WO2022163610A1 - Composition de résine photosensible, feuille de résine photosensible, produit durci, structure creuse, composant électronique et filtre à ondes élastiques - Google Patents

Composition de résine photosensible, feuille de résine photosensible, produit durci, structure creuse, composant électronique et filtre à ondes élastiques Download PDF

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WO2022163610A1
WO2022163610A1 PCT/JP2022/002548 JP2022002548W WO2022163610A1 WO 2022163610 A1 WO2022163610 A1 WO 2022163610A1 JP 2022002548 W JP2022002548 W JP 2022002548W WO 2022163610 A1 WO2022163610 A1 WO 2022163610A1
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photosensitive resin
resin composition
mass
radically polymerizable
cured product
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PCT/JP2022/002548
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English (en)
Japanese (ja)
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桂田悠基
小林悠太
金森大典
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東レ株式会社
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Priority to CN202280012404.5A priority Critical patent/CN116830039A/zh
Priority to KR1020237023729A priority patent/KR20230141762A/ko
Priority to JP2022510941A priority patent/JPWO2022163610A1/ja
Publication of WO2022163610A1 publication Critical patent/WO2022163610A1/fr

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    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • 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
    • 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
    • G03F7/025—Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive resin sheet, a cured product, a hollow structure, an electronic component, and an elastic wave filter.
  • Photosensitive resin compositions are widely used as insulating films for wiring boards because they can be microfabricated by photolithography. Furthermore, materials obtained by forming photosensitive resin compositions into sheets are being applied to roofing materials for forming hollow structures of electronic parts, taking advantage of the sheet-like characteristics. In recent years, the photosensitive resin sheet forming the roof of the hollow structure is required to have pattern workability for forming fine through holes and pressure resistance to withstand the sealing process. In order to improve pressure resistance, a method of adding an inorganic filler to increase the elastic modulus has been proposed. In addition to improving pressure resistance by adding a filler, it is expected that scattering of light used for exposure can be suppressed and pattern processability can be compatible.
  • the photosensitive resin composition described in Patent Document 1 has the problem that it does not have sufficient pattern workability and pressure resistance in adapting to roofing materials for hollow structures, for which the required properties are increasing.
  • An object of the present invention is to solve the above problems, and to provide a photosensitive resin composition excellent in pattern workability and pressure resistance.
  • a photosensitive resin composition comprising (A) a polymer, (B) a radically polymerizable compound, (C) a photopolymerization initiator, and (D) an inorganic filler,
  • the photosensitive resin composition, wherein the (B) radically polymerizable compound has an average radically polymerizable functional group equivalent of 70 g/eq or more and 200 g/eq or less.
  • the present invention it is possible to form an insulating film that is finely processed and has excellent pressure resistance.
  • the photosensitive resin composition of the present invention can be suitably used for substrate applications requiring high resolution and high elastic modulus, and electronic component applications having hollow structures requiring pressure resistance.
  • FIG. 2 is a schematic plan view showing one mode in which convex portions are formed for forming the hollow structural body of the present invention. It is a schematic diagram showing an example of a method of forming a hollow structure using the photosensitive resin sheet of the present invention.
  • the present invention provides a photosensitive resin composition
  • a photosensitive resin composition comprising (A) a polymer, (B) a radically polymerizable compound, (C) a photopolymerization initiator, and (D) an inorganic filler, wherein the (B) radically polymerizable compound is a photosensitive resin composition having an average radically polymerizable functional group equivalent weight of 70 g/eq or more and 200 g/eq or less. Details of this are given below.
  • the photosensitive resin composition of the present invention contains (A) a polymer.
  • a polymer By including the polymer (A), it becomes easy to form a thick film of the photosensitive resin composition, and it becomes easy to adjust the film thickness according to the application.
  • the main skeleton of the polymer is not particularly limited, but (meth)acrylic polymer, epoxy polymer, polyurethane, polybenzoxazine, polybenzoxazole precursor, polybenzoxazole, polyimide precursor, polyimide, etc. can be used.
  • the polymer (A) contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, precursors thereof, and copolymers thereof, that is, poly It preferably contains benzoxazole precursors, polybenzoxazole, polyimide precursors, polyimides, and copolymers thereof.
  • the polymer (A) more preferably contains a polyimide precursor or polyimide, and particularly preferably contains polyimide from the viewpoint of lowering the heat treatment temperature after patterning.
  • the resin contained in the polymer is preferably soluble in a developer, and particularly preferably alkali-soluble.
  • alkali-soluble as used herein means that the solubility in a 2.38% by weight tetramethylammonium hydroxide (TMAH) aqueous solution is 0.1 g/100 mL or more.
  • a functional group that imparts alkali solubility to a polymer that is, an alkali-soluble group includes a phenolic hydroxyl group, a thiol group, a carboxyl group, a sulfonic acid group and the like. It is preferred to have either or both groups.
  • polyimide As the polymer, it preferably contains one or more polyimides having a structural unit represented by the following general formula (1), and one type represented by the following general formula (2) or (3) It is more preferable to contain the above polyimides.
  • X represents a monovalent organic group having at least one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group.
  • Y represents a divalent organic group having at least one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group.
  • X and Y preferably have a phenolic hydroxyl group or a thiol group, and particularly preferably have a phenolic hydroxyl group.
  • R 1 represents a 4- to 14-valent organic group
  • R 2 represents a 2- to 12-valent organic group
  • R3 and R4 each independently represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group.
  • R 3 and R 4 are preferably phenolic hydroxyl groups or carboxyl groups, particularly preferably phenolic hydroxyl groups.
  • ⁇ and ⁇ each independently represent an integer ranging from 0 to 10. Among such ⁇ and ⁇ , it is preferable that ⁇ + ⁇ is 1 or more.
  • n represents the number of repeating structural units of the polymer. The range of n is 3-200. If n is 3 or more, the thick film workability of the photosensitive resin composition can be further improved. From the viewpoint of improving the thick film workability, n is preferably 5 or more. On the other hand, when n is 200 or less, the solubility of the alkali-soluble polyimide (a) in an alkali developer can be improved. From the viewpoint of improving the solubility, n is preferably 100 or less.
  • R 1 is a tetravalent to 14valent organic group having a structure derived from tetracarboxylic dianhydride.
  • R 1 is preferably an organic group having 5 to 40 carbon atoms containing an aromatic group or a cycloaliphatic group.
  • tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.
  • aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3 '-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1, 1-bis
  • examples of tetracarboxylic dianhydrides include acid dianhydrides having the structures shown below.
