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WO2007108172A1 - Composition photosensible, film photosensible, produit en couches photosensible, produit de formation d'un motif permanent, et carte à circuits imprimés - Google Patents

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

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Publication number
WO2007108172A1
WO2007108172A1 PCT/JP2006/323425 JP2006323425W WO2007108172A1 WO 2007108172 A1 WO2007108172 A1 WO 2007108172A1 JP 2006323425 W JP2006323425 W JP 2006323425W WO 2007108172 A1 WO2007108172 A1 WO 2007108172A1
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WO
WIPO (PCT)
Prior art keywords
group
exposure
photosensitive
compound
pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/323425
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English (en)
Japanese (ja)
Inventor
Masanobu Takashima
Kazuhiro Fujimaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
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Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006072693A external-priority patent/JP2007248843A/ja
Priority claimed from JP2006072747A external-priority patent/JP2007248846A/ja
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2007108172A1 publication Critical patent/WO2007108172A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • Photosensitive composition photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed circuit board
  • the present invention relates to a photosensitive composition, a photosensitive film, a photosensitive laminate, and a photosensitive laminate 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 using a laminate, and a printed 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 and drying a photosensitive composition on a support has been used.
  • a method for producing the permanent pattern for example, a laminate is formed by laminating the photosensitive film on a substrate such as a copper clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed. After the exposure, the photosensitive layer is developed to form a pattern, and then subjected to a curing process or the like to form the permanent pattern.
  • the photosensitive composition for the purpose of improving stability and the like, a copolymer of a (meth) acrylic monomer having an aliphatic hydrocarbon group having 1 to 6 carbon atoms and (meth) acrylic acid is used.
  • a photosensitive composition containing a polymer compound obtained by adding a (meth) acrylate compound having an epoxy group to a polymer see Patent Document 1.
  • a photosensitive composition comprising a polymer compound in which an unsaturated compound having an alicyclic epoxy group is added to a copolymer having a carboxyl group in a side chain for the same purpose as the above proposal is proposed. (See Patent Document 2).
  • the epoxy compound is roughly classified into a liquid form and a solid form.
  • the former has fluidity, so that the melt viscosity is lowered and the embedding property in the obtained film is good, while the glass transition temperature (Tg) and elastic modulus of the film are lowered.
  • Tg glass transition temperature
  • the latter is advantageous in that it lacks fluidity but does not lower the Tg of the resulting film and has a high elastic modulus. Therefore, in a photosensitive composition generally used for forming a liquid resist type permanent pattern, both are used together so that both advantages can be exhibited as much as possible.
  • the polymerizable compound is composed only of an aliphatic ester monomer (for example, dipentaerythritol hexaatalylate, trimethylolpropane tritalylate, trimethylolpropane trimethacrylate).
  • an aliphatic ester monomer for example, dipentaerythritol hexaatalylate, trimethylolpropane tritalylate, trimethylolpropane trimethacrylate.
  • PET polyethylene terephthalate
  • Patent Document 1 Japanese Patent Laid-Open No. 3-172301
  • Patent Document 2 Japanese Patent Laid-Open No. 10-10726
  • Patent Document 3 JP-A-7-199457
  • 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.
  • Photosensitive composition, photosensitive film, photosensitive laminate, and method for forming permanent pattern using photosensitive laminate which can efficiently form patterns (protective film, interlayer insulating film, solder resist pattern, etc.) And a printed circuit board on which a pattern is formed by the permanent pattern forming method.
  • the present invention contains a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, and the binder includes an acidic group and an ethylene.
  • the photosensitive composition containing a high molecular compound having a ionic unsaturated bond in the side chain and the thermal cross-linking agent containing two or more types of rosins defines a binder and a thermal cross-linking agent used in combination. It was discovered that high-definition permanent patterns can be efficiently formed with high sensitivity and high resolution, excellent electroless gold plating resistance, and via and through-hole embedding.
  • the polymer composition includes a binder, two or more polymerizable compounds, a photopolymerization initiator, and a thermal crosslinking agent, and the binder has a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain.
  • Photosensitive composition containing two or more types of monomers and excellent in sensitivity, resolution, tackiness, electroless gold plating resistance, storage stability, and high-efficiency permanent pattern We found that it was possible to form well. [0009]
  • the present invention is based on the above findings of the present inventor, and means for solving the above problems are as follows. That is,
  • the binder includes a polymer compound having an acidic group and an ethylenically unsaturated bond in the side chain, and is polymerizable.
  • the photosensitive composition is characterized in that at least one of the ionic compound and the thermal crosslinking agent contains two or more compounds.
  • a 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.
  • Thermal crosslinking agent is an epoxy compound, oxetane compound, polyisocyanate compound, compound obtained by reacting polyisocyanate compound with a blocking agent, and melamine derivative power
  • the photosensitive composition according to any one of ⁇ 1> to ⁇ 2>, wherein two or more selected.
  • the thermal crosslinking agent is an epoxy compound, and the epoxy compound is selected from a novolac epoxy compound, a bisphenol epoxy compound, a heterocyclic ring-containing epoxy compound, and an alicyclic epoxy compound.
  • Thermal crosslinking agent power The photosensitive composition according to ⁇ 4>, comprising an epoxy compound having an epoxy equivalent of 90 to 400 gZeq. And an epoxy compound having an epoxy equivalent of 150 to 9, OOOg / eq.
  • thermosensitive composition according to any one of ⁇ 1> to ⁇ 5>, wherein at least one of the thermal crosslinking agents is alkali-insoluble.
  • thermosetting accelerator a thermosetting accelerator
  • ⁇ 12> The photosensitive composition according to any one of ⁇ 10> and ⁇ 11>, comprising a monomer having a mass average molecular weight of 200 to 9,000.
  • Noinda Noinda
  • ⁇ 16> The photosensitive composition according to any one of ⁇ 1> to ⁇ 15>, wherein the polymer compound contains 0.5 to 3. OmeqZg of an ethylenically unsaturated bond.
  • the acid group of the polymer compound is a carboxyl group, and the content of the carboxyl group in the polymer compound is 1.0 to 4. OmeqZg. It is a photosensitive composition.
  • ⁇ 18> The photosensitive composition according to any one of ⁇ 1> to ⁇ 17>, wherein the polymer compound has a mass average molecular weight of 10,000 or more and less than 100,000.
  • 1 2 and 3 represent a hydrogen atom or a monovalent organic group.
  • L represents an organic group and may be omitted.
  • Ar represents an aromatic group.
  • the photopolymerization initiator is a halogenated hydrocarbon derivative, hexaryl biimidazole, an oxime derivative, an organic peroxide, a thio compound, a ketone compound, or an aromatic onium salt.
  • ⁇ 21> The photosensitive composition according to any one of ⁇ 1> to ⁇ 20>, wherein the photosensitive composition contains a sensitizer.
  • a photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of 1) to 22) on the support. .
  • ⁇ 26> The photosensitive film according to any one of ⁇ 23> to ⁇ 25>, which is long and wound in a roll.
  • a photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of ⁇ 1> to 22 above on a substrate.
  • ⁇ 29> The photosensitive laminate according to ⁇ 28>, wherein the photosensitive layer is formed of the photosensitive film according to any one of ⁇ 23> to ⁇ 27>.
  • ⁇ 30> The photosensitive laminate according to any one of ⁇ 28> to ⁇ 29>, wherein the photosensitive layer has a thickness of 1 to 100 / ⁇ ⁇ .
  • a pattern forming apparatus comprising: a light irradiating unit capable of irradiating light; and a light modulating unit that modulates light from the light irradiating unit and exposes the photosensitive layer in the photosensitive film. It is.
  • the light irradiation 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 modulating means is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the pattern forming apparatus according to ⁇ 31> 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 according to
  • the light modulation means has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts.
  • the pattern forming apparatus according to ⁇ 33> can be controlled in accordance with pattern information.
  • the light from the light irradiating means is modulated at high speed by controlling any less than n pixel parts arranged continuously from the pixel parts in accordance with the pattern information.
  • ⁇ 34> The pattern forming apparatus according to any one of ⁇ 31>, ⁇ 33>, wherein the light modulation means is a spatial light modulation element.
  • ⁇ 35> The pattern forming apparatus according to ⁇ 34>, wherein the spatial light modulation element is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • ⁇ 36> The pattern forming apparatus according to any one of ⁇ 33>, ⁇ 35>, wherein the pixel part is a micromirror.
  • the light irradiation unit can synthesize and irradiate two or more lights.
  • the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth.
  • the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is developed thereafter, an extremely fine pattern is formed.
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated with the plurality of laser forces, respectively, and couples them to the multimode optical fiber.
  • the pattern forming apparatus according to any one of the above 31> Karaku 37>.
  • the light irradiation unit may collect the laser beams irradiated with the plurality of laser forces by the collective optical system and couple the laser beams to the multimode optical fiber.
  • exposure is performed with exposure light having a deep focal depth.
  • the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • a permanent pattern forming method comprising exposing the photosensitive layer in the photosensitive laminate according to any one of ⁇ 28> to ⁇ 30>.
  • ⁇ 40> The method for forming a permanent pattern according to ⁇ 39>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
  • 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 42.
  • the permanent pattern forming method according to any one of ⁇ 39> to 41, which is performed by relatively moving the exposure head in a scanning direction.
  • the exposure head is subjected to N-exposure (where N is a natural number greater than or equal to 2) out of the usable pixel parts by the use pixel part designating unit. ) Is specified, and 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.
  • N is a natural number greater than or equal to 2
  • the pixel part control means so that only the pixel part specified by the use pixel part specifying means is involved in exposure.
  • the exposure is performed by a plurality of exposure heads, and the drawing element specifying means is used for exposure of a joint area between the heads, which is an overlapped exposure area on the exposed surface formed by the plurality of exposure heads.
  • the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapped exposure region on an exposed surface formed by the plurality of exposure heads.
  • the picture element part used for realizing the N-fold exposure in the head-to-head joint area is designated, so that the mounting of the exposure head Variations in the resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to a shift in the position and the mounting angle are equalized.
  • the photosensitive layer is exposed with high definition. For example, a high-definition pattern is then formed by developing the photosensitive layer.
  • the exposure is performed by a plurality of exposure heads, and the used pixel part specifying means is involved in exposure other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads.
  • the permanent pattern forming method according to ⁇ 43> wherein the pixel part used to realize N double exposure in an area other than the head-to-head connection area among the picture element parts is designated.
  • the exposure is performed by a plurality of exposure heads, and the used pixel portion specifying unit overlaps the exposed surface formed by the plurality of exposure heads.
  • ⁇ 46> The method for forming a permanent pattern according to any one of ⁇ 42> to ⁇ 45>, wherein the N force of N exposure is a natural number of 3 or more.
  • the N force of N exposure is a natural number of 3 or more.
  • multiple drawing is performed by using a natural number of N force 3 or more in N double exposure.
  • a light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface
  • a pixel part selection means for selecting a pixel part to be
  • the used pixel part specifying means specifies the used pixel part to be used for realizing the N double exposure in units of rows.
  • the permanent pattern formation according to any one of ⁇ 42> to ⁇ 47> Is the method.
  • a light spot position detection unit based on at least two light spot positions detected, a light spot column direction on the surface to be exposed and a scanning direction of the exposure head when the exposure head is tilted
  • the actual inclination angle ⁇ 'formed by the image is determined, 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 ⁇ .
  • This is a permanent pattern forming method as described in the above.
  • the actual inclination angle ⁇ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined.
  • the pixel parts from the first line to the T line are selected as the used pixel parts from ⁇ 47> to ⁇ 50>, the permanent pattern forming method according to any one of the above.
  • the permanent pattern forming method according to any one of the above ⁇ 47> Karaku 51, wherein the pixel part excluding the unused pixel part is selected as the used pixel part.
  • connection area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads
  • the number of pixel units in the overexposed area is equal to the number of pixel units in the underexposed area.
  • N (N ⁇ 1) column-by-column drawings are used for N of N double 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 rows constituting 1ZN rows are configured.
  • N of N double 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 used pixel part specifying means includes a slit and a photodetector as light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means ⁇ 57> !, a method for forming a permanent pattern as described in any of the above.
  • ⁇ 59> The method for forming a permanent pattern according to any one of ⁇ 42> to ⁇ 58>, which is a natural number of N force 3 or more and 7 or less in N double exposure.
  • 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 the light emitted from the light irradiation unit.
