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WO2007108171A1 - Composition photosensible, film photosensible, produit en couches photosensible, procédé de formation de motif permanent et carte à circuits imprimés - Google Patents

Composition photosensible, film photosensible, produit en couches photosensible, procédé de formation de motif permanent et carte à circuits imprimés Download PDF

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Publication number
WO2007108171A1
WO2007108171A1 PCT/JP2006/323318 JP2006323318W WO2007108171A1 WO 2007108171 A1 WO2007108171 A1 WO 2007108171A1 JP 2006323318 W JP2006323318 W JP 2006323318W WO 2007108171 A1 WO2007108171 A1 WO 2007108171A1
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WO
WIPO (PCT)
Prior art keywords
group
exposure
photosensitive
pattern
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/323318
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English (en)
Japanese (ja)
Inventor
Masanobu Takashima
Kazuhiro Fujimaki
Toshiaki Hayashi
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to JP2008506161A priority Critical patent/JP5144495B2/ja
Publication of WO2007108171A1 publication Critical patent/WO2007108171A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • 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
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • Photosensitive composition photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed circuit board
  • the present invention relates to a permanent pattern (a protective film, an interlayer insulating film, and a solder) that has no edge fusion (end face fusion), is excellent in tackiness and stability over time, is easily formed into a film, and has a high definition. Resist pattern, etc.) can be efficiently formed, a photosensitive film, a photosensitive laminate, a permanent pattern formation method using the photosensitive laminate, and a permanent pattern formed by the permanent pattern formation method. Relates to a printed circuit board.
  • a photosensitive film in which a photosensitive layer is formed by applying and drying a photosensitive composition on a support has been used.
  • a method for producing the permanent pattern for example, a laminate is formed by laminating the photosensitive film on a substrate such as a copper clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed. After the exposure, the photosensitive layer is developed to form a pattern, and then subjected to a curing process or the like to form the permanent pattern.
  • Solder resists for use in flexible substrates such as a knock substrate and a flexible substrate in the permanent pattern are required to relieve stress in order to prevent cracks.
  • the substrate and the components used therefor have also been miniaturized.
  • a liquid resist type photosensitive composition is used, it is difficult to apply smoothly because it is applied and dried on the substrate.
  • an acid-modified vinyl group-containing epoxy resin (A), an elastomer (B), a photopolymerization initiator may be used.
  • a photocurable resin composition containing (C), a diluent (D), and a curing agent (E) as essential components has been proposed (see Patent Document 1).
  • edge fusion end-face fusion
  • excellent tackiness and stable performance over time easy filming
  • high-definition permanent patterns protection film, interlayer insulating film, and solder resist pattern
  • a photosensitive film a photosensitive laminate
  • a permanent pattern forming method using the photosensitive laminate a permanent pattern formed by the permanent pattern forming method.
  • the printed circuit board to be used has not been provided yet, and further improvement and development are desired.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11 240930
  • the present invention has been made in view of the current situation, and it is an object of the present invention to solve the above-described problems and achieve the following objects. That is, the present invention has no edge fusion (end face fusion), excellent tackiness and stable performance over time, easy to form into a film, and has a high-definition permanent pattern (protective film, interlayer insulating film, and solder resist).
  • the binder includes a binder, a polymerizable compound, a photopolymerization initiator, an elastomer, and a thermal cross-linking agent.
  • a photosensitive composition containing a polymer compound having an ethylenically unsaturated bond in the side chain is superior in tackiness and stability of performance over time without edge fusion (end face fusion), and can be easily formed into a film. We found that high-definition permanent patterns can be formed efficiently.
  • a binder a polymerizable compound, a photopolymerization initiator, an elastomer, and a thermal crosslinking agent, wherein the binder contains a polymer compound having an acidic group and an ethylenically unsaturated bond in the side chain. It is the photosensitive composition characterized by these.
  • Noinda Is the photosensitive composition according to ⁇ 1>, including a polymer compound having an acidic group, an aromatic group that may include a heterocyclic ring, and an ethylenically unsaturated bond in a side chain. .
  • ⁇ 3> Polymer compound strength The photosensitive composition according to any one of ⁇ 1>, ⁇ 2>, and ⁇ 2> containing 0.5 to 3. OmeqZg of an ethylenically unsaturated bond.
  • the acid group of the polymer compound is a carboxyl group, and the content of the carboxyl group in the polymer compound is 1.0 to 4.
  • OmeqZg. ⁇ 1> to ⁇ 3> It is a photosensitive composition as described above.
  • ⁇ 5> The photosensitive composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer compound has a mass average molecular weight of 10,000 or more and less than 100,000.
  • ⁇ 6> The photosensitive composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer compound contains 20 mol% or more of a structural unit represented by the following structural formula (I).
  • L represents an organic group and may be omitted.
  • Ar represents an aromatic group.
  • ⁇ 7> The photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, wherein the elastomer exhibits either swellability or solubility in an alkaline aqueous solution.
  • Elastomer is at least one selected from styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, acrylic elastomer, and silicone elastomer. Certain The pattern forming method according to any one of 1> Karaku 7>.
  • Photopolymerization initiators are halogenated hydrocarbon derivatives, hexarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, 11.
  • ⁇ 12> The photosensitive composition according to any one of ⁇ 1> to ⁇ 11>, wherein the photopolymerization initiator includes an oxime derivative.
  • thermosensitive composition according to any one of ⁇ 1> to ⁇ 14>, wherein the thermal crosslinking agent is alkali-insoluble.
  • a thermal crosslinking agent is produced from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative.
  • the photosensitive composition according to the above item 15> which is at least one selected.
  • ⁇ 17> The photosensitive composition according to any one of ⁇ 1> to ⁇ 16>, wherein the photosensitive composition includes a sensitizer, and the sensitizer is a hetero-fused ring ketone.
  • a photosensitive film comprising a ⁇ 18> support and a photosensitive layer comprising the photosensitive composition according to any one of ⁇ 1> to ⁇ 17> on the support. .
  • ⁇ 22> The photosensitive film according to any one of ⁇ 18> to ⁇ 21>, wherein the photosensitive film has a protective film on the photosensitive layer.
  • a photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of ⁇ 1> to 17 above on a substrate.
  • ⁇ 25> The photosensitive laminate according to any one of ⁇ 23> to ⁇ 24>, wherein the photosensitive layer has a thickness of 1 to 100 / ⁇ .
  • a pattern forming apparatus comprising: a light irradiating unit capable of irradiating light; and a light modulating unit that modulates light from the light irradiating unit and exposes the photosensitive layer in the photosensitive film. It is.
  • the light irradiation means irradiates light toward the light modulation means.
  • the light modulation means modulates light received from the light irradiation means.
  • the light modulated by the light modulating means is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the pattern forming apparatus according to ⁇ 26> wherein the pattern is modulated according to a signal.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit.
  • the light modulation means has n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts.
  • n pieces of light modulating means The light from the light irradiating means is modulated at high speed by controlling any less than n pixel parts arranged continuously from among the picture element parts according to the pattern information.
  • ⁇ 29> The pattern forming apparatus according to any one of ⁇ 26>, ⁇ 28>, wherein the light modulation means is a spatial light modulation element.
  • ⁇ 30> The pattern forming apparatus according to ⁇ 29>, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • ⁇ 31> The pattern forming apparatus according to any one of ⁇ 28>, ⁇ 30>, wherein the pixel part is a micromirror.
  • ⁇ 32> The pattern forming apparatus according to any one of the above items ⁇ 26>, ⁇ 31>, wherein the light irradiation means can synthesize and irradiate two or more lights.
  • the pattern forming apparatus described in ⁇ 32> exposure is performed by exposure light having a deep depth of focus because the light irradiation means can synthesize and irradiate two or more lights.
  • the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is developed thereafter, an extremely fine pattern is formed.
  • the light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated with the plurality of laser forces and couples the laser beams to the multimode optical fiber.
  • the pattern forming apparatus according to any one of the above 26> Karaku 32> having In the pattern forming apparatus according to ⁇ 33>, the light irradiation unit can collect the laser beams irradiated with the plurality of laser forces by the collective optical system and couple the laser beams to the multimode optical fiber.
  • exposure is performed with exposure light having a deep focal depth.
  • the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • Sensation in the photosensitive laminate as described above, wherein 34> said 25>25> It is a permanent pattern formation method characterized by including exposing with respect to an optical layer.
  • ⁇ 35> The method for forming a permanent pattern according to ⁇ 34>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
  • ⁇ 36> The method for forming a permanent pattern according to any one of ⁇ 34> and ⁇ 35>, wherein the exposure is performed imagewise based on pattern information to be formed.
  • Exposure includes light irradiation means and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means,
  • An exposure head provided with a light modulation means capable of controlling the picture element portion according to pattern information, wherein the column direction of the picture element portion is 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 permanent pattern forming method according to any one of ⁇ 34>, [36], wherein the exposure head is moved relatively in the scanning direction.
  • the exposure head is subjected to N-exposure (where N is a natural number equal to or greater than 2) among the usable pixel parts by the use pixel part designating unit.
  • the pixel part is controlled by the pixel part control means so that only the pixel part specified by the use pixel part specifying means is involved in exposure.
  • The By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. 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 pattern.
  • 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.
  • N-exposure in the joint area between the heads The method for forming a permanent pattern according to ⁇ 37>, wherein the picture element portion used for realizing is specified.
  • the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapped exposure region on an exposed surface formed by the plurality of exposure heads.
  • the picture element part used for realizing the N-fold exposure in the head-to-head joint area is designated, so that the mounting of the exposure head Variations in the resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to a shift in the position and the mounting angle are equalized.
  • the photosensitive layer is exposed with high definition. For example, a high-definition pattern is then formed by developing the photosensitive layer.
  • the exposure is performed by a plurality of exposure heads, and the used pixel part specifying means is involved in exposures other than the inter-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 ⁇ 38> 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 portion specifying unit overlaps the exposed surface formed by the plurality of exposure heads.
  • the permanent pattern forming method according to any one of 7> to ⁇ 39>.
  • ⁇ 41> The method for forming a permanent pattern according to any one of the above ⁇ 37> to 40, which is a natural number of N force of 3 or more and N force of 3 or more.
  • N force a natural number of N force of 3 or more and N force of 3 or more.
  • multiple drawing is performed by using a natural number of N force 3 or more in N double exposure.
  • 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
  • the used pixel part designation means designates the used pixel part to be used for realizing N double exposure in units of lines. Permanent pattern formation according to any one of ⁇ 37> to ⁇ 42> above Is the method.
  • the light spot position detection means based on at least two light spot positions detected, the light spot column direction on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted
  • the actual inclination angle ⁇ 'formed by the image and the pixel part selection means select the pixel part to be used so as to absorb the error between the actual inclination angle ⁇ ' and the set inclination angle ⁇ . It is a permanent pattern forming method described in the above.
  • 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 permanent pattern forming method according to any one of ⁇ 42>, ⁇ force>, and ⁇ 45>, wherein a picture element part is selected as a use picture element part.
  • the permanent pattern forming method according to any one of the above ⁇ 42> Force et al. ⁇ 46>, wherein the pixel part excluding the unused pixel part is selected as the used pixel part.
  • ⁇ 48> In a region including at least a multiple exposure region on an exposed surface formed by a plurality of pixel part columns,
  • the number of pixel units in the overexposed area is equal to the number of pixel units in the underexposed area.
  • N (N-1) pixel part columns for every N exposures are used among the pixel parts that can be used.
  • N of N multiple exposures among the usable pixel parts can be specified.
  • (N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. The pixel part in the region is easily specified.
  • the pixel part line for each 1ZN line is configured.
  • the permanent pattern forming method according to any one of the above items 37>, 50, 50>, in which reference exposure is performed using only the pixel part.
  • N of N double exposure is used in order to designate the use pixel part in the use pixel part designating means, among the usable picture element parts.
  • the picture element constituting the picture element sub-sequence for each 1ZN row The reference exposure is performed using only the part, and a simple pattern of approximately single drawing is obtained. As a result, the picture element part in the head-to-head connection region is easily specified.
  • the used pixel part specifying means includes a slit and a photodetector as light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means ⁇ 52> is a permanent pattern forming method as described in!
