WO2017126536A1 - Composition de résine, feuille de résine avec support, carte imprimée multicouche et dispositif semi-conducteur - Google Patents

Composition de résine, feuille de résine avec support, carte imprimée multicouche et dispositif semi-conducteur Download PDF

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Publication number
WO2017126536A1
WO2017126536A1 PCT/JP2017/001510 JP2017001510W WO2017126536A1 WO 2017126536 A1 WO2017126536 A1 WO 2017126536A1 JP 2017001510 W JP2017001510 W JP 2017001510W WO 2017126536 A1 WO2017126536 A1 WO 2017126536A1
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WIPO (PCT)
Prior art keywords
resin composition
mass
parts
resin
meth
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PCT/JP2017/001510
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English (en)
Japanese (ja)
Inventor
鈴木　卓也
慎也 喜多村
誠司 四家
Original Assignee
三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to KR1020187010037A priority Critical patent/KR20180103819A/ko
Priority to JP2017562838A priority patent/JP6858351B2/ja
Priority to CN201780007395.XA priority patent/CN108495878B/zh
Publication of WO2017126536A1 publication Critical patent/WO2017126536A1/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
    • C08F2/46—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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • 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
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to a resin composition, a resin sheet with a support using the same, a multilayer printed wiring board, and a semiconductor device.
  • thermosetting resin is mainly used as a resin composition as a material for the insulating layer, and a hole for obtaining conduction between insulating layers is generally performed by laser processing.
  • drilling by laser processing has a problem that the processing time becomes longer as the high-density substrate having a larger number of holes is obtained. Therefore, in recent years, there has been a demand for a resin sheet that can be collectively punched in a development process by using a resin composition that is cured by light or the like and dissolved by development.
  • Patent Document 1 discloses a composition that can be developed into an aqueous alkaline solution using an acid-modified novolak epoxy acrylate.
  • Patent Document 2 the photosensitive resin composition which improved the mechanical characteristic by containing a specific hardening
  • Patent Document 3 discloses a photosensitive resin composition for use in an interlayer insulating layer of a multilayer printed wiring board.
  • a cured product using a conventional acrylate cannot provide sufficient physical properties, and there is a limit to the formation of a protective film having high heat resistance and an interlayer insulating layer.
  • the use is limited to an etching resist or a solder resist for printed wiring boards, and the heat resistance is not sufficient for use as an interlayer insulating layer.
  • the glass transition temperature is 115 ° C., and the heat resistance is not sufficient.
  • the photosensitive resin composition described in Patent Document 3 is developed using an organic solvent as a developing solution, and is an aqueous type that does not use an organic solvent such as an alkaline aqueous solution that is mainly used in developing solutions in the field of printed wiring boards. The developability with a developer is not sufficient.
  • the present invention has been made in view of the above problems, and when used in a multilayer printed wiring board, a resin composition having excellent heat resistance and developability, a resin sheet with a support, and the like To provide a multilayer printed wiring board and a semiconductor device using the above.
  • the present inventors represent a compound (A) represented by the following formula (1) and having an acid value of 30 mgKOH / g or more and 120 mgKOH / g or less, a photocuring initiator (B), a maleimide compound (C) and / or
  • the present inventors have found that the above problems can be solved by using a resin composition containing blocked isocyanate (D), and have completed the present invention.
  • each of the plurality of R 1 independently represents a hydrogen atom or a methyl group
  • each of the plurality of R 2 independently represents a hydrogen atom or a methyl group
  • each of the plurality of R 3 represents, Independently, it represents a substituent represented by the following formula (2), a substituent represented by the following formula (3), or a hydroxy group.
  • R 4 represents a hydrogen atom or a methyl group
  • E an epoxy resin
  • the resin composition according to [1] or [2] further including a compound (F) having an ethylenically unsaturated group other than the compound (A).
  • a resin sheet with a support comprising the resin composition according to any one of [1] to [4], which is applied to the support.
  • a multilayer printed wiring board having the resin composition according to any one of [1] to [4].
  • a semiconductor device comprising the resin composition according to any one of [1] to [4].
  • cured with the active energy ray which is excellent in coating-film property, heat resistance, and developability, and has a suitable property for the protective film of a multilayer printed wiring board, and an interlayer insulation layer, Resin with support Sheets, multilayer printed wiring boards using them, and semiconductor devices can be provided.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
  • the present invention can be appropriately modified within the scope of the gist.
  • (meth) acryloyl group means both “acryloyl group” and the corresponding “methacryloyl group”
  • “(meth) acrylate” means “acrylate” and the corresponding “methacrylate”.
  • (Meth) acrylic acid” means both "acrylic acid” and the corresponding "methacrylic acid”.
  • “resin solid content” or “resin solid content in the resin composition” means a component excluding the solvent and the inorganic filler (G) in the resin composition unless otherwise specified.
  • the “resin solid content of 100 parts by mass” means that the total of the components excluding the solvent and the inorganic filler (G) in the resin composition is 100 parts by mass.
  • the resin composition of this embodiment contains the compound (A), a photocuring initiator (B), a maleimide compound (C) and / or a blocked isocyanate (D).
