TW201204798A - Adhesive composition, connecting structure and fabricating method thereof, and use of adhesive composition - Google Patents

Adhesive composition, connecting structure and fabricating method thereof, and use of adhesive composition Download PDF

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Publication number
TW201204798A
TW201204798A TW100119007A TW100119007A TW201204798A TW 201204798 A TW201204798 A TW 201204798A TW 100119007 A TW100119007 A TW 100119007A TW 100119007 A TW100119007 A TW 100119007A TW 201204798 A TW201204798 A TW 201204798A
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Taiwan
Prior art keywords
group
circuit member
adhesive composition
formula
resin
Prior art date
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TW100119007A
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Chinese (zh)
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TWI445792B (en
Inventor
Hiroyuki Izawa
Shigeki Katogi
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Hitachi Chemical Co Ltd
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Publication of TW201204798A publication Critical patent/TW201204798A/en
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Publication of TWI445792B publication Critical patent/TWI445792B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
    • H01L24/92—Specific sequence of method steps
    • 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
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • 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
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  • Engineering & Computer Science (AREA)
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  • Polymers & Plastics (AREA)
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  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Wire Bonding (AREA)

Abstract

This invention provides an adhesive composition for connecting a first circuit part having a first connecting terminal on a main surface and a second circuit part having a second connecting terminal on a main surface; the first circuit part and/or second circuit part include substrates having thermal plastic resin with a glass transition temperature of 200 DEG C or less. The adhesive composition includes (a) a thermal plastic resin, (b) a radical polymerization compound and (c) a radical polymerization initiator, and (b) the redical polymerization compound includes a urethane (meth)acrylate having a critical surface tension of 25 to 40 mN/m.

Description

201204798201204798

^ L 六、發明說明： 【發明所屬之技術領域】 本實施形態是有關於一種黏著劑組成物、連接結構 體、連接結構體的製造方法以及黏著劑組成物的應用。 【先前技術】 於半導體元件及液晶顯示元件中，為了使元件中的各 種構件結合的目的，自先前以來使用各種黏著劑。對黏著 劑的要求是以黏著性為代表’涉及耐熱性、高溫高濕狀態 下的可靠性等。另外，用於黏著的被黏附體是印刷配線板 或以聚醯亞胺（polyimide )、聚對苯二甲酸乙二酯 (polyethylene terephthalate，PET )、聚碳酸酯 (polycarbonate，PC )、聚萘二曱酸乙二醋（p〇lyethylene naphthalate，PEN)等有機基材為代表，使用銅、鋁等金 屬或ITO (indium tin oxide，銦與錫的複合氧化物）、SiN、[Embodiment of the Invention] [Technical Field] The present embodiment relates to an adhesive composition, a bonded structure, a method for producing a bonded structure, and an application of an adhesive composition. [Prior Art] In the semiconductor element and the liquid crystal display element, various adhesives have been used since the purpose of bonding various members in the element. The requirement for the adhesive is represented by adhesiveness, which relates to heat resistance, reliability in a high-temperature and high-humidity state, and the like. In addition, the adhered body for adhesion is a printed wiring board or polyimide, polyethylene terephthalate (PET), polycarbonate (PC), polynaphthalene. An organic substrate such as p〇ly ethylene naphthalate (PEN) is used, and a metal such as copper or aluminum or ITO (indium tin oxide, a composite oxide of indium and tin), SiN, or the like is used.

