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WO2006025389A1 - Matériau de formation de motifs, appareil de formation de motifs et procédé de formation de motifs - Google Patents

Matériau de formation de motifs, appareil de formation de motifs et procédé de formation de motifs Download PDF

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Publication number
WO2006025389A1
WO2006025389A1 PCT/JP2005/015768 JP2005015768W WO2006025389A1 WO 2006025389 A1 WO2006025389 A1 WO 2006025389A1 JP 2005015768 W JP2005015768 W JP 2005015768W WO 2006025389 A1 WO2006025389 A1 WO 2006025389A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
pattern forming
pattern
forming material
meth
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/JP2005/015768
Other languages
English (en)
Japanese (ja)
Inventor
Masayuki Iwasaki
Yoshiharu Sasaki
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
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of WO2006025389A1 publication Critical patent/WO2006025389A1/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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/70283—Mask effects on the imaging process
    • G03F7/70291—Addressable masks, e.g. spatial light modulators [SLMs], digital micro-mirror devices [DMDs] or liquid crystal display [LCD] patterning devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces

Definitions

  • the present invention relates to a pattern forming material suitable for manufacturing a printed wiring board, a color filter, and the like, a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material.
  • Forming material is used.
  • a method for forming the pattern for example, a layered body is formed by laminating the pattern forming material on a substrate on which a pattern is formed, and the photosensitive layer in the layered body is exposed to light, and then the pattern is formed.
  • a pattern is formed by developing the photosensitive layer, and then a permanent pattern is formed by performing an etching process or the like.
  • a pattern forming material for a color filter having a plurality of colored layers after forming the first color pattern, when the second color pattern is formed, the already formed first color pattern impairs the lamination property of the second color photosensitive layer.
  • the printed wiring board pattern forming material dry film resist
  • the photosensitive layer is made thin in order to obtain high resolution, the laminating property is impaired by the unevenness on the surface of the metal substrate. There is a problem.
  • a cushion layer (thermoplastic resin) is provided between the photosensitive layer and the support.
  • a pattern forming material having a layer) has been developed (see Patent Documents 1 to 16). Due to the presence of the cushion layer, the followability to an already formed pattern or substrate is improved, and the photosensitive layer can be laminated without generating bubbles.
  • the cushion layer is peeled off before exposure (for example, Patent Documents 2 to 10, and 15 to 16). It is difficult to peel off the cushion layer without damaging the photosensitive layer from the thin photosensitive layer to obtain the above.
  • a pattern forming material, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material have not been provided yet, and further improvement and development are desired at present.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-173320
  • Patent Document 2 Japanese Patent Laid-Open No. 7-20309
  • Patent Document 3 Japanese Patent Laid-Open No. 11-72908
  • Patent Document 4 JP-A-11 109124
  • Patent Document 5 Japanese Patent Laid-Open No. 11 174220
  • Patent Document 6 Japanese Patent Laid-Open No. 11 338133
  • Patent Document 7 Japanese Patent Laid-Open No. 2000-250222
  • Patent Document 8 Japanese Patent Laid-Open No. 2000-250221
  • Patent Document 9 Japanese Unexamined Patent Publication No. 2000-266925
  • Patent Document 10 Japanese Patent Laid-Open No. 2001-142223
  • Patent Document 11 Japanese Patent Laid-Open No. 2003-5364
  • Patent Document 12 Japanese Unexamined Patent Publication No. 2003-215793
  • Patent Document 13 Japanese Patent Laid-Open No. 2003-228165
  • Patent Document 14 Japanese Patent Laid-Open No. 2003-302765
  • Patent Document 15 Japanese Patent Application Laid-Open No. 2003-307845
  • Patent Document 16 Japanese Patent Laid-Open No. 5-72724
  • the present invention has been made in view of the current situation, and it is an object of the present invention to solve the above-described problems and achieve the following objects. That is, the present invention has a cushion layer and a photosensitive layer on the support in this order, and the total light transmittance and haze value in the cushion layer are within a certain numerical range, so that the uneven follow-up property and the high sensitivity can be achieved.
  • a pattern forming material that is compatible with resolution and that can efficiently form a high-definition pattern without defects, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material The purpose is to provide.
  • ⁇ 3> The pattern forming material according to any one of ⁇ 1> to ⁇ 2>, wherein an average particle size of the fine particles contained in the cushion layer is less than 1 ⁇ m.
  • the cushion layer upper force is also exposed. As a result, a defect-free pattern is formed.
  • ⁇ 5> The pattern forming material according to any one of ⁇ 1> to ⁇ 4>, wherein the thickness force of the cushion layer is 6 to 100111.
  • ⁇ 6> The pattern forming material according to any one of ⁇ 1> to ⁇ 5> above, which has a noble layer capable of suppressing the movement of a substance between the cushion layer and the photosensitive layer.
  • the pattern forming material described in ⁇ 6> has the barrier layer. As a result, a decrease in sensitivity of the photosensitive layer is suppressed.
  • the first photosensitive layer and the second photosensitive layer having a smaller amount of light energy for curing than the first photosensitive layer are laminated in this order.
  • the pattern forming material according to any one of the above. In the pattern forming material described in ⁇ 7>, three-dimensional modeling with different thicknesses inside the image, increasing the strength of the film only in the desired region, or increasing the image density only in the desired region, etc. It is possible to form a cured resin image or the like having characteristics imparted with one kind of pattern forming material.
  • ⁇ 8> The pattern forming material according to ⁇ 7>, wherein a barrier layer is provided between the first photosensitive layer and the second photosensitive layer.
  • cushion layer strength Formed by applying a cushion layer composition coating solution, in which the composition contained in the cushion layer is dissolved, emulsified, or dispersed, through a filter, and then coating and drying on a support.
  • the fine particles such as fine foreign matters and gellic substances contained in the cushion layer composition coating solution are removed by a filter, so that the cushion layer composition is coated on the cushion layer composition.
  • 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.
  • Device In the pattern forming apparatus described in 11>
  • the light irradiating means irradiates light toward the light modulating 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 means generates a control signal based on the pattern information to be formed
  • the pattern forming device further comprising a pattern signal generation unit, wherein the light emitted from the light irradiation unit is modulated according to a control signal generated by the pattern signal generation unit.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, 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 has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts.
  • the pattern forming apparatus according to any one of the above 11> Karaku 12> which can be controlled according to pattern information.
  • an arbitrary less than n pixel portions arranged continuously from n pixel portions 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.
  • ⁇ 16> The pattern forming apparatus according to any one of ⁇ 11>, ⁇ 15>, wherein the picture element portion is a micromirror.
  • ⁇ 17> The pattern forming apparatus according to any one of the items ⁇ 11> to ⁇ 16>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
  • the pattern forming apparatus described in ⁇ 17> exposure is performed by exposure light having a deep focal depth because the light irradiation means can synthesize and irradiate two or more lights.
  • 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 irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated with the plurality of laser forces and couples the laser beams to the multimode optical fiber.
  • the pattern forming apparatus according to any one of the above items 11> Karaku 17>.
  • the light irradiation unit is configured to receive the laser beams irradiated with the plurality of laser forces. Since the light is condensed by an optical system and can be coupled to the multimode optical fiber, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • ⁇ 21> The pattern forming method according to any one of ⁇ 19>, ⁇ 20>, wherein the exposure is performed imagewise based on pattern information to be formed.
  • the pattern forming method according to any one of the above 19> Karaku 23> which is performed by light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface are arranged. .
  • the pattern forming method according to 24> In this case, the light modulated by the light modulation means passes through the aspherical surface in the microlens array, so that the aberration due to the distortion of the exit surface in the pixel portion is corrected. As a result, distortion of the 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 developed thereafter, an extremely fine pattern is formed.
  • ⁇ 26> The pattern forming method according to any one of the above items ⁇ 19>, ⁇ 25>, wherein the exposure is performed through an aperture array. Further, in the pattern forming method described in 26>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • ⁇ 27> The pattern forming method according to ⁇ 19>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
  • exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • ⁇ 30> The pattern formation method according to ⁇ 29>, 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.
  • ⁇ 31> The pattern forming method according to ⁇ 29>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
  • the conventional problems can be solved, and the cushion layer and the photosensitive layer are provided on the support in this order, and the total light transmittance and the haze value in the cushion layer are constant numerical values. If it is within the range, a pattern forming material capable of simultaneously forming unevenness followability and high resolution, and capable of efficiently forming a defect-free V and high-definition pattern, and a pattern forming apparatus provided with the pattern forming material And a pattern forming method using the pattern forming material.
  • 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 similar to FIG. 2A.
  • FIG. 3A is an example of a plan view showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined.
  • FIG. 3B is an example of a plan view showing a comparison of exposure beam arrangement and scanning lines when the DMD similar to FIG. 3A is not inclined and when it is inclined.
  • FIG. 4A is an example of a diagram illustrating an example of a DMD usage area.
  • FIG. 4B is an example of a diagram showing an example of a DMD usage area similar to FIG. 4A.
  • FIG. 5 is an example of a plan view for explaining an exposure method in which a pattern forming material is exposed by one scanning by a scanner.
  • FIG. 6A is an example of a plan view for explaining an exposure method for exposing a pattern forming material by a plurality of scans by a scanner.
  • FIG. 6B is an example of a plan view for explaining an exposure method for exposing the pattern forming material by a plurality of scans by the same scanner as in FIG. 6A.
  • 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 a pattern forming material.
  • FIG. 9B is an example of a diagram showing an arrangement of exposure areas by each exposure head.
  • FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means.
  • FIG. 11 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG.
  • FIG. 12 shows an example of a controller that controls DMD based on pattern information.
  • FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system.
  • FIG. 13B is an example of a plan view showing an optical image projected onto the exposure surface when a microlens array or the like is not used.
  • FIG. 13C is an example of a plan view showing an optical image projected onto an exposed surface when a microlens array or the like is used.
  • FIG. 14 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines.
  • FIG. 15A 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 a microlens array. is there.
  • 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. 19B, but at different positions.
  • FIG. 19C is an example of a diagram showing a simulation result similar to FIG. 19A at another position.
  • FIG. 19D is an example of a diagram showing a simulation result similar to FIG. 19A at another position.
  • FIG. 20A is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method.
  • FIG. 20B is an example of a diagram showing the same simulation results as in FIG. 20A but at different positions.
  • FIG. 20C 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 a 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 (A)
  • FIG. 27A (C) and (D ) Is an example of a plan view showing an array of light emitting points in the laser emitting portion.
  • 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 is an example of a cross-sectional view along the optical axis showing the difference between the depth of focus in a conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention.
  • FIG. 37B is an example of a cross-sectional view along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention.
  • the pattern forming material of the present invention has a cushion layer and a photosensitive layer in this order on a support.
  • the cushion layer which may have other layers appropriately selected as necessary, satisfies the total light transmittance of 86% or more and a haze value of 10% or less.
  • the cushion layer can be appropriately selected according to the purpose without particular limitation as long as the total light transmittance is 86% or more and the haze value is 10% or less.
  • thermoplastic resin is used as the cushion layer.
  • the inclusion is preferred.
  • the wavelength of light when obtaining the total light transmittance and the haze value is preferably 405 nm! /.
  • the total light transmittance of the cushion layer is preferably 86% or more, more preferably 87% or more, and particularly preferably 89% or more.
  • the cushion layer When the cushion layer is irradiated with 405 nm light, the cushion layer has a haze value of 10% or less, preferably 7% or less, more preferably 5% or less. 3% or less is particularly preferred, and 1% or less is most preferred.
  • the haze value exceeds 10%, the amount of light scattering in the cushion layer increases, the resolution decreases, and the resist shape may be inferior, such as defects.
  • the method for measuring the total light transmittance is appropriately selected according to the purpose without any particular limitation.
  • a measurement method using an integrating sphere and a spectrophotometer capable of irradiating light of 405 nm for example, UV-2400 manufactured by Shimadzu Corporation
  • a spectrophotometer capable of irradiating light of 405 nm for example, UV-2400 manufactured by Shimadzu Corporation
  • a force that can be appropriately selected according to the purpose for which there is no particular limitation, for example, the method described below can be cited.
  • the parallel light transmittance is measured in the same manner as the total light transmittance measurement method except that the integrating sphere is not used.
  • Examples of the fine particles and aggregates thereof present in the cushion layer include precipitated particles and gel-like substances generated during the production process of the cushion layer composition coating liquid.
  • voids may be generated in the photosensitive layer during exposure, and defects may be generated in the formed pattern.
  • the precipitated particles and the gel-like substance are a catalyst at the time of producing the raw material polymer, a high polymerization degree polymer or a thermal decomposition product locally generated at the time of producing the raw material polymer.
  • the average particle size of the fine particles allowed to be present in the cushion layer and the aggregates thereof is preferably a force S of less than 1 ⁇ m, more preferably a force S of less than 0.5 m, Particularly preferred is less than 2 m.