  • A a photocuring initiator
  • B a maleimide compound
  • D a blocked isocyanate
  • Compound (A) used in the present embodiment is a compound represented by the formula (1).
  • Compound (A) may be used alone, may contain isomers such as structural isomers and stereoisomers, and may be used in appropriate combination of two or more compounds having different structures.
  • R ⁇ 1 > represents a hydrogen atom or a methyl group each independently. Among them, it is preferable to include a viewpoint from hydrogen atoms to improve the reactivity of the photocuring reaction, more preferably all of R 1 is a hydrogen atom.
  • R ⁇ 2 > represents a hydrogen atom or a methyl group each independently. Among them, preferably comprises a methyl group from the viewpoint of improving the heat resistance of the cured product, and more preferably all of R 2 is a methyl group.
  • R ⁇ 3 > represents the substituent represented by the said Formula (2), the substituent represented by the said Formula (3), or a hydroxy group each independently. Among these, it is preferable that a hydroxyl group is included from a viewpoint of improving heat resistance. Moreover, in this embodiment, it is also preferable from a viewpoint of improving developability to use the compound (A) containing the substituent represented by said Formula (2) among several R ⁇ 3 >. In the present embodiment, it is also preferable to use the compound (A) containing a substituent represented by the formula (3) among the plurality of R 3 from the viewpoint of improving heat resistance.
  • R 4 represents a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable from the viewpoint of improving the reactivity of the photocuring reaction.
  • the plurality of R 3 have a ratio of the substituent represented by the formula (2) of 20% or more and 85% or less of all the substituents of R 3 , and the formula (3). Is preferably 5% to 70%, and the hydroxy group is preferably 10% to 75%.
  • the compound (A) preferably contains at least one of the following compounds (A1) to (A5) because the reactivity of the photocuring reaction, the heat resistance of the cured product and the developability can be improved. More preferably, at least compound (A1) is included, more preferably any two or more of (A1) to (A5) are included, and any one of compound (A1) and compounds (A2) to (A5) is included. More preferably, it contains more than one species. As the compound (A), it is also preferable that at least the compounds (A2) and (A3) are included.
  • Such compounds may be commercially available, for example, KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR- 6007H (above, trade name, manufactured by Nippon Kayaku Co., Ltd.).
  • the acid value of the compound (A) is 30 mgKOH / g or more from the viewpoint of improving developability, and the developability is further improved, so that it is 50 mgKOH / g or more. preferable.
  • the acid value of the compound (A) is 120 mgKOH / g or less, and since dissolution can be further prevented, it is 110 mgKOH / g or less. Is preferred.
  • the “acid value” in the present embodiment indicates a value measured by a method according to JISK 0070: 1992.
  • the content of the compound (A) is not particularly limited, but from the viewpoint of curing the resin composition with active energy rays, the resin solid content in the resin composition is 100 parts by mass. 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, still more preferably 10 parts by mass or more, even more preferably 25 parts by mass or more. It is still more preferable, and it is still more preferable to set it as 30 mass parts or more. Further, from the viewpoint of sufficiently curing with active energy rays and improving heat resistance and developability, it is preferably 99 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition, and 98 parts by mass. More preferably, it is more preferably 97 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 75 parts by mass or less, and even more preferably 73 parts by mass or less. Most preferred.
  • Photocuring initiator (B) used for this embodiment is not specifically limited, A well-known thing can be used in the field
  • Examples of the photocuring initiator (B) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, and parachlorobenzoyl peroxide.
  • Organic peroxides exemplified by oxides, di-tert-butyl-di-perphthalate, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- Dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- -Acetophenones such as morpholino-propan-1-one, anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone Thioxanthones such as 2-chlorothioxanthone, ket
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (from the viewpoint of reactivity suitable for multilayer printed wiring board applications and high reliability for metal conductors)
  • a radical photocuring initiator of acetophenones such as ISFacure (registered trademark) 369 manufactured by BASF Japan Ltd. is preferable.
  • photocuring initiators (B) can be used alone or in combination of two or more, and both radical and cationic initiators may be used in combination.
  • the content of the photocuring initiator (B) in the resin composition of the present embodiment is not particularly limited. From the viewpoint of sufficiently curing the resin composition with active energy rays and improving heat resistance, the resin composition. It is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the resin solid content therein. It is still more preferable to set it as 1 mass part or more. Further, from the viewpoint of preventing the heat curing after photocuring and preventing the heat resistance from being lowered, the content is preferably 30 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.
  • either the maleimide compound (C) or the blocked isocyanate (D) can be used, and these can be used in combination.
  • the maleimide compound (C) from the viewpoint of improving the coating properties, heat resistance and developability, it is preferable to use the maleimide compound (C), further improving the heat resistance and developability, and further improving the coating properties. More preferably, the maleimide compound (C) and the blocked isocyanate (D) are used in combination.
  • the maleimide compound (C) and the blocked isocyanate (D) are described in detail below.
  • the maleimide compound (C) used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include, for example, N-phenylmaleimide, phenylmethanemaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane.
