WO2007055220A1 - Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern - Google Patents

Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern Download PDF

Info

Publication number
WO2007055220A1
WO2007055220A1 PCT/JP2006/322232 JP2006322232W WO2007055220A1 WO 2007055220 A1 WO2007055220 A1 WO 2007055220A1 JP 2006322232 W JP2006322232 W JP 2006322232W WO 2007055220 A1 WO2007055220 A1 WO 2007055220A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
mass
photosensitive
compound
film
Prior art date
Application number
PCT/JP2006/322232
Other languages
French (fr)
Japanese (ja)
Inventor
Toshiaki Hayashi
Takashi Tamura
Original Assignee
Fujifilm Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Priority to CN2006800424464A priority Critical patent/CN101310222B/en
Publication of WO2007055220A1 publication Critical patent/WO2007055220A1/en

Links

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • Photosensitive composition and photosensitive film and permanent pattern and method for forming the same
  • the present invention includes a compound that does not react at room temperature during storage, initiates a crosslinking reaction by heating, and obtains good film hardness of a cured film, and can form an image by UV exposure.
  • the present invention relates to a photosensitive composition that exhibits properties and the like, a photosensitive film using the same, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) and an efficient formation method thereof.
  • components such as semiconductors, capacitors and resistors are soldered on the printed wiring board.
  • a soldering process such as IR reflow
  • it corresponds to the unnecessary part of soldering as a protective film and an insulating film.
  • a method of forming a permanent pattern is adopted.
  • a solder resist is preferably used as the permanent pattern of the protective film.
  • solder resist a thermosetting material is often used, and a method in which this is applied by screen printing is generally used.
  • the screen printing method has a limit in terms of resolution, and a photo solder resist for forming an image by a photolithographic method has been actively used.
  • alkali development type photo solder resists that can be developed with a weak alkali solution such as sodium carbonate solution are mainly used in terms of working environment and global environment conservation.
  • a liquid solder resist is applied to one side of a substrate on which wiring has been formed by screen printing, spray coating, dip coating, etc., dried, and then applied to the opposite side and dried.
  • the alkali development type photo solder resist as described above, a compound in which an acid group for imparting an ethylenically unsaturated double bond and alkali developability to an epoxy compound as a main component (A composition containing an epoxy acrylate and an addition polymerizable compound (monomer) having an ethylenically unsaturated double bond is generally used, and specifically disclosed in Patent Document 1.
  • the solder resist described in Patent Document 1 has a high surface hardness after post-baking and excellent chemical resistance, but the surface tack remains and dust tends to adhere to increase the defects, or the photo resist. There is a problem of deteriorating handling properties such as contamination of the mask.
  • the tack remains on the surface because the molecular weight of epoxy acrylate, which is a binder soluble in an alkaline aqueous solution, is as low as several hundreds, and the monomer is usually a liquid or semi-solid with a high boiling point. It is dismissed if there is.
  • the exposure sensitivity of such solder resists is usually as low as 300 to 1, OOOiujZcm 2, which is becoming a bottleneck in speeding up the production line, and further improvement in sensitivity is required.
  • the ability to increase the amount of the monomer is effective to increase the sensitivity. If a large amount of monomers are added, the problem that the surface tack is further worsened, and no solution has been found. .
  • LDI laser direct imaging system
  • the solder resist used in the LDI is required to have an exposure sensitivity of lOOmiZcm 2 or more in order to cope with a UV laser of 365 nm or 405 nm. For this reason, A film-type solder resist is required to achieve high sensitivity.
  • the solder resist described in Patent Document 1 is made into a film, the tackiness of the surface is strong, the support or protective film is difficult to peel off from the photosensitive layer, and the handling property is poor. Even frozen storage can only be stored for a few months, and there is a problem of storage stability. In addition, the sensitivity to laser light having a wavelength of 405 nm is inferior.
  • Patent Document 2 uses a binder soluble in a relatively high molecular weight alkaline aqueous solution having a molecular weight of 10,000 or more, has a small surface tackiness, excellent heat resistance, and relatively storage stability.
  • a good solder resist has a problem that the surface hardness is low and the laminate property is poor. Therefore, it is necessary to apply a liquid monomer as an undercoat layer in advance to the outermost layer of a printed wiring board on which wiring has been formed without generating bubbles, which makes the process complicated and inferior in handleability. have.
  • the cured film is flexible as a result of the use of a copolymer component that forms a rigid polymer such as methyl methacrylate and styrene (Tg of each homopolymer is 105 ° C or higher and 100 ° C). It is considered that the surface hardness does not increase due to chipping, and that sufficient fluidity cannot be obtained in the heating and laminating process under vacuum conditions, causing bubbles to be generated. Furthermore, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.
  • Non-Patent Document 1 and Patent Document 3 a proposal has been made that contains a salt of zinc 2-ethylhexylate and triethanolamine, and a salt of triethylenediamine and an aliphatic carboxylic acid! (See Non-Patent Document 1 and Patent Document 3). These are intended to reduce solubility, suppress reaction activity, and improve storage stability by using a complex accelerator as a curing accelerator.
  • an epoxy resin compound as a thermal cross-linking agent has been disclosed to improve storage stability by making it hardly soluble (see Patent Document 8 and Patent Document 9).
  • Patent Document 8 and Patent Document 9 it was difficult to balance storage stability, which has a low exposure sensitivity of 300 to 500 mjZcm 3 , with high sensitivity and developability.
  • thermo crosslinking agent that initiates a crosslinking reaction by heating that does not cause a reaction at room temperature, can form an image by UV exposure, and can be peeled off from a support or the like with a low surface tack.
  • Photosensitivity composition that can exhibit excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development with excellent laminating and handling properties, excellent storage stability, high sensitivity and excellent developability The present situation is that there is still no satisfactory product, and a photosensitive film using the same, a high-definition permanent pattern, and an efficient formation method thereof.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 61-243869
  • Patent Document 2 Japanese Patent Laid-Open No. 02-097502
  • Patent Document 3 Japanese Patent Laid-Open No. 11-246651
  • Patent Document 4 Japanese Patent Laid-Open No. 56-155222
  • Patent Document 5 Japanese Unexamined Patent Publication No. 57-100127
  • Patent Document 6 Japanese Unexamined Patent Publication No. 59-053526
  • Patent Document 7 Japanese Patent Laid-Open No. 2000-001526
  • Patent Document 8 Japanese Patent No. 2746009
  • Patent Document 9 Japanese Patent No. 2707495
  • Non-Patent Document 1 Nippon Oil & Fats, Endooka lj (Tokyo Tech) Network polymer voll9, No. 4, P2 28—235, 1998
  • An object of the present invention is to solve the conventional problems and achieve the following object. That is, the present invention includes a compound that does not react at room temperature during storage, starts a crosslinking reaction by heating, and provides a cured film with good film hardness. Low tackiness, good laminating and handling properties, excellent storage stability, high sensitivity, excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development It is an object of the present invention to provide a photosensitive composition, a photosensitive film using the same, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) and an efficient formation method thereof. To do.
  • a photosensitive composition comprising at least one compound selected from compounds represented by the following general formulas (1) to (3).
  • ⁇ represents any of an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene, and an arylene.
  • Q represents any of a boron atom, a nitrogen atom, alkylene, and arylene.
  • W represents naphthalene having two X moieties and a bond.
  • Ai A 5 represents a single bond, alkylene, or arylene, and ⁇ to 6 represent one of —OCONH—, —NHCOO—, —NHCO—, and —CONH. !
  • ⁇ To 6 represent any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
  • the photosensitive composition according to ⁇ 1> curing does not occur during storage at a low temperature or normal temperature, it has excellent storage stability and handleability, and a reaction is caused by heating, resulting in excellent film hardness of the cured film. Is obtained.
  • a permanent pattern is formed using the photosensitive composition, a highly sensitive pattern can be formed, and the chemical resistance, surface hardness, heat resistance, and dielectric properties of the cured film can be improved, and a high-definition permanent pattern can be obtained. A pattern is obtained.
  • At least one compound selected from the compounds represented by the general formulas (1) to (3) is a compound represented by the following structural formulas (1) to (10) The photosensitive composition according to ⁇ 1>.
  • the thermal crosslinking agent used in combination is an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and at least a melamine derivative selected. It is a photosensitive composition as described in 4> above.
  • thermo crosslinking agent used in combination is a force-induced epoxy compound with a polyhydric phenol compound and j8-alkylephalohydrin. Composition.
  • thermo crosslinking agent used in combination is an epoxy compound having two or more oxosilane groups in the molecule.
  • thermo crosslinking agent used in combination is an oxetane compound having two or more oxetal groups in the molecule. is there.
  • R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
  • R represents any of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms.
  • R ′ represents either a hydrogen atom or CH, and n represents 0.
  • thermo crosslinking agent used in combination is hexamethylated methylolmelamine.
  • X represents any of a hydrogen atom and a substituent containing at least an acidic group
  • Y represents any of a methylene group, an isopropylidene group, and a sulfole group
  • n represents an integer of 1-20.
  • the copolymer 1 is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of a maleic anhydride copolymer. > To ⁇ 5> and ⁇ 10>.
  • the polymer is (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, 0.1 to 1.0 equivalent of a primary amine compound is reacted with an anhydride group of a copolymer consisting of a vinyl monomer having a glass transition temperature (Tg) of less than 80 ° C.
  • Tg glass transition temperature
  • the photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexarylbiimidazole, oxime derivative, organic peroxide, thio compound, keton compound, aromatic onium salt. And ketoxime ether power.
  • the photosensitive composition according to any one of ⁇ 1> to 17>, which contains at least one selected from the group.
  • a photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to any one of ⁇ 1>, 18 and 18 on the support. It is.
  • a photosensitive film according to ⁇ 19> is LOOmjZcm 2.
  • ⁇ 23> The photosensitive film according to any one of ⁇ 19> to ⁇ 22>, which is long and wound in a roll.
  • ⁇ 25> The photosensitive film according to any one of ⁇ 19> to ⁇ 24>, wherein the photosensitive layer has a thickness of 3 to 100111.
  • the photosensitive layer modulates the light from the light irradiation means by the light modulation means having n picture elements for receiving and emitting the light from the light irradiation means, the light is emitted from the light irradiation means.
  • the photosensitive film according to the above ⁇ 19> to ⁇ 25> which is exposed by light passing through a microphone aperture lens array in which microlenses having aspherical surfaces capable of correcting aberration due to surface distortion are arranged.
  • the photosensitive composition according to any one of ⁇ 1> to ⁇ 18> is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. This is a permanent pattern forming method characterized by this.
  • the photosensitive composition is applied to the surface of the substrate, and the applied photosensitive composition is dried to form the photosensitive layer. Is done.
  • the photosensitive layer is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated.
  • a crosslinking reaction is started to increase the film strength of the cured region of the photosensitive layer.
  • an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern.
  • the heat treatment may be a whole surface heat treatment or a heat treatment in a pattern.
  • the photosensitive film according to any one of the above is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed.
  • a permanent pattern forming method characterized by heating.
  • the photosensitive film is laminated on the surface of the substrate under heating and pressing.
  • the photosensitive layer in the laminated photosensitive film is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated.
  • the film strength of the cured region of the photosensitive layer is increased by the crosslinking effect of the compounds represented by the general formulas (1) to (3).
  • an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern.
  • ⁇ 30> The permanent pattern forming method according to any one of ⁇ 27>, ⁇ 29>, wherein the exposure is performed imagewise based on pattern information to be formed.
  • the control signal is generated based on the pattern information to be formed, and the control signal is generated using light modulated in accordance with the control signal. This is a permanent pattern forming method.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the light modulation means has n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts.
  • the permanent pattern forming method according to any one of ⁇ 32> to ⁇ 33>, which can be controlled according to pattern information.
  • any less than n pixel parts arranged continuously from the n pixel parts in the light modulation means may be selected according to the pattern information.
  • ⁇ 36> The permanent pattern forming method according to 35, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • the light modulation means modulates the light, and then passes through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface of the picture element portion in the light modulation means 38.
  • the method for forming a permanent pattern according to any one of 34> Karaku 37>.
  • ⁇ 40> The method for forming a permanent pattern according to any one of the above items 27> to 39>, wherein the exposure is performed through an aperture array.
  • the extinction ratio is improved by performing exposure through the aperture array.
  • the exposure is performed with extremely high definition.
  • the photosensitive layer is developed to form a very fine permanent pattern.
  • ⁇ 41> The method for forming a permanent pattern according to any one of ⁇ 27>, ⁇ 40>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
  • exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
  • ⁇ 42> The method for forming a permanent pattern according to any one of ⁇ 27> to ⁇ 41>, wherein the exposure is performed on a partial region of the photosensitive layer.
  • the light irradiation means can synthesize and irradiate two or more lights.
  • the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth.
  • the exposure to the photosensitive layer is performed with extremely high definition.
  • the photosensitive layer is developed to form an extremely fine permanent pattern.
  • 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 laser forces and couples the laser beams to the multimode optical fiber.
  • the laser light respectively emitted from the plurality of lasers is condensed by the converging optical system by the light irradiation unit and coupled to the multimode optical fiber.
  • exposure is performed with exposure light having a deep focal depth.
  • the exposure of the photosensitive layer is performed with extremely high definition.
  • the photosensitive layer is developed to form a very fine permanent pattern.
  • ⁇ 46> The method for forming a permanent pattern according to any one of ⁇ 27>, et al. ⁇ 45>, which is performed at a heat of 120 to 250 ° C.
  • the film strength of the cured film is increased in the heat treatment performed under the temperature condition.
  • ⁇ 48> The method for forming a permanent pattern according to any one of the above ⁇ 27> and ⁇ 47>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
  • the wiring is externally provided due to the insulation property, heat resistance, etc. of the film. Protected against impacts and bending.
  • the permanent pattern described in 49> is formed by the method for forming a permanent pattern, so that it has excellent chemical resistance, surface hardness, heat resistance, etc., and has high definition, and is a multilayer wiring board for semiconductor components. It is useful for high-density mounting on PCBs and build-up wiring boards.
  • the permanent pattern according to the above item 49 which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in ⁇ 50> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring has an external force or the like depending on the insulating property and heat resistance of the film. Force and bending are protected.
  • Laminate that contains compound can be imaged by UV exposure, and has low surface tack And a photosensitive composition that has good handling properties, excellent storage stability, high sensitivity and excellent developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development, and
  • a high-definition permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern
  • an efficient formation method thereof can be provided.
  • the photosensitive composition of the present invention comprises (A) a polymer having one or more carboxyl groups and ester groups in one molecule, (B) a polymerizable compound, and (C) a photopolymerization initiator. And (D) a compound represented by the following general formulas (1) to (3): at least one selected from at least one compound, and a thermal cross-linking agent used in combination. Depending on the type, it may contain other components such as coloring pigments, extender pigments, thermal polymerization inhibitors, and surfactants.
  • the noinder is preferably a compound exhibiting swellability in an alkaline aqueous solution, and more preferably a compound that is soluble in an alkaline aqueous solution.
  • binder exhibiting swellability or solubility with respect to the alkaline aqueous solution for example, those having an acidic group are preferably mentioned.
  • an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound.
  • Compound (epoxy atalytoyl compound), vinyl copolymer having (meth) taroloyl group and acid group in the side chain, epoxy atalytoyl compound, and (meth) attalyloyl group in the side chain, and A mixture with a vinyl copolymer having an acidic group, a maleamic acid copolymer, and the like are preferable.
  • the acidic group is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From this point of view, a carboxyl group is preferred.
  • it can be obtained by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.
  • Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin ( ⁇ 4000; manufactured by Japan Epoxy Resin Co., Ltd.) or a mixture thereof, a complex having an isocyanurate skeleton, and the like.
  • Cyclic epoxy resin (“TEPIC: manufactured by Nissan Chemical Industries,” “ALALDITE PT810, manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated screw Phenolic A type epoxy resin, Bisphenol S type epoxy resin, Phenolic novolac type epoxy resin, Cresol novolac type epoxy resin, Halogen phenolic novolac type epoxy resin S, Glycidinoreamine type epoxy resin S (e.g., tetraglycidinoresinaminodiphenol methane), hydantoin type Poxy resin, cycloaliphatic epoxy resin, trihydroxyphenyl methane type epoxy resin, bisphenol, novolac epoxy resin, tetraphenylethane epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyle Tan resin, naphthalene group-containing epoxy resin ("ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co
  • polyphenolic compounds obtained by condensation reaction with aromatic aldehydes for example, p-hydroxybenzaldehyde
  • epichlorohydrin Reaction product Polyphenolic compound obtained by addition reaction of phenolic compound with diolefin compound such as dibutenebenzene dicyclopentagen and epichlorohydrin; 4 Opening of vinylcyclohexene-1 oxide Epoxy resin of ring polymer with peracetic acid, etc .; Epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; Epoxy resin with glycidyl metaaterylate copolymer (“CP-50S, CP-50 M "Manufactured by Nippon Oil & Fats Co., Ltd.”), and a copolymerized epoxy resin of cyclohexylmaleimide and glycidylmethacrylate. These may be used alone or in combination of two or more.
  • Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl -Rubenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, a-ciano cinnamic acid, acrylic acid dimer; in addition, 2-hydroxyethyl (meth) An addition reaction product of a monomer having a hydroxyl group such as acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic acid anhydride; a reaction product of a nonogen-containing carboxylic acid compound; ⁇ Carboxy-Poly-Power Pro-Lataton Mono (Meth) Atarylate.
  • commercially available products include ALONIX ⁇ -5300, ⁇ —5400, ⁇ —5500 and ⁇ —5600 manufactured by Toa Gosei Kagaku Kogyo Co., Ltd. ⁇ Ester CB—1 manufactured by Shin-Nakamura And CBX-1, Kyoeisha Yushi Chemical Co., Ltd. ⁇ -MP and ⁇ -MS, Osaka Organic Chemical Industry Co., Ltd. Viscoat # 2100, etc. can be used. These may be used alone or in combination of two or more.
  • polybasic acid anhydride examples include succinic anhydride, methyl succinic anhydride, anhydrous 2,3 dimethyl succinic acid, anhydrous 2,2 dimethyl succinic acid, ethyl succinic anhydride, anhydrous dodecyl succinic acid, and anhydrous Lusuccinic acid, maleic anhydride, methylmaleic anhydride, 2,3 dimethylmaleic anhydride, 2 chloromaleic anhydride, 2,3 dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, ciscacot anhydride Acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetra
  • the epoxy atelar toy compound represented by the following structural formulas (III) and (IV) I like things,
  • X represents any of a hydrogen atom and a substituent containing at least an acidic group
  • ⁇ represents any of a methylene group, an isopropylidene group, and a sulfol group
  • ⁇ Represents an integer of 1-20.
  • ⁇ represents an integer of 1 to 20.
  • epoxy ata relay toy compound represented by the structural formula (III) specifically, a bisphenol F type epoxy ata relay toy compound represented by the following structural formula (V), and A bisphenol-type epoxy atelar toy compound represented by the following structural formula (VI) is more preferred.
  • the molecular weight of the epoxy acrylate compound is preferably 1,000,000-100,000 force, more preferably 2,000-50,000 force S. If the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may increase, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 000, developability may deteriorate. Also, synthesis of the resin becomes difficult.
  • Examples of the vinyl copolymer having a (meth) atalyloyl group and an acidic group in the side chain include (1) a vinyl monomer having an acidic group, and (2) can be used for a polymer reaction described later if necessary.
  • the acidic group of the vinyl monomer having an acidic group (1) can be appropriately selected according to the purpose without any particular limitation, and is described in, for example, [0164] described in JP-A-2005-258431. And the like. These monomers can be May be used alone or in combination of two or more.
  • monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
  • the functional group that can be used for the high molecular reaction includes a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc.
  • the above-mentioned (1) carboxyl group and acid anhydride group are also usable functional groups.
  • Examples of the vinyl monomer having a hydroxyl group include the compounds described in [0182] to [0192] of JP 2005-258431 A.
  • Examples of the butyl monomer having an amino group include benzylbenzylamine, aminoethyl methacrylate, and the like.
  • Examples of the monomer having an isocyanate group include compounds described in [0176] to [0180] of JP-A-2005-258431.
  • Examples of the butyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (45).
  • R represents either H or Me.
  • Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
  • Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
  • Each of the monomers may be used alone or in combination of two or more.
  • the other copolymerizable monomer used as needed in (3) is not particularly limited, and can be appropriately selected according to the purpose.
  • Examples include the compounds described in [0165] to [0174].
  • Examples of a method for synthesizing a bulu monomer having a urethane group or a urea group as the functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, and specifically, an isocyanate group.
  • An addition reaction of a monomer having a hydroxyl group with a compound having one hydroxyl group or a compound having one primary or secondary amino group, a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, Addition reaction with cyanate can be mentioned.
  • Examples of the monomer having an isocyanate group include the compounds described in [0176] to [0180] of JP-A-2005-258431.
  • Examples of the monoisocyanate include the compounds described in [0181] of JP-A-2005-258431.
  • Examples of the monomer having a hydroxyl group include those described in JP-A-2005-258431 [0.
  • Examples of the compound containing one hydroxyl group include compounds described in [0193] of JP-A-2005-258431.
  • Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.
  • Examples of the compound containing one primary or secondary amino group include compounds described in [0195] of JP-A-2005-258431.
  • the vinyl (co) polymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. Example For example, it can be prepared by the method described in JP-A-2005-258431 [0198].
  • an acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It can be obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) atallyloyl group.
  • the functional group having reactivity with at least one of an acidic group in the (co) polymer of the above (4) or a functional group available for a polymer reaction, and a (meth) atallyloyl group As the compound having, the compound shown in the above (2) can be used.
  • Examples of combinations of functional groups for performing these polymer reactions include, for example, a copolymer having an acidic group (such as a carboxyl group) and a butyl monomer having an epoxy group, and a copolymer having an amino group.
  • Combination of polymer and acid group vinyl monomer having a ride group, combination of copolymer having amino group and vinyl monomer having active halide group, combination of copolymer having acid anhydride group and vinyl monomer having hydroxyl group
  • the maleamic acid copolymer is a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer.
  • the copolymer is represented by the following structural formula (VII): a maleamic acid system containing at least maleic acid unit B having maleic acid-formamide structure and unit A having no maleic acid-sulfamide structure.
  • VII structural formula
  • the unit A may be one type or two or more types.
  • the maleamic acid copolymer means a binary copolymer, and the unit A is two types.
  • the maleamic acid copolymer means a terpolymer.
  • the unit A includes an aryl group which may have a substituent and a butyl monomer which will be described later, and the glass transition temperature (Tg) of the butyl monomer homopolymer is less than 80 ° C.
  • Tg glass transition temperature
  • a combination with a certain vinyl monomer (c) is preferred.
  • R 3 and R 4 represent either a hydrogen atom or a lower alkyl group.
  • X and y represent mole fractions of the repeating units, for example, when the unit A is one, X is 85-50 mol 0/0, y is 15 to 50 mole 0/0.
  • R 1 for example, (—COOR 1C> ), (—CONRUR 12 ), an aryl group optionally having a substituent, (—OCOR 13 ), ( -Substituents such as OR 14 ) and (— COR 15 ).
  • R 1U to R 1 & represents one of a hydrogen atom (1H), an alkyl group which may have a substituent, an aryl group, and an aralkyl group.
  • the alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
  • R to R examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butinole, sec-butyl, t-butinole, pentinole, arinole, n-hexyl, cyclohexyl, 2 -Ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, black mouth
  • R 1 examples include benzene derivatives such as, for example, a file, a-methyl file, 2-methyl file, 3 methyl file, 4 methyl file, 2,4 dimethyl file, etc .; n —Propyloxycarbonyl, n-Butyloxycarbonyl, Pentyloxycarbonyl, Hexyloxycarbonyl, n-Butyloxycarbonyl, n-Hexyloxycarbonyl, 2-Ethylhexyloxycarbonyl, Methyloxy Bonyl and the like can be mentioned.
  • R 2 examples include a substituent group! /, But may include an alkyl group, an aryl group, an aralkyl group, and the like. These may have a cyclic structure or a branched structure. Specific examples of R 2 include, for example, benzyl, phenethyl, 3-phenol 1-propyl, 4-phenol 1-butinole, 5 phenol-1-pentinole, 6-phenol 1- Hexinole, a Methylbenzyl, 2 Methylbenzyl, 3 Methylbenzyl, 4 Methylbenzyl, 2 Mono (P-tolyl) ethyl, j8-Methylphenethyl, 1-Methyl-3-phenylpropyl, 2 —Black Benzynole, 3 Black Mouth Benzinore, 4-black mouth Benzore, 2 Fluoro Benzinore, 3— Fluoro Benzinore, 4 Fluoro Benzino
  • the binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, which is a homopolymer of the bull monomer.
  • Vinyl amines with a glass transition temperature (Tg) of less than 80 ° C and primary amines for the anhydride groups of powerful copolymers It is preferably a copolymer obtained by reacting a product.
  • a copolymer comprising the component (a) and the component (b) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties.
  • the copolymer comprising the component (a) and the component (c) although the laminating property can be ensured, it may be difficult to ensure the surface hardness.
  • the aromatic vinyl monomer is not particularly limited and can be appropriately selected according to the purpose.
  • the surface hardness of the photosensitive layer formed using the photosensitive composition of the present invention can be increased.
  • compounds having a glass transition temperature (Tg) of the homopolymer of 80 ° C or higher are preferred, and compounds having a temperature of 100 ° C or higher are more preferable.
  • Preferable examples include styrene derivatives such as C). These may be used alone or in combination of two or more.
  • the vinyl monomer needs to have a glass transition temperature (Tg) of a homopolymer of the vinyl monomer of less than 80 ° C, preferably 40 ° C or less, more preferably 0 ° C or less. .
  • Tg glass transition temperature
  • Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenol-1-propylamine, 4-phenol-l-butylamine, 5-phenol-l-pen. Tyramine, 6 phenyl 1-hexylamine, ⁇ -methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2 ( ⁇ -tolyl) ethylamine, ⁇ -methylphenethylamine Min, 1-Methyl-3 Phenylpropylamine, 2 Chlorobenzylamine, 3 Chlorobenzylamine, 4 Chlorobenzylamine, 2-Fluorobenzylamine, 3-Fluorobenzylamine, 4-Fluorobenzylamine, 4- Bromoethylylamine, 2— (2 black mouth) ethylamine, 2— (3 black mouth) ethylamine, 2— (4 black mouth) etherylamine, 2— (2 fluorophenol) )
  • the primary amine compounds may be used alone or in combination of two or more.
  • the reaction amount of the primary amine compound needs to be 0.1 to 1.2 equivalents, preferably 0.1 to 1.0 equivalents, relative to the anhydride group.
  • the solubility may be remarkably deteriorated when one or more primary amine compounds are reacted.
  • the content of the (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol%. If the content is less than 15 mol%, alkali developability cannot be imparted, and if it exceeds 50 mol%, alkali resistance deteriorates, and the copolymer becomes difficult to synthesize. Permanent pattern shape It may not be possible to complete.
  • the content of the (b) aromatic bule monomer and (c) the bulle monomer having a glass transition temperature (Tg) of the homopolymer of less than 80 ° C in the binder is respectively 20-60 mol% and 15-40 mol% are preferred. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.
  • the molecular weight of the maleamic acid copolymer is preferably 3,000 to 500,000, more preferably 8,000 to 150,000.
  • the molecular weight is less than 3,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later.
  • the molecular weight exceeds 500,000, the photosensitive composition is heated and laminated. The fluidity at the time may be low, and it may be difficult to ensure proper laminating properties, and the developability may deteriorate.
  • the binder may be used in combination with other binders.
  • other binders polyamide (imide) resins described in JP-A-11-288087, polyimide precursors described in JP-A-11-282155, and the like can be used. These can be used alone or in combination of two or more.
  • the molecular weight of the above-mentioned polyamide (imide) or polyimide precursor is preferably 3,000 to 500,000 force ⁇ , 5,000 to 100,000 force ⁇ ! ⁇ . If the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may increase, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 00,000, developability may deteriorate.
  • the solid content in the photosensitive composition solid content of the binder is preferably 5 to 70 mass%, more preferably 10 to 50 mass%. If the solid content is less than 5% by mass, the film strength of the photosensitive layer described later may be weakened or the tackiness of the surface of the photosensitive layer may be deteriorated immediately. If it exceeds 70% by mass, Exposure sensitivity may decrease.
  • the polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, but has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure.
  • the compound is preferably selected from monomers having a (meth) acrylic group Preferably, at least one of the above is mentioned.
  • the monomer having the (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose.
  • polyethylene glycol mono (meth) acrylate, 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 , Trimethylolpropane ditalylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate,
  • Atari rate such; as epoxy ⁇ and (meth) polyfunctional Atari rate and Metatarireto of Epoki Shiatarireto and the like which is a reaction product of acrylic acid.
  • Atari rate such; as epoxy ⁇ and (meth) polyfunctional Atari rate and Metatarireto of Epoki Shiatarireto and the like which is a reaction product of acrylic acid.
  • trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol pent (meth) acrylate are particularly preferred.
  • the solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
  • the photopolymerization initiator is limited as long as it has the ability to initiate polymerization of the polymerizable compound. For example, those having photosensitivity to visible light in the ultraviolet region are preferably photoexcited sensitization. It may be an activator that generates some action with the agent and generates active radicals. An initiator that initiates cationic polymerization according to the type of monomer may be used.
  • the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), phosphine oxides, hexarylbiimidazoles, oximes. Derivatives, organic peroxides, thio compounds, ketonic compounds, aromatic onium salts, metathelons, and the like.
  • halogenated hydrocarbon compound having a triazine skeleton examples include, for example, a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), British Patent 1388 492 Compounds described in JP-A-53-133428, compounds described in German Patent No. 3337024, J. Org. Chem. By FC Schaefer et al .; 29, 1527 (1964), Compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, compounds described in US Pat. No. 4212976 , Etc.
  • Examples of the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969) include, for example, the compounds described in [0291] of JP-A-2005-258431. Can be mentioned.
  • Examples of the compound described in British Patent 1388492 include the compounds described in [0292] of JP-A-2005-258431.
  • Examples of the compound described in JP-A-53-133428 include compounds described in [0293] of JP-A-2005-258431.
  • Examples of the compound described in German Patent 3337024 include compounds described in [0294] of JP-A-2005-258431.
  • Examples of the compound described in JP-A-62-58241 include compounds described in [0296] of JP-A-2005-258431.
  • Examples of the compound described in JP-A-5-281728 include compounds described in [0297] of JP-A-2005-258431.
  • Examples of the compounds described in JP-A-5-34920 include compounds described in [0298] of JP-A-2005-258431.
  • Examples of the compound described in US Pat. No. 4,212,976 include the compound described in [0299] of JP 2005-258431 A.
  • Examples of the phosphine oxide include compounds described in [0307] of JP-A-2005-258431.
  • Examples of the hexarylbiimidazole include 2, 2 'bis (2-clonal ring) 4, 4, 5, 5, 5, monotetraphenyl biimidazole, 2, 2, 1 bis ( o Fluorophore) —4, 4 ,, 5, 5, — Tetraphenol biimidazole, 2, 2, — Bis (2 bromophenol) — 4, 4, 4, 5, 5, monotetraphenol biimidazole, 2 , 2, 1 bis (2, 4 dichlorophenol) 4, 4 ,, 5, 1 tetraphenyl biimidazole, 2, 2, 1 bis (2 x 2 mouthpiece) —4, 4, 5, 5, 1-tetra (3-methoxyphenol) biimidazole, 2, 2, 1-bis (2-cyclophenol) 1, 4, 4, 5, 5, 5, 5, 1-tetra (4-methoxyphenyl) biimidazole, 2, 2, 1 bis (4-methoxyphenyl) 1, 4, 4, 5, 5, 1, tetraphenyl biimidazole 2, 2, 1, bis (2, 4 dich
  • Examples of the oxime derivative suitably used in the present invention include, for example, 3 benzoyloxyiminobutane 2 on, 3 acetoximininobutane 2 on, 3 propionyl oxyiminobutane 2 on, 2 acetoximinopentane 3-one, 2-acetoximino 1-phenolpropane 1-one, 2-benzoyloximino 1-phenolpropan 1-one, 3- (4-toluenesulfo-loxy) iminobutane 2 on, and 2 ethoxycarbo- For example, oxyimino 1-phenol propane 1-on.
  • organic peroxide examples include 3,3 ', 4,4'-tetra (t-butylperoxycarbol) benzophenone.
  • thioi compound examples include 2,4 jetylthioxanthone, 2,4-dichlorothioxanthone, 1 chloro-4 propoxythioxanthone, 2 benzoinolemethylene 3-methylnaphthothiazoline, and the like.
  • Examples of the ketone compound include the compounds described in [0305] of JP-A-2005-258431.
  • aromatic salt examples include diphenyl rhododonium tetrafluoroborate, diphne noredo um hexafnoreo phosphonate, and trifene noles norehonumute.
  • diphenyl rhododonium tetrafluoroborate diphne noredo um hexafnoreo phosphonate
  • trifene noles norehonumute For example, trough noreroborate, triphenol-norethnohexahexolenorophore phosphonate, tetraphenol hexahexafluorophosphate, and the like.
  • meta-port mosses e.g., bis (r 5 -2, 4 cyclopentadiene one 1-I le?) - bis (2, 6-difluoro one 3- (IH-pyrrol-one 1-I le) phenyl) titanium ⁇ 5 —cyclopentagel- 6 —tamale-iron (1 +) -hexafluorophosphate (1 1), and the like.
  • polyhalogen compounds such as vinyl glycine (for example, carbon tetrabromide, felt rib mouth methyl sulfone, phenyl trichloromethyl ketone, etc.), amines (E.g., 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid ⁇ -butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimidoethyl, 4 dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis ( 4-dimethylaminobenzoate), 3-dimethylaminobenzoate Phenethylene of perfume acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2 chloro 4 dimethylaminobenzaldehyde, 4 dimethylamin
  • the sensitizer can be appropriately selected depending on visible light, ultraviolet light, visible light 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.
  • These compounds also have a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation only by improving the sensitivity of the photosensitive layer.
  • the sensitizer can be appropriately selected from known sensitizers that are not particularly limited.
  • known polynuclear aromatics for example, pyrene, perylene, triphenylene
  • Xanthenes for example, fluorescein, eosin, erythrosine synth, rhodamine B, rose bengal
  • cyanines for example, indocarboyanine, thiacarboyanine, oxacarboyanine
  • merocyanines for example, merocyanine, carbomerocyanine
  • Thiazines for example, thionine, methylene blue, toluidine blue
  • atalidines for example, atalidine orange, chloroflavin, acriflavine
  • anthraquinones for example, anthraquinone
  • squaliums for example, squalium
  • Preferred examples of the sensitizer include hetero-fused compounds.
  • the heterocyclic ring-type compound means a polycyclic compound having a hetero element in the ring, and the ring Among these, it is preferable to contain a nitrogen atom.
  • Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound, a quinoline compound, and an atalidine compound.
  • hetero-fused ketone ketone compound examples include attaridone compounds such as attaridone, chloroacridone, N-methyl attaridone, N butyl attaridone, and N butyl chloro attaridone; (2 Benzofuroyl) 7 Jetylaminocoumarin, 3- (2 Benzofuroyl) -7- (1-Pyrrolidyl) coumarin, 3 Benzyl-7 Jetyl aminocoumarin, 3- (2-Methoxybenzoyl) 7 Jet Tyraminocoumarin, 3- (4 dimethylaminobenzoyl) 1-7-jetylaminocoumarin, 3, 3, 1-carborubis (5, 7-di-n-propoxycoumarin), 3, 3 , 1-Carbobis (7-Jetylaminocoumarin), 3-Benzyl 7-Methoxycoumarin, 3- (2-Furoyl) 7-Jetylaminotamarin, 3- (4-Jetylaminominonamoyl) 7 —Jetaridon
  • quinoline compound examples include quinoline, 9-hydroxy 1,2-dihydroquinoline-2 on, 9 ethoxy 1,2 dihydroquinoline-2 on, 9-dibutylamino 1,2 dihydroquinoline 2 on. , 8 hydroxyquinoline, 8 mercaptoquinoline, quinoline 2 -strong rubonic acid, and the like.
  • the atalidine compound examples include 9 phenyllacridin, 1,7-bis (9,9,1 allysyl) heptane, atalidine orange, chloroflavin, acriflavine, and the like. It is done.
  • these hetero-fused compounds those containing a nitrogen element in the ring are more preferable.
  • Preferred examples of the compound containing a nitrogen element in the ring include the acridine compound, a coumarin compound substituted with an amino group, and an attaridone compound. Of these, the talidone, coumarin substituted with an amino group, 9-phenylacridine, and the like are more preferred, and the talidone is particularly preferred.
  • 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 content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, based on all components in the photosensitive composition. 2 to 10% by mass is particularly preferable. If the content is less than 0.05% by mass, the sensitivity to active energy rays may be reduced, the exposure process may take time, and productivity may be reduced. When present, the sensitizer may precipitate from the photosensitive layer.
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • halogenated carbonization having the phosphine oxides, the ⁇ -aminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the later-described exposure.
  • a composite photoinitiator that combines a hydrogen compound and an amine compound, a hexaryl biimidazole compound, a hexaryl biimidazole compound and a hetero-fused compound, or a metaguchicene, And so on.
  • a chain transfer agent for example, a mercapto compound, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenthiazole, etc.
  • a chain transfer agent for example, a mercapto compound, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenthiazole, etc.
  • 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 0.5 to 15% by mass. Is particularly preferred.
  • P represents any of an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene, and an arylene.
  • Q represents any of a boron atom, a nitrogen atom, alkylene, and arylene.
  • W represents naphthalene having two X moieties and a bond.
  • Ai A 5 represents a single bond, alkylene, or arylene, and ⁇ to 6 represent one of —OCONH—, —NHCOO—, —NHCO—, and —CONH. !
  • ⁇ To 6 represent any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
  • the alkylene of P is an unsubstituted alkylene; at least any one of an aryl group, a alkenyl group, and a hydroxyl group, and an alkoxy group, a cyan group, and a halogen atom. At least a substituted-containing alkylene substituted with a shift is shown.
  • the unsubstituted alkylene is preferably one having a total number of carbon atoms of 1 to 20 which may have a double bond or a triple bond which may have a branch, and particularly preferably 1 to 8.
  • alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, and cyclohexylene.
  • aryl substituent in the above-mentioned alkylene containing a substituent those having a total carbon number of 6 to 30 are preferable, and those having 6 to 15 are particularly preferable.
  • substituents include phenyl, naphthyl, and anthracene. Groups, methoxyphenol groups, chlorophenol groups, and the like.
  • the alkenyl substituent in the substituent-containing alkylene preferably has a total carbon number of 2 to 10 and particularly preferably 2 to 6, such as an ethyl group, a propenyl group, a butyryl group, etc. Is mentioned.
  • the alkoxy substituent in the substituent-containing alkylene the total number of carbon atoms of 1 to 10 which may have a branch is preferable, and 1 to 5 is particularly preferable.
  • the substituent include a methoxy group. Ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
  • a double bond which may have a branch or a triple bond which may have a triple bond is preferable, and 2 to 25 is particularly preferable.
  • Examples of such a substitution-containing alkylene include a 2-ethylhexyl group, a chlorobutyl group, a benzyl group, a 2-ethylpropyl group, a phenylethyl group, a cyanopropyl group, and a methoxycetyl group.
  • the P arylene has the same meaning as the Ai A 5 arylene described below.
  • examples of the alkylene of Q include the unsubstituted alkylene, and the unsubstituted alkylene includes a double bond that may have a branch,
  • the total number of carbon atoms that may have a triple bond is preferably 2-30.
  • examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, and cyclohexylene.
  • the Q arylene has the same meaning as the Ai A 5 arylene described below.
  • the binding site with the X portion of W is 1, 2, 1, 3, 1, 5, 5, 1, 6, 1, 7, 8th, 2nd, 3rd, 2nd, 4th, 2nd, 5th, 2nd and 7th positions, and W may be substituted with any of an alkyl group, aryl group, alkoxy group, and halogen atom Good.
  • Ariren of the Ai ⁇ A 5 is a benzene ring, as well as Al kill group, Ariru group, Aruke - group, an alkoxy group, Shiano group, and a halogen atom At least one of the substituents is substituted with a deviation and represents a substituent-containing arylene.
  • a double bond that may have a branch or a total number of carbon atoms that may have a triple bond is preferably 1 to 20.
  • LO Particularly preferred.
  • examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an S butyl group, a t butyl group, a butyryl group, a cyclohexyl group, and a cyclohexenole group.
  • aryl group in the substituent-containing arylene those having a total carbon number of 6 to 30 are preferable, and those having 6 to 15 are particularly preferable.
  • substituent include a phenyl group, a naphthyl group, and an anthracene group. Group, methoxyphenol group, chlorophenol group, and the like.
  • alkyl group in the substituent-containing arylene a double bond that may have a branch or a total number of carbon atoms that may have a triple bond is preferably 1 to 20. : LO is particularly preferred.
  • Examples of such an alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. It is done.
  • the alkenyl substituent in the substituent-containing arylene preferably has a total carbon number of 2 to: LO, and particularly preferably 2 to 6 as the substituent, for example, an ethur group, a propenyl group, a pentyl group, and the like Is mentioned.
  • the alkoxy substituent in the substituent-containing arylene the total number of carbon atoms that may be branched is 1 to: LO is preferable, and 1 to 5 is particularly preferable.
  • the substituent include methoxy. Group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
  • Such a substituent-containing arylene is particularly preferably 2 to 25, preferably having a total of 2 to 40 carbon atoms which may have a double bond or a triple bond.
  • Examples of such a substitution-containing arylene include a methylphenol ring, a dimethylphenol ring, a dibutylphenol ring, a methoxyphenyl ring, a cyclohexylphenol ring, a biphenyl structure, a dichlorophenol ring, and a tribromophenol. Ring, chlorocyanophenyl ring, and the like.
  • the alkylene of Ai A 5 has the same meaning as the alkylene of P.
  • the Xi X 6 is, as described above, OCONH, 1 NHC
  • the alkyl group represented by- is an unsubstituted alkyl group; Substituted with at least one of an alkyl group, a alkenyl group, and a hydroxyl group, and at least one of an alkoxy group, a cyano group, and a halogen atom, and an oxygen atom, a sulfur atom, a carbonyl group, an amide group, a urethane And / or a divalent group of an ester group and / or a substituent-containing alkyl group.
  • the unsubstituted alkyl group is preferably a double bond that may have a branch or a triple bond that preferably has a total carbon number of 1 to 20, more preferably 1 to 10.
  • Examples of such an alkyl group include a methyl group, an ethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, a cyclohexyl group, Etc.
  • aryl substituent in the substituent-containing alkyl group those having a total carbon number of 6 to 30 are preferable, and 6 to 15 are particularly preferable.
  • substituents include a phenyl group and a naphthyl group. , Anthracenyl group, methoxyphenyl group, black mouth phenyl group, and the like.
  • alkenyl substituent in the substituent-containing alkyl group include a total carbon number of 2 to: LO is preferred, and 2 to 6 is particularly preferred.
  • substituent include ethynyl group, propenyl group, and petityl. Group, and the like.
  • alkoxy substituent in the substituent-containing alkyl group examples include a branched group, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples include methoxy group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
  • Such a substituent-containing alkyl group is particularly preferably 2 to 25, preferably having a total of 2 to 40 carbon atoms which may have a double bond or a triple bond.
  • Examples of such a substitution-containing alkyl group include a 2-ethylhexyl group, a chlorobutyl group, a benzyl group, a 2-ethylpropyl group, a phenylethyl group, a cyanopropyl group, and a methoxyethyl group.
  • Specific examples of the compound represented by the general formula (1) include compounds represented by the following structural formulas (1) to (10), but are not limited to these compounds. .
  • the compounds represented by (7) and (9) are particularly preferred U ,.
  • the compounds represented by the general formulas (1) to (3) are compounds having two or more oxysilane rings having a substituent at the oxysilane ring site in one molecule, and these compounds are contained in the photosensitive composition. It can be identified by measuring the H-NMR ⁇ vector.
  • thermal crosslinking agent In addition to the compounds represented by the general formulas (1) to (3) that function as the thermal crosslinking agent, other conventionally known thermal crosslinking agents may be further used in combination.
  • the other thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose.
  • an epoxy compound having at least two oxanyl groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used as long as the developability is not adversely affected. .
  • Examples of the epoxy compound having at least two oxysilane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, an isocyanurate skeleton, etc.
  • Heterocyclic epoxy resin ("TEPIC; manufactured by Nissan Chemical Industries", “ALALDITE PT810; manufactured by Ciba Special Chemicals”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin Bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, Low brominated epoxy resin, high oil, logene epoxy resin, brominated phenolic Novo Type epoxy resin), allylic group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenol methanol type epoxy resin, phenol biphenol-type epoxy resin, di-sicated pentagen type Epoxy resin ("HP-7200, HP-7200H; Dainippon Ink & Chemicals Glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidyl dilin, triglycidyl aminophenol, etc.), g
  • oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3-oxeta-lmethoxy) methyl] ether.
  • 4-methyl-N, N amine compounds such as dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; block isocyanate compounds such as dimethylamine; imidazole, 2-methyl Such as imidazole, 2-ethylimidazole, 2-ethylimidazole, 2-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanethyl-2-phenylimidazole, and 1- (2-cyanethyl) -2-ethyl-4-methylimidazole Imidazole derivative bicyclic amidine compound Salts thereof; phosphorus compounds such as triphenyl-phosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2, 4 diamino 6-methacryloyloxychetyl S triazine, 2 bur 1, 2, 4 diamino 1 S triazine
  • the solid content in the solid content of the photosensitive composition of the epoxy compound, the oxetane compound, and a compound capable of accelerating thermal curing of these with a carboxylic acid is usually as follows.
  • a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is composed of at least two isocyanates. It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing a monoto group.
  • bifunctional isocyanates eg, mixtures of 1,3 and 1,4-phenolic diisocyanates, 2,4 and 2,6 toluene diisocyanates, 1,3 and 1,4 xylates
  • Range isocyanate bis (4-isocyanate monophenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone di-socyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate
  • the body is a burette; norbornane diisocyanate;
  • isocyanate group blocking agent examples include alcohols (eg, isopropanol, tert-butanol, etc.), ratatas (eg, ⁇ -strength prolatatum, etc.), phenols (eg, phenol, crezo-monore, p-tert-butinolephenol) Nore, p-sec butinolevenore, p-sec amylphenol, p-octylphenol, p-norphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline) And the like, and active methylene compounds (for example, dialkyl malonate, methyl ethyl ketoxime, acetyl acetone, alkyl acetoacetonitrile, acetooxime, cyclohexanone oxime, etc.).
  • a melamine derivative can be used as the thermal crosslinking agent.
  • the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, etc.). These may be used alone or in combination of two or more.
  • hexamethylated methylol melamine is particularly preferred because alkylated methylol melamine is preferred because it has good storage stability and the surface hardness of the photosensitive layer is effective in improving the film strength itself of the cured film. preferable.
  • aldehyde condensation products other than melamine, rosin precursors, and the like can be used.
  • the corresponding ethyl or butyl ether, or an ester of acetic acid or propionic acid may be used.
  • Photosensitive compositions of the compounds represented by the general formulas (1) to (3) and other thermal crosslinking agents The solid content in the solid content is preferably 1 to 50% by mass 3 ⁇ 30 mass% force is preferred. When the content is less than 1% by mass, the reaction during the heat treatment is lowered, and the strength of the cured film may not be improved. Decrease and film hardness of the cured film may occur.
  • thermosetting accelerator examples include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) N, N dimethylbenzilamine, 4-methoxy N, N dimethylbenzylamine, 4-methyl-N, N dimethylbenzylamine.
  • Amine compounds such as amine; quaternary ammonium salt compounds such as triethylbenzyl ammonium chloride; block isocyanate compounds blocked with dimethylamine and the like; imidazole, 2-methylimidazole, 2-ethylimidazole, 2 Etyl 4 —Methylimidazole, 2-phenolimidazole, 4-phenolimidazole, 1-cyanethyl-2-phenolimidazole, imidazole bicyclic amidine compounds such as 1- (2-cyanethyl) 2-ethyl-4-methylimidazole, etc.
  • Phosphorus compounds such as triphenylphosphine
  • Guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine
  • 2, 4 diamine 6 methacryloyloxychetyl S triazine 2 bul 1, 2, 4 diamine 1 S triazine, 2 S-triazine derivatives such as bulle 4, 6 diamino 1 S triazine 'isocyanuric acid, 2, 4 diamino-6-methacryloyloxychetyl S-triazine' isocyanuric acid adduct, etc.
  • the These may be used alone or in combination of two or more.
  • thermosetting accelerator is not particularly limited as long as it can accelerate the thermosetting of the epoxy atelar toy compound, and other compounds that can accelerate the thermosetting are used. Also good.
  • thermosetting accelerator in the solid content of the photosensitive composition is 0.01-1.
  • the other components include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other assistants.
  • Agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.
  • the thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
  • thermal polymerization inhibitor examples include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted nanoquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, Cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2, 6 di-tert-butyl-4 Cresol, 2,2, -methylenebis (4-methyl-6t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound -A chelate of a soy compound and A1.
  • the content of the thermal polymerization inhibitor is preferably from 0.001 to 5 mass%, more preferably from 0.005 to 2 mass%, based on the polymerizable compound. Mass% is particularly preferred. When the content is less than 0.001% by mass, the stability during storage may be reduced, and when it exceeds 5% by mass, the sensitivity to active energy rays may be reduced.
  • the coloring pigment can be appropriately selected according to the purpose without any particular limitation.
  • Bikku! J Pure One Blue BO CI 42595
  • Auramin CI 41000
  • Fat 'Black HB CI 26150
  • Monolight Yellow GT CI Pigment Yellow 12
  • Permanent Yellow GR CI Pigment Yellow 17
  • Permanent Yellow HR CI Pigment Yellow 83
  • Permanent Carmine FBB CI Pigment Red 146
  • Hoster Balm Red ESB CI Pigment 'Violet 19
  • Permanent' Ruby FBH CI Pigment 'Red 11
  • Huster's' Pink B Supra CI Pigment 'Red 81
  • Monastral' First 'Blue CI Pigment' Blue 15
  • Monolite 'First' Black B CI Pigment 'Black 1
  • Carbon CI Bigume 'Leg 97
  • 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 at the time of forming a permanent pattern. Different forces depending on the type of face Generally, 0.01 to 10% by mass is preferred 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, and examples thereof include kaolin, barium sulfate, barium titanate, potassium oxide powder, finely divided oxide silica, and vapor phase method silica.
  • the average particle diameter of the inorganic pigment is preferably less than 10 m, more preferably 3 m or less. If the average particle size is 10 m or more, the resolution may deteriorate due to light scattering.
  • the organic fine particles can be appropriately selected according to the purpose without particular limitation, and examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle diameter of 1 to 5 / ⁇ , an oil absorption of about 100 to 200 m 2 Zg, spherical porous fine particles made of a crosslinked resin, and the like can be used.
  • the amount of the extender pigment added is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.
  • a known adhesion promoter may be used for each layer.
  • adhesion promoter examples include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638.
  • the content of the adhesion promoter is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on all components in the photosensitive composition. 0.1 mass% to 5 mass% is particularly preferable.
  • the photosensitive composition of the present invention is capable of forming an image by UV exposure, has a low surface tackiness, good laminating properties and handling properties, and does not react at room temperature during storage, and is stable in storage. Excellent, high sensitivity, excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development. For this reason, displays such as protective films for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be widely used for forming permanent patterns such as members, holograms, micromachines, proofs, etc., and is particularly suitable for use in the photosensitive film, permanent pattern and method of forming the same of the present invention.
  • the photosensitive film of the present invention includes at least a support and a photosensitive layer, preferably includes a protective film, and further includes a cushion layer, an oxygen barrier layer (PC layer) and the like as necessary. It has other layers.
  • the form of the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose.
  • the photosensitive film and the protective film are provided on the support in this order.
  • Form Form in which the PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film on the support. In this order.
  • the photosensitive layer may be a single layer or a plurality of layers.
  • the photosensitive layer is formed by the photosensitive composition of the present invention.
  • the portion provided in the photosensitive film of the photosensitive layer can be appropriately selected according to the purpose without any particular limitation.
  • the photosensitive layer laminated on the support is an exposure step described later.
  • the aberration due to the distortion of the emission surface in the picture element It is preferable to be exposed to light through a microlens array in which microlenses with aspherical surfaces capable of correcting the light are arranged! /.
  • the minimum energy of light used in the exposure is 0.1 to 0.1 mm, without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development.
  • L00 (mj / cm 2) it is preferably a tool l ⁇ 80mj / cm 2 and it is more preferable arbitrariness. If the minimum energy power of light used for the exposure is less than 0.1 ImiZcm 2 , the processing margin may be narrowed, and if it exceeds lOOmiZcm 2 , the tact time becomes long, which is not preferable.
  • 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 is not changed by exposure and development.
  • the method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. (For example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) can be used.
  • the thickness of the photosensitive layer can be appropriately selected depending on the purpose for which there is no particular limitation. For example, 3 to: LOO m force is preferable, and 5 to 70 m is more preferable.
  • a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support.
  • coating a solution directly and drying is mentioned.
  • the solvent of the photosensitive composition solution can be appropriately selected according to the purpose without any particular limitation.
  • methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, n- Alcohols such as hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone; Ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl ethyl propionate, dimethyl phthalate , Esters such as ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichlorethylene, chloroform, 1,
  • the coating method can be appropriately selected depending on the purpose without any particular limitation.
  • 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 support can be appropriately selected according to the purpose without particular limitation, It is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and it is more preferable that the surface smoothness is good.
  • the support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic.
  • plastic films such as butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
  • the support for example, the supports described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, and the like are used. I can do it.
  • the thickness of the support is not particularly limited, and can be appropriately selected according to the purpose.
  • ⁇ column is t, 4 to 300 111 girls, 5 to 175 111 parts 0 girl's dress 1 ⁇ 0
  • the shape of the support is not particularly limited and can be appropriately selected according to the purpose, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include those having a length of 10 m to 20, OOOm.
  • the protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
  • the protective film is appropriately selected depending on the purpose. Usually, it is provided on the photosensitive layer.
  • protective film examples include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, polypropylene, etc. Ren films are preferred.
  • the thickness of the protective film is not particularly limited, and can be appropriately selected according to the purpose. For example, 5 to 100 ⁇ m is preferable, and 8 to 30 ⁇ m is more preferable.
  • the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
  • Examples of the combination of the support and the protective film include, for example, polyethylene terephthalate z polypropylene, polyethylene terephthalate z polyethylene, polychlorinated bur Z cellophane, polyimide Z polypropylene, polyethylene terephthalate z polyethylene terephthalate. Etc.
  • the above-described adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer.
  • a primer layer for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • ultraviolet irradiation treatment for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • One discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like can be mentioned.
  • the coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2 force! / !.
  • the photosensitive film is wound around a cylindrical core and wound and stored in a long roll shape.
  • the length of the long photosensitive film is not particularly limited. For example, a range force of 10-20, OOOm can be appropriately selected.
  • slitting may be performed to make it easy for the user to use, and a long body in the range of 100 to 1,000 m may be rolled. In this case, it is preferable that the support is scraped off so as to be the outermost side.
  • the roll-shaped photosensitive film may be slit into a sheet shape.
  • a separator on the end face especially moisture-proof and with desiccant.
  • the packaging is also low in moisture permeability and it is preferable to use materials.
  • the protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer.
  • an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polybutyl alcohol is formed on the surface of the protective film.
  • the undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C (particularly 50 to 120 ° C) for 1 to 30 minutes. Can do.
  • a cushion layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.
  • PC layer oxygen blocking layer
  • a release layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.
  • PC layer oxygen blocking layer
  • a release layer an adhesive layer, a light absorption layer, a surface protective layer, and the like.
  • the cushion layer is a layer that melts and flows when laminated under vacuum and heating conditions that have no tackiness at room temperature.
  • the PC layer is usually a coating of about 0.5 to 5 / ⁇ ⁇ , which is formed mainly of polybulal alcohol.
  • the photosensitive film of the present invention has low surface tackiness, good laminating properties and handleability, excellent storage stability, high sensitivity and excellent developability, and excellent chemical resistance after development. It has a photosensitive layer on which a photosensitive composition exhibiting surface hardness, heat resistance, dielectric properties and the like is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for a permanent pattern and a method for forming the permanent pattern.
  • the photosensitive film of the present invention since the photosensitive film of the present invention has a uniform thickness, the film is more precisely laminated on the substrate when the permanent pattern is formed.
  • the permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
  • the photosensitive composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. .
  • the photosensitive film of the present invention is laminated on the surface of a substrate under at least one of heating and pressurization. , Expose, develop and heat.
  • the base material can be appropriately selected from publicly known materials that are not particularly limited to those having a high surface smoothness and a surface having an uneven surface, and a plate-like base material (substrate) is preferred.
  • Specific examples include known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, and the like.
  • the printed wiring board forming substrate has already been formed in terms of the fact that high-density mounting of semiconductors and the like can be performed on a multilayer wiring substrate that is preferred for the printed wiring board forming substrate. Is particularly preferred.
  • the substrate is a laminate in which a photosensitive layer made of the photosensitive composition is formed on the substrate as the first aspect, or the photosensitive film in the photosensitive film as the second aspect. It is possible to form and use a laminated body in which the layers are laminated so as to overlap each other. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed area can be cured, and a permanent pattern can be formed by development to be described later.
  • the method for forming the laminate of the first aspect can be appropriately selected according to the purpose without any particular limitation, and is formed by applying and drying the photosensitive composition on the substrate. It is preferable to laminate a photosensitive layer.
  • the method for coating and drying can be appropriately selected according to the purpose without particular limitation.
  • the method for forming the photosensitive composition solution in the photosensitive film which is performed when forming the photosensitive layer in the photosensitive film.
  • a method of applying the photosensitive composition solution by using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be used.
  • the method for forming the laminate of the second aspect is a force that can be appropriately selected depending on the purpose without any particular limitation.
  • the photosensitive film is heated and pressed on the base material at least. It is preferable to perform the lamination while performing either one.
  • the photosensitive film is the front In the case where the protective film is provided, it is preferable that the protective film is peeled off and laminated so that the photosensitive layer overlaps the substrate.
  • the heating temperature can be appropriately selected according to the purpose for which there is no particular limitation. For example, 70 to 130 ° C is preferable, and 80 to 110 ° C is more preferable.
  • the pressure of the pressurization is a force that can be appropriately selected according to the purpose for which there is no particular restriction.
  • ⁇ column; t is preferably 0.01 to: L OMPa force, 0.05 to L: L OMPa force ⁇ More preferred! / ⁇ .
  • the apparatus for performing at least one of the heating and pressurization can be appropriately selected according to the purpose of restriction, and for example, a heat press, a heat roll laminator (for example, Taisei Laminate Earthen, VP 11), a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho) and the like are preferable.
  • a heat press for example, Taisei Laminate Earthen, VP 11
  • a vacuum laminator for example, MVLP500 manufactured by Meiki Seisakusho
  • the exposure step is a step of exposing the photosensitive layer.
  • the subject of the exposure is a material having a photosensitive layer
  • the exposure of the laminate can be appropriately selected depending on the purpose without any particular limitation.
  • the photosensitive layer may be exposed through the support, the cushion layer, and the PC layer. After peeling off the support, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling off the support and cushion layer, the photosensitive layer is exposed through the PC layer. The photosensitive layer may be exposed after the support, cushion layer and PC layer are peeled off.
  • the exposure can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
  • the digital exposure can be appropriately selected according to the purpose without any particular limitation.
  • a control signal is generated based on pattern formation information to be formed, and is modulated according to the control signal. I prefer to use light.
  • the digital exposure means can be appropriately selected according to the purpose without any particular restriction.
  • the light exposure means for irradiating light and the pattern information to be formed examples include light modulating means for modulating light emitted from the light irradiating means.
  • the light modulation means As long as light can be modulated, it is preferable to have a force that can be appropriately selected according to the purpose without particular limitation.
  • the light modulation means preferably has n pixel portions.
  • the light modulation means having the n picture elements can be appropriately selected according to the purpose without any particular limitation, and for example, a spatial light modulation element is preferable.
  • Examples of the spatial light modulation element include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (S LM; Special Light Modulator), and transmission by an electro-optic effect.
  • Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
  • the light modulation means includes pattern signal generation means for generating a control signal based on pattern information to be formed.
  • the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
  • control signal can be appropriately selected according to the purpose for which there is no particular limitation.
  • a digital signal is preferably used.
  • Specific examples of the light modulation means include the means described in [0016] to [0 047] of JP-A-2005-258431.
  • 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.
  • Examples include ultraviolet to visible light, electron beams, X-rays, and laser light.
  • laser light is preferred.
  • Laser light that combines two or more lights hereinafter referred to as “combined laser light”). Is more preferable). Similar light can be used even when the support is peeled off and light is irradiated with force.
  • the wavelength of the ultraviolet ray visible light is preferably 300-1,500 nm, more preferably 320 0 to 800 mn force, and 330 ⁇ ! ⁇ 650mn force ⁇ especially preferred!
  • the wavelength of the laser beam is preferably 200 to 1,500 nm force S, more preferably 300 to 800 nm, more preferably 330 nm to 500 nm force S, and particularly preferably 395 nm to 415 nm.
  • Examples of means capable of irradiating the combined laser beam include, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces to collect the multimode optical fiber.
  • U a means having a collective optical system coupled to U is preferred.
  • means (fiber array light source) that can irradiate the combined laser include means described in paragraphs [0130] to [0177] of Japanese Patent Application Laid-Open No. 2005-316431. It is done.
  • the exposure is preferably performed through the microlens array with the modulated light, and may be performed through an aperture array, an imaging optical system, or the like.
  • the microlens array is a force that can be appropriately selected depending on the purpose without any particular limitation.
  • a microlens having an aspherical surface that can correct aberration due to distortion of the exit surface in the pixel portion Preferred are those arranged.
  • the aspherical surface can be appropriately selected according to the purpose without any particular limitation, and for example, a toric surface is preferable.
  • microlens array for example, paragraph numbers [0051] to [0063] and paragraph number [0065] of JP-A-2005-258431. ], Paragraph numbers [0070] to [0073], and means described in paragraph numbers [0083] to [0088].
  • the permanent pattern forming method of the present invention may be used in combination with other optical systems appropriately selected from known optical systems.
  • the light quantity distribution correction light comprising a pair of combination lenses Academic and so on.
  • the developing step is a step of exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region to form a permanent pattern.
  • the removal method of the uncured region can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include a method of removing using a developer.
  • the developer may be appropriately selected according to the purpose without any particular limitation.
  • an alkali metal or alkaline earth metal hydroxide or carbonate, bicarbonate, aqueous ammonia Preferred examples include aqueous solutions of quaternary ammonium salts. Among these, an aqueous sodium carbonate solution is particularly preferable.
  • the developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, Triethanolamine, etc.) and organic solvents (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination to accelerate development.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or an organic solvent alone.
  • the permanent pattern forming method of the present invention further includes a heat treatment as a curing treatment step, and further includes an entire surface exposure treatment as necessary.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer having a permanent pattern formed after the developing step.
  • the heat treatment is performed in order to sufficiently improve the film hardness due to the thermal crosslinking effect of the compounds represented by the general formulas (1) to (3) contained in the photosensitive composition of the present invention.
  • the heat treatment may be a whole surface heat treatment or a pattern-like heat treatment. Of these, the entire surface heat treatment is preferable.
  • 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 developing step. By heating the entire surface, the crosslinking reaction of the compounds represented by the general formulas (1) to (3) is promoted, and the film strength on the surface of the permanent pattern is increased.
  • the heating temperature for the entire surface heating is 120 to 250, preferably 120 to 200 ° C.
  • the heating temperature is less than 120 ° C.
  • the crosslinking reactivity of the resin in the photosensitive composition by the compounds represented by the general formulas (1) to (3) is lowered, and the film strength is improved by the heat treatment.
  • the temperature exceeds 250 ° C., decomposition of the resin in the photosensitive composition may occur, and the film quality may be weak and brittle.
  • the heating time for the entire surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
  • the apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
  • Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step.
  • the entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
  • the apparatus for performing the entire surface exposure can be appropriately selected according to the purpose without any particular limitation, and a UV exposure machine such as an ultrahigh pressure mercury lamp is preferably exemplified.
  • the substrate is a printed wiring board such as a multilayer wiring board
  • the permanent pattern of the present invention is formed on the printed wiring board, and soldering may be further performed as follows. it can.
  • the hardened layer which is the permanent pattern is formed by the developing step, and the metal layer is exposed on the surface of the printed wiring board.
  • Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed.
  • soldered A semiconductor or a component is mounted on the part.
  • the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.
  • the permanent pattern forming method of the present invention it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
  • the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, it is possible to protect the wiring from an impact or bending force of an external force, particularly when it is the interlayer insulating film. Is useful for high-density mounting of semiconductor components on, for example, multilayer wiring boards and build-up wiring boards.
  • the permanent pattern forming method of the present invention can be widely used for forming various patterns because it can form a pattern at high speed, and can be particularly suitably used for forming a wiring pattern.
  • the permanent pattern formed by the method for forming a permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance, etc., and is suitably used as a protective film, an interlayer insulating film, and a solder resist pattern. be able to.
  • a photosensitive composition was prepared based on the following composition.
  • methyl ethyl ketone was used as a dispersion solvent, and the solid content concentration was adjusted to 55% by mass.
  • Dispersion was performed using a bead mill, and the obtained dispersion was confirmed to be free from aggregation by a particle gauge.
  • the compound represented by the structural formula (1) was synthesized as follows.
  • the obtained photosensitive composition was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 m as the support and dried to form a photosensitive layer having a thickness of 30 / z m.
  • a 12 ⁇ m-thick polypropylene film was laminated as a protective film on the photosensitive layer to produce a photosensitive film.
  • the substrate was prepared by subjecting a surface of a copper-clad laminate (no through-hole, copper thickness 1 2 / z m) on which wiring had been formed, to a chemical polishing treatment.
  • a vacuum laminator manufactured by Nichigo Morton Co., Ltd.
  • the pressure bonding conditions were as follows: vacuuming time 40 seconds, pressure bonding temperature 70 ° C, pressure bonding pressure 0.2 MPa, pressurization time 10 seconds.
  • the tackiness of the surface of the photosensitive layer in the laminate obtained as described above was evaluated based on the following criteria.
  • the protective film on the photosensitive film of Example 1 was peeled off, the peeling itself without strong tackiness on the surface of the photosensitive layer could be easily performed.
  • the results are shown in Table 3.
  • a laser exposure device 405 nm laser light is irradiated from the polyethylene terephthalate film (support) side so that a pattern in which holes having different diameters are formed is applied to the photosensitive layer in the prepared laminate. Then, a portion of the photosensitive layer was cured.
  • the laminate strength was also peeled off from the polyethylene terephthalate film (support), and a 1% by weight sodium carbonate aqueous solution was added as an alkaline developer to the entire surface of the photosensitive layer on the copper clad laminate.
  • a spray pressure of 0.2 MPa at 30 ° C. for 60 seconds the uncured area was dissolved and removed. Thereafter, it was washed with water and dried to form a permanent pattern.
  • the entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 60 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.
  • the photosensitive film produced was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 3.
  • the thickness of the cured area of the remaining photosensitive layer was measured. Subsequently, a sensitivity curve is obtained by plotting the relationship between the irradiation amount of the laser beam and the thickness of the cured layer. Sensitivity curve force obtained in this way The thickness of the cured area on the wiring was 15 m, and the amount of light energy when the surface of the cured area was a glossy surface was the amount of light energy required to cure the photosensitive layer.
  • the amount of light energy required to cure the photosensitive layer is 30 mjZcm 2 Met.
  • the surface of the obtained printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured.
  • the 405 nm laser exposure apparatus uses a 405 nm laser exposure apparatus, the speed at which the exposure light and the photosensitive layer were moved relative to each other was changed, and the speed at which the permanent pattern was formed was determined.
  • the exposure was performed from the polyethylene terephthalate film (support) side to the photosensitive layer in the prepared laminate. It should be noted that an efficient permanent pattern can be formed when the set speed is high.
  • the 405 nm laser exposure apparatus has a light modulation means composed of the DMD, and the exposure speed is to ldmm / sec.
  • the produced photosensitive film was subjected to forced aging for 3 days at 40 ° C., and then the development time of the unexposed film was measured.
  • the printed wiring board on which the permanent pattern had been formed was plated with gold according to a conventional method, and then a water-soluble flux treatment was performed. Next, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JIS K-5400.
  • the pencil hardness was 5H. Further, when visually observed, the cured film in the permanent pattern peeled, blistered, and discolored.
  • the dielectric properties of a 500 m thick cured film were measured at 25 ° C using an LCR meter manufactured by Agilent Technologies and a 4291A type solid electrode.
  • the dielectric constant at 1 GHz was 3.3. Was 0.013.
  • Example 2 A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent film was formed.
  • the pattern was evaluated for pencil hardness and dielectric properties. As a result, the exposure sensitivity was 30 mjZcm 2 , the resolution was 70 m, and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
  • the unit A consists of two types of structural units, in which one of the structural units R 1 is a fail, and in the other structural unit R 1 is a butoxycarbon, R 3 and R 4 is a hydrogen atom.
  • R 2 in unit B is benzyl.
  • the Interview - mole fraction X of recurring units of Tsu DOO A is the one constituent unit Nitsu /, Te is 40 mole 0/0 is 28 mol% for the other structural units, the The mole fraction y of repeating units in unit B is 32 mol%.
  • the reaction amount of the benzylamine with respect to the anhydride group of the styrene Z maleic anhydride Z butyl acrylate copolymer is 1.0 equivalent.
  • Example 2 the content of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 14% by mass.
  • Example 1 the addition amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 0.8 parts by mass, and the structural formula (1) is used.
  • a photosensitive composition was prepared in the same manner as in Example 1 except that the content of the epoxy resin compound in the photosensitive composition was 0.8% by mass (less than 1% by mass).
  • a photosensitive film and a laminate were prepared in the same manner as in 1 to form a permanent pattern.
  • the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ⁇ ⁇ , and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
  • Example 1 the amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 100 parts by mass, and the epoxy represented by the structural formula (1) is used.
  • a photosensitive composition was prepared in the same manner as in Example 1 except that the content of the resin compound in the photosensitive composition was 51% by mass (over 50% by mass). Photosensitive film and laminate Prepared and formed a permanent pattern.
  • the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ⁇ ⁇ , and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
  • Example 1 the compound represented by the structural formula (1) in the photosensitive composition was changed to the compounds represented by the structural formulas (2) to (10) as shown in Table 3.
  • the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, in Examples 5 to 13, the exposure sensitivity was 30 mjZcm 2 , the resolution was 70 / ⁇ ⁇ , and the exposure speed was 13 mjZcm 2 . The other results of each example are shown in Table 3.
  • the solvent of the organic phase is distilled off and silica gel
  • Example 1 40.0 parts by mass of the binder represented by the structural formula (46) in the photosensitive composition, 20.0 parts by mass of the binder represented by the structural formula (46), and the following:
  • a photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to 20 parts by mass of the acrylic resin (B1) having an unsaturated group obtained in Synthesis Example a. Photosensitive film And a laminated body was prepared and the permanent pattern was formed.
  • the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ⁇ ⁇ , and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
  • Example 1 40.0 parts by mass of the binder represented by the structural formula (46) in the photosensitive composition was replaced with 20.0 parts by mass of the binder represented by the structural formula (46).
  • a photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to 20 parts by mass of the acrylic resin (B2) having an unsaturated group obtained in Synthesis Example b shown below.
  • a photosensitive film and a laminate were prepared in the same manner as in 1 to form a permanent pattern.
  • the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ⁇ ⁇ , and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
  • Acrylic resin (B2) solution having an unsaturated group (solid acid value; 104, Mw; 20,000, double bond equivalent 2.0 mmol / g, propylene glycol monomethyl ether) 37 mass 0/0 solution) was obtained.
  • Example 1 except that the exposure apparatus in Examples 1, 5, 7 and 10 was replaced with the pattern forming apparatus described in paragraphs [0383] to [0393] of JP-A-2005-258431.
  • the prepared photosensitive composition and photosensitive film were evaluated for tackiness, exposure sensitivity, resolution, and exposure speed, and for the formed permanent pattern, pencil hardness and dielectric properties were evaluated.
  • the exposure sensitivity is 30 mjZcm 2
  • the resolution is 70 m
  • the exposure speed is 7 mjZcm 2 .
  • Table 3 shows the results for pencil hardness, dielectric properties, and storage stability.
  • Example 1 except that the compound represented by the structural formula (1) in the photosensitive composition was changed to 2,2 ′ bis (4-glycidylphenol) propane, the same as in Example 1.
  • a photosensitive composition was prepared, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 2 the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated.
  • Comparative Example 1 and Comparative Examples 2 and 3 below the exposure sensitivity was 30 miZcm 2 , the resolution was 70 / ⁇ ⁇ , and the exposure speed was 13 m jZcm 2 . Other results are shown in Table 3. [0207] (Comparative Example 2)
  • Example 1 except that the compound represented by the structural formula (1) in the photosensitive composition was changed to Epicote YX4000 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy resin) in Example 1.
  • a photosensitive composition was prepared in the same manner as in Example 1.
  • a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. The results are shown in Table 3.
  • Example 1 the same procedure as in Example 1 was performed except that the compound represented by the structural formula (1) in the photosensitive composition was changed to ⁇ C (manufactured by Nissan Chemical Industries, Ltd., epoxy resin). A photosensitive composition was prepared, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. The results are shown in Table 3.
  • Example 1 Structural formula (1) ⁇ 5H 0. 013 30
  • Example 2 Structural formula (1) ⁇ 4H 0. 014 25
  • Example 3 Structural formula (1) ⁇ 2H 0. 018 25
  • Example 4 Structural formula (1) ⁇ 5H or more 0.013 45
  • Example 5 Structural formula (2) ⁇ 5H or more 0.015 20
  • Example 6 Structural formula (3) ⁇ 5H 0. 015 25
  • Comparative example 2 Epicot ⁇ 5H or more 0. 011 Development impossible Comparative example 3 TEPIC ⁇ 5H or more 0. 013 Development impossible Based on the results in Table 3, selected from compounds represented by general formulas (1) to (3)
  • the photosensitive layer in the photosensitive film produced using the photosensitive composition of Examples 1 to 19 containing at least one compound is excellent in tackiness, exposure sensitivity and resolution, and is formed using the photosensitive film.
  • the surface hardness and dielectric properties of the cured layer in the permanent pattern are excellent, and the storage stability is extremely superior compared to the photosensitive films of Comparative Examples 1 to 3 using a conventionally known epoxy resin compound as a thermal crosslinking agent.
  • the photosensitive films of Examples 1 to 2 and 5 to 19 in which the content of the compound in the photosensitive composition is 0.01 to 15% by mass are extremely excellent in both storage stability and dielectric properties. It turns out that he speaks excellently.
  • Examples 16 to 19 using the same photosensitive film as in Examples 1, 5, 7 and 10 pattern formation is possible with a high-intensity light source and high-speed modulation, and optical system distortion correction by a toric lens. Since the apparatus was used, it was confirmed that the resolution and the exposure speed were excellent, and it was confirmed that a high-definition permanent pattern was formed.
  • the photosensitive composition of the present invention and the photosensitive film using the photosensitive composition do not react at room temperature during storage, start a crosslinking reaction by heating, and have a cured film with good film hardness.
  • Contains the resulting compound can be imaged by UV exposure, has low surface tack, good laminating and handling properties, excellent storage stability, high sensitivity and excellent developability, and excellent after development
  • protective films for printed wiring boards multilayer wiring boards, build-up wiring boards, etc.
  • interlayer insulating films interlayer insulating films
  • solder resist patterns color filters
  • the permanent pattern of the present invention is excellent in chemical resistance, surface hardness, heat resistance, dielectric properties, and electrical insulation.
  • protective films, interlayer insulation films, solder resist patterns, and displays such as color filters, pillar materials, rib materials, spacers, and partition walls It can be suitably used because it can be widely used for forming permanent patterns such as members, holograms, micromachines, and proofs.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Disclosed is a photosensitive composition comprising a compound which causes no reaction under a low temperature or ambient temperature employed for storage, has excellent storage stability, can cause a cross-linking reaction by heating to enhance the curing of a resin, and can impart a good film hardness to a cured film containing the compound. The composition can form an image by the exposure to UV ray, shows a low surface tacking property, has a good laminating property and a good handling property, is excellent in storage stability, has a high sensitivity, is excellent in image-developing property, and can exert excellent chemical resistance, surface hardness, heat resistance, dielectric properties and the like after being developed. Also disclosed is a photosensitive film using the composition. Further disclosed is a highly precise permanent pattern. Still further disclosed is a method for formation of the pattern with good efficiency. The photosensitive composition comprises (A) a polymer having at least one carboxyl group and/or ester group per molecule, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) a specific compound having at least two oxirane groups per molecule.