  • a pattern signal generation unit that generates a control signal based on the pattern information to be formed
  • the pattern signal generation unit outputs the light emitted from the light irradiation unit.
  • ⁇ 42> to ⁇ 59> to be modulated according to the generated control signal
  • the permanent pattern forming method according to any one of the above.
  • the light modulation unit includes the pattern signal generation unit, so that light emitted from the light irradiation unit is transmitted by the pattern signal generation unit. Modulated according to the generated control signal.
  • ⁇ 62> The method for forming a permanent pattern according to the above item 61, wherein the spatial light modulation element is a digital micromirror device (DMD).
  • DMD digital micromirror device
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated with the plurality of laser forces and couples the laser beams to the multimode optical fiber.
  • the light irradiating means can condense the laser light irradiated with each of the plurality of laser forces by the converging optical system and couple it to the multimode optical fiber. Therefore, exposure is performed with exposure light having a deep depth of focus. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, if the photosensitive layer is subsequently developed, A fine pattern is formed.
  • ⁇ 67> The permanent pattern forming method according to any one of ⁇ 39> to ⁇ 66>, wherein the photosensitive layer is developed after the exposure.
  • a high-definition pattern is formed by developing the photosensitive layer after the exposure.
  • ⁇ 68> The method for forming a permanent pattern according to ⁇ 67>, wherein a permanent pattern is formed after development.
  • ⁇ 69> A permanent pattern formed by the pattern forming method according to any one of ⁇ 39> and 68. Since the permanent pattern described in 68> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition, and is a multilayer wiring board for semiconductors and components. This is useful for high-density mounting on PCBs and build-up wiring boards.
  • the pattern according to the above item 69 which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in 70> 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, heat resistance, etc. of the film. Protected from impact and bending.
  • Photosensitive composition capable of efficiently forming high-definition permanent patterns (interlayer insulation film, solder resist pattern, etc.) with excellent accuracy, resolution, tackiness, electroless gold plating resistance, and storage stability. It is possible to provide a permanent laminate, a permanent pattern forming method using the photosensitive laminate, a permanent pattern formed by the permanent pattern forming method, and a printed circuit board on which the permanent pattern is formed.
  • 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 shows the positions of the exposure areas by the two adjacent exposure heads and the corresponding slits. It is the top view which showed arrangement
  • 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 first aspect of the present invention includes a binder, a polymerizable compound, a photopolymerization initiator, and two or more thermal crosslinking agents, preferably includes a thermosetting accelerator, and if necessary. And other ingredients.
  • the thermal crosslinking agent preferably contains two or more compounds, and at least one of them is alkali-insoluble from the viewpoint of gold plating resistance.
  • the compound is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability is improved.
  • 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 are selected. Two or more types can be used.
  • “the thermal crosslinking agent includes two or more compounds” means, for example, that the thermal crosslinking agent includes two or more compounds as a mixture. To do.
  • Examples of the epoxy compound include an epoxy compound having at least two oxysilane groups in one molecule, and an epoxy compound including at least two epoxy groups having an alkyl group at the 3-position in one molecule. Etc.
  • 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 Co., Ltd.") or a mixture thereof.
  • Heterocyclic epoxy resins having an isocyanurate skeleton (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, "Araldite PT810; manufactured by Ciba 'Specialty'Chemicals"), bisphenol A type epoxy resin, novolak Type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, talesol novolac type epoxy resin, halogenated epoxy resin Fats (for example, low brominated epoxy resins, high halogenated epoxy resins, brominated phenols Borak type epoxy resin), aryl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenol dimethanol type epoxy resin, phenol biphenol type epoxy resin, dicyclopentagen Type epoxy resin (“HP-7200, HP-7200H; manufactured by Dainippon Ink Chemical Co., Ltd.”), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, dig
  • an epoxy compound containing at least two epoxy groups having an alkyl group at the ⁇ -position in one molecule can be used.
  • Particularly preferred are compounds containing an epoxy group whose position is substituted with an alkyl group (more specifically, a ⁇ -alkyl-substituted glycidyl group or the like).
  • 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.
  • epoxy compound containing an epoxy group having an alkyl group at the / 3-position for example, an epoxy compound derived from a polyvalent phenol compound and a j8-alkylephalohydrin is preferable.
  • the / 3-alkylepino and rhohydrin are not particularly limited and can be appropriately selected according to the purpose.
  • j8-methylepichlorohydrin, 13 methylepibromohydrin, 13- J8-methylepihalohydrin such as methylepifluorohydrin; 13-ethylepichlorohydrin, j8-ethylepibu mouth mohydrin, —ethylepifluorohydrin, etc.
  • ⁇ -propyle ⁇ -Propinoreepihalohydrin such as chlorohydrin, ⁇ -propylepib mouth mohydrin, ⁇ -propinoreepifluorohydrin; ⁇ 8-butinoreepichlorohydrin, j8-butylepib mouth mohydrin, j8-butylepihydrohydrin, etc. Pihalohydrin; and the like.
  • ⁇ -methylepino and rhohydrin are preferable from the viewpoints of reactivity with the polyhydric phenol and fluidity.
  • the polyhydric phenol 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 A, bisphenol F and bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol-formaldehyde polycondensates, etc.
  • 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 Ruformaldehyde polycondensates, bisphenol compounds such as bisphenol A formaldehyde polycondensates, etc.
  • Formaldehyde polycondensates, copolycondensates of phenol and monoalkyl-substituted phenols having 1 to 10 carbon atoms with formaldehyde, phenol Le compound and polyaddition products of di Bulle benzene and the like are preferable.
  • Examples of the epoxy compound containing an epoxy group having an alkyl group at the / 3-position include di-13-alkyl glycidyl ether of bisphenol A, di- ⁇ -alkyl glycidyl ether of bisphenol F, and bisphenol S 13 bisphenol compounds such as alkyl glycidyl ethers / 3 alkyl glycidyl ethers; biphenols ge 13 alkyl glycidyl ethers, tetramethylbiphenol diols 13 biphenol compounds such as alkyl glycidyl ethers 13 alkyl glycidyl ethers; dihydroxy Naphthalene Gee / 3 Alkyl Glycidyl Ether, Binaphthol Gee 13 Alkyl Glycidyl Ether, etc.
  • phenolic compound of formaldehyde polycondensate represented by the following structural formula (ii): j8-alkyl glycidyl ether.
  • R represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 20.
  • R represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • n is an integer of 0 to 20 Represents.
  • epoxy compounds containing an epoxy group having an alkyl group at the 13-position may be used alone or in combination of two or more. It is also possible to use an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the j8 position.
  • epoxy compound commercially available products and mixtures thereof described in JP-A-2005-182004 [0037] can also be suitably used.
  • Examples of the oxetane compound include oxetane compounds having at least two oxetal groups in one molecule.
  • polyisocyanate compound a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is at least 2 Aliphatic, cycloaliphatic or aromatic substituted aliphatic compounds containing two isocyanate groups may be derivatized.
  • bifunctional isocyanates eg, mixtures of 1,3 and 1,4-phenolic diisocyanates, 2, 4 and 2,6 toluene diisocyanates, 1, 3 —And 1, 4 xylylene diisocyanate, bis (4 —isocyanate monophenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate
  • Polyfunctional alcohols such as trimethylolpropane, pentalysitol, glycerin, etc .; an alkylene oxide adduct of the polyfunctional alcohol and the bifunctional isocyanate Adduct: Cyclic ring such as hexamethylene diisocyanate, hexamethylene 1,6 diisocyanate and its derivatives Trimer; and the like.
  • a compound obtained by reacting a blocking agent with the polyisocyanate compound that is, a compound obtained by reacting a blocking agent with the isocyanate group of polyisocyanate and its derivatives.
  • the agent include alcohols (for example, isopropanol, tert-butanol, etc.), ratatas (for example, epsilon prolatatam, etc.), phenols (for example, phenol, crezo-monore, p-tert-butinorephenol, p— sec Butylphenol, p-sec amylphenol, p-octylphenol, p noninolephenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (For example, dialkyl malonate, methyl ethyl ketoxime, acetyl acetone, alkyl acetoacetoxime, acetooxime, acetooxi
  • Examples of 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. Among these, hexamethylated methylol melamine is particularly preferred, because alkylated methylol melamine is preferred because it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film. .
  • thermo crosslinking agents for example, a combination of bifunctional compounds, a combination of a bifunctional compound and a trifunctional or higher compound, and a combination of a monofunctional compound and a polyfunctional compound are preferable. . Of these, combinations of bifunctional compounds and combinations of bifunctional compounds with trifunctional or higher compounds are particularly preferred.
  • the bifunctional compound is preferably a bisphenol type epoxy compound in an epoxy compound. Specifically, a bisphenol A type, a bisphenol F type, a bisphenol S type, and a biphenol type force are selected. A combination of the two is preferred. Also, combinations of bisphenol type epoxy compounds and novolak type epoxy compounds, combinations of bisphenol type epoxy compounds and heterocyclic ring-containing epoxy compounds, bisphenol type epoxy compounds and alicyclic epoxy compounds. Combinations with products, combinations of novolak epoxy compounds with heterocyclic ring-containing epoxy compounds, and combinations of heterocyclic epoxy compounds and alicyclic epoxy compounds are also preferred.
  • the combination of the thermal crosslinking agents for example, in terms of epoxy equivalent, a combination of an epoxy compound of 90 to 400 gZeq. And an epoxy compound of 150 to 9, OOOg / eq. Is preferable, and 90 to 300 g / eq. Threaded combination of ⁇ composite with 150-8,000g / eq. It is preferable. That is, when the thermal crosslinking agent is a mixture containing two or more kinds of compounds, the epoxy equivalent force of the mixture is preferably 150 to 400 gZeq. More preferably, it is 150 to 300 g / eq. preferable.
  • the epoxy equivalent can be measured based on JIS K 7236.
  • the solid content of the thermal crosslinking agent in the photosensitive composition is preferably 1 to 50% by mass, more preferably 3 to 30% by mass. When the solid content is less than 1% by mass, no improvement in the film strength of the cured film is observed, and when it exceeds 50% by mass, the developability and exposure sensitivity may decrease.
  • examples of the thermal curing accelerator include amine compounds (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, triethylbenzylammo) -Um chloride, etc.), block isocyanate compounds (for example, dimethylamine), imidazole derivative bicyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethylyl 4- Methylimidazole, 2 phenol imidazole, 4 —phenol imidazole, 1-cyanethyl-2 —Phenol imidazole, 1- (2-
  • the solid content in the solid content of the photosensitive composition of the epoxy compound, the oxetane compound, and a thermosetting accelerator capable of accelerating the thermal curing of these with a carboxylic acid is usually 0.01 to 15% by mass. It is.
  • a thermal crosslinking agent other than the epoxy compound or the oxetane compound as the thermal crosslinking agent for example, an amine compound (for example, dicyandiamide, benzyldimethylamine) 4- (dimethylamino) N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methylN, N-dimethylbenzylamine, etc., quaternary ammonium salt compounds (for example, trie Benzylbenzyl ammonium chloride), block isocyanate compounds (eg, dimethylamine), imidazole derivative bicyclic amidine compounds, and salts thereof (eg, imidazole, 2-methylimidazole, 2-ethylimidazole) , 2-ethyl 4-methylimidazole, 2-phenolimidazole, 4-phenolimidazole 1 cyanoethyl 2 phenol imidazole, 1-
  • an amine compound for example, dicyandiamide
  • a curing catalyst for the thermal crosslinking agent or a compound capable of promoting thermal curing other than those described above is not particularly limited as long as it can accelerate the reaction between these and a carboxyl group.
  • the solid content in the photosensitive composition of the thermal crosslinking agent and the thermal curing accelerator capable of accelerating thermal curing between these and a carboxylic acid is preferably 0.01 to 15% by mass.
  • ⁇ Binder> a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain is used.
  • the acidic group include a carboxyl group, a phosphate group, and a sulfonate group.
  • a carboxyl group is preferable from the viewpoint of obtaining raw materials.
  • a compound which is insoluble in water and swells or dissolves in an alkaline aqueous solution is preferable.
  • the binder include at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or a (meth) acrylamide group, a vinyl ester of carboxylic acid, a butyl ether, Various polymerizable double bonds such as aryl ether can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound, for example, a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, or an alicyclic group.
