JP5337034B2 - Adhesives and joints - Google Patents
Adhesives and joints Download PDFInfo
- Publication number
- JP5337034B2 JP5337034B2 JP2009528082A JP2009528082A JP5337034B2 JP 5337034 B2 JP5337034 B2 JP 5337034B2 JP 2009528082 A JP2009528082 A JP 2009528082A JP 2009528082 A JP2009528082 A JP 2009528082A JP 5337034 B2 JP5337034 B2 JP 5337034B2
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- JP
- Japan
- Prior art keywords
- adhesive
- conductive
- adhesive according
- electrode
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 230000001070 adhesive effect Effects 0.000 title claims description 88
- 239000000853 adhesive Substances 0.000 title claims description 86
- 239000002245 particle Substances 0.000 claims description 40
- 239000003822 epoxy resin Substances 0.000 claims description 30
- 229920000647 polyepoxide Polymers 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 30
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000013034 phenoxy resin Substances 0.000 claims description 14
- 229920006287 phenoxy resin Polymers 0.000 claims description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 12
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 11
- -1 polyethylene terephthalate Polymers 0.000 claims description 9
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 8
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 45
- 238000001723 curing Methods 0.000 description 20
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- 229920000515 polycarbonate Polymers 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000013464 silicone adhesive Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Classifications
-
- 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
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
-
- 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
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
-
- 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
- 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
- H05K2201/0162—Silicon containing polymer, e.g. silicone
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
- Manufacturing Of Electrical Connectors (AREA)
- Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)
- Wire Bonding (AREA)
Description
本発明は、回路基板どうしの電気的な接続等に用いられる接着剤に関する。 The present invention relates to an adhesive used for electrical connection between circuit boards.
従来から、導電粒子を含有する接着剤としては、異方導電性接着剤や導電性接着剤が公知である。中でも、異方導電性接着剤は、目的とする接続電極と被接続電極とを導電粒子を介して接続することが可能である。特に、加熱、加圧で導電粒子をある程度変形させて電極間（接続電極および被接続電極）を接続するが、このとき同時に導電粒子を分散させて接着剤の硬化により接合体が得られるものである。 Conventionally, anisotropic conductive adhesives and conductive adhesives are known as adhesives containing conductive particles. Among these, the anisotropic conductive adhesive can connect the target connection electrode and the connection target electrode via conductive particles. In particular, the conductive particles are deformed to some extent by heating and pressurization to connect the electrodes (connection electrode and connected electrode). At this time, the conductive particles are dispersed at the same time, and a bonded body is obtained by curing the adhesive. is there.
異方導電性接着剤に用いられる接着剤としては、エポキシ樹脂やフェノキシ樹脂、潜在性硬化剤を用いてなる接着剤が公知である。（例えば特許文献1及び２）
異方導電性接着剤を用いた場合の接続電極と被接続電極との接続方法を説明する。まず、接続電極を有する基板、例えばフレキシブル基板やガラスパネル上へ、異方導電性接着剤を載せ、被接続電極を有する基材、例えば、ICチップやポリイミドＦＰＣ（フレキシブルプリント配線板）を載せ、構造体とする。次に、該構造体によって異基板の電極間の接続はとりながら、隣り合う電極間は絶縁を保つことができる。As an adhesive used for the anisotropic conductive adhesive, an adhesive using an epoxy resin, a phenoxy resin, or a latent curing agent is known. (For example, Patent Documents 1 and 2)
A method for connecting the connection electrode and the electrode to be connected in the case where the anisotropic conductive adhesive is used will be described. First, an anisotropic conductive adhesive is placed on a substrate having a connection electrode, such as a flexible substrate or a glass panel, and a substrate having a connection electrode, such as an IC chip or a polyimide FPC (flexible printed wiring board), A structure. Next, it is possible to maintain insulation between adjacent electrodes while connecting the electrodes of different substrates with the structure.
特定のフレキシブル基材、例えばポリエチレンテレフタレート（PET）フィルムやポリカーボネート（ＰＣ）といった透明性は高いが耐熱性のないフィルム基材を用いる場合には、低温度で接着する必要がある。 In the case of using a specific flexible base material such as a polyethylene terephthalate (PET) film or polycarbonate (PC) which has high transparency but no heat resistance, it is necessary to bond at a low temperature.
しかしながら、低温で接着した場合には、接続電極を有する基板や被接続電極を有する基材との接着性に劣るといった問題があった。
本発明の目的は、上記問題点を克服し、１５０℃以下という低温で加熱硬化しても、初期及び信頼性試験後の接着性あるいはまたは導電性に優れる接着剤を提供することである。 An object of the present invention is to overcome the above-described problems and provide an adhesive having excellent adhesion or conductivity after initial and reliability tests even when heat-cured at a low temperature of 150 ° C. or lower.
本発明者らは、上記課題を解決すべく鋭意検討した結果、接着剤が所定の粘着特性を有するシリコーン化合物、エポキシ樹脂、フェノキシ樹脂、及び硬化剤を成分として含むことにより、前記目的に適した接着剤をえることができるという知見を得て本発明を完成するに至った。
すなわち、本発明は、以下のとおりである。
（１）シリコーン化合物、エポキシ樹脂、フェノキシ樹脂、及び硬化剤を含有する接着剤であって、該シリコーン化合物は、５０μm厚のポリエチレンテレフタレートフィルム（ＰＥＴ）に、硬化後に４０μmとなるように塗布して粘着シートを作製し、該粘着シートの該シリコーン化合物からなる層をステンレス板に接着し、２３℃で３０分放置した後、０．３m/minで１６０°で剥離した時の値である粘着特性が１５０〜１８００（ｇ／ｉｎｃｈ）（５．９１〜７０．９（ｋｇ／ｍ））であるものである前記接着剤。
（２）導電粒子をさらに含む、前記（１）に記載の接着剤。
（３）前記エポキシ樹脂がテトラメチルビフェノール型エポキシ樹脂を含む、前記（１）又は（２）に記載の接着剤。
（４）前記エポキシ樹脂がジシクロペンタジエン型エポキシ樹脂を含む、前記（１）〜（３）のいずれかに記載の接着剤。
（５）前記シリコーン化合物の平均重量分子量が１００万以下である、前記（１）〜（４）のいずれかに記載の接着剤。
（６）前記シリコーン化合物の平均重量分子量が６０万以下である、前記（１）〜（５）のいずれかに記載の接着剤。
（７）前記シリコーン化合物がエポキシ変性シリコーンでない、前記（１）〜（６）のいずれかに記載の接着剤。
（８）前記導電粒子の平均粒子径が１〜２０μmである、前記（２）〜（７）のいずれかに記載の接着剤。
（９）前記硬化剤が潜在性硬化剤である、前記（１）〜（８）のいずれかに記載の接着剤。
（１０）前記導電粒子を０．１体積％以上３０体積％未満含有し、異方導電性を示す、前記（２）〜（９）のいずれかに記載の接着剤。
（１１）前記導電粒子を３０体積％以上８０体積％以下で含有する、前記（２）〜（９）のいずれかに記載の接着剤。
（１２）第一の導電電極を有する基材、第二の導電電極を有する基材、及び前記（１）〜（１１）のいずれかに記載の接着剤を有する接合体。
（１３）前記（１）〜（１１）のいずれかに記載の接着剤を、導電電極を有する基板又は導電電極上に配し、電子部品を加熱圧着する工程を含む請求項１２に記載の接合体の製造方法。
As a result of intensive studies to solve the above problems, the present inventors have found that the adhesive contains a silicone compound having a predetermined adhesive property, an epoxy resin, a phenoxy resin, and a curing agent as components and is suitable for the above purpose. The present invention has been completed by obtaining the knowledge that an adhesive can be obtained.