Description

明 細 書  Specification
感光性組成物及び感光性フィルム、並びに、永久パターン及びその形成 方法  Photosensitive composition and photosensitive film, and permanent pattern and method for forming the same
技術分野  Technical field
[0001] 本発明は、保存時の常温下では反応を生じず、加熱により架橋反応を開始して、 硬化膜の良好な膜硬度が得られる化合物を含み、 UV露光により画像形成可能で、 表面のタック性が小さぐラミネート性及び取扱い性が良好で、保存安定性に優れ、 高感度で現像性にも優れ、現像後に優れた耐薬品性、表面硬度、耐熱性、誘電特 性、電気絶縁性などを発現する感光性組成物、及びこれを用いた感光性フィルム、 並びに高精細な永久パターン (保護膜、層間絶縁膜、ソルダーレジストパターンなど） 及びその効率的な形成方法に関する。  [0001] The present invention includes a compound that does not react at room temperature during storage, initiates a crosslinking reaction by heating, and obtains good film hardness of a cured film, and can form an image by UV exposure. Low tackiness, good laminating and handling properties, excellent storage stability, high sensitivity and excellent developability, excellent chemical resistance after development, surface hardness, heat resistance, dielectric properties, electrical insulation The present invention relates to a photosensitive composition that exhibits properties and the like, a photosensitive film using the same, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) and an efficient formation method thereof.
背景技術  Background art
[0002] プリント配線基板の分野では、半導体やコンデンサ、抵抗等の部品がプリント配線 基板の上に、半田付けされる。この場合、例えば、 IRリフロー等のソルダリング工程に おいて、半田が、半田付けの不必要な部分に付着するのを防ぐため、保護膜、絶縁 膜として、前記半田付けの不要部分に相当する永久パターンを形成する方法が採用 されている。また、保護膜の永久パターンとしては、ソルダーレジストが好適に用いら れている。  In the field of printed wiring boards, components such as semiconductors, capacitors and resistors are soldered on the printed wiring board. In this case, for example, in a soldering process such as IR reflow, in order to prevent solder from adhering to an unnecessary part of soldering, it corresponds to the unnecessary part of soldering as a protective film and an insulating film. A method of forming a permanent pattern is adopted. Also, a solder resist is preferably used as the permanent pattern of the protective film.
[0003] 従来、ソルダーレジストとしては、熱硬化型の材料が多く用いられ、これをスクリーン 印刷法で印刷して施す方法が一般的であった。しかし、近年、プリント配線板の配線 の高密度化に伴い、スクリーン印刷法では解像度の点で限界が生じ、フォトリソグラフ ィ一法で画像形成を行うフォトソルダーレジストが盛んに用いられるようになってきて いる。中でも、炭酸ソーダ溶液等の弱アルカリ溶液で現像可能なアルカリ現像型のフ オトソルダーレジストが、作業環境、地球環境保全の点で主流になっている。また、一 般には液状ソルダーレジストをスクリーン印刷、スプレーコート、ディップコート等によ り配線形成済みの基板の片面に塗布して乾燥し、引き続き反対面に塗布して乾燥す る製造方法が用いられて 、る。 [0004] また、前記のようなアルカリ現像型のフォトソルダーレジストとしては、主成分として エポキシィ匕合物にエチレン性不飽和二重結合及びアルカリ現像性を付与するため の酸基を導入した化合物（エポキシアタリレート）と、エチレン性不飽和二重結合を有 する付加重合性化合物 (モノマー）と、を含む組成物が一般に用いられており、具体 的には特許文献 1に開示されている。しかし、特許文献 1に記載のソルダーレジスト は、ポストべイク後に高い表面硬度が得られ、耐薬品性に優れるものの、表面のタツ クが残り、ゴミが付着し易くなり欠陥が増大する、あるいはフォトマスクを汚染するなど 、取扱い性を悪ィ匕させるという問題がある。ここで、表面にタックが残るのは、アルカリ 水溶液に可溶性のバインダーであるエポキシアタリレートの分子量が数 100程度と低 分子量であり、モノマーが通常沸点の高い液体又は半固体であることによるものであ ると考免られる。 [0003] Conventionally, as the solder resist, a thermosetting material is often used, and a method in which this is applied by screen printing is generally used. However, in recent years, with the increase in the wiring density of printed wiring boards, the screen printing method has a limit in terms of resolution, and a photo solder resist for forming an image by a photolithographic method has been actively used. ing. Among them, alkali development type photo solder resists that can be developed with a weak alkali solution such as sodium carbonate solution are mainly used in terms of working environment and global environment conservation. In general, a liquid solder resist is applied to one side of a substrate on which wiring has been formed by screen printing, spray coating, dip coating, etc., dried, and then applied to the opposite side and dried. Being [0004] Further, as the alkali development type photo solder resist as described above, a compound in which an acid group for imparting an ethylenically unsaturated double bond and alkali developability to an epoxy compound as a main component ( A composition containing an epoxy acrylate and an addition polymerizable compound (monomer) having an ethylenically unsaturated double bond is generally used, and specifically disclosed in Patent Document 1. However, the solder resist described in Patent Document 1 has a high surface hardness after post-baking and excellent chemical resistance, but the surface tack remains and dust tends to adhere to increase the defects, or the photo resist. There is a problem of deteriorating handling properties such as contamination of the mask. Here, the tack remains on the surface because the molecular weight of epoxy acrylate, which is a binder soluble in an alkaline aqueous solution, is as low as several hundreds, and the monomer is usually a liquid or semi-solid with a high boiling point. It is dismissed if there is.
また、このようなソルダーレジストの露光感度は通常 300〜1, OOOiujZcm2と低く、 製造ラインのスピードアップのネックになりつつあり、更に感度アップが要請されてい る。該感度アップのためにはモノマーの配合量の増量が効果的である力 モノマー 類を多く配合してしまうと前記表面タックが更に悪ィ匕するという問題が生じ、解決策が 見出されていない。 In addition, the exposure sensitivity of such solder resists is usually as low as 300 to 1, OOOiujZcm 2, which is becoming a bottleneck in speeding up the production line, and further improvement in sensitivity is required. The ability to increase the amount of the monomer is effective to increase the sensitivity. If a large amount of monomers are added, the problem that the surface tack is further worsened, and no solution has been found. .
[0005] また、近年高密度実装が急速に進みつつあり、高密度実装を実現する上での、ソ ルダーレジストの課題は、ウエット現像やウエットエッチングを繰り返す、フォトリソダラ フィープロセス中での基板の伸縮やフォトマスクフィルムの温湿度変化に基づく伸縮 に起因する配線パターンやスルーホールランドパターンの位置ズレである。  [0005] Also, in recent years, high-density mounting has been rapidly progressing, and the problem of solder resist in realizing high-density mounting is that the substrate is being processed during the photolithography process, in which wet development and wet etching are repeated. This is the misalignment of wiring patterns and through-hole land patterns due to expansion and contraction due to expansion and contraction and changes in temperature and humidity of the photomask film.
位置ズレ防止には、これまでは、基板の変形度の少ないロットを選別したり、予め各 種のパラメータで修正した複数のフィルムマスクを準備したり、高価なガラスマスクを 使用するといつた対策が採られてきた。また、この位置ズレ問題の解決のため、レー ザ一ダイレクトイメージングシステム（LDI)の適用が進んでいる。ここで、 LDIは、デジ タルデータの高速処理による補正により、基板の変形に対応した露光パターンを形 成する技術に基づくものである。  To prevent misalignment, it has been necessary to select lots with a low degree of substrate deformation, prepare multiple film masks that have been corrected in advance using various parameters, or use expensive glass masks. Have been taken. In addition, the application of laser direct imaging system (LDI) is progressing to solve this misalignment problem. Here, LDI is based on a technology that forms an exposure pattern corresponding to the deformation of the substrate by correcting the digital data by high-speed processing.
[0006] 前記 LDIに用いられるソルダーレジストには、 365nm、あるいは 405nmなどの UV レーザーに対応するため、 lOOmiZcm2以上の露光感度が要求される。このため、 高感度が得られやす 、フィルムタイプのソルダーレジストが必要となってきて 、る。し かし、特許文献 1に記載のソルダーレジストをフィルム化すると、表面のタック性が強く 、支持体や保護膜と感光層とが剥離しにくぐ取扱い性が悪ぐ更に— 20°C以下の 冷凍保存でも 2、 3ヶ月の保存しか出来ず、保存安定性の問題がある。また波長 405 nmのレーザ光に対する感度が無 、と 、う欠点を有して 、る。 [0006] The solder resist used in the LDI is required to have an exposure sensitivity of lOOmiZcm 2 or more in order to cope with a UV laser of 365 nm or 405 nm. For this reason, A film-type solder resist is required to achieve high sensitivity. However, when the solder resist described in Patent Document 1 is made into a film, the tackiness of the surface is strong, the support or protective film is difficult to peel off from the photosensitive layer, and the handling property is poor. Even frozen storage can only be stored for a few months, and there is a problem of storage stability. In addition, the sensitivity to laser light having a wavelength of 405 nm is inferior.
[0007] 一方、特許文献 2には、分子量 10, 000以上の比較的高分子量のアルカリ水溶液 に可溶性のバインダーを用いた、表面のタック性が小さぐ耐熱性に優れ、比較的保 存安定性が良好なソルダーレジストが開示されている。しかしながら、該ソルダーレジ ストは表面硬度が低ぐラミネート性に劣るという問題がある。したがって、気泡を生ず ることなぐ配線形成済みのプリント配線基板の最外層に予め液状のモノマーを下引 き層として塗布しておく必要があり、工程が煩雑になり、取扱い性に劣るという欠点を 有している。その理由としては、メチルメタタリレート、スチレンという硬質のポリマーを 形成する共重合成分 (各々のホモポリマーの Tgは 105°C以上、 100°Cである）を用 いた結果、硬化膜が柔軟性に欠けて脆くなり、表面硬度が上がらず、また、真空条件 下の加熱積層工程で、十分な流動性が得られず、気泡発生を引き起こしていること が考えられる。更に、波長 405nmのレーザ光に対する感度が無いという欠点を有し ている。 [0007] On the other hand, Patent Document 2 uses a binder soluble in a relatively high molecular weight alkaline aqueous solution having a molecular weight of 10,000 or more, has a small surface tackiness, excellent heat resistance, and relatively storage stability. Has disclosed a good solder resist. However, the solder resist has a problem that the surface hardness is low and the laminate property is poor. Therefore, it is necessary to apply a liquid monomer as an undercoat layer in advance to the outermost layer of a printed wiring board on which wiring has been formed without generating bubbles, which makes the process complicated and inferior in handleability. have. The reason is that the cured film is flexible as a result of the use of a copolymer component that forms a rigid polymer such as methyl methacrylate and styrene (Tg of each homopolymer is 105 ° C or higher and 100 ° C). It is considered that the surface hardness does not increase due to chipping, and that sufficient fluidity cannot be obtained in the heating and laminating process under vacuum conditions, causing bubbles to be generated. Furthermore, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.
[0008] また、先端電子機器分野では、高周波環境での高速伝搬性が要求されており、特 に電子計算機や移動体通信機器に代表される電子機器にぉ ヽては、処理速度や信 号伝播速度の高速化、使用帯域の高周波化に伴い、積層板用材料には低誘電率 ィ匕、低誘電正接化が求められている。プリント配線板製造におけるソルダーレジスト にも低誘電率化、低誘電正接化が求められてきている。しカゝしながら、現状のアル力 リ現像型のソルダーレジストでは、高周波数領域での誘電特性が悪ぐ高周波数用 榭脂として満足な特性が得られて!/、な!、のが現状である。  [0008] In the field of advanced electronic equipment, high-speed propagation in a high-frequency environment is required, and processing speed and signal are particularly high for electronic equipment typified by electronic computers and mobile communication equipment. With higher propagation speeds and higher frequency bands, laminated board materials are required to have low dielectric constants and low dielectric loss tangents. Lowering the dielectric constant and lowering the dielectric loss tangent are also required for solder resists in the production of printed wiring boards. However, with the current Al re-development type solder resist, satisfactory characteristics can be obtained as a high frequency resin with poor dielectric properties in the high frequency range! It is.
[0009] また、前記フィルムタイプのソルダーレジストとして、一般に市販されている製品では 、このフィルム化に伴い、感光層中においてバインダー及びモノマーと、熱架橋剤と が混在するため、架橋反応が生じて保存安定性に乏しいことが問題となっている。 一方、エポキシ榭脂組成物などの熱硬化性榭脂組成物の硬化促進剤として、前記 保存安定性の観点から、保存時には反応を生じないが、加熱により反応して硬化す る性質を持つ、いわゆる潜在性硬化促進剤を使用した提案がされている。例えば、 2 ェチルへキシル酸亜鉛とトリエタノールアミンカ なる塩、トリエチレンジァミンと脂 肪族カルボン酸からなる塩を配合した提案がされて！/ヽる（非特許文献 1及び特許文 献 3参照)。これらは、硬化促進剤を錯塩とすることにより、溶解性を低下させて、反応 活性を抑制し、保存安定性を向上させようとするものである。 [0009] In addition, in the product that is generally marketed as the film type solder resist, a binder and a monomer and a thermal cross-linking agent are mixed in the photosensitive layer as the film is formed, so that a crosslinking reaction occurs. The problem is poor storage stability. On the other hand, as a curing accelerator for a thermosetting resin composition such as an epoxy resin composition, From the viewpoint of storage stability, a proposal has been made to use a so-called latent curing accelerator that does not cause a reaction during storage but has a property of being cured by heating. For example, a proposal has been made that contains a salt of zinc 2-ethylhexylate and triethanolamine, and a salt of triethylenediamine and an aliphatic carboxylic acid! (See Non-Patent Document 1 and Patent Document 3). These are intended to reduce solubility, suppress reaction activity, and improve storage stability by using a complex accelerator as a curing accelerator.
また、エポキシ榭脂にジメチルアミンゃジアルキルアミンを反応させて得られる付カロ 物 (特許文献 4及び特許文献 5参照）、エポキシ榭脂に 3級ァミンを反応させて得られ る付加物 (特許文献 6及び特許文献 7参照)などを使用した提案もされている。このよ うにエポキシ榭脂にアミンィ匕合物を付加させて高分子化、不溶化させることにより、保 存安定性の向上を図っている。  Also, adducts obtained by reacting epoxy resin with dimethylamine dialkylamine (see Patent Document 4 and Patent Document 5) and adducts obtained by reacting epoxy resin with tertiary amine (Patent Document) 6 and Patent Document 7) are also proposed. Thus, the storage stability is improved by adding an amine compound to the epoxy resin to polymerize and insolubilize it.
し力しながら、これらの文献では、ソルダーレジストに使用した開示がないし、十分 満足し得る高い保存安定性能が得られ、かつ、安価な原料を用いて簡単に得られる 熱架橋剤として作用する化合物は未だ提供されておらず、更なる改良が望まれてい る。  However, in these documents, there is no disclosure used for a solder resist, a compound that acts as a thermal cross-linking agent can be obtained with a sufficiently satisfactory high storage stability and can be easily obtained using inexpensive raw materials. Is not yet provided, and further improvements are desired.
[0010] また、熱架橋剤としてのエポキシ榭脂化合物を、難溶性にすることで、保存安定性 の向上を図ったものが開示されている（特許文献 8及び特許文献 9参照)。し力しなが ら、この場合、露光感度が 300〜500mjZcm3と低ぐ保存安定性と、高感度や現像 性などとをバランスよく両立させるのは難し力つた。 [0010] In addition, an epoxy resin compound as a thermal cross-linking agent has been disclosed to improve storage stability by making it hardly soluble (see Patent Document 8 and Patent Document 9). However, in this case, it was difficult to balance storage stability, which has a low exposure sensitivity of 300 to 500 mjZcm 3 , with high sensitivity and developability.
[0011] したがって、常温では反応を生じることがなぐ加熱により架橋反応を開始する熱架 橋剤を含み、 UV露光により画像形成可能で、表面のタック性が小さぐ支持体などと の剥離性に優れ、ラミネート性及び取扱い性が良好で、保存安定性に優れ、高感度 で現像性にも優れ、現像後に優れた耐薬品性、表面硬度、耐熱性、誘電特性などを 発現可能な感光性組成物、及びこれを用いた感光性フィルム、並びに、高精細な永 久パターン及びその効率的な形成方法も、未だ十分満足し得るものが提供されて ヽ ないのが現状である。  [0011] Therefore, it contains a thermal crosslinking agent that initiates a crosslinking reaction by heating that does not cause a reaction at room temperature, can form an image by UV exposure, and can be peeled off from a support or the like with a low surface tack. Photosensitivity composition that can exhibit excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development with excellent laminating and handling properties, excellent storage stability, high sensitivity and excellent developability The present situation is that there is still no satisfactory product, and a photosensitive film using the same, a high-definition permanent pattern, and an efficient formation method thereof.
[0012] 特許文献 1：特開昭 61— 243869号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 61-243869
特許文献 2 :特開平 02— 097502号公報 特許文献 3：特開平 11― 246651号公報 Patent Document 2: Japanese Patent Laid-Open No. 02-097502 Patent Document 3: Japanese Patent Laid-Open No. 11-246651
特許文献 4：特開昭 56— 155222号公報  Patent Document 4: Japanese Patent Laid-Open No. 56-155222
特許文献 5 :特開昭 57— 100127号公報  Patent Document 5: Japanese Unexamined Patent Publication No. 57-100127
特許文献 6：特開昭 59— 053526号公報  Patent Document 6: Japanese Unexamined Patent Publication No. 59-053526
特許文献 7：特開 2000— 001526号公報  Patent Document 7: Japanese Patent Laid-Open No. 2000-001526
特許文献 8：特許第 2746009号公報  Patent Document 8: Japanese Patent No. 2746009
特許文献 9：特許第 2707495号公報  Patent Document 9: Japanese Patent No. 2707495
非特許文献 1 :日本油脂、遠藤岡 lj (東工大)ネットワークポリマー voll9, No. 4, P2 28— 235、 1998  Non-Patent Document 1: Nippon Oil & Fats, Endooka lj (Tokyo Tech) Network polymer voll9, No. 4, P2 28—235, 1998
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0013] 本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題と する。即ち、本発明は、保存時の常温下では反応を生じず、加熱により架橋反応を 開始して、硬化膜の良好な膜硬度が得られる化合物を含み、 UV露光により画像形 成可能で、表面のタック性が小さぐラミネート性及び取扱い性が良好で、保存安定 性に優れ、高感度で現像性にも優れ、現像後に優れた耐薬品性、表面硬度、耐熱 性、誘電特性などを発現する感光性組成物、及びこれを用いた感光性フィルム、並 びに、高精細な永久パターン (保護膜、層間絶縁膜、及びソルダーレジストパターン など)及びその効率的な形成方法を提供することを目的とする。 [0013] An object of the present invention is to solve the conventional problems and achieve the following object. That is, the present invention includes a compound that does not react at room temperature during storage, starts a crosslinking reaction by heating, and provides a cured film with good film hardness. Low tackiness, good laminating and handling properties, excellent storage stability, high sensitivity, excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development It is an object of the present invention to provide a photosensitive composition, a photosensitive film using the same, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) and an efficient formation method thereof. To do.
課題を解決するための手段  Means for solving the problem
[0014] 前記課題を解決するための手段としては、以下の通りである。即ち、 [0014] Means for solving the above problems are as follows. That is,
< 1 > (A) 1分子中に 1個以上のカルボキシル基及びエステル基の少なくとも ヽ ずれかを有する重合体と、（B)重合性化合物と、（C)光重合開始剤と、（D)下記一 般式（ 1)〜（3)で表される化合物から選択される少なくとも 1種の化合物を含むことを 特徴とする感光性組成物である。  <1> (A) a polymer having at least one of at least one carboxyl group and ester group in one molecule, (B) a polymerizable compound, (C) a photopolymerization initiator, (D) A photosensitive composition comprising at least one compound selected from compounds represented by the following general formulas (1) to (3).
[化 14]  [Chemical 14]
A1— P— -般式 (υ [化 15] 一般式（2)
Figure imgf000008_0001
A 1 — P—-General formula (υ [Chemical formula 15] General formula (2)
Figure imgf000008_0001
[化 16]
Figure imgf000008_0002
[Chemical 16]
Figure imgf000008_0002
ただし、前記一般式（1)、 (2)、及び (3)中、 Ρは、酸素原子、カルボニル基、アミド 基、ウレタン基、アルキレン、及びァリーレンのいずれかを表す。 Qは、ホウ素原子、 窒素原子、アルキレン、及びァリーレンのいずれかを表す。 Wは、 2つの X部と結合を 有するナフタレンを表す。 Ai A5は、単結合、アルキレン、及びァリーレンのいずれ かを表し、 丄〜 6は、— OCONH―、— NHCOO—、— NHCO—、及び— CONH 一のいずれかを表す。！^〜尺6は、水素原子、ハロゲン原子、アルキル基、及びァリー ル基のいずれかを表す。 However, in the general formulas (1), (2), and (3), Ρ represents any of an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene, and an arylene. Q represents any of a boron atom, a nitrogen atom, alkylene, and arylene. W represents naphthalene having two X moieties and a bond. Ai A 5 represents a single bond, alkylene, or arylene, and 丄 to 6 represent one of —OCONH—, —NHCOO—, —NHCO—, and —CONH. ! ^ To 6 represent any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
該< 1 >に記載の感光性組成物においては、低温又は常温での保存時には硬化 を生じず、保存安定性及び取り扱い性などに優れ、加熱により反応を生じて、硬化膜 の優れた膜硬度が得られる。前記感光性組成物を用いて永久パターンを形成した場 合、高感度なパターン形成ができ、硬化膜の耐薬品性、表面硬度、耐熱性、誘電特 性の向上が図られ、高精細な永久パターンが得られる。  In the photosensitive composition according to <1>, curing does not occur during storage at a low temperature or normal temperature, it has excellent storage stability and handleability, and a reaction is caused by heating, resulting in excellent film hardness of the cured film. Is obtained. When a permanent pattern is formed using the photosensitive composition, a highly sensitive pattern can be formed, and the chemical resistance, surface hardness, heat resistance, and dielectric properties of the cured film can be improved, and a high-definition permanent pattern can be obtained. A pattern is obtained.
< 2> (D)一般式（ 1)〜（3)で表される化合物から選択される少なくとも 1種の化 合物が、下記構造式（1)〜（10)で表される化合物である前記 < 1 >に記載の感光 性組成物である。  <2> (D) At least one compound selected from the compounds represented by the general formulas (1) to (3) is a compound represented by the following structural formulas (1) to (10) The photosensitive composition according to <1>.
[化 17]  [Chemical 17]
0 0、 0 0 0 0, 0 0
、oへ 構造式（1 )  To o Structural formula (1)
H  H
[化 18] 構造式 (2) [Chemical formula 18] Structural formula (2)
Figure imgf000008_0003
構造式 (3)
Figure imgf000008_0003
Structural formula (3)
Figure imgf000009_0001
Figure imgf000009_0001
[化 20] 構造式 (4) [Chemical formula 20] Structural formula (4)
Figure imgf000009_0002
Figure imgf000009_0002
[化 21]  [Chemical 21]
ο- Η Η  ο- Η Η
-0、，Ν- - Μ、，0- 構造式（5)  -0,, Ν--Μ,, 0- Structural formula (5)
[化 22][Chemical 22]
Figure imgf000009_0003
構造式 (6)
Figure imgf000009_0003
Structural formula (6)
[化 23] 構造式 (7) [Chemical formula 23] Structural formula (7)
Figure imgf000009_0004
Figure imgf000009_0004
[化 24]  [Chemical 24]
構造式 (8)Structural formula (8)
Figure imgf000009_0005
Figure imgf000009_0005
[化 25] [Chemical 25]
Figure imgf000009_0006
構造式 (9)
Figure imgf000009_0006
Structural formula (9)
[化 26]  [Chemical 26]
構造式（1 0)Structural formula (1 0)
Figure imgf000009_0007
Figure imgf000009_0007
< 3 > (D)一般式（ 1)〜（3)で表される化合物から選択される少なくとも 1種の化 合物の含有量の含有量が、 1〜50質量％である前記 < 1 >から < 2>のいずれ力に 記載の感光性組成物である。 < 4 > (D)一般式（ 1)〜（3)で表される化合物から選択される少なくとも 1種の化 合物と併用する熱架橋剤を更に含む前記 < 1 >から < 3 >の 、ずれかに記載の感 光性組成物である。 <3> (D) The above <1>, wherein the content of at least one compound selected from the compounds represented by the general formulas (1) to (3) is 1 to 50% by mass To <2>. The photosensitive composition according to any one of the above. <4> (D) <1> to <3>, further comprising a thermal crosslinking agent used in combination with at least one compound selected from the compounds represented by formulas (1) to (3): The photosensitive composition according to any one of the above.
< 5 > 併用する熱架橋剤が、エポキシィ匕合物、ォキセタンィ匕合物、ポリイソシァネ ート化合物、ポリイソシァネート化合物にブロック剤を反応させて得られる化合物、及 びメラミン誘導体力 選択される少なくとも 1種である前記く 4 >に記載の感光性組成 物である。  <5> The thermal crosslinking agent used in combination is an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and at least a melamine derivative selected. It is a photosensitive composition as described in 4> above.
< 6 > 併用する熱架橋剤が、多価フエノール化合物と j8—アルキルェピハロヒドリ ンと力 誘導されたエポキシィ匕合物である前記 <4>力 < 5 >の 、ずれかに記載の 感光性組成物である。  <6> The photosensitivity according to any one of <4>, <5>, wherein the thermal crosslinking agent used in combination is a force-induced epoxy compound with a polyhydric phenol compound and j8-alkylephalohydrin. Composition.
< 7> 併用する熱架橋剤が、分子内に 2つ以上のォキシラン基を有するエポキシ 化合物である前記 < 4 >から < 6 >のいずれかに記載の感光性組成物である。  <7> The photosensitive composition according to any one of <4> to <6>, wherein the thermal crosslinking agent used in combination is an epoxy compound having two or more oxosilane groups in the molecule.
< 8 > 併用する熱架橋剤が、分子内に 2つ以上のォキセタ-ル基を有するォキセ タンィ匕合物である前記く 4 >から < 7 >の 、ずれかに記載の感光性組成物である。  <8> The photosensitive composition according to any one of <4> to <7>, wherein the thermal crosslinking agent used in combination is an oxetane compound having two or more oxetal groups in the molecule. is there.
< 9 > 併用する熱架橋剤が、下記構造式 (I)及び (II)のいずれかで表される前記 < 4 >力 < 8 >の!、ずれかに記載の感光性組成物である。  <9> The photosensitive composition according to any one of <4> force <8> represented by any one of the following structural formulas (I) and (II):
[化 27]
Figure imgf000010_0001
[Chemical 27]
Figure imgf000010_0001
構造式（ 1〕 Structural formula (1)
[化 28] [Chemical 28]
構造式 (II)Structural formula (II)
Figure imgf000010_0002
Figure imgf000010_0002
ただし、前記構造式 (I)中、 Rは水素原子及び炭素数 1〜6のアルキル基のいずれ かを表し、 nは 0〜20の整数を表す。  However, in said structural formula (I), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
ただし、前記構造式 (II)中、 Rは水素原子及び炭素数 1〜6のアルキル基のいずれ かを表し、 R'は水素原子、及び CHのいずれかを表し、 nは 0 However, in the structural formula (II), R represents any of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. R ′ represents either a hydrogen atom or CH, and n represents 0.
3 〜20の整数を表す。 Represents an integer from 3 to 20.
< 10> 併用する熱架橋剤が、へキサメチル化メチロールメラミンである前記く 4 >から < 6 >の!、ずれかに記載の感光性組成物である。 <10> The photosensitive composition according to any one of <4> to <6>, wherein the thermal crosslinking agent used in combination is hexamethylated methylolmelamine.
< 11 > (A)重合体力 エポキシアタリレートイ匕合物である前記く 1 >からく 10> の!ヽずれかに記載の感光性組成物である。  <11> (A) Polymer power The photosensitive composition according to any one of the above <1> and <10>, which is an epoxy atareto toy compound.
< 12 > (A)重合体が、側鎖に (メタ)アタリロイル基、及び酸性基を有するビニル 共重合体の少なくとも 1種を含む前記 < 1 >からく 11 >のいずれかに記載の感光性 組成物である。  <12> The photosensitivity according to any one of <1> and <11>, wherein the (A) polymer contains at least one kind of vinyl copolymer having a (meth) ataryloyl group and an acidic group in a side chain. It is a composition.
< 13 > (A)重合体力 エポキシアタリレートイ匕合物と、側鎖に (メタ）アタリロイル基 、及び酸性基を有するビニル共重合体の少なくとも 1種を含む前記 < 1 >から < 12 >の 、ずれかに記載の感光性組成物である。  <13> (A) Polymer power of <1> to <12>, comprising an epoxy ataretoy compound, and at least one vinyl copolymer having a (meth) attalyloyl group and an acidic group in the side chain The photosensitive composition described in any of the above.
< 14> (A)重合体力 下記構造式 (III)で表される前記く 11 >からく 13 >のい ずれかに記載の感光性組成物である。  <14> (A) Polymer strength The photosensitive composition according to any one of the above 11> Karaku 13> represented by the following structural formula (III).
[化 29] [Chemical 29]
O X OX 0 X O X OX 0 X
CHfCH、c 、 2 。 。、 2 2 。 、 CH f CH , c, 2 . . , 2 2 . ,
0 0 構造式 （I I I )  0 0 Structural formula (I I I)
ただし、前記構造式 (III)中、 Xは水素原子、及び少なくとも酸性基を含む置換基の いずれかを表し、 Yはメチレン基、イソプロピリデン基、及びスルホ-ル基のいずれか を表し、 nは、 1〜20の整数を表す。  However, in the structural formula (III), X represents any of a hydrogen atom and a substituent containing at least an acidic group, Y represents any of a methylene group, an isopropylidene group, and a sulfole group, n Represents an integer of 1-20.
< 15 > (A)重合体力 無水マレイン酸共重合体の無水物基に対して 0. 1〜1. 2 当量の 1級アミンィ匕合物を反応させて得られる共重合体である前記く 1 >から < 5 > 及びく 10 >の 、ずれかに記載の感光性組成物である。  <15> (A) Polymer strength As described above, the copolymer 1 is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of a maleic anhydride copolymer. > To <5> and <10>.
< 16 > (A)重合体が、（a)無水マレイン酸と、（b)芳香族ビニル単量体と、（c)ビ -ル単量体であって、該ビュル単量体のホモポリマーのガラス転移温度 (Tg)が 80 °C未満であるビニル単量体とからなる共重合体の無水物基に対して 0. 1〜1. 0当量 の 1級アミンィ匕合物を反応させて得られる共重合体である前記 < 1 >からく 5 >、 < 1 0 >及びく 15 >の 、ずれかに記載の感光性組成物である。 < 17> (B)重合性化合物が、（メタ)アクリル基を有するモノマーから選択される 少なくとも 1種を含む前記 < 1 >からく 16 >のいずれかに記載の感光性組成物であ る。 <16> (A) The polymer is (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, 0.1 to 1.0 equivalent of a primary amine compound is reacted with an anhydride group of a copolymer consisting of a vinyl monomer having a glass transition temperature (Tg) of less than 80 ° C. The photosensitive composition according to any one of <1> Karaku 5>, <10> and 15>, which is a copolymer to be obtained. <17> The photosensitive composition according to any one of <1> to Karaku16, wherein the polymerizable compound (B) includes at least one selected from monomers having a (meth) acryl group.
< 18> (C)光重合開始剤が、ハロゲン化炭化水素誘導体、ホスフィンオキサイド 、へキサァリールビイミダゾール、ォキシム誘導体、有機過酸化物、チォ化合物、ケト ン化合物、芳香族ォ -ゥム塩、及びケトォキシムエーテル力 選択される少なくとも 1 種を含む前記 < 1 >からく 17 >のいずれかに記載の感光性組成物である。  <18> (C) The photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexarylbiimidazole, oxime derivative, organic peroxide, thio compound, keton compound, aromatic onium salt. And ketoxime ether power. The photosensitive composition according to any one of <1> to 17>, which contains at least one selected from the group.
< 19> 支持体と、該支持体上に、前記 < 1 >からく 18>のいずれかに記載の感 光性組成物が積層されてなる感光層とを有することを特徴とする感光性フィルムであ る。  <19> A photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to any one of <1>, 18 and 18 on the support. It is.
< 20> 感光層を露光し現像する場合において、該感光層の露光する部分の厚 みを該露光及び現像後にお 、て変化させな 、前記露光に用いる光の最小エネルギ 一が 0. 1〜： LOOmjZcm2である前記 < 19 >に記載の感光性フィルムである。 <20> When the photosensitive layer is exposed and developed, the minimum energy of the light used for the exposure is 0.1 to 0.1% without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development. : a photosensitive film according to <19> is LOOmjZcm 2.
< 21 > 支持体が、合成樹脂を含み、かつ透明である前記く 19>からく 21 >の V、ずれかに記載の感光性フィルムである。  <21> The photosensitive film according to any one of V and deviations of <19> to <21>, wherein the support contains a synthetic resin and is transparent.
< 22> 支持体が、長尺状である前記く 19>からく 21 >のいずれかに記載の感 光性フィルムである。  <22> The photosensitive film according to any one of the above <19> and <21>, wherein the support has a long shape.
< 23> 長尺状であり、ロール状に巻かれてなる前記 < 19>から < 22>のいず れかに記載の感光性フィルムである。  <23> The photosensitive film according to any one of <19> to <22>, which is long and wound in a roll.
< 24 > 感光層上に保護フィルムを有してなる前記く 19 >力らく 23 >の!、ずれ かに記載の感光性フィルムである。  <24> The photosensitive film according to any one of [19] above, [23] above, which has a protective film on the photosensitive layer.
< 25> 感光層の厚みが、 3〜100 111でぁる前記< 19>から< 24>のぃずれ かに記載の感光性フィルムである。  <25> The photosensitive film according to any one of <19> to <24>, wherein the photosensitive layer has a thickness of 3 to 100111.
< 26> 感光層が、光照射手段からの光を受光し出射する描素部を n個有する光 変調手段により、前記光照射手段からの光を変調させた後、前記描素部における出 射面の歪みによる収差を補正可能な非球面を有するマイクロレンズを配列したマイク 口レンズアレイを通した光で、露光される前記く 19 >からく 25 >に記載の感光性フ イルムである。 < 27> 前記く 1 >からく 18 >のいずれかに記載の感光性組成物を、基材の表 面に塗布し、乾燥して感光層を形成した後、露光し、現像し、加熱することを特徴とす る永久パターン形成方法である。該< 27 >に記載の永久パターン形成方法にお!ヽ ては、前記感光性組成物が前記基材の表面に塗布され、該塗布された感光性組成 物が乾燥されて前記感光層が形成される。該感光層が露光され、該露光された感光 層が現像され、該現像された感光層が加熱される。該感光層が加熱されることにより 、架橋反応を開始して、前記感光層の硬化領域の膜強度が高められる。その結果、 表面硬度が高ぐ保護膜、層間絶縁膜、及びソルダーレジストパターンなどに最適な 永久パターンが形成される。該加熱処理は、全面加熱処理であってもよいし、パター ン状に加熱する処理であってもよ ヽ。 <26> After the photosensitive layer modulates the light from the light irradiation means by the light modulation means having n picture elements for receiving and emitting the light from the light irradiation means, the light is emitted from the light irradiation means. The photosensitive film according to the above <19> to <25>, which is exposed by light passing through a microphone aperture lens array in which microlenses having aspherical surfaces capable of correcting aberration due to surface distortion are arranged. <27> The photosensitive composition according to any one of <1> to <18> is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. This is a permanent pattern forming method characterized by this. In the method for forming a permanent pattern according to <27>, the photosensitive composition is applied to the surface of the substrate, and the applied photosensitive composition is dried to form the photosensitive layer. Is done. The photosensitive layer is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated. When the photosensitive layer is heated, a crosslinking reaction is started to increase the film strength of the cured region of the photosensitive layer. As a result, an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern. The heat treatment may be a whole surface heat treatment or a heat treatment in a pattern.
< 28 > 前記 < 19 >から < 26 >の!、ずれかに記載の感光性フィルムを、加熱及 び加圧の少なくともいずれかの下において基材の表面に積層した後、露光し、現像 し、加熱することを特徴とする永久パターン形成方法である。該く 28 >に記載の永 久パターン形成方法においては、前記感光性フィルム力 加熱及び加圧下にて前記 基材の表面に積層される。該積層された感光性フィルムにおける前記感光層が露光 され、該露光された感光層が現像され、該現像された感光層が加熱される。該感光 層が加熱されることで、前記一般式（1)〜（3)で表される化合物の架橋効果により、 前記感光層の硬化領域の膜強度が高められる。その結果、表面硬度が高ぐ保護膜 、層間絶縁膜、及びソルダーレジストパターンなどに最適な永久パターンが形成され る。  <28> From the above <19> to <26> !, the photosensitive film according to any one of the above is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed. And a permanent pattern forming method characterized by heating. In the permanent pattern forming method described in the above item 28>, the photosensitive film is laminated on the surface of the substrate under heating and pressing. The photosensitive layer in the laminated photosensitive film is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated. By heating the photosensitive layer, the film strength of the cured region of the photosensitive layer is increased by the crosslinking effect of the compounds represented by the general formulas (1) to (3). As a result, an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern.
< 29 > 基材が、配線形成済みのプリント配線基板である前記く 27 >からく 28 > の!、ずれかに記載の永久パターン形成方法である。該永久パターン形成方法を利 用することにより、半導体部品の多層配線基板ゃビルドアップ配線基板などへの高 密度実装が可能である。  <29> The method for forming a permanent pattern according to any one of [27] to [28], wherein the substrate is a printed wiring board on which wiring is formed. By using the permanent pattern forming method, high-density mounting of semiconductor components on a multilayer wiring board or a build-up wiring board is possible.
< 30> 露光が、形成するパターン情報に基づいて像様に行われる前記く 27 > からく 29 >のいずれかに記載の永久パターン形成方法である。  <30> The permanent pattern forming method according to any one of <27>, <29>, wherein the exposure is performed imagewise based on pattern information to be formed.
< 31 > 露光が、形成するパターン情報に基づいて制御信号を生成し、該制御信 号に応じて変調させた光を用いて行われる前記く 27 >から < 30 >の 、ずれかに記 載の永久パターン形成方法である。 <31> The control signal is generated based on the pattern information to be formed, and the control signal is generated using light modulated in accordance with the control signal. This is a permanent pattern forming method.
< 32> 露光が、光を照射する光照射手段と、形成するパターン情報に基づいて 前記光照射手段から照射される光を変調させる光変調手段とを用いて行われる前記 < 27 >から < 31 >の!、ずれかに記載の永久パターン形成方法である。  <32> From the above <27> to <31, wherein the exposure is performed using a light irradiation unit that emits light and a light modulation unit that modulates light emitted from the light irradiation unit based on pattern information to be formed >! Is a permanent pattern forming method as described in any of the above.
< 33 > 光変調手段が、形成するパターン情報に基づいて制御信号を生成する パターン信号生成手段を更に有してなり、前記光照射手段から照射される光を該パ ターン信号生成手段が生成した制御信号に応じて変調させる前記 < 32 >に記載の 永久パターン形成方法である。  <33> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit. The method for forming a permanent pattern according to <32>, wherein modulation is performed according to a control signal.
< 34> 光変調手段が、 n個の描素部を有してなり、該 n個の描素部の中から連続 的に配置された任意の n個未満の前記描素部を、形成するパターン情報に応じて制 御可能である前記 < 32 >から < 33 >のいずれかに記載の永久パターン形成方法 である。該く 34 >に記載の永久パターン形成方法においては、前記光変調手段に おける n個の描素部の中から連続的に配置された任意の n個未満の描素部をパター ン情報に応じて制御することにより、前記光照射手段からの光が高速で変調される。  <34> The light modulation means has n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts. The permanent pattern forming method according to any one of <32> to <33>, which can be controlled according to pattern information. In the permanent pattern forming method described in 34>, any less than n pixel parts arranged continuously from the n pixel parts in the light modulation means may be selected according to the pattern information. By controlling the light, the light from the light irradiation means is modulated at high speed.
< 35 > 光変調手段が、空間光変調素子である前記く 32>からく 34>のいずれ かに記載の永久パターン形成方法である。  <35> The method for forming a permanent pattern according to any one of the items <32> to <34>, wherein the light modulation means is a spatial light modulation element.
< 36 > 空間光変調素子が、デジタル 'マイクロミラー'デバイス (DMD)である前 記く 35 >に記載の永久パターン形成方法である。  <36> The permanent pattern forming method according to 35, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
< 37> 描素部が、マイクロミラーである前記く 34>からく 36 >のいずれかに記 載の永久パターン形成方法である。  <37> The permanent pattern forming method according to any one of the above <34>, <36>, wherein the pixel part is a micromirror.
< 38 > 露光が、光変調手段により光を変調させた後、前記光変調手段における 描素部の出射面の歪みによる収差を補正可能な非球面を有するマイクロレンズを配 列したマイクロレンズアレイを通して行われる前記く 34 >からく 37 >のいずれかに 記載の永久パターン形成方法である。  <38> After exposure, the light modulation means modulates the light, and then passes through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface of the picture element portion in the light modulation means 38. The method for forming a permanent pattern according to any one of 34> Karaku 37>.
< 39 > 非球面が、トーリック面である前記く 38 >に記載の永久パターン形成方 法である。該< 39 >に記載の永久パターン形成方法においては、前記非球面がト 一リック面であることにより、前記描素部における放射面の歪みによる収差が効率よく 補正され、前記感光層上に結像させる像の歪みが効率よく抑制される。その結果、前 記感光層への露光が高精細に行われる。その後、前記感光層を現像することにより、 高精細な永久パターンが形成される。 <39> The method for forming a permanent pattern according to <38>, wherein the aspherical surface is a toric surface. In the method for forming a permanent pattern according to <39>, since the aspherical surface is a toric surface, the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected and is formed on the photosensitive layer. The distortion of the image to be imaged is efficiently suppressed. As a result, before The photosensitive layer is exposed with high definition. Thereafter, the photosensitive layer is developed to form a high-definition permanent pattern.
<40> 露光が、アパーチャアレイを通して行われる前記く 27>からく 39 >のい ずれかに記載の永久パターン形成方法である。該< 40 >に記載の永久パターン形 成方法においては、露光が前記アパーチャアレイを通して行われることにより、消光 比が向上する。その結果、露光が極めて高精細に行われる。その後、前記感光層を 現像することにより、極めて高精細な永久パターンが形成される。  <40> The method for forming a permanent pattern according to any one of the above items 27> to 39>, wherein the exposure is performed through an aperture array. In the method for forming a permanent pattern according to <40>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<41 > 露光が、露光光と感光層とを相対的に移動させながら行われる前記く 27 >からく 40 >のいずれかに記載の永久パターン形成方法である。該く 41 >に記載 の永久パターン形成方法においては、前記変調させた光と前記感光層とを相対的に 移動させながら露光することにより、露光が高速に行われる。  <41> The method for forming a permanent pattern according to any one of <27>, <40>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the method for forming a permanent pattern described in 41>, exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
<42> 露光が、感光層の一部の領域に対して行われる前記 < 27>から <41 > のいずれかに記載の永久パターン形成方法である。  <42> The method for forming a permanent pattern according to any one of <27> to <41>, wherein the exposure is performed on a partial region of the photosensitive layer.