  • 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 converts the light emitted from the light irradiation unit.
  • the permanent pattern forming method according to any one of the above 37> to 54>, which is modulated in accordance with a generated control signal.
  • the light modulation unit includes the pattern signal generation unit, so that light emitted from the light irradiation unit is transmitted by the pattern signal generation unit. Modulated according to the generated control signal.
  • ⁇ 60> The method for forming a permanent pattern according to any one of the above items ⁇ 37> to ⁇ 59>, wherein the light irradiation means 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 by exposure light having a deep focal depth. .
  • the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated with the plurality of laser forces and couples them to the multimode optical fiber.
  • the light irradiating means can condense the laser light irradiated with each of the plurality of laser forces by the converging optical system and couple it to the multimode optical fiber. Therefore, exposure is performed with exposure light having a deep depth of focus. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine pattern is formed.
  • ⁇ 62> The method for forming a permanent pattern according to any one of ⁇ 34> to ⁇ 61>, wherein the photosensitive layer is developed after the exposure.
  • a high-definition pattern is formed by developing the photosensitive layer after the exposure.
  • ⁇ 64> A permanent pattern formed by the pattern forming method according to any one of ⁇ 34> and 63. Since the permanent pattern described in 64> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition, and is a multilayer wiring board for semiconductors and components. This is useful for high-density mounting on PCBs and build-up wiring boards.
  • the pattern according to the above item 64> which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in ⁇ 65> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring has an external force or the like depending on the insulating property and heat resistance of the film. Protected from impact and bending.
  • ⁇ 66> According to the permanent pattern forming method described in any one of ⁇ 34> to ⁇ 63>.
  • the printed circuit board is characterized in that a permanent pattern is formed.
  • edge fusion end face fusion
  • tackiness and performance stability over time are excellent
  • film formation is easy
  • high-definition permanent Photosensitive composition capable of efficiently forming patterns (protective film, interlayer insulating film, solder resist pattern, etc.), photosensitive film and photosensitive laminate using the same, and permanent pattern formation using the photosensitive laminate
  • a method and a printed circuit board on which a permanent pattern is formed can be provided.
  • 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 view showing an example of unevenness occurring in a no-turn on the 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.
  • Photosensitive composition It includes a noinder, a polymerizable compound, a photopolymerization initiator, an elastomer, and a thermal crosslinking agent, and if necessary, other components.
  • a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain is used.
  • the acidic group include a carboxyl group, a phosphate group, and a sulfonate group.
  • a carboxyl group is preferable from the viewpoint of obtaining raw materials.
  • the noinder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
  • the binder include 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 vinyl ester of carboxylic acid, a butyl ether, Various polymerizable double bonds such as aryl ether can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound, for example, a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, or an alicyclic group.
  • an acrylic resin containing a carboxyl group as an acidic group a cyclic ether group-containing polymerizable compound, for example, a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidy
  • an epoxy group-containing polymerizable compound such as an epoxy group (for example, an epoxy group such as cyclohexenoxide in the same molecule) and a compound having a (meth) aryryl group, etc.
  • an isocyanate group-containing polymerizable compound such as isocyanatoethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group.
  • examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as hydroxyalkyl (meth) acrylate to fat.
  • a cyclic ether group-containing polymerizable compound such as glycidyl metatalylate is copolymerized with a butyl monomer such as (meth) atalyloyl alkyl ester, and (meth) acrylic acid is added to the side chain epoxy group.
  • a cyclic ether group-containing polymerizable compound such as glycidyl metatalylate is copolymerized with a butyl monomer such as (meth) atalyloyl alkyl ester, and (meth) acrylic acid is added to the side chain epoxy group.
  • the compound etc. which are obtained by making it also include.
  • Examples of these include Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, Japanese Patent Application Laid-Open No. 2000-232264, and the like.
  • the binder is obtained by adding a polymerizable compound containing a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) to a part of the acidic group of the polymer compound, and A part or all of the cyclic ether group of the polymer compound It is more preferable that the polymer compound is selected from any of those to which a boxyl group-containing polymerizable compound is added. At this time, it is preferable that the addition reaction between the acidic group and the compound having a cyclic ether group is carried out in the presence of a catalyst. In particular, the catalyst selects an acidic compound and a neutral compound force. Preferably there is.
  • a catalyst selects an acidic compound and a neutral compound force. Preferably there is.
  • the binder contains a carboxyl group and a heterocycle in the side chain, or a polymer containing an aromatic group and an ethylenically unsaturated bond in the side chain.
  • Compound preferred.
  • aromatic group including the heterocycle examples include a benzene ring, and 2 to 3 benzene rings formed a condensed ring. And those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
  • aromatic group examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indur group, an acenaphthyl group, a fluorene group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, Pyrazole ring group, isoxazole ring group, isothiazole ring group, indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benz Oxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group,
  • the aromatic group may have a substituent.
  • substituents include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, An ether group, a thiol group, a thioether group, a silyl group, a nitro group, a cyano group, each of which may have a substituent, an alkyl group, an alkyl group, an alkyl group, an aryl group, a heterocyclic group, etc. Can be mentioned.
  • alkyl group include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups, and cyclic alkyl groups.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Hexadecyl group, Octadecyl group, Eicosyl group, Isopropyl group, Isobutyl group, sbutyl group, tbutyl group, isopentyl group, neopentyl group, 1 methylbutyl group, isohexyl group, 2-ethylhexyl group, 2- Examples include a methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl
  • Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • substituents include halogen atoms (one F, one Br, one Cl, one), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group.
  • sulfonate group alkoxysulfol group, aryloxysulfol group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N dialkylsulfinaimoyl group, N Lylsulfinamoyl group, N, N dialylsulfinamoyl group, N-alkyl-N arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N dialkylsulfamoyl group, N-arylsulfamoyl group Group, N, N diallylsulfamoyl group, N alkyl—Narylsulfamoyl group, phosphono group (one PO H) and its conjugate base group (phosphonate group and
  • Dialkylphosphono group (one PO (alkyl)) (hereinafter “alkyl” means an alkyl group)
  • a diarylphosphono group (one PO (aryl)) (hereinafter “aryl” means an aryl group)
  • Alkylaryl phosphono group PO (alkyl) (aryl)
  • monoalkyl phosphono group PO (alkyl) (aryl)
  • alkyl and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group
  • Phonoxy group (one OPO H) and its conjugate base group (referred to as phosphonatoxy group), dia
  • alkylaryl phosphonoxy group one OPO (alkyl) (aryl)
  • aryl phosphonatoxy group cyano group, nitro group, aryl group, alkenyl Group, alkynyl group, heterocyclic group, silyl group and the like.
  • alkyl group in these substituents include the aforementioned alkyl groups.
  • aryl group in the above substituent examples include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a phthalyl group, a chlorophenol group, a bromophenyl group, a chloromethyl group.
  • Phenyl group hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxylphenol group, benzoylphenol group, methylthiophenyl group, phenolthiol group Group, methylaminophenol group, dimethylaminophenol group, acetylaminophenol group, carboxyphenol group, methoxycarbonyl group, ethoxyphenol group, phenoxycarbon group , N-phenylcarbamoyl file group, cyanophyl group, sulfophenyl group, sulfonaphthoyl group, phosphonophenol group, phosphonatophenol group, etc. That.
  • alkenyl group in the substituent examples include a bur group, a 1 probe group, a 1-butur group, a cinnamyl group, and a 2-chloro 1-etul group.
  • alkyl group in the substituent include an ethur group, a 1-propynyl group, a 1-buturyl group, and a trimethylsilylethynyl group.
  • Examples 1 Ashiru in the substituent group (1 .. I) are a hydrogen atom, the above-described alkyl group, such as Ariru group.
  • halogen atoms (1 F, 1 Br, 1 Cl, 1 1), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N alkylamino groups, N, N-dialkylamino groups, Acyloxy group, N-alkyl-force rubermoyloxy group, N-aryl force-rubamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbol group, force-rubamoyl group, N-alkyl-force rubermoyl Group, N, N dialkyl-force rubamoyl group, N allyl force rubamoyl group, N alkyl N allyl force rubamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N dialkyl
  • examples of the heterocyclic group in the substituent include a pyridyl group and a piperidyl group
  • examples of the silyl group in the substituent include a trimethylsilyl group.
  • the alkylene group in the alkyl group is, for example, a divalent organic residue obtained by removing one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms.
  • a linear alkylene group having 1 to 12 carbon atoms a branched alkylene group having 3 to 12 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, etc. Is preferred.
  • substituted alkyl group obtained by combining such a substituent with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, isopropoxymethyl.
  • Examples of the aryl group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. .
  • aryl group examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a acenaphthenyl group, and a fluorenyl group.
  • a phenol group and a naphthyl group are preferable.
  • the alkyl group may have a substituent or an aryl group having such a substituent (hereinafter also referred to as “substituted aryl group”), for example, ring formation of the aforementioned aryl group
  • substituent on the carbon atom include a group consisting of a monovalent nonmetallic atomic group other than a hydrogen atom.
  • the aryl group may have, for example, the alkyl group, the substituted alkyl group, or the alkyl group that is described above as the substituent may be preferable.
  • substituted aryl group examples include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a tamale group, a chlorophenol group, a bromophenol group, a fluorophenol group, a chloromethyl group.
  • Phenyl group trifluoromethylphenol group, hydroxyphenyl group, methoxyphenyl group, methoxymethoxyphenyl group, aryloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, Tolylthiophenyl group, ethylaminophenyl group, germanaminophenyl group, morpholinophenol group, acetyloxyphenyl group, benzoylphenyl group, N cyclohexylcarbamoylphenyl group, N Phenylcarbamoyl phenyl group, Acetylaminophenol group, N-Methylbenzoylaminophenol group, Carboxyphenol group, Methoxycarbol Benzyl group, allyloxyl hydroxyl group, chlorophenoxy carbonyl group, rubamoyl group N-methylcarbamoyl file group, N, N dipropyl-powered rubamoyl file group,
  • the Aruke - Le group (C (R 02) C (R 03) (R 04)) and alkyl - as Le group (an C ⁇ C (R ° 5)) , for example, R ° 2, R ° 3 , R ° 4 , and R ° 5 are groups having a non-valent nonmetallic atomic group.
  • Examples of 2 , R ° 3 , R ° 4 , and R ° 5 include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above-mentioned examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.
  • alkenyl group and alkyl group! / Preference is given to the above-mentioned alkenyl group and alkyl group! /, And specific examples include vinyl group, 1-port perl group, 1-butul group, 1 pentale group, 1 hex. -Luyl group, 1-Otatur group, 1-Methyl-1 Propyl group, 2-Methyl-1 Propyl group, 2-Methyl-1-Butur group, 2-Fu Russellu 1-Ethul group, 2-Chrome- 1-Ethul group, Etul group, 1-Propyl group, 1-Butul group, and Feule group.
  • the heterocyclic group include a pyridyl group exemplified as a substituent for a substituted alkyl group.
  • Examples of the oxy group (R 60 ) include those in which 6 is a group consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • Examples of such oxy groups include, for example, alkoxy groups, aryloxy groups, acyloxy groups, rubamoyloxy groups, N-alkyl rubamoyloxy groups, N-aryl carbamoyloxy groups, N, N-dialkyl rubamoyloxy groups, N, N dialyl rubamoyloxy groups, N alkyl N aryl group ruberamoyloxy group, alkyl sulreoxy group, arenores noreoxy group, phosphono oxy group, phosphonato xy group and the like are preferable.
  • alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above.
  • examples of the acyl group (R 7 CO 2) in the acyloxy group include those in which R 7 is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group exemplified above. Of these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
  • preferred oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxyethyloxy, methoxy Carbo-ruethyloxy group, ethoxycarbo-ruethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxy group, ethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, aralkyloxyethoxy group, phenoxy group, triloxy Group, xylyloxy group, mesityloxy group, mesityloxy group, tamoxy group, methoxyphenyl group, ethoxyphenyl group, black-end phenol group , Buromofue - Ruokishi group, Ase
  • An amido group (R 8 NH-, (R 09 ) (R 01 °) N-) includes, for example, R ° 8 , 9 , and R G1G are monovalent except for a hydrogen atom. Non-metallic atomic groups are also included. In addition, R 9 may be bonded to form a ring.