  • the tetracarboxylic dianhydride two types of the aromatic tetracarboxylic dianhydride described above, the aliphatic tetracarboxylic dianhydride, and the acid dianhydride having the structure shown below The above may be used.
  • R5 is an oxygen atom, a group selected from C ( CF3 ) 2 , C(CH3)2 and SO2 ; and represents a group selected from a thiol group.
  • R 2 is a divalent to dodecavalent organic group having a diamine-derived structure.
  • an organic group having 5 to 40 carbon atoms containing an aromatic group or a cycloaliphatic group is preferred.
  • Diamines include, for example, hydroxyl group-containing diamines, carboxyl group-containing diamines, thiol group-containing diamines, aromatic diamines, compounds in which at least some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, fatty group diamines and the like.
  • hydroxyl group-containing diamines include bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane. , bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl) fluorene and the like.
  • Carboxyl group-containing diamines include, for example, 2,2-bis[3-amino-4-carboxyphenyl]propane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 2,2-bis[3 -amino-4-carboxyphenyl]hexafluoropropane, 4,4'-diamino-2,2',5,5'-tetracarboxydiphenylmethane, 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4 ,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2,2',5,5'-tetracarboxy Diphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenylsulfone
  • aromatic diamines examples include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4, 4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, benz
  • diamines include, for example, diamines having the structures shown below.
  • diamines having the structures shown below as the diamine, at least part of the hydroxyl group-containing diamine, the carboxyl group-containing diamine, the thiol group-containing diamine, the aromatic diamine, and the hydrogen atoms of these aromatic rings are substituted with an alkyl group or a halogen atom.
  • aliphatic diamines, and diamines having the structures shown below may be used.
  • R 5 is an oxygen atom, a group selected from C(CF 3 ) 2 , C(CH 3 ) 2 and SO 2
  • R 6 to R 9 are each independently a carboxyl group, hydroxyl group, sulfonic acid group and represents a group selected from thiol groups.
  • R 3 and R 4 each independently represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group, as described above.
  • an aliphatic group having a siloxane structure at R2 may be copolymerized within a range that does not reduce the heat resistance.
  • the diamine component bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, etc. may be copolymerized in an amount of 1 to 10 mol %.
  • X is derived from a primary monoamine that is a terminal blocking agent.
  • Primary monoamines used as terminal blockers include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1 -hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6- aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid , 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid,
  • Y is derived from a dicarboxylic anhydride that is a terminal blocking agent.
  • acid anhydride used as the terminal blocking agent 4-carboxyphthalic anhydride, 3-hydroxyphthalic anhydride, cis-aconitic anhydride and the like are preferable. These are used alone or in combination of two or more.
  • the alkali-soluble polyimide used in the present invention may consist of only the structures represented by the general formulas (1) to (3), or may be a mixture with other structures having alkali solubility. good.
  • the alkali-soluble polyimide having the structure represented by the general formulas (1) to (3) is contained in an amount of 30% by weight or more based on the total weight of the alkali-soluble polyimide.
  • it is preferably 60% by weight or more. If it is 30% by weight or more, shrinkage during thermosetting can be suppressed, and it is suitable for producing a thick film.
  • the type and amount of polyimide to be mixed is preferably selected within a range that does not impair the heat resistance of the polyimide obtained by the final heat treatment.
  • Alkali-soluble polyimide is obtained by replacing part of the diamine with a terminal blocking agent monoamine, or replacing tetracarboxylic dianhydride with a terminal blocking agent dicarboxylic anhydride, using a known method.
  • a polyimide precursor is obtained by using a method such as a method of obtaining a diester with an alcohol, and then reacting a diamine, a monoamine, and a condensing agent. After that, the obtained polyimide precursor can be completely imidized using a known imidization reaction method to synthesize a polyimide.
  • the imidization rate of the alkali-soluble polyimide can be easily determined by, for example, the following method.
  • the imidization rate means what mol % of the polyimide precursor is converted to polyimide when the polyimide is synthesized via the polyimide precursor as described above.
  • the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (near 1780 cm ⁇ 1 and 1377 cm ⁇ 1 ) of the imide structure due to polyimide.
  • the infrared absorption spectrum is measured again, and the peak intensity near 1377 cm ⁇ 1 before and after the heat treatment is compared. Assuming that the imidization rate of the polymer after the heat treatment is 100%, the imidization rate of the polymer before the heat treatment is obtained.
  • the imidization rate of the polymer is preferably 90% or more.
  • the terminal blocking agent introduced into the alkali-soluble polyimide can be detected by the following method.
  • a polyimide into which a terminal blocking agent has been introduced is dissolved in an acidic solution to decompose into an amine component and a carboxylic acid anhydride component, which are constituent units of polyimide, and this is analyzed by gas chromatography (GC) or NMR. Measure.
  • GC gas chromatography
  • NMR NMR
  • the content of the polymer is preferably 20% by mass or more, preferably 30% by mass or more, based on 100% by mass of the solid content of the photosensitive resin composition excluding (D) the inorganic filler described later. is more preferable, and 40% by mass or more is even more preferable.
  • the content of the polymer (A) is preferably 80% by mass or less, preferably 70% by mass or less, in 100% by mass of the solid content of the photosensitive resin composition excluding the (D) inorganic filler described later. It is more preferable that the content is 60% by mass or less.
  • the lower the content of the polymer the more the lamination property of the photosensitive resin sheet can be improved.
  • the photosensitive resin composition of the present invention contains (B) a radically polymerizable compound.
  • the radically polymerizable compound has a radically polymerizable functional group in its molecule.
  • functional groups exhibiting radical polymerizability include vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, propargyl groups, and the like.
  • compounds having an acryloyl group or a methacryloyl group are preferable from the standpoint of polymerizability.
  • a compound having an acryloyl group or a methacryloyl group is hereinafter referred to as a (meth)acrylic compound.
  • the radically polymerizable functional group equivalent of (B) the radically polymerizable compound is 70 g/eq or more and 200 g/eq or less on average.
  • the radically polymerizable functional group equivalent of the radically polymerizable compound is on average 70 g/eq or more, more preferably 80 g/eq or more, further preferably 90 g/eq or more, and 100 g/eq. It is particularly preferable that it is above.
  • the greater the equivalent weight of the radically polymerizable functional group the more the elongation of the cured product can be improved, and the more the occurrence of cracks can be suppressed.
  • the average radically polymerizable functional group equivalent of (B) the radically polymerizable compound is 200 g/eq or less, more preferably 180 g/eq or less, further preferably 160 g/eq or less, 140 g/eq or less is particularly preferred.
  • the radically polymerizable functional group equivalent is obtained from the following formula.
