WO2019216425A1 - Substrat conducteur, substrat de câblage, dispositif étirable et procédé de fabrication de substrat de câblage - Google Patents

Substrat conducteur, substrat de câblage, dispositif étirable et procédé de fabrication de substrat de câblage Download PDF

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Publication number
WO2019216425A1
WO2019216425A1 PCT/JP2019/018795 JP2019018795W WO2019216425A1 WO 2019216425 A1 WO2019216425 A1 WO 2019216425A1 JP 2019018795 W JP2019018795 W JP 2019018795W WO 2019216425 A1 WO2019216425 A1 WO 2019216425A1
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WO
WIPO (PCT)
Prior art keywords
resin layer
conductor
rubber
stretchable resin
conductive
Prior art date
Application number
PCT/JP2019/018795
Other languages
English (en)
Japanese (ja)
Inventor
禎宏 小川
剛史 正木
崇司 川守
タンイー シム
Original Assignee
日立化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to JP2020518362A priority Critical patent/JP7338621B2/ja
Priority to KR1020207029968A priority patent/KR20210007956A/ko
Priority to CN201980030870.4A priority patent/CN112088089A/zh
Publication of WO2019216425A1 publication Critical patent/WO2019216425A1/fr
Priority to JP2022203298A priority patent/JP7468610B2/ja
Priority to JP2022203296A priority patent/JP7468609B2/ja
Priority to JP2022203303A priority patent/JP7468611B2/ja

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00Compositions of unspecified rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/0011Working of insulating substrates or insulating layers
    • H05K3/0017Etching of the substrate by chemical or physical means
    • H05K3/002Etching of the substrate by chemical or physical means by liquid chemical etching
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061Etching masks
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061Etching masks
    • H05K3/064Photoresists

