WO2020066974A1 - 樹脂組成物、膜、積層体、接合構造体、積層体の製造方法および接合構造体の製造方法 - Google Patents

樹脂組成物、膜、積層体、接合構造体、積層体の製造方法および接合構造体の製造方法 Download PDF

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Publication number
WO2020066974A1
WO2020066974A1 PCT/JP2019/037186 JP2019037186W WO2020066974A1 WO 2020066974 A1 WO2020066974 A1 WO 2020066974A1 JP 2019037186 W JP2019037186 W JP 2019037186W WO 2020066974 A1 WO2020066974 A1 WO 2020066974A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
resin
capsule
protrusion
insulating base
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PCT/JP2019/037186
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English (en)
French (fr)
Japanese (ja)
Inventor
堀田　吉則
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富士フイルム株式会社
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Priority to JP2020549193A priority Critical patent/JP7057432B2/ja
Publication of WO2020066974A1 publication Critical patent/WO2020066974A1/ja

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    • 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
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B3/30—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 formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits

Definitions

  • the present invention relates to a resin composition containing a resin and a capsule containing a core material. More specifically, the present invention relates to a resin composition used for joining members having a projection serving as an electrically conductive terminal. In addition, the present invention relates to a film, a laminate, a joint structure, a method for producing a laminate, and a method for producing a joint structure using a resin composition.
  • a metal-filled microstructure in which metal is filled in micropores provided in an insulating base material is one of the fields that have attracted attention in nanotechnology in recent years, and is expected to be used, for example, as an anisotropic conductive member.
  • This anisotropic conductive member can be inserted between an electronic component such as a semiconductor element and a circuit board and pressurized to obtain an electrical connection between the electronic component and the circuit board.
  • electrical connection members and connectors for testing when performing a function test are widely used as electrical connection members and connectors for testing when performing a function test.
  • Patent Literatures 1 and 2 disclose an insulating base made of an inorganic material and a plurality of conductive paths made of a conductive member penetrating in a thickness direction of the insulating base and provided in a state of being insulated from each other. It describes that a plurality of conductive paths are joined to a wiring board having a plurality of electrodes by using an anisotropic conductive member having a protrusion protruding from a surface of an insulating base material. In Patent Literatures 1 and 2, when a protrusion of an anisotropic conductive member is bonded to an electrode of a wiring board, the protrusion is bonded using a thermosetting resin.
  • an object of the present invention is to provide a resin composition that can suppress generation of voids between members having projections when the members are joined to each other.
  • Another object of the present invention is to provide a film, a laminate, a joint structure, a method for producing a laminate, and a method for producing a joint structure using a resin composition.
  • the present invention provides the following.
  • a resin composition containing a resin and a capsule containing a core material The capsule has an arithmetic mean of the maximum diameter of 3 ⁇ m or less,
  • the resin composition, wherein the core material includes at least one selected from a compound that decomposes the resin and a plasticizer.
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the capsule is contained in an amount of 5 to 50% by mass in the total solid content of the resin composition.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the capsule is contained in an amount of 10 to 50 parts by mass with respect to 100 parts by mass of the resin.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the capsule is broken when a pressure of 10 kPa to 50 MPa is applied.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the capsule is broken at 120 to 300 ° C.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the viscosity of the core material at 23 ° C. is 100 mPa ⁇ s or less.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the core material includes at least one selected from an oxidizing agent, a reducing agent, and a reactive plasticizer.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the resin composition further contains a plasticizer.
  • ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, wherein the resin is a thermosetting resin.
  • ⁇ 11> A film formed using the resin composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 12> The membrane according to ⁇ 11>, wherein the volume fraction of the capsule in the membrane is 5% or more.
  • ⁇ 13> A member having a protrusion serving as an electrically conductive terminal, and the resin composition according to any one of ⁇ 1> to ⁇ 10> provided on a surface of the member having a protrusion. And a film formed using the same.
  • ⁇ 14> The laminate according to ⁇ 13>, wherein the member has protrusions on both surfaces of the insulating base material, and the film has on both surfaces of the insulating base material.
  • the member has an insulating base material and a plurality of conductive paths formed of conductive members penetrating in the thickness direction of the insulating base material and provided in a state of being insulated from each other.
  • a passage is an anisotropic conductive member having a protrusion protruding from the surface of the insulating base material
  • ⁇ 17> The laminate according to ⁇ 16>, wherein the capsules in the film are unevenly distributed in a surface layer on a side opposite to a surface where the insulating substrate and the film are in contact.
  • ⁇ 18> a first member having a projection serving as an electrically conductive terminal; A second member having a projection serving as an electrically conductive terminal; A film formed using the resin composition according to any one of ⁇ 1> to ⁇ 10>, provided between the first member and the second member; A joint structure in which the projection of the first member and the projection of the second member are electrically joined.
  • One of the first member and the second member penetrates the insulating base material in a thickness direction of the insulating base material and a plurality of conductive paths formed of conductive members provided in a state of being insulated from each other.
  • the plurality of conductive paths are anisotropically conductive members having protrusions protruding from the surface of the insulating base material, and the other is a wiring board.
  • the resin composition according to any one of ⁇ 1> to ⁇ 10> is applied to a member having a protrusion serving as an electrically conductive terminal, and is in contact with the protrusion and the height of the protrusion.
  • a method for producing a laminate comprising: a resin composition layer forming step of forming a resin composition layer having a thickness exceeding 3 mm.
  • the resin composition according to any one of ⁇ 1> to ⁇ 10> is applied to a first member having a protrusion serving as an electrically conductive terminal, and is in contact with the protrusion and a protrusion.
  • the present invention it is possible to provide a resin composition that can suppress generation of voids between members having a projection when joining members having a projection. Further, the present invention can provide a film, a laminate, a joint structure, a method for producing a laminate, and a method for producing a joint structure using a resin composition.
  • FIG. 5 is a diagram illustrating a manufacturing process of the joint structure of FIG. 4.
