WO2021025055A1 - 樹脂多層基板および樹脂多層基板の製造方法 - Google Patents

樹脂多層基板および樹脂多層基板の製造方法 Download PDF

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Publication number
WO2021025055A1
WO2021025055A1 PCT/JP2020/029985 JP2020029985W WO2021025055A1 WO 2021025055 A1 WO2021025055 A1 WO 2021025055A1 JP 2020029985 W JP2020029985 W JP 2020029985W WO 2021025055 A1 WO2021025055 A1 WO 2021025055A1
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Prior art keywords
group
resin
multilayer substrate
resin layer
resin layers
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English (en)
French (fr)
Japanese (ja)
Inventor
亮介 ▲高▼田
道治 西村
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2021537342A priority Critical patent/JP7127745B2/ja
Priority to CN202080054610.3A priority patent/CN114208401A/zh
Publication of WO2021025055A1 publication Critical patent/WO2021025055A1/ja
Priority to US17/584,589 priority patent/US12120817B2/en
Anticipated expiration legal-status Critical
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    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/034—Organic insulating material consisting of one material containing halogen
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K3/0011—Working of insulating substrates or insulating layers
    • 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
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or 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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or 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 halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or 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 halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or 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 halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • H05K1/118—Printed elements for providing electric connections to or between printed circuits specially for flexible printed circuits, e.g. using folded portions
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0141—Liquid crystal polymer [LCP]
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/06—Lamination
    • H05K2203/065—Binding insulating layers without adhesive, e.g. by local heating or welding, before lamination of the whole PCB
    • 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
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits

Definitions

  • the present invention relates to a resin multilayer substrate formed by laminating a plurality of resin layers and a method for manufacturing a resin multilayer substrate.
  • the norbornene-based polymer which is conventionally known as a material having a low dielectric constant and low loss, is expected as a material for a high-frequency circuit board (Patent Document 1).
  • An object of the present invention is to provide a resin multilayer substrate and a method for producing a resin multilayer substrate in which a plurality of resin layers containing a norbornene-based polymer are laminated, and the adhesion of the interface between the resin layers is improved. ..
  • the resin multilayer substrate of the present invention It has a base material formed by laminating a plurality of resin layers.
  • the plurality of resin layers have a plurality of first resin layers using a norbornene-based polymer containing at least one of the repeating units represented by the following general formula (1).
  • one of at least two first resin layers adjacent to each other in the stacking direction has an altered portion altered by surface treatment on the interface side with the other first resin layer.
  • the adhesion between the altered portions and the adhesion between the non-altered portion and the altered portion are higher than the adhesion between the non-altered portions.
  • X represents O, -CH 2- or -CH 2- CH 2-
  • the substituents R 1 , R 2 , R 3 and R 4 are hydrogen, linear or branched, respectively.
  • the organic group is, for example, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
  • aralkyl group alkoxysilyl group, organic group containing epoxy group, organic group containing ether group, organic group containing (meth) acrylic group, organic group containing ester group, organic containing ketone group Groups. These groups may be attached via an alkyl group, an ether group, an ester group, and may be the same or different.
  • M is an integer of 10 to 10000, and n 1 is 0 to 0. It is an integer up to 5).
  • the resin multilayer substrate of the present invention It has a base material formed by laminating a plurality of resin layers.
  • the plurality of resin layers include a plurality of first resin layers using a norbornene-based polymer containing at least one of the repeating units represented by the following general formula (1), and a second resin layer.
  • the second resin layer has higher adhesion to the first resin layer than the adhesion between the plurality of first resin layers.
  • the first resin layer at least one of the plurality of first resin layers is bonded to the second resin layer.
  • X represents O, -CH 2- or -CH 2- CH 2-
  • the substituents R 1 , R 2 , R 3 and R 4 are hydrogen, linear or branched, respectively.
  • the organic group is, for example, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
  • aralkyl group alkoxysilyl group, organic group containing epoxy group, organic group containing ether group, organic group containing (meth) acrylic group, organic group containing ester group, organic containing ketone group Groups. These groups may be attached via an alkyl group, an ether group, an ester group, and may be the same or different.
  • M is an integer of 10 to 10000, and n 1 is 0 to 0. It is an integer up to 5).
  • the method for manufacturing a resin multilayer substrate of the present invention is A method for manufacturing a resin multilayer substrate having a substrate formed by laminating a plurality of resin layers.
  • the plurality of resin layers have at least one first resin layer using a norbornene-based polymer containing at least one of the repeating units represented by the following general formula (1).
  • the first resin layer contains an additive that reacts with the norbornene-based polymer, and contains an additive.
  • the norbornene-based polymer of the first resin layer and the additive are reacted by surface treatment, and the composition of the material before the reaction and the material after the reaction is inclined in the thickness direction as the effect of the surface treatment is attenuated. Is characterized by producing.
  • X represents O, -CH 2- or -CH 2- CH 2-
  • the substituents R 1 , R 2 , R 3 and R 4 are hydrogen, linear or branched, respectively.
  • the organic group is, for example, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
  • the present invention in a configuration in which a plurality of resin layers using a norbornene-based polymer are laminated, it is possible to realize a resin multilayer substrate having improved adhesion at the interface between the resin layers.
  • FIG. 1A is a cross-sectional view of the resin multilayer substrate 101 according to the first embodiment
  • FIG. 1B is an exploded sectional view of the resin multilayer substrate 101
  • FIG. 2 is a cross-sectional view showing the manufacturing method of the resin multilayer substrate 101 in order.