Definitions

  • Patent Document 1 describes a method of sealing a semiconductor element such as a memory chip using a stretchable resin composition.
  • application of a stretchable resin composition to sealing applications is mainly studied.
  • one aspect of the present invention is a conductor substrate having a stretchable resin layer and a conductive foil provided on the stretchable resin layer, wherein the stretchable resin layer is Provided is a conductor substrate including a cured product of a resin composition containing (A) a rubber component, (B) a crosslinking component having an epoxy group, and (C) an ester curing agent.
  • Another aspect of the present invention is a conductor substrate having a stretchable resin layer and a conductor plating film provided on the stretchable resin layer, wherein the stretchable resin layer is (A) a rubber component. And (B) a cross-linking component having an epoxy group and (C) an ester-based curing agent, and a cured product of the resin composition.
  • (B) a crosslinking component having an epoxy group as a crosslinking component and (C) an ester curing agent as a curing agent are used in combination to greatly suppress the formation of hydroxyl groups during the curing reaction of the crosslinking component.
  • the inventors have found that this is possible. This is because the curing reaction between the epoxy group of the crosslinking component and the ester curing agent does not involve the generation of a hydroxyl group, and it is difficult to generate a hydroxyl group even after curing. Furthermore, these hardened
  • Another aspect of the present invention is a step of preparing a laminate having a stretchable resin layer and a conductive foil laminated on the stretchable resin layer, a step of forming an etching resist on the conductive foil, Exposing the etching resist, developing the exposed etching resist to form a resist pattern covering a part of the conductor foil, and removing the conductor foil in a portion not covered by the resist pattern.
  • a method for producing the wiring board of the present invention comprising a step and a step of removing the resist pattern.
  • the method for providing the conductor foil is not particularly limited.
  • a method for directly applying a resin composition for forming a stretchable resin layer to a metal foil and a resin composition for forming a stretchable resin layer are provided.
  • a resin layer an elastic resin layer before curing
  • the formed resin layer is laminated on a conductor foil.
  • the conductor plating film can be formed by a normal plating method used for the additive method or the semi-additive method. For example, after applying a plating catalyst for depositing palladium, the stretchable resin layer is immersed in an electroless plating solution, and an electroless plating layer (conductor layer) having a thickness of 0.3 to 1.5 ⁇ m is formed on the entire surface of the primer. To precipitate. If necessary, electrolytic plating (electroplating) can be further performed to adjust to a necessary thickness. As an electroless plating solution used for electroless plating, any electroless plating solution can be used, and there is no particular limitation. An ordinary method can be employed for electrolytic plating, and there is no particular limitation.
  • the conductor plating film (electroless plating film, electrolytic plating film) may be a copper plating film from the viewpoint of cost and resistance.
  • the relative dielectric constant (Dk) of the stretchable resin layer may be 4.0 or less.
  • the relative dielectric constant may be 3.5 or less, 3.0 or less, or 2.5 or less.
  • Examples of commercially available products of isoprene rubber include ZEON Corporation “Nipol IR Series”.
  • fluororubber examples include Daikin Corporation “DAIEL Series”.
  • R 1 , R 2 and R 3 each independently represent a monovalent organic group, but since the effects of the present invention can be obtained more sufficiently, the monovalent organic group having an aromatic ring is Also good.
  • the resin composition may contain (C) a curing agent other than the ester curing agent as long as the effects of the present invention are not significantly impaired.
  • the content of the other curing agent is preferably less than 10 parts by mass with respect to 100 parts by mass of the (C) ester-based curing agent, from the viewpoint of sufficiently reducing the dielectric loss tangent of the stretchable resin layer.
  • the content ratio of (B) crosslinking component to (C) ester curing agent is equivalent ratio of epoxy group in (B) epoxy resin and ester bond in (C) ester curing agent. And preferably in the range of 4: 5 to 5: 4.
  • the content ratio is in the above range, more sufficient curing is easily obtained, and the stretchable resin layer tends to have particularly excellent characteristics in terms of adhesion, insulation reliability, and heat resistance.
  • the content of the (D) curing accelerator is 0.1 to 10 with respect to 100 parts by mass of the total amount of (A) the rubber component, (B) the crosslinking component, and (C) the ester curing agent. A mass part may be sufficient.
  • content of a hardening accelerator is 0.1 mass part or more, there exists a tendency for more sufficient hardening to be easy to be obtained.
  • content of a hardening accelerator is 10 mass parts or less, there exists a tendency for more sufficient heat resistance to be acquired easily. From the above viewpoint, the content of the (D) curing accelerator may be 0.3 to 7 parts by mass, or 0.5 to 5 parts by mass.
  • the phenolic antioxidant may be a compound having a sterically hindered substituent such as a t-butyl group (tertiary butyl group) and a trimethylsilyl group at the ortho position of the phenolic hydroxyl group.
  • the phenolic antioxidant is also referred to as a hindered phenolic antioxidant.
  • phenolic antioxidant examples include 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-4-ethylphenol, and 2,2′- Methylene-bis (4-methyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t) Selected from the group consisting of -butyl-4-hydroxybenzyl) benzene and tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane It may be a species or more compounds.
  • Thermal stabilizers include metal soaps or inorganic acid salts such as combinations of higher fatty acid zinc and barium salts, organotin compounds such as organotin maleates and organotin mercaptides, and fullerenes (eg, Fullerene hydroxide).
  • hydrolysis inhibitor examples include carbodiimide derivatives, epoxy compounds, isocyanate compounds, acid anhydrides, oxazoline compounds, and melamine compounds.
  • a protective film may be attached on the stretchable resin layer to form a laminated film having a three-layer structure including a conductor foil or a carrier film, a stretchable resin layer, and a protective film.
  • the thickness of the protective film may be appropriately changed depending on the intended flexibility, but may be 10 to 250 ⁇ m. When the thickness is 10 ⁇ m or more, the film strength tends to be sufficient, and when it is 250 ⁇ m or less, sufficient flexibility tends to be obtained. From the above viewpoint, the thickness may be 15 to 200 ⁇ m, or 20 to 150 ⁇ m.
  • Etching resists used for etching include, for example, Photec H-7005 (trade name, manufactured by Hitachi Chemical Co., Ltd.), Fotec H-7030 (trade name, manufactured by Hitachi Chemical Co., Ltd.), X-87 (manufactured by Taiyo Holdings Co., Ltd., Product name).
  • the etching resist is usually removed after the wiring pattern is formed.
  • Example 1 ⁇ Preparation of resin varnish for forming elastic resin layer> (A) 80 parts by mass of maleic anhydride-modified styrene ethylene butadiene rubber (trade name “FG1924GT” manufactured by KRATON Co., Ltd.) diluted with toluene and adjusted to have a nonvolatile content of 25% by mass as component (B) ) Dicyclopentadiene type epoxy resin diluted with toluene as a component and adjusted to a nonvolatile content of 25% by mass (manufactured by DIC Corporation, trade name “EPICLON HP7200H”) 11.1 parts by mass (mixed amount of nonvolatile component), (C) 8.9 parts by mass (non-volatile content) of an ester-based curing agent (manufactured by DIC Corporation, trade name “HPC8000-65T”, dicyclopentadiene type diphenol compound) diluted with toluene as a component and adjusted to a non-vola
  • the protective film of the laminated film is peeled off and the exposed resin layer has a roughened surface with a surface roughness Ra of 1.5 ⁇ m (Furukawa Electric Co., Ltd., trade name “F2-WS-12”) Were stacked in such a direction that the roughened surface was on the resin layer side.
  • the electrolytic copper foil was applied to the resin layer under the conditions of a pressure of 0.5 MPa, a temperature of 90 ° C. and a pressurization time of 60 seconds using a vacuum pressure laminator (trade name “V130” manufactured by Nikko Materials Co., Ltd.). Laminated. After that, by heating for 60 minutes at 180 ° C. in a dryer (trade name “MSO-80TPS” manufactured by Futaba Kagaku Co., Ltd.), an elastic resin layer, which is a cured product of the resin layer, and an electrolytic copper foil as a conductor layer A conductive substrate having
  • the etching resist is removed with a stripping solution, and the wiring substrate 1 having a conductor layer 5 on the stretchable resin layer 3 having a wiring width of 50 ⁇ m and forming a wavy wiring pattern meandering along a predetermined direction X. Got.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Structure Of Printed Boards (AREA)

