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WO2006075633A1 - Materiau pour formation de motif, appareil de formation de motif et procede de formation de motif indelebile - Google Patents

Materiau pour formation de motif, appareil de formation de motif et procede de formation de motif indelebile Download PDF

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Publication number
WO2006075633A1
WO2006075633A1 PCT/JP2006/300233 JP2006300233W WO2006075633A1 WO 2006075633 A1 WO2006075633 A1 WO 2006075633A1 JP 2006300233 W JP2006300233 W JP 2006300233W WO 2006075633 A1 WO2006075633 A1 WO 2006075633A1
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WO
WIPO (PCT)
Prior art keywords
pattern forming
light
photosensitive layer
forming material
exposure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/300233
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English (en)
Japanese (ja)
Inventor
Masanobu Takashima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Fujifilm Corp
Original Assignee
Fujifilm Corp
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 Fujifilm Corp, Fuji Photo Film Co Ltd filed Critical Fujifilm Corp
Priority to JP2006552948A priority Critical patent/JPWO2006075633A1/ja
Publication of WO2006075633A1 publication Critical patent/WO2006075633A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0082—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the exposure method of radiation-sensitive masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a pattern forming material suitable for forming a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist, a pattern forming apparatus provided with the pattern forming material, and a permanent using the pattern forming material
  • the present invention relates to a pattern forming method.
  • a pattern forming material is used in which a photosensitive resin composition is applied on a support and dried to form a photosensitive layer.
  • a laminate is formed by laminating the pattern forming material on a substrate such as a copper-clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed. After the exposure, the photosensitive layer is imaged to form a pattern, followed by an etching process or the like to form a permanent pattern.
  • a pattern forming material for photoresist using a highly transparent substance having a haze value of 5.0% or less such as polyethylene terephthalate (PET) as the support is known.
  • PET polyethylene terephthalate
  • the binder can be copolymerized with (meth) acrylic acid and (meth) acrylic acid alkyl ester, for the purpose of mainly improving sensitivity, resolution, adhesion and the like.
  • a pattern forming material containing a copolymer obtained by copolymerizing a vinyl monomer see Patent Document 1.
  • the photosensitive layer contains a carboxyl group-containing polymer, an ethylenically unsaturated compound, a mouth fin dimer, a photopolymerization initiator, and a mouth dye (Patent Document). 2).
  • a pattern forming material includes a carboxyl group-containing binder, a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and a photopolymerization initiator (patent).
  • the photosensitive layer is transparent to ultraviolet rays with a wavelength of 365 nm.
  • a pattern forming material having a rate of 5 to 75% has been proposed (see Patent Document 4).
  • the thickness is 10 ⁇ m or more and 25 ⁇ m or less, and the polycondensation metal catalyst A support having a residue of less than 150 ppm and an antimony metal content of 15 mmol% or less based on the total acid component has been proposed (see Patent Document 5).
  • Patent Document 6 discloses a solder resist film having a total thickness of 90 ⁇ m, comprising a support thickness of 40 ⁇ m, a photosensitive layer thickness of 30 ⁇ m, and a protective film thickness of 20 ⁇ m.
  • Patent Document 7 discloses a solder resist film having a total thickness of 86 ⁇ m comprising a support having a thickness of 25 m, a photosensitive layer having a thickness of 50 m, and a protective film having a thickness of 11 m.
  • the conventional techniques relating to these solder resists have low exposure sensitivity as large as 500 to 3000 mjZcm 2 .
  • Patent Document 1 Japanese Patent No. 3452597
  • Patent Document 2 Japanese Patent No. 3100040
  • Patent Document 3 International Publication No. 00Z79344 Pamphlet
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-13681
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2002-60598
  • Patent Document 6 International Publication No.OOZ73510 Pamphlet
  • Patent Document 7 JP-A-11-240109
  • the present invention uses a highly transparent material as a support for the purpose of forming a permanent pattern such as a solder resist, and by defining the total thickness of the support, the photosensitive layer, and the protective film, High sensitivity, good resist surface shape, curl prevention
  • An object of the present invention is to provide a pattern forming material capable of forming a higher-definition pattern, a pattern forming apparatus including the pattern forming material, and a permanent pattern forming method using the pattern forming material. To do.
  • the total thickness of the photosensitive member, the photosensitive layer, and the protective film is 30 to 200 / zm, and when the photosensitive layer is exposed and developed, the thickness of the exposed portion of the photosensitive layer is determined after the exposure and development.
  • the pattern forming material is characterized in that the minimum energy of light used for the exposure is 0.1 to 200 mj / cm 2 without being changed.
  • a highly transparent substance is used as a support, and the total thickness of the support, the photosensitive layer, and the protective film is defined, thereby obtaining a high sensitivity.
  • the resist surface shape is good, curling can be prevented, and a higher definition pattern can be formed.
  • G (; zm) satisfies the following formula: G ⁇ G and G ⁇ G
  • the pattern forming material according to ⁇ 1> In the pattern forming material according to ⁇ 2>!
  • a solid core is formed in the middle of the pattern forming material, so that curling can be prevented.
  • the photosensitive layer thickness (G) is 1 m or more thicker than the support thickness (G).
  • the thickness (G) of the layer is 1 m or more thicker than the thickness (G) of the protective film.
  • ⁇ 4> The pattern forming material according to any one of ⁇ 1> to ⁇ 3>, wherein the support has a haze value of 5.0% or less.
  • ⁇ 5> The pattern forming material according to any one of ⁇ 1> to ⁇ 4>, wherein the support has a total light transmittance of 86% or more.
  • ⁇ 6> The pattern forming material according to any one of ⁇ 1> to ⁇ 5>, wherein the haze value of the support and the total light transmittance of the support are 405 nm. is there.
  • ⁇ 8> The deviation from ⁇ 1> to ⁇ 7>, wherein the binder is at least one selected from an epoxy acrylate relay compound and an acrylic resin having at least one group polymerizable with an acidic group.
  • the pattern forming material according to any one of the above.
  • the binder is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of the maleic anhydride copolymer.
  • ⁇ 8> V a pattern forming material according to any of the above.
  • the binder is (a) maleic anhydride, (b) an aromatic bull monomer, and (c) a vinyl monomer, and the glass transition temperature (Tg ) which is obtained by reacting a vinyl monomer having a force of less than 3 ⁇ 4o ° c with 0.1 to 1.0 equivalent of a primary amine compound with respect to the anhydride group of the powerful copolymer.
  • Tg glass transition temperature
  • Thermal crosslinker is an epoxy compound, oxetane compound, polyisocyanate compound, compound obtained by reacting polyisocyanate compound with blocking agent, and melamine derivative power
  • ⁇ 12> The pattern forming material according to any one of the above ⁇ 1> strong ⁇ 1>, wherein the melamine derivative is an alkylated methylol melamine.
  • the photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexaryl biimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, or acyl phosphine oxidoxide compound.
  • the pattern forming material according to any one of ⁇ 1> to ⁇ 12>, which contains at least one selected from aromatic onium salts and ketoxime ethers.
  • the photosensitive layer modulates the light from the light irradiating means by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means, the light is emitted from the light emitting means.
  • Microphone with an aspherical microlens that can correct aberrations due to surface distortion
  • the light irradiation unit irradiates light toward the light modulation unit.
  • the n picture elements in the light modulating means receive and emit light from the light irradiating means, thereby modulating the light received from the light irradiating means.
  • the light modulated by the light modulation means passes through the aspheric surface in the microlens array, so that the aberration due to the distortion of the exit surface in the pixel portion is corrected, and the distortion of the image formed on the photosensitive layer. Is suppressed.
  • the exposure to the photosensitive layer is performed with high definition. Thereafter, when the photosensitive layer is developed, a high-definition permanent pattern is formed.
  • ⁇ 15> The pattern forming material according to any one of ⁇ 1> to ⁇ 14>, wherein the support contains a synthetic resin and is transparent.
  • ⁇ 17> The pattern forming material according to any one of ⁇ 1> to ⁇ 16>, which is long and wound in a roll shape.
  • ⁇ 18> The pattern forming material according to any one of ⁇ 1> to 17>, wherein the photosensitive layer has a thickness of 3 to 100 m.
  • a pattern forming apparatus comprising at least light modulation means for exposing a photosensitive layer in a material.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the pattern forming apparatus according to ⁇ 19>, wherein the pattern is modulated according to a signal.
  • the light modulation unit includes the pattern signal generation unit, the light irradiated from the light irradiation unit Modulation is performed according to the control signal generated by the signal generating means.
  • the light modulation means has n pixel parts, and forms any less than n of the pixel parts continuously arranged from the n pixel parts.
  • the pattern forming apparatus according to any one of the above 19> Karaku 20>, which is controllable according to pattern information.
  • n light modulation means in the light modulation means Light of the light irradiation means force is modulated at high speed by controlling any less than n pixel parts arranged continuously from the pixel parts according to the pattern information.
  • ⁇ 24> The pattern forming apparatus according to any one of ⁇ 21>, ⁇ 23>, wherein the picture element portion is a micromirror.
  • the pattern forming apparatus since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is developed thereafter, an extremely fine pattern is formed.
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated with the plurality of laser forces, respectively, and couples them to the multimode optical fiber.
  • the pattern forming apparatus according to any one of the above items 19> Karaku 25>.
  • the light irradiation unit can collect the laser light respectively emitted from the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber.
  • exposure is performed with exposure light having a deep focal depth.
  • the pattern forming material is exposed with extremely high precision. It is. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • a method for forming a permanent pattern comprising at least exposing the photosensitive layer in the pattern forming material according to any one of ⁇ 1> to 18 above.
  • ⁇ 28> The permanent film according to ⁇ 27>, wherein the pattern forming material according to any one of ⁇ 1> and ⁇ 18> is laminated on the substrate while being heated and pressurized and exposed. This is a pattern forming method.
  • ⁇ 29> The method for forming a permanent pattern according to any one of ⁇ 27> to ⁇ 28>, wherein the base material is a printed circuit board on which wiring is formed.
  • ⁇ 30> The method for forming a permanent pattern according to any one of ⁇ 27>, ⁇ 29>, wherein the exposure is performed imagewise based on pattern information to be formed.
  • the control signal is generated based on the pattern information to be formed, and the control signal is generated using light modulated in accordance with the control signal. This is a permanent pattern forming method.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the light modulation means includes n pixel portions, and forms any less than n of the pixel portions continuously arranged from the n pixel portions.
  • the permanent pattern forming method according to any one of ⁇ 32> to ⁇ 33>, which can be controlled according to pattern information.
  • pattern information is obtained by adding any less than n pixel parts arranged continuously from n pixel parts in the light modulation means. By controlling according to the light, the light from the light irradiation means is modulated at high speed.
  • ⁇ 36> The permanent pattern forming method according to 35, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • the light modulation means modulates the light, and then passes through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface of the picture element portion in the light modulation means are arranged. 38.
  • the aspherical surface is a toric surface
  • the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected, and an image is formed on the photosensitive layer.
  • Image distortion is efficiently suppressed.
  • the photosensitive layer is exposed with high definition. Thereafter, the photosensitive layer is developed to form a high-definition permanent pattern.
  • the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high precision. Thereafter, the photosensitive layer is developed to form an extremely fine permanent pattern.
  • ⁇ 41> The method for forming a permanent pattern according to any one of ⁇ 27>, ⁇ 40>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
  • exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
  • ⁇ 42> The method for forming a permanent pattern according to any one of ⁇ 27> to ⁇ 41>, wherein the exposure is performed on a partial region of the photosensitive layer.
  • the light irradiation means can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated with the plurality of laser forces and couples them to the multimode optical fiber.
  • the permanent pattern forming method according to any one of ⁇ 33> to ⁇ 43>.
  • the laser light emitted from each of the plurality of lasers is condensed by the collective optical system by the light irradiation unit, and can be coupled to the multimode optical fiber. By doing so, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Then, by developing the photosensitive layer, a very high-definition permanent pattern is formed.
  • ⁇ 45> The method for forming a permanent pattern according to any one of ⁇ 44>, wherein the exposure is performed using a laser beam having a wavelength of 340 to 415 nm.
  • ⁇ 46> The method for forming a permanent pattern according to any one of ⁇ 27> to ⁇ 45>, wherein the photosensitive layer is developed after the exposure.
  • ⁇ 47> The method for forming a permanent pattern according to any one of ⁇ 27> to ⁇ 46>, wherein the photosensitive layer is subjected to a curing treatment after development.
  • ⁇ 48> Whole surface heat treatment where the curing process is performed at 120 to 200 ° C. 47.
  • the method for forming a permanent pattern according to the above item 47> which is at least one of the following.
  • curing of the resin in the pattern forming material is promoted in the entire surface exposure process. Further, the film strength of the cured film is increased in the entire surface heat treatment performed under the temperature condition.
  • the wiring has an external force due to the insulating property, heat resistance, etc. of the film. Your shock and bends are protected.
  • ⁇ 50> A permanent pattern formed by the method for forming a permanent pattern described in ⁇ 27> to ⁇ 49>.
  • the permanent pattern according to ⁇ 50> is formed by the permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance and the like, and has high definition, and multi-layer wiring of semiconductors and parts This is useful for high-density mounting on boards and build-up wiring boards.
  • the permanent pattern according to ⁇ 50> which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
  • the permanent pattern described in 51> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern
  • the wiring may be subjected to an external force shock or bending due to the insulating property, heat resistance, etc. of the film. Power is protected.
  • FIG. 1 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD).
  • DMD digital micromirror device
  • FIG. 2A is an example of an explanatory diagram for explaining the operation of the DMD.
  • FIG. 2B is an example of an explanatory diagram for explaining the operation of the DMD.
  • FIG. 3A is an example of a plan view showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined.
  • Fig. 3B shows the exposure beam when the DMD is not tilted and when the DMD is tilted. It is an example of the top view which compared and showed the arrangement
  • FIG. 4A is an example of a diagram illustrating an example of a DMD usage area.
  • FIG. 4B is an example of a diagram illustrating an example of a DMD usage area.
  • FIG. 5 is an example of a plan view for explaining an exposure method for exposing a photosensitive layer by one scanning by a scanner.
  • FIG. 6A is an example of a plan view for explaining an exposure method for exposing a photosensitive layer by a plurality of scans by a scanner.