<43 > 光照射手段が、 2以上の光を合成して照射可能である前記く 32>からく 42 >の 、ずれかに記載の永久パターン形成方法である。該< 43 >に記載の永久 パターン形成方法にぉ 、ては、前記光照射手段が 2以上の光を合成して照射可能 であることにより、露光が焦点深度の深い露光光で行われる。その結果、前記感光層 への露光が極めて高精細に行われる。その後、前記感光層を現像することにより、極 めて高精細な永久パターンが形成される。  <43> The permanent pattern forming method according to any one of the above <32> and <42>, wherein the light irradiation means can synthesize and irradiate two or more lights. In the permanent pattern forming method described in <43>, 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. As a result, the exposure to the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form an extremely fine permanent pattern.
<44> 光照射手段が、複数のレーザと、マルチモード光ファイバと、該複数のレ 一ザ力 それぞれ照射されたレーザ光を集光して前記マルチモード光ファイバに結 合させる集合光学系とを有する前記く 32>からく 43 >のいずれかに記載の永久パ ターン形成方法である。該< 44 >に記載の永久パターン形成方法においては、前 記光照射手段により、前記複数のレーザからそれぞれ照射されたレーザ光が前記集 合光学系により集光され、前記マルチモード光ファイバに結合可能とすることにより、 露光が焦点深度の深い露光光で行われる。その結果、前記感光層への露光が極め て高精細に行われる。その後、前記感光層を現像することにより、極めて高精細な永 久パターンが形成される。 <45 > 露光が、 395〜415nmの波長のレーザ光を用いて行われる前記く 27> 力ら< 44 >の!、ずれかに記載の永久パターン形成方法である。 <44> 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 laser forces and couples the laser beams to the multimode optical fiber. The method for forming a permanent pattern according to any one of the above items 32> to 43>. In the method for forming a permanent pattern described in <44>, the laser light respectively emitted from the plurality of lasers is condensed by the converging optical system by the light irradiation unit and coupled to the multimode optical fiber. By making it possible, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern. <45> The method for forming a permanent pattern according to <44>, wherein the exposure is performed using a laser beam having a wavelength of 395 to 415 nm.
<46 > カロ熱力 120〜250oCで行われる前記 < 27>カら<45 >のいずれ力に 記載の永久パターン形成方法である。該く 46 >に記載の永久パターン形成方法で は、前記温度条件で行われる加熱処理において、硬化膜の膜強度が高められる。 <46> The method for forming a permanent pattern according to any one of <27>, et al. <45>, which is performed at a heat of 120 to 250 ° C. In the permanent pattern forming method described in 46>, the film strength of the cured film is increased in the heat treatment performed under the temperature condition.
<47> 現像が行われた後、感光層に対して全面露光処理を行う前記く 27>か らく 46 >に記載の永久パターン形成方法である。該< 46 >に記載の永久パターン 形成方法では、前記全面露光処理において、前記感光性組成物中の榭脂の硬化が 促進される。  <47> The method for forming a permanent pattern according to <27> to <46>, wherein after the development, the photosensitive layer is subjected to an entire surface exposure process. In the method for forming a permanent pattern according to <46>, curing of the resin in the photosensitive composition is promoted in the overall exposure process.
<48 > 保護膜、層間絶縁膜、及びソルダーレジストパターンの少なくともいずれ かを形成する前記く 27 >からく 47 >の 、ずれかに記載の永久パターン形成方法 である。該く 48 >に記載の永久パターン形成方法では、保護膜、層間絶縁膜及び ソルダーレジストパターンの少なくともいずれかが形成されるので、該膜の有する絶 縁性、耐熱性などにより、配線が外部からの衝撃や曲げなどカゝら保護される。  <48> The method for forming a permanent pattern according to any one of the above <27> and <47>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. In the permanent pattern forming method described in 48>, since at least one of a protective film, an interlayer insulating film and a solder resist pattern is formed, the wiring is externally provided due to the insulation property, heat resistance, etc. of the film. Protected against impacts and bending.
[0017] <49 > 前記 < 27>から <48 >のいずれかに記載の永久パターン形成方法によ り形成されることを特徴とする永久パターンである。該く 49 >に記載の永久パターン は、前記永久パターン形成方法により形成されるので、優れた耐薬品性、表面硬度、 耐熱性などを有し、かつ高精細であり、半導体部品の多層配線基板やビルドアップ 配線基板などへの高密度実装に有用である。 [0017] <49> A permanent pattern formed by the method for forming a permanent pattern according to any one of <27> to <48>. The permanent pattern described in 49> is formed by the method for forming a permanent pattern, so that it has excellent chemical resistance, surface hardness, heat resistance, etc., and has high definition, and is a multilayer wiring board for semiconductor components. It is useful for high-density mounting on PCBs and build-up wiring boards.
< 50> 保護膜、層間絶縁膜、及びソルダーレジストパターンの少なくともいずれ かである前記く 49 >に記載の永久パターンである。該< 50 >に記載の永久パター ンは、保護膜、層間絶縁膜及びソルダーレジストパターンの少なくともいずれかであ るので、該膜の有する絶縁性、耐熱性などにより、配線が外部力ゝらの衝撃や曲げなど 力 保護される。  <50> The permanent pattern according to the above item 49, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in <50> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring has an external force or the like depending on the insulating property and heat resistance of the film. Force and bending are protected.
発明の効果  The invention's effect
[0018] 本発明によると、従来における問題を解決することができ、保存時の常温下では反 応を生じず、加熱により架橋反応を開始して、硬化膜の良好な膜硬度が得られる化 合物を含み、 UV露光により画像形成可能で、表面のタック性が小さぐラミネート性 及び取扱い性が良好で、保存安定性に優れ、高感度で現像性にも優れ、現像後に 優れた耐薬品性、表面硬度、耐熱性、誘電特性などを発現する感光性組成物、及び これを用いた感光性フィルム、並びに、高精細な永久パターン (保護膜、層間絶縁膜 、及びソルダーレジストパターンなど)及びその効率的な形成方法を提供することが できる。 [0018] According to the present invention, conventional problems can be solved, and no reaction occurs at room temperature during storage, and a crosslinking reaction is initiated by heating, whereby a good film hardness of the cured film can be obtained. Laminate that contains compound, can be imaged by UV exposure, and has low surface tack And a photosensitive composition that has good handling properties, excellent storage stability, high sensitivity and excellent developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development, and The photosensitive film used, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) and an efficient formation method thereof can be provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0019] (感光性組成物）  [0019] (Photosensitive composition)
本発明の感光性組成物は、（A) 1分子中に 1個以上のカルボキシル基及びエステ ル基のいずれかを有する重合体と、（B)重合性化合物と、（C)光重合開始剤と、 (D) 後述の一般式（1)〜（3)で表される化合物力 選択される少なくとも 1種の化合物と を少なくとも含み、併用する熱架橋剤を含んでいてもよぐ更に、必要に応じて、着色 顔料、体質顔料、熱重合禁止剤、及び界面活性剤などのその他の成分を含んでなる  The photosensitive composition of the present invention comprises (A) a polymer having one or more carboxyl groups and ester groups in one molecule, (B) a polymerizable compound, and (C) a photopolymerization initiator. And (D) a compound represented by the following general formulas (1) to (3): at least one selected from at least one compound, and a thermal cross-linking agent used in combination. Depending on the type, it may contain other components such as coloring pigments, extender pigments, thermal polymerization inhibitors, and surfactants.
[0020] 〔(A)バインダー（重合体)〕 [0020] [(A) Binder (Polymer)]
前記ノインダーとしては、アルカリ性水溶液に対して膨潤性を示すィ匕合物が好まし く、アルカリ性水溶液に対して可溶性である化合物がより好ま 、。  The noinder is preferably a compound exhibiting swellability in an alkaline aqueous solution, and more preferably a compound that is soluble in an alkaline aqueous solution.
アルカリ性水溶液に対して膨潤性又は溶解性を示すバインダーとしては、例えば、 酸性基を有するものが好適に挙げられ、具体的には、エポキシ化合物にエチレン性 不飽和二重結合と酸性基とを導入した化合物 (エポキシアタリレートイ匕合物）、側鎖に (メタ)アタリロイル基、及び酸性基を有するビニル共重合体、エポキシアタリレートイ匕 合物と、側鎖に (メタ)アタリロイル基、及び酸性基を有するビニル共重合体との混合 物、マレアミド酸系共重合体、などが好ましい。  As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound. Compound (epoxy atalytoyl compound), vinyl copolymer having (meth) taroloyl group and acid group in the side chain, epoxy atalytoyl compound, and (meth) attalyloyl group in the side chain, and A mixture with a vinyl copolymer having an acidic group, a maleamic acid copolymer, and the like are preferable.
前記酸性基としては、特に制限はなぐ 目的に応じて適宜選択することができ、例え ば、カルボキシル基、スルホン酸基、リン酸基、などが挙げられ、これらの中でも、原 料の入手性などの観点から、カルボキシル基が好ましく挙げられる。  The acidic group is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From this point of view, a carboxyl group is preferred.
[0021] <エポキシアタリレート化合物 > [0021] <Epoxy Atalylate Compound>
前記エポキシィ匕合物にエチレン性不飽和二重結合と酸性基とを導入したィ匕合物（ エポキシアタリレートイ匕合物）としては、特に制限は無ぐ 目的に応じて適宜選択する ことができ、例えば、多官能エポキシィ匕合物とカルボキシル基含有モノマーとを反応 させ、更に多塩基酸無水物を付加させる方法などで得られる。 There is no particular limitation on the compound obtained by introducing an ethylenically unsaturated double bond and an acidic group into the epoxy compound (epoxy atelar toy compound), which is appropriately selected according to the purpose. For example, it can be obtained by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.
[0022] 前記多官能エポキシィ匕合物としては、例えば、ビキシレノール型もしくはビスフエノ ール型エポキシ榭脂（ ΓΥΧ4000；ジャパンエポキシレジン社製」等）又はこれらの混 合物、イソシァヌレート骨格等を有する複素環式エポキシ榭脂（「TEPIC ;日産化学 工業社製」、「ァラルダイト PT810 ;チバ'スペシャルティ'ケミカルズ社製」等）、ビスフ ェノール A型エポキシ榭脂、ビスフエノール F型エポキシ榭脂、水添ビスフエノール A 型エポキシ榭脂、ビスフエノール S型エポキシ榭脂、フエノールノボラック型エポキシ 榭脂、クレゾ ルノボラック型エポキシ榭脂、ハロゲンィ匕フエノールノボラック型ェポキ シ榭 S旨、グリシジノレアミン型エポキシ榭 S旨（ί列えばテトラグリシジノレジアミノジフエ二ノレ メタン等）、ヒダントイン型エポキシ榭脂、脂環式エポキシ榭脂、トリヒドロキシフエニル メタン型エポキシ榭脂、ビスフエノール Αノボラック型エポキシ榭脂、テトラフエ二ロー ルェタン型エポキシ榭脂、グリシジルフタレート榭脂、テトラグリシジルキシレノィルェ タン榭脂、ナフタレン基含有エポキシ榭脂（「ESN— 190, ESN— 360 ;新日鉄化学 社製」、「HP— 4032, EXA-4750, EXA— 4700 ;大日本インキイ匕学工業社製」 等）、ジシクロペンタジェン骨格を有するエポキシ榭脂（「HP— 7200, HP- 7200H ；大日本インキ化学工業社製」等）；フエノール、 o クレゾール、ナフトール等のフエノ ール化合物と、フエノール性水酸基を有する芳香族アルデヒド (例えば、 p ヒドロキ シベンズアルデヒド）との縮合反応により得られるポリフエノールイ匕合物とェピクロルヒ ドリンとの反応物；フエノール化合物とジビュルベンゼンゃジシクロペンタジェン等の ジォレフインィ匕合物との付加反応によって得られるポリフエノールイ匕合物と、ェピクロ ルヒドリンとの反応物； 4 ビニルシクロへキセン— 1 オキサイドの開環重合物を過 酢酸等でエポキシィ匕したもの；トリグリシジルイソシァヌレート等の複素環を有するェポ キシ榭脂；グリシジルメタアタリレート共重合系エポキシ榭脂（「CP— 50S, CP - 50 M ;日本油脂社製」等）、シクロへキシルマレイミドとグリシジルメタアタリレートとの共 重合エポキシ榭脂などが挙げられる。これらは 1種単独で使用してもよいし、 2種以上 を併用してもよい。  [0022] Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin (ΓΥΧ4000; manufactured by Japan Epoxy Resin Co., Ltd.) or a mixture thereof, a complex having an isocyanurate skeleton, and the like. Cyclic epoxy resin (“TEPIC: manufactured by Nissan Chemical Industries,” “ALALDITE PT810, manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated screw Phenolic A type epoxy resin, Bisphenol S type epoxy resin, Phenolic novolac type epoxy resin, Cresol novolac type epoxy resin, Halogen phenolic novolac type epoxy resin S, Glycidinoreamine type epoxy resin S ( e.g., tetraglycidinoresinaminodiphenol methane), hydantoin type Poxy resin, cycloaliphatic epoxy resin, trihydroxyphenyl methane type epoxy resin, bisphenol, novolac epoxy resin, tetraphenylethane epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyle Tan resin, naphthalene group-containing epoxy resin ("ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.") Epoxy resin having a dicyclopentagen skeleton (“HP-7200, HP-7200H; manufactured by Dainippon Ink and Chemicals”, etc.); phenolic compounds such as phenol, o cresol, naphthol, and phenolic hydroxyl groups. The reaction between polyphenolic compounds obtained by condensation reaction with aromatic aldehydes (for example, p-hydroxybenzaldehyde) and epichlorohydrin Reaction product: Polyphenolic compound obtained by addition reaction of phenolic compound with diolefin compound such as dibutenebenzene dicyclopentagen and epichlorohydrin; 4 Opening of vinylcyclohexene-1 oxide Epoxy resin of ring polymer with peracetic acid, etc .; Epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; Epoxy resin with glycidyl metaaterylate copolymer (“CP-50S, CP-50 M "Manufactured by Nippon Oil & Fats Co., Ltd."), and a copolymerized epoxy resin of cyclohexylmaleimide and glycidylmethacrylate. These may be used alone or in combination of two or more.
[0023] また、前記カルボキシル基含有モノマーの例としては、例えば (メタ）アクリル酸、ビ -ル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、ィタコン酸 、クロトン酸、桂皮酸、ソルビン酸、 a—シァノ桂皮酸、アクリル酸ダイマー；この他、 2 ーヒドロキシェチル (メタ）アタリレート等の水酸基を有する単量体と無水マレイン酸、 無水フタル酸、シクロへキサンジカルボン酸無水物等の環状酸無水物との付加反応 物；ノヽロゲン含有カルボン酸化合物との反応生成物、 ω カルボキシーポリ力プロラ タトンモノ (メタ)アタリレート、などが挙げられる。さらに、市販品としては、東亜合成化 学工業 (株）製のァロニックス Μ— 5300、 Μ— 5400、 Μ— 5500および Μ— 5600、 新中村ィ匕学工業 (株)製の ΝΚエステル CB— 1および CBX— 1、共栄社油脂化学ェ 業 (株)製の ΗΟΑ— MPおよび ΗΟΑ— MS、大阪有機化学工業 (株)製のビスコート # 2100などを用いることができる。これらは 1種単独で使用してもよいし、 2種以上を 併用してちょい。 [0023] Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl -Rubenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, a-ciano cinnamic acid, acrylic acid dimer; in addition, 2-hydroxyethyl (meth) An addition reaction product of a monomer having a hydroxyl group such as acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic acid anhydride; a reaction product of a nonogen-containing carboxylic acid compound; ω Carboxy-Poly-Power Pro-Lataton Mono (Meth) Atarylate. In addition, commercially available products include ALONIX Μ-5300, Μ—5400, Μ—5500 and Μ—5600 manufactured by Toa Gosei Kagaku Kogyo Co., Ltd. ΝΚEster CB—1 manufactured by Shin-Nakamura And CBX-1, Kyoeisha Yushi Chemical Co., Ltd. ΗΟΑ-MP and ΗΟΑ-MS, Osaka Organic Chemical Industry Co., Ltd. Viscoat # 2100, etc. can be used. These may be used alone or in combination of two or more.
また、前記多塩基酸無水物としては、例えば、無水コハク酸、無水メチルコハク酸、 無水 2, 3 ジメチルコハク酸、無水 2, 2 ジメチルコハク酸、無水ェチルコハク酸、 無水ドデセ -ルコハク酸、無水ノネ-ルコハク酸、無水マレイン酸、無水メチルマレイ ン酸、無水 2, 3 ジメチルマレイン酸、無水 2 クロロマレイン酸、無水 2, 3 ジクロ ロマレイン酸、無水ブロモマレイン酸、無水ィタコン酸、無水シトラコン酸、無水シスァ コット酸、無水フタル酸、テトラヒドロ無水フタル酸、テトラクロ口無水フタル酸、テトラブ ロモ無水フタル酸、へキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチ ルへキサヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメ チレンテトラヒドロ無水フタル酸、無水クロレンド酸および 5— (2, 5 ジォキソテトラヒ ドロフリル） 3—メチル 3 シクロへキセン一 1, 2 ジカルボン酸無水物などの二 塩基酸無水物、無水トリメリット酸、無水ピロメリット酸、 3, 3' , 4, 4'一べンゾフエノン テトラカルボン酸等の多塩基酸無水物なども使用できる。これらは 1種単独で使用し てもよいし、 2種以上を併用してもよい。  Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, anhydrous 2,3 dimethyl succinic acid, anhydrous 2,2 dimethyl succinic acid, ethyl succinic anhydride, anhydrous dodecyl succinic acid, and anhydrous Lusuccinic acid, maleic anhydride, methylmaleic anhydride, 2,3 dimethylmaleic anhydride, 2 chloromaleic anhydride, 2,3 dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, ciscacot anhydride Acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Methyl endomethylene tetrahydrophthalic anhydride Lendic acid and dibasic anhydrides such as 5- (2,5 dioxotetrahydrofuryl) 3-methyl 3 cyclohexene mono 1,2 dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, 3, 3 ', Polybasic acid anhydrides such as 4,4 'monobenzophenone tetracarboxylic acid can also be used. These may be used alone or in combination of two or more.
それぞれを順次反応させて、エポキシアタリレートを得るが、それらを反応させる比 率は、多官能エポキシィ匕合物のエポキシ基 1当量に対して、カルボキシル基含有モ ノマーのカルボキシル基。. 8〜1. 2当量、好ましくは、 0. 9〜1. 1当量であり、多塩 基酸無水物 0. 1〜1. 0当量、好ましくは、 0. 3〜1. 0当量である。 [0025] また、特開平 5— 70528号公報記載のフルオレン骨格を有するエポキシアタリレー ト (カルボキシル基を有しては 、な 、化合物）に前記多塩基酸無水物を付加させて得 られる化合物なども本発明のエポキシアタリレートとして利用できる。 Each of them is reacted sequentially to obtain an epoxy acrylate, and the ratio of reacting them is the carboxyl group of the carboxyl group-containing monomer with respect to 1 equivalent of the epoxy group of the polyfunctional epoxy compound. 8-1.2 equivalents, preferably 0.9-1.1 equivalents, polybasic acid anhydrides 0.1-1.0 equivalents, preferably 0.3-1.0 equivalents . [0025] In addition, compounds obtained by adding the polybasic acid anhydrides to epoxy atrelates having a fluorene skeleton (compounds having a carboxyl group) described in JP-A-5-70528, etc. Can also be used as the epoxy acrylate of the present invention.
[0026] 前記エポキシィ匕合物にエチレン性不飽和二重結合と酸性基とを導入したィ匕合物の 中でも、下記構造式 (III)及び (IV)で表されるエポキシアタリレートイ匕合物が好まし 、  [0026] Among the compounds obtained by introducing an ethylenically unsaturated double bond and an acidic group into the epoxy compound, the epoxy atelar toy compound represented by the following structural formulas (III) and (IV) I like things,
[化 30] [Chemical 30]
O X OX 0 X  O X OX 0 X
<CH、C 、 。、 、 。 γ 、 <C H, C,. ,,. γ ,
構造式 （I I I )  Structural formula (I I I)
ただし、前記一般式 (in)中、 Xは水素原子、及び少なくとも酸性基を含む置換基の いずれかを表し、 Υはメチレン基、イソプロピリデン基、及びスルホ-ル基のいずれか を表し、 ηは、 1〜20の整数を表す。  However, in the general formula (in), X represents any of a hydrogen atom and a substituent containing at least an acidic group, Υ represents any of a methylene group, an isopropylidene group, and a sulfol group, and η Represents an integer of 1-20.
[0027] [化 31]  [0027] [Chemical 31]
Figure imgf000020_0001
Figure imgf000020_0001
ただし、前記一般式 (IV)中、 ηは、 1〜20の整数を表す。  However, in the general formula (IV), η represents an integer of 1 to 20.
また、前記構造式 (III)で表されるエポキシアタリレートイ匕合物としては、具体的には 、下記構造式 (V)で表されるビスフエノール F型エポキシアタリレートイ匕合物、及び下 記構造式 (VI)で表されるビスフエノール Α型エポキシアタリレートイ匕合物がより好まし い。  In addition, as the epoxy ata relay toy compound represented by the structural formula (III), specifically, a bisphenol F type epoxy ata relay toy compound represented by the following structural formula (V), and A bisphenol-type epoxy atelar toy compound represented by the following structural formula (VI) is more preferred.
[化 32]
Figure imgf000021_0001
構造式 （ν)[Chemical 32]
Figure imgf000021_0001
Structural formula (ν)
[化 33] [Chemical 33]
Figure imgf000021_0002
Figure imgf000021_0002
構造式 (VI ) Structural formula (VI)
[0029] 前記エポキシアタリレート化合物の分子量としては、 1, 000〜100, 000力 子ましく 、 2, 000-50, 000力 Sより好ましい。該分子量が 1, 000未満であると、感光層表面 のタック性が強くなることがあり、後述する感光層の硬化後において、膜質が脆くなる 、あるいは、表面硬度が劣化することがあり、 100, 000を超えると、現像性が劣化す ることがある。また樹脂の合成も困難となる。 [0029] The molecular weight of the epoxy acrylate compound is preferably 1,000,000-100,000 force, more preferably 2,000-50,000 force S. If the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may increase, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 000, developability may deteriorate. Also, synthesis of the resin becomes difficult.
[0030] く側鎖に (メタ)アタリロイル基、及び酸性基を有するビニル共重合体 >  [0030] Vinyl Copolymer Having (Meth) Ataliloyl Group and Acid Group in Side Chain>
前記側鎖に (メタ)アタリロイル基、及び酸性基を有するビニル共重合体としては、例 えば（1)酸性基を有するビニルモノマー、 （2)必要に応じて後述する高分子反応に 利用可能な官能基を有するビニルモノマー、及び（3)必要に応じてその他の共重合 可能なビュルモノマーのビュル (共)重合で得られた（共)重合体を合成し、更に (4) 該 (共)重合体中の酸性基、又は高分子反応に利用可能な官能基の少なくとも 1種に 対して反応性を有する官能基と (メタ)アタリロイル基を有する化合物とを高分子反応 させること〖こよって得られる。  Examples of the vinyl copolymer having a (meth) atalyloyl group and an acidic group in the side chain include (1) a vinyl monomer having an acidic group, and (2) can be used for a polymer reaction described later if necessary. A vinyl copolymer having a functional group, and (3) a (co) polymer obtained by the (co) polymerization of other copolymerizable bull monomers as necessary, and (4) the (co) polymer It is obtained by polymerizing a functional group having reactivity with at least one of an acidic group in the polymer or a functional group available for polymer reaction and a compound having a (meth) attalyloyl group. It is done.
前記（1)酸性基を有するビニルモノマーの酸性基としては、特に制限はなぐ目的 に応じて適宜選択することができ、例えば、特開 2005— 258431号公報に記載の〔 0164〕に記載されている化合物などが挙げられる。またこれらのモノマーは、 1種単 独で使用してもよぐ 2種以上を併用してもよい。 The acidic group of the vinyl monomer having an acidic group (1) can be appropriately selected according to the purpose without any particular limitation, and is described in, for example, [0164] described in JP-A-2005-258431. And the like. These monomers can be May be used alone or in combination of two or more.
また、カルボキシル基の前駆体として無水マレイン酸、無水ィタコン酸、無水シトラコ ン酸等の無水物を有するモノマーを用いてもょ 、。  Alternatively, monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
前記（2)の高分子反応に利用可能な官能基を有するビニルモノマーにおける、高 分子反応に利用可能な官能基としては水酸基、アミノ基、イソシァネート基、エポキシ 基、酸ハライド基、活性ハライド基、などが挙げられる。また前述（1)のカルボシキル 基や酸無水物基も利用可能な官能基として挙げられる。  In the vinyl monomer having a functional group that can be used for the polymer reaction of (2) above, the functional group that can be used for the high molecular reaction includes a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. In addition, the above-mentioned (1) carboxyl group and acid anhydride group are also usable functional groups.
[0031] 前記水酸基を有するビニルモノマーとしては、例えば、特開 2005— 258431号公 報の〔0182〕〜〔0192〕に記載されて 、る化合物が挙げられる。 Examples of the vinyl monomer having a hydroxyl group include the compounds described in [0182] to [0192] of JP 2005-258431 A.
[0032] 前記アミノ基を有するビュルモノマーとしては、例えば、ビュルベンジルァミン、アミ ノエチルメタタリレート、などが挙げられる。 [0032] Examples of the butyl monomer having an amino group include benzylbenzylamine, aminoethyl methacrylate, and the like.
[0033] 前記イソシァネート基を有するモノマーとしては、例えば、特開 2005— 258431号 公報の〔0176〕〜〔0180〕に記載されて 、る化合物が挙げられる。  [0033] Examples of the monomer having an isocyanate group include compounds described in [0176] to [0180] of JP-A-2005-258431.
[0034] 前記エポキシ基を有するビュルモノマーとしては、例えば、グリシジル (メタ)アタリレ ート、下記構造式 (45)で表される化合物などが挙げられる。  [0034] Examples of the butyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (45).
[0035] [化 46] [0035] [Chemical 46]
構造式 (45)Structural formula (45)
Figure imgf000022_0001
Figure imgf000022_0001
但し、前記構造式 (45)中、 Rは H及び Meのいずれかを表す。  However, in said structural formula (45), R represents either H or Me.
[0036] 前記酸ハライド基を有するビニルモノマーとしては、例えば、（メタ)アクリル酸クロリド 、などが挙げられる。 [0036] Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
前記活性ハライド基を有するビニルモノマーとしては、例えば、クロロメチルスチレン 、などが挙げられる。  Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
これらの市販品としては、例えば、「カネカレジン AXE ;鐘淵化学工業 (株)製」、「サ イクロマー（CYCLOMER) A— 200 ;ダイセル化学工業 (株）製」、「サイクロマー（ CYCLOMER) M— 200 ;ダイセル化学工業 (株）製」、「SPCP1X、 SPCP2X、 S PCP3X;昭和高分子 (株)製」などを用いることができる。 These commercially available products include, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Co., Ltd.”, “CYCLOMER A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER” M— 200; Daicel Chemical Industries, Ltd. ”,“ SPCP1X, SPCP2X, S PCP3X; manufactured by Showa Polymer Co., Ltd. "can be used.
また、前記各モノマーは、 1種単独で使用してもよぐ 2種以上を併用してもよい。  Each of the monomers may be used alone or in combination of two or more.
[0037] 前記（3)の必要に応じて用いられるその他の共重合可能なモノマーとしては、特に 制限はなぐ 目的に応じて適宜選択することができる力 例えば、特開 2005— 2584 31号公報の〔0165〕〜〔0174〕に記載されている化合物などが挙げられる。  [0037] The other copolymerizable monomer used as needed in (3) is not particularly limited, and can be appropriately selected according to the purpose. For example, in JP-A-2005-258431 Examples include the compounds described in [0165] to [0174].
[0038] 前記官能基としてウレタン基又はウレァ基を有するビュルモノマーの合成方法とし ては、例えば、イソシアナ一ト基と水酸基又はアミノ基の付加反応が挙げられ、具体 的には、イソシアナ一ト基を有するモノマーと、水酸基を 1個含有する化合物又は 1級 若しくは 2級アミノ基を 1個有する化合物との付加反応、水酸基を有するモノマー又 は 1級若しくは 2級アミノ基を有するモノマーと、モノイソシァネートとの付加反応が挙 げられる。  [0038] Examples of a method for synthesizing a bulu monomer having a urethane group or a urea group as the functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, and specifically, an isocyanate group. An addition reaction of a monomer having a hydroxyl group with a compound having one hydroxyl group or a compound having one primary or secondary amino group, a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, Addition reaction with cyanate can be mentioned.
[0039] 前記イソシアナ一ト基を有するモノマーとしては、例えば、特開 2005— 258431号 公報の〔0176〕〜〔0180〕に記載されて 、る化合物が挙げられる。  [0039] Examples of the monomer having an isocyanate group include the compounds described in [0176] to [0180] of JP-A-2005-258431.
前記モノイソシァネートとしては、例えば、特開 2005— 258431号公報の〔0181〕 に記載されて 、る化合物等が挙げられる。  Examples of the monoisocyanate include the compounds described in [0181] of JP-A-2005-258431.
前記水酸基を有するモノマーとしては、例えば、特開 2005— 258431号公報の〔0 Examples of the monomer having a hydroxyl group include those described in JP-A-2005-258431 [0.
182]〜〔0192〕に記載されて 、る化合物が挙げられる。 182] to [0192].
[0040] 前記水酸基を 1個含有する化合物としては、例えば、特開 2005— 258431号公報 の〔0193〕に記載されている化合物等が挙げられる。 [0040] Examples of the compound containing one hydroxyl group include compounds described in [0193] of JP-A-2005-258431.
[0041] 前記 1級又は 2級アミノ基を有するモノマーとしては、例えば、ビニルベンジルァミン などが挙げられる。 [0041] Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.
[0042] 前記 1級又は 2級アミノ基を 1個含有する化合物としては、例えば、特開 2005— 25 8431号公報の〔0195〕に記載されている化合物などが挙げられる。  [0042] Examples of the compound containing one primary or secondary amino group include compounds described in [0195] of JP-A-2005-258431.
[0043] また、これらのモノマーは、 1種単独で使用してもよぐ 2種以上を併用してもよい。  [0043] These monomers may be used alone or in combination of two or more.
これらをビニル (共)重合させることにより酸性基、酸無水物基および必要に応じて 水酸基、アミノ基、イソシァネート基、エポキシ基、酸ハライド基、活性ノヽライド基など を含有する（共)重合体が得られる。前記ビニル (共)重合体は、それぞれ相当するモ ノマーを公知の方法により常法に従って共重合させることで調製することができる。例 えば、特開 2005— 258431号公報の〔0198〕に記載されている方法により調製する ことができる。 These are vinyl (co) polymerized to contain an acid group, an acid anhydride group and, if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. Is obtained. The vinyl (co) polymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. Example For example, it can be prepared by the method described in JP-A-2005-258431 [0198].
このようにして得られた (共)重合体に対して、前記 (4)として、これらの共重合体中 の酸性基、および必要に応じて水酸基、アミノ基、イソシァネート基、グリシジル基、 酸ハライド基の少なくとも 1種に対して反応性を有する官能基と (メタ)アタリロイル基を 有する化合物とを高分子反応させることによって得られる。  With respect to the (co) polymer thus obtained, as the above (4), an acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It can be obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) atallyloyl group.
[0044] 前記該 (4)の (共)重合体中の酸性基、又は高分子反応に利用可能な官能基の少 なくとも 1種に対して反応性を有する官能基と (メタ)アタリロイル基を有する化合物と しては、前述の（2)に示したィ匕合物などが利用できる。 [0044] The functional group having reactivity with at least one of an acidic group in the (co) polymer of the above (4) or a functional group available for a polymer reaction, and a (meth) atallyloyl group As the compound having, the compound shown in the above (2) can be used.
これらの高分子反応を行なう場合の官能基の組合せの例としては、例えば、酸性基 (カルボキシル基など）を有する共重合体とエポキシ基を有するビュルモノマーの組 合せ、アミノ基を有する共重合体とエポキシ基を有するビニルモノマーの組合せ、アミ ノ基を有する共重合体とイソシァネート基を有するビニルモノマーの組合せ、水酸基 を有する共重合体とイソシァネート基を有するビニルモノマーの組合せ、水酸基を有 する共重合体と酸ノ、ライド基を有するビニルモノマーの組合せ、アミノ基を有する共 重合体と活性ハライド基を有するビニルモノマーの組合わせ、酸無水物基を有する 共重合体と水酸基を有するビニルモノマーの組合せ、イソシァネート基を有する共重 合体とアミノ基を有するビニルモノマーの組合せ、イソシァネート基を有する共重合体 と水酸基を有するビニルモノマーの組合せ、活性ハライド基を有する共重合体とアミ ノ基を有するビュルモノマーの組合わせ、などが挙げられる。またこれらの組合せは 2 種以上を併用しても構わない。  Examples of combinations of functional groups for performing these polymer reactions include, for example, a copolymer having an acidic group (such as a carboxyl group) and a butyl monomer having an epoxy group, and a copolymer having an amino group. And a vinyl monomer having an epoxy group, a copolymer having an amino group and a vinyl monomer having an isocyanate group, a combination of a copolymer having a hydroxyl group and a vinyl monomer having an isocyanate group, and a copolymer having a hydroxyl group Combination of polymer and acid group, vinyl monomer having a ride group, combination of copolymer having amino group and vinyl monomer having active halide group, combination of copolymer having acid anhydride group and vinyl monomer having hydroxyl group A combination of a copolymer having an isocyanate group and a vinyl monomer having an amino group, Combinations of vinyl monomer having a copolymer and a hydroxyl group having over preparative group, a combination of Bulle monomer having a copolymer and the amino group having an active halide groups, and the like. Two or more of these combinations may be used in combination.
[0045] <マレアミド酸系共重合体 > <Maleamic acid copolymer>
前記マレアミド酸系共重合体は、無水マレイン酸共重合体の無水物基に対して 1級 ァミン化合物を 1種以上反応させて得られる共重合体である。該共重合体は下記構 造式 (VII)で表される、マレイン酸ノ、ーフアミド構造を有するマレアミド酸ユニット Bと、 前記マレイン酸ノヽーフアミド構造を有しないユニット Aと、を少なくとも含むマレアミド 酸系共重合体であるのが好まし 、。  The maleamic acid copolymer is a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer. The copolymer is represented by the following structural formula (VII): a maleamic acid system containing at least maleic acid unit B having maleic acid-formamide structure and unit A having no maleic acid-sulfamide structure. Preferably it is a copolymer.
前記ユニット Aは 1種であってもよいし、 2種以上であってもよい。例えば、前記ュニ ット Bが 1種であるとすると、前記ユニット Aが 1種である場合には、前記マレアミド酸系 共重合体が 2元共重合体を意味することになり、前記ユニット Aが 2種である場合には 、前記マレアミド酸系共重合体が 3元共重合体を意味することになる。 The unit A may be one type or two or more types. For example, the unit Assuming that there is one type of unit A, when the unit A is one type, the maleamic acid copolymer means a binary copolymer, and the unit A is two types. In some cases, the maleamic acid copolymer means a terpolymer.
前記ユニット Aとしては、置換基を有していてもよいァリール基と、後述するビュル単 量体であって、該ビュル単量体のホモポリマーのガラス転移温度 (Tg)が 80°C未満 であるビニル単量体 (c)との組合せが好適に挙げられる。  The unit A includes an aryl group which may have a substituent and a butyl monomer which will be described later, and the glass transition temperature (Tg) of the butyl monomer homopolymer is less than 80 ° C. A combination with a certain vinyl monomer (c) is preferred.
[0046] [化 47] [0046] [Chemical 47]
構造式 (V I I ) Structural formula (V I I)
Figure imgf000025_0001
Figure imgf000025_0001
A B  A B
ただし、前記構造式 (VII)中、 R3及び R4は水素原子及び低級アルキル基のいずれ かを表す。 X及び yは繰り返し単位のモル分率を表し、例えば、前記ユニット Aが 1種 の場合、 Xは 85〜50モル0 /0であり、 yは 15〜50モル0 /0である。 However, in the structural formula (VII), R 3 and R 4 represent either a hydrogen atom or a lower alkyl group. X and y represent mole fractions of the repeating units, for example, when the unit A is one, X is 85-50 mol 0/0, y is 15 to 50 mole 0/0.
[0047] 前記構造式 (VI)中、 R1としては、例えば、（― COOR1C>)、（― CONRUR12)、置換 基を有していてもよいァリール基、（― OCOR13)、 ( - OR14) , (— COR15)などの置 換基が挙げられる。ここで、前記 R1U〜R1&は、水素原子（一 H)、置換基を有していて もよいアルキル基、ァリール基及びァラルキル基のいずれかを表す。該アルキル基、 ァリール基及びァラルキル基は、環状構造又は分岐構造を有して 、てもよ 、。 In the structural formula (VI), as R 1 , for example, (—COOR 1C> ), (—CONRUR 12 ), an aryl group optionally having a substituent, (—OCOR 13 ), ( -Substituents such as OR 14 ) and (— COR 15 ). Here, R 1U to R 1 & represents one of a hydrogen atom (1H), an alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
前記 R 〜R としては、例えば、メチル、ェチル、 n—プロピル、 i—プロピル、 n—ブ チル、 iーブチノレ、 sec—ブチル、 tーブチノレ、ペンチノレ、ァリノレ、 n—へキシル、シクロ へキシル、 2—ェチルへキシル、ドデシル、メトキシェチル、フエニル、メチルフエニル 、メトキシフエ-ル、ベンジル、フエネチル、ナフチル、クロ口フエ-ルなどが挙げられ る。 Examples of R to R include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butinole, sec-butyl, t-butinole, pentinole, arinole, n-hexyl, cyclohexyl, 2 -Ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, black mouth The
前記 R1の具体例としては、例えば、フエ-ル、 a—メチルフエ-ル、 2—メチルフエ -ル、 3 メチルフエ-ル、 4 メチルフエ-ル、 2, 4 ジメチルフエ-ル等のベンゼ ン誘導体； n—プロピルォキシカルボ-ル、 n ブチルォキシカルボ-ル、ペンチルォ キシカルボニル、へキシルォキシカルボニル、 n ブチルォキシカルボニル、 n—へ キシルォキシカルボニル、 2—ェチルへキシルォキシカルボニル、メチルォキシカル ボニルなどが挙げられる。 Specific examples of R 1 include benzene derivatives such as, for example, a file, a-methyl file, 2-methyl file, 3 methyl file, 4 methyl file, 2,4 dimethyl file, etc .; n —Propyloxycarbonyl, n-Butyloxycarbonyl, Pentyloxycarbonyl, Hexyloxycarbonyl, n-Butyloxycarbonyl, n-Hexyloxycarbonyl, 2-Ethylhexyloxycarbonyl, Methyloxy Bonyl and the like can be mentioned.
[0048] 前記 R2としては、置換基を有して!/、てもよ 、アルキル基、ァリール基、ァラルキル基 などが挙げられる。これらは、環状構造又は分岐構造を有していてもよい。前記 R2の 具体例としては、例えば、ベンジル、フエネチル、 3—フエ-ルー 1—プロピル、 4 フ ェ-ノレ一 1—ブチノレ、 5 フエ-ノレ一 1—ペンチノレ、 6 フエ-ノレ一 1—へキシノレ、 a メチルベンジル、 2 メチルベンジル、 3 メチルベンジル、 4 メチルベンジル、 2 一（P—トリル）ェチル、 j8—メチルフエネチル、 1ーメチルー 3—フエ-ルプロピル、 2 —クロ口べンジノレ、 3 クロ口べンジノレ、 4 クロ口べンジノレ、 2 フロロべンジノレ、 3— フロロべンジノレ、 4 フロロべンジノレ、 4 ブロモフエネチノレ、 2— (2 クロ口フエ二ノレ) ェチル、 2- (3 クロ口フエ-ル）ェチル、 2—（4 クロ口フエ-ル）ェチル、 2—（2— フロロフエ-ノレ)ェチノレ、 2— (3—フロロフエ-ノレ)ェチノレ、 2— (4—フロロフエ-ノレ)ェ チル、 4 フロロ一 α , a—ジメチルフエネチル、 2—メトキシベンジル、 3—メトキシべ ンジル、 4—メトキシベンジル、 2 エトキシベンジル、 2—メトキシフエネチル、 3—メト キシフエネチル、 4ーメトキシフエネチル、メチル、ェチル、プロピル、 i—プロピル、ブ チル、 tーブチノレ、 sec ブチル、ペンチノレ、へキシル、シクロへキシル、ヘプチル、ォ クチル、ラウリル、フエ-ル、 1 ナフチル、メトキシメチル、 2—メトキシェチル、 2—ェ トキシェチル、 3—メトキシプロピル、 2 ブトキシェチル、 2 シクロへキシルォキシェ チル、 3—エトキシプロピル、 3—プロポキシプロピル、 3—イソプロポキシプロピルアミ ンなどが挙げられる。 [0048] Examples of R 2 include a substituent group! /, But may include an alkyl group, an aryl group, an aralkyl group, and the like. These may have a cyclic structure or a branched structure. Specific examples of R 2 include, for example, benzyl, phenethyl, 3-phenol 1-propyl, 4-phenol 1-butinole, 5 phenol-1-pentinole, 6-phenol 1- Hexinole, a Methylbenzyl, 2 Methylbenzyl, 3 Methylbenzyl, 4 Methylbenzyl, 2 Mono (P-tolyl) ethyl, j8-Methylphenethyl, 1-Methyl-3-phenylpropyl, 2 —Black Benzynole, 3 Black Mouth Benzinore, 4-black mouth Benzore, 2 Fluoro Benzinore, 3— Fluoro Benzinore, 4 Fluoro Benzinole, 4 Bromophenetinore, 2— (2 Black mouth Fueninore) Ethyl, 2- (3 Black mouth Hue -Ru) ethyl, 2— (4 black mouth fuer) ethyl, 2— (2—floro-nore) echinore, 2— (3-floro-nore) echinore, 2— (4-floro-nore) til , 4 Fluoro 1 α, a-Dime Ruphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl, ethyl, propyl, i-propyl , Butyl, tert-butynole, sec butyl, pentinole, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenol, 1 naphthyl, methoxymethyl, 2-methoxyethyl, 2-methoxyl, 3-methoxypropyl, Examples include 2-butoxychetyl, 2-cyclohexyloxychetyl, 3-ethoxypropyl, 3-propoxypropyl, and 3-isopropoxypropylamine.
[0049] 前記バインダーは、特に、（a)無水マレイン酸と、（b)芳香族ビニル単量体と、（c)ビ -ル単量体であって、該ビュル単量体のホモポリマーのガラス転移温度 (Tg)が 80 °C未満であるビニル単量体と、力 なる共重合体の無水物基に対して 1級アミンィ匕合 物を反応させて得られる共重合体であるのが好ましい。該 (a)成分と、該 (b)成分と、 からなる共重合体では、後述する感光層の高い表面硬度を得ることはできるものの、 ラミネート性の確保が困難になることがある。また、該 (a)成分と、該 (c)成分と、から なる共重合体では、ラミネート性は確保することができるものの、前記表面硬度の確 保が困難になることがある。 [0049] The binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, which is a homopolymer of the bull monomer. Vinyl amines with a glass transition temperature (Tg) of less than 80 ° C and primary amines for the anhydride groups of powerful copolymers It is preferably a copolymer obtained by reacting a product. A copolymer comprising the component (a) and the component (b) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties. In addition, in the copolymer comprising the component (a) and the component (c), although the laminating property can be ensured, it may be difficult to ensure the surface hardness.
[0050] - - (b)芳香族ビニル単量体 [0050]--(b) Aromatic vinyl monomer
前記芳香族ビニル単量体としては、特に制限はなぐ 目的に応じて適宜選択するこ とができるが、本発明の感光性組成物を用いて形成される感光層の表面硬度を高く することができる点で、ホモポリマーのガラス転移温度 (Tg)が 80°C以上である化合 物が好ましぐ 100°C以上である化合物がより好ましい。  The aromatic vinyl monomer is not particularly limited and can be appropriately selected according to the purpose. However, the surface hardness of the photosensitive layer formed using the photosensitive composition of the present invention can be increased. In view of this, compounds having a glass transition temperature (Tg) of the homopolymer of 80 ° C or higher are preferred, and compounds having a temperature of 100 ° C or higher are more preferable.
前記芳香族ビュル単量体の具体例としては、例えば、スチレン (ホモポリマーの Tg = 100°C)、 α—メチルスチレン（ホモポリマーの Tg= 168°C)、 2—メチルスチレン（ ホモポリマーの Tg= 136°C)、 3—メチルスチレン（ホモポリマーの Tg = 97°C)、 4— メチルスチレン（ホモポリマーの Tg = 93°C)、 2, 4 ジメチルスチレン（ホモポリマー の Tg = 112°C)などのスチレン誘導体が好適に挙げられる。これらは 1種単独で使用 してもよいし、 2種以上を併用してもよい。  Specific examples of the aromatic bur monomer include, for example, styrene (homopolymer Tg = 100 ° C), α-methylstyrene (homopolymer Tg = 168 ° C), 2-methylstyrene (homopolymer Tg = 136 ° C), 3-methylstyrene (homopolymer Tg = 97 ° C), 4-methylstyrene (homopolymer Tg = 93 ° C), 2,4 dimethylstyrene (homopolymer Tg = 112 °) Preferable examples include styrene derivatives such as C). These may be used alone or in combination of two or more.
[0051] - - (c)ビニル単量体 [0051]--(c) Vinyl monomer
前記ビニル単量体は、該ビニル単量体のホモポリマーのガラス転移温度 (Tg)が 80 °C未満であることが必要であり、 40°C以下が好ましぐ 0°C以下がより好ましい。  The vinyl monomer needs to have a glass transition temperature (Tg) of a homopolymer of the vinyl monomer of less than 80 ° C, preferably 40 ° C or less, more preferably 0 ° C or less. .
前記ビュル単量体としては、例えば、 n—プロピルアタリレート（ホモポリマーの Tg = Examples of the bull monomer include n-propyl acrylate (Tg = homopolymer)
— 37°C)、 n—ブチルアタリレート（ホモポリマーの Tg=— 54°C)、ペンチルァクリレー ト、あるいはへキシルアタリレート（ホモポリマーの Tg=— 57°C)、 n—ブチノレメタクリレ ート（ホモポリマーの Tg=— 24°C)、 n—へキシノレメタタリレート（ホモポリマーの Tg=— 37 ° C), n-butyl acrylate (homopolymer Tg = —54 ° C), pentyl acrylate, or hexyl acrylate (Tg = —57 ° C. of homopolymer), n-butynole Methacrylate (Tg of homopolymer = 24 ° C), n-hexenoremethacrylate (Tg = of homopolymer)
— 5°C)などが挙げられる。これらは 1種単独で使用してもよいし、 2種以上を併用して ちょい。 — 5 ° C). These may be used alone or in combination of two or more.
[0052] 1級ァミン化合物  [0052] Primary amine compound
前記 1級アミンィ匕合物としては、例えば、ベンジルァミン、フエネチルァミン、 3 フエ -ル— 1—プロピルァミン、 4—フエ-ルー 1—ブチルァミン、 5—フエ-ルー 1—ペン チルァミン、 6 フエ二ルー 1一へキシルァミン、 α メチルベンジルァミン、 2—メチ ルベンジルァミン、 3—メチルベンジルァミン、 4—メチルベンジルァミン、 2 (ρ トリ ル）ェチルァミン、 β—メチルフエネチルァミン、 1—メチル—3 フエ-ルプロピルァ ミン、 2 クロ口ベンジルァミン、 3 クロ口ベンジルァミン、 4 クロ口ベンジルァミン、 2 —フロロベンジルァミン、 3—フロロベンジルァミン、 4—フロロベンジルァミン、 4—ブ ロモフエネチルァミン、 2— (2 クロ口フエ-ル）ェチルァミン、 2— (3 クロ口フエ-ル )ェチルァミン、 2— (4 クロ口フエ-ル）ェチルァミン、 2— (2 フロロフエ-ル）ェチ ルァミン、 2 - (3—フロロフエ-ル）ェチルァミン、 2— (4—フロロフエ-ル）ェチルアミ ン、 4 フロロ一 α , a—ジメチルフエネチルァミン、 2—メトキシベンジルァミン、 3— メトキシベンジルァミン、 4ーメトキシベンジルァミン、 2 エトキシベンジルァミン、 2— メトキシフエネチルァミン、 3—メトキシフエネチルァミン、 4ーメトキシフエネチルァミン 、メチルァミン、ェチルァミン、プロピルァミン、 1—プロピルァミン、ブチルァミン、 t— ブチルァミン、 sec ブチルァミン、ペンチルァミン、へキシルァミン、シクロへキシル ァミン、ヘプチルァミン、ォクチルァミン、ラウリルァミン、ァ-リン、ォクチルァ-リン、 ァニシジン、 4 クロルァニリン、 1 ナフチルァミン、メトキシメチルァミン、 2—メトキ シェチルァミン、 2 エトキシェチルァミン、 3—メトキシプロピルァミン、 2 ブトキシェ チルァミン、 2 シクロへキシルォキシェチルァミン、 3 エトキシプロピルァミン、 3— プロポキシプロピルァミン、 3—イソプロポキシプロピルァミンなどが挙げられる。これら の中でも、ベンジルァミン、フエネチルァミンが特に好ましい。 Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenol-1-propylamine, 4-phenol-l-butylamine, 5-phenol-l-pen. Tyramine, 6 phenyl 1-hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2 (ρ-tolyl) ethylamine, β-methylphenethylamine Min, 1-Methyl-3 Phenylpropylamine, 2 Chlorobenzylamine, 3 Chlorobenzylamine, 4 Chlorobenzylamine, 2-Fluorobenzylamine, 3-Fluorobenzylamine, 4-Fluorobenzylamine, 4- Bromoethylylamine, 2— (2 black mouth) ethylamine, 2— (3 black mouth) ethylamine, 2— (4 black mouth) etherylamine, 2— (2 fluorophenol) ) Ethylamine, 2- (3-Fluorophenyl) Ethylamine, 2- (4-Fluorophenyl) Ethylamine, 4-Fluoro-α, a-Dimethylphenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine , Methylamine, ethylamine, propylamine, 1-propylamine, butylamine, t-butylamine, sec butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, arrin, octylamine, 1 aniline, 1 chloraniline Naphthylamine, Methoxymethylamine, 2-Methoxy Shetylamine, 2 Ethoxyethylamine, 3-Methoxypropylamine, 2 Butoxyche Tyramine, 2 Cyclohexoxyl Chetilamine, 3 Ethoxypropyla Min, 3-propoxypropylamine, 3-isopropoxypropylamine and the like. Of these, benzylamine and phenethylamine are particularly preferred.
