WO2005083522A1 - Pattern forming process - Google Patents

Pattern forming process Download PDF

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Publication number
WO2005083522A1
WO2005083522A1 PCT/JP2005/003707 JP2005003707W WO2005083522A1 WO 2005083522 A1 WO2005083522 A1 WO 2005083522A1 JP 2005003707 W JP2005003707 W JP 2005003707W WO 2005083522 A1 WO2005083522 A1 WO 2005083522A1
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WO
WIPO (PCT)
Prior art keywords
pattern forming
process according
forming process
laser
meth
Prior art date
Application number
PCT/JP2005/003707
Other languages
French (fr)
Inventor
Masanobu Takashima
Yuichi Wakata
Hiromi Ishikawa
Yuji Shimoyama
Original Assignee
Fuji Photo Film Co., Ltd.
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 Fuji Photo Film Co., Ltd. filed Critical Fuji Photo Film Co., Ltd.
Publication of WO2005083522A1 publication Critical patent/WO2005083522A1/en

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216Mask projection systems
    • G03F7/70275Multiple projection paths, e.g. array of projection systems, microlens projection systems or tandem projection systems
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • G03F7/2051Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2057Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using an addressed light valve, e.g. a liquid crystal device
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/092Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/107Using laser light

Definitions

  • the present invention relates to pattern forming processes in which laser beams modulated by laser modulators such as spatial light modulators are imaged on pattern forming materials, thereby exposing the pattern forming materials.
  • o Exposing devices have become popular in which lights or laser beams modulated by spatial light modulators and the like are directed to imaging optical systems and optical images are formed on pattern forming materials so as to expose the pattern forming materials.
  • exposing devices are comprised of a spatial light modulator that is equipped with planar arrays of many imaging portions 5 that modulate an incident light or laser beam depending on various controlling signals, a laser source that irradiates a laser beam to the spatial light modulator, and an imaging optical system that forms an image from the modulated laser beam through the spatial light modulator onto a pattern forming material
  • akito Ishikawa "Shortening of Research and Application to Massproduction by Mas less Exposure"
  • o Electronics Jisso Gijyutsu edd.
  • the spatial light modulators include liquid crystal displays (LCD), digital micromiriOr devices (DMD), and the like.
  • the DMD refers to a mirror device that is equipped with planar arrays of many micromirrors as imaging 5 portions that change the reflecting angle depending on the controlling signal.
  • images to be projected on the pattern forming material are often desired to magnify, thus a magnified imaging optical system is utilized as the imaging optical system for responding to such a desire.
  • the means to solely direct the modulated light from the spatial light modulator into the magnified imaging optical system leads to magnify the light flux from the respective imaging portions of the spatial light modulator, resulting in a disadvantage that clearness of pixels decreases due to magnified pixel size within the projected pattern.
  • JP-A 2004-1244 set forth above proposes a magnified projection, wherein a first imaging optical device is on a path of laser beam modulated by the spatial light modulator, an array of microlenses is disposed on the imaging surface of the first imaging optical device, the microlenses respectively correspond to the imaging portions of the spatial light modulator, a second imaging optical device is disposed on the path of laser beam from the array of microlenses that images the modulated light on a pattern forming material or a screen, and images are magnified by the first and the second imaging optical devices.
  • JP-A Nos. 57-21890 and 57-21891 propose processes in which water is sprayed on a substrate then a photosensitive film for o forming a circuit is laminated on the substrate.
  • JP-A No. 52-154363 proposes a process in which a liquid resin is coated on a substrate to form an adhesive intermediate layer, then a photosensitive film for forming a circuit is laminated on the substrate.
  • JP-B Japanese Patent Application Publication
  • 51-63702 propose a laminating process by means of a vacuum laminator under a reduced pressure.
  • the apparatus is expensive and reducing the pressure is time consuming.
  • pattern forming processes have not been provided yet that may 5 form highly fine and precise permanent patterns with sufficient efficiency owing to suppressing deformation of images formed on pattern forming materials as well as employing a pattern forming material that exhibits high conf ormability to nonunif ormity of substrates on which permanent patters are to be formed; and the improvement of such pattern forming processes has been demanded currently.
  • An object of the present invention is to provide pattern forming processes that may form highly fine and precise permanent patterns with sufficient efficiency owing to suppressing deformation of images formed on pattern forming materials as well as employing a pattern forming material that exhibits high conf ormability to nonunif ormity of substrates on which permanent patters are to be formed.
  • the object may be attained by the pattern forming process according to the present invention which comprises modulating a laser beam irradiated from a laser source, compensating the modulated laser beam, and exposing a photosensitive layer in a pattern forming material by means of the modulated and compensated laser beam, wherein the pattern forming material comprises a support, a cushioning layer, and the photosensitive layer in order, the modulating is performed by a laser modulator which comprises plural imaging portions each capable of receiving the laser beam and outputting the modulated laser beam, and the compensating is performed by transmitting the modulated laser beam through plural microlenses each having a non-spherical surface capable of compensating the aberration due to distortion of the output surface of the imaging portion, and the plural microlenses are arranged to a microlens array.
  • the cushioning layer of the pattern forming material may bring about high conf ormability to nonunif ormity of substrate surface on which permanent patters are to be formed.
  • the laser source irradiates the laser beam toward the laser modulator, the laser beam received by the plural imaging portions is modulated through irradiating the laser beam from the imaging portions, the aberration due to distortion of the output surface of the imaging portion is compensated by transmitting the modulated laser beam through plural microlenses and thus the distortion of images formed on the pattern forming material is controlled efficiently. Consequently, exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns.
  • the cushioning layer comprises a thermoplastic resin.
  • the Nicat softening temperature of the thermoplastic resin is 80 °C 5 or less.
  • the cushioning layer is swellable or soluble in an alkaline liquid.
  • the cushioning layer is insoluble in an alkaline liquid.
  • the thickness of the cushioning layer is 5 ⁇ m to 50 ⁇ m.
  • a barrier layer capable of suppressing migration of substances is o formed between the cushioning layer and the photosensitive layer.
  • the barrier layer is soluble or dispersible in water.
  • oxygen gas permeability of the barrier layer is 100 cm 3 /(m 2 - day- atm) or less under a temperature of 23 °C and a relative humidity of 60 %.
  • the barrier layer comprises at least one of vinyl polymers and vinyl copolymers.
  • the thickness of the photosensitive layer is 0.1 to 10 ⁇ m.
  • the pattern forming material is laminated to the substrate while the pattern forming material is being subjected to at least one of heating and pressing, o then the pattern forming material is subjected to the exposing.
  • the non-spherical surface is a toric surface.
  • the laser modulator is capable of controlling a part of the plural imaging portions depending on pattern information. Controlling a part of the plural imaging portions depending on pattern information may result in the modulation of laser beam with higher velocity.
  • the laser modulator is a spatial light modulator, more preferably, the spatial light modulator is a digital micromirror device (DMD).
  • the exposing is performed by a laser beam transmitted through an aperture array.
  • Such exposing by a laser beam transmitted through an aperture array may increase the extinction ratio. Consequently, exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns.
  • the exposing is performed while moving relatively the laser beam and the photosensitive layer. Such exposing while moving relatively the laser beam and the photosensitive layer may lead to exposing with higher velocity.
  • developing the photosensitive layer is performed following the exposing; preferably, forming a permanent pattern is performed following the developing.
  • the permanent pattern is a wiring pattern, and the permanent pattern is formed by means of at least one of etching treatment and plating treatment, which may lead to a highly fine and precise wiring patterns.
  • the laser source is capable of irradiating two or more types of laser beams which are combined with. Such irradiation of two or more types of lasers may lead to exposing with a longer focal depth. Consequently, exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns.
  • the laser source comprises plural lasers, a multimode optical fiber, and a collective optical system which collects the laser beams from the plural lasers into the multimode optical fiber.
  • the photosensitive layer comprises a binder, a polymerizable compound, and a photopolymerization initiator.
  • the binder contains an acidic group.
  • the binder contains a vinyl copolymer.
  • acid value of the binder is 70 mgKOH/g to 250 mgKOH/g.
  • the polymerizable compound comprises a monomer which contains at least one of urethane group and aryl group.
  • the photopolymerization initiator comprises a compound selected from the group consisting of halogenated hydrocarbon derivatives, hexaaryl-biimidazols, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acylphosphine oxides, and metallocenes.
  • the photosensitive layer comprises 10 % by mass to 90 % by mass of binder, 5 % by mass to 60 % by mass of polymerizable compound, and 0.1 % by mass to 30 % by mass of photopolymerization initiator.
  • the support comprises a synthetic resin and is transparent.
  • the support is of an elongated shape.
  • the pattern forming material is of an elongated shape formed by winding into a roll shape.
  • a protective film is formed on the photosensitive layer of the pattern forming material.
  • FIG. 1 is a partially enlarged view that shows exemplarily a construction of a digital micromirror device (DMD).
  • FIG. 2A is a view that explains exemplarily the motion of the DMD.
  • FIG. 2B is a view that explains exemplarily the motion of the DMD.
  • FIG. 3A is an exemplary plan view that shows the exposing beam and the scanning line in the case that the DMD is not inclined.
  • FIG. 3B is an exemplary plan view that shows the exposing beam and the scanning line in the case that the DMD is inclined.
  • FIG. 4A is an exemplary view that shows an available region of the DMD.
  • FIG.4B is an exemplary view that shows another available region of the DMD.
  • FIG. 5 is an exemplary plan view that explains a way to expose a photosensitive layer in one scanning by means of a scanner.
  • FIG. 6A is an exemplary plan view that explains a way to expose a photosensitive layer in plural scannings by means of a scanner.
  • FIG. 6B is another exemplary plan view that explains a way to expose a photosensitive layer in plural scannings by means of a scanner.
  • FIG. 7 is a schematic perspective view that shows exemplarily a pattern forming apparatus.
  • FIG. 8 is a schematic perspective view that shows exemplarily a scanner construction of a pattern forming apparatus.
  • FIG. 9A is an exemplary plan view that shows exposed regions formed on a photosensitive layer.
  • FIG. 9B is an exemplary plan view that shows regions exposed by respective exposing heads.
  • FIG. 10 is a schematic perspective view that shows exemplarily an exposing head containing a laser modulator.
  • FIG. 11 is an exemplary cross section that shows the construction of the exposing head shown in FIG. 10 in the sub-scanning direction along the optical axis.
  • FIG. 12 shows an exemplary controller to control the DMD based on pattern information.
  • FIG. 13A is an exemplary cross section that shows a construction of another exposing head in other connecting optical system along the optical axis.
  • FIG. 13B is an exemplary plan view that shows an optical image projected on an exposed surface when a microlens array is not employed.
  • FIG. 13C is an exemplary plan view that shows an optical image projected on an exposed surface when a microlens array is employed.
  • FIG. 14 is an exemplary view that shows distortion of a reflective surface of a micromirror that constitutes a DMD by means of contour lines.
  • FIG 15A is an exemplary graph that shows height displacement of a micromirror along the X direction.
  • FIG 15B is an exemplary graph that shows height displacement of a micromirror along the Y direction.
  • FIG. 16A is an exemplary front view that shows a microlens array employed in a pattern forming apparatus.
  • FIG. 16B is an exemplary side view that shows a microlens array employed in a pattern forming apparatus.
  • FIG. 17A is an exemplary front view that shows a microlens of a microlens array.
  • FIG. 17B is an exemplary side view that shows a microlens of a microlens array.
  • FIG. 18 A is an exemplary view that schematically shows a laser collecting condition in a cross section of a microlens.
  • FIG. 18B is an exemplary view that schematically shows a laser collecting condition in another cross section of a microlens.
  • FIG. 19A is an exemplary view that shows a simulation of beam diameters near the focal point of a microlens in accordance with the present invention.
  • FIG. 19B is an exemplary view that shows another simulation similar to FIG. 19A in terms of other sites in accordance with the present invention.
  • FIG. 19C is an exemplary view that shows still another simulation similar to FIG. 19A in terms of other sites in accordance with the present invention.
  • FIG. 19D is an exemplary view that shows still another simulation similar to
  • FIG. 19A in terms of other sites in accordance with the present invention.
  • FIG. 20A is an exemplary view that shows a simulation of beam diameters near the focal point of a microlens in a conventional pattern forming process.
  • FIG. 20B is an exemplary view that shows another simulation similar to FIG. 20A in terms of other sites.
  • FIG. 20C is an exemplary view that shows still another simulation similar to FIG. 20 A in terms of other sites.
  • FIG. 20D is an exemplary view that shows still another simulation similar to FIG. 20A in terms of other sites.
  • FIG. 21 is an exemplary plan view that shows another construction of a combined laser source.
  • FIG. 22A is an exemplary front view that shows a microlens of a microlens array.
  • FIG. 22A is an exemplary front view that shows a microlens of a microlens array.
  • FIG. 22B is an exemplary side view that shows a microlens of a microlens array.
  • FIG. 23A is an exemplary view that schematically shows a laser collecting condition in the cross section of the microlens shown in FIG. 22B.
  • FIG. 23B is an exemplary view that schematically shows a laser collecting condition in another cross section of the microlens shown in FIG. 22B.
  • FIG. 24A is an exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation.
  • FIG. 24B is another exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation.
  • FIG. 24C is another exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation.
  • FIG. 24A is an exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation.
  • FIG. 24B is another exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation.
  • FIG. 24C is another exemplary view that
  • FIG. 25 is an exemplary graph that shows an optical quantity distribution of Gaussian distribution without compensation of optical quantity.
  • FIG. 26 is an exemplary graph that shows a compensated optical quantity distribution by an optical system of optical quantity distribution compensation.
  • FIG. 27A (A) is an exemplary perspective view that shows a constitution of a fiber array laser source.
  • FIG. 27A (B) is a partially enlarged view of FIG. 27A (A).
  • FIG. 27 A (C) is an exemplary plan view that shows an arrangement of emitting sites of laser output.
  • FIG. 27A (D) is an exemplary plan view that shows another arrangement of laser emitting sites.
  • FIG. 27B is an exemplary front view that shows an arrangement of laser 5 emitting sites in a fiber array laser source.
  • FIG. 28 is an exemplary view that shows a construction of a multimode optical fiber.
  • FIG. 29 is an exemplary plan view that shows a construction of a combined laser source.
  • FIG. 30 is an exemplary plan view that shows a construction of a laser module.
  • FIG. 31 is an exemplary side view that shows a construction of the laser module shown in FIG. 30.
  • FIG. 32 is a partial side view that shows a construction of the laser module 5 shown in FIG. 30.
  • FIG. 33 is an exemplary perspective view that shows a construction of a laser array.
  • FIG. 34A is an exemplary perspective view that shows a construction of a multi cavity laser.
  • FIG.34B is an exemplary perspective view that shows a multi cavity laser array in which the multi cavity lasers shown in FIG.
  • FIG. 35 is an exemplary plan view that shows another construction of a combined laser source.
  • FIG. 36A is an exemplary plan view that shows still another construction of a5 combined laser source.
  • FIG. 36B is an exemplary cross section of FIG. 36A along the optical axis.
  • FIG. 37A is an exemplary cross section of an exposing device that shows focal depth in the pattern f ori ing process of the prior art.
  • FIG. 37B is an exemplary cross section of an exposing device that shows focal depth in the pattern forming process according to the present invention.
  • the pattern forming process comprises an exposing step, and other steps selected properly.
  • a pattern forming process is provided that comprises modulating a laser beam irradiated from a laser source, compensating the modulated l o laser beam, and exposing a photosensitive layer in a pattern forming material by means of the modulated and compensated laser beam, wherein the pattern forming material comprises a support, a cushioning layer, and the photosensitive layer in order, the modulating is performed by a laser modulator that comprises plural imaging portions each capable of receiving the laser beam and outputting the 15 modulated laser beam, and the compensating is performed by transmitting the modulated laser beam through plural microlenses each having a non-spherical surface capable of compensating the aberration due to distortion of the output surface of the imaging portion, and the plural microlenses are arranged to a microlens array.
  • the laser modulator may be properly selected depending on the application as long as it comprises plural imaging portions.
  • Preferable examples of the laser modulator include a spatial light modulator.
  • Specific examples of the spatial light modulator include a digital micromirror 25 device (DMD), spatial light modulator of micro electro mechanical system type, PLZT element, and liquid crystal shatter; among these, the DMD is preferable.
  • DMD 50 is a mirror device that has lattice arrays of many micromirrors 62, e.g. 1024 x 768, on SRAM cell or memory cell 60 as shown in FIG. 1, wherein each of the micromirrors performs as a imaging portion.
  • micromirror 62 is supported by a pillar.
  • a material having a higher reflectivity such as aluminum is vapor deposited on the surface of the niicromirror.
  • the reflectivity of the micromirrors 62 is 90 % or more; the array pitches in longitudinal and width directions are respectively 13.7 ⁇ m, for example.
  • SRAM cell 60 of a silicon gate CMOS produced by conventional semiconductor memory producing processes is disposed just below each micromirror 62 through a pillar containing a hinge and yoke.
  • the mirror device is entirely constricted as a monolithic body.
  • FIG. 2A indicates the condition that -rucrornirror 62 is inclined + alpha degrees at on state
  • FIG. 2B indicates the condition that micromirror 62 is inclined - alpha degrees at off state.
  • FIG. 1 exemplarily shows a magnified condition of DMD 50 partly in which micromirrors 62 are controlled at an angel of - alpha degrees or + alpha degrees.
  • Controller 302 connected to DMD 50 carries out on-off controls of the respective micromirrors 62.
  • An optical absorber (not shown) is disposed on the way of laser beam B reflected by rnicromirrors 62 at off state.
  • DMD 50 is slightly inclined in the condition that the shorter side presents a pre ⁇ determined angle, e.g. 0.1 to 5 degrees against the sub-scanning direction.
  • FIG. 3A shows scanning traces of reflected laser image or exposing beam 53 by the respective micromirrors when DMD 50 is not inclined;
  • FIG. 3A shows scanning traces of reflected laser image or exposing beam 53 by the respective micromirrors when DMD 50 is not inclined;
  • FIG. 3A shows scanning traces of reflected laser image or exposing beam 53 by the respective micromirrors when DMD
  • 3B shows scanning traces of reflected laser image or exposing beam 53 by the respective micromirrors when DMD 50 is inclined.
  • DMD 50 many micromirrors, e.g. 1024, are disposed in the longer direction to form one array, and many arrays, e.g. 756, are disposed in the shorter direction.
  • the pitch Pi of scanning traces or lines of exposing beam 53 from each micromirror may be reduced than the pitch P 2 of scanning traces or lines of exposing beam 53 without inclining DMD 50, thereby the resolution may be improved remarkably.
  • the inclined angle of DMD 50 is small, therefore, the scanning direction W2 when DMD 50 is inclined and the scanning direction Wi when DMD 50 is not inclined are approximately the same.
  • the process to accelerate the modulation rate of the laser modulator (hereinafter referring to as "high rate modulation") will be explained in the following.
  • the laser modulator is able to control any imaging portions of less than "ft" disposed successively among the imaging portions depending on the pattern information ("ft": an integer of 2 or more). Since there exist a limit in the data processing rate of the laser modulator and the modulation rate per one line is defined with proportional to the utilized imaging portion number, the modulation rate per one line may be increased through only utilizing the imaging portions of less than "ft" disposed successively.
  • the high rate modulation will be explained with reference to figures in the following.
  • the reflected laser beam at the micromirrors of DMD 50 being on state, is imaged on pattern forming material 150 by lens systems 54, 58.
  • the laser beam irradiated from the fiber array laser source is turned into on or off by the respective imaging portions, and the pattern forming material 150 is exposed in approximately the same number of imaging portion units or exposing areas 168 as the imaging portions utilized in DMD 50.
  • micromirrors are disposed on DMD 50 as 1024 arrays in the main-scanning direction and 768 arrays in sub-scanning direction as shown in FIGs. 4A and 4B.
  • a part of rmcromirrors e.g. 1024 x 256, may be controlled and driven by controller 302.
  • the micromirror arrays disposed at the central area of DMD 50 may be employed as shown in FIG.4A; alternatively, the micromirror arrays disposed at the edge portion of DMD 50 may be employed as shown in FIG. 4B.
  • the utilized micromirrors may be properly altered depending on the situations such that micromirrors with no damage are utilized. Since there exist a limit in the data processing rate of DMD 50 and the modulation rate per one line is defined with proportional to the utilized imaging portion number, partial utilization of micromirror arrays leads to higher modulation rate per one line.
  • the entire imaging portions are not necessarily required in the sub-scanning direction.
  • the stage 152 returns to the original site at the most upstream of gate 160 along guide 158, and the stage 152 is moved again from upstream to downstream of gate 160 along guide 158 at a constant rate.
  • the modulation rate may be enhanced two times compared to utilizing all of 768 arrays; further, when 256 arrays are utilized among the 768 arrays of micromirrors, the modulation rate may be enhanced three times compared to utilizing all of 768 arrays.
  • DMD 50 is provided with 1024 micromirror arrays in the mam-scanning direction and 768 micromirror arrays in the sub-scanning direction, controlling and driving of partial micromirror arrays may lead to higher modulation rate per one line compared to controlling and driving of entire micromirror arrays.
  • elongated DMD on which many micromirrors are disposed on a substrate in planar arrays may increase similarly the modulation rate when the each angle of reflected surface is changeable depending on the various controlling signals, and the substrate is longer in a specific direction than its perpendicular direction.
  • the exposing is performed while moving relatively the exposing laser and the thermosensitive layer; more preferably, the exposing is combined with the high rate modulation set forth before, thereby exposing may be carried out with higher rate in a shorter period.
  • pattern forming material 150 may be exposed on the entire surface by one scanning of scanner 162 in X direction; alternatively, as shown in FIGs.
  • pattern forming material 150 may be exposed on the entire surface by repeated plural exposing such that pattern forming material 150 is scanned in X direction by scanner 162, then the scanner 162 is moved one step in Y direction, followed by scanning in X direction.
  • scanner 162 comprises eighteen exposing heads 166; each exposing head comprises a laser source and the laser modulator. The exposure is performed on a partial region of the photosensitive layer, thereby the partial region is hardened, followed by un-hardened region other than the partial hardened region is removed in developing step as set forth later, thus a pattern is formed.
  • a pattern forming apparatus comprising the laser modulator will be exemplarily explained with reference to figures in the following.
  • the pattern forming apparatus comprising the laser modulator is equipped with flat stage 152 that absorbs and sustains sheet-like pattern forming material 150 on the surface.
  • Stage 152 is disposed such that the elongated direction faces the stage moving direction, and supported by guide 158 in reciprocally movable manner.
  • a driving device is equipped with the pattern forming apparatus (not shown) so as to drive stage 152 along guide 158.
  • gate 160 is provided such that the gate 160 strides the path of stage 152.
  • the respective ends of gate 160 are fixed to both sides of table 156.
  • Scanner 162 is provided at one side of gate 160, plural (e.g.
  • scanner 162 comprises plural (e.g. fourteen) exposing heads 166 that are arrayed in substantially matrix of "m rows x n lines" (e.g. three x five). In this example, four exposing heads 166 are disposed at third line considering the width of pattern forming material 150.
  • the specific exposing head at "m" th row and "ft" th line is expressed as exposing head 166mn hereinafter.
  • the exposing area 168 by exposing head 166 is rectangular having the shorter side in the sub-scanning direction. Therefore, exposed areas 170 are formed on pattern forming material 150 of a band shape that corresponds to the respective exposing heads 166 along with the movement of stage 152.
  • the specific exposing area corresponding to the exposing head at "m” th row and "n" th line is expressed as exposing area 168mn hereinafter. As shown in FIGs.
  • each of the exposing heads at each line is disposed with a space in the line direction (space: (longer side of exposing area) x natural number; two times in this example) so that exposed regions 170 of band shape are arranged without space in the perpendicular direction to the sub-scanning direction. Therefore, the non-exposing area between exposing area I68 1 1 and I6812 at the first raw can be exposed by exposing area I6821 of the second raw and exposing area I6831 of the third raw.
  • Each of exposing heads I6611 to 166mn comprises a digital micromirror device (DMD) 50 (by US Texas Instruments Inc.) as a laser modulator or spatial light modulator that modulates the incident laser beam depending on the pattern information as shown in FIGs. 10 and 11.
  • DMD 50 is connected to controller 302 that comprises a data processing part and a mirror controlling part as shown in FIG. 12.
  • controller 302 The data processing part of controller 302 generates controlling signals to control and drive the respective micromirrors in the areas to be controlled for the respective exposing heads 166, based on the input pattern information.
  • the area to be controlled will be explained later.
  • the mirror driving-controlling part controls the reflective surface angle of each micromirror of DMD 50 per each exposing head 166 based on the control signals generated at the pattern information processing part.
  • the control of the reflective surface angle will be explained later.
  • fiber array laser source 66 that is equipped with a laser irradiating part where irradiating ends or en itting sites of optical fibers are arranged in an array along the direction corresponding with the longer side of exposing area 168, lens system 67 that compensate the laser beam from fiber array laser source 66 and collect it on the DMD, and mirrors 69 that reflect laser beam through lens system 67 toward DMD 50 are disposed in this order.
  • FIG. 10 schematically shows lens system 67.
  • Lens system 67 is comprised of collective lens 71 that collects laser beam B for illumination from fiber array laser source 66, rod-like optical integrator 72 (hereinafter, referring to as "rod integrator") inserted on the optical path of the laser passed through collective lens 71, and image lens 74 disposed in front of rod integrator 72 or the side of mirror 69, as shown FIG. 11.
  • rod integrator rod-like optical integrator 72
  • image lens 74 disposed in front of rod integrator 72 or the side of mirror 69, as shown FIG. 11.
  • Collective lens 71, rod integrator 72, and image lens 74 make the laser beam irradiated from fiber array laser source 66 enter into DMD 50 as an luminous flux of approximately parallel beam with uniform intensity in the cross section. The shape and effect of the rod 5 integrator will be explained in detail later.
  • Laser beam B irradiated from lens system 67 is reflected by mirror 69, and is irradiated to DMD 50 through a total internal reflection prism 70 (not shown in FIG. 10).
  • imaging system 51 is disposed that images o laser beam B reflected by DMD 50 onto pattern forming material 150.
  • the imaging system 51 is equipped with the first imaging system of lens systems 52, 54, the second imaging system of lens systems 57, 58, and microlens array 55 and aperture array 59 interposed between these imaging systems as shown in FIG. 11.
  • Arranging two-dimensionally many microlenses 55a each corresponding to 5 the respective imaging portions of DMD 50 forms Microlens array 55.
  • micromirrors of 1024 rows x 256 lines among 1024 rows x 768 lines of DMD 50 are driven, therefore, 1024 rows x 256 lines of microlenses are disposed correspondingly.
  • the pitch of disposed microlenses 55a is 41 ⁇ m in both of raw and line directions.
  • Microlenses 55a have a focal length of 0.19 mm and a numerical o aperture (NA) of 0.11 for example, and are formed of optical glass BK7. The shape of microlenses will be explained later.
  • the beam diameter of laser beam B is 41 ⁇ m at the site of microlens 55a.
  • Aperture array 59 is formed of many apertures 59a each corresponding to the respective microlenses 55a of microlens array 55.
  • the diameter of aperture 59a is 10 5 ⁇ m, for example.
  • the first imaging system forms the image of DMD 50 on microlens array 55 as a three times magnified image.
  • the second imaging system forms and projects the image through microlens array 55 on pattern forming material 150 as a 1.6 times magnified image. Therefore, the image by DMD 50 is formed and projected on pattern forming material 150 as a 4.8 times magnified image.
  • prism pair 73 is installed between the second imaging system and pattern forming material 150; through the operation to move up and down the prism pair 73, the image pint may be adjusted on the image forming material 150.
  • pattern forming material 150 is fed to the direction of arrow F as sub-sca-nning.
  • the imaging portions may be properly selected depending on the application provided that the imaging portions can receive the laser beam from the laser source or irradiating means and can output the laser beam; for example, the imaging o portions are pixels when the pattern formed by the pattern forming process according to the present invention is an image pattern, alternatively the imaging portions are micromirrors when the laser modulator contains a DMD.
  • the number of imaging portions contained in the laser modulator may be properly selected depending on the application. 5
  • the alignment of imaging portions in the laser modulator may be properly selected depending on the application; preferably, the imaging portions are arranged two dimensionally, more preferably are arranged in a lattice pattern.
  • microlens array may be properly selected depending on the application, o provided that microlenses have a non-spherical surface capable of compensating the aberration due to strain at irradiating surface of the imaging portion.
  • the non-spherical surface may be properly selected depending on the application; preferably, the non-spherical surface is toric surface, for example.
  • the microlens array, aperture array, imaging system set forth above will be 5 explained with reference to figures. FIG.
  • FIG. 13 A shows an exposing head that is equipped with DMD 50, laser source 144 to irradiate laser beam onto DMD 50, lens systems or imaging optical systems 454 and 458 that magnify and image the laser beam reflected by DMD 50, microlens array 472 that arranges many microlenses 474 corresponding to the respective imaging portions of DMD 50, aperture array that aligns many apertures 478 corresponding to the respective microlenses of microlens array 472, and lens systems or imaging systems 480 and 482 that image laser beam through the apertures onto exposed surface 56.
  • FIG. 14 shows the flatness data as to the reflective surface of irricromirrors 62 of DMD 50.
  • contour lines express the respective same heights of the reflective surface; the pitch of the contour lines is five nano meters.
  • X direction and Y direction are two diagonal directions of micromirror 62, the micromirror 62 rotates around the rotation axis extending in Y direction.
  • FIGs. 15A o and 15B show the height displacements of micromirrors 62 along the X and Y directions respectively. As shown in FIG. 14, FIGs. 15A and 15B, there exist strains on the reflective surface of micromirror 62, the strains of one diagonal direction (Y direction) is larger than another diagonal direction (X direction) at the central region of the mirror in 5 particular.
  • FIGs. 16A and 16B show the front shape and side shape of the entire o microlens array 55 in detail. In FIGs. 16A and 16B, various parts of the microlens array are indicated as the unit of mm (millimeter).
  • micromirrors of 1024 rows x 256 lines of DMD 50 are driven as explained above; microlens array 55 are correspondingly constructed as 1024 arrays in length direction and 256 arrays in width direction.
  • FIG. 16A the 5 site of each microlens is expressed as ")" th line and "k" th row.
  • FIGs. 17A and 17B show respectively the front shape and side shape of one microlens 55a of microlens array 55.
  • FIG. 17A shows also the contour lines of microlens 55a.
  • the end surface of each microlens 55a of irradiating side is of non-spherical shape to compensate the strain aberration of reflective surface of micromirrors 62.
  • microlens 55a is a toric lens; the curvature radius of optical X direction Rx is - 0.125 mm, and the curvature radius of optical Y direction Ry is - 0.1 mm. Accordingly, the collecting condition of laser beam B within the cross section 5 parallel to the X and Y directions are approximately as shown in FIGs. 18A and 18B respectively. Namely, comparing the X and Y directions, the curvature radius of microlens 55a is shorter and the focal length is also shorter in Y direction.
  • FIGs. 19A, 19B, 19C, and 19D show the simulations of beam diameter near the focal point of microlens 55a in the above noted shape by means of a computer. l o For the reference, FIGs.
  • the values of "z" in the figures are expressed as the evaluation sites in the focus direction of microlens 55a by the distance from the beam irradiating surface of microlens 55a.
  • the surface shape of microlens 55a in the simulation may be calculated by 15 the following equation.
  • X means the distance from optical axis O in X direction
  • Y means the distance from optical axis O in Y direction.
  • Aperture arrays 59 disposed near the collecting site of microlens array 55 are constructed such that each aperture 59a receives only the laser beam through the corresponding microlens 55a.
  • aperture array 59 may afford the respective apertures with the insurance that the light incidence from the adjacent apertures 55a may be prevented and the extinction ratio may be enhanced.
  • smaller diameter of apertures 59a provided for the above noted purpose may afford the effect to reduce the strain of beam shape at the collecting site of microlens 55a.
  • such a construction inevitably increases the optical quantity interrupted by the aperture array 59, resulting in lower efficiency of optical quantity.
  • the non-spherical shape of microlenses 55a does not bring about the light interruption, thus leading to maintain the higher efficiency of optical quantity.
  • the microlenses 55a may be non-spherical shape of secondary or higher order such as fourth or sixth.
  • the employment of higher order non-spherical surface may lead to higher accuracy of beam shape.
  • the end surface of irradiating side of microlens 55a is non-spherical or toric; alternatively, substantially the same effect may be derived by constructing one of the end surface as a spherical surface and the other surface as cylindrical surface and thus providing the microlens.
  • microlens 55a of microlens array 55 is non-spherical so as to compensate the aberration due to the strain of reflective surface of micromirror 62; alternatively, substantially the same effect may be derived by providing each microlens of the microlens array with the distribution of refractive index so as to compensate the aberration due to the strain of reflective surface of micromirror 62.
  • FIGs. 22A and 22B show exemplarily such a microlens 155a.
  • FIGs. 22B respectively show the front shape and side shape of microlens 155a.
  • the entire shape of microlens 155a is a planar plate as shown in FIGs.22A and 22B.
  • the X and Y directions in FIGs. 22A and 22B mean the same as set forth above.
  • FIGs. 23A and 23B schematically show the condition to collect laser beam B by microlens 155a in the cross section parallel with X and Y directions respectively.
  • the microlens 155a exhibits a refractive index distribution that the refractive index increases gradually from the optical axis O to outward direction; the broken lines in FIGs. 23A and 23B indicate the positions where the refractive index decreases a certain level from that of optical axis O. As shown in FIGs.
  • the microlens array having such a refractive index distribution may provide the similar effect as the microlens array 55 set forth above.
  • the microlens having a non-spherical surface as shown in FIGs. 17A, 17B, 18A and 18B may be provided with such a refractive index distribution, and both of the surface shape and the refractive index distribution may compensate the aberration due to strain of the reflective surface of micromirror 62.
  • the aberration due to strain of reflective surface of micromirror 62 in DMD 50 is compensated; similarly, in the pattern forming process according to the present invention that employs a spatial light modulator other than DMD, the possible aberration due to strain may be compensated and the strain of beam shape may be prevented when the strain appears at the surface of imaging portion of the spatial light modulator.
  • the imaging optical system set forth above will be explained in the following. In the exposing head, when laser beam is irradiated from the laser source 144, the cross section of luminous flux reflected to on-direction by DMD 50 is magnified several times, e.g. two times, by lens systems 454, 458.
  • the magnified laser beam is collected by each microlens of microlens array 472 correspondingly with each imaging portion of DMD 50, then passes through the corresponding apertures of aperture array 476.
  • the laser beam passed through the aperture is imaged on exposed surface 56 by lens systems 480, 482.
  • the laser beam reflected by DMD 50 is magnified into several times by magnifying lenses 454, 458, and is projected onto exposed surface 56, therefore, the entire image region is enlarged.
  • each beam spot BS projected on exposed surface 56 is enlarged depending on the size of exposed area 468, thus MTF (modulation transfer function) property that is a measure of sharpness at exposing area 468 is decreased, as shown in FIG. 13B.
  • MTF modulation transfer function
  • the spot size of each beam spot BS may be reduced into the desired size, e.g. 10 ⁇ m x 10 ⁇ m, even when the exposing area is magnified, as shown in FIG.
  • the decrease of MFT property may be prevented and the exposure may be carried out with higher accuracy.
  • inclination of exposing area 468 is caused by the DMD 50 that is disposed with inclination in order to eliminate the spaces between imaging portions.
  • the beam shape may be arranged by the aperture array so as to form spots on exposed surface 56 with a constant size, and the crosstalk between the adjacent imaging portions may be prevented by passing the beam through the aperture array provided correspondingly to each imaging portion.
  • laser source 144 may lead to prevention of partial entrance of luminous flux from adjacent imaging portions, since the angle of incident luminous flux is narrowed that enters into each microlens of microlens array 472 from lens 458; namely, higher extinction ratio may be achieved.
  • the other optical system may be combined that is properly selected from conventional systems, for example, an optical system to compensate the optical quantity distribution may be employed additionally.
  • the optical system to compensate the optical quantity distribution alters the luminous flux width at each output site such that the ratio of the luminous flux width at the periphery region to the luminous flux width at the central region near the optical axis is higher in the output side than the input side, thus the optical quantity distribution at the exposed surface is compensated to be approximately constant when the parallel luminous flux from the laser source is irradiated to DMD.
  • the optical system to compensate the optical quantity distribution will be explained with reference to figures in the following.
  • the optical system will be explained as for the case that the entire luminous flux widths HO and HI are the same between the input luminous flux and the output luminous flux, as shown in FIG. 24A.
  • the portions denoted by reference numbers 51, 52 in FIG. 24A indicate imaginarily the input surface and output surface of the optical system to compensate the optical quantity distribution.
  • the optical system to compensate the optical quantity distribution affects the laser beam that has the same luminous fluxes hO, hi at the input side, and acts to magnify the luminous flux width hO for the input luminous flux at the central region, and acts to reduce the luminous flux width hi for the input luminous flux at the periphery region conversely. Namely, the optical system affects the output luminous flux width hlO at the central region and the output luminous flux width hll at the periphery region to turn into 5 hll ⁇ hlO.
  • the luminous flux at the central o region representing higher optical quantity may be supplied to the periphery region where the optical quantity is insufficient; thereby the optical quantity distribution is approximately uniformed at the exposed surface without decreasing the utilization efficiency.
  • the level for uniformity is controlled such that the nonuniformity of optical quantity is 30 % or less in the effective region for example, preferably is 20 %5 or less.
  • FIG. 24B shows the case that the entire optical flux bundle HO is reduced and o outputted as optical flux bundle H2 (HO > H2).
  • the optical system to compensate the optical quantity distribution tends to process the laser beam, in which luminous flux width hO is the same as hi at input side, into that the luminous flux width hlO at the central region is larger than the spherical region and the luminous flux width hll is smaller than the central region in the output side.
  • the optical system affects to decrease the reduction ratio of input luminous flux at the central region compared to the peripheral region, and affects to increase the reduction ratio of input luminous flux at the peripheral region compared to the central region.
