WO2007000885A1 - Procédé de mise en motif permanent - Google Patents

Procédé de mise en motif permanent Download PDF

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Publication number
WO2007000885A1
WO2007000885A1 PCT/JP2006/311503 JP2006311503W WO2007000885A1 WO 2007000885 A1 WO2007000885 A1 WO 2007000885A1 JP 2006311503 W JP2006311503 W JP 2006311503W WO 2007000885 A1 WO2007000885 A1 WO 2007000885A1
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WO
WIPO (PCT)
Prior art keywords
exposure
pixel part
area
pixel
permanent pattern
Prior art date
Application number
PCT/JP2006/311503
Other languages
English (en)
Japanese (ja)
Inventor
Masanobu Takashima
Katsuto Sumi
Kazuteru Kowada
Issei Suzuki
Takayuki Uemura
Original Assignee
Fujifilm Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Publication of WO2007000885A1 publication Critical patent/WO2007000885A1/fr

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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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70691—Handling of masks or workpieces
    • G03F7/70791—Large workpieces, e.g. glass substrates for flat panel displays or solar panels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/70358—Scanning exposure, i.e. relative movement of patterned beam and workpiece during imaging
    • 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
    • G03F7/70425—Imaging strategies, e.g. for increasing throughput or resolution, printing product fields larger than the image field or compensating lithography- or non-lithography errors, e.g. proximity correction, mix-and-match, stitching or double patterning
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0082—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the exposure method of radiation-sensitive masks

Definitions

  • the present invention forms an image of light modulated in accordance with image data on a photosensitive layer, exposes the photosensitive layer, and performs high-performance in the printed wiring board field including a package substrate or in the semiconductor field.
  • the present invention relates to a permanent pattern forming method for efficiently forming fine permanent patterns (protective film, interlayer insulating film, and solder resist pattern).
  • An exposure apparatus that passes light modulated by a spatial light modulator or the like through an imaging optical system, forms an image of this light on a predetermined photosensitive layer, and exposes the photosensitive layer is known.
  • the exposure apparatus includes a spatial light modulation element in which a large number of pixel portions that modulate irradiated light according to control signals are arranged in a two-dimensional manner, and a light source that irradiates the spatial light modulation element with light.
  • an imaging optical system that forms an image of the light modulated by the spatial light modulation element on the photosensitive layer, and the exposure head is placed on the exposed surface of the photosensitive layer.
  • Patent Document 2 a plurality of exposure heads each having a DMD in which micromirrors are arranged in a rectangular lattice shape are inclined with respect to the scanning direction, and the triangles on both sides of the DMD are inclined.
  • An exposure apparatus in which each exposure head is attached is described in such a manner that the shape portion complements each other between DMDs adjacent to each other in a direction perpendicular to the scanning direction.
  • Patent Document 3 discloses a direction in which a plurality of exposure heads having a rectangular grid DMD are not tilted with respect to the scanning direction or tilted by a minute angle and are orthogonal to the scanning direction. Each exposure head is attached so that the exposure areas by the DMD adjacent to each other overlap by a predetermined width, and the number of micromirrors to be driven is determined at the position corresponding to the overlap between the exposure areas of each DMD.
  • An exposure apparatus is described in which the exposure area by each DMD is made into a parallelogram shape that is gradually reduced or increased at a constant rate.
  • the exposure head is used so as to coincide with the scanning line force of the light beam from one pixel part to match the scanning line of the light beam of another pixel part force.
  • an exposure apparatus of a multiple exposure type in which each point on an exposed surface of a layer is exposed by overlapping a plurality of times substantially.
  • Patent Document 4 discloses a plurality of micromirrors (drawing) in order to improve the resolution of a two-dimensional pattern formed on an exposed surface and to express a pattern including a smooth diagonal line.
  • An exposure apparatus that uses rectangular DMDs that are two-dimensionally arranged in a two-dimensional manner and is tilted with respect to the scanning direction so that adjacent exposure spots with micromirror forces partially overlap on the exposed surface. It is described.
  • Patent Document 5 uses a rectangular DMD that is inclined with respect to the scanning direction, thereby superimposing exposure spots on the exposed surface to change the total illumination chromaticity.
  • An exposure apparatus capable of suppressing imaging errors caused by factors such as color image expression and microlens partial defects is described.
  • the mounting angle of the exposure head is deviated from an ideal setting inclination angle force, so that at a place on the exposed surface of the photosensitive layer to be exposed, The density and arrangement of the exposure spots will be different from the other parts, resulting in unevenness in the resolution and density of the image formed on the photosensitive layer, and the edge roughness of the pattern formed will increase. There's a problem.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-1244
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-9595
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-195512
  • Patent Document 4 U.S. Patent No. 6493867
  • Patent Document 5 Special Table 2001-500628
  • Non-patent document 1 Akito Ishikawa “Development shortening and mass production application by maskless exposure”, “ELECROTOKUS mounting technology”, Technical Research Committee, Vol.18, No.6, 2002, p.74- 79 Disclosure of the Invention
  • the present invention has been made in view of the current situation, and it is an object of the present invention to solve the conventional problems and achieve the following objects. That is, the present invention relates to deviations in the mounting position and mounting angle of the exposure head, various aberrations of the optical system between the image element and the exposed surface of the photosensitive layer, distortion of the image element itself, and the like. By leveling out the effect of variations in exposure due to pattern distortion caused by the pattern, and reducing variations in resolution and density of the pattern formed on the exposed surface of the photosensitive layer, a protective film, an insulating film, Permanent pattern that can form permanent patterns such as solder resists with high definition and efficiency. It is an object of the present invention to provide a method for forming a film.
  • a photosensitive layer After forming a photosensitive layer on the surface of the substrate using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, Light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel elements that receive and emit light from the light irradiating means.
  • An exposure head provided with a light modulation means capable of controlling a picture element portion, wherein the exposure element is arranged such that a column direction of the picture element portion forms a predetermined set inclination angle ⁇ with respect to a scanning direction of the exposure head.
  • the used pixel part specifying means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) out of the usable pixel parts, and the exposure head
  • the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure, and
  • a method of forming a permanent pattern characterized in that the exposure head is moved relative to the scanning direction for exposure and image formation.
  • the exposure head is subjected to N multiple exposures (where N is 2 or more) of the usable pixel parts by the used pixel part specifying means.
  • the pixel part to be used for (natural number) is specified, and the pixel part is assigned by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in the exposure. Be controlled. Exposure is performed by moving the exposure head relative to the photosensitive layer in the scanning direction, so that the exposure head is formed on the exposed surface of the photosensitive layer due to a mounting position or mounting angle shift. Variations in resolution and unevenness in density of the pattern are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition permanent pattern.
  • ⁇ 2> The method for forming a permanent pattern according to ⁇ 1>, wherein the formation of the photosensitive layer is performed by applying the photosensitive composition to the surface of the substrate and drying.
  • the photosensitive composition is applied to the surface of the substrate. Dried. As a result, the photosensitive layer is formed on the substrate.
  • a photosensitive layer is formed by applying a photosensitive film having a support and a photosensitive layer obtained by laminating a photosensitive composition on the support under at least one of heating and pressurization.
  • the method for forming a permanent pattern according to ⁇ 1> wherein the method is carried out by laminating on the surface.
  • the photosensitive film having the support and a photosensitive layer obtained by laminating a photosensitive composition on the support is at least one of heating and pressurization. It is laminated on the surface of the base material underneath. As a result, the photosensitive layer is formed by being transferred onto the substrate.
  • ⁇ 4> The method for forming a permanent pattern according to ⁇ 3>, wherein the support contains a synthetic resin and is transparent.
  • ⁇ 5> The method for forming a permanent pattern according to any one of ⁇ 3> to ⁇ 4>, wherein the support is elongated.
  • ⁇ 6> The method for forming a permanent pattern according to any one of ⁇ 3> to ⁇ 5>, wherein the photosensitive film is long and is wound into a roll.
  • ⁇ 8> The method for forming a permanent pattern according to any one of ⁇ 1> to ⁇ 7>, wherein the photosensitive layer has a thickness of 3 to 100111.
  • ⁇ 9> The permanent pattern forming method according to any one of ⁇ 1> to ⁇ 8>, wherein the substrate is a printed wiring board on which wiring is formed.
  • the substrate is a printed wiring board on which wiring is formed.
  • the base material is a printed wiring board on which wiring has been formed, a multilayer wiring board for semiconductors and components can be obtained by using the permanent pattern forming method. High-density mounting on build-up wiring boards is possible.
  • the exposure is performed by a plurality of exposure heads, and the drawing element specifying means is used for the exposure of the joint area between the heads, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads.
  • the permanent pattern forming method according to any one of ⁇ 1> to ⁇ 9>, wherein, among the element parts, the picture element part used for realizing N double exposure in the head-to-head connection region is designated.
  • the exposure is performed by a plurality of exposure heads, and the used pixel part specifying means is involved in the exposure of the joint area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads.
  • the picture element used for realizing the N-fold exposure in the head-to-head connection region is designated, so that the exposure of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head is performed. Variations in the resolution and uneven density of the pattern formed in the connecting area between the heads on the exposure surface are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition permanent pattern.
