WO2007102261A1 - 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板 - Google Patents

感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板 Download PDF

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Publication number
WO2007102261A1
WO2007102261A1 PCT/JP2006/323468 JP2006323468W WO2007102261A1 WO 2007102261 A1 WO2007102261 A1 WO 2007102261A1 JP 2006323468 W JP2006323468 W JP 2006323468W WO 2007102261 A1 WO2007102261 A1 WO 2007102261A1
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Prior art keywords
group
exposure
alkyl
photosensitive
photosensitive composition
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PCT/JP2006/323468
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English (en)
French (fr)
Japanese (ja)
Inventor
Kimi Ikeda
Akinori Fujita
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Fujifilm Corporation
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Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Priority to KR1020087024502A priority Critical patent/KR101291638B1/ko
Priority to CN2006800545219A priority patent/CN101438210B/zh
Publication of WO2007102261A1 publication Critical patent/WO2007102261A1/ja

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • 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 uses a photosensitive composition, a photosensitive film, and the photosensitive composition capable of efficiently forming a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern).
  • the present invention relates to a permanent pattern forming method and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.
  • a photosensitive film in which a photosensitive layer is formed by applying a photosensitive composition on a support and drying it 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 imaged to form a pattern, followed by a curing process or the like to form the permanent pattern.
  • the photosensitive film can be preserved in life such as the sensitivity over time. In some cases, the sexiness was lowered.
  • liquid registration type a dispersion in which components other than the thermal crosslinking agent are dispersed; Prepare a liquid in which a thermal cross-linking agent is dispersed or dissolved, and then mix and prepare both. If the so-called two-component type is used, the above-mentioned raw storage stability can be secured, but a one-component type that does not require mixing work is desired.
  • film type a film in which a photosensitive layer made of the photosensitive composition is formed on a support and then laminated on a substrate such as a printed board. Therefore, it is difficult to adopt an aspect like the above liquid cashier type because handling is required.
  • an alkali-soluble binder having an unsaturated double bond a photopolymerizable oxime compound, a sensitizer thixanthone compound, a polymerizable compound, and two or more epoxies.
  • a photosensitive composition containing an epoxy compound containing a xyl group has been proposed (see Patent Documents 2 and 3).
  • a permanent pattern such as a solder resist, a photosensitive composition, a photosensitive film, and the photosensitive composition that have good sensitivity and excellent raw storability also in the film type.
  • the permanent pattern forming method used and the printed circuit board on which the pattern is formed by the permanent pattern forming method have not yet been provided, and the present situation is that further improvement development is desired.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-232264
  • Patent Document 2 Japanese Translation of Special Publication 2002—519732
  • Patent Document 3 JP 2005-182004
  • the present invention has been made in view of the current situation, and it is an object of the present invention to solve the conventional problems and achieve the following objects. That is, the present invention uses a photosensitive composition, a photosensitive film, and the photosensitive composition, which have good sensitivity and excellent raw storage stability, for the purpose of forming a permanent pattern such as a solder resist. Another object is to provide a permanent pattern forming method and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method. Means for solving the problem
  • the photosensitive layer is laminated on a substrate, and 24 ° C 60% RH
  • the thickness of the exposed portion of the photosensitive layer after being sealed for 3 days at 40 ° C is not changed after the exposure and development, and the minimum energy (E) of light used for the exposure is not changed. Fluctuation rate log (E / E) is within ⁇ 0.3 against the minimum energy (E) of light used for the exposure after storage at 24 ° C for 30 minutes
  • the minimum energy (E) of light used for exposure immediately after preparation of the photosensitive layer is 0.1.
  • the photosensitive composition according to the above ⁇ 1> which is ⁇ 200 miZcm 2 .
  • Photopolymerization initiator power The photosensitive composition according to any one of ⁇ 1> to ⁇ 2>, comprising a neutral radical generator.
  • Ar represents either an aromatic group or a heterocyclic group
  • Y 1 represents any one of a hydrogen atom and a monovalent substituent
  • Y 2 is an aliphatic group, aromatic group, heterocyclic group
  • COY 3 CO
  • And 5 represents an aliphatic group, an aromatic group, or a heterocyclic group, and m represents an integer of 1 or more.
  • Ar in the general formulas (A) and (B) is a difference between a phenyl group and a naphthyl group.
  • Ar in the general formulas (A) and (B) is a naphthyl group having a deviation.
  • R is the same as Y 1 in the general formulas (A) and (B).
  • Y 12 represents the same meaning as Y 2 in the general formulas (A) and (B).
  • ⁇ 9> The photosensitive composition according to any one of ⁇ 1> to ⁇ 8>, wherein the binder includes a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain.
  • Noinda One of the above ⁇ 1> to ⁇ 9>, which includes a polymer compound having an acidic group, an aromatic group that may contain a heterocyclic ring, and an ethylenically unsaturated bond in the side chain. It is a photosensitive composition as described in above.
  • the polymer compound has a carboxyl group in a side chain, and the content power of the carboxyl group in the polymer compound is 1.0 to 4. OmeqZg. Of the photosensitive composition.
  • the polymer compound contains 20 mol% or more of a structural unit represented by the following structural formula (I)
  • 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.
  • Polymerizable strength is a photosensitive composition according to any one of the above ⁇ 1> to ⁇ 14> including at least one monomer power having a (meth) acryl group. .
  • the thermal crosslinking agent is 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 power.
  • the thermal crosslinking agent contains an epoxy compound, and the epoxy compound is selected from bisphenol type epoxy resin, novolac type epoxy resin, alicyclic group-containing type epoxy resin, and poorly soluble epoxy resin.
  • the photosensitive composition according to the above item 16> which is at least one kind.
  • ⁇ 18> The photosensitive composition according to any one of ⁇ 1> to 17>, which contains a sensitizer.
  • a photosensitive material comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of ⁇ 1> to 20> on the support. It is a sex film.
  • ⁇ 22> The photosensitive film according to ⁇ 21>, wherein the photosensitive layer has a thickness of 1 to: LOO ⁇ m.
  • ⁇ 23> The photosensitive film according to any one of V and deviations of ⁇ 21> to ⁇ 22>, wherein the support contains a synthetic resin and is transparent.
  • ⁇ 25> The photosensitive film according to any one of ⁇ 21> to ⁇ 24>, which is long and wound in a roll.
  • ⁇ 26> The photosensitive film according to any one of ⁇ 21> and ⁇ 25>, wherein a protective film is provided on the photosensitive layer.
  • the light irradiation unit irradiates light toward the light modulation unit.
  • the light modulation means modulates light received from the light irradiation means.
  • the light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the control generated by the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the pattern forming apparatus according to ⁇ 27> wherein the pattern is modulated according to a signal.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
  • the light modulation means has n pixel portions, and forms any less than n of the pixel portions continuously arranged from the n pixel portions.
  • the pattern forming apparatus according to any one of the above 27> Karaku 28>, which can be controlled according to pattern information.
  • an arbitrary less than n pixel parts arranged continuously among n pixel parts in the light modulation unit are controlled according to pattern information As a result, the light of the light irradiation means power is modulated at high speed.
  • the optical modulation means is a spatial light modulation element.
  • ⁇ 31> The pattern forming apparatus according to ⁇ 30>, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • ⁇ 32> The pattern forming apparatus according to any one of the above ⁇ 29>, ⁇ 31>, ⁇ 31>, wherein the picture element portion is a micromirror.
  • ⁇ 33> The pattern forming apparatus according to any one of the above ⁇ 27>, ⁇ 32>, wherein the light irradiation means can synthesize and irradiate two or more lights.
  • the light irradiating means can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • the light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system 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 items 27> to 33>.
  • the light irradiating means can collect the laser light respectively emitted from the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber.
  • exposure is performed with exposure light having a deep focal depth.
  • the 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.
  • a method for forming a permanent pattern comprising exposing a photosensitive layer formed of the photosensitive composition according to any one of ⁇ 1> to ⁇ 20>.
  • ⁇ 36> The method for forming a permanent pattern according to ⁇ 35>, wherein the photosensitive layer is formed of the photosensitive film according to any one of ⁇ 21> to ⁇ 26>.
  • ⁇ 37> The method for forming a permanent pattern according to ⁇ 36>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
  • the exposure is performed imagewise based on pattern information to be formed.
  • 37. The permanent pattern forming method according to any one of 37.
  • Exposure has a 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 ⁇ 36> and [38], 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 portions by using pixel portion specifying means.
  • 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 the overlapping exposure area on the exposed surface formed by the plurality of exposure heads.
  • the permanent pattern forming method according to ⁇ 39> wherein, among the element parts, the picture element part used for realizing N double exposure in the inter-head connecting region is designated.
  • 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 photosensitive layer due to a deviation in the attachment position or attachment angle of the exposure head is designated. Variations in the resolution and density unevenness of the pattern formed in the head-to-head connection region on the exposed surface are leveled. As a result, 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 portion specifying means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads.
  • the permanent pattern forming method according to ⁇ 40> wherein the pixel part used for realizing N double exposure in an area other than the inter-head connecting area among the picture element parts is designated.
  • the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit overlaps the exposed surface formed by the plurality of exposure heads.
  • 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 light spot position detecting means detects the light spot column direction on the surface to be exposed and the exposure head running direction when the exposure head is tilted based on the detected at least two light spot positions.
  • the actual inclination angle ⁇ 'formed by and the pixel part selection means selects the pixel part to be used so as to absorb the error between the actual inclination angle ⁇ ' and the set inclination angle ⁇ . It is a permanent pattern forming method described in any of 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.
  • T represents a natural number greater than or equal to 2
  • the previous pixel part of the (T + 1) line power m-th line is specified as an unused pixel part, and the unused pixel part is excluded.