前記 1級アミンィ匕合物は、 1種単独で使用してもよいし、 2種以上を併用してもよい。  The primary amine compounds may be used alone or in combination of two or more.
[0053] 前記 1級アミンィ匕合物の反応量としては、前記無水物基に対して 0. 1〜1. 2当量 であることが必要であり、 0. 1〜1. 0当量が好ましい。該反応量が 1. 2当量を超える と、前記 1級ァミン化合物を 1種以上反応させた場合に、溶解性が著しく悪ィ匕すること がある。 [0053] The reaction amount of the primary amine compound needs to be 0.1 to 1.2 equivalents, preferably 0.1 to 1.0 equivalents, relative to the anhydride group. When the reaction amount exceeds 1.2 equivalents, the solubility may be remarkably deteriorated when one or more primary amine compounds are reacted.
[0054] 前記（a)無水マレイン酸の前記バインダーにおける含有量は、 15〜50mol%が好 ましぐ 20〜45mol%がより好ましぐ 20〜40mol%が特に好ましい。該含有量が 15 mol%未満であると、アルカリ現像性の付与ができず、 50mol%を超えると、耐アル カリ性が劣化し、また、前記共重合体の合成が困難になり、正常な永久パターンの形 成を行うことができないことがある。また、この場合における、前記 (b)芳香族ビュル単 量体、及び (c)ホモポリマーのガラス転移温度 (Tg)が 80°C未満であるビュル単量体 の前記バインダーにおける含有量は、それぞれ 20〜60mol%、 15〜40mol%が好 ましい。該含有量が該数値範囲を満たす場合には、表面硬度及びラミネート性の両 立を図ることができる。 [0054] The content of the (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol%. If the content is less than 15 mol%, alkali developability cannot be imparted, and if it exceeds 50 mol%, alkali resistance deteriorates, and the copolymer becomes difficult to synthesize. Permanent pattern shape It may not be possible to complete. In this case, the content of the (b) aromatic bule monomer and (c) the bulle monomer having a glass transition temperature (Tg) of the homopolymer of less than 80 ° C in the binder is respectively 20-60 mol% and 15-40 mol% are preferred. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.
[0055] 前記マレアミド酸系共重合体の分子量は、 3, 000〜500, 000力 子ましく、 8, 000 〜150, 000力 Sより好ましい。該分子量が 3, 000未満であると、後述する感光層の硬 化後において、膜質が脆くなり、表面硬度が劣化することがあり、 500, 000を超える と、前記感光性組成物の加熱積層時の流動性が低くなり、適切なラミネート性の確保 が困難になることがあり、また、現像性が悪ィヒすることがある。  [0055] The molecular weight of the maleamic acid copolymer is preferably 3,000 to 500,000, more preferably 8,000 to 150,000. When the molecular weight is less than 3,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later. When the molecular weight exceeds 500,000, the photosensitive composition is heated and laminated. The fluidity at the time may be low, and it may be difficult to ensure proper laminating properties, and the developability may deteriorate.
[0056] <その他のバインダー >  [0056] <Other binders>
前記ノインダーとしては、その他のバインダーを併用してもよい。前記その他バイン ダ一としては、特開平 11— 288087号公報記載のポリアミド (イミド)榭脂、特開平 11 — 282155号公報記載のポリイミド前駆体などを用いることができる。これらは 1種単 独で使用してもょ 、し、 2種以上を混合して使用してもょ 、。  The binder may be used in combination with other binders. As the other binders, polyamide (imide) resins described in JP-A-11-288087, polyimide precursors described in JP-A-11-282155, and the like can be used. These can be used alone or in combination of two or more.
[0057] 前記ポリアミド (イミド）、あるいは、ポリイミド前駆体などのノインダ一の分子量として ίま、 3, 000〜500, 000力好まし <、 5, 000〜100, 000力 ^より好まし!/ヽ。該分子量 が 3, 000未満であると、感光層表面のタック性が強くなることがあり、後述する感光 層の硬化後において、膜質が脆くなる、あるいは、表面硬度が劣化することがあり、 5 00, 000を超えると、現像性が劣化することがある。  [0057] The molecular weight of the above-mentioned polyamide (imide) or polyimide precursor is preferably 3,000 to 500,000 force <, 5,000 to 100,000 force ^!ヽ. If the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may increase, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 00,000, developability may deteriorate.
[0058] 前記バインダーの前記感光性組成物固形分中の固形分含有量は、 5〜70質量％ が好ましぐ 10〜50質量％がより好ましい。該固形分含有量が、 5質量％未満である と、後述する感光層の膜強度が弱くなりやすぐ該感光層の表面のタック性が悪化す ることがあり、 70質量％を超えると、露光感度が低下することがある。  [0058] The solid content in the photosensitive composition solid content of the binder is preferably 5 to 70 mass%, more preferably 10 to 50 mass%. If the solid content is less than 5% by mass, the film strength of the photosensitive layer described later may be weakened or the tackiness of the surface of the photosensitive layer may be deteriorated immediately. If it exceeds 70% by mass, Exposure sensitivity may decrease.
[0059] 〔(Β)重合性化合物〕  [0059] [(Β) Polymerizable compound]
前記重合性化合物としては、特に制限はなぐ 目的に応じて適宜選択することがで きるが、分子中に少なくとも 1個の付加重合可能な基を有し、沸点が常圧で 100°C以 上である化合物が好ましぐ例えば、（メタ)アクリル基を有するモノマーから選択され る少なくとも 1種が好適に挙げられる。 The polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, but has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, the compound is preferably selected from monomers having a (meth) acrylic group Preferably, at least one of the above is mentioned.
[0060] 前記 (メタ）アクリル基を有するモノマーとしては、特に制限はなぐ 目的に応じて適 宜選択することができ、例えば、ポリエチレングリコールモノ (メタ)アタリレート、ポリプ ロピレングリコールモノ（メタ）アタリレート、フエノキシェチル (メタ）アタリレート等の単 官能アタリレートや単官能メタタリレート；ポリエチレングリコールジ (メタ)アタリレート、 ポリプロピレングリコールジ (メタ）アタリレート、トリメチロールェタントリアタリレート、トリ メチロールプロパントリアタリレート、トリメチロールプロパンジアタリレート、ネオペンチ ルグリコールジ (メタ）アタリレート、ペンタエリスリトールテトラ (メタ）アタリレート、ペンタ エリスリトールトリ（メタ）アタリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、 ジペンタエリスリトールペンタ（メタ）アタリレート、へキサンジオールジ (メタ）アタリレー ト、トリメチロールプロパントリ（アタリロイルォキシプロピル）エーテル、トリ（アタリロイル ォキシェチル)イソシァヌレート、トリ（アタリロイルォキシェチル）シァヌレート、グリセリ ントリ（メタ）アタリレート、トリメチロールプロパンやグリセリン、ビスフエノール等の多官 能アルコールに、エチレンオキサイドやプロピレンオキサイドを付加反応した後で (メ タ）アタリレートイ匕したもの、特公昭 48— 41708号、特公昭 50— 6034号、特開昭 51 — 37193号等の各公報に記載されているウレタンアタリレート類;特開昭 48— 6418 3号、特公昭 49 43191号、特公昭 52— 30490号等の各公報に記載されているポ リエステルアタリレート類；エポキシ榭脂と (メタ)アクリル酸の反応生成物であるェポキ シアタリレート類等の多官能アタリレートやメタタリレートなどが挙げられる。これらの中 でも、トリメチロールプロパントリ (メタ)アタリレート、ペンタエリスリトールテトラ (メタ)ァ タリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、ジペンタエリスリトールぺ ンタ (メタ)アタリレートが特に好ま 、。 [0060] The monomer having the (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose. For example, polyethylene glycol mono (meth) acrylate, 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 , Trimethylolpropane ditalylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylol propane tri (atalylooxypropyl) ether, tri (atalyloyloxychetyl) isocyanurate, tri (atalyloyl) Oxetyl) cyanurate, glycerin tri (meth) acrylate, trimethylol propane, glycerin, bisphenol and other multifunctional alcohols after addition reaction of ethylene oxide and propylene oxide (meth) atelolito Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, etc .; JP-A-48-6183, JP-B-49 No. 43191, JP-B 52-30490, etc. Atari rate such; as epoxy 榭脂 and (meth) polyfunctional Atari rate and Metatarireto of Epoki Shiatarireto and the like which is a reaction product of acrylic acid. Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol pent (meth) acrylate are particularly preferred.
[0061] 前記重合性化合物の前記感光性組成物固形分中の固形分含有量は、 5〜50質 量％が好ましぐ 10〜40質量％がより好ましい。該固形分含有量が 5質量％未満で あると、現像性の悪化、露光感度の低下などの問題を生ずることがあり、 50質量％を 超えると、感光層の粘着性が強くなりすぎることがあり、好ましくない。  [0061] The solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
[0062] 〔(C)光重合開始剤〕  [0062] [(C) Photopolymerization initiator]
前記光重合開始剤としては、前記重合性化合物の重合を開始する能力を有する限 り、特に制限はなぐ公知の光重合開始剤の中から適宜選択することができるが、例 えば、紫外線領域力 可視の光線に対して感光性を有するものが好ましぐ光励起さ れた増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよぐ モノマーの種類に応じてカチオン重合を開始させるような開始剤であってもよい。 また、前記光重合開始剤は、約 300〜800nm (より好ましくは 330〜500nm)の範 囲内に少なくとも約 50の分子吸光係数を有する成分を少なくとも 1種含有して ヽるこ とが好ましい。 The photopolymerization initiator is limited as long as it has the ability to initiate polymerization of the polymerizable compound. For example, those having photosensitivity to visible light in the ultraviolet region are preferably photoexcited sensitization. It may be an activator that generates some action with the agent and generates active radicals. An initiator that initiates cationic polymerization according to the type of monomer may be used. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).
[0063] 前記光重合開始剤としては、例えば、ハロゲンィ匕炭化水素誘導体 (例えば、トリアジ ン骨格を有するもの、ォキサジァゾール骨格を有するもの、など）、ホスフィンォキサイ ド、へキサァリールビイミダゾール、ォキシム誘導体、有機過酸化物、チォ化合物、ケ トンィ匕合物、芳香族ォ -ゥム塩、メタセロン類、などが挙げられる。  [0063] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), phosphine oxides, hexarylbiimidazoles, oximes. Derivatives, organic peroxides, thio compounds, ketonic compounds, aromatic onium salts, metathelons, and the like.
[0064] 前記トリァジン骨格を有するハロゲンィ匕炭化水素化合物としては、例えば、若林ら 著、 Bull. Chem. Soc. Japan, 42、 2924 (1969)記載のィ匕合物、英国特許 1388 492号明細書記載の化合物、特開昭 53— 133428号公報記載の化合物、独国特 許 3337024号明細書記載の化合物、 F. C. Schaefer等による J. Org. Chem. ; 2 9、 1527 (1964)記載の化合物、特開昭 62— 58241号公報記載の化合物、特開平 5— 281728号公報記載の化合物、特開平 5— 34920号公報記載ィ匕合物、米国特 許第 4212976号明細書に記載されている化合物、などが挙げられる。  [0064] Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), British Patent 1388 492 Compounds described in JP-A-53-133428, compounds described in German Patent No. 3337024, J. Org. Chem. By FC Schaefer et al .; 29, 1527 (1964), Compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, compounds described in US Pat. No. 4212976 , Etc.
[0065] 前記若林ら著、 Bull. Chem. Soc. Japan, 42、 2924 (1969)記載の化合物とし ては、例えば、特開 2005— 258431号公報の〔0291〕に記載されている化合物など が挙げられる。  [0065] Examples of the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969) include, for example, the compounds described in [0291] of JP-A-2005-258431. Can be mentioned.
[0066] 前記英国特許 1388492号明細書記載の化合物としては、例えば、特開 2005— 2 58431号公報の〔0292〕に記載されている化合物などが挙げられる。  [0066] Examples of the compound described in British Patent 1388492 include the compounds described in [0292] of JP-A-2005-258431.
前記特開昭 53— 133428号公報記載の化合物としては、例えば、特開 2005— 25 8431号公報の〔0293〕に記載されている化合物などが挙げられる。  Examples of the compound described in JP-A-53-133428 include compounds described in [0293] of JP-A-2005-258431.
[0067] 前記独国特許 3337024号明細書記載の化合物としては、例えば、特開 2005— 2 58431号公報の〔0294〕に記載されている化合物などが挙げられる。  [0067] Examples of the compound described in German Patent 3337024 include compounds described in [0294] of JP-A-2005-258431.
[0068] 前記 F. C. Schaefer等による J. Org. Chem. ; 29、 1527 (1964)記載のィ匕合物 としては、例えば、特開 2005— 258431号公報の〔0295〕に記載されている化合物 などが挙げられる。 [0068] The compound according to J. Org. Chem .; 29, 1527 (1964) by FC Schaefer et al. Examples thereof include compounds described in [0295] of JP-A-2005-258431.
[0069] 前記特開昭 62— 58241号公報記載の化合物としては、例えば、特開 2005— 258 431号公報の〔0296〕に記載されている化合物などが挙げられる。  [0069] Examples of the compound described in JP-A-62-58241 include compounds described in [0296] of JP-A-2005-258431.
[0070] 前記特開平 5— 281728号公報記載の化合物としては、例えば、特開 2005— 258 431号公報の〔0297〕に記載されている化合物などが挙げられる。  [0070] Examples of the compound described in JP-A-5-281728 include compounds described in [0297] of JP-A-2005-258431.
[0071] 前記特開平 5— 34920号公報記載化合物としては、例えば、特開 2005— 25843 1号公報の〔0298〕に記載されている化合物などが挙げられる。  [0071] Examples of the compounds described in JP-A-5-34920 include compounds described in [0298] of JP-A-2005-258431.
[0072] 前記米国特許第 4212976号明細書に記載されている化合物としては、例えば、特 開 2005— 258431号公報の〔0299〕に記載されている化合物などが挙げられる。  [0072] Examples of the compound described in US Pat. No. 4,212,976 include the compound described in [0299] of JP 2005-258431 A.
[0073] 前記ホスフィンオキサイドとしては、例えば、特開 2005— 258431号公報の [0307 〕に記載されている化合物、などが挙げられる。  [0073] Examples of the phosphine oxide include compounds described in [0307] of JP-A-2005-258431.
[0074] 前記へキサァリールビイミダゾールとしては、例えば、 2, 2' ビス（2 クロ口フエ- ル） 4, 4，， 5, 5，一テトラフエ-ルビイミダゾール、 2, 2，一ビス（o フロロフエ-ル )—4, 4，， 5, 5，—テトラフエ-ルビイミダゾール、 2, 2，—ビス（2 ブロモフエ-ル） —4, 4，， 5, 5，一テトラフエ-ルビイミダゾール、 2, 2，一ビス（2, 4 ジクロロフエ- ル） 4, 4，， 5, 5，一テトラフエ-ルビイミダゾール、 2, 2，一ビス（2 クロ口フエ-ル） —4, 4，， 5, 5，一テトラ（3—メトキシフエ-ル）ビイミダゾール、 2, 2，一ビス（2 クロ 口フエ-ル）一 4, 4，， 5, 5，一テトラ（4—メトキシフエ-ル）ビイミダゾール、 2, 2，一ビ ス（4—メトキシフエ-ル）一 4, 4，， 5, 5，一テトラフエ-ルビイミダゾール、 2, 2，一ビ ス（2, 4 ジクロロフエ-ル）一 4, 4，， 5, 5，一テトラフエ-ルビイミダゾール、 2, 2，一 ビス（2 -トロフエ-ル）一 4, 4，， 5, 5，一テトラフエ-ルビイミダゾール、 2, 2，一ビ ス（2—メチルフエ-ル）一 4, 4，， 5, 5，一テトラフエ-ルビイミダゾール、 2, 2，一ビス (2 トリフルォロメチルフエ-ル）— 4, 4' , 5, 5，—テトラフエ-ルビイミダゾール、 W 000/52529号公報に記載の化合物、などが挙げられる。  [0074] Examples of the hexarylbiimidazole include 2, 2 'bis (2-clonal ring) 4, 4, 5, 5, 5, monotetraphenyl biimidazole, 2, 2, 1 bis ( o Fluorophore) —4, 4 ,, 5, 5, — Tetraphenol biimidazole, 2, 2, — Bis (2 bromophenol) — 4, 4, 4, 5, 5, monotetraphenol biimidazole, 2 , 2, 1 bis (2, 4 dichlorophenol) 4, 4 ,, 5, 5, 1 tetraphenyl biimidazole, 2, 2, 1 bis (2 x 2 mouthpiece) —4, 4, 5, 5, 1-tetra (3-methoxyphenol) biimidazole, 2, 2, 1-bis (2-cyclophenol) 1, 4, 4, 5, 5, 5, 1-tetra (4-methoxyphenyl) biimidazole, 2, 2, 1 bis (4-methoxyphenyl) 1, 4, 4, 5, 5, 1, tetraphenyl biimidazole 2, 2, 1, bis (2, 4 dichlorophenol) 1, 4, 4, , 5, 5, one tetra Erbiimidazole, 2, 2, 1 Bis (2-Trophenyl) 1, 4, 4, 5, 5, 5, 1 Tetraphenol Biimidazole, 2, 2, 1 Bis (2-Methylphenol) 1 4 , 4 ,, 5, 5, 1-tetrafluorobiimidazole, 2, 2, 1-bis (2 trifluoromethylphenol) — 4, 4 ′, 5, 5, —tetraphenylbiimidazole, W 000/52529 And the compounds described in the Japanese Patent Publication.
前記ビイミダゾール類は、例えば、 Bull. Chem. Soc. Japan, 33, 565 (1960)、 及び J. Org. Chem, 36 (16) 2262 (1971)に開示されている方法により容易に合 成することができる。 [0075] 本発明で好適に用いられる前記ォキシム誘導体としては、例えば、 3 べンゾイロ キシイミノブタン 2 オン、 3 ァセトキシィミノブタン 2 オン、 3 プロピオニル ォキシイミノブタン 2 オン、 2 ァセトキシィミノペンタンー3 オン、 2 ァセトキシ ィミノ 1—フエ-ルプロパン一 1―オン、 2 -ベンゾイロキシィミノ 1—フエ-ルプロ パン 1 オン、 3—（4 トルエンスルホ -ルォキシ）イミノブタン 2 オン、及び 2 エトキシカルボ-ルォキシイミノー 1 フエ-ルプロパン 1 オンなどが挙げられ る。 The biimidazoles are easily synthesized by methods disclosed in Bull. Chem. Soc. Japan, 33, 565 (1960), and J. Org. Chem, 36 (16) 2262 (1971), for example. be able to. [0075] Examples of the oxime derivative suitably used in the present invention include, for example, 3 benzoyloxyiminobutane 2 on, 3 acetoximininobutane 2 on, 3 propionyl oxyiminobutane 2 on, 2 acetoximinopentane 3-one, 2-acetoximino 1-phenolpropane 1-one, 2-benzoyloximino 1-phenolpropan 1-one, 3- (4-toluenesulfo-loxy) iminobutane 2 on, and 2 ethoxycarbo- For example, oxyimino 1-phenol propane 1-on.
[0076] 前記有機過酸化物としては、例えば、 3, 3' , 4, 4'ーテトラ (t ブチルパーォキシ カルボ-ル）ベンゾフエノン、などが挙げられる。  [0076] Examples of the organic peroxide include 3,3 ', 4,4'-tetra (t-butylperoxycarbol) benzophenone.
前記チオイ匕合物としては、例えば、 2, 4 ジェチルチオキサントン、 2, 4ージクロ口 チォキサントン、 1 クロロー 4 プロポキシチォキサントン、 2 べンゾイノレメチレン 3—メチルナフトチアゾリン、などが挙げられる。  Examples of the thioi compound include 2,4 jetylthioxanthone, 2,4-dichlorothioxanthone, 1 chloro-4 propoxythioxanthone, 2 benzoinolemethylene 3-methylnaphthothiazoline, and the like.
[0077] 前記ケトンィ匕合物としては、例えば、特開 2005— 258431号公報の〔0305〕に記 載されて!ヽる化合物などが挙げられる。  [0077] Examples of the ketone compound include the compounds described in [0305] of JP-A-2005-258431.
[0078] 前記芳香族ォ -ゥム塩としては、例えば、ジフエ二ルョードニゥムテトラフルォロボレ ート、ジフエ-ノレョード -ゥムへキサフノレオ口ホスホネート、トリフエ-ノレスノレホニゥムテ トラフノレオロボレート、トリフエ-ノレスノレホ-ゥムへキサフノレオ口ホスホネート、テトラフエ -ルホスホ-ゥム一へキサフルォロホスフェート、などが挙げられる。  [0078] Examples of the aromatic salt include diphenyl rhododonium tetrafluoroborate, diphne noredo um hexafnoreo phosphonate, and trifene noles norehonumute. For example, trough noreroborate, triphenol-norethnohexahexolenorophore phosphonate, tetraphenol hexahexafluorophosphate, and the like.
前記メタ口セン類としては、例えば、ビス（ r? 5—2, 4 シクロペンタジェン一 1—ィル )—ビス（2, 6 ジフロロ一 3— (1H ピロール一 1—ィル） フエニル）チタニウム、 η 5—シクロペンタジェ -ル一 6—タメ-ル一アイアン（1 + )—へキサフロロホスフエ ート（1一）、などが挙げられる。 As the meta-port mosses, e.g., bis (r 5 -2, 4 cyclopentadiene one 1-I le?) - bis (2, 6-difluoro one 3- (IH-pyrrol-one 1-I le) phenyl) titanium Η 5 —cyclopentagel- 6 —tamale-iron (1 +) -hexafluorophosphate (1 1), and the like.
[0079] また、上記以外の光重合開始剤として、 Ν フエ-ルグリシンなど、ポリハロゲンィ匕 合物（例えば、四臭化炭素、フエ-ルトリブ口モメチルスルホン、フエ-ルトリクロロメチ ルケトンなど）、アミン類 (例えば、 4—ジメチルァミノ安息香酸ェチル、 4—ジメチルァ ミノ安息香酸 η—ブチル、 4ージメチルァミノ安息香酸フエネチル、 4ージメチルァミノ 安息香酸 2 フタルイミドエチル、 4 ジメチルァミノ安息香酸 2—メタクリロイルォキシ ェチル、ペンタメチレンビス（4ージメチルァミノべンゾエート）、 3—ジメチルァミノ安息 香酸のフエネチル、ペンタメチレンエステル、 4ージメチルァミノべンズアルデヒド、 2 クロル 4 ジメチルァミノべンズアルデヒド、 4 ジメチルァミノべンジルアルコ一 ル、ェチル（4ージメチルァミノべンゾィル）アセテート、 4ーピベリジノアセトフエノン、 4 —ジメチルァミノべンゾイン、 N, N ジメチルー 4—トルイジン、 N, N—ジェチルー 3 —フエネチジン、トリベンジルァミン、ジベンジルフエ-ルァミン、 N—メチル N フ ェニルベンジルァミン、 4—ブロム一 N, N ジメチルァニリン、トリドデシルァミン、タリ スタルバイオレツトラクトン、ロイコクリスタルバイオレットなど）、特開昭 53— 133428 号公報、特公昭 57— 1819号公報、同 57— 6096号公報、及び米国特許第 36154 55号明細書に記載されたィ匕合物などが挙げられる。 [0079] In addition to photopolymerization initiators other than those mentioned above, polyhalogen compounds such as vinyl glycine (for example, carbon tetrabromide, felt rib mouth methyl sulfone, phenyl trichloromethyl ketone, etc.), amines (E.g., 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid η-butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimidoethyl, 4 dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis ( 4-dimethylaminobenzoate), 3-dimethylaminobenzoate Phenethylene of perfume acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2 chloro 4 dimethylaminobenzaldehyde, 4 dimethylaminobenzil alcohol, ethyl (4-dimethylaminobenzol) acetate, 4-piberidinoacetophenone, 4 — Dimethylaminobenzoin, N, N Dimethyl-4-toluidine, N, N-Jetylu 3 -Phenetidine, Tribenzylamine, Dibenzylphenylamine, N-Methyl Nphenylbenzylamine, 4-Bromo N, N Dimethylaniline , Tridodecylamine, tarristal bioretactone, leuco crystal violet, etc.), JP-A 53-133428, JP-B 57-1819, 57-6096, and US Pat. No. 36154 55 Examples include the compound described in the book.
[0080] また、後述する感光層への露光における露光感度や感光波長を調整する目的で、 前記光重合開始剤に加えて、増感剤を添加することが可能である。  [0080] In addition to the photopolymerization initiator, it is possible to add a sensitizer for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to the photosensitive layer described later.
前記増感剤は、後述する光照射手段としての可視光線や紫外光及び可視光レー ザなどにより適宜選択することができる。  The sensitizer can be appropriately selected depending on visible light, ultraviolet light, visible light laser or the like as a light irradiation means described later.
前記増感剤は、活性エネルギー線により励起状態となり、他の物質 (例えば、ラジカ ル発生剤、酸発生剤等）と相互作用（例えば、エネルギー移動、電子移動等)するこ とにより、ラジカルや酸等の有用基を発生することが可能である。  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.
尚、これらの化合物は、感光層の感度の向上を図るだけでなぐ光励起により前記 モノマーの重合を開始させるような光重合開始剤としての機能をも有している。  These compounds also have a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation only by improving the sensitivity of the photosensitive layer.
[0081] 前記増感剤としては、特に制限はなぐ公知の増感剤の中から適宜選択することが できるが、例えば、公知の多核芳香族類 (例えば、ピレン、ペリレン、トリフエ二レン）、 キサンテン類（例えば、フルォレセイン、ェォシン、エリス口シン、ローダミン B、ローズ ベンガル）、シァニン類（例えば、インドカルボシァニン、チアカルボシァニン、ォキサ カルボシァニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、チア ジン類（例えば、チォニン、メチレンブルー、トルイジンブルー）、アタリジン類（例えば 、アタリジンオレンジ、クロロフラビン、ァクリフラビン）、アントラキノン類（例えば、アント ラキノン）、スクァリウム類 (例えば、スクァリウム）、などが挙げられる。  [0081] The sensitizer can be appropriately selected from known sensitizers that are not particularly limited. For example, 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 (for example, thionine, methylene blue, toluidine blue), atalidines (for example, atalidine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), etc. .
[0082] 前記増感剤としては、更に、ヘテロ縮環系化合物が好ましく挙げられる。前記へテ 口縮環系化合物とは、環の中にヘテロ元素を有する多環式化合物を意味し、前記環 の中に、窒素原子を含むのが好ましい。前記へテロ縮環系化合物としては、例えば、 ヘテロ縮環系ケトン化合物、キノリンィ匕合物、アタリジン化合物が挙げられる。 [0082] Preferred examples of the sensitizer include hetero-fused compounds. The heterocyclic ring-type compound means a polycyclic compound having a hetero element in the ring, and the ring Among these, it is preferable to contain a nitrogen atom. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound, a quinoline compound, and an atalidine compound.
前記へテロ縮環系ケトンィ匕合物としては、具体的には、例えば、アタリドン、クロロア クリドン、 N—メチルアタリドン、 N ブチルアタリドン、 N ブチルークロロアタリドン、 などのアタリドン化合物； 3—（2 べンゾフロイル） 7 ジェチルァミノクマリン、 3— ( 2 ベンゾフロイル）—7— (1—ピロリジ -ル）クマリン、 3 ベンゾィル—7 ジェチル アミノクマリン、 3— (2—メトキシベンゾィル） 7 ジェチルァミノクマリン、 3- (4 ジ メチルァミノベンゾィル）一7—ジェチルァミノクマリン、 3, 3，一カルボ-ルビス（5, 7 —ジ一 n—プロポキシクマリン）、 3, 3，一カルボ-ルビス（7—ジェチルァミノクマリン） 、 3—ベンゾィル 7—メトキシクマリン、 3— (2—フロイル） 7—ジェチルァミノタマリ ン、 3—（4ージェチルァミノシンナモイル） 7—ジェチルァミノクマリン、 7—メトキシ —3— (3—ピリジルカルボ-ル）クマリン、 3—ベンゾィル 5, 7—ジプロポキシタマリ ン、 7 ベンゾトリアゾール 2—イルクマリン、 7 ジェチルァミノ一 4—メチルタマリ ン、また、特開平 5— 19475号、特開平 7— 271028号、特開 2002— 363206号、 特開 2002— 363207号、特開 2002— 363208号、特開 2002— 363209号公報等 に記載のクマリンィ匕合物、などのクマリン類;などが挙げられる。  Specific examples of the hetero-fused ketone ketone compound include attaridone compounds such as attaridone, chloroacridone, N-methyl attaridone, N butyl attaridone, and N butyl chloro attaridone; (2 Benzofuroyl) 7 Jetylaminocoumarin, 3- (2 Benzofuroyl) -7- (1-Pyrrolidyl) coumarin, 3 Benzyl-7 Jetyl aminocoumarin, 3- (2-Methoxybenzoyl) 7 Jet Tyraminocoumarin, 3- (4 dimethylaminobenzoyl) 1-7-jetylaminocoumarin, 3, 3, 1-carborubis (5, 7-di-n-propoxycoumarin), 3, 3 , 1-Carbobis (7-Jetylaminocoumarin), 3-Benzyl 7-Methoxycoumarin, 3- (2-Furoyl) 7-Jetylaminotamarin, 3- (4-Jetylaminominonamoyl) 7 —Jetylaminocoumarin, 7-methoxy —3 -— (3-Pyridylcarbole) coumarin, 3-benzoyl 5,7-dipropoxytamarin, 7 Benzotriazole 2-ylcoumarin, 7 Jetylamino 4-methyltamarin, In addition, the coumarin candy described in JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc. Compound, and the like;
前記キノリン化合物としては、具体的には、例えば、キノリン、 9ーヒドロキシ 1, 2 ージヒドロキノリンー2 オン、 9 エトキシ 1, 2 ジヒドロキノリンー2 オン、 9ージ ブチルアミノー 1, 2 ジヒドロキノリンー2 オン、 8 ヒドロキシキノリン、 8 メルカプ トキノリン、キノリン 2—力ルボン酸、などが挙げられる。  Specific examples of the quinoline compound include quinoline, 9-hydroxy 1,2-dihydroquinoline-2 on, 9 ethoxy 1,2 dihydroquinoline-2 on, 9-dibutylamino 1,2 dihydroquinoline 2 on. , 8 hydroxyquinoline, 8 mercaptoquinoline, quinoline 2 -strong rubonic acid, and the like.
前記アタリジンィ匕合物としては、具体的には、例えば、 9 フエ二ルァクリジン、 1, 7 —ビス（9, 9，一アタリジ-ル）ヘプタン、アタリジンオレンジ、クロロフラビン、ァクリフラ ビン、などが挙げられる。これらへテロ縮環系化合物の中でも、環の中に窒素元素を 含有するものがより好ましい。前記環内に窒素元素を含有するものとしては、前記ァ クリジンィ匕合物、アミノ基により置換されたクマリンィ匕合物、アタリドンィ匕合物、などが 好適に挙げられる。この中でも前記アタリドン、アミノ基により置換されたクマリン、 9— フエ二ルァクリジン、などが更に好ましぐこれらの中でも、前記アタリドンが特に好まし い。 [0084] 前記光重合開始剤と前記増感剤との組合せとしては、例えば、特開 2001 - 3057 34号公報に記載の電子移動型開始系 [ (1)電子供与型開始剤及び増感色素、 (2) 電子受容型開始剤及び増感色素、（3)電子供与型開始剤、増感色素及び電子受容 型開始剤 (三元開始系）]などの組合せが挙げられる。 Specific examples of the atalidine compound include 9 phenyllacridin, 1,7-bis (9,9,1 allysyl) heptane, atalidine orange, chloroflavin, acriflavine, and the like. It is done. Among these hetero-fused compounds, those containing a nitrogen element in the ring are more preferable. Preferred examples of the compound containing a nitrogen element in the ring include the acridine compound, a coumarin compound substituted with an amino group, and an attaridone compound. Of these, the talidone, coumarin substituted with an amino group, 9-phenylacridine, and the like are more preferred, and the talidone is particularly preferred. [0084] 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.
[0085] 前記増感剤の含有量としては、前記感光性組成物中の全成分に対し、 0. 05-30 質量％が好ましぐ 0. 1〜20質量％がより好ましぐ 0. 2〜10質量％が特に好ましい 。該含有量が、 0. 05質量％未満であると、活性エネルギー線への感度が低下し、露 光プロセスに時間がかかり、生産性が低下することがあり、 30質量％を超えると、保 存時に前記感光層から前記増感剤が析出することがある。  [0085] The content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, based on all components in the photosensitive composition. 2 to 10% by mass is particularly preferable. If the content is less than 0.05% by mass, the sensitivity to active energy rays may be reduced, the exposure process may take time, and productivity may be reduced. When present, the sensitizer may precipitate from the photosensitive layer.
[0086] 前記光重合開始剤は、 1種単独で使用してもよぐ 2種以上を併用してもよい。  [0086] The photopolymerization initiator may be used alone or in combination of two or more.
前記光重合開始剤の特に好ましい例としては、後述する露光において、波長が 40 5nmのレーザ光に対応可能である、前記ホスフィンオキサイド類、前記 α—アミノア ルキルケトン類、前記トリァジン骨格を有するハロゲンィ匕炭化水素化合物とアミンィ匕 合物とを組合せた複合光開始剤、へキサァリールビイミダゾールイ匕合物、へキサァリ 一ルビイミダゾールイ匕合物とヘテロ縮環系化合物、あるいは、メタ口セン類、などが挙 げられる。  As a particularly preferred example of the photopolymerization initiator, halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the later-described exposure. A composite photoinitiator that combines a hydrogen compound and an amine compound, a hexaryl biimidazole compound, a hexaryl biimidazole compound and a hetero-fused compound, or a metaguchicene, And so on.
更にこれらの開始剤とともに、連鎖移動剤 (例えば、メルカプト化合物、より具体的 には、 2—メルカプトべンズイミダゾール、 2—メルカプトべンズォキサゾール、 2—メル カプトべンズチアゾール、など）を併用してもよい。  Furthermore, a chain transfer agent (for example, a mercapto compound, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenthiazole, etc.) may be used in combination with these initiators. Good.
[0087] 前記光重合開始剤の前記感光性組成物における含有量としては、 0. 1〜30質量 %が好ましぐ 0. 5〜20質量％がより好ましぐ 0. 5〜15質量％が特に好ましい。  [0087] 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 0.5 to 15% by mass. Is particularly preferred.
[0088] 〔 (D)一般式（1)〜（3)で表される化合物力も選択される少なくとも 1種の化合物〕 下記一般式（1)〜（3)で表される化合物は、低温又は常温では反応を生じることが なぐ加熱により架橋反応を開始する熱架橋剤としての機能を有する。該化合物を本 発明の感光性組成物に含有させることにより、該感光性組成物が低温又は常温では 反応することがなぐ優れた保存安定性が図れるとともに、加熱処理時には、該熱処 理温度で速やかな反応を示して硬化し、表面硬度、及び耐アルカリ性などに優れる 硬化物が得られる。 [化 48] 一般式（1 )[(D) At least one compound in which the compound powers represented by the general formulas (1) to (3) are also selected] The compounds represented by the following general formulas (1) to (3) It functions as a thermal cross-linking agent that initiates a cross-linking reaction by heating that does not cause a reaction at room temperature. By containing the compound in the photosensitive composition of the present invention, the photosensitive composition can have excellent storage stability that does not react at a low temperature or normal temperature, and at the time of heat treatment, the heat treatment temperature is maintained. It cures with rapid reaction, and a cured product with excellent surface hardness and alkali resistance can be obtained. [Chemical formula 48] General formula (1)
Figure imgf000037_0001
Figure imgf000037_0001
[化 49]  [Chemical 49]
一般式（2)
Figure imgf000037_0002
General formula (2)
Figure imgf000037_0002
[化 50] 一般式（3) [Chemical formula 50] General formula (3)
Figure imgf000037_0003
ノ 2
Figure imgf000037_0003
2
ただし、前記一般式（1)、 (2)、及び (3)中、 Pは、酸素原子、カルボニル基、アミド 基、ウレタン基、アルキレン、及びァリーレンのいずれかを表す。 Qは、ホウ素原子、 窒素原子、アルキレン、及びァリーレンのいずれかを表す。 Wは、 2つの X部と結合を 有するナフタレンを表す。 Ai A5は、単結合、アルキレン、及びァリーレンのいずれ かを表し、 丄〜 6は、— OCONH―、— NHCOO—、— NHCO—、及び— CONH 一のいずれかを表す。！^〜尺6は、水素原子、ハロゲン原子、アルキル基、及びァリー ル基のいずれかを表す。 However, in the general formulas (1), (2), and (3), P represents any of an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene, and an arylene. Q represents any of a boron atom, a nitrogen atom, alkylene, and arylene. W represents naphthalene having two X moieties and a bond. Ai A 5 represents a single bond, alkylene, or arylene, and 丄 to 6 represent one of —OCONH—, —NHCOO—, —NHCO—, and —CONH. ! ^ To 6 represent any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
前記一般式（1)〜（3)中、前記 Pのアルキレンは、無置換アルキレン;ァリール基、 ァルケ-ル基、及びヒドロキシル基の少なくともいずれ力、並びにアルコキシ基、シァ ノ基、及びハロゲン原子の少なくとも 、ずれかで置換されて 、る置換基含有アルキレ ンを示す。  In the general formulas (1) to (3), the alkylene of P is an unsubstituted alkylene; at least any one of an aryl group, a alkenyl group, and a hydroxyl group, and an alkoxy group, a cyan group, and a halogen atom. At least a substituted-containing alkylene substituted with a shift is shown.
前記無置換アルキレンとしては、分岐を有していてもよぐ二重結合、三重結合を有 していてもよぐ総炭素数は 1〜20のものが好ましぐ 1〜8が特に好ましい。このよう なアルキレンとしては、エチレン、プロピレン、 i—プロピレン、ブチレン、 iーブチレン、 シクロへキシレン、などが挙げられる。  The unsubstituted alkylene is preferably one having a total number of carbon atoms of 1 to 20 which may have a double bond or a triple bond which may have a branch, and particularly preferably 1 to 8. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, and cyclohexylene.
前記置換基含有アルキレン中のァリール置換基としては、総炭素数 6〜30のもの が好ましぐ 6〜15が特に好ましぐ前記置換基として、例えば、フエニル基、ナフチ ル基、アントラセ-ル基、メトキシフエ-ル基、クロロフヱ-ル基、などが挙げられる。 前記置換基含有アルキレン中のアルケニル置換基としては、総炭素数 2〜10が好 ましぐ 2〜6が特に好ましぐ置換基として、例えば、ェチュル基、プロぺニル基、ブ チリル基、などが挙げられる。 As the aryl substituent in the above-mentioned alkylene containing a substituent, those having a total carbon number of 6 to 30 are preferable, and those having 6 to 15 are particularly preferable. Examples of the substituent include phenyl, naphthyl, and anthracene. Groups, methoxyphenol groups, chlorophenol groups, and the like. The alkenyl substituent in the substituent-containing alkylene preferably has a total carbon number of 2 to 10 and particularly preferably 2 to 6, such as an ethyl group, a propenyl group, a butyryl group, etc. Is mentioned.
前記置換基含有アルキレン中のアルコキシ置換基としては、分岐を有していてもよ ぐ総炭素数 1〜10が好ましぐ 1〜5が特に好ましぐ前記置換基として、例えば、メト キシ基、エトキシ基、プロピルォキシ基、 2—メチルプロピルォキシ基、ブトキシ基、な どが挙げられる。  As the alkoxy substituent in the substituent-containing alkylene, the total number of carbon atoms of 1 to 10 which may have a branch is preferable, and 1 to 5 is particularly preferable. Examples of the substituent include a methoxy group. Ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
このような置換基含有アルキレンとしては、分岐を有していてもよぐ二重結合、三 重結合を有していてもよぐ総炭素数 2〜40が好ましぐ 2〜25が特に好ましい。この ような置換含有アルキレンとしては、例えば、 2—ェチルへキシル基、クロロブチル基 、ベンジル基、 2—ェチュルプロピル基、フエ-ルェチル基、シァノプロピル基、メトキ シェチル基、などが挙げられる。  As such a substituent-containing alkylene, a double bond which may have a branch or a triple bond which may have a triple bond is preferable, and 2 to 25 is particularly preferable. . Examples of such a substitution-containing alkylene include a 2-ethylhexyl group, a chlorobutyl group, a benzyl group, a 2-ethylpropyl group, a phenylethyl group, a cyanopropyl group, and a methoxycetyl group.
前記 Pのァリーレンとしては、後述する Ai A5のァリーレンと同義である。 The P arylene has the same meaning as the Ai A 5 arylene described below.
[0090] 前記一般式（1)〜（3)中、前記 Qのアルキレンとしては、前記無置換アルキレンが 挙げられ、前記無置換アルキレンとしては、分岐を有していてもよぐ二重結合、三重 結合を有していてもよぐ総炭素数は 2〜30のものが好ましい。このようなアルキレン としては、エチレン、プロピレン、 i プロピレン、ブチレン、 iーブチレン、シクロへキシ レン、などが挙げられる。 In the general formulas (1) to (3), examples of the alkylene of Q include the unsubstituted alkylene, and the unsubstituted alkylene includes a double bond that may have a branch, The total number of carbon atoms that may have a triple bond is preferably 2-30. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, and cyclohexylene.
前記 Qのァリーレンとしては、後述する Ai A5のァリーレンと同義である。 前記一般式（1)〜（3)中、前記 Wの X部との結合部位は、 1, 2位、 1, 3位、 1, 5位 、 1, 6位、 1, 7位、 1, 8位、 2, 3位、 2, 4位、 2, 5位、 2, 7位であり、前記 Wとしては 、アルキル基、ァリール基、アルコキシ基、ハロゲン原子のいずれかで置換されてい てもよい。 The Q arylene has the same meaning as the Ai A 5 arylene described below. In the general formulas (1) to (3), the binding site with the X portion of W is 1, 2, 1, 3, 1, 5, 5, 1, 6, 1, 7, 8th, 2nd, 3rd, 2nd, 4th, 2nd, 5th, 2nd and 7th positions, and W may be substituted with any of an alkyl group, aryl group, alkoxy group, and halogen atom Good.
[0091] 前記一般式（1)〜（3)中、前記 Ai〜A5のァリーレンとは、ベンゼン環、並びにアル キル基、ァリール基、ァルケ-ル基、アルコキシ基、シァノ基、及びハロゲン原子の少 なくとも 、ずれかで置換されて 、る置換基含有ァリーレンを示す。 [0091] In the general formula (1) to (3), and Ariren of the Ai～A 5 is a benzene ring, as well as Al kill group, Ariru group, Aruke - group, an alkoxy group, Shiano group, and a halogen atom At least one of the substituents is substituted with a deviation and represents a substituent-containing arylene.
前記置換基含有ァリーレン中のアルキル基としては、分岐を有していてもよぐ二重 結合、三重結合を有していてもよぐ総炭素数は 1〜20のものが好ましぐ 1〜： LOが 特に好ましい。このようなアルキル基としては、メチル基、ェチル基、プロピル基、イソ プロピル基、ブチル基、 S ブチル基、 t ブチル基、ブチリル基、シクロへキシル基、 シクロへキセニノレ基、などが挙げられる。 As the alkyl group in the substituent-containing arylene, a double bond that may have a branch or a total number of carbon atoms that may have a triple bond is preferably 1 to 20. : LO Particularly preferred. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an S butyl group, a t butyl group, a butyryl group, a cyclohexyl group, and a cyclohexenole group.
前記置換基含有ァリーレン中のァリール置換基としては、総炭素数 6〜30のものが 好ましぐ 6〜15が特に好ましぐ前記置換基としては、例えば、フエニル基、ナフチ ル基、アントラセ-ル基、メトキシフエ-ル基、クロロフヱ-ル基、などが挙げられる。 前記置換基含有ァリーレン中のアルキル基としては、分岐を有していてもよぐ二重 結合、三重結合を有していてもよぐ総炭素数は 1〜20のものが好ましぐ 1〜： LOが 特に好ましい。このようなアルキル基としてはメチル基、ェチル基、ェチニル基、プロ ピル基、イソプロピル基、ブチル基、 s ブチル基、 t ブチル基、ブチリル基、シクロ へキシル基、シクロへキセニル基、などが挙げられる。  As the aryl group in the substituent-containing arylene, those having a total carbon number of 6 to 30 are preferable, and those having 6 to 15 are particularly preferable. Examples of the substituent include a phenyl group, a naphthyl group, and an anthracene group. Group, methoxyphenol group, chlorophenol group, and the like. As the alkyl group in the substituent-containing arylene, a double bond that may have a branch or a total number of carbon atoms that may have a triple bond is preferably 1 to 20. : LO is particularly preferred. Examples of such an alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. It is done.
置換基含有ァリーレン中のアルケニル置換基としては、総炭素数 2〜： LOが好ましく 、 2〜6が特に好ましぐ前記置換基としては、例えば、ェチュル基、プロぺニル基、 プチリル基、などが挙げられる。  The alkenyl substituent in the substituent-containing arylene preferably has a total carbon number of 2 to: LO, and particularly preferably 2 to 6 as the substituent, for example, an ethur group, a propenyl group, a pentyl group, and the like Is mentioned.
置換基含有ァリーレン中のアルコキシ置換基としては、分岐を有していてもよぐ総 炭素数 1〜： LOが好ましぐ 1〜5が特に好ましぐ前記置換基としては、例えば、メトキ シ基、エトキシ基、プロピルォキシ基、 2—メチルプロピルォキシ基、ブトキシ基、など が挙げられる。  As the alkoxy substituent in the substituent-containing arylene, the total number of carbon atoms that may be branched is 1 to: LO is preferable, and 1 to 5 is particularly preferable. Examples of the substituent include methoxy. Group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
このような置換基含有ァリーレンとしては、分岐を有していてもよぐ二重結合、三重 結合を有していてもよぐ総炭素数 2〜40が好ましぐ 2〜25が特に好ましい。  Such a substituent-containing arylene is particularly preferably 2 to 25, preferably having a total of 2 to 40 carbon atoms which may have a double bond or a triple bond.
このような置換含有ァリーレンとしては、例えば、メチルフエ-ル環、ジメチルフエ- ル環、ジブチルフエ-ル環、メトキシフエ-ル環、シクロへキシルフェ-ル環、ビフエ- ル構造、ジクロロフエ-ル環、トリブロモフエ-ル環、クロロシアノフエ-ル環、などが挙 げられる。  Examples of such a substitution-containing arylene include a methylphenol ring, a dimethylphenol ring, a dibutylphenol ring, a methoxyphenyl ring, a cyclohexylphenol ring, a biphenyl structure, a dichlorophenol ring, and a tribromophenol. Ring, chlorocyanophenyl ring, and the like.
なお、前記 Ai A5のアルキレンは、前記 Pのアルキレンと同義である。 The alkylene of Ai A 5 has the same meaning as the alkylene of P.
[0092] 前記一般式（1)〜（3)中、前記 Xi X6は、前述のように、 OCONH 、 一 NHC[0092] In the general formulas (1) to (3), the Xi X 6 is, as described above, OCONH, 1 NHC
OO 、 一 NHCO—、及び CONH のいずれかを表す。 One of OO, NHCO—, and CONH.
[0093] 前記一般式（1)〜（3)中、前記 〜 のアルキル基とは、無置換アルキル基;ァリ ール基、ァルケ-ル基、及びヒドロキシル基の少なくともいずれ力、並びにアルコキシ 基、シァノ基、及びハロゲン原子の少なくともいずれかで置換されており、酸素原子、 硫黄原子、カルボニル基、アミド基、ウレタン基、及びウレァ基の少なくともいずれか、 並びにエステル基の 2価の基の!/、ずれかを有して!/、てもよ!/、置換基含有アルキル基 を示す。 [0093] In the general formulas (1) to (3), the alkyl group represented by-is an unsubstituted alkyl group; Substituted with at least one of an alkyl group, a alkenyl group, and a hydroxyl group, and at least one of an alkoxy group, a cyano group, and a halogen atom, and an oxygen atom, a sulfur atom, a carbonyl group, an amide group, a urethane And / or a divalent group of an ester group and / or a substituent-containing alkyl group.
前記無置換アルキル基としては、分岐を有していてもよぐ二重結合、三重結合を 有していてもよぐ総炭素数は 1〜20のものが好ましぐ 1〜10が特に好ましい。この ようなアルキル基としては、メチル基、ェチル基、ェチュル基、プロピル基、イソプロピ ル基、ブチル基、 s ブチル基、 t ブチル基、ブチリル基、シクロへキシル基、シクロ へキセ-ル基、などが挙げられる。  The unsubstituted alkyl group is preferably a double bond that may have a branch or a triple bond that preferably has a total carbon number of 1 to 20, more preferably 1 to 10. . Examples of such an alkyl group include a methyl group, an ethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, a cyclohexyl group, Etc.
前記置換基含有アルキル基中のァリール置換基としては、総炭素数 6〜30のもの が好ましぐ 6〜15が特に好ましぐ前記置換基としては、例えば、フエ-ル基、ナフ チル基、アントラセニル基、メトキシフエニル基、クロ口フエニル基、などが挙げられる。 前記置換基含有アルキル基中のアルケニル置換基としては、総炭素数 2〜： LOが好 ましぐ 2〜6が特に好ましぐ前記置換基としては、例えば、ェチニル基、プロぺニル 基、プチリル基、などが挙げられる。  As the aryl substituent in the substituent-containing alkyl group, those having a total carbon number of 6 to 30 are preferable, and 6 to 15 are particularly preferable. Examples of the substituent include a phenyl group and a naphthyl group. , Anthracenyl group, methoxyphenyl group, black mouth phenyl group, and the like. Examples of the alkenyl substituent in the substituent-containing alkyl group include a total carbon number of 2 to: LO is preferred, and 2 to 6 is particularly preferred. Examples of the substituent include ethynyl group, propenyl group, and petityl. Group, and the like.
前記置換基含有アルキル基中のアルコキシ置換基としては、分岐を有して 、てもよ ぐ総炭素数 1〜10が好ましぐ 1〜5が特に好ましぐ前記置換基としては、例えば、 メトキシ基、エトキシ基、プロピルォキシ基、 2—メチルプロピルォキシ基、ブトキシ基、 などが挙げられる。  Examples of the alkoxy substituent in the substituent-containing alkyl group include a branched group, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples include methoxy group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
このような置換基含有アルキル基は、分岐を有していてもよぐ二重結合、三重結合 を有していてもよぐ総炭素数 2〜40が好ましぐ 2〜25が特に好ましい。このような置 換含有アルキル基としては、例えば、 2—ェチルへキシル基、クロロブチル基、ベンジ ル基、 2—ェチュルプロピル基、フエ-ルェチル基、シァノプロピル基、メトキシェチ ル基、などが挙げられる。  Such a substituent-containing alkyl group is particularly preferably 2 to 25, preferably having a total of 2 to 40 carbon atoms which may have a double bond or a triple bond. Examples of such a substitution-containing alkyl group include a 2-ethylhexyl group, a chlorobutyl group, a benzyl group, a 2-ethylpropyl group, a phenylethyl group, a cyanopropyl group, and a methoxyethyl group. .
前記一般式（1)で表される化合物としては、具体的には、下記構造式（1)〜（10) で表される化合物などが挙げられるが、これらの化合物に限定されるものではない。  Specific examples of the compound represented by the general formula (1) include compounds represented by the following structural formulas (1) to (10), but are not limited to these compounds. .
[化 51] 構造式（1 )
Figure imgf000041_0001
[Chemical 51] Structural formula (1)
Figure imgf000041_0001
[化 52] 構造式 (2)
Figure imgf000041_0002
[Formula 52] Structural formula (2)
Figure imgf000041_0002
[化 53] 構造式 (3) [Formula 53] Structural formula (3)
Figure imgf000041_0003
Figure imgf000041_0003
[化 54]  [Chemical 54]
0 。、- o Ο 0 . , -O Ο