That is, the present invention is as follows.
(1) a silicone compound, an epoxy resin, a adhesives you containing phenoxy resin, and curing agent, the silicone compound, a 50μm thick polyethylene terephthalate film (PET), coated to a 40μm after curing The pressure-sensitive adhesive sheet was prepared, and the silicone compound layer of the pressure-sensitive adhesive sheet was adhered to a stainless steel plate, left at 23 ° C. for 30 minutes, and then peeled at 160 ° at 0.3 m / min. The adhesive having an adhesive property of 150 to 1800 (g / inch) (5.91 to 70.9 (kg / m)).
(2) The adhesive according to (1), further including conductive particles.
(3) the epoxy resin comprises a tetramethylbiphenol type epoxy resin, adhesive agent according to (1) or (2).
(4) the epoxy resin comprises a dicyclopentadiene type epoxy resin, adhesive according to any one of (1) to (3).
(5) The adhesive according to any one of (1) to (4) , wherein the silicone compound has an average weight molecular weight of 1,000,000 or less.
(6) The adhesive according to any one of (1) to (5) , wherein the silicone compound has an average weight molecular weight of 600,000 or less.
(7) The adhesive according to any one of (1) to (6) , wherein the silicone compound is not an epoxy-modified silicone.
(8) Average particle diameter of the conductive particles is 1 ~ 20 [mu] m, the adhesive according to any one of (2) to (7).
(9) The adhesive according to any one of (1) to (8) , wherein the curing agent is a latent curing agent.
(10) the conductive particles contain less than 0.1 vol% to 30 vol%, it shows the anisotropic conductive adhesive according to any one of (2) to (9).
(11) containing at said conductive particles 80 vol% to 30 vol% or less, the adhesive according to any one of (2) to (9).
(12) A joined body having a base material having a first conductive electrode, a base material having a second conductive electrode, and the adhesive according to any one of (1) to (11).
(13) The bonding according to claim 12, comprising a step of disposing the adhesive according to any one of (1) to (11) on a substrate having a conductive electrode or a conductive electrode and thermocompression bonding the electronic component. Body manufacturing method.
本発明の接着剤は、１５０℃以下という低温で加熱硬化しても、初期及び信頼性試験後に接着力にすぐれまたはかつ導電性に優れるという効果を有する。 The adhesive of the present invention has an effect that it has excellent adhesion or excellent electrical conductivity after the initial and reliability tests even if it is heat-cured at a low temperature of 150 ° C. or lower.
本発明の接着剤は、少なくとも、粘着特性を有するシリコーン化合物、エポキシ樹脂、フェノキシ樹脂及び硬化剤を含有する。 The adhesive of the present invention contains at least a silicone compound having an adhesive property, an epoxy resin, a phenoxy resin, and a curing agent.
粘着特性を有するシリコーン化合物としては、シリコーン粘着剤を用いる。その粘着特性は、１５０から１８００ｇ／ｉｎｃｈであることが好ましい。粘着特性の評価条件は、５０μm厚のポリエチレンテレフタレートフィルム（ＰＥＴ）に、硬化後に４０μmとなるようにシリコーン粘着剤を塗布して粘着シートを作成し、ステンレス板に粘着シートのシリコーン粘着剤からなる層を接着し、２３℃で３０分放置した後、０．３m/minで１６０°で剥離した時の値である。 A silicone adhesive is used as the silicone compound having adhesive properties. The adhesive property is preferably 150 to 1800 g / inch. The adhesive property was evaluated by applying a silicone adhesive to a 50 μm thick polyethylene terephthalate film (PET) to 40 μm after curing to create an adhesive sheet. Is a value when peeled at 160 ° at 0.3 m / min after being left to stand at 23 ° C. for 30 minutes.
粘着特性を有するシリコーン化合物としては、例えば、付加反応型シリコーン粘着剤、過酸化物硬化型シリコーン粘着剤が挙げられる。付加反応型シリコーン粘着剤とは、８０〜１２０℃で１〜５分で硬化する特性をもつシリコーン粘着剤である。中でも、付加反応型シリコーン粘着剤が好ましい。付加反応型シリコーン粘着剤としては、例えば、東レダウコーニング社製のＳＤ４５８０、ＳＤ４５８１、ＳＤ４５８４、ＳＤ４５８５、ＳＤ４５８６、ＳＤ４５８７、ＳＤ４８９０、ＳＤ４５９２、ＳＤ４５６０、ＢＹ２４−７３８、ＢＹ２４−７４０が挙げられる。本発明でいう粘着特性を有するシリコーン化合物はエポキシ変性シリコーンでないのが好ましい。シリコーン粘着剤の平均重量分子量は１００万以下が好ましく、さらには、６０万以下が適度な粘着性を与えるため好ましい。このましくは、平均重量分子量が１０００から60万である。シリコーン粘着剤の配合量は、接着剤中に０．０１〜２０体積％含有することが好ましく、さらに０．１〜１５体積％が好ましい。接着性の効果発現の観点から、０．０１体積％以上が好ましく、エポキシ樹脂の硬化阻害を防止する観点から、２０体積％以下が好ましい。本発明でいうシリコーン粘着剤とエポキシ樹脂とも併用することで導電粒子の固定化による導電性確保と優れた接着力を同時に満足することができる。 Examples of the silicone compound having adhesive properties include addition reaction type silicone adhesives and peroxide-curing type silicone adhesives. The addition reaction type silicone pressure-sensitive adhesive is a silicone pressure-sensitive adhesive having a property of curing at 80 to 120 ° C. in 1 to 5 minutes. Among these, addition reaction type silicone pressure-sensitive adhesives are preferable. Examples of the addition reaction type silicone pressure-sensitive adhesive include SD4580, SD4581, SD4584, SD4585, SD4586, SD4587, SD4890, SD4592, SD4560, BY24-738 and BY24-740 manufactured by Toray Dow Corning. The silicone compound having adhesive properties as referred to in the present invention is preferably not an epoxy-modified silicone. The average weight molecular weight of the silicone pressure-sensitive adhesive is preferably 1,000,000 or less, and more preferably 600,000 or less because appropriate adhesiveness is imparted. Preferably, the average weight molecular weight is 1000 to 600,000. The compounding amount of the silicone pressure-sensitive adhesive is preferably 0.01 to 20% by volume, more preferably 0.1 to 15% by volume in the adhesive. From the viewpoint of expression of the adhesive effect, 0.01% by volume or more is preferable, and from the viewpoint of preventing curing inhibition of the epoxy resin, 20% by volume or less is preferable. By using both the silicone pressure-sensitive adhesive and the epoxy resin in the present invention, it is possible to simultaneously satisfy the securing of conductivity and the excellent adhesive force by fixing the conductive particles.