  • 4,4-diphenylmethane bismaleimide bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4 -Maleimidophenyl) methane, polytetramethylene oxide-bis (4-maleimidobenzoate), o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide , P-fe Renbiscitraconimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6-bismaleimide- (2,
  • a maleimide compound represented by the following formula (4) and a maleimide compound represented by the following formula (5) are preferable, and the following formula (4) ) Is more preferred.
  • a commercially available product can be used as the maleimide compound represented by the following formula (4), and examples thereof include BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.).
  • the maleimide compound represented by the following formula (5) a commercially available product can be used, and examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.).
  • These maleimide compounds (C) can be used singly or in appropriate combination of two or more.
  • each of the plurality of R 5 independently represents a hydrogen atom or a methyl group.
  • N 1 represents an integer of 1 or more, preferably an integer of 1 to 10).
  • each of the plurality of R 6 independently represents a hydrogen atom or a methyl group.
  • N 2 represents an integer of 1 or more, preferably an integer of 1 to 5).
  • the content of the maleimide compound (C) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, the resin solid content 100 in the resin composition is 100%. It is preferable to set it as 0.01 mass part or more with respect to a mass part, It is more preferable to set it as 0.02 mass part or more, It is still more preferable to set it as 0.03 mass part or more, 0.5 mass part or more Even more preferably.
  • the blocked isocyanate (D) used in the present embodiment is not particularly limited as long as it is inactive at room temperature (25 ° C.), but the blocking agent is reversibly dissociated to regenerate isocyanate groups when heated.
  • Examples of the blocked skeleton of the blocked isocyanate (D) include isocyanurate type, biuret type, and adduct type, and isocyanurate type is preferable from the viewpoint of heat resistance. These blocked isocyanates (D) can be used singly or in appropriate combination of two or more.
  • Examples of the blocking agent that is inactive at room temperature (25 ° C.) but reversibly dissociates when heated include at least one compound selected from diketones, oximes, phenols, alkanols, and caprolactams. Specific examples include methyl ethyl ketone oxime and ⁇ -caprolactam.
  • the dissociation temperature of the blocking agent is not particularly limited, but is preferably 120 ° C. or higher from the viewpoint of sufficiently curing the resin composition and improving heat resistance. Moreover, the thing below 200 degreeC is preferable from a viewpoint of making a block agent fully dissociate and hardening a resin composition.
  • the above blocking agent is dissociated during heating and discharged as a gas. Therefore, it is preferable to use a blocking agent having a small molecular weight because it causes a volume reduction. Specifically, it is preferable to use a methyl ethyl ketone oxime type.
  • Such blocked isocyanates are readily available as commercial products, for example, Sumidur (registered trademark) BL-3175, BL-4265, BL-5375, BL-1100, BL-1265, , Sumika Covestrourethane Co., Ltd.), Coronate (registered trademark) 2507, Coronate (registered trademark) 2554 (trade name, manufactured by Tosoh Corporation), Duranate (registered trademark) TPA-B80E, Duranate (Registered Trademark) 17B-60PX (above, trade name, manufactured by Asahi Kasei Chemicals Corporation) and the like.
  • the blocked skeleton is at least one selected from the group of isocyanurate type, selected from Sumidur (registered trademark) BL-3175 and Duranate (registered trademark) TPA-B80E.
  • isocyanurate type selected from Sumidur (registered trademark) BL-3175 and Duranate (registered trademark) TPA-B80E.
  • the content of the blocked isocyanate (D) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, the resin solid content in the resin composition It is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.3 parts by mass or more, and 0.5 parts by mass with respect to 100 parts by mass. It is even more preferable to use the above. Further, from the viewpoint of suppressing the volume reduction of the resin composition and being excellent in developability, it is 5.0 parts by mass or less or less than 5.0 parts by mass with respect to 100 parts by mass of resin solid content in the resin composition. It is preferably 4.0 parts by mass or less or less than 4.0 parts by mass, more preferably 3.0 parts by mass or less or less than 3.0 parts by mass.
  • the maleimide compound (C) and the blocked isocyanate (D) are used in combination, their content is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, It is preferable to set it as 0.11 mass part or more with respect to 100 mass parts of resin solid content of this, It is more preferable to set it as 0.5 mass part or more, It is still more preferable to set it as 1 mass part or more, 3 mass parts It is even more preferable to use the above. Moreover, from a viewpoint that the volume reduction of a resin composition is suppressed, it is excellent in developability, and a more favorable coating film is obtained, it shall be 55 mass parts or less with respect to 100 mass parts of resin solid content in a resin composition. It is preferably 25 parts by mass or less, more preferably 15 parts by mass, still more preferably 13 parts by mass or less, and still more preferably 10 parts by mass.
  • epoxy resin (E) In order to improve the developability and the heat resistance of the cured product, the epoxy resin (E) can be used in combination with the resin composition of the present embodiment.
  • the epoxy resin (E) used in the present embodiment is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolak type epoxy resin, xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, Trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, triglycidyl isocyanurate, glycidyl ester epoxy resin, alicyclic Poxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novol
  • biphenyl aralkyl type epoxy resins it is preferably at least one selected from the group consisting of biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins, and biphenyl aralkyl type epoxy resins are more preferable. .