Si〇2等具有多種多樣的表面狀態的基材，必需根據各被黏 附體來進行分子設計。 自先前以來’上述半導體元件或液晶顯示元件用的黏 著劑是使用利用高黏著性且表現出高可靠性的環氧樹脂的 ，硬化性樹脂（例如參照專利文獻1)。樹脂的構成成分通 常使用環氧樹脂、與環氧樹脂具有反應性的酚樹脂等硬化 劑、促進環氧樹脂與硬化劑的反應的熱潛在性觸媒。熱潛 f性觸媒是在室溫等儲存溫度下不反應而在加熱時表現出 南反f性=物質’成為決定硬化溫度及硬化速度的重要因 f ’就黏著劑的於室溫下的儲存穩定性及加熱時的硬化速 4 201204798 而言’使用各種化合物。實際步驟中的硬化條件 :二170 C〜250°C的溫度下硬化1小時〜3小時，而 獲传所需的黏著。 ，而，、最近，有在PET、pc、腦等耐熱性低的有機 /成半導體元件或液晶騎元件及崎的情況，但 3 = ί化時的加熱而對有機基材及周邊構件造成不良 來達成低溫下快速硬化，必需使=; 的熱潛在性觸媒’但難以兼具室溫附近的儲存穩定性。 物！述巾，將丙触S旨衍生物或甲基㈣酸醋衍生 合性化合物與作為自由基聚合起始劑的過氧 =併用的自*基硬化難著敝卿注。由於作為反應 =性種的自由基富有反應性，故而自由基硬化可短時間硬 由專利文獻2)。然而，自由基硬化系的黏著劑 ^加熱時的硬化收縮大，故而與使用環氧樹脂的情況相 =較，黏著強度差。關於如上所述的黏著強度的下降，提 ^有藉由應用胺基甲酸g旨丙_自旨（ufethane_iate) @ ^予可撓性改善黏著強度的方法（例如參照專利文獻 。另外，提出有藉由對被黏附體為ΙΤ〇、⑽、&〇2等的 無機基材添加石夕烧偶合劑等點著助劑，而改 方法（例如參照專利文獻4)。 先前技術文獻 專利文獻 專利文獻1 :日本專利特開平1-113·號公報 201204798 專利文獻2 :國際公開第98/44〇67號小冊子 專利文獻3:日本專利第35〇374〇號公報 專利文獻4:曰本專利特開昭62_62874號公報 然而，作為熱塑性樹脂的pET、pc、pEN等有機基材 為直鏈狀，另外，利用由苯環引起的分子間的相互作用而 容易形成結晶部分，因此極其難以形成與黏著劑組成物或 矽烷偶合劑的共價鍵。因此，上述專利文獻4中記載的方 法中，未獲得充分的黏著強度。另外，由於pET、pC、pEN 等的表面平滑，故而由物理性錨固效果（增黏效果）引起 的黏著效果小。因此’必需制獲得對被黏_的潤濕性 或充分可齡_著敝成物，但上述補讀3所記載 的方法中，未獲得對被黏附體的充分龍性或可挽性。 【發明内容】 因此，本發明的目的在於提供一種對於聚對苯二甲 乙二醋、聚魏S旨、聚萘二甲酸乙二酯等有機基材，即便 =低f的硬化條件下亦可獲得優異的㈣ 溫高濕試驗)後亦可維持穩定的性= 黏著劑組成物的應用。連接結構_造方法以及 為了達成上述目的，本發明接徂 ^ ^ 用於將主面上具有第-連接 上具有第二連接端子的第二電路構件 /、面 構件及/或上述第-電路^接上述第一電路 第一電路構件疋由包含玻璃轉移溫度為 6 201204798 200°C以下的熱塑性樹脂的基材所構成，上述黏著劑組成物 含有（a)熱塑性樹脂、（b)自由基聚合性化合物及（c) 自由基聚合起始劑，且上述（b)自由基聚合性化合物包含 具有25 mN/m〜40 mN/m的臨界表面張力的胺基甲酸酯 (曱基）丙稀酸醋（urethane (meth)acrylate)。 上述黏著劑組成物藉由含有包含具有25 mN/m〜40 mN/m的臨界表面張力的胺基曱酸酯（甲基）丙烯酸酯的（b) 自由基聚合性化合物，與包含Tg為20(rCw下的熱塑性樹 脂的基材（例如PET、PC、PEN等）的潤濕性提高，可進 行低溫硬化下的黏著，可提高電路構件間的黏著強度。另 外，即便於長時間的可靠性試驗後亦可維持穩 另外，本發明的黏著劑組成物中，性 化合物中所含的胺基甲酸酯（甲基）丙烯酸酯較佳為下述通 式（A)所表示的化合物。 [化1] CHj—C-C—Ο—R3—O-C—N—R*—N—C- 〇-Rs-〇~c-. C-C=CH, (A) [式（A)中，R1及R2分別獨立地表示氮原子或者甲 基，R3表示伸乙基、伸丙基、自ε_己内§旨（e eapn)iaet_ ) 的開環化合物所衍生的基團、或者下述通式（B)所表二 的基團’ R4表示下述通式⑻所表示的基圑，r5表示= 和脂肪族基或者飽和脂環基，a表示上〜扣的整數。 [化2] 正。 201204798 / x P 〇 〇"^Re—〇^~c—R7—c一七q—r6^—〇一 · · · (B) b *. b [式（B)中，R6及R7分別獨立地表示碳數2〜12的 直鏈或者分支鏈的伸烷基，b表示1〜1〇的整數，〇表示1 〜25的整數；此外，式中，R6彼此、R7彼此、|3彼此以及 C彼此分別可相同，亦可不同。] 臨界表面張力與凝集能量密度之間存在比例關係，因 此考慮藉由導入凝集能量密度高的官能基而提高臨界表面 張力。因此，藉由（b)自由基聚合性化合物中所含的胺基 曱酸，（曱基)丙烯酸酯為上述通式（A)所表示的結構，凝 集能篁密度提高，與包含黏著劑組成物及Tg為20(rc以下 的熱塑性樹脂的基材（例如PET、PC、pEN等）的潤濕性 提高’由包含PET或PC、PEN等熱塑性樹脂的基材所構 成的電路構件_黏著強度提高，可獲得優異的連接可靠 性。另外’藉由（b)自由基聚合性化合物中所含的胺基甲 酸醋（甲基)丙烯酸醋為上述通式⑷所表示的結構，而對 黏著劑域物解適度料撓性，*包含pET或冗、酿 f熱塑性樹脂的基材所構成的電路構件_黏著強度提 尚，可獲得優異的連接可靠性。 另外本發明提供—種黏著冑彳組成物，用於將主面上 具有第-連接端子的第―電路構件、與主面上 上述第-電路構件及/或二 第一電路構件疋由包含玻璃轉移溫度為以下的熱塑 8 201204798 JO JJnpn' t月曰的基材所構成，上述黏著劑組成物含有（a)熱塑性 月曰、、（b)自由基聚合性化合物及（C)自由基聚合起始劑， 且上述（b)自由基聚合性化合物包含下述通式（A)所表 不的胺基曱酸㉟（曱基)丙稀酸醋。 [化3] R2 0-r3-O-C-C=CH2 •(A) | r CH2=C-C—〇~R3〜A ~ 1A substrate having a variety of surface states such as Si〇2 must be molecularly designed according to each adherend. The adhesive for the above-mentioned semiconductor element or liquid crystal display element is a curable resin which uses an epoxy resin which exhibits high adhesion and exhibits high reliability (for example, see Patent Document 1). As the constituent component of the resin, a curing agent such as an epoxy resin, a phenol resin reactive with an epoxy resin, or a thermal latent catalyst that promotes a reaction between the epoxy resin and the curing agent is usually used. The thermal latent f-catalyst does not react at room temperature and other storage temperatures, and exhibits a south anti-f property when heated = the substance 'is an important factor determining the hardening temperature and the hardening rate f' at the room temperature of the adhesive Storage stability and rate of hardening upon heating 4 201204798 For the use of various compounds. Hardening conditions in the actual steps: Hardening at a temperature of 170 C to 250 ° C for 1 hour to 3 hours, and obtaining the desired adhesion. Recently, there are cases in which an organic/semiconductor element or a liquid crystal riding element having low heat resistance such as PET, pc, or brain is in the form of a liquid crystal riding element, but 3 = heating causes deterioration of the organic substrate and peripheral members. In order to achieve rapid hardening at low temperatures, it is necessary to make the thermal latent catalyst of =; but it is difficult to achieve storage stability near room temperature. Things! In the case of the towel, it is difficult to use a C-synthesis derivative or a methyl (tetra) acid vinegar-derived compound and a peroxygen as a radical polymerization initiator. Since the radical which is a reaction = sex is highly reactive, radical hardening can be hardened for a short time by Patent Document 2). However, since the adhesive of the radical hardening type has a large hardening shrinkage upon heating, the adhesive strength is inferior to that in the case of using an epoxy resin. With regard to the decrease in the adhesive strength as described above, there is a method of improving the adhesive strength by applying urethane for the purpose of improving the adhesive strength by applying urethane formic acid (for example, refer to the patent literature. An additive is added to an inorganic substrate to which the adherend is ruthenium, (10), & 〇2, etc., and the like is added, and the method is modified (for example, refer to Patent Document 4). [Patent Document 2: International Publication No. 98/44〇67, pamphlet Patent Document 3: Japanese Patent No. 35〇374〇 Patent Document 4: 曰本专利专开昭However, the organic base material such as pET, pc, or pEN which is a thermoplastic resin is linear, and the crystal part is easily formed by the interaction between molecules by the benzene ring. Therefore, it is extremely difficult to form an adhesive composition. The covalent bond of the substance or the decane coupling agent. Therefore, in the method described in the above Patent Document 4, sufficient adhesion strength is not obtained. Further, since the surfaces of pET, pC, pEN, etc. are smooth, The effect of the rational anchoring effect (the viscosity-increasing effect) is small. Therefore, it is necessary to obtain the wettability of the viscous _ or the sufficient age, but the method described in the above supplementary reading 3 is not obtained. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an organic group such as polyethylene terephthalate, poly-weis, and polyethylene naphthalate. Material, even under the hardening condition of low f, excellent (four) temperature and humidity test can be obtained to maintain stable properties = application of adhesive composition. The connection structure-making method and the above-described first object are provided for the purpose of achieving the above object, the second circuit member having the second connection terminal on the main surface and the surface member and/or the first circuit The first circuit member is connected to the first circuit member, and comprises a substrate comprising a thermoplastic resin having a glass transition temperature of 6 201204798 200 ° C or less. The adhesive composition contains (a) a thermoplastic resin and (b) a radical polymerizable property. a compound and (c) a radical polymerization initiator, and the above (b) radical polymerizable compound contains a urethane (mercapto) acrylic acid having a critical surface tension of 25 mN/m to 40 mN/m. Urethane (meth)acrylate. The above adhesive composition comprises a (b) radical polymerizable compound containing an amino phthalate (meth) acrylate having a critical surface tension of 25 mN/m to 40 mN/m, and a Tg of 20 (The substrate of the thermoplastic resin under rCw (for example, PET, PC, PEN, etc.) has improved wettability, can be adhered under low-temperature curing, and can improve the adhesion strength between circuit members. Moreover, reliability over a long period of time Further, in the adhesive composition of the present invention, the urethane (meth) acrylate contained in the compound is preferably a compound represented by the following formula (A). 1] CHj—CC—Ο—R3—OC—N—R*—N—C— 〇-Rs-〇~c-. CC=CH, (A) [In equation (A), R1 and R2 are independent The ground represents a nitrogen atom or a methyl group, and R3 represents a group derived from a ring-opening compound of an ethyl group, a propyl group, or an e-eap iaet_), or a group of the following formula (B) The group 'R4 of Table 2> represents a group represented by the following formula (8), r5 represents = and an aliphatic group or a saturated alicyclic group, and a represents an integer of the upper to the deduction. [Chemical 2] Positive. 201204798 / x P 〇〇"^Re—〇^~c—R7—c一七q—r6^—〇一· · · (B) b *. b [In equation (B), R6 and R7 are independent The ground represents a linear or branched alkyl group having a carbon number of 2 to 12, b represents an integer of 1 to 1 〇, and 〇 represents an integer of 1 to 25; further, in the formula, R6, R7, and |3 are each C may be the same or different from each other. There is a proportional relationship between the critical surface tension and the agglomerated energy density, so it is considered to increase the critical surface tension by introducing a functional group having a high energy density. Therefore, (b) the amino phthalic acid contained in the radically polymerizable compound, (mercapto) acrylate is a structure represented by the above formula (A), the aggregation energy density is increased, and the composition is composed of an adhesive. The material and the substrate having a Tg of 20 or less (for example, PET, PC, pEN, etc.) have improved wettability. 'The circuit member consisting of a base material containing a thermoplastic resin such as PET, PC, or PEN_Adhesive strength When the (b) radically polymerizable compound contains the amino methacrylate (meth) acrylate, the structure represented by the above formula (4) is used, and the adhesive is added. The domain material is moderately flexible, and the circuit member composed of a substrate comprising pET or a redundant thermoplastic resin has excellent adhesion reliability, and the present invention provides an adhesive composition. The first circuit member having the first connection terminal on the main surface and the first circuit member and/or the second first circuit member on the main surface are made of a thermoplastic containing glass transition temperature of 8 201204798 JO JJnpn't month base The adhesive composition comprises (a) a thermoplastic polymer, (b) a radical polymerizable compound, and (C) a radical polymerization initiator, and the (b) radical polymerizable compound comprises the following Amino decanoic acid 35 (mercapto) acrylic acid vinegar represented by the general formula (A) [Chemical 3] R2 0-r3-OCC=CH2 • (A) | r CH2=CC—〇~R3~A ~ 1

O N-c- -Rs—C-N-R —NO N-c- -Rs-C-N-R —N

[式（A)中’ Rl及R2分別獨立地表示氫原子或者曱 基，R3表示伸乙基、伸丙基、由ε-己内酯的開環化合物所 衍生的基團、或者下述通式（Β)所表示的基團，R4表示 下述通式（Β)所表示的基團，R5表示飽和脂肪族基或者 飽和脂環基，a表示1〜40的整數。] [化4][In the formula (A), R1 and R2 each independently represent a hydrogen atom or a fluorenyl group, and R3 represents an ethyl group, a propyl group, a group derived from a ring-opening compound of ε-caprolactone, or the following The group represented by the formula (Β), R4 represents a group represented by the following formula (Β), R5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents an integer of 1 to 40. ] [Chemical 4]