  • FIG. 24C explains the case that the entire luminous flux width HO at input side is magnified and output into width H3 (HO ⁇ H3).
  • the 5 optical system to compensate the optical quantity distribution tends to process the laser beam, in which luminous flux width hO is the same as hi at input side, into that the luminous flux width hlO at the central region is larger than the spherical region and the luminous flux width hll is smaller than the central region in the output side.
  • the optical system affects to o increase the magnification ratio of input luminous flux at the central region compared to the peripheral region, and affects to decrease the magnification ratio of input luminous flux at the peripheral region compared to the central region.
  • the optical system to compensate the optical quantity distribution alters the luminous flux width at each input site, and lowers the ratio (output luminous flux width at periphery region) / (output luminous flux width at central region) at output side compared to the input side; therefore, the laser beam having o the same luminous flux turns into the laser beam at output side that the luminous flux width at central region is larger compared to that at the peripheral region and the luminous flux at the peripheral region is smaller compared to the central region.
  • the luminous flux at the central region may be supplied to the periphery region, thereby the optical quantity distribution is approximately 5 uniformed at the luminous flux cross section without decreasing the utilization efficiency of the entire optical system.
  • lens data of a pair of combined lenses will be set forth exemplarily that is utilized for the optical system to compensate the optical quantity distribution.
  • the lens data will be explained in the case that the optical quantity distribution shows Gaussian distribution at the cross section of the output luminous flux, such as the case that the laser source is a laser array as set forth above.
  • the optical quantity distribution of output luminous flux from the optical fiber shows Gaussian distribution.
  • the pattern forming process according to the present invention may be applied, in addition, to such a case that the optical quantity near the central region is significantly larger than the optical quantity at the peripheral region as the case that the core diameter of multimode optical fiber is reduced and constructed similarly to a single mode optical fiber, for example.
  • Table 1 The essential data for the lens are summarized in Table 1 below. Table 1
  • a pair of combined lenses is constructed from two non-spherical lenses of rotational symmetry.
  • the surfaces of the lenses are defined that the surface of input side of the first lens disposed at the light input side is the first surface; the opposite surface at light output side is the second surface; the surface of input side of the second lens disposed at the light input side is the third surface; and the opposite surface at light output side is the fourth surface.
  • the first and the fourth surfaces are non-spherical.
  • the non-spherical data set forth above may be expressed by means of the coefficients of the following equation (A) that represent the non-spherical shape.
  • FIG. 26 shows the optical quantity distribution of illumination light obtained by a pair of combined lenses shown in Table 1 and Table 2.
  • FIG. 25 shows the optical quantity distribution (Gaussian distribution) of illumination light without the compensation.
  • the compensation by means of the optical system to compensate the optical quantity distribution brings about an approximately uniform optical quantity distribution significantly exceeding that without the compensation, thus uniform exposing may be achieved by means of uniform laser beam without decreasing the optical utilization efficiency.
  • optical irradiating Means may be properly selected depending on the application; examples thereof include an extremely high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, fluorescent tube, LED, semiconductor laser, and the other conventional laser source, and also combination of these means.
  • the means capable of irradiating two or more types of lights or laser beams is preferable.
  • the light or laser beam irradiated from the optical irradiating means or laser source include UV-rays, visual light, X-ray, laser beam, and the like.
  • laser beam is preferable, more preferably are those containing two or more types of laser beams (hereinafter, sometimes referring to as "combined laser").
  • the wavelength of the UV-rays and the visual light is preferably 300 to 1500 nm, more preferably is 320 to 800 ran, most preferably is 330 to 650 nm.
  • the wavelength of the laser beam is preferably 200 to 1500 nm, more preferably is 300 to 800 nm, still more preferably is 330 to 500 nm, and most preferably is 400 to 450 nm.
  • a means to irradiate the combined laser such a means is preferably exemplified that comprises plural laser irradiating devices, a multimode optical fiber, and a collecting optical system that collect a respective laser beams and connect them to a multimode optical fiber.
  • the means to irradiate combined laser or the fiber array laser source will be explained with reference to figures in the following.
  • Fiber array laser source 66 is equipped with plural (e.g. fourteen) laser modules 64 as shown in FIG.27A.
  • each multimode optical fiber 30 is connected to each laser module 64.
  • the ends of multimode optical fibers 31 at the opposite end of multimode optical fiber 30 are aligned as seven ends along the main scanning direction perpendicular to the sub-scanning direction, and the seven ends are aligned as two rows, thereby laser output portion 68 is constructed.
  • the laser output portion 68, formed of the ends of multimode optical fibers 31, is fixed by being interposed between two flat support plates 65 as shown in FIG.
  • a transparent protective plate such as a glass plate is disposed on the output end surface of multimode optical fibers 31 in order to protect the output end surface.
  • the output end surface of multimode optical fibers 31 tends to bear dust and to degrade due to its higher optical density; the protective plate set forth above may prevent the dust deposition on the end surface and may retard the degradation.
  • multimode optical fiber 30 is stacked between two multimode optical fibers 30 that contact at the larger clad diameter, and the output end of optical fiber 31 connected to the stacked multimode optical fiber 30 is interposed between two output ends of optical fibers 31 connected to two multimode optical fibers 30 that contact at the larger clad diameter.
  • Such optical fibers may be produced by connecting concentrically optical 5 fibers 31 having a length of 1 to 30 cm and a smaller clad diameter to the tip portions of laser beam output side of multimode optical fiber 30 having a larger clad diameter, for example, as shown in FIG. 28.
  • Two optical fibers are connected such that the input end surface of optical fiber 31 is fused to the output end surface of multimode optical fiber 30 so as to coincide the center axises of the two optical fibers.
  • the o diameter of core 31a of optical fiber 31 is the same as the diameter of core 30a of multimode optical fiber 30 as set forth above.
  • a shorter optical fiber produced by fusing an optical fiber having a smaller clad diameter to an optical fiber having a shorter length and a larger clad diameter may be connected to the output end of multimode optical fiber through a 5 ferrule, optical connector or the like.
  • Optical fiber 31 is sometimes referred to as "output end o portion" of multimode optical fiber 30.
  • Multimode optical fiber 30 and optical fiber 31 may be any one of step index type optical fibers, grated index type optical fibers, and combined type optical fibers.
  • step index type optical fibers produced by Mitsubishi Cable Industries, Ltd. are available.
  • Laser beams at infrared region typically increase the propagation loss while the clad diameter of optical fibers decreases. Accordingly, a proper clad diameter is defined usually depending on the wavelength region of the laser beam.
  • the clad diameter of optical fiber utilized for conventional fiber array laser sources is 125 ⁇ m; the smaller is the clad diameter, the deeper is the focal depth; 5 therefore, the clad diameter of the multimode optical fiber is preferably 80 ⁇ m or less, more preferably is 60 ⁇ m or less, still more preferably is 40 ⁇ m or less.
  • the clad diameter of optical fiber 31 is preferably 10 ⁇ m or more.
  • Laser module 64 is constructed from the combined laser source or the fiber o array laser source as shown in FIG. 29. The combined laser source is constructed from plural (e.g.
  • the number of semiconductor lasers is not limited to seven. 5
  • GaN semiconductor lasers LD1 to LD7 have a common oscillating wavelength e.g.
  • the GaN semiconductor lasers LD1 to LD7 may be those having an oscillating wavelength of other than 405 nm as long as within the wavelength of 350 to 450 nm.
  • the combined laser source is housed into a box package 40 having an upper opening with other optical elements as shown in FIGs. 30 and 31.
  • the package 40 is equipped with package lid 41 for shutting the opening. Introduction of sealing gas after evacuating procedure and shutting the opening of package 40 by means of package lid 41 presents a closed space or sealed volume constructed by package 40 and package lid 41, and the combined laser source is disposed in a sealed condition.
  • Base plate 42 is fixed on the bottom of package 40; the heat block 10, collective lens holder 45 to support collective lens 20, and fiber holder 46 to support the input end of multimode optical fiber 30 are mounted to the upper surface of the base plate 42.
  • the output end of multimode optical fiber 30 is drawn out of the package from the aperture provided at the wall of package 40.
  • Collimator lens holder 44 is attached to the side wall of heat block 10, and collimator lenses 11 to 17 are supported thereby.
  • An aperture is provided at the side wall of package 40, and wiring 47 that supplies driving power to GaN semiconductor lasers LD1 to LD7 is directed through the aperture out of the package.
  • FIG.31 only the GaN semiconductor laser LD7 is indicated with a reference mark among plural GaN semiconductor laser, and only the collimator lens 17 is indicated with a reference number among plural collimators, in order not to make the figure excessively complicated.
  • FIG.32 shows a front shape of attaching part for collimator lenses 11 to 17.
  • Each of collimator lenses 11 to 17 is formed into a shape that a circle lens containing a non-spherical surface is cut into an elongated piece with parallel planes at the region containing the optical axis.
  • the collimator lens with the elongated shape may be produced by a molding process.
  • the collimator lenses 11 to 17 are closely disposed in the aligning direction of emitting points such that the elongated direction is perpendicular to the alignment of the emitting points of GaN semiconductor lasers LD1 to LD7.
  • the following laser may be employed that comprises an active layer having an emitting 5 width of 2 ⁇ m and emits the respective laser beams Bl to B7 at a condition that the divergence angle is 10 degrees and 30 degrees for the parallel and perpendicular directions against the active layer.
  • the GaN semiconductor lasers LD1 to LD7 are disposed such that the emitting sites align as one line in parallel to the active layer.
  • laser beams Bl to B7 emitted from the respective emitting sites o enter into the elongated collimator lenses 11 to 17 in a condition that the direction having a larger divergence angle coincides with the length direction of each collimator lens and the direction having a less divergence angle coincides with the width direction of each collimator lens.
  • the width is 1.1 mm and the length is 4.6 mm with respect to respective collimator lenses 11 to 17, and the beam diameter5 is 0.9 mm in the horizontal direction and is 2.6 mm in the vertical direction with respect to laser beams Bl to B7 that enter into the collimator lenses.
  • Collective lens 20 formed into a shape that a part of circle lens containing the 0 optical axis and non-spherical surface is cut into an elongated piece with parallel planes and is arranged such that the elongated piece is longer in the direction of disposing collimator lens 11 to 17 i.e. horizontal direction, and is shorter in the perpendicular direction.
  • the collective lens 20 may be produced by molding a resin or optical glass, for5 example.
  • a pattern forming apparatus may be attained that exhibits a higher output and a deeper focal depth.
  • the higher output of the respective fiber array laser sources may lead to less number of fiber array laser sources required to take a necessary output as well as a lower cost of the pattern forming apparatus.
  • the clad diameter at the output ends of the optical fibers is 5 smaller than the clad diameter at the input ends, therefore, the diameter at emitting sites is reduced still, resulting in higher luminance of the fiber array laser source. Consequently, pattern forming apparatuses with a deeper focal depth may be achieved.
  • the pattern forming apparatus is appropriate for the exposure of thin film transistor (TFT) that requires high resolution.
  • the illumination means is not limited to the fiber array laser source that is equipped with plural combined laser sources; for example, such a fiber array laser5 source may be employed that is equipped with one fiber laser source, and the fiber laser source is constructed by one arrayed optical fiber that outputs a laser beam from one semiconductor laser having an emitting site. Further, as for the illumination means having plural emitting sites, such a laser array may be employed that comprises plural (e.g.
  • multi cavity laser 110 comprises plural (e.g. five) emitting sites 110a disposed in a certain direction as shown in FIG. 34A.
  • the emitting sites can be arrayed with higher dimensional accuracy compared to arraying tip-like semiconductor lasers, thus laser beams emitted from 5 the respective emitting sites can be easily combined.
  • the number of emitting sites 110a is five or less, since deflection tends to generate on multi cavity laser 110 at the laser production process when the number increases.
  • the multi cavity laser 110 set forth above, or the multi cavity array disposed such that plural multi cavity lasers 110 are arrayed in the same direction as emitting sites 110a of each tip as shown in FIG.34B may be employed for the laser source.
  • the combined laser source is not limited to the types that combine plural laser beams emitted from plural tip-like semiconductor lasers.
  • such a combined laser source is available that comprises tip-like multi cavity laser 110 having plural (e.g. three) emitting sites 110a as shown in FIG. 21.
  • the combined laser source is equipped with multi cavity laser 110, one multimode optical fiber 130, and collecting lens 120.
  • the multi cavity laser 110 may be constructed from GaN laser diodes having an oscillating wavelength of 405 nm, for example.
  • each laser beam B emitted from each of plural emitting sites 110a of multi cavity laser 110 is collected by collective lens 120 and enters into core 130a of multimode optical fiber 130.
  • the laser beams entered into core 130a propagate inside the optical fiber and combine as one laser beam then output from the optical fiber.
  • the connection efficiency of laser beam B to multimode optical fiber 130 may be enhanced by way of arraying plural emitting sites 110a of multi cavity laser 110 into a width that is approximately the same as the core diameter of multimode optical fiber 130, and employing a convex lens having a focal length of approximately the same as the core diameter of multimode optical fiber 130, and also employing a rod lens that collimates the output beam from multi cavity laser 110 at only within the surface perpendicular to the active layer.
  • a combined laser source may be employed that is equipped with laser array 140 formed by arraying on heat block 111 plural (e.g. nine) multi cavity lasers 110 with an identical space between them by employing multi cavity lasers 110 equipped with plural (e.g. three) emitting sites.
  • the plural multi cavity lasers 110 are arrayed and fixed in the same direction as emitting sites 110a of the respective tips.
  • the combined laser source is equipped with laser array 140, plural lens arrays 114 that are disposed correspondingly to the respective multi cavity lasers 110, one rod lens 113 that is disposed between laser array 140 and plural lens arrays 114, one multimode optical fiber 130, and collective lens 120.
  • Lens arrays 114 are equipped with plural micro lenses each corresponding to emitting sites of multi cavity lasers 110. 5
  • laser beams B that are emitted from plural ermtting sites 110a of plural multi cavity lasers 110 are collected in a certain direction by rod lens 113, then are paralleled by the respective microlenses of microlens arrays 114.
  • the paralleled laser beams L are collected by collective lens 120 and are inputted into core 130a of multimode optical fiber 130.
  • the laser beams entered into o core 130a propagate inside the optical fiber and combine as one beam then output from the optical fiber.
  • Another combined laser source will be exemplified in the following.
  • heat block 182 having a cross section of L-shape in the optical axis direction is installed on rectangular heat block 180 as shown in FIGs. 36A and 5 36B, and a housing space is formed between the two heat blocks.
  • plural (e.g. two) multi cavity lasers 110 in which plural (e.g. five) emitting sites are arrayed, are disposed and fixed each with an identical space between them in the same direction as the aligning direction of respective tip-like emitting sites.
  • a concave portion is provided on the rectangular heat block 180; plural (e.g. two) multi cavity lasers 110 are disposed on the upper surface of heat block 180, plural emitting sites (e.g.
  • collimate lens arrays 184 are disposed such that collimate lenses are arrayed correspondingly with the emitting sites 110a of the respective tips.
  • the length direction of each collimate lens coincides with the direction at which the laser beam represents wider divergence angle or the fast axis direction
  • the width direction of each collimate lens coincides with the direction at which the laser beam represents less divergence angle or the slow axis direction.
  • the integration by arraying the collimate lenses may increase the space efficiency of laser beam, thus the output power of the combined laser source may be enhanced, and also the number of parts may be reduced, resulting advantageously in lower production cost.
  • collimate lens arrays 184 disposed are one multimode optical fiber 130 and collective lens 120 that collects laser beams at the input end of multimode optical fiber 130 and combines them.
  • the respective laser beams B emitted from the respective emitting sites 110a of plural multi cavity lasers 110 disposed on laser blocks 180, 182 are paralleled by collimate lens array, are collected by collective lens 120, then enter into core 130a of multimode optical fiber 130.
  • the laser beams entered into core 130a propagate inside the optical fiber and combine as one beam then output from the optical fiber.
  • the combined laser source may be made into a higher output power source by multiple arrangement oi the multi cavity lasers and the array of collimate lenses in particular.
  • the combined laser source allows to construct a fiber array laser source and a bundle fiber laser source, thus is appropriate for the fiber laser source to construct the laser source of the pattern forming apparatus in the present invention.
  • a laser module may be constructed by housing the respective combined laser sources into a casing, and drawing out the output end of multimode optical fiber 130.
  • the higher luminance of fiber array laser source is exemplified that the output end of the multimode optical fiber of the combined laser source is connected to another optical fiber that has the same core diameter as that of the multimode optical fiber and a clad diameter smaller than that of the multimode optical fiber; alternatively a multimode optical fiber having a clad diameter of 125 ⁇ m, 80 ⁇ m, 60 ⁇ m or the like may be utilized without connecting another optical fiber at the output end, for example.
  • the pattern forming process according to the present invention will be explained further. As shown in FIG.
  • the respective laser beams Bl, B2, B3, B4, B5, B6, and B7, emitted from GaN semiconductor lasers LDl to LD 7 that constitute the combined laser source of fiber array laser source 66, are paralleled by the corresponding collimator lenses 11 to 17.
  • the paralleled laser beams Bl to B7 are collected by collective lens 20, and converge at the input end surface of core 30a of multimode optical fiber 30.
  • the collective optical system is constructed from collimator lenses 11 to 17 and collective lens 20, and the combined optical system is constructed from the collective optical system and multimode optical fiber 30.
  • laser beams Bl to B7 that are collected by collective lens 20 enter into core 30a of multimode optical fiber 30 and propagate inside the optical fiber, combine into one laser beam B, then output from optical fiber 31 that is connected at the output end of multimode optical fiber 30.
  • Laser emitting portions 68 of fiber array source 66 are arrayed such that the higher luminous emitting sites are aligned along the main scanning direction.
  • the conventional fiber laser source that connects laser beam from one semiconductor laser to one optical fiber is of lower output, therefore, a desirable output cannot be attained unless many lasers are arrayed; whereas the combined laser source of lower number (e.g. one) array can produce the desirable output since the combined laser source may generate a higher output.
  • a semiconductor laser of about 30 mW output is usually employed, and a multimode optical fiber that has a core diameter of 50 ⁇ m, a clad diameter of 125 ⁇ m, and a numerical aperture of 0.2 is employed as the optical fiber.
  • the luminance at laser emitting portion 68 is 123 x IO 6 (W/m 2 ), which corresponds to about 80 times the luminance of conventional means.
  • the luminance per one optical fiber is 90 x IO 6 (W/m 2 ), which corresponds to about 28 times the luminance of conventional means.
  • the diameter of exposing head is 0.675 mm in the sub-scanning direction of the emitting region of the bundle-like fiber laser source, and the diameter of exposing head is 0.025 mm in the sub-scanning direction of the emitting region of the fiber array laser source.
  • the emitting region of illuminating means or bundle-like fiber laser source 1 is larger, therefore, the angle of laser bundle that enters into DMD3 is larger, resulting in larger angle of laser bundle that enters into scanning surface 5. Therefore, the beam diameter tends to increase in the collecting direction, resulting in a deviation in focus direction. 5
  • FIG. 37A in the o conventional exposing head, the emitting region of illuminating means or bundle-like fiber laser source 1 is larger, therefore, the angle of laser bundle that enters into DMD3 is larger, resulting in larger angle of laser bundle that enters into scanning surface 5. Therefore, the beam diameter tends to increase in the collecting direction, resulting in a deviation in focus direction. 5 On the other hand, as shown in FIG.
  • the exposing head of the pattern forming apparatus in the present invention has a smaller diameter of the emitting region of fiber array laser source 66 in the sub-scanning direction, therefore, the angle of laser bundle is smaller that enters into DMD50 through lens system 67, resulting in lower angle of laser bundle that enters into scanning surface 56, i.e. larger focal depth.
  • the diameter of the err tting region is about 30 times the diameter of prior art in the sub-scanning direction, thus the focal depth approximately corresponding to the limited diffraction may be obtained, which is appropriate for the exposing at extremely small spots.
  • the effect on the focal depth is more significant as the optical quantity required at the exposing head comes to larger.
  • the size of one imaging portion projected on the exposing surface is 10 ⁇ m x 10 ⁇ m.
  • the DMD is a spatial light modulator of reflected type; in FIGs. 37A and 37B, it is shown as developed views to explain the optical relation.
  • the pattern information corresponding to the exposing pattern is inputted into a controller (not shown) connected to DMD50, and is memorized once to a flame memory within the controller.
  • the pattern information is the data that expresses the concentration of each imaging portion that constitutes the pixels by means of two-values i.e. presence or absence of the dot recording.
  • Stage 152 that absorbs pattern forming material 150 on the surface is conveyed from upstream to downstream of gate 160 along guide 158 at a constant velocity by a driving device (not shown).
  • a driving device not shown
  • the tip of pattern forming material 150 is detected by detecting sensor 164 installed at gate 160 while stage 152 passes under gate 160
  • the pattern information memorized at the flame memory is read plural lines by plural lines sequentially, and controlling signals are generated for each exposing head 166 based on the pattern information read by the data processing portion.
  • each micromirror of DMD50 is subjected to on-off control for each exposing head 166 based on the generated controlling signals.
  • the laser beam reflected by the micromirror of DMD50 at on-condition is imaged on exposed surface 56 of pattern forming material 150 by means of lens systems 54, 58.
  • the laser beams emitted from fiber array laser source 66 are subjected to on-off control for each imaging portion, and pattern forming material 150 is exposed by imaging portions or exposing area 168 of which the number is approximately the same as that of imaging portions employed in DMD50.
  • pattern forming material 150 is subjected to sub-scanning in the direction opposite to the stage moving direction by means of scanner 162, and band-like exposed region 170 is formed for each exposing head 166.
  • the material to be exposed is properly selected without particular limitations as long as the material is a pattern forming material that comprises a photosensitive layer.
  • the exposing is carried out for the laminate that comprises the pattern forming material on a substrate.
  • the exposing of the laminated body may be properly selected depending on the application; for example, the photosensitive layer may be exposed through the support and the cushioning layer and the barrier layer, the photosensitive layer may be exposed through the cushioning layer and the barrier layer after the support being peeled away, the photosensitive layer may be exposed through the barrier layer after 5 the support and the cushioning layer being peeled away, or the photosensitive layer may be exposed after the support and the cushioning layer and the barrier layer being peeled away.
  • Pattern Forming Material > The pattern forming material may be properly selected depending on the o application without particular limitations as long as the pattern forming material comprises a cushioning layer and a photosensitive layer on a substrate.
  • the pattern forming material may comprise a barrier layer that suppresses migration of substances between the cushioning layer and the photosensitive layer depending on the requirements.5 « Cushioning Layer »
  • the cushioning layer may be properly selected depending on the application; preferably the cusMoning layer comprises a thermoplastic resin.
  • the cushioning layer may be swellable, soluble, or insoluble in alkaline liquids.
  • thermoplastic resins include saponification products from copolymers of styrene and acrylate, saponification products from copolymers of styrene and (meth)acrylate, saponification products from copolymers of vinyltoluene and (meth)acrylate, poly(meth)acrylates, saponification products from (meth)acrylate copolymers of (meth)butylacrylate and vinyl acetate, copolymers of (meth)acrylate and (meth)acrylic acid, and copolymers of styrene and (meth)acrylate and (meth)acrylic acid.
  • the Nicat softening temperature of these thermoplastic resins may be properly selected depending on the application; preferably the softening temperature of these thermoplastic resins is 80 °C or less.
  • the thermoplastic resins that have a softening temperature of 80 °C or less and are soluble in alkaline liquids are exemplified in "Plastic Property Handbook, edited by Japan Plastic Molding Industry Union of The Japan Plastics Industry Federation, published by Kogyo Chosakai Publishing Inc., Oct. 25, 1968".
  • organic polymer materials having a softening temperature of above 80 °C may be decreased in many cases for the softening temperature by incorporating a plasticizer compatible with the organic polymer material for example.
  • the adhesive strength between the pattern f orrning material and the other layers may be properly adjusted depending on the application; preferably, the adhesive strength between the support and the cushioning layer is the lowest among the interlayer adhesive strengths.
  • interlayer adhesive strengths may bring about the situation that only the support is peeled from the laminated body, the photosensitive layer is exposed through the cushioning layer, then the photosensitive layer is developed by an alkaline developing liquid; alternatively, the photosensitive layer is exposed while remaining the support, then only the support is peeled from the laminated body, followed by developing the photosensitive layer by the alkaline developing liquid.
  • the adjustment of the interlayer adhesive strength may be properly performed depending on the application, for example, through incorporating into the thermoplastic resin a substance selected from conventional polymers, supercooled substances, adhesion promoters, surfactants, releasing agent, and the like.
  • plasticizers set forth above may be properly selected depending on the application; examples of the plasticizers include alcohols and esters such as polypropylene glycol, polyethylene glycol, dioctylphthalate, diheptylphthalate, dibutylphthalate, tricresylphosphate, ⁇ resyldiphenylphosphate, and biphenyldiphenylphosphate; amides such as toluenesulfone amide.
  • thermoplastic resins include copolymers that contain ethylene as the essential component.
  • examples of the copolymers that contain ethylene as the essential component include ethylene-vinylacetate copolymers (EVA), ethylene-ethylacrylate copolymers (EEA) and the like.
  • EVA ethylene-vinylacetate copolymers
  • ESA ethylene-ethylacrylate copolymers
  • the adhesive strength between the pattern forming material and the other layers may be properly adjusted depending on the application; preferably, the adhesive strength between the photosensitive layer and the cushioning layer is the lowest among the interlayer adhesive strengths.
  • interlayer adhesive strengths may bring about the situation that the support and the cushioning layer are peeled from the laminated body, then the photosensitive layer is exposed and the photosensitive layer is developed by an alkaline developing liquid; alternatively, the photosensitive layer is exposed while remaining the support, then the support and the cushioning layer are peeled from the laminated body, followed by developing the photosensitive layer by the alkaline developing liquid.
  • the adjustment of the interlayer adhesive strength may be properly performed depending on the application, for example, through incorporating into the thermoplastic resin a substance selected from conventional polymers, supercooled substances, adhesion promoters, surfactants, releasing agent, and the like, and also through adjusting the copolymerization ratio of ethylene as explained following..
  • the copolymerization ratio of ethylene in a copolymer that contains ethylene as the essential component may be properly selected depending on the application; preferably the copolymerization ratio is 60 to 90 % by mass, more preferably is 60 to 80 % by mass, still more preferably is 65 to 80 % by mass.
  • the thickness of the cushioning layer may be properly selected depending on the application; for example, the thickness is 5 to 50 ⁇ m, more preferably is 10 to 50 ⁇ m, and still more preferably is 15 to 40 ⁇ m.
  • the photosensitive layer may be properly selected from conventional pattern forming materials without particular limitations; preferably the photosensitive layer comprises a binder, a polymerizable compound, a photopolymerization initiator, for example, and other components if necessary.
  • the laminated number of the photosensitive layer may be properly selected without particular limitations; the laminated number may be of one, or no less than two.
  • the binder is swellable in alkaline liquids, more preferably, the 5 binder is soluble in alkaline liquids.
  • the binder that is swellable or soluble in alkaline liquids is those having an acidic group, for example.
  • the acidic group may be properly selected depending on the application without particular limitations; examples thereof include a carboxyl group, sulf onic acid group, phosphoric acid group, and the like. Among these groups, a carboxyl o group is preferable.
  • the binders that contain the carboxyl group include vinyl copolymers, polyurethane resins, polyamide acid resins, and modified epoxy resins that contain a carboxyl group.
  • vinyl copolymers containing a carboxyl group are preferable from the viewpoints of solubility in coating solvents,5 solubility in alkaline developers, ability to be synthesized, easiness to adjust film properties, and the like.
  • the vinyl copolymers containing a carboxyl group may be synthesized by copolymerizing at least (i) a vinyl polymer containing a carboxyl group, and (ii) a monomer capable of copolymerizing with the vinyl monomer.
  • vinyl polymers containing a carboxyl group examples include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkylester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, adducts of a monomer containing a hydroxy group such as 2-hydroxyethyl(meth)acrylate and a cyclic anhydride such as maleic acid anhydride, phthalic acid anhydride, and 5 cyclohexane dicarbonic acid anhydride, and ⁇ -carboxy-polycaprolactone mono(meth)acrylate.
  • (meth)acrylic acid is preferable in particular from the view points of copolymerizing ability, cost, solubility, and the like.
  • monomers containing anhydride such as maleic acid anhydride, itaconic acid anhydride, and citraconic acid anhydride may be employed.
  • the monomer capable of copolymerizing may be properly selected depending on the application; examples thereof include (meth)acrylate esters, crotonate esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid 5 diesters, (meth)acrylic amides, vinyl ethers, vinyl alcohol esters, styrenes, metacrylonitrile; heterocyclic compounds with a substituted vinyl group such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; N-vinyl f ormamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone, 2-acrylamide-2-methylpropane sulfonic acid, phosphoric acid mono(2-acryloyloxyethylester), phosphoric acid l o mono(l-methyl ⁇ 2-acryloyloxyethylester), and vinyl monomers containing a functional group such as a urethane group, urea group,
  • n-butyl(meth)acrylate isobutyl(meth)acrylate, t-butyl(meth)acrylate, n ⁇ hexyl(meth)acrylate, cyclohexyl(meth)acrylate, t-butyl cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, t-octyl(meth)acrylate, dodecyl(meth)acrylate, octadecyl(meth)acrylate, acetoxyethyl(meth)acry late, phenyl(meth)acry late, 2-hydroxyethyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,
  • polyethyleneglycol monomethylether (meth)acrylate polyethyleneglycol monoethylether (meth)acrylate, ⁇ -phenoxy ethoxy ethyl (meth)acrylate, nonylphenoxy polyethyleneglycol (meth)acrylate, dicyclopentanyl (meth) aery late, dicyclopentenyl oxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, tribromophenyl (meth)acrylate, and tribromophenyloxyethyl (meth)acrylate.
  • Examples of crotonate esters include butyl crotonate, and hexyl crotonate.
  • Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinylmethoxy acetate, and vinyl benzoate.
  • maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
  • Examples of itaconic acid diesters include dimethyl itaconate, diethyl o itaconate, and dibutyl itaconate.
  • Examples of (meth)acrylic amides include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-t-butyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-(2-methoxyethyl)5 (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-benzil (meth)acrylamide, (meth)acryloyl morpholine, and diacetone acrylamide.
  • styrenes examples include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, o methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene; hydroxystyrene with a protective group such as t-Boc capable of being de-protected by an acid substance; vinylmethyl benzoate, and -methylstyrene.
  • styrene styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene,
  • Examples of vinyl ethers include methyl vinylether, butyl vinylether, hexyl 5 vinylether, and methoxyethyl vinylether.
  • the process to synthesize the vinyl monomer containing a functional group is an addition reaction of an isocyanate group and a hydroxy group or amino group for example; specifically, an addition reaction between a monomer containing an isocyanate group and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, and an addition reaction between a monomer containing a hydroxy group or a monomer containing a primary or secondary amino group and a mono isocyanate are exemplified.
  • Examples of the monomers containing an isocyanate group include the compounds expressed by the following formulas (1) to (3).
  • R 1 represents a hydrogen atom or a methyl l o group.
  • mono isocyanates set forth above include cyclohexyl isocyanate, n-butyl isocyanate, toluic isocyanate, benzil isocyanate, and phenyl isocyanate.
  • monomers containing a hydroxyl group include the compounds expressed by the following formulas (4) to (12).
  • Ri represents a hydrogen atom or a methyl grotip
  • "ft" represents an integer of one or more.
  • the compounds containing one hydroxyl group include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzil alcohol, and phenylethyl alcohol; phenols such as phenol, cresol, and naphthol; examples of the compounds containing additionally a substituted group include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, and acet
  • Examples of monomers containing a primary or secondary amino group set forth above include vinylbenzil amine.
  • Examples of compounds containing a primary or secondary amino group include alkylamines such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexylamine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, and dioctylamine; cyclic alkylamines such as cyclopentylamine and cyclohexylamine; aralkylamines such as benzilamine and phenethylamine; arylamines such as aniline, toluicamine, xylylamine, and naphthylamine; combination thereof such as N-methyl-N-benzilamine
  • copolymerizable monomers other than set forth above examples include methyl (meth) aery late, ethyl (meth)acrylate, butyl (meth)acrylate, benzil (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.
  • the above noted copolymerizable monomers may be used alone or in combination.
  • the vinyl copolymers set forth above may be prepared by copolymerizing the appropriate monomers in accordance with conventional processes; for example, such a solution polymerization process is available as dissolving the monomers into an appropriate solvent, adding a radical polymerization initiator, thereby causing a polymerization in the solvent; alternatively such a so-called emulsion polymerization process is available as polymerizing the monomers under the condition that the monomers are dispersed in an aqueous solvent.
  • the solvent utilized in the solution polymerization process may be properly selected depending on the monomers, solubility of the resultant copolymer and the like; examples of the solvents include methanol, ethanol, propanol, isopropanol, l-methoxy-2-propanol, acetone, methyl ethyl ketone, methylisobutylketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, o dimethylf ormamide, ⁇ hlorof orm, and toluene. These solvents may be used alone or in combination.
  • the radical polymerization initiator set forth above may be properly selected without particular limitations; examples thereof include azo compounds such as 2,2'-azobis(isobutyronitrile) (AIBN) and 2,2'-azobis-(2,4'-dimethylvaleronitrile);5 peroxides such as benzoyl peroxide; persulfates such as potassium persulfate and ammonium persulfate.
  • the content of the polymerizable compound having a carboxyl group in the vinyl copolymers set forth above may be properly selected without particular limitations; preferably, the content is 5 to 50 mole %, more preferably is 10 to 40 o mole %, and still more preferably is 15 to 35 mole % .
  • the content When the content is less than 5 mole %, the developing ability in alkaline solution may be insufficient, and when the content is more than 50 mole %, the durability of the hardening portion or imaging portion is insufficient against the developing liquid. 5
  • the molecular weight of the binder having a carboxyl group set forth above may be properly selected without particular limitations; preferably the weight-averaged molecular weight is 2000 to 300000, more preferably is 4000 to 150000. When the weight-averaged molecular weight is less than 2000, the film strength is likely to be insufficient, and also the production process tends to be unstable, and when the weight-averaged molecular weight is more than 300000, the developing ability tends to decrease.
  • the binder having a carboxyl group set forth above may be used alone or in 5 combination.
  • such combination may be exemplified as two or more of binders having different copolymer components, two or more of binders having different weight-averaged molecular weight, and two or more of binders having different dispersion levels.
  • a part or all of the o carboxyl groups may be neutralized by a basic substance.
  • the binder may be combined with a resin of different type selected from polyester resins, polyamide resins, polyurethane resins, epoxy resins, polyvinyl alcohols, gelatin, and the like.
  • the binder having a carboxyl group set forth above may be resins soluble in an alkaline aqueous solution as described in Japanese Patent No. 2873889. 5
  • the content of the binder in the photosensitive layer set forth above may be properly selected without particular limitations; preferably the content is 10 to 90 % by mass, more preferably is 20 to 80 % by mass, and still more preferably is 40 to 80 % by mass. When the content is less than 10 % by mass, the developing ability in alkaline o solutions or the adhesive property with substrates for forming printed wiring boards such as a cupper laminated board tends to decrease, and when the content is more than 90 % by mass, the stability of developing period or the strength of the hardening film or the tenting film may be insufficient.
  • the content of the binder may be considered as the entire content of the binder content and the additional polymer 5 binder content combined depending on requirements.
  • the acid value of the binder may be properly selected depending on the application; preferably the acid value is 70 to 250 mgKOH/g, more preferably is 90 to 200 mgKOH/g, still more preferably is 100 to 180 mgKOH/g.
  • the acid value is less than 70 mgKOH/g, the developing ability may be insufficient, the resolving property may be poor, or the permanent pattern such as wiring patterns cannot be formed precisely
  • the acid value is more than 250 mgKOH/g, the durability of pattern against the developer and/ or adhesive property of pattern tends to degrade, thus the permanent pattern such as wiring 5 patterns cannot be formed precisely.
  • the polymerizable compound may be properly selected without particular limitations; preferably, the polymerizable compound is the monomer or oligomer that contains a urethane group and/ or an aryl group; preferably, the polymerizable o compound contains two or more types of polymerizable groups.
  • the polymerizable group include ethylenically unsaturated bonds such as (meth)acryloyl groups, (meth)acrylamide groups, styryl groups, vinyl groups (e.g. of vinyl esters, vinyl ethers), and allyl groups (e.g.
  • - Monomer Containing Urethane Group The monomer containing a urethane group set forth above may be properly selected without particular limitations; examples thereof include those described in Japanese Patent Application Publication (JP-B) No.48-41708, Japanese Patent o Application Laid-Open (JP-A) No. 51-37193, JP-B Nos. 5-50737, 7-7208, and JP-A Nos.
  • the adducts may be exemplified between polyisocyanate compounds having two or more isocyanate groups in the molecule and vinyl monomers having a hydroxyl group in the molecule.
  • polyisocyanate compounds having two or more isocyanate 5 groups in the molecule set forth above include diisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, and S / S'-dimethyl ⁇ '-diphenyl diisocyanate; polyaddition products of these diisocyanates and two-functional alcohols wherein each of both ends of the polyaddition product is an isocyanate group
  • vinyl monomers having a hydroxyl group in the molecule set forth above include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethyleneglycol mono(meth)acrylate, o triethyleneglycol monp(meth)acrylate, tetraethyleneglycol mono(meth)acrylate, octaethyleneglycol mono(meth)acrylate, polyethyleneglycol mono(meth)acrylate, dipropyleneglycol mono(meth)acrylate, tripropyleneglycol mono(meth)acrylate, tetrapropyleneglycol mono(meth)acrylate, octapropyleneglycol mono(meth)acrylate, polypropyleneglycol mono(meth)acrylate, dibutyleneglycol mono(meth)acrylate, 5 ttibutyleneglycol mono(meth)acrylate, tetrabutylene
  • such a vinyl monomer may be exemplified that has a (meth)acrylate component at one end of diol molecule having different alkylene oxides such as of random or block o copolymer of ethylene oxide and propylene oxide for example.
  • the monomer containing a urethane group set forth above include the compounds having an isocyanurate ring such as tri(meth)acryloyloxyethyl isocyanurate, di(meth)acrylated isocyanurate, and tri(meth) aery late of ethylene oxide modified isocyanuric acid.