  • amino group examples include an N-alkylamino group, an N, N dialkylamino group, an N arylamino group, an N, N dialylamino group, and an N-alkyl-N arylamino.
  • alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
  • Ashiruamino group, N-alkyl ⁇ sill ⁇ amino group, N ⁇ reel ⁇ sill ⁇ amino group definitive Ashiru group (R 7 CO-) of 7 are as defined above.
  • an N alkylamino group, an N, N dialkylamino group, an N arylamino group, and an acylamino group are more preferable.
  • preferred amino groups include methylamino group, ethylamino group, jetylamino group, morpholino group, piperidino group, pyrrolidino group, phenolamino group, benzoylamino group, acetylamino group and the like.
  • Examples of the sulfo group ( 11 SO—) include, for example, a 11 -valent nonmetallic atomic group.
  • the power group is mentioned.
  • a sulfo group for example, an alkyl sulfo group, an aryl sulfo group and the like are preferable.
  • the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
  • Specific examples of the sulfo group include a butyl sulfo group, a phenol sulfo group, and a closed-end phenol sulfo group.
  • the sulfonate group (one SO-) is a conjugate base group of the sulfo group (one SO H).
  • oniums for example, ammoniums, sulfomes, phosphomes
  • sodium ions for example, azimuths, etc.
  • metal ions for example, Na +, K +, Ca 2+ , Zn 2+, etc.
  • Examples of the carbo group include those in which R 13 is a group having a nonvalent nonmetallic atomic group.
  • carbol groups include formyl, acyl, carboxyl, alkoxycarbol, aryloxycarbol, strong rubamoyl, N alkyl, rubamoyl, N, N dialkyl.
  • Examples include a rubermoyl group, an N-aryl force rubermoyl group, an N, N-diaryl force rubermoyl group, and an N-alkyl N, -aryl force-rubamoyl group.
  • alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
  • Examples of the carbonyl group include formyl group, acyl group, carboxyl group, alkoxy group, aryloxycarbo group, rubamoyl group, N-alkyl group rubamoyl group, N, N dialkyl group rubamoyl.
  • Group, N-aryl rubamoyl group is preferable, and formyl group, acyl group, alkoxycarbol group, and aryloxycarbol group are more preferable.
  • the carbonyl group include a formyl group, a acetyl group, a benzoyl group, a carboxy group, a methoxy carbo ol group, an ethoxy carbo yl group, an ar aroxy carboxy group, a dimethylamino pheno group.
  • Preferred examples include a ruthel carbol group, a methoxy carbo methoxy carbo ol group, an N-methyl carbamoyl group, an N phen carbamoyl group, an N, N decyl rubamoyl group, a morpholino carbo ol group and the like.
  • the sulfiel group (R 14 — SO 3) is composed of “a non-valent non-metallic atomic group”. Examples of groups are mentioned.
  • sulfier groups include alkyl sulfier groups, aryl sulfier groups, sulfinamoyl groups, N-alkyl sulfinamoyl groups, N, N dialsulfyl amoyl groups, N aryl sulfinamoyl groups, N, N And diarylsulfinamoyl group, N alkyl N arylsulfinamoyl group and the like.
  • alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, the alkylsulfur group and the arylsulfier group are preferred.
  • substituted sulfiel group examples include a hexyl sulfiel group, a benzyl sulfyl group, and a tolyl sulfyl group.
  • the phosphono group means a group in which one or two of the hydroxyl groups on the phosphono group are substituted with another organic oxo group.
  • dialkylphosphono group, diarylphosphono group, A reel phosphono group, a monoalkyl phosphono group, a monoaryl phosphono group and the like are preferable.
  • dialkylphosphono groups and diarylphosphono groups are more preferred.
  • the phosphono group include a jetyl phosphono group, a dibutyl phosphono group, and a diphenyl phosphono group.
  • the phosphonate group (PO H-, -PO H-) is a phosphono group (PO
  • H means a conjugated base anion group derived from acid first dissociation or acid second dissociation
  • counter cation generally known ones can be appropriately selected. For example, various kinds of atoms (ammonium, sulfo-ums, phospho-umms, ododoniums) ), Metal ions (Na +, K +, Ca 2+ , Zn 2+ etc.).
  • the phosphonato group may be a conjugated basic anion group obtained by substituting one of the phosphono groups with one organic oxo group.
  • 1 PO H (alkyl) a conjugated salt of a monoarylphosphono group (PO H (aryl))
  • the aromatic group includes at least one radical polymerizable compound containing an aromatic group and, if necessary, Accordingly, one or more other radically polymerizable compounds can be produced as a copolymerization component by a conventional radical polymerization 12 method.
  • Examples of the radical polymerization method generally include a suspension polymerization method and a solution polymerization method.
  • a compound represented by the structural formula (A) and a compound represented by the structural formula (B) are preferable.
  • R, R, and R represent a hydrogen atom or a monovalent organic group.
  • L represents an organic group and may be omitted.
  • Ar represents an aromatic group that may contain a heterocycle.
  • the organic group of L is, for example, a polyvalent organic group consisting of non-metallic nuclear power, including 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 atoms. Of oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur nuclear powers.
  • examples of the organic group of L include those formed by combining the following structural units, polyvalent naphthalene, polyvalent anthracene and the like.
  • the linking group of L may have a substituent.
  • substituents include the aforementioned halogen atom, hydroxyl group, carboxyl group, sulfonate group, nitro group, cyan group, amide group, amino group.
  • the structural formula (A) is more preferable in terms of sensitivity.
  • those having a linking group that are preferred from the viewpoint of stability are L 1-4 organic groups, which are C 1-4 alkylene groups in the non-image area. Preferred in terms of removability (developability).
  • the compound represented by the structural formula (A) is a compound containing a structural unit of the following structural formula (I).
  • the compound represented by the structural formula (B) is a compound containing a structural unit represented by the following structural formula ( ⁇ ). Of these, the structural unit of the structural formula (I) is preferable from the viewpoint of storage stability.
  • R, R, R, and Ar are the structural formulas (I) and ( ⁇ ).
  • R and R are hydrogen atoms, and R is a methyl group.
  • an alkylene group having 1 to 4 carbon atoms is preferable in terms of removability (imageability) of a non-image area.
  • the compound represented by the structural formula (A) or the compound represented by the structural formula (B) is not particularly limited, and examples thereof include the following exemplified compounds (1) to (30). It is done.
  • the content of the aromatic group that may contain a hetero ring in the binder is not particularly limited, but when the total structural unit of the polymer compound is 100 mol%, the structural formula (I) It is preferred to contain 20 mol% or more of the structural unit represented. It is more preferred to contain 30 to 45 mol%. When the content is less than 20 mol, storage stability may be lowered, and when it exceeds 45 mol%, developability may be lowered. [0063] ethylenically unsaturated bond
  • the ethylenically unsaturated bond is not particularly limited and may be appropriately selected according to the purpose.
  • those represented by the following structural formulas (III) to (v) are preferable.
  • R to R are each independently an l-valent organic group.
  • X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R.
  • Z represents an oxygen atom, a sulfur atom, -N-R, or a phenylene group.
  • R is a hydrogen atom
  • Or represents a monovalent organic group.
  • each R independently represents, for example, a hydrogen atom, an optionally substituted alkyl group, a hydrogen atom, or a methyl group is radically reactive. Is more preferable because it is high.
  • R and R are each independently, for example, a hydrogen atom, a halogen atom,
  • It has a mino group, a carboxyl group, an alkoxycarbo group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent.
  • Examples include a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and a substituent.
  • Aryl basic force More preferable because of high radical reactivity.
  • Examples of R include a hydrogen atom that is preferably an alkyl group which may have a substituent.
  • examples of the substituent that can be introduced include an alkyl group, an alkyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, and a carboxyl group.
  • R to R include, for example, a hydrogen atom, a halogen atom, and R
  • Mino group dialkylamino group, carboxyl group, alkoxycarbo group, sulfo group, nitrogen group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, substituent Having an alkoxy group that may have a substituent, an allyloxy group that may have a substituent, an alkylamino group that may have a substituent, an arylamino group that may have a substituent, and a substituent.
  • an aryl group may preferably have a hydrogen atom, a carboxyl group, an alkoxy carbo yl group or a substituent, an alkyl group. Even if it has a substituent, the aryl group is more preferred! /.
  • R may have, for example, a hydrogen atom or a substituent. Good
  • Alkyl groups and the like are more preferred because of high hydrogen atom and methyl group s radical reactivity.
  • R 1 and R 2 are each independently, for example, hydrogen atom, halogen atom, amino
  • Z represents an oxygen atom, a sulfur atom, -NR-, or a phenyl group optionally having a substituent.
  • R represents an alkyl group which may have a substituent, a hydrogen atom,
  • a til group, an ethyl group, and an isopropyl group are preferable because they have high radical reactivity.
  • the content of the ethylenically unsaturated bond in the polymer compound is not particularly limited. Repulsive force 0.5 to 3. Omeq / g force is preferable, 1.0 to 3. Omeq / g force ⁇ is more preferable, 1. 5-2.8 meqZg is particularly preferred. If the content is less than 0.5 meqZg, the sensitivity may be low because the amount of curing reaction is small. 3. If the content is more than OmeqZg, the storage stability may deteriorate.
  • the content (meqZg) can be measured, for example, by iodine value titration.
  • the method of introducing the ethylenically unsaturated bond represented by the structural formula (III) into the side chain is not particularly limited, and examples thereof include a polymer compound containing a carboxyl group in the side chain and ethylene. It can be obtained by addition reaction of a compound having an unsaturated bond and an epoxy group.
  • the polymer compound containing a carboxyl group in the side chain is, for example, one or more radically polymerizable compounds containing a carboxyl group and, if necessary, one other radically polymerizable compound as a copolymerization component.
  • the above can be produced by a normal radical polymerization method, and examples of the radical polymerization method include suspension polymerization method and solution polymerization method.
  • the compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these.
  • the compound represented by the following structural formula (VI) and (VII) are preferred.
  • the use of the compound represented by the structural formula (VI) is preferable from the viewpoint of increasing sensitivity.
  • R represents a hydrogen atom or a methyl group.
  • L represents an organic group
  • the W represents a 4- to 7-membered aliphatic hydrocarbon group.
  • L is More preferred is an alkylene group having 1 to 4 carbon atoms.
  • the compound represented by the structural formula (VI) or the compound represented by the structural formula (VII) is not particularly limited, and examples thereof include the following exemplified compounds (31) to (40).
  • radical polymerizable compound containing a carboxyl group examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, ink-mouthed tonic acid, maleic acid, and p-carboxyl styrene. Particularly preferred are acrylic acid and methacrylic acid.
  • Examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonia such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride.
  • the reaction can be carried out by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours using a -um salt, pyridine, triphenylphosphine or the like as a catalyst.
  • the structural unit having an ethylenically unsaturated bond in the side chain is not particularly limited.
  • the structure represented by the following structural formula (i), the structure represented by the structural formula (ii), And those represented by a mixture of these are preferred.
  • Ra to Rc represent a hydrogen atom or a monovalent organic group.
  • 1 ⁇ represents a hydrogen atom or a methyl group.
  • the content in the polymer compound having the structure represented by the structural formula (i) or the structural formula (ii) is preferably 20 mol% or more, more preferably 20 to 50 mol%. 25-45 mol% is particularly preferred. If the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. If the content is more than 50 mol%, the storage stability may be deteriorated.
  • the polymer compound of the present invention may have a carboxyl group in order to improve various performances such as non-image area removability.
  • the carboxyl group can be imparted to the polymer compound by copolymerizing a radical polymerizable compound having an acid group.
  • Examples of the acid group having such radical polymerizability include carboxylic acid, sulfonic acid, and phosphoric acid group, and carboxylic acid is particularly preferable.
  • the radically polymerizable compound having a carboxyl group can be appropriately selected depending on the purpose, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, cucumber tonic acid, and ink fountain. Examples include acid, maleic acid, and ⁇ -carboxyl styrene. Among these, acrylic acid, methacrylic acid, and p-carboxyl styrene are preferable. These may be used alone or in combination of two or more.