  • an acrylic resin containing a carboxyl group as an acidic group a cyclic ether group-containing polymerizable compound, for example, a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidy
  • an epoxy group-containing polymerizable compound such as an epoxy group (for example, an epoxy group such as cyclohexenoxide in the same molecule) and a compound having a (meth) aryryl group, etc.
  • an isocyanate group-containing polymerizable compound such as isocyanatoethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group.
  • examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as hydroxyalkyl (meth) acrylate to fat.
  • a cyclic ether group-containing polymerizable compound such as glycidyl metatalylate is copolymerized with a butyl monomer such as (meth) atalyloyl alkyl ester, and (meth) acrylic acid is added to the side chain epoxy group.
  • a cyclic ether group-containing polymerizable compound such as glycidyl metatalylate is copolymerized with a butyl monomer such as (meth) atalyloyl alkyl ester, and (meth) acrylic acid is added to the side chain epoxy group.
  • the compound etc. which are obtained by making it also include.
  • Examples of these include Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, Japanese Patent Application Laid-Open No. 2000-232264, and the like.
  • the binder is obtained by adding a polymerizable compound containing a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) to part of an acidic group of the polymer compound, and a polymer compound
  • a polymerizable compound containing a cyclic ether group for example, a group having an epoxy group or an oxetane group in a partial structure
  • 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.
  • the addition reaction between the acidic group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. It is preferable that the physical strength and neutral strength are also selected.
  • the binder contains a carboxyl group and a heterocycle in the side chain, or a polymer containing an aromatic group and an ethylenically unsaturated bond in the side chain.
  • Compound preferred.
  • aromatic group including the heterocycle examples include a benzene ring, and 2 to 3 benzene rings formed a condensed ring. And those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
  • aromatic group examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indur group, an acenaphthyl group, a fluorene group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, Pyrazole ring group, isoxazole ring group, isothiazole ring group, indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benz Oxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group,
  • the aromatic group may have a substituent.
  • substituents include, 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 a methyl group, an ethyl group, a propyl group, a butyl group, Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, Sbutyl, t butyl, isopentyl, neopentyl, 1 methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl, etc.
  • a linear alkyl group having 1 to 12 carbon atoms a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are preferable.
  • Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • substituents include halogen atoms (one F, one Br, one Cl, one), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group.
  • sulfonate group alkoxysulfol group, aryloxysulfol group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N dialkylsulfinaimoyl group, N Lylsulfinamoyl group, N, N dialylsulfinamoyl group, N-alkyl-N arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N dialkylsulfamoyl group, N-arylsulfamoyl group Group, N, N diallylsulfamoyl group, N alkyl—Narylsulfamoyl group, phosphono group (one PO H) and its conjugate base group (phosphonate group and
  • Dialkylphosphono group (one PO (alkyl)) (hereinafter “alkyl” means an alkyl group)
  • a diarylphosphono group (one PO (aryl)) (hereinafter “aryl” means an aryl group)
  • Alkylaryl phosphono group PO (alkyl) (aryl)
  • monoalkyl phosphono group PO (alkyl) (aryl)
  • alkyl and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group, monoarylphosphonate group
  • Phonoxy group (one OPO H) and its conjugate base group (referred to as phosphonatoxy group), dia
  • alkylaryl phosphonoxy group one OPO (alkyl) (aryl)
  • 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 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, methylthiophenol 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-ether group.
  • alkyl group in the substituent examples include an ethur group, a 1-propynyl group, a 1-buturyl group, and a trimethylsilylethynyl group.
  • Examples 1 Ashiru in the substituent group (1 .. I) are a hydrogen atom, the above-described alkyl group, such as Ariru group.
  • halogen atoms (1 F, 1 Br, 1 Cl, 1 1), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N alkylamino groups, N, N-dialkylamino groups, Aryloxy group, N-alkyl-force rubermoyloxy group, N-aryl force-rubamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbol group, force-rubamoyl group, N-alkyl-force rubermoyl Group, N, N dialkyl-force rubamoyl group, N allyl force rubamoyl group, N alkyl N allyl force rubamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N dialkyls
  • heterocyclic group in the substituent examples include, for example, a pyridyl group, a piperidyl group.
  • silyl group in the substituent examples include a trimethylsilyl group.
  • the alkylene group in the alkyl group is, for example, a divalent organic residue obtained by removing one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms.
  • a linear alkylene group having 1 to 12 carbon atoms a branched alkylene group having 3 to 12 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, etc. Is preferred.
  • substituted alkyl group obtained by combining such a substituent with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, isopropoxymethyl.
  • Examples of the aryl group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. .
  • aryl group examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a acenaphthenyl group, and a fluorenyl group.
  • a phenol group and a naphthyl group are preferable.
  • the alkyl group may have a substituent or an aryl group having such a substituent (hereinafter also referred to as “substituted aryl group”), for example, ring formation of the aforementioned aryl group
  • substituent on the carbon atom include a group consisting of a monovalent nonmetallic atomic group other than a hydrogen atom.
  • the aryl group may have, for example, the alkyl group, the substituted alkyl group, or the alkyl group that is described above as the substituent may be preferable.
  • substituted aryl group examples include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a tamale group, a chlorophenol group, a bromophenol group, a fluorophenol group, a chloromethyl group.
  • Phenyl group trifluoromethylphenol group, hydroxyphenyl group, methoxyphenyl group, methoxymethoxyphenyl group, aryloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, Tolylthiophenyl group, ethylaminophenyl group, germanaminophenyl group, morpholinophenol group, acetyloxyphenyl group, benzoylphenyl group, N cyclohexylcarbamoylphenyl group, N Phenylcarbamoyl phenyl group, Acetylaminophenol group, N-Methylbenzoylaminophenol group, Carboxyphenol group, Methoxycarbol Benzyl group, aryloxy-hydroxyl-phenyl group, chlorophenol-oxyl-hydroxyl-phenyl group, strong rubamoyl-phenol group, N-methylcarbamoyl-phenol group, N, N
  • the Aruke - Le group (C (R 02) C (R 03) (R 04)) and alkyl - as Le group (an C ⁇ C (R. 5)), for example, R ° 2, R ° 3 , R ° 4 , and R ° 5 are groups having a non-valent nonmetallic atomic group.
  • Examples of 2 , R ° 3 , R ° 4 , and R ° 5 include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above-mentioned examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.
  • alkenyl group and alkyl group! / Specific examples include vinyl group, 1-port perl group, 1-butul group, 1 pentale group, 1 hex. -Luyl group, 1-Otatur group, 1-Methyl-1 Propyl group, 2-Methyl-1 Propyl group, 2-Methyl-1-Butur group, 2-Fuilleru 1-Ethul group, 2-Chrome- 1-Ethul group, Etul group, 1-Propyl group, 1-Butul group, and Feule 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 alkaryl carbamoyloxy groups, N, N dialkyl rubamoyloxy groups, N, N diaryl forces.
  • a ruberamoyloxy group, an N alkyl N aryl group, a rubermoyloxy group, an alkyl snoreoxy group, an arenoresnoreoxy group, a phosphono-oxy group, and a phosphonato-oxy group are preferred.
  • 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, carboxyethyloxy, methoxy Carbo-ruethyloxy group, ethoxycarbo-ruethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxy group, ethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, aralkyloxyethoxy group, phenoxy group, triloxy Group, xylyloxy group, mesityloxy group, mesityloxy group, tamoxy group, methoxyphenyl group, ethoxyphenyl group, black-end phenol group , Buromofue - Ruokishi group, Ase
  • An amido group (R 8 NH-, (R 09 ) (R 01 °) N-) includes, for example, R ° 8 , 9 , and R G1G are monovalent except for a hydrogen atom. Non-metallic atomic groups are also included. In addition, R 9 may be bonded to form a ring.
  • amino group examples include an N-alkylamino group, an N, N dialkylamino group, an N allylamino group, an N, N dialylamino group, an N-alkyl-N allylamino group, an acylamine group, and an N-alkylacylamino group.
  • alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
  • 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.
  • 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, as described above, a conjugate base group of the sulfo group (one SO H). It means an ionic group and is usually preferably used together with a counter cation. As such counter cations, generally known ones can be appropriately selected and used. For example, oniums (for example, ammoniums, sulfomes, phosphomes) And sodium ions, azimuths, etc.) and metal ions (for example, Na +, K +, Ca 2+ , Zn 2+, etc.).
  • Examples of the carbo group include those in which 13 is a group having a non-valent atomic group with 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.
  • alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
  • Examples of the carbonyl group include formyl group, acyl group, carboxyl group, alkoxy group, aryloxycarbo group, rubamoyl group, N-alkyl group rubamoyl group, N, N dialkyl group rubamoyl.
  • Group, N-aryl rubamoyl group is preferable, and formyl group, acyl group, alkoxycarbol group, and aryloxycarbol group are more preferable.
  • the carbonyl group include a formyl group, a acetyl group, a benzoyl group, a carboxy group, a methoxy carbo ol group, an ethoxy carbo yl group, an ar aroxy carboxy group, a dimethylamino pheno group.
  • Preferred examples include a ruthel carbol group, a methoxy carbo methoxy carbo ol group, an N-methyl carbamoyl group, an N phen carbamoyl group, an N, N decyl rubamoyl group, a morpholino carbo ol group and the like.
  • Examples of the sulfiel group (R 14 — SO) include those having a group consisting of a non-valent nonmetallic atomic group.
  • Examples of such sulfiel groups include alkyl sulfiel groups, aryl sulfiel groups, sulfinamoyl groups, N-alkyl sulfinamoyl groups, N, N dialkyl groups. Examples include a rusulfinamoyl group, an N-arylsulfinamoyl group, an N, N-diarylsulfinamoyl group, and an N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, the alkylsulfur group and the arylsulfier group are preferred.
  • substituted sulfiel group examples include a hexyl sulfiel group, a benzyl sulfyl group, and a tolyl sulfyl group.
  • the phosphono group means a group in which one or two of the hydroxyl groups on the phosphono group are substituted with another organic oxo group.
  • dialkylphosphono group, diarylphosphono group, A reel phosphono group, a monoalkyl phosphono group, a monoaryl phosphono group and the like are preferable.
  • dialkylphosphono groups and diarylphosphono groups are more preferred.
  • the phosphono group include a jetyl phosphono group, a dibutyl phosphono group, and a diphenyl phosphono group.
  • the phosphonato group (PO H-, -PO H-) is, as described above, a phosphono group (PO
  • H means a conjugated base anion group derived from acid first dissociation or acid second dissociation
  • counter cation generally known ones can be appropriately selected. For example, various kinds of atoms (ammonium, sulfo-ums, phospho-umms, ododoniums) ), Metal ions (Na +, K +, Ca 2+ , Zn 2+ etc.).
  • the phosphonato group may be a conjugated basic anion group obtained by substituting one of the phosphono groups with an organic oxo group.
  • 1 PO H (alkyl) a conjugated salt of a monoarylphosphono group (PO H (aryl))
  • the aromatic group includes one or more radically polymerizable compounds containing an aromatic group and, if necessary, one or more other radically polymerizable compounds as copolymerization components. It can be manufactured legally.
  • radical polymerization method examples include a suspension polymerization method or a solution polymerization method. Etc.
  • 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, polyvalent anthracene and the like.
  • 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 more preferable in terms of sensitivity.
  • those having a linking group that are preferred from the viewpoint of stability are L 1-4 organic groups, which are C 1-4 alkylene groups in the non-image area. Preferred in terms of removability (developability).
  • the compound represented by the structural formula (A) is a compound containing a structural unit of the following structural formula (I).
  • the compound represented by the structural formula (B) is a compound containing a structural unit represented by the following structural formula ( ⁇ ). Of these, the structural unit of the structural formula (I) is preferable from the viewpoint of storage stability.
  • R, R, R, and Ar are the structural formulas (I) and ( ⁇ ).
  • R and R are hydrogen atoms, and R is a methyl group.
  • an alkylene group having 1 to 4 carbon atoms is preferable in terms of removability (imageability) of a non-image area.
  • the compound represented by the structural formula (A) or the compound represented by the structural formula (B) is not particularly limited, and examples thereof include the following exemplified compounds (1) to (30). It is done.
  • the content of the aromatic group that may contain a hetero ring in the binder is not particularly limited, but when the total structural unit of the polymer compound is 100 mol%, the structural formula (I) It is preferred to contain 20 mol% or more of the structural unit represented. It is more preferred to contain 30 to 45 mol%. When the content is less than 20 mol, storage stability may be lowered, and when it exceeds 45 mol%, developability may be lowered. [0085] Ethylenically unsaturated bond
  • the ethylenically unsaturated bond is not particularly limited and may be appropriately selected according to the purpose.