  • the 5 compounds expressed by formula (13) or formula (14) are preferable; at least the compounds expressed by formula (14) are preferably included in particular from the view point of tenting property. These compounds may be used alone or in combination.
  • R 1 to R 3 represent a hydrogen atom or a methyl group respectively;
  • Xi to X3 represent alkylene oxide groups, which may be identical or different each other.
  • alkylene oxide group include ethylene oxide group, propylene oxide group, butylene oxide group, pentylene oxide group, hexylene oxide group, and combined groups thereof in random or block. Among these, ethylene oxide group, propylene oxide group, butylene oxide group, and combined groups thereof are preferable; and ethylene oxide group and propylene oxide group are more preferable.
  • ml to m3 represent integers of 1 to 60 respectively, preferably is 2 to 30, more preferably is 4 to 15.
  • each of Y 1 and Y 2 represent a divalent organic group having 2 to 30 carbon atoms such as alkylene group, arylene group, alkenylene group, alkynylene group, carbonyl group (-CO-), oxygen atom, sulfur atom, imino group (-NH-), substituted imino group wherein a hydrogen atom on the imino group is substituted by a monovalent hydrocarbon group, sulf onyl group (-S0 2 -), and combination thereof; among these, an alkylene group, arylene group, and combination thereof are preferable.
  • the alkylene group set forth above may be of branched or cyclic structure; examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, ttimethylhexylene group, cyclohexylene group, heptylene, group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, dodecylene group, octadecylene group, and the groups expressed by the following formulas.
  • the arylene group may be substituted by a hydrocarbon group; examples of the arylene group include phenylene group, thrylene group, diphenylene group, naphthylele group, and the following group.
  • the group of combination thereof set forth above is exemplified by xylylene group.
  • the alkylene group, arylene group, and combination thereof set forth above may contain a substituted group additionally; examples of the substituted group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and
  • aryl groups alkoxy groups such as methoxy group, ethoxy group, and 2-ethoxyethoxy group; aryloxy groups such as phenoxy group; acyl groups such as acetyl group and propionyl group; acyloxy groups such as acetoxy group and butylyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; and aryloxycarbonyl groups such as phenoxycarbonyl group.
  • ft represents an integer of 3 to 6, preferably, "ft” is 3, 4, or 6 from the view point of the available feedstock for synthesizing the polymerizable monomer.
  • ft represents an integer of 3 to 6;
  • X 4 represents an alkylene oxide
  • m4 represents an integer of 1 to 20
  • "ft” represents an integer of 3 to 6
  • Example of A of the organic group set forth above include n- valence aliphatic groups, n-valence aromatic groups, and combinations of these groups and alkylene groups, arylene groups, alkenylene groups, alkynylene groups, carbonyl group, oxygen atom, sulfur atom, imino group, substituted imino groups wherein a hydrogen atom on the imino group is substituted by a monovalent hydrocarbon group, and sulfonyl group (-SO2-); more preferably are n-valence aliphatic groups, n-valence aromatic groups, and combinations of these groups and alkylene groups, arylene groups, or an oxygen atom; particularly preferably are n-valence aliphatic groups, and combinations of n-valence aliphatic groups
  • the number of carbon atoms in the A of the organic group set forth above is preferably 1 to 100, more preferably is 1 to 50, and most preferably is 3 to 30.
  • the n-valence aliphatic group set forth above may be of branched or cyclic structure.
  • the number of carbon atoms in the aliphatic group is preferably 1 to 30, more preferably is 1 to 20, and most preferably is 3 to 10.
  • the number of carbon atoms in the aromatic group set forth above is preferably 6 to 100, more preferably is 6 to 50, and most preferably is 6 to 30.
  • the n-valence aliphatic group and the n-valence aromatic group may contain a substituted group additionally; examples of the substituted group include hydroxyl group, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; aryl groups; alkoxy groups such as methoxy group, ethoxy group, and 2-ethoxyethoxy group; aryloxy groups such as phenoxy group; acyl groups such as acetyl group and propionyl group; acyloxy groups such as acetoxy group and butylyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; and aryloxycarbonyl groups such as phenoxycarbonyl group.
  • the substituted group include hydroxyl group, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; aryl groups; alkoxy groups
  • the alkylene group set forth above may be of branched or cyclic structure.
  • the number of carbon atoms in the alkylene group is preferably 1 to 18, and more preferably is 1 to 10.
  • the arylene group set forth above may be further substituted by a hydrocarbon group.
  • the number of carbon atoms in the arylene group is preferably 6 to 18, and more preferably is 6 to 10.
  • the number of carbon atoms in the hydrocarbon group of the substituted imino group set forth above is preferably 1 to 18, and more preferably is 1 to 10.
  • Preferable examples of A of the organic group set forth above are as follows.
  • each of "n”, nl, n2, and “m” represents an integer of 1 to 60; "1" represents an integer of 1 to 20; and R represents a hydrogen atom or a methyl group.
  • - Monomer Containing Aryl Group The monomers containing an aryl group set forth above may be properly selected as long as the monomer contains an aryl group; examples of the monomers containing an aryl group include esters and amides between at least one of polyvalent alcohol compounds, polyvalent amine compounds, and polyvalent amino alcohol compounds containing an aryl group and at least one of unsaturated carboxylic acids.
  • polystyrene oxide polystyrene oxide
  • xylylenediol di( ⁇ -hydroxyethoxy)benzene
  • l,5-dihydroxy-l,2,3,4-tetrahydronaphthalene 2,2-diphenyl-l,3-propanediol
  • hydroxybenzyl alcohol hydroxyethyl resorcinol
  • l-phenyl-l,2-ethanediol 5 2,3,5,6-tetramethyl-p-xylene- , ⁇ '-diol, l,l,4,4-tetraphenyl-l,4-butanediol, l,l,4,4-tetraphenyl-2-butine-l,4-diol, 1,1 '-bi-2-naphthol, dihydroxynaphthalene, l / l'-
  • xylylene-bis-(meth)acrylamide adducts of novolac epoxy resins or glycidyl compounds such as bisphenol A diglycidylether and ⁇ , ⁇ -unsaturated 5 carboxylic acids; ester compounds from acids such as phthalic acid and ttimellitic acids and vinyl monomers containing a hydroxide group; diallyl phthalate, triallyl trimellitate, diallyl benzene sulfonate, cationic polymerizable divinylethers as a polymerizable monomer such as bisphenol A divinylether; epoxy compounds such as novolac epoxy resins and bisphenol A diglycidylethers; vinyl esters such as o divinyl phthalate, divinyl terephthalate, and divinylbenzene-l,3-disulf onate; and styrene compounds such as divinyl benzene, p-allyl styrene, and p-is
  • R 4 and R 5 represent respectively a hydrogen atom or an alkyl group.
  • X5 and X 6 represent an alkylene oxide group respectively, the alkylene oxide group may be one species or two or more species.
  • the alkylene oxide group include ethylene oxide group, propylene oxide group, butylene oxide group, pentylene oxide group, hexylene oxide group, and combined groups in random or block thereof. Among these, ethylene oxide group, propylene oxide group, butylene oxide group, and combined groups thereof are preferable; and ethylene oxide group and propylene oxide group are more preferable.
  • m5 and m6 represent respectively an integer of 1 to 60, preferably is 2 to 30, and more preferably is 4 to 15.
  • T represents a divalent connecting group such as methylene group, ethylene group, MeCMe, CF3CCF3, CO, and SO2.
  • Ari and Ar2 represent respectively an aryl group that may contain a substituted group; examples of An and A ⁇ 2 include phenylene and naphthyene; and examples of the substituted group include alkyl groups, aryl groups, aralkyl groups, halogen groups, alkoxy groups, and combinations thereof.
  • the monomer containing an aryl group set forth above include 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane; 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane in which the number of ethoxy groups substituted for one phenolic OH group is 2 to 20 such as 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxytetraethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxypentaethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxydecaethoxy)phenyl]pro ⁇ ane, and 2,2-bis[4-((me
  • 2,2 ⁇ bis[4 ⁇ ((meth)acryloyloxypolypropoxy)phenyl]propane in which the number of ethoxy groups substituted for one phenolic OH group is 2 to 20 such as 2,2-bis[4-((meth)acryloyloxydipropoxy)phenyl]propane, 2,2-bis[4-(.(meth)acryloyloxytetrapropoxy) ⁇ henylJpro ⁇ ane, 2,2-bis[4-((meth)acryIoyloxypentapropoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxydeca ⁇ ropoxy) ⁇ henyl]pro ⁇ ane, 2,2-bis[4-((meth)acryloyloxypentadecapropoxy)phenyl]propane; compounds having a polyethylene oxide skeleton as well as a polypropylene skeleton in one molecule as the ether site of these compounds such as described in International Public
  • WO 01/98832 and commercial products of BPE-200, BPE-500, and BPE-1000 (by Shin-nakamura Chemical Co.); and polymerizable compounds having a polyethylene oxide skeleton as well as a polypropylene skeleton.
  • the site resultant from bisphenol A may be changed into the site resultant from bisphenol F, bisphenol S, or the like.
  • Examples of the polymerizable compounds having a polyethylene oxide skeleton as well as a polypropylene skeleton include the adducts of bisphenols and ethylene oxides or propylene oxides, and the compounds having a hydroxyl group at the end wherein the compound is formed as a polyaddition product and the compound has an isocyanate group and a polymerizable group such as 2-isocyanate ethyl(meth)acrylate and ⁇ , -dimethylviny benzilisocyanate, and the like.
  • the polymerizable monomers other than the monomers having a urethane group or an aryl group set forth above may be employed together within a range that the properties of the pattern forming material are not deteriorated.
  • monomers other than the monomers having a urethane group or an aromatic ring include the esters between unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and isocrotonic acid and aliphatic polyvalent alcohols, and amides between unsaturated carboxylic acids and polyvalent amines.
  • esters between unsaturated carboxylic acids and aliphatic polyvalent alcohols set forth above include, as (meth) aery late esters, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 18 ethylene groups such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol 5 di(meth)acrylate, dodecaethylene glycol di(meth)acrylate, and tetradecaethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate having 2 to 18 propylene groups such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, and dodecapropylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate
  • ethylene glycol di(meth)acrylate polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylates of alkyleneglyc ⁇ l chains having at least each one of ethyleneglycol chain and propyleneglycol chain, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol triacrylate, 5 pentaerythritol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, glycerin di(meth)acrylate, 1,3-propanediol di(meth)acrylate,
  • esters between the itaconic acid and the aliphatic polyvalent alcohol compounds i.e. itaconate
  • esters between the itaconic acid and the aliphatic polyvalent alcohol compounds set forth above include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol5 tetraitaconate.
  • esters between the crotonic acid and the aliphatic polyvalent alcohol compounds i.e.
  • crotonate set forth above include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • esters between the isocrotonic acid and the aliphatic polyvalent alcohol compounds, i.e. isocrotonate set forth above include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
  • esters between the maleic acid and the aliphatic polyvalent alcohol compounds i.e.
  • amides derived from the polyvalent amine compounds and the unsaturated carboxylic acids set forth above include methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, l,6-hexamethylenebis(meth)acrylamide, octamethylenebis(meth)acrylamide, diethylenettiamine tris(meth)acrylamide, and diethylenetriamine bis(meth)acrylamide.
  • the following compounds may be exemplified additionally: compounds that are obtained by 5 adding , ⁇ -unsaturated carboxylic acids to compounds containing a glycidyl group such as butanediol-l,4-diglycidylether, cyclohexane dimethanol glycidylether, ethyleneglycol diglycidylether, diethyleneglycol diglycidylether, dipropyleneglycol diglycidylether, hexanediol diglycidylether, trimethylolpropane triglycidylether, pentaerythritol tetraglycidylether, and glycerin triglycidylether; polyester acrylates o and polyester (meth)acrylate oligomers described in JP-A No.48-64183, and JP-B Nos.
  • a glycidyl group such as butanediol-l,4-diglycid
  • multifunctional acrylate or methacrylate such as epoxy acrylates obtained from the reaction between methacrylic acid epoxy compounds such as butanediol-l,4-diglycidylether, cyclohexane dimethanol glycidylether, diethyleneglycol diglycidylether, dipropyleneglycol diglycidylether, hexanediol5 diglycidylether, trimethylolpropane triglycidylether, pentaerythritol tetraglycidylether, and glycerin triglycidylether; photocurable monomers and oligomers described in Journal of Adhesion Society of Japan, Vol.
  • allyl esters such as diallyl phthalate, diallyl adipate, and diallyl malonate
  • diallyl amides such as diallyl acetamide
  • cationic polymerizable o divinylethers such as butanediol-l,4-divinylether, cyclohexane dimethanol divinylether, ethyleneglycol divinylether, diethyleneglycol divinylether, dipropyleneglycol divinylether, hexanediol divinylether, trimethylolpropane trivinylether, pentaerythritol tetravinylether, and glycerin vinylether; epoxy compounds such as butanediol-l,4-diglycidylether, cyclohexane dimethanol 5 glycidylether, ethyleneglycol diglycidylether, diethyleneglycol diglycidylylether, diethyleneglycol
  • WO 01/22165 compounds having two or more of ethylenically unsaturated double bonds of different types such as N- ⁇ -hydroxyethyl- ⁇ -methacrylamide ethylacrylate, N,N-bis( ⁇ -methacryloxyethyl)acrylamide, acrylmetahcrylate.
  • vinyl esters set forth above include divinyl succinate and 5 divinyl adipate. These polyfunctional monomers or oligomers may be used alone or in combination.
  • the polymerizable monomers set forth above may be combined with a polymerizable compound having one polymerizable group in the molecule, i.e. o monof unctional monomer.
  • Examples of the mono functional monomers include the compounds exemplified as the raw materials for the binder set forth above, dibasic monofunctional monomer such as mono-(meth)acryloyloxyalkylester, mono-hydroxyalkylester, and5 ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate, and the compounds described in JP-A No. 06-236031, JP-B Nos. 2744643 and 2548016, and International Publication No. WO 00/52529.
  • dibasic monofunctional monomer such as mono-(meth)acryloyloxyalkylester, mono-hydroxyalkylester, and5 ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate
  • the content of the polymerizable compound in the photosensitive layer is 5 to 60 % by mass, more preferably is 15 to 60 % by mass, and still more o preferably is 20 to 50 % by mass.
  • the strength of the tent film may be lower, and when the content is more than 90 % by mass, the edge fusion at storage period is insufficient and bleeding trouble may be induced.
  • the content of the polyfunctional monomer having two or more 5 polymerizable groups set forth above in the molecule is preferably 5 to 100 % by mass, more preferably is 20 to 100 % by mass, still more preferably is 40 to 100 % by mass.
  • the photopolymerization initiator may be properly selected from conventional ones without particular limitations as long as having the property to initiate polymerization; preferably is the initiator that exhibits photosensitivity from ultraviolet rays to visual lights.
  • the initiator may be an active substance that generates a radical due to an effect with a photo-exited photosensitizer, or a substance that initiates cation polymerization depending on the monomer species.
  • the photopolymerization initiator contains at least one component that has a molecular extinction coefficient of about 50 M ⁇ cm in a range of about 300 to 800 nm, more preferably about 330 to 500 nm.
  • the photopolymerization initiator examples include halogenated hydrocarbon derivatives such as having a ttiazine skeleton or an oxadiazole skeleton, hexaaryl-biimidazols, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acylphosphine oxides, and metallocenes.
  • halogenated hydrocarbon compounds having a ttiazine skeleton, oxime derivatives, ketone compounds, and hexaaryl-biimidazol compounds are preferable from the view points of sensitivity of photosensitive layers, self stability, adhesive ability between the photosensitive layers and substrates for printed wiring boards.
  • hexaaryl-biimidazol compounds examples include 2,2 l -bis(2-chlorophenyl)-4,4 l ,5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-fluorophenyl)-4,4 , ,5,5 , -tetraphenyl-biimidazole,
  • WO 00/52529 The biimidazoles set forth above can be easily prepared by the methods described, for example, in Bulletin of the Chemical Society of Japan, 33, 565 (1960) and Journal of Organic Chemistry, 36, [16], 2262 (1971).
  • Examples of the halogenated hydrocarbon compounds 1 having a ttiazine skeleton include the compounds described in Bulletin of the Chemical Society of Japan.
  • Examples of the compounds described in GB Pat. No. 1388492 set forth above include 2-styryl-4,6-bis(trichloromethyl)-l,3,5-triazine,
  • 3337024 set forth above include 2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 5 2-(4-(4-methoxystyryl)phenyl)-4,6-bis(ttichloromethyl)-l,3,5-triazine, 2-(l-na ⁇ hthylvinylene ⁇ henyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-thiophene-2-vinylenephenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-thiophene-3-vinylenephenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, o 2-(4-furan-2-vinylenephen
  • Examples of the compounds described in Journal of Organic Chemistry, by RG Schaefer et. al. 29, 1527 (1964) set forth above include 2-methyl-4,6-bis(tribromomethyl)-l,3,5-triazine, 5 2,4,6-tris(tribromomethyl)-l,3,5-triazine, 2,4,6-tris(dibromomethyl)-l,3,5-triazine, 2-amino-4-n ethyl-6-tribrornomethyl-l,3,5-ttiazine and 2-meth ⁇ xy-4-methyl-6-trichloromethyl-l,3,5-triazine. Examples of the compounds described in JP-A No.
  • 62-58241 set forth above o include 2-(4- ⁇ henylethylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-naphthyl-l-ethynylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-(4-triethynyl)phenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-(4-methoxyphenyl)ethynyl ⁇ henyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-(4-isopropylphenylethynyl)phenyl)-4,6-bis(tticWorometl yl)-l,3,5-triazine, and5 2-(4-(4-ethylpheny
  • Examples of the compounds described in JP-A No. 5-281728 set forth above include 2-(4-trifluoromethylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(2,6-difluorophenyl)- ,6-bis(trichloromethyl)-l,3,5-triazine, 2-(2,6-dichloro ⁇ henyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, and 2-(2,6-dibromophenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine.
  • 5-34920 set forth above mclude 2,4-bis(tticWoromethyl)-6-[4-(N,N-diethoxycarbonylmethylamino)- 3-bromophenyl]-l,3,5-triazine, trihalomethyl-s-triazine compounds described in US 5 Pat. No.4239850, and also 2,4,6-tris(ttichloromethyl)-s-triazine, and 2-(4-chlorophenyl)-4,6-bis(tribromomethyl)-s-triazine. Examples of the compounds described in US Pat. No.
  • 4212976 set forth above include the compounds having an oxadiazole skeleton such as 2-trichloromethyl-5-phenyl-l,3,4-oxadiazole, o 2-ttichloromethyl-5-(4-chlorophenyl)-l,3,4-oxadiazole, 2-trichloromethyl-5-(l-naphthyl)-l,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-l,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-l,3,4-oxadiazole, 2-tribromomethyl-5-(2-naphthyl)-l,3,4-oxadiazole, 5 2-trichloromethyI-5-styryl-l,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyryl)-l,3,4-oxadiazole, 2-trichloromethyl
  • ketone compounds set forth above include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone-tetracarboxylic acid and its tetramethyl ester; 4,4'-bis(dialkylamino)benzophenones such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(cyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4 ⁇ methoxy-4 , -dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, and 5 4-dimethylamin
  • metallocenes include bis( ⁇ 5-2,4-cyclopentadiene-l ⁇ yl) ⁇ bis(2,6-dmuoro-3-(lH-pyrrole-l-yl)-phenyl)titaniurn, ⁇ 5-cyclopentadienyl- ⁇ 6-cumenyl-iron(l+)-hexafluorophosphate(l-), and the compounds described in JP-A No. 53-133428, JP-B Nos. 57-1819 and 57-6096, and US
  • photopolymerization initiators other than set forth above, the following substances are further exemplified: acridine derivatives such as 9-phenyl acridine and l,7-bis(9,9'-acridinyl)heptane; polyhalogenated compounds such as carbon tetrabromide, phenyltribromosulf one, and phenyltrichloromethylketone;
  • acridine derivatives such as 9-phenyl acridine and l,7-bis(9,9'-acridinyl)heptane
  • polyhalogenated compounds such as carbon tetrabromide, phenyltribromosulf one, and phenyltrichloromethylketone
  • 25 coumarins such as 3-(2-benzofuroyl)-7-diethyIaminocoumarin, 3-(2-benzofuroyl)-7-(l-pyrrolidinyl)coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-(2-methoxybenzoyl)-7-diethylaminocoumarin, 3-(4-dimethyla_rmnobenzoyl)-7-diethylaminocoumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3-(2-furoyl)-7-diethylaminocoumarin, 3-(4-diethylammocinnan oyl)-7-diethylaminocoumarin,
  • amines such as ethyl 4-dimethylamibenzoate, n-butyl 4-dimethylamibenzoate, phenethyl 4-dimethylamibenzoate, 2-phthalimide 4-dimethylamibenzoate, 2-methacryloyloxyethyl 4-dirnethylamibenzoate, pentamethylene-bis(4-dimethylaminobenzoate), phenethyl 3-dimethylamibenzoate, pentamethylene esters, 4-dimethylamino benzaldehyde, 2-c oro-4-dimethylamino benzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl(4-dimethylaminobenzoyl)acetate, 4-piperidine acetophenone, 4-dimethyamino benzoin, N,N-dimethyl
  • photopolymerization initiators may be used alone or in combination.
  • the combination of two or more photopolymerization initiators may be for example the combination of hexaaryl-biimidazol compounds and amino ketones described in US Pat. No.3549367; combination of benzothiazole compounds and trihalomethyl-s-triazine compounds as described in JP-B No.
  • the content of the photopolymerization initiator in the photosensitive layer is preferably 0.1 to 30 % by mass, more preferably is 0.5 to 20 % by mass, and still more preferably is 0.5 to 15 % by mass.
  • photosensitizer, thermal polymerization inhibitor, plasticizer, coloring agent, and colorant are exemplified; in addition, the other auxiliaries such as adhesion promoter on substrate surface, pigment, conductive particles, filler, defoamer, fire retardant, leveling agent, peeling promoter, antioxidant, perfume, thermocrosslinker, adjustor of surface tension, chain transfer agent, and the like may be utilized together with.
  • desirable properties of the pattern forming material such as stability with time, photographic property, developing property, film property, and the like may be tailored.
  • Photosensitizer The photosensitizer may be properly selected depending on the types of laser beam utilized in the pattern forming process and the like.
  • the photosensitizer may be exited by active irradiation, and may generate a radical, an available acidic group and the like through interaction with other substances such as radical generators and acid generators by transferring energy or electrons.
  • the photosensitizer may be properly selected without particular limitations from conventional substances; examples of the photosensitizer include polynuclear aromatics such as pyrene, perylene, and triphenylene; xanthenes such as fluorescein, Eosine, erythrosine, rhodamine B, and Rose Bengal; cyanines such as indocarbocianine, thiacarbocianine, and oxacarbocianine; merocianines such as 5 merocianine and carbomerocianine; thiazins such as thionine, methylene blue, and toluidine blue; acridines such as acridine orange, chloroflavine, and acriflavine; anthraquinones such as anthraquinone; scariums such as scarium; acridones such as acridone, chloroacridone, N-methylacridone, N-butylacridone, N-but
  • the initiating mechanism that involves electron transfer may be exemplified such as combinations of (1) an electron donating initiator and a5 photosensitizer dye, (2) an electron accepting initiator and a photosensitizer dye, and (3) an electton donating initiator, and an electron accepting initiator, and a photosensitizer dye (ternary mechanism) as described in JP-A No. 2001-305734.
  • the content of the photosensitizer is preferably 0.05 to 30 % by mass based on the entire composition of the photosensitive resin, more preferably is 0.1 to 20 % by mass, and still more preferably is 0.2 to 10 % by mass.
  • the content is less than 0.05 % by mass, the sensitivity toward the active energy ray may decrease, longer period may be required for exposing process, and the productivity tends to lower, and when the content is more than 30 % by mass, the photosensitizer may precipitate from the photosensitive layer during preservation period.
  • Thermal Polymerization Inhibitor The thermal polymerization inhibitor may be effectively incorporated into the photosensitive layer in order to prevent the polymerization due to higher temperature or with time.
  • thermal polymerization inhibitors examples include 4-methoxy phenol, hydroquinone, hydroquinones substituted by an alkyl or aryl group, t-butylcatechol, p rogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methyleneblue, reaction products of cupper and organic chelating agents, methyl salicylate, nitroso compounds, chelate compounds between nitroso compounds and Al, and the like.
  • the content of the thermal polymerization inhibitor is preferably 0.001 to 5 % by mass based on the polymerizable compound in the photosensitive layer, more preferably is 0.005 to 2 % by mass, and still more preferably is 0.01 to 1 % by mass.
  • the content is less than 0.001 % by mass, the storage stability may be insufficient, and when the content is more than 5 % by mass, the sensitivity toward the active energy ray may decrease.
  • Plasticizer The plasticizer set forth above may be incorporated into in order to adjust the film property i.e. flexibility of the photosensitive layer.
  • plasticizer examples include phthalic acid esters such as dimethylphthalate, dibutylphthalate, diisobutylphthalate, diheptylphthalate, dioctylphthalate, dicyclohexylphthalate, dittidecylphthalate, butylbenzylphthalate, diisodecylphthalate, diphenylphthalate, diallylphthalate, and octylcaprylphthalate; glycol esters such as triethyleneglycol diacetate, tetraethyleneglycol diacetate, dimethylglycose phthalate, ethylphthalyl ethylglycolate, methylphthalyl ethylglycolate, buthylphthalyl buthylglycolate, triethylene glycol dicaprylate; phosphoric acid esters such as tricresylphosphate and triphenylphosphate; amides such as 4-toluenesulfone amide,
  • the content of the plasticizer set forth above is preferably 0.1 to 50 % by mass, more preferably is 0.5 to 40 % by mass, and still more preferably is 1 to 30 % by mass.
  • Coloring Agent The coloring agent may be utilized to provide visible images or to afford developing property on the photosensitive layer set forth above after exposure.
  • coloring agent examples include aminotriarylmethanes such as tris(4-dimethylaminophenyl)methane (leucocrystal violet), tris(4-diethylaminophenyl)methane, ttis(4-dimethylamino-2-methylphenyl)rnethane, tris(4-diethylamino-2-methylphenyl)methane, bis(4-dibutylaminophenyl)-[4-(2-cyanoethyl)methylaminophenyl]methane, bis(4-dimethylaminophenyl)-2-quinolylmethane, and ttis(4-dipropylaminophenyl)methane; aminoxanthenes such as 3,6-bis(diethyIamino)-9-phenylxanthene and
  • aminothioxanthenes such as
  • amino-9,10-dihydroacridines such as 3,6-bis(diethylamino)-9,l O-dihydro-9-phenylacridine and 3,6-bis(benzylar-vino)-9,10-dihydro-9-methylacridine
  • aminophenoxazines such as 3,7-bis(diethylamino)phenoxazines
  • ammophenothiazines such as 3,7-bis(ethylamino)phenothiazine
  • arninodihydrophenazines such as 5 3,7-bis(diethylamino)-5-hexyl-5,10-dihydrophenazine
  • aminophenylmethanes such as bis(4-di ⁇ -nethylaminopheny
  • organic amines capable of being oxidized to colored forms as described in US Pat. Nos. 3042515 and 3042517 such as 4,4'-ethylenediamine, diphenylamine, N,N-dimethylaniline, 4,4'-methylenediaminetriphenylamine, and N-vinylcarbazole.
  • triarylmethanes such as leucocrystal violet are preferable in particular.
  • the coloring agents set forth above may be combined with halogenated compounds in order to develop a color from the leuco compounds.
  • halogenated compounds include halogenated hydrocarbons such as tetrabromocarbon, iodoform, ethylene bromide, methylene bromide, amyl
  • bromide isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, diphenylmethyl bromide, hexachloromethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, l,2-dibromo-l,l,2-trichloroethane, 1,2,3-tribromopropane, l-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, and l,l,l-ttichloro-2,2-bis(4-chlorophenyl)ethane; halogenated alcohol compounds such as 2,2,2,-trichloroethanol, tribromoethanol, l,3-dichloro-2-propano;
  • organic halogenated compounds preferably are those containing two or more halogen atoms that are attached to one carbon atom, more preferably are those containing three halogen atoms that are attached to one carbon atom.
  • the organic halogenated compounds may be used alone or in combination.
  • tribromomethyl phenylsulfone and 2,4-bis(trichloromethyl)-6-phenyltriazole are preferable.
  • the content of the coloring agent is preferably 0.01 to 20 % by mass based on the total components in the photosensitive layer, more preferably is 0.05 to 10 % by mass, and still more preferably is 0.1 to 5 % by mass.
  • the content of the halogenated compound is preferably 0.001 to 5 % by mass based on the total components in the photosensitive layer, more preferably is 0.005 to 1 % by mass.
  • - Dye To the photosensitive layer set forth above, a dye may be incorporated into in order to add a color so as to make easy the handling or to enhance the storage 5 stability.
  • the dye examples include Brilliant Green, eosin, Ethyl Violet, Erythrosine B, Methyl Green, Crystal Violet, Basic Fuchsine, phenolphthalein, 1,3-diphenyltriazine, Alizarin Red S, Thymolphthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengale, Metanil- Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl o Orange, Orange IV, diphenyl thiocarbazone, 2,7-dichlorofluorescein, Para Methyl Red, Congo Red, Benzopurpurine 4B, ⁇ -Naphthyl Red, Nile Blue 2B, Nile Blue A, phenacetarin, Methyl Violet, Malachite Green, Para Fuchsine, Oil Blue #603 (produced by Orient Chemical Industry Co., Ltd.), Rhodamine B, Rhodamine 6G, and Victoria Pure Blue BOH.
  • these dyes preferably are cation dyes such as 5 oxalate of Malachite Green and sulf ate of Malachite Green.
  • the pair anion of the cation dyes may be residues of organic acid or inorganic acid such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methane sulfonic acid, and toluene sulfonic acid.
  • the content of the dye is preferably 0.001 to 10 % by mass based on the total o components in the photosensitive layer, more preferably is 0.01 to 5 % by mass, and still more preferably is 0.1 to 2 % by mass.
  • Adhesion Promoter In order to enhance the adhesion between layers or between the pattern forming material and the substrate, so-called adhesion promoters may be employed. 5 Examples of the adhesion promoters set forth above include those described in JP-A Nos.
  • adhesion promoters include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-l-phenyl-triazole-2-thion, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thion, 5-amino-3-morpholmornethyl-thiadiazole-2-thion, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzottiazole, benzotriazole containing an amino group, and silane coupling agents.
  • the content of the adhesion promoter is preferably 0.001 to 20 % by mass based on the total components in the photosensitive layer, more preferably is 0.01 to 10 % by mass, and still more preferably is 0.1 to 5 % by mass.
  • the photosensitive layer may contain, as described in "Light Sensitive Systems, chapter 5th, by J. Curser", organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreductive dyes, or organic halogen compounds.
  • organic sulfur compounds examples include di-n-butyldisulfide, dibenzyldisulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyl ttichloromethane sulfonate, and 2-mercaptobenzimidazole.
  • peroxides examples include di-t-butyl peroxide, benzoyl peroxide, and methyethylketone peroxide.
  • the redox compounds set forth above are a combination of a peroxide and a reducer such as persulfate ion and ferrous ion, peroxide and ferric ion, or the like.
  • azo or diazo compound set forth above examples include diazoniums such as ⁇ , ⁇ '-azobis-isobutylonitrile, 2-azobis-2-methylbutylonitrile, and 4-aminodiphenylamine.
  • examples of the photoreductive dye set forth above include Rose Bengale, Erythrosine, Eosine, acriflavine, riboflavin, and thionine.
  • Surfactant In order to improve surface nonuniformity generated at producing the pattern forming material in the present invention, conventional surfactants may be employed. The surfactant may be properly selected from anionic surfactants, cationic surfactants, nonionic surfactants, ampholytic surfactants, fluorine-containing surfactant, and the like.
  • the content of the surfactant is preferably 0.001 to 10 % by mass based on the solid content of the photosensitive resin composition.
  • the content is less than 0.001 % by mass, the effect to improve the nonuniformity may be insufficient, and when the content is more than 10 % by mass, the adhesion ability may be deteriorated.
  • such polymer surfactants containing fluorine may be preferably exemplified as containing 40 % by mass or more of fluorine atoms, having, a carbon chain of 3 to 20 carbon atoms, and having a copolymerized component of acrylate or methacrylate containing an aliphatic group of which the hydrogen atoms bonded on the terminal carbon atom to the third of the carbon atom are substituted by fluorine atoms.
  • the thickness of the photosensitive layer may be properly selected without particular limitations; preferably, the thickness is 0.1 to 10 ⁇ m. « Barrier Layer » The barrier layer may be properly selected depending on the application as long as migration of substances may be suppressed.
  • the barrier layer When the barrier layer is insoluble in water, preferably is dispersible into water.
  • the barrier layer is soluble in water and/ or alkaline liquids.
  • the barrier layer should be removed in a process other than that of removing the photosensitive layer with the alkaline liquid, thus possibly resulting in an additional production process.
  • the substances of which the migration should be suppressed by the barrier layer are, for example, oxygen, water, component contained in the photosensitive layer or the cushioning layer.
  • the barrier layer may be properly selected depending on the application, preferably the barrier layer contain a resin.
  • the resin may be soluble or insoluble in water; preferably the resin is soluble in water or dispersible into water.
  • the resin is preferably soluble in a concenttation of 0.1 % by mass or more in water at 25 °C, more preferably 1 % by mass or more.
  • the resin may be properly selected depending on the application; examples of the resins include various resins soluble in alcohols, water, or alkaline liquids, various resins dispersible into alcohols or water, and resins capable of emulsified.
  • the resins may be vinyl polymers such as polyvinyl alcohols, modified polyvinyl alcohols, polyvinyl pyrrolidones, vinyl copolymers set forth above, water soluble polyamides, gelatin, celluloses, derivatives thereof, or various resins and compounds described in JP-B No. 2794242.
  • the oxygen gas permeability of the barrier layer may be properly selected depending on the application; preferably, the oxygen gas permeability is 100 cm 3 / (m 2 - day arm) or less, more preferably is 50 cm 3 / (m 2 - day arm) or less under a temperature of 23 °C and a relative humidity of 60 %.
  • the pattern forming material contains a barrier layer between the cushioning layer and the photosensitive layer, among the respective interlayer adhesive strengths between the respective layers, the interlayer adhesive strength between the support and the cushioning layer may be minimum, the interlayer adhesive strength between the cushioning layer and the barrier layer may be minimum, or the interlayer adhesive strength between the barrier layer and the photosensitive layer may be minimum.
  • the thickness of the barrier layer may be properly selected depending on the application; preferably the thickness is less than 10 ⁇ m, more preferably is 0.1 to 6 ⁇ m, and still more preferably is 1 to 5 ⁇ m. When the thickness is more than 10 ⁇ m, laser scattering tends to be induced at the barrier layer during the exposure, resulting in degradation of resolution and/ or adhesive property.
  • the pattern forming material may be produced as follows. Initially, a solution of photosensitive resin composition, a coating liquid for cushioning layer, and a coating liquid for barrier layer are prepared by dissolving, emulsifying, or dispersing the various components or materials set forth above into water or solvents.
  • the solvent of the solution of photosensitive resin composition, coating liquid for cushioning layer, and coating liquid for barrier layer may be properly selected depending on the application; examples of the solvent include alcohols such as ethanol, methanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; ektones such as acetone, methyl ethyl ketone, methylisobutylketone, cyclohexanone, o and diisobutylketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, and ethyl benzene; halogenated hydrocarbons such
  • the coating liquid for cushioning layer is coated on the support to dry o the coating thereby to form a cushioning layer
  • the coating liquid for barrier layer is coated on the cushioning layer to dry the coating thereby to form a barrier layer
  • the solution of photosensitive resin composition is coated on the barrier layer to dry the coating thereby to form a photosensitive layer, thus a pattern forming material may be produced.
  • the solution of photosensitive resin composition, the coating liquid for cushioning layer, and the coating liquid for barrier layer may be properly coated depending on the application; examples of the coating method include spraying method, roll coating method, rotary coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, gravure coating method, wire bar coating method, and knife coating method.
  • the drying conditions at the coating methods depend on the various components, species of solvent, and the solvent amount in general; usually, the temperature is 60 to 110 °C and the period is 30 seconds to 15 minutes.
  • the support is formed from a transparent synthetic resin; o examples of the synthetic resin include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, diacetyl cellulose, polyalkyl methacrylate, polymethacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinylchloride-vinylacetate copolymer, polytettafluoroethylene, polytrifluoroethylene, 5 cellulose film, and nylon film; among these resins, polyethylene terephthalate is particularly preferable. These resins may be used alone or in combination.
  • the thickness of the support may be properly selected depending on the application; preferably, the thickness is 2 to 150 ⁇ m, more preferably is 5 to 100 ⁇ m, and still more preferably is 8 to 50 ⁇ m.
  • the shape of the support may be properly selected depending on the application; preferably the shape is elongated. The length of the elongated support is selected from 10 to 20000 meters, for example.
  • a protective film may be provided on the photosensitive layer.
  • the material of the protective film may be those exemplified 5 with respect to the support set forth above, and also may be paper, polyethylene, paper laminated with polypropylene, or the like. Among these materials, polyethylene film and polypropylene film are preferable.
  • the thickness of the protective film may be properly selected without particular limitations; preferably, the thickness is 5 to 100 ⁇ m, more preferably is 8 to 50 ⁇ m, and still more preferably is 10 to 30 ⁇ m.
  • the adhesive strength A between the photosensitive layer and the support, and the adhesive strength B between the photosensitive layer and the protective film represent the following 5 relation: adhesive strength A > adhesive strength B.
  • support/ protective film are exemplified by (polyethylene terephthalate/ polypropylene), (polyethylene terephthalate/ polyethylene), (polyvinyl chloride/ cellophane), (polyimide/polypropylene), and (polyethylene o terephthalate/ polyethylene terephthalate).
  • the surface treatment of the support and/ or the protective film may result in the relation of the adhesive strength set forth above.