  • FIG. 3 is an external perspective view of the resin multilayer substrate 101A according to the first embodiment.
  • FIG. 4A is a plan view of the inside of the housing 1 of the electronic device 301 using the resin multilayer substrate 101A
  • FIG. 4B is a cross-sectional view of the electronic device 301.
  • FIG. 5A is a cross-sectional view of the resin multilayer substrate 102 according to the second embodiment
  • FIG. 5B is an exploded sectional view of the resin multilayer substrate 102.
  • FIG. 6A is a sectional view of the resin multilayer substrate 103 according to the third embodiment
  • FIG. 6B is an exploded sectional view of the resin multilayer substrate 103.
  • FIG. 1A is a cross-sectional view of the resin multilayer substrate 101 according to the first embodiment
  • FIG. 1B is an exploded sectional view of the resin multilayer substrate 101.
  • the altered parts D1 and D2 are shown by cross-hatching in order to make the structure easy to understand.
  • the resin multilayer substrate 101 includes a base material 10, conductor patterns 31, 32, an interlayer connection conductor V1, and the like.
  • the resin multilayer substrate 101 includes other configurations, but is not shown in FIGS. 1A and 1B.
  • the base material 10 is a rectangular flat plate having flexibility, and has a first main surface VS1 and a second main surface VS2 facing each other.
  • the conductor patterns 31 and 32 and the interlayer connection conductor V1 are formed inside the base material 10.
  • the base material 10 is formed by laminating the first resin layers 11, 12, and 13 in this order.
  • the first main surface VS1 and the second main surface VS2 are planes orthogonal to the stacking direction (Z-axis direction) of the plurality of first resin layers 11 to 13.
  • the first resin layers 11, 12, and 13 are resin sheets using a norbornene-based polymer containing at least one of the repeating units represented by the following general formula (1), for example.
  • X represents O, -CH 2- or -CH 2- CH 2-
  • the substituents R 1 , R 2 , R 3 and R 4 are hydrogen, linear or branched, respectively.
  • An organic group or a group containing a group selected from a derivative in which a part of these organic groups is substituted with a halogen or a nitrile group is shown.
  • the organic group contains, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkoxysilyl group, an organic group containing an epoxy group, an organic group containing an ether group, and a (meth) acrylic group.
  • m is an integer from 10 to 10000
  • n 1 is an integer from 0 to 5.
  • X is -CH 2-
  • m is 1000 or more
  • n 1 is 0 or 1
  • at least one of R 1 , R 2 , R 3 and R 4 contains an ester group, an ether group or a hydroxyl group.
  • m is 5000 or more
  • n 1 is 0, and at least one of R 1 , R 2 , R 3 and R 4 contains an ester group or a hydroxyl group.
  • Examples of the alkyl group include linear or branched saturated hydrocarbons having 1 to 10 carbon atoms, cyclic saturated hydrocarbons, and the like.
  • Examples of the alkenyl group include vinyl, allyl, butynyl, cyclohexenyl group and the like.
  • Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, hexynyl, octynyl, and heptynyl groups.
  • Examples of the aryl group include phenyl, trill, naphthyl, anthracenyl group and the like.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • the epoxy group include a glycidyl ether group and the like, and examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group and a triethoxysilylethyl group.
  • examples of the (meth) acrylic group include a methacryloxymethyl group, and examples of the ester group include methyl ester, ethyl ester, n-propyl ester, n-butyl ester, t-butyl ester group and the like.
  • a conductor pattern 31 is formed on the surface of the first resin layer 11.
  • the conductor pattern 31 is a rectangular conductor pattern arranged near the center of the first resin layer 11.
  • the conductor pattern 31 is a conductor pattern such as a Cu foil.
  • the first resin layer 11 has an altered portion D1 that has been altered by surface treatment (described in detail later) on the surface (interface FS1 with the first resin layer 12 that is adjacent to and adheres in the Z-axis direction). ..
  • the altered portion D1 is formed between non-altered portions ND1, ND2, ND3 (parts other than the altered portions D1 and D2 of the first resin layers 11 to 13 of FIGS. 1A and 1B) that have not been altered.
  • Tg glass transition temperature
  • a conductor pattern 32 is formed on the surface of the first resin layer 12.
  • the conductor pattern 32 is a rectangular conductor pattern arranged near the center of the first resin layer 12.
  • the conductor pattern 32 is a conductor pattern such as a Cu foil.
  • the interlayer connection conductor V1 is formed in the first resin layer 12. Further, on the surface side of the first resin layer 12 (the interface FS2 with the first resin layer 13 adjacent to and in close contact with each other in the Z-axis direction), there is an altered portion D2 that has been altered by surface treatment (described in detail later).
  • the altered portion D2 is a portion in which the adhesion to the first resin layer (altered portion or non-altered portion) is enhanced rather than the adhesion between the non-altered portions ND1, ND2, and ND3 that have not been altered.
  • the altered portion D2 of the present embodiment has a glass transition temperature (Tg) lower than that of the non-altered portion ND2.
  • the conductor patterns 31 and 32 are electrically connected via the interlayer connection conductor V1.
  • the adhesion of the altered parts D1 and D2 to the first resin layers 11 and 12 is higher than the adhesion between the non-altered parts ND1, ND2 and ND3.
  • the altered portions D1 and D2 of the present embodiment have a glass transition temperature (Tg) lower than that of the non-altered portions ND1, ND2 and ND3.
  • Tg glass transition temperature
  • the main chain skeleton of a norbornene-based polymer has a high glass transition temperature of about 300 ° C. and low molecular mobility with respect to heat.