  • force ⁇ 48> wherein the pixel part is selected as a use pixel part.
  • connection area between the heads which is the overlapping exposure area on the exposed surface formed by a plurality of exposure heads,
  • the number of pixel units in the overexposed area is equal to the number of pixel units in the underexposed area.
  • N (N ⁇ 1) column-by-column plots for N of N multiple exposures In order to specify the used pixel part in the used pixel part specifying means, out of the usable pixel parts, N (N ⁇ 1) column-by-column plots for N of N multiple exposures.
  • 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 simple single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
  • the above-mentioned pixel part row constituting each 1ZN line is configured.
  • N of the multiple exposures among the usable pixel parts can be specified. The reference exposure is performed using only the pixel part constituting the pixel part column for each 1ZN row, and a simple single-drawn pattern is obtained. As a result, the picture element part in the head-to-head connection region is easily specified.
  • the ⁇ 39> force wherein the used pixel part specifying means includes a slit and a photodetector as the light spot position detecting means, and an arithmetic unit connected to the photodetector as the pixel part selecting means.
  • ⁇ 56> The method for forming a permanent pattern according to ⁇ 39>, wherein the N force is a natural number of 3 or more and 7 or less in N double exposure, and the V of the above ⁇ 39> is 55.
  • 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 outputs light emitted from the light irradiation unit.
  • the permanent pattern forming method according to any one of the above items 39>, 56, 56>, which is modulated in accordance with a generated control 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 generated by the pattern signal generation unit. Modulated according to the control signal.
  • ⁇ 58> The method for forming a permanent pattern according to ⁇ 57>, wherein the light modulation means is a spatial light modulation element.
  • the frame having conversion means for converting the pattern information so that the dimension of the predetermined part of the pattern represented by the pattern information matches the dimension of the corresponding part that can be realized by the designated used pixel part.
  • 60> The method for forming a permanent pattern according to any one of the above.
  • ⁇ 62> The permanent pattern forming method according to any one of the above items 39> Karaku 61>, in which the light irradiation unit can synthesize and irradiate two or more lights.
  • the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed by exposure light having a deep focal depth. .
  • the photosensitive film is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • the light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated with the plurality of laser forces and couples them to the multimode optical fiber.
  • the permanent pack according to any one of 39> Karaku 62> This is a turn formation method.
  • the light irradiation unit can collect the laser beams irradiated with the plurality of laser forces respectively by the collecting optical system and couple the laser light 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.
  • ⁇ 0023> ⁇ 64> The method for forming a permanent pattern according to any one of ⁇ 36> to ⁇ 63>, wherein the photosensitive layer is developed after the exposure.
  • a high-definition pattern is formed by developing the photosensitive layer after the exposure.
  • ⁇ 66> The method for forming a permanent pattern according to ⁇ 65>, wherein after the development, the photosensitive layer is cured.
  • ⁇ 67> A permanent pattern formed by the pattern forming method according to any one of ⁇ 35> and 65. Since the permanent pattern described in the above 67> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, etc., 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.
  • ⁇ 68> The pattern according to ⁇ 67>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in ⁇ 68> 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.
  • a printed circuit board wherein a permanent pattern is formed by the permanent pattern forming method according to any one of ⁇ 36> to ⁇ 66>.
  • 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.
  • the photosensitive composition of the present invention contains a binder, a polymerizable compound, a photopolymerization initiator, a sensitizer, and a thermal crosslinking agent, and further contains other components as necessary.
  • the photosensitive layer formed of the photosensitive composition When the photosensitive layer formed of the photosensitive composition is exposed and developed, The photosensitive layer is laminated on a substrate, sealed at 24 ° C and 60% RH, and stored at 40 ° C for 3 days. The thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development. Fluctuation rate log (E /) of minimum energy (E) of light used for exposure to minimum energy (E) of light used for exposure after storage at 24 ° C for 30 minutes
  • E) is within ⁇ 0.3, and within ⁇ 0.2 is preferred ⁇ 0. Within 15 is more preferred ⁇ 0.
  • the variation rate is not within ⁇ 0.3, the pattern shape and resolution when stored for a long time in a refrigerator or at room temperature will deteriorate.
  • the minimum amount of light used for the exposure is not changed without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development.
  • energy one it is particularly preferred that a 0. l ⁇ 200mi / cm 2 is preferred instrument 0. 2 ⁇ 100mj / cm 2 preferably instrument 0. 5 ⁇ 50mjZcm 2 Ri good to be.
  • 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. .
  • development sensitivity for example, the amount of light energy (exposure amount) used for the exposure when the photosensitive layer is exposed, and the curing generated by the development process following the exposure. It can be obtained from a graph (sensitivity curve) showing the relationship with the layer thickness.
  • the thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure.
  • the development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
  • the thickness of the cured layer is not changed by exposure and development.
  • the method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. (For example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) can be used.
  • the variation rate (%) of the minimum energy of light in light having a wavelength of 400 to 410 nm is preferably within 20%. If the fluctuation rate exceeds 20%, the pattern shape in the plane may vary.
  • the variation rate is measured by sequentially measuring the minimum energy of the light up to the light having a wavelength of 410 nm by shifting the wavelength by lnm. From the difference between the maximum value (Emax) and the minimum value (Emin) of the minimum energy of light, it can be obtained by the following equation.
  • the thickness of the photosensitive layer is not particularly limited, and can be appropriately selected according to the purpose. 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 photopolymerization initiator is not particularly limited.
  • the neutral radical generators preferred are neutral radical generators, acyl acylphosphine compounds, ketal compounds, hydroxyalkyl ketones.
  • oxime derivatives and oxime derivatives are particularly preferred.
  • other photopolymerization initiators may be included.
  • the neutral radical generator is not particularly limited as long as it is neutral, and is appropriately selected from an electron-accepting radical generator and an electron-donating active radical generator. Although it can be used, an electron-accepting active radical generator is preferred because it gives higher sensitivity.
  • the neutral radical generator is a compound that does not contain a basic group such as an amino group or an acidic group such as a carboxylic acid group or a sulfonic acid group in the molecule. It is appropriately selected from those neutralized by bonding with an acidic group or basic group, or by bonding with another acidic molecule or basic molecule.
  • a neutral radical generator monoacylphosphine oxide, bisacylphosphine oxide, triacylphosphine oxide compound, ketal compound, hydroxyalkylketone compound, and oxime derivative are preferable.
  • acyl phosphinoxide compound examples include compounds represented by the following general formula (II).
  • R 11 and R 12 are each independently an alkyl group having 1 to 12 carbon atoms, a benzyl group, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.
  • the group represented by 13 represents a deviation
  • R 11 may be one OR 14 and a group represented by the following formula (i).
  • R 13 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, or a phenyl group substituted 1 to 4 times by a halogen atom.
  • R 14 represents any of an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a benzyl group.
  • Y represents any one of a phenylene group, an alkylene group having 1 to 12 carbon atoms, and a cyclohexylene group
  • X represents an alkylene group having 1 to 18 carbon atoms and a group represented by the following formula (iii) Represents one of the following.
  • Specific examples of the compound represented by the general formula (II) include bis (2,6-dimethoxybenzoyl) phenol phosphine oxide, bis (2,6 dimethoxybenzoyl) (2, 4, 4 Trimethylpentyl) phosphine oxide, bis (2,6 dimethoxybenzoyl) n-butylphosphine oxide, bis (2,6 dimethoxybenzoyl) mono (2 methylpropane-1-yl) phosphine oxide, Bis (2, 6 dimethoxybenzoyl) mono (1-methylpropan-1-yl) phosphine oxide, bis (2, 6 dimethoxybenzoyl) t-butyl phosphinoxide, bis (2, 6 dimethoxybenzo) Cyclohexylphosphine oxide, bis (2,6 dimethoxybenzoyl) octylphosphine oxide, bis (2-methoxybenzoyl) (2-methylpropane 1yl) pho
  • Examples of the ketal compound include Irgacure 651 as benzylmethyl ketal.
  • hydroxyalkyl ketone compound examples include Irgacure 184, Darocur 1173, Irgacure 2959, and Irgacure 127 as hydroxyalkylphenones.
  • the oxime derivative is not particularly limited and may be appropriately selected depending on the purpose, but it is preferably a compound having at least an aromatic group, and the following general formula (A) and the following general formula ( B) is a compound having a partial structure represented by slippage. More preferable. Two or more oxime derivatives may be used in combination.
  • Ar represents either an aromatic group or a heterocyclic group
  • Y 1 represents any one of a hydrogen atom and a monovalent substituent
  • Y 2 represents an aliphatic group, an aromatic group, a heterocyclic group, COY 3 , CO
  • And 5 represents an aliphatic group, an aromatic group, or a heterocyclic group, and m represents an integer of 1 or more.
  • Y 1 is preferably a hydrogen atom, an aliphatic group, or an aromatic group.
  • Examples of Y 2 include an aliphatic group, CO (aliphatic group), CO (aromatic group), CO— (heterocyclic group), CO (aliphatic group), CO (aromatic group), and CO (complex). ring
  • Y 3 and Y 4 are preferably any of an aliphatic group and an aromatic group.
  • the oxime derivative may be a compound in which a plurality of structures represented by the general formula (A) and the general formula (B) are bonded via a linking group.
  • the aliphatic group represents an alkyl group, a alkenyl group, or an alkyl group, each of which may have a substituent.
  • the aromatic group represents an aryl group or a heterocyclic (heterocyclic) group, each of which may have a substituent, and the monovalent substituent may have a halogen atom or a substituent.