  • the content of the carboxyl group in the binder is 1.0 to 4. OmeqZg, preferably 1.5 to 3. Omeq / g. If the content is less than 1. Omeq / g, developability may be insufficient. 4. If it exceeds OmeqZg, image strength damage due to alkaline water development may occur. May be easier to receive.
  • the polymer compound of the present invention may be copolymerized with another radical polymerizable compound in addition to the above-described radical polymerizable compound for the purpose of improving various performances such as image strength. It is preferable.
  • radical polymerizable compound examples include radically polymerizable compounds such as acrylic acid esters, methacrylate esters, and styrenes.
  • acrylic acid esters such as alkyl acrylate, methacrylate esters such as aryl acrylate, alkyl methacrylate, styrenes such as aryl methacrylate, styrene, alkyl styrene, alkoxy
  • acrylic acid esters such as alkyl acrylate, methacrylate esters such as aryl acrylate, alkyl methacrylate, styrenes such as aryl methacrylate, styrene, alkyl styrene, alkoxy
  • styrene and halogen styrene include styrene and halogen styrene.
  • acrylates those having 1 to 20 carbon atoms in the alkyl group are preferable.
  • methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, and ethyl acrylate are preferable.
  • examples include atarylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate.
  • Examples of the aryl acrylate include a file acrylate.
  • methacrylic acid esters those having 1 to 20 carbon atoms of the alkyl group are preferable.
  • Rate amyl methacrylate, hexyl methacrylate, cyclohexenomethacrylate, benzyl methacrylate, chlorbendyl methacrylate, octyl methacrylate, ginseng, 4-hydroxybutynole methacrylate, 5 hydroxy Examples include pentinoremetatalylate, 2, 2 dimethyl-3-hydroxypropyl metatalylate, trimethylolpropane monometatalate, pentaerythritol monometatalate, glycidyl metatalylate, furfuryl metatalylate, tetrahydrofurfuryl metatalylate, etc.
  • Be Examples of the aryl methacrylate include phenyl methacrylate, credinole methacrylate, naphthyl methacrylate, and the like.
  • styrenes examples include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, jetyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, and chloromethyl.
  • examples include styrene, trifluoromethyl styrene, ethoxymethyl styrene, and acetomethyl styrene.
  • alkoxystyrene examples include methoxystyrene, 4-methoxy-13-methylstyrene, dimethoxystyrene, and the like.
  • halogen styrene examples include chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromo styrene, dibromo styrene, odo styrene, fluor styrene, trifluoro styrene, 2-bromo trifluoromethyl styrene. 4 Fluoro 3-trifluoromethylstyrene and the like.
  • radically polymerizable compounds may be used alone or in combination of two or more.
  • the solvent used in the synthesis of the polymer compound of the present invention is not particularly limited, and can be appropriately selected according to the purpose.
  • the molecular weight of the polymer compound of the present invention is preferably a mass average molecular weight of 10,000 or more, more preferably 10,000 to 50,000 force! /. If the mass average molecular weight force S is less than 10,000, the cured film strength may be insufficient, and if it exceeds 50,000, the developability tends to be lowered. Further, the polymer compound of the present invention may contain an unreacted monomer. this In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less.
  • the polymer compound according to the present invention may be used alone or in a combination of two or more. Moreover, you may mix and use another high molecular compound. In this case, the content of the other polymer compound in the polymer compound of the present invention is preferably 50% by mass or less, more preferably 30% by mass or less.
  • the solid content of the binder in the photosensitive composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
  • the elastomer is polymerized in combination with the above-mentioned noinder to improve the cure shrinkage and flexibility of the cured film, and to operate in the temperature range of 200 to 220 ° C, which is the temperature during reflow.
  • the elastic modulus can be reduced to 1 to: LOOMPa by dynamic viscoelasticity measurement, and there is a function to improve the shear adhesion with the sealing material. That is, by adding a flexible elastomer, the stress of the cured film can be relaxed and the cured coating film can be modified. If the elastic modulus is less than 1 MPa, the mechanical strength decreases, and if it exceeds lOOMPa, the shear adhesive strength decreases.
  • the elastomer can be appropriately selected according to the purpose without any particular limitation.
  • styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer, polyamide elastomer Acrylic elastomers and silicone elastomers are composed of hard segment components and soft segment components. Generally, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. is doing.
  • the properties of the elastomer are not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably alkali-soluble or swellable in terms of production efficiency in the development process. ⁇ .
  • the styrene-based elastomer can be appropriately selected according to the purpose without any particular limitation.
  • styrene butadiene styrene block copolymer styrene isoprene styrene block copolymer
  • styrene ethylene-butylene styrene block copolymer styrene ethylene Propylene styrene block copolymer I can get lost.
  • styrene derivatives such as a-methylol styrene, 3-methylol styrene, 4-propyl styrene and 4-cyclohexyl styrene can be used.
  • Tufprene examples include RIKEN BULL
  • the olefin-based elastomer is not particularly limited and can be appropriately selected according to the purpose.
  • ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, etc. 2-20 ⁇ -olefin copolymers such as ethylene propylene copolymer (EPR), ethylene propylene copolymer (EPDM), etc., and dicyclopentaene, 1, 4 Examples thereof include non-conjugated digen having 2 to 20 carbon atoms such as hexagen, cyclooctagen, methylene norbornene, ethylidene norbornene, butadiene and isoprene, and ⁇ -olefin copolymers.
  • carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-atari mouth-tolyl copolymer.
  • ethylene 'a Orefuin copolymer rubber ethylene' a Orefuin 'non-conjugated diene copolymer rubber, propylene.
  • Miralastoma Mitsubishi Chemical
  • EXA CT Escon Chemical
  • ENG A GE Hydroated styrene butadiene rubber
  • DYNABON HSBR Hydroated styrene butadiene rubber
  • Butadiene-acrylo-tolyl copolymer “NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.), there is! /, “XER” of the carboxyl group-modified butadiene-acrylonitrile copolymer having both cross-linking points. Series "(manufactured by Nippon Synthetic Rubber Co., Ltd.).
  • the urethane-based elastomer is not particularly limited and is appropriately selected depending on the purpose.
  • it consists of a structural unit of a hard segment composed of a low molecular weight glycol and diisocyanate and a soft segment composed of a polymer (long chain) diol and a diisocyanate.
  • the number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000 force S.
  • short chain diols such as propylene glycol, 1,4 butanediol, and bisphenol diol can be used, and the number average molecular weight of the short chain diol is preferably 48 to 500 force S.
  • Specific examples of urethane elastomers include PANDEX T-2185, T-2983N (Dainippon Ink), and sylactolan E790.
  • the polyester elastomer is not particularly limited and may be appropriately selected depending on the purpose.
  • the polyester elastomer is obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
  • dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and hydrogen nuclear S of these aromatic nuclei, aromatic dicarboxylic acids that are substituted with methyl, ethyl, phenyl, etc.
  • Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as acid, adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more.
  • Specific examples of the diol compound include fats such as ethylene glycol, 1,3 propanediol, 1,4 butanediol, 1,6 hexanediol, 1,10 decanediol, and 1,4 hexane hexanediol.
  • Group diol and alicyclic diol, or divalent phenol represented by the following structural formula.
  • Y represents any one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, and —SO—,
  • R 1 and R 2 represent halogen or an alkyl group having 1 to 12 carbon atoms.
  • 1 and m represent an integer of 0 to 4, and p is 0 or 1.
  • polyester elastomer examples include bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-1-methylphenol) propane, resorcin and the like. These compounds can be used alone or in combination of two or more. Further, as the polyester elastomer, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a node segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component. You can use your body.
  • aromatic polyester for example, polybutylene terephthalate
  • aliphatic polyester for example, polytetramethylene glycol
  • Examples of the multi-block copolymer include various grades depending on the types, ratios, and molecular weights of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by DuPont Toray Industries, Inc.), Perprene (manufactured by Toyobo Co., Ltd.), Espel (manufactured by Hitachi Chemical Co., Ltd.), and the like.
  • the polyamide-based elastomer is not particularly limited and can be appropriately selected according to the purpose.
  • a polyether block amide type using a polyamide as a hard phase and a polyether or polyester as a soft phase.
  • the polyamide is roughly divided into two types, such as polyamide 6, 11, 12 and the like, and the polyether is polyoxyethylene, polyoxypropylene, polytetramethylene glycol, etc. Used.
  • UBE polyamide elastomer manufactured by Ube Industries, Ltd.
  • Daiamide manufactured by Daicel Huls Co., Ltd.
  • PEB AX manufactured by Toray Industries, Inc.
  • Daliron ELY manufactured by Ems Japan Ltd.
  • Novamid (Mitsubishi Chemical Co., Ltd.) and Glais (Dainippon Ink Co., Ltd.).
  • the acrylic elastomer is not particularly limited and may be appropriately selected according to the purpose.
  • the acrylic elastomer is mainly composed of an acrylate ester, and includes ethyl acetate, butyrate, methoxyethyl acrylate, Ethoxyethyl talylate or the like is used, and glycidyl metatalylate, allyl glycidyl ether or the like is used as a crosslinking point monomer. It is done.
  • acrylonitrile and ethylene can be copolymerized.
  • acrylo-tolyl butyl acrylate copolymer examples include acrylo-tolyl butyl acrylate copolymer, acrylonitrile butyl acrylate relay acrylate copolymer, acrylonitrile butyl acrylate relay glycidyl methacrylate copolymer, and the like.
  • the silicone elastomer is not particularly limited and may be appropriately selected depending on the purpose.
  • the silicone elastomer is mainly composed of an organopolysiloxane, such as polydimethylsiloxane, polymethylphenol siloxane. And polydiphenylsiloxane. Some of them are modified with a bur group or an alkoxy group.
  • Specific examples include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the SE series, the CY series, and the SH series (above, manufactured by Toray Dowco-One Silicone Co., Ltd.).
  • rubber-modified epoxy resins can be used.
  • the rubber-modified epoxy resin is, for example, the above-mentioned bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol monovolak type epoxy resin or cresol novolac type epoxy resin. This is obtained by modifying a part or all of the epoxy groups with a carboxylic acid-modified butadiene-acrylonitrile rubber or a terminal amino-modified silicone rubber.
  • both end carboxyl group-modified butadiene acrylate-tolyl copolymer Espel which is a polyester elastomer having a hydroxyl group (manufactured by Hitachi Chemical Co., Ltd., Espel) 1612, 1620) are preferred.
  • the content of the elastomer is not particularly limited and can be appropriately selected according to the purpose. For example, 2 to 50 parts by mass is preferable with respect to 100 parts by mass of the binder. Part is more preferred. If it is less than 2 parts by mass, the modulus of elasticity in the high temperature region of the cured film tends not to decrease, and if it exceeds 50 parts by mass, the unexposed part tends not to be eluted with the developer.
  • the polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose.
  • a compound having one or more ethylenically unsaturated bonds is preferable.
  • Examples of the ethylenically unsaturated bond include a (meth) atalyloyl group, a (meth) acrylamido group, a styryl group, a butyl group such as a butyl ester and a butyl ether, and a aryl ether. And aryl groups such as ryalyl esters.
  • the compound having one or more ethylenically unsaturated bonds is not particularly limited, and can be appropriately selected depending on the purpose.
  • a monomer having a (meth) acryl group is selected. At least one is preferably mentioned.
  • 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 methallylates such as rate and phenoxychetyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate Rate, trimethylolpropane ditalylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta erythritol tri (meth) acrylate, dipentaerythritol hexane (Meth) acrylate, dipentaerythritol penta (meth) acrylate,
  • 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 poor developability and reduced exposure sensitivity may occur. If it exceeds, the adhesiveness of the photosensitive layer may become too strong.
  • the photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light may have some effect with photo-excited sensitizers, and may be active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates.
  • the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 to 800 nm. The above wavelength is more preferable than 330 ⁇ 500mn force! / ⁇ .
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexarylbiimidazole, oxime derivatives, organic peroxides. Products, thio compounds, ketone compounds, aromatic onium salts, meta-octenes, and the like.
  • a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, a ketone compound, Hexaarylbiimidazole compounds are preferred.