  • the surface treatment of the support may be utilized for enhancing the adhesive strength with the photosensitive layer; examples of the surface treatment include deposition of under-coat layer, corona discharge treatment, flame5 treatment, UV-rays treatment, RF exposure treatment, glow discharge tteatment, active plasma treatment, and laser beam treatment.
  • the static friction coefficient between the support and the protective film is preferably 0.3 to 1.4, more preferably is 0.5 to 1.2.
  • winding displacement o may generate in roll configuration due to excessively high slipperiness, and when the static friction coefficient is more than 1.4, winding of the material in a roll configuration tends to be difficult.
  • the pattern forming material is wound on a cylindrical winding core, and is stored in an elongated roll configuration.
  • the length of the elongated 5 pattern forming material may be properly selected without particular limitations, for example the length is from 10 to 20000 meters.
  • the pattern forming material may be subjected to slit processing for easy handling in the usages, and may be provided as a roll configuration for every 100 to 1000 meters. Preferably, the pattern forming material is wound such that the support exists at outer most side of the roll configuration. Further, the pattern forming material may be slit into a sheet configuration.
  • a separator of moistureproof with desiccant in particular is provided at the end surface of the pattern forming material, and the package is performed by a material of higher moistureproof for preventing 5 edge fusion.
  • the protective film may be subjected to surface treatment in order to control the adhesive property between the protective film and the photosensitive layer.
  • the surface treatment is performed, for example, by providing an under-coat layer of polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and o polyvinyl alcohol on the surface of the protective film.
  • the under-coat layer may be formed by coating the liquid of the polymer on the surface of the protective film, then drying the coating at 30 to 150 °C, in particular 50 to 120 °C for 1 to 30 minutes.
  • other layers such as a peeling layer, adhesive layer, optical absorbing layer, and surface 5 protective layer may be provided.
  • the substrate may be properly selected from commercially available materials, which may be of nonuniform surface other than of highly smooth surface.
  • the substrate is plate-like; specifically, the substrate selected from the o materials such as printed wiring boards e.g. cupper-laminated plate, glass plates e.g. soda glass plate, synthetic resin films, paper, and metal plates.
  • the substrate is utilized such that the photosensitive layer of the pattern forming material is duplicated on the substrate to form a consolidated laminate.
  • a pattern may be formed by a developing step, for example, 5 through exposing the photosensitive layer of the pattern forming material on the laminate thereby hardening the exposed region.
  • the process for forming the laminated body may be properly selected depending on the application; preferably, the pattern forming material is laminated to the substrate while the pattern forming material is being subjected to at least one of heating and pressing.
  • the heating temperature may be properly selected depending on the application; preferably the temperature is 15 to 180 °C, more preferably is 60 to 140 °C.
  • the pressure may be properly selected depending on the application; 5 preferably the pressure is 0.1 to 1.0 MPa, more preferably is 0.2 to 0.8 MPa.
  • the apparatus for conducting the heating and/ or pressing may be properly selected depending on the application; examples of the apparatus include a laminator, vacuum laminator and the like.
  • the pattern forming material i ⁇ the present invention may be applied to o printed wiring boards, color filters; display members such as column member, rib member, spacer, and partition member; holograms, micro machines, and proofs. Also, the pattern forming material may be applied to the pattern forming processes according to the present invention.
  • the other steps may be properly conducted by applying the conventional steps for forming patterns such as developing step, etching step, and plating step. These steps may be employed singly or in combination.
  • the developing step the photosensitive layer of the pattern forming material is exposed, the exposed region of the photoconductive layer is hardened, o then the unhardened region is removed, thereby a pattern is produced.
  • the method to remove the unhardened region may be properly selected without particular limitations; for example, the unhardened region may be removed by a developer.
  • the developer may be properly selected depending on the application;5 examples of the developers include alkaline aqueous solutions, aqueous developing liquids, and organic solvents; among these, weak alkali aqueous solutions are preferable.
  • the basic components of the weak alkali aqueous solutions are exemplified by lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, and borax.
  • the weak alkali aqueous solution exhibits a pH of about 8 to 12, more preferably is about 9 to 11. Examples of such a solution are aqueous solutions 5 of sodium carbonate and potassium carbonate at a concentration of 0.1 to 5 % by mass.
  • the temperature of the developer may be properly selected depending on the developing ability of the developer; for example, the temperature of the developer is about 25 to 40 °C.
  • the developer may be combined with surfactants, defoamers; organic bases o such as ethylene diamine, ethanol amine, tetramethylene ammonium hydroxide, diethylene ttiamine, triethylene pentamine, morpholine, and triethanol amine; organic solvents to promote developing such as alcohols, ketones, esters, ethers, amides, and lactones.
  • the developer set forth above may be an aqueous developer selected from aqueous solutions, aqueous alkali solutions, combined solutions of 5 aqueous solutions and organic solvents, or an organic developer.
  • the etching may be carried out by a method selected properly from conventional etching method.
  • the etching liquid in the etching method may be properly selected depending on the application; when the metal layer set forth above is formed of o copper, exemplified are cupric chloride solution, ferric chloride solution, alkali etching solution, and hydrogen peroxide solution for the etching liquid; among these, ferric chloride solution is preferred in light of the etching factor.
  • the etching treatment and the removal of the pattern forming material may form a permanent pattern on the substrate.
  • the permanent pattern may be properly 5 selected depending on the application; for example, the pattern is of wiring.
  • the plating step may be performed by a method selected from conventional plating treatment methods.
  • plating treatment examples include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, nickel plating such as watt bath (nickel sulf ate-nickel chloride) plating and nickel sulf amate plating, and gold plating such as hard gold plating and soft gold plating.
  • a permanent pattern may be formed by performing a plating treatment in the plating step, followed by removing the pattern forming material and optional etching treatment on unnecessary portions.
  • permanent patterns may be precisely and effectively formed by suppressing the distortion of images formed on the pattern forming material, therefore, the pattern forming process may be successfully applied to various patterns that require highly precise exposure, in particular to highly precise wiring patterns.
  • the pattern forming process according to the present invention may be successfully applied to the production of printed wiring boards, in particular the printed wiring boards having through holes pr via holes.
  • the process for producing printed wiring boards based on the pattern forming process according to the present invention will be explained in the following.
  • a pattern may be formed by (i) laminating the pattern forming material on a substtate of a printed wiring board having holes such that the photosensitive layer faces the substrate thereby to form a laminated body, (ii) irradiating a light onto the regions for forming wiring patterns and holes from the opposite side of the substrate of the laminated body thereby to harden the photosensitive layer, (iii) removing the support of the pattern forming material from the laminated body, and (iv) developing the photosensitive layer of the laminated body to remove unhardened portions in the laminated body.
  • removing the support of (iii) may be carried out between the (i) and (ii) instead of between (ii) and (iv) set forth above.
  • etching treatment or plating treatment of the substrate of the printed wiring board by means of conventional subtractive or additive method e.g. semi-additive or full-additive method may produce the printed wiring board.
  • the subtractive method is preferable in order to form printed wiring boards by industrially advantageous tenting. After the treatment, the hardened resin remaining on the substrate of the printed wiring board is peeled, or copper thin film is etched after the peeling in the case of semi-additive process, thereafter the intended printed wiring board is obtained.
  • the substrate of printed wiring board is prepared in which the surface of the substrate is covered with a metal plating layer.
  • the substrate of printed wiring board may be a copper-laminated layer substrate, a substrate that is produced by forming a copper plating layer on a insulating substrate such as glass or epoxy resin, or a substrate that is laminated on these substrate and formed into a copper plating layer.
  • the protective film is peeled, and the photosensitive layer of the pattern forming material is contact bonded to the surface of the printed wiring board by means a pressure roller as a laminating process, thereby a laminated body may be obtained that contains the substrate of the printed wiring board and the laminated body set forth above.
  • the laminating temperature of the pattern forming material may be properly selected without particular limitations; the temperature may be about room temperature such as 15 to 30 °C, or higher temperature such as 30 to 180 °C, preferably it is substantially warm temperature such as 60 to 140 °C.
  • the roll pressure of the contact bonding roll may be properly selected without particular limitations; preferably the pressure is 0.1 to 1 MPa; the velocity of the contact bonding may be properly selected without particular limitations, preferably, the velocity is 1 to 3 meter/ minute.
  • the substrate of the printed wiring board may be pre-heated before the contact bonding; and the substrate may be laminated under a reduced pressure.
  • the laminated body may be formed by laminating the pattern forming material on the substrate of the printed wiring board; alternatively by coating the solution of the photosensitive resin composition for pattern forming material directly on the substtate of the printed wiring board, followed by drying the solution, thereby laminating the photosensitive layer on the substrate of the printed wiring board.
  • a laser beam is irradiated onto the photosensitive layer from the opposite side of the substtate of the laminated body thereby to harden the photosensitive layer.
  • the irradiation is performed after the support is peeled, depending on the requirement such that the transparency of the support is lower.
  • the support is peeled from the laminated body as the support peeling step.
  • the un-hardened region of the photosensitive layer on the substtate of the printed wiring board is dissolved away by means of an appropriate developer, a pattern is formed that contains a hardened layer for forming a wiring pattern and a hardened layer for protecting a metal layer of through holes, and the metal layer is exposed at the substrate surface of the printed wiring board as the developing step.
  • Additional treatment to promote the hardening reaction may be performed by means of post-heating or post-exposing optionally.
  • the developing may be of a wet method set forth above or a dry developing method. Then, the metal layer exposed on the substrate surface of the printed wiring board is dissolved away by an etching liquid as an etching process.
  • the apertures of the through holes are covered by cured resin or tent film, therefore, the etching liquid does not infiltrate into the through holes to corrode the metal plating within the through holes, and the metal plating may maintain the specific shape, thus a wiring pattern may be formed on the substrate of the printed wiring board.
  • the etching liquid may be properly selected depending on the application; cupric chloride solution, ferric chloride solution, alkali etching solution, and hydrogen peroxide solution are exemplified for the etching liquid when the metal layer set forth above is formed of copper; among these, ferric chloride solution is preferred in light of the etching factor.
  • the hardened layer is removed from the substtate of the printed wiring board by means of a strong alkali aqueous solution for example as the removing step of hardened material.
  • the basic component of the strong alkali aqueous solution may be properly selected without particular limitations, examples of the basic component include sodium hydroxide and potassium hydroxide.
  • the pH of the strong alkali aqueous solution may be about 12 to 14 for example, preferably is about 13 to 14.
  • the strong alkali aqueous solution may be an aqueous solution of sodium hydroxide or potassium hydroxide at a concentration of 1 to 10 % by mass.
  • the printed wiring board may be of multi-layer construction.
  • the plating method may be copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating.
  • solder plating such as high flow solder plating
  • nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating
  • gold plating such as hard gold plating and soft gold plating.
  • Example 1 Production of Pattern Forming Material -
  • the coating liquid for cushioning layer of the following ingredients was coated on a polyethylene terephthalate film of 16 ⁇ m thick as the support and the coating was dried to form a cushioning layer of 15 ⁇ m thick.
  • [Ingredients of Coating Liquid for Cushioning Layer] Copolymer of methyl methacrylate/2-ethylhexyl acrylate/ benzyl
  • the photosensitive layer was contact bonded while the protective film of the pattern forming material was peeled away by means of Laminator (Model 8B-720-PH, by Taisei-Laminator Co.) so as to contact the photosensitive layer with the copper laminated plate, thereby a laminated body was obtained which comprises the copper laminated plate, the photosensitive layer, the cushioning layer, and the polyethylene terephthalate as the support in order.
  • the maximum height Rz of the surface of the photosensitive layer laminated on the copper laminated plate was 3 ⁇ m in accordance with JIS B 0601.
  • the conditions of the contact bonding were such that temperature of contact bonding roll: 105 °C, pressure of contact bonding roll: 0.3 MPa, and laminating rate: 1 meter/ minute (m/min).
  • the resulting laminated body was evaluated as to the resolution, exposure rate, and etching property. The result is shown in Table 3.
  • the period from the initial spraying to the dissolving away of the photosensitive layer on the copper laminated plate was measured, and the period was defined as the shortest developing period. As the result, the shortest developing period was 15 seconds.
  • Laser beam was irradiated to the photosensitive layer of the pattern forming material in the laminated body, in which the laser beam was varied as to the optical energy quantity from 0.1 mj/cm 2 to 100 mj/cm 2 in every increments of 2 1 / 2 times, the laser beam was irradiated from the side of the polyethylene terephthalate film by means of a pattern forming apparatus set forth later, thereby a part of the 5 photosensitive layer was hardened.
  • the polyethylene terephthalate film as the support was peeled away from the laminated body, then an aqueous solution of sodium carbonate at 1 % by mass concentration was sprayed on the entire surface of the photosensitive layer on the copper laminated plate at 30 °C o and 0.15 MPa for the period of two times the shortest developing period obtained in (1) set forth above, thereby the un-hardened portion was removed away, and the thickness of the remaining hardened layer was measured. Then, a sensitivity curve was prepared by plotting the relation between irradiated optical quantity and the thicknesses of the hardened layers.
  • the optical 5 energy quantity at which the thickness of the hardened region came to 5 ⁇ m was determined, and the optical energy quantity was defined as the optical energy quantity that was necessary to harden the photosensitive layer.
  • the optical energy quantity that was necessary to harden the photosensitive layer was 2 mj/cm 2 .
  • a pattern forming apparatus was employed that comprised the combined laser source shown in FIGs. 27A to 32 as a laser source; DMD50 as the laser modulator, in which 1024 micromirrors are arrayed as one array in the main 5 scanning direction shown in FIGs.
  • microlens array 472 in which microlenses 474, of which one surface is toric surface as shown in FIG. 13 A, are arrayed; and optical systems 480, 482 that images the laser through the microlens array onto the pattern forming material.
  • optical systems 480, 482 that images the laser through the microlens array onto the pattern forming material.
  • the micromirror 62 may rotate around the rotating axis extending to Y direction.
  • the height displacements of micromirrors 62 are shown along the X and Y directions respectively.
  • the central portion of the micromirror With respect to the central portion of the micromirror,
  • the distortion in one diagonal direction i.e. Y direction is larger than the other diagonal direction. Therefore, the shape of laser beam B should be distorted at the collected site through microlenses 55a of microlens array 55.
  • FIGs. 16A and 16B the front shape and side shape of the entire microlens array 55 are shown in detail, and also shown the sizes of various portions in the unit
  • microlens array 55 is constructed such that 1024 of microlenses 55a are aligned in width direction to form one row and the 256 rows are arrayed in length direction.
  • each of the site of microlenses 55a is expressed by "j" in the width direction and "k" in the length direction.
  • FIGs. 17A and 17B the front shape and the side shape of microlens 55a of microlens array 55 are shown respectively.
  • contour lines of microlens 55a are also shown.
  • microlens 55a is non-spherical 5 surface in order to compensate the aberration due to the distortion of the reflective surface of micromirror 62.
  • microlens 55a is a toric lens; the curvature radius of optical X direction Rx is - 0.125 mm, and the curvature radius of optical Y direction Ry is - 0.1 mm.
  • the collecting condition of laser beam B within the cross section o parallel to the X and Y directions are approximately as shown in FIGs. 18 A and 18B respectively. Namely, comparing the X and Y directions, the curvature radius of microlens 55a is shorter and the focal length is also shorter in Y direction.
  • the values of "z" in the figures are expressed as the evaluation sites in focus direction of microlens 55a by the distance from the laser beam irradiating surface of microlens 55a.
  • the surface shape of microlens 55a in the simulation may be calculated by o the following equation.
  • X means the distance from optical axis O in X direction
  • Y means the distance from optical axis O in Y5 direction.
  • aperture arrays 59 disposed near the collecting site of microlens array 55 is constricted such that each aperture 59a receive only the light through the corresponding microlens 55a. Namely, aperture array 59 may afford the respective apertures with the insurance that the light incidence from the adjacent apertures 59a may be prevented and the extinction ratio may be enhanced.
  • the polyethylene terephthalate film as the support was peeled away from the laminated body, then an aqueous solution of sodium carbonate at 1 % by mass concenttation was sprayed on the entire surface of the photosensitive layer on the copper laminated plate at 30 °C and 0.15 MPa for the period of two times the shortest developing period obtained in (1) set forth above, thereby the un-hardened portion was removed away.
  • the resultant copper laminated plate with hardened resin pattern was observed by means of an optical microscope; and the narrowest line width, at which abnormality of lines such as clogging, deformation, or the like does not exist, was determined, then the narrowest widths were defined as the resolution. Namely, the smaller value means the better resolution.
  • Exposing Rate > By means of the pattern forming apparatus set forth above, the exposing laser and relative transferring rate of the photosensitive layer were changed, thus the velocity to form usual patterns was measured. The exposing was carried out from the side of polyethylene terephthalate film onto the photosensitive layer of the pattern forming material of the laminated body. The higher exposing rate may enable to form patterns more effectively.
  • a ferric chloride etchant etching solution containing ferric chloride, 40° baume, solution temperature: 40 °C
  • Example 2 A pattern forming material was produced in the same manner as Example 1, except that the coating liquid for cushioning layer was changed into the coating liquid of which the ingredient is shown below, the thickness of the cushioning layer was changed into 17 ⁇ m, and a barrier layer was not coated. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. Further, the resultant pattern forming material was forced to peel, then the peeled sites were inspected by way of measuring the thicknesses of the peeled pattern f orming material; consequently, it is demonstrated that the peeling was caused at the interface between the cushioning layer and the photosensitive layer. The shortest developing period was 4 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/ cm 2 . [Ingredients of Coating Liquid for Cushioning Layer]
  • Example 3 A pattern forming material was produced in the same manner as Example 1, except that the coating liquid for cushioning layer was changed into the coating liquid of which the ingredient is shown below. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. Further, the resultant pattern forming material was forced to peel, then the peeled sites were inspected by way of measuring the thicknesses of the peeled pattern forming material; consequently, it is demonstrated that the peeling was caused at the interface between the cushioning layer and the photosensitive layer. The shortest developing period was 6 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/cm 2 . [Ingredients of Coating Liquid for Cushioning Layer]
  • a pattern forming material was produced in the same manner as Example 1, except that a cushioning layer and a barrier layer were not coated on the pattern forming material. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. o Further, the shortest developing period was 4 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/cm 2 .
  • Comparative Example 2 A pattern forming material was produced in the same manner as Example 1, except that a cushioning layer and a barrier layer were not coated on the pattern5 forming material and that all of the micromirrors of the DMD (1024 x768) were driven under control.
  • Example 3 A pattern forming material was produced in the same manner as Example 1, except that a cushioning layer and a barrier layer were not coated on the pattern forming material, all of the micrornirrors of the DMD (1024 x768) were driven under 5 control, and the combined laser source in the pattern forming apparatus was changed into GaN semiconductor laser LDl shown in FIG. 29. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. The shortest developing period was 4 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/cm 2 Table 3
  • the present invention may be appropriately applied to produce highly o fine and precise permanent patterns, in particular highly fine and precise wiring patterns.

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Abstract

The object of the present invention is to provide pattern forming processes that may form permanent patterns such as a wiring pattern with high fineness and preciseness, and sufficient efficiency due to suppressing the image deformation formed on pattern forming materials. In order to attain the object, a pattern forming process is provided which comprises modulating a laser beam irradiated from a laser source, compensating the modulated laser beam, and exposing a photosensitive layer by the modulated and compensated laser beam, wherein the photosensitive layer is disposed on a substrate to form a pattern forming material, the modulating is performed by a laser modulator which comprises plural imaging portions each capable of receiving the laser beam and outputting the modulated laser beam, and the compensating is performed by transmitting the modulated laser beam through plural microlenses each having a non-spherical surface capable of compensating the aberration due to distortion of the output surface of the imaging portion, and the plural microlenses are arranged to a microlens array.

Description

DESCRIPTION PATTERN FORMING PROCESS
Technical Field 5 The present invention relates to pattern forming processes in which laser beams modulated by laser modulators such as spatial light modulators are imaged on pattern forming materials, thereby exposing the pattern forming materials.
Background Art o Exposing devices have become popular in which lights or laser beams modulated by spatial light modulators and the like are directed to imaging optical systems and optical images are formed on pattern forming materials so as to expose the pattern forming materials. Typically, such exposing devices are comprised of a spatial light modulator that is equipped with planar arrays of many imaging portions 5 that modulate an incident light or laser beam depending on various controlling signals, a laser source that irradiates a laser beam to the spatial light modulator, and an imaging optical system that forms an image from the modulated laser beam through the spatial light modulator onto a pattern forming material (Akito Ishikawa, "Shortening of Research and Application to Massproduction by Mas less Exposure", o Electronics Jisso Gijyutsu, edd. by Gicho Publishing & Advertising Co., Ltd., vol. 18, No. 6, pp.74-79 (2002); Japanese Patent Application Laid-Open (JP-A) No. 2004-1244). Examples of the spatial light modulators include liquid crystal displays (LCD), digital micromiriOr devices (DMD), and the like. The DMD refers to a mirror device that is equipped with planar arrays of many micromirrors as imaging 5 portions that change the reflecting angle depending on the controlling signal. In the exposing devices, images to be projected on the pattern forming material are often desired to magnify, thus a magnified imaging optical system is utilized as the imaging optical system for responding to such a desire. However, the means to solely direct the modulated light from the spatial light modulator into the magnified imaging optical system leads to magnify the light flux from the respective imaging portions of the spatial light modulator, resulting in a disadvantage that clearness of pixels decreases due to magnified pixel size within the projected pattern. In order to address such a disadvantage, JP-A 2004-1244 set forth above proposes a magnified projection, wherein a first imaging optical device is on a path of laser beam modulated by the spatial light modulator, an array of microlenses is disposed on the imaging surface of the first imaging optical device, the microlenses respectively correspond to the imaging portions of the spatial light modulator, a second imaging optical device is disposed on the path of laser beam from the array of microlenses that images the modulated light on a pattern forming material or a screen, and images are magnified by the first and the second imaging optical devices. In this proposal, while the size of images projected on the pattern forming material or screen may be magnified, the laser beam from the respective imaging portions of the spatial light modulator is collected by the respective microlenses of the array; therefore, the drawing size or spot size of the projected image is focused and reduced, resulting in higher sharpness of images. In addition, exposure devices that combine DMD as the spatial light modulator and a microlens array are proposed (see JP-A No. 2001-305663). Similar exposure devices are also proposed in which a perforated plate having apertures corresponding to the microlens of the array is disposed behind the microlens array, such that only the laser beam through the microlenses pass through the apertures (see JP-A No. 2001-500628). In these exposure devices, excluding the incident laser beam from the adjacent microlenses that do not correspond to the respective apertures may enhance extinction ratio. However, these proposals suffer from a problem that images formed on the pattern forming materials are deformed through utilizing the laser beam collected by the microlenses of the array. The problem is significant in particular when the DMD is utilized as the spatial light modulator. Further, in addition to the problems set forth above, when substrates on which permanent patterns such as wiring patterns are to be formed contain nonunif ormity on the surface, when fine dusts are deposited on the substrates, or when bubbles generate at laminating a pattern orming material on the substrates, 5 non-adhesive regions generate between the substrate and the pattern forming material, thus there arise a problem that highly fine and precise pattern are hardly obtainable. In order solve such a problem, JP-A Nos. 57-21890 and 57-21891 propose processes in which water is sprayed on a substrate then a photosensitive film for o forming a circuit is laminated on the substrate. However, in this proposal, the substrate surface should be cleaned so as to coat uniformly the thin layer of water; and small through halls tend to induce a reaction between the water in the through halls and the photosensitive layer, resulting another problem that the developing property is deteriorated. 5 JP-A No. 52-154363 proposes a process in which a liquid resin is coated on a substrate to form an adhesive intermediate layer, then a photosensitive film for forming a circuit is laminated on the substrate. However, in this proposal, there exist such problems that the developing property and the peeling property at the through halls are insufficient, and the cost for coating the liquid resin is significant. o Japanese Patent Application Publication (JP-B) No. 53-31670 and JP-A No. 51-63702 propose a laminating process by means of a vacuum laminator under a reduced pressure. However, in this proposal, there exist such problems that the apparatus is expensive and reducing the pressure is time consuming. As such, pattern forming processes have not been provided yet that may 5 form highly fine and precise permanent patterns with sufficient efficiency owing to suppressing deformation of images formed on pattern forming materials as well as employing a pattern forming material that exhibits high conf ormability to nonunif ormity of substrates on which permanent patters are to be formed; and the improvement of such pattern forming processes has been demanded currently. Disclosure of Invention An object of the present invention is to provide pattern forming processes that may form highly fine and precise permanent patterns with sufficient efficiency owing to suppressing deformation of images formed on pattern forming materials as well as employing a pattern forming material that exhibits high conf ormability to nonunif ormity of substrates on which permanent patters are to be formed. The object may be attained by the pattern forming process according to the present invention which comprises modulating a laser beam irradiated from a laser source, compensating the modulated laser beam, and exposing a photosensitive layer in a pattern forming material by means of the modulated and compensated laser beam, wherein the pattern forming material comprises a support, a cushioning layer, and the photosensitive layer in order, the modulating is performed by a laser modulator which comprises plural imaging portions each capable of receiving the laser beam and outputting the modulated laser beam, and the compensating is performed by transmitting the modulated laser beam through plural microlenses each having a non-spherical surface capable of compensating the aberration due to distortion of the output surface of the imaging portion, and the plural microlenses are arranged to a microlens array. In the pattern forming process, the cushioning layer of the pattern forming material may bring about high conf ormability to nonunif ormity of substrate surface on which permanent patters are to be formed. Further, in the pattern forming process, the laser source irradiates the laser beam toward the laser modulator, the laser beam received by the plural imaging portions is modulated through irradiating the laser beam from the imaging portions, the aberration due to distortion of the output surface of the imaging portion is compensated by transmitting the modulated laser beam through plural microlenses and thus the distortion of images formed on the pattern forming material is controlled efficiently. Consequently, exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns. Preferably, the cushioning layer comprises a thermoplastic resin. Preferably, the Nicat softening temperature of the thermoplastic resin is 80 °C 5 or less. Preferably, the cushioning layer is swellable or soluble in an alkaline liquid. Preferably, the cushioning layer is insoluble in an alkaline liquid. Preferably, the thickness of the cushioning layer is 5 μm to 50 μm. Preferably, a barrier layer capable of suppressing migration of substances is o formed between the cushioning layer and the photosensitive layer. Preferably, the barrier layer is soluble or dispersible in water. Preferably, oxygen gas permeability of the barrier layer is 100 cm3/(m2- day- atm) or less under a temperature of 23 °C and a relative humidity of 60 %. 5 Preferably, the barrier layer comprises at least one of vinyl polymers and vinyl copolymers. Preferably, the thickness of the photosensitive layer is 0.1 to 10 μm. Preferably, the pattern forming material is laminated to the substrate while the pattern forming material is being subjected to at least one of heating and pressing, o then the pattern forming material is subjected to the exposing. Preferably, the non-spherical surface is a toric surface. The toric surface of the non-spherical surface may lead to efficient compensation of the aberration due to distortion of the output surface of the imaging portion, and the distortion of images formed on the pattern forming material may be controlled efficiently. Consequently, 5 exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns. Preferably, the laser modulator is capable of controlling a part of the plural imaging portions depending on pattern information. Controlling a part of the plural imaging portions depending on pattern information may result in the modulation of laser beam with higher velocity. Preferably, the laser modulator is a spatial light modulator, more preferably, the spatial light modulator is a digital micromirror device (DMD). Preferably, the exposing is performed by a laser beam transmitted through an aperture array. Such exposing by a laser beam transmitted through an aperture array may increase the extinction ratio. Consequently, exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns. Preferably, the exposing is performed while moving relatively the laser beam and the photosensitive layer. Such exposing while moving relatively the laser beam and the photosensitive layer may lead to exposing with higher velocity. Preferably, developing the photosensitive layer is performed following the exposing; preferably, forming a permanent pattern is performed following the developing. Preferably, the permanent pattern is a wiring pattern, and the permanent pattern is formed by means of at least one of etching treatment and plating treatment, which may lead to a highly fine and precise wiring patterns. Preferably, the laser source is capable of irradiating two or more types of laser beams which are combined with. Such irradiation of two or more types of lasers may lead to exposing with a longer focal depth. Consequently, exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns. Preferably, the laser source comprises plural lasers, a multimode optical fiber, and a collective optical system which collects the laser beams from the plural lasers into the multimode optical fiber. This configuration may lead to exposing with a longer focal depth. Consequently, exposing on the pattern forming material may be highly fine and precise, and developing of the photosensitive layer may result in highly fine and precise patterns. Preferably, the photosensitive layer comprises a binder, a polymerizable compound, and a photopolymerization initiator. Preferably, the binder contains an acidic group. Preferably, the binder contains a vinyl copolymer. Preferably, acid value of the binder is 70 mgKOH/g to 250 mgKOH/g. Preferably, the polymerizable compound comprises a monomer which contains at least one of urethane group and aryl group. Preferably, the photopolymerization initiator comprises a compound selected from the group consisting of halogenated hydrocarbon derivatives, hexaaryl-biimidazols, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acylphosphine oxides, and metallocenes. Preferably, the photosensitive layer comprises 10 % by mass to 90 % by mass of binder, 5 % by mass to 60 % by mass of polymerizable compound, and 0.1 % by mass to 30 % by mass of photopolymerization initiator. Preferably, the support comprises a synthetic resin and is transparent. Preferably, the support is of an elongated shape. Preferably, the pattern forming material is of an elongated shape formed by winding into a roll shape. Preferably, a protective film is formed on the photosensitive layer of the pattern forming material.
Brief Description of Drawings FIG. 1 is a partially enlarged view that shows exemplarily a construction of a digital micromirror device (DMD). FIG. 2A is a view that explains exemplarily the motion of the DMD. FIG. 2B is a view that explains exemplarily the motion of the DMD. FIG. 3A is an exemplary plan view that shows the exposing beam and the scanning line in the case that the DMD is not inclined. FIG. 3B is an exemplary plan view that shows the exposing beam and the scanning line in the case that the DMD is inclined. FIG. 4A is an exemplary view that shows an available region of the DMD. FIG.4B is an exemplary view that shows another available region of the DMD. FIG. 5 is an exemplary plan view that explains a way to expose a photosensitive layer in one scanning by means of a scanner. FIG. 6A is an exemplary plan view that explains a way to expose a photosensitive layer in plural scannings by means of a scanner. FIG. 6B is another exemplary plan view that explains a way to expose a photosensitive layer in plural scannings by means of a scanner. FIG. 7 is a schematic perspective view that shows exemplarily a pattern forming apparatus. FIG. 8 is a schematic perspective view that shows exemplarily a scanner construction of a pattern forming apparatus. FIG. 9A is an exemplary plan view that shows exposed regions formed on a photosensitive layer. FIG. 9B is an exemplary plan view that shows regions exposed by respective exposing heads. FIG. 10 is a schematic perspective view that shows exemplarily an exposing head containing a laser modulator. FIG. 11 is an exemplary cross section that shows the construction of the exposing head shown in FIG. 10 in the sub-scanning direction along the optical axis. FIG. 12 shows an exemplary controller to control the DMD based on pattern information. FIG. 13A is an exemplary cross section that shows a construction of another exposing head in other connecting optical system along the optical axis. FIG. 13B is an exemplary plan view that shows an optical image projected on an exposed surface when a microlens array is not employed. FIG. 13C is an exemplary plan view that shows an optical image projected on an exposed surface when a microlens array is employed. FIG. 14 is an exemplary view that shows distortion of a reflective surface of a micromirror that constitutes a DMD by means of contour lines. FIG 15A is an exemplary graph that shows height displacement of a micromirror along the X direction. FIG 15B is an exemplary graph that shows height displacement of a micromirror along the Y direction. FIG. 16A is an exemplary front view that shows a microlens array employed in a pattern forming apparatus. FIG. 16B is an exemplary side view that shows a microlens array employed in a pattern forming apparatus. FIG. 17A is an exemplary front view that shows a microlens of a microlens array. FIG. 17B is an exemplary side view that shows a microlens of a microlens array. FIG. 18 A is an exemplary view that schematically shows a laser collecting condition in a cross section of a microlens. FIG. 18B is an exemplary view that schematically shows a laser collecting condition in another cross section of a microlens. FIG. 19A is an exemplary view that shows a simulation of beam diameters near the focal point of a microlens in accordance with the present invention. FIG. 19B is an exemplary view that shows another simulation similar to FIG. 19A in terms of other sites in accordance with the present invention. FIG. 19C is an exemplary view that shows still another simulation similar to FIG. 19A in terms of other sites in accordance with the present invention. FIG. 19D is an exemplary view that shows still another simulation similar to
FIG. 19A in terms of other sites in accordance with the present invention. FIG. 20A is an exemplary view that shows a simulation of beam diameters near the focal point of a microlens in a conventional pattern forming process. FIG. 20B is an exemplary view that shows another simulation similar to FIG. 20A in terms of other sites. FIG. 20C is an exemplary view that shows still another simulation similar to FIG. 20 A in terms of other sites. FIG. 20D is an exemplary view that shows still another simulation similar to FIG. 20A in terms of other sites. FIG. 21 is an exemplary plan view that shows another construction of a combined laser source. FIG. 22A is an exemplary front view that shows a microlens of a microlens array. FIG. 22B is an exemplary side view that shows a microlens of a microlens array. FIG. 23A is an exemplary view that schematically shows a laser collecting condition in the cross section of the microlens shown in FIG. 22B. FIG. 23B is an exemplary view that schematically shows a laser collecting condition in another cross section of the microlens shown in FIG. 22B. FIG. 24A is an exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation. FIG. 24B is another exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation. FIG. 24C is another exemplary view that explains the concept of compensation by an optical system of optical quantity distribution compensation. FIG. 25 is an exemplary graph that shows an optical quantity distribution of Gaussian distribution without compensation of optical quantity. FIG. 26 is an exemplary graph that shows a compensated optical quantity distribution by an optical system of optical quantity distribution compensation. FIG. 27A (A) is an exemplary perspective view that shows a constitution of a fiber array laser source. FIG. 27A (B) is a partially enlarged view of FIG. 27A (A). FIG. 27 A (C) is an exemplary plan view that shows an arrangement of emitting sites of laser output. FIG. 27A (D) is an exemplary plan view that shows another arrangement of laser emitting sites. FIG. 27B is an exemplary front view that shows an arrangement of laser 5 emitting sites in a fiber array laser source. FIG. 28 is an exemplary view that shows a construction of a multimode optical fiber. FIG. 29 is an exemplary plan view that shows a construction of a combined laser source. o FIG. 30 is an exemplary plan view that shows a construction of a laser module. FIG. 31 is an exemplary side view that shows a construction of the laser module shown in FIG. 30. FIG. 32 is a partial side view that shows a construction of the laser module 5 shown in FIG. 30. FIG. 33 is an exemplary perspective view that shows a construction of a laser array. FIG. 34A is an exemplary perspective view that shows a construction of a multi cavity laser. o FIG.34B is an exemplary perspective view that shows a multi cavity laser array in which the multi cavity lasers shown in FIG. 34A are arranged in an array. FIG. 35 is an exemplary plan view that shows another construction of a combined laser source. FIG. 36A is an exemplary plan view that shows still another construction of a5 combined laser source. FIG. 36B is an exemplary cross section of FIG. 36A along the optical axis. FIG. 37A is an exemplary cross section of an exposing device that shows focal depth in the pattern f ori ing process of the prior art. FIG. 37B is an exemplary cross section of an exposing device that shows focal depth in the pattern forming process according to the present invention.