  • epoxy resins (E) can be used singly or in appropriate combination of two or more.
  • the content of the epoxy resin (E) is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, the resin solid content in the resin composition is 100 parts by mass. 1.0 part by mass or more, preferably 1.5 parts by mass or more, more preferably 2.0 parts by mass or more, and even more preferably 8 parts by mass or more. . Further, from the viewpoint of improving the developability of the resin composition, it is preferably 90 parts by mass or less and more preferably 70 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, it is 50 mass parts or less, More preferably, it is 25 mass parts or less.
  • the resin composition of the present embodiment is used in combination with a compound (F) having an ethylenically unsaturated group in order to increase the reactivity to active energy rays (for example, ultraviolet rays) and improve the developability and heat resistance. Is also possible.
  • the compound (F) having an ethylenically unsaturated group used in the present embodiment is other than the compound (A) represented by the formula (1) and having an acid value of 30 mgKOH / g or more and 120 mgKOH / g or less.
  • a compound having a (meth) acryloyl group methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether , Phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylenedi (meth) a Relate,
  • urethane (meth) acrylates that have (meth) acryloyl groups and urethane bonds in the same molecule
  • polyester (meth) acrylates that have (meth) acryloyl groups and ester bonds in the same molecule
  • epoxy resins Epoxy (meth) acrylates derived from the above and having a (meth) acryloyl group, and reactive oligomers in which these bonds are used in combination.
  • the urethane (meth) acrylate is a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as necessary.
  • hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin (meta) such as glycerin mono (meth) acrylate, glycerin di (meth) acrylate, etc.
  • Sugar alcohol (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , Isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate Dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.
  • polyisocyanates such as buret reactants, the urethane (meth) acrylates.
  • the above epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid.
  • phenol novolac type epoxy (meth) acrylate cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolak type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy ( And (meth) acrylate and the like, and acid anhydride-modified epoxy (meth) acrylate and the like.
  • Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether.
  • Examples of styrenes include styrene, methyl styrene, ethyl styrene, divinyl benzene, ⁇ -methyl styrene, and oligomers thereof.
  • Other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, bisallyl nadiimide and the like.
  • the heat resistance of the resulting cured product tends to be further improved.
  • the content of the compound (F) having an ethylenically unsaturated group is not particularly limited, but from the viewpoint of improving developability, the resin solid content in the resin composition is 100 mass. 0.5 parts by mass or more with respect to parts, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, and more preferably 5 parts by mass or more. Is more preferable, and it is most preferable to set it to 15 parts by mass or more. Further, from the viewpoint of improving the heat resistance of the cured product, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. 50 parts by mass or less, more preferably 25 parts by mass or more.
  • an inorganic filler (G) can be used in combination in order to improve various properties such as coating properties, developability and heat resistance.
  • the inorganic filler (G) used in the present embodiment is not particularly limited as long as it has insulating properties.
  • silica for example, natural silica, fused silica, amorphous silica, hollow silica, etc.
  • an aluminum compound for example, Boehmite, aluminum hydroxide, alumina, etc.
  • magnesium compounds eg, magnesium oxide, magnesium hydroxide, etc.
  • calcium compounds eg, calcium carbonate, etc.
  • molybdenum compounds eg, molybdenum oxide, zinc molybdate, etc.
  • barium compounds eg, sulfuric acid
  • talc eg, natural talc, calcined talc, etc.
  • mica mica
  • glass eg, short fiber glass, spherical glass, fine powder glass (eg, E glass, T glass, D glass, etc.)) Etc.) and silicone powder.
  • glass eg, short fiber glass, spherical glass, fine powder glass (eg, E glass, T glass, D glass, etc.)) Etc
  • one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, magnesium hydroxide, and barium sulfate is preferable.
  • These inorganic fillers (G) may be surface-treated with a silane coupling agent described later.
  • silica is preferable and fused silica is particularly preferable from the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties.
  • Specific examples of silica include SFP-130MC manufactured by Denka Corporation, SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Corporation.
  • These inorganic fillers (G) can be used singly or in appropriate combination of two or more.
  • the content of the inorganic filler (G) is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, the resin solid content in the resin composition is 100 parts by mass. It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. Further, from the viewpoint of improving the developability of the resin composition, it is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, the amount is 300 parts by mass or less, and more preferably 100 parts by mass or less.
  • a silane coupling agent and / or a wet dispersant is used in combination. It is also possible.
  • silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for inorganic surface treatment.
  • Specific examples include, for example, aminosilanes such as ⁇ -aminopropyltriethoxysilane and N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane; epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane Acrylic silanes such as ⁇ -acryloxypropyltrimethoxysilane; cationic silanes such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride; phenylsilane silane cups A ring agent is mentioned.
  • These silane coupling agents can be used alone or in combination of two or more.
  • the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • the wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints.
  • Specific examples include wet dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, and W903 manufactured by Big Chemie Japan Co., Ltd. . These wetting and dispersing agents can be used singly or in appropriate combination of two or more.