  • the photopolymerization initiator include phosphine oxides, a-aminoalkyl ketones, and halogenated amines having the triazine skeleton, which are compatible with laser light having a wavelength of 405 nm in the later-described exposure.
  • examples thereof include a composite photoinitiator in which a hydrocarbon compound and an amine compound as a sensitizer described later are combined, the oxime derivative, the hexane monorubiimidazole compound, and titanocene.
  • a-aminoalkyl ketones and an aromatic ketone compound such as thixanthone as a sensitizer.
  • an oxime derivative is preferable because of its high sensitivity.
  • the content of the photopolymerization initiator in the photosensitive composition is 0.1 to 30% by mass. 0.5 to 20% by mass is more preferable, and 0.5 to 15% by mass is particularly 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 compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
  • the thermal crosslinking agent is preferably alkali-insoluble from the viewpoint of gold plating resistance.
  • Examples of the epoxy compound having at least two oxysilane groups in one molecule include, for example, bixylenol type or biphenol type epoxy resin ("YX4000 Japan Epoxy Resin Co., Ltd.") or a mixture thereof.
  • Heterocyclic epoxy resins having an isocyanurate skeleton (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, "Araldite PT810; manufactured by Ciba 'Specialty'Chemicals"), bisphenol A type epoxy resin, novolak Type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, talesol novolac type epoxy resin, halogenated epoxy resin Fats (for example, low brominated epoxy resins, high halogenated epoxy resins, brominated phenols Borak type epoxy resin), aryl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenol dimethanol type epoxy resin, phenol biphenol type epoxy resin, dicyclopentagen Type epoxy resin (“HP-7200, HP-7200H; manufactured by Dainippon Ink Chemical Co., Ltd.”), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, dig
  • epoxy resin having a linear phosphorus-containing structure epoxy resin having a cyclic phosphorus-containing structure, a methyl stilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenol Type liquid crystal epoxy resin, azomethine file type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, and glycidyl metatalylate copolymer epoxy resin (“CP-50S, CP-50M; Co., Ltd.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane Forces such as type epoxy resin are not limited to these.
  • an epoxy compound having at least two epoxy groups having an alkyl group at the ⁇ -position in one molecule may be used.
  • Particularly preferred is a compound containing an epoxy group (more specifically, a 13-alkyl-substituted glycidyl group or the like) in which the ⁇ -position is substituted with an alkyl group.
  • the epoxy compound containing at least the epoxy group having an alkyl group at the j8 position is composed of at least one epoxy group in which all of two or more epoxy groups contained in one molecule may be 13 alkyl-substituted glycidyl groups.
  • the group may be a j8-alkyl substituted glycidyl group.
  • the / 3 alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose.
  • ⁇ -methyldaricidyl group ⁇ -ethyldaricidyl group, ⁇ Propyl glycidyl group, ⁇ -butyl daricidyl group, and the like.
  • j8-methyl A daricidyl group is preferred.
  • the epoxy compound containing an epoxy group having an alkyl group at the / 3-position is preferably, for example, an epoxy compound derived from a polyvalent phenol compound and a j8-alkylepihalohydrin.
  • the / 3-alkylepino and rhohydrin are not particularly limited and can be appropriately selected according to the purpose.
  • j8-methylepichlorohydrin, 13 methylepibromohydrin, 13- J8-methylepihalohydrin such as methylepifluorohydrin; 13-ethylepichlorohydrin, j8-ethylepibu mouth mohydrin, —ethylepifluorohydrin, etc.
  • ⁇ -propyle ⁇ -Propinoreepihalohydrin such as chlorohydrin, ⁇ -propylepib mouth mohydrin, ⁇ -propinoreepifluorohydrin; ⁇ 8-butinoreepichlorohydrin, j8-butylepib mouth mohydrin, j8-butylepihydrohydrin, etc. Pihalohydrin; and the like.
  • ⁇ -methylepino and rhohydrin are preferable from the viewpoints of reactivity with the polyhydric phenol and fluidity.
  • the polyhydric phenolic compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose.
  • bisphenol compounds such as bisphenol ⁇ ⁇ , bisphenol F and bisphenol S
  • biphenol compounds such as biphenol and tetramethylbiphenol
  • naphthol compounds such as dihydroxynaphthalene and binaphthol
  • phenol-formaldehyde polycondensates C1-C10 monoalkyl substituted phenol-formaldehyde polycondensate such as phenol novolac resin, creso-one formaldehyde polycondensate, etc.
  • C1-C10 dialkyl substituted phenol such as xylenol-formaldehyde polycondensate Ruholmaldehyde polycondensate, bisphenol A formaldehyde Bisphenol compounds such as polycondensates Formaldehyde polycondensates, copolycondensates of phenol and monoalkyl-substituted phenols with 1 to 10 carbon atoms and formaldehyde, polyadducts of phenolic compounds and dibutenebenzene It is done.
  • the above-mentioned bisphenol compound is preferable.
  • Examples of the epoxy compound containing an epoxy group having an alkyl group at the B position include bisphenol A di- 13-alkyl glycidyl ether, bisphenol F di- ⁇ -alkyl glycidyl ether, bisphenol S G Bisphenol compounds such as alkyl glycidyl ethers / 3 alkyl glycidyl ethers; Biphenols ge 13 alkyl glycidyl ethers, tetramethylbiphenols ge 13 alkyl glycidyl ethers and other biphenol compounds ge 13 alkyl glycidyl ethers; dihydroxynaphthalene Of naphthyl compounds such as alkyl glycidyl ether and binaphthol 13 alkyl glycidyl ether such as alkyl glycidyl ether; poly 13a of phenol-formaldehyde polycondensate Cylglycidyl ether; poly 13 alkyl glycid
  • R represents either a hydrogen atom or an alkyl group having 16 carbon atoms, and n represents an integer of 0-20.
  • R represents either a hydrogen atom or an alkyl group having 16 carbon atoms
  • R ′′ represents either a hydrogen atom or CH
  • n represents an integer of 0-20.
  • epoxy compounds containing an epoxy group having an alkyl group at the 13-position may be used alone or in combination of two or more. It is also possible to use an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the j8 position.
  • 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 rates or their oligomers or copolymers of In addition to polyfunctional oxetanes, compounds with oxetane groups, novolac resin, poly (p-hydroxystyrene groups,
  • an amine compound for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N dimethylbenzyl Amine, 4-methyl N, N dimethylbenzylamine, etc., quaternary ammonium salt compounds (eg, triethylbenzylammochloride), block isocyanate compounds (eg, dimethylamine), Imidazole derivatives Bicyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenolimidazole, 4-phenolimidazole, 1 — Cyanethyl-2 phenolimidazole, 1- (2 Cyanethyl) -2 ethyl-4-methyl
  • the epoxy resin compound or the oxetane compound is 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. May be used.
  • the solid content in the solid content of the photosensitive composition of the epoxy compound, 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.
  • 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, bifunctional isocyanates (eg, mixtures of 1,3 and 1,4-phenolic diisocyanates, 2,4 and 2,6 toluene diisocyanates, 1,3 and 1,4 xylates) Range isocyanate, bis (4-isocyanate monophenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone di-socyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Etc.), the bifunctional isocyanate, trimethylolpropane, pentalysitol, Dali Polyfunctional alcohols with serine and
  • a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate or its derivative may be used.
  • isocyanate group blocking agent examples include alcohols (for example, isopropanol, tert-butanol, etc.), ratatas (for example, epsilon-prolactam, etc.), phenols (for example, phenol, crezo-monore, p-tert-butinolephenol) Nore, p-sec butinolevenore, p-sec amylphenol, p-octylphenol, p-norphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline) And the like, and active methylene compounds (for example, dialkyl malonate, methyl ethyl ketoxime, acetyl acetone, alkyl acetoacetonitrile, acetooxime, cyclohexanone oxime, etc.).
  • compounds having at least one polymerizable double bond and at least one block isocyanate group examples include alcohols
  • a melamine derivative can be used as the thermal crosslinking agent.
  • the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, etc.). These may be used alone or in combination of two or more.
  • hexamethylated methylol melamine is particularly preferred because alkylated methylol melamine is preferred because it has good storage stability and the surface hardness of the photosensitive layer is effective in improving the film strength itself of the cured film. preferable.
  • an amine compound eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) N, N dimethylbenzilamine, 4-methoxy N , N dimethylbenzylamine, 4-methyl-N, N dimethylbenzylamine, etc.
  • quaternary ammonium salt compounds eg, triethylbenzylamine
  • dimethyl chloride block isocyanate compounds (for example, dimethylamine)
  • imidazole bicyclic amidine compounds and salts thereof for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 cyanoethyl, 2-phenolimidazole, 1 (2 cyanoethyl) 2-ethyl-4-methylimidazole, etc.
  • phosphonaminoethyl e.g., 2-ethylimid
  • a compound capable of accelerating thermal curing other than the above may be used without particular limitation.
  • the solid content in the photosensitive composition of the thermal crosslinking agent and the compound capable of accelerating thermal curing of these and a carboxylic acid is preferably 0.01 to 15% by mass.
  • the solid content of the thermal crosslinking agent in the photosensitive composition is preferably 1 to 50% by mass, more preferably 3 to 30% by mass. When the solid content is less than 1% by mass, no improvement in the film strength of the cured film is observed, and when it exceeds 50% by mass, the developability and exposure sensitivity may decrease.
  • Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and others.
  • sensitizers thermal polymerization inhibitors, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and others.
  • plasticizers for example, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like
  • adhesion promoters to the substrate surface and others.
  • conductive particles fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.
  • Sensitizer By appropriately containing these components, it is possible to adjust properties such as stability, photosensitivity, and film physical properties of the intended photosensitive composition. [0123] Sensitizer
  • 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.
  • Examples of combinations of the photopolymerization initiator and the sensitizer include, for example, an electron transfer-type initiator system described in JP-A-2001-305734 [(1) an electron-donating initiator and a sensitizing dye (2) Electron-accepting initiators and sensitizing dyes, (3) Electron-donating initiators, sensitizing dyes and electron-accepting initiators (ternary initiation system)], and the like.
  • the sensitizer can be appropriately selected from known sensitizers that are not particularly limited.
  • known polynuclear aromatics for example, pyrene, perylene, triphenylene
  • Xanthenes for example, fluorescein, eosin, erythrosine synth, rhodamine B, rose bengal
  • cyanines for example, indocarboyanine, thiacarboyanine, oxacarboyanine
  • merocyanines for example, merocyanine, carbomerocyanine
  • Thiazines eg, thionine, methylene blue, toluidine blue
  • atalidines eg, ataridin orange, chloroflavin, acriflavine, 9 phenyllacridin, 1,7-bis (9,9,1 ataridinyl) heptane
  • anthraquinone for example, anthraquinone
  • squalium for example, squalium ( For
  • hetero-fused ketone compounds (ataridon compounds, thixanthone compounds, coumarin compounds, etc.), and atalidine compounds are more preferable.
  • attaridone compounds and thixanthone compounds are particularly preferable.
  • the amine compound substituted with any one of the at least two aromatic hydrocarbon rings and aromatic heterocycles is a sensitizer having an absorption maximum with respect to light in a wavelength range of 330 to 450 nm.
  • a di-substituted aminobenzene compound having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, an amino group on the benzene ring In contrast, a di-substituted amino-benzene compound having a substituent containing a sulfo-limino group at the carbon atom at the para position, a di-substituted amino-benzene compound having a carbostyryl skeleton, and at least two aromatics Examples thereof include compounds having a di-substituted amino-benzene as a partial structure, such as a compound having a structure in which a ring is bonded to a nitrogen atom.
  • the sensitizers may be used alone or in combination of two or more.
  • the content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and 0.05 to 1% by mass with respect to all components of the photosensitive composition. Particularly preferred.
  • the thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
  • thermal polymerization inhibitor examples include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted nanoquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, Cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2,6 di-t-butyl-4 cresol, 2,2, -methylenebis (4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 Toluidine, methylene blue, copper and organic chelating agent reactants, methyl salicylate, and phenothiazine, nitroso compounds, and chelates of troso compounds with A1.
  • 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 of the photosensitive layer. 01 to 1% by mass is particularly preferred.