  • those represented by the following structural formulas (III) to (v) are preferable.
  • R to R are each independently an l-valent organic group.
  • X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R.
  • Z represents an oxygen atom, a sulfur atom, -N-R, or a phenylene group.
  • R is a hydrogen atom
  • Or represents a monovalent organic group.
  • each R is independently, 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.
  • R to R may be, for example, a hydrogen atom, a halogen atom, or 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 includes, for example, a hydrogen atom and a substituent. But
  • Alkyl groups and the like are more preferred because of high hydrogen atom and methyl group s radical reactivity.
  • R 1 and R 2 are each independently, for example, hydrogen atom, halogen atom, amino
  • Z represents an oxygen atom, a sulfur atom, -NR-, or a phenyl group optionally having a substituent.
  • R represents an alkyl group which may have a substituent, a hydrogen atom,
  • a til group, an ethyl group, and an isopropyl group are preferable because they have high radical reactivity.
  • the content of the ethylenically unsaturated bond in the polymer compound is not particularly limited. Repulsive force 0.5 to 3. Omeq / g force is preferable, 1.0 to 3. Omeq / g force ⁇ is more preferable, 1. 5-2.8 meqZg is particularly preferred. If the content is less than 0.5 meqZg, the sensitivity may be low because the amount of curing reaction is small. 3. If the content is more than OmeqZg, the storage stability may deteriorate.
  • the content (meqZg) can be measured, for example, by iodine value titration.
  • the method of introducing an ethylenically unsaturated bond represented by the structural formula (III) into the side chain is not particularly limited, but examples thereof include a polymer compound containing a carboxyl group in the side chain and ethylene. It can be obtained by addition reaction of a compound having an unsaturated bond and an epoxy group.
  • the polymer compound containing a carboxyl group in the side chain is, for example, one or more radically polymerizable compounds containing a carboxyl group and, if necessary, one other radically polymerizable compound as a copolymerization component.
  • the above can be produced by a normal radical polymerization method, and examples of the radical polymerization method include suspension polymerization method and solution polymerization method.
  • the compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these, and examples thereof include a compound represented by the following structural formula (VI) and (VII). Are preferred. In particular, the use of the compound represented by the structural formula (VI) is preferable from the viewpoint of increasing sensitivity.
  • R represents a hydrogen atom or a methyl group.
  • L represents an organic group
  • the W represents a 4- to 7-membered aliphatic hydrocarbon group.
  • L is More preferred is an alkylene group having 1 to 4 carbon atoms.
  • the compound represented by the structural formula (VI) or the compound represented by the structural formula (VII) is not particularly limited, and examples thereof include the following exemplified compounds (31) to (40).
  • radical polymerizable compound containing a carboxyl group examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, ink-mouthed tonic acid, maleic acid, and p-carboxyl styrene. Particularly preferred are acrylic acid and methacrylic acid.
  • Examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonia such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride.
  • the reaction can be carried out by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours using a -um salt, pyridine, triphenylphosphine or the like as a catalyst.
  • the structural unit having an ethylenically unsaturated bond in the side chain is not particularly limited.
  • a structure represented by the following structural formula (m), a structure represented by the structural formula (iv), and a mixture thereof are preferable.
  • 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 (iii) to the structure represented by the structural formula (iv) is preferably 20 mol% or more, more preferably 20 to 50 mol%. 25-45 mol% is particularly preferred. If the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. If the content is more than 50 mol%, the storage stability may be deteriorated.
  • the polymer compound of the present invention may have a carboxyl group in order to improve various performances such as non-image area removability.
  • the carboxyl group can be imparted to the polymer compound by copolymerizing a radical polymerizable compound having an acid group.
  • Examples of the acid group having such radical polymerizability include carboxylic acid, sulfonic acid, and phosphoric acid group, and carboxylic acid is particularly preferable.
  • the radically polymerizable compound having a carboxyl group can be appropriately selected depending on the purpose, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, cucumber tonic acid, and ink fountain. Examples include acid, maleic acid, and ⁇ -carboxyl styrene. Among these, acrylic acid, methacrylic acid, and p-carboxyl styrene are preferable. These may be used alone or in combination of two or more.
  • the content of the carboxyl group in the binder is 1.0 to 4. OmeqZg, preferably 1.5 to 3. Omeq / g.
  • 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. 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, methacrylic esters such as aryl acrylate, alkyl methacrylate, styrene such as aryl methacrylate, styrene, alkyl styrene, alkoxy
  • acrylic esters such as alkyl acrylate, methacrylic 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 1 to 20 carbon atoms of the alkyl group are preferable.
  • Rate amyl methacrylate, hexyl methacrylate, cyclohexenomethacrylate, benzyl methacrylate, chlorbendyl methacrylate, octyl methacrylate, ginseng, 4-hydroxybutynole methacrylate, 5 hydroxy
  • Examples include pentinoremetatalylate, 2, 2 dimethyl-3-hydroxypropyl metatalylate, trimethylolpropane monometatalate, pentaerythritol monometatalate, glycidyl metatalylate, furfuryl metatalylate, tetrahydrofurfuryl metatalylate, etc.
  • 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.
  • the molecular weight of the polymer compound of the present invention is preferably 10,000 or more in terms of mass average molecular weight, 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 singly or in combination of two or more. Moreover, you may mix and use another high molecular compound. In this case, the content of the other polymer compound in the polymer compound of the present invention is preferably 50% by mass or less, more preferably 30% by mass or less.
  • the solid content of the binder in the photosensitive composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
  • the polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose.
  • a compound having one or more ethylenically unsaturated bonds is preferable.
  • Examples of the ethylenically unsaturated bond include, for example, a (meth) ataryloyl group, a (meth) acrylamido group, a styryl group, a butyl group such as butyl ester and butyl ether, and a allylic group such as allyl ether allyl ester, and the like. Is mentioned.
  • the compound having one or more ethylenically unsaturated bonds is not particularly limited, and can be appropriately selected depending on the purpose.
  • a monomer having a (meth) acryl group is selected. At least one is preferably mentioned.
  • the monomer having a (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monofunctional acrylates and monofunctional methallylates such as rate and phenoxychetyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate Rate, trimethylolpropane ditalylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta erythritol tri (meth) acrylate, dipentaerythritol hexane (Meth) acrylate, dipentaerythritol penta (meth) acrylate,
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • the 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. is there.
  • the photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light may have some effect with photo-excited sensitizers, and may be active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates.
  • the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexarylbiimidazole, oxime derivatives, organic peroxides. Products, thio compounds, ketone compounds, aromatic onium salts, meta-octenes, and the like.
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.
  • hexarylbiimidazole for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.
  • hexarylbiimidazole for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.
  • oxime derivatives for example, those having a triazine skeleton, those
  • photopolymerization initiators include the compounds described in [0288] to [0309] of JP-A-2005-258431.
  • the photopolymerization initiators may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator in the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass. preferable.
  • Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and others.
  • sensitizers thermal polymerization inhibitors, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and others.
  • plasticizers for example, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like
  • adhesion promoters to the substrate surface and others.
  • conductive particles fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.
  • the sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible laser, or the like as a light irradiation means described later.
  • the sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals and It is possible to generate useful groups such as acids.
  • substances for example, radical generator, acid generator, etc.
  • energy transfer, electron transfer, etc. for example, energy transfer, electron transfer, etc.
  • Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer-type initiator system described in JP-A-2001-305734 [(1) an electron-donating initiator and a sensitizing dye (2) Electron-accepting initiators and sensitizing dyes, (3) Electron-donating initiators, sensitizing dyes and electron-accepting initiators (ternary initiation system)], and the like.
  • the sensitizer can be appropriately selected from known sensitizers without particular limitations.
  • known polynuclear aromatics for example, pyrene, perylene, triphenylene
  • Xanthenes for example, fluorescein, eosin, erythrosine synth, rhodamine B, rose bengal
  • cyanines for example, indocarboyanine, thiacarboyanine, oxacarboyanine
  • merocyanines for example, merocyanine, carbomerocyanine
  • Thiazines eg, thionine, methylene blue, toluidine blue
  • atalidines eg, ataridin orange, chloroflavin, acriflavine, 9 phenyllacridin, 1,7-bis (9,9,1 ataridinyl) heptane
  • anthraquinone E.g., anthraquinone
  • squalium e.g.,
  • thixanthone compounds thixanthone, isopropyl thixanthone, 2,4 jetylthioxanthone, 1-clooxy-4 propyloxythixanthone, QuantacureQTX, etc.
  • Preferred are compounds in which a heterocyclic ring is condensed with a heterocyclic ring (condensed ring-based compound), and an amine compound substituted with at least two aromatic hydrocarbon rings and V of the aromatic heterocyclic ring.
  • hetero condensed ring ketone compounds (ataridon compounds, thixanthone compounds, coumarin compounds, etc.) and atalidine compounds are more preferable.
  • attaridone compounds and thixanthone compounds are particularly preferable.
  • the amine compound substituted with any one of the at least two aromatic hydrocarbon rings and aromatic heterocyclic rings is a sensitizer having an absorption maximum with respect to light in a wavelength range of 330 to 450 nm.
  • a di-substituted aminobenzene compound having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, an amino group on the benzene ring In contrast, a di-substituted amino-benzene compound having a substituent containing a sulfo-limino group at the carbon atom at the para position, a di-substituted amino-benzene compound having a carbostyryl skeleton, and at least two aromatics Examples thereof include compounds having a di-substituted amino-benzene as a partial structure, such as a compound having a structure in which a ring is bonded to a nitrogen atom.
  • one type may be used alone, or two or more types may be used in combination.
  • the content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and particularly preferably 0.05 to 1% by mass in the total solid content of the photosensitive composition. preferable.
  • 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 thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
  • thermal polymerization inhibitor examples include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted nanoquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, Cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2,6 di-t-butyl-4 cresol, 2,2, -methylenebis (4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 Toluidine, methylene blue, copper and organic chelating agent reactants, methyl salicylate, and phenothiazine, nitroso compounds, and chelates of troso compounds with A1.
  • the content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass with respect to the polymerizable compound of the photosensitive layer. 01 to 1% by mass is particularly preferred. When 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, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diphenyl phthalate.
  • Phthalic acid esters such as ril phthalate and octyl capryl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl dallicose phthalate, ethino retino eno ethino reglycolate, methyl phthal yl acetyl dalicolate, buty Glycol esters such as norephthalino lebutinoglycolate and triethylene glycol dicabrylate; tricresyl phosphate, triphenyl Phosphate esters such as sulfate; 4 Amides such as toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl seba Aliphatic dibasic acid esters such as keto, dibutyl sebac
  • the content of the plasticizer is preferably 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 'Pink B Splash (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 coloring pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during the formation of a permanent pattern. Different forces depending on the type of facial material Generally 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.
  • the photosensitive composition is used for the purpose of improving the surface hardness of the permanent pattern or keeping the coefficient of linear expansion low, or keeping the dielectric constant or dielectric loss tangent of the cured film low, if necessary.
  • Inorganic pigments and organic fine particles can be added.
  • the inorganic pigment can be appropriately selected from known ones that are not particularly limited.
  • kaolin barium sulfate, barium titanate, key oxide powder, fine powder oxide oxide, vapor phase method silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and my strength.
  • the average particle diameter of the inorganic pigment is preferably less than 10 m, more preferably 3 m or less. If the average particle size is 10 m or more, the resolution may deteriorate due to light scattering.
  • the organic fine particles can be appropriately selected according to the purpose without particular limitation, and examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle diameter of 1 to 5 / ⁇ , an oil absorption of about 100 to 200 m 2 Zg, spherical porous fine particles made of a crosslinked resin, and the like can be used.
  • the amount of the extender is preferably 5 to 60% by mass.
  • the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced.
  • the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.
  • a loose adhesion promoter can be used.
  • adhesion promoter examples include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638.
  • the content of the adhesion promoter is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on all components of the photosensitive layer. % To 5% by mass is particularly preferred.