  • the molecular motility of the altered portions D1 and D2 located on the interface FS1 and FS2 sides of the first resin layers with respect to heat is higher than that of the non-altered portions ND1 and ND2. Therefore, the adhesion between the plurality of first resin layers 11 to 13 is enhanced, and a resin multilayer substrate having a low dielectric constant and low loss (low dielectric loss tangent) using the first resin layers 11 to 13 can be realized.
  • the interface between the first resin layers 11 to 13 is not peeled off, and the resin multilayer substrate 101 is coagulated and broken inside any one of the first resin layers 11 to 13.
  • the term "aggregate fracture” as used herein means, for example, a case where (aggregate fracture rate) / (interface fracture rate) as an area ratio is 10% or more.
  • the (aggregate fracture rate) / (interfacial fracture rate) as an area ratio is preferably 50% or more, more preferably 80% or more.
  • the peeling test is, for example, a 90-degree peel strength test (IPC-TM-650 2.4.9 or JIS C 6471 8.1) or a land pull strength test.
  • the "aggregation fracture” in the present specification means that the fracture occurs inside the resin layers, not at the interface between the resin layers.
  • the altered parts D1 and D2 of the present embodiment are the portions of the interfaces FS1 and FS2 of the first resin layers 11 to 13 that are in contact with the conductor patterns 31 and 32 (the first resin layers 11 to 11 to sandwich the conductor patterns 31 and 32). It is not formed in the portion where 13 are joined to each other). However, after the plurality of first resin layers 11 to 13 are laminated to form the base material 10 (after heat pressing), the resin constituting the first resin layers 11 to 13 is fine on the surfaces of the conductor patterns 31 and 32. It gets into unevenness (anchor effect or anchoring effect). Therefore, in the base material 10, the adhesion between the first resin layers 11 to 13 via the conductor patterns 31 and 32 is high.
  • the resin multilayer substrate 101 according to this embodiment is manufactured by, for example, the following manufacturing method.
  • FIG. 2 is a cross-sectional view showing the manufacturing method of the resin multilayer substrate 101 in order.
  • the “aggregate substrate” refers to a substrate including a plurality of resin multilayer substrates 101.
  • first resin layers 11, 12, and 13 are prepared.
  • the first resin layers 11 to 13 are sheets using, for example, a norbornene-based polymer.
  • conductor patterns 31 and 32 are formed on the first resin layers 11 and 12, respectively.
  • a metal foil for example, Cu foil
  • the metal foil is patterned by photolithography.
  • the conductor pattern 31 is formed on the surface of the first resin layer 11, and the conductor pattern 32 is formed on the surface of the first resin layer 12.
  • the interlayer connecting conductor V1 is formed on the first resin layer 12.
  • the interlayer connection conductor V1 is provided with holes in the first resin layer 12 by, for example, laser irradiation or a drill, and then a conductive paste containing a metal powder such as Cu, Sn or an alloy thereof and a resin material is arranged in the holes. It is provided by setting (filling) and solidifying the conductive paste by a subsequent heating press.
  • the surfaces of the first resin layers 11 and 12 are altered by surface treatment.
  • the surface of the first resin layer 11 is subjected to either plasma discharge, corona discharge, electron beam irradiation, laser irradiation or light irradiation (for example, UV treatment) ((2) in FIG. 2). ) Refer to the white arrow).
  • the altered portion D1 is formed on a part of the surface side of the first resin layer 11 (a portion where the conductor pattern 31 is not formed. A portion which becomes an interface with the first resin layer 12 at the time of later lamination).
  • the altered portion D2 is formed on a part of the surface side of the first resin layer 12 (a portion where the conductor pattern 32 is not formed. A portion which becomes an interface with the first resin layer 13 at the time of later lamination). ..
  • the glass transition temperature (Tg) of the altered portions D1 and D2 is altered to be lower than that of the non-altered portions ND1, ND2 and ND3.
  • the first resin layers 11, 12, and 13 are laminated (placed) in this order.
  • the altered portion D1 of the first resin layer 11 abuts on the first resin layer 12 (non-altered portion ND2) adjacent in the Z-axis direction, and the altered portion D2 of the first resin layer 12 is Z. It comes into contact with the first resin layer 13 (non-altered portion ND3) adjacent in the axial direction.
  • the plurality of laminated first resin layers 11 to 13 are heat-pressed (collectively pressed) to form the base material 10 (resin multilayer substrate 101) shown in (4) in FIG.
  • alteration portions D1 and D2 having high molecular mobility with respect to heat are provided on the interface side of the first resin layers 11 and 12 with the other first resin layers, respectively. Be done. Therefore, as compared with the case where the non-altered portions ND1, ND2, and ND3 of the first resin layers 11 to 13 are directly bonded to each other, it is possible to easily manufacture a resin multilayer substrate having high adhesion at the interface between the plurality of resin layers.
  • the base material 10 can be easily formed by hot-pressing (collectively pressing) the laminated first resin layers 11, 12, and 13, so that the manufacturing process of the resin multilayer substrate 101 is reduced. And the cost can be kept low. Further, according to the above manufacturing method, it is possible to easily manufacture a resin multilayer substrate that can be plastically deformed and can maintain (retain) a desired shape.
  • the conductive paste is arranged in the holes provided in the first resin layer 12, and the conductive paste is solidified by a heating press (collective press) to form the interlayer connection conductor V1.
  • a heating press collector press
  • FIG. 3 is an external perspective view of the resin multilayer substrate 101A according to the first embodiment.
  • FIG. 4A is a plan view of the inside of the housing 1 of the electronic device 301 using the resin multilayer substrate 101A, and
  • FIG. 4B is a cross-sectional view of the electronic device 301.