  • Radically polymerizable functional group equivalent (molecular weight/number of functional groups exhibiting radical polymerizability in the same molecule) The average is obtained by averaging the radically polymerizable functional group equivalents of each (B) radically polymerizable compound in terms of mass ratio.
  • the average number of functional groups of the radically polymerizable compound is preferably 2 or more, more preferably 3 or more. As the average number of functional groups increases, the heat resistance of the cured product can be improved. On the other hand, the average number of functional groups of the radically polymerizable compound (B) is preferably 6 or less, more preferably 4 or less. The smaller the average number of functional groups, the more it is possible to suppress the occurrence of cracks in the cured product.
  • the radically polymerizable compound is not particularly limited as long as the average radically polymerizable functional group equivalent is 70 g/eq or more and 200 g/eq or less.
  • the content of the radically polymerizable compound (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and 50 parts by mass or more with respect to 100 parts by mass of the polymer (A). is particularly preferred. When the content is 10 parts by mass or more, it is possible to reduce film loss in the exposed portion during development.
  • the content of the radical polymerizable compound (B) is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 100 parts by mass or less, with respect to 100 parts by mass of the polymer (A). Part by mass or less is particularly preferred. By making it 300 mass parts or less, the heat resistance of hardened
  • R 10 represents a hydrocarbon group having 1 to 5 carbon atoms
  • R 11 represents hydrogen or a methyl group
  • Z represents an organic group.
  • a represents an integer of 0-1, and b represents an integer of 2-10.
  • a is 0.
  • b is preferably 4 to 8.
  • Z has a cyclic skeleton b is preferably 2 to 4.
  • the cyclic skeleton is an alicyclic ring. A skeleton is preferred.
  • the content of the compound represented by the following general formula (4) is preferably 70% by mass or more and 100% by mass or less, and 80% by mass. % or more and 100 mass % or less, more preferably 90 mass % or more and 100 mass % or less. It is possible to improve the storage elastic modulus and pressure resistance of the cured product, and it becomes possible to maintain the shape of the roof during the sealing process. In addition, it is possible to suppress pattern swelling derived from the (D) inorganic filler, which will be described later, and to form a high-resolution pattern.
  • the (B) radically polymerizable compound in the photosensitive resin composition of the present invention is (B1) a radically polymerizable compound having no cyclic structure and having a radically polymerizable functional group equivalent weight of 80 to 120 g/eq (hereinafter referred to as (B1) component) is preferably contained.
  • (B1) component a radically polymerizable compound having no cyclic structure and having a radically polymerizable functional group equivalent weight of 80 to 120 g/eq
  • the number of functional groups of component (B1) is preferably 3 or more, more preferably 4 or more. By setting the number of functional groups to 3 or more, it is possible to improve the heat resistance of the cured product. On the other hand, the number of functional groups of component (B1) is preferably 10 or less, more preferably 8 or less. By setting the number of functional groups to 10 or less, it becomes possible to suppress the generation of cracks in the cured product.
  • component (B1) include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, and ditrimethylol.
  • Non-limiting examples include propane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.
  • the radically polymerizable compound contains (B2) a radically polymerizable compound having an alicyclic structure and a radically polymerizable functional group equivalent weight of 130 to 200 g/eq (hereinafter referred to as component (B2)). is preferred.
  • component (B2) By containing the component (B2), it is possible to improve the elongation while improving the storage elastic modulus and pressure resistance of the cured product.
  • the number of functional groups of component (B2) is preferably 2 or more. By setting the number of functional groups to 2 or more, it is possible to improve the heat resistance of the cured product. On the other hand, the number of functional groups of component (B2) is preferably 6 or less, more preferably 4 or less. By setting the number of functional groups to 6 or less, it becomes possible to suppress the generation of cracks in the cured product.
  • component (B2) include dimethyloltricyclodecane diacrylate, dimethyloltricyclodecane dimethacrylate, 1,3-adamantane diacrylate, 1,3-adamantane dimethacrylate, 1,3,5-adamantane tri Acrylates, 1,3,5-adamantane trimethacrylate, 5-hydroxy-1,3-adamantane diacrylate, 5-hydroxy-1,3-adamantane dimethacrylate, bis-(2-acryloxyethyl) isocyanurate, tris- (2-Acryloxyethyl)isocyanurate and the like can be mentioned, but not limited to these.
  • the total mass of the component (B1) and the component (B2) is preferably 70% by mass or more and 100% by mass or less, preferably 80% by mass or more. It is more preferably 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less. It is possible to improve the storage elastic modulus and pressure resistance of the cured product, and it becomes possible to maintain the shape of the roof during the sealing process. In addition, it is possible to suppress pattern swelling derived from the (D) inorganic filler, which will be described later, and to form a high-resolution pattern.
  • the content of component (B1) is preferably 20% by mass or more and 80% by mass or less when the total mass of components (B1) and (B2) is 100% by mass. That is, when the total mass of the components (B1) and (B2) is 100% by mass, the content of the component (B1) is preferably 20% by mass or more, more preferably 30% by mass or more. It is preferably 40% by mass or more, and more preferably 40% by mass or more. By making it 20% by mass or more, it is possible to improve the storage elastic modulus and pressure resistance of the cured product. On the other hand, when the total mass of components (B1) and (B2) is 100% by mass, the content of component (B1) is preferably 80% by mass or less, and preferably 70% by mass or less. More preferably, it is 60% by mass or less. By making it 80% by mass or less, it is possible to improve the elongation of the cured product.
  • the photosensitive resin composition of the present invention contains (C) a photopolymerization initiator.
  • C a photopolymerization initiator.
  • the radical polymerization of the radically polymerizable compound (B) described above proceeds, and the exposed portion of the film of the resin composition becomes insoluble in an alkaline developer, thereby producing a negative film.
  • a pattern of molds can be formed.
  • photopolymerization initiators examples include benzophenones, glycines, mercaptos, oximes, acylphosphines, ⁇ -aminoalkylphenones, etc. Among them, acylphosphines and oximes are preferred.
  • a photoinitiator may be used by 1 type, and may be used in combination of 2 or more type.
  • photopolymerization initiator examples include benzophenones such as benzophenone, Michler's ketone, 4,4,-bis(diethylamino)benzophenone, and 3,3,4,4,-tetra(t-butylperoxycarbonyl)benzophenone.
  • benzylidenes such as 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone, 7-diethylamino-3-nonylcoumarin , 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylmethylbenzimidazolyl)coumarin, 3-(2-benzothiazolyl)-7 - coumarins such as diethylaminocoumarin, anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2,4 -
  • acylphosphines and oximes examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1-phenyl -1,2-propanedione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, bis( ⁇ -isonitrosopropiophenone oxime) isophthalate , 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-1-(o-acetyloxime), ADEKA Co., Ltd. ADEKA Arkles (registered trademark) N-1919, NCI-831
  • the content of the photopolymerization initiator (C) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 2 parts by mass or more in 100 parts by mass of the polymer (A). is more preferred.