  • the photosensitive composition according to the first aspect of the present invention has high sensitivity and high resolution, electroless gold plating resistance, and via and through-through resistance by specifying a binder and a thermal crosslinking agent to be used together. It is excellent in the embedding property of the tool, and a high-definition permanent pattern can be efficiently formed. Therefore, it can be widely used as a printed wiring board, color filter, pillar material, rib material, spacer, partition member and other display members, holograms, micromachines, proofs and other permanent patterns. It can be suitably used for forming a permanent pattern on a printed circuit board.
  • the photosensitive composition according to the second aspect of the present invention contains a binder, two or more polymerizable compounds, a photopolymerization initiator, and a thermal crosslinking agent, and if necessary, other components.
  • the noinder, photopolymerization initiator, and other components are as already described in the first embodiment.
  • the polymerizable compound includes two or more monomers.
  • the monomer is not particularly limited and can be appropriately selected depending on the purpose. For example, the number of functional groups is different.
  • Two or more monomers are preferred.
  • Examples of the two or more monomers having different numbers of functional groups include a combination of a monofunctional monomer and a polyfunctional monomer, and a combination of polyfunctional monomers.
  • Examples of the combination of the polyfunctional monomers include a combination of a bifunctional monomer and a trifunctional or higher monomer, and a combination of a bifunctional to tetrafunctional monomer and a pentafunctional or higher monomer. Of these, at least one is more preferably a monomer having 4 or more functional groups.
  • the monomer is preferably a monomer having at least one of urethane groups, aryl groups, ester groups, ether groups, and groups derived from an epoxy compound.
  • the monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose.
  • JP-A-2005-258431 [
  • the monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose.
  • a polyhydric alcohol compound having an aryl group a polyvalent amine compound.
  • esters or amides of unsaturated carboxylic acids with at least any of the above compounds and polyamino amino alcohol compounds for example, JP-A-2005-258431, [0264] to [0271]. And the like.
  • the monomer having an ester group is not particularly limited as long as it has an ester group, and can be appropriately selected depending on the purpose.
  • polyester acrylic oligomer (CN series manufactured by Sartoma Co., Ltd.), Daicel Examples include polyester acrylic oligomers manufactured by Cytec.
  • the monomer having an ether group is not particularly limited as long as it has an ether group, and can be appropriately selected according to the purpose. Examples thereof include monomers containing alkylene oxide as a structural unit.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, and a mixture thereof (for example, a mixture of ethylene oxide and propylene oxide).
  • Examples of the monomer containing an alkylene oxide as a structural unit include polyalkylene glycol di (meth) acrylate and polyalkylene glycol mono (meth) acrylate.
  • polyethylene glycol di (meth) acrylate polyethylene glycol mono (meth) acrylate
  • polyethylene glycol mono (meth) acrylate polypropylene di (meth) acrylate
  • the monomer having a group derived from the epoxy compound is not particularly limited as long as it has this, and may be appropriately selected depending on the purpose.
  • a commercially available epoxy compound may be (meth) acrylic. Examples include compounds to which an acid has been added.
  • the mass average molecular weight of the monomer having at least one of the urethane group, aryl group, ester group, ether group, and epoxy compound strength is, for example, 200 to 9,000 force S Preferable ⁇ , Preferable over 250 to 8,000 force S ⁇ , 300 to 7,000 force S Particularly preferred.
  • examples of the polymerizable compound include aliphatic groups. It is preferable to include at least one selected from ester monomers.
  • the aliphatic ester-based monomer is not particularly limited and can be appropriately selected depending on the purpose.
  • Atalylate trimethylolpropane tri Atalylate, trimethylolpropane ditalylate, neopentylglycol di (meth) talarate, pentaerythritol tetra (meth) atalylate, pentaerythritol tri (meth) attalylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, and the like.
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferred.
  • the content ratio of the monomer having at least one of the urethane group, aryl group, ester group, ether group, and epoxy compound force-derived group to the aliphatic ester monomer is expressed by mass ratio. 1: 100-100: 1 is preferred 1: 20-20: 1 is more preferred 1: 10 to 10: 1 is particularly preferred.
  • the total solid content in the photosensitive composition solid content of the polymerizable compound is 5 to
  • the adhesiveness of the photosensitive layer may become too strong.
  • the thermal cross-linking agent can be appropriately selected according to the purpose for which there is no particular limitation.
  • thermal cross-linking agent examples include epoxy resins in a range that does not adversely affect developability and the like in order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition.
  • the photosensitive composition according to the second embodiment of the present invention combines sensitivity, resolution, tackiness, electroless plating resistance, and storage by combining monomers other than aliphatic ester monomers as the polymerizable compound. Excellent stability and high-definition permanent patterns can be formed efficiently. For this reason, it can be suitably used for the same application as the photosensitive composition of the first embodiment.
  • the photosensitive film of the present invention has at least a support and a photosensitive layer having the above-mentioned photosensitive composition of the present invention on the support, and a thermoplastic resin layer or the like is appropriately selected depending on the purpose. Other layers are laminated.
  • the photosensitive layer is formed using the photosensitive composition of the present invention.
  • the minimum energy of light used for the exposure is not changed after the exposure and development. Scratch, it is Ri preferably good it is preferred instrument 0. 2 ⁇ 100mj / cm 2 It is 0. l ⁇ 200mi / cm 2, and still more preferably is 0. 5 ⁇ 50mjZcm 2 instrument l ⁇ Particularly preferred is 30 miZcm 2 .
  • capri may occur in the processing step, and if it exceeds 200 mjZcm 2 , the time required for exposure may become longer and the processing speed may become slower. .
  • the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is so-called development sensitivity. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure when exposed and the thickness of the cured layer generated by the development process following the exposure. .
  • the thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure.
  • the development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
  • the thickness of the cured layer and the thickness of the photosensitive layer before exposure are within ⁇ 1 m, it is considered that the thickness of the cured layer is not changed by exposure and development.
  • a method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a film thickness measuring device for example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.
  • the thickness of the photosensitive layer can be appropriately selected according to the purpose for which there is no particular limitation. However, if it is omitted, 1 to: L00 ⁇ m force S, preferably 2 to 50 ⁇ m force S 4-30 ⁇ m force S is particularly preferable.
  • the support can be appropriately selected according to the purpose for which there is no particular limitation. However, it is preferable that the photosensitive layer is peelable and has good light transmittance. Further, the surface is smooth. It is more preferable that the sex is good.
  • the support and protective film Specifically, for example, it is described in JP-A-2005-258431, [0342] to [0348].
  • a cushion layer an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface
  • a protective layer may be provided on the photosensitive layer.
  • the cushion layer is not particularly limited and may be appropriately selected depending on the purpose, and may be swellable or soluble or insoluble in an alkaline liquid.
  • thermoplastic resin examples include, for example, an ethylene / acrylate copolymer copolymer, styrene, and (meth) (Meth) such as saponified acrylate copolymer, kento of butyltoluene and (meth) acrylic ester copolymer, poly (meth) acrylate, butyl (meth) acrylate and vinyl acetate Acrylic ester copolymers, etc., (meth) acrylic acid ester and (meth) acrylic acid copolymer, styrene, (meth) acrylic acid ester and (meth) acrylic acid copolymer Etc.
  • an ethylene / acrylate copolymer copolymer styrene
  • (meth) (Meth) such as saponified acrylate copolymer, kento of butyltoluene and (meth) acrylic ester copolymer, poly (meth) acrylate, butyl (meth) acryl
  • the softness point (Vicat) of the thermoplastic resin in this case is a force that can be appropriately selected according to the purpose without any particular limitation. For example, 80 ° C or less is preferable.
  • the above-mentioned thermoplastic resin has a softness point of 80 ° C or less, as well as “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, Issued on October 25, 1968).
  • the organic polymers whose soft spot is about 80 ° C or less those that are soluble in alkaline liquids are listed.
  • various plasticizers compatible with the organic polymer material are added to the organic polymer material so that a substantial softness can be obtained. It is also possible to lower the point below 80 ° C.
  • the interlayer adhesive strength of the photosensitive film is not particularly limited, and can be appropriately selected according to the purpose.
  • the support and the cushion layer can be selected. It is preferable that the interlayer adhesion between them is the smallest.
  • 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 according to 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.
  • Alcohols and esters such as zircphosphate, uddernoresiphosphate and biphenyldiphosphate, amides such as toluenesulfonamide, and the like.
  • thermoplastic resin examples include a copolymer whose main component is an essential copolymer component of ethylene.
  • the copolymer having ethylene as an essential copolymer component is not particularly limited and can be appropriately selected according to the purpose.
  • ethylene vinyl acetate copolymer (EV A) ethylene-ethyl acrylate. Copolymer (EEA) and the like.
  • the interlayer adhesive force of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose.
  • the adhesive strength between the photosensitive layer and the cushion layer is preferably the smallest.
  • the method for adjusting the interlayer adhesive force can be appropriately selected depending on the purpose without any particular limitation.
  • various polymers, supercooling substances, adhesion improvers in the thermoplastic resin can be selected.
  • the ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component can be appropriately selected according to the purpose without any particular limitation, but is preferably 60 to 90 mass%, for example. 60-80% by mass is more preferred. 65-80% by mass is particularly preferred.
  • the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. If the amount exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled off. It may be difficult to produce the photosensitive film.
  • the thickness of the cushion layer can be selected as appropriate according to the purpose for which there is no particular limitation.
  • Force 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. First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution for a photosensitive film.
  • the solvent can be appropriately selected depending on the purpose without any particular limitation.
  • Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and n-xanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisoptyl ketone;
  • Esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; aromatic carbonization such as toluene, xylene, benzene, and ethylbenzene Hydrogens: Halogenated hydrocarbons such as tetrasalt carbon, trichloroethylene, blackform, 1, 1, 1-trichlor
  • the photosensitive resin composition solution is coated on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.
  • the method for applying the photosensitive composition solution is not particularly limited.
  • the force can be selected appropriately according to the purpose.
  • spray method roll coating method, spin coating method, slit coating method, etatrusion.
  • the coating method include a coating method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
  • the drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
  • the photosensitive film is preferably stored, for example, by winding it around a cylindrical core and winding it into a long roll.
  • the length of the long photosensitive film is not particularly limited. For example, a range force of 10-20,000 m can be appropriately selected. In addition, slitting may be performed for the convenience of the user, and a long body in the range of 100 1,000 m may be rolled. In this case, it is preferable that the support is wound up so as to be the outermost side.
  • the roll-shaped photosensitive film may be slit into a sheet shape. From the viewpoint of protecting the end face and preventing edge fusion during storage, the end face should have a separator (especially moisture-proof, desiccant). It is preferable to use materials with low moisture permeability.
  • 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 appropriately selected depending on the purpose without particular limitation. 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 boards (printed boards), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.
  • Examples of the method for producing the photosensitive laminate include, as the first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as the second aspect, in the photosensitive film of the present invention.
  • a method of laminating by transferring at least one of heating and pressurizing at least one of the photosensitive layer and transferring force is mentioned.
  • the photosensitive composition is applied and dried on the substrate to form a photosensitive layer.
  • the coating and drying method can be appropriately selected according to the purpose without any particular limitation.
  • the photosensitive composition is dissolved, emulsified or dispersed on the surface of the substrate in water or a solvent.
  • a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.
  • the solvent of the photosensitive composition solution can be appropriately selected depending on the purpose without particular limitation, and examples thereof include the same solvents as those used for the photosensitive film. They are
  • One type may be used alone or two or more types may be used in combination. Also, add a known surfactant.
  • the coating method and drying conditions are appropriately selected depending on the purpose without any particular limitation.
  • the same method and conditions as those used for the photosensitive film can be used.
  • the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing.
  • the protective film it is preferable that the protective film is peeled off and laminated so that the photosensitive layer overlaps the substrate.
  • the heating temperature is not particularly limited, and can be appropriately selected according to the purpose. For example, 15 to 180 ° C is preferable, and 60 to 140 ° C is more preferable.
  • the pressure of the pressurization is not particularly limited, and can be appropriately selected depending on the purpose. 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 is not particularly limited and may be appropriately selected depending on the purpose.
  • a laminator for example, Taisei Laminanee VP-II,-Chigo Morton Co., Ltd.
  • Preferable examples include VP130).
  • the photosensitive film and the photosensitive laminate of the present invention can efficiently form a high-definition permanent pattern by using the photosensitive composition of the present invention, a protective film, an interlayer insulating film, And various patterns such as permanent patterns such as solder resist patterns, color filters, pillar materials, rib materials, spacers, manufacturing liquid crystal structural members such as partition walls, holograms, micromachines, proofs, etc.