  • the exposure is performed by a plurality of exposure heads, and the used picture element designation means is involved in exposures other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads.
  • the permanent pattern forming method according to ⁇ 10> wherein the pixel part used to realize N double exposure in an area other than the head-to-head connection area among the picture element parts is designated.
  • the exposure is performed by a plurality of exposure heads, and the used pixel part designating unit overlaps the exposed surface formed by the plurality of exposure heads.
  • ⁇ 13> The method for forming a permanent pattern according to any one of ⁇ 1> to ⁇ 12>, wherein the N force of N exposure is a natural number of 3 or more.
  • the permanent pattern forming method according to 13> According to the law, multiple drawing is performed by using a natural number of N force 3 or more in N double exposure. As a result, due to the effect of offsetting, variations in resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to deviations in the mounting position and mounting angle of the exposure head are more accurately leveled. .
  • a light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface
  • a pixel part selecting means for selecting a picture element part to be used for realizing N double exposure
  • ⁇ 16> Based on at least two light spot positions detected by the light spot position detecting means, the row direction of the light spots on the surface to be exposed and the running direction of the exposure head in a state where the exposure head is tilted
  • the actual inclination angle ⁇ ′ formed by the image element is specified, and the pixel part selection means selects the pixel part to be used so as to absorb the error between the actual inclination angle ⁇ ′ and the set inclination angle ⁇ .
  • the permanent pattern forming method according to any one of 15>.
  • the actual inclination angle ⁇ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined.
  • the ⁇ 16> force is selected as the pixel portion to be used as the pixel portion to be used from the first row to the T-th row in the arranged pixel portion.
  • the power of the mth line is specified as the unused pixel part, and the pixel part excluding the unused pixel part is selected as the used pixel part.
  • the permanent pattern forming method according to any one of the above.
  • ⁇ 20> In an area including at least a multiple exposure area on an exposed surface formed by a plurality of pixel part rows,
  • connection area between the heads which is the overlapping exposure area on the exposed surface formed by a plurality of exposure heads
  • the number of pixel units in the overexposed area is equal to the number of pixel units in the underexposed area.
  • N (N ⁇ 1) column-by-column drawings for N of N double exposures.
  • the N double exposure of the usable pixel parts is designated. For N, reference exposure is performed using only the pixel part constituting the pixel part sequence for each (N-1) column, and a simple pattern of simple single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
  • the above-described drawing element specifying unit includes a slit and a photodetector as a light spot position detection unit, and an arithmetic unit connected to the photodetector as a drawing unit selection unit.
  • V is a method for forming a permanent pattern described in any of the above.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit.
  • V is a method for forming a permanent pattern described in any of the above.
  • 27. A method for forming a permanent pattern according to any one of the above.
  • ⁇ 29> The method for forming a permanent pattern according to any one of ⁇ 1>, ⁇ 28>, wherein the light modulation means is a spatial light modulation element.
  • ⁇ 30> The method for forming a permanent pattern according to 29 above, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • ⁇ 32> The method for forming a permanent pattern according to any one of ⁇ 1> to Kara 31, wherein the light irradiation unit can synthesize and irradiate two or more lights.
  • the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. .
  • the photosensitive layer is exposed with extremely high definition, and then the photosensitive layer is developed to form a very high definition permanent pattern.
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated with the plurality of laser forces and couples the laser beams to the multimode optical fiber.
  • the method for forming a permanent pattern according to any one of ⁇ 1> to ⁇ 32>.
  • the laser beams irradiated by the light irradiation means respectively with the plurality of laser forces. Is condensed by the collective optical system and can be coupled to the multimode optical fiber, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive layer is performed with extremely high definition, and then the photosensitive layer is developed to form an extremely fine permanent pattern.
  • ⁇ 34> The method for forming a permanent pattern according to ⁇ 33>, wherein the wavelength of the laser beam is 395 to 415 nm.
  • ⁇ 36> The method for forming a permanent pattern according to ⁇ 35>, wherein the curing process is at least a shift between an overall exposure process and an overall heating process performed at 120 to 200 ° C.
  • the permanent pattern forming method described in ⁇ 36> curing of the resin in the photosensitive composition is accelerated through the entire surface exposure treatment. Further, the film strength of the cured film is increased in the entire surface heat treatment performed under the temperature condition.
  • ⁇ 37> The method for forming a permanent pattern according to any one of ⁇ 1> and ⁇ 36>, 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, the displacement of the mounting position and mounting angle of the exposure head, and the optical system between the picture element portion and the exposed surface of the photosensitive layer. Equalizes the effects of variations in exposure due to various aberrations and pattern distortion caused by the distortion of the image area itself, etc., and eliminates variations in resolution and density of the pattern formed on the exposed surface of the photosensitive layer.
  • a permanent pattern forming method capable of forming a permanent pattern such as a protective film, an insulating film, and a solder resist with high definition and efficiency.
  • FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus.
  • FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus.
  • FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer.
  • FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head.
  • FIG. 4 is a perspective view showing an example of a schematic configuration of an exposure head.
  • FIG. 5A is a top view showing an example of a detailed configuration of an exposure head.
  • FIG. 5B is a side view showing an example of a detailed configuration of the exposure head.
  • FIG. 6 is a partially enlarged view showing an example of a DMD of the pattern forming apparatus in FIG.
  • FIG. 7A is a perspective view for explaining the operation of the DMD.
  • FIG. 7B is a perspective view for explaining the operation of the DMD.
  • FIG. 8 is an explanatory view showing an example of unevenness that occurs in a pattern on an exposed surface when there is an attachment head angle error and pattern distortion.
  • FIG. 9 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit.
  • FIG. 10 is a top view for explaining a method for measuring the position of a light spot on a surface to be exposed using a slit.
  • FIG. 11 is an explanatory view showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure.
  • FIG. 12 is an explanatory diagram showing an example of unevenness that occurs in a pattern on an exposed surface when there is a relative position shift between adjacent exposure heads.
  • FIG. 13 is a top view showing a positional relationship between an exposure area by two adjacent exposure heads and a corresponding slit.
  • FIG. 14 is a top view for explaining a technique for measuring the position of a light spot on an exposed surface using a slit.
  • FIG. 15 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 12 are actually moved, and unevenness in the pattern on the exposed surface is improved.
  • FIG. 16 is an explanatory diagram showing an example of unevenness that occurs in a pattern on an exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads.
  • FIG. 17 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG.
  • FIG. 18A is an explanatory view showing an example of magnification distortion.
  • FIG. 18B is an explanatory diagram showing an example of beam diameter distortion.
  • FIG. 19A is an explanatory view showing a first example of reference exposure using a single exposure head.
  • FIG. 19B is an explanatory view showing a first example of reference exposure using a single exposure head.
  • FIG. 20 is an explanatory view showing a first example of reference exposure using a plurality of exposure heads.
  • FIG. 21A is an explanatory view showing a second example of reference exposure using a single exposure head.
  • FIG. 21B is an explanatory diagram showing a second example of reference exposure using a single exposure head.
  • FIG. 22 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads.
  • FIG. 23 is an explanatory view showing an example of unevenness generated in the pattern on the exposed surface due to “angle distortion” in which the inclination angle of each pixel column is not uniform in Comparative Example 1.
  • the permanent pattern forming method of the present invention includes at least an exposure step and a development step, preferably includes a curing treatment step, and further includes other steps appropriately selected as necessary.
  • the exposure step is performed on the photosensitive layer.
  • An exposure head provided with a light modulation means capable of controlling a picture element portion, and arranged such that the column direction of the picture element portion forms a predetermined set inclination angle ⁇ with respect to the scanning direction of the exposure head.
  • the used pixel part specifying means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) out of the usable pixel parts, and the exposure head
  • the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure, and The exposure is performed by moving the exposure head relatively in the scanning direction.
  • N-exposure exposure refers to a straight line parallel to the scanning direction of the exposure head on the surface to be exposed in almost all of the exposure region on the surface to be exposed of the photosensitive layer.
  • the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit.
  • the arrangement of the picture element portions does not necessarily have to be a rectangular lattice, for example, an arrangement of parallelograms.
  • substantially all areas of the exposure area is described as being parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of picture element rows in the use picture element part that intersect with the straight line is reduced, even if it is used to connect multiple exposure heads when it is applied, errors due to the mounting angle and arrangement of the exposure head, etc. The number of pixel parts in the used pixel part that intersects the straight line parallel to the scanning direction may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is less than the resolution.
  • N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”.
  • N-fold drawing and N-fold drawing are used as terms corresponding to “N-double exposure” and “multiple exposure” for the embodiment in which the exposure method in the permanent pattern forming method of the present invention is implemented as a drawing method.
  • multiple drawing t is used.
  • N is a natural number of 2 or more
  • N is not particularly limited for the purpose of N-exposure. Forces that can be selected at the same time. Natural numbers of 3 or more are preferred. Natural numbers of 3 or more and 7 or less are preferred.
  • the pattern forming apparatus is a V flat-bed type exposure apparatus, and as shown in FIG. 1, a sheet-shaped photosensitive material 12 (hereinafter referred to as a sheet-shaped photosensitive material 12) formed by laminating the photosensitive layer on the substrate.
  • the plate-shaped moving stage 14 holds the “photosensitive layer 12” (which may be absorbed) on the surface.
  • Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation base 18 supported by the four legs 16.
  • the stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable.
  • the pattern forming apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.
  • a U-shaped gate 22 is provided at the center of the installation base 18 so as to straddle the moving path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18.
  • a scanner 24 is provided on one side of the gate 22, and a plurality of (for example, two) sensors 26 for detecting the front and rear ends of the photosensitive material 12 are provided on the other side.
  • the scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14.
  • the scanner 24 and the sensor 26 are connected to a controller (not shown) for controlling them.
  • an X axis and a Y axis that are orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.
  • a " ⁇ " shape that opens in the direction of the X-axis.
  • Ten slits 28 are formed at regular intervals.
  • Each slit 28 also has a force with a slit 28a located on the upstream side and a slit 28b located on the downstream side.
  • the slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of ⁇ 45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.
  • the position of the slit 28 is substantially coincident with the center of the exposure head 30.
  • each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30. Further, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34. In this case, the size of each slit 28 is set to a size that sufficiently covers the width of the overlapping portion between the exposed regions 34.
  • each slit 28 in the stage 14 a single cell type as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part specifying process to be described later.
  • a photodetector (not shown) is incorporated.
  • each photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in the used pixel part specifying process described later. .
  • the operation form of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while the exposure head is constantly moved, or each pattern is moved while the exposure head is moved step by step.
  • the exposure operation may be performed with the exposure head stationary at the destination position.
  • Each exposure head 30 is connected to a scanner 24 so that each pixel portion (micromirror) row direction of an internal digital 'micromirror' device (DMD) 36 described later forms a predetermined set inclination angle ⁇ with the scanning direction. Is attached. Therefore, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed for each exposure head 30 in the photosensitive layer 12.
  • the scanner 24 includes ten exposure heads arranged in a matrix of 2 rows and 5 columns.
  • the individual exposure heads arranged in the mth row and the nth column are indicated, they are represented as an exposure head 30, and the exposure by the individual exposure heads arranged in the mth row and the nth column is indicated.
  • each row arranged in a line is performed so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34.
  • Each of the heads 30 is arranged at a predetermined interval (a natural number times the long side of the exposure area, twice in this embodiment) in the arrangement direction. Therefore, the exposure area 32 in the first row and the exposure area
  • the part that cannot be exposed to the rear 32 can be exposed by the exposure area 32 in the second row.
  • each of the exposure heads 30 has a light modulation means (spatial light modulated for each pixel portion) that modulates incident light for each pixel portion in accordance with image data.
  • DMD36 (manufactured by Texas Instruments Inc., USA) is provided as a modulation element.
  • the DMD 36 is connected to a controller as a pixel part control means having a data processing part and a mirror drive control part.
  • the data processing unit of the controller generates a control signal for driving and controlling each micromirror in the use area on the DMD 36 for each exposure head 30 based on the input image data.
  • the mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.
  • a laser in which the emission end portion (light emission point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32.
  • a fiber array light source 38 having an emission part, a lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and reflecting the laser light transmitted through the lens system 40 toward the DMD 36
  • the mirrors 42 to be used are arranged in this order.
  • the lens system 40 is schematically shown.
  • the lens system 40 includes a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38, and a light quantity distribution of the collimated laser light. It is composed of a pair of combination lenses 46 that correct the light so as to be uniform, and a condensing lens 48 that condenses the laser light whose light intensity distribution has been corrected on the DMD 36.
  • a lens system 50 that forms an image of the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed.
  • the lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.
  • the laser beam emitted from the fiber array light source 38 is substantially five times larger. After being expanded, the light from each micromirror on the DMD 36 is set to be reduced to about 5 ⁇ m by the lens system 50!
  • n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements are provided, and according to the pattern information
  • Any device that can control the picture element portion can be appropriately selected according to the purpose without any particular restriction.
  • a spatial light modulator is preferable.
  • Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), and transmission by an electro-optic effect.
  • Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
  • the light modulation means includes pattern signal generation means for generating a control signal based on pattern information to be formed.
  • the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
  • control signal can be appropriately selected according to the purpose for which there is no particular limitation.
  • a digital signal is preferably used.
  • the DMD 36 has a mirror structure in which a large number of micromirrors 58 are arranged in a lattice pattern as a pixel portion constituting each pixel (pixel). It is a device.
  • the power to use DMD36 in which micromirrors 58 of 1024 columns x 768 rows are arranged.
  • micromirrors 58 that can be driven by a controller connected to DMD36, that is usable are only 1024 columns x 256 rows.
  • the data processing speed of DMD36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors used. Thus, by using only some of the micromirrors in this way, Modulation speed increases.
  • Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof.
  • the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof Is 13.7 m in both vertical and horizontal directions.
  • the SRAM cell 56 is a silicon gate CMOS manufactured on an ordinary semiconductor memory manufacturing line via a support including a hinge and a yoke, and is configured monolithically (integrated) as a whole.
  • each micromirror 58 supported by the column is Inclined to one of ⁇ ⁇ degrees (for example, ⁇ 10 degrees) with respect to the substrate side on which the DMD 36 is disposed with the diagonal line as the center.
  • FIG. 7 (b) shows a state tilted to + ⁇ degrees when the micromirror 58 is in the on state
  • FIG. 7 (b) shows a state tilted to ⁇ degrees when the micromirror 58 is in the off state.
  • FIG. 6 shows an example of a state in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + ⁇ degrees or ⁇ degrees.
  • the on / off control of each micromirror 58 is performed by the controller connected to the DM D36.
  • a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.
  • the light irradiating means can be appropriately selected according to the purpose without any particular restriction.
  • (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copying machine For example, a fluorescent tube, a known light source such as an LED or a semiconductor laser, or a means capable of combining and irradiating two or more lights.
  • a means capable of combining and irradiating two or more lights is 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 force 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! /,
  • a means capable of irradiating the combined laser for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber.
  • a means having a collective optical system for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber.
  • a means having a collective optical system for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber.
  • means (fiber array light source) that can irradiate the combined laser include means described in paragraphs [0109] to [0146] of Japanese Patent Application Laid-Open No. 20 05-258431.
  • the used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot as a pixel unit on the exposed surface, and a detection result by the light spot position detecting means. It is preferable to have at least a pixel part selection means for selecting a pixel part to be used for realizing N double exposure.
  • the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and the variation in resolution and density unevenness due to the mounting angle error of each exposure head 30 are reduced.
  • the set tilt angle ⁇ in the column direction of the image area (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used in an ideal state where there is no mounting angle error of the exposure head 30. From the angle ⁇ , which is exactly double exposure using a 1024 column x 256 row pixel part
  • the ideal also uses a slightly larger angle.
  • This angle ⁇ is the number of N exposures N, the number of usable micromirrors 58 in the row direction s
  • the angle ⁇ is about 0.45 degrees according to the equation 3. Therefore, the set tilt angle ⁇ is, for example, 0.5 ideal
  • FIG. 8 shows unevenness that occurs in the pattern on the exposed surface due to the effect of the mounting angle error of one exposure head 30 and the pattern distortion in the pattern forming apparatus 10 that is initially adjusted as described above. It is explanatory drawing which showed the example.
  • the light spot as the pixel unit generated by each pixel part (micromirror) and constituting the exposure region on the exposed surface the light spot in the m-th row 3 ⁇ 4 ⁇ (m), the light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).
  • FIG. 8 shows a pattern of light spots from the usable micromirror 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is The pattern of the light spot group as shown in the upper part appears, and the state of the exposure pattern formed on the exposed surface is shown when the stage 14 is moved in this state and continuous exposure is performed. Is.
  • FIG. 8 for convenience of explanation, the exposure pattern by the odd-numbered columns of the micromirrors 58 that can be used and the exposure pattern by the even-numbered columns are shown separately. However, the actual exposure patterns on the exposed surface are shown in FIG. It is a superposition of two exposure patterns.
  • the set inclination angle 0 is set to a slightly larger angle than the angle 0 described above.
  • FIG. 8 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” in which the inclination angle of each pixel column projected on the surface to be exposed is not uniform has occurred.
  • the Causes of this angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, and micromirror placement errors.
  • the angular distortion appearing in the example of FIG. 8 is a distortion in which the tilt angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure.
  • the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.
  • the light spot position detecting means includes the slit 28 and the photodetector.
  • the actual inclination angle ⁇ ′ is specified for each exposure head 30, and the arithmetic unit connected to the photodetector is used as the pixel part selection unit based on the actual inclination angle ⁇ ′.
  • a process of selecting a micromirror to be used for actual exposure is performed. Based on at least two light spot positions detected by the light spot position detecting means until the actual tilt angle ⁇ , the light spot column direction on the surface to be exposed and the exposure head when the exposure head is tilted. It is specified by the angle formed by the scanning direction.
  • FIG. 9 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28.
  • the size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
  • the angle formed by the 512-th light spot array positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle ⁇ ′.
  • the micromirror 58 in the first row and the 512th column on the DMD 36 and the micromirror 58 in the 256th row and the 512th column are turned on, and the light spots on the exposure surface corresponding to each of them are turned on.
  • the positions of P (l, 512) and P (256, 512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual tilt angle ⁇ ′.