  • the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.
  • the plasticizer should be added to control the film physical properties (flexibility) of the photosensitive layer.
  • plasticizer examples include dimethyl phthalate, dibutyl phthalate, diisopropyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diphenyl phthalate.
  • Phthalic acid esters such as ril phthalate and octyl capryl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl dallicose phthalate, ethino retino eno ethino reglycolate, methyl phthal yl acetyl glycolate Glycol esters such as norephthalino lebutinoglycolate and triethylene glycol dicabrylate; tricresyl phosphate, triphenyl Phosphate esters such as sulfate; 4 Toluenesulfonamide, Benzenesulfonamide Amides such as N-n-butylbenzenesulfonamide, N-n-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sepacate, dioct
  • the content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive layer. preferable.
  • the coloring pigment is not particularly limited and can be appropriately selected according to the purpose.
  • 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 'Carmine 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), Monolite 'Fast' Black B (CI Pigment 'Black 1), Carbon, CI Pigment' Red 97 CI Pigment 'Red 122, CI Pigment' Red 149, CI Pigment 'Red 168
  • the solid content in the solid content of the photosensitive composition of the colored pigment is a permanent pattern. It can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer at the time of formation, and a force that varies depending on the type of the colored pigment is generally preferably from 0.01 to 10% by mass. ⁇ 5% by mass 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 pigment added is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.
  • a loose adhesion promoter can be used.
  • adhesion promoter examples include JP-A-5-11439 and JP-A-5-34153.
  • Preferable examples include adhesion promoters described in JP-A No. 2 and JP-A-6-43638.
  • the content of the adhesion promoter is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on all components of the photosensitive layer. % To 5% by mass is particularly preferred.
  • the photosensitive composition of the present invention has no edge fusion (end face fusion), is excellent in tackiness and stability of performance over time, is easily formed into a film, and efficiently forms a high-definition permanent pattern. Is possible. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, columns, ribs, spacers, partition walls, display members, holograms, micromachines, proofs, etc. It can be suitably used for forming a permanent pattern on a substrate.
  • the photosensitive film of the present invention has at least a support and a photosensitive layer made of the photosensitive composition of the present invention formed on the support, and a thermoplastic resin layer or the like as needed. It is preferable to have other layers.
  • the photosensitive layer is as described above.
  • the photosensitive layer is formed using the photosensitive composition of the present invention.
  • the minimum energy of light used for the exposure is 0.1 l without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development. it is that it is ⁇ 200mi / cm 2 is the preferred tool 0. 2 ⁇ 100mj / cm 2 Ri preferably, and particularly preferably it is 0. 5 ⁇ 50mjZcm 2 is more preferably tool l ⁇ 30miZcm 2.
  • capri may occur in the processing step, and if it exceeds 200 mjZcm 2 , the time required for exposure may become longer and the processing speed may become slower. .
  • the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is so-called development sensitivity. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure when exposed and the thickness of the cured layer generated by the development process following the exposure. .
  • the thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure.
  • the development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
  • the thickness of the cured layer and the thickness of the photosensitive layer before exposure are within ⁇ 1 m, it is considered that the thickness of the cured layer is not changed by exposure and development.
  • a method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a film thickness measuring device for example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.
  • the thickness of the photosensitive layer can be appropriately selected according to the purpose for which there is no particular restriction. However, if it is omitted, 1 to: LOO ⁇ m force S, preferably 2 to 50 ⁇ m force S 4-30 ⁇ m force S is particularly preferable.
  • the support can be appropriately selected according to the purpose for which there is no particular limitation. However, it is preferable that the photosensitive layer is peelable and has good light transmittance. Further, the surface is smooth. It is more preferable that the sex is good. Specific examples of the support and the protective film are described in, for example, JP-A-2005-258431, [0342] to [0348]. ing.
  • a cushion layer an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface
  • a protective layer may be provided on the photosensitive layer.
  • the cushion layer is not particularly limited and may be appropriately selected depending on the purpose, and may be swellable or soluble or insoluble in an alkaline liquid.
  • thermoplastic resin examples include, for example, an ethylene / acrylate copolymer copolymer, styrene, and (meth) (Meth) such as saponified acrylate copolymer, kento of butyltoluene and (meth) acrylic ester copolymer, poly (meth) acrylate, butyl (meth) acrylate and vinyl acetate Acrylic ester copolymers, etc., (meth) acrylic acid ester and (meth) acrylic acid copolymer, styrene, (meth) acrylic acid ester and (meth) acrylic acid copolymer Etc.
  • an ethylene / acrylate copolymer copolymer styrene
  • (meth) (Meth) such as saponified acrylate copolymer, kento of butyltoluene and (meth) acrylic ester copolymer, poly (meth) acrylate, butyl (meth) acryl
  • the softness point (Vicat) of the thermoplastic resin in this case is a force that can be appropriately selected according to the purpose without any particular limitation. For example, it is preferably 80 ° C or lower.
  • the above-mentioned thermoplastic resin has a softness point of 80 ° C or less, as well as “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, Issued on October 25, 1968).
  • the organic polymers whose soft spot is about 80 ° C or less those that are soluble in alkaline liquids are listed.
  • various plasticizers compatible with the organic polymer material are added to the organic polymer material so that a substantial softness can be obtained. It is also possible to lower the point below 80 ° C.
  • the interlayer adhesive strength of the photosensitive film is not particularly limited and is appropriately selected according to the purpose.
  • the interlayer adhesion between the support and the cushion layer is the smallest among the interlayer adhesion of each layer.
  • the interlayer adhesive strength only the support is peeled off from the photosensitive film, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is removed using an alkaline developer. Can be developed. Further, after exposing the photosensitive layer while leaving the support, the photosensitive film force is peeled off, and the photosensitive layer is developed using an alkaline developer.
  • the method for adjusting the interlayer adhesion can be appropriately selected depending on the purpose without any particular limitation.
  • a known polymer, supercooling substance, or adhesion improver in the thermoplastic resin can be selected.
  • a method of adding a surfactant, a release agent and the like can be selected.
  • the plasticizer can be appropriately selected depending on the purpose without any particular limitation.
  • polypropylene glycol polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutino phthalate, tricres.
  • Alcohols and esters such as zircphosphate, uddernoresiphosphate and biphenyldiphosphate, amides such as toluenesulfonamide, and the like.
  • thermoplastic resin examples include a copolymer whose main component is an essential copolymer component of ethylene.
  • the copolymer having ethylene as an essential copolymer component is a force that can be appropriately selected according to the purpose without any particular limitation.
  • ethylene vinyl acetate copolymer (EV A) ethylene-ethyl acrylate. Copolymer (EEA) and the like.
  • the interlayer adhesive force of the photosensitive film can be appropriately selected according to the purpose without any particular limitation.
  • the adhesive strength between the photosensitive layer and the cushion layer is preferably the smallest.
  • the support and cushion layer are peeled off from the photosensitive film carrier, the photosensitive layer is exposed, and then the photosensitive layer is developed using an alkaline developer. be able to.
  • the support and the cushion are exposed from the photosensitive film. It is also possible to peel the layer and develop the photosensitive layer using an alkaline developer.
  • the method for adjusting the interlayer adhesive force can be appropriately selected depending on the purpose without any particular limitation.
  • various polymers, supercooling substances, adhesion improvers in the thermoplastic resin can be selected.
  • the ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component can be appropriately selected according to the purpose without any particular limitation, and is preferably 60 to 90% by mass, for example. 60-80% by mass is more preferred. 65-80% by mass is particularly preferred.
  • the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. If the amount exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled off. It may be difficult to produce the photosensitive film.
  • the thickness of the cushion layer can be appropriately selected according to the purpose for which there is no particular restriction.
  • the force f row; t is 5-50 111 girls, 10-50 111 girls Preferably, 15-40111.
  • the thickness is less than 5 m, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition permanent pattern may not be formed. Problems such as increased load may occur.
  • the oxygen barrier layer is preferably a film having a thickness of preferably about 0.5 to 5 ⁇ m, and is preferably formed mainly of polybulal alcohol.
  • the said photosensitive film can be manufactured as follows, for example. First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution for a photosensitive film.
  • the solvent can be appropriately selected according to the purpose without any particular limitation.
  • examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec. -Alcohols such as butanol and n-xanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone; Ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, Esters such as ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; tetrasalt carbon, trichloroethylene, and blackform 1, 1, 1-trichloroe
  • the photosensitive resin composition solution is coated on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.
  • the method for applying the photosensitive composition solution is not particularly limited.
  • the force can be selected appropriately according to the purpose.
  • spray method roll coating method, spin coating method, slit coating method, etatrusion.
  • the coating method include a coating method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
  • the drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
  • the photosensitive film is preferably stored, for example, by being wound around a cylindrical core and wound into a long roll.
  • the length of the long photosensitive film is not particularly limited. For example, a range force of 10-20,000 m can be appropriately selected. In addition, slitting may be performed for the convenience of the user, and a long body in the range of 100 1,000 m may be rolled. In this case, it is preferable that the support is wound up so as to be the outermost side.
  • the roll-shaped photosensitive film may be slit into a sheet shape. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (particularly moisture-proof, with desiccant) on the end face, and the packaging should be made of a material with low moisture permeability. Prefer to use That's right.
  • the photosensitive film of the present invention has no edge fusion (end face fusion), excellent tackiness and stable performance over time, and can be easily formed into a film. Therefore, it is possible to efficiently form high-definition permanent patterns, so that various patterns such as protective films, interlayer insulation films, and permanent patterns such as solder resist patterns can be formed, color filters, pillar materials, rib materials, spacers. It can be suitably used for the production of liquid crystal structural members such as a substrate and partition walls, and for the formation of patterns such as holograms, micromachines, and proofs, and particularly for the formation of permanent patterns on printed boards.
  • the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned in the formation of the permanent pattern, it is possible to increase the thickness. Ion migration does not occur in the acceleration test (HAST) High-definition permanent patterns with excellent heat resistance and moisture resistance can be obtained, so that lamination to the substrate is performed more precisely.
  • HAST acceleration test
  • the photosensitive laminate of the present invention comprises at least a photosensitive layer comprising the photosensitive composition of the present invention on a substrate, and other layers appropriately selected according to the purpose.
  • the substrate is a substrate to be processed on which a photosensitive layer is formed, or a transfer target to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and is appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having a high surface smoothness to those having a rough surface.
  • a so-called substrate in which a plate-like substrate is preferred is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.
  • Examples of the method for producing the photosensitive laminate include, as the first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as the second aspect, in the photosensitive film of the present invention. A method of laminating by transferring at least one of heating and pressurizing at least one of the photosensitive layer and transferring force is mentioned. [0168] In the method for producing a photosensitive laminate of the first aspect, the photosensitive composition is applied and dried on the substrate to form a photosensitive layer.
  • 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 substrate 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 can be appropriately selected depending on the purpose without particular limitation, and examples thereof include the same solvents as those used for the photosensitive film. They are
  • One type may be used alone or two or more types may be used in combination. Also, add a known surfactant.
  • the coating method and drying conditions can be appropriately selected according to the purpose without any particular limitation, and the same methods and conditions as those used for the photosensitive film are used.
  • the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing.
  • the protective film it is preferable that the protective film is peeled off and laminated so that the photosensitive layer overlaps the substrate.
  • the heating temperature can be appropriately selected according to the purpose for which there is no particular limitation. For example, 15 to 180 ° C is preferable, and 60 to 140 ° C is more preferable.
  • the pressure of the pressurization can be appropriately selected according to the purpose for which there is no particular restriction. For example, 0.1 to 1. OMPa force is preferable, 0.2 to 0.8 MPa force is more preferable! / ⁇ .
  • the apparatus for performing at least one of the heating can be appropriately selected depending on the purpose without any particular limitation.
  • a laminator for example, VP-II, manufactured by Taisei Laminatene Earth, Inc.-Chigo I Morton Co., Ltd.
  • Preferable examples include VP130).
  • the photosensitive laminate of the present invention has excellent edge tack (end face fusion), excellent tackiness and stability of performance over time, and high definition. Because permanent patterns can be formed efficiently, it can be used to form various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. For manufacturing liquid crystal structural members, holograms, It can be suitably used for pattern formation such as thin and proof, and can be particularly suitably used for permanent pattern formation on printed circuit boards.