  • FIG. 5 is a diagram illustrating a manufacturing process of the joint structure of FIG. 4.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “(meth) acryl” represents both or “acryl” and “methacryl”.
  • the term "step” is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
  • the physical property values in the present invention are values at a temperature of 23 ° C. and a pressure of 101325 Pa unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) and are defined as polystyrene equivalent values, unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, for example, using HLC-8220 (manufactured by Tosoh Corporation), and using guard columns HZ-L, TSKgel Super HZM-M, and TSKgel as columns. It can be determined by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • THF tetrahydrofuran
  • UV rays ultraviolet rays
  • the resin composition of the present invention is a resin composition containing a resin and a capsule containing a core material,
  • the capsule has an arithmetic mean of the maximum diameter of 3 ⁇ m or less
  • the core material includes at least one selected from a compound that decomposes a resin and a plasticizer.
  • the reason for obtaining such an effect is as follows. Since the arithmetic mean of the maximum diameter of the capsule contained in the resin composition is 3 ⁇ m or less, it is estimated that the variation in height when the projections of both members are joined can be reduced. For this reason, when joining the protrusions of both members, it is presumed that the capsule is easily broken, and the core material can efficiently seep out from the inside of the capsule. Then, it is presumed that the resin is plasticized by the core material exuding from the inside of the capsule, or the resin is decomposed to lower the viscosity and improve the fluidity.
  • the generation of voids between both members can be suppressed by joining the members having the protrusions using the resin composition of the present invention. Further, even when the members are joined at a low temperature (for example, 250 ° C. or lower), the generation of voids can be effectively suppressed, which is particularly effective when joining at a low temperature.
  • the arithmetic mean of the maximum diameter of the capsule is 3 ⁇ m or less, the dispersibility of the capsule in the resin composition is good.
  • the protrusions of each member can be firmly joined. For this reason, when the projections of each member are to be electrically conductive terminals, the projections of each member can be electrically firmly joined to each other, and the joining resistance between the members is reduced. And the bonding property (bonding probability) can be improved.
  • the resin composition of the present invention is preferably used as a composition for joining members having a projection. Further, the resin composition used in the present invention is also preferably an insulating resin composition. Such a resin composition is preferably used as a composition for joining members having a projection serving as an electrically conductive terminal.
  • the resin composition of the present invention will be described in more detail.
  • the resin composition of the present invention contains a resin.
  • the resin may be a thermoplastic resin or a thermosetting resin.
  • a thermosetting resin is preferable because it is easy to maintain the adhesive strength between devices and to ensure the reliability under high humidity.
  • the thermoplastic resin is a resin that is softened or melted by heating
  • the thermosetting resin is a resin that is cured by heating.
  • the resin used in the resin composition of the present invention is preferably a non-conductive resin, and more preferably a non-conductive resin having a volume resistivity of 10 10 ⁇ ⁇ cm or more. Further, a thermosetting resin is preferable.
  • the weight average molecular weight (Mw) of the resin is preferably from 1,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 2000 or more, and more preferably 3000 or more.
  • resins include (meth) acrylic resin, epoxy resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, polycarbonate resin, polyether resin, polyester resin, styrene resin, phenol resin, maleimide resin, and urea-formaldehyde resin.
  • epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and aliphatic epoxy resin.
  • bisphenol A type epoxy resins include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, and jER1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (all manufactured by DIC Corporation) and the like.
  • Bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (all manufactured by DIC Corporation), LCE-21, RE-602S (Nippon Kayaku Co., Ltd.) and the like.
  • Examples of the phenol novolak type epoxy resin include jER152, jER154, jER157S70, jER157S65 (all manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, and EPICLON N-775 (all manufactured by DIC). Is mentioned.
  • Cresol novolak type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DIC Corporation). ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • ADEKA RESIN EP-4080S, EP-4085S, EP-4088S manufactured by ADEKA Corporation
  • Celloxide 2021P Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB3600, PB # 4700 (all manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Corporation) and the like.
  • ADEKA Resin EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation) and the like.
  • the thermal expansion coefficient of the resin used in the present invention is preferably 50 ⁇ 10 ⁇ 6 K ⁇ 1 or less, more preferably 5 ⁇ 10 ⁇ 6 K ⁇ 1 to 50 ⁇ 10 ⁇ 6 K ⁇ 1. And more preferably 5 ⁇ 10 ⁇ 6 K ⁇ 1 to 30 ⁇ 10 ⁇ 6 K ⁇ 1 .
  • the coefficient of thermal expansion of the mixture of two or more resins is preferably 50 ⁇ 10 ⁇ 6 K ⁇ 1 or less, and preferably 5 ⁇ 10 ⁇ 5. It is more preferably from 6 K -1 to 50 ⁇ 10 -6 K -1 , further preferably from 5 ⁇ 10 -6 K -1 to 30 ⁇ 10 -6 K -1 .
  • the content of the resin is preferably 20 to 80% by mass based on the total solid content of the resin composition.
  • the lower limit is preferably 25% by mass or more, more preferably 50% by mass or more.
  • the upper limit is preferably 75% by mass or less.
  • the resin may contain only one kind, or may contain two or more kinds. When two or more resins are contained, the total thereof is preferably within the above range.
  • the resin composition of the present invention contains a capsule containing a core material.
  • the core material of the capsule used in the resin composition of the present invention contains at least one selected from a compound that decomposes the resin and a plasticizer.
  • a compound that decomposes the resin contained in the resin composition of the present invention and has low decomposability or solubility in the wall material of the capsule is used.
  • an oxidizing agent, a reducing agent and the like can be mentioned, and it is preferable to select and use as appropriate according to the type of the resin contained in the resin composition and the type of the material constituting the wall material of the capsule.
  • a carboxylic acid compound and a sulfonic acid compound are preferable.
  • the carboxylic acid compound include acetic acid, oxalic acid, propionic acid, 1,10-dodecanedicarboxylic acid, 1,11-undecanedicarboxylic acid, sebacic acid, benzoic acid, phthalic acid, terephthalic acid, 1,3-dicarboxylate -1,1,3,3-tetramethyldisiloxane and the like.
