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WO2006051761A1 - Composition de formation de motif et matériau de formation de motif, et appareil de formation de motif et procédé de formation de motif - Google Patents

Composition de formation de motif et matériau de formation de motif, et appareil de formation de motif et procédé de formation de motif Download PDF

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Publication number
WO2006051761A1
WO2006051761A1 PCT/JP2005/020391 JP2005020391W WO2006051761A1 WO 2006051761 A1 WO2006051761 A1 WO 2006051761A1 JP 2005020391 W JP2005020391 W JP 2005020391W WO 2006051761 A1 WO2006051761 A1 WO 2006051761A1
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WIPO (PCT)
Prior art keywords
pattern forming
group
light
pattern
compound
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/JP2005/020391
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English (en)
Japanese (ja)
Inventor
Kousaku Yoshimura
Morimasa Sato
Hirotaka Matsumoto
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
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Filing date
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Application filed by Fujifilm Corp, Fuji Photo Film Co Ltd filed Critical Fujifilm Corp
Publication of WO2006051761A1 publication Critical patent/WO2006051761A1/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
    • G03F7/028—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

Definitions

  • the present invention relates to a pattern forming material suitable for dry film resist (DFR) and the like, a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material.
  • DFR dry film resist
  • a pattern forming material is used in which a photosensitive layer is formed by applying and drying a pattern forming composition on a support.
  • 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 developed to form a pattern, and then an etching process or the like is performed to form the permanent pattern.
  • the pattern forming material is a compound having a phenolic hydroxyl group, an aromatic sensation, a heterocyclic ring, an imino group or the like in the pattern forming composition for the purpose of improving storage stability or improving the resolution.
  • the proposal which added the polymerization inhibitor of this is made (refer patent documents 1-4). However, there was a problem that the sensitivity was lowered by adding a polymerization inhibitor.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-268211
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-29399
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-4527
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-4528
  • Patent Document 5 JP 2002-220409 A
  • the present invention has been made in view of the current situation, and it is an object of the present invention to solve the conventional problems and achieve the following objects. That is, according to the present invention, the sensitivity and resolution are good, a high-definition pattern is obtained, the adhesiveness with a substrate such as a printed wiring board is excellent, and the pattern shape after pattern formation is good. It is an object of the present invention to provide a pattern forming composition and a pattern forming material, and a pattern forming apparatus and a pattern forming method using the pattern forming material.
  • the content of the chain transfer compound having a plurality of substituents capable of chain transfer is 100 to 50,000 parts by mass when the content of the polymerization inhibitor is 100 parts by mass. 4>, the pattern forming composition according to any one of the above. ⁇ 6> The pattern formation according to any one of ⁇ 1> to ⁇ 5>, wherein the polymerization inhibitor is a compound having at least one selected from an aromatic ring, a heterocyclic ring, an imino group, and a phenolic hydroxyl group power Composition.
  • the polymerization inhibitor is selected from a compound having at least two phenolic hydroxyl groups, a compound having an aromatic ring substituted with an imino group, a compound having a heterocyclic ring substituted with an imino group, and a hindered amine compound.
  • ⁇ 8> The pattern forming composition according to any one of ⁇ 1> to ⁇ 7>, wherein the polymerization inhibitor is at least one selected from catechol, phenothiazine, phenoxazine, hindered amine, and derivatives thereof. is there.
  • ⁇ 9> The pattern forming composition according to any one of ⁇ 1> to ⁇ 8>, wherein the polymerization inhibitor is at least one selected from phenothiazine and a phenothiazine derivative.
  • ⁇ 12> The pattern forming composition according to any one of ⁇ 1> to 11 described above, wherein the photosensitive layer contains a sensitizer.
  • ⁇ 15> The pattern forming composition according to any one of the above ⁇ 12> to ⁇ 14>, wherein the sensitizer is at least one selected from ataridons, atalidines, and coumarins.
  • Binder strength Any one of the above-mentioned options 1> Karaku 15 having an acidic group The pattern forming composition.
  • ⁇ 18> The pattern forming composition according to any one of ⁇ 1> to ⁇ 17>, wherein the binder contains a copolymer of at least one of styrene and a styrene derivative.
  • ⁇ 20> The pattern forming composition according to any one of ⁇ 1> to 19, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.
  • the polymerizable compound has a bisphenol skeleton 1> Karaku 20>
  • V the composition for pattern formation according to any one of the above.
  • ⁇ 23> The pattern forming composition according to any one of ⁇ 1> to 22, wherein the photosensitive layer contains 10 to 90% by mass of a noinder and 5 to 90% by mass of a polymerizable compound.
  • a pattern comprising: a support; and a photosensitive layer obtained by laminating the pattern forming composition according to any one of 1) to 23) on the support. It is a forming material.
  • ⁇ 25> The pattern forming material according to any one of ⁇ 24>, wherein the photosensitive layer has a thickness of 1 to 100 / ⁇ .
  • V is a pattern forming material described in any of the above.
  • ⁇ 27> The pattern forming material according to any one of ⁇ 24> to ⁇ 26>, wherein the support is a long shape.
  • Pattern forming material force The pattern forming material according to any one of ⁇ 24> to ⁇ 27>, which is long and wound in a roll shape.
  • ⁇ 29> The pattern forming material according to any one of ⁇ 24> to ⁇ 28>, wherein the pattern forming material has a protective film on the photosensitive layer.
  • Pattern formation characterized by comprising at least light irradiation means capable of irradiating light and light modulation means for modulating light from the light irradiation means and exposing the photosensitive layer in the pattern forming material.
  • the light irradiation means irradiates light toward the light modulation means.
  • the light modulation means modulates light received from the light irradiation means.
  • the light modulated by the light modulating means is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • 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 control generated by the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the pattern forming apparatus according to ⁇ 30> wherein the pattern is modulated according to a signal.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
  • the light modulation means includes n pixel parts, and any less than n of the pixel parts arranged continuously from the n pixel parts.
  • the pattern forming apparatus according to any one of ⁇ 30> to ⁇ 31>, which can be controlled according to pattern information to be formed.
  • an arbitrary less than n pixel parts arranged continuously from n pixel parts in the light modulation unit are controlled according to pattern information As a result, the light of the light irradiation means power is modulated at high speed.
  • ⁇ 33> The pattern forming apparatus according to any one of ⁇ 30> to ⁇ 32>, wherein the light modulation unit is a spatial light modulation element.
  • the spatial light modulator is a digital micromirror device (DMD).
  • DMD digital micromirror device
  • ⁇ 35> The pattern forming apparatus according to any one of the above ⁇ 32> to ⁇ 34>, wherein the pixel part is a micromirror.
  • ⁇ 36> The pattern forming apparatus according to any one of the above ⁇ 30> and ⁇ 35>, wherein the light irradiation means can synthesize and irradiate two or more lights.
  • the light irradiating means 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 subsequently developed, an extremely fine pattern is formed.
  • the light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system for condensing and coupling the laser beams irradiated with the plurality of laser forces respectively to the multimode optical fiber.
  • the pattern forming apparatus according to any one of the above items 30> to 36>.
  • the light irradiating means may collect the laser light emitted from each of 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. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • the method includes at least exposing the photosensitive layer of the pattern forming material according to any one of ⁇ 1> to ⁇ 29>.
  • exposure is performed on the pattern forming material. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • the exposure generates a control signal based on the pattern information to be formed, and the control signal
  • the pattern forming method according to any one of ⁇ 38> to ⁇ 40>, wherein the pattern forming method is performed using light modulated in accordance with a signal.
  • a control signal is generated based on the pattern formation information to be formed, and light is modulated in accordance with the control signal.
  • the pattern forming method according to any one of the above.
  • the light is modulated by the light modulation means, and then passes through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means are arranged.
  • the pattern forming method according to the above item 42> In the pattern forming method described in the above item 43>, 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. The As a result, distortion of an image formed on the pattern forming material is suppressed, and exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine pattern is formed.
  • ⁇ 45> The pattern forming method according to any one of the above ⁇ 38> and ⁇ 44>, wherein the exposure is performed through an aperture array.
  • the extinction ratio is improved by performing exposure through the aperture array.
  • the exposure is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • ⁇ 46> The exposure is performed while the exposure light and the photosensitive layer are relatively moved.
  • Karaku 45> The pattern forming method according to any one of the above.
  • the exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • ⁇ 48> The pattern forming method according to any one of ⁇ 38> to ⁇ 47>, wherein the photosensitive layer is developed after the exposure.
  • a high-definition pattern is formed by developing the photosensitive layer after the exposure.
  • ⁇ 50> The pattern formation method according to ⁇ 49>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.
  • a high-definition pattern with good sensitivity and resolution is obtained, and the force is excellent in adhesion to a substrate such as a printed wiring board, and the pattern shape after pattern formation is good.
  • a pattern forming apparatus and a pattern forming method using the pattern forming material are provided.
  • the high-definition pattern referred to in the present invention means that a pattern having a rectangular cross-section with an intended width is obtained at an intended location.
  • 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 shows the exposure beam arrangement and scanning lines when the DMD is not inclined. It is an example of the top view shown in comparison.
  • FIG. 3B 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 inclined and arranged.
  • 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 a diagram showing the distortion of the reflection surface of the micromirrors constituting the DMD with contour lines. It is an example.
  • FIG. 15A is an example of a graph showing distortion of the reflecting surface of the micromirror in two diagonal directions of the mirror.
  • 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 shows the same simulation results as FIG. 20A, but at different positions. It is an example of a figure.
  • FIG. 20C is an example of a diagram illustrating the simulation result similar to FIG. 20A at another position.
  • 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 composition of the present invention contains a chain transfer compound having a plurality of substituents capable of chain transfer, a polymerization inhibitor, a binder, a polymerizable compound, and a photopolymerization initiator, and other components as necessary. Can be added.
  • Chain transfer compound having a plurality of substituents capable of single chain transfer
  • the chain transfer compound having a plurality of substituents capable of chain transfer can be appropriately selected according to the purpose without particular limitation.
  • the chain transferable substituent refers to a substituent capable of easily causing a chain transfer reaction.
  • the chain transfer reaction is a polymerization by a chain reaction and is activated by a reaction with a growing species. It is a reaction where the sex point is transferred to the substance present in the system and the polymerization starts again.
  • the chain transferable substituent is not particularly limited as long as it has the above-described action, for example, an aralkyl group such as an aryl group or a benzyl group, a mercapto group, an active methylene group, a methine group, Examples thereof include a disulfide group and a sulfide group.
  • chain transfer compounds having a plurality of chain transferable substituents chain transfer compounds having a mercapto group as a chain transferable substituent are preferred because of their high reactivity.
  • a chain transfer compound having a plurality of mercapto groups By using a chain transfer compound having a plurality of mercapto groups, a more sensitive pattern forming composition can be obtained.
  • the chain transfer compound having a plurality of mercapto groups is selected from, for example, aliphatic mercabtans represented by the following general formula (1) or general formula (2), aromatic mercabtans, and heterocyclic rings having mercapto groups. Examples include compounds having a plurality of one or more substituents.
  • R represents a divalent or higher organic linking group
  • n represents an integer of 2 or higher.
  • R represents a divalent or higher valent organic linking group
  • R is an aliphatic group
  • n represents an integer of 2 or more.
  • the chain transfer compound having a plurality of mercapto groups has an ester bond or an aliphatic group as a partial structure of R or R in the general formula (1) and the general formula (2).
  • chain transfer compound having a plurality of mercapto groups various chain transfer compounds without particular limitation can be used.
  • a chain transfer compound having two mercapto groups in one molecule examples include a chain transfer compound having 3 mercapto groups, a chain transfer compound having 4 or more mercapto groups in one molecule, and the like.