エポキシ樹脂とは、１分子中に２個以上のエポキシ基を有する化合物であり、具体的には、ビスフェノールA型樹脂、ビスフェノールＦ型樹脂、ナフタレン型樹脂、ビスフェノールＳ型樹脂、フェノールノボラック型樹脂、クレゾールノボラック型樹脂、脂環式型樹脂、ビフェニル型樹脂、ジシクロペンタジエン型樹脂、グリシジルアミン型樹脂、グリシジルエステル型樹脂などを含むものが挙げられる。 An epoxy resin is a compound having two or more epoxy groups in one molecule. Specifically, a bisphenol A resin, a bisphenol F resin, a naphthalene resin, a bisphenol S resin, a phenol novolac resin, Examples include cresol novolac resins, alicyclic resins, biphenyl resins, dicyclopentadiene resins, glycidyl amine resins, glycidyl ester resins, and the like.
中でも、ビスフェノールA型樹脂、ビスフェノールF型樹脂、ジシクロペンタジエン型樹脂、テトラメチルビフェノール型樹脂を含むものが高接着性、導電性の高湿度信頼性試験下での安定性の観点でさらに好ましい。これらの樹脂は、複数で用いるのが好ましい。
テトラメチルビフェノール型エポキシ樹脂としては、例えば、ＹＸ４０００Ｋ、ＹＸ４０００、ＹＸ４０００Ｈ、ＹＬ６１２Ｈ、ＹＬ６６４０、ＹＬ６６７７などが挙げられる。テトラメチルビフェノール型エポキシ樹脂としては、ビフェニル構造がエーテル結合を介して２個結合してなる構造を有するものが好ましい。テトラメチルビフェノール型エポキシ樹脂の配合量は、接着剤成分中０．１体積以上４０体積％以下が好ましい。Among these, those containing bisphenol A type resin, bisphenol F type resin, dicyclopentadiene type resin, and tetramethylbiphenol type resin are more preferable from the viewpoint of stability under high adhesion and conductivity high humidity reliability tests. A plurality of these resins are preferably used.
Examples of the tetramethylbiphenol type epoxy resin include YX4000K, YX4000, YX4000H, YL612H, YL6640, and YL6677. As the tetramethylbiphenol type epoxy resin, one having a structure in which two biphenyl structures are bonded via an ether bond is preferable. The blending amount of the tetramethylbiphenol type epoxy resin is preferably 0.1 volume or more and 40 volume% or less in the adhesive component.
また、本発明の接着剤は、ジシクロペンタジエン型エポキシ樹脂を含有することが好ましい。ジシクロペンタジエン型エポキシ樹脂を含有することで、高湿度下で接続信頼性の低下を防止できる。また、異方導電性接着剤や導電性接着剤として用いる場合には、吸湿による導電性粒子の劣化も抑制できる点にある。ジシクロペンタジエン型エポキシ樹脂の配合量は、接着剤中に１〜４０体積％が好ましい。 The adhesive of the present invention preferably contains a dicyclopentadiene type epoxy resin. By containing the dicyclopentadiene type epoxy resin, it is possible to prevent a decrease in connection reliability under high humidity. Moreover, when using as an anisotropic conductive adhesive or a conductive adhesive, it exists in the point which can also suppress deterioration of the electroconductive particle by moisture absorption. As for the compounding quantity of a dicyclopentadiene type epoxy resin, 1-40 volume% is preferable in an adhesive agent.
本発明の接着剤は、フェノキシ樹脂を含有する。フェノキシ樹脂としては、分子量１００００から２０００００以下を含んでいるものが溶解性や取り扱い性から好ましい。具体的には、ビスフェノールA型フェノキシ樹脂、ビスフェノールＦ型フェノキシ樹脂、カプロラクタム変性フェノキシ樹脂、ポリオール変性フェノキシ樹脂が挙げられる。また、必要に応じて、アクリル樹脂、エポキシ変性アクリル樹脂などを添加して用いることもできる。フェノキシ樹脂の配合量は、接着剤成分中５〜７０体積％が好ましい。 The adhesive of the present invention contains a phenoxy resin. As the phenoxy resin, those containing a molecular weight of 10,000 to 200,000 are preferable from the viewpoint of solubility and handleability. Specifically, bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, caprolactam modified phenoxy resin, and polyol modified phenoxy resin can be mentioned. Moreover, an acrylic resin, an epoxy-modified acrylic resin, etc. can also be added and used as needed. As for the compounding quantity of a phenoxy resin, 5-70 volume% is preferable in an adhesive agent component.
本発明の接着剤に用いる硬化剤は、前記エポキシ樹脂を硬化できるものであればよい。本発明の接着剤は加熱硬化を行う場合には、使用開始までの保存性のために、潜在性硬化剤を用いることがより好ましい。例えば、酸無水物、ポリアミン、アミン化合物、フェノール化合物、イミダゾール類を用いることが好ましい、中でも、マイクロカプセル化硬化剤がより好ましい。 The curing agent used for the adhesive of the present invention may be any one that can cure the epoxy resin. In the case where the adhesive of the present invention is heat-cured, it is more preferable to use a latent curing agent for storage stability until the start of use. For example, it is preferable to use acid anhydrides, polyamines, amine compounds, phenol compounds, and imidazoles, and among these, microencapsulated curing agents are more preferable.