  • the sulfonic acid compound include toluenesulfonic acid, benzenesulfonic acid, and methanesulfonic acid.
  • the reducing agent examples include a metal alkoxide compound.
  • the metal alkoxide compound is a compound represented by M (OR) n .
  • M represents a metal element
  • R represents an alkyl group
  • n represents the oxidation number of the metal element M.
  • the metal element represented by M include sodium (Na), potassium (K), and calcium (Ca).
  • the number of carbon atoms of the alkyl group represented by R is preferably from 1 to 30, more preferably from 1 to 10, and still more preferably from 1 to 5.
  • Preferred specific examples of the metal alkoxide compound include methoxy sodium (CH 3 ONa) and methoxy potassium (CH 3 OK).
  • epoxy resin when used as the resin, oxalic acid, benzenesulfonic acid, methoxy potassium, and the like can be used.
  • polyester plasticizers a compound that reduces the viscosity of the resin is preferably used.
  • polyester plasticizers glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, phthalic acid diester plasticizers such as dibutyl phthalate, di (2-ethylhexyl) phthalate, and adipine
  • phthalic acid diester plasticizers such as dibutyl phthalate, di (2-ethylhexyl) phthalate, and adipine
  • aliphatic dibasic acid ester-based plasticizers such as di (2-ethylhexyl) acid
  • phosphate triester-based plasticizers such as tricresyl phosphate
  • glycol ester-based plasticizers such as polyethylene glycol ester.
  • a reactive plasticizer is more preferable.
  • the reactive plasticizer is a plasticizer having a reactive group.
  • the reactive group include an epoxy group and a phenol group, and an epoxy group is preferable. That is, the reactive plasticizer is preferably a plasticizer having an epoxy group.
  • a glycidyl ester compound which is an epoxidized product of a chain dimer or an ester compound thereof may be mentioned.
  • polyester plasticizer examples include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and rosin, and propylene glycol, 1,3-butanediol, and 1,4-butanediol.
  • polyesters composed of diol components such as 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be terminal-blocked with a monofunctional carboxylic acid or monofunctional alcohol, or may be terminal-blocked with an epoxy compound or the like.
  • glycerin-based plasticizer examples include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonoolate, glycerin monoacetomonomontanate, and glycerin tribenzoate.
  • polycarboxylic acid ester-based plasticizer examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and the like, tributyl trimellitate, Trimellitate such as trioctyl trimellitate, trihexyl trimellitate, tri (2-ethylhexyl) trimellitate, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, adipin Adipates such as benzylmethyldiglycolate and benzylbutyldiglycolate, citrates such as triethyl acetylcitrate and tributylacetylcitrate, and di-2-ethyl azelate Azelaic acid
  • polyalkylene glycol plasticizer examples include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and propylene oxide of bisphenols.
  • polyalkylene glycols such as addition polymers and tetrahydrofuran addition polymers of bisphenols, and terminal-modified compounds thereof.
  • the reactive plasticizer examples include a glycidyl ester compound which is an epoxidized product of a chain dimer or an ester compound thereof.
  • plasticizers include benzoic acid esters of aliphatic polyols such as ethylene glycol, neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, and fatty acid amides such as stearamide.
  • carboxylic acid esters such as butyl oleate, oxyacid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, pentaerythritol, and various sorbitols.
  • the core material contained in the capsule may contain only one of the compound that decomposes the resin and the plasticizer, or may contain both.
  • the core material contains a compound that decomposes the resin, it is easy to suppress the curing reaction of the resin.
  • the core material contains a plasticizer, it is easy to improve the fluidity of the resin.
  • the core material contains a compound that decomposes the resin and a plasticizer, the mobility (fluidity) of the resin is more likely to be improved by a synergistic effect of the two.
  • the core material contains a compound that decomposes the resin and a plasticizer
  • the core material preferably contains 10 to 90 parts by mass, and more preferably 20 to 70 parts by mass of the plasticizer based on 100 parts by mass of the compound that decomposes the resin. More preferably, it is more preferably 40 to 60 parts by mass.
  • the core material does not substantially contain a compound that decomposes the resin.
  • the case where the core material does not substantially contain the compound that decomposes the resin means that the content of the compound that decomposes the resin in the core material is 1% by mass or less, and 0.5% by mass or less. Is more preferably 0.1% by mass or less, and particularly preferably not contained.
  • the core material does not substantially contain a plasticizer.
  • the case where the core material does not substantially contain a plasticizer means that the content of the plasticizer in the core material is 1% by mass or less, and preferably 0.5% by mass or less, The content is more preferably 0.1% by mass or less, and particularly preferably not contained.
  • the core material contained in the capsule used in the resin composition of the present invention preferably contains a compound that decomposes the resin and a plasticizer in total of 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more. More preferably, it is contained by mass% or more.
  • the upper limit can be 100% by mass or less, and can be 90% by mass or less.
  • the core material contained in the capsule may further contain a component (other component) other than the above-mentioned compound that decomposes the resin and the plasticizer.
  • Other components include metal antioxidants (eg, imidazole), crosslinking agents, surfactants, and the like.
  • the content of the other components is preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less in the core material.
  • the core material contained in the capsule preferably has a viscosity at 23 ° C. of not more than 1000 mPa ⁇ s, more preferably not more than 200 mPa ⁇ s, and still more preferably not more than 100 mPa ⁇ s.
  • the lower limit can be, for example, 10 mPa ⁇ s or more.
  • the capsule used in the resin composition of the present invention is one that is broken by application of heat or pressure. More specifically, it is preferable that the wall material of the capsule is broken by application of heat or pressure.
  • the capsule is broken by applying a pressure of 10 kPa to 50 MPa (preferably 1 MPa to 5 MPa, more preferably 1 MPa to 3 MPa).
  • the wall material is broken.