  • the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • thermosetting accelerator In the resin composition of the present embodiment, a thermosetting accelerator can be used in combination as long as the characteristics of the present embodiment are not impaired.
  • thermosetting accelerator is not particularly limited, and examples thereof include organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, and the like.
  • Azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline , N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, tertiary amines such as N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, stearic acid lead, Organic metal salts such as zinc phthalate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and acetylacetone iron; these organic metal salts are dissolved in hydroxyl-containing compounds such as phenol and bisphenol Inorganic metal salts
  • thermosetting accelerators can be used singly or in appropriate combination of two or more.
  • the content of the thermosetting accelerator is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • the resin composition of the present embodiment may contain a solvent as necessary.
  • a solvent for example, when an organic solvent is used, the viscosity at the time of preparing the resin composition can be adjusted.
  • the kind of solvent will not be specifically limited if it can melt
  • organic solvents can be used singly or in appropriate combination of two or more.
  • thermosetting resins thermoplastic resins and oligomers thereof, elastomers, etc.
  • Flame retardant compound not mentioned so far; combined use of additives and the like is also possible. These are not particularly limited as long as they are generally used.
  • flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters.
  • Additives include UV absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface conditioners, brighteners, polymerization inhibitors, etc. It is done. These components can be used alone or in appropriate combination of two or more.
  • the content of other components is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • the resin composition of the present embodiment comprises a compound (A), a photocuring initiator (B), a maleimide compound (C) and / or a blocked isocyanate (D), and, if desired, an epoxy resin (E), ethylenic It is prepared by appropriately mixing a compound (F) having an unsaturated group, an inorganic filler (G), a silane coupling agent, a wetting and dispersing agent, a thermosetting accelerator, an organic solvent and other components.
  • the resin composition of this embodiment can be used suitably as a varnish at the time of producing the resin sheet with a support body of this embodiment mentioned later.
  • the manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix
  • a known process for uniformly dissolving or dispersing each component can be performed as necessary.
  • the dispersibility of the inorganic filler (G) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability.
  • the stirring, mixing, and kneading processes described above are, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll, ball mill, bead mill, and sand mill, or a revolving or rotating type.
  • an organic solvent can be used as needed.
  • the type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.
  • the resin composition of the present embodiment can be used for applications where an insulating resin composition is required, and is not particularly limited, but a photosensitive film, a photosensitive film with a support, a resin sheet with a support, Used for insulating resin sheets such as prepreg, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-filling resins, etc. be able to. Especially, it can be conveniently used as a resin composition for insulating layers of a multilayer printed wiring board or a solder resist.
  • the resin sheet with a support of the present embodiment comprises the support and a resin composition layer that is formed on the surface of the support and includes the resin composition of the present embodiment. It is the resin sheet with a support body apply
  • the resin sheet with a support can be produced by applying the resin composition onto a support and drying.
  • the support used in the resin sheet with a support of the present embodiment is not particularly limited, but a known one can be used, and a resin film is preferable.
  • the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, and polyvinyl alcohol.
  • resin films such as films and triacetyl acetate films. Among these, a PET film is preferable.
  • the resin film having a release agent coated on the surface thereof can be suitably used in order to facilitate peeling from the resin composition layer.
  • the thickness of the resin film is preferably in the range of 5 ⁇ m to 100 ⁇ m, and more preferably in the range of 10 ⁇ m to 50 ⁇ m. If the thickness is less than 5 ⁇ m, the support tends to be broken when the support is peeled off before development, and if the thickness exceeds 100 ⁇ m, the resolution when exposed from the support tends to decrease. is there.
  • the resin film has excellent transparency.
  • the resin composition layer may be protected with a protective film.
  • a protective film By protecting the resin composition layer side with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer.
  • the protective film a film made of the same material as the above resin film can be used.
  • the thickness of the protective film is not particularly limited, but is preferably in the range of 1 ⁇ m to 50 ⁇ m, and more preferably in the range of 5 ⁇ m to 40 ⁇ m. When the thickness is less than 1 ⁇ m, the handleability of the protective film tends to be lowered, and when it exceeds 50 ⁇ m, the inexpensiveness tends to be inferior.
  • the protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support.
  • the production method of the resin sheet with a support of the present embodiment is not particularly limited.
  • the resin sheet of the present embodiment is applied to a support such as a PET film and the organic solvent is removed by drying.
  • Examples thereof include a method for producing a body-attached resin sheet.
  • the coating can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, squeeze coater or the like.
  • the drying can be performed, for example, by a method of heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes.
  • the amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less with respect to the total mass of the resin composition layer from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
  • the thickness of the resin composition layer with respect to the support is preferably 1.0 ⁇ m or more in terms of the resin composition layer thickness of the resin sheet with the support, from the viewpoint of improving the handleability. Further, from the viewpoint of improving the transmittance and improving the developability, the thickness is preferably 300 ⁇ m or less.
  • the resin sheet with a support of the present embodiment can be used as an interlayer insulating layer of a multilayer printed wiring board.