  • the content of the photopolymerization initiator (C) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and 150 parts by mass or less in 100 parts by mass of the polymer (A). is more preferred.
  • (C) By setting the content of the photopolymerization initiator to 30 parts by mass or less, light can be transmitted to a deep portion, and a favorable pattern shape can be obtained.
  • the photosensitive resin composition of the present invention contains (D) an inorganic filler.
  • (D) an inorganic filler By containing an inorganic filler, mechanical properties such as storage elastic modulus and chemical resistance can be improved. This makes it possible to retain the shape of the roof during the sealing process.
  • Inorganic fillers include silicon oxides such as talc, amorphous silica, crystalline silica, fused silica and spherical silica, titanium oxide, aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, Fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite , potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, xonolite, boron nitride, aluminum borate, glass, silica balloon, glass balloon, steel slag, copper, iron, iron oxide, sendust, alnico magnet, various ferrites magnetic powder, cement, Neuburg silica, diatomaceous earth, antimony trioxide, magnesium oxysul, titanium
  • the glass of the present invention refers to an inorganic substance having amorphous properties and having a plurality of inorganic oxides bonded together.
  • fused silica exhibits amorphous properties, it is not included in glass in the present invention because it is a single inorganic substance.
  • the amorphousness and the presence or absence of bonding can be confirmed by a broad X-ray diffraction peak. Whether or not there are multiple inorganic oxides can be confirmed by a composition analysis method such as fluorescent X-ray analysis.
  • the inorganic filler preferably contains a glass filler because it can suppress light scattering and improve resolution by adjusting the refractive index.
  • the glass filler content is preferably 50% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass, based on 100% by mass of the inorganic filler (D).
  • the glass filler preferably has a refractive index of 1.55 to 1.75 at a wavelength of 405 nm.
  • the glass filler preferably contains at least two selected from the group consisting of silicon oxide, aluminum oxide, and boron oxide, and further contains rare earth oxides.
  • the rare earth oxides contained in the glass filler may be of one kind or may be used in combination of two or more kinds.
  • the glass filler preferably has a low content of magnesium oxide, calcium oxide, and zinc oxide, which cause elution of components under the influence of humidity, and more preferably does not contain these. Furthermore, it is more preferable that the glass filler does not contain an alkali metal oxide from the viewpoint of insulation reliability.
  • yttrium oxide or lanthanide oxide is preferable as the glass filler because it is easily mixed with at least two oxides selected from among silicon oxide, aluminum oxide, and boron oxide. It is more preferable to use yttrium oxide from the viewpoint of fine adjustment of the refractive index of the filler.
  • the content of magnesium oxide, calcium oxide, and zinc oxide in the glass filler is small.
  • the total amount of calcium ions and zinc ions is preferably 100 ppm (by weight) or less in the glass filler.
  • the measurement can be performed by the method described in Examples described later.
  • the total amount of magnesium ions, calcium ions, and zinc ions detected in the extract after 24 hours of extraction treatment at 121 ° C. saturated water vapor pressure conditions is 100 ppm (weight basis) or less in the glass filler, and the refractive index at 405 nm is 1.
  • the total content of at least two selected from the group consisting of silicon oxide, aluminum oxide, and boron oxide is 65 to 85% by mass in 100% by mass of the glass filler.
  • the total content of rare earth oxides is preferably 15 to 35% by mass.
  • the glass contains 40 to 50% by mass of silicon oxide, 20 to 30% by mass of aluminum oxide, 0 to 10% by mass of boron oxide, and 15 to 35% by mass of rare earth oxide, based on 100% by mass of the glass filler. It is to be a filler.
  • the content of rare earth oxides contained in the glass filler can be measured by a generally known quantitative measurement method for inorganic elements. It can be measured by combining analysis, X-ray diffraction, electron beam diffraction, and the like.
  • SEM-EDX means scanning electron microscope-energy dispersive X-ray spectroscopy
  • TEM-EDX means transmission electron microscope-energy dispersive X-ray spectroscopy
  • ICP-MS means inductively coupled plasma mass spectrometry.
  • the glass filler in the present invention refers to one that does not have a sharp peak (half width of 2° or less) representing the crystal structure of a specific component in 2 ⁇ - ⁇ powder X-ray diffraction measurement.
  • the refractive index of the inorganic filler can be measured by the V-block method, and in the present invention, the refractive index is the result of measurement at a wavelength of 405 nm.
  • the absolute value of the difference between the refractive index of (D) the inorganic filler and the refractive index of (D) the solid content of the photosensitive resin composition excluding the inorganic filler should be 0.5. 05 or less.
  • the refractive index of the solid content of the photosensitive resin composition excluding the inorganic filler is largely due to the refractive index of the (A) polymer, and when the (A) polymer is polyimide, the refractive index is from 1.55 to 1.75.
  • the refractive index of the solid content of the photosensitive resin composition excluding the inorganic filler was 405 nm at 25° C. by the ellipsometry method after the coating and drying steps by preparing only the organic component of the photosensitive resin composition. can be obtained by measuring the wavelength of light.
  • the refractive index of the inorganic filler and (D) The absolute value of the difference between the refractive index of the solid content of the photosensitive resin composition excluding the inorganic filler is preferably as small as possible, and there is no difference, that is, the absolute value of the difference A value of 0 is particularly preferred.
  • the inorganic filler preferably has an average particle size of 0.1 to 3.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m. The smaller the average particle size, the smoother the insulating film surface after patterning.
  • the average particle size of the (D) inorganic filler referred to in the present invention is the value of the 50% volume particle size measured using a particle size distribution meter (Microtrac particle size analyzer MODEL MT3000) using a laser diffraction scattering method. Measurement is carried out by taking about 1 g of a sample and dispersing it in purified water for 1 to 3 minutes with ultrasonic waves at an output of 40 W.
  • the average particle size obtained by the laser diffraction scattering method represents the diameter of a volume-equivalent sphere.
  • the diameter is preferably within the above range.
  • the shape of the (D) inorganic filler includes, but is not particularly limited to, spherical, needle-like, fibrous, amorphous granular, plate-like, and crushed shapes.
  • the content of the inorganic filler is 30% by mass or more when the total mass of the solid content of the photosensitive resin composition is 100% by mass, from the viewpoint of improving mechanical properties such as storage elastic modulus and chemical resistance. , more preferably 50% by mass or more, and even more preferably 60% by mass or more.