  • FIG. 10 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
  • the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is
  • the slit 28 is positioned at an arbitrary position between the upstream slit 28a and the downstream slit 28b.
  • the value of this coordinate (XO, YO) is determined and recorded by the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position force of the slit 28.
  • the stage 14 is moved, and the slit 28 is relatively moved along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 10, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector.
  • the coordinates (XO, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).
  • the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. Then, as indicated by a two-dot chain line in FIG. 10, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector.
  • the coordinates (XO, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).
  • the coordinates indicating the position of P (l, 512) are also determined, and the inclination angle formed by the straight line connecting the coordinates and the scanning direction of the exposure head 30 is derived, and this is the actual inclination angle.
  • a natural number T is derived that is closest to the value t satisfying the above relationship, and the micromirrors in the 1st to Tth rows on the DMD 36 are selected as the micromirrors that are actually used during the main exposure.
  • a micromirror that minimizes the total area of the overexposed area and the underexposed area for the ideal double exposure is actually realized. It can be selected as a micromirror to be used for.
  • the smallest natural number equal to or greater than the value t may be derived.
  • a micromirror that minimizes the area of the overexposed area and produces an insufficient exposure area for ideal double exposure. Can be selected as the actual micromirror to be used.
  • a micromirror that minimizes the area of the underexposed area and does not produce an overexposed area with respect to the ideal double exposure It can be selected as a micromirror to be actually used.
  • FIG. 11 shows the unevenness on the exposed surface shown in FIG. 8 in the exposure performed using only the light spot generated by the micromirror selected as the micromirror actually used as described above. It is explanatory drawing which showed how it is improved.
  • T 253 is derived as the natural number T and the micromirror on the 253rd line is selected as the first line force.
  • the force of the 254th line that has not been selected is also sent to the micromirror on the 256th line by the pixel part control means to send a signal for setting the angle to the off state at all times.
  • Is not involved in exposure As shown in Fig. 11, overexposure and underexposure are almost completely eliminated in the exposure area near the 512th column, and uniform exposure very close to ideal double exposure is realized.
  • the inclination angle of the light spot sequence on the exposure surface is near the center (c (512 in the figure)) due to the angular distortion. It is smaller than the angle of inclination of the ray train in the area of). Therefore, the exposure using only the micromirrors selected based on the actual inclination angle ⁇ ⁇ measured with c (512) as a reference, is ideal for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. A slight under-exposure area is generated for the double exposure.
  • the overexposed areas are complemented with each other, and the density unevenness due to the angular distortion is It can be minimized by the effect of offset by double exposure.
  • the actual inclination angle ⁇ ′ of the 512th ray array is measured, and the actual inclination angle ⁇ is used to derive the equation (4).
  • the micromirror 58 to be used is selected based on T.
  • the actual inclination angle ⁇ ′ the column direction (light spot column) of a plurality of pixel portions and the scanning direction of the exposure head are used.
  • a plurality of actual tilt angles are respectively measured, and any one of the average value, median value, maximum value, and minimum value is specified as an actual tilt angle ⁇ '.
  • an exposure with a good balance between an overexposed area and an underexposed area can be realized with respect to an ideal N double exposure. Can do. For example, the total area of overexposed areas and underexposed areas is minimized, and the number of pixel units (number of light spots) in overexposed areas and underexposed areas It is possible to achieve an exposure that makes the number of pixel units (number of light spots) equal to the maximum number of pixels. It is possible to achieve exposure that places more importance on eliminating excessive regions, for example, to achieve exposure that minimizes the area of underexposed regions and prevents overexposed regions. Is possible.
  • the minimum value is the actual inclination angle ⁇ ′, it is possible to realize exposure that places more emphasis on the exclusion of areas that are insufficient for the ideal N double exposure. Thus, it is possible to realize an exposure that minimizes the area of the region and prevents an underexposed region from occurring.
  • the identification of the actual inclination angle ⁇ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row).
  • the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in a row in the vicinity of c (n) may be specified.
  • one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on the straight line and in the vicinity along the scanning direction of the exposure head are detected.
  • the actual inclination angle ⁇ ′ can be obtained from these positional information.
  • the angle obtained based on the position of at least two light spots in the light spot array in the vicinity of the c (n) line is obtained.
  • the actual inclination angle ⁇ ′ may be specified.
  • the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and is a head that is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads 30.
  • Two exposure heads for example, exposure head 30 as an example
  • And 30 due to the deviation of the relative position in the X-axis direction from the ideal state.
  • each exposure head 30 that is, each DMD 36
  • the set tilt angle ⁇ of each exposure head 30, that is, each DMD 36 can be used as long as there is no mounting angle error or the like of the exposure head 30. 58 and adopt an angle ⁇ that is exactly double exposure.
  • This angle ⁇ is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1).
  • FIG. 12 shows an ideal relationship between the relative positions of the two exposure heads (for example, the exposure heads 30 and 30) in the X-axis direction in the pattern forming apparatus 10 initially adjusted as described above.
  • FIG. 6 is an explanatory view showing an example of density unevenness generated in a pattern on an exposed surface due to the influence of deviation from the state. Deviations in the relative position of each exposure head in the X-axis direction can occur because it is difficult to fine-tune the relative position between exposure heads.
  • FIG. 12 The upper part of FIG. 12 is a micromirror 58 that can be used for the DMD 36 of the exposure heads 30 and 30 that is projected onto the exposed surface of the photosensitive material 12 with the stage 14 stationary.
  • Fig. 12 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and continuous exposure is performed with the light spot group pattern shown in the upper part appearing.
  • every other column exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B.
  • the actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.
  • the light spot position detection is performed. Using a set of slit 28 and photodetector as means, exposure head 30 and 30 force
  • the position (coordinates) of some of the light spots that constitute the inter-head connecting area formed on the exposed surface is detected from among the 12 21 light spot groups. Based on the position (coordinates), processing for selecting a micromirror to be used in actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel part selection means.
  • FIG. 13 shows the positional relationship between the exposure areas 32 and 32 similar to those in FIG.
  • the size from 12 21 is sufficiently large to cover the connecting area between the heads formed on the exposed surface.
  • FIG. 14 shows an example of detecting the position of the light spot P (256, 1024) in the exposure area 32 as an example.
  • the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream.
  • the slit 28 is positioned at an arbitrary position between the slit 28a on the side and the slit 28b on the downstream side.
  • the coordinates of the intersection of the slit 28a and the slit 28b are (XO, Y0).
  • the value of this coordinate (XO, Y0) is determined and recorded by the movement distance of the stage 14 to the above position indicated by the drive signal given to the stage 14 and the known X-direction position force of the slit 28.
  • the stage 14 is moved, and the slit 28 is relatively moved along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 14, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector.
  • the coordinates (XO, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).
  • the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. Then, as indicated by a two-dot chain line in FIG.
  • the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector.
  • the coordinates (XO, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).
  • Detection is performed by a combination of a slit 28 and a photodetector as a position detection means. Next, exposure area 32
  • each light spot on the light spot line r (256) of the 256th line of 21 is detected in order of ⁇ (256, 1024), P (256, 10 23) ... X coordinate greater than 32 light spots P (256, 1)
  • the micromirror to be used is identified as a micromirror (unused pixel part) that is not used during the main exposure.
  • the detection operation ends.
  • the 1021 row power in the exposure area 32 corresponding to the portion 70 covered by the diagonal line is also the light spot that forms the 1024th row.
  • the micromirror force corresponding to is specified as a micromirror that is not used during the main exposure.
  • the micromirrors that are not used during the main exposure described above are used.
  • the positions of the light spots that make up the rightmost column 1020 are the P (l, 1020) forces in the order P (l, 1020), P (2, 1020) ... and spot P (m, 1020) indicating an X coordinate larger than spot P (256, 2) in exposure area 32
  • the detection operation is terminated.
  • an exposure area 32 Thereafter, in an arithmetic unit connected to the photodetector, an exposure area 32
  • the X coordinate of the light spot P (m, 1020) in the exposure area 32 is the exposure area 3
  • the micromirror corresponding to the force P (m-1, 1020) is also identified as the micromirror that is not used during the main exposure.
  • the X coordinate of the light spot P (m–1, 1020) in the exposure area 32 is the light in the exposure area 32.
  • micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 15 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set their micromirror angle to the off-state angle, and these micromirrors are essentially not used for exposure.
  • exposure areas 32 and 32 are selected. Ideal double dew in the area between the heads
  • the total area of areas that are overexposed and underexposed to light can be minimized, and uniform exposure very close to ideal double exposure is achieved, as shown in the lower part of Fig. 15. can do.
  • the light spot P (l, 1020) force in the exposure area 32 immediately increases P (m— 2, 1020) May be specified as a micromirror that is not used during the main exposure.
  • a micromirror that minimizes the area of the overexposed region with respect to the ideal double exposure and does not generate an underexposed region in the connecting region between the heads It can be selected as a micromirror to be actually used.
  • the light spot P (l, 1020) force in the exposure area 32 corresponds to P (m— 1, 1020).
  • a micromirror which is not used for this exposure. In that case, in the connecting area between the heads, a micromirror that minimizes the area of the area that is underexposed with respect to the ideal double exposure and that does not cause an overexposed area is actually used. It can be selected as the micromirror to be used.