Abstract

L'invention concerne un substrat conducteur ayant une couche de résine étirable et une feuille conductrice disposée sur la couche de résine étirable, la couche de résine étirable contenant un produit durci d'une composition de résine contenant : (A) un composant de caoutchouc, (B) un composant de réticulation ayant un groupe époxy, et (C) un agent de durcissement à base d'ester.
PCT/JP2019/018795 2018-05-11 2019-05-10 Substrat conducteur, substrat de câblage, dispositif étirable et procédé de fabrication de substrat de câblage WO2019216425A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2020518362A JP7338621B2 (ja) 2018-05-11 2019-05-10 導体基板、配線基板、ストレッチャブルデバイス及び配線基板の製造方法
KR1020207029968A KR20210007956A (ko) 2018-05-11 2019-05-10 도체 기판, 배선 기판, 스트레처블 디바이스 및 배선 기판의 제조 방법
CN201980030870.4A CN112088089A (zh) 2018-05-11 2019-05-10 导体基板、配线基板、可伸缩元件和配线基板的制造方法
JP2022203298A JP7468610B2 (ja) 2018-05-11 2022-12-20 導体基板、配線基板、ストレッチャブルデバイス及び配線基板の製造方法
JP2022203296A JP7468609B2 (ja) 2018-05-11 2022-12-20 導体基板、配線基板、ストレッチャブルデバイス及び配線基板の製造方法
JP2022203303A JP7468611B2 (ja) 2018-05-11 2022-12-20 導体基板、配線基板、ストレッチャブルデバイス及び配線基板の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018092105 2018-05-11
JP2018-092105 2018-05-11

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WO2019216425A1 true WO2019216425A1 (fr) 2019-11-14

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PCT/JP2019/018795 WO2019216425A1 (fr) 2018-05-11 2019-05-10 Substrat conducteur, substrat de câblage, dispositif étirable et procédé de fabrication de substrat de câblage

Country Status (5)

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JP (4) JP7338621B2 (fr)
KR (1) KR20210007956A (fr)
CN (1) CN112088089A (fr)
TW (1) TW201946777A (fr)
WO (1) WO2019216425A1 (fr)

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WO2024014435A1 (fr) * 2022-07-12 2024-01-18 株式会社レゾナック Composition de résine durcissable, film durcissable, et film stratifié

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JP7468609B2 (ja) 2024-04-16
JP2023029400A (ja) 2023-03-03
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