〜…⑻ [式（B)中，R6及R7分別獨立地表示碳數2〜12的 直鏈或者分支鏈的伸烷基，b表示1〜1〇的整數，c表示又 〜25的整數；此外，式中，R6彼此、R7彼此、b彼此以及 c彼此分別可相同，亦可不同。] 藉由（b)自由基聚合性化合物中所含的胺基曱酸酷（甲 201204798^ 基)丙烯酸酯為上述通式（A)所表示的結構，本黏著劑組 成物的凝集能量密度提高，與包含黏著劑組成物及Tg為 200°C以下的熱塑性樹脂的基材（例如pET、pc、PEN等） 的潤濕性提高，由包含PET或PC、PEN等熱塑性樹脂的 基材所構成的電路構件間的黏著強度提高，可獲得優異的 連接可靠性。另外，藉由（b)自由基聚合性化合物中所含 的胺基甲酸酯（曱基）丙烯酸酯為上述通式（A)所表示的結 構，而對黏著劑組成物賦予適度的可撓性，由包含pET或 PC、PEN等熱塑性樹脂的基材所構成的電路構件間的黏著 強度提尚，可獲得優異的連接可靠性。進而，即便於長時 間的可靠性試驗後亦可維持穩定的性能。 本發明的黏著劑組成物中較佳為，胺基曱酸酯（甲基) 丙婦酸S旨為使用脂肪族聚g旨二醇而獲得的化合物。藉由胺 基甲is曰（甲基)丙烯酸醋為使用脂肪族聚醋二醇而獲得的 化s物，黏著劑組成物的可撓性提高由包含ρΕτ或pc、 等熱錄細旨的基材所構成的電路構件_黏著強度 知:尚，可獲得優異的連接可靠性。 为夕卜 界發月的黏著劑組成物中較佳為，胺基甲酸酯 乂甲基)丙，酸S旨的重量平均分子量為8_以上且小於 5000藉由胺基曱酸§旨（甲基)丙稀酸㈣重量平均分 内，與PET、pc、pEN等有機基材的黏著強度 進Y耠尚，可獲得優異的連接可靠性。 有1種以上的具有磷酸基的乙烯基化合 201204798 物、及1種以上的具有磷酸基的乙烯基化合物以外的自由 基聚合性化合物。藉由（b)自由基聚合性化合物具備如上 所述的構成’尤其與包含金屬的基材的黏著強度進一步提 向。 另外，本發明的黏著劑組成物中較佳為，（a)熱塑性 樹脂含有選自由苯氧基（phenoxy)樹脂、聚胺基曱酸酯 (polyurethane)樹脂、聚酉旨胺基甲酸醋（p〇lyester虹她孤） 樹脂、丁醛（butyral)樹脂、丙烯酸樹脂及聚醯亞胺樹脂 所組成組群中的至少丨種。藉由含有如上所述的樹脂作為 (a)熱塑性樹脂，黏著劑組成物的耐熱性、黏著性進一步 提南。 另外，本發明的黏著劑組成物中亦較佳為更含有（d) 導電性粒子。藉由含有⑷導電餘子，可對黏著劑组成 物賦予良好的導電性或者異向導電性，因此可更適合用於 具有連接端子的f路構件彼此的黏著用料。另外，可更 分降低經由上述黏著敝成物而f性連接的電路構件的 運接電阻。 主面有供一種電路構件的連接結構體，包括 子的第二電路構件、及連接構件，並且叹2 知子及第一連接端子對向的方式配置上 件及上述第二電路構件，立由七人Η ^電路構 轉劑組成物的連 之間 而且第-連接…：構 第二電路構件 上述第一 第連接^子及第二連接端子為電性連接，(8) [In the formula (B), R6 and R7 each independently represent a linear or branched alkyl group having 2 to 12 carbon atoms, b represents an integer of 1 to 1 ,, and c represents an integer of ～25; Further, in the formula, R6, R7, b, and c may be the same or different from each other. By the structure represented by the above formula (A) in the (b) radically polymerizable compound, the acridine acid (A 201204798 alkyl) acrylate is a structure represented by the above formula (A), and the aggregation energy density of the adhesive composition is improved. It has improved wettability with a substrate (for example, pET, pc, PEN, etc.) containing an adhesive composition and a thermoplastic resin having a Tg of 200 ° C or lower, and is composed of a substrate containing a thermoplastic resin such as PET, PC, or PEN. The adhesion strength between the circuit members is improved, and excellent connection reliability can be obtained. In addition, the urethane (mercapto) acrylate contained in the (b) radical polymerizable compound is a structure represented by the above formula (A), and the adhesive composition is moderately flexible. The adhesion strength between circuit members composed of a base material comprising a thermoplastic resin such as pET or PC or PEN is improved, and excellent connection reliability can be obtained. Further, stable performance can be maintained even after a long-term reliability test. In the adhesive composition of the present invention, it is preferred that the amino phthalate (methyl) acetoic acid S is a compound obtained by using an aliphatic poly glycerol. By using an aminomethicone (meth)acrylic acid vinegar as a chemical substance obtained by using an aliphatic polyester diol, the flexibility of the adhesive composition is improved by a composition including ρΕτ or pc, etc. The circuit member made of the material _ the adhesion strength is known: excellent connection reliability can be obtained. Preferably, the adhesive composition of the present invention is a urethane 乂methyl) propyl group, and the acid S has a weight average molecular weight of 8 Å or more and less than 5,000 by an amine decanoic acid § In the weight average of methyl (meth) acrylate (4), the adhesion strength to organic substrates such as PET, pc, and pEN is improved, and excellent connection reliability can be obtained. There are one or more kinds of free-radical polymerizable compounds other than the vinyl compound 201204798 having a phosphoric acid group and one or more vinyl compounds having a phosphoric acid group. The (b) radically polymerizable compound has the above-described constitution, and particularly the adhesion strength to the metal-containing substrate is further improved. Further, in the adhesive composition of the present invention, (a) the thermoplastic resin contains a compound selected from the group consisting of a phenoxy resin, a polyurethane resin, and a polyamine carboxylic acid vinegar (p). 〇lyester rainbow her orphan) At least one of the group consisting of resin, butyral resin, acrylic resin and polyimide resin. By containing the resin as described above as the (a) thermoplastic resin, the heat resistance and adhesion of the adhesive composition are further advanced. Further, it is preferable that the adhesive composition of the present invention further contains (d) conductive particles. By containing (4) a conductive remainder, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition, and therefore it is more suitable for use in an adhesive material for f-members having connection terminals. Further, the transfer resistance of the circuit member which is f-connected via the above-described adhesive composition can be further reduced. The main surface has a connecting structure for a circuit member, the second circuit member including the sub-connector, and the connecting member, and the upper member and the second circuit member are disposed in a manner opposite to the first connecting terminal, and the second circuit member is provided Between the connection of the circuit composition of the circuit and the first connection: the second circuit member is electrically connected to the first connection and the second connection terminal,

201204798 L 上述第二電路構件是由含有玻璃轉移溫度 '、、 以下的熱塑性樹脂的基材所構成。 ，由第—電路構件及/或第二電路構件為由含有玻璃 播ί溫度為2啊以下的熱塑性繼的基材所構成的電路 牛，與黏著劑組成物的潤濕性提高，黏著強度進一步接 高，可獲得優異的連接可靠性。 移溫度為2(Krc:以下的_性樹脂較佳為 、聚對苯二甲酸乙二酯、聚碳酸酯及聚萃二曱酸乙二 成組群中的至少1種。藉由上述電路構件為由含ΐ ▲、本一甲酸乙二酯等的基材所構成的電路構件，與 =組成物的潤濕性提高，黏著強度進—步提高;蔓 異的連接可靠性。 付1愛 另外，本發明的電路構件的連接結構體中較佳 :電路構件或者第二電路構件中的—方的電路構件是 一選自由聚對苯二㈣乙二g旨、聚碳酸酯及聚蔡二 二醋所組成組群中的至少！種的基材所構成，且第 ^件或者第二電路構件巾的另-方的電路構件是由含 ^由聚醢亞胺樹脂及聚對苯二甲酸乙二賴組歧群中的 >1種的基材所構成。藉由第—電路構件與第二電路 ，由如上所述的基材所構成，本連接結構體的與201204798 L The second circuit member is made of a base material containing a thermoplastic resin having a glass transition temperature of ' or less. The circuit board comprising the first circuit member and/or the second circuit member is composed of a thermoplastic substrate having a glass temperature of 2 Å or less, and the wettability of the adhesive composition is improved, and the adhesion strength is further increased. When connected high, excellent connection reliability can be obtained. The migration temperature is 2 (Krc: the following _ resin is preferably at least one of polyethylene terephthalate, polycarbonate, and polyacetic acid diacetate.) In order to form a circuit member made of a substrate containing ΐ ▲ or ethyl methacrylate, the wettability with the composition is improved, the adhesion strength is further improved, and the connection reliability of the vine is different. Preferably, in the connection structure of the circuit member of the present invention, the circuit member or the circuit member in the second circuit member is selected from the group consisting of poly(p-phenylene) (tetra)ethylene, and polycarbonate and polycaene. a substrate composed of at least a species of vinegar, and the other circuit component of the second member or the second circuit member is composed of a polyimide resin and polyethylene terephthalate A substrate of one type in the group of the two groups. The first circuit member and the second circuit are composed of the substrate as described above, and the connection structure is