  • the number of pixel units (the number of light spots) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light spots) in an area that is underexposed are: It is good also as selecting the micromirror actually used so that it may become equal.
  • the solution caused by the relative position shift in the X-axis direction of the plurality of exposure heads reduces image variability and density unevenness, and realizes ideal N double exposure.
  • the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30.
  • the relative position of the two exposure heads (for example, exposure heads 30 and 30) in the X-axis direction deviates from the ideal state, as well as each exposure.
  • each exposure head 30 that is, each DMD 36
  • the set tilt angle of each exposure head 30, that is, each DMD 36 can be used as long as there is no mounting angle error or the like of the exposure head 30.
  • the degree shall be adopted.
  • the set inclination angle 0 for example, an angle of about 0.50 degrees may be adopted. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle ⁇ within an adjustable range.
  • FIG. 16 shows a mounting angle error between two exposure heads (for example, exposure heads 30 and 30) in the pattern forming apparatus 10 in which the mounting angles of each exposure head 30, that is, each DMD 36 are initially adjusted as described above. And relative mounting angle error between each exposure head 30 and 30
  • FIG. 6 is an explanatory diagram showing an example of unevenness that occurs in a pattern on an exposed surface due to the influence of a shift in relative position.
  • phase of the exposure heads 30 and 30 in the X-axis direction is the same as the example of FIG.
  • the set inclination angle ⁇ of each exposure head is changed to an angle ⁇ satisfying the above equation (1).
  • Use pixel selection processing is performed to reduce density unevenness due to the influence of the angle difference. Specifically, a set of the slit 28 and the photodetector is used as the light spot position detecting means, and the actual inclination angle ⁇ ′ is specified for each of the exposure heads 30 and 30, and the actual inclination angle is determined.
  • an arithmetic unit connected to a photodetector is used as the pixel part selection means.
  • a process of selecting a micromirror to be used for actual exposure is performed.
  • the actual inclination angle ⁇ ′ is specified by the light spot P (l,
  • the arithmetic device connected to the photodetector using the actual inclination angle ⁇ ′ thus specified is similar to the arithmetic device in the above-described embodiment (1), as shown in the following equation 4
  • the (T + 1) line force on the DMD 36 is also identified as a micromirror that is not used for the main exposure.
  • the micromirror force corresponding to the light spots constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 is specified as a micromirror that is not used in the main exposure.
  • the micromirror force corresponding to the light spots constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 is specified as a micromirror that is not used in the main exposure.
  • the total area of the overexposed and underexposed areas with respect to the ideal double exposure can be minimized.
  • the smallest natural number equal to or greater than the value t may be derived. In that case, to multiple exposures in exposure areas 32 and 32
  • exposure areas 32 and 32 overlapped exposure areas on the exposed surface formed by multiple exposure heads.
  • the number of pixel units in the overexposed area for the ideal double exposure in each area other than the joint area between the heads, which is the overlapping exposure area on the exposed surface formed by multiple exposure heads It is also possible to specify a micromirror that is not used during the main exposure so that the number of pixel units (number of light spots) in the underexposed area is equal to the number of light spots!
  • micromirror corresponding to the light spot other than the light spots constituting the regions 78 and 80 covered by the oblique lines in FIG. 17 this is the same as the embodiment (3) described with reference to FIGS.
  • the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 in FIG. 17 were identified and should not be used during the main exposure! And added as a micromirror. Is done.
  • the pixel unit control means sends a signal for setting the angle of the always-off state, and these microphone mirrors substantially Not involved in exposure.
  • the relative position shifts in the X-axis direction of the plurality of exposure heads and the respective exposure Variations in resolution and density unevenness due to the mounting angle error of the optical head and the relative mounting angle error between the exposure heads can be reduced, and ideal N-fold exposure can be realized.
  • a set of the slit 28 and the single cell type photodetector is used as a means for detecting the position of the light spot on the surface to be exposed.
  • the force that was used is not limited to this, V, or any other form can be used.
  • a two-dimensional detector can be used.
  • the actual inclination angle ⁇ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle is obtained.
  • a micromirror to be used is selected based on ⁇ ⁇
  • a usable micromirror may be selected without going through the derivation of the actual inclination angle ⁇ ′.
  • all available A mode in which a micromirror used by an operator is manually designated by performing reference exposure using a simple micromirror and confirming the unevenness of resolution and density by visual observation of the reference exposure result is also included in the scope of the present invention. It is.
  • magnification distortion that reaches the exposure area 32 on the exposure surface at different magnifications from the light power from each micromirror 58 on the DMD 36.
  • beam diameter distortion that reaches the exposure area 32 on the exposed surface with different beam diameters, the light power from each micromirror 58 on the DMD 36.
  • this light distortion is due to the positional dependence of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the single lenses 52 and 54 in FIG. 5) and the DMD 36 itself. This is caused by unevenness in the amount of light.
  • These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.
  • the residual elements of these forms of pattern distortion are As with the residual elements, it can be leveled by the effect of multiple exposure, and the unevenness in resolution and density can be reduced over the entire exposure area of each exposure head.
  • every (N-1) micromirror columns or adjacent to 1ZN rows of all light spot rows The reference exposure is performed using only the group of micromirrors that make up the row, and the microphone mirror that is not used during actual exposure is identified among the micromirrors used for the reference exposure so that uniform exposure can be achieved. You can do it.
  • the result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is subjected to analysis such as confirmation of resolution variation and density unevenness and estimation of the actual inclination angle.
  • the analysis of the result of the reference exposure is a visual analysis by the operator.
  • FIG. 19 is an explanatory diagram showing an example of a mode in which reference exposure is performed using only (N-1) -row micromirrors using a single exposure head.
  • reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot arrays indicated by solid lines in FIG. 19A, and the reference exposure results are output as samples. Based on the reference exposure result output from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and uneven density, or estimating the actual tilt angle.
  • a microphone aperture mirror other than the micromirror corresponding to the light spot array shown by hatching in FIG. 19B is designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. Is done.
  • a separate reference exposure may be performed in the same manner to specify a micromirror to be used during the main exposure, or the same pattern as that for odd-numbered light spot arrays may be applied. Good.
  • FIG. 20 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) -row micromirrors using a plurality of exposure heads.
  • Exposure is performed, and a reference exposure result is output as a sample. Based on the output result of the reference exposure, the two exposure heads check resolution variations and density unevenness in areas other than the head-to-head connection area formed on the exposed surface, and estimate the actual inclination angle. Therefore, it is possible to specify the micromirror to be used during the main exposure. For example, the micromirror force other than the micromirror corresponding to the light spot array in the area 86 shown by hatching in FIG. Designated as actually used. For even-numbered light spot arrays, a separate reference exposure may be performed in the same manner, and the micromirror used for the main exposure may be designated, or the same pattern as that for the odd-numbered pixel lines may be applied. .
  • the two exposure heads form the surface to be exposed.
  • a state close to ideal double exposure can be achieved in areas other than the head-to-head connection area.
  • FIG. 21 illustrates an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1ZN rows of the total number of light spots. It is a figure.
  • a microphone mouth mirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 21B is actually used during the main exposure in the micromirrors in the first to 128th rows.
  • micromirror By specifying the micromirror to be used during the main exposure in this way, it is possible to achieve a state close to an ideal double exposure in the main exposure using the entire micromirror.
  • Fig. 22 shows two exposure heads that use a plurality of exposure heads and are adjacent in the X-axis direction ( As an example, exposure heads 30 and 30) are equivalent to 1ZN rows of the total number of light spots.
  • FIG. 10 is an explanatory diagram showing an example of a form in which reference exposure is performed using only micromirror groups constituting adjacent rows.
  • the micro-mirror force other than the micro-mirror corresponding to the light spot array in the area 90 shown shaded in FIG. 22 and the area 92 shown by shading is the main exposure in the micro-mirrors in the first to 128th rows. Designated as actually used at the time.
  • a separate reference exposure may be performed in the same manner to specify the micromirror to be used for the main exposure, and the first to 128th lines are designated. The same pattern as that of the micromirror may be applied.
  • micromirror By specifying the micromirror to be used during the main exposure in this way, a state close to ideal double exposure is realized in areas other than the joint area between the heads formed on the exposed surface by the two exposure heads. it can.
  • the power described in the case where the main exposure is double exposure is not limited to this, and any multiple exposure over double exposure is possible. It is good.
  • the triple exposure power is set to approximately seven exposures, it is possible to achieve exposure with high resolution and reduced resolution variation and density unevenness.
  • the size of the predetermined portion of the two-dimensional pattern represented by the image data matches the size of the corresponding portion that can be realized by the selected use pixel. It is preferable that a mechanism for converting image data is provided. By converting the image data in this way, it is possible to form a high-definition pattern on the exposed surface according to the desired two-dimensional pattern.
  • the object of exposure is a photosensitive layer formed on the surface of a substrate using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent.
  • a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent.
  • it can be appropriately selected according to the purpose for which there is no restriction.
  • the photosensitive composition of the first aspect formed by applying the photosensitive composition to the surface of a substrate and drying, and the support and the photosensitive composition on the support
  • the photosensitive layer of the second aspect is formed by laminating a photosensitive film having a photosensitive layer on which is laminated on the surface of the substrate under at least one of heating and pressing. I can get lost.