  • Examples of the aromatic group include those in which 1 to 3 benzene rings form a condensed ring, benzene And a 5-membered unsaturated ring forming a condensed ring.
  • Specific examples include a phenol group, a naphthyl group, an anthryl group, a phenanthryl group, an indur group, a acenaphthyl group, a fluorenyl group.
  • a group having a naphthyl group which is preferably a group having either a phenol group or a naphthyl group, is particularly preferable.
  • these aromatic groups may have a substituent.
  • a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • the alkyl group, the substituted alkyl group, or the substituents in the substituted alkyl group described later can be used.
  • the heterocyclic (heterocyclic) group includes a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, Isothiazole ring group, indazole ring group, benzisoxazol ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring Group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline
  • heterocyclic groups may have a substituent.
  • substituents include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.
  • the monovalent substituent may have a halogen atom, a substituent, an amino group, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, A cyano group, an alkyl group optionally having a substituent, an alkyl group, an alkyl group; A alkynyl group, an aryl group, and a heterocyclic group are preferred.
  • an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent is preferable. .
  • alkyl group which may have a substituent examples include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include , Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl Group, isopropyl group, isobutyl group, sec- butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group , Cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 20
  • the substituent of the alkyl group may have a substituent which is also a monovalent non-metallic nuclear energy excluding a hydrogen atom, and a preferable example is a halogen atom (one F, — Br, 1 Cl, 1 1), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, arylidothio group, amino group, N-aminorequinoleamino group, N , N dianolenoamino group, N aryleno amino group, N, N diaryl amino group, N-alkyl-N aryl amino group, acyloxy group, rubamoyloxy group, N alkyl rubamoyloxy group, N aralkyl rubamoyloxy group , N, N dialkyl force ruberamoyloxy group, N, N diaryl force ruberamoyloxy group, N, N diary
  • Functional base group (referred to as sulfonate group), alkoxysulfol group, aryloxysulfol group
  • Alkylphosphonate group monoarylphosphono group (one PO H (arvl)) and their
  • a functional base group (referred to as an arylphosphonate group), a phosphonoxy group (one OPO H),
  • a functional base group (referred to as a phosphonatoxy group), a dialkylphosphonoxy group (one OPO H (alk
  • alkyl group in these substituents include the above-described alkyl groups
  • specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, Tolyl group, xylyl group, mesityl group, tame group, chlorophenol group, bromophenol group, chloromethylphenol group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenol group , Cetoxyphenyl group, benzoylphenyl group, methylthiophenyl group, phenylthiol group, methylaminophenol group, dimethylaminophenol group, acetylaminophenol group, carboxyphenyl group Group, methoxypolyphenyl group, ethoxyphenol group, phenoxycarbon group, N-phenol carbamoyl group, cyanophenol group, sulfo group Examples thereof include
  • Examples of the alkenyl group in the substituent include a bur group, a 1-probe group, a 1-butur group, a cinnamyl group, a 2-chloro-1-ethenyl group, and the like.
  • Examples of the alkyl group in the group include an ethur group, a 1 propyl group, a 1-butynyl group, a trimethylsilyl ether group, and the like.
  • heterocyclic group in the substituent examples include a pyridyl group and a piperidinyl group.
  • Examples of the silyl group in the substituent include a trimethylsilyl group.
  • Examples of the acyl group in which the substituent may include an acyl group (I ⁇ CO 2) include those in which R G1 is a hydrogen atom, the above alkyl group, or an aryl group.
  • the R Q1 of Ashiru group (R Q1 CO), hydrogen atom, and the alkyl group include a Ariru group. Of these substituents, more preferred are a halogen atom (one F, —Br, —Cl, ⁇ 1), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N , N dialkylamino group, acyloxy group, N alkyl group ruberamoyloxy group, N aryl group rubermoyloxy group, acyl Mino group, formyl group, acyl group, carboxyl group, alkoxy carbonyl group, aryloxy carbonyl group, strong rubamoyl group, N-alkyl rubamoyl group, N, N dialkyl carbamoyl group, N allyl rubamoyl group, N alkyl N arylcarbamoyl, s
  • examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above.
  • Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, isopropoxymethyl.
  • Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
  • Specific examples include Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phantolyl group, an indur group, an acenaphthyl group, and a fluorenyl group.
  • a phenyl group and a naphthyl group are more preferable.
  • substituted aryl group those having a monovalent non-metallic atomic group group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used.
  • substituent include the aforementioned alkyl group, substituted alkyl group, and those previously shown as substituents in the substituted alkyl group.
  • 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,
  • R ° 2 , R ° 3 , R ° 4 and R ° 5 are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Examples of these can be mentioned. Among these, a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms are more preferable.
  • heterocyclic group examples include the pyridyl group exemplified as the substituent of the substituted alkyl group.
  • substituted oxy group examples include alkoxy groups, aryloxy groups, acyloxy groups, rubamoyloxy groups, N alkylcarbamo groups. Nyloxy group, N allyl force ruberamoyloxy group, N, N dialkyl force ruberamoyloxy group, N, N diaryl force ruberamoyloxy group, N alkyl N allyl force ruberamoyloxy group, alkylsulfoxy group, arlylsulfoxy group, phosphonoxy group, phosphonatoxy group Can be mentioned.
  • alkyl group and aryl group in these include the aforementioned alkyl groups, substituted alkyl groups, and those shown as aryl groups and substituted aryl groups.
  • acyl group (R ° 7 CO 2) in the acyloxy group include those in which R ° 7 is the alkyl group, substituted alkyl group, aryl group, and substituted aryl group listed above. Of these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
  • preferred substituted oxy groups include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, arryloxy group, phenethyloxy group, and force ruboxy group.
  • Shetyloxy group methoxycarbo-lethyloxy group, ethoxycarbo-tinoyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyl group Xyl group, aryloxyethoxyethoxy group, phenoxy group, triloxy group, xylyloxy group, mesityloxy group, mesityloxy group, tamoxy group, methoxyphenyloxy group, ethoxyphenyloxy group, black mouth phenol
  • Examples thereof include an oxy group, a bromophenyl group, an acetyloxy group, a benzoyloxy group, a naphthyloxy group, a phenylsulfooxy group, a phosphonoxy group, and a phosphonatoxy group.
  • R ° 8 NH—, (R 09 ) (R 01 °) N-) including amide groups R ° 8 , R ° 9 and R 010 are monovalent nonmetallic atoms excluding hydrogen atoms
  • a group of groups can be used. Note that 9 and R 1 () may combine to form a ring.
  • Preferred examples of the substituted amino group include N alkylamino group, N, N dialkylamino group, N arylamino group, N, N dialylamino group, N alkyl—N arylamino group, acylamino group, N alkyl acylamino group, N aryl group.
  • alkyl groups and aryl groups include those described above as alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups, including acylamino groups, N alkylalkylamino groups, and N arylarylamino groups.
  • R ° 7 of definitive Ashiru group R ° 7 CO
  • N alkylamino group, N, N dialkylamino group, N arylamino group, and acylamine group are more preferable.
  • the preferred substituted amino group include methylamino group, ethylamino group, jetylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.
  • substituted sulfo - Le group (11 SO -) as the 11 consists over-valent non-metal atomic group
  • the basic one can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group.
  • alkyl group and aryl group in these include the aforementioned alkyl group, substituted alkyl group, and those shown as aryl group and substituted aryl group.
  • Specific examples of such a substituted sulfol group include a butyl sulfol group, a phenol sulfol group, and a black-ended phenol sulfol group.
  • the sulfonate group (one SO ) is a conjugate base anion of the sulfo group (one SO H).
  • Counter-ions include those generally known, ie, various hums (ammo-ums, sulfomes, phospho- ummes, jordanums, azimuths). Um), and metal ions (Na +, K +, Ca 2+ , Zn 2+ etc.).
  • the substituted carbo group (R 13 — CO 2), a group in which 13 is a non-valent nuclear energy can also be used.
  • the substituted carbo group include formyl group, acyl group, carboxyl group, alkoxy carbo group, aryloxy carbo ol group, force rubamoyl group, N alkyl force rubamoyl group, N, N dialkyl force rubamoyl.
  • alkyl group and aryl group in these include the aforementioned alkyl group, substituted alkyl group, and those shown as aryl group and substituted aryl group.
  • substituted carbo groups include formyl, acyl, carboxyl, alkoxy carbo, aryloxy carbo, rubamoyl, N alkyl rubamoyl, N, N dialkyl-powered rubermoyl group and N-aryl-powered rubermoyl group may be mentioned, and even more preferred are formyl, acyl, alkoxycarbol and aryloxycarbol.
  • preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxy carbo ol group, ethoxy carbo ol group, aralkyl carboxy group, dimethylamino phen tert carbo ol group.
  • R 14 SO can use a group R 14 consists of over-valent non-metal atomic group.
  • Preferable examples include alkylsulfiel group, arylsulfyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N dialkyl sulfinamoyl group, N arylsulfinamoyl group, N, N diarylsulfur group.
  • Examples include a finamoyl group and an N-alkyl-N arylsulfinamoyl group.
  • alkyl group and aryl group in these include the above-described alkyl groups, substituted alkyl groups, and those shown as aryl groups and substituted aryl groups. Of these, more preferred examples include an alkyl sulfiel group and an aryl sulfiel group. Specific examples of such a substituted sulfiel group include a hexyl sulfiel group, a benzyl sulfiel group, a tolyl sulfyl group, and the like.
  • the substituted phosphono group means a group in which one or two of the hydroxyl groups on the phosphono group are substituted with other organic oxo groups.
  • Preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group. Group, alkylaryl phosphono group, monoalkyl phosphono group and monoaryl phosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a jetyl phosphono group, a dibutyl phosphono group, and a diphenyl phosphono group.