  • the pattern forming apparatus of the present invention includes the photosensitive layer and includes at least a light irradiation unit and a light modulation unit.
  • the permanent pattern forming method of the present invention includes at least an exposure step and other steps such as an appropriately selected imaging step.
  • the photosensitive layer in the photosensitive film of the present invention is exposed.
  • the photosensitive film and the base material of the present invention are as described above.
  • the subject of the exposure is not particularly limited as long as it is the photosensitive layer in the photosensitive film, and can be appropriately selected depending on the purpose. It is preferable that this is performed on a laminated body formed by laminating the optical film while performing at least one of heating and pressing.
  • the exposure is not particularly limited, and can be appropriately selected according to the purpose. Among these, digital exposure, analog exposure, and the like are preferred. Digital exposure is preferable.
  • the analog exposure is not particularly limited and may be appropriately selected depending on the purpose. For example, exposure is performed with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like through a negative mask having a predetermined pattern. A method is mentioned.
  • the digital exposure is not particularly limited, and can be appropriately selected according to the purpose.
  • a control signal is generated based on pattern formation information to be formed and modulated according to the control signal.
  • light For example, n light (where n is a natural number of 2 or more) two-dimensional light receiving means and receiving light from the light irradiating means.
  • the usable picture element part of the exposure head is specified by the use picture element specifying means.
  • the pixel part to be used for N double exposure (where N is a natural number of 2 or more) is specified, and the exposure head is specified by the pixel part specifying unit by the pixel part control means. It is preferable to control the drawing unit so that only the drawing unit is involved in exposure, and move the exposure head relative to the photosensitive layer in the scanning direction.
  • N-exposure exposure means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. It refers to exposure with settings that intersect with N light spots (pixel array).
  • 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. Refers to a sequence of The arrangement of the picture element portions does not necessarily have to be a rectangular lattice, for example, an arrangement of parallelograms.
  • the “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part row at both side edges of each pixel part. Since the number of picture element parts in the used picture element part is reduced, even if a plurality of exposure heads are connected together in such a case, scanning may occur due to errors such as the mounting angle or arrangement of the exposure heads.
  • the number of pixel parts in the used pixel part that intersects the straight line parallel to the direction may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is less than the resolution.
  • N double exposure and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” with respect to an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method.
  • 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-type flatbed type exposure apparatus, and as shown in FIG. 1, a sheet-like photosensitive material 12 in which at least the photosensitive layer in the photosensitive film is laminated.
  • a plate-like moving stage 14 is provided that adsorbs and holds the surface (hereinafter also referred to as “photosensitive layer 12”).
  • 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 device 10 is provided with a stage driving device (not shown) for driving 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 movement 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.
  • 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 process of specifying a used pixel part 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, 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 of the 30 slots is arranged at a predetermined interval in the arrangement direction (a natural number multiple of the long side of the exposure area. They are shifted by a factor of 2). 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 is a light modulation unit that modulates incident light for each pixel part according to image data (modulation for each pixel part).
  • DMD36 (made by Texas Instruments Inc., USA) as a spatial light modulator.
  • This 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 this 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 collimated laser. It is composed of a pair of combination lenses 46 that correct the light amount distribution of light so that it is uniform, and a condensing lens 48 that condenses the laser light whose light amount 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 light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is transmitted by the lens system 50 described above. It is set to be reduced to about 5 ⁇ m!
  • the light modulating means has n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements, and the picture elements can be controlled according to the pattern information As long as it is a thing, it can select suitably according to the objective without a restriction
  • Examples of the spatial light modulation element include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (S LM; Spatial Light Modulator), and transmission by an electro-optic effect.
  • Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
  • the light modulation means preferably includes pattern signal generation means for generating a control signal based on pattern information to be formed.
  • the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
  • control signal can be appropriately selected according to the purpose for which there is no particular limitation.
  • a digital signal is preferably used.
  • the DMD 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 the vertical direction and the horizontal direction.
  • SRAM cell 56 includes hinges and yokes. This is a silicon gate CMO S manufactured on an ordinary semiconductor memory manufacturing line via a supporting column, and is configured monolithically as a whole.
  • each micromirror 58 supported by the support 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 irradiation means can be appropriately selected according to the purpose without any particular limitation.
  • a known light source such as a semiconductor laser or means capable of combining and irradiating two or more lights can be mentioned. Among these, means capable of combining and irradiating two or more lights are preferable.
  • the light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • ultraviolet to visible light, electron beams, X-rays, laser light, etc. are mentioned, and among these, laser light is preferred.
  • Laser that combines two or more lights hereinafter sometimes referred to as “combined laser”) ) Is more preferable. Even when the support is peeled off and the light is irradiated with light, the same light can be used.
  • the wavelength of the ultraviolet to visible light is preferably 300-1, 500 nm, for example. 320-8 OOrnn force is preferred, 330 ⁇ 650mn force is particularly preferred! /, 0
  • the wavelength of the laser beam is, for example, 200 to 1,500 nm force S, more preferably 300 to 800 nm force, more preferably 330 to 500 mn force, and 400 to 450 mn force.
  • 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.
  • 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 pixel part (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 etc. 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 inclination angle ⁇ is ideal, for example, about 0.50 degrees.
  • 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 above angle 0.
  • FIG. 8 is an example of pattern distortion appearing on the surface to be exposed, and "angular distortion" occurs in which the inclination angle of each pixel row projected on the surface to be exposed is not uniform.
  • 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 slit 28 and the photodetector are used as the light spot position detecting means.
  • 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 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. It is specified as ⁇ .
  • 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. It does not participate 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 angle distortion of the light spot sequence on the exposed surface is near the center (c (512 in the figure)) due to the angular distortion.
  • 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 tilt angle ⁇ ′ of the 512th ray array is measured, and the actual tilt 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 ⁇ '.
  • the micro mirror to be used As a form to select the micro mirror to be used.
  • the average value or the median value is set to the actual inclination angle ⁇ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure.
  • the total area of overexposed areas and underexposed areas can be minimized, and the number of pixel units (number of light spots) in overexposed areas and underexposure. Exposure with the same number of pixel units (number of light spots) in the area to be used can be realized. It is possible to achieve exposure that places more emphasis on eliminating overexposed areas, for example, achieving exposure that minimizes the area of underexposed areas and prevents overexposed areas. 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.
  • Pixels used to achieve ideal double exposure by reducing variations in image density and uneven density A method for designating a part will be described.
  • each DMD 36 is an ideal state where there is no mounting angle error or the like of the exposure head 30, a usable 1024 column x 256 row pixel part micromirror can be used. 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, 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 by the DMD 36 of the exposure heads 30 and 30 that is projected onto the exposed surface of the photosensitive material 12 while the stage 14 is 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.
  • Figure 14 shows an example of detecting the position of light spot P (256, 1024) in exposure area 32.
  • 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 shown by the two-dot chain line in FIG. 14, the light spot P (25 The stage 14 is stopped when the light of 6,1024) 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 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.
  • 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 X coordinate of the light spot P (256, 2) of the exposure area 32 and the exposure area are determined when specifying the light spot that forms the shaded area 72 in FIG. 32 of
  • micromirror May be specified as a micromirror that is not used during the main exposure.
  • the area of the over-exposed region with respect to the ideal double exposure is the largest in the connecting region between the heads.
  • a micromirror that is small and does not generate an underexposed region 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, in an ideal state where there is no mounting angle error of the exposure head 30, a usable 1024 column x 256 row pixel part (micrometer) Angle slightly larger than angle ⁇ , which is exactly double exposure using mirror 58)
  • the degree shall be adopted.
  • This angle ⁇ is obtained in the same manner as in the above embodiment (1) using the above equations 1-3.
  • the set inclination angle ⁇ is an angle of about 0.50 degrees, for example. Adopt it. 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 0 within the 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.
  • processing for selecting a micromirror used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel portion selection means.
  • 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 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.
  • the (T + 1) line force on the DMD 36 is also identified as the 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
  • the exposure areas 32 and 32 overlapped exposure areas on the exposed surface formed by multiple exposure heads.
  • the area of the underexposed region is minimized with respect to the ideal double exposure, and an overexposed region is not generated. it can.
  • 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!
  • the same processing was performed, and micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 in FIG. 17 were identified and added as micromirrors that are not used during the main exposure. 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 ⁇ ′.
  • a reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by checking the resolution and density unevenness by visual observation of the reference exposure results. It is included in the scope of the present invention.
  • 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 can be attributed to the positional dependence of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIGS. 5A and 5B, which are single lenses). This is caused by unevenness in the amount of light caused by DMD36 itself.
  • These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.
  • the residual elements of the pattern distortion of these forms are also the above-mentioned angular distortion. 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.
  • Sample output of the result of reference exposure by the reference exposure means confirm variation in resolution and uneven density in the output reference exposure result, and estimate the actual tilt angle. Which analysis to do.
  • the analysis of the result of the reference exposure is a visual analysis by the operator.
  • FIG. 19A and FIG. 19B are explanatory views showing an example of a form in which reference exposure is performed using only (N-1) rows of 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) 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.
  • 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.
  • FIGS. 21A and 21B show an example of a mode in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to IZN rows of the total number of light spot rows. It is explanatory drawing shown.
  • 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 the use of multiple exposure heads, and two adjacent exposure heads in the X-axis direction (for example, exposure heads 30 and 30), each corresponding to 1ZN rows of the total number of light spots
  • 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 development is performed by removing an unexposed portion of the photosensitive layer.
  • the method for removing the uncured region can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a method using a developer.
  • the developer can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include alkaline aqueous solutions, aqueous developers, organic solvents, etc. Among these, weakly alkaline aqueous solutions are mentioned. preferable.
  • Examples of the base component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and phosphoric acid.
  • the pH of the weak alkaline aqueous solution is more preferably, for example, about 9 to about 8 to 12, preferably L1.
  • Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.
  • the temperature of the developer is a force that can be appropriately selected according to the developability of the photosensitive layer. For example, about 25 to 40 ° C. is preferable.
  • the developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.)
  • an organic solvent for example, alcohols, ketones, esters, ethers, amides, latatones, etc.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
  • the curing treatment step can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include full-surface exposure treatment and full-surface heat treatment.
  • Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure promotes curing of the resin in the photosensitive composition forming the photosensitive layer, and the permanent pattern The surface of the coating is cured.
  • a force that can be appropriately selected according to the purpose without particular limitation a UV exposure machine such as an ultra-high pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine, etc. are suitable.
  • the exposure dose is usually 10 to 2,000 mj / cm 2 .
  • Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
  • the heating temperature in the entire surface heating is preferably 120 to 250 ° C, more preferably 120 to 200 ° C. If the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment. If the heating temperature exceeds 250 ° C, the resin in the photosensitive composition may be decomposed, resulting in film quality. May be weak and brittle.
  • the heating time in the whole surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
  • the apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
  • the pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern
  • the pattern is permanently formed on the printed wiring board by the permanent pattern forming method.
  • a pattern can be formed and soldering can be performed as follows.
  • the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), and a solder resist, and prevents external impact and conduction between adjacent electrodes.
  • the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film
  • the wiring may be subjected to impact or bending by an external force.
  • the interlayer insulating film is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board and a build-up wiring board.
  • a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern is used. It can be used suitably for the manufacture of liquid crystal structural members such as filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., especially for the formation of permanent patterns on printed circuit boards. It can be preferably used.
  • the mass average molecular weight (Mw) of the obtained polymer compound was 15,000 as a result of measurement by gel permeation chromatography (GPC) using polystyrene as a standard substance. From the titration with sodium hydroxide sodium salt, the acid value per solid content (content of force lpoxyl group) was 2.2 meqZg.
  • * 1 represents a mixture of the structure represented by the following structural formula (a) and the structure represented by the following structural formula (b).
  • the mass average molecular weight (Mw) of the obtained polymer compound was 15,000 as measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and 7 pieces.
  • the acid value per solid content is 2.3 meqZg based on titration with sodium hydroxide.
  • * 1 represents a mixture of the structure represented by the structural formula (a) and the structure represented by the structural formula (b).