  • Examples of the chain transfer compound having two mercapto groups in one molecule include 1, 2 Ethanedithiol, 1,3 Propanedithiol, 1,4 Butanedithiol, 2,3 Butanedithiol, 1,5 Pentanedithiol, 1,6 Hexanedithiol, 1,8 Octanedithiol, 1,9-nonanedithiol, 2, 3 Dimercapto 1 propanol, Dithioerythritol, 2, 3 Dimercaptosuccinic acid, 1, 2 Benzene dithiol, 1, 2 Benzene dimethane thiol, 1, 3 Benzene dithiol, 1, 3 Benzene dimethane thiol, 1 , 4 Benzenedimethanethiol, 3, 4 Dimercaptotoluene, 4 Chloro-1, 3 Benzenedithionole, 2, 4, 6 Trimethinole 1,3 Benzenedimethanethanol, 4, 4 'Thiod
  • Examples of the chain transfer compound having three mercapto groups in one molecule include 1, 2, 6 hexanetriol trithioglycolate, 1, 3, 5 trithiocyanouric acid, 2, 4, 6-trimercapto 1, 3, 5 triazine, trimethylol propane tris (3-mercapto-pionate), trimethylol propane tris mercaptoacetate, and the like.
  • Examples of the compound having four or more mercapto groups in one molecule include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakismercaptoacetate, dipentaerythritol hexakis (3-mercaptopropionate). Pionate) and dipentaerythritol hexakismercaptoacetate.
  • the organic linking group may have a polymer structure, and examples thereof include a compound represented by the following structural formula (5).
  • n and n are integers, and Z represents any residue.
  • esters of polyhydric alcohols and carboxylic acids having mercapto groups are preferred.
  • the ester of the polyhydric alcohol and the carboxylic acid having a mercapto group is not particularly limited.
  • polyhydric alcohol examples include sugars such as glucose and fructose, and polymers having a hydroxyl group such as polybutanol and polybutyral.
  • the number of substituents capable of chain transfer in the chain transfer compound is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
  • the pattern forming composition is more sensitive than when a chain transfer compound having 2 or 3 chain transferable substituents is used. You can get things.
  • the content of the chain transfer compound having a plurality of chain transferable substituents is preferably 0.01 to 5% by mass when the solid content of the pattern forming composition is 100% by mass. 0.1 to 1% by mass is more preferred.
  • the content of the chain transfer compound having a plurality of substituents capable of chain transfer is less than 0.01% by mass, improvement in sensitivity may not be observed. If the content exceeds 5% by mass, after development, The chain transfer compound may remain as a residue on the substrate.
  • the polymerization inhibitor can be appropriately selected according to the purpose without particular limitation.
  • the polymerization inhibitor provides hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to the radical component of polymerization initiation generated from the photopolymerization initiator by the exposure. ) And the like to deactivate polymerization initiation radicals and inhibit polymerization initiation.
  • Examples of the polymerization inhibitor include a compound having a lone electron pair (for example, a compound having oxygen, nitrogen, sulfur, metal, etc.), a compound having a pi electron (for example, an aromatic compound), etc.
  • a compound having a phenolic hydroxyl group, a compound having an imino group, a compound having a nitro group, a compound having a nitroso group, a compound having an aromatic ring, a compound having a heterocyclic ring, a metal atom And the like including complexes with organic compounds.
  • a compound having a phenolic hydroxyl group, a compound having an imino group, a compound having an aromatic ring, and a compound having a heterocyclic ring are preferable.
  • the compound having a phenolic hydroxyl group is not particularly limited, and can be appropriately selected according to the purpose.
  • a compound having at least two phenolic hydroxyl groups is preferable.
  • at least two phenolic hydroxyl groups may be substituted with different aromatic rings in the same molecule, which may be substituted with the same aromatic ring.
  • the compound having at least two phenolic hydroxyl groups is more preferably a compound represented by the following structural formula (6), for example.
  • Z represents a substituent
  • m represents an integer of 2 or more
  • n represents an integer of 0 or more.
  • Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, and a halogen atom.
  • alkoxy carbo group having 30 or less carbon atoms for example, methoxy carbo ol group, ethoxy carbo ol group, benzyloxy carbo ol group
  • carbon number 30 or less aryloxycarbonyl groups for example, phenyl carbonyl groups
  • alkyl sulfo-laminocarbo groups having 30 or less carbon atoms for example, methyl sulfo-laminocarbol groups, octyl sulfo-laminocarbo yl groups
  • aryl sulfo -Laminocarbo group for example, toluenesulfo-luaminocar
  • an acyl acylsulfol group having 30 or less carbon atoms for example, benzoylaminosulfol group, acetylaminosulfo
  • Examples of the compound represented by the structural formula (6) include alkyl catechol (for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatenole, 4-methinole teconole, 2 ethinole Force Teconole, 3 Ethinore Force Teconole, 4 Ethylcatechol, 2 Propylcatechol, 3 Propylcatechol, 4 Propyl Power Teconole, 2— n-Butinore Force Teconole, 3— n-Butinore Force Teconole, 4 n-Butinorecate Conole, 2 tert —Butinore force Teconole, 3 tert-Butinole force Teconole, 4 tert-Butylcatechol, 3,5-Ditert-Butylcatechol, etc., Alkylresorcinol (eg 2-Methylresorcinol, 4-Methylresorcinol, 1,
  • the compound having a phenolic hydroxyl group is also preferably a compound in which aromatic rings having at least one phenolic hydroxyl group are linked to each other by a divalent linking group.
  • Examples of the divalent linking group include groups having 1 to 30 carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, SO, SO and the like.
  • the sulfur atom, oxygen atom, SO, And SO may be directly bonded.
  • Examples of the substituent on which the carbon atom and oxygen atom may have a substituent include Z in the structural formula (6) described above.
  • the aromatic ring may have a substituent.
  • substituents include Z in the structural formula (6) described above.
  • the compound having a phenolic hydroxyl group examples include bisphenol A, bisphenol S, bisphenol M, a known bisphenol compound used as a color developer for thermal paper, and JP2003-305945A. And hindered phenolic compounds used as acid-proofing agents. Also included are monophenolic compounds having substituents such as 4-methoxyphenol, 4-methoxy-2-hydroxybenzophenone, 13-naphthol, 2,6-ditert-butyl-4-cresol, methyl salicylate, and jetylaminophenol. It is done.
  • Examples of commercially available compounds having a phenolic hydroxyl group include bisphenol compounds manufactured by Honshu Chemical Co., Ltd.
  • the compound having an imino group is not particularly limited and can be appropriately selected depending on the purpose.
  • a compound having a molecular weight of 50 or more is preferable, and a compound having a molecular weight of 70 or more is more preferable.
  • the compound having an imino group preferably has a cyclic structure substituted with an imino group.
  • the cyclic structure is more preferably one in which at least one of an aromatic ring and a heterocyclic ring is condensed, and a preferable aromatic ring is condensed.
  • the annular structure In the annular structure,
  • Specific examples of the compound having an imino group include phenothiazine, phenoxazine, dihydrophenazine, hydroquinoline, or a compound obtained by substituting these compounds with Z in the structural formula (6) described above. Can be mentioned.
  • a hindered amine derivative having a hindered amine as a part is preferable.
  • the hindered amine examples include hindered amines described in JP-A-2003-246138.
  • the compound having a nitro group or the compound having a nitroso group is not particularly limited and can be appropriately selected according to the purpose.
  • a molecular weight having a molecular weight of 50 or more is preferable. Is more preferably 70 or more.
  • the compound having a nitro group or the compound having a nitroso group include nitrobenzene, a chelate compound of nitroso compound and aluminum, and the like.
  • the compound having an aromatic ring can be appropriately selected depending on the purpose without any particular limitation.
  • the aromatic ring has a substituent having a lone electron pair (for example, an oxygen atom, a nitrogen atom).
  • substituent having a sulfur atom or the like include, for example, the above-described compound having a phenolic hydroxyl group, the above-described compound having an imino group, and a compound partially having an aniline skeleton (for example, methylene blue, crystal Violet).
  • the compound having a heterocyclic ring can be appropriately selected depending on the purpose without any particular limitation.
  • the heterocyclic ring includes an atom having a lone pair of electrons such as nitrogen, oxygen, and sulfur. What has is preferable.
  • Specific examples of the compound having a heterocyclic ring include pyridine and quinoline.
  • the compound having a metal atom can be appropriately selected depending on the purpose without any particular limitation.
  • the metal atom can be appropriately selected according to the purpose without any limitation as long as it is a metal atom having an affinity for a radical generated from the polymerization initiator, and examples thereof include copper, aluminum, and titanium. Can be mentioned.
  • compounds having at least two phenolic hydroxyl groups, compounds having an aromatic ring substituted with an imino group, and compounds having a heterocyclic ring substituted with an imino group are preferred.
  • Particularly preferred are compounds in which the imino group constitutes part of the cyclic structure, and hindered amine compounds.
  • catechol, phenothiazine, phenoxazine, hindered amine, or derivatives thereof are preferable.
  • the polymerization inhibitor is generally contained in a trace amount in a commercially available polymerizable compound, in the present invention, it is contained in the commercially available polymerizable compound from the viewpoint of improving the resolution.
  • the polymerization inhibitor described above is included. Therefore, the polymerization inhibitor is preferably a compound other than monophenolic compounds such as 4-methoxyphenol contained in the commercially available polymerizable compound for imparting stability.
  • the content of the polymerization inhibitor is preferably 0.005 to 0.5 mass% with respect to the polymerizable compound of the pattern forming composition. 0.02-0. 2% by weight is particularly preferred.
  • the resolution may decrease, and when it exceeds 0.5% by mass, the sensitivity to active energy rays may decrease.
  • the content of the polymerization inhibitor represents a content excluding monophenolic compounds such as 4-methoxyphenol contained in the commercially available polymerizable compound for imparting stability.
  • the content of the chain transfer compound having a plurality of substituents capable of chain transfer is preferably 100-50, 000 parts by mass when the content of the polymerization inhibitor is 100 parts by mass.
  • the power is more preferably 500 to 10000 mass%, and particularly preferably 500 to 5,000 mass%.
  • the cross section of the resulting pattern shape is a trapezoidal trapezoidal shape.
  • a high-definition pattern shape cannot be obtained, for example, the area of the bottom surface of the pattern is larger than the area of the top surface of the pattern, and if the amount is less than 100 parts by mass, the sensitivity improvement rate may be low.
  • the high-definition pattern referred to in the present invention indicates that a pattern having a rectangular cross section with an intended width can be obtained at an intended location.
  • Examples of the other components include a binder and a photopolymerization initiator.
  • the noinder is more preferably soluble in an alkaline liquid, preferably swellable in an alkaline liquid.
  • binder exhibiting swellability or solubility in an alkaline liquid
  • acidic Those having a group are preferred.
  • the acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyxenore group is preferable. .
  • binder having a carboxyl group examples include a vinyl copolymer having a carboxyl group, polyurethane resin, polyamic acid resin, and modified epoxy resin.
  • solubility in a coating solvent Viewpoints such as solubility in alkaline developer, suitability for synthesis, and ease of adjustment of film properties.
  • Vinyl copolymers having a carboxyl group are preferred. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.
  • the vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.
  • Examples of the butyl monomer having a carboxyl group include (meth) acrylic acid, belbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid.
  • (meth) acrylic acid is particularly preferred from the viewpoint of copolymerization cost and solubility.
  • monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
  • the other copolymerizable monomer is not particularly limited, and can be appropriately selected according to the purpose.
  • Examples of the (meth) acrylic acid esters include methyl (meth) acrylate and ethyl.
  • crotonic acid esters examples include butyl crotonic acid and hexyl crotonic acid. Etc.
  • Examples of the vinyl esters include vinyl acetate, vinyl propionate, butyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
  • maleic acid diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate, and the like.
  • Examples of the itaconic acid diesters include dimethyl itaconate, dimethyl itaconate, and dibutyl itaconate.
  • Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-Butylacrylic (meth) acrylamide, N-tert butyl (meth) acrylamide, N cyclohexyl (meth) acrylamide, N— (2-methoxyethyl) (meth) acrylamide, N, N dimethyl (meth) acrylamide, N, Examples thereof include N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) atalyloylmorpholine, diacetone acrylamide and the like.
  • styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropylino styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, Examples include dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (eg, tert-butyloxycarbonyl group), methyl benzoate, a-methylstyrene, etc. .
  • an acidic substance eg, tert-butyloxycarbonyl group
  • butyl ethers examples include methyl butyl ether, butyl benzene ether, hexyl butyl ether, methoxyethyl butyl ether, and the like.