  • FIG. 6B is an example of a plan view for explaining an exposure method for exposing a photosensitive layer by a plurality of scans by a scanner.
  • FIG. 7 is an example of a schematic perspective view showing an appearance of an example of a pattern forming apparatus.
  • FIG. 8 is an example of a schematic perspective view showing the configuration of the scanner of the pattern forming apparatus.
  • FIG. 9A is an example of a plan view showing an exposed region formed in the photosensitive layer.
  • FIG. 9B is an example of a diagram showing an arrangement of exposure areas by each exposure head.
  • FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means.
  • FIG. 11 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG.
  • FIG. 12 shows an example of a controller that controls DMD based on pattern information.
  • FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system.
  • FIG. 13B is an example of a plan view showing an optical image projected onto the exposure surface when a microlens array or the like is not used.
  • FIG. 13C is an example of a plan view showing an optical image projected onto an exposed surface when a microlens array or the like is used.
  • FIG. 14 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines.
  • FIG. 15A shows the distortion of the reflection surface of the micromirror in two diagonal directions of the mirror. This is an example of the graph shown.
  • FIG. 15B is an example of a graph showing distortion of the reflecting surface of the micromirror similar to that in FIG. 15A in two diagonal directions of the mirror.
  • FIG. 16A is an example of a front view of a microlens array used in the pattern forming apparatus.
  • FIG. 16B is an example of a side view of the microlens array used in the pattern forming apparatus.
  • FIG. 17A is an example of a front view of a microlens constituting a microlens array.
  • FIG. 17B is an example of a side view of a microlens constituting the microlens array.
  • FIG. 18A is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
  • FIG. 18B is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
  • FIG. 19A is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention.
  • FIG. 19B is an example of a diagram showing the same simulation results as in FIG. 19A but at different positions.
  • FIG. 19C is an example of a diagram showing a simulation result similar to FIG. 19A at another position.
  • FIG. 19D is an example of a diagram showing a simulation result similar to FIG. 19A at another position.
  • FIG. 20A is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method.
  • FIG. 20B is an example of a diagram showing the same simulation results as in FIG. 20A but at different positions.
  • Fig. 20C shows the same simulation results as Fig. 20A, but at different positions. It is an example of a figure.
  • FIG. 20D is an example of a diagram showing a simulation result similar to FIG. 20A at another position.
  • FIG. 21 is an example of a plan view showing another configuration of the combined laser light source.
  • FIG. 22A is an example of a front view of a microlens constituting a microlens array.
  • FIG. 22B is an example of a side view of a microlens constituting a microlens array.
  • FIG. 23A is an example of a schematic view showing a condensing state by the microlens of FIG. 22A and FIG. 22B in one cross section.
  • FIG. 23B is an example of a schematic diagram showing another cross section of the example of FIG. 23A.
  • FIG. 24A is an example of an explanatory diagram of the concept of correction by the light quantity distribution correcting optical system.
  • FIG. 24B is an example of an explanatory diagram of the concept of correction by the light quantity distribution correcting optical system.
  • FIG. 24C is an example of an explanatory diagram of the concept of correction by the light quantity distribution correction optical system.
  • FIG. 25 is an example of a graph showing the light amount distribution when the light irradiation means is a Gaussian distribution and the light amount distribution is not corrected.
  • FIG. 26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system.
  • FIG. 27A is a perspective view showing the configuration of the fiber array light source
  • FIG. 27A (B) is an example of a partially enlarged view of FIG. 27A (C)
  • FIG. (D) is an example of a plan view showing an array of light emitting points in the laser emitting section.
  • FIG. 27B is an example of a front view showing an array of light emitting points in a laser emitting section of a fiber array light source.
  • FIG. 28 is an example of a diagram showing a configuration of a multimode optical fiber.
  • FIG. 29 is an example of a plan view showing a configuration of a combined laser light source.
  • FIG. 30 is an example of a plan view showing a configuration of a laser module.
  • FIG. 31 is an example of a side view showing the configuration of the laser module shown in FIG. 30.
  • FIG. 32 is a partial side view showing the configuration of the laser module shown in FIG. 30.
  • FIG. 33 is an example of a perspective view showing a configuration of a laser array.
  • FIG. 34A is an example of a perspective view showing a configuration of a multi-cavity laser.
  • FIG. 34B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 34A are arranged in an array.
  • FIG. 35 is an example of a plan view showing another configuration of the combined laser light source.
  • FIG. 36A is an example of a plan view showing another configuration of the combined laser light source.
  • FIG. 36B is an example of a cross-sectional view along the optical axis of FIG. 36A.
  • FIG. 37A shows the depth of focus in the conventional exposure apparatus and the pattern forming method of the present invention.
  • FIG. 3 is an example of a cross-sectional view along an optical axis showing a difference from a depth of focus by a (pattern forming device).
  • FIG. 37B is an example of a cross-sectional view along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention.
  • the pattern forming material of the present invention comprises at least a support and a photosensitive layer and a protective film on the support, and further comprises other layers as necessary.
  • the protective film is preferably provided on the photosensitive layer.
  • the pattern forming material is used in a pattern forming method to be described later, and the pattern forming method is performed by laminating a photosensitive layer of the pattern forming material on a substrate.
  • the total thickness of the support, the photosensitive layer, and the protective finem is 30 to 200 ⁇ m, preferably 30 to 150 ⁇ m force S, and 50 to L00 ⁇ m.
  • m Force S is preferable. If the total thickness is less than 30 m, laminating properties such as wrinkles during auto-cut lamination and meandering when winding the protective film are poor. In addition, the photosensitive layer may become thin and the function as an insulating film may not be sufficiently achieved. On the other hand, if the total thickness exceeds 200 m, the drawing force of the pattern forming material during auto-cut laminating will be poor, and if it is laminated on a thin copper clad laminate, curling will occur on the laminate substrate. May end up.
  • the detailed structure including the thickness of the support, the photosensitive layer, and the protective film will be described later.
  • the thickness G (m) of the support the thickness G (m) of the photosensitive layer, the protective film
  • Thickness Gm satisfies at least one of the following formulas: G ⁇ G and G ⁇ G
  • G ⁇ G and G ⁇ G are satisfied at the same time.
  • the thickness G of the photosensitive layer is preferably 1 m or more thicker than the thickness G of the support.
  • a thickness of 3 m or more is more preferable.
  • a thickness of 5 m or more is particularly preferable.
  • the thickness G of the photosensitive layer is preferably 1 m or more thicker than the thickness G of the protective film.
  • a thickness of 3 m or more is more preferable.
  • a thickness of 5 m or more is particularly preferable.
  • a tenacious core is formed in the middle of the pattern forming material, so that curling can be effectively prevented.
  • the thicknesses of the support, the photosensitive layer, and the protective film can be measured by, for example, an optical microscope, a laser microscope, a contact digital displacement meter, or the like.
  • the pattern forming material of the present invention does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development when the photosensitive layer is exposed and developed while satisfying the above thickness condition.
  • the minimum energy of light used for the exposure is 0.1 to 200 mjZcm 2 .
  • the thickness of the exposed portion of the photosensitive layer is not changed before and after the exposure and development.
  • it can be selected as appropriate according to the purpose for which there is no particular restriction. For example, 0.5 ⁇ : L00mj / cm 2 is preferred l ⁇ 50 mj / cm 2 is more preferred, 1 5-30 mj / cm 2 is particularly preferred.
  • capri may occur in the processing step. If it exceeds 200 mjZcm 2 , the time required for exposure becomes longer and the processing speed is increased. May slow down.
  • the "minimum energy of light used in the exposure without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development" means so-called development sensitivity, for example, It is obtained from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for exposure when the photosensitive layer is exposed and the thickness of the cured layer generated by the development processing following the exposure. be able to.
  • the thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure.
  • the development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
  • the thickness of the cured layer is not changed by exposure and development.
  • the method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and can be appropriately selected depending on the purpose.
  • a film thickness measuring device for example, a surface roughness measuring device (for example, , Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.
  • the support can be appropriately selected according to the purpose without any particular limitation, but a synthetic resin film that can peel off the photosensitive layer and has good light transmittance is preferred. A synthetic resin film having good properties is more preferable. From the viewpoint of transparency, the haze value of the support is preferably 5.0% or less.
  • the haze value of the support is required to be 5.0% or less with respect to light of 405 nm, and preferably 3.0% or less, more preferably 1.0% or less. Preferred. When the haze value exceeds 5.0%, the amount of light scattering in the photosensitive layer increases, and the resolution when obtaining fine pitch may be lowered.
  • the total light transmittance of the support with respect to 405 nm light is preferably 86% or more, more preferably 87% or more.
  • the method for measuring the haze value and the total light transmittance can be appropriately selected according to the purpose for which there is no particular limitation, and examples thereof include the methods described below.
  • the total light transmittance is measured.
  • the method for measuring the total light transmittance is not particularly limited and can be appropriately selected according to the purpose.
  • an integrating sphere and a spectrophotometer capable of irradiating light of 405 ⁇ m for example, Shimadzu Corporation
  • UV-2400 for example, Shimadzu Corporation
  • the parallel light transmittance is measured in the same manner as the measurement method of the total light transmittance except that the integrating sphere is not used.
  • the diffuse light transmittance obtained from the total light transmittance—the parallel light transmittance is calculated, and (4) the following calculation formula, the diffuse light transmittance Z, the total light:
  • the haze value can also be obtained for the line transmittance X 100 and force.
  • the thickness of the measurement sample for obtaining the total light transmittance and the haze value is 1 ⁇ m &).
  • the support may be coated with inert fine particles on at least one surface.
  • the inactive fine particles are preferably applied on the surface opposite to the surface on which the photosensitive layer is formed.
  • Examples of the inert fine particles include crosslinked polymer particles, inorganic particles (for example, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite). , Molybdenum sulfate, etc.), organic particles (eg, hexamethylenebisbehenamide, hexamethylenebisstearylamide, N, N'-distearyl terephthalamide, silicone, calcium oxalate, etc.), produced during polyester polymerization Among these, silica, calcium carbonate, and hexamethylenebisbehenamide are preferred.
  • inorganic particles for example, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite.
  • Molybdenum sulfate, etc. organic particles
  • the precipitated particles are, for example, those precipitated in a reaction system by polymerizing a system using an alkali metal or alkaline earth metal compound as a transesterification catalyst according to a conventional method. It may be the one precipitated by adding terephthalic acid during the polycondensation reaction.
  • phosphoric acid trimethyl phosphate, triethyl phosphate, tributyl phosphate, acidic ethyl phosphate, phosphorous acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, etc.
  • One or more of the phosphorus compounds May be present.
  • the average particle size of the inert fine particles is preferably 0.01-2. 0 ⁇ m, more preferably 0.02-1.
  • Force S, 0.03-: L 0 m force S more preferably. 0.04 to 0.5 111 is particularly preferred.
  • the pattern forming material may have poor transportability.
  • the inert fine particles are contained in a large amount. By doing so, the haze value of the support may increase. Further, when the average particle diameter of the inert fine particles exceeds 2.0 m, the resolution force S may be reduced due to scattering of exposure light.
  • the method for applying the inert fine particles is not particularly limited, and can be appropriately selected according to the purpose.
  • a method of applying a coating solution containing the inert fine particles by a known method after the production of the synthetic resin film as the support is mentioned.
  • the synthetic resin containing the inert fine particles may be melted and discharged from a die cutter to be molded on a synthetic resin film to be the support. Further, it may be formed by the method described in JP-A-2000-221688.
  • the thickness of the coating layer containing the inert fine particles in the support is from 0.02 to 3.
  • the synthetic resin film used as the support is preferably a transparent film, for example, a biaxially stretched polyester film, which is preferably a polyester resin film.
  • polyester resin examples include polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylate copolymer, poly (meth) acrylate alkyl ester, polyethylene 2,6 naphthalate, polytetramethylene terephthalate, poly Examples include tetramethylene 1, 2, 6 naphthalate. These may be used alone or in combination of two or more.
  • Examples of the resin other than the polyester resin include polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polychlorinated bur, polybulal alcohol, poly Carbonate, polystyrene, cellophane, polysalt-vinylidene copolymer, polyamide, polyimide, butyl chloride butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulosic resin, nylon resin, etc. Is mentioned. These may be used alone or in combination of two or more.
  • the synthetic resin film may be composed of one layer, or may be composed of two or more layers. In the case of comprising two or more layers, it is preferred that the inert fine particles are contained in a layer located farthest from the photosensitive layer.
  • the synthetic resin film is preferably a biaxially stretched polyester film from the viewpoint of mechanical strength characteristics and optical characteristics.
  • the biaxial orientation method of the biaxially stretched polyester film can be appropriately selected depending on the purpose without any particular limitation.
  • the polyester resin is melt-extruded into a sheet shape, rapidly cooled to form an unstretched film, and when the unstretched film is biaxially stretched, the stretching temperature is 85 to 145 ° C., stretching in the machine and transverse directions. It can be prepared by setting the magnification to 2.6 to 4.0 times and heat-fixing the film after biaxial stretching as necessary at 150 to 210 ° C.
  • the biaxial stretching is a sequential biaxial stretching method in which an unstretched film is stretched in the longitudinal direction or the transverse direction to form a uniaxially stretched film, and then the -axially stretched film is stretched in the transverse direction or the longitudinal direction.
  • a simultaneous biaxial stretching method may be used in which the unstretched film is stretched simultaneously in the machine direction and the transverse direction.
  • the biaxially stretched film can be further stretched in at least one of the longitudinal direction and the transverse direction as necessary.
  • the thickness of the support is not particularly limited, and can be appropriately selected according to the purpose.
  • F column; t is 2-150 ⁇ m force S girlish, 5-: LOO ⁇ m force SJ-like girls, 8-50 ⁇ m force S Particularly preferred. If the thickness is less than 2 m, uneven coating at the time of coating the photosensitive layer may easily occur, and if it exceeds 150 / z m, the auto-peeler suitability of the support may be poor.
  • the shape of the support is not particularly limited and can be appropriately selected according to the purpose, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include a length of 10 m to 20000 m.
  • the photosensitive layer contains a solder, a polymerizable compound, a photopolymerization initiator, and a thermal cross-linking agent, and may contain a sensitizer and other components appropriately selected as necessary.