  • the content of (D) the inorganic filler is preferably 80% by mass or less with respect to 100% by mass of the total solid content of the photosensitive resin composition, from the viewpoint of improving elongation.
  • silane coupling agents include Shin-Etsu Chemical's vinyltrimethoxysilane (KBM-1003), 3-glycidoxypropyltrimethoxysilane (KBM-403), 3-methacryloxypropyltrimethoxysilane (KBM- 503), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573) and the like can be used.
  • the (D) inorganic filler can be surface-treated by a dry surface treatment in which a silane coupling agent and a small amount of water are added to the (D) inorganic filler and stirred.
  • the photosensitive resin composition of the present invention preferably contains (E) a thermal cross-linking agent.
  • the thermal cross-linking agent is a component that is cured by heat treatment after patterning, and can improve the mechanical properties and chemical resistance of the cured product.
  • a compound containing at least one of an alkoxymethyl group, a methylol group and an epoxy group is preferable, and a compound containing at least two of an alkoxymethyl group, a methylol group and an epoxy group is more preferable. preferable.
  • compounds having an alkoxymethyl group or a methylol group include, for example, 46DMOC, 46DMOEP (trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML- OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC- Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TM
  • compounds having an epoxy group include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl(glycidyloxypropyl) , epoxy group-containing silicone, and the like.
  • the content of (E) the thermal cross-linking agent in the photosensitive resin composition of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, relative to 100% by mass of the (A) polymer.
  • the content of (E) the thermal cross-linking agent is preferably 50% by mass or less, more preferably 30% by mass or less, relative to 100% by mass of the (A) polymer.
  • the content of the thermal cross-linking agent By setting the content of the thermal cross-linking agent to 50% by mass or less, it is possible to improve the storage stability of the photosensitive resin composition.
  • the photosensitive resin composition of the present invention can further contain a polymerization inhibitor. Since the exciton concentration is adjusted by containing the polymerization inhibitor, a pattern having a rectangular cross section can be formed. In addition, the polymerization inhibitor can suppress excessive photoresponsivity, and the exposure margin can be widened.
  • polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, phenolic polymerization inhibitors such as t-butylcatechol, phenothiazine, 2-methoxyphenothiazine, 1-naphthol, 1,4-dihydroxynaphthalene, 4-methoxy- 1-naphthol, 1-methoxynaphthalene, 1,4-dimethoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 2,6-diethoxynaphthalene, 2,7- Diethoxynaphthalene, 2,6-dibutoxynaphthalene, 2-ethyl-1,4-diethoxynaphthalene, 1,4-dibutoxynaphthalene, 1,4-diphenethyloxynaphthalene, 1,4-naphthoquinone,
  • the photosensitive resin composition of the present invention may contain sensitizers, adhesion improvers, colorants, dispersants, etc., if necessary.
  • One form of the photosensitive resin composition of the present invention is a varnish material prepared by dissolving and diluting various raw materials in a solvent. Dissolving methods include ultrasonic waves, blade agitation, ball milling, and the like, and filter filtration may be performed as necessary. Although the filtration method is not particularly limited, a method of filtration by pressure filtration using a filter having a retained particle size of 1 ⁇ m to 50 ⁇ m is preferred.
  • the solvent for dilution is not particularly limited, but ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate and butyl lactate , acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, ketones such
  • the photosensitive resin composition of the present invention is obtained by coating the photosensitive resin composition in the form of the above-described varnish material on a supporting film (also referred to as a support film), drying, and forming a layer composed of the photosensitive resin composition. is formed on the support film to form a photosensitive resin sheet. That is, the photosensitive resin sheet of the present invention is a photosensitive resin sheet having a support film and a layer (referred to as a photosensitive resin layer) comprising the photosensitive resin composition of the present invention on the support film.
  • the support film used in the photosensitive resin sheet of the present invention is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used.
  • PET polyethylene terephthalate
  • the bonding surface between the support film and the photosensitive resin layer may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like, in order to improve adhesion and releasability.
  • the thickness of the support film is not particularly limited, it is preferably in the range of 10 to 100 ⁇ m from the viewpoint of workability.
  • the haze of the support film is preferably 2.0% or less because the exposure can be performed through the support film. If the haze is more than 2.0%, scattering of exposure light occurs, resulting in poor pattern workability.
  • a protective film may be provided on the layer side of the photosensitive resin sheet composed of a layer made of a photosensitive resin composition and a support film.
  • a protective film may be provided on the layer side of the photosensitive resin sheet composed of a layer made of a photosensitive resin composition and a support film.
  • Protective films include polyethylene films, polypropylene (PP) films, polyester films, polyvinyl alcohol films, and the like.
  • the protective film is preferably such that the layer made of the photosensitive resin composition and the protective film are not easily peeled off.
  • Methods for applying the photosensitive resin composition to the support film include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma Methods such as roll coater, gravure coater, screen coater and slit die coater can be used.
  • the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., it is generally preferable that the film thickness after drying is 3 ⁇ m or more and 100 ⁇ m or less.
  • the layer made of the photosensitive resin composition preferably has a thickness of 10 to 50 ⁇ m.
  • the thickness of the layer comprising the photosensitive resin composition is preferably 10 ⁇ m or more, preferably 20 ⁇ m or more, from the viewpoint of pressure resistance. It is more preferable that the thickness is 30 ⁇ m or more.
  • the thickness of the layer made of the photosensitive resin composition is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less. Ovens, hot plates, infrared rays, etc. can be used for drying.
  • the drying temperature and drying time may be within a range in which the organic solvent can be volatilized, and it is preferable to appropriately set a range such that the photosensitive resin sheet is in an uncured or semi-cured state. Specifically, it is preferable to carry out at a temperature in the range of 40° C. to 120° C. for 1 minute to several tens of minutes. Further, these temperatures may be combined and the temperature may be increased stepwise, for example, heat treatment may be performed at 50° C., 60° C., and 70° C. for 1 minute each.
  • the visible light transmittance T25 of the photosensitive resin layer when the thickness of the photosensitive resin layer is 25 ⁇ m is preferably 40% or more and 100% or less, and preferably 50% or more and 100%. % or less.
  • the visible light transmittance T25 can be calculated by measuring the transmittance at a wavelength of 400 to 800 nm with an ultraviolet-visible spectrophotometer and averaging the values.
  • the cured product of the present invention is a cured product of the photosensitive resin composition of the present invention.
  • the cured product of the present invention can be obtained by photocuring and thermally curing the photosensitive resin composition of the present invention.