  • permanent patterns such as solder resist patterns, color filters, pillar materials, rib materials, spacers, manufacturing liquid crystal structural members such as partition walls, holograms, micromachines, proofs, etc.
  • it can be suitably used for forming a permanent pattern on a printed circuit board.
  • the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned in the formation of the permanent pattern, the photosensitive film of the present invention is high. Ion migration does not occur in the acceleration test (HAST) High-definition permanent patterns with excellent heat resistance and moisture resistance can be obtained, so that lamination to the substrate is performed more precisely.
  • HAST acceleration test
  • the 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 an appropriately selected imaging step.
  • the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention.
  • 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 exposure target 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 can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure and analog exposure are preferable. Among these, digital exposure is preferable.
  • the analog exposure can be appropriately selected depending on the purpose without any particular limitation. For example, exposure is performed with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like through a negative mask having a predetermined pattern. A method is mentioned.
  • the digital exposure can be appropriately selected according to the purpose without any particular limitation.
  • a control signal is generated based on pattern formation information to be formed, and modulated according to the control signal.
  • light For example, n light (where n is a natural number of 2 or more) two-dimensional light receiving means and receiving light from the light irradiating means.
  • the 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 on the exposed surface in almost all of the exposed region on the exposed surface of the photosensitive layer. Refers to exposure with a setting that intersects the N light spot rows (pixel rows) irradiated to the.
  • 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 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 flat moving stage 14 is provided.
  • 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 moving path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18.
  • a scanner 24 is provided on one side of the gate 22, and a plurality of (for example, two) sensors 26 for detecting the front and rear ends of the photosensitive material 12 are provided on the other side.
  • the scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14.
  • the scanner 24 and the sensor 26 are connected to a controller (not shown) for controlling them.
  • an X axis and a Y axis that are orthogonal to each other are defined in a plane parallel to the surface of the stage 14, as shown in FIG.
  • the "U" shape 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 is a light spot position detecting means for detecting a light spot as a pixel unit in the used pixel part specifying process described later.
  • a single cell type 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 mode of the pattern forming apparatus at the time of exposure may be a mode 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 the scanning direction. Is attached. Therefore, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed for each exposure head 30 in the photosensitive layer 12.
  • the scanner 24 includes ten exposure heads arranged in a matrix of 2 rows and 5 columns.
  • the individual exposure heads arranged in the m-th column and the n-th column are indicated, they are represented as exposure heads 30, and the exposure by the individual exposure heads arranged in the m-th row and the n-th column mn
  • 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 is a light modulation unit that modulates incident light for each pixel part according to image data (modulation for each pixel part).
  • DMD36 (made by Texas Instruments Inc., USA) as a spatial light modulator.
  • This DMD36 is a controller as a pixel part control means having a data processing part and a mirror drive control part. Connected to the trawler.
  • 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 (light emission point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32.
  • a fiber array light source 38 having an emission part, a lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and reflecting the laser light transmitted through the lens system 40 toward the DMD 36
  • the mirrors 42 to be used are arranged in this order.
  • the lens system 40 is schematically shown.
  • the lens system 40 includes a pair of combination lenses 44 for collimating the laser light emitted from the fiber array light source 38, and a collimated laser. It is composed of a pair of combination lenses 46 that correct the light amount distribution of light so that it is uniform, and a condensing lens 48 that condenses the laser light whose light amount distribution has been corrected on the DMD 36.
  • a lens system 50 that forms an image of the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed.
  • the lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.
  • the laser light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is 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). , MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), optical element that modulates transmitted light by electro-optic effect (PLZT element), liquid crystal light shirter (FLC), etc.
  • DMD digital micromirror device
  • MEMS Micro Electro Mechanical Systems
  • PZT element optical element that modulates transmitted light by electro-optic effect
  • FLC liquid crystal light shirter
  • 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 support is Inclined to one of ⁇ ⁇ degrees (for example, ⁇ 10 degrees) with respect to the substrate side on which the DMD 36 is disposed with the diagonal line as the center.
  • Fig. 7 ⁇ ⁇ shows a state tilted to + ⁇ degrees when the micromirror 58 is on
  • Fig. 7 ⁇ shows a state tilted to ⁇ degrees when the micromirror 58 is off Show the state.
  • the laser light B incident on the DMD 36 moves in the inclination direction of each micromirror 58. Reflected.
  • FIG. 6 shows an example in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + ⁇ degrees or ⁇ degrees.
  • the on / off control of each micromirror 58 is performed by the controller connected to the DM D36.
  • a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.
  • the light irradiation means can be appropriately selected according to the purpose without any particular limitation.
  • a known light source such as a semiconductor laser or means capable of combining and irradiating two or more lights can be mentioned. Among these, means capable of combining and irradiating two or more lights are preferable.
  • the light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • ultraviolet to visible light, electron beams, X-rays, laser light, etc. are mentioned, and among these, laser light is preferred.
  • Laser that combines two or more lights hereinafter sometimes referred to as “combined laser”) ) Is more preferable. Even when the support is peeled off and the light is irradiated with light, the same light can be used.
  • the wavelength of the ultraviolet to visible light is preferably 300-1,500 nm, more preferably 320-8 OOrnn force, particularly preferably 330-650 mn force! / ,.
  • the wavelength of the laser light is, for example, 200 to 1,500 nm force, more preferably 300 to 800 nm force, more preferably 330 to 500 mn force, and 400 to 450 mn force.
  • a means capable of irradiating the combined laser for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber.
  • a means having a collective optical system for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber.
  • a means having a collective optical system for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber.
  • the used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot as a pixel unit on the exposed surface, and a detection result by the light spot position detecting means. It is preferable to have at least a pixel part selection means for selecting a pixel part to be used for realizing N double exposure.
  • the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and the variation in resolution and density unevenness due to the mounting angle error of each exposure head 30 are reduced.
  • the set tilt angle ⁇ in the column direction of the pixel part (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 etc. From the angle ⁇ , which is exactly double exposure using a 1024 column x 256 row pixel part
  • the ideal also uses a slightly larger angle.
  • This angle ⁇ is the number of N exposures N, the number of usable micromirrors 58 in the row direction s
  • the angle ⁇ is about 0.45 degrees according to the equation 3. Therefore, the set inclination angle ⁇ is, for example, about 0.50 degrees. An angle of degrees should be adopted. It is assumed that the pattern forming apparatus 10 is initially adjusted within an adjustable range so that the mounting angle of each exposure head 30, that is, each DMD 36 is an angle close to the set inclination angle ⁇ .
  • FIG. 8 shows unevenness generated 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 initially adjusted as described above. It is explanatory drawing which showed the example.
  • the light spot as the pixel unit generated by each pixel part (micromirror) and constituting the exposure region on the exposed surface the light spot in the m-th row 3 ⁇ 4 ⁇ (m), the light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).
  • FIG. 8 shows a pattern of light spots from the usable micromirror 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is The pattern of the light spot group as shown in the upper part appears, and the state of the exposure pattern formed on the exposed surface is shown when the stage 14 is moved in this state and continuous exposure is performed. Is.
  • FIG. 8 for convenience of explanation, the exposure pattern by the odd-numbered columns of the micromirrors 58 that can be used and the exposure pattern by the even-numbered columns are shown separately. However, the actual exposure patterns on the exposed surface are shown in FIG. It is a superposition of two exposure patterns.
  • the set tilt angle 0 is set to a slightly larger angle than the above angle 0.
  • FIG. 8 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” is generated in which the inclination angle of each pixel column projected on the surface to be exposed is not uniform.
  • the cause of this angular distortion is the various aberrations and misalignment of the optical system between the DMD36 and the exposed surface, the distortion of the DMD36 itself, and the placement error of the micromirrors. Etc.
  • 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, 512).
  • the stage 14 is slowly moved to relatively move the slit 28 along the ⁇ axis direction, and the light spot ⁇ (256, 512
  • the slit 28 is positioned at an arbitrary position such that) comes between the upstream slit 28a and the downstream slit 28b.
  • the value of this coordinate (XO, YO) is determined and recorded by the movement distance of the stage 14 to the 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.
  • the micro area is such that the total area of the overexposed area and the underexposed area is minimized with respect to the ideal double exposure.
  • the mirror can be selected as the micromirror that is actually used.
  • the smallest natural number equal to or greater than the value t may be derived.
  • a micromirror that minimizes the area of the overexposed area and produces an insufficient exposure area for ideal double exposure. Can be selected as the actual micromirror to be used.
  • a micromirror that minimizes the area of the underexposed area and does not produce an overexposed area with respect to the ideal double exposure It can be selected as a micromirror to be actually used.
  • FIG. 11 shows the unevenness on the exposed surface shown in FIG. 8 in the exposure performed using only the light spot generated by the micromirror selected as the micromirror actually used as described above. It is explanatory drawing which showed how it is improved.
  • T 253 is derived as the natural number T and the micromirror on the 253rd line is selected as the first line force.
  • a signal for setting the angle in the always-off state is sent by the pixel part control means. Is not involved in exposure. As shown in Fig. 11, overexposure and underexposure are almost completely eliminated in the exposure area near the 512th column, and uniform exposure very close to ideal double exposure is realized.
  • the inclination angle of the light spot sequence on the 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.
  • a plurality of actual tilt angles are respectively measured, and any one of the average value, median value, maximum value, and minimum value is specified as an actual tilt angle ⁇ '.
  • the 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 exposure is not ideal for ideal N double exposure. It is possible to realize exposure that places more importance on the elimination of areas that become legs, for example, to realize exposure that minimizes the area of areas that are overexposed and does not cause areas that are underexposed. Is possible.
  • 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).
  • the pattern forming apparatus 10 includes each exposure head 30, that is, each DM. It is assumed that D36 is initially adjusted so that the mounting angle of D36 becomes this angle ⁇ .
  • 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 a superposition of these two exposure patterns.
  • the light spot position detection is performed. Using a combination 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. [0242] Detection of one position (coordinate)
  • FIG. 13 shows the positional relationship between the exposure areas 32 and 32 similar to those in FIG.
  • the size from 12 21 is sufficiently large to cover the connecting area between the heads formed on the exposed surface.
  • Figure 14 shows an example of detecting the position of light spot P (256, 1024) in exposure area 32.
  • the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream.
  • the slit 28 is positioned at an arbitrary position between the slit 28a on the side and the slit 28b on the downstream side.
  • the coordinates of the intersection of the slit 28a and the slit 28b are (XO, Y0).
  • the value of this coordinate (XO, Y0) is determined and recorded by the movement distance of the stage 14 to the above position indicated by the drive signal given to the stage 14 and the known X-direction position force of the slit 28.
  • the stage 14 is moved, and the slit 28 is relatively moved along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 14, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector.
  • the coordinates (XO, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).
  • the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. Then, as 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).
  • the position of light spot ⁇ (256, 1) in exposure area 32 is Detection is performed by a combination of a slit 28 and a photodetector as a position detection means.
  • exposure area 32 is a combination of a slit 28 and a photodetector as a position detection means.
  • each light spot on the light spot line r (256) of the 256th line of 21 is detected in order of P (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 position of the light spot P (256, N) in the exposure area 32 is detected for the number N of N double exposures.
  • the positions of the light spots that make up the rightmost 1020th column are represented by P (l , 1020)
  • the force is also detected in order as P (l, 1020), P (2, 1020) ..., and light spot P indicating an X coordinate larger than light spot P (256, 2) in exposure area 32 (m, 1020)
  • 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.
  • the light spot P (l, 1020) force of exposure area 32 is also P (m -Micromirror force corresponding to 2, 1020) Specified as a micromirror not used in this exposure.
  • micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 15 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set their micromirror angle to the off-state angle, and these micromirrors are essentially not used for exposure.
  • the total area of areas that are overexposed and underexposed to light can be minimized, and uniform exposure very close to ideal double exposure is achieved, as shown in the lower part of Fig. 15. can do.
  • the X coordinate of the light spot P (256, 2) of the exposure area 32 and the exposure area are determined when specifying the light spot that constitutes 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 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, making it possible to achieve ideal N double exposure.
  • the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30.
  • the relative position of the two exposure heads (for example, exposure heads 30 and 30) in the X-axis direction deviates from the ideal state, as well as each exposure.