構造式 (4) Structural formula (4)
Η Η
[化 55]  [Chemical 55]
Η Η  Η Η
-0 Ν. 構造式（5)  -0 Ν. Structural formula (5)
[化 56] [Chemical 56]
ο  ο
ο [ 。 。 構造式 (6) ο [. . Structural formula (6)
[化 57] 構造式 (7)
Figure imgf000041_0004
[Chemical formula 57] Structural formula (7)
Figure imgf000041_0004
[化 58]  [Chemical 58]
構造式 (8)Structural formula (8)
Figure imgf000041_0005
Figure imgf000041_0005
[化 59]  [Chemical 59]
0  0
° ¾ 構造式 (9)  ° ¾ Structural formula (9)
[化 60] 構造式（1 0)[Chemical 60] Structural formula (1 0)
Figure imgf000042_0001
Figure imgf000042_0001
[0095] 前記構造式 (1)〜（10)で表される化合物の中でも、前記構造式 (1)、（2)、（4)〜  Among the compounds represented by the structural formulas (1) to (10), the structural formulas (1), (2), (4) to
(7)、及び（9)で表される化合物が特に好ま U、。  The compounds represented by (7) and (9) are particularly preferred U ,.
前記一般式（1)〜（3)で表される化合物は、ォキシラン環部位に置換基を持つォ キシラン環を 1分子中に 2個以上有する化合物であり、これらの化合物が感光性組成 物中に含まれることは、 H—NMR ^ベクトルを測定して同定することができる。  The compounds represented by the general formulas (1) to (3) are compounds having two or more oxysilane rings having a substituent at the oxysilane ring site in one molecule, and these compounds are contained in the photosensitive composition. It can be identified by measuring the H-NMR ^ vector.
[0096] 〔併用する熱架橋剤〕 [0096] [Heat crosslinking agent used in combination]
前記熱架橋剤として機能する一般式（1)〜（3)で表される化合物のほかにも、従来 公知のその他の熱架橋剤を更に併用してもよい。  In addition to the compounds represented by the general formulas (1) to (3) that function as the thermal crosslinking agent, other conventionally known thermal crosslinking agents may be further used in combination.
前記その他の熱架橋剤としては、特に制限はなぐ 目的に応じて適宜選択すること ができ、前記感光性組成物を用いて形成される感光層の硬化後の膜強度を改良す るために、現像性等などに悪影響を与えない範囲で、例えば、 1分子内に少なくとも 2 つのォキシラン基を有するエポキシィ匕合物、 1分子内に少なくとも 2つのォキセタニル 基を有するォキセタンィ匕合物を用いることができる。  The other thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, For example, an epoxy compound having at least two oxanyl groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used as long as the developability is not adversely affected. .
前記 1分子中に少なくとも 2つのォキシラン基を有するエポキシィ匕合物としては、例 えば、ビキシレノール型もしくはビフエノール型エポキシ榭脂（「YX4000ジャパンェ ポキシレジン社製」等)又はこれらの混合物、イソシァヌレート骨格等を有する複素環 式エポキシ榭脂（「TEPIC ;日産化学工業社製」、「ァラルダイト PT810 ;チバ'スぺシ ャルティ'ケミカルズ社製」等）、ビスフエノール A型エポキシ榭脂、ノボラック型ェポキ シ榭脂、ビスフエノール F型エポキシ榭脂、水添ビスフエノール A型エポキシ榭脂、ビ スフエノール S型エポキシ榭脂、フエノールノボラック型エポキシ榭脂、クレゾ ルノボ ラック型エポキシ榭脂、ハロゲンィ匕エポキシ榭脂 (例えば低臭素化エポキシ榭脂、高 ノ、ロゲンィ匕エポキシ榭脂、臭素化フエノールノボラック型エポキシ榭脂など）、ァリル 基含有ビスフエノール A型エポキシ榭脂、トリスフエノールメタン型エポキシ榭脂、ジフ ェ -ルジメタノール型エポキシ榭脂、フエノールビフエ-レン型エポキシ榭脂、ジシク 口ペンタジェン型エポキシ榭脂（「HP— 7200, HP— 7200H；大日本インキ化学ェ 業社製」等）、グリシジルァミン型エポキシ榭脂（ジアミノジフエニルメタン型エポキシ 榭脂、ジグリシジルァ二リン、トリグリシジルァミノフエノール等）、グリジジルエステル型 エポキシ榭脂（フタル酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、へ キサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステル等）ヒダン トイン型エポキシ榭脂、脂環式エポキシ榭脂（3, 4—エポキシシクロへキシルメチル - 3' , 4' エポキシシクロへキサン力ノレボキシレート、ビス（3, 4—エポキシシクロへ キシルメチル）アジペート、ジシクロペンタジェンジエポキシド、 「GT— 300、 GT-40 0、 ZEHPE3150 ;ダイセルィ匕学工業製」等、）、イミド型脂環式エポキシ榭脂、トリヒド ロキシフエニルメタン型エポキシ榭脂、ビスフエノール Aノボラック型エポキシ榭脂、テ トラフエ-ロールエタン型エポキシ榭脂、グリシジルフタレート榭脂、テトラグリシジル キシレノィルエタン榭脂、ナフタレン基含有エポキシ榭脂（ナフトールァラルキル型ェ ポキシ榭脂、ナフトールノボラック型エポキシ榭脂、 4官能ナフタレン型エポキシ榭脂 、市販品としては「ESN— 190, ESN— 360 ;新日鉄化学社製」、「HP— 4032, EX A-4750, EXA— 4700 ;大日本インキ化学工業社製」等）、フエノールイ匕合物とジ ビュルベンゼンゃジシクロペンタジェン等のジォレフイン化合物との付カ卩反応によつ て得られるポリフエノール化合物と、ェピクロルヒドリンとの反応物、 4 ビュルシクロへ キセン— 1 オキサイドの開環重合物を過酢酸等でエポキシィ匕したもの、線状含リン 構造を有するエポキシ榭脂、環状含リン構造を有するエポキシ榭脂、 α—メチルスチ ルベン型液晶エポキシ榭脂、ジベンゾィルォキシベンゼン型液晶エポキシ榭脂、ァ ゾフエ-ル型液晶エポキシ榭脂、ァゾメチンフエ-ル型液晶エポキシ榭脂、ビナフチ ル型液晶エポキシ榭脂、アジン型エポキシ榭脂、グリシジルメタアタリレート共重合系 エポキシ榭脂（「CP— 50S, CP- 50M ;日本油脂社製」等）、シクロへキシルマレイミ ドとグリシジルメタアタリレートとの共重合エポキシ榭脂、ビス（グリシジルォキシフエ- ル）フルオレン型エポキシ榭脂、ビス（グリシジルォキシフエ-ル）ァダマンタン型ェポ キシ榭脂などが挙げられる力 これらに限られるものではない。これらのエポキシ榭脂 は、 1種単独で使用してもよいし、 2種以上を併用してもよい。 Examples of the epoxy compound having at least two oxysilane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, an isocyanurate skeleton, etc. Heterocyclic epoxy resin ("TEPIC; manufactured by Nissan Chemical Industries", "ALALDITE PT810; manufactured by Ciba Special Chemicals", etc.), bisphenol A type epoxy resin, novolak type epoxy resin Bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, Low brominated epoxy resin, high oil, logene epoxy resin, brominated phenolic Novo Type epoxy resin), allylic group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenol methanol type epoxy resin, phenol biphenol-type epoxy resin, di-sicated pentagen type Epoxy resin ("HP-7200, HP-7200H; Dainippon Ink & Chemicals Glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidyl dilin, triglycidyl aminophenol, etc.), glycidyl ester type epoxy resin (phthalic acid diglycidyl ester, Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, cycloaliphatic epoxy resin (3, 4-epoxycyclohexylmethyl-3 ', 4' Epoxycyclohexane power noroxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentagen diepoxide, “GT-300, GT-40 0, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc.), imide Type cycloaliphatic epoxy resin, trihydroxyphenylmethane type epoxy resin, Sufenol A novolac type epoxy resin, tetrahethane-rollethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenol ethane resin, naphthalene group-containing epoxy resin (naphthol aralkyl epoxy resin, Naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, "ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EX A-4750, EXA-4700; Dainippon Ink Chemical Industries Co., Ltd.), polyphenolic compounds obtained by the addition reaction of phenolic compounds with diolefin compounds such as dibutylbenzene dicyclopentagen, and epichlorohydrin Reaction product, 4-Buylcyclohexene-1 ring-opened polymer of epoxy with peracetic acid etc., epoxy with linear phosphorus-containing structure Resin, epoxy resin having a cyclic phosphorus-containing structure, α-methyl styrene-type liquid crystal epoxy resin, dibenzoyl benzene type liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethine phenolic liquid crystal epoxy Resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl meta acrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), cyclohexylmaleimide Copolymerization with glycidyl meta acrylate, epoxy resin, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. It is not limited. These epoxy resins may be used alone or in combination of two or more.
前記ォキセタンィ匕合物としては、例えば、ビス [ (3—メチルー 3—ォキセタニルメトキ シ）メチル]エーテル、ビス [ ( 3—ェチル— 3—ォキセタ -ルメトキシ)メチル]エーテル 、 1, 4 ビス [ (3—メチル 3—ォキセタ -ルメトキシ)メチル]ベンゼン、 1, 4 ビス [ ( 3 -ェチル 3—ォキセタ -ルメトキシ)メチル]ベンゼン、（ 3 -メチル 3—ォキセ タ -ル)メチルアタリレート、 （3ーェチルー 3ーォキセタ -ル)メチルアタリレート、 (3- メチル 3—ォキセタ -ル)メチルメタタリレート、 ( 3 ェチル 3—ォキセタ -ル)メチ ルメタタリレート又はこれらのオリゴマーあるいは共重合体等の多官能ォキセタン類の 他、ォキセタン基を有する化合物と、ノボラック榭脂、ポリ（p ヒドロキシスチレン）、力 ルド型ビスフエノール類、カリックスァレーン類、力リックスレゾルシンアレーン類、シル セスキォキサン等の水酸基を有する榭脂など、とのエーテルィ匕合物が挙げられ、この 他、ォキセタン環を有する不飽和モノマーとアルキル (メタ）アタリレートとの共重合体 なども挙げられる。 Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3-oxeta-lmethoxy) methyl] ether. 1,4 bis [(3-methyl-3-oxeta-lmethoxy) methyl] benzene, 1,4 bis [(3-ethyl-3-oxeta-lmethoxy) methyl] benzene, (3-methyl-3-oxetal) methyl Atari rate, (3 Echiru 3 Okiseta -) methyl Atari rate, (3-methyl 3-Okiseta -) methyl meth Tari rate, (3 Echiru 3 Okiseta - Le) methylate Rume Tatari rate or oligomers thereof or co In addition to polyfunctional oxetanes such as polymers, compounds with oxetane groups, novolac resin, poly (p-hydroxystyrene), force-type bisphenols, calixarenes, force-resorcinarenes, silsesquioxanes, etc. As well as ether compounds such as those having a hydroxyl group, an unsaturated monomer having an oxetane ring and an alkyl (meth ) It may also be mentioned, such as copolymers of Atari rate.
また、前記エポキシ化合物や前記ォキセタン化合物の熱硬化を促進するため、例 えば、ジシアンジアミド、ベンジルジメチルァミン、 4— (ジメチルァミノ） N, N ジメ チルベンジルァミン、 4ーメトキシ N, N ジメチルベンジルァミン、 4ーメチルー N, N ジメチルベンジルァミンなどのアミン化合物；トリェチルベンジルアンモ -ゥムクロ リドなどの 4級アンモ-ゥム塩化合物；ジメチルァミンなどのブロックイソシァネートイ匕 合物；イミダゾール、 2—メチルイミダゾール、 2 ェチルイミダゾール、 2 ェチルー 4 —メチルイミダゾール、 2 フエ-ルイミダゾール、 4 フエ-ルイミダゾール、 1—シァ ノエチルー 2 フエ-ルイミダゾール、 1一（2 シァノエチル） 2 ェチルー 4ーメチ ルイミダゾールなどのイミダゾール誘導体二環式アミジンィ匕合物及びその塩；トリフエ -ルホスフィンなどのリン化合物；メラミン、グアナミン、ァセトグアナミン、ベンゾグアナ ミンなどのグアナミン化合物； 2, 4 ジァミノ 6—メタクリロイルォキシェチル S ト リアジン、 2 ビュル一 2, 4 ジァミノ一 S トリァジン、 2 ビュル一 4, 6 ジァミノ一 S トリアジン'イソシァヌル酸付カ卩物、 2, 4 ジァミノ一 6—メタクリロイルォキシェチ ル一 S トリァジン'イソシァヌル酸付加物などの S トリァジン誘導体；などを用いるこ とができる。これらは 1種単独で使用してもよぐ 2種以上を併用してもよい。なお、前 記エポキシィ匕合物や前記ォキセタンィ匕合物の硬化触媒、あるいは、これらとカルボキ シル基の反応を促進することができるものであれば、特に制限はなぐ上記以外の熱 硬化を促進可能な化合物を用いてもょ 、。 前記エポキシ化合物、前記ォキセタン化合物、及びこれらとカルボン酸との熱硬化 を促進可能な化合物の前記感光性組成物固形分中の固形分含有量としては、通常In order to accelerate the thermal curing of the epoxy compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) N, N dimethylbenzylamine, 4-methoxy N, N dimethylbenzylamine. , 4-methyl-N, N amine compounds such as dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; block isocyanate compounds such as dimethylamine; imidazole, 2-methyl Such as imidazole, 2-ethylimidazole, 2-ethylimidazole, 2-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanethyl-2-phenylimidazole, and 1- (2-cyanethyl) -2-ethyl-4-methylimidazole Imidazole derivative bicyclic amidine compound Salts thereof; phosphorus compounds such as triphenyl-phosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2, 4 diamino 6-methacryloyloxychetyl S triazine, 2 bur 1, 2, 4 diamino 1 S triazine , 2 Bull 1,4,6 Diamino 1 S Triazine 'isocyanuric acid, 2, 4 Diamino 6-methacryloyloxy-S Triazine, isocyanuric acid adduct, etc. You can. These may be used alone or in combination of two or more. It is possible to promote thermal curing other than the above as long as it is a curing catalyst for the epoxy compound or the oxetane compound, or any catalyst that can accelerate the reaction between these and the carboxyl group. You can use the right compounds. The solid content in the solid content of the photosensitive composition of the epoxy compound, the oxetane compound, and a compound capable of accelerating thermal curing of these with a carboxylic acid is usually as follows.
0. 01〜15質量0 /0である。 0.01 to 15 weight 0/0.
[0099] また、前記熱架橋剤としては、特開平 5— 9407号公報記載のポリイソシァネートイ匕 合物を用いることができ、該ポリイソシァネートイ匕合物は、少なくとも 2つのイソシァネ 一ト基を含む脂肪族、環式脂肪族又は芳香族基置換脂肪族化合物から誘導されて いてもよい。具体的には、 2官能イソシァネート（例えば、 1, 3 フエ-レンジイソシァ ネートと 1, 4 フエ-レンジイソシァネートとの混合物、 2, 4 及び 2, 6 トルエンジ イソシァネート、 1, 3 及び 1, 4 キシリレンジイソシァネート、ビス（4 イソシァネー ト一フエ-ル)メタン、ビス（4—イソシァネートシクロへキシル)メタン、イソフォロンジィ ソシァネート、へキサメチレンジイソシァネート、トリメチルへキサメチレンジイソシァネ ート等）、該 2官能イソシァネートと、トリメチロールプロパン、ペンタリスルトール、ダリ セリン等との多官能アルコール;該多官能アルコールのアルキレンオキサイド付加体 と、前記 2官能イソシァネートとの付加体;へキサメチレンジイソシァネート、へキサメ チレン 1 , 6 ジイソシァネート及びその誘導体等の環式三量体ゃビュレット体;ノ ルボルナンジイソシァネート；などが挙げられる。 [0099] As the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is composed of at least two isocyanates. It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing a monoto group. Specifically, bifunctional isocyanates (eg, mixtures of 1,3 and 1,4-phenolic diisocyanates, 2,4 and 2,6 toluene diisocyanates, 1,3 and 1,4 xylates) Range isocyanate, bis (4-isocyanate monophenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone di-socyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Polyfunctional alcohols of the bifunctional isocyanates and trimethylolpropane, pentalysitol, dariserine, etc .; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; Cyclic trimers such as diisocyanate, hexamethylene 1,6 diisocyanate and its derivatives The body is a burette; norbornane diisocyanate;
[0100] 更に、本発明の感光性組成物及び後述の感光性フィルムの保存性を向上させるこ とを目的として、前記ポリイソシァネート及びその誘導体のイソシァネート基にブロック 剤を反応させて得られる化合物を用いてもょ ヽ。 [0100] Further, for the purpose of improving the preservability of the photosensitive composition of the present invention and the photosensitive film described later, it is obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivatives. Use compounds.
前記イソシァネート基ブロック剤としては、アルコール類 (例えば、イソプロパノール 、tert ブタノール等）、ラタタム類 (例えば、 ε 一力プロラタタム等）、フエノール類（ 例えば、フエノーノレ、クレゾ一ノレ、 p— tert ブチノレフエノーノレ、 p— sec ブチノレフエ ノーノレ、 p— sec ァミルフエノール、 p—ォクチルフエノール、 p ノ-ルフエノール等 )、複素環式ヒドロキシルイ匕合物（例えば、 3—ヒドロキシピリジン、 8—ヒドロキシキノリ ン等）、活性メチレン化合物（例えば、ジアルキルマロネート、メチルェチルケトキシム 、ァセチルアセトン、アルキルァセトアセテートォキシム、ァセトォキシム、シクロへキ サノンォキシム等)などが挙げられる。これらの他、特開平 6— 295060号公報記載の 分子内に少なくとも 1つの重合可能な二重結合及び少なくとも 1つのブロックイソシァ ネート基の 、ずれかを有する化合物などを用いることができる。 Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert-butanol, etc.), ratatas (eg, ε-strength prolatatum, etc.), phenols (eg, phenol, crezo-monore, p-tert-butinolephenol) Nore, p-sec butinolevenore, p-sec amylphenol, p-octylphenol, p-norphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline) And the like, and active methylene compounds (for example, dialkyl malonate, methyl ethyl ketoxime, acetyl acetone, alkyl acetoacetonitrile, acetooxime, cyclohexanone oxime, etc.). In addition to these, at least one polymerizable double bond and at least one block isocyanate in the molecule described in JP-A-6-295060 A compound having a deviation from the nate group can be used.
[0101] また、前記熱架橋剤として、メラミン誘導体を用いることができる。該メラミン誘導体と しては、例えば、メチロールメラミン、アルキル化メチロールメラミン (メチロール基を、 メチル、ェチル、ブチルなどでエーテルィ匕した化合物）などが挙げられる。これらは 1 種単独で使用してもよいし、 2種以上を併用してもよい。これらの中でも、保存安定性 が良好で、感光層の表面硬度ある ヽは硬化膜の膜強度自体の向上に有効である点 で、アルキル化メチロールメラミンが好ましぐへキサメチル化メチロールメラミンが特 に好ましい。  [0101] A melamine derivative can be used as the thermal crosslinking agent. 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 the surface hardness of the photosensitive layer is effective in improving the film strength itself of the cured film. preferable.
[0102] また、その他の熱架橋剤として、メラミン以外のアルデヒド縮合生成物、榭脂前駆体 などを用いることができる。具体的には、 N, N，一ジメチロール尿素、 N, N，一ジメチ ロールマロンアミド、 N, N，—ジメチロールスクシンイミド、 1, 3-N, N，—ジメチロー ルテレフタルアミド、 2, 4, 6 トリメチロールフエノール、 2, 6 ジメチロールー4ーメ チロア-ノール、 1, 3 ジメチロール 4, 6 ジイソプロピルベンゼン、などが挙げら れる。また、これらのメチロールイ匕合物の代わりに、対応するェチルもしくはブチルェ 一テル、又は酢酸あるいはプロピオン酸のエステルを使用してもよ 、。  [0102] As other thermal crosslinking agents, aldehyde condensation products other than melamine, rosin precursors, and the like can be used. Specifically, N, N, dimethylol urea, N, N, dimethylol malonamide, N, N, dimethylol succinimide, 1, 3-N, N, dimethylol terephthalamide, 2, 4, 6 Trimethylol phenol, 2, 6 dimethylol-4-methylo-anol, 1,3 dimethylol 4, 6 diisopropylbenzene, and the like. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or an ester of acetic acid or propionic acid may be used.
[0103] 前記一般式（1)〜（3)で表される化合物及びその他の熱架橋剤の感光性組成物 固形分中における固形分含有量としては、 1〜50質量％が好ましぐ 3〜30質量％ 力 り好ましい。前記含有量が、 1質量％未満であると、加熱処理時の反応が低下し 、硬化膜の膜強度の向上が図れないことがあり、 50質量％超であると、現像性、露光 感度の低下、及び硬化膜の膜硬度の低下を生ずることがある。  [0103] Photosensitive compositions of the compounds represented by the general formulas (1) to (3) and other thermal crosslinking agents The solid content in the solid content is preferably 1 to 50% by mass 3 ~ 30 mass% force is preferred. When the content is less than 1% by mass, the reaction during the heat treatment is lowered, and the strength of the cured film may not be improved. Decrease and film hardness of the cured film may occur.
[0104] 熱硬化促進剤  [0104] Thermosetting accelerator
前記ノインダ一中のエポキシアタリレートイ匕合物の熱硬化を促進するため、従来公 知の熱硬化促進剤を配合することができる。前記熱硬化促進剤としては、例えば、ジ シアンジアミド、ベンジルジメチルァミン、 4— (ジメチルァミノ） N, N ジメチルベン ジルァミン、 4ーメトキシ N, N ジメチルベンジルァミン、 4ーメチルー N, N ジメ チルベンジルァミン等のアミン化合物；トリェチルベンジルアンモ -ゥムクロリド等の 4 級アンモ-ゥム塩化合物；ジメチルァミン等でブロックされたブロックイソシァネートイ匕 合物；イミダゾール、 2—メチルイミダゾール、 2 ェチルイミダゾール、 2 ェチルー 4 —メチルイミダゾール、 2 フエ-ルイミダゾール、 4 フエ-ルイミダゾール、 1—シァ ノエチルー 2 フエ-ルイミダゾール、 1一（2 シァノエチル） 2 ェチルー 4ーメチ ルイミダゾール等のイミダゾール誘導体二環式アミジンィ匕合物及びその塩；トリフエ- ルホスフィン等のリン化合物；メラミン、グアナミン、ァセトグアナミン、ベンゾグアナミン 等のグアナミン化合物； 2, 4 ジァミノ 6 メタクリロイルォキシェチル S トリアジ ン、 2 ビュル一 2, 4 ジァミノ一 S トリアジン、 2 ビュル一 4, 6 ジァミノ一 S ト リアジン'イソシァヌル酸付カ卩物、 2, 4 ジアミノー 6—メタクリロイルォキシェチルー S -トリァジン'イソシァヌル酸付加物等の S -トリァジン誘導体；などを用いることができ る。これらは 1種単独で使用してもよぐ 2種以上を併用してもよい。 In order to accelerate the thermal curing of the epoxy atelar toy compound in the noinder, a conventionally known thermal curing accelerator can be blended. Examples of the thermosetting accelerator include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) N, N dimethylbenzilamine, 4-methoxy N, N dimethylbenzylamine, 4-methyl-N, N dimethylbenzylamine. Amine compounds such as amine; quaternary ammonium salt compounds such as triethylbenzyl ammonium chloride; block isocyanate compounds blocked with dimethylamine and the like; imidazole, 2-methylimidazole, 2-ethylimidazole, 2 Etyl 4 —Methylimidazole, 2-phenolimidazole, 4-phenolimidazole, 1-cyanethyl-2-phenolimidazole, imidazole bicyclic amidine compounds such as 1- (2-cyanethyl) 2-ethyl-4-methylimidazole, etc. Its salts; Phosphorus compounds such as triphenylphosphine; Guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2, 4 diamine 6 methacryloyloxychetyl S triazine, 2 bul 1, 2, 4 diamine 1 S triazine, 2 S-triazine derivatives such as bulle 4, 6 diamino 1 S triazine 'isocyanuric acid, 2, 4 diamino-6-methacryloyloxychetyl S-triazine' isocyanuric acid adduct, etc. can be used. The These may be used alone or in combination of two or more.
なお、前記熱硬化促進剤としては、前記エポキシアタリレートイ匕合物の熱硬化を促 進することができるものであれば、特に制限はなぐ上記以外の熱硬化を促進可能な 化合物を用いてもよい。  The thermosetting accelerator is not particularly limited as long as it can accelerate the thermosetting of the epoxy atelar toy compound, and other compounds that can accelerate the thermosetting are used. Also good.
[0105] 前記熱硬化促進剤の前記感光性組成物固形分中の固形分含有量は、 0. 01〜1 [0105] The solid content of the thermosetting accelerator in the solid content of the photosensitive composition is 0.01-1.
5質量％であることが好まし 、。  Preferably 5% by weight.
[0106] 〔その他の成分〕 [0106] [Other ingredients]
前記その他の成分としては、例えば、熱重合禁止剤、可塑剤、着色剤 (着色顔料あ るいは染料)、体質顔料、などが挙げられ、更に基材表面への密着促進剤及びその 他の助剤類 (例えば、導電性粒子、充填剤、消泡剤、難燃剤、レべリング剤、剥離促 進剤、酸化防止剤、香料、表面張力調整剤、連鎖移動剤など)を併用してもよい。こ れらの成分を適宜含有させることにより、目的とする感光性組成物あるいは感光性フ イルムの安定性、写真性、膜物性などの性質を調整することができる。  Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other assistants. Agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination. Good. By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.
[0107] 熱重合禁止剤 [0107] Thermal polymerization inhibitor
前記熱重合禁止剤は、前記重合性化合物の熱的な重合又は経時的な重合を防止 するために添カ卩してもよい。  The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
前記熱重合禁止剤としては、例えば、 4—メトキシフエノール、ハイドロキノン、アル キルまたはァリール置換ノヽイドロキノン、 tーブチルカテコール、ピロガロール、 2—ヒド ロキシベンゾフエノン、 4—メトキシ一 2 ヒドロキシベンゾフエノン、塩化第一銅、フエ ノチアジン、クロラニル、ナフチルァミン、 13 ナフトール、 2, 6 ジ tーブチルー 4 クレゾール、 2, 2，ーメチレンビス（4ーメチルー 6 t—ブチルフエノール）、ピリジン 、ニトロベンゼン、ジニトロベンゼン、ピクリン酸、 4ートルイジン、メチレンブルー、銅と 有機キレート剤反応物、サリチル酸メチル、及びフエノチアジン、ニトロソィ匕合物、 -ト 口ソィ匕合物と A1とのキレート等が挙げられる。 Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted nanoquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, Cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2, 6 di-tert-butyl-4 Cresol, 2,2, -methylenebis (4-methyl-6t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound -A chelate of a soy compound and A1.
[0108] 前記熱重合禁止剤の含有量としては、前記重合性化合物に対して 0. 001〜5質 量％が好ましぐ 0. 005〜2質量％がより好ましぐ 0. 01〜1質量％が特に好ましい 。該含有量が、 0. 001質量％未満であると、保存時の安定性が低下することがあり、 5質量％を超えると、活性エネルギー線に対する感度が低下することがある。  [0108] The content of the thermal polymerization inhibitor is preferably from 0.001 to 5 mass%, more preferably from 0.005 to 2 mass%, based on the polymerizable compound. Mass% is particularly preferred. When the content is less than 0.001% by mass, the stability during storage may be reduced, and when it exceeds 5% by mass, the sensitivity to active energy rays may be reduced.
[0109] 一着色顔料  [0109] Monochromatic pigment
前記着色顔料としては、特に制限はなぐ目的に応じて適宜選択することができ、 例えば、ビク卜! J ピュア一ブルー BO (C. I. 42595)、オーラミン（C. I. 41000)、 フアット'ブラック HB (C. I. 26150)、モノライト'イェロー GT(C. I.ビグメント 'イエロ 一 12)、パーマネント 'イェロー GR(C. I.ビグメント 'イェロー 17)、パーマネント 'イエ ロー HR(C. I.ビグメント 'イェロー 83)、パーマネント 'カーミン FBB (C. I.ビグメント 'レッド 146)、ホスターバームレッド ESB (C. I.ビグメント 'バイオレット 19)、パーマネ ント 'ルビー FBH (C. I.ビグメント 'レッド 11)、フアステル 'ピンク Bスプラ（C. I.ピグメ ント 'レッド 81)モナストラル'ファースト 'ブルー（C. I.ピグメント 'ブルー 15)、モノライ ト 'ファースト 'ブラック B (C. I.ビグメント 'ブラック 1)、カーボン、 C. I.ビグメント 'レツ ド 97、 C. I.ビグメント 'レッド 122、 C. I.ビグメント 'レッド 149、 C. I.ビグメント 'レッド 168、 C. I.ビグメント 'レッド 177、 C. I.ビグメント 'レッド 180、 C. I.ビグメント 'レッド 192、 C. I.ピグメント.レッド 215、 C. I.ピグメント.グリーン 7、 C. I.ピグメント.グリー ン 36、 C. I.ピグメント.ブルー 15 : 1、 C. I.ピグメント.ブルー 15 :4、 C. I.ビグメント 'ブルー 15 : 6、 C. I.ピグメント.ブルー 22、 C. I.ピグメント.ブルー 60、 C. I.ピグメ ント 'ブルー 64などが挙げられる。これらは 1種単独で用いてもよいし、 2種以上を併 用してちょい。  The coloring pigment can be appropriately selected according to the purpose without any particular limitation. For example, Bikku! J Pure One Blue BO (CI 42595), Auramin (CI 41000), Fat 'Black HB (CI 26150) , Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146 ), Hoster Balm Red ESB (CI Pigment 'Violet 19), Permanent' Ruby FBH (CI Pigment 'Red 11), Huster's' Pink B Supra (CI Pigment 'Red 81) Monastral' First 'Blue (CI Pigment' Blue) 15), Monolite 'First' Black B (CI Pigment 'Black 1), Carbon, CI Bigume 'Leg 97, CI Pigment' Red 122, CI Pigment 'Red 149, CI Pigment' Red 168, CI Pigment 'Red 177, CI Pigment' Red 180, CI Pigment 'Red 192, CI Pigment. Red 215, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15: 1, CI Pigment Blue 15: 4, CI Pigment 'Blue 15: 6, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment 'Blue 64 and so on. These may be used alone or in combination of two or more.
[0110] 前記着色顔料の前記感光性組成物固形分中の固形分含有量は、永久パターン形 成の際の感光層の露光感度、解像性などを考慮して決めることができ、前記着色顔 料の種類により異なる力 一般的には 0. 01〜10質量％が好ましぐ 0. 05〜5質量 %がより好ましい。 [0110] 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 at the time of forming a permanent pattern. Different forces depending on the type of face Generally, 0.01 to 10% by mass is preferred 0.05 to 5% by mass % Is more preferable.
[0111] 一体質顔料  [0111] Solid pigment
前記感光性組成物には、必要に応じて、永久パターンの表面硬度の向上、あるい は線膨張係数を低く抑えること、あるいは、硬化膜自体の誘電率や誘電正接を低く 抑えることを目的として、無機顔料や有機微粒子を添加することができる。  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.
前記無機顔料としては、特に制限はなぐ公知のものの中から適宜選択することが でき、例えば、カオリン、硫酸バリウム、チタン酸バリウム、酸化ケィ素粉、微粉状酸ィ匕 ケィ素、気相法シリカ、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タルク、 クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、 マイ力などが挙げられる。  The inorganic pigment can be appropriately selected from known ones that are not particularly limited, and examples thereof include kaolin, barium sulfate, barium titanate, potassium oxide powder, finely divided oxide silica, and vapor phase method silica. Amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, My strength and the like.
前記無機顔料の平均粒径は、 10 m未満が好ましぐ 3 m以下がより好ましい。 該平均粒径が 10 m以上であると、光錯乱により解像度が劣化することがある。 前記有機微粒子としては、特に制限はなぐ目的に応じて適宜選択することができ 、例えば、メラミン榭脂、ベンゾグアナミン榭脂、架橋ポリスチレン榭脂などが挙げられ る。また、平均粒径 1〜5 /ζ πι、吸油量 100〜200m2Zg程度のシリカ、架橋樹脂から なる球状多孔質微粒子などを用いることができる。 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 / ζπι, 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.
[0112] 前記体質顔料の添加量は、 5〜60質量％が好ましい。該添加量が 5質量％未満で あると、十分に線膨張係数を低下させることができないことがあり、 60質量％を超える と、感光層表面に硬化膜を形成した場合に、該硬化膜の膜質が脆くなり、永久バタ ーンを用いて配線を形成する場合にお!、て、配線の保護膜としての機能が損なわれ ることがある。  [0112] The amount of the extender pigment added is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.
[0113] 密着促進剤  [0113] Adhesion promoter
各層間の密着性、又は感光層と基材との密着性を向上させるために、各層に公知 の 、わゆる密着促進剤を用いることができる。  In order to improve the adhesion between each layer or the adhesion between the photosensitive layer and the substrate, a known adhesion promoter may be used for each layer.
[0114] 前記密着促進剤としては、例えば、特開平 5— 11439号公報、特開平 5— 34153 2号公報、及び特開平 6—43638号公報などに記載の密着促進剤が好適挙げられ る。具体的には、ベンズイミダゾール、ベンズォキサゾール、ベンズチアゾール、 2— メルカプトべンズイミダゾール、 2—メルカプトべンズォキサゾール、 2—メルカプトベン ズチアゾール、 3 モルホリノメチルー 1 フエ二ルートリアゾールー 2 チオン、 3— モルホリノメチル 5 フエニル ォキサジァゾール 2 チオン、 5 アミノー 3 モ ルホリノメチル チアジアゾール - 2-チオン、及び 2 メルカプト 5—メチルチオ ーチアジアゾール、トリァゾール、テトラゾール、ベンゾトリァゾール、カルボキシベン ゾトリァゾール、アミノ基含有べンゾトリァゾール、シランカップリング剤などが挙げられ る。 [0114] Preferred examples of the adhesion promoter include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptoben Thiothiazole, 3 morpholinomethyl-1 phenyltriazole 2 thione, 3— morpholinomethyl 5 phenyloxadiazole 2 thione, 5 amino-3 morpholinomethyl thiadiazole-2-thione, and 2 mercapto-5-methylthiothiadiazole, triazole, tetrazole, Examples thereof include benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.
[0115] 前記密着促進剤の含有量としては、前記感光性組成物中の全成分に対して 0. 00 1質量％〜20質量％が好ましぐ 0. 01〜10質量％がより好ましぐ 0. 1質量％〜5 質量％が特に好ましい。  [0115] 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 in the photosensitive composition. 0.1 mass% to 5 mass% is particularly preferable.
[0116] 本発明の感光性組成物は、 UV露光により画像形成可能で、表面のタック性が小さ ぐラミネート性及び取扱い性が良好で、保存時の常温下では反応を生じず保存安 定性に優れ、高感度で現像性にも優れ、現像後に優れた耐薬品性、表面硬度、耐 熱性、誘電特性、電気絶縁性などを発現する。このため、プリント配線板 (多層配線 基板、ビルドアップ配線基板等)の保護膜、層間絶縁膜、及びソルダーレジストパタ ーン、カラーフィルタや柱材、リブ材、スぺーサ一、隔壁などのディスプレイ用部材、 ホログラム、マイクロマシン、プルーフなどの永久パターン形成用として広く用いること ができ、特に本発明の感光性フィルム、永久パターン及びその形成方法に好適に用 いることがでさる。  [0116] The photosensitive composition of the present invention is capable of forming an image by UV exposure, has a low surface tackiness, good laminating properties and handling properties, and does not react at room temperature during storage, and is stable in storage. Excellent, high sensitivity, excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development. For this reason, displays such as protective films for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be widely used for forming permanent patterns such as members, holograms, micromachines, proofs, etc., and is particularly suitable for use in the photosensitive film, permanent pattern and method of forming the same of the present invention.
[0117] (感光性フィルム）  [0117] (Photosensitive film)
本発明の感光性フィルムは、少なくとも支持体と、感光層とを有してなり、好ましくは 保護フィルムを有してなり、更に必要に応じて、クッション層、酸素遮断層（PC層）な どのその他の層を有してなる。  The photosensitive film of the present invention includes at least a support and a photosensitive layer, preferably includes a protective film, and further includes a cushion layer, an oxygen barrier layer (PC layer) and the like as necessary. It has other layers.
[0118] 前記感光性フィルムの形態としては、特に制限はなぐ 目的に応じて適宜選択する ことができ、例えば、前記支持体上に、前記感光層、前記保護膜フィルムをこの順に 有してなる形態、前記支持体上に、前記 PC層、前記感光層、前記保護フィルムをこ の順に有してなる形態、前記支持体上に、前記クッション層、前記 PC層、前記感光 層、前記保護フィルムをこの順に有してなる形態などが挙げられる。なお、前記感光 層は、単層であってもよいし、複数層であってもよい。 [0119] 〔感光層〕 [0118] The form of the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive film and the protective film are provided on the support in this order. Form: Form in which the PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film on the support. In this order. The photosensitive layer may be a single layer or a plurality of layers. [Photosensitive layer]
前記感光層は、本発明の前記感光性組成物により形成される。  The photosensitive layer is formed by the photosensitive composition of the present invention.
前記感光層の前記感光性フィルムにおいて設けられる箇所としては、特に制限は なぐ目的に応じて適宜選択することができるが、通常、前記支持体上に積層される 前記感光層は、後述する露光工程において、光照射手段からの光を受光し出射す る描素部を n個有する光変調手段により、前記光照射手段からの光を変調させた後、 前記描素部における出射面の歪みによる収差を補正可能な非球面を有するマイクロ レンズを配列したマイクロレンズアレイを通した光で、露光されるのが好まし！/、。  The portion provided in the photosensitive film of the photosensitive layer can be appropriately selected according to the purpose without any particular limitation. Usually, the photosensitive layer laminated on the support is an exposure step described later. In this embodiment, after the light from the light irradiating means is modulated by the light modulating means having n number of picture elements for receiving and emitting the light from the light irradiating means, the aberration due to the distortion of the emission surface in the picture element It is preferable to be exposed to light through a microlens array in which microlenses with aspherical surfaces capable of correcting the light are arranged! /.
[0120] 前記感光層を露光し現像する場合において、該感光層の露光する部分の厚みを 該露光及び現像後にお 、て変化させな 、前記露光に用いる光の最小エネルギーは 、0. 1〜： L00 (mj/cm2)であることが好ましぐ l〜80mj/cm2であることがより好ま しい。前記露光に用いる光の最小エネルギー力 0. ImiZcm2未満であると、加工 マージンが狭くなることがあり、 lOOmiZcm2を超えると、タクト時間が長くなるため好 ましくない。 [0120] In the case where the photosensitive layer is exposed and developed, the minimum energy of light used in the exposure is 0.1 to 0.1 mm, without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development. : L00 (mj / cm 2) it is preferably a tool l~80mj / cm 2 and it is more preferable arbitrariness. If the minimum energy power of light used for the exposure is less than 0.1 ImiZcm 2 , the processing margin may be narrowed, and if it exceeds lOOmiZcm 2 , the tact time becomes long, which is not preferable.
[0121] ここで、「該感光層の露光する部分の厚みを該露光及び現像後において変化させ ない前記露光に用いる光の最小エネルギー」とは、いわゆる現像感度であり、例えば 、前記感光層を露光したときの前記露光に用いた光のエネルギー量 (露光量）と、前 記露光に続く前記現像処理により生成した前記硬化層の厚みとの関係を示すグラフ (感度曲線)から求めることができる。  [0121] Here, "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. .
前記硬化層の厚みは、前記露光量が増えるに従い増加していき、その後、前記露 光前の前記感光層の厚みと略同一かつ略一定となる。前記現像感度は、前記硬化 層の厚みが略一定となったときの最小露光量を読み取ることにより求められる値であ る。  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.
ここで、前記硬化層の厚みと前記露光前の前記感光層の厚みとの差が ± 1 μ m以 内であるとき、前記硬化層の厚みが露光及び現像により変化していないとみなす。 前記硬化層及び前記露光前の前記感光層の厚みの測定方法としては、特に制限 はなく、目的に応じて適宜選択することができるが、膜厚測定装置、表面粗さ測定機 (例えば、サーフコム 1400D (東京精密社製) )などを用いて測定する方法が挙げら れる。 Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development. The method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. (For example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) can be used.
[0122] 前記感光層の厚みとしては、特に制限はなぐ目的に応じて適宜選択することがで きるが、例えば、 3〜： LOO m力好ましく、 5〜70 mがより好ましい。  [0122] The thickness of the photosensitive layer can be appropriately selected depending on the purpose for which there is no particular limitation. For example, 3 to: LOO m force is preferable, and 5 to 70 m is more preferable.
[0123] 前記感光層の形成方法としては、前記支持体の上に、本発明の前記感光性組成 物を、水又は溶剤に溶解、乳化又は分散させて感光性組成物溶液を調製し、該溶 液を直接塗布し、乾燥させることにより積層する方法が挙げられる。  [0123] As the method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support. The method of laminating | stacking by apply | coating a solution directly and drying is mentioned.
[0124] 前記感光性組成物溶液の溶剤としては、特に制限はなぐ目的に応じて適宜選択 することができ、例えば、メタノール、エタノール、 n—プロパノール、イソプロパノール 、 n—ブタノール、 sec ブタノール、 n—へキサノール等のアルコール類；アセトン、メ チルェチルケトン、メチルイソブチルケトン、シクロへキサノン、ジイソプチルケトンなど のケトン類；酢酸ェチル、酢酸ブチル、酢酸 n—ァミル、硫酸メチル、プロピオン酸 ェチル、フタル酸ジメチル、安息香酸ェチル、及びメトキシプロピルアセテートなどの エステル類；トルエン、キシレン、ベンゼン、ェチルベンゼンなどの芳香族炭化水素類 ；四塩化炭素、トリクロロエチレン、クロ口ホルム、 1, 1, 1—トリクロロェタン、塩化メチ レン、モノクロ口ベンゼンなどのハロゲン化炭化水素類；テトラヒドロフラン、ジェチル エーテノレ、エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノエチノレエ 一テル、 1ーメトキシー 2—プロパノールなどのエーテル類；ジメチルホルムアミド、ジメ チルァセトアミド、ジメチルスルホオキサイド、スルホランなどが挙げられる。これらは、 1種単独で使用してもよぐ 2種以上を併用してもよい。また、公知の界面活性剤を添 カロしてちょい。  [0124] The solvent of the photosensitive composition solution can be appropriately selected according to the purpose without any particular limitation. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, n- Alcohols such as hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone; Ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl ethyl propionate, dimethyl phthalate , Esters such as ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichlorethylene, chloroform, 1, 1, 1-trichloroethane, chloride Such as methylene and monochrome benzene. Genated hydrocarbons; Tetrahydrofuran, Jetyl etherenole, Ethylene glycol monomethino ethenore, Ethylene glyconoreno ethinore ether, ethers such as 1-methoxy-2-propanol; Dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane Etc. These may be used alone or in combination of two or more. Also, add a known surfactant.
[0125] 前記塗布の方法としては、特に制限はなぐ目的に応じて適宜選択することができ 、例えば、スピンコーター、スリットスピンコーター、ロールコーター、ダイ =1一ター、力 一テンコーターなどを用いて、前記支持体に直接塗布する方法が挙げられる。  [0125] The coating method can be appropriately selected depending on the purpose without any particular limitation. For example, a spin coater, a slit spin coater, a roll coater, a die = 1 ter, a force tenser coater, or the like is used. And a method of directly applying to the support.
前記乾燥の条件としては、各成分、溶媒の種類、使用割合等によっても異なるが、 通常 60〜 110°Cの温度で 30秒間〜 15分間程度である。  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.
[0126] 〔支持体〕  [Support]
前記支持体としては、特に制限はなぐ目的に応じて適宜選択することができるが、 前記感光層を剥離可能であり、かつ光の透過性が良好であるのが好ましぐ更に表 面の平滑性が良好であるのがより好ましい。 The support can be appropriately selected according to the purpose without particular limitation, It is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and it is more preferable that the surface smoothness is good.
[0127] 前記支持体は、合成樹脂製で、かつ透明であるものが好ましぐ例えば、ポリエチレ ンテレフタレート、ポリエチレンナフタレート、ポリプロピレン、ポリエチレン、三酢酸セ ルロース、二酢酸セルロース、ポリ（メタ）アクリル酸アルキルエステル、ポリ（メタ）アタリ ル酸エステル共重合体、ポリ塩化ビュル、ポリビュルアルコール、ポリカーボネート、 ポリスチレン、セロファン、ポリ塩ィ匕ビユリデン共重合体、ポリアミド、ポリイミド、塩ィ匕ビ -ル '酢酸ビュル共重合体、ポリテトラフロロエチレン、ポリトリフロロエチレン、セル口 ース系フィルム、ナイロンフィルム等の各種のプラスチックフィルムが挙げられ、これら の中でも、ポリエチレンテレフタレートが特に好ましい。これらは、 1種単独で使用して もよぐ 2種以上を併用してもよい。  [0127] The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Acid alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated butyl, polybulal alcohol, polycarbonate, polystyrene, cellophane, polysalt-vinylidene copolymer, polyamide, polyimide, salt-vinyl Various plastic films such as butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
なお、前記支持体としては、例えば、特開平 4- 208940号公報、特開平 5— 8050 3号公報、特開平 5— 173320号公報、特開平 5— 72724号公報などに記載の支持 体を用いることちできる。  As the support, for example, the supports described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, and the like are used. I can do it.
[0128] 前記支持体の厚みとしては、特に制限はなぐ 目的に応じて適宜選択することがで さる力 ί列; tは、、 4〜300 111カ^女子ましく、 5〜175 111カ^0り女子まし1ヽ0 [0128] The thickness of the support is not particularly limited, and can be appropriately selected according to the purpose. 列 column is t, 4 to 300 111 girls, 5 to 175 111 parts 0 girl's dress 1 ヽ0
[0129] 前記支持体の形状としては、特に制限はなぐ 目的に応じて適宜選択することがで きるが、長尺状が好ましい。前記長尺状の支持体の長さとしては、特に制限はなぐ 例えば、 10m〜20, OOOmの長さのものが挙げられる。  [0129] The shape of the support is not particularly limited and can be appropriately selected according to the purpose, but is preferably long. The length of the long support is not particularly limited, and examples thereof include those having a length of 10 m to 20, OOOm.
[0130] 〔保護フィルム〕  [0130] [Protective film]
前記保護フィルムは、前記感光層の汚れや損傷を防止し、保護する機能を有する 前記保護フィルムの前記感光性フィルムにお 、て設けられる箇所としては、特に制 限はなく、 目的に応じて適宜選択することができるが、通常、前記感光層上に設けら れる。  The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged. There are no particular restrictions on the location of the protective film provided on the photosensitive film, and the protective film is appropriately selected depending on the purpose. Usually, it is provided on the photosensitive layer.
前記保護フィルムとしては、例えば、前記支持体に使用されるもの、シリコーン紙、 ポリエチレン、ポリプロピレンがラミネートされた紙、ポリオレフイン又はポリテトラフルォ ルエチレンシート、などが挙げられ、これらの中でも、ポリエチレンフィルム、ポリプロピ レンフィルムが好ましい。 Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, polypropylene, etc. Ren films are preferred.
前記保護フィルムの厚みとしては、特に制限はなぐ 目的に応じて適宜選択するこ とができる力 例えば、 5-100 μ mが好ましぐ 8〜30 μ mがより好ましい。  The thickness of the protective film is not particularly limited, and can be appropriately selected according to the purpose. For example, 5 to 100 μm is preferable, and 8 to 30 μm is more preferable.
前記保護フィルムを用いる場合、前記感光層及び前記支持体の接着力 Aと、前記 感光層及び保護フィルムの接着力 Bとが、接着力 A>接着力 Bの関係であることが好 ましい。  When the protective film is used, it is preferable that the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
前記支持体と保護フィルムとの組合せ (支持体 Z保護フィルム）としては、例えば、 ポリエチレンテレフタレート zポリプロピレン、ポリエチレンテレフタレート zポリエチレ ン、ポリ塩化ビュル Zセロファン、ポリイミド Zポリプロピレン、ポリエチレンテレフタレ ート zポリエチレンテレフタレートなどが挙げられる。また、支持体及び保護フィルム の少なくとも 、ずれかを表面処理することにより、上述のような接着力の関係を満たす ことができる。前記支持体の表面処理は、前記感光層との接着力を高めるために施 されてもよぐ例えば、下塗層の塗設、コロナ放電処理、火炎処理、紫外線照射処理 、高周波照射処理、グロ一放電照射処理、活性プラズマ照射処理、レーザ光線照射 処理などを挙げることができる。  Examples of the combination of the support and the protective film (support Z protective film) include, for example, polyethylene terephthalate z polypropylene, polyethylene terephthalate z polyethylene, polychlorinated bur Z cellophane, polyimide Z polypropylene, polyethylene terephthalate z polyethylene terephthalate. Etc. In addition, the above-described adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment, One discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like can be mentioned.
[0131] また、前記支持体と前記保護フィルムとの静摩擦係数としては、 0. 3〜1. 4が好ま しく、 0. 5〜1. 2力より好まし!/ヽ。  [0131] The coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2 force! / !.
前記静摩擦係数が、 0. 3未満であると、滑り過ぎるため、ロール状にした場合に卷 ズレが発生することがあり、 1. 4を超えると、良好なロール状に巻くことが困難となるこ とがある。  If the coefficient of static friction is less than 0.3, slipping may occur excessively, so that a deviation may occur when the roll is formed, and if it exceeds 1.4, it is difficult to wind in a good roll. Sometimes.
[0132] 前記感光性フィルムは、例えば、円筒状の卷芯に巻き取って、長尺状でロール状 に卷かれて保管されるのが好ま 、。前記長尺状の感光性フィルムの長さとしては、 特に制限はなぐ例えば、 10-20, OOOmの範囲力も適宜選択することができる。ま た、ユーザーが使いやすいようにスリット加工し、 100〜1, 000mの範囲の長尺体を ロール状にしてもよい。なお、この場合には、前記支持体が一番外側になるように卷 き取られるのが好ましい。また、前記ロール状の感光性フィルムをシート状にスリットし てもよい。保管の際、端面の保護、エッジフュージョンを防止する観点から、端面には セパレーター（特に防湿性のもの、乾燥剤入りのもの）を設置するのが好ましぐまた 梱包も透湿性の低 、素材を用いるのが好ま 、。 [0132] It is preferable that the photosensitive film is wound around a cylindrical core and wound and stored in a long roll shape. The length of the long photosensitive film is not particularly limited. For example, a range force of 10-20, OOOm can be appropriately selected. In addition, slitting may be performed to make it easy for the user to use, and a long body in the range of 100 to 1,000 m may be rolled. In this case, it is preferable that the support is scraped off so as to be the outermost side. The roll-shaped photosensitive film may be slit into a sheet shape. In order to protect the end face and prevent edge fusion during storage, it is preferable to install a separator on the end face (especially moisture-proof and with desiccant). The packaging is also low in moisture permeability and it is preferable to use materials.