  • Examples of a method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group. Specifically, a monomer having an isocyanate group and a hydroxyl group An addition reaction with a compound containing one or a compound having one primary or secondary amino group, a monomer having a hydroxyl group or a primary or secondary amino group The addition reaction of the monomer which has and a monoisocyanate is mentioned.
  • Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (7) to (9).
  • IT represents a hydrogen atom or a methyl group.
  • Examples of the monoisocyanate include cyclohexenoisocyanate, n-butynoleisocyanate, trail isocyanate, benzylisocyanate, phenylisocyanate, and the like.
  • Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (10) to (18).
  • Structural formula (1 8) In the structural formulas (10) to (18), represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.
  • Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n -propanol, i-propanol, n-butanol, sec-butanol, tert-butanol, n —Hexanol, 2-ethinolehexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol ethyl alcohol, etc.), phenols (eg, phenol, Cresole, naphthol, etc.) and those containing further substituents include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, and acetophenol.
  • alcohols for example, methanol, ethanol, n -propanol, i-propanol
  • Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.
  • Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec butylamine, tertbutylamine, hexylamine, 2 —Ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, jetylamine, dibutylamine, dioctylamine), cyclic alkylamines (cyclopentylamine, cyclohexylamine, etc.), aralkylamines (benzylamine, phenethylamine, etc.), arylamine (A-lin, tolylamine, xylylamine, naphthylamine, etc.), combinations of these (N-methyl-N-benzylamine, etc.), and further amines containing substituents (trifluoro
  • Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate. Suitable examples include (meth) acrylic acid 2-ethylhexyl, styrene, chlorostyrene, bromostyrene, hydroxystyrene and the like.
  • the other copolymerizable monomers may be used alone or in combination of two or more.
  • the vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Further, it can be prepared by utilizing polymerization such as so-called emulsion polymerization in a state where the monomer is dispersed in an aqueous medium.
  • the suitable solvent used in the solution polymerization method can be appropriately selected according to the monomer to be used without particular limitation and the solubility of the copolymer to be produced.
  • These may be used alone or in combination of two or more.
  • the radical polymerization initiator is not particularly limited.
  • 2, 2'-azobis isobutyoritol-tolyl) (AIBN)
  • peracids such as benzoyl peroxide
  • persulfates such as potassium persulfate and ammonium persulfate.
  • [0094] is the content of the polymerizable compound having a carboxyl group in the vinyl copolymer, a force such as especially limited can be appropriately selected depending on the Nag purpose, preferably 5 to 50 mol 0/0 ingredients 10 to 40 mole 0/0, more preferably tool 15-35 mole 0/0 are particularly preferred. If the content is less than 5 mol%, developability in alkaline water may be insufficient.
  • the developer resistance of the cured part (image part) may be insufficient.
  • the molecular weight of the binder having a carboxyl group is a force that can be appropriately selected according to the purpose without particular limitation.
  • the mass average molecular weight is 2,000 to 3
  • the noinder having a carboxyl group may be used alone or in combination of two or more. Examples of the case where two or more binders are used in combination include, for example, two or more binders having different copolymer component forces, two or more binders having different mass average molecular weights, two or more binders having different dispersities, And the like.
  • the binder having a carboxyl group a part or all of the carboxyl group may be neutralized with a basic substance.
  • the binder may be used in combination with different types of resins such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.
  • binder for example, a resin soluble in an alkaline liquid described in Japanese Patent No. 2873889 can be used.
  • the content of the binder in the pattern-forming composition is not particularly limited.
  • a force that can be appropriately selected according to the purpose For example, 10 to 90% by mass is preferable, and 20 to 80% by mass. 40 to 80% by mass is particularly preferable.
  • the content is less than 10% by mass, the alkali developability and the adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability against image time and the strength of the cured film (tent film) may be reduced.
  • the above content may be the total content of the binder and the polymer binder used in combination as necessary.
  • the acid value of the binder is not particularly limited and may be appropriately selected depending on the Nag purpose, for example, preferably 70 ⁇ 250mgKOHZg force s, preferably Ri by 90 ⁇ 200mgKOHZg force s, 100 ⁇ 180mgKOH / g Is particularly preferred.
  • the acid value is less than 70 mg KOHZg, developability may be insufficient or resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained in high definition. At least the developer resistance and adhesiveness of the film may deteriorate, and a permanent pattern such as a wiring pattern may not be obtained with high definition.
  • the polymerizable compound is not particularly limited and may be appropriately selected according to the purpose.
  • the polymerizable compound may be a monomer or a monomer having at least one of a urethane group and an aryl group. Is preferably an oligomer. These preferably have two or more polymerizable groups.
  • Examples of the polymerizable group include an ethylenically unsaturated bond (for example, a (meth) atarylyl group, a (meth) acrylamide group, a styryl group, a beryl group such as a bull ester or a bull ether, Aryl groups such as aryl esters) and polymerizable cyclic ether groups (for example, epoxy groups, oxetane groups, etc.), among which ethylenically unsaturated bonds are preferred.
  • an ethylenically unsaturated bond for example, a (meth) atarylyl group, a (meth) acrylamide group, a styryl group, a beryl group such as a bull ester or a bull ether, Aryl groups such as aryl esters
  • polymerizable cyclic ether groups for example, epoxy groups, oxetane groups, etc.
  • the monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose.
  • JP-B-48-41708 JP-B-48-41708
  • polyisocyanate compounds having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate. , Xylene diisocyanate, toluene diisocyanate, phenol-diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, 3, 3, 1 dimethyl 4, Diisocyanates such as 4'-diphenyl diisocyanate; the diisocyanate further added with a bifunctional alcohol (in this case, both ends are isocyanate groups); a trimer such as a burette of the diisocyanate or an isocyanurate; The diisocyanate or diisocyanates and trimethylolpropane, Taeritoritoru, polyfunctional alcohols such as glycerin, or the like adducts of other functional
  • Examples of the butyl monomer having a hydroxyl group in the molecule include 2 hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 4 hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate.
  • the monomer having a urethane group tri ((meth) acryloyloxy) isocyanurate, di (meth) acrylated isocyanurate, ethylene oxide-modified isocyanuric acid tri (meth) atalyte.
  • examples thereof include compounds having an isocyanurate ring such as a rate.
  • the compound represented by the following structural formula (19) or the structural formula (20) includes at least the compound represented by the structural formula (20) from the viewpoint of the preferred tent property. .
  • these compounds may be used alone or in combination of two or more.
  • X to ⁇ represent alkylene oxides, which may be used alone or in combination of two or more.
  • alkylene oxide group examples include, for example, an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, a combination of these (random and block combinations) Among them, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is more preferable an ethylene oxide group or a propylene oxide group.
  • ml to m3 represent an integer of 1 to 60, preferably 2 to 30, more preferably 4 to 15 force! / ⁇ .
  • Y 1 and Y 2 represent a divalent organic group having 2 to 30 carbon atoms, such as an alkylene group, an arylene group, an alkylene group, Alkynylene group, carbonyl group (one CO), oxygen atom (one O), sulfur atom (one S), imino group (one NH), imino group hydrogen atom is replaced with monovalent hydrocarbon group ⁇ Mino group, sulfonyl group (So) or a combination of these are preferred, and among these, alkyl
  • Rene group, arylene group, or a combination of these is preferred.
  • the alkylene group may have a branched structure or a cyclic structure.
  • Examples of the arylene group that may be substituted with a hydrocarbon group include, for example, a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and the following groups. It is done.
  • Examples of the group in which these are combined include a xylylene group.
  • the alkylene group, arylene group, or a combination of these may further have a substituent.
  • substituents include a halogen atom (for example, a fluorine atom, a chlorine atom, Bromine atom, iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group Groups (for example, acetooxy groups, butyryloxy groups), alkoxy carbo yl groups (for example, methoxy carbo yl groups, ethoxy carbo ol groups), aryl carbo yl groups (for example, phenoxy carbo ol groups), etc. Is mentioned.
  • n represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of the raw material supply ability for synthesizing the polymerizable monomer.
  • Z represents an n-valent (trivalent to hexavalent) linking group, and examples thereof include any of the groups shown below.
  • X represents an alkylene oxide.
  • m4 represents an integer of 1 to 20.
  • n is 3-6
  • A represents an n-valent (trivalent to hexavalent) organic group.
  • Examples of A include, for example, an n-valent aliphatic group, an n-valent aromatic group, or an alkylene group, an arylene group, an alkylene group, an alkylene group, a carbonyl group, oxygen, and the like.
  • Preferred is an atom, sulfur atom, imino group, a substituted amino group in which a hydrogen atom of an imino group is substituted with a monovalent hydrocarbon group, or a group in combination with a sulfo group, an n-valent aliphatic group, An n-valent aromatic group or a group in which these are combined with an alkylene group, an arylene group, or an oxygen atom is more preferable.
  • the group is particularly preferred.
  • the number of carbon atoms of A is, for example, preferably an integer of 1 to 100, an integer of 1 to 50 Strongly preferred An integer of 3 to 30 is particularly preferred.
  • the n-valent aliphatic group may have a branched structure or a cyclic structure.
  • the number of carbon atoms of the aliphatic group for example, an integer of 1 to 30 is preferable, and an integer of 1 to 20 is more preferable, and an integer of 3 to 10 is particularly preferable.
  • an integer of 6 to: an integer of LOO is preferred
  • An integer of 6 to 50 is more preferred
  • An integer of 6 to 30 is particularly preferred.
  • the n-valent aliphatic group or aromatic group may further have a substituent.
  • substituents include a hydroxyl group and a halogen atom (for example, a fluorine atom, a chlorine atom, Oxygen atom, iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example,
  • Acetyl group, propionyl group acyloxy group (for example, acetooxy group, butyryloxy group), alkoxy carbo yl group (for example, methoxy carbo yl group, ethoxy carbo yl group), aryloxy carbo yl group (For example, phenoxycarbonyl group) and the like.
  • the alkylene group may have a branched structure or a cyclic structure! /.
  • the number of carbon atoms of the alkylene group for example, an integer of 1 to 18 is preferable, and an integer of 1 to 10 is more preferable.
  • the arylene group may be further substituted with a hydrocarbon group.
  • the number of carbon atoms of the arylene group is preferably an integer of 6 to 18, more preferably an integer of 6 to 10.
  • the number of carbon atoms of the monovalent hydrocarbon group of the substituted imino group is preferably an integer of 1 to 18, more preferably an integer of 1 to 10.
  • Examples of the compounds represented by the structural formulas (19) and (20) include the following structural formulas (21),
  • n, nl, n2 and m represent 1 to 60, 1 represents 1 to 20, and R represents a hydrogen atom or methyl. Represents a group.
  • the monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected depending on the purpose.
  • a polyhydric alcohol compound having an aryl group a polyvalent amine compound.
  • esters or amides of unsaturated carboxylic acids with at least any of the above compounds and polyamino amino alcohol compounds are examples of the above compounds.
  • Examples of the polyalcohol compound, polyamine compound or polyamino amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di--hydroxyethoxy) benzene, 1,5 dihydroxy-1, 2, 3, 4—tetrahydronaphthalene, 2, 2 diphenyl 1,3 propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1 phenyl 1,2 ethanediol, 2, 3, 5, 6— Tetramethyl- ⁇ -xylene ⁇ , ⁇ ′ -diol, 1, 1, 4, 4-tetraphenol 2 1,4-butanediol, 1, 1, 4, 4-tetrafluoro ninole 2 butyne 1,4-diol 1, 1 '—Bee 2-naphthol, dihydroxynaphthalene, 1, 1' -methylene oxy-2 naphthol, 1, 2, 4 benzenetriol, biphenol,
  • R 4 and R 5 represent a hydrogen atom or an alkyl group.
  • X and X each represents an alkylene oxide group, and may be one kind alone.
  • alkylene oxide group examples include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a combination of these (which may be combined in any of random and block), Among these, ethylene oxide groups, propylene oxide groups, butylene oxide groups, or ethylene oxide groups and propylene oxide groups, which are preferred in combination thereof, are more preferable.