  • the noinder is more preferably soluble in an alkaline aqueous solution, which is preferably swellable in an alkaline aqueous solution. It is also preferable that the binder contains a polymerizable group.
  • binder exhibiting swellability or solubility with respect to the alkaline aqueous solution for example, those having an acidic group are preferably exemplified.
  • the noinder is not particularly limited and can be appropriately selected according to the purpose.
  • JP-A-51-131706, JP-A-52-94388, JP-A-64H5 examples thereof include epoxy atalate toy compounds having acidic groups described in Kaihei 2-97513, JP-A-3-289656, JP-A-61-243869, JP-A-2002-296776, and the like.
  • phenol novolak type epoxy acrylate, tarezol novolak epoxy acrylate, bisphenol A type epoxy acrylate, etc. for example, epoxy resin is mixed with polyfunctional epoxy compound (meth) acrylic acid.
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, and succinic anhydride are added.
  • the molecular weight of the epoxy vacancy compound is preferably 1,000 to 200,000 force S, more preferably 2,000 to 100,000.
  • the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and the film quality becomes brittle or the surface hardness deteriorates after curing of the photosensitive layer described later. Yes, if it exceeds 200,000, developability may deteriorate.
  • Acrylic resin having at least one polymerizable group such as an acidic group and a double bond described in JP-A-6-295060 can also be used.
  • at least one polymerizable double bond in the molecule for example, an acrylic group such as a (meth) acrylate group or a (meth) acrylamido group, a carboxylic acid bull ester, a bull ether, a valyl group.
  • Various polymerizable double bonds such as tellurium can be used.
  • an acidic group In addition, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexenoxide and (meth) attalyloyl groups are included in the acrylic resin containing carboxyl groups. Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound. In addition, an acrylic resin containing an acid group and a hydroxyl group is added to an isocyanate group-containing polymerizable compound such as isocyanatoethyl (meth) acrylate, and an acrylic resin containing an anhydride group.
  • reaction product of hydroxyalkyl attalylate or hydroxyalkyl metatalylate described in JP-A-50-59315 with any one of polycarboxylic acid anhydride and epihalohydrin can be used.
  • the polyimide precursors described in JP-A-2-097502 and JP-A-11-282155 can be used. These may be used alone or as a mixture of two or more.
  • a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer can also be used.
  • the copolymer is a maleamic acid system comprising at least a maleamic acid unit B having a maleic acid-formamide structure represented by the following structural formula (1) and a unit A not having the maleic acid-sulfamide structure.
  • it is a copolymer.
  • the unit A may be one type or two or more types.
  • the maleamic acid-based copolymer means a binary copolymer
  • the unit A includes an aryl group which may have a substituent and a butyl monomer which will be described later, and the glass transition temperature (Tg) of the butyl monomer homopolymer is less than 80 ° C.
  • Tg glass transition temperature
  • a combination with a certain vinyl monomer (c) is preferred.
  • R 3 and R 4 represent either a hydrogen atom or a lower alkyl group.
  • X and y represent mole fractions of the repeating units, for example, when the unit A is one, X is 85-50 mol 0/0, y is 15 to 50 mole 0/0.
  • R lu to R ia represent any one of a hydrogen atom (1H), an optionally substituted alkyl group, an aryl group, and an aralkyl group.
  • the alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
  • R to R examples include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butinole, sec butyl, t-butinole, pentinole, arinole, n-hexyl, cyclohexyl, 2- Examples include ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, and black-mouthed phenyl.
  • R 1 examples include benzene derivatives such as, for example, a file, a-methyl file, 2-methyl file, 3 methyl file, 4 methyl file, 2,4 dimethyl file, etc .;
  • n Propyloxycarbol, n-butyloxycarbol, pentylo Examples include xyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-xyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl, and the like.
  • R 2 examples include a substituent! /, But may include an alkyl group, an aryl group, an aralkyl group, and the like. These may have a cyclic structure or a branched structure. Specific examples of R 2 include, for example, benzyl, phenethyl, 3-phenol 1-propyl, 4-phenol 1-butinole, 5 phenol-1-pentinole, 6-phenol 1- Hexinole, a Methylbenzyl, 2 Methylbenzyl, 3 Methylbenzyl, 4 Methylbenzyl, 2 Mono (P-Tolyl) ethyl, j8-Methylphenethyl, 1-Methyl-3 Phenylpropyl, 2 —Black Benzynole, 3 Black Ninore, 4-Black Benzore, 2-Fluoro-Benenore, 3-—Fluoro-Benore, 4-Fluoro-Benz
  • the binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, which is a homopolymer of the bull monomer.
  • a copolymer obtained by reacting a primary amine compound with a vinyl monomer having a glass transition temperature (Tg) of less than 80 ° C and an anhydride group of a powerful copolymer is a copolymer. preferable.
  • a copolymer comprising the component (a) and the component (b) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties.
  • the laminating property can be ensured, but the surface hardness is ensured. May be difficult to maintain.
  • the aromatic vinyl monomer is not particularly limited and can be appropriately selected according to the purpose.
  • the surface hardness of the photosensitive layer formed using the pattern forming material of the present invention can be increased.
  • a compound having a glass transition temperature (Tg) of the homopolymer of 80 ° C or higher is preferred, and a compound having a temperature of 100 ° C or higher is more preferable.
  • Preferable examples include styrene derivatives such as C). These may be used alone or in combination of two or more.
  • the vinyl monomer needs to have a glass transition temperature (Tg) of a homopolymer of the vinyl monomer of less than 80 ° C, preferably 40 ° C or less, more preferably 0 ° C or less. .
  • Tg glass transition temperature
  • Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenol-1-propylamine, 4-phenol-l-butylamine, 5-ferro-l-pentylamine, and 6-phenylamine. Hexylamine, ⁇ -methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2 ( ⁇ -tolyl) ethylamine, ⁇ -methylphenethylamine, 1-methyl-3 phenol -Rupropylamine, 2 Chlorobenzylamine, 3 Chlorobenzylamine, 4 Chlorobenzylamine, 2 —Fluorobenzylamine, 3-Fluorobenzylamine, 4-Fluorobenzylamine, 4-Bromophenethylamine, 2 -— (2-Black) Ethylamine, 2-— (3 Black-hole) ) Ethylamine, 2— (4 Phlorophenyl) Ethylamine,
  • the primary amine compounds may be used alone or in combination of two or more.
  • the reaction amount of the primary amin compound is required to be 0.1 to 1.2 equivalents, preferably 0.1 to 1.0 equivalents, relative to the anhydride group. When the reaction amount exceeds 1.2 equivalents, the solubility may be remarkably deteriorated when one or more primary amine compounds are reacted.
  • the content of (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol%. If the content is less than 15 mol%, alkali developability cannot be imparted, and if it exceeds 50 mol%, alkali resistance deteriorates, and the copolymer becomes difficult to synthesize. Permanent pattern formation may not be possible.
  • the content of the (b) aromatic bule monomer and (c) the bulle monomer having a glass transition temperature (Tg) of the homopolymer of less than 80 ° C in the binder is respectively 20-60 mol% and 15-40 mol% are preferred. When the content satisfies the numerical range, both surface hardness and laminating properties Can stand up.
  • the molecular weight of the binder such as 3,000-500,000 force S, is more preferable than 5,000-100,000 force! / ,. If the molecular weight force is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 000, the developability may be inferior.
  • the content of the noinder in the photosensitive layer is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
  • the content is less than 5% by mass, the film strength of the photosensitive layer may be weakened or the tackiness of the surface of the photosensitive layer may be deteriorated.
  • the content exceeds 50% by mass, the exposure sensitivity is increased. May decrease.
  • the polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, but has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure.
  • at least one selected from monomers having a (meth) acryl group is preferable.
  • the monomer having the (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose.
  • the monofunctional acrylate or monofunctional methacrylate for example, polyethylene glycol mono (meth)
  • (Meth) atrelate toys after the addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols eg acrylate, polypropylene glycol mono (meth) acrylate, phenoxychetyl (meth) acrylate, etc.
  • polyfunctional acrylate and metatalylate for example, reaction formation of epoxy resin and (meth) acrylic acid
  • epoxy acrylates Such as epoxy acrylates.
  • trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • the content of the polymerizable compound in the photosensitive layer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
  • the content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur.
  • it exceeds 50% by mass the adhesiveness of the photosensitive layer may become too strong. It is not preferable.
  • the photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light may have some effect with photo-excited sensitizers, and may be active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates.
  • the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having an oxadiazole skeleton, etc.), phosphine oxides, hexaryl hydrocarbons. Imidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, acyl phosphine oxide compounds, aromatic compounds Examples include aromatic o-um salts and ketoxime ethers.
  • halogenated hydrocarbon compound having a triazine skeleton examples include, for example, a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), British Patent No. 138 8492 Compounds described in JP-A-53-133428, compounds described in German Patent No. 3337024, J. Org. Chem .; 29, 1527 (1964) by FC Schaefer et al. Compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4212976 And compounds described in the specification.
  • Examples of the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969) include, for example, 2 phenol-4, 6 bis (trichloromethyl) -1, 3, 5 Triazine, 2 — (4 Chlorphenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (4 Tolyl) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2— (4-Methoxyphenyl) —4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (2,4 Dichlorophenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2, 4, 6 Tris (trichloromethyl) -1, 3, 5 Triazine, 2-methyl-4, 6 Bis (trichloromethyl) -1,
  • Examples of the compounds described in the British Patent 1388492 include 2-styryl-4,6bis (trichloromethyl) -1,3,5 triazine, 2- (4-methylstyryl)-
  • Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (4 ethoxy-naphth-1-yl) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- [4- (2 ethoxyethyl) -naphth-1-yl] -4, 6 Bis (trichloromethyl)-1, 3, 5 triazine, 2— (4, 7 Dimethoxy mononaphthone 1-yl) 4, 6 Bis (tri Chloromethyl) -1,3,5 triazine, 2- (acenaphtho-5-yl) 4,6 bis (trimethyl) 1,3,5 triazine and the like.
  • Examples of the compound described in German Patent No. 3337024 include 2- (4-styrylphenol) -4, 6bis (trichloromethyl) -1,3,5 triazine, 2- ( 4— (4 —Methoxystyryl) phenol) 1,4,6 bis (trichloromethyl) 1,3,5 triazine, 2 -— (1-naphthylbi-phenylenephenol) 1,4,6 bis (trichloromethyl) 1, 3, 5 Triazine, 2 Chlorostyrylphenol 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4 Thiophene-2-bilenphenol) 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4 thiophene, 3 bilenphenol), 1, 4, 5 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4 furan, 1 biphenylene) 1, 4, 6-Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4-Benzofur
  • Examples of the compounds described in J. Org. Chem., 29, 1527 (1964) by FC Schaefer et al. include 2-methyl-4,6 bis (tribromomethyl) -1,1,3,5 Triazine, 2, 4, 6 Tris (tribromomethyl) 1, 3, 5 Triazine, 2, 4, 6 Tris (dibromomethyl) 1, 3, 5 Triazine, 2 Amamino-4-methyl-6 Tri (Bromomethyl) — 1, 3, 5 triazine, 2-methoxy-4-methyl 6-trichloromethyl 1, 3, 5 triazine.
  • the compounds described in JP-A-62-58241 include, for example, 2- (4 phenolic phenol) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (4 Naphthyl 1-Ethurhu-Lu 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4 Tril-Ethyl) Cel) —4, 6 Bis (Trichloromethyl) —1, 3, 5 Triazine, 2— (4— (4-Methoxyphenyl) ether), 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4-Isopropylphenol) ) -4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4 ethyl fuerture) fuer) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triadine.
  • Examples of the compound described in JP-A-5-281728 include 2- (4-trif Fluoromethylphenol) — 4, 6 bis (trichloromethyl) —1, 3, 5 triazine, 2- (2, 6 difluorophenol) —4, 6 bis (trichloromethyl) —1, 3, 5 triazine, 2 -(2, 6 Dichlorophenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (2, 6 Dibromophenyl) 1, 4, 6 Bis (trichloromethyl) 1, 3, 5 For example, triazine.
  • Examples of the compound described in JP-A-5-34920 include 2,4 bis (trichloromethyl) -6- [4- (N, N diethoxycarbomethylmethylamino) -3-bromophenol- 1, 3, 5 triazine, trihalomethyl-s triazine compound described in US Pat. No. 4,239,850, 2, 4, 6 tris (trichloromethyl) -s triazine, 2- (4-chloro) Mouth file) 4, 6-bis (tribromomethyl) s triazine.
  • Examples of the compound described in US Pat. No. 4,212,976 include compounds having an oxadiazole skeleton (for example, 2 trichloromethyl-5 phenol-l, 3, 4 -oxadiazole, 2 trichloromethyl mono 5 — (4 Chlorophthalate) 1 1, 3, 4-Oxadiazole, 2 Trichloromethyl— 5— (1-Naphthyl) —1, 3, 4-Oxadiazole, 2 Trichloromethyl 5— (2 —Naphthyl) -1, 3, 4 oxadiazole, 2 Tribromomethyl-5 Feniruru 1, 3, 4 oxaziazole, 2 Trimethyl-methyl 5 — (2 Naphthyl) 1, 3, 4-Oxadiazole; 2 Trichloromethyl— 5-styryl —1, 3, 4-Oxadiazole, 2 Trichloromethyl mono 5— (4 Chlorstyryl) mono 1, 3, 4-Oxadiazole, 2 Trichloromethyl mono
  • Examples of the oxime derivatives include 3 benzoylimiminobutane 2 on, 3 acetoxy iminobutane 2 on, 3 propionyloxy iminobutane 2 on, 2 -acetoximinopentane 3 on, 2 -Acetoximino 1-phenol propane — 1—one, 2 benzoyloximino 1—phenol propane 1—one, 3— (4-to Ruensulfonyloxy) iminobutane 2-one, 2-ethoxycarbonyloxyimino-1-phenolpropane-1-one and the like.
  • isylphosphine oxides are used, for example, bis (2,4,6 trimethylbenzoyl) -phenolphosphine oxide, bis (2,6 dimethoxy). (Benzyl) -2, 4, 4 Trimethyl-pentylphenylphosphine oxide, LucirinTPO, etc.