[0133] 前記保護フィルムは、前記保護フィルムと前記感光層との接着性を調整するために 表面処理してもよい。前記表面処理は、例えば、前記保護フィルムの表面に、ポリオ ルガノシロキサン、弗素化ポリオレフイン、ポリフルォロエチレン、ポリビュルアルコー ル等のポリマーからなる下塗層を形成させる。該下塗層の形成は、前記ポリマーの塗 布液を前記保護フィルムの表面に塗布した後、 30〜150°C (特に 50〜120°C)で 1 〜30分間乾燥させることにより形成させることができる。 [0133] The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polybutyl alcohol is formed on the surface of the protective film. The undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C (particularly 50 to 120 ° C) for 1 to 30 minutes. Can do.
また、前記感光層、前記支持体、前記保護フィルムの他に、クッション層、酸素遮断 層 (PC層）、剥離層、接着層、光吸収層、表面保護層などの層を有してもよい。  In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included. .
前記クッション層は、常温ではタック性が無ぐ真空及び加熱条件で積層した場合 に溶融し、流動する層である。  The cushion layer is a layer that melts and flows when laminated under vacuum and heating conditions that have no tackiness at room temperature.
前記 PC層は、通常ポリビュルアルコールを主成分として形成された 0. 5〜5 /ζ πι程 度の被膜である。  The PC layer is usually a coating of about 0.5 to 5 / ζ πι, which is formed mainly of polybulal alcohol.
[0134] 本発明の感光性フィルムは、表面のタック性が小さぐラミネート性及び取扱い性が 良好で、保存安定性に優れ、高感度で現像性にも優れ、現像後に優れた耐薬品性 、表面硬度、耐熱性、誘電特性などを発現する感光性組成物が積層された感光層を 有してなる。このため、プリント配線板、カラーフィルタや柱材、リブ材、スぺーサ一、 隔壁などのディスプレイ用部材、ホログラム、マイクロマシン、プルーフなどの永久パ ターン形成用として広く用いることができ、本発明の永久パターン及びその形成方法 に好適に用いることができる。  [0134] The photosensitive film of the present invention has low surface tackiness, good laminating properties and handleability, excellent storage stability, high sensitivity and excellent developability, and excellent chemical resistance after development. It has a photosensitive layer on which a photosensitive composition exhibiting surface hardness, heat resistance, dielectric properties and the like is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for a permanent pattern and a method for forming the permanent pattern.
特に、本発明の感光性フィルムは、該フィルムの厚みが均一であるため、永久パタ ーンの形成に際し、基材への積層がより精細に行われる。  In particular, since the photosensitive film of the present invention has a uniform thickness, the film is more precisely laminated on the substrate when the permanent pattern is formed.
[0135] (永久パターン及び永久パターン形成方法） [0135] (Permanent pattern and permanent pattern forming method)
本発明の永久パターンは、本発明の永久パターン形成方法により得られる。  The permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
本発明の永久パターン形成方法は、第 1の態様として、本発明の感光性組成物を、 基材の表面に塗布し、乾燥して感光層を形成した後、露光し、現像し、加熱する。 また、本発明の永久パターン形成方法は、第 2の態様として、本発明の感光性フィ ルムを、加熱及び加圧の少なくともいずれかの下において基材の表面に積層した後 、露光し、現像し、加熱する。 In the method for forming a permanent pattern of the present invention, as a first aspect, the photosensitive composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. . Further, in the method for forming a permanent pattern of the present invention, as a second aspect, the photosensitive film of the present invention is laminated on the surface of a substrate under at least one of heating and pressurization. , Expose, develop and heat.
以下、本発明の永久パターン形成方法の説明を通じて、本発明の永久パターンの 詳細も明らかにする。  Hereinafter, the details of the permanent pattern of the present invention will be clarified through the description of the method for forming a permanent pattern of the present invention.
[0136] 〔基材〕  [Substrate]
前記基材としては、特に制限はなぐ公知の材料の中から表面平滑性の高いもの 力も凸凹のある表面を有するものまで適宜選択することができ、板状の基材 (基板)が 好ましぐ具体的には、公知のプリント配線板形成用基板 (例えば、銅張積層板)、ガ ラス板 (例えば、ソーダガラス板等）、合成樹脂性のフィルム、紙、金属板などが挙げ られるが、これらの中でも、プリント配線板形成用基板が好ましぐ多層配線基板ゃビ ルドアップ配線基板などへの半導体等の高密度実装化が可能となる点で、該プリント 配線板形成用基板が配線形成済みであるのが特に好ましい。  The base material can be appropriately selected from publicly known materials that are not particularly limited to those having a high surface smoothness and a surface having an uneven surface, and a plate-like base material (substrate) is preferred. Specific examples include known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, and the like. Among these, the printed wiring board forming substrate has already been formed in terms of the fact that high-density mounting of semiconductors and the like can be performed on a multilayer wiring substrate that is preferred for the printed wiring board forming substrate. Is particularly preferred.
[0137] 前記基材は、前記第 1の態様として、該基材上に前記感光性組成物による感光層 が形成されてなる積層体、又は前記第 2の態様として、前記感光性フィルムにおける 感光層が重なるようにして積層されてなる積層体を形成して用いることができる。即ち 、前記積層体における前記感光層に対して後述する露光することにより、露光した領 域を硬化させ、後述する現像により永久パターンを形成することができる。  [0137] The substrate is a laminate in which a photosensitive layer made of the photosensitive composition is formed on the substrate as the first aspect, or the photosensitive film in the photosensitive film as the second aspect. It is possible to form and use a laminated body in which the layers are laminated so as to overlap each other. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed area can be cured, and a permanent pattern can be formed by development to be described later.
[0138] —積層体—  [0138] —Laminate—
前記第 1の態様の積層体の形成方法としては、特に制限はなぐ目的に応じて適宜 選択することができるが、前記基材上に、前記感光性組成物を塗布及び乾燥して形 成した感光層を積層するのが好ましい。  The method for forming the laminate of the first aspect can be appropriately selected according to the purpose without any particular limitation, and is formed by applying and drying the photosensitive composition on the substrate. It is preferable to laminate a photosensitive layer.
前記塗布及び乾燥の方法としては、特に制限はなぐ目的に応じて適宜選択するこ とができ、例えば、前記感光性フィルムにおける感光層を形成する際に行われる、前 記感光性組成物溶液の塗布及び乾燥と同様な方法で行うことができ、例えば、該感 光性組成物溶液をスピンコーター、スリットスピンコーター、ロールコーター、ダイコー ター、カーテンコーターなどを用いて塗布する方法が挙げられる。  The method for coating and drying can be appropriately selected according to the purpose without particular limitation. For example, the method for forming the photosensitive composition solution in the photosensitive film, which is performed when forming the photosensitive layer in the photosensitive film. For example, a method of applying the photosensitive composition solution by using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be used.
[0139] 前記第 2の態様の積層体の形成方法としては、特に制限はなぐ目的に応じて適宜 選択することができる力 前記基材上に前記感光性フィルムを加熱及び加圧の少な くともいずれかを行いながら積層するのが好ましい。なお、前記感光性フィルムが前 記保護フィルムを有する場合には、該保護フィルムを剥離し、前記基材に前記感光 層が重なるようにして積層するのが好まし 、。 [0139] The method for forming the laminate of the second aspect is a force that can be appropriately selected depending on the purpose without any particular limitation. The photosensitive film is heated and pressed on the base material at least. It is preferable to perform the lamination while performing either one. The photosensitive film is the front In the case where the protective film is provided, it is preferable that the protective film is peeled off and laminated so that the photosensitive layer overlaps the substrate.
前記加熱温度としては、特に制限はなぐ目的に応じて適宜選択することができる 力 例えば、 70〜130°Cが好ましぐ 80〜110°Cがより好ましい。  The heating temperature can be appropriately selected according to the purpose for which there is no particular limitation. For example, 70 to 130 ° C is preferable, and 80 to 110 ° C is more preferable.
前記加圧の圧力としては、特に制限はなぐ目的に応じて適宜選択することができ る力 ί列; tは、、 0. 01〜： L OMPa力好ましく、 0. 05〜： L OMPa力 ^より好まし!/ヽ。  The pressure of the pressurization is a force that can be appropriately selected according to the purpose for which there is no particular restriction. Ί column; t is preferably 0.01 to: L OMPa force, 0.05 to L: L OMPa force ^ More preferred! / ヽ.
[0140] 前記加熱及び加圧の少なくともいずれかを行う装置としては、特に制限はなぐ目 的に応じて適宜選択することができ、例えば、ヒートプレス、ヒートロールラミネーター（ 例えば、大成ラミネータネ土製、 VP— 11)、真空ラミネーター (例えば、名機製作所製、 MVLP500)などが好適に挙げられる。  [0140] The apparatus for performing at least one of the heating and pressurization can be appropriately selected according to the purpose of restriction, and for example, a heat press, a heat roll laminator (for example, Taisei Laminate Earthen, VP 11), a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho) and the like are preferable.
[0141] 〔露光工程〕  [0141] [Exposure process]
前記露光工程は、前記感光層に対し、露光を行う工程である。  The exposure step is a step of exposing the photosensitive layer.
[0142] 前記露光の対象としては、感光層を有する材料である限り、特に制限はなぐ目的 に応じて適宜選択することができる力 例えば、基材上に前記感光性組成物又は前 記感光性フィルムが形成されてなる前記積層体に対して行われることが好ましい。  [0142] As long as the subject of the exposure is a material having a photosensitive layer, a force that can be appropriately selected according to the purpose without any particular limitation. It is preferable to be performed on the laminate formed with a film.
[0143] 前記積層体への露光としては、特に制限はなぐ目的に応じて適宜選択することが でき、例えば、前記支持体、クッション層及び PC層を介して前記感光層を露光しても よぐ前記支持体を剥離した後、前記クッション層及び PC層を介して前記感光層を 露光してもよぐ前記支持体及びクッション層を剥離した後、前記 PC層を介して前記 感光層を露光してもよぐ前記支持体、クッション層及び PC層を剥離した後、前記感 光層を露光してもよい。  [0143] The exposure of the laminate can be appropriately selected depending on the purpose without any particular limitation. For example, the photosensitive layer may be exposed through the support, the cushion layer, and the PC layer. After peeling off the support, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling off the support and cushion layer, the photosensitive layer is exposed through the PC layer. The photosensitive layer may be exposed after the support, cushion layer and PC layer are peeled off.
[0144] 前記露光としては、特に制限はなぐ目的に応じて適宜選択することができ、デジタ ル露光、アナログ露光等が挙げられる力 これらの中でもデジタル露光が好ましい。  [0144] The exposure can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
[0145] 前記デジタル露光としては、特に制限はなぐ目的に応じて適宜選択することがで きるが、例えば、形成するパターン形成情報に基づいて制御信号を生成し、該制御 信号に応じて変調させた光を用いて行うのが好ま 、。 [0145] The digital exposure can be appropriately selected according to the purpose without any particular limitation. For example, a control signal is generated based on pattern formation information to be formed, and is modulated according to the control signal. I prefer to use light.
[0146] 前記デジタル露光の手段としては、特に制限はなぐ目的に応じて適宜選択するこ とができ、例えば、光を照射する光照射手段、形成するパターン情報に基づいて該 光照射手段から照射される光を変調させる光変調手段などが挙げられる。 [0146] The digital exposure means can be appropriately selected according to the purpose without any particular restriction. For example, the light exposure means for irradiating light and the pattern information to be formed Examples include light modulating means for modulating light emitted from the light irradiating means.
[0147] <光変調手段 >  [0147] <Light modulation means>
前記光変調手段としては、光を変調することができる限り、特に制限はなぐ目的に 応じて適宜選択することができる力 例えば、 n個の描素部を有するのが好ましい。 前記 n個の描素部を有する光変調手段としては、特に制限はなぐ目的に応じて適 宜選択することができるが、例えば、空間光変調素子が好ましい。  As the light modulation means, as long as light can be modulated, it is preferable to have a force that can be appropriately selected according to the purpose without particular limitation. For example, the light modulation means preferably has n pixel portions. The light modulation means having the n picture elements can be appropriately selected according to the purpose without any particular limitation, and for example, a spatial light modulation element is preferable.
[0148] 前記空間光変調素子としては、例えば、デジタル ·マイクロミラー ·デバイス (DMD) 、 MEMS (Micro Electro Mechanical Systems)タイプの空間光変調素子（S LM ; Special Light Modulator)、電気光学効果により透過光を変調する光学素 子（PLZT素子）、液晶光シャツタ（FLC)などが挙げられ、これらの中でも DMDが好 適に挙げられる。  [0148] Examples of the spatial light modulation element include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (S LM; Special Light Modulator), and transmission by an electro-optic effect. Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
[0149] また、前記光変調手段は、形成するパターン情報に基づ!、て制御信号を生成する パターン信号生成手段を有するのが好ましい。この場合、前記光変調手段は、前記 パターン信号生成手段が生成した制御信号に応じて光を変調させる。  [0149] Further, it is preferable that the light modulation means includes pattern signal generation means for generating a control signal based on pattern information to be formed. In this case, the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
前記制御信号としては、特に制限はなぐ目的に応じて適宜選択することができ、 例えば、デジタル信号が好適に挙げられる。  The control signal can be appropriately selected according to the purpose for which there is no particular limitation. For example, a digital signal is preferably used.
[0150] 前記光変調手段の具体例としては、特開 2005— 258431号公報の〔0016〕〜〔0 047]に記載されている手段などが挙げられる。  [0150] Specific examples of the light modulation means include the means described in [0016] to [0 047] of JP-A-2005-258431.
[0151] 一光照射手段  [0151] Single light irradiation means
前記光照射手段としては、特に制限はなぐ目的に応じて適宜選択することができ 、例えば、（超)高圧水銀灯、キセノン灯、カーボンアーク灯、ハロゲンランプ、複写機 用などの蛍光管、 LED,半導体レーザ等の公知光源、又は 2以上の光を合成して照 射可能な手段が挙げられ、これらの中でも 2以上の光を合成して照射可能な手段が 好ましい。  The light irradiation means can be appropriately selected according to the purpose without any particular limitation. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, etc. fluorescent tube, LED, 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.
前記光照射手段から照射される光としては、例えば、支持体を介して光照射を行う 場合には、該支持体を透過し、かつ用いられる光重合開始剤や増感剤を活性化す る電磁波、紫外から可視光線、電子線、 X線、レーザ光などが挙げられ、これらの中 でもレーザ光が好ましぐ 2以上の光を合成したレーザ光（以下、「合波レーザ光」と称 することがある）がより好ましい。また支持体を剥離して力も光照射を行う場合でも、同 様の光を用いることができる。 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. Examples include ultraviolet to visible light, electron beams, X-rays, and laser light. Among these, laser light is preferred. Laser light that combines two or more lights (hereinafter referred to as “combined laser light”). Is more preferable). Similar light can be used even when the support is peeled off and light is irradiated with force.
[0152] 前記紫外力 可視光線の波長としては、例えば、 300-1, 500nmが好ましぐ 32 0〜800mn力より好ましく、 330ηπ！〜 650mn力 ^特に好まし!/、。  [0152] The wavelength of the ultraviolet ray visible light is preferably 300-1,500 nm, more preferably 320 0 to 800 mn force, and 330 ηπ! ~ 650mn force ^ especially preferred!
前記レーザ光の波長としては、 ί列えば、、 200〜1, 500nm力 S好ましく、 300〜800n mがより好ましぐ 330nm〜500nm力 S更に好ましく、 395nm〜415nmが特に好まし い。  The wavelength of the laser beam is preferably 200 to 1,500 nm force S, more preferably 300 to 800 nm, more preferably 330 nm to 500 nm force S, and particularly preferably 395 nm to 415 nm.
[0153] 前記合波レーザ光を照射可能な手段としては、例えば、複数のレーザと、マルチモ ード光ファイバと、該複数のレーザ力 それぞれ照射したレーザ光を集光して前記マ ルチモード光ファイバに結合させる集合光学系とを有する手段が好ま U、。  [0153] Examples of means capable of irradiating the combined laser beam include, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces to collect the multimode optical fiber. U, a means having a collective optical system coupled to U is preferred.
[0154] 前記合波レーザを照射可能な手段 (ファイバアレイ光源）としては、例えば、特開 20 05— 316431号公報の段落番号〔0130〕〜〔0177〕に記載されている手段などが挙 げられる。 また、前記露光は、前記変調させた光を、マイクロレンズアレイを通して行うのが好 ましぐ更にアパーチャアレイ、結像光学系等などを通して行ってもよい。  Examples of means (fiber array light source) that can irradiate the combined laser include means described in paragraphs [0130] to [0177] of Japanese Patent Application Laid-Open No. 2005-316431. It is done. The exposure is preferably performed through the microlens array with the modulated light, and may be performed through an aperture array, an imaging optical system, or the like.
[0156] 前記マイクロレンズアレイとしては、特に制限はなぐ目的に応じて適宜選択するこ とができる力 例えば、前記描素部における出射面の歪みによる収差を補正可能な 非球面を有するマイクロレンズを配列したものが好適に挙げられる。  [0156] The microlens array is a force that can be appropriately selected depending on the purpose without any particular limitation. For example, a microlens having an aspherical surface that can correct aberration due to distortion of the exit surface in the pixel portion. Preferred are those arranged.
[0157] 前記非球面としては、特に制限はなぐ目的に応じて適宜選択することができるが、 例えば、トーリック面が好ましい。  [0157] The aspherical surface can be appropriately selected according to the purpose without any particular limitation, and for example, a toric surface is preferable.
[0158] また、前記マイクロレンズアレイ、前記アパーチャアレイ、及び前記結像光学系等と しては、例えば、特開 2005— 258431号公報の段落番号〔0051〕〜〔0063〕、段落 番号〔0065〕、段落番号〔0070〕〜〔0073〕、及び段落番号〔0083〕〜〔0088〕に記 載されて!ヽる手段などが挙げられる。  [0158] The microlens array, the aperture array, the imaging optical system, and the like are, for example, paragraph numbers [0051] to [0063] and paragraph number [0065] of JP-A-2005-258431. ], Paragraph numbers [0070] to [0073], and means described in paragraph numbers [0083] to [0088].
[0159] <その他の光学系 >  [0159] <Other optical systems>
本発明の永久パターン形成方法では、公知の光学系の中から適宜選択したその 他の光学系と併用してもよぐ例えば、 1対の組合せレンズからなる光量分布補正光 学系などが挙げられる。 In the permanent pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems. For example, the light quantity distribution correction light comprising a pair of combination lenses Academic and so on.
前記光量分布補正光学系としては、具体的には、例えば、特開 2005— 258431 号公報の段落番号〔0090〕〜〔0105〕に記載されて 、る手段などが挙げられる  Specific examples of the light quantity distribution correcting optical system include the means described in paragraph numbers [0090] to [0105] of JP-A-2005-258431.
[0160] 〔現像工程〕 [Development process]
前記現像工程は、前記露光工程により前記感光層を露光し、該感光層の露光した 領域を硬化させた後、未硬化領域を除去することにより現像し、永久パターンを形成 する工程である。  The developing step is a step of exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region to form a permanent pattern.
[0161] 前記未硬化領域の除去方法としては、特に制限はなぐ目的に応じて適宜選択す ることができ、例えば、現像液を用いて除去する方法などが挙げられる。  [0161] The removal method of the uncured region can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include a method of removing using a developer.
[0162] 前記現像液としては、特に制限はなぐ目的に応じて適宜選択することができるが、 例えば、アルカリ金属又はアルカリ土類金属の水酸ィ匕物若しくは炭酸塩、炭酸水素 塩、アンモニア水、 4級アンモニゥム塩の水溶液等が好適に挙げられる。これらの中 でも、炭酸ナトリウム水溶液が特に好ましい。  [0162] The developer may be appropriately selected according to the purpose without any particular limitation. For example, an alkali metal or alkaline earth metal hydroxide or carbonate, bicarbonate, aqueous ammonia Preferred examples include aqueous solutions of quaternary ammonium salts. Among these, an aqueous sodium carbonate solution is particularly preferable.
[0163] 前記現像液は、界面活性剤、消泡剤、有機塩基 (例えば、ベンジルァミン、ェチレ ンジァミン、エタノールァミン、テトラメチルアンモ -ゥムハイドロキサイド、ジエチレント リアミン、トリエチレンペンタミン、モルホリン、トリエタノールアミン等)や、現像を促進さ せるため有機溶剤（例えば、アルコール類、ケトン類、エステル類、エーテル類、アミ ド類、ラタトン類等)などと併用してもよい。また、前記現像液は、水又はアルカリ水溶 液と有機溶剤を混合した水系現像液であってもよぐ有機溶剤単独であってもよい。  [0163] The developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, Triethanolamine, etc.) and organic solvents (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination to accelerate development. The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or an organic solvent alone.
[0164] 〔硬化処理工程〕  [0164] [Curing treatment process]
本発明の永久パターン形成方法は、更に、硬化処理工程として、加熱処理を含み 、更に必要に応じて全面露光処理を含む。  The permanent pattern forming method of the present invention further includes a heat treatment as a curing treatment step, and further includes an entire surface exposure treatment as necessary.
前記硬化処理工程は、前記現像工程が行われた後、形成された永久パターン〖こ おける感光層に対して硬化処理を行う工程である。  The curing treatment step is a step of performing a curing treatment on the photosensitive layer having a permanent pattern formed after the developing step.
[0165] 加熱処理  [0165] Heat treatment
前記加熱処理は、前記本発明の感光性組成物に含まれる前記一般式（1)〜（3) で表される化合物の熱架橋効果による膜硬度の充分な向上を図るために行うもので ある。前記加熱処理としては、全面加熱処理であってもよいし、パターン状に加熱処 理を行うものであってもよぐこの中でも、全面加熱処理が好ましい。 The heat treatment is performed in order to sufficiently improve the film hardness due to the thermal crosslinking effect of the compounds represented by the general formulas (1) to (3) contained in the photosensitive composition of the present invention. . The heat treatment may be a whole surface heat treatment or a pattern-like heat treatment. Of these, the entire surface heat treatment is preferable.
全面加熱処理の方法としては、前記現像工程の後に、前記永久パターンが形成さ れた前記積層体上の全面を加熱する方法が挙げられる。該全面加熱により前記一 般式（1)〜（3)で表される化合物の架橋反応が促進され、前記永久パターンの表面 の膜強度が高められる。  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 developing step. By heating the entire surface, the crosslinking reaction of the compounds represented by the general formulas (1) to (3) is promoted, and the film strength on the surface of the permanent pattern is increased.
前記全面加熱における加熱温度としては、 120〜250でカ 子ましく、 120〜200°C 力 り好ましい。該加熱温度が 120°C未満であると、前記一般式（1)〜（3)で表され る化合物による感光性組成物中の樹脂の架橋反応性が低下し、加熱処理による膜 強度の向上が得られないことがあり、 250°Cを超えると、前記感光性組成物中の榭脂 の分解が生じ、膜質が弱く脆くなることがある。  The heating temperature for the entire surface heating is 120 to 250, preferably 120 to 200 ° C. When the heating temperature is less than 120 ° C., the crosslinking reactivity of the resin in the photosensitive composition by the compounds represented by the general formulas (1) to (3) is lowered, and the film strength is improved by the heat treatment. When the temperature exceeds 250 ° C., decomposition of the resin in the photosensitive composition may occur, and the film quality may be weak and brittle.
前記全面加熱における加熱時間としては、 10〜120分が好ましぐ 15〜60分がよ り好ましい。  The heating time for the entire surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
前記全面加熱を行う装置としては、特に制限はなぐ公知の装置の中から、目的に 応じて適宜選択することができ、例えば、ドライオーブン、ホットプレート、 IRヒーター などが挙げられる。  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.
[0166] 全面露光処理 [0166] Full exposure process
前記全面露光処理の方法としては、例えば、前記現像工程の後に、前記永久バタ ーンが形成された前記積層体上の全面を露光する方法が挙げられる。該全面露光 により、前記感光層を形成する感光性組成物中の榭脂の硬化が促進され、前記永久 パターンの表面が硬化される。  Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
前記全面露光を行う装置としては、特に制限はなぐ目的に応じて適宜選択するこ とができるが、例えば、超高圧水銀灯などの UV露光機が好適に挙げられる。  The apparatus for performing the entire surface exposure can be appropriately selected according to the purpose without any particular limitation, and a UV exposure machine such as an ultrahigh pressure mercury lamp is preferably exemplified.
[0167] なお、前記基材が多層配線基板などのプリント配線板である場合には、該プリント 配線板上に本発明の永久パターンを形成し、更に、以下のように半田付けを行うこと ができる。 [0167] When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention is formed on the printed wiring board, and soldering may be further performed as follows. it can.
即ち、前記現像工程により、前記永久パターンである硬化層が形成され、前記プリ ント配線板の表面に金属層が露出される。該プリント配線板の表面に露出した金属 層の部位に対して金メッキを行った後、半田付けを行う。そして、半田付けを行った 部位に、半導体や部品などを実装する。このとき、前記硬化層による永久パターンが 、保護膜あるいは絶縁膜 (層間絶縁膜)としての機能を発揮し、外部からの衝撃や隣 同士の電極の導通が防止される。 That is, the hardened layer which is the permanent pattern is formed by the developing step, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. And soldered A semiconductor or a component is mounted on the part. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.
[0168] 本発明の永久パターン形成方法においては、保護膜、層間絶縁膜、及びソルダー レジストパターンの少なくともいずれかを形成するのが好ましい。前記永久パターン 形成方法により形成される永久パターンが、前記保護膜又は前記層間絶縁膜である と、配線を外部力もの衝撃や曲げ力も保護することができ、特に、前記層間絶縁膜で ある場合には、例えば、多層配線基板ゃビルドアップ配線基板などへの半導体部品 の高密度実装に有用である。  In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern. When the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, it is possible to protect the wiring from an impact or bending force of an external force, particularly when it is the interlayer insulating film. Is useful for high-density mounting of semiconductor components on, for example, multilayer wiring boards and build-up wiring boards.
[0169] 本発明の永久パターン形成方法は、高速でパターン形成が可能であるため、各種 ノターンの形成に広く用いることができ、特に配線パターンの形成に好適に使用する ことができる。  [0169] The permanent pattern forming method of the present invention can be widely used for forming various patterns because it can form a pattern at high speed, and can be particularly suitably used for forming a wiring pattern.
また、本発明の永久パターン形成方法により形成される永久パターンは、優れた表 面硬度、絶縁性、耐熱性などを有し、保護膜、層間絶縁膜、及びソルダーレジストパ ターンとして好適に使用することができる。  The permanent pattern formed by the method for forming a permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance, etc., and is suitably used as a protective film, an interlayer insulating film, and a solder resist pattern. be able to.
実施例  Example
[0170] 以下、本発明の実施例について説明するが、本発明は下記実施例に何ら限定され るものではない。  [0170] Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.
[0171] (実施例 1) [Example 1]
感光性組成物の調製  Preparation of photosensitive composition
下記組成に基づいて、感光性組成物を調製した。なお、分散溶媒としてメチルェチ ルケトンを用い、固形分濃度を 55質量％として調製した。分散は、ビーズミルを用い て行い、得られた分散液は、粒ゲージにより凝集が無いことを確認した。  A photosensitive composition was prepared based on the following composition. In addition, methyl ethyl ketone was used as a dispersion solvent, and the solid content concentration was adjusted to 55% by mass. Dispersion was performed using a bead mill, and the obtained dispersion was confirmed to be free from aggregation by a particle gauge.
〔感光性組成物溶液の組成〕  [Composition of photosensitive composition solution]
•硫酸バリウム (堺化学工業社製、 B30) 33. 4質量部  • Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) 33.4 parts by mass
，下記構造式 (46)で表されるバインダー 40. 0質量部  , 40.0 parts by mass of a binder represented by the following structural formula (46)
•前記構造式 (1)で表される化合物 (熱架橋剤） 15. 7質量部  • Compound represented by the structural formula (1) (thermal crosslinking agent) 15.7 parts by mass
'ジペンタエリスリトールへキサアタリレート 16. 0質量部 •IRGACURE819 (チノく'スペシャルティ一'ケミカルズ製） 5. 8質 'Dipentaerythritol hexaatalylate 16.0 parts by mass • IRGACURE819 (made by Chinoku 'Specialty One' Chemicals) 5. 8 quality
•ハイドロキノンモノメテノレエーテノレ 0. 056質量咅  • Hydroquinone Monomethenoleetenole 0.05 mass
•ジシアンジアミド 0. 77質量部  • Dicyandiamide 0.77 parts by mass
• 2MAOK 0. 47質量部  • 2MAOK 0.47 parts by weight
* 1 : 2ΜΑΟΚは、下記構造式 (47)で表される 2, 4 ジアミノー 6—〔2' メチルイミ ダゾリル—（1，）〕—ェチル—s トリァジンのイソシァヌル酸付加物（四国化成工業（ 株)製)である。  * 1: 2ΜΑΟΚ is an isocyanuric acid adduct of 2,4 diamino-6- [2 'methylimidazolyl- (1,)]-ethyl-s-triazine represented by the following structural formula (47) (Shikoku Chemicals Co., Ltd.) Made).
[0172] [化 61]  [0172] [Chemical 61]
Figure imgf000063_0001
Figure imgf000063_0001
[0173] 構造式（1)で表される化合物の合成  [0173] Synthesis of Compound Represented by Structural Formula (1)
なお、前記構造式（1)で表される化合物は、次のようにして合成した。  The compound represented by the structural formula (1) was synthesized as follows.
4 ヒドロキシベンジルアルコール 50質量部とェピクロロヒドリン 83. 7質量部とを反 応釜に入れ、 80°Cに加熱した。反応釜に 48%水酸化ナトリウム水溶液 31. 6質量部 を 3時間かけて滴下した。その後 3時間反応させた。放冷後、酢酸ェチル 100質量部 で抽出し、飽和食塩水で分液し有機相を硫酸マグネシウムで乾燥した。有機相の溶 媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸ェチル = 3Z7 )で精製し、第一中間生成物 59質量部 (収率 84%)を得た。  4 50 parts by mass of hydroxybenzyl alcohol and 83.7 parts by mass of epichlorohydrin were placed in a reaction kettle and heated to 80 ° C. To the reaction kettle, 31.6 parts by mass of 48% aqueous sodium hydroxide solution was added dropwise over 3 hours. The reaction was then continued for 3 hours. After allowing to cool, the mixture was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 3Z7) to obtain 59 parts by mass (yield 84%) of the first intermediate product.
次に、 m キシリレンジイソシァネート 4. 84質量部と、前記第一中間生成物 10質 量部と酢酸ェチル 14質量部とを反応釜に入れ、 90°Cに加熱した。反応釜にスタノク ト (吉富製薬社製)を 0. 02質量部加えた。その後、 2時間反応させた。放冷後、反応 溶液をろ過し、ろ液の溶媒を留去し、酢酸ェチルで再結晶することにより白色固体 12 . 5質量部 (収率 84%)を得た。  Next, 4.84 parts by mass of m-xylylene diisocyanate, 10 parts by mass of the first intermediate product, and 14 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 90 ° C. To the reaction kettle was added 0.02 parts by mass of stanoc (Yoshitomi Pharmaceutical Co., Ltd.). Then, it was made to react for 2 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 12.5 parts by mass (yield 84%) of a white solid.
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 7. 67 (t, 2H) , 7. 28- 7. 08 (m, 8H) , 6. 88 (d, 4H) , 4. 28 (d, 2H) , 4. 1 2 (q, 8H) , 3. 79 (q, 2H) , 2. 85— 2. 77 (m, 8H) , 2. 70 (q, 2H)であった。 また、前記構造式（1)で表される化合物の感光性組成物中の含有量は、 14質 である。 7.67 (t, 2H), 7. 28- 7. 08 (m, 8H), 6. 88 (d, 4H), 4. 28 (d, 2H), 4.1 2 (q, 8H ), 3.79 (q, 2H), 2.85— 2.77 (m, 8H), 2.70 (q, 2H). The content of the compound represented by the structural formula (1) in the photosensitive composition is 14%.
[0174] [化 62] [0174] [Chemical 62]
2MAOK
Figure imgf000064_0001
2MAOK
Figure imgf000064_0001
[0175] 感光性フィルムの製造  [0175] Production of photosensitive film
得られた感光性組成物を、前記支持体としての厚み 20 mの PET (ポリエチレンテ レフタレート）フィルム上に、塗布し、乾燥させて、膜厚 30 /z mの感光層を形成した。 次いで、該感光層の上に、前記保護フィルムとして 12 μ m厚のポリプロピレンフィル ムをラミネートで積層し、感光性フィルムを製造した。  The obtained photosensitive composition was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 m as the support and dried to form a photosensitive layer having a thickness of 30 / z m. Next, a 12 μm-thick polypropylene film was laminated as a protective film on the photosensitive layer to produce a photosensitive film.
[0176] 永久パターンの形成  [0176] Formation of permanent pattern
積層体の調製  Preparation of laminate
次に、前記基材として、配線形成済みの銅張積層板 (スルーホールなし、銅厚み 1 2 /z m)の表面に化学研磨処理を施して調製した。該銅張積層板上に、前記感光性 フィルムの感光層が前記銅張積層板に接するようにして前記感光性フィルムにおけ る保護フィルムを剥がしながら、真空ラミネーター（二チゴーモートン (株)社製、 VP1 30)を用いて積層させ、前記銅張積層板と、前記感光層と、前記ポリエチレンテレフ タレートフィルム (支持体)とがこの順に積層された積層体を調製した。  Next, the substrate was prepared by subjecting a surface of a copper-clad laminate (no through-hole, copper thickness 1 2 / z m) on which wiring had been formed, to a chemical polishing treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd.) was peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate VP1 30) to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
圧着条件は、真空引きの時間 40秒間、圧着温度 70°C、圧着圧力 0. 2MPa、加圧 時間 10秒間とした。  The pressure bonding conditions were as follows: vacuuming time 40 seconds, pressure bonding temperature 70 ° C, pressure bonding pressure 0.2 MPa, pressurization time 10 seconds.
[0177] <タック性の評価 >  [0177] <Evaluation of tackiness>
前述のようにして得られた積層体における感光層の表面のタック性について、下記 基準に基づ 、て評価した。前記実施例 1の感光性フィルムにおける保護フィルムを剥 がした時点では、前記感光層の表面に強いタック性がなぐ剥離自体も容易に行うこ とができた。結果を表 3に示す。  The tackiness of the surface of the photosensitive layer in the laminate obtained as described above was evaluated based on the following criteria. When the protective film on the photosensitive film of Example 1 was peeled off, the peeling itself without strong tackiness on the surface of the photosensitive layer could be easily performed. The results are shown in Table 3.
〔評価基準〕 〇：感光層の表面に強いタック性が認められな力つた 〔Evaluation criteria〕 ○: Strong tackiness was not recognized on the surface of the photosensitive layer.
△：感光層の表面にややタック性が認められた  Δ: Slight tackiness was observed on the surface of the photosensitive layer
X：感光層の表面に強いタック性が認められた  X: Strong tackiness was recognized on the surface of the photosensitive layer
[0178] 露光工程 [0178] Exposure process
前記調製した積層体における感光層に対し、ポリエチレンテレフタレートフィルム（ 支持体)側から、レーザ露光装置を用いて、 405nmのレーザ光を、直径の異なる穴 部が形成されるパターンが得られるように照射して露光し、前記感光層の一部の領 域を硬化させた。  Using a laser exposure device, 405 nm laser light is irradiated from the polyethylene terephthalate film (support) side so that a pattern in which holes having different diameters are formed is applied to the photosensitive layer in the prepared laminate. Then, a portion of the photosensitive layer was cured.
[0179] 現像工程 [0179] Development process
室温にて 10分間静置した後、前記積層体力もポリエチレンテレフタレートフィルム（ 支持体)を剥がし取り、銅張積層板上の感光層の全面に、アルカリ現像液として、 1質 量％炭酸ソーダ水溶液を用い、スプレー圧 0. 2MPa、 30°Cにて 60秒間シャワー現 像し、未硬化の領域を溶解除去した。その後、水洗し、乾燥させ、永久パターンを形 成した。  After standing at room temperature for 10 minutes, the laminate strength was also peeled off from the polyethylene terephthalate film (support), and a 1% by weight sodium carbonate aqueous solution was added as an alkaline developer to the entire surface of the photosensitive layer on the copper clad laminate. Using a spray pressure of 0.2 MPa at 30 ° C. for 60 seconds, the uncured area was dissolved and removed. Thereafter, it was washed with water and dried to form a permanent pattern.
[0180] 硬化処理工程  [0180] Curing process
前記永久パターンが形成された積層体の全面に対して、 160°Cで 60分間、加熱処 理を施し、永久パターンの表面を硬化し、膜強度を高めた。該永久パターンを目視 で観察したところ、永久パターンの表面に気泡は認められな力つた。  The entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 60 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.
[0181] 前記製造した感光性フィルムについて、露光感度、解像度、露光速度、及び保存 安定性の評価を行い、前記形成した永久パターンについて鉛筆硬度、及び誘電特 性の評価を行った。結果を表 3に示す。  [0181] The photosensitive film produced was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 3.
[0182] <露光感度 >  [0182] <Exposure sensitivity>
得られた前記永久パターンにお 、て、残った前記感光層の硬化領域の厚みを測定 した。次いで、レーザ光の照射量と、硬化層の厚さとの関係をプロットして感度曲線を 得る。こうして得た感度曲線力 配線上の硬化領域の厚さが 15 mとなり、硬化領域 の表面が光沢面である時の光エネルギー量を、感光層を硬化させるために必要な光 エネルギー量とした。  In the obtained permanent pattern, the thickness of the cured area of the remaining photosensitive layer was measured. Subsequently, a sensitivity curve is obtained by plotting the relationship between the irradiation amount of the laser beam and the thickness of the cured layer. Sensitivity curve force obtained in this way The thickness of the cured area on the wiring was 15 m, and the amount of light energy when the surface of the cured area was a glossy surface was the amount of light energy required to cure the photosensitive layer.
その結果、前記感光層を硬化させるために必要な光エネルギー量は、 30mjZcm2 であった。 As a result, the amount of light energy required to cure the photosensitive layer is 30 mjZcm 2 Met.
[0183] <解像度 >  [0183] <Resolution>
得られた前記永久パターン形成済みのプリント配線基板の表面を光学顕微鏡で観 察し、硬化層パターンの穴部に残膜が無い、最小の穴径を測定し、これを解像度とし た。該解像度は数値が小さいほど良好である。その結果、解像度は、 70 mであつ た。  The surface of the obtained printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. The smaller the numerical value, the better the resolution. As a result, the resolution was 70 m.
[0184] <露光速度 >  [0184] <Exposure speed>
405nmレーザ露光装置を用いて、露光光と前記感光層とを相対的に移動させる速 度を変更し、永久パターンが形成される速度を求めた。露光は、前記調製した積層 体における感光層に対して、ポリエチレンテレフタレートフィルム（支持体)側から行つ た。なお、この設定速度が速い方が効率的な永久パターン形成が可能となる。なお、 前記 405nmレーザ露光装置は、前記 DMDからなる光変調手段を有し、露光速度 は、 ldmm/ secで toつた。  Using a 405 nm laser exposure apparatus, the speed at which the exposure light and the photosensitive layer were moved relative to each other was changed, and the speed at which the permanent pattern was formed was determined. The exposure was performed from the polyethylene terephthalate film (support) side to the photosensitive layer in the prepared laminate. It should be noted that an efficient permanent pattern can be formed when the set speed is high. The 405 nm laser exposure apparatus has a light modulation means composed of the DMD, and the exposure speed is to ldmm / sec.
[0185] <保存安定性 > [0185] <Storage stability>
前記製造した感光性フィルムを 40°Cで 3日間の強制経時後、未露光膜の現像時間 を測定した。  The produced photosensitive film was subjected to forced aging for 3 days at 40 ° C., and then the development time of the unexposed film was measured.
[0186] <鉛筆硬度 > [0186] <Pencil hardness>
前記永久パターン形成済みのプリント配線基板に対して、常法に従 、金メッキを行 つた後、水溶性フラックス処理を行った。次いで、 260°Cに設定された半田槽に 5秒 間にわたって、 3回浸漬し、フラックスを水洗で除去した。そして、該フラックス除去後 の永久パターンについて、 JIS K— 5400に基づいて、鉛筆硬度を測定した。  The printed wiring board on which the permanent pattern had been formed was plated with gold according to a conventional method, and then a water-soluble flux treatment was performed. Next, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JIS K-5400.
その結果、鉛筆硬度は 5Hであった。また、 目視観察を行ったところ、前記永久バタ ーンにおける硬化膜の剥がれ、ふくれ、変色は認められな力つた。  As a result, the pencil hardness was 5H. Further, when visually observed, the cured film in the permanent pattern peeled, blistered, and discolored.
[0187] <誘電特性の測定 > [0187] <Measurement of dielectric properties>
膜厚 500 mの硬化膜の誘電特性を、アジデント'テクノロジ一社製 LCRメーターと 4291A型固体電極を用いて 25°Cで測定した結果、 1GHzでの誘電率は 3. 3であり 、誘電正接は 0. 013であった。  The dielectric properties of a 500 m thick cured film were measured at 25 ° C using an LCR meter manufactured by Agilent Technologies and a 4291A type solid electrode. The dielectric constant at 1 GHz was 3.3. Was 0.013.
[0188] (実施例 2) 下記組成に基づいて、感光性組成物を調製し、実施例 1と同様にして感光性フィル ム及び積層体を調製し、永久パターンを形成した。 [0188] (Example 2) A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性組成物及び感光性フィルムにつ ヽ て、タック性、露光感度、解像度、露光速度、及び保存安定性の評価を行い、前記形 成した永久パターンについて鉛筆硬度、及び誘電特性の評価を行った。その結果、 露光感度は 30mjZcm2、解像度は 70 m、露光速度は 13mjZcm2であった。その 他の結果を表 3に示す。 In addition, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent film was formed. The pattern was evaluated for pencil hardness and dielectric properties. As a result, the exposure sensitivity was 30 mjZcm 2 , the resolution was 70 m, and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
〔感光性組成物溶液の組成〕 [Composition of photosensitive composition solution]
•硫酸バリウム 33. 4質量部  • Barium sulfate 33.4 parts by mass
'スチレン Z無水マレイン酸 Zブチルアタリレート共重合体（モル比 40Z32Z28) とベンジルァミン (該共重合体の無水物基に対して 1. 0当量）との付加反応物 *2 'Addition reaction product of styrene Z maleic anhydride Z butyl acrylate copolymer (molar ratio 40Z32Z28) and benzylamine (1.0 equivalent to the anhydride group of the copolymer) * 2
40. 0質量部  40.0 parts by mass
•前記構造式 (1)で表される化合物 (熱架橋剤） 15. 7質量部  • Compound represented by the structural formula (1) (thermal crosslinking agent) 15.7 parts by mass
'ジペンタエリスリトールへキサアタリレート 16. 0質量部  'Dipentaerythritol hexaatalylate 16.0 parts by mass
• IRGACURE819 (チノく'スペシャルティ一'ケミカルズ製） 5. 8質量部  • IRGACURE819 (manufactured by Chinoku 'Specialty One' Chemicals) 5. 8 parts by mass
•ノヽイドロキノンモノメチルエーテル 0. 056質量部  • Neuroquinone monomethyl ether 0.056 parts by mass
'ジシアンジアミド 0. 77質量部 'Dicyandiamide 0.77 parts by mass
•2MAOK 0. 47質量部 • 2 MAOK 0.47 parts by mass
* 2：下記構造式 (VII)で表されるユニット A及びユニット Bを有するマレアミド酸系 共重合体である。該ユニット Aは 2種の構成単位カゝらなり、その内の一の構成単位に おける R1はフエ-ルであり、他の構成単位における R1はブチルォキシカルボ-ル、 R 3及び R4は水素原子である。上記ユニット Bにおける R2はべンジルである。上記ュ-ッ ト Aにおける繰り返し単位のモル分率 Xは、前記一の構成単位につ!/、ては 40モル0 /0 であり、前記他の構成単位については 28モル％であり、上記ユニット Bにおける繰り 返し単位のモル分率 yは 32モル％である。また、前記スチレン Z無水マレイン酸 Zブ チルアタリレート共重合体の無水物基に対する前記ベンジルァミンの反応量は 1. 0 当量である。 * 2: A maleamic acid copolymer having units A and B represented by the following structural formula (VII). The unit A consists of two types of structural units, in which one of the structural units R 1 is a fail, and in the other structural unit R 1 is a butoxycarbon, R 3 and R 4 is a hydrogen atom. R 2 in unit B is benzyl. The Interview - mole fraction X of recurring units of Tsu DOO A is the one constituent unit Nitsu /, Te is 40 mole 0/0 is 28 mol% for the other structural units, the The mole fraction y of repeating units in unit B is 32 mol%. In addition, the reaction amount of the benzylamine with respect to the anhydride group of the styrene Z maleic anhydride Z butyl acrylate copolymer is 1.0 equivalent.