  • the average particle size of the fine particles and aggregates present in the cushion layer exceeds 1 ⁇ m, the resolution may decrease due to scattering of exposure light.
  • the average particle size is
  • the haze value may decrease if it is contained in a large amount.
  • Examples of the method for measuring the average particle diameter of the fine particles and the aggregates thereof include a method of taking a photograph of a large number of foreign matters with a scanning electron microscope (SEM) and measuring the diameter of the foreign matters on the photograph. It is done.
  • SEM scanning electron microscope
  • the thermoplastic resin preferably contains a thermoplastic resin having a glass transition temperature (Tg) and a softening point of at least 80 ° C.
  • Tg glass transition temperature
  • the softening point of the thermoplastic resin is preferably 80 ° C or less, preferably 60 ° C or less, according to the Vicat method (American material test method ASTMD1235 polymer softening point measurement method). It is particularly preferable that the temperature is 50 ° C or less.
  • thermoplastic resin having a softness point by the Vicat method of 80 ° C. or higher When a thermoplastic resin having a softness point by the Vicat method of 80 ° C. or higher is used, it is necessary to laminate the pattern forming material on a substrate at a high temperature, which is disadvantageous in terms of work.
  • thermoplastic resin examples include polyolefins such as polyethylene and polypropylene, and copolymers thereof; ethylene copolymers such as ethylene vinyl acetate copolymer, ethylene vinyl acetate copolymer kenich; ethylene acrylic acid Ester copolymer and saponified product thereof; polyvinyl chloride; vinyl chloride copolymer such as vinyl chloride-vinyl acetate copolymer and saponified product thereof; polysalt vinylidene; vinylidene chloride copolymer; polystyrene; Styrene copolymer such as styrene (meth) acrylate ester and saponified product thereof; polytoluene toluene; butyltoluene; methacrylic acid ester copolymer and butyltoluene copolymer such as kenicate Poly (meth) acrylic acid esters; butyl (meth) acrylate and butyl
  • thermoplastic resin having a softening point of 80 ° C or less includes the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Organic polymers with a softening point of about 80 ° C or less as of October 25, 1968).
  • thermoplastic resin having a soft softening point of 80 ° C or higher various plasticizers compatible with the thermoplastic resin are added to obtain a substantial soft softening point. Can be lowered below 80 ° C.
  • the plasticizer is not particularly limited and may be appropriately selected according to the purpose. For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutino phthalate, tricresyl phosphate , Krezhno Regihue -Alcohols and esters such as ruphosphate and biphenyl diphosphate; amides such as toluenesulfonamide and the like.
  • the cushion layer is prepared by dissolving the thermoplastic resin and, if necessary, other components in a solvent to prepare a coating solution (cushion layer composition coating solution). It can be formed by coating or the like.
  • a coating solution cushion layer composition coating solution
  • the solvent include organic solvents such as methyl ethyl ketone and 1-methoxy-2-propanol, water, and a mixed solution of water and an organic solvent miscible with water.
  • the thermoplastic resin may have a solubility characteristic that is soluble in a solvent in which the composition of the photosensitive layer does not dissolve at all. Good.
  • the cushion layer composition coating liquid is used as the thermoplastic layer.
  • Preferred is an aqueous dispersion of oily polymer fine particles.
  • the cushion layer may be swellable or soluble in an alkaline liquid, or may be insoluble.
  • the thermoplastic resin mainly contains an alkali-soluble thermoplastic polymer, and optionally contains other components.
  • the acid value (mgKOH / g) of the thermoplastic polymer is not particularly limited.
  • a force that can be appropriately selected according to the purpose 50 to 300 force S, preferably 60 to 270 parts S, more preferably 70 to 250 is particularly preferred.
  • the acid value is within the above range, the developability of the cushion layer can be ensured.
  • the acid value is less than 50, development failure may occur.
  • the acid value exceeds 300, the cushion layer becomes too hard, and uneven followability and laminating properties may be deteriorated.
  • the weight average molecular weight of the thermoplastic polymer is not particularly limited and may be appropriately selected according to the purpose.
  • Force S capable of being 1,000 to 300,000 power S, preferably 3,000 to 200,000 A force of 5,000 to 150,000 is particularly preferred.
  • the weight average molecular weight is in the above range, developability of the cushion layer can be ensured, and the viscosity r? It becomes easy to save. Further, the effect can be further obtained by the combination with the above acid value range. If the weight average molecular weight is less than 1,000, the membrane may become fragile or the cushion layer may exude during lamination. If it exceeds 300,000, the cushion layer may become too hard, and the unevenness followability and laminating properties may deteriorate.
  • a copolymer of a carboxylic acid-containing monomer and a (meth) acrylic acid ester monomer can also be used.
  • the carboxylic acid-containing monomer include acrylic acid, methacrylic acid, and derivatives thereof.
  • (Meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Etc.
  • the copolymer may be a binary polymer of a carboxylic acid-containing monomer and an acrylate ester monomer or a multi-polymer, such as methyl metatalate or 2-ethylhexyl meta methacrylic acid.
  • a methacrylic acid Z-methyl methacrylate / Z2-ethylhexyl acrylate / Z-benzyl methacrylate copolymer is particularly preferred.
  • the interlayer adhesive force of the pattern forming material is not particularly limited and can be appropriately selected according to the purpose.
  • the interlayer adhesive force between the support and the cushion layer is the smallest among the interlayer adhesive strengths of the respective layers.
  • the interlayer adhesive strength only the support is peeled off from the laminate, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. be able to.
  • the photosensitive layer can be developed using an alkaline developer.
  • the method for adjusting the interlayer adhesive force is not particularly limited and may be appropriately selected depending on the purpose.
  • a known polymer, supercooling substance, or adhesion improver in the thermoplastic resin is used.
  • the thermoplastic resin include a copolymer whose main component is an essential copolymer component of ethylene.
  • the copolymer having ethylene as an essential copolymer component is a force that can be appropriately selected according to the purpose without any particular limitation.
  • ethylene vinyl acetate copolymer (EV A) ethylene-ethyl acrylate. Copolymer (EEA) and the like.
  • the interlayer adhesive force of the pattern forming material can be appropriately selected according to the purpose without any particular limitation.
  • the adhesive strength between the photosensitive layer and the cushion layer is preferably the smallest.
  • the photosensitive layer is exposed while leaving the support, and then the support and the cushion layer are peeled off from the laminate, and an alkaline developer is used.
  • the photosensitive layer can also be developed.
  • the photosensitive layer can be developed using an alkaline developer.
  • the method for adjusting the interlayer adhesive force can be appropriately selected according to the purpose without any particular limitation.
  • various polymers, supercooling substances, adhesion improvers in the thermoplastic resin can be selected.
  • the ethylene copolymerization ratio in the copolymer having ethylene as an essential copolymerization component is a force that can be appropriately selected according to the purpose without any particular limitation. For example, 60 to 90% by mass is preferable. 60-80% by mass is more preferred. 65-80% by mass is particularly preferred.
  • the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. If the amount exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled off. It may be difficult to produce a pattern forming material containing
  • the cushion layer is insoluble in an alkaline solution and a barrier layer is present between the cushion layer and the photosensitive layer, the sensitivity is increased in the interlayer adhesion of each layer. It is preferable that the interlayer adhesion between the optical layer and the barrier layer is the smallest!
  • the photosensitive layer is exposed through the cushion layer while leaving the support without peeling, and then the support, the cushion layer, and It is also possible to peel off the barrier layer and develop the photosensitive layer using an alkaline developer.
  • this photosensitive layer can also be developed using an alkaline developing solution.
  • the method for adjusting the interlayer adhesive force can be appropriately selected according to the purpose without any particular limitation.
  • a method of containing a release agent in the photosensitive layer, the cushion layer and the barrier Content of at least one selected from a method for surface-treating an adhesive surface with a layer, a method for surface-treating an adhesive surface between the support and the cushion layer, and a component contained in at least one of the layers And a method of containing or applying a component for improving the adhesive strength. These methods may be used alone or in combination of two or more.
  • the release agent can be appropriately selected from known release agents without particular limitations, and examples thereof include silicone compounds and compounds having a fluorinated alkyl group.
  • silicone compound examples include Daicel UCB, Evecril 1360, 350, Toshiba Silicone Dimethyl Silicone Oil TSF400, Methylphenol Silco 1-year-old Inole TSF4300, TSF4446, TSF4460, TSF4452 etc. are listed.
  • Examples of the compound having a fluorinated alkyl group include a fluorine-based surfactant (for example, perfluoroalkyl group 'hydrophilic group-containing oligomer F-171, manufactured by Dainippon Ink & Chemicals, Inc.
  • a fluorine-based surfactant for example, perfluoroalkyl group 'hydrophilic group-containing oligomer F-171, manufactured by Dainippon Ink & Chemicals, Inc.
  • Examples of the surface treatment include plasma treatment, electron beam treatment, glow discharge treatment, corona discharge treatment, and ultraviolet irradiation treatment.
  • Examples of the component for improving the adhesive strength include phenolic substances (for example, cresol monovolak resin, phenol resin, and the like), polysalt-vinylidene resin, styrene butadiene rubber, gelatin, polybulal alcohol, cellulose. And the like. These may be included in at least one of the support, the cushion layer, and the barrier layer as needed, and the contact surface between the support and the cushion layer, the cushion layer, and the barrier layer. You may apply
  • crosslinking agent examples include borax, boric acid, borates (for example, orthoborate, InBO
  • Aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chlorodiethylurea) -2 hydroxy 4, 6 dichloro 1, 3, 5 Active halogen compounds such as triazine, 2, 4 dichloro-6-S-triazine 'sodium salt; divinylsulfonic acid, 1,3 berylsulfoluol 2-propanol, ⁇ , ⁇ , monoethylenebis (birusulfuluolacetamide) ), 1, 3, 5 Triarylloyl-hexahydro S Triazine and other active bur compounds; dimethylol urea, methyloldimethylhydantoin and other ⁇ -methylol compounds; melamine linseed (eg, methyl
  • silane coupling agent examples include N-2 (aminoethyl) 3 aminopropyl methyldimethoxysilane, N-2 (aminoethyl) 3 aminopropyltrimethoxysilane, N-2 (aminoethyl) 3 Minopropyltriethoxysilane, 3 aminopropyltrimethoxysilane, 3 aminopropyltriethoxysilane, 3 triethoxysilyl mono N— (1, 3 dimethyl)
  • a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be suitably used.
  • the layer containing at least one of the cross-linking agent and the silane coupling agent can be appropriately selected according to the purpose without any particular limitation.
  • the cushion layer and the noria layer are preferable. More preferably, the cushion layer alone is more preferable.
  • At least one selected from the components included in the support layer at least one selected from the components included in the tack layer, and the components included in the barrier layer.
  • the component force contained in the cushion layer is selected from the components contained in the photosensitive layer, wherein at least one selected from the component force and at least one selected from the components contained in the barrier layer are made into a hydrophobic substance.
  • the component is polybulal alcohol
  • the polybulal alcohol having a saponification degree of 85% or less, or a modified polybulal alcohol can be appropriately selected and used.
  • the polybulal alcohol may be used in combination with the crosslinking agent, the silane coupling agent, or the like.
  • modified polybulal alcohol examples include cation-modified polybulal alcohol (for example, carboxy-modified polybulal alcohol), cation-modified polybulal alcohol, acetoacetylated polybulal alcohol, silanol-modified polybulal alcohol, hydrophobic group-modified polybutyl alcohol.
  • examples include polybulal alcohol (for example, terminal alkylpolybulal alcohol), hydrophilic group-modified polyvinyl alcohol (for example, ethylene oxide-modified polybulal alcohol), terminal thiol polybulal alcohol, exeval (manufactured by KURARENE), and the like.
  • thermoplastic resins described above the laminating property to the substrate is good, the releasability from the noria layer is good, and the photosensitive layer component migration prevention property is excellent, and the production is advantageous.
  • Ethylene vinyl acetate copolymer and olefin fin ionomer are particularly preferred.
  • the cushion layer may be formed by filtering a cushion layer composition coating solution in which the above-described composition is dissolved, emulsified, or dispersed, through a filter, and coating and drying on a support.
  • a filter preferably has a pore diameter of 30 m or less.
  • the thickness of the cushion layer can be appropriately selected according to the purpose for which there is no particular limitation, but f column; t is 6 to: LOO / zm force S girlish, 10 to 50 111 15 to 40
  • the thickness is less than 6 m, unevenness on the surface of the substrate or unevenness followability to bubbles and the like may be deteriorated, and a high-definition permanent pattern may not be formed. Problems such as increased drying load may occur.
  • the photosensitive layer can be appropriately selected from known pattern forming materials with no particular restrictions.
  • the photosensitive layer includes a noinder, a polymerizable compound, and a photopolymerization initiator, and is appropriately selected. Those containing other components are preferred.