  • the phosphonato group (—PO 2 H—, —PO 2 H_) is the phosphono group (—PO 2 H).
  • Such counter cations include those commonly known, ie, various hums (ammo-ums, sulfo-ums, phosphor-ums, jordanums, azimuths). beam, etc.), as well as metal ions (Na +, K +, Ca 2 +, Zn 2+ etc.).
  • the substituted phosphonate group is a conjugated base anion group obtained by replacing one hydroxyl group with an organic oxo group among the above-mentioned substituted phosphono groups.
  • Specific examples thereof include the above-described monoalkylphosphono groups (one PO H (alkyl)), monoarylphosphono group (one PO H (aryl)) conjugate base
  • the oxime derivative is more preferably a compound represented by any of the following general formulas (C) and (D).
  • R is the same as Y 1 in the general formulas (A) and (B).
  • Y 12 represents the same meaning as Y z in the general formulas (A) and (B).
  • R is preferably a hydrogen atom or an aliphatic group, particularly a carbon atom.
  • Aliphatic groups having 1 to 10 children are preferred.
  • Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, an octyl group, and an aryl group.
  • Y 12 is particularly preferably —CO— (aliphatic group).
  • the aliphatic group in ⁇ 12 is preferably an aliphatic group having 1 to 10 carbon atoms.
  • methyl group, ethyl group, propyl group, butyl group, octyl group, cyclohexyl group, benzyl group and the like are preferable.
  • oxime derivative examples include, for example, compounds disclosed in JP-A-2001-233842, JP-T-2004-534797, JP-T-2002-519732, etc. And compounds represented by the following structural formulas.
  • R represents any one of n-C H, n-C H, camphor and p-CH C H.
  • R represents either n-C H or p-CH C H.
  • the content of the neutral radical generator in the photosensitive composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and 0.5 to 15% by mass. Further preferred is 1 to 10 parts by mass.
  • the other photopolymerization initiator has the ability to initiate polymerization of the polymerizable compound.
  • Power that can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has, for example, those that are sensitive to visible light from the ultraviolet region are preferred.
  • Photoexcited sensitizers It may be an activator that produces some kind of action and generates an active radical, and may be an initiator that initiates cationic polymerization according to the type of monomer.
  • the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).
  • Examples of the other photopolymerization initiators include, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexyl biimidazole, organic peroxides, thiols.
  • Examples thereof include compounds, ketone compounds, ataridin compounds, metacenes and the like. Among these, ketone compounds and atrazine compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate.
  • halogenated hydrocarbon compound having the triazine skeleton examples include, for example, a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), British Patent 1388 492 Compounds described in JP-A-53-133428, compounds described in German Patent No. 3337024, J. Org. Chem. By FC Schaefer et al .; 29, 1527 (1964), Compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, compounds described in US Pat. No. 4212976 , Etc.
  • Examples of the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969) include, for example, 2 phenol-4, 6 bis (trichloromethyl) -1, 3, 5 Triazine, 2 — (4 Chlorphenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (4 Tolyl) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2— (4-Methoxyphenyl) —4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (2,4 Dichlorophenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2, 4, 6 Tris (trichloromethyl) -1,3,5 Triazine, 2-Methyl-4,6 Bis (trichloromethyl) -1,3,5 Triazine, 2-N-nor 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine
  • Examples of the compound described in the British Patent 1388492 include 2-styryl 4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (4-methylstyryl) -4, 6 — Bis (trichloromethyl) -1,3,5 triazine, 2- (4-methoxystyryl) — 4, 6-bis (trichloromethyl) -1,3,5 triazine, 2 -— (4-methoxystyryl) — 4 Amino — 6 Trichloromethyl-1, 3, 5 Triazine.
  • Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (4-Ethoxy-naphtho-1-yl) -4,6 bis ( ⁇ lichloromethyl) -1,3,5 ⁇ riadine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4 , 6 bis (trichloromethyl) 1, 3, 5 triazine, 2- (4, 7 dimethoxy mononaphtho 1-yl) 4, 6 bis (trichloromethyl) — 1, 3, 5 ⁇ lyazine, and 2— (acenaphth ⁇ -5-yl) -4,6 bis (trichloromethyl) -1,3,5 triazine.
  • Examples of the compound described in the specification of German Patent 3337024 include, for example, 2— (4-stilinorefenenore) 4, 6 bis (trichloromethinole) -1,3,5 triazine, 2- (4— (4-methoxystyryl) phenol) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (1-naphthyl vinylenephenol) 1,4 bis (trichloromethyl) 1,3 , 5 Triazine, 2 Chlorostyryl 1,4,6 Bis (trichloromethyl) 1, 3,5 Triazine, 2— (4 Thiophene-1,2 Bilenphenol) 1,4,6 Bis (trichloromethyl) 1, 3, 5— Triazine, 2— (4 thiophene, 3 bilenfir), 1, 4, 6 bis (trichloromethyl), 1, 3, 5 Triazine, 2— (4 furan, 1 bilene) 1,6 bis (trichloromethyl) 1, 3,5 triazine, and 2—
  • Examples of the compound described in J. Org. Chem .; 29, 1527 (1964) by FC Schaefer et al. include 2-methyl-4,6 bis (tribromomethyl) -1,1,3,5 Triazine, 2, 4, 6 Tris (tribromomethyl) 1, 3, 5 Triazine, 2, 4, 6 Tris (dibromomethyl) 1, 3, 5 Triazine, 2 Amino 1 4-Methyl 6 Tri (bromomethyl) 1 13, 5 Triazine and 2-methoxy-4-methyl-6 trichloromethyl-1,3,5 triazine.
  • Examples of the compound described in JP-A-62-58241 include 2- (4-phenylethyl-sulfur) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (4-Naphthyl 1-etulfur-loop 4, 6 bis (trichloromethyl) 1, 3, 5 triazine, 2— (4— (4 trityl) phenol) — 4, 6 bis (trichloromethyl) —1 , 3, 5 — Triazine, 2- (4— (4-Methoxyphenyl) ether furol) 4, 6—Bis (Trimethylromethyl) 1, 3, 5 Triazine, 2— (4— (4-Isopropylphenol) -Luture) Hue) 4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— (4— (4 ethyl fuse-rucheur) Grav) 1, 4, 6 Bis (trichloromethyl) 1, 3 , 5 Triazines.
  • Examples of the compounds described in JP-A-5-281728 include 2- (4 trifluoromethylphenol) -4,6 bis (trichloromethyl) -1,3,5 triazine, 2- (2, 6—Difluorophenol) —4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2- (2, 6 Dichlorophenol) — 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine 2- (2, 6 dibromophenol) 1,6,6 bis (trichloromethyl) 1, 3, 5 triazine and the like.
  • Examples of the compound described in JP-A-5-34920 include 2,4bis (trichloromethyl) -6- [4- (N, N-diethoxycarbomethylmethylamino) -3-bromophenol. ] — 1, 3, 5 triazine, trihalomethyl-s triazine compounds described in US Pat. No. 4,239,850, and 2, 4, 6 tris (trichloromethyl) —s triazine, 2- (4-chloro) (Fuel) 4, 6-bis (tribromomethyl) s triazine.
  • Examples of the compounds described in the above-mentioned US Pat. No. 4,212,976 include compounds having an oxadiazole skeleton (for example, 2 trichloromethyl-5 phenyl 1,3,4-oxadiazole, 2 trichloromethyl).
  • Examples of the hexarylbiimidazole include 2, 2 ′ bis (2-clonal ring) 4, 4, 5, 5, 5, monotetraphenyl biimidazole, 2, 2, 1 bis ( o Fluorophore) —4, 4 ,, 5, 5, — Tetraphenol biimidazole, 2, 2, — Bis (2 bromophenol) — 4, 4, 4, 5, 5, monotetraphenol biimidazole, 2 , 2, 1 bis (2, 4 dichlorophenol) 4, 4 ,, 5, 1 tetraphenyl biimidazole, 2, 2, 1 bis (2 x 2 mouthpiece) —4, 4, 5, 5, 1-tetra (3-methoxyphenol) biimidazole, 2, 2, 1-bis (2-cyclophenol) 1, 4, 4, 5, 5, 5, 5, 1-tetra (4-methoxyphenyl) biimidazole, 2, 2, 1 bis (4-methoxyphenyl) 1, 4, 4, 5, 5, 1, tetraphenyl biimidazole 2, 2, 1, bis (2, 4 dichlorophenol
  • the biimidazoles are easily synthesized by methods disclosed in Bull. Chem. Soc. Japan, 33, 565 (1960), and J. Org. Chem, 36 (16) 2262 (1971), for example. be able to.
  • organic peroxide examples include 3,3 ', 4,4'-tetra (t-butylperoxycarbol) benzophenone.
  • Examples of the thioi compound include 2-benzomethylene 3-methylnaphthothiazoline.
  • Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-clobenzobenzoneone.
  • Atalidine complex examples include 9 phenyllacridin, 1,7 bis (9,9 'aterigidyl) heptane, and the like.
  • the meta-port mosses such as bis (7 5 -2, 4 cyclopentadiene one 1-I le?) - bis (2, 6-difluoro one 3- (IH-pyrrol-one 1-I le) Phenyl) titanium, ⁇ 5 —cyclopentagel- 6- thamale iron (1 +) -hexafluorophosphate (11), and the like.