  • the base material can be appropriately selected from publicly known materials that are not particularly limited to those having a high surface smoothness and a surface having an uneven surface, and a plate-like base material (substrate) is preferred.
  • Specific examples include 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.
  • the printed wiring board forming substrate has already been formed in terms of the fact that high-density mounting of semiconductors and the like can be performed on a multilayer wiring substrate that is preferred for the printed wiring board forming substrate. Is particularly preferred.
  • the photosensitive composition includes at least a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, and if necessary, a coloring pigment, an extender pigment, a thermal polymerization inhibitor, a surfactant. Including other ingredients.
  • the noinder is more preferably soluble in an alkaline aqueous solution, which is preferably swellable 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 noinder can be appropriately selected according to the purpose for which there is no particular restriction.
  • JP-A-51-131706, JP-A-52-94388, JP-A-64H5 examples thereof include an epoxy atelar toy compound having an acidic group described in JP-A-2-97513, JP-A-3-289656, JP-A-61-243869, JP-A-2002-296776, and the like.
  • phenol novolac type epoxy acrylate, tarezol novolak epoxy acrylate, bisphenol A type epoxy acrylate, etc. for example, epoxy resin is mixed with polyfunctional epoxy compound (meth) acrylic acid.
  • a carboxylic group-containing monomer such as phthalic acid is reacted, and a dibasic acid anhydride such as phthalic anhydride is further added.
  • the molecular weight of the epoxy vacancy compound is preferably 1,000 to 200,000 force S, more preferably 2,000 to 100,000.
  • the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and the film quality becomes brittle or the surface hardness deteriorates after curing of the photosensitive layer described later. Yes, if it exceeds 200,000, developability may deteriorate.
  • an acrylic resin having at least one polymerizable group such as an acidic group and a double bond described in JP-A-6-295060 can also be used.
  • at least one polymerizable double bond in the molecule for example, an acrylic group such as a (meth) acrylate group or a (meth) acrylamide group, a carboxylic acid bull ester, a bull ether, a aryl ether.
  • Various polymerizable double bonds such as tellurium can be used.
  • acrylic resin containing a carboxyl group as an acidic group glycidyl ester of unsaturated fatty acid such as glycidyl atylate, glycidyl methacrylate, cinnamic acid, or cyclohexenoxide in the same molecule.
  • examples thereof include a compound obtained by adding an epoxy group-containing polymerizable compound such as a compound having an epoxy group and a (meth) attalyloyl group.
  • compounds obtained by adding a polymerizable compound containing a hydroxyl group such as hydroxyalkyl (meth) acrylate include “Kaneka Resin AX, manufactured by Kaneka Chemical Co., Ltd.”, “CYCLOM ER A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER M” —200; manufactured by Daicel Chemical Industries, Ltd. ”can be used.
  • a reaction product of hydroxyalkyl attalylate or hydroxyalkyl metatalylate described in JP-A-50-59315 with any one of polycarboxylic acid anhydride and epihalohydrin can be used.
  • the molecular weight of the binder such as the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), amide group-containing styrene Z acid anhydride copolymer, or polyimide precursor, 3, 000 to 500,000 force S preferred ⁇ , 5, 000 to 100,000 force S preferred.
  • the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 500,000, developability may deteriorate.
  • the solid content in the photosensitive composition solid content of the binder is preferably 5 to 80 mass%, more preferably 10 to 70 mass%. If the solid content is less than 5% by mass, the film strength of the photosensitive layer may be weakened or the tackiness of the surface of the photosensitive layer may be deteriorated. If it exceeds 80% by mass, Exposure sensitivity may decrease.
  • the polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, but has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure.
  • at least one selected from monomers having a (meth) acryl group is preferable.
  • the monomer having a (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monofunctional acrylates and monofunctional methacrylates such as rate, phenoxychetyl (meth) acrylate, polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, trimethylol propane dialate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedi
  • polyfunctional acrylates and methacrylates such as epoxide acrylate which is a reaction product of epoxy resin and (meth) acrylic acid.
  • epoxide acrylate which is a reaction product of epoxy resin and (meth) acrylic acid.
  • trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • the solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
  • the photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light may have some effect with photo-excited sensitizers, and may be active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates.
  • the photopolymerization initiator may have a wavelength of about 300 to 800 nm and at least about 50. It is preferable to contain at least one component having a molecular extinction coefficient. The wavelength ⁇ to 330-500mn force is particularly preferred!
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having an oxadiazole skeleton, etc.), phosphine oxides, hexaryl reels.
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having an oxadiazole skeleton, etc.
  • phosphine oxides for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having an oxadiazole skeleton, etc.
  • Examples include imidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and ketoximate.
  • photopolymerization initiator examples include compounds described in paragraphs [0290] to [0299] and paragraphs [0305] to [0307] of JP-A-2005-258431. Etc.
  • Examples of the oxime derivative suitably used in the present invention include, for example, 3 benzoyloxy minobutane 2 on, 3 acetoximininobutane 2 on, 3 propionyloxy iminobutane 2 on, 2 acetoximinopentane 3 on, 2-acetoximino — 1-phenolpropane 1-one, 2-benzoyloximino 1-phenolpropane — 1-one, 3-— (4-toluenesulfo-loxy) iminobutane-2-one, and 2 eth Xylcarboloxymino 1-phenolpropane-1-one.
  • the sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible laser, or the like as a 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 can be appropriately selected from known sensitizers that are not particularly limited. For example, in paragraphs [0313] to [0314] of JP-A-2005-258431, Examples of compounds that are described!
  • the content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, based on all the components in the photosensitive composition. ⁇ 10% by weight is particularly preferred.
  • the sensitizer may be precipitated from the photosensitive layer.
  • the photopolymerization initiators may be used singly or in combination of two or more.
  • halogenated carbonization having the phosphine oxides, the ⁇ -aminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the later-described exposure.
  • examples thereof include a composite photoinitiator in which a hydrogen compound and an amine compound as a sensitizer described later are combined, a hexaarylbiimidazole compound, or titanocene.
  • the content of the photopolymerization initiator in the photosensitive composition 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. preferable.
  • 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 of the epoxy resin compound or oxetane compound in the solid content of the photosensitive composition 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.
  • the epoxy resin compound or the oxetane compound may be a curing catalyst, or a compound capable of promoting thermal curing other than the above as long as it can promote the reaction of these with a carboxyl group. Use it.
  • 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 isocyanate groups. It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing Specifically, 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
  • a blocking agent is reacted with the isocyanate group of the polyisocyanate and its derivatives. You can use the compound obtained in this way.
  • 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 rosin precursors, and the like 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.
  • Hexamethylated methylol melamine which consists of a formaldehyde condensation product of melamine and urea, or butyl ether of a melamine and formaldehyde condensation product may also be used.
  • 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.
  • Agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • the thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
  • thermal polymerization inhibitor examples include compounds described in paragraph No. [0 316] of JP-A-2005-258431.
  • the content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass with respect to the polymerizable compound, and 0.01 to 1% by mass. Is particularly preferred. If the content is less than 0.001% by mass, the stability during storage may be reduced, and if it exceeds 5% by mass, the sensitivity to active energy rays may be reduced.
  • the coloring pigment can be appropriately selected according to the purpose without any particular limitation.
  • Bikku! J Pure One Blue BO CI 42595
  • Auramin CI 41000
  • Fat 'Black HB CI 26150
  • Monolight 'Yellow GT CI Pigment' Yellow 1 2
  • Permanent 'Yellow GR CI Pigment' Yellow 17
  • Permanent 'Yellow HR CI Pigment' Yellow 83
  • Permanent 'Carmin FBB CI Pigment' Red 146)
  • Hoster Balm Red ESB CI Pigment 'Violet 19
  • Permanent' Rubi I FBH CI Pigment 'Red 11
  • Huster's' Pink B Supra CI Pigment 'Red 81
  • Monastral' First 'Blue CI Pigment' Blue 15
  • Monolight 'Fast' Black B CI Pigment 'Black 1
  • Carbon CI Pigment' Red 97, CI Pigment 'Red 122, CI Pigment 'Red 149,
  • Pigment 'Blue 15 1, CI Pigment' Blue 15: 4, CI Pigment 'Blue 15: 6, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, etc. These may be used alone or in combination of two or more. If necessary, a dye appropriately selected from known dyes can be used.
  • the solid content in the solid content of the photosensitive composition of the coloring pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during the formation of a permanent pattern. Different forces depending on the type of facial material Generally 0.05-: LO mass% is preferred 0.1-5 mass% Force is more preferred.
  • the photosensitive composition is used for the purpose of improving the surface hardness of the permanent pattern or keeping the coefficient of linear expansion low, or keeping the dielectric constant or dielectric loss tangent of the cured film low, if necessary.
  • Inorganic pigments and organic fine particles can be added.
  • the inorganic pigment can be appropriately selected from known ones that are not particularly limited.
  • kaolin barium sulfate, barium titanate, key oxide powder, fine powder oxide oxide, vapor phase method silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and my strength.
  • the average particle diameter of the inorganic pigment is preferably less than 10 m, more preferably 3 m or less. If the average particle size is 10 m or more, the resolution may deteriorate due to light scattering.