成物的潤雜及料強度進—倾高，可獲 S 可靠性。 逆钱 本發明提供-種電路構件的連接結構體的製 包括以下步驟：將主面上具有第—連接端子的第—電路構 12 201204798 :連=====第二電路構件，以使第 述第-電路構件與上述第二電路構其:介於上 物；以及將黏著劑組成物加埶二述3考劑組成 件與第二電路構件連接。依硬化而將第—電路構 構件以上述黏著劑組成物來連接，可獲 付U異的連接可靠性的電路構件的連接結構體。 你”本㈣提供—種作為轉敝成物的應用，用 物電路構件與第二電路構件連接，上述黏著劑組成 物3有U)熱塑性樹脂、⑴自由基聚合性化合物及（c) 自由基聚合起始劑，且上述⑴自由絲合性化合物包含 具有25 i^iN/m〜40 mN/m的臨界表面張力的胺基甲酸酯 (甲基)丙烯酸酯，上述第一電路構件於主面上具有第一連 接&子，上述第二電路構件於主面上具有第二連接端子， 且至少一方的電路構件是由包含玻璃轉移溫度200°C以下 的熱塑性樹脂的基材所構成。含有包含具有25 mN/m〜4〇 mN/m的臨界表面張力的胺基曱酸酯（甲基)丙烯酸酯的（b) 自由基聚合性化合物的本黏著劑組成物由於與包含Tg為 200°C以下的熱塑性樹脂的基材（例如PET、PC、PEN等） 的润濕性提高，可進行於低溫硬化下的黏著，故而適宜作 為用於連接電路構件的黏著劑組成物來應用。 上述應用中較佳為，胺基曱酸酯（曱基)丙烯酸酯為下 述通式（A)所表示的胺基曱酸酯（曱基)丙烯酸酯。藉由胺 基曱酸酯（曱基)丙烯酸酯為下述通式（A)所表示的結構， 13 201204798 電路構件間的黏著強度提高，可獲得優異的連接可靠性。 [化 5] ° N-C- --Rs—C-N-R4—N-C- Ο Η H〇 R2 〇-R3-〇-c4=CH2 , 〇 (A)中’Rl及R2分別獨立地表示氫原子或者甲 R3表示伸乙基、伸丙基、由ε•己内酯的開環化合物所 衍生的基團、或者下述通式（Β)所表示的基團，R4表示 下述通式（Β)所表示的基團，R5表示飽和脂肪族基或者 飽和脂環基’ a表示1〜40的整數。] [化6] R午〇一…⑻The complexity of the product and the strength of the material are high - and the reliability of S can be obtained. The invention provides a connection structure for a circuit component comprising the steps of: a first circuit structure having a first connection terminal on the main surface 12 201204798: a ===== second circuit component, so that The first circuit member and the second circuit are configured to be interposed; and the adhesive composition is coupled to the second circuit member. The first circuit member is connected by the above-described adhesive composition in accordance with the hardening, and the connection structure of the circuit member having the connection reliability of U can be obtained. You (4) provide an application for transferring a sputum, the circuit component is connected to the second circuit component, and the adhesive composition 3 has U) a thermoplastic resin, (1) a radical polymerizable compound, and (c) a radical. a polymerization initiator, and the above (1) free silk compound comprises a urethane (meth) acrylate having a critical surface tension of 25 μM/m 40 mN/m, and the first circuit member is mainly The surface has a first connection & the second circuit member has a second connection terminal on the main surface, and at least one of the circuit members is made of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C or lower. The present adhesive composition containing (b) a radically polymerizable compound containing an amino phthalate (meth) acrylate having a critical surface tension of 25 mN/m to 4 〇 mN/m, and a Tg of 200 The substrate of the thermoplastic resin (for example, PET, PC, PEN, etc.) having a temperature of ° C or less is improved in wettability and can be adhered under low-temperature curing, and therefore it is suitably used as an adhesive composition for connecting circuit members. Preferred in the application The amino decanoate (mercapto) acrylate is an amino phthalate acrylate represented by the following formula (A), which is represented by an amino phthalate acrylate. The structure represented by the general formula (A), 13 201204798 The adhesion strength between the circuit components is improved, and excellent connection reliability can be obtained. [Chemical 5] ° NC- --Rs—CN-R4—NC- Ο Η H〇 R2 〇-R3-〇-c4=CH2 , 〇(A) wherein 'Rl and R2 each independently represent a hydrogen atom or A3 represents an exoethyl group, a propyl group, and is derived from a ring-opening compound of ε•caprolactone. a group or a group represented by the following formula (Β), R 4 represents a group represented by the following formula (Β), and R 5 represents a saturated aliphatic group or a saturated alicyclic group ' a represents 1 to 40 The integer.] [Chem. 6] R 〇一一...(8)

Jc [式（B)中，汉6及r7分別獨立地表示碳數2〜12的 直鏈或者分支鏈的伸絲，b表示的整數，c表示i 整數；此外’式巾’R6彼此、R?彼此、b彼此以及 彼此为別可相同，亦可不同。] 於將Ϊ外*t發明提供—種作為黏著劑組成物的應用，用 牛與第二電路構件連接，上述黏著劑組成 自由基聚麵㈣，且」^自^絲合齡合物及⑴ 上述（b)自由基聚合性化合物包含 201204798, 下述通式（A)所表示的胺基曱酸酯（曱基)丙烯酸酯，上述 第-電路構件於主面上具有第—連接端子，上述第二電路 ，件於主面上具有第二連接端子，且至少—方的電路構件 是由包含玻稱移溫度200°(:町的熱齡概的基材所 構成。藉由胺基曱酸酯（曱基）丙烯酸酯為下述通式（A)所 表示的結構，電路構件間的黏著強度提高，可獲得優異 連接可靠性。 一 [化7] 〇—R3- 0Jc [In the formula (B), Han 6 and r7 each independently represent a straight or branched chain of carbon 2 to 12, an integer represented by b, and c represents an integer of i; in addition, 'type towel' R6 and R ? Each other, b and each other may be the same or different. In the application of the invention as an adhesive composition, the cattle are connected to the second circuit member, and the above-mentioned adhesive constitutes a free radical gather (4), and "^ from the silk composite compound and (1) The (b) radically polymerizable compound includes 201204798, an amino phthalate acrylate represented by the following formula (A), and the first circuit member has a first connection terminal on the main surface, a second circuit, the member having a second connection terminal on the main surface, and at least the square circuit member is composed of a substrate containing a glass transition temperature of 200° (: the thermal age of the town). The ester (mercapto) acrylate is a structure represented by the following general formula (A), and the adhesion strength between circuit members is improved, and excellent connection reliability can be obtained. [Chemical 7] 〇-R3- 0

-O-C-N-R4—N-C- U | I It Ο H HO ΤΓΤΕ. ψ -Ο—R3—〇—C-C-CH, II * ο •(A) [式（Α)中，R及R分別獨立地表示氫原子或者曱 基’ R3表示伸乙基、伸丙基、由ε-己内醋的開環化合物所 衍生的基團、或者下述通式⑻所表示的基團，r4表示 下述通式⑻所表示的基團，R5表示飽和脂肪族基或者 飽和脂環基，a表示1〜40的整數。] [化8] * Ο 〇 O+R6—O^C—R7—C一 +0—妒卜。—…(B) [式（B)中，R6及R7分別獨立地表示碳數之〜Η的 直鏈或者分支鏈的伸烷基，b表示1〜1〇的整數，c表示i 15 201204798 〜25的整數；此外，式中，R6彼此、R7彼此、^^彼此以及 c彼此分別可相同，亦可不同。] 上述應用中較佳為，胺基曱酸酯（曱基）丙烯酸酯為使 用脂肪族聚酯二醇而獲得的化合物。藉由胺基曱酸酯（曱基) 丙烯酸酯為使用脂肪族聚酯二醇而獲得的化合物，黏著& 組成物的可撓性提高，由包含pET或pc、pEN等熱塑性-OCN-R4—NC- U | I It Ο H HO ΤΓΤΕ. ψ -Ο—R3—〇—CC—CH, II * ο • (A) [In the formula (Α), R and R independently represent hydrogen The atom or thiol group R3 represents an ethyl group, a propyl group, a group derived from a ring-opening compound of ε-hexyl vinegar, or a group represented by the following formula (8), and r4 represents the following formula (8) The group represented, R5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents an integer of 1 to 40. ] [Chem. 8] * Ο 〇 O+R6—O^C—R7—C—+0—妒卜. —(B) [In the formula (B), R6 and R7 each independently represent a straight or branched alkyl group having a carbon number of Η, b represents an integer of 1 to 1 ,, and c represents i 15 201204798 〜 In addition, in the formula, R6 and R7 may be the same or different from each other, and each other may be the same. In the above application, the amino phthalate acrylate is a compound obtained by using an aliphatic polyester diol. By using an amino phthalate acrylate as a compound obtained using an aliphatic polyester diol, the adhesion of the composition is improved, and the thermoplastic is composed of pET or pc, pEN or the like.