  • polyhalogen compounds such as vinyl glycine (for example, carbon tetrabromide, felt rib momethyl sulfone, phenyl trichloromethyl ketone, etc.), amines (E.g., 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid ⁇ -butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2 phthalimidoethyl, 4 dimethylaminobenzoic acid 2-methacryloyloxy Ethyl, pentamethylenebis (4-dimethylaminobenzoate), 3-dimethylaminobenzoic acid phenethyl, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2 chloro 4 dimethylaminobenzaldehyde, 4 dimethyla
  • the content of all photopolymerization initiators including the neutral radical generator in the photosensitive layer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass. 0.5 to 15% by mass is particularly preferable.
  • a sensitizer may be included.
  • the sensitizer improves the minimum energy (sensitivity) of the light when the photosensitive layer is exposed and developed without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferable to use in combination.
  • the sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light and visible light laser).
  • the light irradiation means for example, visible light, ultraviolet light and visible light laser.
  • the sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals and It is possible to generate useful groups such as acids.
  • substances for example, radical generator, acid generator, etc.
  • energy transfer, electron transfer, etc. for example, energy transfer, electron transfer, etc.
  • the sensitizer is at least selected from a condensed ring compound, an aminophenol ketone compound, a polynuclear aromatic, an acid nucleus, a basic nucleus, and a fluorescent brightener nucleus. 1 type may be included and another sensitizer may be included as needed.
  • a hetero-fused compound and an amaminobenzophenone compound are more preferred in terms of improving sensitivity, and a hetero-fused compound is particularly preferred.
  • a hetero condensed ring compound is preferable as a compound (condensed ring compound) in which an aromatic ring or a heterocyclic ring is condensed.
  • the hetero-fused ring system compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring.
  • Examples of the hetero-fused ring compound include a hetero-fused ketone compound.
  • the hetero-fused ketone compounds attaridone compounds and thixanthone compounds are more preferable, and thixanthone compounds are particularly preferable.
  • hetero-fused ketone ketone compound examples include, for example, attaridone compounds such as attaridone, chloroacridone, N-methyl attaridone, N butyl attaridone, N butyl chloro attaridone, thixanthone, Thioxanthone compounds such as isopropyl thixanthone, 2,4 jetylthioxanthone, 1 chloro-4 propyloxy thixanthone, and QuantacureQT X; (1-Pyrrolidyl) coumarin, 3 Benzyl 7-Jetylaminocoumarin, 3- (2-Methoxybenzoyl) 7 Jetylaminocoumarin, 3 1 (4-Dimethylaminobenzol) 1 7-Jetylva Minocoumarin, 3,3, 1 carborubis (5, 7-di-n-propoxycoumarin), 3, 3, 1 carbo- Bis (7-jetylaminocoumarin), 3-benzoyl 7-
  • polynuclear aromatics for example, pyrene, perylene, triphenylene
  • xanthenes for example, fluorescein, eosin, erythrucine, rhodamine B, rose bengal
  • cyanines for example, indocarbocyanine, Thiacarbocyanine, oxacarbocyanine
  • merocyanines eg, merocyanine, carbomerocyanine
  • thiazines eg, thionine, methylene blue, toluidine blue
  • anthraquinones eg, anthrax
  • squalium for example, squalium
  • the content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, based on all components of the photosensitive composition for photosensitive film. 05-1% by mass is particularly preferred.
  • the sensitivity When the content is less than 0.01% by mass, the sensitivity may be lowered, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.
  • the mass ratio of the sensitizer in the photosensitive composition to the content of the photopolymerization initiator is:
  • the mass ratio of the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may decrease and the change in sensitivity over time may be adversely affected.
  • the combination of the sensitizer and the photopolymerization initiator is particularly preferably a combination of a thixanthone compound and an oxime derivative from the viewpoint of increasing sensitivity.
  • the oxime derivative may be used in combination with another neutral radical generator and a photopolymerization initiator compound containing a small amount of an aminoalkyl group or aminophenyl group in a partial structure.
  • a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain is preferable.
  • the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and the carboxyl group is preferable from the viewpoint of obtaining raw materials.
  • the binder 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
  • Epoxy groups for example, epoxy groups such as cyclohexenoxide in the same molecule
  • (meth) atariloy examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an alkyl 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 More preferably, the polymer compound is selected from any of those obtained by adding a carboxyl group-containing polymerizable compound to a part or all of the cyclic ether group of the polymer compound.
  • the addition reaction between the acidic group and the compound having a cyclic ether group is carried out in the presence of a catalyst.
  • the 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. Preferred compounds.
  • 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, benzoxazole 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, for example, 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 examples 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.
  • N alkylamino group N, N dialkylamino group, N allylamino group, N, N dialylamino group, N-alkyl-N allylamino group, acyloxy group, carbamoyloxy group, N alkyl force ruvamoyloxy group, N allyl force rubermoyl Oxy group, N, N dialkyl force ruberamoyloxy group, N, N diaryl force rubermoyloxy group, N-alkyl-N allyl force ruberamoyloxy group, alkylsulfoxy group, allylsulfoxy group, acyl thio group, acylamino group, N— Alkyl acylamino group, N arylyl silamino group, ureido group, N 'alkyl ureido group, N, N, monodialkyl ureido group, N, aryl ureido group,
  • sulfonate group alkoxysulfol group, aryloxysulfol group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N dialkylsulfinaimoyl group, N Lillesulfinamoyl group, N, N dialylsulfinamoyl group, N-alkyl-N arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N dialkylsulfamoyl group, N 1 sulfamoyl group, N, N dialyl sulfamoyl group, N alkyl — N allylsulfamoyl 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)
  • alkylphosphonate 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)
  • a group (referred to as an aryl phosphonatoxy group), a cyan group, a nitro group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, a 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-ester group.
  • alkyl group in the substituent examples include an ethur group, 1 propynyl Group, 1-buturyl group, trimethylsilylethynyl group and the like.
  • Examples of 1 of the acyl group (R ⁇ CO 2) in the substituent include a hydrogen atom, the aforementioned alkyl group, and aryl 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 ruberamoyloxy group, N-allyl force ruberamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbol group, force rubermoyl group, N alkyl force Rubamoyl group, N, N dialkyl-force rubamoyl group, N-aryl force-rubamoyl group, N-alkyl N-aryl force-rubamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N dialkyls
  • 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.
  • aryl group examples 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 A group consisting of a monovalent nonmetallic atomic group other than a hydrogen atom as a substituent on a carbon atom The thing which has is mentioned.
  • 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.
  • the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a tamphenol group, a black-mouthed phenyl group, a bromophenol group, a fluorophenol group, Chloromethylphenyl group, trifluoromethylphenol group, hydroxyphenol group, methoxyphenyl group, methoxyphenyl group, aryloxyphenyl group, phenoxyphenyl group, methylthiophene Group, tolylthiophene group, ethylaminophenol group, germanaminophenol group, morpholinophenol group, acetyloxyphenyl group, benzoyloxyphenyl group, N cyclohexylcarbamoyloxyphenyl group , N-phenylcarbamoyl phenyl group, acetylaminophenol group, N-methylbenz
  • 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, a substituted aryl group and the like can be mentioned. 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, and a branched alkyl group
  • a cyclic alkyl group is preferred.
  • alkenyl group and alkyl group! / Preference is given to the above-mentioned alkenyl group and alkyl group! /, And specific examples thereof include a vinyl group, a 1-port perl group, a 1-butul group, a 1 pentale group, and a 1-hexyl group.
  • heterocyclic group include a pyridyl group exemplified as a substituent for a substituted alkyl group.
  • R 6 0 has 6 include Chino a group comprising a monovalent nonmetallic atom group exclusive of a hydrogen atom.
  • 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 7 is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group exemplified in the above examples.
  • 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, carboxy Tyroxy group, methoxycarbo-lethyloxy group, ethoxycarbo-rethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxy group, ethoxyethoxychetoxy group, morpholinoethoxy group, morpholinopropyloxy group, aralkyloxyethoxy group, Phenoxy group, triloxy group, xylyloxy group, mesityloxy group, mesityloxy group, tamoxy group, methoxyphenyl group, ethoxyphenyl group, chlorophenol group, bromophenol group, acetyloxy group, benzoyloxy group,
  • Examples of the amino group (R 8 NH-, (R 09 ) (R 01 °) N-) that may contain an amide group include, for example, R ° 8 , R 9 , and R G1 are monovalent non-excluding hydrogen atoms. Examples include groups that can also be metal atom groups. 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, an N alkyl-N arylamino group, an acylamino group, an N-alkyl acylamino group, N arylamine, ureido, N 'alkylureido, ⁇ ,, N, dialkylureido, N'-arylureido, ⁇ ,, N, diarylureido, N' Alkyl—N′—aryl ureido group, N alkyl ureido group, N aryl ureido group, N, monoalkyl N alkyl ureido group, N′—alkyl—N aryl ureido group, N ,, N′—dialkyl—N Alkylureido group, N, monoalkyl N alkyl ureido group
  • alkyl group and aryl group in these examples thereof include a reel group and a 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 (SO-) include a 11 -valent non-metallic 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.
  • alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
  • sulfo group examples include a butyl sulfo group, a phenol sulfo group, and a closed-end phenol sulfo group.
  • the sulfonate group (one SO-) is a conjugate 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 13 is a non-valent atomic group having a valence of ⁇ .
  • 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.
  • the alkyl group and aryl group in these are the aforementioned alkyl groups. 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.
  • Examples of the sulfiel group (R 14 —SO 2) include those having a group consisting of a “-valent non-metallic atomic group”.
  • 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 other organic oxo groups.
  • dialkylphosphono group, diarylphosphono group, alkyloxy group are preferable.
  • dialkylphosphono groups and diarylphosphono groups are more preferred.
  • More preferred specific examples of the phosphono group include a jetyl phosphono group, a diptyl phosphono group, and a diphenyl phosphono group.