  • m5 and m6 are preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and an integer of 4 to 15 is particularly preferable.
  • T represents a divalent linking group, and examples thereof include methylene, ethylene, MeC Me, CF CCF, CO, SO and the like.
  • ⁇ Ar 2 represents an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene.
  • substituent include al A kill group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.
  • the monomer having an aryl group examples include 2, 2 bis [4 (3 (meth) acryloxy 2 hydroxypropoxy) phenol] propane, 2, 2 bis [4 ((meth) acrylic. Oxyethoxy) phenol] propane, a phenolic OH group substituted with 2 to 20 ethoxy groups with 2, 2 bis (4- ((meth) attaroyloxypolyethoxy) ) Phenol) propane (eg, 2, 2 bis (4 — ((meth) attayloxyoxy) phenol) propane, 2,2 bis (4 — ((meth) attayloxytetra) Ethoxy) phenol) propane, 2,2 bis (4-(((meth)) aryloxypentaethoxy) phenol) Propane, 2,2 bis (4-(((meth)) aryloxydecaethoxy) (Phenol) propane, 2, 2 Bis (4— ((meth) atariloy) Oxypentadecaethoxy) (Pheno
  • Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include a hydroxyl group at the terminal obtained as an adduct such as bisphenol and ethylene oxide or propylene oxide, or a polyaddition product.
  • a compound having an isocyanate group and a polymerizable group Compound (for example, 2-isocyanate ethyl (meth) acrylate, oc, ⁇ -dimethyl-benzylbenzyl isocyanate) and the like.
  • a polymerizable monomer other than the monomer having a urethane group and the monomer having an aryl group is used in combination as long as the characteristics as the pattern forming composition are not deteriorated.
  • Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, And an amide of an unsaturated carboxylic acid and a polyvalent amine compound.
  • an unsaturated carboxylic acid for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, And an amide of an unsaturated carboxylic acid and a polyvalent amine compound.
  • Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) atrelate, and a number of ethylene groups of 2 to Polyethylene glycol di (meth) acrylate (eg, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) ) Phthalate, dodecaethylene glycol di (meth) acrylate, tetradeca ethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (2-18 propylene groups) (Meta) attalate (eg Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di
  • an ester of the itaconic acid and the aliphatic polyhydric alcohol compound for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3 butanediol diitaconate, 1,4 monobutanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
  • ester (crotonic acid ester) of the crotonic acid and the aliphatic polyhydric alcohol compound examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol. Examples include tetradicrotonate.
  • esters (isocrotonic acid ester) of the isocrotonic acid and the aliphatic polyhydric alcohol compound examples include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Etc.
  • esters (maleic acid ester) of the maleic acid and the aliphatic polyhydric alcohol compound examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol. Examples include tetramaleate.
  • Examples of the amide from which the polyvalent amine compound and the unsaturated carboxylic acid compound are also derived include, for example, Samethylene bis (meth) acrylamide, Ottamethylene bis (meth) acrylamide, Jetylene triamine tris (meth) acrylamide, Diethylene Triamine bis (meth) acrylamide.
  • the polymerizable monomer for example, butanediol-1,4 diglycidyl ether, cyclohexane dimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diester
  • Glycidyl group-containing compounds such as glycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and glycerin triglycidyl ether are added with ⁇ , ⁇ -unsaturated carboxylic acid.
  • Ethers e.g., butanediol 1,4-dibutyl ether, cyclohexane dimethanol dibutyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol resino vinylenoreethenole, hexane dino Resininoleateolene, trimethylonorepropan trivinyl ether, pentaerythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (eg, butanediol 1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene Glycol diglycidyl ester, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether , Trimethylolpropan trig
  • bull esters examples include divinyl succinate and dibula adipate.
  • polymerizable monomer may be used alone or in combination of two or more.
  • the polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule, if necessary.
  • Examples of the monofunctional monomer include a compound exemplified as a raw material for the binder, a dibasic mono ((meth) atallylooxyalkyl ester) mono (noro) described in JP-A-6-236031.
  • Monofunctional monomers such as hydroxyalkyl esters (for example, ⁇ -chloro-j8-hydroxypropyl j8′-methacryloyloxychetilo o-phthalate, etc.), Patent 2744643, WOOOZ52529 Pamphlet, Patent 2548 016 And the like.
  • the content of the polymerizable compound in the composition for pattern formation is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass. I like it.
  • the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (extruding failure of the roll end force) may be deteriorated. is there.
  • LOO mass% is preferable 20-: LOO mass% is more preferable 40-: LOO Mass% is particularly preferred.
  • 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, etc.), Examples include dazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and meta-octenes.
  • a halogenated hydrocarbon having a triazine skeleton from the viewpoints of the sensitivity and storability of the photosensitive layer obtained by the pattern forming composition and the adhesion between the photosensitive layer and the printed wiring board forming substrate, a halogenated hydrocarbon having a triazine skeleton, An oxime derivative, a ketone compound, and a hexaarylbiimidazole compound are preferred.
  • Examples of the hexarylbiimidazole include 2, 2 'bis (2-clonal phenol) 4, 4', 5, 5'-tetraphenyl biimidazole, 2, 2'-bis ( o Fluoro-phenyl) 4, 4 ', 5, 5' — Tetraphenyl bibiimidazole, 2, 2 ′ — Bis (2 bromophenol) 1, 4, 4 ', 5, 5' — Tetra-phenol biimidazole, 2, 2 '— Bis (2, 4 Diclonal Membrane) 4, 4', 5, 5 '— Tetraphenol Biimidazole, 2, 2' — Bis (2 — Diclonal Membrane) 4 , 4 ', 5, 5' — Tetra (3-methoxyphenol) biimidazole, 2, 2 '— Bis (2-chlorophenol) 1, 4, 4', 5, 5 '— Tetra (4-methoxyphenol) -L) biimidazole, 2,2'-bis (4-meth
  • the biimidazoles can be easily prepared by the methods disclosed in Bull. Chem. Soc. Japan, 33, 565 (1960), and J. Org. Chem, 36 (16) 2262 (1971), for example. Can be synthesized.
  • halogenated hydrocarbon compounds having a triazine skeleton examples include compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), described in British Patent 1388492 A compound described in JP-A-53-133428, a compound described in DE 3337 024, a compound described in J. Org. Chem .; 29, 1527 (1964) by FC Schaefer et al.
  • Examples of the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969) include, for example, 2-Ferreux 4, 6 bis (trichloromethyl) 1, 3, 5 triazine.
  • Examples of the compound described in the British Patent 1388492 include, for example, 2-styryl 4,6 bis (trichloromethinole) -1,3,5 triazine, 2- (4-methinorestyrinole) 4, 6-bis (trichloromethyl) 1, 3, 5 triazine, 2- (4-methoxystyryl) mono 4,6 bis (trichloromethyl) 1, 3, 5 triazine, 2- (4-methoxystyryl) mono 4 Amino 1 -Trichloromethylol 1, 3, 5 Triazine.
  • Examples of the compound described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6 bis (trichloromethyl) -1,3,5 triazine. , 2— (4-Ethoxy mononaphtho 1-yl) 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2- [4- (2-Ethoxyethyl) mononaphtho 1-yl] 4, 6 Bis (trichloromethyl) 1, 3, 5 triazine, 2- (4, 7 dimethoxy mononaphtho 1-yl) 4, 6 Bis (trichloromethyl) — 1, 3, 5 ⁇ lyazine, and 2— (acenaphtho) — 5—yl) —4, 6 Bis (methyl bromide) 1, 3, 5 Triazine.
  • Examples of the compounds described in the specification of the German Patent 3337024 include 2- (4-Styrene Norefiniore) 4, 6 Bis (trichloromethinole) 1, 1, 3, 5 Triazine, 2- (4— (4-methoxystyryl) phenol) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (1-naphthyl vinylenephenol) 1,4 bis (trichloromethyl) 1,3 , 5 Triazine, 2 Chlorostyrylphenol 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4 thiophene 1 2-bilenphenol) 1,4,6 bis (trichloromethyl) 1, 3, 5— triazine, 2— (4-thiophene 1—bi-bienphenol) 1, 4, 6-bis ( Trichloromethyl) 1 1,3,5 Triazine, 2— (4 Furan 1 2 Bilenphenol) 1,4,6 Bis (trichloromethyl) 1, 3, 5 Triazine,
  • Examples of the compounds described in J. Org. Chem .; 29, 1527 (1964) by FC Schaefer et al. include 2-methyl-4,6 bis (tribromomethyl) -1,3,5 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 and 2-methoxy-4-methyl 6-trichloromethyl 1, 3, 5 triazine.
  • Examples of the compounds described in JP-A-62-58241 include 2- (4-phenylethyl-sulfur) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2— (4— Naphthyl 1-Ethurhue-Lu 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4 Tril-Ethyl) phenol) — 4, 6 Bis (trichloromethyl) —1 , 3, 5 — Triazine, 2- (4— (4-Methoxyphenyl) ether furol) 4, 6—Bis (Trimethylromethyl) 1, 3, 5 Triazine, 2— (4— (4-Isopropylphenol) -Luture) Hue) 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4 ethyl fuse-rucheur) Grav) 1, 4, 6 Bis (trichloromethyl) 1, 3 , 5 Triazines.
  • Examples of the compounds described in JP-A-5-281728 include 2- (4 trifluoromethylphenol) -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 dibromophenol) 1,6,6 bis (trichloromethyl) 1, 3, 5 triazine and the like.
  • Examples of the compound described in JP-A-5-34920 include 2,4 bis (trichloromethyl) -6- [4- (N, N-diethoxycarboromethylamino) -3-bromophenol. ] — 1, 3, 5 triazine, trihalomethyl-s triazine compounds described in US Pat. No. 4,239,850, and 2, 4, 6 tris (trichloromethyl) —s triazine, 2- (4-chloro) (Fuel) 4, 6-bis (tribromomethyl) s triazine.
  • Examples of the compounds described in the above-mentioned US Pat. No. 4,212,976 include compounds having an oxadiazole skeleton (for example, 2 trichloromethyl-5 phenyl 1,3,4-oxadiazole, 2 trichloromethyl).
  • Examples of the oxime derivative suitably used in the present invention include the following structural formulas (43) to (43)
  • ketone compound examples include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromo.
  • meta-octenes examples include bis (7? -2, 4 cyclopentagen 1-yl.
  • Atalidine derivatives for example, 9-phenol lysine, 1,7 bis (9,9--ataridyl) heptane, etc.
  • Halogen compounds eg, carbon tetrabromide, felt rib mouth methylsulfone, felt trichloromethyl ketone, etc.
  • coumarins eg, 3- (2-benzofuroyl) -7-jetylaminocoumarin, 3- (2 Benzofuroyl)-7-(1-Pyrrolidyl) coumarin, 3 Benzoyl 7 Jetylaminocoumarin, 3— (2-Methoxybenzoyl) 7 Jetylamino nocoumarin, 3— (4-Dimethylaminobenzol) 7-Jetyl Aminocoumarin, 3,3,1 Carborubis (5, 7-di-n-propoxycoumarin), 3, 3, -carborubis (7-deethyla
  • the photopolymerization initiators may be used singly or in combination of two or more.
  • combinations of two or more include, for example, a combination of hexarylbiimidazole and 4 aminoketones described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516 and trihalomethyl-s—
  • the content of the photopolymerization initiator in the pattern forming composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and 0.5 to 15% by mass. Is particularly preferred
  • the pattern forming composition of the present invention does not change the thickness of the exposed portion of the photosensitive layer before and after the development.
  • the sensitizer it is particularly preferable to use the sensitizer together.
  • the sensitizer together for example, the sensitivity of the photosensitive layer can be very easily adjusted to 0.1 to: LOmjZcm 2 .
  • the sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.) without particular limitation.
  • the light irradiation means for example, visible light, ultraviolet light, visible light laser, etc.
  • a sensitizer having a maximum absorption wavelength of 380 to 450 nm is preferable.
  • 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 may be appropriately selected from known sensitizers that are not particularly limited.