樹脂的基材所構成的電路構件間的黏著強度提高，可庐得 優異的連接可靠性。 X 、，上述應用中較佳為，胺基曱酸酯（甲基）丙烯酸酯的重 量平均分子量為8000以上且小於25〇〇〇。藉由胺基甲酸酯 (甲基）丙烯酸酯的重量平均分子量在上述範圍内，與 PET、PC、PEN等有機基材的黏著強度進一步提高可 得優異的連接可靠性。 上述應用中較佳為，（b)自由基聚合性化合物含有i 種以上的具有磷酸基的乙烯基化合物、及丨種以上的具有 磷酸基的乙烯基化合物以外的自由基聚合性化合物。藉由 ⑴自由基聚合性化合物具備如上所述的構成，尤其與包 含金屬的基材的黏著強度進一步提高。 ^ 上述應用中較佳為’（a)熱塑性樹脂含有選自由苯氧 基樹脂、聚胺基甲酸酯樹脂、聚酯胺基甲酸醋樹脂、丁醛 樹脂」丙烯酸樹脂及聚醯亞胺樹脂所組成組群中的至少ι 種。藉由含有如上所述的樹脂作為（a)熱塑性樹脂 ，耐熱 性、黏著性進一步提高。 … 上述應用中較佳為，黏著劑组成物更含有⑷導電性 201204798 粒子 有⑷導電性粒子’可對黏著劑組成物賦予 性或者異向導，另外，可更充分地降低電 性連接的電路構件的連接電阻。 _ [發明的效果] 依據本發明，可提供一種對於 聚碳酸酯、聚萘二曱酸乙—萨笪古德09 T敎乙一s曰專有機基材，即便於低溫的 土 _'、下亦可獲得優異的黏著強度，且即便於長時間的 可罪性麟（高溫高_驗）後亦可轉穩定的性能（黏 者強度或連接電阻）的黏著劑組成物，使用該黏著劑 物的電路構件的連接結構體，電路構件的連接結構體的製 造方法以及黏著劑組成物的應用。 【實施方式】 、下根據清況，一邊參照圖式一邊對本發明的較佳 實施形態進行詳細說明。此外，圖式中，對同一或者相當 部分標註同一符號，省略重複的說明。另外，本實施形^ 中’所謂（甲基)丙稀酸是表示丙稀酸或者與其對應的甲^ 丙烯酉夂所明（曱基)丙烯酸g旨是表示丙稀酸醋或者與其對 應的曱基丙’所謂（甲基)丙烯酿基是表示丙稀酿基 或者曱基丙烯醯基。 本貫施形態中的所謂「玻璃轉移溫度（Tg)」，是指使 用TAInstmments公司製造的黏彈性分析儀「RSA 3」（商 品名）。，於升溫速度5t/min、頻率10Hz、測定溫度_15(rc 300 C的條件下，對膜狀的有機基材測定而得的附近 的tanS峰值溫度的值。 17 201204798The adhesion strength between the circuit members formed of the base material of the resin is improved, and excellent connection reliability can be obtained. X, in the above application, it is preferred that the amino phthalate (meth) acrylate has a weight average molecular weight of 8,000 or more and less than 25 Å. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, the adhesion strength to an organic substrate such as PET, PC or PEN is further improved to obtain excellent connection reliability. In the above-mentioned application, the (b) radically polymerizable compound preferably contains at least one vinyl compound having a phosphoric acid group and a radical polymerizable compound other than a vinyl compound having a phosphoric acid group. (1) The radically polymerizable compound has the above-described configuration, and in particular, the adhesion strength to the metal-containing substrate is further improved. ^ In the above application, it is preferred that '(a) the thermoplastic resin contains a phenolic resin, a polyurethane resin, a polyester urethane resin, a butyral resin, an acrylic resin, and a polyimide resin. Form at least ι in the group. By containing the resin as described above as the (a) thermoplastic resin, heat resistance and adhesion are further improved. In the above application, it is preferable that the adhesive composition further contains (4) conductivity 201204798 particles have (4) conductive particles' impartability or anisotropy to the adhesive composition, and further, the electrically connected circuit member can be more sufficiently reduced Connection resistance. _ [Effects of the Invention] According to the present invention, it is possible to provide a special organic substrate for polycarbonate, polyethylene naphthyl sulphate, and the like, even at low temperatures. Excellent adhesion strength, and even after prolonged suspicion (high temperature and high temperature), the adhesive composition can be stabilized (adhesive strength or joint resistance), and the adhesive can be used. A connection structure of a circuit member, a method of manufacturing a connection structure of a circuit member, and an application of an adhesive composition. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding components are designated by the same reference numerals, and the repeated description is omitted. In addition, in the present embodiment, 'the so-called (meth)acrylic acid means that acrylic acid or the corresponding propylene sulfonate (mercapto)acrylic acid g is an acrylic acid acrylate or a hydrazine corresponding thereto. The propyl group 'the so-called (meth) propylene aryl group means an acryloyl group or a fluorenyl fluorenyl group. The "glass transition temperature (Tg)" in the present embodiment refers to a viscoelastic analyzer "RSA 3" (trade name) manufactured by TA Instmments. The value of the tanS peak temperature in the vicinity of the film-shaped organic substrate measured under the conditions of a temperature rise rate of 5 t/min, a frequency of 10 Hz, and a measurement temperature of -15 (rc 300 C.) 17 201204798