  • the number of photosensitive layers to be laminated is appropriately selected according to the purpose for which there is no particular limitation.
  • it may be a single layer or two or more layers.
  • the noinder is preferably swellable in an alkaline aqueous solution and more preferably soluble in an alkaline aqueous solution.
  • binder exhibiting swellability or solubility with respect to the alkaline aqueous solution for example, those having an acidic group are preferably exemplified.
  • 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.
  • 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 monomers are not particularly limited and can be appropriately selected depending on the purpose.
  • Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate.
  • crotonic acid esters examples include butyl crotonic acid and hexyl crotonic acid.
  • 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) amide, N-t-butyl (meth) acrylamide, N cyclohexyl (meth) acrylamide, N— (2-methoxyethyl) (meth) acrylamide, N, N dimethyl (meth) acrylamide N, N Jetyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) attalyloylmorpholine, diacetone acrylamide and the like.
  • styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropylene styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, aceto styrene, chlorostyrene, Examples thereof include dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, and a-methylstyrene.
  • an acidic substance for example, t-Boc, etc.
  • butyl ethers examples include methyl butyl ether, butyl benzene ether, hexyl butyl ether, methoxyethyl butyl ether, and the like.
  • a method for synthesizing a vinyl monomer having a urethane group or a urea group as the functional group examples thereof 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 compound containing one hydroxyl group or a primary or secondary amino group Addition reaction with a compound having one of these, and addition reaction of a monomer having a hydroxyl group or a monomer having a primary or secondary amino group with a monoisocyanate.
  • Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).
  • R 1 represents a hydrogen atom or a methyl group.
  • Examples of the monoisocyanate include cyclohexylenoisocyanate, n-butynoleisocyanate, tolylisocyanate, benzylisocyanate, phenylisocyanate, and the like.
  • Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).
  • R 1 represents a hydrogen atom or a methyl group
  • n, nl, and n 2 represent 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, t-butanol, n-hexanol).
  • alcohols for example, methanol, ethanol, n -propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol.
  • phenols eg, phenol, cresol, Naphthol and the like, and those further containing a substituent include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, black mouth phenol, dichloro phenol, methoxy phenol, and acetophenol.
  • 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, t-butylamine, hexylamine, 2 —Ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, jetylamine, Dibutylamine, dioctylamine), cyclic alkylamines (cyclopentylamine, cyclohexylamine, etc.), aralkylamines (benzylamine, phenethylamine, etc.), arylamines (allin, tolylamine, xylylamine, naphthylamine, etc.), and combinations thereof (N— Methyl-N benzylamine, etc.), and amines having further substituents (trifluor fluor
  • 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.
  • solvents 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)
  • Etc. peroxy compounds such as benzoyl peroxide, potassium persulfate, ammonium persulfate Persulfates such as um.
  • [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.
  • the content is less than 5 mol%, the developability to alkaline water may be insufficient, and when it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.
  • the molecular weight of the binder having a carboxyl group is not particularly limited.
  • the force can be appropriately selected according to the purpose.
  • the mass average molecular weight is preferably 2,000 to 300,000, and preferably 4,000. ⁇ 150,000 power ⁇ Preferred more! / ⁇ .
  • the mass average molecular weight is less than 2,000, the strength of the film may be insufficient and stable production may be difficult immediately. If it exceeds 300,000, developability may be deteriorated.
  • 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 aqueous solution described in Japanese Patent No. 2873889 can be used.
  • the content of the binder in the photosensitive layer is not particularly limited, and can be appropriately selected according to the purpose. For example, 10 to 90% by mass is preferable 20 to 80% by mass
  • 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 can be appropriately selected according to the purpose.
  • 70 to 250 (mgKOH / g) is preferable, and 90 to 200 (mgKOH / g) is preferable. More preferred is 100 to 180 (mg KOH / g).
  • the acid value is less than 70 (mgKOHZg)
  • developability may be insufficient
  • resolution may be inferior
  • permanent patterns such as wiring patterns may not be obtained in high definition
  • the polymerizable compound is not particularly limited and may be appropriately selected according to the purpose.
  • a monomer or oligomer having at least one of a urethane group and an aryl group is preferably exemplified. 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.
  • Diisocyanates such as' -diphenyl diisocyanate; an adduct of the diisocyanate with a bifunctional alcohol (in this case, both ends are also isocyanate groups); a trimer such as a burette or isocyanurate of the diisocyanate; Diisocyanate or diisocyanates and trimethylolpropane, penta Examples thereof include adducts with other functional alcohols such as polyfunctional alcohols such as erythritol and glycerin, or these ethylene oxide adducts.
  • 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, triethylene glycol mono (meth) acrylate, tetraethylene dallicol mono (meth) acrylate, otaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono ( (Meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono ) Atalylate, dibutylene glycol mono (meth) acrylate, tribubutylene glycol mono (meth) acrylate, tetra
  • 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.
  • compounds represented by the following structural formula (13) or structural formula (14) are preferable. From the viewpoint of tentability, it is particularly preferable that at least the compound represented by the structural formula (14) is included. In addition, these compounds may be used alone or in combination of two or more.
  • ⁇ ⁇ represents a hydrogen atom or a methyl group, respectively.
  • X to X 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 alkkelene 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
  • 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 preferably an integer of 1 to 100, for example, an integer of 1 to 50, more preferably an integer of 3 to 30 is particularly preferable.
  • 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.
  • 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,
  • 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 (13) and (14) include the following structural formulas (15)
  • 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.
  • polyhydric alcohol compound examples include polystyrene oxide, xylylenediol, di--hydroxyethoxy) benzene, 1, 5 Dihydroxy mono 1, 2, 3, 4-tetrahydronaphthalene, 2, 2 diphenyl 2, 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-nor 1, 4-butanediol, 1, 1, 4, 4-tetrafluoro ninole 2 butyne 1, 4-diol 1, 1'—Bee 2—Naphthol, dihydroxynaphthalene, 1, 1'-methylene oji 2 Naphthol, 1, 2, 4 benzenetriol, bi
  • xylylene bis (meth) acrylamide, novolac-type epoxy resin bisphenol A diglycidyl ether and other glycidyl compounds 0 compounds obtained by adding ⁇ unsaturated carboxylic acid, phthalic acid N trimellit Vinyl monomers that contain acid and other hydroxyl groups in the molecule Esterified products obtained, diallyl phthalate, triallyl trimellitic acid, diallyl benzendisulfonate, cationically polymerizable dibule ethers as polymerizable monomers (for example, bisphenol ⁇ Dibutyl ether), epoxy compounds (for example, novolak type epoxy resin, bisphenol A diglycidyl ether, etc.), bur esters (for example, dibutyl phthalate, dibuter terephthalate, divinylbenzene 1,3 disulfonate, etc.) , Still Compounds such as dibutenebenzene, p-aryl styrene, p-iso
  • 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 them, among these, ethylene oxide An ethylene oxide group and a propylene oxide group, which are preferred are a group, a propylene oxide group, a butylene oxide group, or a combination thereof.
  • m5 and m6 are preferably integers of 1 to 60, more preferably integers of 2 to 30, and particularly preferably integers of 4 to 15.
  • T represents a divalent linking group, for example, methylene, ethylene, MeC
  • Examples include Me, CF CCF, CO, and SO.
  • ⁇ Ar 2 represents an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene.
  • substituent include an alkyl 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, 2, 2 bis (4-(((meth)) allyloyloxypolyethoxy) Phenol) propane (eg, 2, 2 bis (4 ((meth) acryloyloxydiethoxy) phenol) propane, 2, 2 bis (4— ((meth) acryloyloxytetraethoxy) phenol) -Ru) propane, 2,2 bis (4-(((meth)) aryloxypentaethoxy) fele) pouch pan, 2,2 bis (4 — (((meth) attayloxydedecaethoxy) wee -Lu) propane, 2,2bis (4 — ((meth) atarylloyl
  • 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.
  • Examples of the compound include a compound having an isocyanate group and a polymerizable group (for example, 2-isocyanate ethyl (meth) acrylate, ⁇ , ⁇ -dimethyl-benzylbenzyl isocyanate) and the like.
  • a polymerizable monomer other than the monomer containing a urethane group and the monomer having an aryl group may be used in combination as long as the characteristics as the pattern forming material 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.
  • ester monomer of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound examples include, for example, (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 Jipuropire glycol di (meth) Atari rate, tripropylene glycol di (meth) Atari rate, tetrapropylene glyco
  • ethylene glycol di (meth) acrylate polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, ethylene glycol chain Z Dialkyl (ethylene) chain with at least one propylene glycol chain (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( (Meta) Atalylate, Pentaerythritol Triatalylate, Pen Taerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, diglycerol di (meth) acrylate, 1, 3 propane Diol di (meth) acrylate, 1, 3 propane Diol di (meth) acrylate
  • ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound examples include ethylene glycol diitaconate, propylene glycol diitaconate, and 1,3 butanediol diitaco. 1,4,1 butanediol 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.
  • examples of the polymerizable monomer include butanediol 1, 4 Diglycidyl ether, cyclohexane dimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether , Compounds obtained by adding ⁇ , ⁇ -unsaturated carboxylic acid to glycidyl group-containing compounds such as glyceryl triglycidyl ether, JP-A 48-64183, JP-B 49 43191, JP-B Polyester acrylate, polyester (meth) acrylate oligomers and epoxy compounds (for example, butanediol 1,4-diglycidy
  • Photo-curing properties described in polyfunctional ata such as epoxy acrylates reacted with acrylic acid and metatareres ⁇ , Journal of the Adhesion of Japan, vol.20, ⁇ .7, pages 300 to 308 (1984) Monomers and oligomers, allylic esters (eg, diaryl phthalate, diaryl adipate, diaryl malonate, diaryl amide (eg, diaryl acetate amide), cationically polymerizable dibule ethers (eg, butanedio 1,4-dibutyl ether, cyclohexane dimethanol dibulle ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol Conorozorino Resinino Reinenore, Hexan di Resorinino Reinenore , Trimethylonorepropan trivinyl ether, pentaerythritol tetravinyl ether, gly
  • bull esters examples include divinyl succinate, dibula adipate and the like.
  • polyfunctional monomers or oligomers 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, Patent 2548016, etc. And the compounds described.
  • the content of the polymerizable compound in the photosensitive layer is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.
  • 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. Photoexcitations that are sensitive to visible light are preferred. It may be an activator that causes some action with the sensitizer and generates active radicals. An initiator that initiates cationic polymerization according to the type of monomer may be used.
  • 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.), hexarylbiimidazole, oxime derivatives, organic peroxides. Products, thio compounds, ketone compounds, aromatic onium salts, meta-octenes, and the like.
  • a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, a ketone compound, Hexaarylbiimidazole compounds 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 method disclosed in Bull. Chem. Soc. Japan, 33, 565 (1960), and J. Org. Chem, 36 (16) 2262 (1971), for example. Together Can be made.
  • halogenated hydrocarbon compounds having a triazine skeleton examples include compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), and described in British Patent 1388492.
  • Examples thereof include compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, and compounds described in US Pat. No. 421 2976.
  • Examples of the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969) include, for example, 2 phenol-4, 6 bis (trichloromethyl) -1, 3, 5 Triazine, 2 — (4 Chlorphenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (4 Tolyl) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2— (4-Methoxyphenyl) —4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (2,4 Dichlorophenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2, 4, 6 Tris (trichloromethyl) -1, 3, 5 Triazine, 2-methyl-4, 6 Bis (trichloromethyl) -1,
  • Examples of the compounds described in the British Patent 1388492 include 2-styryl
  • 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-naphtho-1-yl) -4,6 bis ( ⁇ chloromethyl) -1,3,5 riadine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl ] -4,6 bis (trichloromethyl) 1,3,5 triazine, 2- (4,7 dimethoxymononaphtho-1-yl) 4,6 bis (trichloro) Rumethyl) —1, 3, 5 ⁇ lyazine, and 2- (acenaphtho-5-yl) -4,6 bis (trichloromethyl) -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) -1,3,5 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 Chlorostyryl 1,4,6 Bis (trichloromethyl) 1, 3,5 Triazine, 2— (4 Thiophene-1,2 Bilenphenol) 1,4,6 Bis (trichloromethyl) 1, 3, 5— Triazine, 2— (4 thiophene, 3 bilenphenol), 1, 4, 6 Bis (trichloromethyl), 1, 3, 5 Triazine, 2— (4 furan, 1 biphenylene) 1,6 bis (trichloromethyl) 1, 3,5 triazine, and 2— (4— (4-
  • Examples of the compound described in FC Schaefer et al., J. Org. Chem .; 29, 1527 (1964) 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—Naphthyru 1-Ethurhu-Lu 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4 Trilluture) Fuel) — 4, 6 Bis (Trichloromethyl) —1, 3, 5 —Triazine, 2- (4— (4-Methoxyphenyl) 4,4-methyl (4-methoxyphenyl) 4,6-triphenyl) 1,6,5-triazine, 2— (4— (4-Isopropylphenol) (Phenol) 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4-Ethylfe-Luture) Grav) 1, 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine And so on.