  • each exposure head 30 that is, each DMD 36
  • the set tilt angle of each exposure head 30, that is, each DMD 36 can be used as long as there is no mounting angle error of the exposure head 30 and the 1024 columns x 256 rows of usable pixel parts (micrometers).
  • 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 each exposure head 30, that is, each DMD 36 are initially adjusted as described above. , And relative mounting angle error between each exposure head 30 and 30
  • 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.
  • Use pixel selection processing is performed to reduce density unevenness due to the influence of the angle difference. Specifically, a set of the slit 28 and the photodetector is used as the light spot position detecting means, and the actual inclination angle ⁇ ′ is specified for each of the exposure heads 30 and 30, and the actual inclination angle is determined.
  • processing for selecting a micromirror used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel portion selection means.
  • the actual inclination angle ⁇ ′ is specified by the light spot P (l,
  • a computing device connected to the photodetector is used. As with the arithmetic unit in the embodiment (1) described above,
  • the natural number T that is closest to the value t that satisfies this relationship is assigned to each of the exposure heads 30 and 30.
  • the (T + 1) line force on the DMD 36 is also identified as the micromirror that is not used for the main exposure.
  • the micromirror force corresponding to the light spots constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 is specified as a micromirror that is not used in the main exposure.
  • the micromirror force corresponding to the light spots constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 is specified as a micromirror that is not used in the main exposure.
  • the total area of the overexposed and underexposed areas with respect to the ideal double exposure can be minimized.
  • the smallest natural number equal to or greater than the value t may be derived. In that case, to multiple exposures in exposure areas 32 and 32
  • the 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 shift 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.
  • Figure 18B from each micromirror 58 on the DMD 36, There is also a form of beam diameter distortion that reaches the exposure area 32 on the exposed surface with different beam powers and different beam diameters.
  • magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposed light surface.
  • 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.
  • every (N-1) micromirror columns or adjacent to 1ZN rows of all light spot rows The reference exposure is performed using only the group of micromirrors that make up the row, and the microphone mirror that is not used during actual exposure is identified among the micromirrors used for the reference exposure so that uniform exposure can be achieved. You can do it.
  • the result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is subjected to analysis such as confirmation of resolution variation and density unevenness and estimation of the actual inclination angle.
  • the analysis of the result of the reference exposure is a visual analysis by the operator.
  • FIG. 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.
  • the sampled reference exposure Based on the results, it is possible to specify the micromirror to be used during the main exposure by checking the variation in resolution and uneven density, or by estimating the actual tilt angle.
  • a microphone aperture mirror other than the micromirror corresponding to the light spot array shown by hatching in FIG. 19B is designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. Is done.
  • a separate reference exposure may be performed in the same manner to specify a micromirror to be used during the main exposure, or the same pattern as that for odd-numbered light spot arrays may be applied. Good.
  • FIG. 20 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) -row micromirrors using a plurality of exposure heads.
  • Exposure is performed, and a reference exposure result is output as a sample. Based on the output result of the reference exposure, the two exposure heads check resolution variations and density unevenness in areas other than the head-to-head connection area formed on the exposed surface, and estimate the actual inclination angle. Therefore, it is possible to specify the micromirror to be used during the main exposure.
  • 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. Ideal for areas other than the head-to-head connection area A state close to a typical double exposure can be realized.
  • FIGS. 21A and 21B show an example of a mode in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to IZN rows of the total number of light spot rows. It is explanatory drawing shown.
  • a microphone mouth mirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 21B is actually used during the main exposure in the micromirrors in the first to 128th rows.
  • micromirror By specifying the micromirror to be used during the main exposure in this way, it is possible to achieve a state close to an ideal double exposure in the main exposure using the entire micromirror.
  • Figure 22 shows multiple exposure heads, and two adjacent exposure heads in the X-axis direction (for example, exposure heads 30 and 30), each corresponding to 1ZN rows of the total number of light spots
  • 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-micrometer used during the main exposure Can be specified.
  • the micro-mirror force other than the micro-mirror corresponding to the light spot array in the area 90 shown shaded in FIG. 22 and the area 92 shown by shading is the main exposure in the micro-mirrors in the first to 128th rows. Designated as actually used at the time.
  • a separate reference exposure may be performed in the same manner to specify the micromirror to be used for the main exposure, and the first to 128th lines are designated. The same pattern as that of the micromirror may be applied.
  • micromirror By specifying the micromirror to be used during the main exposure in this way, a state close to ideal double exposure is realized in areas other than the joint area between the heads formed on the exposed surface by the two exposure heads. it can.
  • the power described in the case where the main exposure is double exposure is not limited to this, and any multiple exposure over double exposure is possible. It is good.
  • the triple exposure power is set to approximately seven exposures, it is possible to achieve exposure with high resolution and reduced resolution variation and density unevenness.
  • the size of the predetermined portion of the two-dimensional pattern represented by the image data matches the size of the corresponding portion that can be realized by the selected use pixel. It is preferable that a mechanism for converting image data is provided. By converting the image data in this way, it is possible to form a high-definition pattern on the exposed surface according to the desired two-dimensional pattern.
  • the development is performed by removing an unexposed portion of the photosensitive layer.
  • the removal method of the uncured region can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a method of removing using a developer.
  • the developer can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include alkaline aqueous solutions, aqueous developers, organic solvents, etc. Among these, weakly alkaline aqueous solutions are mentioned. preferable.
  • Examples of the base component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and phosphoric acid.
  • Examples include lithium, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, and borax.
  • the pH of the weakly alkaline aqueous solution is, for example, preferably about 9 to about 8 to 12: L 1 is more preferable.
  • Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.
  • the temperature of the developer is a force that can be appropriately selected according to the developability of the photosensitive layer. For example, about 25 to 40 ° C. is preferable.
  • the developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.)
  • an organic solvent for example, alcohols, ketones, esters, ethers, amides, latatones, etc.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
  • the curing treatment step can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include full-surface exposure treatment and full-surface heat treatment.
  • Examples of the overall 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 permanent The film strength on the surface of the permanent pattern is increased.
  • the heating temperature in the entire surface heating is preferably 120 to 250 ° C, more preferably 120 to 200 ° C. If the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment. If the heating temperature exceeds 250 ° C, the resin in the photosensitive composition may be decomposed, resulting in film quality. May be weak and brittle.
  • the heating time in the whole surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
  • the apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
  • the pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern
  • the pattern is permanently formed on the printed wiring board by the permanent pattern forming method.
  • a pattern can be formed and soldering can be performed as follows.
  • the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), and a solder resist, and prevents external impact and conduction between adjacent electrodes.
  • the wiring may be subjected to impact or bending by an external force.
  • the interlayer insulating film is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board and a build-up wiring board.
  • a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, etc. It can be suitably used for various pattern formation, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for forming a permanent pattern on a substrate.
  • a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, etc. It can be suitably used for various pattern formation, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for forming a permanent pattern on a substrate.
  • the mass average molecular weight (Mw) of the obtained polymer compound was 15,000 as a result of measurement by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • * 1 represents a mixture of the structure represented by the following structural formula (a) and the structure represented by the following structural formula (b).
  • the mass average molecular weight (Mw) of the obtained polymer compound was polystyrene as a standard substance. As a result of measuring by gel permeation chromatography (GPC), it is 25,000 and 7 pieces.
  • Photopolymerization initiator I-1 (Ciba Specialty Chemicals Inc., Irgacure 819 (Arylphosphine oxide compound)) ⁇ 6 parts by mass
  • Sensitizer thixanthone compound represented by the following formula S— 1 (6) parts by mass
  • the barium sulfate dispersion is composed of 30 parts by mass of barium sulfate (manufactured by Nigaku Kogyo Co., Ltd., ⁇ 30), the polymer compound 1 (solid mass in the 1-methoxy-2-propanol solution) 30 parts by weight) 29.2 parts by weight, CI pigment 'Blue 15: 3 0.2 parts by weight, CI pigment' Yellow 185 0.05 parts by weight, and methyl ethyl ketone 40.55 parts by weight premixed Thereafter, it was prepared by using a motor mill ⁇ -200 (manufactured by Eiger) and dispersing for 3.5 hours at a peripheral speed of 9 mZs using Zircoyu beads having a diameter of 1. Omm.
  • the substrate was prepared by subjecting the surface of a copper-clad laminate (no through hole, copper thickness 1 2 / z m) on which wiring had been formed, to a chemical polishing treatment.
  • the photosensitive composition was applied by screen printing using a 120 mesh Tetron screen so that the thickness after drying was 30 m, and hot air circulation type at 80 ° C. for 15 minutes.
  • a photosensitive layer was formed by drying with a dryer, and a photosensitive laminated body in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared.
  • the photosensitive laminates were evaluated by the following methods for the shortest development time, sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness.
  • Table 2 shows the results other than the shortest development time.
  • the photosensitive layer in the photosensitive laminate prepared above by using a pattern forming apparatus described below, from 0. lruJ / cm 2 until lOOruJ / cm 2 at 2 1/2 times the interval of light energy of different light Were exposed twice to cure a part of the photosensitive layer.
  • a 1 mass% sodium carbonate aqueous solution at 30 ° C is sprayed on the entire surface of the photosensitive layer on the copper-clad laminate at a spray pressure of 0.15 MPa, twice the minimum development time. After spraying, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured.
  • a sensitivity curve was obtained by plotting the relationship between the amount of light irradiation and the thickness of the cured layer. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 m as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.
  • DMD 36 controlled to drive only 1024 ⁇ 256 6 rows, and optical for imaging the light shown in FIGS. 5A and 5B on the photosensitive film
  • a pattern forming apparatus 10 having an exposure head 30 having a system was used.
  • each exposure head 30, ie each DMD 36 is slightly larger than the angle ⁇ that is exactly double exposure using the available 1024 rows x 256 rows micromirror 58
  • This angle 0 is the number of N exposures N, the available micromirrors
  • the power shown for every other column of micromirrors 58 that can be used is divided into the exposure pattern by pixel column group A and the exposure pattern by pixel column group B.
  • the exposure pattern is a superposition of these two exposure patterns.
  • a set of a slit 28 and a photodetector is used as the light spot position detecting means, and an exposure head 30 is used.
  • the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head was measured.
  • the natural number T that is closest to the value t that satisfies this relationship is assigned to each of the exposure heads 30 and 30.
  • micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 were identified as micromirrors that are not used during the main exposure.
  • micromirrors corresponding to the light spots other than the light spots constituting the areas 78 and 80 covered by the oblique lines in FIG. 17 the area 82 covered by the oblique lines in FIG.
  • micromirrors corresponding to the light spots constituting the shaded area 84 were identified and added as micromirrors not used during the main exposure.
  • a signal for setting the angle of the always-off state is sent by the pixel unit control means, and these microphone mirrors are substantially It was controlled so that it was not involved in exposure.
  • the exposure areas formed by a plurality of the exposure heads in the exposure areas 32 and 32 are formed by a plurality of the exposure heads in the exposure areas 32 and 32.
  • test substrate is subjected to electroless gold plating according to the process described below, the appearance of the test substrate is changed, and a peeling test using a cellophane adhesive tape is performed. It was evaluated with.
  • test substrate as a printed circuit board that has been subjected to heat treatment (post-beta treatment) to form a solder resist pattern (permanent pattern), is a 30 ° C acid degreasing solution (Mexdermit Japan, Metex L-5B 20% by mass)
  • the sample was immersed in an aqueous solution for 3 minutes and then immersed in running water for 3 minutes and washed with water.
  • this substrate was immersed in a 30 ° C catalyst solution (Meltex, 10 mass% aqueous solution of Metal Plate Actuator 350) for 7 minutes, then immersed in running water for 3 minutes, washed with water, then 8 5 ° nickel plating solution of C (Meltex Co., Melplate Ni-865M, 20 volume 0/0 aqueous solution, pH 4. 6) was immersed for 20 minutes, after the electroless nickel plating, 10 wt After being immersed in a 1% sulfuric acid solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water.
  • a 30 ° C catalyst solution Mobalx, 10 mass% aqueous solution of Metal Plate Actuator 350
  • 8 5 ° nickel plating solution of C Meltex Co., Melplate Ni-865M, 20 volume 0/0 aqueous solution, pH 4. 6
  • 10 wt After being immersed in a 1% sulfuric acid solution at room temperature for 1 minute, it was immersed
  • a copper-clad laminate having an insulating layer thickness of 200 ⁇ m, a copper thickness of 18 ⁇ m, and a through hole having a diameter of 100 ⁇ m at a pitch of 5 mm was prepared by subjecting the surface to chemical polishing treatment.