  • the capsule may be further broken at a temperature of 120 to 300 ° C. (preferably 150 to 250 ° C., more preferably 180 to 200 ° C.), or may not be broken at the aforementioned temperature. You may. From the viewpoint of developing the fluidity of the resin at the time of joining, it is preferable that the resin be broken at the above temperature. Further, from the viewpoint of storage stability after forming a coating film, it is preferable that the coating film is not broken at the above temperature.
  • the capsule is one which is broken at a temperature of 120 to 300 ° C. (preferably 150 to 250 ° C., more preferably 180 to 200 ° C.), more specifically, a capsule which is broken at the above temperature range.
  • the wall material is broken.
  • the capsule is further broken by applying a pressure of 10 kPa to 50 MPa (preferably 1 MPa to 5 MPa, more preferably 1 MPa to 3 MPa), more specifically, the capsule wall material is broken. It is also preferred.
  • the material constituting the wall material of the capsule is not particularly limited.
  • examples include polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, urea-formaldehyde resin, melamine resin, polystyrene resin, (meth) acrylic resin, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, etc., and polyurethane resin, polyurea.
  • Resins, polyamide resins, polyester resins and polycarbonate resins are preferred, and polyurethane resins and polyurea resins are more preferred.
  • the capsule used in the present invention is obtained by emulsifying a core material containing at least one selected from a compound decomposing a resin and a plasticizer, and then encapsulating by forming a wall of a polymer substance around the oil droplets. Is preferred. In this case, the reactant that forms the polymer substance is added inside the oil droplet and / or outside the oil droplet. Details of capsules that can be preferably used in the present invention, such as a preferred method for producing capsules, are described in the specifications of US Pat. Nos. 3,726,804 and 3,796,696, the contents of which are incorporated herein. .
  • the polyvalent isocyanate and the second substance which reacts with the polyisocyanate to form the wall material are contained in the aqueous phase or the oily liquid to be encapsulated.
  • a polymer forming reaction occurs at the oil droplet interface to form a wall material.
  • the second material is, for example, a polyamine or nothing is added, a polyurea resin is formed.
  • polyvalent isocyanate examples include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene Diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4 Diisocyanates
  • polyol examples include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, hydroxypolyalkylene ethers, and the like. Specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, Propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl-1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol , 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-phenylpropylene
  • polyamine examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxy Trimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, amine adducts of epoxy compounds and the like can be mentioned.
  • the water phase mixed with the oil phase may contain a surfactant.
  • the surfactant include known surfactants.
  • the surfactant can be appropriately selected from an anionic surfactant and a nonionic surfactant.
  • Specific examples of the surfactant include sodium alkylbenzene sulfonate (eg, sodium lauryl sulfate), dioctyl sulfosuccinate sodium salt, polyalkylene glycol (eg, polyoxyethylene nonyl phenyl ether) and the like.
  • the arithmetic mean of the maximum diameter of the capsule contained in the resin composition of the present invention is 3 ⁇ m or less, preferably 2.5 ⁇ m or less, more preferably 2 ⁇ m or less, and preferably 1.5 ⁇ m or less. More preferred.
  • the lower limit is preferably 0.1 ⁇ m or more.
  • the maximum diameter of the capsule can be adjusted by a method such as controlling the number of revolutions of the homogenizer and controlling the state of phase separation when forming the capsule. For example, the maximum diameter of the capsule can be increased by reducing the rotation speed of the homogenizer, and the maximum diameter of the capsule can be reduced by increasing the rotation speed of the homogenizer.
  • the term “maximum diameter of the capsule” refers to the particle diameter (length) of the long axis when the capsule has a long axis and a short axis.
  • the long axis is determined as an axis (straight line) that can take the longest capsule length.
  • the short axis is determined as the axis having the longest length when the particle length is taken along a straight line orthogonal to the long axis.
  • the average particle diameter can be determined as a volume average particle diameter by a laser diffraction / scattering method using LA-910 (manufactured by HORIBA, Ltd.) manufactured by HORIBA. After confirming the workmanship, the arithmetic mean of the maximum diameter of the capsule can be obtained by randomly extracting 50 capsules and observing the shape with an electron microscope.
  • the content of the capsule is preferably 5 to 50% by mass based on the total solid content of the resin composition.
  • the lower limit is preferably 6% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the resin composition of the present invention preferably contains 10 to 50 parts by mass of a capsule with respect to 100 parts by mass of the resin.
  • the lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
  • the upper limit is preferably 45 parts by mass or less, more preferably 30 parts by mass or less.
  • the content of the capsule is preferably such that the volume fraction of the capsule in the film formed using the resin composition is 5% or more, more preferably 10% or more. , And more preferably 15% or more, and particularly preferably 20% or more.
  • the upper limit is preferably 80% or less, more preferably 50% or less, even more preferably 30% or less.
  • the resin composition of the present invention may contain only one type of capsule, or may contain two or more types of capsules. When two or more capsules are contained, the total of them is preferably within the above range.
  • the resin composition of the present invention contains two or more capsules, one or more capsules containing a compound that decomposes resin as a core material and one or more capsules containing a plasticizer as a core material are used in combination. You may. In this case, an effect of improving reliability by separating functions can be expected. Further, two or more capsules containing the same core material and differing only in the capsule wall material may be included. In the case of this embodiment, the joining condition is easily relaxed by controlling the timing of function development.
  • the resin composition of the present invention preferably further contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone , ⁇ -valerolactone, alkyl alkyloxyacetates (eg, methyl alkyloxyacetate, ethylalkyloxyacetate, butylalkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, etc.) )), Alkyl 3-alkyloxypropionates (eg, methyl 3-alkyloxypropionate, ethyl 3-
  • alkyl 2-alkyloxypropionates eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 Propyl alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvate Chill, propyl
  • ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
  • Suitable aromatic hydrocarbons include, for example, toluene, xylene, anisole, limonene and the like.
  • Suitable sulfoxides include, for example, dimethyl sulfoxide.
  • Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like. From the viewpoint of improving the properties of the coated surface, a form in which two or more solvents are mixed is also preferable.