  • known polynuclear aromatics for example, pyrene, perylene, triphenylene
  • xanthenes for example, fluorescein, eosin, erythrucine, rhodamine B, rose bengal
  • cyanines for example, indocarbo Cyanine, thiacarbocyanine, oxacarbyanine
  • merocyanines eg, merocyanine, carbomerocyanine
  • thiazines eg, thionine, methylene blue, toluidine blue
  • atalidines eg, atalidine orange, chloroflavin, acriflavine
  • anthraquinones eg, anthraquinone
  • squaliums eg,
  • Examples of the combination 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 initiator systems)]
  • the content of the sensitizer is 0.01 to 4 with respect to all components of the pattern forming composition. 0.02 to 2% by mass is more preferable 0.05 to 1% by mass is particularly preferable When the content is less than 0.01% by mass, the sensitivity may decrease, If it exceeds 4 mass%, the shape of the pattern may deteriorate.
  • the other components include surfactants, plasticizers, color formers, colorants, and the like, and further adhesion promoters and other auxiliary agents (for example, pigments, conductive particles, fillers). Agents, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, etc.) may be used in combination. In addition, by appropriately containing these components, properties such as stability, photographic properties, print-out properties, and film physical properties of the target pattern forming composition can be adjusted.
  • the plasticizer may be added to control the film physical properties (flexibility) of the photosensitive layer obtained from the pattern forming composition.
  • plasticizer examples include dimethyl phthalate, dibutyl phthalate, diisopropyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diphenyl phthalate.
  • Phthalic acid esters such as ril phthalate and octyl capryl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl dallicose phthalate, ethino retino eno ethino reglycolate, methyl phthal yl acetyl dalicolate, buty Glycol esters such as norephthalino lebutinoglycolate and triethylene glycol dicabrylate; tricresyl phosphate, triphenyl Phosphate esters such as sulfate; 4 Amides such as toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl seba Aliphatic dibasic acid esters such as keto, dibutyl sebac
  • the content of the plasticizer is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 40% by mass, based on all the components of the pattern forming composition. Mass% is particularly preferred.
  • the color former may be added to give a visible image (printing function) after exposing the photosensitive layer obtained by the pattern forming composition.
  • Examples of the color former include tris (4-dimethylaminophenol) methane (leucocrystal violet), tris (4-jetylaminophenol) methane, and tris (4-dimethylamino-2-methylphenol).
  • Methane Tris (4-Jetylamino 2-methylphenol) Methane, Bis (4-dibutylaminophenol) One [4 (2-Cyanethyl) methylaminophenol] Methane, Bis (4-dimethylaminophenol) 2 Aminotriarylmethanes such as quinolylmethane and tris (4 dipropylaminophenol) methane; 3, 6-bis (dimethylamino) 9-phenyl-xanthine, 3 —amino 6 dimethylamino mono 2-methyl 9— (2 Mouthphenyl) Aminoxanthines such as xanthine; 3, 6 bis (jetylamino) 9 (2 etoxycarbol) thixanthene, 3,
  • Leuco-like compounds eg., leucoin digoid dyes; organic amines that can oxidize to colored forms as described in US Pat. Nos. 3,042,515 and 3,042,517 (eg, 4,4,1 ethylenediamine, diphenylamine, N, N dimethylaniline, 4,4'-methylenediamintriphenylamine, N vinylcarbazole), among these, such as leuco crystal violet Triarylmethane compounds are preferred.
  • the color former is combined with a halogen compound for the purpose of coloring the leuco body.
  • organic halogen compounds halogen compounds having two or more halogen atoms bonded to the same carbon atom are preferred. Halogen compounds having three halogen atoms per carbon atom are more preferred.
  • the organic halogen compounds may be used alone or in combination of two or more. Among these, tribromomethyl phenyl sulfone and 2,4 bis (trichloromethyl) 6 -phenol triazole are preferable.
  • the content of the color former is preferably from 0.01 to 20% by mass, more preferably from 0.05 to 10% by mass, based on all the components of the pattern forming composition. 1 to 5% by mass is particularly preferable. Further, the content of the halogen compound is preferably 0.005 to 5% by mass, more preferably 0.001 to 1% by mass, based on all components of the pattern forming composition.
  • the colorant is not particularly limited and can be appropriately selected according to the purpose.
  • a known pigment such as red, green, blue, yellow, purple, magenta, cyan, black, etc.
  • dyes such as Victoria 'Pure One Blue BO (CI 4 2595), Auramin (CI 41000), Fats-Black HB (CI 26150), Monorai-Yellow GT (CI Pigment Yellow 12), Permanent 'Yellow GR (CI Pigment' Yellow 17), Permanent 'Yellow HR (CI Pigment' Yellow 83), Permanent 'Carmin FBB (CI Pigment' Red 146), Hoster Balm Red ESB (CI Pigment 'Violet 19), Permanent 'Ruby FBH (CI Pigment' Red 11), Huster's Pink B Supra (CI Pigment 'Red 81), Monastral' First 'Blue (CI Pigment' Blue 15 ), Monolight 'First' Black B (CI Pigment'Black 1), Power One Bon Black is mentioned.
  • colorant suitable for producing a color filter for example, C. I. pigment
  • the average particle diameter of the colorant is not particularly limited, and can be appropriately selected according to the purpose. For example, 5 m or less is preferable, and 1 m or less is more preferable. In the case of producing a color filter, the average particle diameter is 0.
  • a dye can be used for the purpose of coloring the pattern forming composition for improving the handleability or imparting storage stability.
  • the dye examples include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythine cin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3 diphenyltriazine, alizarin red S, Thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, meta-youro, thymolsulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2, 7 diclonal fluorescein, paramethyl red , Congo Red, Benzopurpurin 4B, a Naphthyl Red, Nile Blue A, Phenacetalin, Methyl Violet, Malachite Green, Parafuchsin, Oil Blue # 603 (manufactured by Orient Chemical Industries), -Damine B, Rhodamine 6G, Victoria Pure Blue BOH and the like can be mentioned, and among these, and
  • the cationic dye may be a residue of an organic acid or an inorganic acid.
  • an organic acid or an inorganic acid for example, bromic acid, iodic acid, sulfuric acid, phosphoric acid, Residues such as oxalic acid, methanesulfonic acid, toluenesulfonic acid and the like are included.
  • the content of the dye is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on all components of the pattern forming composition. ⁇ 2% by weight is particularly preferred.
  • a known adhesion promoter may be used for each layer.
  • adhesion promoter examples include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638.
  • the content of the adhesion promoter is preferably 0.001% by mass to 20% by mass with respect to all the components of the pattern forming composition, and more preferably 0.01% by mass to 10% by mass. 0.1% by mass to 5% by mass is particularly preferred.
  • the pattern forming composition includes, for example, organic sulfur compounds, peroxides, redox compounds, and the like described in Chapter 5 of “Light Sensitive Systems” by J. Kosa. Zo or diazo compound, photoreducible dye, organic halogen compound and the like may be contained.
  • organic sulfur compound examples include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenthiazole, 2-mercaptobenzoxazole, thiophenol, etyltrichloromethanesulfenate, 2- Mercaptobens imidazo And the like.
  • peroxide examples include diethyl butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.
  • the redox compound also serves as a combination force of a peroxy compound and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peracid compounds. .
  • Examples of the azo and diazo compound include ⁇ , ⁇ '-azobis-living mouth-tolyl.
  • Examples of the photoreducible dyes include rose bengal, erythricin, eosin, acriflavine, riboflavin, and thionine.
  • a known surfactant can be added.
  • the surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a non-one surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.
  • the content of the surfactant is preferably 0.001 to 10% by mass based on the solid content of the pattern forming composition! /.
  • the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be lowered.
  • a fluorosurfactant contains 40 mass% or more of fluorine atoms in a carbon chain of 3 to 20, and is small from the number of non-bonded ends.
  • Preferable examples also include polymer surfactants having acrylate or metatalylate having a fluoroaliphatic group in which a hydrogen atom bonded to at least 3 carbon atoms is fluorine-substituted as a copolymerization component.
  • the pattern forming material of the present invention is a laminate having at least a photosensitive layer on a support and having other layers appropriately selected as necessary. In addition, it is possible to improve long-term storage by laminating a protective film on the surface of the photosensitive layer.
  • the photosensitive layer is formed from the photosensitive composition.
  • the portion provided in the pattern forming material of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose, and is usually laminated on a support.
  • the photosensitive layer may be a single layer or a plurality of layers.
  • the thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1 to 100 ⁇ m is preferable, and 2 to 50 ⁇ m is more preferable. ⁇ 30 ⁇ m is particularly preferred.
  • the support is not particularly limited, and can be appropriately selected according to the purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance. Further, the surface is smooth. It is more preferable that the property is good.
  • the support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated butyl, polybulal alcohol, polycarbonate, polystyrene, cellophane, polysalt-vinylidene copolymer, polyamide, polyimide, salt-vinyl or more
  • plastic films such as a butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, nylon film, etc. can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
  • the thickness of the support is not particularly limited, and can be appropriately selected according to the purpose.
  • F row; t is a force of 2 to 150 m, S is a woman, 5 to: LOO ⁇ m Force SJ-like girls, 8-50 ⁇ m force S Especially preferred.
  • 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. For example, the length of 10m-20, OOOm is mentioned.
  • the pattern forming material may form a protective film on the photosensitive layer.
  • Examples of the protective film include those used for the support, paper, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.
  • the thickness of the protective film is not particularly limited and can be appropriately selected according to the purpose. For example, 5 to: LOO / zm force is preferable, 8 to 50 111 is preferable, and 10 to 30 / zm is preferable. Particularly preferred.
  • 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 interlayer adhesion can be adjusted by subjecting at least one of the support and the protective film to a surface treatment. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer.
  • coating of an undercoat layer corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • ultraviolet irradiation treatment for example, coating of an undercoat 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, and can be selected as appropriate, for example, in the range of 10 m to 20,000 m.
  • slitting may be performed so that the user can use it easily, and a long body in the range of 100 m to l, 000 m may be formed into a roll shape.
  • the support is wound up so as to be the outermost side.
  • the roll-shaped pattern forming material is a sheet. You may slit in the shape.
  • a separator especially moisture-proof and desiccant-containing
  • the packaging has low moisture permeability. I prefer to use materials.
  • 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.
  • the other layer can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a cushion layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, and the like.
  • the pattern forming material and the permanent pattern forming material may have one of these layers alone, or two or more of them.
  • the photosensitive layer receives light from the light irradiation unit and receives light from the light irradiation unit. After modulating the light, it is preferable that the exposure is performed with the light that has passed through the distortion of the exit surface of the pixel portion. Details of the light irradiating means, the pixel part, the light modulating means, the aspherical surface, the microlens, and the microlens array will be described later.
  • the pattern forming material can be manufactured, for example, as follows. First, the pattern forming composition is dissolved, emulsified or dispersed in water or a solvent to prepare a pattern forming composition solution.
  • the solvent is not particularly limited and may be appropriately selected according to the purpose.
  • examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol.
  • the pattern forming composition can be produced by applying the pattern forming composition solution on the support and drying it to form a photosensitive layer.
  • the pattern forming composition solution coating method is not particularly limited and can be appropriately selected according to the purpose.
  • spray method roll coating method, spin coating method, slit coating method, eta
  • Various coating methods such as a stretch coating method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method can be 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 pattern forming material of the present invention is advantageous in that it can suppress a decrease in sensitivity of the photosensitive layer, so that it can be exposed with light of a smaller amount of V and energy, and the exposure speed increases, so that the processing speed increases. is there.
  • the pattern forming material of the present invention can suppress a decrease in sensitivity of the photosensitive layer and can form a pattern with high definition, it can be used for forming various patterns and forming permanent patterns such as wiring patterns.
  • 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 pattern forming method of the present invention includes at least an exposure step, and includes other steps appropriately selected.
  • 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 of the present invention is as described above.
  • the subject of the exposure can be appropriately selected according to the purpose without any limitation as long as it is the photosensitive layer in the pattern forming material.
  • the pattern forming material is formed on a substrate. It is preferable to be performed on the laminated body.