硬化剤の配合量は、エポキシ樹脂総量１００体積％に対して、５〜４００体積％が好ましく、さらに好ましくは５〜３００体積％である。
また、必要に応じて、公知のシランカップリング剤やチタンカップリング剤、アルミカップリング剤を用いることができる。シランカップリング剤としては、例えばＫＢＭ４０３、ＫＢＥ４０３、ＫＢＥ９１０３、ＫＢＭ９１０３、ＫＢＭ９０３、ＫＢＥ９０３、ＫＢＥ５７３、ＫＢＭ５７３などを用いることができる。カップリング剤としては、接着剤１００体積％あたり、０．０１から１０体積％が好ましい。As for the compounding quantity of a hardening | curing agent, 5-400 volume% is preferable with respect to 100 volume% of epoxy resin total amount, More preferably, it is 5-300 volume%.
Moreover, a well-known silane coupling agent, a titanium coupling agent, and an aluminum coupling agent can be used as needed. Examples of the silane coupling agent that can be used include KBM403, KBE403, KBE9103, KBM9103, KBM903, KBE903, KBE573, and KBM573. The coupling agent is preferably 0.01 to 10% by volume per 100% by volume of the adhesive.
また、本発明の接着剤は、導電粒子を含有するものである。導電粒子としては、その平均粒子径が１〜２０μmであるものが好ましい。また、接着剤としてフィルム状にした場合の取り扱い性の観点から、２０μm以下が好ましい。加熱接続時に接続電極間での高さばらつきを吸収し、十分な電気的な接続を得る観点から、平均粒子径は１μm以上１０μm以下がより好ましい。さらに好ましくは２μm以上１０μm以下である。導電粒子の平均粒子径は、気流式粒度分布計（RODOS ＳＲ）のレーザー回折により測定された体積積算粒度分布の積算値５０％における値を用いる。 The adhesive of the present invention contains conductive particles. The conductive particles are preferably those having an average particle diameter of 1 to 20 μm. Moreover, from a viewpoint of the handleability at the time of making it into a film form as an adhesive agent, 20 micrometers or less are preferable. The average particle diameter is more preferably 1 μm or more and 10 μm or less from the viewpoint of absorbing the height variation between the connection electrodes during heating connection and obtaining sufficient electrical connection. More preferably, it is 2 μm or more and 10 μm or less. As the average particle diameter of the conductive particles, a value at an integrated value of 50% of the volume integrated particle size distribution measured by laser diffraction of an airflow particle size distribution analyzer (RODOS SR) is used.
導電粒子としては、公知の導電粒子を用いることができる。導電粒子としては、例えば、プラスチック粒子上にニッケルや金、銅、銀をメッキした粒子や、銅、銀、ニッケル、金、すず、はんだ、非鉛はんだ粉やこれらの粒子上にメッキした粒子を用いることができる。中でも、金属粒子、特に銅、銀、銅または銀の合金が柔らかくかつ非破壊性であるために好ましく、そのため、０．５ＭＰａ以下の低圧での接続も可能であり、フレキシブル基材上のＩＴＯやＩＺＯ電極を破壊することがない利点を有する。 Known conductive particles can be used as the conductive particles. Examples of the conductive particles include particles obtained by plating nickel, gold, copper, and silver on plastic particles, copper, silver, nickel, gold, tin, solder, non-lead solder powder, and particles plated on these particles. Can be used. Among them, metal particles, particularly copper, silver, copper or an alloy of silver are preferable because they are soft and nondestructive. Therefore, connection at a low pressure of 0.5 MPa or less is also possible. This has the advantage of not destroying the IZO electrode.
本発明の接着剤は、接着剤中に導電粒子を０．１体積％以上３０体積％未満含有させる場合には、異方導電性を示しうる導電性接着剤（以下、「異方導電性接着剤」という）として用いることができる。導電粒子の含有量は、０．５〜１５体積％とすることがより好ましい。導電粒子の体積％は、接着剤の質量を測定し、さらに比重から換算することができる。また、異方導電性接着剤はペースト状、あるいはフィルム状のどちらの形態で用いても良い。 The adhesive of the present invention is a conductive adhesive that can exhibit anisotropic conductivity (hereinafter referred to as “anisotropic conductive adhesion” when the conductive particles are contained in an amount of 0.1 to 30% by volume in the adhesive. Can be used as an agent). The content of the conductive particles is more preferably 0.5 to 15% by volume. The volume% of the conductive particles can be converted from the specific gravity by measuring the mass of the adhesive. The anisotropic conductive adhesive may be used in either a paste form or a film form.
フィルム状で用いる場合には、接着剤の厚みは１０μm以上５０μm以下であることが好ましく、１３μｍ以上３５μｍ以下であることがより好ましい。 When used in the form of a film, the thickness of the adhesive is preferably 10 μm or more and 50 μm or less, and more preferably 13 μm or more and 35 μm or less.
ペースト状で用いる場合には、適当な溶剤または反応性希釈剤を用いて適度な粘度に調整した後用いるのが好ましい。希釈剤としては、液状のビスフェノールA型エポキシ樹脂やビスフェノールＦ型エポキシ樹脂や硬化剤に影響を与えないような溶剤を用いるのが好ましい。溶剤としては、例えばトルエン、酢酸エチル、γ―ブチロラクトンなど含むものが好ましい。溶剤などは、本発明でいう接着剤の仕込み体積％からは除外される。 When used in a paste form, it is preferably used after adjusting to an appropriate viscosity using an appropriate solvent or reactive diluent. As the diluent, it is preferable to use a liquid bisphenol A type epoxy resin, bisphenol F type epoxy resin, or a solvent that does not affect the curing agent. As the solvent, for example, those containing toluene, ethyl acetate, γ-butyrolactone and the like are preferable. Solvents and the like are excluded from the charged volume% of the adhesive referred to in the present invention.