  • the content of the solvent is preferably such that the total solid content of the resin composition of the present invention is 1 to 70% by mass, and more preferably 5 to 50% by mass. More preferably, the amount is more preferably 10 to 30% by mass.
  • the solvent may contain only one kind, or may contain two or more kinds. When two or more solvents are contained, the total thereof is preferably within the above range.
  • the resin composition of the present invention can further contain a plasticizer.
  • the resin composition of the present invention preferably further contains a plasticizer.
  • the plasticizer by having the plasticizer also outside the capsule, the plasticizer that has exuded from the capsule can be mixed with the plasticizer existing outside the capsule, and the fluidity of the resin can be more easily improved.
  • the plasticizer include the materials described in the section of the core material of the capsule described above.
  • the resin composition of the present invention contains a plasticizer
  • its content is preferably 1% to 50% by mass in the resin composition.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 20% by mass or less.
  • the plasticizer may contain only one type, or may contain two or more types. When two or more plasticizers are contained, the total thereof is preferably within the above range.
  • the resin composition of the present invention may contain a curing agent.
  • a resin containing an epoxy resin is used as the resin, it is preferable to contain a curing agent.
  • the curing agent include amine compounds such as diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine and dicyandiamide; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Acid anhydrides such as tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride and trimellitic anhydride; imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- Phenylimidazole, 2-und
  • the content is preferably 0.1 to 10% by mass based on the total solid content of the resin composition.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 5% by mass or less, more preferably 3% by mass or less.
  • the content of the curing agent is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin.
  • the lower limit is preferably at least 0.5 part by mass, more preferably at least 1 part by mass.
  • the upper limit is preferably 5 parts by mass or less, more preferably 2 parts by mass or less.
  • the curing agent may contain only one kind, or may contain two or more kinds. When two or more curing agents are contained, the total of them is preferably within the above range.
  • the resin composition of the present invention can further contain other additives such as a curing accelerator and a metal oxidation inhibitor, if necessary.
  • the total content of other additives is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less based on the total solid content of the resin composition. .
  • the resin composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited, and can be performed by a conventionally known method.
  • a filter it is preferable to use a filter having a pore size about twice as large as the desired capsule size.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore sizes or materials may be used in combination. Further, various materials may be filtered plural times. When filtration is performed a plurality of times, circulation filtration may be used. Also, filtration may be performed under pressure. In the case of performing filtration by applying pressure, the pressure to be applied is preferably 0.05 MPa or more and 0.3 MPa or less.
  • a treatment for removing impurities using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • the adsorbent a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • a conventionally known storage container can be used as the storage container for the resin composition of the present invention.
  • the inner wall of the container is formed into a multi-layer bottle composed of six types and six layers of resin, or six types of resin is formed into a seven-layer structure. It is also preferred to use a bottle that has been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the film of the present invention is a film formed using the above-described resin composition of the present invention.
  • the film thickness of the film of the present invention can be appropriately selected depending on the application and the application site. For example, it can be 0.1 ⁇ m or more, and can be 0.5 ⁇ m or more. In addition, the upper limit may be 10 ⁇ m or less, may be 2 ⁇ m or less, and may be 1 ⁇ m or less.
  • the volume fraction of the capsule in the film is preferably 5% or more, more preferably 10% or more, further preferably 15% or more, and particularly preferably 20% or more.
  • the upper limit is preferably at most 80%, more preferably at most 50%, even more preferably at most 30%.
  • the laminate of the present invention includes a member having a protrusion serving as an electrically conductive terminal, and a film formed using the resin composition of the present invention provided on the surface of the member having the protrusion.
  • the member is not particularly limited as long as it has a protrusion serving as an electrically conductive terminal.
  • the shape and height of the projection It can be appropriately selected according to the application. Further, a plurality of protrusions may be provided on the member.
  • Examples of the member having a protrusion serving as an electrically conductive terminal include a wiring board, an anisotropic conductive member, a semiconductor device (a processor (CPU (Central Processing Unit), an MPU (Microprocessor Unit)), a memory, a power generation element, a MEMS ( Micro Electro Mechanical Systems), GPU (Graphics Processing Unit), communication element, and the like.
  • a processor CPU (Central Processing Unit), an MPU (Microprocessor Unit)
  • a memory a power generation element
  • MEMS Micro Electro Mechanical Systems
  • GPU Graphics Processing Unit
  • the protrusion of the member is preferably covered with a film formed using the resin composition of the present invention, and the protrusion is formed of a film having a thickness exceeding the height of the protrusion. More preferably, it is covered.
  • the member preferably has protrusions on both surfaces of the insulating base material.
  • the film is preferably provided on both surfaces of the insulating substrate, more preferably the protrusions on both surfaces of the insulating substrate are covered with the film, and provided on both surfaces of the insulating substrate. More preferably, the protrusion is covered with a film having a thickness exceeding the height of the protrusion.
  • a member having a plurality of protrusions is preferably used as the member.
  • the distance between the protrusions of the anisotropic conductive member is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm. More preferably, it is 20 nm to 60 nm.
  • the interval between the projections is preferably less than the arithmetic average of the maximum diameter of the capsule included in the membrane, more preferably 95% or less of the arithmetic average of the maximum diameter of the capsule, and more preferably less than 95% of the arithmetic average of the maximum diameter of the capsule. It is still more preferably 90% or less of the arithmetic mean, more preferably 80% or less of the arithmetic mean of the maximum diameter of the capsule, particularly preferably 50% or less.
  • the lower limit of the interval between the projections is preferably 10% or more of the maximum diameter of the capsule included in the film from the viewpoint of maintaining insulation.
  • the capsule 21 included in the membrane 20 may be unevenly distributed above the projection 11. it can. That is, the capsules 21 in the film 20 can be unevenly distributed on the surface layer opposite to the surface where the insulating base material 12 and the film 20 are in contact. Since the capsules in the film are unevenly distributed as described above, the capsule 21 included in the film 20 is easily broken when the protrusion of another member such as a wiring board is joined to the protrusion 11 of this member. As a result, the fluidity of the film at the time of bonding is improved, and the generation of voids between the two members can be more effectively suppressed.