  • Atalidine derivatives for example, 9-phenol lysine, 1,7 bis (9,9,1 tert-aryl) heptane, etc.
  • N-phenol glycine etc.
  • Rehalogen compounds eg, carbon tetrabromide, felt rib mouth methylsulfone, phenyl trichloromethyl ketone, etc.
  • coumarins eg, 3- (2-benzofuroyl) 7-jetaluminocoumarin, 3- (2 benzofuroyl) -7 -(1-Pyrrolidyl) coumarin, 3 Benzoyl 7 Jetylaminocoumarin, 3- (2-Methoxybenzoyl) 7 Jetylamino nocoumarin, 3- (4-Dimethylaminobenzoyl) 7-Jetylaminocoumarin, 3,3,1 carborubis (5, 7-di-n-propoxycoumarin), 3, 3, -carborubis (7-deethylaminocoumarin), 3-benzoyl 7- Toxicoumarin, 3- (2-Furoyl) 7-Jetylaminocoumarin, 3- (4-Jetylaminocinnamoyl) 7-Jet
  • Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-clobenzobenzoneone.
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • Particularly preferable examples of the photopolymerization initiator include halogenated hydrocarbons having the phosphine oxides, the ⁇ -aminoalkyl ketones, and the triazine skeleton, which are compatible with laser light having a wavelength of 405 nm in the later-described exposure.
  • Examples thereof include a composite photoinitiator obtained by combining a compound and an amine compound as a sensitizer described later, a hexaarylbiimidazole compound, or titanocene.
  • the content of the photopolymerization initiator in the photosensitive layer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and 0.5 to 15% by mass. Particularly preferred.
  • the sensitizer can be appropriately selected depending on visible light, ultraviolet light, or visible light laser as a light irradiation means to be described later.
  • the sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals and It is possible to generate useful groups such as acids.
  • substances for example, radical generator, acid generator, etc.
  • energy transfer, electron transfer, etc. for example, energy transfer, electron transfer, etc.
  • the sensitizer can be appropriately selected from known sensitizers that are not particularly limited.
  • known polynuclear aromatics for example, pyrene, perylene, triphenylene
  • Xanthenes eg, fluorescein, eosin, erythrosine, rhodamine ⁇ , rose bengal
  • cyanines eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine
  • merocyanines eg, merocyanine, carbomerocyanine
  • Thiazines eg, thionine, methylene blue, toluidine blue
  • atalidines eg, atalidine orange, chloroflavin, acriflavine
  • anthraquinones eg, anthraquinone
  • squaliums eg, squalium
  • atalidones eg, , Ataridon, Kuro Ataridon,
  • Examples of combinations of the photopolymerization initiator and the sensitizer include, for example, an electron transfer-type initiator system described in JP-A-2001-305734 [(1) an electron-donating initiator and a sensitizing dye. (2) Electron-accepting initiators and sensitizing dyes, (3) Electron-donating initiators, sensitizing dyes and electron-accepting initiators (ternary initiation system)].
  • the content of the sensitizer in the photosensitive layer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.2 to 10% by mass. If the content is less than 0.05% by mass, the sensitivity to active energy rays may be reduced, the exposure process may take time, and productivity may be reduced. If the content exceeds 30% by mass, The sensitizer may precipitate from the photosensitive layer during storage.
  • the thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, the image property, etc. A compound obtained by reacting a blocking agent with an epoxy compound, an oxetane compound, a polyisocyanate compound, a polyisocyanate compound, and the like. Melamine derivative power At least one selected can be used.
  • Examples of the epoxy compound include bixylenol-type or biphenol-type epoxy resin ("YX4000 Japan Epoxy Resin Co., Ltd.") or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton, etc.
  • Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxeta-lmethoxy) methyl] ether, 1, 4-bis [(3-methyl-3-oxeta-lmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxeta-lmethoxy) methyl] benzene, (3-methyl-3-oxeta-l) methyl acrylate , (3 Echiru 3 Okiseta -) methyl Atari rate, (3-methyl 3-Okiseta -) methyl meth Tari rate, (3 Echiru 3 Okiseta - Le) methylate Rume Tatari rate or oligomers thereof or copolymers
  • novolac resin poly (p-hydroxystyl)
  • an amine compound for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N dimethylbenzylamine.
  • a curing catalyst for the epoxy compound or the oxetane compound, or a compound capable of promoting thermal curing other than the above is used as long as it can accelerate the reaction of the carboxyl group with these. May be.
  • the content of the epoxy compound, the oxetane compound, and a compound capable of accelerating thermal curing of these with a carboxylic acid in the photosensitive layer is usually 0.01 to 15% by mass.
  • polyisocyanate compound for example, a polyisocyanate compound described in JP-A-5-9407 can be used.
  • the polyisocyanate compound may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing at least two isocyanate groups.
  • bifunctional isocyanates eg, mixtures of 1,3 and 1,4-phenolic diisocyanates, 2, 4 and 2,6 toluene diisocyanates, 1, 3 And 1,4 xylylene diisocyanate, bis (4-isocyanate monophenyl) methane, bis (4-isocyanate cyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate Trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, Polyfunctional alcohols with pentalysitol, glycerin, etc .; Alkylene oxide adducts of the polyfunctional alcohols and adducts with the above-mentioned bifunctional isocyanates; Cyclic rings such as hexamethylene disocyanate, hexamethylene 1,6 diisocyanate and derivatives thereof Trimer; and the like.
  • bifunctional isocyanates e
  • a compound obtained by reacting the polyisocyanate compound with a blocking agent may be used.
  • the isocyanate blocker include alcohols (for example, isopropanol, tert-butanol, etc.), ratatas (for example, ⁇ -strength prolatatum, etc.), phenols (for example, phenol, crezo-monore, p-tert-butinolephenol) Nore, p-sec butinolevenore, p-sec amylphenol, p-octylphenol, p-norphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline) Etc.), active methylene compounds (for example, dialkyl malonate, methyl ethyl ketoxime, acetyl acetone, alkyl acetoacetoxime,
  • alcohols for example, isopropanol, tert-butanol, etc
  • Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, etc.). These may be used alone or in combination of two or more. Among these, hexamethylated methylol melamine is particularly preferred, because alkylated methylol melamine is preferred because it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film. .
  • the content of the thermal crosslinking agent in the photosensitive layer is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and particularly preferably 3 to 20% by mass. If the content is less than 1% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation properties, solder heat resistance, electroless resistance, and the like. If it exceeds mass%, the developability may deteriorate and the exposure sensitivity may decrease.
  • Other ingredients include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other assistants.
  • Agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • properties such as stability, photographic properties and film properties of the target pattern forming material can be adjusted.
  • the thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
  • thermal polymerization inhibitor examples include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted nanodroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy1-2hydroxybenzophenone, Cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2,6 di-tert-butyl-4 cresol, 2,2, -methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 —Toluidine, methylene blue, copper and organic chelating agent reactants, methyl salicylate, and phenothiazine, nitroso compounds, chelates of nitroso compounds with A1, and the like.
  • the content of the thermal polymerization inhibitor is preferably from 0.001 to 5% by mass, more preferably from 0.005 to 2% by mass, based on the polymerizable compound. Mass% is particularly preferred. If the content is less than 0.001% by mass, the stability during storage may be reduced, and if it exceeds 5% by mass, the sensitivity to active energy rays may be reduced.
  • the color pigment can be appropriately selected according to the purpose without any particular limitation.
  • phthalocyanine green Victoria 'Pure One Blue BO (CI 42595), olamine (CI 41000), Fat. Black HB ( CI 26150), Monolite Yellow GT (C.I.Pigment 'Yellow 12), Permanent' Yellow GR (CI Pigment 'Yellow 17), Non-Minute' Yellow HR '(CI Pigment' Yellow 83), Permanent 'Carmine FBB (CI Pigment 'Red 146), Hoster Balm Red ESB (CI Pigment' Violet 19 ), Permanent 'Ruby FBH (CI Pigment' Red 11) Huster 'Pink B Supra (CI Pigment' Red 81) Monastral 'First' Blue (CI Pigment 'Blue 1 5), Monolite' First 'Black B (CI Pigment') Black 1), Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment 'Red 168,
  • These may be used alone or in combination of two or more. If necessary, a dye appropriately selected from known dyes can be used.
  • the content of the colored pigment in the photosensitive layer can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer at the time of forming a permanent pattern, and varies depending on the type of the colored pigment. Specifically, 0.05 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable.
  • Inorganic pigments and organic fine particles can be added.
  • the inorganic pigment can be appropriately selected from known ones that are not particularly limited, and examples thereof include kaolin, barium sulfate, barium titanate, potassium oxide powder, finely divided oxide silica, and vapor phase method silica.
  • the average particle diameter of the inorganic pigment is preferably less than 10 m, more preferably 3 m or less. If the average particle size is 10 m or more, the resolution may deteriorate due to light scattering.
  • the organic fine particles are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include melamine resin, benzoguanamine resin, and cross-linked polystyrene resin. Also, from silica and crosslinked resin with an average particle size of 1-5 / ⁇ ⁇ , oil absorption of about 100-200m 2 Zg Spherical porous fine particles can be used.
  • the addition amount of the extender pigment in the photosensitive layer is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when a cured film is formed on the surface of the photosensitive layer, The film quality becomes brittle, and when a wiring is formed using a permanent pattern, the function as a protective film for the wiring may be impaired.
  • a known adhesion promoter may be used for each layer.
  • adhesion promoter for example, the adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638 are preferably exemplified.
  • Specific examples include benzimidazole, benzoxazole, benzthiazole, 2 mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3 morpholinomethyl-1 phenyroot triazole-2 thione, 3 morpholino Methyl 5 phenyloxadiazole 2 thione, 5 amino-3 morpholinomethyl thiadiazole 2 thione, 2 mercapto 5-methylthiothiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, etc.
  • the adhesion promoter for example, the adhesion promoters described in JP-A-5-11439, JP
  • the content of the adhesion promoter in the photosensitive layer is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and 0.1 to 5% by mass. Is particularly preferred.
  • the method for producing the pattern forming material can be appropriately selected according to the purpose without any particular restrictions.
  • the pattern forming material can be formed on the support such as the above-described photosensitive layer such as a binder, a polymerizable compound, and a photopolymerization initiator. It is preferable to form a photosensitive layer by applying and drying the contained material (hereinafter sometimes referred to as “photosensitive composition”).
  • the coating and drying method can be appropriately selected according to the purpose without particular limitation.
  • the photosensitive composition is dissolved on the surface of the support in water or a solvent.
  • a method is preferred in which a photosensitive composition is prepared by dissolving, emulsifying or dispersing, and the solution is applied and dried.
  • the solvent of the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose.
  • methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, n Alcohols such as hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone, etc .; Ethyl acetate, butyl acetate, n-amyl acetate, methyl acetate, ethyl ethyl propionate, phthalic acid Esters such as dimethyl, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; tetrasalt-carbon, trich
  • Hydrocarbons Tetrahydrofurans, Jetyl ethers, Ethylene Glycolanol Monomethine Reetenore, Ethylene Glycol Nole Mono Ethenore Ethenore, 1-methoxy 2-propanol, etc .; Dimethylformamide, Dimethylacetamide, Dimethyl Sulphoxide, Sulfolane Etc. These may be used alone or in combination of two or more. A known surfactant may be added.
  • the coating method is not particularly limited and can be appropriately selected depending on the purpose.
  • coating is mentioned.
  • the drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
  • the thickness of the photosensitive layer is not particularly limited.
  • a force that can be appropriately selected according to the purpose is 3 to 150 111, more preferably 10 to: LOO / zm force. 15 to 80 / ⁇ ⁇ is more preferable. 20 to 70 / ⁇ ⁇ is particularly preferable. If the thickness is less than 3 m, insulation may be poor, and if it exceeds 150 / z m, photocuring may be insufficient.
  • the pattern forming material forms a protective film on the photosensitive layer.
  • Examples of the protective film include those used for the support, silicone paper, Examples thereof include polyethylene, polypropylene laminated paper, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film and polypropylene film are preferable.
  • the thickness of the protective film is not particularly limited. It can be appropriately selected depending on the purpose. Force S that can be applied f: 2 to: L 00 m force S preferred, 5 to 80 111 preferred, 8 ⁇ 50 m is particularly preferred. If the thickness is less than 2 m, wrinkles may easily occur when the protective film is applied to the photosensitive layer, and if it exceeds 100 / zm, the protective film may be wound poorly in an auto-cut laminating machine. There is.
  • the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B. Good.
  • Examples of the combination of the support and the protective film include, for example, polyethylene terephthalate z polypropylene, polyethylene terephthalate z polyethylene, polychlorinated bur Z cellophane, polyimide Z polypropylene, polyethylene terephthalate z polyethylene terephthalate. Etc.
  • the above-described adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer.
  • a primer layer for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • ultraviolet irradiation treatment for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • One discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like can be mentioned.
  • the coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2 force! / !.
  • the pattern forming material is preferably stored, for example, wound around a cylindrical core and wound into a long roll.
  • the length of the long pattern forming material is not particularly limited. For example, a range force of 10 m to 20, OOOm can be appropriately selected. wear.
  • slitting may be performed so that it is easy for the user to use, and a long body in the range of 100 m to l, OOOm may be rolled.
  • the support is wound so that the outermost side is the outermost side.
  • the roll-shaped pattern forming material may be slit into a sheet shape.
  • a separator particularly moisture-proof and desiccant-containing
  • the protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer.
  • an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polybutyl alcohol is formed on the surface of the protective film.
  • the undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C (particularly 50 to 120 ° C) for 1 to 30 minutes. Can do.
  • a cushion layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorbing layer, a surface protective film, and the like may be included.
  • the cushion layer is a layer that melts and flows when laminated under vacuum heating conditions that have no tackiness at room temperature.
  • the PC layer is usually a coating of about 0.5 to 5 / ⁇ ⁇ , which is formed mainly of polybulal alcohol.
  • a laminate is formed by laminating a photosensitive layer of the pattern forming material on a substrate.
  • the substrate can be appropriately selected from known materials that are not particularly limited in medium force, those having high surface smoothness, and those having an uneven surface.
  • a plate-like substrate Specifically, a known printed wiring board forming substrate (eg, copper-clad laminate), glass plate (eg, soda glass plate), synthetic resin film, paper, metal plate, etc. Can be mentioned.