  • the multilayer printed wiring board of the present embodiment can be obtained by, for example, stacking and curing one or more of the above-described resin sheets with a support.
  • the multilayer printed wiring board of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and can be specifically manufactured by the following method.
  • the resin composition layer side of the resin sheet with a support of the present embodiment is laminated on one or both sides of a circuit board using a vacuum laminator.
  • the circuit board include a glass epoxy board, a metal board, a ceramic board, a silicon board, a semiconductor sealing resin board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board.
  • the circuit board refers to a board on which a conductor layer (circuit) patterned on one or both sides of the board is formed.
  • the surface of the conductor layer may be previously roughened by blackening treatment, copper etching, or the like.
  • the laminating step when the resin sheet with a support has a protective film, the protective film is peeled and removed, and then the resin sheet with the support and the circuit board are preheated as necessary, and the resin composition layer is removed. Crimp to circuit board while pressing and heating.
  • a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used.
  • the conditions for the laminating step are not particularly limited.
  • the pressure bonding temperature (laminating temperature) is preferably 50 ° C. to 140 ° C.
  • the pressure bonding pressure is preferably 1 kgf / cm 2 to 15 kgf / cm 2
  • the pressure bonding time Is preferably 5 seconds to 300 seconds
  • lamination is performed under reduced pressure so that the air pressure is 20 mmHg or less.
  • the laminating step may be a batch type or a continuous type using a roll.
  • the vacuum laminating method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a 2-stage build-up laminator manufactured by Nikko Materials Co., Ltd. can be exemplified.
  • an exposure process is performed in which a predetermined portion of the resin composition layer is irradiated with active energy rays to cure the resin composition layer of the irradiated portion.
  • the active energy ray may be irradiated through a mask pattern or a direct drawing method in which an active energy ray is directly irradiated.
  • Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable.
  • the irradiation amount of ultraviolet rays is about 10 mJ / cm 2 to 1000 mJ / cm 2 .
  • There are two methods for exposing the mask pattern a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board, and a non-contact exposure method in which exposure is carried out using parallel light rays without being brought into close contact. It doesn't matter.
  • the support body exists on a resin composition layer, you may expose from a support body and may expose after a support body peels.
  • the developer is not particularly limited as long as it selectively elutes an unexposed portion, but a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. .
  • a development step using an alkaline aqueous solution is particularly preferable.
  • These developers can be used singly or in combination of two or more.
  • a developing method it can carry out by well-known methods, such as spraying, rocking immersion, brushing, and scraping, for example.
  • the alkaline aqueous solution used as the developer is not particularly limited.
  • potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, 4-sodium borate, ammonia And amines are examples of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, 4-sodium borate, ammonia And amines.
  • the concentration of the alkaline aqueous solution is preferably 0.1% by mass to 60% by mass with respect to the total amount of the developer. Moreover, the temperature of aqueous alkali solution can be adjusted according to developability. Furthermore, these aqueous alkali solutions can be used singly or in combination of two or more.
  • development methods include a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is suitable for improving the resolution.
  • the spray pressure when the spray method is employed is preferably 0.02 MPa to 0.5 MPa.
  • a post-bake step is performed to form an insulating layer (cured product).
  • the post-bake process include an ultraviolet irradiation process using a high-pressure mercury lamp and a heating process using a clean oven. Case of ultraviolet irradiation can adjust its dose optionally, the irradiation can be carried out, for example 0.05J / cm 2 ⁇ 10J / cm 2 of about dose.
  • the heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. It is selected in the range of 30 minutes to 150 minutes at ⁇ 200 ° C.
  • a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating.
  • dry plating known methods such as vapor deposition, sputtering, and ion plating can be used.
  • vapor deposition method vacuum vapor deposition method
  • a metal film can be formed on the insulating layer by placing the support in a vacuum vessel and evaporating the metal by heating.
  • sputtering method for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, the ionized inert gas is made to collide with the target metal, and the struck metal is used.
  • a metal film can be formed on the insulating layer.
  • the surface of the insulating layer is roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.
  • the swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 1 to 20 minutes.
  • the swelling liquid include an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution.
  • Examples of commercially available swelling liquids include Updes (registered trademark) MDS-37 manufactured by Uemura Kogyo Co., Ltd.
  • the roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 5 to 30 minutes.
  • the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can.
  • the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
  • Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Updes (registered trademark) MDE-40 and Updes (registered trademark) ELC-SH manufactured by Uemura Kogyo Co., Ltd.
  • the neutralization treatment with the neutralizing solution is performed by immersing in the neutralizing solution at 30 to 50 ° C. for 1 to 10 minutes.
  • the neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is Updes (registered trademark) MDN-62 manufactured by Uemura Kogyo Co., Ltd.
  • a conductor layer is formed by combining electroless plating and electrolytic plating.
  • a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
  • a pattern formation method thereafter for example, a subtractive method, a semi-additive method, or the like can be used.
  • the semiconductor device of this embodiment includes an interlayer insulating layer containing the resin composition of this embodiment, and can be specifically manufactured by the following method.
  • a semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present embodiment.