  • the laminate of the present invention has, as the member, an insulating base material, and a plurality of conductive paths formed of a conductive member penetrating in the thickness direction of the insulating base material and provided in an insulated state from each other.
  • an anisotropic conductive member having a plurality of conductive paths having protrusions protruding from the surface of the insulating base material is used. The anisotropic conductive member will be described below.
  • the insulating base material constituting the anisotropic conductive member may be any material as long as it is made of a material having an insulating property.
  • a material having an insulating property for example, metal oxides, metal nitrides, glasses, ceramics (eg, silicon carbide, silicon nitride, etc.), carbons (eg, diamond-like carbon, etc.), polyimides, and composites of these materials are mentioned.
  • a material formed by forming an inorganic material containing a ceramic material or a carbon material at 50% by mass or more on an organic material may be used.
  • the insulating substrate is preferably a metal oxide substrate because micropores having a desired average opening diameter are formed as through-holes and easy to form conductive paths, and is preferably an anodized film of valve metal. More preferably, there is.
  • specific examples of the valve metal include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony.
  • an anodic oxide film (base material) of aluminum is preferable because of good dimensional stability and relatively low cost.
  • the thickness of the insulating base material is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 1 ⁇ m to 500 ⁇ m, and still more preferably 1 ⁇ m to 100 ⁇ m.
  • the thickness of the insulating base material refers to the average value of the thickness measured at 10 points by observing the cross section of the anisotropic conductive member with a field emission scanning electron microscope.
  • the interval between the conductive paths in the insulating substrate is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm, and further preferably 20 nm to 60 nm.
  • the insulating base material sufficiently functions as an insulating partition.
  • the interval between the conductive paths means the width between adjacent conductive paths, and the cross section of the anisotropic conductive member is observed with a field emission scanning electron microscope at a magnification of 200,000 times. An average value obtained by measuring the width between the points at 10 points.
  • the plurality of conductive paths constituting the anisotropic conductive member are conductive paths formed of a conductive member and penetrated in the thickness direction of the insulating base material and provided in a state of being insulated from each other. Further, the conduction path has a protruding portion projecting from the surface of the insulating base material.
  • the conductive member constituting the conductive path is not particularly limited as long as the material has an electric resistivity of 10 3 ⁇ ⁇ cm or less. Specific examples thereof include gold (Au), silver (Ag), and copper (Cu). ), Aluminum (Al), magnesium (Mg), nickel (Ni), tin oxide doped with indium (ITO), and the like. Among them, from the viewpoint of electric conductivity, copper, gold, aluminum, and nickel are preferable, and copper and gold are more preferable.
  • the protrusion of the conduction path is a part where the conduction path protrudes from the surface of the insulating base material.
  • the aspect ratio (height of the projection / diameter of the projection) of the projection of the conductive path is 0.5 or more and less than 50, And more preferably 1 to 10.
  • the height of the protrusion of the conductive path is preferably 50 nm to 3000 nm, and more preferably 100 nm to 2000 nm, from the viewpoint of following the surface shape of the member to be joined such as a wiring board. Is more preferable, and the thickness is more preferably 200 to 1000 nm.
  • the diameter of the protrusion of the conduction path is preferably more than 5 nm and 10 ⁇ m or less, and more preferably 20 nm to 1000 nm.
  • the height of the projection of the conduction path is determined by observing the cross section of the anisotropic conductive member at a magnification of 20,000 times using a field emission scanning electron microscope, and setting the height of the projection of the conduction path at 10 points. It refers to the average value measured.
  • the diameter of the protrusion of the conduction path refers to an average value obtained by observing the cross section of the anisotropic conductive member with a field emission scanning electron microscope and measuring the diameter of the protrusion of the conduction path at 10 points.
  • the method of producing the anisotropic conductive member is not particularly limited.
  • a conductive path forming step of forming the conductive path by arranging the conductive material in a through hole provided in the insulating base material; After the formation step, a trimming step of partially removing only the surface of the insulating base material and projecting the conductive path is exemplified.
  • a method described in paragraph numbers 0031 to 0050 of JP-A-2018-033759 can be used, and the contents thereof are incorporated herein.
  • the laminate shown in FIG. 1 is a preferred embodiment of the laminate of the present invention.
  • 1 is an anisotropic conductive member.
  • the anisotropic conductive member 10 has an insulating base material 12 and a plurality of conductive paths 15 made of a conductive member penetrating in the thickness direction of the insulating base material 12 and provided in a state of being insulated from each other.
  • the plurality of conductive paths 15 have a structure having the protruding portions 11 protruding from the surface of the insulating base material 12.
  • the protrusion 11 protruding from the insulating base material 12 is covered with a film 20 made of the resin composition of the present invention. More specifically, the protrusion 11 is covered with a film having a thickness exceeding the height of the protrusion 11.
  • the ratio (H1 / H2) of the height H1 of the protrusion 11 to the thickness H2 of the film 20 is preferably 1 to 5, and is preferably 1 to 1.5, because it is easy to secure insulation. Is more preferred.
  • the capsule 21 included in the film is unevenly distributed above the projection 11. That is, the capsules 21 are unevenly distributed on the surface layer opposite to the surface where the insulating base material 12 and the film are in contact.
  • the protrusions 11 are provided only on one surface of the insulating base material 12, but the protrusions 11 may be provided on both surfaces of the insulating base material 12.
  • the protrusions 11b and 11c protruding from both surfaces of the insulating substrate 12 are formed of the film 20 made of the resin composition of the present invention. It is preferable that it is covered with.
  • the joining structure of the present invention includes a first member having a projection serving as an electrical conduction terminal, a second member having a projection serving as an electrical conduction terminal, a first member and a second member.
  • a film formed by using the resin composition of the present invention provided between the first member and the second member. The protrusion of the first member and the protrusion of the second member are electrically connected to each other. .
  • one of the first member and the second member penetrates the insulating base member in a thickness direction of the insulating base member and includes a conductive member provided in a state in which the members are insulated from each other.