  • the photosensitive composition was applied by a screen printing method using a 120 mesh Tetron screen so that the thickness after drying was 30 m, and a hot-air circulating drier at 80 ° C for 15 minutes.
  • the photosensitive layer is formed by applying and drying to a thickness of 30 m after drying.
  • a photosensitive laminate in which a photosensitive layer was formed on both sides of the copper clad laminate was prepared. Thereafter, the vicinity of the through-hole portion was cut with scissors and polished with a sandpaper (roughing: # 600 and main cutting: # 1200) until the cross-section of the through-hole portion could be observed. The through-hole cross section was observed and the embedding property was evaluated based on the following criteria.
  • the photosensitive laminate is irradiated with double exposure so that a horizontal line pattern in a direction orthogonal to the scanning direction of the exposure head is formed, and a part of the photosensitive layer is exposed.
  • a pattern was formed on the area in the same manner as (3) in the resolution measurement.
  • any five points of a line with a line width of 50 m were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ⁇ ), and the edge position in the field of view was observed.
  • edge roughness is preferably as the value is small because it exhibits good performance.
  • the photosensitive composition solution obtained in Example 1 was applied to a PET (polyethylene terephthalate) film having a thickness of 16 m, a width of 30 Omm, and a length of 200 m as the support with a bar coater, and 80 ° C.
  • a photosensitive layer having a thickness of 30 m was formed by drying in a hot air circulation dryer.
  • a polypropylene film having a thickness of 20 ⁇ m, a width of 310 mm, and a length of 210 m was formed as a protective film on the photosensitive layer. Were laminated by lamination to produce the photosensitive film.
  • the photosensitive film of the photosensitive film is in contact with the copper-clad laminate, and the protective film on the photosensitive film is peeled off, and a vacuum laminator (A photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) are laminated in this order. Prepared.
  • the crimping conditions were as follows: vacuuming time 40 seconds, crimping temperature 70 ° C, crimping pressure 0.2 MPa, pressurization time 10 seconds.
  • the photosensitive laminate was evaluated for sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness.
  • the resolution, electroless gold plating resistance, and edge roughness were evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • a part of the photosensitive layer is cured from the support side in the same manner as in Example 1 by the pattern forming apparatus described in Example 1. I let you. After standing at room temperature for 10 minutes, the support was peeled from the photosensitive laminate, and the amount of light energy required to cure the photosensitive layer was measured in the same manner as in Example 1.
  • the substrate was prepared by subjecting a surface of a copper clad laminate having an insulating layer thickness of 200 ⁇ m, a copper thickness of 18 ⁇ m, and a through hole having a diameter of 100 m at a pitch of 5 mm to chemical polishing.
  • the photosensitive layer of the photosensitive film is in contact with the copper-clad laminate on both sides of the copper-clad laminate. In this way, while peeling off the protective film on the photosensitive film, it was laminated using a vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130), the copper-clad laminate, the photosensitive layer, and the polyethylene
  • a vacuum laminator manufactured by Nichigo Morton Co., Ltd., VP130
  • the crimping conditions were as follows: vacuuming time 40 seconds, crimping temperature 70 ° C, crimping pressure 0.2 MPa, pressurization time 10 seconds.
  • Example 2 a mixture of a bisphenol A-based epoxy compound and a bisphenol F-based epoxy compound is combined with a bisphenol F-type epoxy compound (Epototo manufactured by Tohto Kasei Co., Ltd.) as shown in Table 1.
  • Novolak type epoxy compound epoxy equivalent 210 g / eq.
  • Example 2 a mixture of a bisphenol A epoxy compound and a bisphenol F epoxy compound is prepared as shown in Table 1, bisphenol F epoxy resin (manufactured by Tohto Kasei Co., Ltd., Epototo YDF— 8170C, epoxy equivalent 160g / eq.) 3 parts by mass and heterocycle-containing epoxy compound (Nissan Chemical Co., TEPIC-S, epoxy equivalent 100g / eq.) 2 parts by mass.
  • TEPIC-S epoxy equivalent 100g / eq.
  • Example 2 a mixture of a bisphenol A epoxy compound and a bisphenol F epoxy compound is prepared as shown in Table 1, bisphenol F epoxy resin (manufactured by Tohto Kasei Co., Ltd., Epototo YDF— 8170C, epoxy equivalent 160g / eq.) 3 parts by mass and alicyclic ring-containing epoxy compound (Nippon Kayaku Co., Ltd., XD-100, epoxy equivalent 250g / eq.) 2 parts by mass Except for the above, sensitivity, resolution, electroless gold plating resistance, The embedding property of the luhole and the edge roughness were evaluated. The results are shown in Table 2.
  • Example 2 a mixture of a bisphenol A epoxy compound and a bisphenol F epoxy compound is prepared as shown in Table 1, bisphenol F epoxy resin (manufactured by Tohto Kasei Co., Ltd., Epototo YDF— 8170C, epoxy equivalent 160g / eq.) 4 parts by mass and novolac epoxy compound obtained in Synthesis Example 3 (epoxy equivalent 5, OOOg / eq.) 2 parts by mass.
  • the sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 2 as shown in Table 1, the thermal crosslinking agent was 3 parts by mass of epototo ZX-1059 and a novolac type epoxy compound (Etototo YDCN-704L, epoxy equivalent 210 g, manufactured by Toto Kasei Co., Ltd.) / eq.)
  • a novolac type epoxy compound (Etototo YDCN-704L, epoxy equivalent 210 g, manufactured by Toto Kasei Co., Ltd.) / eq.)
  • the sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness were evaluated in the same manner as in Example 2 except that the amount was changed to 2 parts by mass. The results are shown in Table 2.
  • Example 2 a mixture of a bisphenol A epoxy compound and a bisphenol F epoxy compound is prepared as shown in Table 1, bisphenol F epoxy resin (manufactured by Tohto Kasei Co., Ltd., Epototo YDF— 8170C, epoxy equivalent 160g / eq.) 3 parts by weight and 1,4 bis [(3 methyl 3 oxeta-lmethoxy) methyl] benzene (oxetane compound) 2 parts by weight.
  • the sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 2 the polymer compound 1 was replaced with the polymer compound 2 obtained in Synthesis Example 2 as shown in Table 1, except that it was replaced with 87.4 parts by mass. Sensitivity, resolution, electroless gold plating resistance, through-hole embedding, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 10 (Example 10) In Example 2, the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by the following formula I 2 and the sensitizer was replaced with 0.6 parts by mass of N-methyl attaridone. , Sensitivity, resolution, electroless gold plating resistance, through-hole embedding, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 3 the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by Formula I 2 as shown in Table 1, in the same manner as in Example 3, the sensitivity, resolution, The electroless gold plating resistance, through hole embedding, and edge roughness were evaluated. Table the results
  • Example 4 the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by the following formula I 3 as shown in Table 1, in the same manner as in Example 4, the sensitivity, resolution, The electroless gold plating resistance, through hole embedding, and edge roughness were evaluated. Table the results
  • Example 5 the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by the following formulas 1-4 as shown in Table 1.
  • electroless gold plating resistance, through-hole embedding, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 2 instead of the pattern forming apparatus, a glass negative mask having a pattern similar to the above was prepared separately, and this negative mask was brought into contact with the photosensitive laminate, and an exposure amount of 40 miZcm 2 was obtained using an ultrahigh pressure mercury lamp. And exposed. After that, the sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness were evaluated in the same manner as in Example 2 except that development was performed in the same manner as in Example 2 and the resolution was measured. It was. The results are shown in Table 2.
  • Example 14 a mixture of a bisphenol A-based epoxy compound and a bisphenol F-based epoxy compound was combined with a bisphenol F-type epoxy compound as shown in Table 1 (Epototo manufactured by Tohto Kasei Co., Ltd.). YDF— 8170C, epoxy equivalent 160g / eq.) 3 parts by mass and Novolak type epoxy compound (Etototo YDCN— 704L, epoxy equivalent 210 g / eq.) 2 parts by mass Except for the above, sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness were evaluated in the same manner as in Example 14. The results are shown in Table 2.
  • Example 14 a mixture of a bisphenol A epoxy compound and a bisphenol F epoxy compound was prepared as shown in Table 1, bisphenol F type epoxy resin (manufactured by Tohto Kasei Co., Ltd. Epototo YDF— 8170C, epoxy equivalent 160g / eq.) 3 parts by mass and heterocycle-containing epoxy compound (Nissan Chemical Co., TEPIC-S, epoxy equivalent 100g / eq.) 2 parts by mass Except for the above, in the same manner as in Example 14, the sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
  • Example 14 a mixture of a bisphenol A epoxy compound and a bisphenol F epoxy compound was prepared as shown in Table 1, as shown in Table 1. Seisha, Epototo YDF-8170C, epoxy equivalent 160g / eq.) 3 parts by mass and alicyclic ring-containing epoxy compound (Nippon Kayaku Co., Ltd., XD-100, epoxy equivalent 250g / eq.) 2 mass The sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness were evaluated in the same manner as in Example 14 except that the part was replaced with the part. The results are shown in Table 2.
  • Example 14 the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by the following formula 1-4 as shown in Table 1.
  • electroless gold plating resistance, through hole embedding, and edge roughness were evaluated. The results are shown in Table 2.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Une composition photosensible pouvant être formée efficacement avec un motif permanent de haute précision (film protecteur, diélectrique intercouches, motif de résine de protection 'solder resist' etc.); un film photosensible; un produit en couches photosensible; un procédé de formation d'un motif permanent sur le produit en couches photosensible; et une carte de circuits imprimés ayant un motif formé selon le procédé de formation de motif permanent. La composition photosensible comprend un liant, au moins un composé polymérisable, un initiateur de photopolymérisation et un agent de réticulation thermique, le liant contenant un polymère doté d'un groupe acide et d'une liaison éthyléniquement insaturée dans une chaîne latérale et au moins le composé polymérisable ou bien l'agent de réticulation thermique contient au moins deux composés.
PCT/JP2006/323425 2006-03-16 2006-11-24 Composition photosensible, film photosensible, produit en couches photosensible, produit de formation d'un motif permanent, et carte à circuits imprimés Ceased WO2007108172A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-072693 2006-03-16
JP2006072693A JP2007248843A (ja) 2006-03-16 2006-03-16 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
JP2006-072747 2006-03-16
JP2006072747A JP2007248846A (ja) 2006-03-16 2006-03-16 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、永久パターン、及びプリント基板

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JP6607811B2 (ja) * 2016-03-11 2019-11-20 マクセルホールディングス株式会社 メッキ部品の製造方法、メッキ部品、触媒活性妨害剤及び無電解メッキ用複合材料

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WO2006068048A1 (fr) * 2004-12-24 2006-06-29 Fujifilm Corporation Matériau de formation de motifs, appareil de formation de motifs et procédé de formation de motifs
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JP2002287353A (ja) * 2001-03-28 2002-10-03 Nippon Paint Co Ltd フォトソルダーレジスト組成物
JP2002363231A (ja) * 2001-06-06 2002-12-18 Taiyo Ink Mfg Ltd 樹脂組成物
JP2003029402A (ja) * 2001-07-19 2003-01-29 Goo Chemical Co Ltd 紫外線硬化性樹脂組成物及びドライフィルム
JP2003165827A (ja) * 2001-11-29 2003-06-10 Mitsubishi Gas Chem Co Inc 感光性熱硬化樹脂組成物
JP2003270786A (ja) * 2002-03-14 2003-09-25 Goo Chemical Co Ltd 感光性樹脂組成物、フォトソルダーレジストインク、プリント配線板、フレキシブルプリント配線板及びドライフィルム
JP2003280193A (ja) * 2002-03-26 2003-10-02 Taiyo Ink Mfg Ltd アルカリ現像型感光性樹脂組成物及びそれを用いたプリント配線基板
JP2005114992A (ja) * 2003-10-07 2005-04-28 Mitsubishi Chemicals Corp 光硬化性組成物、並びにそれを用いた光硬化性画像形成材料、光硬化性画像形成材、及び画像形成方法
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JP2006047501A (ja) * 2004-08-02 2006-02-16 Hitachi Chem Co Ltd 感光性樹脂組成物、永久レジスト用感光性フィルム、レジストパターンの形成方法及びプリント配線基板
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