  • the substrate can be appropriately selected from known materials having no particular limitation to those having a high surface smoothness, a force having an uneven surface, and a plate-like substrate (substrate). More specifically, a known printed wiring board forming substrate (for example, copper-clad laminate), a glass plate (for example, soda glass plate), a synthetic resin film, paper, a metal plate, etc. may be mentioned. .
  • the layer structure in the laminate can be appropriately selected according to the purpose without any particular limitation.
  • a layer structure having the base, the photosensitive layer, and the support in this order is preferable. .
  • the method for forming the laminate can be appropriately selected depending on the purpose without any particular limitation, but at least one of heating and pressurizing the pattern forming material on the substrate is performed! While preferred, laminating.
  • the heating temperature can be appropriately selected according to the purpose for which there is no particular restriction. For example, 15 to 180 ° C is preferable, and 60 to 140 ° C is more preferable.
  • the pressure of the pressurization is a force that can be appropriately selected according to the purpose for which there is no particular limitation.
  • F column; t is preferably 0.1 to 1. OMPa force, 0.2 to 0.8 MPa force ⁇ More preferred! / ⁇ .
  • the apparatus for performing at least one of the heating and pressurization can be appropriately selected according to the purpose of restriction, for example, a laminator (for example, VP-II manufactured by Taisei Laminator), A vacuum laminator (for example, MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) is preferable.
  • the exposure can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure and analog exposure are preferable. 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. It is preferable to use a 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 modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SL M; Special Light Modulator), and transmitted light by an electro-optic effect.
  • DMD digital micromirror device
  • MEMS Micro Electro Mechanical Systems
  • SL M Special Light Modulator
  • transmitted light by an electro-optic effect Modulating optical elements (PLZT elements), liquid crystal light shirts (FLC), etc. are mentioned.
  • PZT elements liquid crystal light shirts (FLC), etc.
  • FLC liquid crystal light shirts
  • the light modulation means preferably includes pattern signal generation means for generating a control signal based on pattern information to be formed.
  • 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 (eg, 1024 x 768) of micromirrors 62, each of which constitutes a 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.
  • a silicon gate CMOS SRAM cell 60 manufactured on a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke. The entire structure is monolithically configured. ing.
  • 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.
  • a controller 302 (see FIG. 12) connected to the DMD 50.
  • a light absorber (not shown) is disposed in the direction in which the laser beam reflected by the micromirror 62 in the off state 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.
  • Fig. 3 (b) shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted
  • Fig. 3 (b) shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted.
  • the DMD50 has a number of micromirrors arranged in the longitudinal direction (for example, 1024) Micromirror array force A number of ⁇ 1_ (for example, 756 threads) in the short direction As shown, by tilting the DMD 50, the exposure beam 53 of each micromirror Scanning path (scanning line) pitch P 1S Scanning line pitch P when DMD50 is not tilted P
  • 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 (see FIG. 12) performs control so that only a part of the micromirror rows (for example, 1024 ⁇ 256 rows) is driven.
  • the micromirror array arranged at the end of DMD50 may be used as shown in FIG. 4B. May be used.
  • a defect occurs in some micromirrors, use a micromirror array that does not have a defect, such as using a micromirror array that is suitable for the situation. It may be changed at any time.
  • the data processing speed of the 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.
  • the 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 row force in which 1024 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 a direction corresponding to the predetermined direction is longer than a length in a 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.
  • 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 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 in the development step described later, an uncured area other than the cured partial area. 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 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.
  • 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. did. 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 the 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.
  • each of the exposure heads 166 to 166 has an incident optical beam.
  • a digital micromirror device (DM D) 50 manufactured by Texas Instruments Inc. of the United States is provided as the light modulation means (spatial light modulation element that modulates each pixel in accordance with pattern information).
  • the DMD 50 is connected to the controller 302 (see FIG. 12) having a data processing unit and a mirror drive control unit. Based on the input pattern information, 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. The area to be controlled will be described later. Further, the mirror drive control unit controls the angle of the reflecting 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.
  • a fiber array light source having a laser emitting portion in which the emitting end portion (light emitting point) of the optical fiber is arranged in a line along the direction corresponding to the long side direction of the exposure area 168 66, a lens system 67 for correcting the laser light emitted from the fiber array light source 66 and collecting it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order.
  • the lens system 67 is schematically shown. As shown in detail in FIG.
  • the lens system 67 has a condensing lens 71 that condenses the laser light B as illumination light emitted from the fiber array light source 66, and an optical path of light that has passed through the condensing 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 microlens 55a is arranged by 1024 x 256 rows.
  • the arrangement pitch of microlenses 55a is 41 ⁇ m in both the vertical and horizontal directions.
  • the micro lens 55a has a focal length of 0.19 mm, an NA (numerical aperture) of 0.11, and is formed of the optical glass BK7.
  • 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.
  • Aperture 59a The diameter is, for example, 10 / zm.
  • the first imaging optical system forms an image on the microlens array 55 by magnifying the image by the DMD 50 three times. 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 pixel part 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 part 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.
  • a known light source such as a semiconductor laser or means capable of combining and irradiating two or more lights can be mentioned. Among these, means capable of combining and irradiating two or more lights are preferable.
  • 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.
  • a laser that combines two or more light beams that are preferred by laser light (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 ultraviolet power is preferably, for example, 300 to 1500 nm 320
  • the wavelength of the laser light is, for example, 200 to 1500 nm force S, preferably 300 to 800 nm force S, more preferably 330 to 500 mn force, and 400 to 450 mn force.
  • 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 as shown in FIG. 27A, and one end of the multimode optical fiber 30 is coupled to each laser module 64. ing.
  • 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.
  • the end portion of the multimode optical fiber 31 opposite to the optical fiber 30 is arranged along the main scanning direction orthogonal to the sub-scanning direction, and is arranged in two rows.
  • a laser emitting unit 68 is configured.
  • the laser emitting portion 68 formed by the end portion 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 multimode optical fiber 30 between two adjacent multimode optical fibers 30 with a large cladding diameter is arranged.
  • Stack optical fiber 30 and stack multi-mode optical fiber 30 The output ends of the combined optical fibers 31 are arranged so as to be sandwiched between the two output ends of the optical fibers 31 connected to the two adjacent multimode optical fibers 30 in the portion where the cladding diameter is large. .
  • Such an optical fiber is, for example, as shown in FIG. 28, a light with a small cladding diameter of 1 to 30 cm in length at the tip of the laser light emission side of the multimode optical fiber 30 with a large cladding diameter. 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. As described above, 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 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 / zm.
  • 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 all have the same maximum output (for example, 100 mW for the multimode laser and 30 mW for the single mode laser).
  • As the GaN-based semiconductor lasers LD1 to LD7 lasers having an oscillation wavelength other than the above-mentioned 405 nm in a wavelength range of 350 to 450 nm may be used.
  • the combined laser light source is housed together with other optical elements in a box-shaped package 40 having an upper opening.
  • the package 40 is provided with a package lid 41 created so as to close the opening thereof. After the degassing process, a sealing gas is introduced, and the opening of the knocker 40 is closed by the package lid 41, whereby the package 40 and the package 40 are packaged.
  • the combined laser light source is hermetically sealed in a closed space (sealed space) formed by the die lid 41.
  • a base plate 42 is fixed to the bottom surface of the package 40. 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 the front shape of the 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 the optical axis of a circular lens having an aspherical surface into an elongated shape with a parallel plane.
  • This elongated collimator lens can be formed, for example, by molding a 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 LD 7 (left and right direction in FIG. 32). Yes.
  • each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having an emission width of 2 m, and the divergence angles in the direction parallel to the active layer and in the direction perpendicular thereto are, 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.
  • each collimator lens 11-17 has a width of 1. lmm and a length of 4.6m.
  • the horizontal and vertical beam diameters of the laser beams B1 to B7 incident on them are 0.9 mm and 2.6 mm, respectively.
  • 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 parallel plane, and perpendicular to the arrangement direction of the collimator lenses 11 to 17, that is, in the horizontal direction. It is formed in a shape that is short in the direction.
  • 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 made 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
  • the light irradiation means is not limited to a fiber array light source including a plurality of the combined laser light sources.
  • laser light incident from a single semiconductor laser having one light emitting point is used.
  • a fiber array light source in which a fiber light source including one optical fiber emitting light is arrayed can be used.
  • 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.
  • Multi-Cavity Laser 110 is an array of chip-shaped semiconductor lasers Compared to the case, since the light emitting points can be arranged with high positional accuracy, it is easy to multiplex the laser light emitted from each light emitting point force. However, as the number of light emitting points increases, it becomes easy for the multi-cavity laser 110 to stagnate during laser manufacturing. Therefore, 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 also emitted from each of the plurality of emission 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 light emitting points 110a of the multi-cavity laser 110 are juxtaposed within a width substantially equal to the core diameter of the multi-mode optical fiber 130, and as the condenser lens 120, the multi-mode optical fiber 130
  • the multimode optical fiber 130 By using a convex lens with a focal length approximately equal to the core diameter or a rod lens that collimates the outgoing beam from the multi-cavity laser 110 only in a plane perpendicular to its active layer, the multimode of laser light B
  • the coupling efficiency to the optical fiber 130 can be increased.
  • 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 Viti lasers 110 are arranged at equal intervals is used. Can be.
  • 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.
  • the combined laser light source is disposed between the laser array 140, the plurality of lens arrays 114 disposed 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 a plurality of light emitting points (for example, five) are arranged on the space side upper surface of the heat block 180 (for example, five).
  • the two multi-cavity lasers 110 are arranged so that their emission points are located on the same vertical plane as the emission points of the laser chips arranged on the upper surface of the heat block 182.
  • 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 As a result, the space utilization efficiency of the laser beam can be improved, the output of the combined laser light source can be increased, and the number of components can be reduced and the cost can be reduced.
  • the collimating lens array 184 there is a single multimode optical fiber 130 and a condensing unit that condenses 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 power by using a multi-stage arrangement of multi-cavity lasers and an 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.
  • a fiber array is formed by coupling another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber to the output end of the multimode optical fiber of the combined laser light source.
  • Another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber to the output end of the multimode optical fiber of the combined laser light source.
  • the example of increasing the brightness of the light source has been explained.
  • a multimode optical fiber with a cladding diameter of 125 m, 80 m, 60 ⁇ m, etc. can be used without connecting another optical fiber to the output end. Also good.
  • 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 And converged 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, and the core diameter is used as the optical fiber.
  • Multimode optical fiber with 50 m, clad diameter 125 m, NA (numerical aperture) 0.2 is used, so if you want to obtain an output of about 1 W (watt), 48 multimode optical fibers ( 8 X 6)
  • the luminous area is 0.62 mm 2 (0.675 mm X O. 925 mm)
  • the brightness at the laser emitting section 68 is 1.6 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 mmX 0.025 mm), laser emission
  • the brightness at section 68 is 123 ⁇ 10 6 (WZm 2 ), which is about 80 times higher than before.
  • 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 emission 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.
  • the DMD is a reflective spatial light modulator, but FIGS. 37A and 37B are developed views for explaining the optical relationship.
  • Pattern information power corresponding to the exposure pattern is input 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 the surface thereof is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown).
  • a detection sensor attached to the gate 160 is used.
  • the pattern information stored in the frame memory is sequentially read out for each of a plurality of lines, and each exposure head 166 is read based on the pattern information read out by the data processing unit.
  • a control signal is generated every time. Then, 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 according to 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 any particular limitation, and 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 imaging the laser light reflected by DMD50.
  • the laser light that has passed through the exposed surface 5 6 represents an exposure head composed of a lens system (imaging optical system) 480 and 482 that forms an image.
  • 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.
  • FIG. 16A and FIG. 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.
  • the 55 is composed of 256 rows of 1024 microlenses 55a arranged in the horizontal direction and arranged in parallel in the vertical direction.
  • the arrangement order of the microlens array 55 is indicated by j for the horizontal direction and k for 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 micro 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. More specifically, the microlens 55a is a toric lens, and light is emitted in the X direction.
  • 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.
  • the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. ing.
  • the surface shape of the microlens 55a used in the simulation is calculated by the following calculation formula.