另外，本實施形態中的所謂「臨界表面張力（γ。）」， 是指實際測量剛對製成膜狀的胺基曱酸酯（甲基)丙烯酸酯 分別在23°C下滴加1 μΐ的純水、潤濕張力試驗用混合溶液 Νο.50、60 (和光純藥工業（股）製造）之後的與胺基曱酸 酯（曱基)丙烯酸酯表面所形成的角（接觸角Θ)，以各液體 的表面張力為X軸且以cose為y軸而製圖時，通過3點 的直線成為Y=1時的表面張力。此外，關於當通過上述 純水、Νο·50、60的測定所得的3點的直線為γ=1時X 成為負值的情況，亦可使用純水、潤濕張力試驗用混合溶 液No.60、1-溴萘（和光純藥工業（股）製造）來進行與 上述相同的測定’使用通過所得的3點的直線成為Y=1 時的表面張力的值。 另外，本實施形態中，所謂「重量平均分子量」及「數 量平均分子量」’是指依據表1所示的條件，藉由凝膠滲透 層析法（gel permeation chromatograph，GPC )，使用標準 聚笨乙烯的校正曲線進行測定而得的值。 [表1] 「_ 裝置 ___逢測器 Tosoh股瘀有限公司製造，GPC-8020 Tosoh股份有限公司製造，RI-8020 管柱 日立化成工業股份有限公司製造，Gelpack _ GL-A-160-S + GL-A150-SG2000Hhr ^試料濃庶 _____120 mg/3 ml__ 四氫呋喃 60 μΐ __壓力 — 流量 ----30 kg£W__ 1.00 ml/min 18 201204798 本實施形態的黏著劑組成物是用於將主面上具有第一 連接端子的第一電路構件、與主面上具有第二連接端子的 第一電路構件連接的黏著劑組成物，第一電路構件及/或第 二電路構件是由包含玻璃轉移溫度為2〇〇〇C以下的熱塑性 树月曰的基材所構成，上述黏著劑組成物含有（a)熱塑性樹 脂、（b)自由基聚合性化合物及（c)自由基聚合起始劑， 且⑴自由基聚合性化合物包含具有25mN/m〜4〇mN/m 的臨界表面張力的胺基甲酸酯（曱基)丙烯酸酯。 本實施形態的黏著劑組成物中所含有的（a)熱塑性樹 脂f指具有如下性質的樹脂（高分子）：藉由加熱而成為黏 度高的液狀狀態，利用外力而自由變形，若加以冷卻並去 除外力，則於保持其形狀的狀態下變硬，將該過程重複進 行。另外，亦包括包含具有上述性質的反應性官能基的樹 脂（高分子Wa)熱塑性樹脂的“較佳為π〜19(rc， 更佳為20°C〜170°C。 如上所述的熱塑性樹脂可使用：聚醯亞胺樹脂、聚醢 胺（polyamide)樹脂、苯氧基樹脂、（甲基)丙烯酸樹脂、 胺基甲酸酯樹脂、聚酯胺基甲酸酯樹脂、聚乙烯基丁醛 (polyvinylbutyral)樹脂等。該些樹脂可單獨使用或者將2 種以上混合使用。進而，該些熱塑性樹脂中亦可包含矽氧 烷（s^loxane)鍵或氟取代基。該些樹脂若為所混合的樹脂 彼此完全相溶，或者產生微相分離而白濁的狀態，則可適 宜使用。 於將黏著劑組成物製成臈狀而利用的情況，上述熱塑 19 201204798 性樹脂的分子魏大，齡賴射请㈣ I將對作為膜雜㈣組成物麟祕產生 佳為5_〜15_ ^I平均分子量較 漏，則存在難叫得良好的卿祕的^， 150000 =存在難赠得與其域分的良好姉性的傾向。 貧施形態的黏著劑組成物中，以黏著劑組成物總量 為基準’（a)熱塑性樹脂的含量較佳為5質量％〜肋 %’更佳為15質量％〜70質量％。若該含量小於5質量 則於將黏著劑組成物製成膜狀而利用的情況， ° 以獲得良好的膜形成性的傾向，若超過8〇質量％，、則存在 難以獲得良好的黏著劑組成物的流動性的傾向。 本貫施形態的黏著劑組成物中所含有的（b)自由基聚 合性化合物是指藉由自由基聚合起始劑的作用而產生自由 基聚合的化合物，亦可為藉由賦予光或熱等活化能而使其 自身產生自由基的化合物。（b)自由基聚合性化合物例如 可適宜使用具有藉由乙烯基、（曱基）丙烯醯基、烯丙基、 順丁烯二醯亞胺基等活性自由基而聚合的官能基的化合 物。 (b)自由基聚合性化合物具體而言可列舉：環氧（甲 基)丙烯酸酯（epoxy (meth)acrylate )寡聚物、胺基曱酸醋（甲 基）丙烯酸酯寡聚物、聚醚（曱基）丙烯酸酯（polyether (meth)acrylate)寡聚物、聚酯（曱基）丙烯酸酯（polyester (meth)acrylate)寡聚物等寡聚物；三羥曱基丙烧三（曱基) 20 201204798 丙稀酸醋（trimethylolpropane tri(meth)acrylate )、聚乙二醇 二（曱基）丙烯酸酯（p〇1yethylene di(meth)acrylate)、 聚伸烧基二酵二（曱基）丙稀酸酯（polyalkylene glycol di(meth)acrylate )、（曱基）丙烯酸二環戊烯酉旨 (dicyclopentenyl (meth)acrylate )、（甲基）丙稀酸二環戊烯 氧基乙酯（dicyclopentenyloxy ethyl (meth)acrylate)、新戊 二醇二（曱基）丙稀酸酷（neopentyl glycol di(meth)acrylate )、二季戊四醇六（曱基）丙烯酸酯 (dipentaerythritol hexa(meth)acrylate )、異三聚氰酸 (isocyanuricacid)改質2官能（曱基）丙烯酸酯、異三聚氰 酸改質3官能（甲基)丙浠酸酯、雙笨氧基乙醇第丙婦酸酯 (bisphenoxyethanol fluorene acrylate )、使（曱基）丙烯酸加 成於雙紛苐二縮水甘油醚（biSphen〇i f|u〇rene diglyddyl ether)的縮水甘油基上而成的環氧（曱基）丙烯酸酯、雙苯 氧基乙醇第丙烯酸g旨、使（曱基)丙烯酸加成於雙紛第二縮 水甘油趟的縮水甘油基上而成的環氧（？基)輯酸醋、於 使乙二醇或L成於雙_二縮水甘油_縮水甘油 基上而成的化合物中導入有（甲基）丙烯醯基氧基的化合 物、下述通式（C)及通式（D)所表示的化合物等。In addition, the "critical surface tension (γ.)" in the present embodiment means that an amino phthalate (meth) acrylate which has been formed into a film form is actually added dropwise at 23 ° C for 1 μΐ. The angle formed by the surface of the amino phthalate (mercapto) acrylate after the mixed solution of pure water and wetting tension test Νο.50, 60 (manufactured by Wako Pure Chemical Industries, Ltd.) (contact angle Θ) When the surface tension of each liquid is the X-axis and the cose is the y-axis, the straight line passing through three points becomes the surface tension at Y=1. In addition, when the straight line of the three points obtained by the measurement of the above-mentioned pure water, Νο.50, 60 is γ = 1 and X is a negative value, pure water or a mixed solution for wet tension test No. 60 may be used. The same measurement as described above was carried out by using 1-bromonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.). The value of the surface tension when the straight line obtained by the three points obtained was Y = 1. In the present embodiment, the "weight average molecular weight" and the "number average molecular weight" mean that the gel permeation chromatograph (GPC) is used according to the conditions shown in Table 1, and the standard polystyrene is used. The value obtained by measuring the calibration curve of ethylene. [Table 1] "_ Device___Manufactured by Tosoh Co., Ltd., manufactured by GPC-8020 Tosoh Co., Ltd., manufactured by RI-8020 Pipeline Hitachi Chemical Co., Ltd., Gelpack _ GL-A-160- S + GL-A150-SG2000Hhr ^Sample concentrate _____120 mg/3 ml__ Tetrahydrofuran 60 μΐ __Pressure - Flow rate - -30 kg£W__ 1.00 ml/min 18 201204798 The adhesive composition of this embodiment is used for a first circuit member having a first connection terminal on the main surface and an adhesive composition connected to the first circuit member having the second connection terminal on the main surface, the first circuit member and/or the second circuit member being included The substrate having a glass transition temperature of 2 〇〇〇C or less is composed of a thermoplastic resin, (b) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiation. And (1) the radically polymerizable compound contains a urethane (mercapto) acrylate having a critical surface tension of 25 mN/m to 4 〇 mN/m. The adhesive composition of the present embodiment contains ( a) thermoplastic resin f means having the following properties Resin (polymer): a liquid state which is highly viscous by heating, and is freely deformed by an external force. When it is cooled and the external force is removed, it is hardened while maintaining its shape, and the process is repeated. Further, the resin (polymer Wa) thermoplastic resin containing a reactive functional group having the above-described properties is preferably "p 19 to 19 (rc, more preferably 20 ° C to 170 ° C.) The thermoplastic resin as described above may be used. Use: polyimine resin, polyamide resin, phenoxy resin, (meth)acrylic resin, urethane resin, polyester urethane resin, polyvinyl butyral ( The resin may be used singly or in combination of two or more. Further, the thermoplastic resin may further contain a siloxane or a fluorine substituent. The resin is completely compatible with each other, or is in a state of microphase separation and white turbidity, and can be suitably used. In the case where the adhesive composition is used in the form of a crucible, the above-mentioned thermoplastic 19 201204798 The age of Lai, please (4) I will be good as the composition of the film (4). The average molecular weight of the product is 5_~15_^I, and the average molecular weight is more than the leak, then there is a difficult secret. ^, 150000 = It is difficult to give it and its domain The adhesive composition of the lean form is based on the total amount of the adhesive composition. (a) The content of the thermoplastic resin is preferably 5% by mass to rib%, and more preferably 15% by mass. When the content is less than 5, the adhesive composition is used in a film form, and ° is used to obtain good film formability. If it exceeds 8% by mass, it is difficult to obtain. Good propensity for the fluidity of the adhesive composition. (b) The radically polymerizable compound contained in the adhesive composition of the present embodiment is a compound which generates radical polymerization by the action of a radical polymerization initiator, and may also impart light or heat by imparting A compound that activates energy to generate free radicals by itself. (b) The radically polymerizable compound, for example, a compound having a functional group polymerized by an active radical such as a vinyl group, a (fluorenyl) acrylonitrile group, an allyl group or a maleimide group can be suitably used. (b) The radical polymerizable compound specifically includes an epoxy (meth)acrylate oligomer, an amine phthalic acid (meth)acrylate oligomer, and a polyether. Oligomers such as polyether (meth)acrylate oligomers, polyester (meth)acrylate oligomers; trishydroxypropylpropane tris(sulfonate) 20 201204798 Trimethylolpropane tri(meth)acrylate, p〇1yethylene di(meth)acrylate, poly(diethyl)dithiomethane Polyalkylene glycol di(meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy ethyl (dicyclopentenyloxy ethyl) (meth)acrylate), neopentyl glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, heterotrimerization Isocyanuric acid modified bifunctional (fluorenyl) acrylate, Iso-cyanuric acid modified trifunctional (methyl) propionate, bisphenoxyethanol fluorene acrylate, and (mercapto)acrylic acid added to di-di- diglycidyl ether Epoxy (mercapto) acrylate, bisphenoxyethanol acrylate, and glycidyl acrylate based on the glycidyl group of (biSphen〇if|u〇rene diglyddyl ether) An epoxy (?-based) acid vinegar formed on the glycidyl group of diglycidyl hydrazine, which is introduced into a compound obtained by forming ethylene glycol or L on bis-diglycidyl-glycidyl group. The compound of the acryloyloxy group, the compound represented by the following formula (C) and the formula (D), and the like.

21 201204798 [式（C)中’R及R9分別獨立地表示氫原子或者甲 基，d及e分別獨立地表示1〜8的整數。] [化 10]21 201204798 [In the formula (C), 'R and R9 each independently represent a hydrogen atom or a methyl group, and d and e each independently represent an integer of 1 to 8. ] [Chem. 10]