第一の導電電極を有する基材、例えばFPC、又は電子部品例えばICチップに代表される電子部品を第二の導電電極を有する基材上に異方導電性接着剤を用いて接続する場合には、第二の導電電極を有する基材上にデイスペンサーやシリンジを用いて異方導電性接着剤を適量塗布し、第一の導電電極を有する基材または電子部品と、第二の導電電極を有する基材の対向電極を位置あわせしたのちに第一の導電電極を有する基材または電子部品側から加熱して硬化させる方法が好ましい。また、この方法により、第一の導電電極を有する基材と第二の導電電極を有する基材の接合体が得られる。 When connecting a base material having a first conductive electrode, for example, an FPC, or an electronic component, for example, an electronic component represented by an IC chip, onto a base material having a second conductive electrode by using an anisotropic conductive adhesive Apply a suitable amount of anisotropic conductive adhesive on a substrate having a second conductive electrode using a dispenser or syringe, and a substrate or electronic component having the first conductive electrode, and a second conductive electrode A method is preferred in which the counter electrode of the substrate having s is aligned and then heated and cured from the substrate or electronic component side having the first conductive electrode. Moreover, the joined body of the base material which has the 1st conductive electrode, and the base material which has the 2nd conductive electrode by this method is obtained.
異方導電性を有する接着剤のフィルム状で用いる場合にも同様にして、第二の導電電極を有する基材上にフィルムを貼り付けて、１１０〜１５０℃の加熱、０．２〜３MPaの加圧により硬化させる方法が好ましい。また、この方法により、第一の導電電極を有する基材と第二の導電電極を有する基材との接合体が得られる。 Similarly, when used in the form of an anisotropic conductive adhesive film, the film is pasted onto the substrate having the second conductive electrode, heated at 110 to 150 ° C., and 0.2 to 3 MPa. A method of curing by pressurization is preferred. Moreover, the joined body of the base material which has a 1st conductive electrode, and the base material which has a 2nd conductive electrode is obtained by this method.
第一の導電電極を有する基材、電子部品、及び第二の導電電極を有する基材に設けられた電極は、ＩＴＯ、銅、金、銀、アルミ、タンタル、すず、はんだ、チタン、ニッケル、ＩＺＯから選ばれた１種類以上の成分を含有してなる電極であることが好ましい。この場合には、第一の導電電極と第二の導電電極とは同じであっても異なっていても構わない。 The electrode provided on the substrate having the first conductive electrode, the electronic component, and the substrate having the second conductive electrode are ITO, copper, gold, silver, aluminum, tantalum, tin, solder, titanium, nickel, An electrode comprising one or more components selected from IZO is preferable. In this case, the first conductive electrode and the second conductive electrode may be the same or different.
さらに、本発明の異方導電性接着剤は、第一の導電電極を有する基材、及び第二の導電電極を有する基材の少なくとも一方が耐熱性に乏しいフレキシブル基材でも用いることができる。耐熱性に乏しいフレキシブル基材とは、１６０℃以上での加熱に耐えられない基材であり、例えばＰＥＴフィルム、ＰＣフィルムである。 Furthermore, the anisotropic conductive adhesive of the present invention can be used even on a flexible substrate in which at least one of the substrate having the first conductive electrode and the substrate having the second conductive electrode has poor heat resistance. A flexible base material with poor heat resistance is a base material that cannot withstand heating at 160 ° C. or higher, such as a PET film or a PC film.
また、本発明の接着剤は、接着剤中に導電粒子を３０〜８０体積％含有させて、導電性接着剤として用いることができる。導電粒子の含有量は、４０体積％〜６０体積％とすることがより好ましい。 Moreover, the adhesive agent of this invention can be made to contain 30-80 volume% of electroconductive particles in an adhesive agent, and can be used as a conductive adhesive agent. The content of the conductive particles is more preferably 40% by volume to 60% by volume.
第一の導電電極を有する基材、例えばＦＰＣ、又は電子部品例えばＩＣチップに代表される電子部品を、第二の導電電極を有する基材上に導電性接着剤を用いて接続する場合には、導電性接着剤を第一の導電電極を有する基材、又は電子部品や、第二の導電電極を有する基材の電極上に塗布や印刷によって塗りつけて、１１０〜１５０℃で加熱硬化する方法を用いることができる。このときは、必要に応じて０．２〜３MPaで加圧することもできる。また、この方法により、第一の導電電極を有する基材、第二の導電電極を有する基材、及び接着剤を有する接合体が得られる。 When connecting a base material having a first conductive electrode, for example, an FPC, or an electronic component, for example, an electronic component represented by an IC chip, on a base material having a second conductive electrode, using a conductive adhesive A method of applying a conductive adhesive to a substrate having a first conductive electrode, or an electronic component, or an electrode of a substrate having a second conductive electrode by coating or printing, and heat curing at 110 to 150 ° C. Can be used. At this time, pressurization can be performed at 0.2 to 3 MPa as necessary. Moreover, the joined body which has a base material which has a 1st conductive electrode, a base material which has a 2nd conductive electrode, and an adhesive agent by this method.
例えば、耐熱性に乏しいフィルムを用いたフレキシブル基材上のＩＴＯ電極接続において、１５０℃以下という低温で接続した場合にも、接着性に優れる接合体ができるようになった。 For example, in an ITO electrode connection on a flexible substrate using a film having poor heat resistance, a bonded body having excellent adhesiveness can be formed even when connected at a low temperature of 150 ° C. or lower.