  • the phosphonato group (—PO 1 H, —PO 2 H—) is a phosphono group (—PO 2
  • 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 an organic oxo group.
  • 1 PO H (alkyl) a conjugated salt of a monoarylphosphono group (—PO H (aryl))
  • the aromatic group comprises one or more radically polymerizable compounds containing an aromatic group and, if necessary, one or more other radically polymerizable compounds as a copolymerization component. It can be manufactured legally.
  • 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 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, and valent anthracene.
  • the linking group of L may have a substituent.
  • substituents include the halogen atom, hydroxyl group, carboxyl group, sulfonate group, nitro group, cyan group, amide group, amino group described above.
  • the structural formula (A) is preferable in terms of sensitivity.
  • those having a linking group that are preferred from the viewpoint of stability are the organic groups having 1 to 4 carbon atoms.
  • the Kiren group is preferred in terms of removal (developability) of non-image areas.
  • the compound represented by RR 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 the structural unit of the following structural formula (II). Of these, the structural unit of the structural formula (I) is preferred from the viewpoint of storage stability.
  • 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, the storage stability is low. If it exceeds 45 mol%, the developability may decrease.
  • 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 R is independently
  • X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R 4.
  • Z represents an oxygen atom, a sulfur atom, —N—R 4 or a phenylene group.
  • R 4 represents a hydrogen atom or a monovalent organic group.
  • each R independently represents, for example, a hydrogen atom, a hydrogen atom that may have a substituent or an alkyl group, and a methyl group that are 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.
  • examples of R to R include 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 for introducing an ethylenically unsaturated bond represented by the structural formula (III) into the side chain is not particularly limited.
  • a polymer compound containing a carboxyl group in the side chain and ethylene It can be obtained by addition reaction with a compound having a polymerizable 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, and for example, a compound represented by the following structural formula (VI) and (VII) The compounds represented by
  • 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. It 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.
  • tertiary amines such as triethylamine and benzylmethylamine
  • quaternary ammonia such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride. It 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
  • the structural unit having an ethylenically unsaturated bond in the side chain is not particularly limited.
  • a structure represented by the following structural formula (i), a 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) to the structure represented by 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, and preferably 1.5 to 3. Omeq / g. When the content is less than 1. Omeq / g, the developability may be insufficient, and when it exceeds 4. OmeqZg, image strength damage may be easily caused by alkaline water development.
  • the polymer compound of the present invention may be copolymerized with another radical polymerizable compound in addition to the above-mentioned 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 esters such as alkyl acrylate, methacrylate esters such as aryl acrylate, alkyl methacrylate, styrene such as aryl methacrylate, styrene, alkyl styrene, alkoxy
  • acrylic esters such as alkyl acrylate, methacrylate esters such as aryl acrylate, alkyl methacrylate, styrene 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 an alkyl group having 1 to 20 carbon atoms are preferred.
  • 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 methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monometatalate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate.
  • aryl methacrylate examples include phenyl methacrylate and uddernore methacrylate. Rate, naphthylmetatalate 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, 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. Examples thereof include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone.
  • 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. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less. Yes.
  • 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. If the solid content is less than 5% by mass, the film strength of the photosensitive layer may be weakened, and the tackiness of the surface of the photosensitive layer may be deteriorated. If it exceeds 80% by mass, The exposure sensitivity may decrease.
  • the polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, but has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure.
  • at least one selected from monomers having a (meth) acryl group is preferable.
  • the “polymerizable compound” does not include a polymerizable compound that can be contained in the binder.
  • 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 deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
  • the 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 film, it is possible to develop it.
  • 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 as long as no adverse effect is exerted.
  • Examples of the epoxy compound having at least two oxysilane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, an isocyanurate skeleton, etc.
  • Heterocyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries", “ALALDITE PT810; manufactured by Ciba Special Chemicals”, etc.), 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, cresol novolac type epoxy resin, halogenated epoxy resin (for example, , Low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novola Click type such as epoxy ⁇ ), ⁇ Li Le-containing bisphenol A type epoxy ⁇ , tris phenol methane type epoxy ⁇ , Diphenyldimethanol type epoxy resin, phenol biphenol type epoxy resin, dicyclopentagen type epoxy resin (“HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.”), glycidylamine Type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidyl dilin, trig
  • Epoxy resin, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy I do not like is limited to the force mentioned sheet ⁇ . These epoxy resins may be used alone or in combination of two or more.
  • an epoxy compound having at least two epoxy groups having an alkyl group at the ⁇ -position in one molecule may be used.
  • 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 is particularly preferable.
  • 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 epoxy compound containing an epoxy group having an alkyl group at the 13-position is based on the total amount of the epoxy compound contained in the photosensitive composition.
  • the ratio power of the / 3-alkyl-substituted glycidyl group in all epoxy groups is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the j8-alkyl-substituted glycidyl group is not particularly limited and can be appropriately selected according to the purpose.
  • j8-methyldaricidyl group 13-ethyldaricidyl group, 13 propylglycidyl group, 13- And a butyldaricidyl group.
  • a j8-methyldaricidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive composition and the ease of synthesis.
  • 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 may 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 picrohydrin, ⁇ -propylepib mouth mohydrin, ⁇ -propinoreepifluorohydrin; ⁇ -butinoreepichlorohydrin, j8-butylepib mouth mohydrin, and j8-bub such as 8-butylepephrohydrin Chillephalohydrin; 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 / 3-position include bisphenol A di- 13-alkyl glycidyl ether, bisphenol F di- ⁇ -alkyl glycidyl ether, bisphenol.
  • G of S 13 Bisphenol compounds such as alkyl glycidyl ethers / 3 Alkyl glycidyl ethers; Biphenols of G 13 Alkyl glycidyl ethers, tetramethyl biphenols of G 13 Alkyl glycidyl ethers of G of 13 phenols Ether: dihydroxynaphthalene diol / 3 alkyl glycidyl ether, binaphthol diol 13 alkyl glycidyl ether 13 alk glycidyl ether; phenol-formaldehyde polycondensate polycondensate 13 alkyl glycidyl ethers; poly 13 alkyl glycidyl ethers of monoalkyl substituted phenol-formaldehyde polycondensates of 1 to 10 carbon atoms such as poly 13 alkyl glycidyl ethers of crezo-ru formaldehyde polyconden
  • 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.
  • An epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the j8 position can be used in combination.
  • the skeleton of the epoxy compound is selected from bisphenol type epoxy resin, novolac type epoxy resin, alicyclic group-containing type epoxy resin, and poorly soluble epoxy resin. Preferred at least one kind.
  • Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxeta-lmethoxy) methyl] ether, 1, 4-bis [(3-methyl-3-oxeta-lmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxeta-lmethoxy) methyl] benzene, (3-methyl-3-oxeta-l) methyl acrylate , (3 Echiru 3 Okiseta -) methyl Atari rate, (3-methyl 3-Okiseta -) methyl meth Tari rate, (3 Echiru 3 Okiseta - Le) methylate Rume Tatari rate or oligomers thereof or copolymers In addition to these polyfunctional oxetanes, compounds having an oxetane group, novolac resin, poly (p-hydroxy
  • an amine compound for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N dimethylbenzylamine, 4-methoxy-N, N dimethylbenzylamine, 4-methyl N, N dimethylbenzylamine, etc.
  • quaternary ammonium salt compounds eg, triethylbenzyl ammonium chloride
  • Block isocyanate compounds for example, dimethylamine
  • imidazole derivative bicyclic amidine compounds and their salts for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl
  • Imidazole 2 phenol imidazole, 4 phenol imidazole, 1-cyanoethyl-2 phenol imidazole, 1- (2 cyanoethyl) -2 ethyl-4-methylimi
  • 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 isocyanates. It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing a monoto group.
  • 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
  • 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 (eg, isopropanol, tert-butanol, etc.), ratatas (eg, ⁇ -strength prolatatum, etc.), phenols (eg, 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-hydroxyquinolyl) 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 examples include alcohol
  • 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.
  • the solid content of the thermal crosslinking agent in the solid content of 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, improvement in the film strength of the cured film is not observed, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.
  • the other components include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other assistants.
  • Agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • properties such as stability, photographic properties, and film properties of the intended photosensitive film.
  • 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 nanodroquinone, t-butylcatechol, pyrogallol, 2-hydride.
  • the content of the thermal polymerization inhibitor is preferably from 0.001 to 5 mass%, more preferably from 0.005 to 2 mass%, based on the polymerizable compound of the photosensitive layer. 01 to 1% by mass is particularly preferred.
  • the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.
  • the plasticizer should be added to control the film physical properties (flexibility) of the photosensitive layer.
  • plasticizer examples include dimethyl phthalate, dibutyl phthalate, diisopropyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diphenyl phthalate.
  • Phthalic acid esters such as ril phthalate and octyl capryl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl dallicose phthalate, ethino retino eno ethino reglycolate, methyl phthal yl acetyl glycolate Glycol esters such as norephthalino lebutinoglycolate and triethylene glycol dicabrylate; tricresyl phosphate, triphenyl Phosphate esters such as sulfate; 4 Amides such as toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl seba Aliphatic dibasic acid esters such as keto, dibutyl sebacate, dioc
  • 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 color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during the formation of a permanent pattern. Different forces depending on the type of facial material Generally 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.
  • the surface hardness of the permanent pattern is improved, or Inorganic pigments and organic fine particles can be added for the purpose of keeping the linear expansion coefficient low or keeping the dielectric constant and dielectric loss tangent of the cured film itself low.
  • 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 size of 0.01 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 1 to 60% by mass.
  • the addition amount is less than 1% by mass, the linear expansion coefficient may not be sufficiently reduced.
  • the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, 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 known adhesion promoter may be used for each layer.