  • the electronic device 301 includes a resin multilayer board 101A, a housing 1, a battery pack 2, circuit boards 201, 202, electronic components 71, 72, and the like.
  • the electronic device 301 also includes elements other than the above, but is not shown in FIG. 4 (B).
  • the resin multilayer board 101A is, for example, a cable for connecting a plurality of circuit boards.
  • the resin multilayer substrate 101A has connection portions CN1 and CN2 and a line portion SL.
  • the connection portions CN1 and CN2 are portions that are connected to other circuit boards.
  • the line section SL includes a transmission line connecting the connecting sections CN1 and CN2.
  • the connecting portion CN1, the line portion SL, and the connecting portion CN2 are arranged in this order in the + X direction.
  • the resin multilayer substrate 101A includes a substrate 10A, plugs 51, 52, and the like.
  • the base material 10A is a substantially rectangular flat plate whose longitudinal direction coincides with the X-axis direction.
  • the basic configuration of the resin multilayer substrate 101A is substantially the same as that of the resin multilayer substrate 101 described above.
  • the plug 51 is provided in the connection portion CN1, and the plug 52 is provided in the connection portion CN2.
  • a resin multilayer board 101A, a battery pack 2, circuit boards 201, 202, electronic components 71, 72, and the like are arranged in the housing 1.
  • the circuit boards 201 and 202 are, for example, printed wiring boards.
  • the electronic components 71 and 72 are, for example, chip components such as chip inductors and chip capacitors, RFIC elements, antenna devices, impedance matching circuits, and the like.
  • a plurality of electronic components 71 are mounted on the surface of the circuit board 201, and a plurality of electronic components 72 are mounted on the surface of the circuit board 202.
  • the battery pack 2 is arranged between the circuit boards 201 and 202.
  • the resin multilayer board 101A connects the circuit boards 201 and 202. Specifically, the plug 51 of the resin multilayer board 101A is connected to the receptacle 61 arranged on the surface of the circuit board 201. Further, the plug 52 of the resin multilayer board 101A is connected to the receptacle 62 arranged on the surface of the circuit board 201.
  • the heights of the surfaces of the circuit boards 201 and 202 and the upper surface of the battery pack 2 in the Z-axis direction are different.
  • the resin multilayer board 101A is connected to the circuit boards 201 and 202 in a bent state (only the line portion of the resin multilayer board 101A is in contact with the upper surface of the battery pack 2). That is, the base material 10A of the resin multilayer substrate 101A has a bent portion.
  • the resin multilayer substrate 101A of the present invention has high adhesion between the resin layers and can suppress peeling (delamination) at the interface between the resin layers, so that it can also be used when connecting by bending.
  • ⁇ Deformation example of altered part >>
  • the first resin layers 11 and 12 are formed with altered portions D1 and D2 having a glass transition temperature lower than that of other portions (non-altered portions ND1 to ND3).
  • the altered part with enhanced molecular motility is not limited to this.
  • the loss tangent of the altered portions D1 and D2 is higher than that of the non-altered portions ND1 to ND3, the adhesion between the first resin layers is enhanced.
  • the loss tangent (tan ⁇ ) is calculated by the formula shown below.
  • E “ Imaginary part of complex elastic modulus (loss elastic modulus)
  • E' Real part of complex modulus (storage modulus)
  • the loss modulus (E "), storage modulus (E') and loss tangent (tan ⁇ ) are measured, for example, by dynamic viscoelasticity measurements.
  • the altered portions D1 and D2 in which the adhesion to the first resin layer is enhanced by increasing the molecular mobility with respect to heat are shown, but the altered portion of the present invention is limited to this. is not it.
  • the altered portion may be a portion whose adhesion to the first resin layer has been improved by a chemical reaction, bond, or the like.
  • the functional group is, for example, an organic group such as a hydroxyl group or a carboxylic acid.
  • additives to the first resin layer >> Further, in the first resin layers 11 to 13, in the process of manufacturing the resin layer, an additive having a predetermined function according to the application (for example, a known deterioration inhibitor, ultraviolet inhibitor, ultraviolet absorber, plasticizer or (Infrared absorber, etc.) may be added (kneading, coating, segregation, etc.).
  • the types of the additives include, for example, (a) a material added to the first resin layer to promote surface treatment, or (b) a material added to change the physical characteristics and chemical properties of the first resin layer. And so on.
  • the additive is a material added to the first resin layer in order to promote the surface treatment
  • the surface treatment of the first resin layer is performed by UV treatment, it has a function of enhancing UV absorption. It is preferable that the material is added in advance to the first resin layers 11 and 12 as an additive.
  • the additive is a material to be added to change the physical properties and chemical properties of the first resin layer
  • the additive is, for example, a known stabilizer, deterioration inhibitor, ultraviolet inhibitor, plasticizer, or the like.
  • it may be a material having a function of lowering the glass transition temperature of the first resin layers 11 to 13 (or increasing the loss tangent).
  • a long-chain carboxylic acid or a long-chain alcohol
  • the glass transition temperature can be lowered.
  • R 1 , R 2 , R 3 and R 4 of the general formula (1) are alcohols
  • a long-chain carboxylic acid (R-COOH) is added, and the substituents R 1 , R 2 are added.
  • R 3 and R 4 are carboxylic acids, alcohol may be added.
  • the additive may be, for example, a material having a function of increasing the flexibility of the first resin layers 11 to 13.
  • the additive may be a ring-opening olefin polymer (COC / COP) containing at least one cyclic repeating unit represented by the general formula (2).