  • the 180°C storage modulus of the cured product of the present invention is preferably 10 GPa or more, more preferably 12 GPa or more, even more preferably 13 GPa or more, and particularly preferably 14 GPa or more.
  • the 180° C. storage elastic modulus of the cured product is preferably 20 GPa or less, more preferably 18 GPa or less, and even more preferably 16 GPa or less.
  • the elongation of the cured product obtained by heat treatment is preferably 0.5% or more, more preferably 1.0% or more, and even more preferably 2.0%. By setting the elongation to 0.5% or more, it is possible to suppress the occurrence of cracks during the sealing process when applied as a roofing material.
  • the cured product of the present invention preferably satisfies the relationship 15 ⁇ TG-TE ⁇ 25, where TE (°C) is the temperature at which the loss modulus is maximized and TG (°C) is the glass transition temperature.
  • TE (°C) is the temperature at which the loss modulus is maximized
  • TG (°C) is the glass transition temperature.
  • the cured product of the present invention satisfies the relationship of 1.5 ⁇ EMAX/E180 ⁇ 3.2, where EMAX (GPa) is the maximum value of the loss elastic modulus and E180 (GPa) is the loss elastic modulus at 180°C. is preferred.
  • EMAX/E180 higher than 1.5 makes it easier to withstand the sealing process when applied as a roofing material.
  • EMAX/E180 smaller than 3.2 cracks can be suppressed.
  • the hollow structure of the present invention is a hollow structure having a cured product of the photosensitive resin composition of the present invention as a roofing material.
  • the hollow structure referred to here includes a substrate, a convex portion formed on the substrate so as to surround a part of the surface of the substrate, and a film-like object (hereinafter referred to as a roofing material) in contact with the top of the convex portion. ), a closed space (hereinafter referred to as a hollow portion) is formed by a substrate, a convex portion, and a roofing material, and the roofing material contains the cured product of the present invention.
  • the hollow structure of the present invention includes a substrate, a convex portion formed on the substrate so as to surround part of the surface of the substrate, and a film-like object (hereinafter referred to as a A hollow structure having a roof material), a closed space (hereinafter referred to as a hollow portion) is formed by the substrate, the convex portion, and the roof material, and the roof material contains the cured product of the present invention.
  • the projections formed on the substrate of the hollow structure are sometimes called walls or wall materials.
  • the film-like material provided so as to be in contact with the top of the convex portion is sometimes called a roof or a roofing material.
  • the convex portion of the hollow structure may be formed on the substrate by printing a resin material or photolithographic processing of a photosensitive material. may be formed.
  • a photosensitive material it preferably contains polyimide from the viewpoint of reliability.
  • the thickness of the convex portion is 5 to 25 ⁇ m, and the width of the short side of the substrate in the hollow portion is 200 to 400 ⁇ m.
  • the width of the short side of the substrate in the hollow portion is 200 ⁇ m or more, it becomes easy to dispose the internal electrodes in the hollow portion, and when it is 400 ⁇ m or less, it becomes easy to maintain the shape of the roof during the sealing process.
  • the inner side surrounded by the convex portions may have an independent convex portion or a convex portion continuous with the outer wall.
  • the width of the short side of the substrate in the hollow portion is the width of the inner short side surrounded by the projections of the substrate (y1 in FIG. 1), and can be measured with a length-measuring microscope.
  • the roof material preferably has through holes. Since the roofing material has a through-hole, wiring can be formed inside the roofing material. This eliminates the need to form wiring on the outer wall of the hollow structure, making it possible to reduce the size of the electronic component.
  • a method for forming a hollow structure using the photosensitive resin sheet of the present invention has the following steps. Step 1: forming a convex portion on the substrate; Step 2: a step of bonding the photosensitive resin layer side of the photosensitive resin sheet onto the convex portion of the substrate; Step 3: a step of exposing the photosensitive resin layer, Step 4: a step of peeling off the support film; Step 5: a step of developing the photosensitive resin layer, Step 6: A step of thermally curing the photosensitive resin layer to obtain a cured product.
  • protrusions are formed on a substrate by printing a resin material or photolithography processing of a photosensitive material, and a method such as dry etching is used to scrape the substrate to form recesses, thereby making the protrusions relatively convex.
  • a convex portion is formed on the substrate by a method for forming a portion, or the like.
  • the photosensitive resin layer side of the photosensitive resin sheet is pasted onto the convex portion of the substrate.
  • the width x of the projection 2 is 50 ⁇ m
  • the height z of the projection 2 is 20 ⁇ m
  • the width y1 of the short side of the substrate 1 in the hollow is 300 ⁇ m
  • the width y1 of the short side of the hollow is 300 ⁇ m.
  • the width y2 of the long side of the substrate 1 of is set to 500 ⁇ m, but the dimensions are not limited to this.
  • the protective film is peeled off from the photosensitive resin sheet, the layer 4 made of the photosensitive resin composition is arranged so as to face the substrate 1 on which the projections 2 are formed, and the roll is rolled from the support film 3 side with a roll laminator. They are affixed together (FIG. 2(b)).
  • the bonding temperature and pressure are preferably 50 to 80° C. and 0.05 to 0.3 MPa, although they depend on the shape of the projections formed on the substrate.
  • a photomask capable of forming a pattern covering the projections 2 with an exposure machine using an ultra-high pressure mercury lamp, LED, laser, or the like that emits light containing ultraviolet light with a wavelength of 405 nm as a light source.
  • Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc.
  • the layer 4 made of the photosensitive resin composition becomes a layer 5 in which a desired pattern is photocured by exposure (FIG. 2(c)).
  • post-exposure baking the reaction proceeds favorably, and effects such as an improvement in resolution after development and an increase in the allowable range of development conditions can be expected.
  • an oven, a hot plate, an infrared ray, a flash annealing device, a laser annealing device, or the like can be used.
  • the post-exposure bake temperature is preferably 40 to 150°C, more preferably 60 to 150°C.
  • the post-exposure bake time is preferably 10 seconds to several hours.
  • the support film 3 is peeled off (FIG. 2(d)).
  • the support film may be peeled off before exposure, may be peeled off immediately after exposure, or may be peeled off after heat treatment after exposure.
  • a developer is used to remove the unexposed portion (FIG. 2(e)).
  • the developer include tetramethylammonium hydroxide (TMAH) aqueous solution, alkaline aqueous solution such as sodium carbonate aqueous solution, and organic solvent such as cyclohexanone and propylene glycol methyl ether acetate (PGMEA). can be selected.
  • TMAH tetramethylammonium hydroxide
  • PMEA propylene glycol methyl ether acetate
  • the temperature of the developer and the development time are appropriately set depending on the pattern shape and the like, but 20 to 30° C. and 30 seconds to 10 minutes are preferable, respectively.