Best Mode for Carrying Out the Invention (Pattern Forming Process) 5 The pattern forming process according to the present invention comprises an exposing step, and other steps selected properly. [Exposing Step] In the exposing step, a pattern forming process is provided that comprises modulating a laser beam irradiated from a laser source, compensating the modulated l o laser beam, and exposing a photosensitive layer in a pattern forming material by means of the modulated and compensated laser beam, wherein the pattern forming material comprises a support, a cushioning layer, and the photosensitive layer in order, the modulating is performed by a laser modulator that comprises plural imaging portions each capable of receiving the laser beam and outputting the 15 modulated laser beam, and the compensating is performed by transmitting the modulated laser beam through plural microlenses each having a non-spherical surface capable of compensating the aberration due to distortion of the output surface of the imaging portion, and the plural microlenses are arranged to a microlens array. 20 - Laser Modulator - The laser modulator may be properly selected depending on the application as long as it comprises plural imaging portions. Preferable examples of the laser modulator include a spatial light modulator. Specific examples of the spatial light modulator include a digital micromirror 25 device (DMD), spatial light modulator of micro electro mechanical system type, PLZT element, and liquid crystal shatter; among these, the DMD is preferable. The laser modulator will be exemplarily explained with reference to figures in the following. DMD 50 is a mirror device that has lattice arrays of many micromirrors 62, e.g. 1024 x 768, on SRAM cell or memory cell 60 as shown in FIG. 1, wherein each of the micromirrors performs as a imaging portion. At the upper most portion of the each imaging portion, micromirror 62 is supported by a pillar. A material having a higher reflectivity such as aluminum is vapor deposited on the surface of the niicromirror. The reflectivity of the micromirrors 62 is 90 % or more; the array pitches in longitudinal and width directions are respectively 13.7 μm, for example. Further, SRAM cell 60 of a silicon gate CMOS produced by conventional semiconductor memory producing processes is disposed just below each micromirror 62 through a pillar containing a hinge and yoke. The mirror device is entirely constricted as a monolithic body. When a digital signal is written into SRAM cell 60 of DMD 50, micromirror 62 supported by a pillar is inclined toward the substrate, on which DMD 50 is disposed, within ± alpha degrees e.g. 12 degrees around the diagonal as the rotating axis. FIG. 2A indicates the condition that -rucrornirror 62 is inclined + alpha degrees at on state, FIG. 2B indicates the condition that micromirror 62 is inclined - alpha degrees at off state. As such, each incident laser beam B on DMD 50 is reflected depending on each inclined direction of micromirrors 62 by controlling each inclined angle of micromirrors 62 in imaging portions of DMD 50 depending on pattern information as shown in FIG. 1. By the way, FIG. 1 exemplarily shows a magnified condition of DMD 50 partly in which micromirrors 62 are controlled at an angel of - alpha degrees or + alpha degrees. Controller 302 connected to DMD 50 carries out on-off controls of the respective micromirrors 62. An optical absorber (not shown) is disposed on the way of laser beam B reflected by rnicromirrors 62 at off state. Preferably, DMD 50 is slightly inclined in the condition that the shorter side presents a pre~determined angle, e.g. 0.1 to 5 degrees against the sub-scanning direction. FIG. 3A shows scanning traces of reflected laser image or exposing beam 53 by the respective micromirrors when DMD 50 is not inclined; FIG. 3B shows scanning traces of reflected laser image or exposing beam 53 by the respective micromirrors when DMD 50 is inclined. In DMD 50, many micromirrors, e.g. 1024, are disposed in the longer direction to form one array, and many arrays, e.g. 756, are disposed in the shorter direction. Thus, by means of inclining DMD 50 as shown in FIG. 3B, the pitch Pi of scanning traces or lines of exposing beam 53 from each micromirror may be reduced than the pitch P2 of scanning traces or lines of exposing beam 53 without inclining DMD 50, thereby the resolution may be improved remarkably. On the other hand, the inclined angle of DMD 50 is small, therefore, the scanning direction W2 when DMD 50 is inclined and the scanning direction Wi when DMD 50 is not inclined are approximately the same. The process to accelerate the modulation rate of the laser modulator (hereinafter referring to as "high rate modulation") will be explained in the following. Preferably, the laser modulator is able to control any imaging portions of less than "ft" disposed successively among the imaging portions depending on the pattern information ("ft": an integer of 2 or more). Since there exist a limit in the data processing rate of the laser modulator and the modulation rate per one line is defined with proportional to the utilized imaging portion number, the modulation rate per one line may be increased through only utilizing the imaging portions of less than "ft" disposed successively. The high rate modulation will be explained with reference to figures in the following. When laser beam B is irradiated from fiber array laser source 66 to DMD 50, the reflected laser beam, at the micromirrors of DMD 50 being on state, is imaged on pattern forming material 150 by lens systems 54, 58. As such, the laser beam irradiated from the fiber array laser source is turned into on or off by the respective imaging portions, and the pattern forming material 150 is exposed in approximately the same number of imaging portion units or exposing areas 168 as the imaging portions utilized in DMD 50. In addition, when pattern forming material 150 is conveyed with stage 152 at a constant rate, pattern forming material 150 is sub-scanned to the direction opposite to the stage moving direction by scanner 162, thus exposed regions 170 of band shape are formed correspondingly to the respective exposing heads 166. In this example, micromirrors are disposed on DMD 50 as 1024 arrays in the main-scanning direction and 768 arrays in sub-scanning direction as shown in FIGs. 4A and 4B. Among these micromirrors, a part of rmcromirrors, e.g. 1024 x 256, may be controlled and driven by controller 302. In such control, the micromirror arrays disposed at the central area of DMD 50 may be employed as shown in FIG.4A; alternatively, the micromirror arrays disposed at the edge portion of DMD 50 may be employed as shown in FIG. 4B. In addition, when micromirrors are partly damaged, the utilized micromirrors may be properly altered depending on the situations such that micromirrors with no damage are utilized. Since there exist a limit in the data processing rate of DMD 50 and the modulation rate per one line is defined with proportional to the utilized imaging portion number, partial utilization of micromirror arrays leads to higher modulation rate per one line. Further, when exposing is carried out by moving continuously the exposing head relative to the exposing surface, the entire imaging portions are not necessarily required in the sub-scanning direction. When the sub-scanning of pattern forming material 150 is completed by scanner 162, and the rear end of pattern forming material 150 is detected by sensor 164, the stage 152 returns to the original site at the most upstream of gate 160 along guide 158, and the stage 152 is moved again from upstream to downstream of gate 160 along guide 158 at a constant rate. For example, when 384 arrays are utilized among the 768 arrays of micromirrors, the modulation rate may be enhanced two times compared to utilizing all of 768 arrays; further, when 256 arrays are utilized among the 768 arrays of micromirrors, the modulation rate may be enhanced three times compared to utilizing all of 768 arrays As explained above, when DMD 50 is provided with 1024 micromirror arrays in the mam-scanning direction and 768 micromirror arrays in the sub-scanning direction, controlling and driving of partial micromirror arrays may lead to higher modulation rate per one line compared to controlling and driving of entire micromirror arrays. In addition to the controlling and driving of partial rnicromirror arrays, elongated DMD on which many micromirrors are disposed on a substrate in planar arrays may increase similarly the modulation rate when the each angle of reflected surface is changeable depending on the various controlling signals, and the substrate is longer in a specific direction than its perpendicular direction. Preferably, the exposing is performed while moving relatively the exposing laser and the thermosensitive layer; more preferably, the exposing is combined with the high rate modulation set forth before, thereby exposing may be carried out with higher rate in a shorter period. As shown in FIG. 5, pattern forming material 150 may be exposed on the entire surface by one scanning of scanner 162 in X direction; alternatively, as shown in FIGs. 6A and 6B, pattern forming material 150 may be exposed on the entire surface by repeated plural exposing such that pattern forming material 150 is scanned in X direction by scanner 162, then the scanner 162 is moved one step in Y direction, followed by scanning in X direction. In this example, scanner 162 comprises eighteen exposing heads 166; each exposing head comprises a laser source and the laser modulator. The exposure is performed on a partial region of the photosensitive layer, thereby the partial region is hardened, followed by un-hardened region other than the partial hardened region is removed in developing step as set forth later, thus a pattern is formed. A pattern forming apparatus comprising the laser modulator will be exemplarily explained with reference to figures in the following. The pattern forming apparatus comprising the laser modulator is equipped with flat stage 152 that absorbs and sustains sheet-like pattern forming material 150 on the surface. On the upper surface of thick plate table 156 supported by four legs 154, two guides 158 are disposed that extend along the stage moving direction. Stage 152 is disposed such that the elongated direction faces the stage moving direction, and supported by guide 158 in reciprocally movable manner. A driving device is equipped with the pattern forming apparatus (not shown) so as to drive stage 152 along guide 158. At the middle of the table 156, gate 160 is provided such that the gate 160 strides the path of stage 152. The respective ends of gate 160 are fixed to both sides of table 156. Scanner 162 is provided at one side of gate 160, plural (e.g. two) detecting sensors 164 are provided at the opposite side of gate 160 in order to detect the front and rear ends of pattern forming material 150. Scanner 162 and detecting sensor 164 are mounted on gate 160 respectively, and disposed stationarily above the path of stage 152. Scanner 162 and detecting sensor 164 are connected to a controller (not shown) that controls them. As shown in FIGs. 8 and 9B, scanner 162 comprises plural (e.g. fourteen) exposing heads 166 that are arrayed in substantially matrix of "m rows x n lines" (e.g. three x five). In this example, four exposing heads 166 are disposed at third line considering the width of pattern forming material 150. The specific exposing head at "m" th row and "ft" th line is expressed as exposing head 166mn hereinafter. The exposing area 168 by exposing head 166 is rectangular having the shorter side in the sub-scanning direction. Therefore, exposed areas 170 are formed on pattern forming material 150 of a band shape that corresponds to the respective exposing heads 166 along with the movement of stage 152. The specific exposing area corresponding to the exposing head at "m" th row and "n" th line is expressed as exposing area 168mn hereinafter. As shown in FIGs. 9A and 9B, each of the exposing heads at each line is disposed with a space in the line direction (space: (longer side of exposing area) x natural number; two times in this example) so that exposed regions 170 of band shape are arranged without space in the perpendicular direction to the sub-scanning direction. Therefore, the non-exposing area between exposing area I6811 and I6812 at the first raw can be exposed by exposing area I6821 of the second raw and exposing area I6831 of the third raw. Each of exposing heads I6611 to 166mn comprises a digital micromirror device (DMD) 50 (by US Texas Instruments Inc.) as a laser modulator or spatial light modulator that modulates the incident laser beam depending on the pattern information as shown in FIGs. 10 and 11. Each DMD 50 is connected to controller 302 that comprises a data processing part and a mirror controlling part as shown in FIG. 12. The data processing part of controller 302 generates controlling signals to control and drive the respective micromirrors in the areas to be controlled for the respective exposing heads 166, based on the input pattern information. The area to be controlled will be explained later. The mirror driving-controlling part controls the reflective surface angle of each micromirror of DMD 50 per each exposing head 166 based on the control signals generated at the pattern information processing part. The control of the reflective surface angle will be explained later. At the incident laser side of DMD 50, fiber array laser source 66 that is equipped with a laser irradiating part where irradiating ends or en itting sites of optical fibers are arranged in an array along the direction corresponding with the longer side of exposing area 168, lens system 67 that compensate the laser beam from fiber array laser source 66 and collect it on the DMD, and mirrors 69 that reflect laser beam through lens system 67 toward DMD 50 are disposed in this order. FIG. 10 schematically shows lens system 67. Lens system 67 is comprised of collective lens 71 that collects laser beam B for illumination from fiber array laser source 66, rod-like optical integrator 72 (hereinafter, referring to as "rod integrator") inserted on the optical path of the laser passed through collective lens 71, and image lens 74 disposed in front of rod integrator 72 or the side of mirror 69, as shown FIG. 11. Collective lens 71, rod integrator 72, and image lens 74 make the laser beam irradiated from fiber array laser source 66 enter into DMD 50 as an luminous flux of approximately parallel beam with uniform intensity in the cross section. The shape and effect of the rod 5 integrator will be explained in detail later. Laser beam B irradiated from lens system 67 is reflected by mirror 69, and is irradiated to DMD 50 through a total internal reflection prism 70 (not shown in FIG. 10). At the reflecting side of DMD 50, imaging system 51 is disposed that images o laser beam B reflected by DMD 50 onto pattern forming material 150. The imaging system 51 is equipped with the first imaging system of lens systems 52, 54, the second imaging system of lens systems 57, 58, and microlens array 55 and aperture array 59 interposed between these imaging systems as shown in FIG. 11. Arranging two-dimensionally many microlenses 55a each corresponding to 5 the respective imaging portions of DMD 50 forms Microlens array 55. In this example, micromirrors of 1024 rows x 256 lines among 1024 rows x 768 lines of DMD 50 are driven, therefore, 1024 rows x 256 lines of microlenses are disposed correspondingly. The pitch of disposed microlenses 55a is 41 μm in both of raw and line directions. Microlenses 55a have a focal length of 0.19 mm and a numerical o aperture (NA) of 0.11 for example, and are formed of optical glass BK7. The shape of microlenses will be explained later. The beam diameter of laser beam B is 41 μm at the site of microlens 55a. Aperture array 59 is formed of many apertures 59a each corresponding to the respective microlenses 55a of microlens array 55. The diameter of aperture 59a is 10 5 μm, for example. The first imaging system forms the image of DMD 50 on microlens array 55 as a three times magnified image. The second imaging system forms and projects the image through microlens array 55 on pattern forming material 150 as a 1.6 times magnified image. Therefore, the image by DMD 50 is formed and projected on pattern forming material 150 as a 4.8 times magnified image. By the way, prism pair 73 is installed between the second imaging system and pattern forming material 150; through the operation to move up and down the prism pair 73, the image pint may be adjusted on the image forming material 150. 5 In FIG. 11, pattern forming material 150 is fed to the direction of arrow F as sub-sca-nning. The imaging portions may be properly selected depending on the application provided that the imaging portions can receive the laser beam from the laser source or irradiating means and can output the laser beam; for example, the imaging o portions are pixels when the pattern formed by the pattern forming process according to the present invention is an image pattern, alternatively the imaging portions are micromirrors when the laser modulator contains a DMD. The number of imaging portions contained in the laser modulator may be properly selected depending on the application. 5 The alignment of imaging portions in the laser modulator may be properly selected depending on the application; preferably, the imaging portions are arranged two dimensionally, more preferably are arranged in a lattice pattern. < Microlens Array > The microlens array may be properly selected depending on the application, o provided that microlenses have a non-spherical surface capable of compensating the aberration due to strain at irradiating surface of the imaging portion. The non-spherical surface may be properly selected depending on the application; preferably, the non-spherical surface is toric surface, for example. The microlens array, aperture array, imaging system set forth above will be 5 explained with reference to figures. FIG. 13 A shows an exposing head that is equipped with DMD 50, laser source 144 to irradiate laser beam onto DMD 50, lens systems or imaging optical systems 454 and 458 that magnify and image the laser beam reflected by DMD 50, microlens array 472 that arranges many microlenses 474 corresponding to the respective imaging portions of DMD 50, aperture array that aligns many apertures 478 corresponding to the respective microlenses of microlens array 472, and lens systems or imaging systems 480 and 482 that image laser beam through the apertures onto exposed surface 56. 5 FIG. 14 shows the flatness data as to the reflective surface of irricromirrors 62 of DMD 50. In FIG. 14, contour lines express the respective same heights of the reflective surface; the pitch of the contour lines is five nano meters. In FIG. 14, X direction and Y direction are two diagonal directions of micromirror 62, the micromirror 62 rotates around the rotation axis extending in Y direction. FIGs. 15A o and 15B show the height displacements of micromirrors 62 along the X and Y directions respectively. As shown in FIG. 14, FIGs. 15A and 15B, there exist strains on the reflective surface of micromirror 62, the strains of one diagonal direction (Y direction) is larger than another diagonal direction (X direction) at the central region of the mirror in 5 particular. Accordingly, a problem may be induced that the shape is distorted at the site that collects laser beam B by microlenses 55a of microlens array 55. In order to prevent such a problem, microlenses 55a of microlens array 55 are of special shape that is different from the prior art as explained later. FIGs. 16A and 16B show the front shape and side shape of the entire o microlens array 55 in detail. In FIGs. 16A and 16B, various parts of the microlens array are indicated as the unit of mm (millimeter). In the pattern forming process according to the present invention, micromirrors of 1024 rows x 256 lines of DMD 50 are driven as explained above; microlens array 55 are correspondingly constructed as 1024 arrays in length direction and 256 arrays in width direction. In FIG. 16A, the 5 site of each microlens is expressed as ")" th line and "k" th row. FIGs. 17A and 17B show respectively the front shape and side shape of one microlens 55a of microlens array 55. FIG. 17A shows also the contour lines of microlens 55a. The end surface of each microlens 55a of irradiating side is of non-spherical shape to compensate the strain aberration of reflective surface of micromirrors 62. Specifically, microlens 55a is a toric lens; the curvature radius of optical X direction Rx is - 0.125 mm, and the curvature radius of optical Y direction Ry is - 0.1 mm. Accordingly, the collecting condition of laser beam B within the cross section 5 parallel to the X and Y directions are approximately as shown in FIGs. 18A and 18B respectively. Namely, comparing the X and Y directions, the curvature radius of microlens 55a is shorter and the focal length is also shorter in Y direction. FIGs. 19A, 19B, 19C, and 19D show the simulations of beam diameter near the focal point of microlens 55a in the above noted shape by means of a computer. l o For the reference, FIGs. 20A, 20B, 20C, and 20D show the similar simulations for microlens of Rx = Ry = - 0.1 mm. The values of "z" in the figures are expressed as the evaluation sites in the focus direction of microlens 55a by the distance from the beam irradiating surface of microlens 55a. The surface shape of microlens 55a in the simulation may be calculated by 15 the following equation.
C χ 2 X 2 + C v 2 γ 2 Z = 1 +S Q R T ( 1 - C X 2 - C 2 Y 2)
In the above equation, Cx means the curvature radius (= 1/Rx) in X direction, Cy means the curvature radius (= 1/Ry) in Y direction, X means the distance from optical axis O in X direction, Y means the distance from optical axis O in Y direction.
2 o From the comparison of FIGs. 19A to 19D, and FIGs. 20A to 20D, it is apparent in the pattern forming process according to the present invention that the employment of the toric lens as the microlens 55a that has a shorter focal length in the cross section parallel to Y direction than the focal length in the cross section parallel to X direction may reduce the strain of the beam shape near the collecting
25 site. Accordingly, images are able to be exposed on pattern forming material 150 with more clearness and without strain. In addition, it is apparent that the inventive mode shown in FIGs. 19A to 19D may bring about a wider region with smaller beam diameter, i.e. longer focal depth. By the way, when the larger or smaller strain at the central region appears at the central region of micromirror 62 inversely with those set forth above, the employment of microlenses that has a shorter focal length in the cross section parallel to X direction than the focal length in the cross section parallel to Y direction may make possible to expose images on pattern forming material 150 with more clearness and without strain. Aperture arrays 59 disposed near the collecting site of microlens array 55 are constructed such that each aperture 59a receives only the laser beam through the corresponding microlens 55a. Namely, aperture array 59 may afford the respective apertures with the insurance that the light incidence from the adjacent apertures 55a may be prevented and the extinction ratio may be enhanced. Essentially, smaller diameter of apertures 59a provided for the above noted purpose may afford the effect to reduce the strain of beam shape at the collecting site of microlens 55a. However, such a construction inevitably increases the optical quantity interrupted by the aperture array 59, resulting in lower efficiency of optical quantity. On the contrary, the non-spherical shape of microlenses 55a does not bring about the light interruption, thus leading to maintain the higher efficiency of optical quantity. In the pattern forming process according to the present invention, the microlenses 55a may be non-spherical shape of secondary or higher order such as fourth or sixth. The employment of higher order non-spherical surface may lead to higher accuracy of beam shape. In the mode set forth above, the end surface of irradiating side of microlens 55a is non-spherical or toric; alternatively, substantially the same effect may be derived by constructing one of the end surface as a spherical surface and the other surface as cylindrical surface and thus providing the microlens. Further, in the mode set forth above, microlens 55a of microlens array 55 is non-spherical so as to compensate the aberration due to the strain of reflective surface of micromirror 62; alternatively, substantially the same effect may be derived by providing each microlens of the microlens array with the distribution of refractive index so as to compensate the aberration due to the strain of reflective surface of micromirror 62. FIGs. 22A and 22B show exemplarily such a microlens 155a. FIGs. 22A and
22B respectively show the front shape and side shape of microlens 155a. The entire shape of microlens 155a is a planar plate as shown in FIGs.22A and 22B. The X and Y directions in FIGs. 22A and 22B mean the same as set forth above. FIGs. 23A and 23B schematically show the condition to collect laser beam B by microlens 155a in the cross section parallel with X and Y directions respectively. The microlens 155a exhibits a refractive index distribution that the refractive index increases gradually from the optical axis O to outward direction; the broken lines in FIGs. 23A and 23B indicate the positions where the refractive index decreases a certain level from that of optical axis O. As shown in FIGs. 23A and 23B, comparing the cross section parallel to the X direction and the cross section parallel to the Y direction, the latter represents a rapid change in the refractive index distribution, and shorter focal length. Thus, the microlens array having such a refractive index distribution may provide the similar effect as the microlens array 55 set forth above. In addition, the microlens having a non-spherical surface as shown in FIGs. 17A, 17B, 18A and 18B may be provided with such a refractive index distribution, and both of the surface shape and the refractive index distribution may compensate the aberration due to strain of the reflective surface of micromirror 62. In the mode set forth above, the aberration due to strain of reflective surface of micromirror 62 in DMD 50 is compensated; similarly, in the pattern forming process according to the present invention that employs a spatial light modulator other than DMD, the possible aberration due to strain may be compensated and the strain of beam shape may be prevented when the strain appears at the surface of imaging portion of the spatial light modulator. The imaging optical system set forth above will be explained in the following. In the exposing head, when laser beam is irradiated from the laser source 144, the cross section of luminous flux reflected to on-direction by DMD 50 is magnified several times, e.g. two times, by lens systems 454, 458. The magnified laser beam is collected by each microlens of microlens array 472 correspondingly with each imaging portion of DMD 50, then passes through the corresponding apertures of aperture array 476. The laser beam passed through the aperture is imaged on exposed surface 56 by lens systems 480, 482. In the imaging optical system, the laser beam reflected by DMD 50 is magnified into several times by magnifying lenses 454, 458, and is projected onto exposed surface 56, therefore, the entire image region is enlarged. When microlens array 472 and aperture array 476 are not disposed, one drawing size or spot size of each beam spot BS projected on exposed surface 56 is enlarged depending on the size of exposed area 468, thus MTF (modulation transfer function) property that is a measure of sharpness at exposing area 468 is decreased, as shown in FIG. 13B. On the other hand, when microlens array 472 and aperture array 476 are disposed, the laser beam reflected by DMD 50 is collected correspondingly with each imaging portion of DMD 50 by each microlens of microlens array 472. Thereby, the spot size of each beam spot BS may be reduced into the desired size, e.g. 10 μm x 10 μm, even when the exposing area is magnified, as shown in FIG. 13C, and the decrease of MFT property may be prevented and the exposure may be carried out with higher accuracy. By the way, inclination of exposing area 468 is caused by the DMD 50 that is disposed with inclination in order to eliminate the spaces between imaging portions. Further, even when bean thickening exists due to aberration of microlenses, the beam shape may be arranged by the aperture array so as to form spots on exposed surface 56 with a constant size, and the crosstalk between the adjacent imaging portions may be prevented by passing the beam through the aperture array provided correspondingly to each imaging portion. In addition, employment of higher luminance laser source as laser source 144 may lead to prevention of partial entrance of luminous flux from adjacent imaging portions, since the angle of incident luminous flux is narrowed that enters into each microlens of microlens array 472 from lens 458; namely, higher extinction ratio may be achieved.
< Other Optical System > In the pattern forming process according to the present invention, the other optical system may be combined that is properly selected from conventional systems, for example, an optical system to compensate the optical quantity distribution may be employed additionally. The optical system to compensate the optical quantity distribution alters the luminous flux width at each output site such that the ratio of the luminous flux width at the periphery region to the luminous flux width at the central region near the optical axis is higher in the output side than the input side, thus the optical quantity distribution at the exposed surface is compensated to be approximately constant when the parallel luminous flux from the laser source is irradiated to DMD. The optical system to compensate the optical quantity distribution will be explained with reference to figures in the following. Initially, the optical system will be explained as for the case that the entire luminous flux widths HO and HI are the same between the input luminous flux and the output luminous flux, as shown in FIG. 24A. The portions denoted by reference numbers 51, 52 in FIG. 24A indicate imaginarily the input surface and output surface of the optical system to compensate the optical quantity distribution. In the optical system to compensate the optical quantity distribution, it is assumed that the luminous flux width hO of the luminous flux entered at central region near the optical axis Zl and luminous flux width hi of the luminous flux entered at peripheral region near are the same (hO = hi). The optical system to compensate the optical quantity distribution affects the laser beam that has the same luminous fluxes hO, hi at the input side, and acts to magnify the luminous flux width hO for the input luminous flux at the central region, and acts to reduce the luminous flux width hi for the input luminous flux at the periphery region conversely. Namely, the optical system affects the output luminous flux width hlO at the central region and the output luminous flux width hll at the periphery region to turn into 5 hll < hlO. In other words concerning the ratio of luminous flux width, (output luminous flux width at periphery region) / (output luminous flux width at central region) is smaller than the ratio of input, namely [hll/hlOJ is smaller than (hl/hO = 1) or (hll/hlO < 1). Owing to altering the luminous flux width, the luminous flux at the central o region representing higher optical quantity may be supplied to the periphery region where the optical quantity is insufficient; thereby the optical quantity distribution is approximately uniformed at the exposed surface without decreasing the utilization efficiency. The level for uniformity is controlled such that the nonuniformity of optical quantity is 30 % or less in the effective region for example, preferably is 20 %5 or less. When the luminous flux width is entirely altered for the input side and the output side, the operation and effect due to the optical system to compensate the optical quantity distribution are similar to those shown in FIGs. 24A, 24B, and 24C. FIG. 24B shows the case that the entire optical flux bundle HO is reduced and o outputted as optical flux bundle H2 (HO > H2). In such a case also, the optical system to compensate the optical quantity distribution tends to process the laser beam, in which luminous flux width hO is the same as hi at input side, into that the luminous flux width hlO at the central region is larger than the spherical region and the luminous flux width hll is smaller than the central region in the output side. 5 Considering the reduction ratio of the luminous flux, the optical system affects to decrease the reduction ratio of input luminous flux at the central region compared to the peripheral region, and affects to increase the reduction ratio of input luminous flux at the peripheral region compared to the central region. In the case also, (output luminous flux width at periphery region) / (output luminous flux width at central region) is smaller than the ratio of input, namely [H11/H10] is smaller than (hl/hO = 1) or (hll/hlO < 1). FIG. 24C explains the case that the entire luminous flux width HO at input side is magnified and output into width H3 (HO < H3). In such a case also, the 5 optical system to compensate the optical quantity distribution tends to process the laser beam, in which luminous flux width hO is the same as hi at input side, into that the luminous flux width hlO at the central region is larger than the spherical region and the luminous flux width hll is smaller than the central region in the output side. Considering the magnification ratio of the luminous flux, the optical system affects to o increase the magnification ratio of input luminous flux at the central region compared to the peripheral region, and affects to decrease the magnification ratio of input luminous flux at the peripheral region compared to the central region. In the case also, (output luminous flux width at periphery region) / (output luminous flux width at central region) is smaller than the ratio of input, namely [H11/H10] is 5 smaller than (hl/hO = 1) or (hll/hlO < 1). As such, the optical system to compensate the optical quantity distribution alters the luminous flux width at each input site, and lowers the ratio (output luminous flux width at periphery region) / (output luminous flux width at central region) at output side compared to the input side; therefore, the laser beam having o the same luminous flux turns into the laser beam at output side that the luminous flux width at central region is larger compared to that at the peripheral region and the luminous flux at the peripheral region is smaller compared to the central region. Owing to such effect, the luminous flux at the central region may be supplied to the periphery region, thereby the optical quantity distribution is approximately 5 uniformed at the luminous flux cross section without decreasing the utilization efficiency of the entire optical system. Specific lens data of a pair of combined lenses will be set forth exemplarily that is utilized for the optical system to compensate the optical quantity distribution. In this discussion, the lens data will be explained in the case that the optical quantity distribution shows Gaussian distribution at the cross section of the output luminous flux, such as the case that the laser source is a laser array as set forth above. In a case that one semiconductor laser is connected to an input end of single mode optical fiber, the optical quantity distribution of output luminous flux from the optical fiber shows Gaussian distribution. The pattern forming process according to the present invention may be applied, in addition, to such a case that the optical quantity near the central region is significantly larger than the optical quantity at the peripheral region as the case that the core diameter of multimode optical fiber is reduced and constructed similarly to a single mode optical fiber, for example. The essential data for the lens are summarized in Table 1 below. Table 1
Figure imgf000030_0001
As demonstrated in Table 1, a pair of combined lenses is constructed from two non-spherical lenses of rotational symmetry. The surfaces of the lenses are defined that the surface of input side of the first lens disposed at the light input side is the first surface; the opposite surface at light output side is the second surface; the surface of input side of the second lens disposed at the light input side is the third surface; and the opposite surface at light output side is the fourth surface. The first and the fourth surfaces are non-spherical. In Table 1, 'Si (surface No.)' indicates "i" th surface (i = 1 to 4), 'ri (curvature radius)' indicates the curvature radius of the "i" th surface, di (surface distance) means the surface distance between "i" th surface and "i+1" surface. The unit of di (surface distance) is millimeter (mm). Ni (refractive index) means the refractive index of the optical element comprising "i" th surface for the light of wavelength 405 nm. In Table 2 below, the non-spherical data of the first and the fourth surface are summarized. Table 2
Figure imgf000031_0002
The non-spherical data set forth above may be expressed by means of the coefficients of the following equation (A) that represent the non-spherical shape.
Figure imgf000031_0001
In the above formula (A), the coefficients are defined as follows: Z: length of perpendicular that extends from a point on non-spherical surface at height p from optical axis (mm) to tangent plane at vertex of non-spherical surface or plane vertical to optical axis; p: distance from optical axis (mm); K: coefficient for circular conic; C: paraxial curvature (1/r, r: radius of paraxial curvature); ai: "i" st non-spherical coefficient (i = 3 to 10). FIG. 26 shows the optical quantity distribution of illumination light obtained by a pair of combined lenses shown in Table 1 and Table 2. The abscissa axis represents the distance from the optical axis, the ordinate axis represents the proportion of optical quantity (%). FIG. 25 shows the optical quantity distribution (Gaussian distribution) of illumination light without the compensation. As is apparent from FIGs.25 and 26, the compensation by means of the optical system to compensate the optical quantity distribution brings about an approximately uniform optical quantity distribution significantly exceeding that without the compensation, thus uniform exposing may be achieved by means of uniform laser beam without decreasing the optical utilization efficiency. - Optical Irradiating Means or Laser Source - The optical irradiating means may be properly selected depending on the application; examples thereof include an extremely high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, fluorescent tube, LED, semiconductor laser, and the other conventional laser source, and also combination of these means.
Among these means, the means capable of irradiating two or more types of lights or laser beams is preferable. Examples of the light or laser beam irradiated from the optical irradiating means or laser source include UV-rays, visual light, X-ray, laser beam, and the like. Among these, laser beam is preferable, more preferably are those containing two or more types of laser beams (hereinafter, sometimes referring to as "combined laser"). The wavelength of the UV-rays and the visual light is preferably 300 to 1500 nm, more preferably is 320 to 800 ran, most preferably is 330 to 650 nm. The wavelength of the laser beam is preferably 200 to 1500 nm, more preferably is 300 to 800 nm, still more preferably is 330 to 500 nm, and most preferably is 400 to 450 nm. As for the means to irradiate the combined laser, such a means is preferably exemplified that comprises plural laser irradiating devices, a multimode optical fiber, and a collecting optical system that collect a respective laser beams and connect them to a multimode optical fiber. The means to irradiate combined laser or the fiber array laser source will be explained with reference to figures in the following. Fiber array laser source 66 is equipped with plural (e.g. fourteen) laser modules 64 as shown in FIG.27A. One end of each multimode optical fiber 30 is connected to each laser module 64. To the other end of each multimode optical fiber 30 is connected optical fiber 31 of which the core diameter is the same as that of multimode optical fiber 30 and of which the clad diameter is smaller than that of multimode optical fiber 30. As shown in FIG.27B specifically, the ends of multimode optical fibers 31 at the opposite end of multimode optical fiber 30 are aligned as seven ends along the main scanning direction perpendicular to the sub-scanning direction, and the seven ends are aligned as two rows, thereby laser output portion 68 is constructed. The laser output portion 68, formed of the ends of multimode optical fibers 31, is fixed by being interposed between two flat support plates 65 as shown in FIG.