  • the substituents R 5, R 6, R 7 and R 8 each represents hydrogen, straight-chain or branched organic group or part of these organic groups, it is replaced with a halogen or a nitrile group
  • a group containing a group selected from the above derivatives is shown.
  • the organic group includes, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkoxysilyl group, an organic group containing an epoxy group, and an ether group. It is an organic group containing, an organic group containing a (meth) acrylic group, an organic group containing an ester group, and an organic group containing a ketone group. These groups are via an alkyl group, an ether group, and an ester group. They may be combined and may be the same or different.
  • N 2 is an integer from 0 to 5).
  • the additive may be a material having a function of lowering the coefficient of thermal expansion of the first resin layers 11 to 13, for example, by increasing the molecular orientation of the first resin layers 11 to 13 in the plane direction.
  • the additive includes a glass filler having a small coefficient of thermal expansion, a liquid crystal polymer (LCP), and the like.
  • the coefficient of thermal expansion of the first resin layers 11 to 13 in the surface direction (X-axis direction or Y-axis direction) is preferably 10 ppm / ° C. or higher and 20 ppm / ° C. or lower.
  • the coefficient of thermal expansion of the conductor patterns 31 and 32 which are Cu foils, is about 16 ppm / ° C.
  • the difference in the coefficient of thermal expansion between the first resin layers 11 to 13 and the conductor patterns 31 and 32 can be made extremely small. Therefore, due to this configuration, the base material 10 is warped or delaminated due to the difference in the coefficient of thermal expansion between the resin layer and the conductor pattern during manufacturing (for example, during heating press) and later heating process (during reflow process). (Or, the peeling of the resin layer and the conductor pattern) is suppressed.
  • the additive may be, for example, a material having a function of reducing the combustibility of the first resin layers 11 to 13.
  • the additive is a known flame retardant, and is, for example, an inorganic material such as aluminum hydroxide, magnesium hydroxide, a boron compound or ammonium carbonate, an organic material such as a bromine compound or a phosphoric acid ester, or the like.
  • the altered portion may be formed by modifying the surface of the first resin layer, and the surface of the first resin layer is irradiated with light (for example, polarized light). The altered portion may be formed by increasing the molecular orientation in a certain direction.
  • the surfaces of the first resin layers 11 to 13 may be reacted with each other by a chemical treatment.
  • the chemical treatment includes, for example, a case where a cross-linking agent or the like is applied to the surfaces of the first resin layers 11 to 13 to change the surface of the first resin layers 11 to 13.
  • Second Embodiment an example of a resin multilayer substrate formed by laminating two first resin layers is shown.
  • FIG. 5A is a sectional view of the resin multilayer substrate 102 according to the second embodiment
  • FIG. 5B is an exploded sectional view of the resin multilayer substrate 102.
  • the altered portion D2 is shown by cross-hatching in order to make the structure easy to understand.
  • the resin multilayer substrate 102 is different from the resin multilayer substrate 101 according to the first embodiment in that the substrate 10A is provided.
  • Other configurations of the resin multilayer substrate 102 are substantially the same as those of the resin multilayer substrate 101.
  • the resin multilayer substrate 102 includes a substrate 10A, a conductor pattern 31, and the like.
  • the base material 10A is formed by laminating the first resin layers 11a and 12a in this order.
  • the first resin layers 11a and 12a are substantially the same as the first resin layers 11 and 12 described in the first embodiment.
  • a conductor pattern 31 is formed on the surface of the first resin layer 11a.
  • the conductor pattern 31 is the same as that described in the first embodiment.
  • the first resin layer 12a has an altered portion D2 that has been altered by surface treatment on the back surface (interface FS1 with the first resin layer 11a that is adjacent to and adheres in the Z-axis direction).
  • the altered portion D2 is formed on the entire back surface of the first resin layer 12a.
  • Third Embodiment an example of a resin multilayer substrate provided with a second resin layer other than the first resin layer is shown.
  • FIG. 6A is a cross-sectional view of the resin multilayer substrate 103 according to the third embodiment
  • FIG. 6B is an exploded sectional view of the resin multilayer substrate 103.
  • the altered portions D2 and D3 are shown by cross-hatching in order to make the structure easy to understand.
  • the resin multilayer substrate 103 is different from the resin multilayer substrate 101 according to the first embodiment in that the substrate 10B is provided.
  • the other parts of the resin multilayer substrate 103 are substantially the same as those of the resin multilayer substrate 101.
  • the base material 10B is formed by laminating the first resin layer 11b, the second resin layer 20, the first resin layer 12b, and the first resin layer 13b in this order.
  • the first resin layers 11b, 12b, and 13b are the same as the first resin layers 11 to 13 described in the first embodiment.
  • the second resin layer 20 is an adhesive layer having higher adhesion to the first resin layers 11b to 13b (non-altered portion) than to adhesion between the first resin layers 11b to 13b (non-altered portion).
  • the second resin layer 20 is a fluororesin such as perfluoroalkoxy alkane (PFA) or polytetrafluoroethylene (PTFE), or a resin sheet such as bismaleimide, styrene elastomer, or epoxy.
  • PFA perfluoroalkoxy alkane
  • PTFE polytetrafluoroethylene
  • resin sheet such as bismaleimide, styrene elastomer, or epoxy.
  • first resin layers 11b and 12b adjacent to each other in the Z-axis direction are joined via the second resin layer 20.
  • the thickness of the second resin layer 20 is thinner than the thickness of each of the first resin layers 11b to 13b.