  • Examples of the compound 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 compounds represented by the following structural formulas (36) to (69). [0191] [Chemical 40]
  • ketone compound examples include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzo Phenon, 2-Kanoreboki Cibenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4, 4, monobis (dialkylamino) benzophenones (eg, 4, 4, monobis (dimethylamino) benzophenone, 4, 4, 1-bisdicyclohexylamino) benzophenone, 4, 4, 1-bis (jetylamino) benzophenone, 4, 4, 1-bis (dihydroxyethylamino) benzophenone, 4-methoxy-1-4′-dimethylaminobenzophenone, 4, 4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone,
  • meta-octenes examples include bis (7? 5-2, 4-cyclopentagen 1-yl) -bis (2, 6 difluoro 3- (1H pyrrole-1-yl). —Phenol) Titanium, 7? 5 Cyclopentagel-6 Tame-Lu Iron (1 +) —Hexafluorophosphate (1), JP-A-53-133428, JP-B-57-1819, And compounds described in US Pat. No. 57-6096 and US Pat. No. 3,615,455.
  • Atalidine derivatives for example, 9-phenol lysine, 1,7 bis (9,9, -ataridyl) heptane, etc.
  • N-phenol glycine 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 Ben Zoyl 7 Jetylaminocoumarin, 3— (2-Methoxybenzoyl) 7 Jetylamino Nocoumarin, 3 -— (4-Dimethylaminobenzol) 7—Jetylaminocoumarin, 3,3, 1 Carborubbis (5, 7
  • Amines e.g., ethyl 4-dimethylaminobenzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxychetyl, pentamethylenebis (4 Dimethylaminobenzoate), 3 Dimethylaminobenzoic acid phenethyl, pentamethylene ester, 4 Dimethylaminobenzaldehyde, 2 Chlorone 4-Dimethylaminobenzaldehyde, 4-Dimethylaminobenzil alcohol, Ethyl (4-dimethylaminobenzoyl) acetate , 4-piberidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N jetyl
  • Acylphosphine oxides eg, bis (2, 4, 6 trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6 dimethoxybenzoyl) -1,2,4,4 trimethyl monopentylphenol -Luphosphinoxide, LucirinTPO, etc.
  • 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 photosensitive layer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass.
  • Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, color formers, colorants, thermal crosslinking agents, and the like, and further adhesion promoters to the substrate surface and other auxiliary agents.
  • sensitizers thermal polymerization inhibitors, plasticizers, color formers, colorants, thermal crosslinking agents, and the like
  • further adhesion promoters to the substrate surface and other auxiliary agents.
  • pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc. Also good.
  • properties such as the stability, photographic properties, print-out properties, and film properties of the target pattern forming material can be adjusted.
  • the sensitizer can be appropriately selected by using visible light, ultraviolet light, visible light laser, or the like as light irradiation means described later.
  • the sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals and It is possible to generate useful groups such as acids.
  • substances for example, radical generator, acid generator, etc.
  • energy transfer, electron transfer, etc. for example, energy transfer, electron transfer, etc.
  • the sensitizer may be appropriately selected from known sensitizers without particular limitations.
  • 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, squalium
  • attaridones eg, attaridone, chloroatalidone, N-methyl at
  • Examples of combinations of the photopolymerization initiator and the sensitizer include, for example, an electron transfer-type initiator system described in JP-A-2001-305734 [(1) an electron-donating initiator and a sensitizing dye (2) Electron-accepting initiators and sensitizing dyes, (3) Electron-donating initiators, sensitizing dyes and electron-accepting initiators (ternary initiation system)], and the like.
  • the content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, based on all components of the photosensitive resin composition. 2-10% by weight is particularly preferred.
  • the content is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease.
  • the photosensitive layer May precipitate during storage.
  • the thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
  • thermal polymerization inhibitor examples include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted nanoquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, Cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2,6 di-tert-butyl-4 cresol, 2,2, -methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 Toluidine, methylene blue, copper and organic chelating agent reactants, methyl salicylate, and phenothiazine, nitrosoy compounds, -tosoy compounds and chelates of A1.
  • the content of the thermal polymerization inhibitor is preferably 0.005 to 5% by mass, more preferably 0.005 to 2% by mass, based on the polymerizable compound of the photosensitive layer. 01 to 1% by mass is particularly preferred.
  • the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.
  • the plasticizer should be added to control the film physical properties (flexibility) of the photosensitive layer.
  • 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 Toluenesulfonamide, Benzenesulfonamide Amides such as N-n-butylbenzenesulfonamide, N-n-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sepacate
  • the content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive layer. preferable.
  • the color former should be added to give a visible image (printing function) to the photosensitive layer after exposure.
  • 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,
  • the color former is combined with a halogen compound for the purpose of coloring the leuco body.
  • halogen compound examples include halogenated hydrocarbons (for example, carbon tetrabromide, iodine form, bromoethylene, odorous methylene, amyl bromide, odorous isoamyl, yowiyamyl, isobutylene bromide, iodine Butyl bromide, diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dib-mouthed 1,1,2-trichloroethane, 1, 2,3-tribromopronokun, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1, 1,1-trichrome 1, 2, bis (4-chlorophenol), etc .
  • 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 preferable. .
  • the organic halogen compounds may be used alone or in combination of two or more. Among these, tribromomethyl phenol sulfonate and 2,4 bis (trichloromethyl) 6 phenol triazole are preferable.
  • the content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass with respect to all components of the photosensitive layer, and 0.1 to 5% by mass. % Is particularly preferred.
  • 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 photosensitive layer.
  • 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 Blue BO (CI 425 95), Auramin (CI 41000), Huatu ⁇ 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 ' Carmine FBB (CI Pigment 'Red 146), Hoster Balm Red ESB (CI Pigment' Violet 19), Permanent 'Ruby FBH (CI Pigment' Red 11), Fastel 'Pink B Supra (CI Pigment' Red 81), Monastral 'First' Blue (C.I. Pigment 'Blue 15), Monolite' First 'Black B (CI Pigment' Black
  • colorant suitable for producing a color filter for example, C. I. pigment
  • the average particle size of the colorant is not particularly limited, and can be appropriately selected according to the purpose.
  • the force is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the average particle diameter is preferably 0.5 / zm or less.
  • a dye can be used for the purpose of coloring the photosensitive resin composition for improving 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), rhodamine B, rotamine 6G, Victoria 'pure blue BOH, etc., among which
  • the cationic dye may be a residue of an organic acid or an inorganic acid, such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid, etc. Such as residues
  • 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 photosensitive layer, and 0.1 to 2% by mass. Is particularly preferred.
  • the thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability, etc.
  • an epoxy resin compound having at least two oxsilane groups in one molecule and an oxetane compound having at least two oxetal groups in one molecule can be used. .
  • the epoxy resin compound examples include bixylenol type or biphenol type epoxy resin ( ⁇ 4000; manufactured by Japan Epoxy Resin Co., Ltd.) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; "Nissan Chemical Industry Co., Ltd.”, "Araldite PT810; Ciba 'Specialty' Chemicals Co., Ltd.”), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A Type epoxy resin, glycidinoreamine type epoxy resin, hydantoin type epoxy resin, cycloaliphatic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak Type epoxy resin, tetraf-roll ethane type epoxy resin, glycid Ruphthalate resin, tetraglycidyl xylenol ethane resin, naphthalene group-containing epoxy resin ("ESN
  • Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxeta-lmethoxy) methyl] ether, 1, 4-bis [(3-methyl-3-oxeta-lmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxeta-lmethoxy) methyl] benzene, (3-methyl-3-oxeta-l) methyl acrylate , (3 Echiru 3 Okiseta -) methyl Atari rate, (3-methyl 3-Okiseta -) methyl meth Tari rate, (3 Echiru 3 Okiseta - Le) methylate Rume Tatari rate or oligomers thereof or copolymers
  • novolac resin poly (p-hydroxystyl)
  • the solid content in the photosensitive composition solid content of the epoxy resin compound or oxetane compound is preferably 1 to 50 mass%, more preferably 3 to 30 mass%. If the solid content is less than 1% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance, electroless resistance to plating, etc. If it exceeds 50% by mass, poor developability may cause a reduction in exposure sensitivity, which is not preferable.
  • dicyandiamide benzyldimethylamine, 4- (dimethylamino) N, N-dimethylbenzylamine, 4-methoxy N , N Amine compounds such as dimethylbenzylamine, 4-methyl-N, N dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzylammochloride; Block isocyanate compounds such as dimethylamine Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenolimidazole, 4-phenolimidazole, 1-cyan Ethyl 2-phenol imidazole, 1- (2-cyanethyl) 2 Ethyl 4-methyl imidazole and other imidazole derivative bicyclic amidine compounds and salts thereof; Phosphorus compounds such as triphenylphosphine; Melamine
  • the solid content in the solid content of the photosensitive composition of the epoxy resin, the oxetane compound, and a compound capable of accelerating the thermal curing of these with a carboxylic acid is usually 0.01 to 15% by mass. Ah.
  • a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is composed of at least two isocyanates. It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing a monoto group.
  • a mixture of 1,3 phenolic diisocyanate and 1,4 phenolic diisocyanate, 2, 4 and 2,6 toluene diisocyanate, 1, 3 and 1,4 xylylene diisocyanate Bis (4 isocyanate chain) methane, bis (4 isocyanate cyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; Polyfunctional alcohols of a bifunctional isocyanate and trimethylolpropane, pentalysitol, glycerin, etc .; an alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, Cyclic trimers such as xamethylene 1,6 diisocyanate and its derivatives; It is.
  • the isocyanate groups of the polyisocyanate and its derivatives are used. Use a compound obtained by reacting with a blocking agent.
  • isocyanate group blocking agent examples include alcohols such as isopropanol, tert.-butanol; ⁇ — ratatas such as force prolatatum; phenol, cresol, ⁇ -tert.-butinolephenol, p-sec.—butino Phenenoles, p-sec.
  • Phenols such as amino enoenole, p-octylphenol, p-norphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridin, 8-hydroxyquinoline; dialkyl Active methylene compounds such as malonate, methyl ethyl ketoxime, acetyl acetone, alkylacetoacetoxime, acetoxime, cyclohexanone oxime; and the like.
  • compounds having at least one polymerizable double bond and at least one block isocyanate group in the molecule described in JP-A-6-295060 can be used.
  • aldehyde condensation products can be used.
  • methylol compounds instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. You can also use hexamethoxymethylol melamine, which consists of a formaldehyde condensation product of melamine and urea, or butyl ether of melamine and formaldehyde condensation product.
  • the solid content of the thermal crosslinking agent in the solid content of the photosensitive composition is preferably 1 to 40% by mass, more preferably 3 to 20% by mass. When the solid content is less than 1% by mass, no improvement in the strength of the cured film is observed, and when it exceeds 40% by mass, the developability and the exposure sensitivity may decrease.
  • a well-known adhesion promoter can 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 components of the photosensitive layer, and more preferably 0.01 to 10% by mass. A mass% to 5 mass% is particularly preferred.
  • the photosensitive layer may be, for example, an organic sulfur compound, peroxide, redox compound, azo or diazo as described in Chapter 5 of "Light Sensitive Systems" by J. Kosa. It may contain a compound, a photoreducing dye, an organic halogen compound, and the like.
  • organic sulfur compound examples include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaprobenthiazole, 2-mercaptobenzoxazole, thiophenol, etyltrichloromethanesulfate, 2- Examples include mercaptobens imidazole.
  • Examples of the peroxide include diethyl butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.
  • the redox compound also serves as a combination force of peracid compounds and reducing agents, and examples thereof include ferrous ions and persulfate ions, ferric ions and peracid compounds. .
  • Examples of the azo and diazo compounds include ⁇ , ⁇ '-azobis-ylibuchi-tolyl, 2-azobis-2-methylbutyguchi-tolyl, and diaminonium of 4-aminodiphenylamine.
  • 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 mass% with respect to the solid content of the photosensitive resin 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 photosensitive layer has a smaller amount of light energy for curing than the first photosensitive layer and the first photosensitive layer! /, And the second photosensitive layer is laminated on the cushion layer in this order.
  • the number of photosensitive layers is N (the number of photosensitive layers is N)
  • the sensitivity of the photosensitive layer on the side away from the support is relatively high compared to the sensitivity of the photosensitive layer on the side close to the support. If a sheet is used, patterns having different thicknesses in N stages can be formed with one kind of pattern forming material.
  • a barrier layer may be provided between each photosensitive layer.
  • the thickness of the photosensitive layer can be appropriately selected according to the purpose for which there is no particular limitation. For example, 1-100 ⁇ m is preferable, and 2-50 ⁇ m is more preferable. ⁇ 30 ⁇ m is special Is preferred.