  • the layer structure in the laminate is not particularly limited and may be appropriately selected depending on the purpose.
  • the protective film is preferably peeled off and laminated so that the photosensitive layer overlaps the substrate.
  • the method for forming the laminate is not particularly limited and may be appropriately selected. However, at least heating and pressurization of the pattern forming material on the base material! It is preferable to stack the layers while performing any deviation.
  • the heating temperature is not particularly limited, and can be appropriately selected depending on the purpose. For example, 70 to 130 ° C is preferable, and 80 to 110 ° C is more preferable.
  • the pressure of the pressurization is not particularly limited.
  • ⁇ column, t is preferably 0.01-: L OMPa force, 0.05-: L OMPa force ⁇ More preferred! / ⁇ .
  • the apparatus for performing at least one of the heating and pressurization can be appropriately selected depending on the purpose, and for example, a heat press, a heat roll laminator (for example, Taisei Laminate Earthen, VP — 11), vacuum laminator (for example,
  • MVLP500 MVLP500
  • the like are preferable.
  • the pattern forming material of the present invention is smaller because it can suppress a decrease in sensitivity of the photosensitive layer.
  • V and energy can be used for light exposure, which is advantageous in that the processing speed increases because the exposure speed increases.
  • the pattern forming material of the present invention has a good resist surface shape and can form a more precise pattern, a printed wiring plate, a color filter, a column material, a rib material, a spacer, It can be widely used for the formation of permanent patterns such as display members such as partition walls, holograms, micromachines, and proofs, and can be suitably used for the permanent pattern formation method of the present invention.
  • the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, and has at least light irradiation means and light modulation means.
  • the permanent pattern forming method of the present invention preferably includes at least an exposure step, and further includes a development step and a curing treatment step.
  • the pattern forming apparatus according to the present invention includes This will be clarified through the description of the method for forming a permanent pattern of the invention.
  • the said exposure process is a process of exposing with respect to the photosensitive layer in the pattern formation material of this invention.
  • the pattern forming material and the base material of the present invention are as described above.
  • the object of exposure is the photosensitive layer in the pattern forming material
  • a force that can be appropriately selected according to the purpose without any particular limitation for example, as described above, the pattern forming material on the substrate It is preferable that this is performed on a laminate formed by laminating while performing at least one of heating and pressurization.
  • the exposure can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
  • the digital exposure can be appropriately selected according to the purpose without any particular limitation.
  • a control signal is generated based on pattern formation information to be formed, and is modulated according to the control signal. Preferred to do with light.
  • the digital exposure means can be appropriately selected according to the purpose without any particular restriction.
  • Examples thereof include a light modulation unit that modulates the irradiated light.
  • the light modulating means can be appropriately selected according to the purpose without any limitation as long as light can be modulated.
  • the light modulating means preferably has n pixel portions.
  • the light modulation means having the n picture elements can be appropriately selected according to the purpose without any particular limitation, and for example, a spatial light modulation element is preferable.
  • Examples of the spatial light modulation element include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (S LM; Special Light Modulator), and transmission by an electro-optic effect.
  • Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
  • the light modulation means generates a control signal based on pattern information to be formed. It is preferable to have a pattern signal generating means. In this case, the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
  • control signal can be appropriately selected according to the purpose for which there is no particular limitation.
  • a digital signal is preferably used.
  • the DMD 50 has an SRAM cell (memory cell) 60 and a large number of micromirrors 62 (for example, 1024 x 768) that make up each pixel. It is a mirror device arranged in a shape. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a highly reflective material such as aluminum is deposited on the surface of the micromirror 62. Note that the reflectance of the micromirror 62 is 90% or more, and the arrangement pitch thereof is 13. as an example in both the vertical and horizontal directions.
  • CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and the entire structure is monolithically configured. ing.
  • the microphone mirror 62 supported by the support is ⁇ degrees (eg ⁇ 12 °) with respect to the substrate side on which the DMD50 is placed with the diagonal line at the center. ) Tilted within the range.
  • FIG. 2A shows a state tilted to + ⁇ degrees when the micromirror 62 is in the on state
  • FIG. 2B shows a state tilted to ⁇ degrees when the micromirror 62 is in the off state. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 as shown in FIG. 1 according to the pattern information, the laser light incident on the DMD 50 is inclined in the direction of the inclination of each micromirror 62. Reflected to.
  • FIG. 1 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + ⁇ degrees or ⁇ degrees.
  • On / off control of each micromirror 62 is performed by the controller 302 connected to the DMD 50.
  • a light absorber (not shown) is arranged in the direction in which the laser beam reflected by the off-state microphone aperture mirror 62 travels.
  • the DMD 50 is arranged with a slight inclination so that the short side forms a predetermined angle ⁇ (for example, 0.1 ° to 5 °) with the sub-scanning direction.
  • Figure 3 ⁇ shows the DMD50 tilted.
  • FIG. 3B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted.
  • the DMD50 has a micromirror array force in which a large number of micromirrors are arranged in the longitudinal direction (for example, 1024).
  • the scanning width w in this case is substantially the same.
  • high-speed modulation a method for increasing the modulation speed in the optical modulation means (hereinafter referred to as “high-speed modulation”) will be described.
  • the light modulation means can control any less than n pixel elements arranged continuously from the n pixel elements according to pattern information.
  • the modulation speed per line is determined in proportion to the number of pixels to be used. Using only this increases the modulation rate per line.
  • the laser beam reflected when the DMD50 microphone mirror is on is imaged on the pattern forming material 150 by the lens systems 54 and 58. .
  • the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in the DMD 50.
  • the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in a direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposure is performed for each exposure head 166. Region 170 is formed.
  • the DMD 50 has a force in which 768 pairs of micro mirror arrays in which 1024 microphone aperture mirrors are arranged in the main scanning direction are arranged in the sub scanning direction.
  • the controller 302 causes some micromirror rows (eg, 1024 x 2 Control is performed so that only 56 rows) are driven.
  • the micromirror array arranged at the end of DMD50 may be used as shown in FIG. 4B. May be used.
  • the micromirror array used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.
  • the data processing speed of DMD50 is limited, and the modulation speed per line is determined in proportion to the number of pixels to be used. The modulation speed per hit is increased. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.
  • stage 152 is moved along the guide 158 by the stage driving device 304. Returning to the origin on the uppermost stream side of the gate 160, it is moved again along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.
  • modulation can be performed twice as fast per line as compared to using all 768 sets. Also, when only 256 pairs are used in the 768 micromirror array, modulation can be performed three times faster per line than when all 768 pairs are used.
  • the micromirror array force in which 1,024 micromirrors are arranged in the main scanning direction includes the DMD arranged in 768 threads in the subscanning direction.
  • the force described in the example of partially driving the micromirror of the DMD has a length in the direction corresponding to the predetermined direction is longer than the length in the direction intersecting the predetermined direction. Even if a long and narrow DMD in which a number of micromirrors that can change the angle of the reflecting surface are arranged in two dimensions is used, the number of micromirrors that control the angle of the reflecting surface is reduced. Can be fast.
  • the exposure is performed while relatively moving the exposure light and the photosensitive layer. In this case, it is preferable to use in combination with the high-speed modulation. Thereby, high-speed exposure can be performed in a short time.
  • the entire surface of the pattern forming material 150 may be exposed by one scan in the X direction by the scanner 162, as shown in FIGS. 6A and 6B.
  • the scanner 162 is moved one step in the Y direction, and scanning is performed in the X direction.
  • the entire surface of 150 may be exposed.
  • the scanner 162 includes 18 exposure heads 166.
  • the exposure head has at least the light irradiation means and the light modulation means.
  • the exposure is performed on a partial area of the photosensitive layer, whereby the partial area is cured, and an uncured area other than the cured partial area in a development step described later.
  • the area is removed and a pattern is formed.
  • the pattern forming apparatus including the light modulating means includes a flat plate stage 152 for adsorbing and holding a sheet-like pattern forming material 150 on the surface.
  • Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-like installation table 156 supported by the four legs 154.
  • the stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 158 so as to be reciprocally movable.
  • the pattern forming apparatus includes a driving device (not shown) for driving the stage 152 along the guide 158.
  • a U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each end of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156.
  • a scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the pattern forming material 150 are provided on the other side. Yes.
  • the scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. Na
  • the scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.
  • the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in a substantially matrix of m rows and n columns (eg, 3 rows and 5 columns). I have. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the pattern forming material 150. When individual exposure heads arranged in the m-th row and the n-th column are shown, they are expressed as an exposure head 166.
  • An exposure area 168 by the exposure head 166 has a rectangular shape with the short side in the sub-scanning direction.
  • a strip-shaped exposed region 170 is formed in the pattern forming material 150 for each exposure head 166. If the exposure area by each exposure head arranged in the m-th row and the n-th column is shown, the exposure area 168
  • each of the exposure heads in each row arranged in a line so that the strip-shaped exposed region 170 is arranged without a gap in a direction perpendicular to the sub-scanning direction is In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice in this example). Therefore, exposure between the exposure area 168 and the exposure area 168 in the first row is not possible.
  • Unexposed areas are exposed using the exposure area 168 in the second row and the exposure area 168 in the third row.
  • a light modulation means spatial light modulation element that modulates each pixel in accordance with pattern information
  • a digital 'micromirror' device manufactured by Texas Instruments Inc., USA
  • the DMD 50 is connected to a later-described controller 302 (see FIG. 12) that includes a data processing unit and a mirror drive control unit.
  • the data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The areas to be controlled will be described later.
  • the mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit. The control of the angle of the reflecting surface will be described later.
  • the exit end (light emitting point) of the optical fiber is the length of the exposure area 168.
  • a fiber array light source 66 having laser emission units arranged in a line along the direction corresponding to the side direction, a lens system 67 for correcting the laser light emitted from the fiber array light source 66 and collecting it on the DMD 67, a lens A mirror 69 that reflects the laser beam transmitted through the system 67 toward the DMD 50 is arranged in this order.
  • the lens system 67 is schematically shown.
  • the lens system 67 includes a condenser lens 71 that condenses the laser light B as illumination light emitted from the fiber array light source 66, and an optical path of the light that has passed through the condenser lens 71.
  • An inserted rod-shaped optical integrator (hereinafter referred to as a rod integrator) 72, and an imaging lens 74 force arranged in front of the rod integrator 72, that is, on the mirror 69 side, are also configured.
  • the condensing lens 71, the rod integrator 72, and the imaging lens 74 cause the laser light emitted from the fiber array light source 66 to enter the DMD 50 as a light beam that is close to parallel light and has a uniform intensity in the beam cross section.
  • the shape and action of the rod integrator 72 will be described in detail later.
  • the laser beam B emitted from the lens system 67 is reflected by the mirror 69 and irradiated to the DMD 50 via the TIR (total reflection) prism 70.
  • the TIR prism 70 is omitted.
  • an imaging optical system 51 that images the laser beam B reflected by the DMD 50 onto the pattern forming material 150 is disposed on the light reflection side of the DMD 50.
  • This imaging optical system 51 is schematically shown in FIG. 10, but as shown in detail in FIG. 11, the first imaging optical system consisting of lens systems 52 and 54 and lens systems 57 and 58 are used.
  • the second imaging optical system, the microlens array 55 inserted between these imaging optical systems, and the aperture array 59 are also configured.
  • the microlens array 55 is formed by two-dimensionally arranging a number of microlenses 55a corresponding to each picture element of the DMD 50.
  • the arrangement pitch of microlenses 55a is 41 ⁇ m in both the vertical and horizontal directions.
  • this micro lens 55a has a focal length of 0.19 mm, NA (numerical aperture) of 0.11, and is formed from optical glass BK7. It is made.
  • the shape of the microlens 55a will be described in detail later.
  • the beam diameter of the laser beam B at the position of each microlens 55a is 41 ⁇ m.
  • the aperture array 59 is formed by forming a large number of apertures (openings) 59a corresponding to the respective microlenses 55a of the microlens array 55.
  • the diameter of the aperture 59a is, for example, 10 m.
  • the first imaging optical system enlarges the image by the DMD 50 three times and forms an image on the microlens array 55. Then, the second imaging optical system forms an image on the pattern forming material 150 and projects it by enlarging the image that has passed through the microlens array 55 by 1.6 times. Therefore, as a whole, the image formed by the DMD 50 is magnified by 4.8 times and is formed and projected on the pattern forming material 150.
  • a prism pair 73 is disposed between the second imaging optical system and the pattern forming material 150. By moving the prism pair 73 in the vertical direction in FIG. You can adjust the focus of the image above. In the figure, the pattern forming material 150 is sub-scan fed in the direction of arrow F.
  • the picture element portion can be appropriately selected according to the purpose without particular limitation as long as it can receive and emit light from the light irradiation means.
  • the pattern portion of the present invention can be selected.
  • the pattern formed by the forming method is an image pattern, it is a pixel, and when the light modulation means includes a DMD, it is a micromirror.
  • the number of picture element portions (n mentioned above) of the light modulation element can be appropriately selected according to the purpose without particular limitation.
  • the arrangement of the picture element portions in the light modulation element can be appropriately selected according to the purpose for which there is no particular limitation.
  • a two-dimensional arrangement is preferably arranged in a lattice shape. More preferred to be.
  • the light irradiation means can be appropriately selected according to the purpose without any particular limitation.
  • the means which can irradiate is mentioned, Among these, the means which can synthesize
  • the light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • ultraviolet to visible light, electron beams, X-rays, laser light, etc. are mentioned, and among these, laser light is preferred.
  • Laser that combines two or more lights hereinafter sometimes referred to as “combined laser”) ) Is more preferable. Even when the support is peeled off and the light is irradiated with light, the same light can be used.
  • the wavelength of the light irradiated from the light irradiation means can be appropriately selected according to the purpose without particular limitation, as long as the photosensitive layer to be exposed is a wavelength at which the photosensitive layer is exposed and hardened.
  • the wavelength of ultraviolet to visible light is preferably 300 to 1500 nm, more preferably 320 to 800 mn, and 330 ⁇ ! ⁇ 650mn force ⁇ especially preferred!
  • the wavelength of the laser beam includes, for example, 200 to 1500 nm force S, preferably 300 to 800 nm force S, more preferably 330 to 500 nm force S, more preferably 340 to 415 nm force S, and particularly preferably 400 to 410 nm. .