  • adhesion promoter examples include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3 morpholinomethyl-1 phenyroot triazole-2 thione, 3—morpholinomethyl 5 phenyloxadiazole 2 thione, 5 amino-3 morpholinomethyl thiadiazole-2-thione, and 2 mercapto 5-methylthio -Thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.
  • the content of the adhesion promoter is preferably from 0.001 to 20% by mass, more preferably from 0.01 to 10% by mass, based on all components of the photosensitive layer. % To 5% by mass is particularly preferred.
  • 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 support is not particularly limited, and can be appropriately selected according to the purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance. Further, the surface is smooth. It is more preferable that the sex is good. Specific examples of the support and protective film are described in, for example, [0342] to [0348] of JP-A-2005-258431.
  • 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.
  • the thermoplastic resin may be, for example, an ethylene / acrylate copolymer copolymer. Saponified product of styrene and (meth) acrylic acid ester copolymer, saponified product of butyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, butyl (meth) acrylate and acetic acid Kenya such as (meth) acrylic acid ester copolymer such as vinyl, copolymer of (meth) acrylic acid ester and (meth) acrylic acid, styrene, (meth) acrylic acid ester and (meth) acrylic Examples thereof include a copolymer with an acid.
  • 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 force of the photosensitive film is not particularly limited and can be 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 adhesive force is not particularly limited and may be appropriately selected depending on the purpose.
  • a known polymer, supercooling substance, or adhesion improver in the thermoplastic resin is used.
  • a method of adding a surfactant, a release agent and the like is used.
  • the plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polypropylene glycol, polyethylene glycol, dioctyl phthalate, and dithiol. Examples include alcohols and esters such as heptino phthalate, dibutyno phthalate, tricresyl phosphate, credinol resin phosphate, biphenyl-diphenyl phosphate; amides such as toluenesulfonamide.
  • 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 layer can be peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer. .
  • the method for adjusting the interlayer adhesive force can be appropriately selected according to the purpose without any particular restrictions.
  • 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 it exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, so that it is very easy to peel between the cushion layer and the photosensitive layer.
  • the production of a photosensitive film including the cushion layer may be difficult.
  • the thickness of the cushion layer is not particularly limited.
  • the force f can be selected as appropriate according to the purpose.
  • F column; 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.
  • a material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution for a photosensitive film.
  • the solvent is not particularly limited and may be appropriately selected according to the purpose.
  • examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol.
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl acetate propionate, dimethyl phthalate Esters such as ethyl, benzoate, and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; tetrasalt carbon, trichloroethylene, blackform, 1, 1, 1-trichloro Halogenated carbonization of ethane, methylene chloride, monochrome benzene, etc.
  • the photosensitive composition solution is applied onto the support and dried to form a photosensitive layer. And a photosensitive film can be produced.
  • the method for applying the photosensitive composition solution is not particularly limited.
  • the force can be selected as appropriate according to the purpose.
  • spray method roll coating method, spin coating method, slit coating method, ethatrusion.
  • 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 wound around a cylindrical core, wound into a long roll, and stored.
  • the length of the long photosensitive film is not particularly limited. For example, a range force of 10-20, OOOm 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 to 1, OOOm 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.
  • a separator especially moisture-proof and desiccant-containing
  • the photosensitive laminate is formed by laminating at least the photosensitive layer 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.
  • Method for producing photosensitive laminate examples 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.
  • a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
  • the coating and drying method can be appropriately selected according to the purpose without any particular limitation.
  • the photosensitive composition is dissolved, emulsified or dispersed on the surface of the 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 according to the purpose without any 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 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 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 according to the purpose without any particular limitation.
  • Preferable examples include VP130).
  • the photosensitive film of the present invention and the photosensitive laminate are the photosensitive composition of the present invention. Therefore, it is possible to form various patterns such as a permanent pattern such as a protective film, an interlayer insulation film, and a solder resist pattern. It can be suitably used for the production of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, etc., and pattern formation for holograms, micromachines, proofs, etc. It can be suitably used for pattern formation.
  • the photosensitive film of the present invention has a uniform thickness, a permanent pattern (a protective film, an interlayer insulating film, a solder resist, etc.) is thinned when forming a permanent pattern.
  • a permanent pattern a protective film, an interlayer insulating film, a solder resist, etc.
  • HAST high acceleration test
  • 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 includes other steps such as a suitably 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 according to 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 may be appropriately selected depending on the purpose. Among these, digital exposure and analog exposure are preferred. Digital exposure is preferable among these.
  • the digital exposure can be appropriately selected according to the purpose without any particular restriction.
  • a control signal is generated based on pattern formation information to be formed and modulated according to the control signal.
  • 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.
  • An exposure head having light modulation means capable of controlling the drawing unit according to pattern information, the drawing unit being arranged in a scanning direction of the exposure head.
  • the exposure head is arranged so that the column direction of the predetermined inclination angle ⁇ is set, and, for the exposure head, N-exposure (N double exposure) of the usable pixel parts by the used pixel part designating means.
  • N is a natural number of 2 or more
  • N double exposure refers to a straight line parallel to the scanning direction of the exposure head in almost all of the exposure area on the exposed surface of the photosensitive layer. This refers to exposure with a setting that intersects N light spots (pixel array) irradiated on the exposure surface.
  • the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit.
  • the arrangement of the picture element portions does not necessarily have to be a rectangular lattice, for example, an arrangement of parallelograms.
  • 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 rows at both side edges of each picture element part. Since the number of picture element parts in the used picture element part decreases, even if it is used to connect multiple exposure heads in such a case, scanning will occur due to errors in the mounting angle and arrangement of the exposure heads.
  • the number of pixel parts in the used pixel part that intersects a 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 multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”.
  • 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 in the N-exposure is a natural number of 2 or more, a force that can be appropriately selected according to the purpose for which there is no particular limitation, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .
  • 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. [0229]
  • a " ⁇ " shape that opens in the direction of the X-axis Ten slits 28 are formed at regular intervals.
  • Each slit 28 also has a force with a slit 28a located on the upstream side and a slit 28b located on the downstream side.
  • the slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of ⁇ 45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.
  • the position of the slit 28 is substantially coincident with the center of the exposure head 30.
  • the size of each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30.
  • the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34.
  • 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, or each pattern is moved while the exposure head is moved stepwise.
  • 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 respect to the scanning direction. Is attached to. 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 10 exposure heads arranged in a matrix of 2 rows and 5 columns. In the following, when the individual exposure heads arranged in the m-th row and the n-th column are indicated, the exposure heads 30 are represented as exposure heads 30.
  • each of the nodes 30 is arranged with a predetermined interval (natural number times the long side of the exposure area, twice in this embodiment) in the arrangement direction. Therefore, the exposure area 32 in the first row and the exposure area
  • the part that cannot be exposed to the rear 32 can be exposed by the exposure area 32 in the second row.
  • each of the exposure heads 30 includes 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 emitting 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. Further, on the light reflection side of 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 reduced by the lens system 50 described above. It is set to be reduced to 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 modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (S LM), 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 has 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.
  • the SRAM cell 56 is a silicon gate CMOS manufactured on an ordinary semiconductor memory manufacturing line via a support including a hinge and a yoke, and is configured monolithically (integrated) as a whole.
  • DMD36 SRAM cell memory cell 56 mm.
  • each micromirror 58 supported by the column is Inclined to one of ⁇ ⁇ degrees (for example, ⁇ 10 degrees) with respect to the substrate side on which the DMD 36 is disposed with the diagonal line as the center.
  • FIG. 7 (b) shows a state tilted to + ⁇ degrees when the micromirror 58 is in the on state
  • FIG. 7 (b) shows a state tilted to ⁇ degrees when the micromirror 58 is in the off state.
  • FIG. 6 shows an example of a state in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + ⁇ degrees or ⁇ degrees.
  • the on / off control of each micromirror 58 is performed by the controller connected to the DM D36.
  • a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.
  • the light 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.
  • light irradiated from the light irradiation means for example, light irradiation is performed through a support.
  • Examples include electromagnetic waves that pass through the support and activate the used photopolymerization initiator and sensitizer, ultraviolet to visible light, electron beams, X-rays, laser light, and the like.
  • Laser light is preferred A laser combining two or more lights (hereinafter sometimes referred to as “combined laser”) is more preferred. 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, for example, preferably 300-1500 nm 320-8
  • OOrnn force is more preferable, 330 ⁇ 650mn force is especially preferred!
  • 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 is used in an ideal state where there is no mounting angle error of the exposure head 30 or the like. Using the available 1024 columns by 256 rows pixel part, the angle ⁇ is exactly double exposure.
  • 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 the pattern of the light spot group 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.
  • the number of usable micromirrors 58 is an odd number. Although the exposure pattern and the exposure pattern in even columns are shown separately, the actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.
  • the set inclination angle 0 is slightly larger than the angle 0 described above.
  • 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 ⁇ (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 256 (256, 512).
  • the stage 14 is slowly moved to relatively move the slit 28 along the axis direction, and the light spot ⁇ (256, 512) is
  • the slit 28 is positioned at an arbitrary position between the upstream slit 28a and the downstream slit 28b.
  • 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. 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 to be 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.
  • a signal for setting the angle of the always-off state is sent by the pixel part control means, and these micromirrors are not substantially involved in exposure. As shown in Fig. 11, overexposure and underexposure are almost completely eliminated in the exposure area near the 512th column, and uniform exposure very close to ideal double exposure is realized.
  • the 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. It is smaller than the angle of inclination of the ray train in the area of). Therefore, the exposure using only the micromirrors selected based on the actual inclination angle ⁇ ⁇ measured with c (512) as a reference, is ideal for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. A slight under-exposure area is generated for the double exposure.