  • the organic fine particles can be appropriately selected according to the purpose without particular limitation, and examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle diameter of 1 to 5 / ⁇ , an oil absorption of about 100 to 200 m 2 Zg, spherical porous fine particles made of a crosslinked resin, and the like can be used.
  • the amount of the extender is preferably 5 to 60% by mass.
  • the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced.
  • the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, When the film quality becomes fragile and the wiring is formed using permanent patterns, the function of the wiring as a protective film is impaired. Sometimes.
  • a known adhesion promoter may be used for each layer.
  • adhesion promoter examples include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638.
  • the content of the adhesion promoter is preferably 0.001% by mass to 20% by mass with respect to all components in the photosensitive composition, and more preferably 0.01 to 10% by mass. 0.1% by mass to 5% by mass is particularly preferable.
  • Examples of the method for forming the photosensitive layer include a method in which the photosensitive composition is applied to the surface of the base material and dried as the first aspect, and a photosensitive film is used as the second aspect. A method of laminating on the surface of the substrate under at least one of heating and pressurization is mentioned.
  • a photosensitive layer is formed by coating and drying the photosensitive composition on the substrate.
  • the coating and drying method can be appropriately selected according to the purpose without any particular limitation.
  • the photosensitive composition is dissolved, emulsified or dispersed on the surface of the base material in water or a solvent.
  • a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.
  • the solvent of the photosensitive composition solution is appropriately selected depending on the purpose without any particular limitation.
  • Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, n-hexanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone Ketones such as: Ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; aromatics such as toluene, xylene, benzene, and ethylbenzene Group hydrocarbons: Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, black mouth form, 1, 1, 1-t
  • the coating method is not particularly limited and can be appropriately selected depending on the purpose.
  • coating directly to the said base material is mentioned.
  • the drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
  • the thickness of the photosensitive layer is not particularly limited, and can be appropriately selected depending on the purpose. For example, 3 to: LOO 111 or more preferably 5 to 70 m force.
  • a photosensitive film having a support on the surface of the substrate and a photosensitive layer in which a photosensitive composition is laminated on the support is heated and Laminate while performing at least one of pressurization.
  • the said photosensitive film has a protective film mentioned later, it is preferable to peel this protective film and to laminate
  • the photosensitive film comprises at least a support and a photosensitive layer, preferably a protective film, and further comprises a cushion layer, an oxygen barrier layer (PC layer), etc., if necessary. It has other layers.
  • the form of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose.
  • the photosensitive film and the protective film are provided in this order on the support, A form comprising the PC layer, the photosensitive layer, and the protective film in this order on a support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film in this order on the support.
  • the photosensitive layer may be a single layer or a plurality of layers.
  • the support is not particularly limited and may be appropriately selected depending on the purpose. However, it is preferable that the photosensitive layer can be peeled off and the light transmittance is good. Further, the surface is smooth. It is more preferable that the property is good.
  • the support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated bur, polybulal alcohol, polycarbonate, polystyrene, cellophane, polysalt-vinylidene copolymer, polyamide, polyimide, salt-vinyl.
  • a synthetic resin and transparent for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated bur, polybulal alcohol, polycarbonate, polystyrene, cellophane, polysalt-vinylidene copolymer, poly
  • plastic films such as butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, and nylon film can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
  • the support for example, the supports described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, and the like are used. I can do it.
  • the thickness of the support is not particularly limited, and can be appropriately selected according to the purpose.
  • t is preferably 4 to 300 ⁇ m force, more preferably 5 to 175 ⁇ m force ⁇ . It's better!
  • the shape of the support is not particularly limited, and can be appropriately selected depending on the purpose, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include those having a length of 10 to 20, OOOm.
  • Photosensitive layer in photosensitive film is not particularly limited, and can be appropriately selected depending on the purpose, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include those having a length of 10 to 20, OOOm.
  • the photosensitive layer in the photosensitive film is formed of the photosensitive composition.
  • the portion provided in the photosensitive film of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose, but is usually laminated on the support.
  • the thickness of the photosensitive layer in the photosensitive film is not particularly limited.
  • the force can be appropriately selected according to the purpose. For example, 3 to: LOO / zm force S, preferably 5 to 70 / ⁇ ⁇ . I like it.
  • Formation of the photosensitive layer in the photosensitive film is carried out by the same method as the application of the photosensitive composition solution to the substrate and drying (the method for forming the photosensitive layer of the first aspect).
  • the method for forming the photosensitive layer of the first aspect examples thereof include a method of applying the photosensitive composition solution using a spin coater, a slit spin coater, a mouth coater, a die coater, a curtain coater, or the like.
  • the protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
  • the protective film is appropriately selected depending on the purpose. Usually, it is provided on the photosensitive layer.
  • protective film examples include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among them, polyethylene film, polypropylene, and the like. A film is preferred.
  • the thickness of the protective film is not particularly limited and can be appropriately selected according to the purpose. For example, 5 to: LOO / z m force is preferable, and 8 to 30 m is more preferable.
  • the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
  • 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 photosensitive film is preferably stored, for example, wound around a cylindrical core and wound into a long roll.
  • the length of the long photosensitive film is not particularly limited, and can be appropriately selected from the range of 10-20, OOOm, for example.
  • slitting may be performed to make it easy for users to use, and a long body in the range of 100 to 1, OOOm may be rolled.
  • the support is wound up so as to be the outermost side.
  • the roll-shaped photosensitive film may be slit into a sheet shape.
  • a separator especially moisture-proof, with desiccant
  • 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 at 30 to 150 ° C (especially 50 to 120 ° C) after the polymer coating solution is applied to the surface of the protective film. It can be formed by drying for ⁇ 30 minutes.
  • a cushion layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.
  • PC layer oxygen blocking layer
  • a release layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.
  • PC layer oxygen blocking layer
  • a release layer an adhesive layer, a light absorption layer, a surface protective layer, and the like.
  • the cushion layer is a layer that melts and flows when laminated under vacuum heating conditions that have no tackiness at room temperature.
  • the PC layer is usually a coating of about 0.5 to 5 / ⁇ ⁇ , which is formed mainly of polybulal alcohol.
  • the heating temperature can be appropriately selected according to the purpose for which there is no particular limitation. For example, 70 to 130 ° C is preferable, and 80 to 110 ° C is more preferable.
  • the pressure of the pressurization can be appropriately selected according to the purpose for which there is no particular limitation.
  • ⁇ column; t is preferably 0.01 to: L OMPa force, 0.05 to: L OMPa force ⁇ I like it!
  • the apparatus for performing at least one of the heating and the pressurization can be appropriately selected according to the purpose of restriction, for example, a heat press, a heat roll laminator (for example, Taisei Laminate Earthen, VP — 11), vacuum laminator (for example,
  • MVLP500 MVLP500
  • the like are preferable.
  • the photosensitive film comprises a printed wiring board, a color filter, a pillar material, a rib material, and a spacer.
  • the photosensitive film has a uniform thickness, lamination onto the substrate is performed more finely when forming a permanent pattern.
  • the exposure to the laminate having the photosensitive layer formed by the photosensitive layer forming method of the second aspect can be appropriately selected according to the purpose without any particular limitation.
  • the photosensitive layer may be exposed through the support, the cushion layer, and the PC layer. After the support is peeled off, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling off the support and cushion layer, the photosensitive layer may be exposed through the PC layer. After peeling off the support, cushion layer and PC layer, the photosensitive layer is exposed. [0175] [Development process]
  • the developing step is a step of exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region to form a permanent pattern.
  • the removal method of the uncured region can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a method of removing using a developer.
  • the developer may be appropriately selected according to the purpose without any particular limitation.
  • an alkali metal or alkaline earth metal hydroxide or carbonate, bicarbonate, aqueous ammonia Preferred examples include aqueous solutions of quaternary ammonium salts. Among these, an aqueous sodium carbonate solution is particularly preferable.
  • the developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, Triethanolamine, etc.) and organic solvents (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination to accelerate development.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or an organic solvent alone.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer having a permanent pattern formed after the developing step.
  • Examples of the overall exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
  • the apparatus for performing the entire surface exposure can be appropriately selected according to the purpose without any particular limitation, and a UV exposure machine such as an ultrahigh pressure mercury lamp is preferably exemplified.
  • the permanent pattern is shaped after the development step.
  • the method of heating the whole surface on the formed said laminated body is mentioned. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
  • the heating temperature for the entire surface heating is 120 to 250, preferably 120 to 200 ° C.
  • 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 permanent pattern of the present invention may be formed on the printed wiring board, and further soldered as follows. it can.
  • the hardened layer which is the permanent pattern is formed by the developing step, and the metal layer is exposed on the surface of the printed wiring board.
  • Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, semiconductors and parts are mounted on the soldered parts.
  • the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.
  • the permanent pattern formed by the method for forming a permanent pattern can protect the wiring from external impact and bending force.
  • the interlayer insulating film for example, a multilayer wiring board or a build This is useful for high-density mounting of semiconductors and components on up-wiring boards.
  • the permanent pattern forming method of the present invention can efficiently form a permanent pattern with high definition by suppressing distortion of an image formed on the photosensitive layer. It can be suitably used for the formation of various patterns that require light, and can be particularly suitably used for the formation of high-definition permanent patterns.