特に、接続電極を有する基板として、ポリイミド樹脂層に銅箔を積層した構成を有する２層ポリイミドフレキシブル基板を、被接続電極を有する基材として、ポリエチレンテレフタレート（ＰＥＴ）フィルムやポリカーボネート（ＰＣ）、ポリエチレンナフタレート（PEN）、ポリエチレンスルフィド（ＰＥＳ）といった透明性は高いが耐熱性の低いフィルム基材（特に、ＰＥＴ、ＰＣフィルム）を用いた基材同士を本発明の接着剤を用いて接合することに適している。 In particular, as a substrate having connection electrodes, a two-layer polyimide flexible substrate having a structure in which a copper foil is laminated on a polyimide resin layer, and as a substrate having electrodes to be connected, polyethylene terephthalate (PET) film, polycarbonate (PC), polyethylene Bonding substrates using film bases (especially PET, PC film) such as naphthalate (PEN) and polyethylene sulfide (PES) that have high transparency but low heat resistance using the adhesive of the present invention. Suitable for
以下に本発明の実施態様の具体例を実施例に基づいて説明する。
実施例及び比較例で用いた接着剤の原料成分は以下のとおりである。
ビスフェノールA型エポキシ樹脂（旭化成ケミカルズ（株）製、ＡＥＲ２６００）
ビスフェノールＦ型エポキシ樹脂（日本化薬（株）製ＲＥ-３０３Ｓ）
ナフタレン型エポキシ樹脂（大日本インキ（株）製 ＨＰ−４０３２Ｄ）
テトラメチルビフェノール型エポキシ樹脂（ジャパンエポキシレジン社製ＹＸ４０００Ｋ）
ジシクロペンタジエン型エポキシ樹脂（大日本インキ（株）製ＨＰ７２００）
ビスフェノールA型フェノキシ樹脂（インケム（株）製 ＰＫＨＣ、ＰＫＦＥ、ＰＫＨＢ）
ポリオール変性フェノキシ樹脂（インケム（株）製 ＰＫＨＭ３０１）
潜在性硬化剤（旭化成ケミカルズ（株）製 ＨＸ３９３２ＨＰマイクロカプセル型イミダゾール（潜在性硬化剤））
シランカップリング剤（信越化学（株）製ＫＢＭ４０３、ＫＢＭ９０３）
シリコーン粘着剤（東レダウコーニング製 ＳＤ４５８０、ＳＤ４５６０）（平均重量分子量２０から５０万）
ＫＭＰ５９４シリコーンゴム粒子（信越化学社製）（平均重量分子量＞１００万）
エポキシ変性シリコーン樹脂（東レダウコーニング社製 ＢＹ１６-８５５）
アクリル樹脂（三菱レーヨン社製 ダイヤナール）
（導電粒子）
銀銅合金粉 平均３μｍ
金メッキプラスチック粒子 平均８μｍ
金/ニッケルメッキ銅粒子 平均１０μｍ
＜実施例1〜４，比較例４、５＞
［表１］に示す割合で組成１，２，３，４，５、６を酢酸エチル溶剤を用いて厚み５０μのPET上に塗布して、６０℃10分空気中乾燥して、酢酸エチルの溶剤をとばした。こうして、３５μｍ厚みの異方導電性接着剤を作成した。また、試験接続基材として、次の基材を用いた。
（第一の導電電極を有する基材）
銅箔付ポリイミドフレキシブル基板（２層タイプ）（２００μピッチ銅箔配線上にニッケル金メッキを表面に施したもの）
（第二の導電電極を有する基材）
PETフィルム上にITO電極が設けられた基材（３００Ω シート抵抗）/実施例１
PETフィルム上にITO電極が設けられた基材（３００Ω シート抵抗）/実施例２
ＰＣフィルム上にIZO電極が設けられた基材（３００Ω シート抵抗）/実施例３
ＰＣフィルム上にIZO電極が設けられた基材（３００Ω シート抵抗）/実施例４
ＰＣフィルム上にIZO電極が設けられた基材（３００Ω シート抵抗）/比較例４
ＰＣフィルム上にIZO電極が設けられた基材（３００Ω シート抵抗）/比較例５
上記の第一の導電電極を有する基材と第二の導電電極を有する基材とを異方導電性接着剤を用いて接合した。
Specific examples of embodiments of the present invention will be described below based on examples.
The raw material components of the adhesive used in the examples and comparative examples are as follows.
Bisphenol A epoxy resin (AER2600, manufactured by Asahi Kasei Chemicals Corporation)
Bisphenol F epoxy resin (RE-303S manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy resin (HP-4032D manufactured by Dainippon Ink Co., Ltd.)
Tetramethylbiphenol type epoxy resin (YX4000K manufactured by Japan Epoxy Resin)
Dicyclopentadiene type epoxy resin (HP7200 manufactured by Dainippon Ink Co., Ltd.)
Bisphenol A type phenoxy resin (PKHC, PKFE, PKHB manufactured by Inchem Co., Ltd.)
Polyol-modified phenoxy resin (PKHM301 manufactured by Inchem Co., Ltd.)
Latent curing agent (HX3932HP microcapsule type imidazole (latent curing agent) manufactured by Asahi Kasei Chemicals Corporation)
Silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM403, KBM903)
Silicone adhesive (Toray Dow Corning SD4580, SD4560) (average weight molecular weight 200 to 500,000)
KMP594 silicone rubber particles (manufactured by Shin-Etsu Chemical Co., Ltd.) (average weight molecular weight> 1 million)
Epoxy-modified silicone resin (BY16-855, Toray Dow Corning)
Acrylic resin (Dianar manufactured by Mitsubishi Rayon Co., Ltd.)
(Conductive particles)
Silver copper alloy powder average 3μm
Gold-plated plastic particles average 8μm
Gold / nickel plated copper particles, average 10μm
<Examples 1 to 4, Comparative Examples 4 and 5 >
The compositions 1, 2, 3, 4, 5, and 6 were coated on a 50 μm thick PET using an ethyl acetate solvent in the proportions shown in [Table 1], and dried in air at 60 ° C. for 10 minutes. Solvent was skipped. Thus, an anisotropic conductive adhesive having a thickness of 35 μm was prepared. Moreover, the following base material was used as a test connection base material.
(Base material having first conductive electrode)
Polyimide flexible board with copper foil (2 layer type) (200μ pitch copper foil wiring with nickel gold plating on the surface)
(Base material having second conductive electrode)
Base material (300Ω sheet resistance) with ITO electrode on PET film / Example 1
Base material (300Ω sheet resistance) with ITO electrode on PET film / Example 2
Base material (300Ω sheet resistance) with IZO electrode on PC film / Example 3
Base material (300Ω sheet resistance) with IZO electrode on PC film / Example 4
Base material (300Ω sheet resistance) with IZO electrode on PC film / Comparative Example 4
Base material (300Ω sheet resistance) with IZO electrode on PC film / Comparative Example 5
The base material having the first conductive electrode and the base material having the second conductive electrode were joined using an anisotropic conductive adhesive.
接合は、第二の導電電極を有する基材にフィルム状の異方導電性接着剤を貼り付けて、第一の導電電極を有する基材である上記フレキシブル基材側から１３０℃、30秒、１．５MＰaで１．５mmヘッドで加熱加圧することによって行った。 Bonding is performed by attaching a film-like anisotropic conductive adhesive to the substrate having the second conductive electrode, and 130 ° C. for 30 seconds from the flexible substrate side, which is the substrate having the first conductive electrode. This was carried out by heating and pressing with a 1.5 mm head at 1.5 MPa.
このようにして得た接合体について初期接続抵抗値及び接続信頼性テスト後（８５℃８５％で２００時間放置後）の抵抗値を評価した。 The bonded body thus obtained was evaluated for an initial connection resistance value and a resistance value after a connection reliability test (after leaving at 85 ° C. and 85% for 200 hours).