27B. Preferably, a transparent protective plate such as a glass plate is disposed on the output end surface of multimode optical fibers 31 in order to protect the output end surface. The output end surface of multimode optical fibers 31 tends to bear dust and to degrade due to its higher optical density; the protective plate set forth above may prevent the dust deposition on the end surface and may retard the degradation. In this example, in order to align optical fibers 31 having a lower clad diameter into an array without a space, multimode optical fiber 30 is stacked between two multimode optical fibers 30 that contact at the larger clad diameter, and the output end of optical fiber 31 connected to the stacked multimode optical fiber 30 is interposed between two output ends of optical fibers 31 connected to two multimode optical fibers 30 that contact at the larger clad diameter. Such optical fibers may be produced by connecting concentrically optical 5 fibers 31 having a length of 1 to 30 cm and a smaller clad diameter to the tip portions of laser beam output side of multimode optical fiber 30 having a larger clad diameter, for example, as shown in FIG. 28. Two optical fibers are connected such that the input end surface of optical fiber 31 is fused to the output end surface of multimode optical fiber 30 so as to coincide the center axises of the two optical fibers. The o diameter of core 31a of optical fiber 31 is the same as the diameter of core 30a of multimode optical fiber 30 as set forth above. Further, a shorter optical fiber produced by fusing an optical fiber having a smaller clad diameter to an optical fiber having a shorter length and a larger clad diameter may be connected to the output end of multimode optical fiber through a 5 ferrule, optical connector or the like. The connection through a connector and the like in an attachable and detachable manner may bring about easy exchange of the output end portion when the optical fibers having a smaller clad diameter are partially damaged for example, resulting advantageously in lower maintenance cost for the exposing head. Optical fiber 31 is sometimes referred to as "output end o portion" of multimode optical fiber 30. Multimode optical fiber 30 and optical fiber 31 may be any one of step index type optical fibers, grated index type optical fibers, and combined type optical fibers. For example, step index type optical fibers produced by Mitsubishi Cable Industries, Ltd. are available. In one of the best mode according to the present invention, 5 multimode optical fiber 30 and optical fiber 31 are step index type optical fibers; in the multimode optical fiber 30, clad diameter = 125 μm, core diameter = 50 μm, NA = 0.2, transmittance = 99.5 % or more (at coating on input end surface); and in the optical fiber 31, clad diameter = 60 μm, core diameter = 50 μm, NA = 0.2. Laser beams at infrared region typically increase the propagation loss while the clad diameter of optical fibers decreases. Accordingly, a proper clad diameter is defined usually depending on the wavelength region of the laser beam. However, the shorter is the wavelength, the less is the propagation loss; for example, in the 5 laser beam of wavelength 405 nm irradiated from GaN semiconductor laser, even when the clad thickness (clad diameter - core diameter)/2 is made into about 1/2 of the clad thickness at which infrared beam of wavelength 800 nm is typically propagated, or made into about 1/4 of the clad thickness at which infrared beam of wavelength 1.5 μm for cornmunication is typically propagated, the propagation loss o does not increase significantly. Therefore, the clad diameter is possible to be as small as 60 μm. Needless to say, the clad diameter of optical fiber 31 should not be limited to 60 μm. The clad diameter of optical fiber utilized for conventional fiber array laser sources is 125 μm; the smaller is the clad diameter, the deeper is the focal depth; 5 therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, more preferably is 60 μm or less, still more preferably is 40 μm or less. On the other hand, since the core diameter is appropriately at least 3 to 4 μm, the clad diameter of optical fiber 31 is preferably 10 μm or more. Laser module 64 is constructed from the combined laser source or the fiber o array laser source as shown in FIG. 29. The combined laser source is constructed from plural (e.g. seven) multimode or single mode GaN semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 and LD7 disposed and fixed on heat block 10, collimator lenses 11, 12, 13, 14, 15, 16, and 17, one collecting lens 20, and one multimode optical fiber 30. Needless to say, the number of semiconductor lasers is not limited to seven. 5 For example, with respect to the multimode optical fiber having clad diameter = 60 μm, core diameter = 50 μm, NA = 0.2, as much as twenty semiconductor lasers may be inputted, thus the number of optical fibers may be reduced while attaining the necessary optical quantity of the exposing head. GaN semiconductor lasers LD1 to LD7 have a common oscillating wavelength e.g. 405 nm, and a common maximum output e.g. 100 mW as for multimode lasers and 30 mW as for single mode lasers. The GaN semiconductor lasers LD1 to LD7 may be those having an oscillating wavelength of other than 405 nm as long as within the wavelength of 350 to 450 nm. The combined laser source is housed into a box package 40 having an upper opening with other optical elements as shown in FIGs. 30 and 31. The package 40 is equipped with package lid 41 for shutting the opening. Introduction of sealing gas after evacuating procedure and shutting the opening of package 40 by means of package lid 41 presents a closed space or sealed volume constructed by package 40 and package lid 41, and the combined laser source is disposed in a sealed condition. Base plate 42 is fixed on the bottom of package 40; the heat block 10, collective lens holder 45 to support collective lens 20, and fiber holder 46 to support the input end of multimode optical fiber 30 are mounted to the upper surface of the base plate 42. The output end of multimode optical fiber 30 is drawn out of the package from the aperture provided at the wall of package 40. Collimator lens holder 44 is attached to the side wall of heat block 10, and collimator lenses 11 to 17 are supported thereby. An aperture is provided at the side wall of package 40, and wiring 47 that supplies driving power to GaN semiconductor lasers LD1 to LD7 is directed through the aperture out of the package. In FIG.31, only the GaN semiconductor laser LD7 is indicated with a reference mark among plural GaN semiconductor laser, and only the collimator lens 17 is indicated with a reference number among plural collimators, in order not to make the figure excessively complicated. FIG.32 shows a front shape of attaching part for collimator lenses 11 to 17. Each of collimator lenses 11 to 17 is formed into a shape that a circle lens containing a non-spherical surface is cut into an elongated piece with parallel planes at the region containing the optical axis. The collimator lens with the elongated shape may be produced by a molding process. The collimator lenses 11 to 17 are closely disposed in the aligning direction of emitting points such that the elongated direction is perpendicular to the alignment of the emitting points of GaN semiconductor lasers LD1 to LD7. On the other hand, as for GaN semiconductor lasers LD1 to LD7, the following laser may be employed that comprises an active layer having an emitting 5 width of 2 μm and emits the respective laser beams Bl to B7 at a condition that the divergence angle is 10 degrees and 30 degrees for the parallel and perpendicular directions against the active layer. The GaN semiconductor lasers LD1 to LD7 are disposed such that the emitting sites align as one line in parallel to the active layer. Accordingly, laser beams Bl to B7 emitted from the respective emitting sites o enter into the elongated collimator lenses 11 to 17 in a condition that the direction having a larger divergence angle coincides with the length direction of each collimator lens and the direction having a less divergence angle coincides with the width direction of each collimator lens. Namely, the width is 1.1 mm and the length is 4.6 mm with respect to respective collimator lenses 11 to 17, and the beam diameter5 is 0.9 mm in the horizontal direction and is 2.6 mm in the vertical direction with respect to laser beams Bl to B7 that enter into the collimator lenses. As for the respective collimator lenses 11 to 17, focal length fl = 3 mm, NA = 0.6, pitch of disposed lenses = 1.25 mm. Collective lens 20 formed into a shape that a part of circle lens containing the 0 optical axis and non-spherical surface is cut into an elongated piece with parallel planes and is arranged such that the elongated piece is longer in the direction of disposing collimator lens 11 to 17 i.e. horizontal direction, and is shorter in the perpendicular direction. As for the collective lens, focal length f2 = 23 mm, NA = 0.2. The collective lens 20 may be produced by molding a resin or optical glass, for5 example. Further, since a high luminous fiber array laser source is employed that is arrayed at the output ends of optical fibers in the combined laser source for the illumination means to illuminate the DMD, a pattern forming apparatus may be attained that exhibits a higher output and a deeper focal depth. In addition, the higher output of the respective fiber array laser sources may lead to less number of fiber array laser sources required to take a necessary output as well as a lower cost of the pattern forming apparatus. In addition, the clad diameter at the output ends of the optical fibers is 5 smaller than the clad diameter at the input ends, therefore, the diameter at emitting sites is reduced still, resulting in higher luminance of the fiber array laser source. Consequently, pattern forming apparatuses with a deeper focal depth may be achieved. For example, a sufficient focal depth may be obtained even for the extremely high resolution exposure such that the beam diameter is 1 μm or less and o the resolution is 0.1 μm or less, thereby enabling rapid and precise exposure. Accordingly, the pattern forming apparatus is appropriate for the exposure of thin film transistor (TFT) that requires high resolution. The illumination means is not limited to the fiber array laser source that is equipped with plural combined laser sources; for example, such a fiber array laser5 source may be employed that is equipped with one fiber laser source, and the fiber laser source is constructed by one arrayed optical fiber that outputs a laser beam from one semiconductor laser having an emitting site. Further, as for the illumination means having plural emitting sites, such a laser array may be employed that comprises plural (e.g. seven) tip-like o semiconductor lasers LDl to LD7 disposed on heat block 100 as shown in FIG. 33. In addition, multi cavity laser 110 is known that comprises plural (e.g. five) emitting sites 110a disposed in a certain direction as shown in FIG. 34A. In the multi cavity laser 110, the emitting sites can be arrayed with higher dimensional accuracy compared to arraying tip-like semiconductor lasers, thus laser beams emitted from 5 the respective emitting sites can be easily combined. Preferably, the number of emitting sites 110a is five or less, since deflection tends to generate on multi cavity laser 110 at the laser production process when the number increases. Concerning the illumination means, the multi cavity laser 110 set forth above, or the multi cavity array disposed such that plural multi cavity lasers 110 are arrayed in the same direction as emitting sites 110a of each tip as shown in FIG.34B may be employed for the laser source. The combined laser source is not limited to the types that combine plural laser beams emitted from plural tip-like semiconductor lasers. For example, such a combined laser source is available that comprises tip-like multi cavity laser 110 having plural (e.g. three) emitting sites 110a as shown in FIG. 21. The combined laser source is equipped with multi cavity laser 110, one multimode optical fiber 130, and collecting lens 120. The multi cavity laser 110 may be constructed from GaN laser diodes having an oscillating wavelength of 405 nm, for example. In the above noted construction, each laser beam B emitted from each of plural emitting sites 110a of multi cavity laser 110 is collected by collective lens 120 and enters into core 130a of multimode optical fiber 130. The laser beams entered into core 130a propagate inside the optical fiber and combine as one laser beam then output from the optical fiber. The connection efficiency of laser beam B to multimode optical fiber 130 may be enhanced by way of arraying plural emitting sites 110a of multi cavity laser 110 into a width that is approximately the same as the core diameter of multimode optical fiber 130, and employing a convex lens having a focal length of approximately the same as the core diameter of multimode optical fiber 130, and also employing a rod lens that collimates the output beam from multi cavity laser 110 at only within the surface perpendicular to the active layer. In addition, as shown in FIG.35, a combined laser source may be employed that is equipped with laser array 140 formed by arraying on heat block 111 plural (e.g. nine) multi cavity lasers 110 with an identical space between them by employing multi cavity lasers 110 equipped with plural (e.g. three) emitting sites. The plural multi cavity lasers 110 are arrayed and fixed in the same direction as emitting sites 110a of the respective tips. The combined laser source is equipped with laser array 140, plural lens arrays 114 that are disposed correspondingly to the respective multi cavity lasers 110, one rod lens 113 that is disposed between laser array 140 and plural lens arrays 114, one multimode optical fiber 130, and collective lens 120. Lens arrays 114 are equipped with plural micro lenses each corresponding to emitting sites of multi cavity lasers 110. 5 In the above noted construction, laser beams B that are emitted from plural ermtting sites 110a of plural multi cavity lasers 110 are collected in a certain direction by rod lens 113, then are paralleled by the respective microlenses of microlens arrays 114. The paralleled laser beams L are collected by collective lens 120 and are inputted into core 130a of multimode optical fiber 130. The laser beams entered into o core 130a propagate inside the optical fiber and combine as one beam then output from the optical fiber. Another combined laser source will be exemplified in the following. In the combined laser source, heat block 182 having a cross section of L-shape in the optical axis direction is installed on rectangular heat block 180 as shown in FIGs. 36A and 5 36B, and a housing space is formed between the two heat blocks. On the upper surface of L-shape heat block 182, plural (e.g. two) multi cavity lasers 110, in which plural (e.g. five) emitting sites are arrayed, are disposed and fixed each with an identical space between them in the same direction as the aligning direction of respective tip-like emitting sites. 0 A concave portion is provided on the rectangular heat block 180; plural (e.g. two) multi cavity lasers 110 are disposed on the upper surface of heat block 180, plural emitting sites (e.g. five) are arrayed in each multi cavity laser 110, and the emitting sites are situated at the same vertical surface as the surface where are situated the emitting sites of the laser tip disposed on the heat block 182.5 At the laser beam output side of multi cavity laser 110, collimate lens arrays 184 are disposed such that collimate lenses are arrayed correspondingly with the emitting sites 110a of the respective tips. In the collimate lens arrays 184, the length direction of each collimate lens coincides with the direction at which the laser beam represents wider divergence angle or the fast axis direction, and the width direction of each collimate lens coincides with the direction at which the laser beam represents less divergence angle or the slow axis direction. The integration by arraying the collimate lenses may increase the space efficiency of laser beam, thus the output power of the combined laser source may be enhanced, and also the number of parts may be reduced, resulting advantageously in lower production cost. At the laser beam output side of collimate lens arrays 184, disposed are one multimode optical fiber 130 and collective lens 120 that collects laser beams at the input end of multimode optical fiber 130 and combines them. In the above noted construction, the respective laser beams B emitted from the respective emitting sites 110a of plural multi cavity lasers 110 disposed on laser blocks 180, 182 are paralleled by collimate lens array, are collected by collective lens 120, then enter into core 130a of multimode optical fiber 130. The laser beams entered into core 130a propagate inside the optical fiber and combine as one beam then output from the optical fiber. The combined laser source may be made into a higher output power source by multiple arrangement oi the multi cavity lasers and the array of collimate lenses in particular. The combined laser source allows to construct a fiber array laser source and a bundle fiber laser source, thus is appropriate for the fiber laser source to construct the laser source of the pattern forming apparatus in the present invention. By the way, a laser module may be constructed by housing the respective combined laser sources into a casing, and drawing out the output end of multimode optical fiber 130. In the explanations set forth above, the higher luminance of fiber array laser source is exemplified that the output end of the multimode optical fiber of the combined laser source is connected to another optical fiber that has the same core diameter as that of the multimode optical fiber and a clad diameter smaller than that of the multimode optical fiber; alternatively a multimode optical fiber having a clad diameter of 125 μm, 80 μm, 60 μm or the like may be utilized without connecting another optical fiber at the output end, for example. The pattern forming process according to the present invention will be explained further. As shown in FIG. 29, in each exposing head 166 of scanner 162, the respective laser beams Bl, B2, B3, B4, B5, B6, and B7, emitted from GaN semiconductor lasers LDl to LD 7 that constitute the combined laser source of fiber array laser source 66, are paralleled by the corresponding collimator lenses 11 to 17. The paralleled laser beams Bl to B7 are collected by collective lens 20, and converge at the input end surface of core 30a of multimode optical fiber 30. In this example, the collective optical system is constructed from collimator lenses 11 to 17 and collective lens 20, and the combined optical system is constructed from the collective optical system and multimode optical fiber 30. Namely, laser beams Bl to B7 that are collected by collective lens 20 enter into core 30a of multimode optical fiber 30 and propagate inside the optical fiber, combine into one laser beam B, then output from optical fiber 31 that is connected at the output end of multimode optical fiber 30. In each laser module, when the coupling efficiency of laser beams Bl to B7 with multimode optical fiber 30 is 0.85 and each output of GaN semiconductor lasers LDl to LD7 is 30 mW, each optical fiber disposed in an array can take combined laser beam B of output 180 mW (= 30 mW x 0.85 x 7). Accordingly, the output is about 1 W (= 180 mW x 6) at laser emitting portion 68 of the array of six optical fibers 31. Laser emitting portions 68 of fiber array source 66 are arrayed such that the higher luminous emitting sites are aligned along the main scanning direction. The conventional fiber laser source that connects laser beam from one semiconductor laser to one optical fiber is of lower output, therefore, a desirable output cannot be attained unless many lasers are arrayed; whereas the combined laser source of lower number (e.g. one) array can produce the desirable output since the combined laser source may generate a higher output. For example, in the conventional fiber where one semiconductor laser and one optical fiber are connected, a semiconductor laser of about 30 mW output is usually employed, and a multimode optical fiber that has a core diameter of 50 μm, a clad diameter of 125 μm, and a numerical aperture of 0.2 is employed as the optical fiber. Therefore, in order to take an output of about 1 W (Watt), 48 (8 x 6) multimode optical fibers are necessary; since the area of emitting region is 0.62 mm2 5 (0.675 mm x 0.925 mm), the luminance at laser emitting portion 68 is 1.6 x IO6 (W/m2), and the luminance per one optical fiber is 3.2 x IO6 (W/m2). On the contrary, when the laser emitting means is one capable of emitting the combined laser, six multimode optical fibers can produce the output of about 1 W. Since the area of the emitting region in laser emitting portion 68 is 0.0081 mm2 (0.325 o mm x 0.025 mm), the luminance at laser emitting portion 68 is 123 x IO6 (W/m2), which corresponds to about 80 times the luminance of conventional means. The luminance per one optical fiber is 90 x IO6 (W/m2), which corresponds to about 28 times the luminance of conventional means. The difference of focal depth between the conventional exposing head and 5 the exposing head in the present invention will be explained with reference to FIGs. 37A and 37B. For example, the diameter of exposing head is 0.675 mm in the sub-scanning direction of the emitting region of the bundle-like fiber laser source, and the diameter of exposing head is 0.025 mm in the sub-scanning direction of the emitting region of the fiber array laser source. As shown in FIG. 37A, in the o conventional exposing head, the emitting region of illuminating means or bundle-like fiber laser source 1 is larger, therefore, the angle of laser bundle that enters into DMD3 is larger, resulting in larger angle of laser bundle that enters into scanning surface 5. Therefore, the beam diameter tends to increase in the collecting direction, resulting in a deviation in focus direction. 5 On the other hand, as shown in FIG. 37B, the exposing head of the pattern forming apparatus in the present invention has a smaller diameter of the emitting region of fiber array laser source 66 in the sub-scanning direction, therefore, the angle of laser bundle is smaller that enters into DMD50 through lens system 67, resulting in lower angle of laser bundle that enters into scanning surface 56, i.e. larger focal depth. In this example, the diameter of the err tting region is about 30 times the diameter of prior art in the sub-scanning direction, thus the focal depth approximately corresponding to the limited diffraction may be obtained, which is appropriate for the exposing at extremely small spots. The effect on the focal depth is more significant as the optical quantity required at the exposing head comes to larger. In this example, the size of one imaging portion projected on the exposing surface is 10 μm x 10 μm. The DMD is a spatial light modulator of reflected type; in FIGs. 37A and 37B, it is shown as developed views to explain the optical relation. The pattern information corresponding to the exposing pattern is inputted into a controller (not shown) connected to DMD50, and is memorized once to a flame memory within the controller. The pattern information is the data that expresses the concentration of each imaging portion that constitutes the pixels by means of two-values i.e. presence or absence of the dot recording. Stage 152 that absorbs pattern forming material 150 on the surface is conveyed from upstream to downstream of gate 160 along guide 158 at a constant velocity by a driving device (not shown). When the tip of pattern forming material 150 is detected by detecting sensor 164 installed at gate 160 while stage 152 passes under gate 160, the pattern information memorized at the flame memory is read plural lines by plural lines sequentially, and controlling signals are generated for each exposing head 166 based on the pattern information read by the data processing portion. Then, each micromirror of DMD50 is subjected to on-off control for each exposing head 166 based on the generated controlling signals. When a laser beam is irradiated from fiber array laser source 66 onto DMD50, the laser beam reflected by the micromirror of DMD50 at on-condition is imaged on exposed surface 56 of pattern forming material 150 by means of lens systems 54, 58. As such, the laser beams emitted from fiber array laser source 66 are subjected to on-off control for each imaging portion, and pattern forming material 150 is exposed by imaging portions or exposing area 168 of which the number is approximately the same as that of imaging portions employed in DMD50. Further, through moving the pattern forming material 150 at a constant velocity along with stage 152, pattern forming material 150 is subjected to sub-scanning in the direction opposite to the stage moving direction by means of scanner 162, and band-like exposed region 170 is formed for each exposing head 166. 5 [Laminate] The material to be exposed is properly selected without particular limitations as long as the material is a pattern forming material that comprises a photosensitive layer. Preferably, the exposing is carried out for the laminate that comprises the pattern forming material on a substrate. o The exposing of the laminated body may be properly selected depending on the application; for example, the photosensitive layer may be exposed through the support and the cushioning layer and the barrier layer, the photosensitive layer may be exposed through the cushioning layer and the barrier layer after the support being peeled away, the photosensitive layer may be exposed through the barrier layer after 5 the support and the cushioning layer being peeled away, or the photosensitive layer may be exposed after the support and the cushioning layer and the barrier layer being peeled away. < Pattern Forming Material > The pattern forming material may be properly selected depending on the o application without particular limitations as long as the pattern forming material comprises a cushioning layer and a photosensitive layer on a substrate. The pattern forming material may comprise a barrier layer that suppresses migration of substances between the cushioning layer and the photosensitive layer depending on the requirements.5 « Cushioning Layer » The cushioning layer may be properly selected depending on the application; preferably the cusMoning layer comprises a thermoplastic resin. The cushioning layer may be swellable, soluble, or insoluble in alkaline liquids. In the case that the cushioning layer is swellable or soluble in alkaline liquids, examples of the thermoplastic resins include saponification products from copolymers of styrene and acrylate, saponification products from copolymers of styrene and (meth)acrylate, saponification products from copolymers of vinyltoluene and (meth)acrylate, poly(meth)acrylates, saponification products from (meth)acrylate copolymers of (meth)butylacrylate and vinyl acetate, copolymers of (meth)acrylate and (meth)acrylic acid, and copolymers of styrene and (meth)acrylate and (meth)acrylic acid. The Nicat softening temperature of these thermoplastic resins may be properly selected depending on the application; preferably the softening temperature of these thermoplastic resins is 80 °C or less. Examples of the thermoplastic resins that have a softening temperature of 80 °C or less and are soluble in alkaline liquids are exemplified in "Plastic Property Handbook, edited by Japan Plastic Molding Industry Union of The Japan Plastics Industry Federation, published by Kogyo Chosakai Publishing Inc., Oct. 25, 1968". By the way, organic polymer materials having a softening temperature of above 80 °C may be decreased in many cases for the softening temperature by incorporating a plasticizer compatible with the organic polymer material for example. In the case that the cushioning layer is swellable or soluble in alkaline liquids, the adhesive strength between the pattern f orrning material and the other layers may be properly adjusted depending on the application; preferably, the adhesive strength between the support and the cushioning layer is the lowest among the interlayer adhesive strengths. Such interlayer adhesive strengths may bring about the situation that only the support is peeled from the laminated body, the photosensitive layer is exposed through the cushioning layer, then the photosensitive layer is developed by an alkaline developing liquid; alternatively, the photosensitive layer is exposed while remaining the support, then only the support is peeled from the laminated body, followed by developing the photosensitive layer by the alkaline developing liquid. The adjustment of the interlayer adhesive strength may be properly performed depending on the application, for example, through incorporating into the thermoplastic resin a substance selected from conventional polymers, supercooled substances, adhesion promoters, surfactants, releasing agent, and the like. Examples of the plasticizers set forth above may be properly selected depending on the application; examples of the plasticizers include alcohols and esters such as polypropylene glycol, polyethylene glycol, dioctylphthalate, diheptylphthalate, dibutylphthalate, tricresylphosphate, αresyldiphenylphosphate, and biphenyldiphenylphosphate; amides such as toluenesulfone amide. In the case that the cushioning layer is insoluble in alkaline liquids, examples of the thermoplastic resins include copolymers that contain ethylene as the essential component. Examples of the copolymers that contain ethylene as the essential component include ethylene-vinylacetate copolymers (EVA), ethylene-ethylacrylate copolymers (EEA) and the like. In the case that the cushioning layer is insoluble in alkaline liquids, the adhesive strength between the pattern forming material and the other layers may be properly adjusted depending on the application; preferably, the adhesive strength between the photosensitive layer and the cushioning layer is the lowest among the interlayer adhesive strengths. Such interlayer adhesive strengths may bring about the situation that the support and the cushioning layer are peeled from the laminated body, then the photosensitive layer is exposed and the photosensitive layer is developed by an alkaline developing liquid; alternatively, the photosensitive layer is exposed while remaining the support, then the support and the cushioning layer are peeled from the laminated body, followed by developing the photosensitive layer by the alkaline developing liquid. The adjustment of the interlayer adhesive strength may be properly performed depending on the application, for example, through incorporating into the thermoplastic resin a substance selected from conventional polymers, supercooled substances, adhesion promoters, surfactants, releasing agent, and the like, and also through adjusting the copolymerization ratio of ethylene as explained following.. The copolymerization ratio of ethylene in a copolymer that contains ethylene as the essential component may be properly selected depending on the application; preferably the copolymerization ratio is 60 to 90 % by mass, more preferably is 60 to 80 % by mass, still more preferably is 65 to 80 % by mass. When the copolymerization ratio of ethylene is below 60 % by mass, the interlayer adhesive strength of cushioning layer and the photosensitive layer comes to higher, resulting in a hard peeling between the cushioning layer and the photosensitive layer, and when the copolymerization ratio of ethylene is above 90 % by mass, the interlayer adhesive strength of cushioning layer and the photosensitive layer is likely to be excessively low, thus the cushioning layer and the photosensitive layer tend to separate therebetween, resulting in a hard production of pattern forming material containing the cushioning layer. The thickness of the cushioning layer may be properly selected depending on the application; for example, the thickness is 5 to 50 μm, more preferably is 10 to 50 μm, and still more preferably is 15 to 40 μm. When the thickness is below 5 μm, the conformability to nonuniformity on substrate surface or the conformability to nonuniformity on layer surface due to bubbles is likely to be insufficient, thus possibly preventing the production of highly fine and precise permanent patterns, and when the thickness is above 50 μm, the production process tends to be difficult due to disadvantageously enlarged drying load and the like. « Photosensitive Layer » The photosensitive layer may be properly selected from conventional pattern forming materials without particular limitations; preferably the photosensitive layer comprises a binder, a polymerizable compound, a photopolymerization initiator, for example, and other components if necessary. The laminated number of the photosensitive layer may be properly selected without particular limitations; the laminated number may be of one, or no less than two. - Binder - Preferably, the binder is swellable in alkaline liquids, more preferably, the 5 binder is soluble in alkaline liquids. The binder that is swellable or soluble in alkaline liquids is those having an acidic group, for example. The acidic group may be properly selected depending on the application without particular limitations; examples thereof include a carboxyl group, sulf onic acid group, phosphoric acid group, and the like. Among these groups, a carboxyl o group is preferable. Examples of the binders that contain the carboxyl group include vinyl copolymers, polyurethane resins, polyamide acid resins, and modified epoxy resins that contain a carboxyl group. Among these, vinyl copolymers containing a carboxyl group are preferable from the viewpoints of solubility in coating solvents,5 solubility in alkaline developers, ability to be synthesized, easiness to adjust film properties, and the like. The vinyl copolymers containing a carboxyl group may be synthesized by copolymerizing at least (i) a vinyl polymer containing a carboxyl group, and (ii) a monomer capable of copolymerizing with the vinyl monomer. o Examples of vinyl polymers containing a carboxyl group include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkylester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, adducts of a monomer containing a hydroxy group such as 2-hydroxyethyl(meth)acrylate and a cyclic anhydride such as maleic acid anhydride, phthalic acid anhydride, and 5 cyclohexane dicarbonic acid anhydride, and ω-carboxy-polycaprolactone mono(meth)acrylate. Among these, (meth)acrylic acid is preferable in particular from the view points of copolymerizing ability, cost, solubility, and the like. In addition, as for the precursor of carboxyl group, monomers containing anhydride such as maleic acid anhydride, itaconic acid anhydride, and citraconic acid anhydride may be employed. The monomer capable of copolymerizing may be properly selected depending on the application; examples thereof include (meth)acrylate esters, crotonate esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid 5 diesters, (meth)acrylic amides, vinyl ethers, vinyl alcohol esters, styrenes, metacrylonitrile; heterocyclic compounds with a substituted vinyl group such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; N-vinyl f ormamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone, 2-acrylamide-2-methylpropane sulfonic acid, phosphoric acid mono(2-acryloyloxyethylester), phosphoric acid l o mono(l-methyl~2-acryloyloxyethylester), and vinyl monomers containing a functional group such as a urethane group, urea group, sulfonic amide group, phenol group, and imide group. Examples of (meth)acrylate esters include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isoρropyl(meth)acrylate,
15 n-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, n~hexyl(meth)acrylate, cyclohexyl(meth)acrylate, t-butyl cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, t-octyl(meth)acrylate, dodecyl(meth)acrylate, octadecyl(meth)acrylate, acetoxyethyl(meth)acry late, phenyl(meth)acry late, 2-hydroxyethyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,
20 2-ethoxyethyl(meth)acrylate (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl(meth)acrylate, benzil(meth)acrylate, diethyleneglycol monomethylether (meth)acrylate, diethyleneglycol monoethylether (meth)acrylate, diethyleneglycol monophenylether (meth)acrylate, triethyleneglycol monomethylether (meth)acrylate, triethyleneglycol monoethylether (meth)acrylate,
25 polyethyleneglycol monomethylether (meth)acrylate, polyethyleneglycol monoethylether (meth)acrylate, β -phenoxy ethoxy ethyl (meth)acrylate, nonylphenoxy polyethyleneglycol (meth)acrylate, dicyclopentanyl (meth) aery late, dicyclopentenyl oxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, tribromophenyl (meth)acrylate, and tribromophenyloxyethyl (meth)acrylate. Examples of crotonate esters include butyl crotonate, and hexyl crotonate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinylmethoxy acetate, and vinyl benzoate. 5 Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate. Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include dimethyl itaconate, diethyl o itaconate, and dibutyl itaconate. Examples of (meth)acrylic amides include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-t-butyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-(2-methoxyethyl)5 (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-benzil (meth)acrylamide, (meth)acryloyl morpholine, and diacetone acrylamide. Examples of the styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, o methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene; hydroxystyrene with a protective group such as t-Boc capable of being de-protected by an acid substance; vinylmethyl benzoate, and -methylstyrene. Examples of vinyl ethers include methyl vinylether, butyl vinylether, hexyl 5 vinylether, and methoxyethyl vinylether. The process to synthesize the vinyl monomer containing a functional group is an addition reaction of an isocyanate group and a hydroxy group or amino group for example; specifically, an addition reaction between a monomer containing an isocyanate group and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, and an addition reaction between a monomer containing a hydroxy group or a monomer containing a primary or secondary amino group and a mono isocyanate are exemplified. Examples of the monomers containing an isocyanate group include the compounds expressed by the following formulas (1) to (3).
H R1 i I ^\ ^NCO C=C-COO^^ formula (1) I H
H R1 C=C-CO-NCO formula (2) I H
formula (3)
Figure imgf000052_0001
In the above formulas (1) to (3), R1 represents a hydrogen atom or a methyl l o group. Examples of mono isocyanates set forth above include cyclohexyl isocyanate, n-butyl isocyanate, toluic isocyanate, benzil isocyanate, and phenyl isocyanate. Examples of the monomers containing a hydroxyl group include the compounds expressed by the following formulas (4) to (12).
formula (4)
Figure imgf000052_0002
O -r- H formula (5)
Figure imgf000053_0001
formula (6)
formula (7)
formula (8)
formula (9)
formula (10)
Figure imgf000053_0002
ormula (11)
formula (12)
Figure imgf000053_0003
e above formulas (4) to (12), Ri represents a hydrogen atom or a methyl grotip, and "ft" represents an integer of one or more. Examples of the compounds containing one hydroxyl group include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzil alcohol, and phenylethyl alcohol; phenols such as phenol, cresol, and naphthol; examples of the compounds containing additionally a substituted group include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, and acetoxyphenol. Examples of monomers containing a primary or secondary amino group set forth above include vinylbenzil amine. Examples of compounds containing a primary or secondary amino group include alkylamines such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexylamine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, and dioctylamine; cyclic alkylamines such as cyclopentylamine and cyclohexylamine; aralkylamines such as benzilamine and phenethylamine; arylamines such as aniline, toluicamine, xylylamine, and naphthylamine; combination thereof such as N-methyl-N-benzilamine; and amines containing a substituted group such as trifluoroethylamine, hexafluoro isopropylamine, methoxyaniline, and methoxy propylamine. Examples of the copolymerizable monomers other than set forth above include methyl (meth) aery late, ethyl (meth)acrylate, butyl (meth)acrylate, benzil (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, chlorostyrene, bromostyrene, and hydroxystyrene. The above noted copolymerizable monomers may be used alone or in combination. The vinyl copolymers set forth above may be prepared by copolymerizing the appropriate monomers in accordance with conventional processes; for example, such a solution polymerization process is available as dissolving the monomers into an appropriate solvent, adding a radical polymerization initiator, thereby causing a polymerization in the solvent; alternatively such a so-called emulsion polymerization process is available as polymerizing the monomers under the condition that the monomers are dispersed in an aqueous solvent. 5 The solvent utilized in the solution polymerization process may be properly selected depending on the monomers, solubility of the resultant copolymer and the like; examples of the solvents include methanol, ethanol, propanol, isopropanol, l-methoxy-2-propanol, acetone, methyl ethyl ketone, methylisobutylketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, o dimethylf ormamide, ςhlorof orm, and toluene. These solvents may be used alone or in combination. The radical polymerization initiator set forth above may be properly selected without particular limitations; examples thereof include azo compounds such as 2,2'-azobis(isobutyronitrile) (AIBN) and 2,2'-azobis-(2,4'-dimethylvaleronitrile);5 peroxides such as benzoyl peroxide; persulfates such as potassium persulfate and ammonium persulfate. The content of the polymerizable compound having a carboxyl group in the vinyl copolymers set forth above may be properly selected without particular limitations; preferably, the content is 5 to 50 mole %, more preferably is 10 to 40 o mole %, and still more preferably is 15 to 35 mole % . When the content is less than 5 mole %, the developing ability in alkaline solution may be insufficient, and when the content is more than 50 mole %, the durability of the hardening portion or imaging portion is insufficient against the developing liquid. 5 The molecular weight of the binder having a carboxyl group set forth above may be properly selected without particular limitations; preferably the weight-averaged molecular weight is 2000 to 300000, more preferably is 4000 to 150000. When the weight-averaged molecular weight is less than 2000, the film strength is likely to be insufficient, and also the production process tends to be unstable, and when the weight-averaged molecular weight is more than 300000, the developing ability tends to decrease. The binder having a carboxyl group set forth above may be used alone or in 5 combination. As for the combination of two or more of the binders, such combination may be exemplified as two or more of binders having different copolymer components, two or more of binders having different weight-averaged molecular weight, and two or more of binders having different dispersion levels. In the binder having a carboxyl group set forth above, a part or all of the o carboxyl groups may be neutralized by a basic substance. Further, the binder may be combined with a resin of different type selected from polyester resins, polyamide resins, polyurethane resins, epoxy resins, polyvinyl alcohols, gelatin, and the like. In addition, the binder having a carboxyl group set forth above may be resins soluble in an alkaline aqueous solution as described in Japanese Patent No. 2873889. 5 The content of the binder in the photosensitive layer set forth above may be properly selected without particular limitations; preferably the content is 10 to 90 % by mass, more preferably is 20 to 80 % by mass, and still more preferably is 40 to 80 % by mass. When the content is less than 10 % by mass, the developing ability in alkaline o solutions or the adhesive property with substrates for forming printed wiring boards such as a cupper laminated board tends to decrease, and when the content is more than 90 % by mass, the stability of developing period or the strength of the hardening film or the tenting film may be insufficient. The content of the binder may be considered as the entire content of the binder content and the additional polymer 5 binder content combined depending on requirements. The acid value of the binder may be properly selected depending on the application; preferably the acid value is 70 to 250 mgKOH/g, more preferably is 90 to 200 mgKOH/g, still more preferably is 100 to 180 mgKOH/g. When the acid value is less than 70 mgKOH/g, the developing ability may be insufficient, the resolving property may be poor, or the permanent pattern such as wiring patterns cannot be formed precisely, and when the acid value is more than 250 mgKOH/g, the durability of pattern against the developer and/ or adhesive property of pattern tends to degrade, thus the permanent pattern such as wiring 5 patterns cannot be formed precisely. - Polymerizable Compound - The polymerizable compound may be properly selected without particular limitations; preferably, the polymerizable compound is the monomer or oligomer that contains a urethane group and/ or an aryl group; preferably, the polymerizable o compound contains two or more types of polymerizable groups. Examples of the polymerizable group include ethylenically unsaturated bonds such as (meth)acryloyl groups, (meth)acrylamide groups, styryl groups, vinyl groups (e.g. of vinyl esters, vinyl ethers), and allyl groups (e.g. of allyl ethers, allyl esters); and polymerizable cyclic ether groups such as epoxy groups and oxetane 5 group. Among these, the ethylenically unsaturated bond is preferable. - Monomer Containing Urethane Group - The monomer containing a urethane group set forth above may be properly selected without particular limitations; examples thereof include those described in Japanese Patent Application Publication (JP-B) No.48-41708, Japanese Patent o Application Laid-Open (JP-A) No. 51-37193, JP-B Nos. 5-50737, 7-7208, and JP-A Nos. 2001-154346, 2001-356476; specifically, the adducts may be exemplified between polyisocyanate compounds having two or more isocyanate groups in the molecule and vinyl monomers having a hydroxyl group in the molecule. Examples of the polyisocyanate compounds having two or more isocyanate 5 groups in the molecule set forth above include diisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, and S/S'-dimethyl^^'-diphenyl diisocyanate; polyaddition products of these diisocyanates and two-functional alcohols wherein each of both ends of the polyaddition product is an isocyanate group; trimers such as buret of the diisocyanates or isocyanurates; adducts obtained from the diisocyanate of diisocyanates and polyfunctional alcohols such as trimethylolpropane, 5 pentaerythritol, and glycerin or polyfunctional alcohols of adducts with ethylene oxide. Examples of vinyl monomers having a hydroxyl group in the molecule set forth above include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethyleneglycol mono(meth)acrylate, o triethyleneglycol monp(meth)acrylate, tetraethyleneglycol mono(meth)acrylate, octaethyleneglycol mono(meth)acrylate, polyethyleneglycol mono(meth)acrylate, dipropyleneglycol mono(meth)acrylate, tripropyleneglycol mono(meth)acrylate, tetrapropyleneglycol mono(meth)acrylate, octapropyleneglycol mono(meth)acrylate, polypropyleneglycol mono(meth)acrylate, dibutyleneglycol mono(meth)acrylate, 5 ttibutyleneglycol mono(meth)acrylate, tetrabutyleneglycol mono(meth)acrylate, octabutyleneglycol mono(meth)acrylate, polybutyleneglycol mono(meth)acrylate, trimethylolpropane (meth)acrylate, and pentaerythritol (meth)acrylate. Further, such a vinyl monomer may be exemplified that has a (meth)acrylate component at one end of diol molecule having different alkylene oxides such as of random or block o copolymer of ethylene oxide and propylene oxide for example. Examples of the monomer containing a urethane group set forth above include the compounds having an isocyanurate ring such as tri(meth)acryloyloxyethyl isocyanurate, di(meth)acrylated isocyanurate, and tri(meth) aery late of ethylene oxide modified isocyanuric acid. Among these, the 5 compounds expressed by formula (13) or formula (14) are preferable; at least the compounds expressed by formula (14) are preferably included in particular from the view point of tenting property. These compounds may be used alone or in combination.
Figure imgf000059_0001
formula(13)
formula (14)
Figure imgf000059_0002
In the formulas (13) and (14), R1 to R3 represent a hydrogen atom or a methyl group respectively; Xi to X3 represent alkylene oxide groups, which may be identical or different each other. Examples of the alkylene oxide group include ethylene oxide group, propylene oxide group, butylene oxide group, pentylene oxide group, hexylene oxide group, and combined groups thereof in random or block. Among these, ethylene oxide group, propylene oxide group, butylene oxide group, and combined groups thereof are preferable; and ethylene oxide group and propylene oxide group are more preferable. In the formulas (13) and (14), ml to m3 represent integers of 1 to 60 respectively, preferably is 2 to 30, more preferably is 4 to 15. In the formulas (13) and (14), each of Y1 and Y2 represent a divalent organic group having 2 to 30 carbon atoms such as alkylene group, arylene group, alkenylene group, alkynylene group, carbonyl group (-CO-), oxygen atom, sulfur atom, imino group (-NH-), substituted imino group wherein a hydrogen atom on the imino group is substituted by a monovalent hydrocarbon group, sulf onyl group (-S02-), and combination thereof; among these, an alkylene group, arylene group, and combination thereof are preferable. The alkylene group set forth above may be of branched or cyclic structure; examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, ttimethylhexylene group, cyclohexylene group, heptylene, group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, dodecylene group, octadecylene group, and the groups expressed by the following formulas.
Figure imgf000060_0001
The arylene group may be substituted by a hydrocarbon group; examples of the arylene group include phenylene group, thrylene group, diphenylene group, naphthylele group, and the following group.
H CH2 Q-
l o The group of combination thereof set forth above is exemplified by xylylene group. The alkylene group, arylene group, and combination thereof set forth above may contain a substituted group additionally; examples of the substituted group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and
15 iodine atom; aryl groups; alkoxy groups such as methoxy group, ethoxy group, and 2-ethoxyethoxy group; aryloxy groups such as phenoxy group; acyl groups such as acetyl group and propionyl group; acyloxy groups such as acetoxy group and butylyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; and aryloxycarbonyl groups such as phenoxycarbonyl group.
20 In the formulas (13) and (14), "ft" represents an integer of 3 to 6, preferably, "ft" is 3, 4, or 6 from the view point of the available feedstock for synthesizing the polymerizable monomer. In the formulas (13) and (14), "ft" represents an integer of 3 to 6; Z represents a connecting group of "ft" values (n = 3 to 6), examples of Z include the following groups.
T T -NHCOrllCONH - NHO -iNHCOO-fx4 — X-A ' n \ 'm4 /n O
In the above formulas, X4 represents an alkylene oxide; m4 represents an integer of 1 to 20; "ft" represents an integer of 3 to 6; and A represents an organic group having "ft"' values (n = 3 to 6). Example of A of the organic group set forth above include n- valence aliphatic groups, n-valence aromatic groups, and combinations of these groups and alkylene groups, arylene groups, alkenylene groups, alkynylene groups, carbonyl group, oxygen atom, sulfur atom, imino group, substituted imino groups wherein a hydrogen atom on the imino group is substituted by a monovalent hydrocarbon group, and sulfonyl group (-SO2-); more preferably are n-valence aliphatic groups, n-valence aromatic groups, and combinations of these groups and alkylene groups, arylene groups, or an oxygen atom; particularly preferably are n-valence aliphatic groups, and combinations of n-valence aliphatic groups and alkylene groups or an oxygen atom. The number of carbon atoms in the A of the organic group set forth above is preferably 1 to 100, more preferably is 1 to 50, and most preferably is 3 to 30. The n-valence aliphatic group set forth above may be of branched or cyclic structure. The number of carbon atoms in the aliphatic group is preferably 1 to 30, more preferably is 1 to 20, and most preferably is 3 to 10. The number of carbon atoms in the aromatic group set forth above is preferably 6 to 100, more preferably is 6 to 50, and most preferably is 6 to 30. The n-valence aliphatic group and the n-valence aromatic group may contain a substituted group additionally; examples of the substituted group include hydroxyl group, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; aryl groups; alkoxy groups such as methoxy group, ethoxy group, and 2-ethoxyethoxy group; aryloxy groups such as phenoxy group; acyl groups such as acetyl group and propionyl group; acyloxy groups such as acetoxy group and butylyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; and aryloxycarbonyl groups such as phenoxycarbonyl group. The alkylene group set forth above may be of branched or cyclic structure. The number of carbon atoms in the alkylene group is preferably 1 to 18, and more preferably is 1 to 10. The arylene group set forth above may be further substituted by a hydrocarbon group. The number of carbon atoms in the arylene group is preferably 6 to 18, and more preferably is 6 to 10. The number of carbon atoms in the hydrocarbon group of the substituted imino group set forth above is preferably 1 to 18, and more preferably is 1 to 10. Preferable examples of A of the organic group set forth above are as follows.
Figure imgf000062_0001
CH2-CH2-CH— CH2 CH3— CH2-CH2-CH— CH-CH2 CHZ— CH2-CH2-CH2-CH-C 5IH2
H2- CH_CH-CH2 CH2-CH-CH-CH-CH2 CH3-CH2-CH2-CH2-CH-CH-CI H2
Figure imgf000062_0002
Figure imgf000062_0003
The compounds expressed by the formulas (13) and (14) are exemplified specifically by the following formulas (15) to (37).