  • a developing method methods such as spray, puddle, immersion, and ultrasonic waves are possible.
  • Alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.
  • a heat treatment is performed to completely cure the photosensitive resin composition to obtain a hollow structure having a cured product 6 of the photosensitive resin composition (Fig. 2(f)). Heat resistance and chemical resistance can be improved by completely curing the photosensitive resin composition by heat curing.
  • the heating temperature for improving these properties is preferably 150°C or higher, more preferably 180°C or higher.
  • the heating temperature is preferably 350° C. or lower, more preferably 300° C. or lower.
  • a temperature is selected and the temperature is raised stepwise, or a certain temperature range is selected and the temperature is raised continuously for 5 minutes to 5 hours.
  • heat treatment is performed at 150° C. and 250° C. for 30 minutes each.
  • a method of linearly raising the temperature from room temperature to 300° C. over 2 hours can be used.
  • the hollow structure of the present invention is used for electronic components having a hollow structure.
  • An elastic wave filter is mentioned as an electronic component which has a hollow structure.
  • the cured product of the present invention is used for electronic components having the cured product, and particularly preferable electronic components having the cured product of the present invention include elastic wave filters. That is, the electronic component of the present invention has the cured product of the present invention or the hollow structure of the present invention. Also, the elastic wave filter of the present invention has the cured product of the present invention or the hollow structure of the present invention.
  • the cured product of the present invention since the cured product of the present invention has excellent pattern processability and can form a highly reliable insulating film, it can be suitably used for electronic components other than electronic components having a hollow structure.
  • the use of the cured product is not particularly limited, for example, resists such as surface protective films built into substrates and packages that use semiconductors such as mounting substrates and wafer level packages, interlayer insulating films, wiring protective insulating films of circuit boards , various electronic components and devices.
  • resists such as surface protective films built into substrates and packages that use semiconductors such as mounting substrates and wafer level packages, interlayer insulating films, wiring protective insulating films of circuit boards , various electronic components and devices.
  • a permanent resist that is, a patterned interlayer insulating film, a patterned substrate, glass, semiconductor element, etc., and an adherend. can be used.
  • the radically polymerizable compound includes Bx, By, and Bz, and the respective radically polymerizable functional group equivalents are Rx, Ry, and Rz, and the respective masses are Wx, Wy, and Wz. If their sum is W, the average of the radically polymerizable functional group equivalents is Rx (Wx/W) + Ry (Wy/W) + Rz (Wz/W).
  • D After melting 50 g of the inorganic filler in a platinum crucible at 1500° C. for 4 hours, the melt was poured into a carbon mold and slowly cooled to obtain a lump of the (D) inorganic filler.
  • the obtained (D) inorganic filler mass was processed into a rectangular parallelepiped shape of 10 mm or more ⁇ 10 mm or more ⁇ 10 mm or more, and a precision refractometer KPR-2000 manufactured by Shimadzu Device Manufacturing Co., Ltd. was used to measure the refractive index at a wavelength of 405 nm. did.
  • ⁇ (D) Refractive index of solid content of photosensitive resin composition excluding inorganic filler> A solution was prepared by removing (D) the inorganic filler from the photosensitive resin composition, applied onto a silicon wafer and dried. Using a spectroscopic ellipsometer SE-2000 manufactured by Japan Semilab Co., Ltd., the refractive index at a wavelength of 405 nm at 25° C. was measured by the ellipsometry method.
  • the layer composed of the obtained support film and the photosensitive resin composition was exposed with an exposure amount of 400 mJ/cm 2 (using an i-line cut filter, converted to h-line) using an exposure machine using an ultra-high pressure mercury lamp as a light source. After exposure, the support film was peeled off, and heat treatment was performed at 200° C. for 60 minutes in an inert oven to form a cured product on the silicon wafer.
  • a single film was produced by peeling the obtained cured product from the silicon wafer. This single film was cut into 5 mm ⁇ 40 mm pieces with a single edge, and measured by a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd., DMS6100). A maximum value EMAX of the loss elastic modulus and a loss elastic modulus E180 at 180° C. were measured.
  • test mode tensile
  • test temperature room temperature (23°C) to 350°C
  • heating rate 5°C/min
  • test frequency 1Hz
  • distance between chucks 10mm
  • sample width 5mm. implemented.
  • the obtained 180° C. storage elastic modulus was used as the evaluation result.
  • the protective film of the photosensitive resin sheet obtained in each example and each comparative example was peeled off, arranged so that the layer made of the photosensitive resin composition faced the silicon wafer, and heated at 80 ° C. and 0.3 MPa for 4 times. It was roll laminated onto an inch silicon wafer.
  • a photomask having 20 via patterns with via diameters of 5, 10, 15, and 5 ⁇ m increments up to 100 ⁇ m was placed on the layer composed of the obtained support film and the photosensitive resin composition, and an ultra-high pressure mercury lamp was applied. Exposure was performed at an exposure amount of 400 mJ/cm 2 (using an i-line cut filter, converted to h-line) using an exposure machine as a light source. After exposure, the support film was peeled off and heated on a hot plate at 100°C for 5 minutes. Next, using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, the unexposed portion was removed by shower development for 480 seconds, rinsed with water for 60 seconds, and then spin-dried. Further, a heat treatment was performed at 200° C. for 60 minutes in an inert oven to form a cured product having a via pattern processed on the silicon wafer.
  • the via pattern was observed with a microscope, and the minimum dimension of the opening of the via was defined as the resolution.
  • the opening of the via as referred to herein is defined as opening at 50% or more of the design value of the photomask. It was judged as A when a via of 45 ⁇ m or less was opened, and as B when a via of 50 ⁇ m to 100 ⁇ m was opened.
  • This measurement was performed under the conditions of reference: support film, scan speed: 300 nm/min, sampling interval: 0.5 nm.
  • a sample with a visible light transmittance T25 of 40% or more was rated as A, and a sample with a visible light transmittance T25 of less than 40% was rated as B.
  • a single film of a cured product of the photosensitive resin composition was prepared by performing the same treatment as in the evaluation of the 180° C. storage modulus described above. This monolayer was cut into 10 mm ⁇ 100 mm pieces with a single-edged blade, and the elongation was measured with a tensile tester (UTM-4-100 manufactured by Baldwin).
  • this measurement was performed under the conditions of a tensile speed of 50 mm/min, a distance between chucks of 50 mm, and a sample width of 10 mm. A was given when the elongation was 2% or more, B was given when the elongation was 1% or more and less than 2%, and C was given when the elongation was less than 1%.