  • X is the lens optical axis in the X direction. This means the distance of O force
  • Y means the distance of the lens optical axis O force in the y direction.
  • the microlens 55a is cut in parallel to the focal length force direction in the cross section parallel to the y direction.
  • a toric lens that is smaller than the in-plane focal length, distortion of the beam shape near the condensing position is suppressed. If so, the pattern forming material 150 can be exposed to a higher definition image without distortion. Further, it can be understood that the region where the direction beam diameter is small in this embodiment shown in FIGS. 19A to 19D is wider, that is, the depth of focus is larger.
  • the focal length in the cross section parallel to the X direction is parallel to the y direction. If the microlens is made up of a toric lens that is smaller than the focal length in the cross section, similarly, a higher definition image without distortion can be exposed to the pattern forming material 150.
  • the aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged such that only light that has 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 enhance 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 exit side is an aspherical surface.
  • a microlens array is configured with one of the two light-passing end surfaces being a spherical surface and the other being a cylindrical surface, the same effect as in the above embodiment can be obtained. It can also be obtained.
  • 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 reflection surface of the micromirror 62 instead of adopting the spherical shape. .
  • FIGS. 22A and 22B An example of such a microlens 155a is shown in FIGS. 22A and 22B. The same figure The front and side shapes of the microlens 155a are shown, and the outer shape of the microlens 155a is a parallel plate as shown. 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 beam 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 outward, and the broken line shown in the microlens 155a in FIG. The positions changed at equal pitches are shown.
  • the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length is larger. It is getting shorter. Even when a microlens array composed of such a gradient index lens is used, the same effect as when the microlens array 55 is used can be obtained.
  • a microlens having an aspherical surface shape such as the microlens 55a previously shown in Figs. 17A, 17B, 18A, and 18B, and the refractive index as described above. It is possible to give a distribution and correct aberration due to distortion of the reflecting 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 can be applied to correct the aberration due to the distortion and prevent the beam shape from being distorted.
  • 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 DMD50 corresponds to each pixel part of the DMD50 by each microlens of the microlens 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 angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. It is possible to prevent a part of the light beam from entering. That is, a high extinction ratio can be realized.
  • 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 is configured so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller at the exit side than at the entrance side.
  • total luminous flux width (total luminous flux width) HO and HI is the same for the incident luminous flux and the outgoing luminous flux.
  • the portions denoted by reference numerals 51 and 52 virtually represent the entrance surface and the exit surface of the light quantity distribution correcting optical system.
  • 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 outgoing light beam in the central portion and the width hl l of the outgoing light beam in the peripheral portion are set to satisfy hl l ⁇ hlO.
  • the central luminous flux which normally has a large light quantity distribution, can be utilized in the peripheral part where the light quantity is insufficient, and the light utilization as a whole is improved.
  • 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 H0 on the incident side is “reduced” to the width H2 before being emitted (H0
  • 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 luminous flux width hl l at the periphery is made smaller than at the center.
  • the reduction ratio for the incident luminous flux at the center is The effect is to make it smaller than the peripheral part and to increase the reduction ratio of incident light in the peripheral part compared to the central part.
  • FIG. 24C shows a case where the entire luminous flux width HO on the incident side is “expanded” to the width H3 and emitted (HO and H3).
  • 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.
  • the light flux width hi 1 at the peripheral part is made smaller than that at the central part.
  • the light amount distribution correcting optical system changes the light beam width at each emission position, and outputs the ratio of the light beam width in the peripheral part to the light beam width in the central part near 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.
  • FIG. 26 shows the light amount distribution of 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 exposes the photosensitive layer in the pattern forming material in the exposing step, cures the exposed region of the photosensitive layer, and then removes the uncured region to form an image, thereby forming a no-turn. It is a process.
  • the development step can be preferably carried out, for example, by a developing means.
  • the developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose.
  • the means for spraying the developer, and applying the developer And means for immersing in the developer may be used alone or in combination of two or more.
  • the developing unit may include a developing solution replacing unit that replaces the developing solution, a developing solution supply unit that supplies the developing solution, and the like.
  • the developer can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include an alkaline solution, an aqueous developer, an organic solvent, and the like. Among these, a weakly alkaline aqueous solution is used. preferable.
  • the basic component of the weak alkaline liquid include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus
  • Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.
  • the pH of the weakly alkaline aqueous solution is more preferably about 9 to 11 force, for example, preferably about 8 to 12.
  • Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of carbonic acid. Examples thereof include an aqueous sodium solution and an aqueous potassium carbonate solution.
  • the temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and for example, about 25 ° C. to 40 ° C. is preferable.
  • the developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.)
  • an organic solvent for example, alcohols, ketones, esters, ethers, amides, latatones, etc.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.
  • the etching step can be performed by a method appropriately selected from among known etching methods.
  • the etching solution used for the etching treatment can be appropriately selected according to the purpose without any particular limitation.
  • a cupric chloride solution examples thereof include a ferric solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
  • a point strength of etching factor—a salty ferric solution is preferable.
  • a permanent pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.
  • the permanent pattern is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a wiring pattern.
  • the plating step can be performed by an appropriately selected method selected from known plating processes.
  • Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-flow solder plating, and Watt bath (nickel sulfate-salt nickel nickel) plating.
  • nickel plating such as nickel sulfamate
  • gold plating such as hard gold plating and soft gold plating.
  • a permanent pattern can be formed.
  • the pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole such as a through hole or a via hole, and for the production of a color filter.
  • a printed wiring board manufacturing method and a color filter manufacturing method using the pattern forming method of the present invention will be described.
  • the pattern forming material is placed on the substrate for forming a printed wiring board having the hole portion as the substrate, and the photosensitive layer thereof.
  • a desired region is irradiated with light from the opposite side of the laminate to the substrate, and the photosensitive layer is cured.
  • the laminated body force The pattern can be formed by removing the support in the pattern forming material, (4) developing the photosensitive layer in the laminated body, and removing the uncured portion in the laminated body.
  • the removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4). Good.
  • a method of etching or plating the printed wiring board forming substrate using the formed pattern for example, a known subtractive method or additive method (for example, Semi-additive method and full additive method)).
  • the subtractive method is preferable in order to form a printed wiring board with industrially advantageous tenting.
  • the cured resin remaining on the printed wiring board forming substrate is peeled off.
  • the copper thin film portion is further etched after the peeling to produce a desired printed wiring board. can do.
  • a multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.
  • a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared.
  • the printed wiring board forming substrate for example, a copper clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates, and a copper plating layer is formed.
  • a formed substrate (laminated substrate) can be used.
  • the lamination temperature of the pattern forming material is not particularly limited, for example, room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.). Among these, under heating (60 to 140 ° C.) ° C) is preferred.
  • the roll pressure of the crimping roll is not particularly limited, for example, 0.1 to lMPa is preferable.
  • the crimping speed is preferably 1 to 3 mZ, which is not particularly limited.
  • the printed wiring board forming substrate may be preheated or laminated under reduced pressure.
  • the laminated body may be formed by laminating the pattern forming material on the printed wiring board forming substrate.
  • the pattern forming composition solution for producing the pattern forming material may be used as the print. Applying directly to the surface of the substrate for forming a wiring board, and drying it, a photosensitive layer and a support may be laminated on the substrate for forming a printed wiring board.
  • the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate.
  • the support may be peeled off and force exposure may be performed.
  • the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer, and the cured layer for forming the wiring pattern and the curing for protecting the metal layer of the through hole are performed.
  • Form a layer pattern and expose the metal layer on the surface of the printed wiring board forming substrate (Development process).
  • a post-heating treatment or a post-exposure treatment may be performed to further accelerate the curing reaction of the cured portion.
  • the development may be a wet development method as described above or a dry development method.
  • etching step the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal coating of the through hole prevents the etching solution from entering the through hole and corroding the metal plating in the through hole. Will remain in the prescribed shape. Thereby, a wiring pattern is formed on the printed wiring board forming substrate.
  • the etching solution is not particularly limited, and can be appropriately selected according to the purpose.
  • a cupric chloride solution a salt solution
  • examples thereof include a ferric solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like.
  • a salty ferric solution is preferable from the viewpoint of an etching factor.
  • the cured layer is removed from the printed wiring board forming substrate as a release piece with a strong alkaline aqueous solution or the like (cured product removing step).
  • the base component in the strong alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide and potassium hydroxide.
  • the pH of the strong alkaline aqueous solution is, for example, preferably about 13-14, more preferably about 12-14.
  • the strong alkaline aqueous solution is not particularly limited, and examples thereof include 1 to 10% by mass of sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
  • the printed wiring board may be a multilayer printed wiring board.
  • the pattern forming material may be used in a Meki process that is performed only by the etching process.
  • the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-salt nickel nickel) plating, nickel plating such as nickel sulfamate, Examples include hard gold plating and gold plating such as soft gold plating.
  • the photosensitive layer of the pattern forming material of the present invention is bonded onto a substrate such as a glass substrate and the support is peeled off from the pattern forming material, the charged support (film) and the human body are uncomfortable. There is a problem that a shock may be received or dust adheres to the charged support body. For this reason, it is preferable to provide a conductive layer on the support or to perform a treatment for imparting conductivity to the support itself. In addition, when the conductive layer is provided on the support opposite to the photosensitive layer, it is preferable to provide a hydrophobic polymer layer in order to improve scratch resistance.
  • a material and a pattern forming material having a black photosensitive layer are prepared.
  • the red photosensitive layer is laminated on the substrate surface to form a laminate, and then exposed and developed imagewise to form red pixels. .
  • the laminate is heated to cure the uncured portion. This is performed in the same manner for the green and blue pixels, and each pixel is formed.
  • the laminated body may be formed by laminating the pattern forming material on the glass substrate, or by applying a pattern forming composition solution for producing the pattern forming material on the surface of the glass substrate.
  • the photosensitive layer and the support may be laminated on the glass substrate by direct application and drying. Further, when three types of pixels of red, green, and blue are arranged, any arrangement such as mosaic type, triangle type, and four pixel arrangement type may be used.
  • a pattern forming material having the black photosensitive layer is laminated on the surface on which the pixels are formed, pixels are formed, and back exposure is performed from the back side, and development is performed to form a black matrix. By heating the laminate on which the black matrix is formed, the uncured portion can be cured to produce a color filter.
  • the pattern forming method and pattern forming apparatus of the present invention uses a pattern forming material that can suppress a decrease in sensitivity of the photosensitive layer and can form a high-definition pattern. Since exposure is possible and the exposure speed is increased, it is advantageous in that the processing speed is increased.
  • the pattern forming method of the present invention uses the pattern forming material of the present invention, various patterns are formed, permanent patterns such as wiring patterns are formed, color filters, pillar materials, rib materials, and spacers. It can be suitably used for the production of liquid crystal structural members such as partition walls, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.
  • the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it forms various patterns, forms permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls It can be suitably used for the production of liquid crystal structure members such as holograms, micromachines, and proofs, and can be particularly suitably used for the formation of high-definition wiring patterns.
  • Examples of the permanent pattern forming method include the following methods. First, similarly to the method for producing the pattern forming material, the pattern forming composition is dissolved, emulsified or dispersed in water or a solvent to prepare a pattern forming composition solution, which is applied onto a substrate, A permanent pattern forming material is produced by drying.
  • the solvent used in the permanent pattern forming method the method of applying the pattern forming composition solution, and the method of drying, the same solvent and method as the method for producing the pattern forming material can be used.
  • the substrate can be appropriately selected from known materials with no medium force, high surface smoothness, and even a material having an uneven surface, and a plate-like substrate (substrate) can be used. More specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate), a glass plate (for example, a soda glass plate), a synthetic resin film, paper, a metal plate, etc. may be mentioned. However, among these, the printed wiring board forming substrate is preferably a multilayer wiring board that can be mounted on a built-up wiring board, etc. It is particularly preferable that the wiring has been formed.
  • the permanent pattern forming material is exposed and developed, and an exposure apparatus and an exposure method used for the exposure, and a developer and a development method used for the development are the exposure and development of the pattern forming material. Similar developments and methods can be used.