Figure imgf000063_0001
formula (15)
Figure imgf000063_0002
formula (16)
Figure imgf000063_0003
formula (17)
Figure imgf000063_0004
formula (18)
Figure imgf000063_0005
formula (19)
Figure imgf000063_0006
formula (20)
Figure imgf000063_0007
formula (21)
Figure imgf000064_0001
formula (22)
Figure imgf000064_0002
formula (23)
Figure imgf000064_0003
Figure imgf000065_0001
formula (27)
Figure imgf000065_0002
Figure imgf000066_0001
formula (34)
Figure imgf000067_0001
formula (35)
Figure imgf000067_0002
formula (36)
Figure imgf000067_0003
a (37)
In the above formulas (15) to (37), each of "n", nl, n2, and "m" represents an integer of 1 to 60; "1" represents an integer of 1 to 20; and R represents a hydrogen atom or a methyl group. - Monomer Containing Aryl Group - The monomers containing an aryl group set forth above may be properly selected as long as the monomer contains an aryl group; examples of the monomers containing an aryl group include esters and amides between at least one of polyvalent alcohol compounds, polyvalent amine compounds, and polyvalent amino alcohol compounds containing an aryl group and at least one of unsaturated carboxylic acids. Examples of the polyvalent alcohol compounds, polyvalent amine compounds, and polyvalent amino alcohol compounds containing an aryl group include polystyrene oxide, xylylenediol, di(β-hydroxyethoxy)benzene, l,5-dihydroxy-l,2,3,4-tetrahydronaphthalene, 2,2-diphenyl-l,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, l-phenyl-l,2-ethanediol, 5 2,3,5,6-tetramethyl-p-xylene- ,α'-diol, l,l,4,4-tetraphenyl-l,4-butanediol, l,l,4,4-tetraphenyl-2-butine-l,4-diol, 1,1 '-bi-2-naphthol, dihydroxynaphthalene, l/l'-methylene-di^-naphthol, 1,2,4-benzenetriol, biphenol, 2,2'-bis(4-hydroxyphenyl)butane, l,l-bis(4-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, 4-chlororesorcinol, hydroquinone, o hydroxybenzyl alcohol, methylhydroquinone, methylene-2,4,6-trihydroxybenzoate, fluoroglucinol, pyrogallol, resorcinol, α-(l-aminoethyl)-p-hydroxybenzyl alcohol, and 3-amino-4-hydroxyphenyl sulfone. In addition, xylylene-bis-(meth)acrylamide; adducts of novolac epoxy resins or glycidyl compounds such as bisphenol A diglycidylether and α,β -unsaturated 5 carboxylic acids; ester compounds from acids such as phthalic acid and ttimellitic acids and vinyl monomers containing a hydroxide group; diallyl phthalate, triallyl trimellitate, diallyl benzene sulfonate, cationic polymerizable divinylethers as a polymerizable monomer such as bisphenol A divinylether; epoxy compounds such as novolac epoxy resins and bisphenol A diglycidylethers; vinyl esters such as o divinyl phthalate, divinyl terephthalate, and divinylbenzene-l,3-disulf onate; and styrene compounds such as divinyl benzene, p-allyl styrene, and p-isopropene styrene. Among these, the compounds expressed by the following formula (38) are preferable.
formula (38)
Figure imgf000068_0001
5 In the above formula (38), R4 and R5 represent respectively a hydrogen atom or an alkyl group. In the above formula (38), X5 and X6 represent an alkylene oxide group respectively, the alkylene oxide group may be one species or two or more species. Examples of the alkylene oxide group include ethylene oxide group, propylene oxide group, butylene oxide group, pentylene oxide group, hexylene oxide group, and combined groups in random or block thereof. Among these, ethylene oxide group, propylene oxide group, butylene oxide group, and combined groups thereof are preferable; and ethylene oxide group and propylene oxide group are more preferable. In the formula (38), m5 and m6 represent respectively an integer of 1 to 60, preferably is 2 to 30, and more preferably is 4 to 15. In the formula (38), T represents a divalent connecting group such as methylene group, ethylene group, MeCMe, CF3CCF3, CO, and SO2. In the formula (38), Ari and Ar2 represent respectively an aryl group that may contain a substituted group; examples of An and Aτ2 include phenylene and naphthyene; and examples of the substituted group include alkyl groups, aryl groups, aralkyl groups, halogen groups, alkoxy groups, and combinations thereof. Specific examples of the monomer containing an aryl group set forth above include 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane; 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane in which the number of ethoxy groups substituted for one phenolic OH group is 2 to 20 such as 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxytetraethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxypentaethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxydecaethoxy)phenyl]proρane, and 2,2-bis[4-((meth)acryloyloxypentadecaethoxy)phenyl]propane; 2,2-bis[4-((meth)acryloxypropoxy)phenyl]propane,
2,2~bis[4~((meth)acryloyloxypolypropoxy)phenyl]propane in which the number of ethoxy groups substituted for one phenolic OH group is 2 to 20 such as 2,2-bis[4-((meth)acryloyloxydipropoxy)phenyl]propane, 2,2-bis[4-(.(meth)acryloyloxytetrapropoxy)ρhenylJproρane, 2,2-bis[4-((meth)acryIoyloxypentapropoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxydecaρropoxy)ρhenyl]proρane, 2,2-bis[4-((meth)acryloyloxypentadecapropoxy)phenyl]propane; compounds having a polyethylene oxide skeleton as well as a polypropylene skeleton in one molecule as the ether site of these compounds such as described in International Publication No. WO 01/98832 and commercial products of BPE-200, BPE-500, and BPE-1000 (by Shin-nakamura Chemical Co.); and polymerizable compounds having a polyethylene oxide skeleton as well as a polypropylene skeleton. In these compounds, the site resultant from bisphenol A may be changed into the site resultant from bisphenol F, bisphenol S, or the like. Examples of the polymerizable compounds having a polyethylene oxide skeleton as well as a polypropylene skeleton include the adducts of bisphenols and ethylene oxides or propylene oxides, and the compounds having a hydroxyl group at the end wherein the compound is formed as a polyaddition product and the compound has an isocyanate group and a polymerizable group such as 2-isocyanate ethyl(meth)acrylate and α, -dimethylviny benzilisocyanate, and the like. - Other Polymerizable Monomer - In the pattern forming process according to the present invention, the polymerizable monomers other than the monomers having a urethane group or an aryl group set forth above may be employed together within a range that the properties of the pattern forming material are not deteriorated. Examples of monomers other than the monomers having a urethane group or an aromatic ring include the esters between unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and isocrotonic acid and aliphatic polyvalent alcohols, and amides between unsaturated carboxylic acids and polyvalent amines. Examples of the esters between unsaturated carboxylic acids and aliphatic polyvalent alcohols set forth above include, as (meth) aery late esters, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 18 ethylene groups such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol 5 di(meth)acrylate, dodecaethylene glycol di(meth)acrylate, and tetradecaethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate having 2 to 18 propylene groups such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, and dodecapropylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate, ethyleneoxide modified l o neopentyl glycol di(meth)acrylate, propyleneoxide modified neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acryloyloxypropyl ether, trimethylolethane tri(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
15 tetramethylene glycol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,5-pentanediol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth) aery late, dipentaerythritol hexa(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol
20 penta(meth)acrylate, sorbitol hexa(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, tricyclodecan di(meth)acrylate, neopentylglycol modified trimethylolpropane di(meth)acrylate; di(meth)acrylates of alkyleneglycol chains having at least each one of ethyleneglycol chain and propyleneglycol chain such as those compounds described in International Publication No. WO 01/98832;
25 tri(meth)acrylate of trimethylolpropane added by at least one of ethylene oxide and propylene oxide; polybutylene glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, and xylenol di(meth)acrylate. Among the (meth)acrylates set forth above, preferable in light of easy availability are ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylates of alkyleneglycσl chains having at least each one of ethyleneglycol chain and propyleneglycol chain, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol triacrylate, 5 pentaerythritol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, glycerin di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,5-pentanediol (meth)acrylate, neopentyl glycol di(meth)acrylate, and tri(meth)acrylate of o trimethylolpropane added by ethylene oxide. Examples of the esters between the itaconic acid and the aliphatic polyvalent alcohol compounds, i.e. itaconate, set forth above include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol5 tetraitaconate. Examples of the esters between the crotonic acid and the aliphatic polyvalent alcohol compounds, i.e. crotonate, set forth above include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. o Examples of the esters between the isocrotonic acid and the aliphatic polyvalent alcohol compounds, i.e. isocrotonate, set forth above include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the esters between the maleic acid and the aliphatic polyvalent alcohol compounds, i.e. maleate, set forth above include ethylene glycol dimaleate,5 triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tettamaleate. Examples of the amides derived from the polyvalent amine compounds and the unsaturated carboxylic acids set forth above include methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, l,6-hexamethylenebis(meth)acrylamide, octamethylenebis(meth)acrylamide, diethylenettiamine tris(meth)acrylamide, and diethylenetriamine bis(meth)acrylamide. As for the polymerizable monomers set forth above, the following compounds may be exemplified additionally: compounds that are obtained by 5 adding ,β -unsaturated carboxylic acids to compounds containing a glycidyl group such as butanediol-l,4-diglycidylether, cyclohexane dimethanol glycidylether, ethyleneglycol diglycidylether, diethyleneglycol diglycidylether, dipropyleneglycol diglycidylether, hexanediol diglycidylether, trimethylolpropane triglycidylether, pentaerythritol tetraglycidylether, and glycerin triglycidylether; polyester acrylates o and polyester (meth)acrylate oligomers described in JP-A No.48-64183, and JP-B Nos. 49-43191 and 52-30490; multifunctional acrylate or methacrylate such as epoxy acrylates obtained from the reaction between methacrylic acid epoxy compounds such as butanediol-l,4-diglycidylether, cyclohexane dimethanol glycidylether, diethyleneglycol diglycidylether, dipropyleneglycol diglycidylether, hexanediol5 diglycidylether, trimethylolpropane triglycidylether, pentaerythritol tetraglycidylether, and glycerin triglycidylether; photocurable monomers and oligomers described in Journal of Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (1984); allyl esters such as diallyl phthalate, diallyl adipate, and diallyl malonate; diallyl amides such as diallyl acetamide; cationic polymerizable o divinylethers such as butanediol-l,4-divinylether, cyclohexane dimethanol divinylether, ethyleneglycol divinylether, diethyleneglycol divinylether, dipropyleneglycol divinylether, hexanediol divinylether, trimethylolpropane trivinylether, pentaerythritol tetravinylether, and glycerin vinylether; epoxy compounds such as butanediol-l,4-diglycidylether, cyclohexane dimethanol 5 glycidylether, ethyleneglycol diglycidylether, diethyleneglycol diglycidylether, dipropyleneglycol diglycidylether, hexanediol diglycidylether, trimethylolpropane triglycidylether, pentaerythritol tetraglycidylether, and glycerin triglycidylether; oxetanes such as l,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene and those described in International Publication No. WO 01/22165; compounds having two or more of ethylenically unsaturated double bonds of different types such as N-β -hydroxyethyl-β -methacrylamide ethylacrylate, N,N-bis(β -methacryloxyethyl)acrylamide, acrylmetahcrylate. Examples of vinyl esters set forth above include divinyl succinate and 5 divinyl adipate. These polyfunctional monomers or oligomers may be used alone or in combination. The polymerizable monomers set forth above may be combined with a polymerizable compound having one polymerizable group in the molecule, i.e. o monof unctional monomer. Examples of the mono functional monomers include the compounds exemplified as the raw materials for the binder set forth above, dibasic monofunctional monomer such as mono-(meth)acryloyloxyalkylester, mono-hydroxyalkylester, and5 γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate, and the compounds described in JP-A No. 06-236031, JP-B Nos. 2744643 and 2548016, and International Publication No. WO 00/52529. Preferably, the content of the polymerizable compound in the photosensitive layer is 5 to 60 % by mass, more preferably is 15 to 60 % by mass, and still more o preferably is 20 to 50 % by mass. When the content is less than 5 % by mass, the strength of the tent film may be lower, and when the content is more than 90 % by mass, the edge fusion at storage period is insufficient and bleeding trouble may be induced. The content of the polyfunctional monomer having two or more 5 polymerizable groups set forth above in the molecule is preferably 5 to 100 % by mass, more preferably is 20 to 100 % by mass, still more preferably is 40 to 100 % by mass. - Photopolymerization Initiator - The photopolymerization initiator may be properly selected from conventional ones without particular limitations as long as having the property to initiate polymerization; preferably is the initiator that exhibits photosensitivity from ultraviolet rays to visual lights. The initiator may be an active substance that generates a radical due to an effect with a photo-exited photosensitizer, or a substance that initiates cation polymerization depending on the monomer species. Preferably, the photopolymerization initiator contains at least one component that has a molecular extinction coefficient of about 50 M^cm in a range of about 300 to 800 nm, more preferably about 330 to 500 nm. Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives such as having a ttiazine skeleton or an oxadiazole skeleton, hexaaryl-biimidazols, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acylphosphine oxides, and metallocenes. Among these compounds, halogenated hydrocarbon compounds having a ttiazine skeleton, oxime derivatives, ketone compounds, and hexaaryl-biimidazol compounds are preferable from the view points of sensitivity of photosensitive layers, self stability, adhesive ability between the photosensitive layers and substrates for printed wiring boards. Examples of the hexaaryl-biimidazol compounds include 2,2l-bis(2-chlorophenyl)-4,4l,5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-fluorophenyl)-4,4,,5,5,-tetraphenyl-biimidazole,
2,2l-bis(o-bromophenyl)-4,4l,5,5l-tetraphenyl-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4l,5,5l-tetraρhenyl-biimidazole, 2,2l-bis(2-chlorophenyl)-4,4,,5,5l-tetra(3-methoxyρhenyl)biimidazole, 2,2'-bis(2-cl orophenyl)-4,4 5,5,-tetta(4-n ethoxyphenyl)biimid -zole, 2,2'-bis(4-emthoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2l-bis(2,4-dichlorophenyl)-4,4',5,5l-tetraphenyl-biimidazole, 2,2'-bis(2-mttophenyl)-4,4^5,5'-tettaphenyl-birmidazole, 2,2,-bis(2-methylphenyl)-4,4,,5,5'-tetraphenyl-biimidazole, 2,2'-bis(2-ttifluoronιethylphenyl)-4,4V5,5l-tetraρhenyl-biimidazole, and the compounds described in International Publication No. WO 00/52529. The biimidazoles set forth above can be easily prepared by the methods described, for example, in Bulletin of the Chemical Society of Japan, 33, 565 (1960) and Journal of Organic Chemistry, 36, [16], 2262 (1971). Examples of the halogenated hydrocarbon compounds1 having a ttiazine skeleton include the compounds described in Bulletin of the Chemical Society of
Japan, by Wakabayasi, 42, 2924 (1969); GB Pat. No. 1388492; JP-A No. 53-133428; DE
Pat. No. 3337024; Journal of Organic Chemistry, by F.C. Schaefer et. al. 29, 1527
(1964); JP-A Nos. 62-58241, 5-281728, and 5-34920; and US Pat. No. 4212976. Examples of the compounds described in Bulletin of the Chemical Society of
Japan, by Wakabayasi, 42, 2924 (1969) set forth above include
2-phenyl-4,6-bis(trichloromethyl)-l,3,5-triazine,
2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine,
2-(4-tolyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine,
2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine,
2,4,6-tris(ttichloromethyl)-l,3,5-ttiazine,
2-methyl-4,6-bis(trichloromethyl)-l,3,5-triazine,
2-n-nonyl-4,6-bis(trichloromethyl)-l,3,5-ttiazine, and 2-(α,α,β -trichloroethyl)-4,6-bis(trichloromethyl)-l,3,5-ttiazine. Examples of the compounds described in GB Pat. No. 1388492 set forth above include 2-styryl-4,6-bis(trichloromethyl)-l,3,5-triazine,
2-(4-methylstyryl)-4,6-bis(trichloromethyl)-l,3,5-triazine,
2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-l,3,5-triazine, and 2-(4-n ethoxystyryl)-4-amino-6-trichlorornethyl-l,3,5-triazine. Examples of the compounds described in JP-A No. 53-133428 set forth above include 2-(4-methoxynaphtho-l-yl)-4,6-bistrichloromethyl-l,3,5-triazine,
2-(4-ethoxynaphtho-l-yl)-4,6-bistrichloromethyl-l,3,5-triazine,
2-[4-(2-ethoxyethyl)-naphtho-l-yl]-4,6-bistrichloromethyl-l,3,5-ttiazine, 2-(4,7-dimethoxynaptho-l-yl)-4,6-bistrichloromethyl-l,3,5-triazine, and 2-(acenaphtho-5-yl)-4,6-bistrichloromethyl-l,3,5-triazine. Examples of the compounds described in DE Pat. No. 3337024 set forth above include 2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 5 2-(4-(4-methoxystyryl)phenyl)-4,6-bis(ttichloromethyl)-l,3,5-triazine, 2-(l-naρhthylvinyleneρhenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-thiophene-2-vinylenephenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-thiophene-3-vinylenephenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, o 2-(4-furan-2-vinylenephenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, and 2-(4-benzofuran-2-vinylenephenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine. Examples of the compounds described in Journal of Organic Chemistry, by RG Schaefer et. al. 29, 1527 (1964) set forth above include 2-methyl-4,6-bis(tribromomethyl)-l,3,5-triazine, 5 2,4,6-tris(tribromomethyl)-l,3,5-triazine, 2,4,6-tris(dibromomethyl)-l,3,5-triazine, 2-amino-4-n ethyl-6-tribrornomethyl-l,3,5-ttiazine and 2-methσxy-4-methyl-6-trichloromethyl-l,3,5-triazine. Examples of the compounds described in JP-A No. 62-58241 set forth above o include 2-(4-ρhenylethylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-naphthyl-l-ethynylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-(4-triethynyl)phenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-(4-methoxyphenyl)ethynylρhenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(4-(4-isopropylphenylethynyl)phenyl)-4,6-bis(tticWorometl yl)-l,3,5-triazine, and5 2-(4-(4-ethylphenylethynyl)phenyl)-4,6-bis(ttichloromethyl)-l,3,5-triazine. Examples of the compounds described in JP-A No. 5-281728 set forth above include 2-(4-trifluoromethylphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, 2-(2,6-difluorophenyl)- ,6-bis(trichloromethyl)-l,3,5-triazine, 2-(2,6-dichloroρhenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, and 2-(2,6-dibromophenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine. Examples of the compounds described in JP-A No. 5-34920 set forth above mclude 2,4-bis(tticWoromethyl)-6-[4-(N,N-diethoxycarbonylmethylamino)- 3-bromophenyl]-l,3,5-triazine, trihalomethyl-s-triazine compounds described in US 5 Pat. No.4239850, and also 2,4,6-tris(ttichloromethyl)-s-triazine, and 2-(4-chlorophenyl)-4,6-bis(tribromomethyl)-s-triazine. Examples of the compounds described in US Pat. No. 4212976 set forth above include the compounds having an oxadiazole skeleton such as 2-trichloromethyl-5-phenyl-l,3,4-oxadiazole, o 2-ttichloromethyl-5-(4-chlorophenyl)-l,3,4-oxadiazole, 2-trichloromethyl-5-(l-naphthyl)-l,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-l,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-l,3,4-oxadiazole, 2-tribromomethyl-5-(2-naphthyl)-l,3,4-oxadiazole, 5 2-trichloromethyI-5-styryl-l,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyryl)-l,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-l,3,4-oxadiazole, 2-trichloromethyl-5-(l-naphthyl)-l,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-l,3,4-oxadiazole, and o 2-tribromomethyl-5-styryl-l,3,4-oxadiazole. Examples of the oxime derivatives set forth above include the compounds expressed by the following formulas (39) to (72).
Figure imgf000079_0001
formula (39) formula (40)
Figure imgf000079_0002
formula (41) formula (42)
Figure imgf000079_0003
formula (43) formula (44)
Figure imgf000079_0004
formula (45) formula (46)
Figure imgf000079_0005
formula (47) formula (48)
Figure imgf000079_0006
formula (49)
Figure imgf000080_0001
formula (50)
Figure imgf000080_0002
formula (51)
Figure imgf000080_0003
formula (52)
Figure imgf000080_0004
Figure imgf000080_0005
formula (55) formula (56)
Figure imgf000080_0006
formula (57)
Figure imgf000081_0001
formula (58) formula (59)
Figure imgf000081_0002
Figure imgf000081_0003
formula (62)
Figure imgf000081_0004
Figure imgf000081_0005
formula (65)
Figure imgf000082_0001
formula (66)
Figure imgf000082_0002
formula (68) n-C8H17 formula (69) camphor formula (70) p-CH3C6H4
Figure imgf000082_0003
R formula (71) n-C3H7 formula (72) p-CH3C6H4
Examples of the ketone compounds set forth above include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone-tetracarboxylic acid and its tetramethyl ester; 4,4'-bis(dialkylamino)benzophenones such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(cyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4~methoxy-4,-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, and 5 4-dimethylaminobenzophenone; 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorene, 2-benzyl-dimethylamino-l-(4-morpholinophenyl)-l-butanone, l o 2-methyl-l-[4-(methylthio)phenyl]-2-morpholino-l-propanone, 2-hydroxy-2-methyl-[4-(l-methylvinyl)phenyl]propanol oligomer, benzoin; benzoin ethers such as benzoin methylether, benzoin ethylether, benzoin propylether, benzoin isopropylether, benzoin phenylether, and benzyl dimethyl ketal; acridone, chloroacridone, N-methylacridone, N-butylacridone, and
15 N-butyl-chloroacridone. Examples of the metallocenes include bis(η5-2,4-cyclopentadiene-l~yl)~ bis(2,6-dmuoro-3-(lH-pyrrole-l-yl)-phenyl)titaniurn, η5-cyclopentadienyl-η6-cumenyl-iron(l+)-hexafluorophosphate(l-), and the compounds described in JP-A No. 53-133428, JP-B Nos. 57-1819 and 57-6096, and US
20 Pat. No. 3615455. As for photopolymerization initiators other than set forth above, the following substances are further exemplified: acridine derivatives such as 9-phenyl acridine and l,7-bis(9,9'-acridinyl)heptane; polyhalogenated compounds such as carbon tetrabromide, phenyltribromosulf one, and phenyltrichloromethylketone;
25 coumarins such as 3-(2-benzofuroyl)-7-diethyIaminocoumarin, 3-(2-benzofuroyl)-7-(l-pyrrolidinyl)coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-(2-methoxybenzoyl)-7-diethylaminocoumarin, 3-(4-dimethyla_rmnobenzoyl)-7-diethylaminocoumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3-(2-furoyl)-7-diethylaminocoumarin, 3-(4-diethylammocinnan oyl)-7-diethylaminocoumarin,
7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and 7-benzottiazol-2-ylcoumarin, and also the coumarin compounds described in JP-A Nos. 5-19475, 7-271028, 2002-363206, 2002-363207, 2002-363208, and 2002-363209; amines such as ethyl 4-dimethylamibenzoate, n-butyl 4-dimethylamibenzoate, phenethyl 4-dimethylamibenzoate, 2-phthalimide 4-dimethylamibenzoate, 2-methacryloyloxyethyl 4-dirnethylamibenzoate, pentamethylene-bis(4-dimethylaminobenzoate), phenethyl 3-dimethylamibenzoate, pentamethylene esters, 4-dimethylamino benzaldehyde, 2-c oro-4-dimethylamino benzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl(4-dimethylaminobenzoyl)acetate, 4-piperidine acetophenone, 4-dimethyamino benzoin, N,N-dimethyl-4-toluidine, N,N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylarnine, N-methyl-N-phenylbenzylamine, 4-bromo-N,N-diethylaniline, and tridodecyl amine; amino fluorans such as ODB and ODBII; leucocrystal violet; acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphenylphosphine oxide, and Lucirin TPO. In addition, as for still other photopolymerization initiator, the following substances are exemplified: vicinal polyketaldonyl compounds as described in US Pat. No. 2367660; acyloin ether compounds as described in US Pat. No. 2448828; aromatic acyloin compounds substituted with an α-hydrocarbon as described in US Pat. No. 2722512; polynucleic quinone compounds as described in US Pat. Nos. 3046127 and 2951758; various substances described in JP-A No. 2002-229194 such as organic boron compounds, radical generators, triarylsulf onium salts e.g. salts with hexafluoroantimony or hexafluorophosphate, phosphonium salts e.g. (phenylthiophenyl)diphenylsulfonium (effective as cation polymerization initiator), and onium salt compounds described in International Publication No. WO 01/71428. These photopolymerization initiators may be used alone or in combination. The combination of two or more photopolymerization initiators may be for example the combination of hexaaryl-biimidazol compounds and amino ketones described in US Pat. No.3549367; combination of benzothiazole compounds and trihalomethyl-s-triazine compounds as described in JP-B No. 51-48516; combination of aromatic ketone compounds such as thioxanthone and hydrogen donating substance such as dialkylamino-containing compounds or phenol compounds; combination of hexaaryl-biimidazol compounds and titanocens; and combination of coumarins, tinanocens, and phenyl glycines. The content of the photopolymerization initiator in the photosensitive layer is preferably 0.1 to 30 % by mass, more preferably is 0.5 to 20 % by mass, and still more preferably is 0.5 to 15 % by mass.
- Other Components - As for the other components, photosensitizer, thermal polymerization inhibitor, plasticizer, coloring agent, and colorant are exemplified; in addition, the other auxiliaries such as adhesion promoter on substrate surface, pigment, conductive particles, filler, defoamer, fire retardant, leveling agent, peeling promoter, antioxidant, perfume, thermocrosslinker, adjustor of surface tension, chain transfer agent, and the like may be utilized together with. By means of incorporating these components properly, desirable properties of the pattern forming material such as stability with time, photographic property, developing property, film property, and the like may be tailored.
— Photosensitizer — The photosensitizer may be properly selected depending on the types of laser beam utilized in the pattern forming process and the like. The photosensitizer may be exited by active irradiation, and may generate a radical, an available acidic group and the like through interaction with other substances such as radical generators and acid generators by transferring energy or electrons. The photosensitizer may be properly selected without particular limitations from conventional substances; examples of the photosensitizer include polynuclear aromatics such as pyrene, perylene, and triphenylene; xanthenes such as fluorescein, Eosine, erythrosine, rhodamine B, and Rose Bengal; cyanines such as indocarbocianine, thiacarbocianine, and oxacarbocianine; merocianines such as 5 merocianine and carbomerocianine; thiazins such as thionine, methylene blue, and toluidine blue; acridines such as acridine orange, chloroflavine, and acriflavine; anthraquinones such as anthraquinone; scariums such as scarium; acridones such as acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; coumarins such as o 3-(2-benzofuroyl)-7-diethylaminocoumarin, 3-(2-benzofuroyl)-7-(l-pyrrolidinyl)coumarin, 3-benzofuroyl-7-diethylaminocoumarin, 3-(2-methoxybenzoyl)-7-diethylaminocoumarin, 3-(4-dirnethylaminobenzoyl)-7-diethylaminocoumarin, 5 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3-(2-furoyl)-7-diethylaminocoumarin, 3-(4-diethylaminocinnamoyl)-7-diethylaminocoumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and o also the coumarin compounds described in JP-A Nos. 5-19475, 7-271028, 2002-363206, 2002-363207, 2002-363208, and 2002-363209. As for the combination of the photopolymerization initiator and the photosensitizer, the initiating mechanism that involves electron transfer may be exemplified such as combinations of (1) an electron donating initiator and a5 photosensitizer dye, (2) an electron accepting initiator and a photosensitizer dye, and (3) an electton donating initiator, and an electron accepting initiator, and a photosensitizer dye (ternary mechanism) as described in JP-A No. 2001-305734. The content of the photosensitizer is preferably 0.05 to 30 % by mass based on the entire composition of the photosensitive resin, more preferably is 0.1 to 20 % by mass, and still more preferably is 0.2 to 10 % by mass. When the content is less than 0.05 % by mass, the sensitivity toward the active energy ray may decrease, longer period may be required for exposing process, and the productivity tends to lower, and when the content is more than 30 % by mass, the photosensitizer may precipitate from the photosensitive layer during preservation period. — Thermal Polymerization Inhibitor — The thermal polymerization inhibitor may be effectively incorporated into the photosensitive layer in order to prevent the polymerization due to higher temperature or with time. Examples of the thermal polymerization inhibitors include 4-methoxy phenol, hydroquinone, hydroquinones substituted by an alkyl or aryl group, t-butylcatechol, p rogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methyleneblue, reaction products of cupper and organic chelating agents, methyl salicylate, nitroso compounds, chelate compounds between nitroso compounds and Al, and the like. The content of the thermal polymerization inhibitor is preferably 0.001 to 5 % by mass based on the polymerizable compound in the photosensitive layer, more preferably is 0.005 to 2 % by mass, and still more preferably is 0.01 to 1 % by mass. When the content is less than 0.001 % by mass, the storage stability may be insufficient, and when the content is more than 5 % by mass, the sensitivity toward the active energy ray may decrease. -- Plasticizer -- The plasticizer set forth above may be incorporated into in order to adjust the film property i.e. flexibility of the photosensitive layer. Examples of the plasticizer include phthalic acid esters such as dimethylphthalate, dibutylphthalate, diisobutylphthalate, diheptylphthalate, dioctylphthalate, dicyclohexylphthalate, dittidecylphthalate, butylbenzylphthalate, diisodecylphthalate, diphenylphthalate, diallylphthalate, and octylcaprylphthalate; glycol esters such as triethyleneglycol diacetate, tetraethyleneglycol diacetate, dimethylglycose phthalate, ethylphthalyl ethylglycolate, methylphthalyl ethylglycolate, buthylphthalyl buthylglycolate, triethylene glycol dicaprylate; phosphoric acid esters such as tricresylphosphate and triphenylphosphate; amides such as 4-toluenesulfone amide, benzenesulfone amide, N-n-butylsulfone amide, and N-n-aceto amide; aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, and dibutyl maleate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate,
4,5-diepoxy-cyclohexane-l,2-dicarboxylic acid dioctyl; and glycols such as polyethylene glycol and polypropylene glycol. The content of the plasticizer set forth above is preferably 0.1 to 50 % by mass, more preferably is 0.5 to 40 % by mass, and still more preferably is 1 to 30 % by mass. — Coloring Agent - The coloring agent may be utilized to provide visible images or to afford developing property on the photosensitive layer set forth above after exposure. Examples of the coloring agent include aminotriarylmethanes such as tris(4-dimethylaminophenyl)methane (leucocrystal violet), tris(4-diethylaminophenyl)methane, ttis(4-dimethylamino-2-methylphenyl)rnethane, tris(4-diethylamino-2-methylphenyl)methane, bis(4-dibutylaminophenyl)-[4-(2-cyanoethyl)methylaminophenyl]methane, bis(4-dimethylaminophenyl)-2-quinolylmethane, and ttis(4-dipropylaminophenyl)methane; aminoxanthenes such as 3,6-bis(diethyIamino)-9-phenylxanthene and
3-amino-6-dimethylamino-2-methyl-9-(o-chlorophenyl)xanthene; aminothioxanthenes such as
3,6-bis(diethylamino)-9-(2-ethoxycarbonylphenyl)thioxanthene and 3,6-bis(dimethylamino)thioxanthene; amino-9,10-dihydroacridines such as 3,6-bis(diethylamino)-9,l O-dihydro-9-phenylacridine and 3,6-bis(benzylar-vino)-9,10-dihydro-9-methylacridine; aminophenoxazines such as 3,7-bis(diethylamino)phenoxazines; ammophenothiazines such as 3,7-bis(ethylamino)phenothiazine; arninodihydrophenazines such as 5 3,7-bis(diethylamino)-5-hexyl-5,10-dihydrophenazine; aminophenylmethanes such as bis(4-diι-nethylaminophenyl)anilinomethane; aminohydrocinnamic acids such as 4-anιino-4'~dimethylaminodiphenylamine and 4-amino- ,β -dicyanohydrocinnamate methyl ester; hydrazines such as l-(2-naphthyl)2-phenylhydrazine; amino-2,3-dihydroanthraquinones such as l o l,4-bis(ethyIamino)-2,3-dihydroanthraquinone; phenethylanilines such as N,N-diethyl~p-phenethylaniline; acyl derivatives of leuco dyes containing a basic NH group such as 10-acetyl-3,7-bis(dirnethylamino)phenothiazine; leuco-like compounds with no oxidizable hydrogen and capable of being oxidized into colored compounds such as tris(4-diethylamino-2-tolyl)ethoxycarbonylmethane; leucoindigoid dyes;
15 organic amines capable of being oxidized to colored forms as described in US Pat. Nos. 3042515 and 3042517 such as 4,4'-ethylenediamine, diphenylamine, N,N-dimethylaniline, 4,4'-methylenediaminetriphenylamine, and N-vinylcarbazole. Among these coloring agents, triarylmethanes such as leucocrystal violet are preferable in particular.