[式（D)中’ R1Q及R11分別獨立地表示氫原子或者曱 基’ f及g分別獨立地表示0〜8的整數。] 另外，（b)自由基聚合性化合物即便是於單獨在30°c 下靜置的情況為躐（wax)狀、蠛狀、結晶狀、玻璃狀、 粉狀等的無流動性且表現出固體狀態的化合物，亦可無特 別限制地使用。如上所述的（b)自由基聚合性化合物具體 而言可列舉：Ν，Ν·-亞曱基雙丙烯醯胺（N，N，-methylene bisacrylamide)、二丙嗣丙烯醯胺（diacetone acrylamide)、 N-羥曱基丙烯醯胺、N-苯基曱基丙烯醯胺、2-丙烯醯胺-2-曱基丙磺酸、異三聚氰酸三(2-丙烯醯基氧基乙基)醋、N-苯基順丁稀二酿亞胺（N-phenyl maleimide)、N-(鄰曱基苯 基)順丁烯二醯亞胺、N-(間曱基苯基)順丁烯二醯亞胺、 N-(對甲基苯基)-順丁烯二醯亞胺、N_(鄰曱氧基苯基)順丁 稀二醯亞胺、N_(間甲氧基苯基)順丁烯二醯亞胺、N-(對曱 氧基苯基)·順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N- 22 201204798, 乙基順丁稀二醯亞胺、N-辛基順丁稀二醯亞胺、4,4，_二苯 基曱烷雙順丁烯二醯亞胺、間伸苯基雙順丁烯二醯亞胺、 3,3 -—曱基_5,5’·二乙基-4,4’-二苯基曱烷雙順丁烯二醯亞 胺、4-曱基-1，3_伸苯基雙順丁烯二醯亞胺、N_曱基丙烯醯 氧基順丁烯二醯亞胺、N-丙烯醯氧基順丁烯二醯亞胺、丨，6_ 雙順丁烯二醯亞胺_(2,2,4_三曱基）己烷、N-甲基丙烯醯基氧 基丁二酸醯亞胺、N-丙烯醯基氧基丁二酸醯亞胺、曱基丙 烯酸2-萘基酯、丙烯酸2_萘基酯、季戊四醇四丙烯酸酯、 一基伸乙基尿素、二乙烯基伸丙基尿素、曱基丙烯酸 2-聚笨乙烯基乙酯、N_苯基_nl(3_曱基丙烯醯基氧基_2_羥 基丙基)-對苯二胺、N_苯基_N，_(3_丙烯醯基氧基_2_羥基丙 基)-對苯二胺、曱基丙烯酸四曱基哌啶基酯、丙烯酸四曱 基錢基g旨、曱基丙雜五甲基料基自旨、丙烯酸五甲基 娘咬基醋、丙稀酸十八絲a旨、N•第三丁基丙烯醯胺、二 丙酮丙烯醯胺、N_(羥基曱基）丙烯醯胺、下述通式（E)〜 通式（N)所表示的化合物等。 [化 11][In the formula (D), R1Q and R11 each independently represent a hydrogen atom or a thiol group; f and g each independently represent an integer of 0 to 8. In addition, (b) the radically polymerizable compound exhibits no-flow property such as a wax shape, a scorpion shape, a crystal form, a glass form, or a powder form even when it is left alone at 30 ° C. The compound in a solid state can also be used without particular limitation. Specific examples of the (b) radical polymerizable compound as described above include: N, N, -methylene bisacrylamide, diacetone acrylamide, and diacetone acrylamide. , N-hydroxydecyl acrylamide, N-phenylmercapto acrylamide, 2-propenylamine-2-mercaptopropanesulfonic acid, isomeric isocyanuric acid (2-propenyl methoxyethyl) Nitrate, N-phenyl maleimide, N-(o-nonylphenyl) maleimide, N-(m-decylphenyl)-n-butene Dimethyleneimine, N-(p-methylphenyl)-m-butyleneimine, N_(o-nonyloxyphenyl)-cis-butyl diimide, N_(m-methoxyphenyl) cis Butyleneimine, N-(p-methoxyphenyl)·m-butyleneimine, N-methylbutyleneimine, N- 22 201204798, ethyl cis-butyl bismuth Imine, N-octyl cis-butyl diimide, 4,4,-diphenylnonane bis-s-butylene diimide, meta-phenyl bis-bis-succinimide, 3,3 - Mercapto_5,5'·diethyl-4,4'-diphenyldecane bis-s-m-butylene imide, 4-mercapto-1,3_phenylenebis-butylene Amine, N _mercapto propylene oxime oxenyl succinimide, N-propylene decyloxy succinimide, hydrazine, 6 bis bis-succinimide _ (2, 2, 4 _ triterpenes Base) hexane, N-methylpropenyl oxy succinate succinimide, N-propylene decyl oxy succinate, 2-naphthyl methacrylate, 2-naphthyl acrylate , pentaerythritol tetraacrylate, monoethylidene urea, divinyl propyl urea, 2-polystyrene ethyl methacrylate, N_phenyl_nl (3_mercaptopropenyloxy_2_ Hydroxypropyl)-p-phenylenediamine, N_phenyl_N,_(3-propenyloxy-2-hydroxypropyl)-p-phenylenediamine, tetradecylpiperidyl methacrylate, Acrylic acid tetramethyl ketone ke, thiol propylene pentamethyl ruthenium hexahydrate, acrylic acid pentamethyl butyl vinegar, acrylic acid octahydrate, N•t-butyl decyl amide, two Acetone acrylamide, N_(hydroxydecyl) acrylamide, a compound represented by the following formula (E) to formula (N), and the like. [化11]

[式（E)中’h表示1〜1〇的整數。] [化 12] 23 201204798[in the formula (E), 'h represents an integer of 1 to 1 。. ] [Chem. 12] 23 201204798

Hb 13] R12 d13Hb 13] R12 d13

[式（G)中，R12及R13分別獨立地表示氫原子或者曱 基，i表示15〜30的整數。] [化 14]In the formula (G), R12 and R13 each independently represent a hydrogen atom or a fluorenyl group, and i represents an integer of 15 to 30. ] [Chem. 14]

•«•(H) [式（H)中，R14及R15分別獨立地表示氫原子或者曱 基，j表示15〜30的整數。] [化 15] 24 201204798• «•(H) [In the formula (H), R14 and R15 each independently represent a hydrogen atom or a fluorenyl group, and j represents an integer of 15 to 30. ] [Chem. 15] 24 201204798

[式（I)中，R16表示氫原子或者曱基。] [化 16][In the formula (I), R16 represents a hydrogen atom or a fluorenyl group. ] [Chem. 16]

.· .(J) [式（J)中，R17表示氫原子或者曱基，k表示1〜10 的整數。] [化Π] R18 R18 R18(J) In the formula (J), R17 represents a hydrogen atom or a fluorenyl group, and k represents an integer of 1 to 10. ] [Chemistry] R18 R18 R18

[式（K)中，R18表示氫原子或者下述通式（i)或通 式（ii)所表示的有機基，1表示1〜10的整數。] [化 18] 0 ch3 II I 广、In the formula (K), R18 represents a hydrogen atom or an organic group represented by the following formula (i) or formula (ii), and 1 represents an integer of 1 to 10. ] [Chem. 18] 0 ch3 II I wide,

—CH2一CH—CH。—Ο一C一C---CH2 OH 25 201204798 [化 19] Ο (H)—CH 2 —CH—CH. —Ο一C一C---CH2 OH 25 201204798 [Chem. 19] Ο (H)

IIII

-ch2—ch—ch2—o—c—ch=ch2 OH-ch2—ch—ch2—o—c—ch=ch2 OH

[化 20][Chem. 20]

CL) [式（L)中，R19表示氫原子或者下述通式（iii)或通 式（iv)所表示的有機基，m表示1〜10的整數。] [化 21] —ch2- 0 -NH~C~CH=CH [化 22] (iii)CL) [In the formula (L), R19 represents a hydrogen atom or an organic group represented by the following formula (iii) or the formula (iv), and m represents an integer of 1 to 10. ] [Chem. 21] —ch2- 0 —NH~C~CH=CH [Chem. 22] (iii)

Civ) o ch3Civ) o ch3

II I CH2—NH-C—CH=CH2 26 20120479見 [化 23]II I CH2—NH-C—CH=CH2 26 20120479 See [Chemical 23]

[式（Μ)中，r2〇表示氫原子或者曱基。] [化 24] P R21In the formula (Μ), r2〇 represents a hydrogen atom or a fluorenyl group. ] [Chem. 24] P R21

…（N) [式（N)中’R21表示氫原子或者曱基。] 另外’可將屬於（b)自由基聚合性化合物的化合物即 含磷酸基的乙烯基化合物、或選自由N_乙烯基化合物及 N，N-二院基乙烯基化合物所組成組群中的乙烯基系化 合物’與該些化合物m卜的⑻自由絲合性化合物併用。 藉由併用錢縣的乙烯基化合物，可提高骑劑組成物 對金屬基材的黏著性。另外，藉由併用N_乙烯基系化合 物’可提尚黏著劑組成物的交聯率。 27 201204798 仏人1魏基的乙稀基化合物若為具有雜基及乙稀基的 (Q°)所制’較佳為下述通式(〇)〜通式 [化 25] R23 〇lrf十4 七-R22 ·(〇) [式（0)中，R22主_ 氫原子或者甲其 表不（甲基)丙烯醯基氧基，R23表示 外，式中，及&分別獨立地表示1〜8的整數；此 相同，亦可不同。] 彼此、n彼此以及〇彼此分別可 [化 26](N) [In the formula (N), 'R21 represents a hydrogen atom or a fluorenyl group. Further, a compound belonging to the (b) radical polymerizable compound, that is, a phosphate group-containing vinyl compound, or a group selected from the group consisting of an N-vinyl compound and an N,N-divalent vinyl compound may be used. The vinyl compound 'is used in combination with the (8) free silk compound of these compounds. By using a vinyl compound of Qianxian County together, the adhesion of the composition of the rider to the metal substrate can be improved. Further, the crosslinking ratio of the adhesive composition can be improved by using N_vinyl compound in combination. 27 201204798 The ethylene compound of Dean 1 Wei Ke is made of (Q°) having a hetero group and a vinyl group. It is preferably the following formula (〇)~General formula [Chem. 25] R23 〇lrf 十4 七-R22 ·(〇) [In the formula (0), R22 main _ hydrogen atom or methyl group thereof is not (meth) acryl fluorenyloxy group, R23 is represented by a formula, and & An integer of ~8; this is the same or different. ] Each other, n and each other can be different from each other [Chem. 26]

R24-(< CHR24-(< CH

)4-)4-

IIII

[CHg*卜 C—I {CH2)~R24 •(P) [式（p)中，反24 _ 別獨立地表示〗〜8不（甲基)丙烯酿基氧基，p及q分[CHg*卜 C—I {CH2)~R24 •(P) [In the formula (p), the inverse 24 _ is not independently represented] 〜8 is not (meth) acryloyloxy, p and q

此以及q彼此分別可立整數；此外，式令，R24彼此、P彼 [化27] 相同，亦可不同。J 28 201204798 R25- R26 fi叶 ο. οThis and q may each be an integer; in addition, R24 is the same as or different from each other, and may be different. J 28 201204798 R25- R26 fi leaves ο. ο