  • 'Irgacure 819 (acylphosphine oxide compound, photopolymerization initiator I— 1)
  • Sensitizer thioxanthone compound represented by the following formula S— 1 (). 6 parts by mass
  • Thermosetting agent (dicyandiamide) ⁇ 0.77 parts by mass • XSK- 500 (20 mass 0/0 methyl E chill ketone solution, manufactured by Japan Synthetic Rubber Co., Ltd., styrene (styrene-butadiene) elastomer I) - - - 50 parts by weight
  • the barium sulfate dispersion was composed of 10 parts by mass of barium sulfate (manufactured by Nigyo Gaku Kogyo Co., Ltd., ⁇ 30) and polymer compound 1 (solid content in the 1-methoxy-2-propanol solution was 30%. 29.2 parts by weight of the solution, 0.2 parts by weight of CI pigment 'Blue 15: 3, 0.05 part by weight of CI pigment' Yellow 185, 40.55 parts by weight of methyl ethyl ketone
  • a motor mill ⁇ -200 manufactured by Eiger
  • a surface of a copper-clad laminate (no through-hole, copper thickness 12 m) on which a wiring was formed as a printed board was prepared by chemical polishing treatment.
  • the photosensitive composition is applied by a screen printing method using a 120 mesh Tetron screen so that the thickness after drying is 30 m, and a hot air circulation type at 80 ° C. for 15 minutes.
  • a photosensitive layer was formed by drying with a dryer, and a photosensitive laminate in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared.
  • the photosensitive laminates were evaluated for the shortest development time, sensitivity, resolution, tackiness, and edge roughness by the following methods. Table 2 shows the results other than the shortest development time.
  • the photosensitive layer in the photosensitive laminate prepared above by using a pattern forming apparatus described below, from 0. lruJ / cm 2 until lOOruJ / cm 2 at 2 1/2 times the interval of light energy of different light Were exposed twice to cure a part of the photosensitive layer.
  • a 1 mass% sodium carbonate aqueous solution at 30 ° C is sprayed on the entire surface of the photosensitive layer on the copper-clad laminate at a spray pressure of 0.15 MPa, twice the minimum development time. After spraying, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured.
  • a sensitivity curve was obtained by plotting the relationship between the amount of light irradiation and the thickness of the cured layer. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 m as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.
  • DMD 36 controlled to drive only 1024 ⁇ 256 6 rows, and optical for imaging the light shown in FIGS. 5A and 5B on the photosensitive film
  • a pattern forming apparatus 10 having an exposure head 30 having a system was used.
  • each exposure head 30 that is, each DMD 36, is slightly smaller 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 having the same vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
  • pcos ⁇ ⁇ (Equation 2)
  • the power shown for every other column of micromirrors 58 that can be used is divided into the exposure pattern by pixel column group A and the exposure pattern by pixel column group B.
  • the exposure pattern is a superposition of these two exposure patterns.
  • a set of a slit 28 and a photodetector is used as the light spot position detecting means, 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.
  • 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 constituting the shaded area 84 were identified and added as micromirrors 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.
  • Tackiness was not recognized at all on the surface of the photosensitive layer.
  • the surface of the photosensitive layer was strong without strong tackiness being recognized.
  • the photosensitive laminate is irradiated with double exposure so that a horizontal line pattern in a direction orthogonal to the scanning direction of the exposure head is formed, and a part of the photosensitive layer is exposed.
  • a pattern was formed on the area in the same manner as (3) in the resolution measurement.
  • any five points of a line with a line width of 50 m were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ⁇ ), and the edge position in the field of view was observed.
  • edge roughness is preferably as the value is small because it exhibits good performance.
  • the photosensitive composition solution obtained in Example 1 was applied to a PET (polyethylene terephthalate) film having a thickness of 16 m, a width of 30 Omm, and a length of 200 m as the support with a bar coater, and 80 ° C.
  • a photosensitive layer having a thickness of 30 m was formed by drying in a hot air circulation dryer.
  • a polypropylene film having a thickness of 20 ⁇ m, a width of 310 mm, and a length of 210 m was formed as a protective film on the photosensitive layer. Were laminated by lamination to produce the photosensitive film.
  • the photosensitive film of the photosensitive film is in contact with the copper-clad laminate, and the protective film on the photosensitive film is peeled off, and a vacuum laminator ( And laminated with a copper clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support).
  • the photosensitive laminate was prepared by laminating the holder) in this order.
  • the crimping conditions were as follows: vacuuming time 40 seconds, crimping temperature 70 ° C, crimping pressure 0.2 MPa, pressurization time 10 seconds.
  • the photosensitive laminate was evaluated for sensitivity, resolution, tackiness, storage stability, and edge roughness.
  • the resolution, tackiness, and edge roughness were evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • a part of the photosensitive layer is cured from the support side in the same manner as in Example 1 by the pattern forming apparatus described in Example 1. I let you. After standing at room temperature for 10 minutes, the support was peeled from the photosensitive laminate, and the amount of light energy required to cure the photosensitive layer was measured in the same manner as in Example 1.
  • the photosensitive film was wound up with a winder to produce a photosensitive film raw roll.
  • the obtained photosensitive film raw roll was slit with a coaxial slitter, and was 300 mm in length and 76 mm in inner diameter.
  • a cylindrical roll core was wound up to 150 m in a width of 250 mm to produce a photosensitive film roll.
  • the photosensitive film roll thus obtained is wrapped in a black polyethylene cylindrical bag (film thickness: 80 m, water vapor transmission rate: 25 gZm 2 '24 hr or less), and a polypropylene bush is pushed into both ends of the winding core.
  • the obtained photosensitive film roll is wrapped in a black polyethylene cylindrical bag (film thickness: 80 m, water vapor transmission rate: 25 g / m 2 '24 hr or less), and a polypropylene bush is pushed into both ends of the winding core. It is.
  • the roll-shaped sample closed at both ends with the bush was stored at 25 ° C. and 55% RH for 40 days, and then observed for end-face fusion, and the storage stability was evaluated according to the following criteria.
  • ⁇ A part of the end face is glossy, and a slight amount of end face fusion occurs (use limit).
  • X State where the entire end face is glossy and a large amount of end face fusion occurs.
  • Example 2 the polymer compound 1 was replaced with the polymer compound 2 obtained in Synthesis Example 2 as shown in Table 1, except that it was replaced with 87.4 parts by mass. Sensitivity, resolution, tackiness, storage stability, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 2 the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by the following formula I 2 and the sensitizer was replaced with 0.6 parts by mass of N-methyl attaridone. , Feeling Evaluation of degree, resolution, tackiness, storage stability, and edge roughness was performed. The results are shown in Table 2.
  • Example 2 the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by the following formulas 1-3 as shown in Table 1. , Tackiness, storage stability, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 2 instead of the pattern forming apparatus, a glass negative mask having a pattern similar to the above was prepared separately, and this negative mask was brought into contact with the photosensitive laminate, and an exposure amount of 40 miZcm 2 was obtained using an ultrahigh pressure mercury lamp. And exposed. Thereafter, the resolution, tackiness, storage stability, and edge roughness were evaluated in the same manner as in Example 2 except that development was performed in the same manner as in Example 2 and the resolution was measured.
  • N 1
  • Example 2 the polymer compound 1 was replaced with a compound represented by the following formula B-1 (solid content: 30% by mass in 1-methoxy-2-propanol solution); 87.4 parts by mass Less than
  • the evaluation of sensitivity, resolution, tackiness, storage stability, and edge roughness was performed in the same manner as in Example 2 except for the above. The results are shown in Table 2.
  • Example 2 the polymer compound 1, epoxy Atari rate (50 mass 0/0 1-methoxy 2-propanol solution of the following formula B- 2, Mw: 8, 000, acid value: 80 mg KOH / g) 52.
  • the sensitivity, resolution, tackiness, storage stability, and edge roughness were evaluated in the same manner as in Example 2 except that the amount was changed to 4 parts by mass. The results are shown in Table 2.
  • Example 8 Film Styrenic polymer 1 1-2 Laser
  • the photosensitive composition, photosensitive film, and photosensitive laminate of the present invention have no edge fusion (end face fusion), are excellent in tackiness and stability of performance over time, and can be easily formed into a film. Since it is possible to efficiently form fine permanent patterns, various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, color filters, pillar materials, rib materials, spacers, It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, and proofs, and can be suitably used particularly for the formation of permanent patterns on printed circuit boards.
  • the method for forming a permanent pattern of the present invention uses the photosensitive laminate of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, and a column. It can be suitably used for the production of liquid crystal structural members such as materials, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., and particularly suitable for forming permanent patterns on printed circuit boards.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition photosensible dont les bords ne collent pas et qui présente d'excellents pouvoir adhésif et stabilité des performances à long terme, pouvant être facilement formée en film, et pouvant être efficacement formée en un motif permanent de haute précision (film protecteur, diélectrique intercouches, motif de résine de protection 'solder resist' etc.); un film photosensible; un produit en couches photosensible; un procédé de formation d'un motif permanent sur le produit en couches photosensible et une carte à circuits imprimés ayant un motif permanent formé par le procédé de formation de motif permanent. La composition photosensible contient un liant, un composé polymérisable, un initiateur de photopolymérisation, un élastomère et un agent de réticulation thermique, le liant contenant un polymère ayant un groupe acide et une liaison éthyléniquement insaturée dans une chaîne latérale.
PCT/JP2006/323318 2006-03-16 2006-11-22 Composition photosensible, film photosensible, produit en couches photosensible, procédé de formation de motif permanent et carte à circuits imprimés Ceased WO2007108171A1 (fr)

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CN102138104B (zh) * 2008-09-04 2013-01-23 日立化成工业株式会社 半导体封装用印刷电路板的保护膜用感光性树脂组合物
JP2014074927A (ja) * 2013-12-26 2014-04-24 Taiyo Holdings Co Ltd 光硬化性樹脂組成物

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JP5475350B2 (ja) * 2009-07-02 2014-04-16 太陽ホールディングス株式会社 光硬化性熱硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP5495297B2 (ja) * 2009-09-01 2014-05-21 太陽ホールディングス株式会社 アルカリ現像性の光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2011095705A (ja) * 2009-09-30 2011-05-12 Fujifilm Corp 感光性組成物、感光性ソルダーレジスト組成物及び感光性ソルダーレジストフィルム、並びに、永久パターン、その形成方法及びプリント基板
JP5523043B2 (ja) * 2009-09-30 2014-06-18 太陽ホールディングス株式会社 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2011215392A (ja) * 2010-03-31 2011-10-27 Fujifilm Corp 感光性組成物、並びに、感光性積層体、永久パターン形成方法、及びプリント基板
JP5757749B2 (ja) * 2010-05-19 2015-07-29 富士フイルム株式会社 重合性組成物
JP5588847B2 (ja) * 2010-11-30 2014-09-10 富士フイルム株式会社 重合性組成物、並びに、これを用いた感光層、永久パターン、ウエハレベルレンズ、固体撮像素子、及び、パターン形成方法
JP2013029556A (ja) * 2011-07-26 2013-02-07 Fujifilm Corp 感光性組成物
JP5523592B2 (ja) * 2013-01-08 2014-06-18 太陽ホールディングス株式会社 光硬化性熱硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
KR101562964B1 (ko) * 2013-09-02 2015-10-26 주식회사 케이씨씨 신뢰성이 우수한 감광성 수지 조성물 및 그 제조방법
CN106233205B (zh) * 2014-04-25 2020-06-23 日立化成株式会社 感光性元件、层叠体、永久掩模抗蚀剂及其制造方法以及半导体封装体的制造方法
JP6204519B2 (ja) * 2016-03-08 2017-09-27 互応化学工業株式会社 感光性樹脂組成物、ドライフィルム、及びプリント配線板
JP6920838B2 (ja) * 2016-03-31 2021-08-18 東京応化工業株式会社 層間絶縁膜形成用組成物、層間絶縁膜及び層間絶縁膜パターンの形成方法、並びにデバイス

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JP2009014745A (ja) 2009-01-22
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CN101401038A (zh) 2009-04-01
JP5144495B2 (ja) 2013-02-13
KR20080103061A (ko) 2008-11-26

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