  • the first resin layer 12b has an altered portion D2 on the front surface (interface FS3 with the first resin layer 13b adjacent to and in close contact with the Z-axis direction), and the first resin layer 13b has a back surface (Z-axis).
  • the altered portion D3 is provided on the FS3) side of the interface with the first resin layer 12b that is adjacent to and adheres to the direction.
  • the altered portion D2 of the first resin layer 12b and the altered portion D3 of the first resin layer 13b face each other.
  • the two first resin layers 11b and 12b adjacent to each other in the Z-axis direction have the second resin layer 20 (the adhesion with the first resin layer is higher than the adhesion between the first resin layers). It may be joined via.
  • the resin layer is more than the case where the first resin layers (non-altered parts) are directly bonded to each other, as in the case where the altered portion having high adhesion is provided on the interface side between the first resin layers. Improves the adhesion of the interface between each other.
  • the second resin layer (adhesive layer) is capable of realizing a resin multilayer substrate having excellent high-frequency characteristics. ) Is not used, and it is desirable to bond the first resin layers to each other. Further, by joining the first resin layers to each other without using the second resin layer, delamination due to the difference in the coefficient of thermal expansion between the resin layers can be suppressed.
  • the thickness of the second resin layer 20 is the first resin. It is preferably thinner than the thickness of each of the layers 11b to 13b. By making the second resin layer 20 thinner, a resin multilayer substrate having a lower dielectric constant and lower loss (low dielectric loss tangent) can be realized.
  • the second resin layer 20 is preferably a resin sheet made of a fluororesin. This is because the resin sheet made of fluororesin has a low dielectric constant, low loss, and excellent bendability as compared with a sheet made of other materials.
  • the second resin layer 20 may be a resin sheet containing a fluororesin (for example, a resin in which a norbornene-based polymer and a fluororesin are mixed).
  • the second resin layer 20 may be a layer obtained by adding a material having a function of enhancing UV absorption to the first resin layer as an additive and performing laser irradiation or light irradiation.
  • the second resin layer 20 is obtained by causing a transesterification reaction in the entire first resin layer by laser irradiation or light irradiation. That is, the entire second resin layer 20 has a structure equivalent to that of the altered portion of the first resin layer. Therefore, the structure of the second resin layer 20 is different from the structure in which the altered portion D1 is formed on a part of the surface side of the first resin layer 11 as shown in FIG. Further, the second resin layer 20 may be obtained by causing a transesterification reaction in the entire first resin layer by heating.
  • the two first resin layers 12b and 13b that are adjacent to each other in the Z-axis direction and are in close contact with each other have a configuration in which the altered portions D2 and D3 are provided on the interface FS3 side. There may be.
  • the altered portion D2 of the first resin layer 12b and the altered portion D3 of the first resin layer 13b are in close contact with each other (joined) in the Z-axis direction. It is not limited. The altered portions of the two first resin layers adjacent to each other in the Z-axis direction do not have to face each other in the Z-axis direction.
  • Example Examples of the resin multilayer substrate of the present invention will be described below.
  • the inventor of the present application created Comparative Example 1 and Examples 1 to 22 described below in order to clarify the effect of the resin multilayer substrate according to the present invention.
  • the inventor of the present application measured the adhesion force, the cohesive fracture rate / surface fracture rate, and the coefficient of thermal expansion in the plane direction of Comparative Example 1 and Examples 1 to 22.
  • the coefficient of thermal expansion in the plane direction is represented by the following formula (A).
  • ⁇ L ⁇ L ⁇ T ...
  • A Coefficient of thermal expansion in the direction in which the main surface of the resin layer spreads (plane direction): ⁇ Length of resin layer in the direction in which the main surface of the resin layer spreads (plane direction): L Amount of elongation of the resin layer in the direction in which the main surface of the resin layer spreads (plane direction): ⁇ L Temperature rise: ⁇ T
  • the inventor of the present application measured the coefficient of thermal expansion by the following method. The inventor of the present application prepared a sample cut out to a width of 5 mm and a length of 16 mm.
  • thermomechanical analyzer (trade name: TMA Q400) manufactured by TA instruments.
  • TMA Q400 thermomechanical analyzer
  • Table 1 is a table showing the conditions of Comparative Example 1 and Examples 1 to 22.
  • P-1 is the chemical formula (3).
  • the synthesis and film formation of the first resin layer having the structures of P-1 to P-4 are described in, for example, Japanese Patent Application Laid-Open No. 2010-189619 and Japanese Patent Application Laid-Open No. 2010-286837.
  • PIAD is a material having a function of enhancing the UV absorption of the resin layer.
  • PIAD is a solvent-soluble polyimide varnish manufactured by Arakawa Chemical Industries, Ltd.
  • LCP-NF and BN are materials having a function of lowering the coefficient of thermal expansion of the resin layer.
  • LCP-NF is, for example, the liquid crystal polymer powder described in Japanese Patent No. 5904307.
  • BN is Denka Boron Night Ride manufactured by Denka Co., Ltd.
  • PFA is AGC Fluon + EA2000 manufactured by AGC Inc.
  • SAFY is Nikaflex SAFY manufactured by Nikkan Kogyo Co., Ltd.
  • Table 2 is a table showing the experimental results.
  • the adhesion and cohesive failure rate / interface failure rate of Examples 1 to 8, Example 15, Example 17, Example 19 and Example 21 are the adhesion and cohesion failure rate / interface failure rate of Comparative Example 1. It turns out to be higher. The reason is that Examples 1 to 8, Example 15, Example 17, Example 19 and Example 21 include an altered portion that has been altered by surface treatment by UV irradiation, plasma discharge or corona discharge.