  • Polyimide 1 An alkali-soluble polyimide synthesized by the following method was used.
  • NMP N-methyl-2-pyrrolidone
  • the imidization rate of the obtained polyimide was 94%. Further, the solubility of polyimide A1 in a 23° C. tetramethylammonium aqueous solution (2.38% by mass) was 0.5 g/100 g or more.
  • ADDM (Mitsubishi Chemical Corporation). Chemical name: 1,3-adamantane dimethacrylate, radically polymerizable functional group equivalent: 152 g/eq, number of functional groups: 2. (B2) corresponds to the component. Corresponds to general formula (4).
  • Silica 1 SO-E2 (Admatechs Co., Ltd.). Fused silica with 100% silicon oxide by weight. Refractive index (wavelength 405 nm): 1.47, average particle size: 0.5 ⁇ m, amount of extracted ions (total amount of magnesium ions, calcium ions, and zinc ions): 2 ppm (weight basis).
  • Example 1 Preparation of the photosensitive resin composition of Example 1 is shown below as an example.
  • A Polyimide 1 (35 g) as polymer
  • B DPE-6A (20 g) as photopolymerizable compound
  • C OXE-04 (1.5 g) as photopolymerization initiator
  • D Inorganic filler as a glass filler 1 (150 g)
  • E a ⁇ -butyrolactone solution of HMOM-TPHAP as a thermal cross-linking agent (30 g (6 g as solid content)), as a polymerization inhibitor phenothiazine (0.01 g), as an adhesion improver KBM- 403 (2 g) and ethyl lactate (68 g) as a diluting solvent were added and stirred at room temperature for 120 minutes, and the resulting solution was filtered under pressure using a filter with a retention particle size of 10 ⁇ m, thereby obtaining a photosensitive resin.
  • a composition was obtained.
  • the resulting photosensitive resin composition was coated on a support film (50 ⁇ m thick PET film) using a comma roll coater and dried at 65° C. for 5 minutes. was laminated to obtain a photosensitive resin sheet having a photosensitive resin layer with a thickness of 25 ⁇ m.
  • the obtained photosensitive resin sheet was evaluated by the method described above, and the evaluation results of Example 1 are shown in Table 1.
  • (B) the radically polymerizable functional group equivalent of the radically polymerizable compound is on average 70 g/eq or more and 200 g/eq or less in Examples 1 to 11, in which the amount of (D) the inorganic filler is Compared with the same Comparative Example 1, the 180° C. storage elastic modulus was high, and a favorable result of 10 GPa or more was obtained.
  • the inorganic filler is a glass filler, and in Examples 1 to 9 consisting only of the (B) radical polymerizable compound corresponding to the general formula (4), the 180 ° C. storage elastic modulus and the resolution were good. .
  • a cured product with excellent pattern workability and pressure resistance can be formed.
  • the cured product obtained from the photosensitive resin composition of the present invention has excellent electrical properties, mechanical properties and heat resistance, and has high reliability. It is useful for applications such as wiring protective insulating films. Furthermore, it is useful for electronic parts having hollow structures that require pressure resistance, especially hollow structures such as elastic wave filters and crystal devices for roof applications.
  • Substrate 2 Protrusions 3: Support film 4: Layer made of photosensitive resin composition 5: Photocured layer 6: Cured product x: Width of protrusions y1: Inner shortness surrounded by protrusions of substrate Width of side y2: Width of inner long side surrounded by protrusions of substrate z: Height of protrusions

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Abstract

Le but de la présente invention est de fournir une composition de résine photosensible ayant une excellente aptitude au traitement de motifs et une excellente résistance à la pression. La présente invention concerne une composition de résine photosensible comprenant (A) un polymère, (B) un composé polymérisable par voie radicalaire, (C) un initiateur de photopolymérisation, et (D) une charge inorganique, l'équivalent en groupe fonctionnel polymérisable par voie radicalaire du (B) composé polymérisable par voie radicalaire étant en moyenne de 70 à 200 g/éq.
PCT/JP2022/002548 2021-02-01 2022-01-25 Composition de résine photosensible, feuille de résine photosensible, produit durci, structure creuse, composant électronique et filtre à ondes élastiques WO2022163610A1 (fr)

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CN202280012404.5A CN116830039A (zh) 2021-02-01 2022-01-25 感光性树脂组合物、感光性树脂片、固化物、中空结构体、电子部件及弹性波滤波器
KR1020237023729A KR20230141762A (ko) 2021-02-01 2022-01-25 감광성 수지 조성물, 감광성 수지 시트, 경화물, 중공구조체, 전자 부품 및 탄성파 필터
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* Cited by examiner, † Cited by third party
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JP2015187750A (ja) * 2010-05-20 2015-10-29 日立化成株式会社 感光性樹脂組成物、感光性フィルム、リブパターンの形成方法、中空構造とその形成方法及び電子部品
JP2015207284A (ja) * 2014-04-10 2015-11-19 富士フイルム株式会社 パターン形成方法、硬化物、タッチパネル又はディスプレイパネルの製造方法、及び、表示装置
JP2016151753A (ja) * 2015-02-19 2016-08-22 富士フイルム株式会社 感光性組成物、硬化膜の製造方法、硬化膜、液晶表示装置、有機ｅｌ表示装置、タッチパネル及びタッチパネル表示装置
JP2018189851A (ja) * 2017-05-09 2018-11-29 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物および電子部品
JP2020166125A (ja) * 2019-03-29 2020-10-08 東レ株式会社 中空構造体の製造方法

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JP6232997B2 (ja) 2013-12-18 2017-11-22 東レ株式会社 感光性樹脂組成物、それからなる感光性樹脂フィルム、それから形成された絶縁膜およびそれを有する多層配線基板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015187750A (ja) * 2010-05-20 2015-10-29 日立化成株式会社 感光性樹脂組成物、感光性フィルム、リブパターンの形成方法、中空構造とその形成方法及び電子部品
JP2015207284A (ja) * 2014-04-10 2015-11-19 富士フイルム株式会社 パターン形成方法、硬化物、タッチパネル又はディスプレイパネルの製造方法、及び、表示装置
JP2016151753A (ja) * 2015-02-19 2016-08-22 富士フイルム株式会社 感光性組成物、硬化膜の製造方法、硬化膜、液晶表示装置、有機ｅｌ表示装置、タッチパネル及びタッチパネル表示装置
JP2018189851A (ja) * 2017-05-09 2018-11-29 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物および電子部品
JP2020166125A (ja) * 2019-03-29 2020-10-08 東レ株式会社 中空構造体の製造方法

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