接続抵抗は日置９４５５型マルチメータを用いて４端子法で測定した。測定は、ポリイミド側の一対の銅箔の抵抗を４対測定して平均値を求めた。結果を［表２］に示す。 The connection resistance was measured by a 4-terminal method using a Hioki 9455 type multimeter. In the measurement, four pairs of resistances of a pair of copper foils on the polyimide side were measured to obtain an average value. The results are shown in [Table 2].
初期接続抵抗値については、５０Ω以下の場合を「良好」とし、５０Ωを超えた場合には「不良」とした。 As for the initial connection resistance value, the case of 50Ω or less was determined as “good”, and the value exceeding 50Ω was determined as “defective”.
接続信頼性テスト後の抵抗値については、接続抵抗値が１００Ωを超える場合、接続信頼性は「不良」とし、１００Ω以下の場合には、接続信頼性は「良好」とした。 Regarding the resistance value after the connection reliability test, when the connection resistance value exceeds 100Ω, the connection reliability is “defective”, and when it is 100Ω or less, the connection reliability is “good”.
接着性試験については、初期接着性および上記接続信頼性テスト後接着性を島津製作所製オートグラフＡＧＳ−５０を用いて引っ張り速度１００ｍｍ／ｍｉｎにて、９０度剥離条件で測定した。このとき、初期接着性は、０．５ｋｇｆ/ｃｍ以上の場合を「良好」とし、接続信頼性テスト後の接着性は、０．４ｋｇｆ/ｃｍ以上の場合を「良好」とした。
<比較例１、２>
［表１］に示す割合で組成７、８を作成し、厚み５０μｍのＰＥＴフィルム上に、バーコートを用いて塗布し、６０℃１０分間乾燥して３５μｍ厚みのフィルム状の異方導電性接着剤を得た。As for the adhesion test, the initial adhesion and the adhesion after the connection reliability test were measured using an autograph AGS-50 manufactured by Shimadzu Corporation at a pulling rate of 100 mm / min under a 90-degree peeling condition. At this time, the initial adhesiveness was “good” when 0.5 kgf / cm or more, and the adhesiveness after the connection reliability test was “good” when 0.4 kgf / cm or more.
<Comparative Examples 1 and 2>
Compositions 7 and 8 were prepared at the ratios shown in [Table 1], applied on a 50 μm thick PET film using a bar coat, dried at 60 ° C. for 10 minutes, and a 35 μm thick anisotropic conductive adhesive film. An agent was obtained.
試験接続基材として、次の基材を用いた。
（第一の導電電極を有する基材）
銅箔付ポリイミドフレキシブル基板（２００μmピッチに銅箔上にニッケル金メッキを表面に施したもの）
（第二の導電電極を有する基材）
PＣフィルム上にIＺO電極が設けられた基材（３００Ωシート抵抗）/比較例１
PＣフィルム上にIＺO電極が設けられた基材（３００Ωシート抵抗）/比較例２
実施例１と同様にして、上記の第一導電電極を有する基材と第二の導電電極を有する基材とを接合し、得られた接合体について初期接続抵抗値及び接続信頼性テスト後の抵抗値を評価した。結果を［表２］に示す。
<実施例７、８>
［表３］に示す割合で組成９及び１０を作成し、導電性接着剤を得た。The following base materials were used as test connection base materials.
(Base material having first conductive electrode)
Polyimide flexible board with copper foil (Ni-gold plating on the surface of copper foil at a pitch of 200μm)
(Base material having second conductive electrode)
Base material (300Ω sheet resistance) with IZO electrode on PC film / Comparative Example 1
Base material (300Ω sheet resistance) with IZO electrode on PC film / Comparative Example 2
In the same manner as in Example 1, the base material having the first conductive electrode and the base material having the second conductive electrode were joined, and the obtained joined body was subjected to the initial connection resistance value and the connection reliability test. The resistance value was evaluated. The results are shown in [Table 2].
<Examples 7 and 8>
Compositions 9 and 10 were prepared at a ratio shown in [Table 3] to obtain a conductive adhesive.
試験接続基材として、次の基材を用いた。
（第一の導電電極を有する基材）
チップコンデンサー/実施例７
IC（金スタッドバンプ）/実施例８
（第二の導電電極を有する基材）
PETフィルム上にITO電極が設けられた基材（３００Ωシート抵抗）/実施例７
PETフィルム上にITO電極が設けられた基材（３００Ωシート抵抗）/実施例８
接合は、第二の導電電極を有する基材に導電性接着剤を塗布し、第一の導電電極を有する基材である上記フレキシブル基材側から１３０℃、６０秒、０．５MPaで１．５mmヘッドで加圧加熱することによって行った。The following base materials were used as test connection base materials.
(Base material having first conductive electrode)
Chip capacitor / Example 7
IC (Gold Stud Bump) / Example 8
(Base material having second conductive electrode)
Base material (300Ω sheet resistance) with ITO electrode on PET film / Example 7
Base material with ITO electrode on PET film (300Ω sheet resistance) / Example 8
For joining, a conductive adhesive is applied to a base material having a second conductive electrode, and the above flexible base material side, which is the base material having the first conductive electrode, is formed at 130 ° C., 60 seconds, 0.5 MPa at 1. MPa. This was carried out by heating under pressure with a 5 mm head.
このようにして得られた接合体について実施例１と同様にして初期接続抵抗値及び信頼性テスト後の抵抗値を評価した。結果を［表４］に示す。同様に、組成７を用いた実験結果を［表４］の比較例３に示す。 Thus, about the obtained joined body, it carried out similarly to Example 1, and evaluated the initial connection resistance value and the resistance value after a reliability test. The results are shown in [Table 4]. Similarly, the experimental results using the composition 7 are shown in Comparative Example 3 in [Table 4].
導電性接着剤評価基準としては、初期接続抵抗値については、１Ω以下の場合を「良好」とし、１Ωを超えた場合を「不良」とした。接続信頼性テスト後（８５℃湿度８５％で２００時間放置後）の抵抗値については、接続抵抗値が１０Ωを超える場合には、接続信頼性が１０Ω以下の場合、接続信頼性は「良好」とした。 As the evaluation criteria for the conductive adhesive, the initial connection resistance value was determined as “good” when the value was 1Ω or less, and as “bad” when it exceeded 1Ω. Regarding the resistance value after the connection reliability test (after leaving for 200 hours at 85 ° C. and 85% humidity), if the connection resistance value exceeds 10Ω, the connection reliability is “good” if the connection reliability is 10Ω or less. It was.