  • the permanent pattern forming method of the present invention can suppress a decrease in sensitivity of the photosensitive layer. It is advantageous in that it can be exposed with light of a smaller amount of energy, and the processing speed increases because the exposure speed increases.
  • a pattern forming composition solution consisting of the following pattern forming composition and a solvent is applied to a 20 ⁇ m thick polyethylene terephthalate film as the support, and dried to form a 15 ⁇ m thick photosensitive layer. Then, the pattern forming material was manufactured.
  • composition of pattern forming composition solution [0426]
  • Methyl metatalylate Z styrene Z methacrylic acid copolymer (copolymer composition (mass ratio): 19/52/29, mass average molecular weight: 50,000, acid value 189): 16 parts by mass
  • Fluorosurfactant (Dainippon Ink, F780F): 0.03 parts by mass
  • the photosensitive layer of the pattern forming material On the photosensitive layer of the pattern forming material, a 20 ⁇ m-thick polyethylene film was laminated as the protective film. Next, the pattern forming material is exposed to light while the protective film of the pattern forming material is peeled off from the surface of the copper-clad laminate (no through-hole, copper thickness 12 m) whose surface is polished, washed and dried as the substrate.
  • the laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) is used so that the layer is in contact with the copper-clad laminate, and the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film A laminate in which (support) was laminated in this order was prepared.
  • the pressure bonding conditions were a pressure roll temperature: 105 ° C, a pressure roll pressure: 0.3 MPa, and a laminating speed: lmZ.
  • the manufactured laminate was evaluated for resolution, etching property, surface shape of the photosensitive layer, adhesion to the copper-clad laminate, and exposure rate. The results are shown in Table 3.
  • the laminate strength polyethylene terephthalate film (support) is peeled off, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate.
  • the time required from the start of spraying of the aqueous solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. As a result, the shortest development time was 10 seconds.
  • the photosensitive layer of the pattern forming material in the laminate With respect to the photosensitive layer of the pattern forming material in the laminate, from the polyethylene terephthalate film (support) side, using a pattern forming apparatus having a 405 nm laser light source as the light irradiation means, from 0.lmj / cm 2 The exposure was performed by irradiating with light having different light energy amounts up to 100 mj / cm 2 at 2 1/2 times intervals to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the strength of the laminate was peeled off from the polyethylene terephthalate film (support), and an aqueous sodium carbonate solution (30 ° C, 1% by mass) was applied to the entire surface of the photosensitive layer on the copper clad laminate.
  • an aqueous sodium carbonate solution (30 ° C, 1% by mass
  • the pattern forming apparatus has light modulation means made of the DMD and has the pattern forming material.
  • the polyethylene terephthalate film (support) was peeled off from the laminate.
  • a sodium carbonate aqueous solution (30 ° C, 1% by mass) as the image liquid is applied to the entire surface of the photosensitive layer on the copper-clad laminate at a spray pressure of 0.15 MPa, twice the shortest development time obtained in (1) above. Sprayed for a period of time to dissolve and remove uncured areas.
  • the surface of the copper-clad laminate with a cured resin pattern obtained in this way was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and crease was measured on the cured resin pattern line. This was the resolution. The smaller the numerical value, the better the resolution.
  • the cross-sectional shape of the pattern having no abnormality formed when the resolution measurement was evaluated was observed with a microscope.
  • the cross section is a cross section at the end of the pattern, and a rectangular shape is preferred, followed by a trapezoid.
  • Photomask with line Z space 1Z3, line width 10 ⁇ : Except for using LOO / zm, perform the same operation as the resolution evaluation method in (2) above and peel off the cured resin pattern line. Measure the minimum line width without any abnormalities such as The
  • a pattern was obtained in the same manner as in Example 1 except that pentaerythritol tetrakis (3-mercaptopropionate) in the pattern-forming composition solution was replaced with tetraethylenedaricolbis (3-mercaptopropionate) in Example 1.
  • a forming material was produced.
  • a pattern forming material was produced in the same manner as in Example 1 except that pentaerythritol tetrakis (3-mercaptopropionate) was replaced with dipentaerythritol hexakis (3-mercaptopropionate) in Example 1. .
  • a pattern forming material was produced in the same manner as in Example 1, except that pentaerythritol tetrakis (3-mercaptopropionate) was replaced with pentaerythritol tetrakis (2-mercaptoacetate).
  • Example 1 pentaerythritol tetrakis (3-mercaptopropionate) 1.
  • a pattern forming material was produced in the same manner as in Example 1 except that 33 parts by mass was replaced with 0.67 parts by mass.
  • Example 1 a pattern forming material was produced in the same manner as in Example 1 except that 1.33 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) was replaced by 2.00 parts by mass.
  • Example 1 the sensitivity, resolution, pattern cross-sectional shape, adhesion to the copper-clad laminate, and exposure speed were the same as in Example 1 except that the pattern forming apparatus was replaced with the pattern forming apparatus described below. Evaluation of evaluation was performed. The results are shown in Table 3.
  • the shortest development time is 10 seconds, and the light energy required to cure the photosensitive layer is 7mjZ cm (? At 7 pieces).
  • a pattern forming material was produced in the same manner as in Example 1 except that the content of phenothiazine was 0.001 part by mass in Example 1.
  • Example 9 A pattern forming material was produced in the same manner as in Example 1 except that the content of phenothiazine was 0.007 parts by mass in Example 1.
  • a pattern forming material was produced in the same manner as in Example 1 except that the content of phenothiazine was 0.019 part by mass in Example 1.
  • a pattern forming material was produced in the same manner as in Example 1 except that the content of phenothiazine was 0.05 parts by mass in Example 1.
  • a pattern forming material was produced in the same manner as in Example 1 except that the polymerization inhibitor was changed to phenothiazine catechol in Example 1.
  • Example 13 In Example 1, a pattern forming material was produced in the same manner as in Example 1 except that the polymerization inhibitor was changed to phenothiazine force phenoxazine.
  • Example 1 a pattern forming material was produced in the same manner as in Example 1 except that the polymerization inhibitor was changed from phenothiazine to the following structural formula (78) hindered amine.
  • the toric surface of the microlens described below was 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.
  • DMD50 1024 ⁇ 256 rows of micromirrors 62 are driven.
  • microlens array 55 has 1024 in the horizontal direction. It consists of 256 rows of microlenses 55a arranged side by side in the vertical direction.
  • FIG. 4A 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 the front shape and the 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 is formed into 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, a break parallel to the X direction. Comparing the in-plane and the cross section parallel to the y direction, it can be seen that the radius of curvature of the microlens 55a is smaller in the latter cross section and the focal length is shorter.
  • 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 microlens 55a has a focal length in the cross section parallel to the y direction that is greater than the focal length in the cross section parallel to the X direction.
  • the aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged such that only light that has 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. [0448] (Comparative Example 1)
  • Example 1 a pattern forming material was produced in the same manner as in Example 1 except that phenothiazine was not added.
  • the shortest development time is 10 seconds, and the light energy required to cure the photosensitive layer is approximately 4 mj / cm (?
  • a pattern forming material was produced in the same manner as in Example 1 except that pentaerythritol tetrakis (3-mercaptopropionate) was not added.
  • the shortest development time was 12 seconds, and the amount of light energy required to cure the photosensitive layer was 19 mjZcm 2 .
  • a pattern forming material was produced in the same manner as in Example 1 except that pentaerythritol tetrakis (3-mercaptopropionate) was replaced with 2-ethylhexyl-3-mercaptopropionate in Example 1.
  • the shortest development time was 11 seconds, and the light energy required to cure the photosensitive layer was 16mjZ cm (?).
  • Comparative Example 2 a pattern forming material was produced in the same manner as in Comparative Example 1, except that phenothiazine was not added. Using the produced pattern forming material, the sensitivity, resolution, pattern shape of the cross section, adhesion to the copper-clad laminate, and exposure speed were evaluated in the same manner as in Example 1. The results are shown in Table 4.
  • the shortest development time was 12 seconds, and the light energy required to cure the photosensitive layer was 16mjZ cm (?).
  • Examples 1 to 8 do not affect the resolution by containing a chain transfer compound having a plurality of substituents capable of chain transfer in the molecule.
  • the sensitivity was found to be excellent.
  • Examples 2 to 7 using a chain transfer compound having four chain transferable substituents were more sensitive than Example 1 using a chain transfer compound having two chain transferable substituents.
  • Example 7 it was found that the resolution was even better.
  • the pattern forming materials of Examples 1 to 7 can obtain a pattern having a good shape by further containing a polymerization inhibitor.
  • the pattern shape force S is a kamaboko shape (the upper part of the pattern is rounded and narrowed), and a good pattern shape is obtained.
  • the pattern forming composition of the present invention and the pattern forming material of the present invention have good sensitivity and resolution, provide a high-definition pattern, and adherence to a substrate such as a printed wiring board substrate.
  • a substrate such as a printed wiring board substrate.
  • the formation of permanent patterns such as wiring patterns, the manufacture of color filters, pillar materials, rib materials, spacers, partition walls and other liquid crystal structural members, the manufacture of holograms, micromachines, and proofs It can be used suitably, and can be used particularly preferably for forming a high-definition wiring pattern.
  • the pattern forming apparatus of the present invention includes the pattern forming material of the present invention.
  • Suitable for various pattern formation formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, manufacturing of liquid crystal structures such as partition walls, holograms, micromachines, proofs, etc.
  • it can be suitably used for forming a high-definition wiring pattern.
  • the pattern forming method of the present invention uses the pattern forming material of the present invention, formation of various patterns, formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls It can be suitably used for the production of liquid crystal structural members such as holograms, micromachines, and proofs, and can be particularly suitably used for the formation of high-definition wiring patterns.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

La présente invention concerne par exemple une composition de formation de motif d’une bonne sensibilité et d’une bonne définition, susceptible de produire un motif haute définition, tout en présentant une excellente adhérence aux substrats tels que les substrats utilisés pour la formation de connexions imprimées, avec une forme adéquate des motifs une fois réalisés. La composition de formation de motif comprend un composé de transfert de chaîne ayant une pluralité de substituants transférables par chaîne, un initiateur de polymérisation, un liant, un composé polymérisable et un initiateur de photopolymérisation. Dans la composition de formation de motif, de préférence, par exemple, le substituant transférable par chaîne est un groupe mercapté.
PCT/JP2005/020391 2004-11-12 2005-11-07 Composition de formation de motif et matériau de formation de motif, et appareil de formation de motif et procédé de formation de motif Ceased WO2006051761A1 (fr)

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JP4631468B2 (ja) * 2005-02-28 2011-02-16 凸版印刷株式会社 光硬化性樹脂組成物及びそれを用いて形成したフォトスペーサを有するカラーフィルタ
TW200832065A (en) 2006-08-11 2008-08-01 Sumitomo Chemical Co Polymerizable resin composition
JP5023878B2 (ja) * 2006-08-11 2012-09-12 住友化学株式会社 重合性樹脂組成物
JP5051365B2 (ja) * 2006-08-24 2012-10-17 Ｊｓｒ株式会社 感光性樹脂組成物、表示パネル用スペーサーおよび表示パネル
JP2010113349A (ja) * 2008-10-10 2010-05-20 Asahi Kasei E-Materials Corp 感光性樹脂組成物
JP5660774B2 (ja) * 2009-11-04 2015-01-28 住友化学株式会社 着色感光性樹脂組成物、塗膜、パターン及び表示装置
CN103430099B (zh) * 2011-03-23 2018-02-13 三菱化学株式会社 着色树脂组合物、滤色片、液晶显示装置及有机el显示装置
JP6079277B2 (ja) * 2013-02-04 2017-02-15 日本ゼオン株式会社 感放射線樹脂組成物及び電子部品
TWI604272B (zh) * 2013-05-24 2017-11-01 奇美實業股份有限公司 彩色濾光片用藍色感光性樹脂組成物及其應用
WO2017038708A1 (fr) * 2015-08-31 2017-03-09 富士フイルム株式会社 Composition photosensible de coloration, film durci, filtre de couleur, film de protection contre la lumière, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, et procédé de fabrication de film durci

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