  • the first photosensitive layer When the photosensitive layer is formed by laminating the first photosensitive layer and the second photosensitive layer having a smaller amount of light energy for curing than the first photosensitive layer in this order on the cushion layer, the first photosensitive layer
  • the thickness of the second photosensitive layer can be appropriately selected depending on the purpose.
  • the first photosensitive layer preferably has a thickness in the range of 1 to L00 m, and more preferably in the range of 5 to 80 ⁇ m, particularly 10 to 50 ⁇ m. Preferably it has a thickness in the range. If the thickness of the first photosensitive layer is less than 1 ⁇ m, it may be inappropriate for increasing the film strength, and if the thickness exceeds 100 m, development problems such as development residue may remain. May come out.
  • the thickness of the first photosensitive layer is preferably larger than the thickness of the second photosensitive layer.
  • the barrier layer can be appropriately selected according to the purpose without particular limitation as long as the movement of the substance can be suppressed, and is soluble in an alkaline liquid which may be water-soluble or water-dispersible. It may be insoluble.
  • the ability to suppress the movement of the substance means that the increase or decrease in the content of the target substance in the layer adjacent to the noria layer is suppressed as compared to the case where the noria layer is not provided. Means.
  • the substance can be appropriately selected according to the purpose without any particular limitation, and examples thereof include substances contained in at least one of oxygen, water, the photosensitive layer and the cushion layer.
  • the barrier layer is water-soluble or water-dispersible
  • the barrier layer when the barrier layer is soluble in an alkaline liquid that preferably contains a water-soluble or water-dispersible resin, the alkaline liquid It is preferable to contain soluble greaves.
  • the water solubility is preferably, for example, preferably 0.1% by mass or more, and more preferably 1% by mass or more, with respect to 25 ° C. water.
  • the rosin can be appropriately selected according to the purpose for which there is no particular restriction.
  • examples thereof include various alcohol-soluble varieties, water-soluble varieties, alcohol-dispersible varieties, and water-dispersible varieties.
  • examples thereof include fats, emulsifiable fats, and fats that are soluble in alkaline liquids.
  • specific examples include bulle polymers (for example, polybulal alcohols (modified polybulal alcohols are also included). ), Polyvinyl pyrrolidone, etc.), the above-mentioned vinyl copolymers, water-soluble polyamide, gelatin
  • thermoplastic resin described in Japanese Patent No. 2794242 and the compounds used in the intermediate layer, the binder, and the like can also be used. These may be used alone or in combination of two or more.
  • the barrier layer is insoluble in the alkaline liquid, it is preferable that the barrier layer contains a resin insoluble in the alkaline liquid.
  • Examples of the resin insoluble in the alkaline liquid include a copolymer whose main component is ethylene as a necessary copolymer component.
  • the copolymer having ethylene as an essential copolymer component is not particularly limited and can be appropriately selected according to the purpose.
  • ethylene vinyl acetate copolymer (EV A) ethylene-ethyl acrylate. Copolymer (EEA) and the like.
  • the thickness of the barrier layer is not particularly limited and may be appropriately selected depending on the purpose.
  • the thickness is preferably less than 10 ⁇ m, more preferably 0.1 to 6 ⁇ m 1 ⁇ 5 ⁇ m is particularly preferred.
  • the thickness is 10 / z m or more, light scattering occurs in the barrier layer during exposure, and at least one of resolution and adhesion may be deteriorated.
  • the support is not particularly limited and may be appropriately selected depending on the purpose, but preferably has good light transmittance and more preferably has smooth surface.
  • 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.
  • plastic films such as butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These can be used alone 2 or more types may be used in combination.
  • the thickness of the support is not particularly limited, and can be appropriately selected according to the purpose.
  • F column; t is 2-150 ⁇ m force S girlish, 5-: LOO ⁇ m force SJ-like girls, 8-50 ⁇ m force S Particularly preferred.
  • the shape of the support is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include a length of 10 m to 20000 m.
  • the 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 interlayer adhesive strength between the protective film and the photosensitive layer is the smallest among the interlayer adhesive strengths of the other layers.
  • Examples of the combination of the support and the protective film include, for example, polyethylene terephthalate z polypropylene, polyethylene terephthalate z polyethylene, polychlorinated bur Z cellophane, polyimide Z polypropylene, polyethylene terephthalate z polyethylene terephthalate. Etc.
  • the above-described adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer.
  • a primer layer for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • ultraviolet irradiation treatment for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • One discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like can be mentioned.
  • the coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2 force! / !.
  • the pattern forming material is preferably stored, for example, wound around a cylindrical core and wound into a long roll.
  • the length of the long pattern forming material is not particularly limited, and can be appropriately selected, for example, a range force of 10 m to 20, OOOm.
  • slitting may be performed so that it is easy for the user to use, and a long body in the range of 100 m to l, OOOm may be rolled.
  • the support is wound up so as to be the outermost side.
  • the roll-shaped pattern forming material may be slit into a sheet shape.
  • a separator especially moisture-proof and desiccant-containing
  • the protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer.
  • an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polybutyl alcohol is formed on the surface of the protective film.
  • the undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C (particularly 50 to 120 ° C) for 1 to 30 minutes. Can do.
  • the pattern forming material of the present invention includes a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like. You may have a layer of. Each of the layers may have one layer or two or more layers.
  • the pattern forming material can be manufactured, for example, as follows. First, the above-mentioned various materials are dissolved, emulsified or dispersed in water or a solvent to prepare a coating solution.
  • the solvent for preparing the coating solution can be appropriately selected according to the purpose without any particular limitation.
  • methanol, ethanol, n-propanol, isopropanol, n-butanol, sec- Alcohols such as butanol and n-hexanol
  • acetone Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone
  • esters such as methoxypropyl acetate
  • aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene
  • tetrasalt-carbon trichloroethylene, chloroform, 1, 1, 1-
  • the cushion layer composition coating solution in which the cushion layer composition is dissolved, emulsified or dispersed, and the barrier layer composition coating solution in which the barrier layer composition is dissolved, emulsified or dispersed are used in a filter. It is preferable that the fine particles and the aggregates thereof, which are solid contents, are removed by filtering with a filter.
  • the effective pore size of the filter used for filtration is preferably 30 m or less, more preferably 0.05 to 1 ⁇ m force, and more preferably 0.25 to 0.3 ⁇ m force ⁇ / ,.
  • the material of the filter examples include, when the coating solution is solvent-based, for example, tetrafluoroethylene resin, polypropylene, polyethersulfone, stainless steel, and the like. preferable.
  • the coating solution is water-soluble or water-dispersible
  • a filter prepared for an aqueous solvent is preferred.
  • a filter made of a polymer material that hardly generates dust is preferable.
  • Examples of the shape of the filter include a disk type, a roll type, a cylindrical type, and a pleated type.
  • the coating solution may be passed through the filter by feeding or pressurized or reduced pressure.
  • the coating solution is preferably defoamed after filtration because air is taken in by the filtration and bubbles may be formed in the film after coating and drying.
  • the defoaming method examples include defoaming by allowing the coating solution to stand after filtration, a method of defoaming with ultrasonic waves, a method of defoaming under reduced pressure, and a method of defoaming by heating.
  • the defoaming by the ultrasonic wave is preferably performed for 30 seconds to 2 hours, and is preferably performed for 5 minutes to 1 hour. Further, the defoaming by heating is preferably allowed to stand at 30 to 50 ° C. for 3 hours or more.
  • the work described above is preferably performed in a clean space of class 1000 or less, preferably in a clean room or clean bench, in order to prevent foreign matter from entering during the work.
  • the cleanness is a value measured by a dust counter.
  • the cushion layer composition coating solution filtered by the filter is applied onto the support and dried to form the cushion layer, and the barrier layer is formed on the cushion layer.
  • a barrier layer composition coating solution is applied and dried to form a barrier layer
  • the photosensitive resin composition solution is applied onto the noor layer or the cushion layer and dried to be photosensitive. Layers can be formed to produce patterning materials.
  • the coating method of the coating solution is not particularly limited, and can be appropriately selected according to the purpose.
  • spray method roll coating method, spin coating method, slit coating method, etasion coating method
  • examples of the coating method include a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
  • 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 includes a printed wiring board, a protective film, an interlayer insulating film, a solder resist pattern, a color filter, a column material, a rib material, a spacer, a display member such as a partition, a hologram, and a micromachine. It can be widely used for pattern formation such as proofing, and can be particularly suitably used for the pattern forming method and pattern forming apparatus of the present invention.
  • the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, and has at least light irradiation means and light modulation means.
  • the pattern forming method of the present invention comprises at least a laminating step, an exposing step, and a developing step. Including other processes appropriately selected.
  • the laminating step is a step of laminating the pattern forming material on a substrate by at least one of heating and pressurization, and a step of forming a laminate formed by laminating the pattern forming material on the substrate. .
  • the layer structure of the laminate can be appropriately selected according to the purpose without any particular limitation.
  • the layered body, the photosensitive layer, the barrier layer, the cushion layer, and the support are included in this order.
  • Layer structure is preferred ⁇ .
  • the substrate can be appropriately selected from known materials having no particular limitation to materials having high surface smoothness, and having a rough surface.
  • a plate-like substrate (substrate) is preferred.
  • known printed wiring board forming substrates for example, copper-clad laminates
  • glass plates for example, soda glass plates
  • synthetic resin films paper, metal plates, and the like can be given.
  • the pattern forming material is heated and pressed at least slightly on the substrate, while the photosensitive layer in the pattern forming material overlaps the substrate.
  • they can be selected appropriately according to the purpose without any particular limitation.
  • 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, Taisei Laminator).
  • a laminator for example, Taisei Laminator
  • a product made by the company, VP- ⁇ is preferable.
  • the exposing step is a step of exposing the photosensitive layer laminated in the laminating step with light irradiated from a light irradiation means, and the photosensitive layer is the photosensitive layer in the pattern forming material. I like it.
  • the exposure can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
  • the digital exposure can be appropriately selected depending on the purpose without any particular limitation.
  • the digital exposure can be performed by a light modulation unit having ⁇ pixel portions that receive and emit light from the light irradiation unit. After the light from the light irradiating means is modulated, the light is passed by the microphone lens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface in the picture element portion are arranged. Are preferred.
  • the light modulation means as long as it has ⁇ pixel portions, it can be appropriately selected according to the purpose without any restriction.
  • a spatial light modulation element or the like is preferable.
  • the spatial light modulation element include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM; Special Light Modulator), and modulated transmitted light by an electro-optic effect.
  • Optical elements PZT elements
  • FLC liquid crystal light shirts
  • DMD is preferable.
  • 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 the surface of the micromirror 62 is provided with an Al. A highly reflective material such as minium is deposited. 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.
  • the microphone mirror 62 supported by the support column is ⁇ degrees (eg ⁇ 12 °) from the substrate side on which the DMD50 is placed with the diagonal line as the center. ) Tilted within the range.
  • FIG. 2A shows a state tilted to + ⁇ degrees when the micromirror 62 is in the on state
  • FIG. 2B shows a state tilted to ⁇ degrees when the micromirror 62 is in the off state. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 as shown in FIG. 1 according to the pattern information, the laser light incident on the DMD 50 is inclined in the direction of the inclination of each micromirror 62. Reflected to.
  • FIG. 1 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + ⁇ degrees or ⁇ degrees.
  • 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 be 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.
  • micromirror array force with a number of micromirrors arranged in the longitudinal direction (eg, 1024)
  • a force with a lot of ⁇ 1_ eg, 756 threads
  • ⁇ 1_ eg, 756 threads
  • 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
  • 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 light B When the laser light B is irradiated from the fiber array light source 66 to the DMD 50, the laser light reflected when the microphone mouth mirror of the DMD 50 is in the on state is reflected by the lens systems 54 and 58 on the pattern forming material in the stack. An image is formed on the photosensitive layer 150 (hereinafter referred to as “pattern forming material 150”).
  • pattern forming material 150 An image is formed on the photosensitive layer 150 (hereinafter referred to as “pattern forming material 150”).
  • 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 non-turn forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region is provided for each exposure head 166. 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 the DMD50 may be used as shown in FIG. 4B. May be used.
  • the micromirror array used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.
  • the data processing speed of the DMD50 is limited, and the modulation speed per line is determined in proportion to the number of pixels used. Modulation rate per channel increases. 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 array force in which 1024 micromirrors are arranged in the main scanning direction is provided with the DMD arranged in 768 threads in the subscanning direction.
  • the modulation speed per line becomes faster than when all the micromirror arrays are driven.
  • the force described in the example of partially driving the micromirror of the DMD has a length in the direction corresponding to the predetermined direction is longer than the length in the direction intersecting the predetermined direction. Even if a long and narrow DMD in which a number of micromirrors that can change the angle of the reflecting surface are arranged in two dimensions is used, the number of micromirrors that control the angle of the reflecting surface is reduced. Can be fast.