上記ビュル単量体であるブチルアタリレートのホモポリマーのガラス転移温度 (Tg) は、 54°Cである, Glass transition temperature (Tg) of homopolymer of butyl acrylate which is the above bull monomer Is 54 ° C,
[化 63]  [Chemical 63]
構造式 (V I I ) Structural formula (V I I)
Figure imgf000068_0001
Figure imgf000068_0001
A B  A B
実施例 2における、前記構造式（1)で表されるエポキシ榭脂化合物の感光性組成 物中の含有量は 14質量％である。  In Example 2, the content of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 14% by mass.
[0189] (実施例 3) [0189] (Example 3)
実施例 1にお 、て、感光性組成物中の前記構造式（1)で表されるエポキシ榭脂ィ匕 合物の添加量を 0. 8質量部とし、構造式（1)で表されるエポキシ榭脂化合物の感光 性組成物中の含有量を 0. 8質量％(1質量％未満)としたこと以外は、実施例 1と同 様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体 を調製し、永久パターンを形成した。  In Example 1, the addition amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 0.8 parts by mass, and the structural formula (1) is used. A photosensitive composition was prepared in the same manner as in Example 1 except that the content of the epoxy resin compound in the photosensitive composition was 0.8% by mass (less than 1% by mass). A photosensitive film and a laminate were prepared in the same manner as in 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。その結果、露光感度は 30mJ 解像度は 70 /ζ πι、露光速度は 13mjZcm2であった。その他の結果を表 3に 示す。 In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ζ πι, and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
[0190] (実施例 4) [0190] (Example 4)
実施例 1にお 、て、感光性組成物中の前記構造式（1)で表されるエポキシ榭脂ィ匕 合物の添加量を 100質量部とし、構造式（1)で表されるエポキシ榭脂化合物の感光 性組成物中の含有量を 51質量％ (50質量％超)としたこと以外は、実施例 1と同様 にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体を 調製し、永久パターンを形成した。 In Example 1, the amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 100 parts by mass, and the epoxy represented by the structural formula (1) is used. A photosensitive composition was prepared in the same manner as in Example 1 except that the content of the resin compound in the photosensitive composition was 51% by mass (over 50% by mass). Photosensitive film and laminate Prepared and formed a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。その結果、露光感度は 30mJ 解像度は 70 /ζ πι、露光速度は 13mjZcm2であった。その他の結果を表 3に 示す。 In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ζ πι, and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
[0191] (実施例 5〜13)  [0191] (Examples 5 to 13)
実施例 1において、感光性組成物中の前記構造式（1)で表される化合物を、表 3に 示すような前記構造式 (2)〜（10)で表される化合物に変えたこと以外は、実施例 1と 同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層 体を調製し、永久パターンを形成した。  In Example 1, the compound represented by the structural formula (1) in the photosensitive composition was changed to the compounds represented by the structural formulas (2) to (10) as shown in Table 3. Prepared a photosensitive composition in the same manner as in Example 1, prepared a photosensitive film and laminate in the same manner as in Example 1, and formed a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。その結果、実施例 5〜13では 、いずれも露光感度は 30mjZcm2、解像度は 70 /ζ πι、露光速度は 13mjZcm2で あった。各実施例の、その他の結果を表 3に示す。 In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, in Examples 5 to 13, the exposure sensitivity was 30 mjZcm 2 , the resolution was 70 / ζ πι, and the exposure speed was 13 mjZcm 2 . The other results of each example are shown in Table 3.
なお、前記構造式 (2)〜（10)で表される化合物 (熱架橋剤）は、下記のようにして 合成した。  The compounds represented by the structural formulas (2) to (10) (thermal crosslinking agents) were synthesized as follows.
[0192] 構造式（2)で表される化合物の合成  [0192] Synthesis of Compound Represented by Structural Formula (2)
前記実施例 1で得た第一中間生成物 10. 9質量部とへキサメチレンジイソシァネー ト 4. 71質量部と酢酸ェチル 14質量部とを反応釜に入れ、 90°Cに加熱した。反応釜 にスタノタト (吉富製薬社製)を 0. 02質量部加えた。その後、 2時間反応させた。放冷 後、反応溶液をろ過し、ろ液の溶媒を留去し、酢酸ェチルで再結晶することにより白 色固体 13. 2質量部 (収率 85%)を得た。  First intermediate product obtained in Example 1 10.9 parts by mass and hexamethylene diisocyanate 4.71 parts by mass and 14 parts by mass of ethyl acetate were put in a reaction kettle and heated to 90 ° C. . Stanotat (Yoshitomi Pharmaceutical Co., Ltd.) 0.02 parts by mass was added to the reaction kettle. Then, it was made to react for 2 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 13.2 parts by weight of white solid (yield 85%).
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 7. 13 (d, 4H) , 6. 86 (d, 4H) , 4. 69 (br, 2H) , 4. 25—4. 17 (m, 6H) , 3. 94 (q, 2H) , 3. 37— 3. 33 (m, 2H) , 3. 14 (d, 4H) , 2. 75 (q, 2H) , 1. 47 (m, 4H) , 1. 31 (m, 4H)であった。 [0193] 構造式（3)で表される化合物の合成 7.13 (d, 4H), 6.86 (d, 4H), 4.69 (br, 2H), 4.25—4.17 (m, 6H), 3.94 (q, 2H) , 3.37—3.33 (m, 2H), 3.14 (d, 4H), 2.75 (q, 2H), 1.47 (m, 4H), 1.31 (m, 4H) there were. [0193] Synthesis of Compound Represented by Structural Formula (3)
トリレンジイソシァネート 20質量部と 3 メチル 3ブテン 1 オール 21. 8質量部 と酢酸ェチル 80質量部とを反応釜に入れ、 55°Cに加熱した。該反応釜に、スタノタト (吉富製薬社製) 0. 05質量部加えた。その後 6時間反応させた。放冷後、該反応物 力 溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸ェチル = 7/3)で精製し中間生成物 32質量部 (収率 80%)を得た。  20 parts by mass of tolylene diisocyanate, 21.8 parts by mass of 3 methyl 3-butene 1 ol and 80 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 55 ° C. To the reaction kettle, 0.05 mass parts of stanotat (Yoshitomi Pharmaceutical Co., Ltd.) was added. The reaction was then continued for 6 hours. After allowing to cool, the reaction mixture was evaporated, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 7/3) to obtain 32 parts by mass of an intermediate product (yield 80%).
次に、前記中間生成物 28質量部と酢酸ェチル 250質量部と炭酸水素ナトリウム 68 質量部と水 200質量部とアセトン 98質量部とを反応釜に入れた。該反応釜に、 OXO NE115質量部を水 400質量部に溶解させた水溶液を 1時間かけて滴下した。その 後 7時間反応させた。該反応釜に、 10%チォ硫酸ナトリウム水溶液を 300質量部加 え 1時間撹拌し、飽和食塩水で分液し有機相を硫酸マグネシウムで乾燥した。該有 機相の溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸ェチ ル =6Z4)で精製し、油状物質 19. 5質量部（収率 64%)を得た。  Next, 28 parts by mass of the intermediate product, 250 parts by mass of ethyl acetate, 68 parts by mass of sodium hydrogen carbonate, 200 parts by mass of water and 98 parts by mass of acetone were placed in a reaction kettle. An aqueous solution prepared by dissolving 115 parts by mass of OXO NE in 400 parts by mass of water was dropped into the reaction kettle over 1 hour. The reaction was then continued for 7 hours. To the reaction kettle, 300 parts by mass of 10% aqueous sodium thiosulfate solution was added and stirred for 1 hour, followed by separation with saturated brine and drying of the organic phase over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 6Z4) to obtain 19.5 parts by mass (yield 64%) of an oily substance.
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 7. 79 (s, 1H) , 7. 22 (d, IH) , 7. 09 (d, IH) , 6. 68 (s, IH) , 6. 41 (s, IH ) , 4. 37-4. 02 (m, 4H) , 2. 63 (d, 4H) , 2. 20 (s, 3H) , 2. 03— 1. 86 (m, 4 H) , 1. 39 (s, 6H)であった。  7.79 (s, 1H), 7.22 (d, IH), 7.09 (d, IH), 6.68 (s, IH), 6.41 (s, IH), 4.37 -4. 02 (m, 4H), 2. 63 (d, 4H), 2. 20 (s, 3H), 2. 03— 1.86 (m, 4 H), 1. 39 (s, 6H) Met.
[0194] 構造式 (4)で表される化合物の合成 [0194] Synthesis of Compound Represented by Structural Formula (4)
前記実施例 1で得た第一中間生成物 7. 56質量部とメチレンビスフエ-ルイソシァ ネート 4. 87質量部と酢酸ェチル 12質量部とを反応釜に入れ、 90°Cに加熱した。反 応釜にスタノタト (吉富製薬社製)を 0. 02質量部加えた。その後、 2時間反応させた。 放冷後、反応溶液をろ過し、ろ液の溶媒を留去し、酢酸ェチルで再結晶することによ り白色固体 9. 6質量部（収率 77%)を得た。  7.56 parts by mass of the first intermediate product obtained in Example 1 above, 4.87 parts by mass of methylene bisphenol isocyanate, and 12 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 90 ° C. Stanotat (Yoshitomi Pharmaceutical Co., Ltd.) 0.02 part by mass was added to the reaction kettle. Then, it was made to react for 2 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 9.6 parts by mass of white solid (yield 77%).
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 9. 50 (s, 2H) , 7. 34 (d, 4H) , 7. 20 (d, 4H) , 7. 08 (d, 4H) , 6. 90 (d, 4H ) , 4. 30—4. 21 (m, 4H) , 3. 84 (q, 4H) , 3. 32 (s, 2H) , 2. 89— 2. 82 (m, 4 H) , 2. 70 (t, 2H) , 2. 50 (s, 4H)であった。  9.50 (s, 2H), 7.34 (d, 4H), 7.20 (d, 4H), 7.08 (d, 4H), 6.90 (d, 4H), 4.30 —4. 21 (m, 4H), 3. 84 (q, 4H), 3. 32 (s, 2H), 2. 89— 2. 82 (m, 4 H), 2. 70 (t, 2H) 2.50 (s, 4H).
[0195] 構造式（5)で表される化合物の合成 前記実施例 1で得た第一中間生成物 7. 56質量部と 1, 3 ビス（1 イソシァネート 1ーメチルェチル）ベンゼン 5. 66質量部と酢酸ェチル 15質量部とを反応釜に入 れ、 90°Cに加熱した。反応釜にスタノタト (吉富製薬社製)を 0. 02質量部加えた。そ の後、 2時間反応させた。放冷後、酢酸ェチル 50質量部で抽出し、飽和食塩水で分 液し、有機相を硫酸マグネシウムで乾燥した。有機相の溶媒を留去し、シリカゲルクロ マトグラフィー（展開溶媒:へキサン Z酢酸ェチル =5Z5)で精製し、化合物 5. 4質 量部 (収率 37%)を得た。 [0195] Synthesis of Compound Represented by Structural Formula (5) First intermediate product obtained in Example 1 7.56 parts by mass, 1,3 bis (1 isocyanate 1-methylethyl) benzene 5.66 parts by mass and ethyl acetate 15 parts by mass were placed in a reaction kettle at 90 ° Heated to C. Stanotat (Yoshitomi Pharmaceutical Co., Ltd.) 0.02 parts by mass was added to the reaction kettle. Then, it was made to react for 2 hours. After allowing to cool, the mixture was extracted with 50 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 5Z5) to obtain 5.4 parts by mass of compound (yield 37%).
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 7. 47 (s, 2H) , 7. 29 (s, 4H) , 7. 12 (s, 2H) , 6. 86 (d, 4H) , 5. 06 (s, 2H ) , 4. 22-4. 16 (m, 6H) , 3. 94 (q, 2H) , 3. 34 (m, 2H) , 2. 92— 2. 74 (m, 4 H) , 1. 71 (s, 12H)であった。  7.47 (s, 2H), 7.29 (s, 4H), 7.12 (s, 2H), 6.86 (d, 4H), 5.06 (s, 2H), 4.22 -4. 16 (m, 6H), 3.94 (q, 2H), 3.34 (m, 2H), 2.92— 2.74 (m, 4 H), 1.71 (s, 12H) Met.
[0196] 構造式 (6)で表される化合物の合成 [0196] Synthesis of Compound Represented by Structural Formula (6)
トリレンジイソシァネート 20質量部と 2—メチルー 2 プロペン 1 オール 16. 1質 量部と酢酸ェチル 80質量部とを反応釜に入れ、 55°Cに加熱した。該反応釜に、スタ ノクト (吉富製薬社製) 0. 05質量部加えた。その後 6時間反応させた。放冷後反応溶 液をろ過した。該ろ液の溶媒を留去し、へキサン Z酢酸ェチル = 1Z1溶液で再結晶 することにより中間生成物 21質量部（収率 60%)を得た。  20 parts by mass of tolylene diisocyanate, 2-methyl-2-propene 1-ol 16.1 parts by mass and 80 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 55 ° C. To the reaction kettle, 0.05 part by mass of stanoct (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added. The reaction was then continued for 6 hours. After standing to cool, the reaction solution was filtered. The solvent of the filtrate was distilled off, and recrystallization was performed with a hexane Z ethyl acetate = 1Z1 solution to obtain 21 parts by mass of an intermediate product (yield 60%).
次に、前記中間生成物 20質量部と酢酸ェチル 200質量部と炭酸水素ナトリウム 51 質量部と水 200質量部とアセトン 73質量部とを反応釜に入れた。該反応釜に、 OXO NE90質量部を水 400質量部に溶解させた水溶液を 1時間かけて滴下した。その後 7時間反応させた。該反応釜に、 10%チォ硫酸ナトリウム水溶液を 300質量部加え 1 時間撹拌し、飽和食塩水で分液し有機相を硫酸マグネシウムで乾燥した。該有機相 の溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸ェチル = 3/7)で精製し、白色固体 15質量部 (収率 68%)を得た。  Next, 20 parts by mass of the intermediate product, 200 parts by mass of ethyl acetate, 51 parts by mass of sodium hydrogen carbonate, 200 parts by mass of water, and 73 parts by mass of acetone were placed in a reaction kettle. An aqueous solution prepared by dissolving 90 parts by mass of OXO NE in 400 parts by mass of water was dropped into the reaction kettle over 1 hour. The reaction was then continued for 7 hours. To the reaction kettle, 300 parts by mass of a 10% aqueous sodium thiosulfate solution was added, stirred for 1 hour, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 3/7) to obtain 15 parts by mass (yield 68%) of a white solid.
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 7. 34- 7. 19 (m, 4H) , 5. 46 (s, 2H) , 4. 38 (d, 4H) , 4. 30 (d, 2H) , 4. 0 0 (d, 2H) , 2. 78 (d, 2H) , 2. 66 (d, 2H) , 1. 38 (s, 6H)であった。  7.34- 7.19 (m, 4H), 5.46 (s, 2H), 4.38 (d, 4H), 4.30 (d, 2H), 4.00 (d, 2H ), 2.78 (d, 2H), 2.66 (d, 2H), 1.38 (s, 6H).
[0197] 構造式（7)で表される化合物の合成 4ーヒドロキシベンジルアルコール 30質量部と炭酸カリウム 37質量部とジメチルァ セトアミド 100質量部とを反応釜に入れ、 80°Cに加熱した。該反応釜に、 3 クロ口— 2—メチルー 1 プロペン 23. 6質量部を 0. 5時間かけて滴下した。その後 10時間反 応させた。放冷後、該反応物を酢酸ェチル 100質量部で抽出し、飽和食塩水で分液 し有機相を硫酸マグネシウムで乾燥した。該有機相の溶媒を留去し、シリカゲルクロ マトグラフィー (展開溶媒：へキサン Z酢酸ェチル = 5Z5)で精製し、第一中間生成 物 34. 5質量部（収率 89%)を得た。 [0197] Synthesis of Compound Represented by Structural Formula (7) 30 parts by mass of 4-hydroxybenzyl alcohol, 37 parts by mass of potassium carbonate, and 100 parts by mass of dimethylacetamide were placed in a reaction kettle and heated to 80 ° C. To the reaction kettle, 23.6 parts by weight of 3 black mouth-2-methyl-1-propene was added dropwise over 0.5 hours. The reaction was continued for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 5Z5) to obtain 34.5 parts by mass (yield 89%) of the first intermediate product.
次に、前記第一中間生成物 30質量部と酢酸ェチル 200質量部と炭酸水素ナトリウ ム 71質量部と水 200質量部とアセトン 103質量部とを反応釜に入れた。該反応釜に 、 OXONE120質量部を水 500質量部に溶解させた水溶液を 1時間かけて滴下した 。その後 7時間反応させた。該反応釜に、 10%チォ硫酸ナトリウム水溶液を 300質量 部加え 1時間撹拌し、飽和食塩水で分液し有機相を硫酸マグネシウムで乾燥した。 該有機相の溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸 ェチル =5Z5)で精製し、第二中間生成物 19. 5質量部 (収率 60%)を得た。  Next, 30 parts by mass of the first intermediate product, 200 parts by mass of ethyl acetate, 71 parts by mass of sodium hydrogen carbonate, 200 parts by mass of water and 103 parts by mass of acetone were placed in a reaction kettle. An aqueous solution prepared by dissolving 120 parts by mass of OXONE in 500 parts by mass of water was dropped into the reaction kettle over 1 hour. The reaction was then continued for 7 hours. To the reaction kettle, 300 parts by mass of a 10% aqueous sodium thiosulfate solution was added and stirred for 1 hour, followed by separation with saturated brine and drying of the organic phase over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 5Z5) to obtain 19.5 parts by mass (yield 60%) of the second intermediate product.
最後に、 m キシリレンジイソシァネート 5質量部と前記第二中間生成物 10. 6質量 部と酢酸ェチル 50質量部とを反応釜に入れ、 55°Cに加熱した。該反応釜に、スタノ タト (吉富製薬社製) 0. 05質量部加えた。その後 6時間反応させた。放冷後、前記反 応溶液をろ過し、ろ液の溶媒を留去し、酢酸ェチルで再結晶することにより白色固体 7質量部（収率 44%)を得た。該白色固体の融点は、 113— 115°Cであった。  Finally, 5 parts by mass of m-xylylene diisocyanate, 10.6 parts by mass of the second intermediate product, and 50 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 55 ° C. To the reaction kettle, 0.05 part by mass of stanotat (Yoshitomi Pharmaceutical Co., Ltd.) was added. The reaction was then continued for 6 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 7 parts by mass (yield 44%) of a white solid. The melting point of the white solid was 113-115 ° C.
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 7. 32- 7. l l (m, 8H) , 6. 84 (d, 4H) , 4. 97 (br, 2H) , 4. 35—4. 25 (m, 8H) , 3. 99 (q, 4H) , 2. 87 (m, 6H) , 2. 72 (d, 2H) , 1. 48 (s, 6H)であった。 構造式 (8)で表されるエポキシ榭脂化合物の合成 Are 7. 32- 7. ll (m, 8H), 6. 84 (d, 4H), 4. 97 (br, 2H), 4. 35—4. 25 (m, 8H), 3. 99 ( q, 4H), 2.87 (m, 6H), 2.72 (d, 2H), 1.48 (s, 6H). Synthesis of epoxy resin compound represented by structural formula (8)
4ーヒドロキシベンジルアルコール 30質量部と炭酸カリウム 37質量部とジメチルァ セトアミド 100質量部とを反応釜に入れ、 80°Cに加熱した。該反応釜に、 3 クロ口— 2—メチルー 1 プロペン 23. 6質量部を 0. 5時間かけて滴下した。その後 10時間 反応させた。放冷後、該反応物を酢酸ェチル 100質量部で抽出し、飽和食塩水で分 液し有機相を硫酸マグネシウムで乾燥した。該有機相の溶媒を留去し、シリカゲルク 口マトグラフィー (展開溶媒：へキサン Z酢酸ェチル = 5Z5)で精製し、第一中間生 成物 34. 5質量部（収率 89%)を得た。 30 parts by mass of 4-hydroxybenzyl alcohol, 37 parts by mass of potassium carbonate, and 100 parts by mass of dimethylacetamide were placed in a reaction kettle and heated to 80 ° C. To the reaction kettle, 23.6 parts by weight of 3 black mouth-2-methyl-1-propene was added dropwise over 0.5 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase is distilled off and silica gel The product was purified by mouth matography (developing solvent: hexane Z ethyl acetate = 5Z5) to obtain 34.5 parts by mass (yield 89%) of the first intermediate product.
次に、前記第一中間生成物 30質量部と酢酸ェチル 200質量部と炭酸水素ナトリウ ム 71質量部と水 200質量部とアセトン 103質量部とを反応釜に入れた。該反応釜に 、 OXONE120質量部を水 500質量部に溶解させた水溶液を 1時間かけて滴下した 。その後 7時間反応させた。該反応釜に、 10%チォ硫酸ナトリウム水溶液を 300質量 部加え 1時間撹拌し、飽和食塩水で分液し有機相を硫酸マグネシウムで乾燥した。 該有機相の溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸 ェチル =5Z5)で精製し、第二中間生成物 19. 5質量部 (収率 60%)を得た。  Next, 30 parts by mass of the first intermediate product, 200 parts by mass of ethyl acetate, 71 parts by mass of sodium hydrogen carbonate, 200 parts by mass of water and 103 parts by mass of acetone were placed in a reaction kettle. An aqueous solution prepared by dissolving 120 parts by mass of OXONE in 500 parts by mass of water was dropped into the reaction kettle over 1 hour. The reaction was then continued for 7 hours. To the reaction kettle, 300 parts by mass of a 10% aqueous sodium thiosulfate solution was added and stirred for 1 hour, followed by separation with saturated brine and drying of the organic phase over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 5Z5) to obtain 19.5 parts by mass (yield 60%) of the second intermediate product.
最後に、トリレンジイソシァネート 3. 4質量部と前記第二中間生成物 7. 7質量部と 酢酸ェチル 40質量部とを反応釜に入れ、 55°C°Cに加熱した。該反応釜、スタノクト（ 吉富製薬社製) 0. 05質量部加えた。その後 6時間反応させた。放冷後前記有機相 の溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸ェチル = 5/5)で精製することによって油状物質 9. 5質量部（収率 83%)を得た。  Finally, 3.4 parts by mass of tolylene diisocyanate, 7.7 parts by mass of the second intermediate product, and 40 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 55 ° C ° C. The reaction kettle, Stanoct (manufactured by Yoshitomi Pharmaceutical), 0.05 parts by mass was added. The reaction was then continued for 6 hours. After allowing to cool, the solvent of the organic phase was distilled off and purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 5/5) to obtain 9.5 parts by mass of an oily substance (yield 83%). It was.
なお、生成物は1 H— NMR (300MHz : CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl). Each peak in the spectrum
3  Three
は、 7. 73 (s, 1H) , 7. 22 (d, IH) , 7. 15 (d, 4H) , 7. 08 (d, IH) , 6. 87 (d, 4H ) , 6. 59 (s, IH) , 6. 39 (s, IH) , 4. 33 (t, 2H) , 3. 98 (q, 4H) , 3. 83 (t, 2H) , 2. 95-2. 72 (m, 8H) , 2. 19 (s, 3H) , 1. 49 (s, 6H)であった。 7.73 (s, 1H), 7.22 (d, IH), 7.15 (d, 4H), 7.08 (d, IH), 6.87 (d, 4H), 6.59 (s, IH), 6.39 (s, IH), 4.33 (t, 2H), 3.98 (q, 4H), 3.83 (t, 2H), 2. 95-2. 72 ( m, 8H), 2.19 (s, 3H), 1.49 (s, 6H).
構造式（9)で表される化合物の合成  Synthesis of the compound represented by the structural formula (9)
ジフエ-ルメタンジイソシァネート 20質量部と 2—メチル 2—プロペン一 1—ォー ル 11. 8質量部と酢酸ェチル 60質量部とを反応釜に入れ、 55°Cに加熱した。該反 応釜に、スタノタト (吉富製薬社製) 0. 05質量部加えた。その後 6時間反応させた。 放冷後反応溶液をろ過した。該ろ液の溶媒を留去し、へキサン Z酢酸ェチル = 1Z 1溶液で再結晶することにより中間生成物 19. 5質量部（収率 62%)を得た。  20 parts by mass of diphenylmethane diisocyanate, 1-mole of 2-methyl-2-propene and 1-8 parts by mass and 60 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 55 ° C. To the reaction kettle, 0.05 part by mass of stanotat (manufactured by Yoshitomi Pharmaceutical) was added. The reaction was then continued for 6 hours. The reaction solution was filtered after standing_to_cool. The solvent of the filtrate was distilled off, and recrystallization was performed with a hexane Z ethyl acetate = 1Z 1 solution to obtain 19.5 parts by mass of an intermediate product (yield 62%).
次に、前記中間生成物 18質量部と酢酸ェチル 200質量部と炭酸水素ナトリウム 40 質量部と水 200質量部とアセトン 65質量部とを反応釜に入れた。該反応釜に、 OXO NE80質量部を水 350質量部に溶解させた水溶液を 1時間かけて滴下した。その後 7時間反応させた。該反応釜に、 10%チォ硫酸ナトリウム水溶液を 300質量部加え 1 時間撹拌し、飽和食塩水で分液し有機相を硫酸マグネシウムで乾燥した。該有機相 の溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸ェチル =Next, 18 parts by mass of the intermediate product, 200 parts by mass of ethyl acetate, 40 parts by mass of sodium hydrogen carbonate, 200 parts by mass of water, and 65 parts by mass of acetone were placed in a reaction kettle. An aqueous solution prepared by dissolving 80 parts by mass of OXO NE in 350 parts by mass of water was dropped into the reaction kettle over 1 hour. The reaction was then continued for 7 hours. Add 300 parts by mass of 10% aqueous sodium thiosulfate solution to the reaction kettle 1 The mixture was stirred for a period of time, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and silica gel chromatography (developing solvent: hexane Z ethyl acetate =
3Z7)で精製し、白色固体 15.4質量部 (収率 73%)を得た。 3Z7) to obtain 15.4 parts by mass (yield 73%) of a white solid.
なお、生成物は1 H— NMR(300MHz:CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl 3). Each peak in the spectrum
3  Three
は、 7.30 (d, 4H), 7.12(d, 4H), 6.76 (s, 2H), 4.37 (d, 2H), 4.07 (d, 2H ), 3.91 (s, 2H), 2.83 (d, 2H), 2.71 (d, 2H), 1.43 (s, 6H)であった。  Are 7.30 (d, 4H), 7.12 (d, 4H), 6.76 (s, 2H), 4.37 (d, 2H), 4.07 (d, 2H), 3.91 (s, 2H), 2.83 (d, 2H) 2.71 (d, 2H), 1.43 (s, 6H).
[0200] 構造式（31)で表されるエポキシ榭脂化合物の合成 [0200] Synthesis of epoxy resin compound represented by structural formula (31)
トリレンジイソシァネート 20質量部と 2—メチルー 2 プロペン 1 オール 17質量 部と酢酸ェチル 50質量部とを反応釜に入れ 55°Cに加熱した。該反応釜に、スタノク ト (吉富製薬社製) 0.05質量部加えた。その後 6時間反応させた。放冷後反応溶液 をろ過した。該ろ液の溶媒を留去し、へキサン Z酢酸ェチル =1Z1溶液で再結晶す ることにより中間生成物 20.5質量部（収率 56%)を得た。  20 parts by mass of tolylene diisocyanate, 17 parts by mass of 2-methyl-2-propene 1 ol and 50 parts by mass of ethyl acetate were placed in a reaction kettle and heated to 55 ° C. To the reaction kettle, 0.05 part by mass of stanoc (Yoshitomi Pharmaceutical Co., Ltd.) was added. The reaction was then continued for 6 hours. After cooling, the reaction solution was filtered. The solvent of the filtrate was distilled off, and recrystallization was performed with hexane Z ethyl acetate = 1Z1 solution to obtain 20.5 parts by mass of intermediate product (yield 56%).
次に、前記中間生成物 20質量部と酢酸ェチル 150質量部と炭酸水素ナトリウム 53 質量部と水 150質量部とアセトン 77質量部とを反応釜に入れた。該反応釜に、 OXO NE95質量部を水 400質量部に溶解させた水溶液を 1時間かけて滴下した。その後 7時間反応させた。該反応釜に、 10%チォ硫酸ナトリウム水溶液を 300質量部加え 1 時間撹拌し、飽和食塩水で分液し有機相を硫酸マグネシウムで乾燥した。該有機相 の溶媒を留去し、シリカゲルクロマトグラフィー（展開溶媒:へキサン Z酢酸ェチル = 5/5)で精製し、油状物質 11質量部 (収率 50%)を得た。  Next, 20 parts by mass of the intermediate product, 150 parts by mass of ethyl acetate, 53 parts by mass of sodium hydrogen carbonate, 150 parts by mass of water, and 77 parts by mass of acetone were placed in a reaction kettle. An aqueous solution in which 95 parts by mass of OXO NE was dissolved in 400 parts by mass of water was dropped into the reaction kettle over 1 hour. The reaction was then continued for 7 hours. To the reaction kettle, 300 parts by mass of a 10% aqueous sodium thiosulfate solution was added, stirred for 1 hour, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane Z ethyl acetate = 5/5) to obtain 11 parts by mass (yield 50%) of an oily substance.
なお、生成物は1 H— NMR(300MHz:CDCl )で同定した。スペクトルの各ピーク The product was identified by 1 H-NMR (300 MHz: CDCl 3). Each peak in the spectrum
3  Three
は、 7.82 (s, 1H), 7.21 (d, 1H), 7.10 (d, IH), 6.74 (s, IH), 6.51 (s, IH ), 4.36 (t, 2H), 4.05 (d, 2H), 2.82 (m, 2H), 2.76 (m, 2H), 2.21 (s, 3H ), 1.43(s, 6H)である。  Are 7.82 (s, 1H), 7.21 (d, 1H), 7.10 (d, IH), 6.74 (s, IH), 6.51 (s, IH), 4.36 (t, 2H), 4.05 (d, 2H) , 2.82 (m, 2H), 2.76 (m, 2H), 2.21 (s, 3H), 1.43 (s, 6H).
[0201] (実施例 14) [0201] (Example 14)
実施例 1にお!、て、感光性組成物中の前記構造式 (46)で表されるバインダー 40. 0質量部を、該構造式 (46)で表されるバインダー 20.0質量部と、以下に示す合成 例 aで得られた不飽和基を有するアクリル榭脂（B1) 20質量部に変えたこと以外は、 実施例 1と同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム 及び積層体を調製し、永久パターンを形成した。 In Example 1, 40.0 parts by mass of the binder represented by the structural formula (46) in the photosensitive composition, 20.0 parts by mass of the binder represented by the structural formula (46), and the following: A photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to 20 parts by mass of the acrylic resin (B1) having an unsaturated group obtained in Synthesis Example a. Photosensitive film And a laminated body was prepared and the permanent pattern was formed.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。その結果、露光感度は 30mJ 解像度は 70 /ζ πι、露光速度は 13mjZcm2であった。その他の結果を表 3に 示す。 In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ζ πι, and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3.
[0202] —合成例 a (アクリル榭脂 (B1)の合成） - メチルメタタリレート 45. 1質量部、メタクリル酸 47. 3質量部、ァゾイソバレロ-トリル 1質量部、プロピレングリコールモノメチルエーテル 215質量部力もなる混合溶液を 窒素ガス雰囲気下、 90°Cの反応容器中に 3時間かけて滴下した。滴下後 4時間反応 し、アクリル榭脂 (A1)を得た。  [0202] —Synthesis Example a (Synthesis of Acrylic Resin (B1))-Methylmethacrylate 45.1 parts by weight, methacrylic acid 47.3 parts by weight, azoisovalero-tolyl 1 part by weight, propylene glycol monomethyl ether 215 parts by weight The mixed solution, which was also powerful, was dropped into a 90 ° C reaction vessel over 3 hours under a nitrogen gas atmosphere. Reaction was performed for 4 hours after the dropwise addition to obtain acrylic resin (A1).
次に、得られたアクリル榭脂 (A1)溶液にサイクロマー A200 (ダイセル化学工業（ 株）製） 54. 7質量部及びハイドロキノンモノメチルエーテル 0. 2質量部、トリフエ-ル フォスフィン 1質量部を加えて、空気を吹き込みながら 80°Cで 8時間反応させて、不 飽和基を有するアクリル榭脂（B1)溶液（固形分酸価； 111、 Mw; 18, 000、二重結 合当量 2. 3mmolZg、プロピレングリコールモノメチルエーテル 41質量0 /0溶液）を得 た。 Next, 54.7 parts by mass of cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.), 0.2 part by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine were added to the resulting acrylic resin (A1) solution. Then, react for 8 hours at 80 ° C while blowing air, to obtain an acrylic resin (B1) solution with an unsaturated group (solid acid value; 111, Mw; 18,000, double bond equivalent 2.3 mmolZg to obtain a propylene glycol monomethyl ether 41 mass 0/0 solution).
[0203] (実施例 15)  [0203] (Example 15)
実施例 1にお!、て、感光性組成物中の前記構造式 (46)で表されるバインダー 40. 0質量部を、前記構造式 (46)で表されるバインダー 20. 0質量部と、以下に示す合 成例 bで得られた不飽和基を有するアクリル榭脂 (B2) 20質量部に変えたこと以外は 、実施例 1と同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィル ム及び積層体を調製し、永久パターンを形成した。  In Example 1, 40.0 parts by mass of the binder represented by the structural formula (46) in the photosensitive composition was replaced with 20.0 parts by mass of the binder represented by the structural formula (46). A photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to 20 parts by mass of the acrylic resin (B2) having an unsaturated group obtained in Synthesis Example b shown below. A photosensitive film and a laminate were prepared in the same manner as in 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。その結果、露光感度は 30mJ 解像度は 70 /ζ πι、露光速度は 13mjZcm2であった。その他の結果を表 3に 示す。 [0204] —合成例 b (アクリル榭脂 (B2)の合成） - メチルメタタリレート 45. 1質量部、メタクリル酸 47. 3質量部、ァゾイソバレロ-トリル 1質量部、プロピレングリコールモノメチルエーテル 215質量部力もなる混合溶液を 窒素ガス雰囲気下、 90°Cの反応容器中に 3時間かけて滴下した。滴下後 4時間反応 し、アクリル榭脂 (A2)を得た。 In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. As a result, the exposure sensitivity was 30 mJ, the resolution was 70 / ζ πι, and the exposure speed was 13 mjZcm 2 . Other results are shown in Table 3. [0204] —Synthesis Example b (Synthesis of Acrylic Resin (B2))-Methylmethallate 45.1 parts by weight, methacrylic acid 47.3 parts by weight, azoisovalero-tolyl 1 part by weight, propylene glycol monomethyl ether 215 parts by weight The mixed solution, which was also powerful, was dropped into a 90 ° C reaction vessel over 3 hours under a nitrogen gas atmosphere. Reaction was performed for 4 hours after the addition, and acrylic resin (A2) was obtained.
次に、得られたアクリル榭脂 (A2)溶液にグリシジルメタタリレート 35. 9質量部及び ハイドロキノンモノメチルエーテル 0. 2質量部、トリフエ-ルフォスフィン 1質量部をカロ えて、空気を吹き込みながら 80°Cで 8時間反応させて、不飽和基を有するアクリル榭 脂（B2)溶液（固形分酸価； 104、 Mw; 20, 000、二重結合当量 2. 0 mmol/g,プ ロピレンダリコールモノメチルエーテル 37質量0 /0溶液）を得た。 Next, add 35.9 parts by mass of glycidyl metatalylate, 0.2 part by mass of hydroquinone monomethyl ether and 1 part by mass of triphenylphosphine to the resulting acrylic resin (A2) solution, and blown air at 80 ° C. Acrylic resin (B2) solution having an unsaturated group (solid acid value; 104, Mw; 20,000, double bond equivalent 2.0 mmol / g, propylene glycol monomethyl ether) 37 mass 0/0 solution) was obtained.
[0205] (実施例 16〜19)  [0205] (Examples 16 to 19)
前記実施例 1、 5、 7及び 10において、露光装置を特開 2005— 258431号公報の 段落番号〔0383〕〜〔0393〕に記載されて 、るパターン形成装置に代えた以外は、 実施例 1と同様にして前記製造した感光性組成物及び感光性フィルムにつ 、て、タ ック性、露光感度、解像度、露光速度の評価を行い、前記形成した永久パターンに ついて鉛筆硬度、及び誘電特性の評価を行った。実施例 16〜19における露光感度 は 30mjZcm2、解像度は 70 m、露光速度は 7mjZcm2である。鉛筆硬度、誘電 特性、保存安定性についての結果を表 3に示す。 Example 1 except that the exposure apparatus in Examples 1, 5, 7 and 10 was replaced with the pattern forming apparatus described in paragraphs [0383] to [0393] of JP-A-2005-258431. In the same manner as described above, the prepared photosensitive composition and photosensitive film were evaluated for tackiness, exposure sensitivity, resolution, and exposure speed, and for the formed permanent pattern, pencil hardness and dielectric properties were evaluated. Was evaluated. In Examples 16 to 19, the exposure sensitivity is 30 mjZcm 2 , the resolution is 70 m, and the exposure speed is 7 mjZcm 2 . Table 3 shows the results for pencil hardness, dielectric properties, and storage stability.
[0206] (比較例 1)  [0206] (Comparative Example 1)
実施例 1において、感光性組成物中の前記構造式（1)で表される化合物を、 2, 2' ビス (4ーグリシジルフエ-ル)プロパンに変えたこと以外は、実施例 1と同様にして 感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、 永久パターンを形成した。  In Example 1, except that the compound represented by the structural formula (1) in the photosensitive composition was changed to 2,2 ′ bis (4-glycidylphenol) propane, the same as in Example 1. A photosensitive composition was prepared, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。なお、比較例 1及び以降の比 較例 2、 3においても、露光感度は 30miZcm2、解像度は 70 /ζ πι、露光速度は 13m jZcm2であった。その他の結果を表 3に示す。 [0207] (比較例 2) In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. In Comparative Example 1 and Comparative Examples 2 and 3 below, the exposure sensitivity was 30 miZcm 2 , the resolution was 70 / ζ πι, and the exposure speed was 13 m jZcm 2 . Other results are shown in Table 3. [0207] (Comparative Example 2)
実施例 1において、感光性組成物中の前記構造式（1)で表される化合物を、ェピコ ート YX4000 (ジャパンエポキシレジン社製、エポキシ榭脂）に変えたこと以外は、実 施例 1と同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及 び積層体を調製し、永久パターンを形成した。  Example 1 except that the compound represented by the structural formula (1) in the photosensitive composition was changed to Epicote YX4000 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy resin) in Example 1. A photosensitive composition was prepared in the same manner as in Example 1. A photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。結果を表 3に示す。  In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. The results are shown in Table 3.
[0208] (比較例 3) [0208] (Comparative Example 3)
実施例 1において、感光性組成物中の前記構造式（1)で表される化合物を、 ΤΕΡΙ C (日産化学工業社製、エポキシ榭脂）に変えたこと以外は、実施例 1と同様にして感 光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、永 久パターンを形成した。  In Example 1, the same procedure as in Example 1 was performed except that the compound represented by the structural formula (1) in the photosensitive composition was changed to ΤΕΡΙ C (manufactured by Nissan Chemical Industries, Ltd., epoxy resin). A photosensitive composition was prepared, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、タック性、露光 感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。結果を表 3に示す。  In addition, the manufactured photosensitive film was evaluated in the same manner as in Example 1 for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Was evaluated. The results are shown in Table 3.
[0209] [表 3] [0209] [Table 3]
4O°C3 強制経時後 実施例 熱架橋剤 タック性 鉛筆硬度 誘電正接 4O ° C3 After forced aging Example Thermal crosslinking agent Tack property Pencil hardness Dielectric loss tangent
現像時間 （秒） 実施例 1 構造式（1) 〇 5H 0. 013 30 実施例 2 構造式（1) 〇 4H 0. 014 25 実施例 3 構造式（1) 〇 2H 0. 018 25 実施例 4 構造式（1) 〇 5H以上 0. 013 45 実施例 5 構造式 (2) 〇 5H以上 0. 015 20 実施例 6 構造式 (3) 〇 5H 0. 015 25 実施例 7 構造式 (4) 〇 5H 0. 017 20 実施例 8 構造式 (5) 〇 5H以上 0. 014 25 実施例 9 構造式 (6) 〇 5H以上 0. 017 30 実施例 1 ◦ 構造式 (7) 〇 5H以上 0. 016 20 実施例 1 1 構造式 (8) 〇 5H 0. 015 20 実施例 1 2 構造式 (9) 〇 5H以上 0. 015 30 実施例 1 3 構造式（10) 〇 5H 0. 013 25 実施例 1 4 構造式（1) 〇 5H 0. 014 25 実施例 1 5 構造式（1) 〇 5H以上 0. 017 25 実施例 1 6 構造式 (1) 〇 5H 0. 013 30 実施例 1 7 構造式 (2) 〇 5H 0. 017 25 実施例 1 8 構造式 (4) 〇 5H以上 0. 013 25 実施例 1 9 構造式 (7) 〇 5H 0. 013 20  Development time (seconds) Example 1 Structural formula (1) 〇 5H 0. 013 30 Example 2 Structural formula (1) 〇 4H 0. 014 25 Example 3 Structural formula (1) 〇 2H 0. 018 25 Example 4 Structural formula (1) 〇 5H or more 0.013 45 Example 5 Structural formula (2) 〇 5H or more 0.015 20 Example 6 Structural formula (3) 〇 5H 0. 015 25 Example 7 Structural formula (4) 〇 5H 0. 017 20 Example 8 Structural formula (5) 〇 5H or more 0.014 25 Example 9 Structural formula (6) 〇 5H or more 0.017 30 Example 1 ◦ Structural formula (7) 〇 5H or more 0.016 20 Example 1 1 Structural formula (8) 〇 5H 0.015 20 Example 1 2 Structural formula (9) 〇 5H or more 0.015 30 Example 1 3 Structural formula (10) 〇 5H 0. 013 25 Example 1 4 Structural formula (1) 〇 5H 0. 014 25 Example 1 5 Structural formula (1) 〇 5H or more 0. 017 25 Example 1 6 Structural formula (1) 〇 5H 0. 013 30 Example 1 7 Structural formula ( 2) 〇 5H 0. 017 25 Example 1 8 Structural formula (4) 〇 5H or more 0.013 25 Example 1 9 Structural formula (7) 〇 5H 0. 013 20
2, 2' -匕'、ス  2, 2 '-匕', Su
比較例 1 (4, - 1 ル） X 5H以上 0. 013 現像不可 Comparative Example 1 (4, -1 ) X 5H or more 0. 013 Development not possible
7°ロハ。ン  7 ° Loha. N
比較例 2 ェピコ一ト 〇 5H以上 0. 011 現像不可 比較例 3 T E P I C 〇 5H以上 0. 013 現像不可 表 3の結果より、一般式（1)〜（3)で表される化合物から選択される少なくとも 1種の 化合物を含む実施例 1〜 19の感光性組成物を用いて製造した感光性フィルムにお ける感光層は、タック性、露光感度及び解像度に優れ、前記感光性フィルムを用いて 形成した永久パターンにおける硬化層の表面硬度も誘電特性も良好であり、従来公 知のエポキシ榭脂化合物を熱架橋剤として使用した比較例 1〜3の感光性フィルム に比べ、保存安定性に極めて優れていることが確認された。特に、前記化合物の感 光性組成物中での含有量が 0. 01〜15質量％である実施例 1〜2、 5〜19の感光性 フィルムは、保存安定性及び誘電特性の双方が極めて優れて ヽることが判った。 また、実施例 1、 5、 7及び 10と同様の感光性フィルムを用いた実施例 16〜19では 、高輝度光源と高速変調可能であり、かつトーリックレンズによる光学系歪み補正が 可能なパターン形成装置を用いたため、解像度及び露光速度が優れることが認めら れ、高精細な永久パターンが形成されることが確認された。  Comparative example 2 Epicot 〇 5H or more 0. 011 Development impossible Comparative example 3 TEPIC 〇 5H or more 0. 013 Development impossible Based on the results in Table 3, selected from compounds represented by general formulas (1) to (3) The photosensitive layer in the photosensitive film produced using the photosensitive composition of Examples 1 to 19 containing at least one compound is excellent in tackiness, exposure sensitivity and resolution, and is formed using the photosensitive film. The surface hardness and dielectric properties of the cured layer in the permanent pattern are excellent, and the storage stability is extremely superior compared to the photosensitive films of Comparative Examples 1 to 3 using a conventionally known epoxy resin compound as a thermal crosslinking agent. It was confirmed that In particular, the photosensitive films of Examples 1 to 2 and 5 to 19 in which the content of the compound in the photosensitive composition is 0.01 to 15% by mass are extremely excellent in both storage stability and dielectric properties. It turns out that he speaks excellently. In Examples 16 to 19 using the same photosensitive film as in Examples 1, 5, 7 and 10, pattern formation is possible with a high-intensity light source and high-speed modulation, and optical system distortion correction by a toric lens. Since the apparatus was used, it was confirmed that the resolution and the exposure speed were excellent, and it was confirmed that a high-definition permanent pattern was formed.
産業上の利用可能性 本発明の感光性組成物及び該感光性組成物を用いた感光性フィルムは、保存時 の常温下では反応を生じず、加熱により架橋反応を開始して、硬化膜の良好な膜硬 度が得られる化合物を含み、 UV露光により画像形成可能で、表面のタック性が小さ ぐラミネート性及び取扱い性が良好で、保存安定性に優れ、高感度で現像性にも優 れ、現像後に優れた耐薬品性、表面硬度、耐熱性、誘電特性などを発現するため、 プリント配線板 (多層配線基板、ビルドアップ配線基板等)の保護膜、層間絶縁膜、 及びソルダーレジストパターン、並びに、カラーフィルタや柱材、リブ材、スぺーサ一、 隔壁などのディスプレイ用部材、ホログラム、マイクロマシン、プルーフなどの永久パ ターン形成用として広く用いることができる。 Industrial applicability The photosensitive composition of the present invention and the photosensitive film using the photosensitive composition do not react at room temperature during storage, start a crosslinking reaction by heating, and have a cured film with good film hardness. Contains the resulting compound, can be imaged by UV exposure, has low surface tack, good laminating and handling properties, excellent storage stability, high sensitivity and excellent developability, and excellent after development In order to develop chemical resistance, surface hardness, heat resistance, dielectric properties, etc., protective films for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, color filters, It can be widely used for the formation of permanent patterns such as columns, ribs, spacers, partition members, display members, holograms, micromachines, and proofs.
また、本発明の永久パターンは耐薬品性、表面硬度、耐熱性、誘電特性、電気絶 縁性に優れる。このため、プリント配線板 (多層配線基板、ビルドアップ配線基板等） の保護膜、層間絶縁膜、ソルダーレジストパターン、並びに、カラーフィルタや柱材、 リブ材、スぺーサ一、隔壁などのディスプレイ用部材、ホログラム、マイクロマシン、プ ルーフなどの永久パターン形成用として広く用いることができるとして好適に使用す ることがでさる。  The permanent pattern of the present invention is excellent in chemical resistance, surface hardness, heat resistance, dielectric properties, and electrical insulation. For this purpose, for printed circuit boards (multilayer wiring boards, build-up wiring boards, etc.) protective films, interlayer insulation films, solder resist patterns, and displays such as color filters, pillar materials, rib materials, spacers, and partition walls It can be suitably used because it can be widely used for forming permanent patterns such as members, holograms, micromachines, and proofs.