  • Examples 9 to 16 are higher than the adhesive force and cohesive fracture rate / interfacial fracture rate of Comparative Example 1. The reason is that Examples 9 to 16 include a second resin layer as an adhesive layer.
  • Comparative Example 2 and Examples 23 to 26 described below as a second experiment in order to clarify the effect of the resin multilayer substrate according to the present invention. Then, the inventor of the present application measured the amount of decrease ( ⁇ Tg) in the glass transition temperature (Tg) of Comparative Example 2 and Examples 23 to 26, the adhesion force, the cohesive fracture rate / surface fracture rate, and the coefficient of thermal expansion.
  • Table 3 is a table showing the conditions of Comparative Example 2 and Examples 23 to 26.
  • P-5 is the chemical formula (7).
  • the thickness of the first resin layer was 50 ⁇ m.
  • the resin near the surface layer of the first resin layer and the additive reacted, and a altered portion having a P-5 structure was formed near the surface layer of the first resin layer.
  • the thickness of the altered portion was 5 ⁇ m.
  • the intensity of the xenon flash lamp and the heat generated by the xenon flash lamp are attenuated as the depth from the surface layer of the first resin layer increases. Therefore, an altered portion having a P-5 structure is formed near the surface layer of the first resin layer.
  • the proportion of P-5 decreases and the proportion of P-1 increases. That is, the composition of P-5 and P-1 is inclined.
  • a / b is the mass of P-1 on the surface layer of the first resin layer / the mass of P-5 on the surface layer of the first resin layer.
  • the inventor of the present application measured the amount of decrease ( ⁇ Tg) in the glass transition temperature (Tg) and the coefficient of thermal expansion using the first resin layer in which the altered portion was formed as described above. Further, the inventor of the present application bonded the first resin layer on which the altered portion was formed and the resin layer on which the altered portion was not formed as described above, and measured the adhesion and the cohesive fracture rate / surface fracture rate.
  • Table 4 is a table showing the experimental results.
  • Examples 23 to 26 are higher than the adhesive force and cohesive fracture rate / interfacial fracture rate of Comparative Example 2. The reason is that Examples 23 to 26 include an altered portion. As described above, the adhesion force and the cohesive fracture rate / interface fracture rate of the resin multilayer substrate are also improved by the altered portion obtained by altering the structure of P-1 to the structure of P-5 by the transesterification reaction by heating. I understand.
  • Example 25 when a / b is low, ⁇ Tg is large. This means that the molecular motility of the first resin layer with respect to heat is increased, and the adhesion between the first resin layers is enhanced.
  • Example 27 to 29 an altered portion was formed in the first resin layer as shown in Table 5. Therefore, the first resin surface of the single-sided copper-coated plate containing P-1 and diethylene glycol monobutyl ether was irradiated with a xenon flash lamp. The thickness of the first resin layer was 50 ⁇ m. At this time, the amount of ethylene glycol monobutyl ether added was changed from 10 phr to 30 phr. As a result, the resin near the surface layer of the first resin layer and the additive reacted, and a altered portion having a P-5 structure was formed near the surface layer of the first resin layer. In Examples 27 to 29, the thickness of the altered portion was 5 ⁇ m.
  • the intensity of the xenon flash lamp and the heat generated by the xenon flash lamp are attenuated as the depth from the surface layer of the first resin layer increases. Therefore, an altered portion having a P-5 structure is formed near the surface layer of the first resin layer. However, as the distance from the surface layer of the first resin layer increases, the proportion of P-5 decreases and the proportion of P-1 increases. That is, the composition of P-5 and P-1 is inclined. The inclination of the composition of P-5 and P-1 occurred in the range of 5 ⁇ m from the surface layer of the first resin layer.
  • a / b is the mass of P-1 on the surface layer of the first resin layer / the mass of P-5 on the surface layer of the first resin layer.
  • the inventor of the present application measured the amount of decrease ( ⁇ Tg) in the glass transition temperature (Tg) and the coefficient of thermal expansion using the first resin layer in which the altered portion was formed as described above. Further, the inventor of the present application bonded the first resin layer on which the altered portion was formed and the resin layer on which the altered portion was not formed as described above, and measured the adhesion and the cohesive fracture rate / surface fracture rate.
  • Table 6 is a table showing the experimental results.
  • Examples 27 to 29 are higher than the adhesive force and cohesive fracture rate / interfacial fracture rate of Comparative Example 3. The reason is that Examples 27 to 29 include an altered portion. As described above, the adhesion force and the cohesive fracture rate / interface fracture rate of the resin multilayer substrate are also improved by the altered portion obtained by altering the structure of P-1 to the structure of P-5 by the transesterification reaction by heating. I understand.
  • Example 27 when a / b is low, ⁇ Tg is large. This means that the molecular motility of the first resin layer with respect to heat is increased, and the adhesion between the first resin layers is enhanced.
  • the method for manufacturing the resin multilayer substrate of Examples 23 to 29 is as follows.
  • the plurality of resin layers have at least one first resin layer 12 using a norbornene-based polymer containing at least one of the repeating units represented by the following general formula (1).
  • X represents O, -CH 2- or -CH 2- CH 2-
  • the substituents R 1 , R 2 , R 3 and R 4 are hydrogen, linear or branched, respectively.
  • the organic group is, for example, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
  • the first resin layer 12 contains an additive that reacts with the norbornene-based polymer.
  • the additive is PIAD or ethylene glycol monobutyl ether.