  • the exposure method is performed while relatively moving the exposure light and the photosensitive layer.
  • the exposure method is preferably used in combination with the high-speed modulation. Thereby, high-speed exposure can be performed in a short time.
  • the entire surface of the pattern forming material 150 may be exposed by one scan in the X direction by the scanner 162, as shown in FIGS. 6A and 6B. After scanning the pattern forming material 150 in the X direction, the scanner 162 is moved one step in the Y direction, and scanning is performed in the X direction. The entire surface of 150 may be exposed.
  • the skier The na 162 has 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 at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each end of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156.
  • a scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the pattern forming material 150 are provided on the other side. Yes.
  • the scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152.
  • the scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.
  • the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in a substantially matrix of m rows and n columns (eg, 3 rows and 5 columns). I have. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the pattern forming material 150. When individual exposure heads arranged in the m-th row and the n-th column are shown, they are expressed as an exposure head 166.
  • An exposure area 168 by the exposure head 166 has a rectangular shape with the short side in the sub-scanning direction. Accordingly, as the stage 152 moves, 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 is arranged in the arrangement direction so that the strip-shaped exposed areas 170 are arranged without gaps in the direction perpendicular to the sub-scanning direction. Are shifted by a predetermined interval (a natural number multiple of the long side of the exposure area, twice in this example). Therefore, exposure between the exposure area 168 and the exposure area 168 in the first row is not possible.
  • Unexposed areas are exposed using the exposure area 168 in the second row and the exposure area 168 in the third row.
  • a light modulation means spatial light modulation element that modulates each pixel in accordance with pattern information
  • a digital 'micromirror' device manufactured by Texas Instruments Inc., USA
  • the DMD 50 is connected to the controller 302 (see FIG. 12) having a data processing unit and a mirror drive control unit.
  • the data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The areas to be controlled will be described later.
  • the mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit. The control of the angle of the reflecting surface will be described later.
  • a fiber array light source including 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.
  • the lens system 67 includes a condensing lens 71 that condenses 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.
  • Rod-shaped optical integrator inserted into the rod hereinafter referred to as rod integrator
  • 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.
  • the diameter of the aperture 59a is, for example, 10 m.
  • the first imaging optical system magnifies the image by the DMD 50 by a factor of 3 to obtain a microlens array 5 5 forms an image. Then, the second imaging optical system forms an image on the pattern forming material 150 and projects it by enlarging the image that has passed through the microlens array 55 by 1.6 times. Therefore, as a whole, the image formed by the DMD 50 is magnified by 4.8 times and is formed and projected on the pattern forming material 150.
  • a prism pair 73 is disposed between the second imaging optical system and the pattern forming material 150. By moving the prism pair 73 in the vertical direction in FIG. You can adjust the focus of the image above. In the figure, the pattern forming material 150 is sub-scan fed in the direction of arrow F.
  • the picture element portion can be appropriately selected according to the purpose without particular limitation as long as it can receive and emit light from the light irradiation means.
  • the pattern portion of the present invention can be selected.
  • the pattern formed by the forming method is an image pattern, it is a pixel, and when the light modulation means includes a DMD, it is a micromirror.
  • the number of picture element portions (n mentioned above) of the light modulation element can be appropriately selected according to the purpose without particular limitation.
  • the arrangement of the picture element portions in the light modulation element can be appropriately selected according to the purpose for which there is no particular limitation.
  • a two-dimensional arrangement is preferably arranged in a lattice shape. More preferred to be.
  • the microlens array can be appropriately selected depending on the purpose without any limitation as long as microlenses having an aspheric surface capable of correcting aberration due to distortion of the exit surface in the pixel portion are arranged. .
  • the aspherical surface can be appropriately selected depending on the purpose without particular limitation, and for example, a toric surface is preferable.
  • FIG. 13A shows DMD50, light irradiation means 144 for irradiating DMD50 with laser light, and a lens system (imaging optical system) 454, 458, DM D50 for enlarging and imaging the laser light reflected by DMD50.
  • a microlens with multiple microlenses 474 corresponding to each pixel part Aperture array 476 provided with a number of apertures 478 corresponding to each of the microlenses of ray 472 and microlens array 472, and a lens system that forms an image of laser light that has passed through the apertures on exposed surface 56 (imaging optics) System) Represents an exposure head composed of 480 and 482.
  • 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 reflection surface of the micromirror 62 is distorted, and when attention is paid particularly to the center of the mirror, one diagonal direction (y direction) ) Distortion 1S The distortion is larger than the distortion in another diagonal direction (X direction). For this reason, the problem that the shape in the condensing position of the laser beam B condensed by the microlens 55a of the microlens array 55 may be distorted.
  • 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 shape and the side shape 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. It consists of 1024 microlenses 55a aligned in the vertical direction and 256 vertical rows.
  • the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.
  • FIG. 17A and FIG. 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 face of each microlens 55a on the light exit side is In other words, it is an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62.
  • the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively.
  • the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. ing.
  • FIGS. 19A to 19D show simulation results of the beam diameter in the vicinity of the condensing position (focus position) of the microlens 55a when the microlens 55a has the above-described shape.
  • 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 placed in the direction of the focal length force in the cross section parallel to the y direction.
  • a toric lens smaller than the focal length in the cross section parallel to the beam, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, the pattern forming material 150 can be exposed to a higher-definition image without distortion.
  • the region where the beam diameter is small is wider, that is, the depth of focus is larger. It turns out that it is big.
  • 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 so that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. . That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to enhance the extinction ratio.
  • the microlens 55a may be a secondary aspherical shape or a higher order (4th, 6th order, aspherical shape). By adopting the higher-order aspherical shape, the beam shape can be further refined.
  • the end surface of the light exit side of the micro lens 55a is aspheric.
  • 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.
  • An example of such a microlens 155a is shown in Figs. 22A and 22B.
  • FIG. 22A and 22B show the front shape and the side shape of the microlens 155a, respectively, and the external shape of the microlens 155a is a parallel plate as shown in the figure.
  • 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 refractive index as described above is also applied to a microlens having an aspherical surface shape like the microlens 55a previously shown in FIGS. 17A, 17B, 18A, and 18B. 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 enters the lens systems 480 and 482. Further, an image is formed on the exposed surface 56.
  • 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 pattern forming method of the present invention may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light quantity distribution correcting optical system composed of a pair of combination lenses.
  • the light quantity distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to the optical axis is smaller on the exit side than on the entrance side.
  • the light amount distribution on the irradiated surface is corrected so as to be substantially uniform.
  • the light quantity distribution correcting optical system will be described with reference to the drawings.
  • the entire luminous flux width (total luminous flux width) HO and HI is the same for the incident luminous flux and the outgoing luminous flux will be described.
  • 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. On the other hand, 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 light 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 is The light beam with the same luminous flux width h0, hi on the side has a larger luminous flux width hlO in the central part than the peripheral part on the outgoing side, and conversely, the luminous flux width hi 1 in the peripheral part is larger than that in the central part. Try to be small.
  • the reduction rate of the luminous flux the reduction rate for the incident light flux in the central portion is made smaller than that in the peripheral portion, and the reduction rate for the incident light flux in the peripheral portion is made larger than that in the central portion.
  • FIG. 24C shows a case where the entire light flux width H0 on the incident side is “expanded” to the width H3 and emitted (H0 and H3).
  • the light quantity distribution correcting optical system has the same light flux width h0, hi on the incident side, and the light flux width hlO in the central portion is larger than that in the peripheral portion on the outgoing side.
  • the light flux width hi 1 at the peripheral part is made smaller than that at the central part.
  • the light quantity distribution correction optical system changes the light flux width at each emission position, and outputs the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to the optical axis Z1 compared to the incident side. Since the emission side is smaller, the light having the same luminous flux width on the incident side has a larger luminous flux width in the central part than in the peripheral part on the outgoing side, and the luminous flux width in the peripheral part is Smaller than the center. As a result, the light beam in the central part can be utilized to the peripheral part, and a light beam cross-section with a substantially uniform light quantity distribution can be formed without reducing the light use efficiency of the entire optical system.
  • lens data is shown in the case where the light amount distribution in the cross section of the emitted light beam is a Gaussian distribution, as in the case where the light irradiation means is a laser array light source.
  • the light intensity distribution of the emitted light beam from the optical fino becomes a Gaussian distribution.
  • the parameters of the present invention The turn forming method can be applied in 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.
  • ⁇ Length of perpendicular line (mm) drawn from a point on the aspheric surface at a height ⁇ from the optical axis to the tangential plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
  • E indicates that the next numerical value is a power index with a base of 10
  • FIG. 26 shows the light quantity 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 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.
  • electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • ultraviolet to visible light, electron beams, X-rays, laser light, etc. are mentioned, and among these, laser light is preferred.
  • Laser that combines two or more lights hereinafter sometimes referred to as “combined laser”) ) Is more preferable. Even when the support is peeled off and the light is irradiated with light, the same light can be used.
  • the ultraviolet power is preferably 300 to 1500 nm, more preferably 320 to 800 mn, and 330 ⁇ ! ⁇ 650mn force ⁇ especially preferred!
  • the wavelength of the laser beam is, for example, preferably 200 to 1500 nm force S, more preferably 300 to 800 nm force S, and 330 mm! ⁇ 500mn force more preferred, 400 ⁇ ! ⁇ 450mn power ⁇ especially preferred! /,
  • Means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces to collect the multi-beam.
  • Means having a collective optical system coupled to the bimode optical fiber is preferred.
  • 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 constituted by the end of the multimode optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. Further, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the multimode optical fiber 31 for protection.
  • the light exit end face of the multimode optical fiber 31 is easy to collect dust and easily deteriorate due to its high light density, but the protective plate as described above prevents the dust from adhering to the end face and prevents deterioration. Can be delayed.
  • the multimode optical fibers 30 adjacent to each other with a large cladding diameter are multimode.
  • the optical fiber 30 is stacked, and the output end of the optical fiber 31 coupled to the stacked multimode optical fiber 30 is connected to the two multimode optical fibers 30 adjacent to each other at the portion where the cladding diameter is large. They are arranged so as to be sandwiched between the two exit ends.
  • such an optical fiber has a light with a small cladding diameter of 1 to 30 cm in length at the tip of the multimode optical fiber 30 with a large cladding diameter on the laser light emission side. It can be obtained by coupling the fibers 31 coaxially.
  • the two optical fibers are fused and bonded to the incident end face force of the optical fiber 31 and the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide.
  • the diameter of the core 31a of the optical fiber 31 is the same as the diameter of the core 30a of the multimode optical fiber 30.
  • a short optical fiber obtained by fusing an optical fiber having a short length and a large clad diameter to which the clad diameter is fused and the optical fiber is fused is connected to the output end of the multimode optical fiber 30 via a ferrule or 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 m.
  • the cladding diameter of the optical fiber 31 is not limited to 60 ⁇ m.
  • Conventional fiber array The optical fiber used in the light source has a cladding diameter of 125 m.
  • m is preferably 40 m or less.
  • the cladding diameter of the optical fiber 31 is preferably 10 ⁇ m or more.
  • the laser module 64 includes a combined laser light source (fiber array light source) shown in FIG.
  • This combined laser light source is a multiple array array fixed on the heat block 10.
  • Several for example, 7) chip-shaped lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, and LD7, and GaN-based semiconductor lasers LD1 to LD7
  • the collimator lenses 11, 12, 13, 14, 15, 16, and 17 are provided correspondingly, one condenser lens 20, and one multimode optical fiber 30.
  • the number of semiconductor lasers is not limited to seven.
  • the GaN semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and all the maximum outputs are also common (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-described 405 nm in a wavelength range of 350 nm to 450 nm may be used.
  • the combined laser light source is housed in a box-shaped package 40 having an upper opening, together with other optical elements.
  • the package 40 is provided with a package lid 41 created so as to close the opening thereof. After the degassing process, a sealing gas is introduced, and the opening of the knock 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 cage lid 41.
  • a base plate 42 is fixed to the bottom surface of the package 40.
  • the heat block 10 On the top surface of the base plate 42, the heat block 10, the condensing lens holder 45 that holds the condensing lens 20, and the multimode light.
  • a fiber holder 46 that holds the incident end of the fiber 30 is attached. The exit end of the multimode optical fiber 30 is drawn out of the package through an opening formed in the wall surface of the knock 40.
  • a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held.
  • An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.
  • 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 longitudinal direction is perpendicular to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 32). .
  • the GaN-based semiconductor lasers LD1 to LD7 have an active layer with an emission width of 2 ⁇ m, and the divergence angles in a direction parallel to the active layer and a direction perpendicular to the active layer are, for example, 10 ° and 30 °, respectively.
  • the lasers that emit laser beams B1 to B7 are used.
  • These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.
  • the laser beams B1 to B7 emitted from the respective light emission points have a direction in which the direction of the larger divergence angle coincides with the longitudinal direction of each of the elongated collimator lenses 11 to 17 as described above.