  • the conductive paths include an anisotropic conductive member having a protrusion protruding from the surface of the insulating substrate, and the other being a wiring board.
  • the wiring substrate there is a wiring substrate having a substrate, a plurality of electrodes having a height of 10 ⁇ m or less, and further having other members as necessary.
  • the height of the electrode refers to an average value obtained by observing the cross section of the wiring substrate at a magnification of 10,000 times with a field emission scanning electron microscope and measuring the height of the electrode at 10 points.
  • the wiring substrate used in the present invention may be a semiconductor chip in which an integrated circuit is mounted on a substrate (for example, a silicon substrate). Examples of the semiconductor chip include a memory, an image sensor, a logic, and a power semiconductor.
  • the substrate in the wiring substrate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a plastic substrate and a glass substrate. The shape, size, and structure of the substrate are not particularly limited, and can be appropriately selected according to the purpose.
  • the material of the electrode in the wiring board include gold, silver, copper, aluminum and the like.
  • the shape of the electrode is not particularly limited as long as the height is 10 ⁇ m or less, and may be a wiring shape, which can be appropriately selected according to the purpose. Further, the height of the electrode is preferably at least 0.05 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • FIG. 3 shows one embodiment of the joint structure of the present invention.
  • the joint structure has an insulating base material 12 and a plurality of conductive paths 15 made of a conductive member provided in a state of being insulated from each other and penetrating in the thickness direction of the insulating base material 12.
  • FIG. 4 shows another embodiment of the joint structure of the present invention.
  • the joint structure has an insulating base material 12 and a plurality of conductive paths 15 made of a conductive member provided in a state of being insulated from each other and penetrating in the thickness direction of the insulating base material 12.
  • the conductive path 15 includes an anisotropic conductive member 10 a having protrusions 11 b and 11 c protruding from the surface (both surfaces) of the insulating base material 12 and protrusions 31 and 41 serving as electrodes of the wiring boards 30 and 40. It is a joined structure joined.
  • the method for producing a laminate according to the present invention includes applying the resin composition of the present invention to a member having a protrusion serving as an electrically conductive terminal, and contacting the protrusion with a thickness exceeding the height of the protrusion. Forming a resin composition layer having a resin composition layer.
  • the resin composition according to the present invention is applied to a first member having a protrusion serving as an electrically conductive terminal so that the first member is in contact with the protrusion and has a high height.
  • Resin composition layer forming step the resin composition of the present invention is applied to a member having a projection serving as an electrically conductive terminal.
  • the application method of the resin composition is not limited, and includes, for example, conventionally known coating methods such as a gravure coating method, a reverse coating method, a die coating method, a blade coater, a roll coater, an air knife coater, a screen coater, a bar coater, and a curtain coater. Can be used.
  • the drying method is not particularly limited. For example, a treatment of heating at a temperature of 0 to 100 ° C. under atmospheric pressure for several seconds to several tens of minutes, or a temperature of 0 to 80 ° C. under reduced pressure at a temperature of 0 to 80 minutes Time, heat treatment and the like can be mentioned. Further, heat treatment after drying may be performed.
  • the temperature condition in the contacting step is not particularly limited, but is preferably 40 to 100 ° C.
  • the pressure conditions in the contacting step are not particularly limited, but are preferably 10 MPa or less, more preferably 5 MPa or less, and particularly preferably 1 MPa or less.
  • the capsule contained in the resin composition layer may be broken at the time of this contacting step, but is preferably broken at the time of the joining step of the next step.
  • the contacting step is performed by a CoW (Chip ⁇ On ⁇ Wafer) process.
  • the semiconductor wafer and the semiconductor chip wafer are inspected so that the good chip and the bad chip can be known in advance (KGD: Known Good Die), and only the good chip of the semiconductor chip wafer is joined to the good part in the semiconductor wafer. , Loss can be reduced.
  • Joining process After breaking the capsule contained in the resin composition layer or while breaking the capsule, the first member and the second member are pressed against each other and the projection of the first member and the second member are pressed.
  • the protrusions of the member are electrically joined (joining step).
  • the first member and the second member are pressed against each other while pressing the first member and the second member while breaking the capsule contained in the resin composition layer during the bonding step.
  • the temperature condition in the bonding step is preferably from 180 to 300 ° C, more preferably from 200 to 250 ° C.
  • the pressure conditions in the joining step are not particularly limited, but are preferably 10 kPa to 50 MPa, and more preferably 2 to 20 MPa.
  • the time of the bonding step is not particularly limited, but is preferably 1 second to 60 minutes, and more preferably 5 seconds to 10 minutes. Although the bonding step may be performed for each chip, it is preferable to perform the bonding step for all wafers from the viewpoint of reducing the tact time.
  • the method for manufacturing a bonded structure of the present invention can be applied to the manufacture of a multilayer wiring board and the like.
  • a resin composition layer (film) 20 is formed by applying the resin composition of the present invention to both surfaces of the insulating base material 12 of the anisotropic conductive member 10 a and protruded from both surfaces of the insulating base material 12.
  • the protrusions 11b and 11c are covered with the resin composition layer (film) 20 to form a laminate having the structure shown in FIG.
  • the resin composition layer (film) 20 provided on one surface side of the anisotropic conductive member 10a is brought into contact with the protruding portion 41 serving as an electrode of the wiring board 40 ( Temporary joining).
  • FIG. 5 Temporary joining
  • the resin composition layer (film) 20 provided on the other surface side of the anisotropic conductive member 10a is brought into contact with the protruding portions 31 serving as the electrodes of the wiring board 30 ( Temporary joining). Then, the wiring board 30, the anisotropic conductive member 10a, and the wiring board 40 are electrically joined by being pressed in the direction of the arrow. Thus, the joint structure shown in FIG. 4 can be manufactured.
  • a melamine-formaldehyde resin (trade name: Sumirez Resin 615K, manufactured by Sumitomo Chemical), and the mixture was mixed at 60 ° C. to obtain a wall material C1.