  • the norbornene-based polymer of the first resin layer 12 and the additive are reacted by surface treatment, and as the effect of the surface treatment is attenuated, the material (P-1) before the reaction and the material (P-1) after the reaction are reduced in thickness direction.
  • the composition with the material (P-5) is inclined.
  • Surface treatments include heating and UV irradiation.
  • the chemical reaction of the surface treatment includes a transesterification reaction by heating, a UV curing reaction by UV irradiation, and the like. Examples of the method for partially forming the altered portion in the first resin layer 12 as in Examples 23 to 29 include the following methods.
  • a transesterification reaction by heat there is a method in which only the surface of the first resin layer 12 is heated and thermally diffused by irradiating a high energy with a short pulse like a xenon flash lamp. Further, there is a method of partially forming a deteriorated portion in the first resin layer 12 by absorbing the irradiation energy in the first resin layer 12, such as near infrared irradiation treatment and infrared irradiation treatment. On the other hand, in the case of an energy reaction by UV curing, there is a method of partially forming a deteriorated portion in the first resin layer 12 by absorbing irradiation energy.
  • An example of a xenon flash lamp is an instant heating / high temperature firing flash lamp annealing manufactured by Ushio, Inc.
  • An example of the near-infrared irradiation treatment manufactured by Matsumoto Metal Industry Co., Ltd. is, for example, an ultra-near infrared heating device. According to these methods, the composition of the material before the reaction (P-1) and the material after the reaction (P-5) is inclined in the thickness direction.
  • the base material is a rectangular or substantially rectangular flat plate
  • the shape of the base material is not limited to this.
  • the shape of the base material can be appropriately changed within the range in which the action and effect of the present invention are exhibited.
  • the planar shape of the base material may be, for example, polygonal, circular, elliptical, L-shaped, U-shaped, crank-shaped, T-shaped, Y-shaped, or the like.
  • a base material formed by laminating three first resin layers, or a group formed by laminating three first resin layers and one second resin layer is not limited to this structure.
  • the number of layers of the first resin layer and the number of layers of the second resin layer forming the base material can be appropriately changed.
  • a protective layer such as a coverlay film or a resist film may be formed on the surface of the base material.
  • the circuit configuration formed on the resin multilayer substrate is not limited to the configuration of each of the above-described embodiments, and can be appropriately changed as long as the operation and effect of the present invention are exhibited.
  • frequency filters such as coils (inductors) and capacitors formed by a conductor pattern and various filters (low-pass filter, high-pass filter, band-pass filter, band-elimination filter) are formed. You may.
  • various transmission lines may be formed on the resin multilayer substrate.
  • various electronic components such as chip components may be mounted or embedded in the resin multilayer substrate.
  • the shapes, positions, and numbers of the conductor patterns 31 and 32 are not limited to the configurations of the above-described embodiments, and can be appropriately changed within the range in which the actions and effects of the present invention are exhibited.
  • the planar shape of the conductor pattern may be, for example, polygonal, circular, elliptical, arcuate, ring-shaped, L-shaped, U-shaped, T-shaped, crank-shaped, or the like.
  • the conductor patterns 31 and 32 are formed inside the base material, but the conductor pattern (including the electrode for external connection) is formed on the surface of the base material. It may have been done.
  • the resin multilayer substrate may include a dummy electrode (dummy conductor) that is not connected to the circuit.
  • interlayer connection conductor V1 formed by solidifying the conductive paste disposed (filled) in the holes provided in the first resin layer 12 by heat pressing is shown.
  • the interlayer connecting conductor is not limited to this.
  • the interlayer connecting conductors formed on the resin multilayer substrate include, for example, plating vias (through hole plating or filled via plating) provided by plating in the holes formed in the resin layer, and the plating vias (or metal pins, etc.).
  • a conductor or the like having a conductive bonding material to be bonded to the plating via may be used.
  • the first resin layers 11b to 13b may be bonded to the second resin layer 20.
  • the third resin layer may be bonded to the second resin layer 20 instead of the first resin layer 11b.
  • a plurality of one first resin layer 12b is joined to the second resin layer 20.
  • the altered parts D2 and D3 are not indispensable.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/JP2020/029985 2019-08-06 2020-08-05 樹脂多層基板および樹脂多層基板の製造方法 Ceased WO2021025055A1 (ja)

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CN202080054610.3A CN114208401A (zh) 2019-08-06 2020-08-05 树脂多层基板和树脂多层基板的制造方法
US17/584,589 US12120817B2 (en) 2019-08-06 2022-01-26 Resin multilayer substrate and method for manufacturing resin multilayer substrate

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CN115087692B (zh) * 2020-03-06 2024-02-13 株式会社村田制作所 液晶聚合物膜及其制造方法
JP7749349B2 (ja) * 2021-06-14 2025-10-06 株式会社Ｅｎｅｏｓマテリアル フィブリル状液晶ポリマー粒子の製造方法
WO2023032376A1 (ja) * 2021-08-31 2023-03-09 株式会社村田製作所 液晶ポリマーフィルムおよび液晶ポリマーフィルムの製造方法
WO2023210471A1 (ja) * 2022-04-28 2023-11-02 富士フイルム株式会社 フィルム及び積層体
CN116552075A (zh) * 2023-05-30 2023-08-08 深圳聚源新材科技有限公司 一种含热膨胀系数可调材料的复合材料及其应用
CN117024911A (zh) * 2023-05-30 2023-11-10 深圳聚源新材科技有限公司 一种热膨胀系数可调的复合材料及其制备方法
CN116731418A (zh) * 2023-05-30 2023-09-12 深圳聚源新材科技有限公司 一种热膨胀系数可调的复合材料及其制备方法
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