Claims

請求の範囲 (A) 1分子中に 1個以上のカルボキシル基及びエステル基の少なくとも 、ずれかを 有する重合体と、（B)重合性化合物と、（C)光重合開始剤と、（D)下記一般式 (1)〜 (3)で表される化合物から選択される少なくとも 1種の化合物を含むことを特徴とする 感光性組成物。 Claims (A) A polymer having at least one of one or more carboxyl groups and ester groups in one molecule, (B) a polymerizable compound, (C) a photopolymerization initiator, (D) A photosensitive composition comprising at least one compound selected from compounds represented by the following general formulas (1) to (3):
[化 1]  [Chemical 1]
o^ X1_A1_p_ A2_x2^o —般式い） o ^ X 1_ A 1_p_ A 2_ x2 ^ o - general formula physician)
[化 2] [Chemical 2]
一般式（2) General formula (2)
一般式（3)General formula (3)
Figure imgf000080_0001
Figure imgf000080_0001
ただし、前記一般式（1)、 (2)、及び (3)中、 Pは、酸素原子、カルボニル基、アミド 基、ウレタン基、アルキレン、及びァリーレンのいずれかを表す。 Qは、ホウ素原子、 窒素原子、アルキレン、及びァリーレンのいずれかを表す。 Wは、 2つの X部と結合を 有するナフタレンを表す。 Ai A5は、単結合、アルキレン、及びァリーレンのいずれ かを表し、 丄〜 6は、— OCONH―、— NHCOO—、— NHCO—、及び— CONH 一のいずれかを表す。！^〜尺6は、水素原子、ハロゲン原子、アルキル基、及びァリー ル基のいずれかを表す。 However, in the general formulas (1), (2), and (3), P represents any of an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene, and an arylene. Q represents any of a boron atom, a nitrogen atom, alkylene, and arylene. W represents naphthalene having two X moieties and a bond. Ai A 5 represents a single bond, alkylene, or arylene, and 丄 to 6 represent one of —OCONH—, —NHCOO—, —NHCO—, and —CONH. ! ^ To 6 represent any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
[2] (D)一般式（1)〜（3)で表される化合物力も選択される少なくとも 1種の化合物の含 有量が、 1〜50質量％である請求項 1に記載の感光性組成物。  [2] The photosensitive property according to claim 1, wherein the content of at least one compound (D) represented by general formulas (1) to (3) is also 1 to 50% by mass. Composition.
[3] 支持体と、該支持体上に、請求項 1から 2のいずれかに記載の感光性組成物が積 層されてなる感光層とを有することを特徴とする感光性フィルム。  [3] A photosensitive film comprising: a support; and a photosensitive layer in which the photosensitive composition according to any one of claims 1 to 2 is laminated on the support.
[4] 請求項 1から 2の 、ずれかに記載の感光性組成物を、基材の表面に塗布し、乾燥 して感光層を形成した後、露光し、現像し、加熱することを特徴とする永久パターン 形成方法。 [4] The photosensitive composition according to any one of claims 1 to 2 is applied to the surface of a substrate and dried. Then, after forming the photosensitive layer, exposure, development, and heating are carried out.
請求項 3に記載の感光性フィルムを、加熱及び加圧の少なくとも!/、ずれかの下にお いて基材の表面に積層した後、露光し、現像し、加熱することを特徴とする永久バタ ーン形成方法。  A permanent film characterized in that the photosensitive film according to claim 3 is laminated on the surface of the base material under at least one of heating and pressurization and then exposed, developed, and heated. Pattern formation method.
PCT/JP2006/322232 2005-11-14 2006-11-08 Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern WO2007055220A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2006800424464A CN101310222B (en) 2005-11-14 2006-11-08 Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005329030A JP2007133333A (en) 2005-11-14 2005-11-14 Photosensitive composition, photosensitive film, permanent pattern and method for forming the same
JP2005-329030 2005-11-14

Publications (1)

Publication Number Publication Date
WO2007055220A1 true WO2007055220A1 (en) 2007-05-18

Family

ID=38023223

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/322232 WO2007055220A1 (en) 2005-11-14 2006-11-08 Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern

Country Status (4)

Country Link
JP (1) JP2007133333A (en)
KR (1) KR20080066845A (en)
CN (1) CN101310222B (en)
WO (1) WO2007055220A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140144687A (en) * 2012-02-25 2014-12-19 스루포커스 옵틱스 인코포레이티드 Devices and methods for improving vision using laser photomiosis

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5818022B2 (en) * 2010-05-13 2015-11-18 日産化学工業株式会社 Photosensitive resin composition and display device
KR20150102937A (en) * 2012-12-27 2015-09-09 히타치가세이가부시끼가이샤 Photosensitive resin composition, photosensitive film, and method for forming resist pattern
JP6854751B2 (en) * 2015-02-26 2021-04-07 株式会社Adeka Pattern formation method and electronic devices manufactured using it
CN112693212B (en) * 2019-10-23 2022-03-11 乐凯华光印刷科技有限公司 Environment-friendly single-layer thermosensitive plate and preparation method and application method thereof
CN115806754A (en) * 2022-12-07 2023-03-17 连州市祥丰化工有限公司 Photosensitive imaging developing-formed conductive ink, preparation method thereof and circuit board

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0741716A (en) * 1993-07-28 1995-02-10 Nissan Chem Ind Ltd Solder resist ink resin composition
JPH09100458A (en) * 1995-06-07 1997-04-15 Natl Starch & Chem Investment Holding Corp Epoxy resin comprising flexible chain terminated with glycidyloxyphenyl group and used in microelectronics adhesive
JP2003029402A (en) * 2001-07-19 2003-01-29 Goo Chemical Co Ltd Ultraviolet ray-curable resin composition and dry film
JP2003506507A (en) * 1999-08-03 2003-02-18 ザ ダウ ケミカル カンパニー Hydroxy aliphatic functional epoxy resin
JP2005114992A (en) * 2003-10-07 2005-04-28 Mitsubishi Chemicals Corp Photosetting composition, photosetting image forming material using the same, photosetting imaging material and image forming method
JP2005250004A (en) * 2004-03-03 2005-09-15 Tamura Kaken Co Ltd Photosensitive resin composition, composition for solder resist, photosensitive dry film and printed wiring board

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1431325A1 (en) * 2002-12-17 2004-06-23 Sika Technology AG Heat-curable epoxy resin composition with improved low-temperatur impact strength

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0741716A (en) * 1993-07-28 1995-02-10 Nissan Chem Ind Ltd Solder resist ink resin composition
JPH09100458A (en) * 1995-06-07 1997-04-15 Natl Starch & Chem Investment Holding Corp Epoxy resin comprising flexible chain terminated with glycidyloxyphenyl group and used in microelectronics adhesive
JP2003506507A (en) * 1999-08-03 2003-02-18 ザ ダウ ケミカル カンパニー Hydroxy aliphatic functional epoxy resin
JP2003029402A (en) * 2001-07-19 2003-01-29 Goo Chemical Co Ltd Ultraviolet ray-curable resin composition and dry film
JP2005114992A (en) * 2003-10-07 2005-04-28 Mitsubishi Chemicals Corp Photosetting composition, photosetting image forming material using the same, photosetting imaging material and image forming method
JP2005250004A (en) * 2004-03-03 2005-09-15 Tamura Kaken Co Ltd Photosensitive resin composition, composition for solder resist, photosensitive dry film and printed wiring board

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140144687A (en) * 2012-02-25 2014-12-19 스루포커스 옵틱스 인코포레이티드 Devices and methods for improving vision using laser photomiosis
KR102080336B1 (en) 2012-02-25 2020-02-21 스루포커스 옵틱스 인코포레이티드 Devices and methods for improving vision using laser photomiosis

Also Published As

Publication number Publication date
CN101310222A (en) 2008-11-19
JP2007133333A (en) 2007-05-31
KR20080066845A (en) 2008-07-16
CN101310222B (en) 2011-09-07

Similar Documents

Publication Publication Date Title
CN102804066B (en) Photocurable and thermocurable resin composition, and dry film solder resist
TWI704169B (en) Curable resin composition, dry film, cured product and printed circuit board
JP5941180B1 (en) Curable resin composition, dry film, cured product and printed wiring board
TWI653506B (en) Photo-sensitive resin composition, dry film, and printed wiring board
JP2001302871A (en) Photocurable/thermosetting resin composition and printed wiring board having solder resist coating film and resin insulating layer formed by using the same
KR101488138B1 (en) Photosensitive resin composition, dry film, cured product, and printed wiring board
JP2017161859A (en) Alkali-developable solder resist ink and printed wiring board processing method thereof and wiring board thereof
CN102591146B (en) Photocurable resin composition, dry film and cured product thereof, and printed wiring board using the same
WO2007055220A1 (en) Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern
WO2019117162A1 (en) Compound, latent base generator, photosensitive resin composition containing said compound, and cured product
JP2019174824A (en) Curable resin composition, dry film, cured product and printed wiring board
JP2007199205A (en) Photosensitive composition, photosensitive film, permanent pattern forming method and pattern
WO2006134846A1 (en) Curing accelerator, thermosetting resin composition, photosensitive composition, photosensitive film, permanent pattern and method for forming same
WO2007111000A1 (en) Photopolymerization initiator, photosensitive composition, photosensitive film, photosensitive laminate, method of forming permanent pattern and printed board
JP2003280192A (en) Photosetting and thermosetting resin composition
JP7254511B2 (en) Photosensitive resin composition, dry film, and method for producing printed wiring board
JP2001278947A (en) Active energy ray setting resin and photo-setting and thermosetting resin composition by applying the same
US9298096B2 (en) Curable resin composition, cured product thereof, printed circuit board comprising the same, and method for producing the cured product
JP2007106886A (en) Curing accelerator, thermosetting resin composition, photosensitive composition, photosensitive film, permanent pattern and method for forming it
JP6127190B1 (en) Photosensitive resin composition, cured product, printed wiring board having cured product, and optical sensor module provided with printed wiring board
JP2011074213A (en) Carboxyl group-containing resin, composition containing the same and cured product thereof, and method for producing carboxyl group-containing resin
JP5986157B2 (en) Curable resin composition, dry film, cured product and printed wiring board
WO2019188067A1 (en) Curable resin composition, dry film, cured product, and electronic component
KR100499836B1 (en) Photopolymerizable Thermosetting Resin Composition
JP2004037726A (en) Photosensitive resin composition for image formation

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680042446.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 1020087013225

Country of ref document: KR

122 Ep: pct application non-entry in european phase

Ref document number: 06823136

Country of ref document: EP

Kind code of ref document: A1