  • the conduction location is a location for transmitting an electrical signal in the multilayer printed wiring board, and the location may be the surface or an embedded location.
  • the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
  • the semiconductor chip mounting method for manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, a bump Examples include a mounting method using a none buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).
  • BBUL none buildup layer
  • ACF anisotropic conductive film
  • NCF non-conductive film
  • a semiconductor device can be manufactured by laminating the resin sheet with a support of this embodiment on a semiconductor chip. After lamination, it can be produced by using the same method as the above multilayer printed wiring board.
  • Example 1 (Production of resin composition and resin sheet with support)
  • PGMEA propylene glycol monomethyl ether acetate
  • PGMEA propylene glycol monomethyl ether acetate
  • PAYARAD registered trademark
  • ZCR-6002H nonvolatile content 65 mass%, acid value: 60 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.
  • 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.) 5 parts by mass
  • maleimide compound (C) maleimide compound
  • BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • epoxy resin (E) biphenyl aralkyl type epoxy
  • the KAYARAD (registered trademark) ZCR-6002H is a mixture containing at least one of the compound (A1) and the compounds (A2) to (A5).
  • the obtained laminate was subjected to an exposure step of irradiating ultraviolet rays of 200 mJ / cm 2 , the support was peeled off, and developed with a 1% by mass aqueous sodium carbonate solution to obtain a laminate for evaluation.
  • the resin sheet with the support was irradiated with 200 mJ / cm 2 of ultraviolet rays, and further subjected to a post-baking step of heat treatment at 180 ° C. for 120 minutes, and then the support was peeled off to obtain a cured product for evaluation.
  • Example 2 As the compound (A), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6002H, non-volatile content 65% by mass, acid value: 60 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) 82.1 mass Parts (53.4 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.) 5 parts by mass, as blocked isocyanate compound (D), Sumidur (registered trademark) BL-3175 (solvent naphtha solution, non-volatile content: 75% by mass (including blocking agent), manufactured by Sumika Covestro Urethane Co., Ltd.
  • KAYARAD registered trademark
  • ZCR-6002H non-volatile content 65% by mass, acid value: 60 mgKOH
  • Example 3 As compound (A), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6002H, nonvolatile content 65 mass%, acid value: 60 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 80.5 mass Parts (52.3 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.) 5 parts by mass, maleimide compound (C) as maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.5 parts by mass, and blocked isocyanate compound (D) as Sumidur (registered trademark) BL-3175 (Solvent naphtha solution, non-volatile content 75% by mass (including blocking agent), Sumika Cobest wax letter (Product
  • cresol novolac epoxy acrylate (EA-7420, nonvolatile content 73 mass%, acid value: 1 mg KOH / g, manufactured by Shin-Nakamura Chemical Co., Ltd.) 72.3 parts by mass (52 in terms of nonvolatile content) .8 parts by mass) was used in the same manner as in Example 1 to obtain a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation.
  • a finger was lightly pressed against the resin surface edge of each A4-sized resin sheet with a support, and the degree of sticking to the finger was evaluated according to the following criteria.
  • ⁇ Developability> After visually observing the development surface of each evaluation laminate, it was observed with a SEM (magnification 1000 times), and the presence or absence of a residue was evaluated according to the following criteria. ⁇ : There is no development residue in the range of 30 mm square, and the developability is excellent. X: There is a development residue in the range of 30 mm square, and the developability is inferior.
  • Examples 1 to 3 have high heat resistance (Tg) and excellent developability. Among them, Example 3 has particularly good coating properties. On the other hand, Comparative Examples 1 to 5 are insufficient in either heat resistance (Tg) or developability. Therefore, according to this invention, the resin composition excellent in heat resistance and developability, the resin sheet with a support body, a multilayer printed wiring board, and a semiconductor device are obtained.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine qui, lorsqu'elle est utilisée pour produire une carte imprimée multicouche, présente une excellente résistance à la chaleur et une excellente aptitude au développement ; une feuille de résine à laquelle un support est fixé ; une carte imprimée multicouche la comprenant ; et un dispositif semi-conducteur. La composition de résine comprend un composé (A) de formule (1) et ayant un indice d'acidité de 30 à 120 mg de KOH/g, un initiateur de photodurcissement (B), ainsi qu'un composé maléimide (C) et/ou un isocyanate bloqué (D).