  • laser light with a wavelength of 405 nm emitted from a GaN-based semiconductor laser is most preferred!
  • Means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces and coupled to the multimode optical fiber. Means having a collective optical system to be used is preferable.
  • the fiber array light source 66 includes a plurality of (for example, 14) laser modules 64.
  • Each laser module 64 has one end of a multimode optical fiber 30 connected thereto. Are combined.
  • the other end of the multimode optical fiber 30 is coupled with an optical fiber 31 having the same core diameter as the multimode optical fiber 30 and a cladding diameter smaller than the multimode optical fiber 30.
  • seven ends of the multimode optical fiber 31 opposite to the optical fiber 30 are arranged along the main scanning direction orthogonal to the sub-scanning direction.
  • Laser emitting units 68 are arranged in rows. [0157] As shown in Fig.
  • the laser emitting portion 68 constituted by the end of the multimode optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. Further, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the multimode optical fiber 31 for protection.
  • the light exit end face of the multimode optical fiber 31 is easy to collect dust and easily deteriorate due to its high light density, but the protective plate as described above prevents the dust from adhering to the end face and prevents deterioration. Can be delayed.
  • the output ends of the optical fibers 31 with a small cladding diameter are arranged in a line without any gap, so that the multimode optical fibers 30 adjacent to each other with a large cladding diameter are multimode.
  • the optical fiber 30 is stacked, and the output end of the optical fiber 31 coupled to the stacked multimode optical fiber 30 is connected to the two multimode optical fibers 30 adjacent to each other at the portion where the cladding diameter is large. They are arranged so as to be sandwiched between the two exit ends.
  • such an optical fiber has a light with a small cladding diameter of 1 to 30 cm in length at the tip of the multimode optical fiber 30 with a large cladding diameter on the laser light emission side. It can be obtained by coupling the fibers 31 coaxially.
  • the two optical fibers are fused and bonded to the incident end face force of the optical fiber 31 and the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide.
  • the diameter of the core 31a of the optical fiber 31 is the same as the diameter of the core 30a of the multimode optical fiber 30.
  • a short optical fiber obtained by fusing an optical fiber having a short length and a large clad diameter to which the clad diameter and the optical fiber are fused is connected to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. May be combined.
  • the tip portion can be easily replaced when the diameter of the clad or the optical fiber is broken, and the cost required for exposure head maintenance can be reduced.
  • the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.
  • the multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber.
  • a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used.
  • the multimode optical fiber 30 and the optical fiber 31 Is a p-index type optical fiber
  • the multimode optical fiber 30 has a cladding diameter of 125 ⁇
  • NA 0.2
  • the transmittance of the incident end face coat 99.5% or more
  • the cladding thickness ⁇ (cladding diameter, one core diameter) Z2 ⁇ is set to the 800 nm wavelength band. About 1Z2 when propagating infrared light, 1.
  • the cladding diameter can be reduced to 60 m.
  • the cladding diameter of the optical fiber 31 is not limited to 60 ⁇ m.
  • Conventional fiber array The optical fiber used in the light source has a cladding diameter of 125 m.
  • m is preferably 40 m or less.
  • the cladding diameter of the optical fiber 31 is preferably 10 ⁇ m or more.
  • the laser module 64 is configured by a combined laser light source (fiber array light source) shown in FIG.
  • This combined laser light source is composed of a plurality of (for example, 7) chip-shaped lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 arranged and fixed on the heat block 10.
  • LD1, LD2, LD3, LD4, LD5, LD6 arranged and fixed on the heat block 10.
  • And LD7, and GaN-based semiconductor laser L D1 ⁇ Collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of LD7, one condenser lens 20, and 1 And a multimode optical fiber 30.
  • the number of semiconductor lasers is not limited to seven.
  • the GaN-based semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and the maximum output is all the same (for example, 100 mW for a multimode laser, single mode). 30 mW) for a single laser.
  • the GaN-based semiconductor lasers LD1 to LD7 lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 nm to 450 nm may be used.
  • the combined laser light source is housed in a box-shaped package 40 having an upper opening, together with other optical elements.
  • the package 40 is provided with a package lid 41 made so as to close the opening. After the degassing process, a sealing gas is introduced, and the opening of the knock 40 is closed by the package lid 41, so that the package 40 and the package 40 are sealed.
  • the combined laser light source is hermetically sealed in a closed space (sealed space) formed by the cage lid 41.
  • a base plate 42 is fixed to the bottom surface of the package 40.
  • the heat block 10 On the top surface of the base plate 42, the heat block 10, the condensing lens holder 45 that holds the condensing lens 20, and the multimode light.
  • a fiber holder 46 that holds the incident end of the fiber 30 is attached. The exit end of the multimode optical fiber 30 is drawn out of the package through an opening formed in the wall surface of the knock 40.
  • a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held.
  • An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.
  • Fig. 32 shows a front shape of a mounting portion of the collimator lenses 11-17.
  • Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting an area including an optical axis of a circular lens having an aspherical surface into an elongated shape on a parallel plane.
  • the elongated collimator lens can be formed, for example, by molding resin or optical glass.
  • the collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 32).
  • each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having an emission width of 2 m, and each of the divergence angles in a direction parallel to and perpendicular to the active layer is, for example, 10 ° and 30 °, respectively.
  • Lasers that emit laser beams B1 to B7 are used.
  • These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.
  • the laser beams B1 to B7 emitted from the respective light emitting points are spread in the direction in which the divergence angle is large with respect to the elongated collimator lenses 11 to 17 as described above.
  • the incident light enters in a state where the direction with a small angle coincides with the width direction (direction perpendicular to the length direction).
  • the width of each collimator lens 11 to 17 is 1. lmm and the length is 4.6 mm, and the beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2 respectively. 6mm.
  • Each of the collimator lenses 11 to 17 has a focal length f
  • the condensing lens 20 is obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a thin plane in a parallel plane, and a direction perpendicular to that in which the collimator lenses 11 to 17 are arranged, that is, horizontally. It is formed in a short shape.
  • the condensing lens 20 is also formed, for example, by molding a resin or optical glass.
  • the light emitting means for illuminating the DMD uses a high-luminance fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, a high output and deep focus A pattern forming apparatus having a depth can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.
  • the cladding diameter of the output end of the optical fiber is smaller than the cladding diameter of the incident end, the diameter of the light emitting section is further reduced, and the brightness of the fiber array light source can be increased.
  • a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 ⁇ m or less and a resolution of 0.1 ⁇ m or less, a deep focal depth can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.
  • TFT thin film transistor
  • a fiber array including a plurality of the combined laser light sources For example, a fiber array light source in which a fiber light source including one optical fiber that emits laser light incident from a single semiconductor laser having one light emitting point is arrayed is used. Can do.
  • the light irradiation means having a plurality of light emitting points for example, as shown in FIG. 33, a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 on a heat block 100: LD7 Can be used.
  • a chip-shaped multi-cavity laser 110 shown in FIG. 34A in which a plurality of (for example, five) light emitting points 110a are arranged in a predetermined direction is known.
  • the light emitting points can be arranged with higher positional accuracy than in the case where the chip-shaped semiconductor lasers are arranged, so that the laser beams emitted from the respective light emitting point forces can be easily combined.
  • the number of light emitting points 110a is preferably 5 or less.
  • a plurality of multi-cavity lasers 110 are arranged on the heat block 100 as shown in FIG. 34B.
  • a multi-cavity laser array arranged in the same direction can be used as a laser light source.
  • the combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers.
  • a combined laser light source including a chip-shaped multi-cavity laser 110 having a plurality of (for example, three) emission points 110a can be used.
  • the combined laser light source includes a multi-cavity laser 110, a single multimode optical fiber 130, and a condenser lens 120.
  • the multi-cavity laser 110 can be composed of, for example, a GaN-based laser diode having an oscillation wavelength of 405 nm.
  • each of the laser beams B emitted from each of the plurality of light emitting points 110a of the multi-cavity laser 110 is collected by the condenser lens 120 and is incident on the core 130a of the multimode optical fiber 130. To do.
  • the laser light incident on the core 130a is propagated in the optical fiber, combined into one, and emitted.
  • a plurality of emission points 110a of the multi-cavity laser 110 are connected to the multi-mode optical fiber.
  • the condensing lens 120 is arranged in parallel within a width substantially equal to the core diameter of the 130, and a convex lens having a focal length substantially equal to the core diameter of the multimode optical fiber 130 or the output from the multicavity laser 110.
  • a plurality of (for example, nine) multi-carriers are provided on the heat block 111 using a multi-cavity laser 110 having a plurality of (for example, three) emission points.
  • a combined laser light source having a laser array 140 in which the bit lasers 110 are arranged at equal intervals can be used.
  • the plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 110a of each chip.
  • This combined laser light source is arranged between the laser array 140, the plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 110, and the laser array 140 and the plurality of lens arrays 114. Further, it is configured to include one rod lens 113, one multimode optical fiber 130, and a condensing lens 120.
  • the lens array 114 includes a plurality of microlenses corresponding to the emission points of the multi-cavity laser 110.
  • each of the laser beams B emitted from the respective light emitting points 110a of the plurality of multi-cavity lasers 110 is condensed in a predetermined direction by the rod lens 113, and then the lens array 114.
  • the light is collimated by each microlens.
  • the collimated laser beam L is collected by the condenser lens 120 and enters the core 130 a of the multimode optical fiber 130.
  • the laser light incident on the core 130a propagates in the optical fiber, and is combined into one and emitted.
  • this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180, and is stored between two heat blocks. A space is formed.
  • a plurality of (for example, two) multi-cavity lasers in which a plurality of light-emitting points (for example, five) are arranged in an array form 110 power light-emitting points for each chip 110a It is fixed and arranged at equal intervals in the same direction as the direction of arrangement.
  • the substantially rectangular heat block 180 has a recess, and the heat block 180 is empty.
  • a plurality of (for example, two) multi-cavity lasers 110 in which a plurality of light emitting points (for example, five) are arranged in an array are arranged on the upper surface on the intermediate side, and the light emitting points are arranged on the upper surface of the heat block 182.
  • the laser chip is arranged so as to be on the same vertical plane as the light emitting point of the laser chip.
  • a collimating lens array 184 in which collimating lenses are arranged corresponding to the light emitting points 110a of the respective chips is arranged.
  • the length direction of each collimating lens and the divergence angle of the laser beam are large V and the direction (fast axis direction) coincides, and the width direction of each collimating lens is divergence is small! /, Direction It is arranged so as to coincide with (slow axis direction).
  • collimating lenses are arrayed and integrated to improve the space utilization efficiency of the laser beam, increase the output of the combined laser light source, reduce the number of parts, and reduce the cost. it can.
  • the collimating lens array 184 there is a single multimode optical fiber 130 and a condensing unit that condenses and combines the laser light at the incident end of the multimode optical fiber 130.
  • An optical lens 120 is disposed.
  • each of the laser beams B also emitted from the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184. And condensed by the condenser lens 120 and incident on the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, and is combined into one and emitted.
  • the combined laser light source can achieve particularly high output by the multistage arrangement of multi-cavity lasers and the array of collimating lenses.
  • a higher-intensity fiber array light source or bundle fiber light source can be formed, which is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.
  • a laser module in which each of the combined laser light sources is housed in a casing and the emission end portion of the multimode optical fiber 130 is pulled out from the casing can be configured.
  • another optical fiber having the same core diameter as that of the multimode optical fiber and a cladding diameter smaller than that of the multimode optical fiber is provided at the output end of the multimode optical fiber of the combined laser light source.
  • the example of increasing the brightness of the fiber array light source by combining the bars has been described.
  • each exposure head 166 of the scanner 162 laser light Bl, B2, B3, B4, GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66 is emitted in the state of divergent light.
  • Each of B5, B6, and B7 is collimated by the corresponding collimator lenses 11-17.
  • the collimated laser beams B1 to B7 are collected by the condenser lens 20 and converge on the incident end face of the core 30a of the multimode optical fiber 30.
  • the collimator lenses 11 to 17 and the condenser lens 20 constitute a condensing optical system
  • the condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system. That is, the laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30 and propagate through the optical fiber. The light is output from the optical fiber 31 combined and coupled to the output end of the multimode optical fiber 30.
  • the laser emitting section 68 of the fiber array light source 66 light emission points with high luminance are arranged in a line along the main scanning direction as described above.
  • a conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has low output, so if the multiple rows are not arranged, the desired force cannot be obtained. Since the wave laser light source has high output, a desired output can be obtained even with a small number of columns, for example, one column.
  • a laser with an output of about 30 mW (milliwatt) is usually used as the semiconductor laser.
  • a multimode optical fiber with a core diameter of 50 m, a cladding diameter of 125 / ⁇ ⁇ , and ⁇ (numerical aperture) of 0.2 is used.
  • 48 multimode optical fibers (8 X 6) must be bundled, and the light emitting area is 0.62 mm 2 (0.675 mm X O. 925 mm). . 6 X 10 6 (W / m 2), brightness per optical fiber is 3.2 X 10 6 (WZm 2 ).
  • the light irradiation means is a means capable of irradiating a combined laser
  • an output of about 1 W can be obtained with six multimode optical finos. Since the area of the optical region is 0.0081 mm 2 (0.325 mm X 0.025 mm), the brightness at the laser emission section 68 is 123 X 10 6 (WZm 2 ), which is about 80 times higher than the conventional brightness. Can be achieved.
  • the luminance per optical fiber is 90 X 10 6 (WZm 2 ), which is about 28 times higher than before.
  • the diameter of the light emission area of the bundled fiber light source of the conventional exposure head is 0.675 mm, and the diameter of the light emission area of the fiber array light source of the exposure head is 0.025 mm.
  • the light emitting means (bundle fiber light source) 1 has a large light emitting area, so the angle of the light beam incident on the DMD 3 increases, and as a result, the light beam enters the scanning surface 5. The angle of the light beam increases. For this reason, the beam diameter tends to increase with respect to the condensing direction (shift in the focus direction).
  • the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is reduced.
  • the angle of the light beam incident on the scanning surface 56 is decreased. That is, the depth of focus becomes deep.
  • the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot.
  • the effect on the depth of focus becomes more significant and effective as the required light quantity of the exposure head increases.