  • a photosensitive composition (solution) was prepared based on the following composition.
  • PCR- 1157H (manufactured by Nippon Kayaku Co., Ltd., epoxy Atari rate 61.8 mass 0/0 ethylene glycol monomethyl E chill ether Atari acetate solution) 46.14 parts by weight
  • IRGACURE819 manufactured by Chinoku Specialty Chemicals 7. 84 parts by mass MW30HM (manufactured by Sanwa Chemical Co., hexamethoxymethylated melamine) 8.00 parts by mass Hydroquinone monomethyl ether 0.049 parts by mass Phthalocyanine green 3.98 parts by mass Part
  • the barium sulfate dispersion is composed of 30 parts by weight of barium sulfate (manufactured by KK, B30), 34.29 parts by weight of the above-mentioned PCR-1157H diethylene glycol monomethyl ether acetate 61.2 mass% solution, methyl After mixing 35.71 parts by mass of ethyl ketone with Motor Mill M-200 (manufactured by Eiger), disperse for 3.5 hours at a peripheral speed of 9 mZs using Zirco Your beads with a diameter of 1. Omm. Prepared.
  • the obtained photosensitive composition solution was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 m as the support and dried to form a photosensitive layer having a thickness of 35 / zm.
  • a polypropylene film having a thickness of 12 m is used as the protective film on the photosensitive layer.
  • the film was laminated with a laminate to produce a photosensitive film.
  • the substrate was prepared by subjecting a surface of a copper-clad laminate (no through-hole, copper thickness 1 2 / z m) on which wiring had been formed, to a chemical polishing treatment.
  • a vacuum laminator manufactured by Meiki Seisakusho, MVLP500
  • MVLP500 vacuum laminator
  • the crimping conditions were a crimping temperature of 90 ° C, a crimping pressure of 0.4 MPa, and a laminating speed of lmZ.
  • a pattern in which holes having different diameters are formed from a laser beam having a wavelength of 405 nm can be obtained from the support side using a pattern forming apparatus described below. Were exposed to light, and a part of the photosensitive layer was cured.
  • DMD36 controlled to drive only 1024 x 256 6 rows and the optical for imaging the light shown in FIG. 5A or FIG. 5B on the pattern forming material
  • a pattern forming apparatus 10 having an exposure head 30 having a system was used.
  • each exposure head 30, ie each DMD 36 is slightly larger than the angle ⁇ that is exactly double exposure using the available 1024 rows x 256 rows micromirror 58
  • This angle 0 is the number of N exposures N, the available micromirrors
  • the DMD 36 in the present embodiment includes a large number of micromirrors 58 with equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
  • inclination angle 0 for example, 0.50 degrees was adopted.
  • the pattern of light spots from the usable micromirror 58 of DMD36 with 12 21 is shown.
  • the exposure formed on the exposed surface when the stage 14 is moved and continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part.
  • the pattern status is shown for exposure areas 32 and 32.
  • FIG. 16 for convenience of explanation
  • every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on pixel array group A and an exposure pattern based on pixel array group B, but the actual exposure pattern on the exposed surface is These two exposure patterns are superimposed.
  • the light spot position detecting means a set of a slit 28 and a light detector is used, and an exposure head 30 is used.
  • the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head was measured.
  • the natural number T that is closest to the value t that satisfies this relationship is assigned to each of the exposure heads 30 and 30.
  • micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 were identified as micromirrors that are not used during the main exposure.
  • micromirrors corresponding to the light spots other than the light spots constituting the areas 78 and 80 covered by the oblique lines in FIG. 17 the area 82 covered by the oblique lines in FIG.
  • micromirrors corresponding to the light spots constituting the shaded area 84 were identified and added as micromirrors that are not used during the main exposure.
  • a signal for setting the angle of the always-off state is sent by the pixel unit control means, and these microphone mirrors are substantially It was controlled so that it was not involved in exposure.
  • the exposure areas formed by a plurality of the exposure heads in the exposure areas 32 and 32 are formed by a plurality of the exposure heads in the exposure areas 32 and 32.
  • the laminate strength was also peeled off from the polyethylene terephthalate film (support), and a 1% by weight sodium carbonate aqueous solution was added as an alkaline developer to the entire surface of the photosensitive layer on the copper clad laminate. Used and shower developed for 60 seconds at 30 ° C to dissolve and remove uncured areas. Thereafter, it was washed with water and dried to form a permanent pattern.
  • the entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 30 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.
  • the printed wiring board on which the permanent pattern had been formed was subjected to gold plating according to a conventional method and then subjected to a water-soluble flux treatment. Next, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the flux About the permanent pattern after removal, pencil hardness was measured based on JIS K-5400. As a result, the pencil hardness was 5H or more. As a result of visual observation, peeling of the cured film in the permanent pattern, blistering, and discoloration were observed.
  • a light energy amount from 0. lmj / cm 2 to 200 mj / cm 2 at 2 1/2 times intervals is used. Double exposure was performed by irradiating different light, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C was sprayed to a spray pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate.
  • the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured.
  • the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was 35 ⁇ m, which was the same as that of the photosensitive layer before exposure, was determined as the amount of light energy necessary for curing the photosensitive layer.
  • the amount of light energy necessary for curing the photosensitive layer was 25 miZcm 2 .
  • the surface of the obtained printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. The smaller the numerical value, the better the resolution.
  • the patterning device was used to irradiate the photosensitive layer so that a horizontal line pattern in a direction perpendicular to the scanning direction of the exposure head was formed, and double exposure was performed to form a permanent pattern.
  • a laser microscope VK-9500, manufactured by Keyence Corporation; objective lens 50 times
  • VK-9500 manufactured by Keyence Corporation
  • the edge roughness is preferable because a smaller value indicates better performance.
  • Example 1 the photosensitive composition was prepared in the same manner as in Example 1 except that the composition of the photosensitive composition was changed to the following composition and kneaded by a roll mill according to a conventional method.
  • a photosensitive composition was prepared based on the following composition.
  • a permanent pattern was formed using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were observed on the surface of the cured film in the permanent pattern. [0208] The obtained permanent pattern was subjected to (a) exposure sensitivity and (b) resolution in the same manner as in Example 1.
  • FIG. 35 An example of the state of exposure of the exposed surface in Comparative Example 1 is shown in FIG. In FIG. 35, a light spot group from the micromirror 58 that can be used by the DMD 36 of one exposure head (for example, 30) projected onto the exposed surface of the photosensitive layer 12 with the stage 14 being stationary.
  • a light spot group from the micromirror 58 that can be used by the DMD 36 of one exposure head (for example, 30) projected onto the exposed surface of the photosensitive layer 12 with the stage 14 being stationary.
  • a single exposure area (eg 32)
  • Said one exposure head e.g. 30
  • the angular distortion that appears in the example of FIG. 35 is a distortion in which the inclination angle with respect to the scanning direction is larger in the left column of the figure and smaller in the right column of the figure. As a result of this angular distortion, an overexposed region appears on the exposed surface shown on the left side of the figure, and an underexposed region appears on the exposed surface shown on the right side of the figure.
  • Permanent patterns in the field of printed wiring boards, including package substrates by leveling out the effects of variations in exposure and reducing variations in resolution and density of the pattern formed on the exposed surface of the photosensitive layer (Protective films such as interlayer insulating films, solder resist patterns, etc.) can be formed with high definition and efficiency, so it can be suitably used for forming various patterns that require high-definition exposure. In particular, it can be suitably used for forming a high-definition permanent pattern.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

L’invention concerne un procédé de mise en motif permanent capable de former un motif permanent haute résolution de manière efficace en moyennant l’impact de variation de quantité d’exposition due à la distorsion du motif, supprimant ainsi toute distorsion d’une image formée sur une couche photosensible. Dans le procédé de mise en motif permanent, après la formation d’une couche photosensible à la surface d’un substrat à l’aide d’une composition photosensible, une portion écriture étant utilisée pour une exposition d’un nombre de fois N (N est un nombre naturel supérieur ou égal à 2) est spécifiée pour la couche photosensible à l’aide d’une section de spécification de portion écriture à l’aide d’une tête d’exposition comprenant un moyen d’irradiation lumineux et un moyen de modulation optique, et disposée de telle sorte que la direction d’analyse des portions écriture forme un angle d’inclinaison défini prédéterminé θ par rapport à la direction de balayage, un moyen de commande de portion écriture commande les portions écriture de telle sorte que seule une portion écriture spécifiée participe à l’exposition, puis la couche photosensible est exposée et développée en déplaçant la tête d’exposition par rapport à la couche dans la direction de balayage.
PCT/JP2006/311503 2005-06-28 2006-06-08 Procédé de mise en motif permanent WO2007000885A1 (fr)

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US9513551B2 (en) 2009-01-29 2016-12-06 Digiflex Ltd. Process for producing a photomask on a photopolymeric surface
US20120321586A1 (en) * 2010-02-27 2012-12-20 Pieter Van Der Bijl Surfactant composition
US10124015B2 (en) * 2010-02-27 2018-11-13 Stellenbosch University Surfactant composition

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TW200707100A (en) 2007-02-16
KR20080020591A (ko) 2008-03-05
CN101189557A (zh) 2008-05-28

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