PCT/JP2017/001510 2016-01-20 2017-01-18 Composition de résine, feuille de résine avec support, carte imprimée multicouche et dispositif semi-conducteur WO2017126536A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020187010037A KR20180103819A (ko) 2016-01-20 2017-01-18 수지 조성물, 지지체가 부착된 수지 시트, 다층 프린트 배선판 및 반도체 장치
JP2017562838A JP6858351B2 (ja) 2016-01-20 2017-01-18 樹脂組成物、支持体付き樹脂シート、多層プリント配線板及び半導体装置
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018062570A (ja) * 2016-10-13 2018-04-19 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート、プリント配線板及び半導体装置
JP2020030227A (ja) * 2018-08-20 2020-02-27 三菱瓦斯化学株式会社 リソグラフィー用膜形成材料、リソグラフィー用膜形成用組成物、リソグラフィー用下層膜及びパターン形成方法
WO2021033441A1 (fr) * 2019-08-20 2021-02-25 東京応化工業株式会社 Composition durcissable, produit durci ainsi que procede de formation de film isolant
CN113646393A (zh) * 2019-06-28 2021-11-12 三菱瓦斯化学株式会社 树脂组合物、树脂片、多层印刷电路板和半导体装置

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109081355B (zh) * 2018-09-25 2021-10-22 浙江工业职业技术学院 便携式燃料电池汽车动力供给设备
EP3916025B1 (fr) * 2019-06-28 2023-08-09 Mitsubishi Gas Chemical Company, Inc. Composition de résine, feuille de résine, circuit imprimé multicouche et dispositif semi-conducteur
US11643493B2 (en) * 2019-12-11 2023-05-09 Mitsubishi Gas Chemical Company, Inc. Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03100009A (ja) * 1989-09-13 1991-04-25 Nippon Kayaku Co Ltd 不飽和基含有ポリカルボン酸樹脂、これを含む樹脂組成物、ソルダーレジスト樹脂組成物及びそれらの硬化物
JP2010224169A (ja) * 2009-03-23 2010-10-07 Taiyo Ink Mfg Ltd 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板
WO2011010457A1 (fr) * 2009-07-21 2011-01-27 太陽ホールディングス株式会社 Composition de résine photodurcissable
JP2011256271A (ja) * 2010-06-09 2011-12-22 Jnc Corp 硬化性組成物およびその用途、ならびに新規化合物
JP2013068896A (ja) * 2011-09-26 2013-04-18 Fujifilm Corp 重合性化合物および重合性組成物
JP2014074927A (ja) * 2013-12-26 2014-04-24 Taiyo Holdings Co Ltd 光硬化性樹脂組成物
JP2015064546A (ja) * 2013-08-28 2015-04-09 太陽インキ製造株式会社 感光性樹脂組成物、ドライフィルム、硬化物およびプリント配線板

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0717737B2 (ja) * 1987-11-30 1995-03-01 太陽インキ製造株式会社 感光性熱硬化性樹脂組成物及びソルダーレジストパターン形成方法
TW268031B (fr) * 1993-07-02 1996-01-11 Ciba Geigy
JP2003149807A (ja) * 2001-11-15 2003-05-21 Nippon Kayaku Co Ltd フレキシブル性を有する難燃型感光性樹脂組成物およびその硬化物
JP5650477B2 (ja) * 2010-07-23 2015-01-07 太陽ホールディングス株式会社 導電性樹脂組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03100009A (ja) * 1989-09-13 1991-04-25 Nippon Kayaku Co Ltd 不飽和基含有ポリカルボン酸樹脂、これを含む樹脂組成物、ソルダーレジスト樹脂組成物及びそれらの硬化物
JP2010224169A (ja) * 2009-03-23 2010-10-07 Taiyo Ink Mfg Ltd 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板
WO2011010457A1 (fr) * 2009-07-21 2011-01-27 太陽ホールディングス株式会社 Composition de résine photodurcissable
JP2011256271A (ja) * 2010-06-09 2011-12-22 Jnc Corp 硬化性組成物およびその用途、ならびに新規化合物
JP2013068896A (ja) * 2011-09-26 2013-04-18 Fujifilm Corp 重合性化合物および重合性組成物
JP2015064546A (ja) * 2013-08-28 2015-04-09 太陽インキ製造株式会社 感光性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2014074927A (ja) * 2013-12-26 2014-04-24 Taiyo Holdings Co Ltd 光硬化性樹脂組成物

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018062570A (ja) * 2016-10-13 2018-04-19 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート、プリント配線板及び半導体装置
JP2020030227A (ja) * 2018-08-20 2020-02-27 三菱瓦斯化学株式会社 リソグラフィー用膜形成材料、リソグラフィー用膜形成用組成物、リソグラフィー用下層膜及びパターン形成方法
JP7258279B2 (ja) 2018-08-20 2023-04-17 三菱瓦斯化学株式会社 リソグラフィー用膜形成材料、リソグラフィー用膜形成用組成物、リソグラフィー用下層膜及びパターン形成方法
CN113646393A (zh) * 2019-06-28 2021-11-12 三菱瓦斯化学株式会社 树脂组合物、树脂片、多层印刷电路板和半导体装置
CN113646393B (zh) * 2019-06-28 2023-09-19 三菱瓦斯化学株式会社 树脂组合物、树脂片、多层印刷电路板和半导体装置
WO2021033441A1 (fr) * 2019-08-20 2021-02-25 東京応化工業株式会社 Composition durcissable, produit durci ainsi que procede de formation de film isolant
JP2021031541A (ja) * 2019-08-20 2021-03-01 東京応化工業株式会社 硬化性組成物、硬化物、及び絶縁膜の形成方法
JP7428491B2 (ja) 2019-08-20 2024-02-06 東京応化工業株式会社 硬化性組成物、硬化物、及び絶縁膜の形成方法

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