  • the size of one pixel projected on the exposure surface is 10 m x 10 m.
  • DMD is a reflective spatial light modulator, but Fig. 37A and Fig. 37B are developed to explain the optical relationship. It was made into a figure.
  • Pattern information power corresponding to the exposure pattern is inputted to a controller (not shown) connected to the DMD 50 and stored in a frame memory in the controller.
  • This pattern information is data that represents the density of each pixel constituting the image as binary values (whether or not dots are recorded).
  • the stage 152 having the pattern forming material 150 adsorbed on its surface is moved along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed by a driving device (not shown).
  • a driving device not shown
  • the pattern information stored in the frame memory is sequentially read for each of a plurality of lines.
  • a control signal is generated for each exposure head 166 based on the pattern information read out and read out by the data processing unit.
  • each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.
  • the DMD 50 When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the microphone mouth mirror of the DMD 50 is turned on is exposed to the surface of the pattern forming material 150 by the lens systems 54 and 58. Imaged on 56. In this way, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the no-turn forming material 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in DM D50.
  • the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposure is performed for each exposure head 166. Region 170 is formed.
  • the exposure is preferably performed using the modulated light through a microlens array, and may be performed through an aperture array, an imaging optical system, or the like.
  • the microlens array is a force that can be appropriately selected depending on the purpose without any particular limitation.
  • a microlens having an aspherical surface capable of correcting aberration due to distortion of the exit surface in the pixel portion Preferred are those arranged.
  • the aspherical surface can be appropriately selected depending on the purpose without particular limitation, For example, a toric surface is preferable.
  • FIG. 13A shows DMD50, DMD50, light irradiation means 144 for irradiating laser light, and lens system (imaging optical system) 454, 458, DM D50 for enlarging and forming the laser light reflected by DMD50.
  • a microlens array 472 in which a large number of microlenses 474 are arranged corresponding to each pixel part, an aperture array 476 in which a large number of apertures 478 are provided corresponding to each microlens of the microlens array 472, and an aperture
  • FIG. 14 shows the result of measuring the flatness of the reflection surface of the micromirror 62 constituting the DMD 50.
  • the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm.
  • the X direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above.
  • 15A and 15B show the height position displacement of the reflection surface of the micromirror 62 along the X direction and the y direction, respectively.
  • the microlens 55a of the microlens array 55 has a special shape different from the conventional one. This will be described in detail below.
  • FIGS. 16A and 16B respectively show the front and side shapes of the entire microlens array 55 in detail. These figures also show the dimensions of each part of the microlens array 55, and their units are mm.
  • the 1024 ⁇ 256 micromirrors 62 of the DMD 50 are driven. 1024 in the direction
  • the microlens 55a is arranged in 256 rows in the vertical direction.
  • the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.
  • FIGS. 17A and 17B show the front shape and the side shape of one microphone opening lens 55a in the microlens array 55, respectively.
  • FIG. 17A also shows the contour lines of the microphone port lens 55a.
  • the end surface of each microlens 55a on the light emission side has an aspherical shape that corrects aberration due to distortion of the reflection surface of the micromirror 62.
  • the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively. That is, when comparing the parallel cross section in the X direction and the parallel cross section in the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. .
  • FIG. 19A, FIG. 19B, FIG. 19C, and FIG. 19D show the simulation results of the beam diameter in the vicinity of the condensing position (focus position) of the microlens 55a when the microlens 55a has the above shape.
  • X is the lens optical axis in the X direction.
  • Mean distance of O force Y represents the distance of the lens optical axis repulsion in the y direction.
  • the microlens 55a is parallel to the focal length force direction in the cross section parallel to the y direction.
  • a toric lens smaller than the focal length in the cross section, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, the pattern forming material 150 can be exposed to a higher definition image without distortion.
  • the present embodiment shown in FIGS. 19A to 19D has a wider region with a smaller beam diameter, that is, a greater depth of focus.
  • the focal length in the cross section parallel to the X direction is in the cross section parallel to the y direction.
  • the microlens is made up of a toric lens having a focal length smaller than the above-described focal length, the pattern forming material 150 can be exposed to a higher-definition image without distortion.
  • the aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged so that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. . That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.
  • the microlens 55a may have a secondary aspherical shape or a higher order (4th, 6th, aspherical shape). By adopting the higher-order aspherical shape, the beam shape can be further refined.
  • the end surface of the microlens 55a on the light emission side is an aspherical surface.
  • one of the two light-passing end surfaces is a spherical surface and the other is a cylindrical
  • the same effect as that of the above-described embodiment can be obtained by forming a microlens array having a cull surface.
  • the microlens 55a of the microlens array 55 has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62.
  • the same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution that corrects aberration due to distortion of the reflecting surface of the micromirror 62 instead of adopting the shape.
  • FIGS. 22A and 22B An example of such a microlens 155a is shown in FIGS. 22A and 22B.
  • 22A and 22B show the front shape and the side shape of the microlens 155a, respectively.
  • the outer shape of the microlens 155a is a parallel plate.
  • the x and y directions in the figure are as described above.
  • FIG. 23A and FIG. 23B schematically show the condensing state of the laser light B in the cross section parallel to the x direction and the y direction by the microlens 155a.
  • the microlens 155a has a refractive index distribution in which the optical axis O force gradually increases as it is directed outward.
  • the positions changed at a predetermined equal pitch are shown.
  • the ratio of the refractive index change of the microlens 155a is larger and the focal length is shorter in the latter section. It is summer. Even when a microlens array composed of such a refractive index distribution type lens is used, the same effect as in the case of using the microlens array 55 can be obtained.
  • a microlens having an aspherical surface shape like the microlens 55a previously shown in Figs. 17A, 17B, 18A, and 18B, and the refractive index distribution as described above It is possible to correct the aberration caused by the distortion of the reflection surface of the micromirror 62 by both the surface shape and the refractive index distribution.
  • the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected.
  • the pattern forming method of the present invention using a spatial light modulation element other than the DMD.
  • the present invention is applied to correct the aberration caused by the distortion, and the beam shape may be distorted. Can be prevented.
  • the cross-sectional area of the beam line reflected in the ON direction by the DMD 50 is several times (for example, twice) by the lens systems 454 and 458. Enlarged.
  • the expanded laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50, and passes through the corresponding aperture of the aperture array 476.
  • the laser beam that has passed through the aperture is imaged on the exposed surface 56 by the lens systems 480 and 482.
  • the laser beam reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. .
  • the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 13B, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 is the exposure area.
  • MTF Modulation Transfer Function
  • the laser light reflected by the DMD 50 corresponds to each pixel part of the DMD 50 by each micro lens of the micro lens array 472. Focused.
  • the spot size of each beam spot BS can be reduced to a desired size (for example, lO ⁇ mX lO ⁇ m). It is possible to perform high-definition exposure by preventing deterioration of characteristics.
  • the exposure area 468 is tilted because the DMD 50 is tilted in order to eliminate gaps between pixels.
  • the aperture array can shape the beam so that the spot size on the exposed surface 56 is constant. At the same time, by passing through an aperture array provided corresponding to each pixel, crosstalk between adjacent pixels can be prevented.
  • the pattern forming method of the present invention may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light quantity distribution correcting optical system composed of a pair of combination lenses.
  • the light quantity distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to the optical axis is smaller on the exit side than on the entrance side.
  • the light amount distribution on the irradiated surface is corrected so as to be substantially uniform.
  • the light quantity distribution correcting optical system expands the light flux width hO of the incident light flux at the central portion with respect to the light having the same light flux width hO, hi on the incident side.
  • it acts to reduce the luminous flux width hi. That is, the width hlO of the emitted light beam in the central portion and the width hl l of the emitted light beam in the peripheral portion are set to satisfy hl l ⁇ hlO.
  • the ratio of the luminous flux width of the peripheral part to the luminous flux width of the central part on the exit side is “hllZhlO” force. ).
  • the central luminous flux which normally has a large light quantity distribution, can be utilized in the peripheral part where the quantity of light is insufficient, and the light utilization as a whole.
  • the light amount distribution on the irradiated surface is made substantially uniform without reducing the use efficiency.
  • the degree of uniformity is, for example, such that the unevenness in the amount of light within the effective area is within 30%, preferably within 20%.
  • Figure 24B shows the case where the total beam width HO on the incident side is “reduced” to the width H2 before being emitted (HO
  • the light quantity distribution correcting optical system has the same light flux width hO, hi on the incident side, and the light flux width hlO in the central portion is larger than that in the peripheral portion on the outgoing side. Conversely, the light flux width hi 1 at the peripheral part is made smaller than that at the central part. Considering the reduction rate of the luminous flux, the reduction rate for the incident light flux in the central portion is made smaller than that in the peripheral portion, and the reduction rate for the incident light flux in the peripheral portion is made larger than that in the central portion.
  • FIG. 24C shows a case where the entire light flux width H0 on the incident side is “expanded” to the width H3 and emitted (H0 and H3).
  • the light quantity distribution correcting optical system has the same light flux width h0, hi on the incident side, and the light flux width hlO in the central portion is larger than that in the peripheral portion on the outgoing side.
  • the light flux width hi 1 at the peripheral part is made smaller than that at the central part.
  • the light quantity distribution correcting optical system changes the light flux width at each emission position, and outputs the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to the optical axis Z1 compared to the incident side. Since the emission side is smaller, the light having the same luminous flux width on the incident side has a larger luminous flux width in the central part than in the peripheral part on the outgoing side, and the luminous flux width in the peripheral part is Smaller than the center. As a result, the light beam in the central part can be utilized to the peripheral part, and a light beam cross-section with a substantially uniform light quantity distribution can be formed without reducing the light use efficiency of the entire optical system.
  • lens data is shown in the case where the light amount distribution in the cross section of the emitted light beam is a Gaussian distribution, as in the case where the light irradiation means is a laser array light source.
  • the light intensity distribution of the emitted light beam from the optical fino becomes a Gaussian distribution.
  • the pattern forming method of the present invention can be applied to such a case. Also applicable to cases where the core diameter is close to the optical axis by reducing the core diameter of the multimode optical fiber and approaching the configuration of the single mode optical fiber, etc. It is.
  • Table 1 below shows basic lens data.
  • a pair of combination lenses is composed of two rotationally symmetric aspherical lenses. If the light incident side surface of the first lens arranged on the light incident side is the first surface and the light output side surface is the second surface, the first surface is aspherical. In addition, when the surface on the light incident side of the second lens disposed on the light emitting side is the third surface and the surface on the light emitting side is the fourth surface, the fourth surface is aspherical.
  • the unit of the surface distance di value is millimeter (mm).
  • Refractive index Ni indicates the value of the refractive index with respect to the wavelength of 405 nm of the optical element having the i-th surface.
  • Table 2 below shows the aspherical data for the first and fourth surfaces.
  • each coefficient is defined as follows.
  • E indicates that the next numerical value is an exponent that has a base of 10
  • the numerical force E expressed by an exponential function with the base of 10 Number before " To be multiplied. For example, “1. OE—02” indicates “1. 0 X 10 _2 ”.
  • FIG. 26 shows the light amount distribution of the illumination light obtained by the pair of combination lenses shown in Table 1 and Table 2.
  • the horizontal axis indicates coordinates from the optical axis, and the vertical axis indicates the light amount ratio (%).
  • Fig. 25 shows the light intensity distribution (Gaussian distribution) of illumination light when correction is applied.
  • the light amount distribution correction optical system corrects the light amount distribution, which is substantially uniform as compared with the case where the correction is not performed. As a result, it is possible to perform uniform exposure with uniform laser light without reducing the light utilization efficiency.
  • the developing step is a step of exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region to form a permanent pattern.
  • the method for removing the uncured region can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a method of removing using a developer.
  • the developer may be appropriately selected according to the purpose without any particular limitation.
  • an alkali metal or alkaline earth metal hydroxide or carbonate, bicarbonate, aqueous ammonia Preferred examples include aqueous solutions of quaternary ammonium salts. Among these, an aqueous sodium carbonate solution is particularly preferable.
  • the developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, Triethanolamine, etc.) and organic solvents (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination to accelerate development.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or an organic solvent alone.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer having a permanent pattern formed after the developing step.
  • the curing treatment can be appropriately selected depending on the purpose without any particular limitation. For example, a full exposure process, a full heat treatment, and the like are preferable.
  • Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. By this entire surface exposure, curing of the resin in the pattern forming material for forming the photosensitive layer is promoted, and the surface of the permanent pattern is cured.
  • the apparatus for performing the entire surface exposure can be appropriately selected according to the purpose without any particular limitation.
  • a UV exposure machine such as an ultra-high pressure mercury lamp is preferably used.
  • Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
  • the heating temperature for the entire surface heating is 120 to 250, preferably 120 to 200 ° C. If the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment. If the heating temperature exceeds 250 ° C, the resin in the pattern forming material is decomposed, resulting in weak and brittle film quality. May be.
  • the heating time for the entire surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
  • the apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
  • the substrate is a printed wiring board such as a multilayer wiring board
  • the permanent pattern of the present invention is formed on the printed wiring board, and soldering may be performed as follows. it can.
  • the hardened layer which is the permanent pattern is formed by the developing step, and the metal layer is exposed on the surface of the printed wiring board.
  • Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, semiconductors and parts are mounted on the soldered parts.
  • the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film). The conduction between the electrodes is prevented.
  • the permanent pattern forming method of the present invention it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
  • the permanent pattern formed by the permanent pattern forming method is the protective film, the interlayer insulating film, and the solder resist pattern, it is possible to protect the wiring from external impact and bending, especially.
  • the interlayer insulating film for example, it is useful for high-density mounting of semiconductors and components on a multilayer wiring board, a build-up wiring board, and the like.
  • the permanent pattern forming method of the present invention can efficiently form a permanent pattern with high definition by suppressing distortion of an image formed on the photosensitive layer. It can be suitably used for the formation of various patterns that require light, and can be particularly suitably used for the formation of high-definition permanent patterns.
  • a permanent pattern such as a solder resist
  • a highly transparent substance is used as a support, and the support, the light-sensitive layer
  • a pattern forming material that is highly sensitive has a good resist surface shape, can prevent curling, and can form a higher definition pattern
  • a pattern forming apparatus provided with the pattern forming material and a permanent pattern forming method using the pattern forming material can be provided.