  • the incident light is incident in a state in which the direction with the smaller width coincides with the width direction (direction perpendicular to the longitudinal direction).
  • the width of each collimator lens 11 to 17 is 1. lmm and the length is 4.6 mm, and the beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2 respectively. 6mm.
  • Each of the collimator lenses 11 to 17 has a focal length f
  • the condensing lens 20 is obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a thin plane in a parallel plane and 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 is provided with the output end of the optical fiber of the combined laser light source. Since high-intensity fiber array light sources arranged in an array are used, a pattern forming apparatus having a high output and a deep focal 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, and for example, laser light incident from a single semiconductor laser having one light emitting point
  • a fiber array light source in which a fiber light source including one optical fiber emitting light is arrayed can be used.
  • a light irradiation means having a plurality of light emitting points for example, as shown in FIG. 33, a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 on a heat block 100: LD7 Can be used.
  • a chip-shaped multi-cavity laser 110 shown in FIG. 34A in which a plurality of (for example, five) light emitting points 110a are arranged in a predetermined direction is known.
  • the light emitting points can be arranged with higher positional accuracy than in the case where the chip-shaped semiconductor lasers are arranged, so that the laser beams emitted from the respective light emitting point forces can be easily combined.
  • the number of light emitting points 110a is preferably 5 or less.
  • a plurality of multi-cavity lasers 110 are arranged on the heat block 100 as shown in FIG. 34B.
  • a multi-cavity laser array arranged in the same direction can be used as a laser light source.
  • the combined laser light source is a laser beam emitted from a plurality of chip-shaped semiconductor lasers. It is not limited to what combines.
  • 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 light emitting points 110a of the multi-cavity laser 110 is collected by the condenser lens 120 and is incident on the core 130a of the multimode optical fiber 130. To do.
  • the laser light incident on the core 130a is propagated in the optical fiber, combined into one, and emitted.
  • a plurality of 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 bit lasers 110 are arranged at equal intervals can be used.
  • the plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 110a of each chip.
  • This combined laser light source is arranged between the laser array 140, the plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 110, and the laser array 140 and the plurality of lens arrays 114. Further, it is configured to include one rod lens 113, one multimode optical fiber 130, and a condensing lens 120.
  • the lens array 114 includes a plurality of microlenses corresponding to the emission points of the multi-cavity laser 110.
  • each of the laser beams B that has also emitted the respective powers of the plurality of light emitting points 10a of the plurality of multi-cavity lasers 110 is condensed in a predetermined direction by the rod lens 113;
  • the light is collimated by each microlens of the lens array 114.
  • the collimated laser beam L is collected by the condensing lens 120 and enters 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.
  • 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 longitudinal direction of each collimating lens coincides with the direction in which the laser beam has a large divergence angle (fast axis direction), and the width direction of each collimating lens is in the direction in which the divergence angle is small (slow axis). Direction).
  • the collimating lenses are integrated into an array to improve the space utilization efficiency of the laser light, increase the output of the combined laser light source, reduce the number of parts, and reduce the cost. it can.
  • each of the laser beams B also emitted from each of the plurality of light emitting points 10a of the plurality of multi-cavity lasers 110 arranged on the laser blocks 180 and 182 is converted into parallel light by the collimating lens array 184. Is collected by the condenser lens 120 and is It enters the core 130a of the optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, and is combined into one and emitted.
  • the combined laser light source can achieve particularly high output by the multistage arrangement of multi-cavity lasers and the array of collimating lenses.
  • a higher-intensity fiber array light source or bundle fiber light source can be formed, which is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.
  • each of the combined laser light sources is housed in a casing and the emission end of the multimode optical fiber 130 is drawn out from the casing.
  • 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.
  • 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 are collected by the condenser lens 20 and converge on the incident end face of the core 30a of the multimode optical fiber 30.
  • the collimator lenses 11 to 17 and the condenser lens 20 constitute a condensing optical system
  • the condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system. That is, the laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30 and propagate through the optical fiber. The light is output from the optical fiber 31 combined and coupled to the output end of the multimode optical fiber 30.
  • each laser module laser light B1 to: B7 multimode optical fiber 30
  • the output efficiency of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW
  • the high-luminance light emitting points 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 mm X 0.025 mm), the brightness at the laser emission section 68 is 123 X 10 6 (WZm 2 ), which is about 80 times higher than the conventional brightness. Can be achieved.
  • the luminance per optical fiber is 90 X 10 6 (WZm 2 ), which is about 28 times higher than before.
  • the diameter of the light emission area of the bundled fiber light source of the conventional exposure head is 0.675 mm, and the diameter of the light emission area of the fiber array light source of the exposure head is 0.025 mm.
  • the light emitting area of the light irradiation means (bundle-shaped fiber light source) 1 is large. Therefore, the angle of the light beam incident on the DMD 3 increases, and as a result, the angle of the light beam incident on the scanning surface 5 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 inputted to a controller (not shown) connected to the DMD 50, and is 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 adsorbed the non-turn forming material 150 on its surface is moved along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed by a driving device (not shown).
  • a driving device not shown
  • the pattern information stored in the frame memory is sequentially read for each of a plurality of lines.
  • a control signal is generated for each exposure head 166 based on the pattern information read out and read out by the data processing unit.
  • each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.
  • the DMD 50 When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the microphone mouth mirror of the DMD 50 is turned on is exposed to the surface of the pattern forming material 150 by the lens systems 54 and 58. Imaged on 56. In this way, the fiber array light source 66 The laser beam from which the force is also emitted 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 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 developing step exposes the photosensitive layer of a laminate formed by laminating the pattern forming material on a substrate to be processed in the exposing step, cures the exposed region of the photosensitive layer, and then forms an ineffective region. It is a process of developing by removing and forming a pattern.
  • the method for removing the uncured region is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method for removing using a developer.
  • the developer is not particularly limited and may be appropriately selected depending on the purpose.
  • examples thereof include an alkaline aqueous solution, an aqueous developer, and an organic solvent.
  • a weak alkaline aqueous solution is used.
  • examples of the base component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and phosphoric acid.
  • the pH of the weak alkaline aqueous solution is more preferably about 9 to 11 force, for example, about 8 to 12 is preferable.
  • Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous 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 contains water or an alkaline aqueous solution and an organic solvent. It can be a mixed aqueous developer or an organic solvent alone.
  • Examples of the other process include a force that can be appropriately selected from known processes for forming a pattern without limitation. Examples thereof include an etching process, a plating process, and a curing process. These may be used alone or in combination of two or more.
  • 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, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-speed solder plating, plating bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard plating.
  • Examples include gold plating such as gold plating and soft gold plating.
  • a permanent pattern can be formed on the surface of the substrate by removing the pattern after performing a plating process in the plating process, and further removing unnecessary portions by an etching process or the like as necessary.
  • the curing treatment step is a step of performing a curing treatment on the formed pattern after the development step is performed on the photosensitive layer.
  • the curing treatment can be appropriately selected according to the purpose without any particular restriction, and examples thereof include full-surface exposure treatment and full-surface heat treatment.
  • Examples of the entire surface exposure processing method include a method of exposing the entire surface of the photosensitive laminate on which the pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the pattern is cured.
  • the apparatus for performing the entire surface exposure can be appropriately selected according to the purpose without any particular limitation.
  • a UV exposure machine such as an ultra-high pressure mercury lamp can be preferably used.
  • Examples of the entire surface heat treatment method include a method of heating the entire surface of the photosensitive laminate on which the pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the pattern is increased.
  • the heating temperature for the entire surface heating is 120 to 250, preferably 120 to 200 ° C.
  • the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment.
  • the heating temperature exceeds 250 ° C, the resin in the photosensitive composition is decomposed and the film quality is weak. May become brittle.
  • the heating time for the entire surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
  • the apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
  • the pattern forming method of the present invention can form a permanent pattern with high definition and efficiency by suppressing distortion of an image formed on the pattern forming material. It can be suitably used for forming various patterns that require a high degree of wiring, and can be particularly suitably used for forming high-definition wiring patterns.
  • 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.
  • the pattern forming method of the present invention is used. An example of a method for manufacturing a printed wiring board and a method for manufacturing a color filter 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.
  • Light irradiation is performed on a desired region from the opposite side of the laminate to the substrate, and the photosensitive layer is cured.
  • the laminated body force The support and the cushion layer in the pattern forming material are removed, and (4) the photosensitive layer in the laminated body is developed to form a pattern by removing the uncured portion in the laminated body. Can do.
  • the removal of the cushion layer is not particularly limited, and may be performed anywhere after (2) above.
  • the cushion layer is insoluble in the alkaline liquid, it is preferably removed before (4).
  • the removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).
  • the barrier layer may be removed together with the support in (3) or may be removed during development in (4).
  • 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 board 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 protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. And press-bonding using a pressure roller (lamination process). Thereby, the laminated body which has the said board
  • 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 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.
  • a layer pattern is formed to expose the metal layer on the surface of the printed wiring board forming substrate (development process).
  • post-heating treatment or post-exposure treatment may be performed to further accelerate the curing reaction of the cured portion.
  • Development is 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
  • 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-throw solder plating, watt bath (nickel sulfate-salt nickel) plating, nickel plating such as nickel sulfamate, Examples include hard gold plating and gold plating such as soft gold plating.
  • a photosensitive layer in the pattern forming material of the present invention is pasted on a substrate such as a glass substrate.
  • the support when the support is peeled from the pattern forming material, the charged support (film) and the human body may receive an unpleasant electric shock, or dust may adhere to the charged support. There is a problem. 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. Further, 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.
  • any arrangement such as a mosaic type, a triangle type, and a 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 other side, and development is performed to form a black matrix.
  • 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, so that 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. It can be used suitably for formation.
  • 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 structural members such as holograms, micromachines, and proofs, and is particularly suitable for the formation of high-definition wiring patterns and color filters.
  • olefin / emulsion acrylate (trade name: Chemipearl S-100, manufactured by Mitsui Chemicals, Inc., solid content concentration) : 27 mass%) was filtered using a membrane filter (manufactured by Millipore) with a pore size of 0.22 / zm, and the filtrate was applied using a wire bar, dried and dried. A cushion layer was formed.
  • a photosensitive resin composition solution having the following composition is applied onto the cushion layer and dried to form a 20-m-thick photosensitive layer, and the protective layer is formed on the photosensitive layer.
  • a 20 ⁇ m thick polyethylene film was laminated as a film to produce the pattern forming material.
  • a copper-clad laminate manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67, no through-hole, copper thickness 12 m
  • a laminator MODEL8B-720-PH, Taisei Laminator () is formed on the copper-clad laminate while peeling the protective film of the pattern-forming material so that the photosensitive layer of the pattern-forming material is in contact with the copper-clad laminate.
  • a laminate in which the copper-clad laminate, the photosensitive layer, the cushion layer, and the support are laminated in this order.
  • the maximum height (Rz) specified in JIS B 0601 was measured on the surface of the copper clad laminate on which the photosensitive layer was laminated, the Rz was 3 ⁇ m.
  • the pressure bonding conditions were a pressure roll temperature of 105 ° C, a pressure roll pressure of 0.3 MPa, and a laminating speed of lmZ.
  • the cushion layer in the manufactured pattern forming material was measured for total light transmittance and haze value with respect to light having a wavelength of 405 nm, and the manufactured pattern forming material and the laminate were laminated, resolution, and adhesion. And pattern defects were evaluated. The results are shown in Table 3.
  • the sample for measuring the total light transmittance was applied to a cushion layer (length 10 cm, width) by applying the cushion layer composition coating liquid on a Teflon (registered trademark) sheet at a coating amount of 74 gZm 2 and drying. After the formation of 10 cm and a thickness of 20 m), the cushion layer was prepared by peeling from the Teflon (registered trademark) sheet.
  • the total light transmittance of the cushion layer is determined by irradiating the manufactured cushion layer with a laser beam of 405 nm using an apparatus incorporating an integrating sphere into a spectrophotometer (manufactured by Shimadzu Corporation, UV-2400). It was measured by. [0438] ⁇ Haze value of cushion layer>
  • the parallel light transmittance was measured in the same manner as the total light transmittance measurement method except that the integrating sphere was not used for the total light transmittance measurement method.
  • diffuse light transmittance the total light transmittance—one parallel light transmittance
  • haze value diffuse light transmittance Z, total light transmittance X 100 It was obtained by calculating.
  • the presence or absence of bubbles between the photosensitive layer and the substrate was observed with an optical microscope, the presence or absence of stains was visually observed, and evaluation was performed according to the following criteria.
  • the support and the cushion layer are peeled off from the laminate, 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 to the dissolution and removal of the photosensitive layer on the copper clad laminate was measured, and this was taken as the shortest development time.
  • the shortest development time was 15 seconds.
  • a sensitivity curve is obtained by plotting the relationship with the thickness of the cured layer.