  • the overexposed areas are complemented with each other, and the density unevenness due to the angular distortion is It can be minimized by the effect of offset by double exposure.
  • the actual inclination angle ⁇ ′ of the 512th ray array is measured, and the actual inclination angle ⁇ is used to derive the equation (4).
  • the micromirror 58 to be used is selected based on T.
  • the actual inclination angle ⁇ ′ the column direction (light spot column) of a plurality of pixel portions and the scanning direction of the exposure head are used. Measure each of the actual inclination angles to make one of the average value, median value, maximum value, and minimum value. It is specified as the actual inclination angle ⁇ ', and the micromirror to be actually used at the time of actual exposure is selected by the above equation 4 etc.
  • 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. For example, the total area of overexposed areas and underexposed areas is minimized, and the number of pixel units (number of light spots) in overexposed areas and underexposed areas It is possible to achieve an exposure that makes the number of pixel units (number of light spots) equal to the maximum number of pixels. It is possible to achieve exposure that places more importance on eliminating excessive regions, for example, to achieve exposure that minimizes the area of underexposed regions and prevents overexposed regions. Is possible.
  • the minimum value is the actual inclination angle ⁇ ′, it is possible to realize exposure that places more emphasis on the exclusion of areas that are insufficient for the ideal N double exposure. Thus, it is possible to realize an exposure that minimizes the area of the region and prevents an underexposed region from occurring.
  • the identification of the actual inclination angle ⁇ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row).
  • the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in a row in the vicinity of c (n) may be specified.
  • one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on the straight line and in the vicinity along the scanning direction of the exposure head are detected.
  • the actual inclination angle ⁇ ′ can be obtained from these positional information.
  • the angle obtained based on the position of at least two light spots in the light spot array in the vicinity of the c (n) line is obtained.
  • the actual inclination angle ⁇ ′ may be specified.
  • the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and is a head that is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads 30.
  • each exposure head 30 that is, each DMD 36
  • the set tilt angle ⁇ of each exposure head 30, that is, each DMD 36 can be used as long as there is no mounting angle error of the exposure head 30 and 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 with the stage 14 stationary.
  • Fig. 12 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and continuous exposure is performed with the light spot group pattern shown in the upper part appearing.
  • every other column exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B.
  • the actual exposure pattern on the exposed surface is the two exposures. It is a superposition of 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 relative to the right in FIG. 14 along the Y axis. Move. Then, as indicated by a two-dot chain line in FIG. 14, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (XO, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).
  • the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. Then, as indicated by a two-dot chain line in FIG. 14, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (XO, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).
  • Detection is performed by a combination of a slit 28 and a photodetector as a position detection means. Next, exposure area 32
  • each light spot on the light spot line r (256) of the 256th line of 21 is detected in order of ⁇ (256, 1024), P (256, 10 23) ... X coordinate greater than 32 light spots P (256, 1)
  • the micromirror to be used is identified as a micromirror (unused pixel part) that is not used during the main exposure.
  • the detection operation ends.
  • the 1021 row power in the exposure area 32 corresponding to the portion 70 covered by the diagonal line is also the light spot that forms the 1024th row.
  • the micromirror force corresponding to is specified as a micromirror that is not used during the main exposure.
  • the 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
  • an exposure area 32 Thereafter, in an arithmetic unit connected to the photodetector, an exposure area 32
  • the X coordinate of the light spot P (m, 1020) in the exposure area 32 is the exposure area 3
  • the micromirror corresponding to the force P (m-1, 1020) is also identified as the micromirror that is not used during the main exposure.
  • the X coordinate of the light spot P (m–1, 1020) in the exposure area 32 is the light in the exposure area 32.
  • a micromirror corresponding to the light spot that forms the shaded area 72 in FIG. 15 is added as a micromirror that is not used during actual exposure. These micromirrors are always signaled to set their micromirror angle to the off-state angle, and these micromirrors are essentially not used for exposure.
  • exposure areas 32 and 32 are selected. Ideal double dew in the area between the heads
  • the total area of areas that are overexposed and underexposed to light can be minimized, and uniform exposure very close to ideal double exposure is achieved, as shown in the lower part of Fig. 15. can do.
  • the X coordinate of the light spot P (256, 2) in 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.
  • a micromirror that minimizes the area of the overexposed region with respect to the ideal double exposure and does not generate an underexposed region in the connecting region between the heads. It can be selected as a micromirror to be actually used.
  • the light spot P (l, 1020) force in the exposure area 32 corresponds to P (m— 1, 1020).
  • a micromirror which is not used for this exposure. In that case, in the connecting area between the heads, a micromirror that minimizes the area of the area that is underexposed with respect to the ideal double exposure and that does not cause an overexposed area is actually used. It can be selected as the micromirror to be used.
  • the number of pixel units (the number of light spots) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light spots) in an area that is underexposed are: It is good also as selecting the micromirror actually used so that it may become equal.
  • the solution caused by the relative position shift in the X-axis direction of the plurality of exposure heads reduces image variability and density unevenness, and realizes ideal N double exposure.
  • the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30.
  • the relative position of the two exposure heads (for example, exposure heads 30 and 30) in the X-axis direction deviates from the ideal state, as well as each exposure.
  • each exposure head 30 As the set tilt angle of each exposure head 30, that is, each DMD 36, the exposure head 30 is adjusted. In an ideal state with no angle error, an angle that is slightly larger than the angle ⁇ , which is a double exposure using a usable 1024 column x 256 row pixel part (micromirror 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.
  • 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 the exposure heads 30, that is, the DMDs 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 exposure heads 30 and 30 in the X-axis direction is the same as the example of FIG.
  • the exposure area other than the overlapping exposure area on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface In this area, both of the exposure patterns of every other light spot group (pixel array groups A and B) and the pixel that is an overlapped exposure region on the exposed surface formed by a plurality of pixel part rows.
  • a region 76 is formed which is overexposed than the ideal double exposure state, and this causes further density unevenness.
  • the mounting angle error of each exposure head 30 and 30, and the relative Use pixel selection processing is performed to reduce density unevenness due to the influence of the angle difference.
  • 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 actual inclination angle ⁇ ′ is specified by the light spot P (l,
  • the arithmetic device connected to the photodetector using the actual inclination angle ⁇ ′ thus specified is similar to the arithmetic device in the above-described embodiment (1), as shown in the following equation 4
  • the (T + 1) line force on the DMD 36 is also identified as 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 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 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 ⁇ ′.
  • the 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 result. 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 in 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.
  • (N— 1) Perform reference exposure using only micromirror columns that make up adjacent rows corresponding to lZN rows of all light spot rows or all light spot rows, so that uniform exposure can be achieved.
  • a microphone mirror that is not used at the time of actual exposure may be specified.
  • the result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is subjected to analysis such as confirmation of resolution variation and density unevenness and estimation of the actual inclination angle.
  • the analysis of the result of the reference exposure is a visual analysis by the operator.
  • FIG. 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 by using only a plurality of (N-1) micromirrors using a plurality of exposure heads.
  • 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 illustrate an example 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.
  • 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.
  • 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 the two adjacent exposure heads in the X-axis direction (for example, exposure heads 30 and 30) correspond to 1ZN rows of the total number of light spots.
  • FIG. 10 is an explanatory diagram showing an example of a form in which reference exposure is performed using only micromirror groups constituting adjacent rows.
  • the micro-mirror force other than the micro-mirror corresponding to the light spot array in the area 90 shown shaded in FIG. 22 and the area 92 shown by shading is the main exposure in the micro-mirrors in the first to 128th rows. Designated as actually used at the time.
  • a separate reference exposure may be performed in the same manner to specify the micromirror to be used for the main exposure, and the first to 128th lines are designated. The same pattern as that of the micromirror may be applied.
  • micromirror By specifying the micromirror to be used during the main exposure in this way, a state close to ideal double exposure is realized in areas other than the joint area between the heads formed on the exposed surface by the two exposure heads. it can.
  • the power described in the case where the main exposure is double exposure is not limited to this, and any multiple exposure over double exposure is possible. It is good.
  • the triple exposure power is set to approximately seven exposures, it is possible to achieve exposure with high resolution and reduced resolution variation and density unevenness.
  • the exposure apparatus further displays image data. It is preferable that a mechanism for converting image data is provided so that the size of the predetermined portion of the two-dimensional pattern matches the size of the corresponding portion that can be realized by the selected use pixel. 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 is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a method for removing using a developer.
  • the developer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include an alkaline aqueous solution, an aqueous developer, an organic solvent, and the like. Among these, a weak alkaline aqueous solution is used. 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. Sodium, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax, etc.
  • the pH of the weakly alkaline aqueous solution is more preferably, for example, about 9 to about 8 to 12: 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 formation of the pattern may include, for example, a curing process, an etching process, a plating process, and the like. These can be used alone or in combination of two or more You can do it.
  • the pattern forming method is a permanent pattern forming method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter
  • the photosensitive layer is cured after the developing step. It is preferable to provide the hardening process process which processes.
  • 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. By this overall exposure, curing of the resin in the photosensitive composition forming the photosensitive layer is accelerated, and the surface of the permanent pattern 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 can be used to form various patterns that require prevention of sensitivity reduction of the photosensitive layer by oxygen in direct writing by laser exposure at 405 nm. It can be suitably used to form a pattern that is compatible with productivity.
  • the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, it is possible to protect the wiring from external impact and bending 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 measured by gel permeation chromatography (GPC) using polystyrene as a standard material.
  • the acid value per solid content should be 2.2 meqZg.
  • the mass average molecular weight (Mw) of the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a standard material.

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