20 In addition, it is known that the coloring agents set forth above may be combined with halogenated compounds in order to develop a color from the leuco compounds. Examples of the halogenated compounds include halogenated hydrocarbons such as tetrabromocarbon, iodoform, ethylene bromide, methylene bromide, amyl
25 bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, diphenylmethyl bromide, hexachloromethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, l,2-dibromo-l,l,2-trichloroethane, 1,2,3-tribromopropane, l-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, and l,l,l-ttichloro-2,2-bis(4-chlorophenyl)ethane; halogenated alcohol compounds such as 2,2,2,-trichloroethanol, tribromoethanol, l,3-dichloro-2-propanol, l,l,l-ttichloro-2-propanol, di(iodohexamethylene)aminoisopropanol, tribromo-tert-butyl alcohol, and 2,2,3-trichlorobutane-l,4-diσl; halogenated carbonyl compounds such as 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3,4-dibromo-2-butanone, and l,4-dichloro-2-butanone-dibromocyclohexanone; halogenated ether compounds such as 2-bromoethyl methylether, 2-bromoethyl ethylether, di(2-bromoethyl) ether, and 1,2-dichloroethyl ethylether; halogenated ester compounds such as bromoethyl acetate, ethyl ttichloroacetate, ttichloroethyl trichloroacetate, homo- and co-polymers of 2,3-dibromopropyl acrylate, ttichloroethyl dibromopropionate, and ethyl ,β-dichloroacrylate; halogenated amide compounds such as chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, ttibromoacetamide, tticWoroethylttichloroacetamide, 2-bromoisopropionamide, 2,2,2-ttichloropropionamide, N-chlorosuccinimide, and N-bromosuccinimide; compounds containing a sulfur and/ or phosphorus atom such as tribromomethyl phenylsulf one, 4-nitrophenyltribromo methylsulf one, 4-chlorophenyltribromo methylsulfone, tris(2,3-dibromopropyl)phosphate, and 2,4-bis(trichloromethyl)-6-phenyltriazole. In the organic halogenated compounds, preferably are those containing two or more halogen atoms that are attached to one carbon atom, more preferably are those containing three halogen atoms that are attached to one carbon atom. The organic halogenated compounds may be used alone or in combination. Among these halogenated compounds, tribromomethyl phenylsulfone and 2,4-bis(trichloromethyl)-6-phenyltriazole are preferable. The content of the coloring agent is preferably 0.01 to 20 % by mass based on the total components in the photosensitive layer, more preferably is 0.05 to 10 % by mass, and still more preferably is 0.1 to 5 % by mass. The content of the halogenated compound is preferably 0.001 to 5 % by mass based on the total components in the photosensitive layer, more preferably is 0.005 to 1 % by mass. - Dye - To the photosensitive layer set forth above, a dye may be incorporated into in order to add a color so as to make easy the handling or to enhance the storage 5 stability. Examples of the dye include Brilliant Green, eosin, Ethyl Violet, Erythrosine B, Methyl Green, Crystal Violet, Basic Fuchsine, phenolphthalein, 1,3-diphenyltriazine, Alizarin Red S, Thymolphthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengale, Metanil- Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl o Orange, Orange IV, diphenyl thiocarbazone, 2,7-dichlorofluorescein, Para Methyl Red, Congo Red, Benzopurpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, phenacetarin, Methyl Violet, Malachite Green, Para Fuchsine, Oil Blue #603 (produced by Orient Chemical Industry Co., Ltd.), Rhodamine B, Rhodamine 6G, and Victoria Pure Blue BOH. Among these dyes, preferably are cation dyes such as 5 oxalate of Malachite Green and sulf ate of Malachite Green. The pair anion of the cation dyes may be residues of organic acid or inorganic acid such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methane sulfonic acid, and toluene sulfonic acid. The content of the dye is preferably 0.001 to 10 % by mass based on the total o components in the photosensitive layer, more preferably is 0.01 to 5 % by mass, and still more preferably is 0.1 to 2 % by mass. — Adhesion Promoter - In order to enhance the adhesion between layers or between the pattern forming material and the substrate, so-called adhesion promoters may be employed. 5 Examples of the adhesion promoters set forth above include those described in JP-A Nos. 5-11439, 5-341532, and 6-43638; specific examples of adhesion promoters include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-l-phenyl-triazole-2-thion, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thion, 5-amino-3-morpholmornethyl-thiadiazole-2-thion, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzottiazole, benzotriazole containing an amino group, and silane coupling agents. The content of the adhesion promoter is preferably 0.001 to 20 % by mass based on the total components in the photosensitive layer, more preferably is 0.01 to 10 % by mass, and still more preferably is 0.1 to 5 % by mass. The photosensitive layer may contain, as described in "Light Sensitive Systems, chapter 5th, by J. Curser", organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreductive dyes, or organic halogen compounds. Examples of the organic sulfur compounds include di-n-butyldisulfide, dibenzyldisulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyl ttichloromethane sulfonate, and 2-mercaptobenzimidazole. Examples of the peroxides include di-t-butyl peroxide, benzoyl peroxide, and methyethylketone peroxide. The redox compounds set forth above are a combination of a peroxide and a reducer such as persulfate ion and ferrous ion, peroxide and ferric ion, or the like. Examples of azo or diazo compound set forth above include diazoniums such as α,α'-azobis-isobutylonitrile, 2-azobis-2-methylbutylonitrile, and 4-aminodiphenylamine. Examples of the photoreductive dye set forth above include Rose Bengale, Erythrosine, Eosine, acriflavine, riboflavin, and thionine. — Surfactant — In order to improve surface nonuniformity generated at producing the pattern forming material in the present invention, conventional surfactants may be employed. The surfactant may be properly selected from anionic surfactants, cationic surfactants, nonionic surfactants, ampholytic surfactants, fluorine-containing surfactant, and the like. The content of the surfactant is preferably 0.001 to 10 % by mass based on the solid content of the photosensitive resin composition. When the content is less than 0.001 % by mass, the effect to improve the nonuniformity may be insufficient, and when the content is more than 10 % by mass, the adhesion ability may be deteriorated. In addition, as for the surfactants, such polymer surfactants containing fluorine may be preferably exemplified as containing 40 % by mass or more of fluorine atoms, having, a carbon chain of 3 to 20 carbon atoms, and having a copolymerized component of acrylate or methacrylate containing an aliphatic group of which the hydrogen atoms bonded on the terminal carbon atom to the third of the carbon atom are substituted by fluorine atoms. The thickness of the photosensitive layer may be properly selected without particular limitations; preferably, the thickness is 0.1 to 10 μm. « Barrier Layer » The barrier layer may be properly selected depending on the application as long as migration of substances may be suppressed. When the barrier layer is insoluble in water, preferably is dispersible into water. Preferably, the barrier layer is soluble in water and/ or alkaline liquids. When the barrier layer is insoluble in alkaline liquids, the barrier layer should be removed in a process other than that of removing the photosensitive layer with the alkaline liquid, thus possibly resulting in an additional production process. The substances of which the migration should be suppressed by the barrier layer are, for example, oxygen, water, component contained in the photosensitive layer or the cushioning layer. The barrier layer may be properly selected depending on the application, preferably the barrier layer contain a resin. The resin may be soluble or insoluble in water; preferably the resin is soluble in water or dispersible into water. Specifically, the resin is preferably soluble in a concenttation of 0.1 % by mass or more in water at 25 °C, more preferably 1 % by mass or more. The resin may be properly selected depending on the application; examples of the resins include various resins soluble in alcohols, water, or alkaline liquids, various resins dispersible into alcohols or water, and resins capable of emulsified. Specifically, the resins may be vinyl polymers such as polyvinyl alcohols, modified polyvinyl alcohols, polyvinyl pyrrolidones, vinyl copolymers set forth above, water soluble polyamides, gelatin, celluloses, derivatives thereof, or various resins and compounds described in JP-B No. 2794242. These may be used alone or in combination. The oxygen gas permeability of the barrier layer may be properly selected depending on the application; preferably, the oxygen gas permeability is 100 cm3/ (m2- day arm) or less, more preferably is 50 cm3/ (m2- day arm) or less under a temperature of 23 °C and a relative humidity of 60 %. When the pattern forming material contains a barrier layer between the cushioning layer and the photosensitive layer, among the respective interlayer adhesive strengths between the respective layers, the interlayer adhesive strength between the support and the cushioning layer may be minimum, the interlayer adhesive strength between the cushioning layer and the barrier layer may be minimum, or the interlayer adhesive strength between the barrier layer and the photosensitive layer may be minimum. The thickness of the barrier layer may be properly selected depending on the application; preferably the thickness is less than 10 μm, more preferably is 0.1 to 6 μm, and still more preferably is 1 to 5 μm. When the thickness is more than 10 μm, laser scattering tends to be induced at the barrier layer during the exposure, resulting in degradation of resolution and/ or adhesive property. [Production of Pattern Forming Material] The pattern forming material may be produced as follows. Initially, a solution of photosensitive resin composition, a coating liquid for cushioning layer, and a coating liquid for barrier layer are prepared by dissolving, emulsifying, or dispersing the various components or materials set forth above into water or solvents. 5 The solvent of the solution of photosensitive resin composition, coating liquid for cushioning layer, and coating liquid for barrier layer may be properly selected depending on the application; examples of the solvent include alcohols such as ethanol, methanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; ektones such as acetone, methyl ethyl ketone, methylisobutylketone, cyclohexanone, o and diisobutylketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, and ethyl benzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1 -trichloroetahne, methylene chloride, and monochloro benzene; 5 ethers such as tetrahydrofuran, diethylene ether, ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, and l-methoxy-2-propanol; dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, and sulforane. These may be used alone or in combination. Further, a conventional surfactant may be added to the solvent. Then, the coating liquid for cushioning layer is coated on the support to dry o the coating thereby to form a cushioning layer, optionally the coating liquid for barrier layer is coated on the cushioning layer to dry the coating thereby to form a barrier layer, and the solution of photosensitive resin composition is coated on the barrier layer to dry the coating thereby to form a photosensitive layer, thus a pattern forming material may be produced. 5 The solution of photosensitive resin composition, the coating liquid for cushioning layer, and the coating liquid for barrier layer may be properly coated depending on the application; examples of the coating method include spraying method, roll coating method, rotary coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, gravure coating method, wire bar coating method, and knife coating method. The drying conditions at the coating methods depend on the various components, species of solvent, and the solvent amount in general; usually, the temperature is 60 to 110 °C and the period is 30 seconds to 15 minutes. 5 « Support and Protective Film » The support may be properly selected depending on the application; preferably, the support exhibits a peeling ability against the photosensitive layer, and the support is highly transparent and has higher surface flatness. Preferably, the support is formed from a transparent synthetic resin; o examples of the synthetic resin include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, diacetyl cellulose, polyalkyl methacrylate, polymethacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinylchloride-vinylacetate copolymer, polytettafluoroethylene, polytrifluoroethylene, 5 cellulose film, and nylon film; among these resins, polyethylene terephthalate is particularly preferable. These resins may be used alone or in combination. The thickness of the support may be properly selected depending on the application; preferably, the thickness is 2 to 150 μm, more preferably is 5 to 100 μm, and still more preferably is 8 to 50 μm. o The shape of the support may be properly selected depending on the application; preferably the shape is elongated. The length of the elongated support is selected from 10 to 20000 meters, for example. In the pattern forming material, a protective film may be provided on the photosensitive layer. The material of the protective film may be those exemplified 5 with respect to the support set forth above, and also may be paper, polyethylene, paper laminated with polypropylene, or the like. Among these materials, polyethylene film and polypropylene film are preferable. The thickness of the protective film may be properly selected without particular limitations; preferably, the thickness is 5 to 100 μm, more preferably is 8 to 50 μm, and still more preferably is 10 to 30 μm. In the application of the protective film, preferably, the adhesive strength A between the photosensitive layer and the support, and the adhesive strength B between the photosensitive layer and the protective film represent the following 5 relation: adhesive strength A > adhesive strength B. The combinations of the support and the protective film, i.e. (support/ protective film), are exemplified by (polyethylene terephthalate/ polypropylene), (polyethylene terephthalate/ polyethylene), (polyvinyl chloride/ cellophane), (polyimide/polypropylene), and (polyethylene o terephthalate/ polyethylene terephthalate). Further, the surface treatment of the support and/ or the protective film may result in the relation of the adhesive strength set forth above. The surface treatment of the support may be utilized for enhancing the adhesive strength with the photosensitive layer; examples of the surface treatment include deposition of under-coat layer, corona discharge treatment, flame5 treatment, UV-rays treatment, RF exposure treatment, glow discharge tteatment, active plasma treatment, and laser beam treatment. The static friction coefficient between the support and the protective film is preferably 0.3 to 1.4, more preferably is 0.5 to 1.2. When the static friction coefficient is less than 0.3, winding displacement o may generate in roll configuration due to excessively high slipperiness, and when the static friction coefficient is more than 1.4, winding of the material in a roll configuration tends to be difficult. Preferably, the pattern forming material is wound on a cylindrical winding core, and is stored in an elongated roll configuration. The length of the elongated 5 pattern forming material may be properly selected without particular limitations, for example the length is from 10 to 20000 meters. Further, the pattern forming material may be subjected to slit processing for easy handling in the usages, and may be provided as a roll configuration for every 100 to 1000 meters. Preferably, the pattern forming material is wound such that the support exists at outer most side of the roll configuration. Further, the pattern forming material may be slit into a sheet configuration. In the storage, preferably, a separator of moistureproof with desiccant in particular is provided at the end surface of the pattern forming material, and the package is performed by a material of higher moistureproof for preventing 5 edge fusion. The protective film may be subjected to surface treatment in order to control the adhesive property between the protective film and the photosensitive layer. The surface treatment is performed, for example, by providing an under-coat layer of polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and o polyvinyl alcohol on the surface of the protective film. The under-coat layer may be formed by coating the liquid of the polymer on the surface of the protective film, then drying the coating at 30 to 150 °C, in particular 50 to 120 °C for 1 to 30 minutes. In addition to the photosensitive layer, the support, and the protective film, other layers such as a peeling layer, adhesive layer, optical absorbing layer, and surface 5 protective layer may be provided. < Substrate > The substrate may be properly selected from commercially available materials, which may be of nonuniform surface other than of highly smooth surface. Preferably, the substrate is plate-like; specifically, the substrate selected from the o materials such as printed wiring boards e.g. cupper-laminated plate, glass plates e.g. soda glass plate, synthetic resin films, paper, and metal plates. The substrate is utilized such that the photosensitive layer of the pattern forming material is duplicated on the substrate to form a consolidated laminate. In such a construction, a pattern may be formed by a developing step, for example, 5 through exposing the photosensitive layer of the pattern forming material on the laminate thereby hardening the exposed region. The process for forming the laminated body may be properly selected depending on the application; preferably, the pattern forming material is laminated to the substrate while the pattern forming material is being subjected to at least one of heating and pressing. The heating temperature may be properly selected depending on the application; preferably the temperature is 15 to 180 °C, more preferably is 60 to 140 °C. The pressure may be properly selected depending on the application; 5 preferably the pressure is 0.1 to 1.0 MPa, more preferably is 0.2 to 0.8 MPa. The apparatus for conducting the heating and/ or pressing may be properly selected depending on the application; examples of the apparatus include a laminator, vacuum laminator and the like. The pattern forming material iαthe present invention may be applied to o printed wiring boards, color filters; display members such as column member, rib member, spacer, and partition member; holograms, micro machines, and proofs. Also, the pattern forming material may be applied to the pattern forming processes according to the present invention. [Other Steps]5 The other steps may be properly conducted by applying the conventional steps for forming patterns such as developing step, etching step, and plating step. These steps may be employed singly or in combination. In the developing step, the photosensitive layer of the pattern forming material is exposed, the exposed region of the photoconductive layer is hardened, o then the unhardened region is removed, thereby a pattern is produced. The method to remove the unhardened region may be properly selected without particular limitations; for example, the unhardened region may be removed by a developer. The developer may be properly selected depending on the application;5 examples of the developers include alkaline aqueous solutions, aqueous developing liquids, and organic solvents; among these, weak alkali aqueous solutions are preferable. The basic components of the weak alkali aqueous solutions are exemplified by lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, and borax. Preferably, the weak alkali aqueous solution exhibits a pH of about 8 to 12, more preferably is about 9 to 11. Examples of such a solution are aqueous solutions 5 of sodium carbonate and potassium carbonate at a concentration of 0.1 to 5 % by mass. The temperature of the developer may be properly selected depending on the developing ability of the developer; for example, the temperature of the developer is about 25 to 40 °C. The developer may be combined with surfactants, defoamers; organic bases o such as ethylene diamine, ethanol amine, tetramethylene ammonium hydroxide, diethylene ttiamine, triethylene pentamine, morpholine, and triethanol amine; organic solvents to promote developing such as alcohols, ketones, esters, ethers, amides, and lactones. The developer set forth above may be an aqueous developer selected from aqueous solutions, aqueous alkali solutions, combined solutions of 5 aqueous solutions and organic solvents, or an organic developer. The etching may be carried out by a method selected properly from conventional etching method. The etching liquid in the etching method may be properly selected depending on the application; when the metal layer set forth above is formed of o copper, exemplified are cupric chloride solution, ferric chloride solution, alkali etching solution, and hydrogen peroxide solution for the etching liquid; among these, ferric chloride solution is preferred in light of the etching factor. The etching treatment and the removal of the pattern forming material may form a permanent pattern on the substrate. The permanent pattern may be properly 5 selected depending on the application; for example, the pattern is of wiring. The plating step may be performed by a method selected from conventional plating treatment methods. Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, nickel plating such as watt bath (nickel sulf ate-nickel chloride) plating and nickel sulf amate plating, and gold plating such as hard gold plating and soft gold plating. A permanent pattern may be formed by performing a plating treatment in the plating step, followed by removing the pattern forming material and optional etching treatment on unnecessary portions. In the pattern forming process according to the present invention, permanent patterns may be precisely and effectively formed by suppressing the distortion of images formed on the pattern forming material, therefore, the pattern forming process may be successfully applied to various patterns that require highly precise exposure, in particular to highly precise wiring patterns.
[Process for Producing Printed Wiring Board] The pattern forming process according to the present invention may be successfully applied to the production of printed wiring boards, in particular the printed wiring boards having through holes pr via holes. The process for producing printed wiring boards based on the pattern forming process according to the present invention will be explained in the following. In process for producing printed wiring boards having through holes and/ or via holes, a pattern may be formed by (i) laminating the pattern forming material on a substtate of a printed wiring board having holes such that the photosensitive layer faces the substrate thereby to form a laminated body, (ii) irradiating a light onto the regions for forming wiring patterns and holes from the opposite side of the substrate of the laminated body thereby to harden the photosensitive layer, (iii) removing the support of the pattern forming material from the laminated body, and (iv) developing the photosensitive layer of the laminated body to remove unhardened portions in the laminated body. By the way, removing the support of (iii) may be carried out between the (i) and (ii) instead of between (ii) and (iv) set forth above. Then, using the formed pattern, etching treatment or plating treatment of the substrate of the printed wiring board by means of conventional subtractive or additive method e.g. semi-additive or full-additive method may produce the printed wiring board. Among these methods, the subtractive method is preferable in order to form printed wiring boards by industrially advantageous tenting. After the treatment, the hardened resin remaining on the substrate of the printed wiring board is peeled, or copper thin film is etched after the peeling in the case of semi-additive process, thereafter the intended printed wiring board is obtained. In the case of multi-layer printed wiring board, the similar process with the printed wiring board may be applicable. The process for producing printed wiring boards having through holes by means of the pattern forming material will be explained in the following. Initially, the substrate of printed wiring board is prepared in which the surface of the substrate is covered with a metal plating layer. The substrate of printed wiring board may be a copper-laminated layer substrate, a substrate that is produced by forming a copper plating layer on a insulating substrate such as glass or epoxy resin, or a substrate that is laminated on these substrate and formed into a copper plating layer. In a case that a protective layer exists on the pattern forming material, the protective film is peeled, and the photosensitive layer of the pattern forming material is contact bonded to the surface of the printed wiring board by means a pressure roller as a laminating process, thereby a laminated body may be obtained that contains the substrate of the printed wiring board and the laminated body set forth above. The laminating temperature of the pattern forming material may be properly selected without particular limitations; the temperature may be about room temperature such as 15 to 30 °C, or higher temperature such as 30 to 180 °C, preferably it is substantially warm temperature such as 60 to 140 °C. The roll pressure of the contact bonding roll may be properly selected without particular limitations; preferably the pressure is 0.1 to 1 MPa; the velocity of the contact bonding may be properly selected without particular limitations, preferably, the velocity is 1 to 3 meter/ minute. The substrate of the printed wiring board may be pre-heated before the contact bonding; and the substrate may be laminated under a reduced pressure. The laminated body may be formed by laminating the pattern forming material on the substrate of the printed wiring board; alternatively by coating the solution of the photosensitive resin composition for pattern forming material directly on the substtate of the printed wiring board, followed by drying the solution, thereby laminating the photosensitive layer on the substrate of the printed wiring board. Then, a laser beam is irradiated onto the photosensitive layer from the opposite side of the substtate of the laminated body thereby to harden the photosensitive layer. In such a case, the irradiation is performed after the support is peeled, depending on the requirement such that the transparency of the support is lower. In the case that the support exists on the support after the laser irradiation, the support is peeled from the laminated body as the support peeling step. The un-hardened region of the photosensitive layer on the substtate of the printed wiring board is dissolved away by means of an appropriate developer, a pattern is formed that contains a hardened layer for forming a wiring pattern and a hardened layer for protecting a metal layer of through holes, and the metal layer is exposed at the substrate surface of the printed wiring board as the developing step. Additional treatment to promote the hardening reaction, for example, may be performed by means of post-heating or post-exposing optionally. The developing may be of a wet method set forth above or a dry developing method. Then, the metal layer exposed on the substrate surface of the printed wiring board is dissolved away by an etching liquid as an etching process. The apertures of the through holes are covered by cured resin or tent film, therefore, the etching liquid does not infiltrate into the through holes to corrode the metal plating within the through holes, and the metal plating may maintain the specific shape, thus a wiring pattern may be formed on the substrate of the printed wiring board. The etching liquid may be properly selected depending on the application; cupric chloride solution, ferric chloride solution, alkali etching solution, and hydrogen peroxide solution are exemplified for the etching liquid when the metal layer set forth above is formed of copper; among these, ferric chloride solution is preferred in light of the etching factor. Then, the hardened layer is removed from the substtate of the printed wiring board by means of a strong alkali aqueous solution for example as the removing step of hardened material. . The basic component of the strong alkali aqueous solution may be properly selected without particular limitations, examples of the basic component include sodium hydroxide and potassium hydroxide. The pH of the strong alkali aqueous solution may be about 12 to 14 for example, preferably is about 13 to 14. The strong alkali aqueous solution may be an aqueous solution of sodium hydroxide or potassium hydroxide at a concentration of 1 to 10 % by mass. The printed wiring board may be of multi-layer construction. By the way, the pattern forming material set forth above may be applied to plating processes instead of the etching process set forth above. The plating method may be copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating. The present invention will be illustrated in more detailed with reference to examples given below, but these are not to be construed as limiting the present invention. All parts are by weight unless indicated otherwise. (Example 1) - Production of Pattern Forming Material - The coating liquid for cushioning layer of the following ingredients was coated on a polyethylene terephthalate film of 16 μm thick as the support and the coating was dried to form a cushioning layer of 15 μm thick. [Ingredients of Coating Liquid for Cushioning Layer] - Copolymer of methyl methacrylate/2-ethylhexyl acrylate/ benzyl
5 methacrylate/methacrylic acid — 60 parts (mole ratio: 55/10/5/30, weight-averaged molecular weight: 100000) - Copolymer of styrene/ acrylic acid — 140 parts (mole ratio: 65/35, weight-averaged molecular weight: 10000) - 2,2-bis[4-(methacryloyloxypentaethoxy)phenyl]propane ~ 150 parts o (BPE-500, by Shin-nakamura Chemical Co.) - Methyl ethyl ketone ~ 700 parts Then, the coating liquid for barrier layer of the following ingredients was coated on the cushioning layer and the coating was dried to form a barrier layer of 1.6 μm thick. 5 [Ingredients of Coating Liquid for Barrier Layer] - Pol vinyl alcohol (PVA205, by Kuraray Co. Ltd.) - 13 parts - Polyvinyl pyrrolidone — 6 parts (K-30, by International Specialty Products Inc.) - Water - 200 parts0 - Methanol - 180 parts Then, the solution of the photosensitive resin composition of the following ingredients was coated on the barrier layer and the coating was dried to form a photosensitive layer of 5 μm thick on the barrier layer, thereby to form a pattern forming material. 5 [Ingredients of Solution of Photosensitive Resin Composition] - Copolymer of methyl methacrylate/2-ethylhexyl acrylate/ benzyl methacrylate/methacrylic acid — 15 parts (mass ratio: 50/20/7/23, weight-averaged molecular weight: 90000, acid value: 150) - 2,2-bis[4-(methacryloyloxypentaethoxy)phenyl]propane — 7.0 parts (BPE-500, by Shin-nakamura Chemical Co.)
- Adduct of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate (mole ratio: 1/2) — 7.0 parts - N-methyl acridone — 0.11 part
- 2,2 -bis(o-chlorophenyl)-4,4',5,5'-tettaphenyl biimidazole — 2.17 parts
- 2-mercaptobenzimidazole — 0.23 part
- Oxalate of Malachite Green — 0.02 part
- Leucocrystal violet — 0.26 part - Methyl ethyl ketone . — 40 parts
- l-methoxy-2-propanol — 20 parts A polyethylene film of 20 μm thick as the protective film was laminated on the photosensitive layer of the pattern forming material. Then, a copper laminated plate (without through holes, copper thickness: 12 μm, MCL-E-67, by Hitachi Chemical Co. Ltd.), which had been polished, rinsed, and dried was prepared as a substrate. To the copper laminated plate, the photosensitive layer was contact bonded while the protective film of the pattern forming material was peeled away by means of Laminator (Model 8B-720-PH, by Taisei-Laminator Co.) so as to contact the photosensitive layer with the copper laminated plate, thereby a laminated body was obtained which comprises the copper laminated plate, the photosensitive layer, the cushioning layer, and the polyethylene terephthalate as the support in order. The maximum height Rz of the surface of the photosensitive layer laminated on the copper laminated plate was 3 μm in accordance with JIS B 0601. The conditions of the contact bonding were such that temperature of contact bonding roll: 105 °C, pressure of contact bonding roll: 0.3 MPa, and laminating rate: 1 meter/ minute (m/min). The resulting laminated body was evaluated as to the resolution, exposure rate, and etching property. The result is shown in Table 3. < Resolution > (1) Method for Measuring Shortest Developing Period The polyethylene terephthalate film as the support was peeled away from the laminated body, then an aqueous solution of sodium carbonate at 1 % by mass concentration was sprayed on the entire surface of the photosensitive layer on the 5 copper laminated plate at 30 °C and 0.15 MPa. The period from the initial spraying to the dissolving away of the photosensitive layer on the copper laminated plate was measured, and the period was defined as the shortest developing period. As the result, the shortest developing period was 15 seconds. (2) Measurement of Sensitivity o Laser beam was irradiated to the photosensitive layer of the pattern forming material in the laminated body, in which the laser beam was varied as to the optical energy quantity from 0.1 mj/cm2 to 100 mj/cm2 in every increments of 21/2 times, the laser beam was irradiated from the side of the polyethylene terephthalate film by means of a pattern forming apparatus set forth later, thereby a part of the 5 photosensitive layer was hardened. After allowing to stand for 10 minutes at room temperature, the polyethylene terephthalate film as the support was peeled away from the laminated body, then an aqueous solution of sodium carbonate at 1 % by mass concentration was sprayed on the entire surface of the photosensitive layer on the copper laminated plate at 30 °C o and 0.15 MPa for the period of two times the shortest developing period obtained in (1) set forth above, thereby the un-hardened portion was removed away, and the thickness of the remaining hardened layer was measured. Then, a sensitivity curve was prepared by plotting the relation between irradiated optical quantity and the thicknesses of the hardened layers. From the resulting sensitivity curve, the optical 5 energy quantity at which the thickness of the hardened region came to 5 μm was determined, and the optical energy quantity was defined as the optical energy quantity that was necessary to harden the photosensitive layer. As the result, the optical energy quantity that was necessary to harden the photosensitive layer was 2 mj/cm2. « Pattern Forming Apparatus » A pattern forming apparatus was employed that comprised the combined laser source shown in FIGs. 27A to 32 as a laser source; DMD50 as the laser modulator, in which 1024 micromirrors are arrayed as one array in the main 5 scanning direction shown in FIGs. 4A and 4B, 768 sets of the arrays are arranged in the sub-scanning direction, and 1024 rows x 256 lines among these micromirrors can be driven; microlens array 472 in which microlenses 474, of which one surface is toric surface as shown in FIG. 13 A, are arrayed; and optical systems 480, 482 that images the laser through the microlens array onto the pattern forming material. l o The toric surface of the microlens was as follows. In order to compensate the distortion of the output surface of microlenses 474 as the imaging portions, the distortion at the output surface was measured, and the results were shown in FIG. 14. In FIG. 14, contour lines indicate the identical heights of the reflective surface, the pitch of the contour lines is 5 nm. In FIG. 14, X and Y directions are two diagonals
15 of micromirror 62, the micromirror 62 may rotate around the rotating axis extending to Y direction. In FIGs. 15A and 15B, the height displacements of micromirrors 62 are shown along the X and Y directions respectively. As shown in FIGs. 14, 15A, and 15B, there exists distortion at the reflective surface of micromirror 62. With respect to the central portion of the micromirror,
20 the distortion in one diagonal direction i.e. Y direction is larger than the other diagonal direction. Therefore, the shape of laser beam B should be distorted at the collected site through microlenses 55a of microlens array 55. In FIGs. 16A and 16B, the front shape and side shape of the entire microlens array 55 are shown in detail, and also shown the sizes of various portions in the unit
25 of millimeter (mm). As explained before referring to FIGs. 4 A and 4B, 1024 lines x 256 rows of micromirrors 62 in DMD 50 are driven; correspondingly, microlens array 55 is constructed such that 1024 of microlenses 55a are aligned in width direction to form one row and the 256 rows are arrayed in length direction. In FIG. 16A, each of the site of microlenses 55a is expressed by "j" in the width direction and "k" in the length direction. In FIGs. 17A and 17B, the front shape and the side shape of microlens 55a of microlens array 55 are shown respectively. In FIG. 17A, contour lines of microlens 55a are also shown. Each of the end surfaces of the microlenses 55a is non-spherical 5 surface in order to compensate the aberration due to the distortion of the reflective surface of micromirror 62. Specifically, microlens 55a is a toric lens; the curvature radius of optical X direction Rx is - 0.125 mm, and the curvature radius of optical Y direction Ry is - 0.1 mm. Accordingly, the collecting condition of laser beam B within the cross section o parallel to the X and Y directions are approximately as shown in FIGs. 18 A and 18B respectively. Namely, comparing the X and Y directions, the curvature radius of microlens 55a is shorter and the focal length is also shorter in Y direction. FIGs. 19A, 19B, 19C, and 19D show the simulations of beam diameter near the focal point of microlens 55a in the above noted shape. For the reference, FIGs.5 20 A, 20B, 20C, and 20D show the simulations for microlens of Rx = Ry = - 0.1 mm. The values of "z" in the figures are expressed as the evaluation sites in focus direction of microlens 55a by the distance from the laser beam irradiating surface of microlens 55a. The surface shape of microlens 55a in the simulation may be calculated by o the following equation.
C χ X 2+C 2 γ 2 Z = 1 +S Q R T ( 1 - C 2 X 2 - C 2 Y 2)
In the above formula, Cx means the curvature radius (= 1/Rx) in X direction, Cy means the curvature radius (= 1/Ry) in Y direction, X means the distance from optical axis O in X direction, and Y means the distance from optical axis O in Y5 direction. From the comparison of FIGs. 19A to 19D, and FIGs. 20A to 20D, it is apparent in the pattern forming process according to the present invention that the employment of the toric lens as the microlens 55a that has a shorter focal length in the cross section parallel to Y direction than the focal length in the cross section parallel to X direction may reduce the strain of the beam shape near the collecting site. Consequently, images can be exposed on pattern f orrning material 150 with more clearness and without strain. In addition, it is apparent that the inventive mode shown in FIGs. 19A to 19D may bring about a wider region with smaller beam diameter, i.e. longer focal depth. Further, aperture arrays 59 disposed near the collecting site of microlens array 55 is constricted such that each aperture 59a receive only the light through the corresponding microlens 55a. Namely, aperture array 59 may afford the respective apertures with the insurance that the light incidence from the adjacent apertures 59a may be prevented and the extinction ratio may be enhanced. (3) Measurement of Resolution A laminated body was prepared in the same way and condition as the (1) Method for Measuring Shortest Developing Period set forth above, and was allowed to stand in an ambient condition of 23 °C and 55 % relative humidity for 10 minutes. From above the polyethylene terephthalate film as the support of the resulting laminated body, exposure of line pattern was conducted by means of the pattern forming apparatus set forth above in a condition: line/ space = 1/1, line widths: 10 to 50 μm, increment of line: 5 μm/line. The optical amount of the exposure was adjusted to the optical energy quantity necessary to cure the photosensitive layer obtained in (2) Measurement of Sensitivity set forth above. After allowing to stand in an ambient condition for 10 minutes, the polyethylene terephthalate film as the support was peeled away from the laminated body, then an aqueous solution of sodium carbonate at 1 % by mass concenttation was sprayed on the entire surface of the photosensitive layer on the copper laminated plate at 30 °C and 0.15 MPa for the period of two times the shortest developing period obtained in (1) set forth above, thereby the un-hardened portion was removed away. The resultant copper laminated plate with hardened resin pattern was observed by means of an optical microscope; and the narrowest line width, at which abnormality of lines such as clogging, deformation, or the like does not exist, was determined, then the narrowest widths were defined as the resolution. Namely, the smaller value means the better resolution. < Exposing Rate > By means of the pattern forming apparatus set forth above, the exposing laser and relative transferring rate of the photosensitive layer were changed, thus the velocity to form usual patterns was measured. The exposing was carried out from the side of polyethylene terephthalate film onto the photosensitive layer of the pattern forming material of the laminated body. The higher exposing rate may enable to form patterns more effectively. < Etching Property > Using the laminated body with the pattern that was formed in (3) Measurement of Resolution set forth above, an etching treatment was performed such that a ferric chloride etchant (etching solution containing ferric chloride, 40° baume, solution temperature: 40 °C) was sprayed on the surface of bare copper laminated body at 0.25 MPa for 36 seconds, the bare copper layer without the hardened layer was dissolved away. Then, the pattern was removed by spraying an . aqueous solution of sodium hydroxide at 2 % by mass, thereby a printed wiring board was prepared that had a wiring pattern of copper layer as the permanent pattern. The resultant wiring pattern was observed by means of an optical microscope, and the narrowest line width of the wiring pattern was determined. The smaller the narrowest line width means the more precise wiring pattern as well as the better etching property. (Example 2) A pattern forming material was produced in the same manner as Example 1, except that the coating liquid for cushioning layer was changed into the coating liquid of which the ingredient is shown below, the thickness of the cushioning layer was changed into 17 μm, and a barrier layer was not coated. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. Further, the resultant pattern forming material was forced to peel, then the peeled sites were inspected by way of measuring the thicknesses of the peeled pattern f orming material; consequently, it is demonstrated that the peeling was caused at the interface between the cushioning layer and the photosensitive layer. The shortest developing period was 4 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/ cm2. [Ingredients of Coating Liquid for Cushioning Layer]
- Evaflex® EEA701 - 17 parts (Vicat Softening Tern. 73 °C, by DuPont-Mitsui Poly chemicals Co. Ltd.)
- Toluene — 73 parts
- Methyl ethyl ketone — 10 parts (Example 3) A pattern forming material was produced in the same manner as Example 1, except that the coating liquid for cushioning layer was changed into the coating liquid of which the ingredient is shown below. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. Further, the resultant pattern forming material was forced to peel, then the peeled sites were inspected by way of measuring the thicknesses of the peeled pattern forming material; consequently, it is demonstrated that the peeling was caused at the interface between the cushioning layer and the photosensitive layer. The shortest developing period was 6 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/cm2. [Ingredients of Coating Liquid for Cushioning Layer]
- Evaflex® EV45X - 17 parts (Vicat Softening Tern. 30 °C or less, by DuPont-Mitsui Polychemicals Co. Ltd.) - Toluene — 73 parts - Methyl ethyl ketone — 10 parts (Comparative Example 1)
5 A pattern forming material was produced in the same manner as Example 1, except that a cushioning layer and a barrier layer were not coated on the pattern forming material. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. o Further, the shortest developing period was 4 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/cm2. (Comparative Example 2) A pattern forming material was produced in the same manner as Example 1, except that a cushioning layer and a barrier layer were not coated on the pattern5 forming material and that all of the micromirrors of the DMD (1024 x768) were driven under control. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. The shortest developing period was 4 seconds, and the optical energy o quantity required to harden the photosensitive layer was 2 mj/cm2. (Comparative Example 3) A pattern forming material was produced in the same manner as Example 1, except that a cushioning layer and a barrier layer were not coated on the pattern forming material, all of the micrornirrors of the DMD (1024 x768) were driven under 5 control, and the combined laser source in the pattern forming apparatus was changed into GaN semiconductor laser LDl shown in FIG. 29. Evaluations of resolution, exposing rate, and etching property were conducted with respect to the produced pattern forming material. The results were shown in Table 3. The shortest developing period was 4 seconds, and the optical energy quantity required to harden the photosensitive layer was 2 mj/cm2 Table 3
Figure imgf000114_0001
In the evaluations of the pattern forming materials of Comparative Examples 5 1 to 3, there existed a number of broken lines in the resultant patterns since the conformability of the pattern forming material against nonuniformity on the copper laminated plate was insufficient, therefore, the resolution and the etching property could not be measured. The results of Table 3 demonstrate that the wiring patters obtained in o Examples 1 to 3 exhibit higher fineness and preciseness compared to Comparative Examples 1 to 3, owing to superior conformability of the pattern forming material against nonuniformity on the copper laminated plate. In addition, exposure rate is higher in Examples 1 to 3, thus wiring patterns may be formed more efficiently. In the pattern forming process according to the present invention, owing to 5 suppressing deformation of images formed on pattern forming materials as well as employing a pattern forming material that exhibits high conformability to nonuniformity of substrates on which permanent patters are to be formed, highly fine and precise permanent patterns may be formed with sufficient efficiency; accordingly, the present invention may be appropriately applied to produce highly o fine and precise permanent patterns, in particular highly fine and precise wiring patterns.

Claims

1. A pattern forming process comprising: modulating a laser beam irradiated from a laser source, 5 compensating the modulated laser beam, and exposing a photosensitive layer in a pattern forming material by means of the modulated and compensated laser beam, wherein the pattern forming material comprises a support, a cushioning layer, and the photosensitive layer in order, o the modulating is performed by a laser modulator which comprises plural imaging portions each capable of receiving the laser beam and outputting the modulated laser beam, and the compensating is performed by transmitting the modulated laser beam through plural microlenses each having a non-spherical surface capable of 5 compensating the aberration due to distortion of the output surface of the imaging portion, and the plural microlenses are arranged to a microlens array.
2. The pattern forming process according to claim 1, wherein the cushioning layer comprises a thermoplastic resin.
3. The pattern forming process according to claim 2, wherein the Vicat o softening temperature of the thermoplastic resin is 80 °C or less.
4. The pattern forming process according to one of claims 1 to 3, wherein the cushioning layer is at least one of swellable and soluble in an alkaline liquid. 5. The pattern forming process according to one of claims 1 to 3, wherein the cushioning layer is insoluble in an alkaline liquid.
5
6. The pattern forming process according to one of claims 1 to 5, wherein the thickness of the cushioning layer is 5 μm to 50 μm.
7. The pattern forming process according to one of claims 1 to 6, wherein a barrier layer capable of suppressing migration of substances is formed between the cushioning layer and the photosensitive layer.
8. The pattern forming process according to claim 7, wherein the barrier layer is at least one of soluble and dispersible in water.
9. The pattern forming process according to one of claims 7 and 8, wherein oxygen gas permeability of the barrier layer is 100 cm3/(m2day-atm) or less under a
5 temperature of 23 °C and a relative humidity of 60 % .
10. The pattern forming process according to one of claims 7 to 9, wherein the barrier layer comprises at least one of vinyl polymers and vinyl copolymers.
11. The pattern forming process according to one of claims 1 to 10, wherein the thickness of the photosensitive layer is 0.1 μm to 10 μm. o
12. The pattern f orrning process according to one of claims 1 to 11, wherein the pattern forming material is laminated to the substrate while the pattern forming material is being subjected to at least one of heating and pressing, then the pattern forming material is subjected to the exposing.
13. The pattern forming process according to one of claims 1 to 12, wherein 5 the non-spherical surface is a toric surface.
14. The pattern forming process according to one of claims 1 to 13, wherein the laser modulator is capable of controlling a part of the plural imaging portions depending on pattern information.
15. The pattern forming process according to one of claims 1 to 14, wherein 0 the laser modulator is a spatial light modulator.
16. The pattern forming process according to claim 15, wherein the spatial light modulator is a digital micromirror device (DMD).
17. The pattern forming process according to one of claims 1 to 16, wherein the exposing is performed by a laser beam transmitted through an aperture array. 5
18. The pattern forming process according to one of claims 1 to 17, wherein the exposing is performed while moving relatively the laser beam and the photosensitive layer.
19. The pattern forming process according to one of claims 1 to 18, wherein developing the photosensitive layer is performed following the exposing.
20. The pattern forming process according to claim 19, wherein forming a permanent pattern is performed following the developing.
21. The pattern forming process according to claim 20, wherein the permanent pattern is a wiring pattern, and the permanent pattern is formed by
5 means of at least one of etching tteatment and plating tteatment.
22. The pattern forming process according to one of claims 1 to 21, wherein the laser source is capable of irradiating two or more types of laser beams which are combined with.
23. The pattern forming process according to one of claims 1 to 22, wherein o the laser source comprises plural lasers, a multimode optical fiber, and a collective optical system which collects the laser beams from the plural lasers into the multimode optical fiber.
24. The pattern forming process according to one of claims 1 to 23, wherein the photosensitive layer comprises a binder, a polymerizable compound, and a5 photopolymerization initiator.
25. The pattern forming process according to claim 24, wherein the binder contains an acidic group.
26. The pattern forming process according to one of claims 24 and 25, wherein the binder contains a vinyl copolymer. o
27. The pattern forming process according to one of claims 24 to 26, wherein acid value of the binder is 70 mgKOH/g to 250 mgKOH/g.
28. The pattern forming process according to one of claims 24 to 27, wherein the polymerizable compound comprises a monomer which contains at least one of urethane group and aryl group. 5
29. The pattern forming process according to one of claims 24 to 28, wherein the photopolymerization initiator comprises a compound selected from the group consisting of halogenated hydrocarbon derivatives, hexaaryl-biimidazols, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes.
30. The pattern forming process according to one of claims 1 to 29, wherein the photosensitive layer comprises 10 % by mass to 90 % by mass of binder, 5 % by mass to 60 % by mass of polymerizable compound, and 0.1 % by mass to 30 % by mass of photopolymerization initiator. 5 31. The pattern forming process according to one of claims 1 to 30, wherein the support comprises a synthetic resin and is transparent. 32. The pattern forming process according to one of claims 1 to 31, wherein the support is of an elongated shape. 33. The pattern forming process according to one of claims 1 to 32, wherein l o the pattern forming material is of an elongated shape formed by winding into a roll shape. 34. The pattern forming process according to one of claims 1 to 33, wherein a protective film is formed on the photosensitive layer of the pattern forming material.
15
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