  • 100 parts by mass of the emulsifier B1 and 100 parts by mass of the solution A1 were emulsified at 60 ° C. using a homomixer.
  • 50 parts by mass of the wall material C1 was added to this emulsion, and the mixture was stirred at a rotation speed of 1000 rpm for 2 hours to obtain a dispersion liquid (solid content 40%) of capsule 1 (arithmetic average of maximum diameter 2 ⁇ m).
  • capsules 7 to 9 capsules containing oxalic acid as a core material
  • Manufacture of capsule 7 A 5 mol / L aqueous solution of oxalic acid was prepared as solution A3. 100 parts by mass of the emulsifier B1 and 100 parts by mass of the solution A3 were emulsified at 60 ° C. using a homomixer. Next, 50 parts by mass of the wall material C1 was added to this emulsion, and the mixture was stirred at a rotation speed of 1000 rpm for 2 hours to obtain a dispersion liquid (solid content 40%) of capsule 7 (arithmetic average of maximum diameter 2 ⁇ m).
  • capsules 13 to 15 capsules containing glycerin-based plasticizer as core material
  • Manufacture of capsule 13 4 g of polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, polyvinylpyrrolidone K25) was dissolved in 36 g of glycerin diacetmonolaurate (Likemar PL-012: manufactured by Riken Vitamin Co., Ltd.) to obtain a uniform protective colloid solution D1.
  • 0.0g was dispersed and mixed using a homodisper (manufactured by Tokushu Kika Kogyo) at 300 to 500 rpm.
  • 10 g of the resulting mixture were dried after filtration.
  • the capsules described in the following table were added so that the volume fraction of the capsules in the obtained membrane was as shown in the following table, and the temperature was lowered to 15 ° C. using a homodisper at 500 rpm.
  • the resin composition of the example was prepared by dispersing and mixing for 6 hours while maintaining.
  • a TEG (test-element-group) for evaluation of the resin composition was prepared as follows. First, by forming a copper film on a silicon wafer, forming a pattern with a resist, and etching away unnecessary portions of copper, an electrode called a daisy chain that can be alternately joined up and down was formed on the surface of the silicon wafer. .
  • the electrode size is 20 ⁇ m in width and 60 ⁇ m in length, and the upper and lower joints are 20 ⁇ m square.
  • the upper chip wafer is called "CHIP” and the lower chip is called “IP” to distinguish them.
  • the lower IP has 10 drawers between both ends of the daisy chain to measure electrical continuity.
  • Wiring was provided so that it was possible to determine whether or not bonding had been performed in the middle, and the size of IP was larger than that of CHIP.
  • a bonding device is obtained by positioning and aligning (aligning) CHIP on the upper surface of an IP with an anisotropic conductive member having a film formed using various resin compositions therebetween. And bonding was performed, and voids, bonding resistance, and bonding properties were evaluated.
  • the anisotropic conductive member a member in which a plurality of copper electrodes (diameter 60 nm) protruded from above and below an insulating base material (thickness 20 ⁇ m, material anodized aluminum) was used.
  • the distance between the copper electrodes is 20 nm
  • the amount of protrusion of the copper electrodes from the insulating base material is 300 nm on one side
  • the density of the copper electrodes is about 100 million / mm 2 .
  • Each resin composition was spin-coated on both surfaces of the anisotropic conductive member to form a film having a thickness of 400 nm.
  • the size of voids remaining in the film (resin layer) is less than 10 ⁇ m, and the total area of all remaining voids is more than 1% and less than 10% with respect to the area of CHIP.
  • 3 The size of voids remaining in the film (resin layer) is more than 10 ⁇ m and less than 30 ⁇ m, and the total area of all remaining voids is less than 1% with respect to the area of CHIP.
  • 2 The size of voids remaining in the film (resin layer) is more than 10 ⁇ m and less than 30 ⁇ m, and the total area of all remaining voids is more than 1% and less than 10% with respect to the area of CHIP.
  • 1 The total area of all remaining voids is 10% or more of the area of the semiconductor element regardless of the size of voids remaining in the film (resin layer).
  • the resin compositions of Examples were able to suppress generation of voids. Furthermore, the joining resistance was low and the joining property was excellent.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Structures For Mounting Electric Components On Printed Circuit Boards (AREA)
PCT/JP2019/037186 2018-09-27 2019-09-24 樹脂組成物、膜、積層体、接合構造体、積層体の製造方法および接合構造体の製造方法 WO2020066974A1 (ja)

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EP4130125A1 (de) * 2021-08-04 2023-02-08 ContiTech AG Gesteuerter polymerkettenabbau durch mikroverkapselte substanzen

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JP2002163939A (ja) * 2000-11-27 2002-06-07 Showa Electric Wire & Cable Co Ltd 可塑剤入りマイクロカプセル含有被覆層付ケーブル
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JPS59204591A (ja) * 1983-05-09 1984-11-19 Mitsubishi Paper Mills Ltd 記録用媒体及びその処理方法
JP2000294889A (ja) * 1999-04-06 2000-10-20 Sony Corp 実装基板およびこれを用いた回路部品の実装方法
JP2002163939A (ja) * 2000-11-27 2002-06-07 Showa Electric Wire & Cable Co Ltd 可塑剤入りマイクロカプセル含有被覆層付ケーブル
JP2002356623A (ja) * 2001-05-30 2002-12-13 Toyota Motor Corp 微生物を含む生分解性樹脂
JP2004227730A (ja) * 2003-01-27 2004-08-12 Fuji Photo Film Co Ltd 光ディスク、及び光ディスクへの表示用シート貼り付け方法
JP2009288577A (ja) * 2008-05-30 2009-12-10 Ricoh Co Ltd 静電荷像現像用トナー、現像剤、トナー入り容器、プロセスカートリッジ、画像形成装置、画像形成方法
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EP4130125A1 (de) * 2021-08-04 2023-02-08 ContiTech AG Gesteuerter polymerkettenabbau durch mikroverkapselte substanzen

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