  • a photosensitive composition (solution) was prepared based on the following composition.
  • the barium sulfate dispersion is composed of 30 parts by weight of barium sulfate (manufactured by Zhigaku Co., Ltd., ⁇ 30), 34.29 parts by weight of the above-mentioned PCR-1157H diethylene glycol monomethyl ether acetate 61.2 mass% solution, methyl
  • a motor mill ⁇ ⁇ ⁇ ⁇ -200 manufactured by Eiger
  • the obtained photosensitive composition solution was applied to a PET (polyethylene terephthalate) film having a thickness of 16 m, a width of 300 mm, and a length of 200 m as the support with a bar coater, and dried at 80 ° C with hot air circulation It was dried in the machine to form a photosensitive layer having a thickness of 30 m. Then, a polypropylene film having a thickness of 20 ⁇ m, a width of 310 mm, and a length of 210 m was laminated as a protective film on the photosensitive layer by lamination to prepare the pattern forming material. Next, the obtained pattern forming material was wound up with a winder to produce a pattern forming material roll.
  • a PET polyethylene terephthalate
  • the total thickness of the obtained pattern forming material support, photosensitive layer and protective film was 66 m.
  • the thicknesses of the support, the photosensitive layer, and the protective film were measured with a contact digital displacement meter (ID-F150, manufactured by Mitutoyo Corporation).
  • the obtained pattern forming material roll is slit with a coaxial slitter and wound into a cylindrical core made of ABS resin having a length of 300 mm and an inner diameter of 76 mm.
  • a forming material was prepared. Wrapped in a black polyethylene cylindrical bag (thickness: 80 m, water vapor transmission rate: 25 gZm 2 '24hr or less) in the pattern forming material obtained, rolled into a roll shape by pushing a polypropylene push into both ends of the winding core A product was made. Two rolls of each package were packed and packed in a cardboard box.
  • a double-sided copper-clad laminate (with no through holes, size: 20 cm x 20 cm, copper thickness 18 ⁇ m, insulation layer thickness 100 ⁇ m) is used as the base material. Prepared by treatment. An auto-cut laminator (manufactured by Hakuto Co., Ltd.) was peeled off on one side of the copper-clad laminate so that the photosensitive layer of the pattern-forming material roll was in contact with the copper-clad laminate. Mach630up), and cut with 190mm length.
  • the temporary laminate in which the pattern forming material is placed on the copper-clad laminate is then pressure-bonded using a vacuum laminator (manufactured by Nichigo Morton, VP130), and the copper-clad laminate, A laminate in which the photosensitive layer and the polyethylene terephthalate film (support) were laminated in this order was prepared.
  • Temporary mounting conditions using an auto-cut laminator are speed lmZ minutes, temporary mounting temperature 50 ° C, temporary mounting time 4 seconds, cylinder pressure 0.2 MPa, cylinder temperature at room temperature, and pressure bonding conditions with a vacuum laminator are vacuum drawing. The time was 40 seconds, the pressure was 70 ° C, the pressure was 0.2 MPa, and the pressure was 10 seconds.
  • Holes with different diameters are formed from the polyethylene terephthalate film (support) side to the photosensitive layer in the prepared laminate using laser beam having a wavelength of 405 nm using a pattern forming apparatus described below. Irradiation was performed so that a pattern was obtained, and a portion of the photosensitive layer was cured.
  • a pattern forming apparatus having optical systems 480 and 482 for forming an image is used.
  • the strain on the exit surface was measured.
  • the results are shown in FIG. In FIG. 14, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm.
  • the X direction and the y direction shown in the figure are the two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction.
  • 15A and 15B show the height position displacement of the reflection surface of the micromirror 62 along the X direction and the y direction, respectively.
  • FIGS. 16A and 16B show the front and side shapes of the entire microlens array 55 in detail.
  • the dimensions of each part of the microlens array 55 are also entered, and their unit is mm.
  • the 1024 ⁇ 256 micromirrors 62 of the DMD50 are driven, and the microlens array 55 is correspondingly arranged in a horizontal direction with 1024 microarrays.
  • the lens 55a is configured by arranging 256 rows in the vertical direction.
  • FIG. 16A the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and by k in the vertical direction.
  • FIGS. 17A and 17B show a front shape and a side shape of one microlens 55a in the microlens array 55, respectively.
  • FIG. 17A also shows the contour lines of microlens 55a.
  • the end surface on the light exit side of each microlens 55a has an aspherical shape that corrects aberration due to distortion of the reflection surface of the microphone mirror 62.
  • the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively. That is, when comparing the parallel cross section in the X direction and the parallel cross section in the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. I understand that.
  • the value z represents the evaluation position in the focus direction of the microlens 55a as a distance from the beam exit surface of the microlens 55a.
  • the surface shape of the microlens 55a used in the simulation is calculated by the following calculation formula.
  • X is the lens optical axis O in the X direction.
  • Y means the distance of the lens optical axis O force in the y direction.
  • the aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is Each of the apertures 59a is arranged so that only light that has passed through the corresponding microlens 55a is incident thereon. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.
  • the laminate strength was also peeled off from the polyethylene terephthalate film (support), and a 1% by weight sodium carbonate aqueous solution was added as an alkaline developer to the entire surface of the photosensitive layer on the copper clad laminate. Used and shower developed for 60 seconds at 30 ° C to dissolve and remove uncured areas. Thereafter, it was washed with water and dried to form a permanent pattern.
  • the entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 30 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.
  • the printed wiring board on which the permanent pattern had been formed was subjected to gold plating according to a conventional method and then subjected to a water-soluble flux treatment. Next, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JIS K-5400. As a result, the pencil hardness was 5H or more. As a result of visual observation, peeling of the cured film in the permanent pattern, blistering, and discoloration were observed.
  • the laminated body was evaluated for sensitivity, resolution, resist surface shape, and curling property as follows.
  • the photosensitive layer in the laminate from the polyethylene terephthalate film (support) side, using the following exposure apparatus, different optical energy from 0. ImiZcm 2 to LOOmjZc m 2 with 2 1/2 times the interval Exposure was performed by irradiating light, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the laminate strength was also peeled off from the polyethylene terephthalate film (support), and an aqueous sodium carbonate solution (30 ° C, 1 mass) was applied to the entire surface of the photosensitive layer on the copper clad laminate. %) Was used for shower development at 30 ° C. for 60 seconds, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured.
  • a sensitivity curve was obtained by plotting the relationship between the light irradiation amount and the thickness of the hardened layer.
  • the sensitivity curve force obtained in this way was the amount of light energy when the thickness of the cured region was the same as that before exposure, and was the amount of light energy required to cure the photosensitive layer.
  • Table 4 shows the amount of light energy (exposure sensitivity) required to cure the photosensitive layer.
  • the surface of the obtained printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. The smaller the numerical value, the better the resolution.
  • the pattern surface (50 m ⁇ 50 m) formed in the above was photographed with a scanning electron microscope (SEM), and the shape of the formed resist surface was evaluated according to the following evaluation criteria. It was. The results are shown in Table 4.
  • ⁇ ⁇ 'No defect or force with 1 to 5 defects There was no effect on the shape of the pattern formed.
  • ⁇ ⁇ 6- Force with LO defects
  • C ′ ⁇ There are 11 to 20 defects, and the defects cause a shape abnormality on the end face of the pattern.
  • the laminate was exposed with the amount of light energy necessary to cure the photosensitive layer determined by sensitivity measurement, and further heat-treated at 140 ° C. for 60 minutes.
  • the laminated body before and after heating was placed on a flat desk, and the warpage of the edge was measured with a ruler.
  • the curl property was evaluated by the difference in warpage after heating and before heating.
  • Example 1 the thickness of the support was 16 m, the thickness of the photosensitive layer was 25 m, the thickness of the protective film was 12 m, and the total thickness was 53 m. A turn forming material and a laminate were manufactured.
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • Example 1 except that the thickness of the support was 16 m, the thickness of the photosensitive layer was 60 m, the thickness of the protective film (polyethylene film) was 25 ⁇ m, and the total thickness was 101 ⁇ m. In the same manner as above, a pattern forming material and a laminate were produced.
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • Example 1 a pattern forming material and a laminate were prepared in the same manner as in Example 1, except that the support was replaced with a 16 ⁇ m thick PET (polyethylene terephthalate) film (Mitsubishi Polyester, R340G). The body was manufactured.
  • PET polyethylene terephthalate
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • Example 1 except that the support was replaced with a 16 ⁇ m thick PET (polyethylene terephthalate) film (16FB50, manufactured by Toray Industries, Inc.), the pattern forming material and the laminate were prepared in the same manner as in Example 1. Manufactured.
  • PET polyethylene terephthalate
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • a photosensitive composition (solution) was prepared based on the following composition.
  • the acrylic resin added a polymerizable compound (cyclomer A200; manufactured by Daicel Chemical Industries, Ltd.) having an alicyclic epoxy in the molecule to a copolymer of methacrylic acid and methyl methacrylate.
  • Example 1 the photosensitive composition of Example 6 was used, and the thickness of the support having PET (R310) force of 19 ⁇ m was obtained.
  • Example 1 except that the layer thickness was 15 ⁇ m, the protective film made of polypropylene film (E-501, E-501) was 12 m, and the total thickness was 46 m. Then, a pattern forming material and a laminate were manufactured.
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • Example 6 the support is 70 ⁇ m thick PET (polyethylene terephthalate) film (Fuji Photo Film Co., Ltd.), the photosensitive layer is 20 ⁇ m thick, and the protective film is a polyethylene film (Tamapoly Co., Ltd.).
  • PET polyethylene terephthalate
  • the protective film is a polyethylene film (Tamapoly Co., Ltd.).
  • a pattern forming material and a laminate were produced in the same manner as in Example 6 except that the thickness of the film was 23 ⁇ m and the total thickness was 113 ⁇ m.
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • Example 1 the thickness of the support is 12 m, the thickness of the photosensitive layer is 5 m, the thickness of the protective film (polypropylene film) is 12 m, and the total thickness is 29 ⁇ m. Similarly, a pattern forming material and a laminate were manufactured. The followability to the pattern was poor during lamination.
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • Example 1 the thickness of the support was 150 m, the thickness of the photosensitive layer was 50 m, the thickness of the protective film (polyethylene film) was 25 ⁇ m, and the total thickness was 225 ⁇ m.
  • the thickness of the support was 150 m
  • the thickness of the photosensitive layer was 50 m
  • the thickness of the protective film polyethylene film
  • the total thickness was 225 ⁇ m.
  • a pattern forming material and a laminate were produced. When the total thickness was increased to a roll shape, winding slip occurred.
  • the protective film was peeled off and laminated. The laminating property was poor and bubbles were generated.
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • Example 1 the support was changed to a 16 ⁇ m thick PET (polyethylene terephthalate) film (G2) manufactured by Teijin DuPont, and the photosensitive layer had a thickness of 170 m and a protective film of 20 ⁇ m thick polypropylene film.
  • a pattern forming material and a laminate were manufactured in the same manner as in Example 1 except that the total thickness was 206 ⁇ m. When the total thickness was made thicker, slippage occurred. Also, the protective film was peeled off and laminated, and the 1S laminating property was poor and bubbles were generated.
  • Example 2 About the said support body, it carried out similarly to Example 1, and measured the total light transmittance and the haze value.
  • the laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, resist surface shape, and curling property.
  • the pattern forming material of the present invention has a good resist surface shape and a higher Since fine patterns can be formed, it is widely used for forming permanent patterns such as printed wiring plates, color filters, pillars, ribs, spacers, partition walls, and other display members, holograms, micromachines, pulls, etc. It can be used suitably for the permanent pattern formation method of the present invention.
  • the permanent pattern forming method of the present invention uses the pattern forming material of the present invention, a printed wiring plate, a color filter, a pillar material, a rib material, a spacer, a partition member such as a partition, a hologram, a micromachine, It can be suitably used for producing a permanent pattern such as a proof, and can be suitably used particularly for forming a high-definition wiring pattern.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

L'invention concerne un matériau pour formation de motif grâce auquel il est possible de former un motif très sensible et très fin, en utilisant une substance hautement transparente en tant que support et en spécifiant l'épaisseur totale de manière à former un motif indélébile tel qu'une photorésine pour brasure. Le matériau pour formation de motif comprend au moins un support et, sur ce support, une couche photosensible et un film protecteur. La couche photosensible inclut au moins un liant, un composé polymère, un initiateur de photopolymérisation et un agent de réticulation thermique. L'épaisseur totale du support, de la couche photosensible et du film protecteur peut varier de 30 à 200 µm et, lors de l'exposition et du développement de la couche photosensible, une énergie lumineuse minimum de 0,1 à 200 mJ/cm2 est utilisée pour l'exposition, une épaisseur d'une partie de la couche photosensible exposée demeurant inchangée après l'exposition et le développement.
PCT/JP2006/300233 2005-01-17 2006-01-11 Materiau pour formation de motif, appareil de formation de motif et procede de formation de motif indelebile Ceased WO2006075633A1 (fr)

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JP (1) JPWO2006075633A1 (fr)
KR (1) KR20070095947A (fr)
CN (1) CN101107565A (fr)
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WO (1) WO2006075633A1 (fr)

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WO2008026397A1 (fr) * 2006-08-31 2008-03-06 Jsr Corporation Composition de résine isolante sensible aux radiations, article durci et dispositif électronique
WO2023286724A1 (fr) * 2021-07-12 2023-01-19 株式会社ニコン Appareil d'exposition

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KR101107003B1 (ko) 2009-04-09 2012-01-25 제일모직주식회사 이미지 센서 및 그 제조 방법
KR101201831B1 (ko) 2009-07-09 2012-11-15 제일모직주식회사 유-무기 하이브리드　조성물 및 이미지 센서
JP7011386B2 (ja) * 2016-11-16 2022-01-26 キヤノン株式会社 密着層形成組成物および物品製造方法

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WO2008026397A1 (fr) * 2006-08-31 2008-03-06 Jsr Corporation Composition de résine isolante sensible aux radiations, article durci et dispositif électronique
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JPWO2023286724A1 (fr) * 2021-07-12 2023-01-19

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KR20070095947A (ko) 2007-10-01
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JPWO2006075633A1 (ja) 2008-06-12

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