接着性試験については、初期接着性および上記接続信頼性テスト後の接着性を島津製作所製オートグラフAGS−５０を用いて引っ張り速度１００mm/minにて、９０度剥離条件で測定した。このとき、初期接着性は、１ｋｇｆ／ｃｍ以上の場合を良好とし、接続信頼性テスト後の接着性は、０．５ｋｇｆ／ｃｍ以上の場合を良好とした。 As for the adhesion test, the initial adhesion and the adhesion after the connection reliability test were measured using an autograph AGS-50 manufactured by Shimadzu Corporation at a pulling speed of 100 mm / min under a 90-degree peeling condition. At this time, the initial adhesiveness was good when it was 1 kgf / cm or higher, and the adhesiveness after the connection reliability test was good when it was 0.5 kgf / cm or higher.
本発明の接着剤は、電子ペーパー、ウエアラブルデイスプレイ、有機ELや液晶のフレキシブルデイスプレイ、電子部品のフレキシブル基材への実装などに用いることができる。
The adhesive of the present invention can be used for electronic paper, wearable displays, organic EL and liquid crystal flexible displays, and mounting of electronic components on flexible substrates.
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2009528082A JP5337034B2 (en) | 2007-08-10 | 2008-08-05 | Adhesives and joints |
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| JP2007209319 | 2007-08-10 | ||
| JP2007209320 | 2007-08-10 | ||
| JP2007209320 | 2007-08-10 | ||
| JP2007209319 | 2007-08-10 | ||
| JP2009528082A JP5337034B2 (en) | 2007-08-10 | 2008-08-05 | Adhesives and joints |
| PCT/JP2008/064010 WO2009022574A1 (en) | 2007-08-10 | 2008-08-05 | Adhesive and bonded body |
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| JPWO2009022574A1 JPWO2009022574A1 (en) | 2010-11-11 |
| JP5337034B2 true JP5337034B2 (en) | 2013-11-06 |
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| JP (1) | JP5337034B2 (en) |
| KR (1) | KR101139749B1 (en) |
| CN (1) | CN101755025B (en) |
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| DE102008041657A1 (en) | 2008-08-28 | 2010-03-04 | Robert Bosch Gmbh | Method for bonding components to form a temperature-resistant adhesive layer |
| JP2011057793A (en) * | 2009-09-08 | 2011-03-24 | Shin-Etsu Chemical Co Ltd | Adhesive composition, and sheet for forming semiconductor protective film using the same |
| JP5651625B2 (en) * | 2012-03-21 | 2015-01-14 | 京都エレックス株式会社 | Heat curable conductive paste composition |
| SG11201606126RA (en) * | 2014-08-29 | 2016-09-29 | Furukawa Electric Co Ltd | Conductive adhesive film |
| JP2016108461A (en) * | 2014-12-08 | 2016-06-20 | 信越化学工業株式会社 | Adhesive, die-bonding material composed of the adhesive, conductive connection method using the adhesive, optical semiconductor device obtained by the method |
| JP6720814B2 (en) | 2016-09-30 | 2020-07-08 | 日亜化学工業株式会社 | Light emitting device |
| JP6352374B2 (en) * | 2016-12-01 | 2018-07-04 | ダウ・コーニング・タイワン・インコーポレイテッドＤｏｗ Ｃｏｒｎｉｎｇ Ｔａｉｗａｎ Ｉｎｃ | Pressure-sensitive adhesive sheets and methods for producing them |
| JP6800129B2 (en) * | 2017-11-07 | 2020-12-16 | 古河電気工業株式会社 | Manufacturing method of semiconductor package using film-like adhesive and film-like adhesive |
| CN113490725A (en) * | 2019-03-18 | 2021-10-08 | 三键有限公司 | Adhesive composition, cured product, and composite |
| WO2021019932A1 (en) * | 2019-07-29 | 2021-02-04 | 株式会社村田製作所 | Crystal vibrator, electronic component, and electronic device |
| KR20230100416A (en) * | 2021-12-28 | 2023-07-05 | 주식회사 노피온 | Anisotropic conductive adhesive for flexible circuit boards |
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2008
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- 2008-08-05 JP JP2009528082A patent/JP5337034B2/en not_active Expired - Fee Related
- 2008-08-05 KR KR1020107002026A patent/KR101139749B1/en not_active IP Right Cessation
- 2008-08-05 WO PCT/JP2008/064010 patent/WO2009022574A1/en active Application Filing
- 2008-08-07 TW TW97130122A patent/TW200925231A/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0517729A (en) * | 1991-07-11 | 1993-01-26 | Nitto Denko Corp | Adhesive tape |
| JPH06220413A (en) * | 1993-01-21 | 1994-08-09 | Murata Mfg Co Ltd | Conductive adhesive and infrared detector made by using the same |
| JP2001060601A (en) * | 1999-08-19 | 2001-03-06 | Sony Chem Corp | Bonding material and connection of circuit |
| JP2001323249A (en) * | 2000-05-17 | 2001-11-22 | Hitachi Chem Co Ltd | Adhesive for circuit connection |
| JP2003147287A (en) * | 2001-11-14 | 2003-05-21 | Hitachi Chem Co Ltd | Adhesive film for connecting circuit |
| JP2004018720A (en) * | 2002-06-18 | 2004-01-22 | Mitsui Chemicals Inc | Adhesive for semiconductor device |
| JP2004196991A (en) * | 2002-12-19 | 2004-07-15 | Shin Etsu Polymer Co Ltd | Transparent silicone adhesive member for optical display and transparent laminate |
| JP2005029710A (en) * | 2003-07-08 | 2005-02-03 | Nippon Kayaku Co Ltd | Adhesive composition |
| JP2006028521A (en) * | 2005-08-19 | 2006-02-02 | Hitachi Chem Co Ltd | Addhesive for circuit connection |
| JP2006137954A (en) * | 2005-11-16 | 2006-06-01 | Hitachi Chem Co Ltd | Adhesive for circuit connection |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101139749B1 (en) | 2012-04-26 |
| TWI374924B (en) | 2012-10-21 |
| CN101755025A (en) | 2010-06-23 |
| KR20100037124A (en) | 2010-04-08 |
| CN101755025B (en) | 2014-03-12 |
| TW200925231A (en) | 2009-06-16 |
| JPWO2009022574A1 (en) | 2010-11-11 |
| WO2009022574A1 (en) | 2009-02-19 |
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