  • the amount of light energy when the thickness of the cured region reached 5 m was determined as the amount of light energy required to cure the photosensitive layer.
  • the amount of light energy required for curing the photosensitive layer was 2 mjZcm 2 .
  • 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 microphone mirror 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.
  • the reflection surface of the micromirror 62 is distorted, and when attention is paid particularly to the central portion of the mirror, one diagonal direction (y direction) ) Distortion force It can be seen that it is larger than the distortion in another diagonal direction (X direction). For this reason, it can be seen that the shape of the laser beam B collected by the microlens 55a of the microlens array 55 is distorted as it is.
  • FIG. 16A and FIG. 16B show the front shape and side shape of the entire microlens array 55 in detail.
  • the dimensions of each part of the microlens array 55 are also entered, and their unit is mm.
  • the microlens array 55 of the DMD50 is driven by 1024 x 256 rows of micromirrors 62.
  • the microlens array 55 has 256 rows of 1024 microlenses 55a arranged in the horizontal direction. Configured.
  • FIG. 16A the arrangement order of the microlens array 55 is indicated in the horizontal direction, indicated by j, and indicated in the vertical direction by k! /.
  • FIGS. 17A and 17B show a front shape and a side shape of one microlens 55a in the microlens array 55, respectively.
  • FIG. 17A also shows the contour lines of microlens 55a.
  • the end surface on the light exit side of each microlens 55a 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.
  • the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section.
  • FIGS. 19-8 to 190 show the simulation results of the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above-described shape.
  • the value z represents the evaluation position in the focus direction of the microlens 55a as a distance from the beam exit surface of the microlens 55a.
  • the surface shape of the microlens 55a used in the simulation is calculated by the following calculation formula.
  • X is the lens optical axis in the X direction.
  • Mean distance of O force Y represents the distance of the lens optical axis repulsion in the y direction.
  • the aperture array 59 disposed in the vicinity of the light collection position of the microlens array 55 is
  • Each of the apertures 59a is arranged so that only light that has passed through the corresponding microlens 55a is incident thereon. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to enhance the extinction ratio.
  • the laminate is allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes, and then the support is peeled off. From the cushion layer, using the pattern forming apparatus, a line Z strap is removed. Each line width was exposed in increments of 1 ⁇ m from 5 ⁇ m to 20 ⁇ m in line width at lZl, and each line width was exposed in steps of 5 ⁇ m from 20 ⁇ m to 50 ⁇ m in line width.
  • the exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material measured in the above (2).
  • an aqueous solution of sodium carbonate (30 ° C, 1% by mass) was used as the developer at a spray pressure of 0.15 MPa for the shortest development time determined in (1) above.
  • the laminate was prepared under the same method and conditions as in the method (1) for evaluating the shortest development time, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes.
  • the exposure amount at this time is the minimum amount of light energy necessary to cure the photosensitive layer of the pattern forming material measured in (2).
  • the said laminated body After leaving still at room temperature for 10 minutes, the said laminated body force The said cushion layer was peeled off.
  • the entire surface of the photosensitive layer on the copper-clad laminate 2 of the shortest developing time aqueous sodium carbonate (30 ° C, 1 wt 0/0) was determined by the at spray pressure 0. 2 MPa (1) as a developing solution Sprayed for twice the time to dissolve away uncured areas.
  • the surface of the copper clad laminate with a pattern obtained in this way was observed with an optical microscope, and the minimum line width with no abnormalities such as short lines and creases was measured on the pattern line, and this was defined as adhesion. The smaller the value, the better the adhesion.
  • the pattern surface (50 m ⁇ 50 m) formed in this manner was photographed with a scanning electron microscope (SEM), the shape of the formed pattern was observed, and the presence or absence of defects was evaluated.
  • SEM scanning electron microscope
  • Example 1 the same cushion layer composition coating solution as the following composition was prepared, and the cushion layer was formed using the filtrate filtered using a 400 mesh filter. Thus, the pattern forming material of Example 2 and the laminate were prepared. Further, in the same manner as in Example 1, the total light transmittance and haze value of the cushioning layer in the pattern forming material with respect to light having a wavelength of 405 nm were measured, and the pattern forming material and the laminate were laminated. , Adhesion, and pattern defects were evaluated. The results are shown in Table 3.
  • EVAFLEX 45X (vinyl acetate content 46 mass 0/0, manufactured by Mitsui Du Pont Polychemical Co.) 17 parts by weight
  • Example 1 a photosensitive resin composition solution having the following composition was applied onto the cushion layer.
  • the pattern forming material and laminate of Example 3 were the same as Example 1 except that a 15 m thick photosensitive layer was formed by coating and drying, and a 12 m polypropylene film was laminated thereon.
  • the body was prepared. Further, in the same manner as in Example 1, the total light transmittance and haze value of the pattern forming material with respect to light having a wavelength of 405 nm were measured, and the pattern forming material and the laminate were laminated. The adhesion and pattern defects were evaluated. The results are shown in Table 3.
  • the amount of light energy required for curing the photosensitive layer of Example 3 was 2 mjZcm 2 and the shortest development time was 20 seconds.
  • Example 1 a cushion layer composition coating solution having the following composition was prepared, and 400 A 15-m thick cushion layer is formed using the filtrate filtered using a fresh filter, and a Noria layer composition coating solution having the following compositional power is also prepared, and the filtrate filtered using a 400 mesh filter is used.
  • the pattern forming material of Example 4 and the laminate were prepared in the same manner as Example 1 except that a 1.5 m thick noria layer was formed. Further, in the same manner as in Example 1, the total light transmittance and haze value with respect to light having a wavelength of 405 nm of the cushion layer in the pattern forming material were measured, and the pattern forming material and the laminate were laminated. Resolution, adhesion, and pattern defects were evaluated. The results are shown in Table 3.
  • Example 4 the amount of light energy required to cure the photosensitive layer was 2 OmjZcm 2 and the shortest development time was 40 seconds.
  • Fluorosurfactant (trade name: F177P, manufactured by Dainippon Ink Co., Ltd.) 0.3 parts by mass' Methanol 30.0 parts by mass
  • Example 5 In Example 1, except that the micro lens array of the pattern forming apparatus was used, the pattern forming material and the laminate were analyzed for resolution, adhesion, And pattern defects were evaluated. The results are shown in Table 3.
  • Example 1 a pattern forming material and a laminate were produced in the same manner as in Example 1 except that the cushion layer composition coating solution was applied without filtering and a tack layer was formed. Further, in the same manner as in Example 1, the total light transmittance and haze value with respect to light having a wavelength of 405 nm of the cushion layer in the pattern forming material were measured, and the laminate, resolution, Adhesion and pattern defects were evaluated. The results are shown in Table 3.
  • Example 2 a pattern forming material and a laminate were produced in the same manner as in Example 1 except that the cushion layer composition coating solution was applied without filtering and a tack layer was formed. Further, in the same manner as in Example 1, the total light transmittance and haze value with respect to light having a wavelength of 405 nm of the cushion layer in the pattern forming material were measured, and the laminate, resolution, Adhesion and pattern defects were evaluated. The results are shown in Table 3.
  • Example 3 a pattern forming material and a laminate were produced in the same manner as in Example 1 except that the cushion layer composition coating solution was applied without filtering and a tack layer was formed. Further, in the same manner as in Example 1, the total light transmittance and haze value with respect to light having a wavelength of 405 nm of the cushion layer in the pattern forming material were measured, and the laminate, resolution, Adhesion and pattern defects were evaluated. The results are shown in Table 3.
  • Example 4 a pattern forming material and a laminate were produced in the same manner as in Example 1 except that the cushion layer composition coating solution and the barrier layer coating solution were applied without filtering to form a cushion layer. did. Further, in the same manner as in Example 1, the pattern forming material The total light transmittance and haze value of the cushion layer in the material with respect to light having a wavelength of 405 nm were measured, and the pattern forming material and the laminate were evaluated for laminating properties, resolution, adhesion, and pattern defects. The results are shown in Table 3.
  • Examples 1 to 5 are cushion layers formed by filtering the cushion layer composition coating solution as compared with the pattern forming materials and laminates of Comparative Examples 1 to 4. It was found that the pattern forming material and the laminate can obtain a high-definition pattern having no defects after development by making the cushion layer compatible with suitable laminating properties (protrusion following unevenness) and transparency. Further, the pattern of Example 5 formed by a pattern forming apparatus not using a microlens array was inferior in resolution as compared with Example 1.
  • the pattern forming material, pattern forming apparatus, and pattern forming method of the present invention have a cushion layer and a photosensitive layer in this order on a support, and the total light transmittance and haze value in the cushion layer.
  • a pattern forming material that has a certain numerical range, and suppressing distortion of the image formed on the photosensitive layer, it is possible to achieve both concave-convex followability and high resolution, and to produce a high-definition pattern without defects. Since it can be formed efficiently, it forms various patterns, wiring patterns, protective films, interlayer insulating films, solder resist patterns, etc., liquid crystals such as color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be suitably used for the manufacture of structural members, holograms, micromachines, proofs, etc. It can be used suitably for forming fine wiring patterns and manufacturing color filters.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

L’invention porte sur un matériau de formation de motifs permettant de constituer de manière efficace un motif très fin, sans défaut, dont la rugosité de surface des deux côtés a d’excellentes propriétés et une haute définition. L’invention porte également sur un appareil de formation de motifs employant un tel matériau de formation de motifs et un procédé de formation de motifs utilisant un tel matériau de formation de motifs. L’invention porte en particulier sur un matériau de formation de motifs caractérisé par une couche d’amortissement et une couche photosensible sur un corps de support, dans cet ordre. Le matériau de formation de motifs est en outre caractérisé en ce que la couche d’amortissement a une réflectance lumineuse totale supérieure ou égale à 86% et un voile ne dépassant pas 10%. L’invention concerne également un appareil de formation de motifs employant un tel matériau de formation de motifs et un procédé de formation de motifs où l’exposition fait appel à un tel matériau de formation de motifs.
PCT/JP2005/015768 2004-09-01 2005-08-30 Matériau de formation de motifs, appareil de formation de motifs et procédé de formation de motifs Ceased WO2006025389A1 (fr)

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JP2004254907A JP2007327979A (ja) 2004-09-01 2004-09-01 パターン形成材料、並びにパターン形成装置及びパターン形成方法
JP2004-254907 2004-09-01

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Cited By (1)

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US9513551B2 (en) 2009-01-29 2016-12-06 Digiflex Ltd. Process for producing a photomask on a photopolymeric surface

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EP2182410A4 (fr) 2007-11-20 2011-04-13 Hitachi Chemical Co Ltd Composition de resine photosensible, produit de resine photosensible durcie, film de resine photosensible, produit de film de resine photosensible durcie et guide d'ondes optique produit par utilisation de ces produits
JP5782162B2 (ja) * 2014-05-29 2015-09-24 三菱製紙株式会社 サンドブラスト用感光性フィルム
WO2020054075A1 (fr) * 2018-09-14 2020-03-19 日立化成株式会社 Film photosensible de type transfert, procédé de formation de film de résine durci, et procédé de production de substrat de capteur avec film de résine durci
WO2021137443A1 (fr) * 2019-12-31 2021-07-08 코오롱인더스트리 주식회사 Stratifié photosensible, procédé de fabrication de stratifié photosensible et procédé de fabrication de carte de circuit imprimé

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JPH1172908A (ja) * 1997-08-29 1999-03-16 Hitachi Chem Co Ltd 感光性エレメント及びカラ−フィルタの製造法
JP2000250222A (ja) * 1999-02-26 2000-09-14 Hitachi Chem Co Ltd 着色画像形成用感光性フィルム及びこれを用いた着色画像の製造法
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JPH0720309A (ja) * 1992-12-16 1995-01-24 Nippon Paper Ind Co Ltd フォトポリマーの転写材料、それを用いたカラーフィルター及びその製造方法
JPH1172908A (ja) * 1997-08-29 1999-03-16 Hitachi Chem Co Ltd 感光性エレメント及びカラ−フィルタの製造法
JP2000250222A (ja) * 1999-02-26 2000-09-14 Hitachi Chem Co Ltd 着色画像形成用感光性フィルム及びこれを用いた着色画像の製造法
JP2002311208A (ja) * 2001-04-17 2002-10-23 Jsr Corp 反射防止膜用硬化性組成物及びそれを用いた反射防止膜
JP2004001244A (ja) * 2002-04-10 2004-01-08 Fuji Photo Film Co Ltd 露光ヘッド及び露光装置
JP2003307845A (ja) * 2002-04-17 2003-10-31 Hitachi Chem Co Ltd 回路形成用感光性フィルム及びプリント配線板の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9513551B2 (en) 2009-01-29 2016-12-06 Digiflex Ltd. Process for producing a photomask on a photopolymeric surface

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JP2007327979A (ja) 2007-12-20

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