IIII

~Ρ—〇Η OH (Q) 卜[式（Q)中，R25表示（甲基)丙烯醯基氧基，R26表示 氫原子或者甲基，1*及S分別獨立地表示i〜8的整數；此 外，式中，R26彼此以及r彼此分別可相同，亦可不同。] 含磷酸基的乙烯基化合物具體而言可列舉：曱基丙烯 酸酸式磷氧基乙酯（acid phosphoxy ethyl methacryiate)、 丙烯酸酸式磷氧基乙酯、曱基丙烯酸酸式磷氧基丙酯、酸 式鱗氧基聚氧乙一醇單曱基丙烯酸g旨、酸式構氧基聚氧丙 ^醇單甲基丙烯酸酯、磷酸2,2，-二（甲基)丙烯醯氧基二乙 酉曰、環氧乙烧（ethylene oxide，EO )改質填酸二甲基丙烯 酸酯、磷酸改質環氧丙烯酸酯、磷酸乙烯基酯等。 含磷酸基的乙烯基化合物的調配量較佳為與含磷酸基 的乙烯基化合物以外的（b)自由基聚合性化合物的調配量 獨立地相對於（a)熱塑性樹脂1〇〇質量份，設為〇2質量 份〜300質量份，更佳為設為1質量份〜200質量份，尤佳 為设為1質量份〜5〇質量份，特佳為設為i質量份〜15 質量份。若將含磷酸基的乙烯基化合物的調配量設為小於 0·2質篁份，則存在難以獲得高黏著強度的傾向，若超過 300質虿份’則存在硬化後的黏著劑組成物的物性容易下 降，變得難以確保可靠性的傾向。 另一方面’ 乙烯基系化合物具體而言可列舉：N-乙 29 201204798 烯基口米0坐（N-vinyl imidazole)、N-乙烯基0比咬（N-vinyl pyridine)、N-乙稀基0比π各。定酮（N-vinyl pyrrolidone)、N-乙烯基曱酿胺（N-vinyl formamide)、N-乙稀基己内醯胺 (N-vinyl caprolactam)、4,4'-亞乙稀基雙(N，N-二曱基苯胺) (4,4’-vinylidene bis(N，N-dimethyl aniline) )、N·乙烯基乙醯 胺（N-vinyl acetamide )、N，N-二曱基丙烯醯胺 (N，N-dimethyl acrylamide )、N，N-二乙基丙烯醯胺 (N，N-diethyl acrylamide )等。 相對於（a)熱塑性樹脂1〇〇質量份，除上述符合含磷 酸基的乙稀基化合物的化合物以外的（b)自由基聚合性化 合物的調配量較佳為50質量份〜250質量份，更佳為60 質篁份〜150質量份。若上述調配量小於5〇質量份，則存 在硬化後難以獲得充分的对熱性的傾向，另外，若超過250 質量份，則於作為膜來使用的情況，存在難以獲得良好的 膜形成性的傾向。 作為必需成分，本實施形態的黏著劑組成物含有滿足 臨界表面張力為25 mN/m〜40 mN/m的胺基甲酸酯（曱基) 丙烯I自曰、及下述通式（A)所表示的胺基甲酸酯（甲基) 丙烯酸酯中的一種或兩種條件的胺基甲酸酯（甲基）丙烯酸 酉曰作為（b)自由基聚合性化合物。其中，本實施形態中， 更適宜使用滿足上述條件的絲曱酸㈣雜㉜。此處， 1述通式（A)所表示的胺基甲酸酯（甲基)丙烯酸酯可藉由 脂肪族系二異氰酸酯及聚g旨二醇的縮合反應而獲得。 [化 28] 30~Ρ—〇Η OH (Q) 卜 [In the formula (Q), R25 represents a (meth) acryloyloxy group, R26 represents a hydrogen atom or a methyl group, and 1* and S each independently represent an integer of i8. Further, in the formula, R26 and r may be the same or different from each other. Specific examples of the phosphoric acid group-containing vinyl compound include: acid phosphoxy ethyl methacryiate, phosphatidyl acrylate, and phosphatidyl propyl acrylate. , acid squamous polyoxyethylene monohydric monoglycolic acid g, acid oxy oxy allyl monomethacrylate, 2,2,-di(methyl) propylene oxy oxydiethyl phosphide Ethylene oxide, ethylene oxide (EO) is modified with acid dimethacrylate, phosphoric acid modified epoxy acrylate, vinyl phosphate, and the like. The amount of the phosphoric acid group-containing vinyl compound is preferably set to be equal to (a) the thermoplastic resin in an amount of 1 part by mass based on the amount of the (b) radically polymerizable compound other than the phosphoric acid group-containing vinyl compound. It is more preferably 2 parts by mass to 200 parts by mass, more preferably 1 part by mass to 5 parts by mass, even more preferably 1 part by mass to 15 parts by mass. When the compounding amount of the phosphoric acid group-containing vinyl compound is less than 0.2 mass%, it is difficult to obtain high adhesion strength, and if it exceeds 300 mass parts, the physical properties of the adhesive composition after curing are present. It is easy to fall, and it becomes difficult to ensure the reliability. On the other hand, the vinyl compound is specifically mentioned: N-ethyl 29 201204798 N-vinyl imidazole, N-vinyl pyridine, N-ethylene The base 0 is different from π. N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl caprolactam, 4,4'-ethylenebis(double) N,N-dimethylaniline, N-vinyl acetamide, N,N-dimercaptopropene N,N-dimethyl acrylamide, N,N-diethyl acrylamide, and the like. The amount of the (b) radically polymerizable compound other than the above compound containing the phosphoric acid group-containing compound is preferably 50 parts by mass to 250 parts by mass, based on 1 part by mass of the thermoplastic resin (a). More preferably, it is 60 parts by mass to 150 parts by mass. When the amount is less than 5 parts by mass, it is difficult to obtain sufficient heat resistance after hardening, and when it exceeds 250 parts by mass, it tends to be difficult to obtain good film formability when used as a film. . As an essential component, the adhesive composition of the present embodiment contains a urethane (mercapto) propylene I having a critical surface tension of 25 mN/m to 40 mN/m, and the following general formula (A) The urethane (meth) acrylate of one or both of the urethane (meth) acrylates represented is (b) a radically polymerizable compound. In the present embodiment, it is more preferable to use a silk fibric acid (tetra) 32 which satisfies the above conditions. Here, the urethane (meth) acrylate represented by the above formula (A) can be obtained by a condensation reaction of an aliphatic diisocyanate and a polyg diol. [化 28] 30

201204798 ^ WWW •R5—C*N-R4~ R2 一 R3—〇—〇C=CH2 …(A) 其HU)巾，R2分別獨立地表示氫原子或者甲 ^ "伸乙基、伸丙基、由S-己内S旨的開環化合物所 ;ΤΪΪί圑、或者下述通式（B)所表示的基團，R4表示 = ( (B)所表示的基團，R5表示飽和脂肪族基或者 乾和月曰環基，a表示1〜40的整數。] [化 29] •0如6 0 —〇^~C一R7 - _6 0 "0—^·0—R6^—〇 (B) [式（B)中，R6及R7分別獨立地表示碳數2〜I2的 直鍵或者分支鏈的伸烷基，b表示1〜1〇的整數，c表示1 〜25的整數；此外，式中，R6彼此、R7彼此、b彼此以及 c彼此分別可相同，亦可不同。] 構成上述胺基曱酸酯（曱基）丙烯酸酯的脂肪族系二異 氰酸酯是選自以下化合物中：四亞曱基二異氰酸酯、六亞 曱基一異氰酸酯、離胺酸二異氛酸酯、2-曱基戊烧-l，5-二 異氰酸酯、3-曱基戊烷_ι，5_二異氰酸酯、2,2,4-三曱基六亞 曱基·1，6-二異氰^酸酯、2,4,4_三曱基六亞甲基-1，6-二異氰酸 醋、異佛爾酮二異氰酸酯、二異氰酸環己酯、氫化笨二曱 31 201204798 基二異氰酸醋、氫化二苯基甲烷二異氰 苯二曱基二異氰酸酯等。 虱化一甲基 另外，構成上述胺基甲賴（甲旬崎_的 醇例如可使用脂肪族系聚s旨二醇或芳麵 二，二 佳為使用脂肪族系聚酯二醇。脂肪族系聚酯二“二 下化合财：乙二醇、丙二醇、1，2讷二醇、以丙二醇、 1，3-丁二醇、1，4·丁二醇、新戍二醇、12•戊二醇、丨，4戍二 醇、1，5-戊二醇、2,4_戊二醇、2-曱基_2斗戊二醇、 曱基-2,4-戊二醇、2,2,4-三曱基-1，3-戊二醇、i 2-己二醇 1，5-己二醇、M-己二醇、2,5-己二醇、2_乙基分己二醇、、 2.5- 二曱基·2,5-己二醇、ι，2-辛二醇、认辛二醇、i 7庚二 醇、1，9-壬二醇、U癸二醇、U0·癸二醇、U2癸二醇; 十二烷二醇、頻哪醇（pinacol)、1，4-丁炔二醇、三乙二台 二乙二醇、二丙二醇、環己院二曱醇等飽和的低分子^醇 類；藉由至少1種以上的上述二_與域的反應而獲得 的聚碳酸醋二醇類；藉由以至少1種以上的上述二醇類作 為起始劑，利用公知的方法將環氧乙烷、環氧丙院、表氯 醇（epichlorohydrin)等單體的1種或者其以上進行加成聚 合而獲得的聚醚二醇等二醇類；使己二酸、3_曱基己二酸、 2.2.5.5- 四甲基己二酸、順丁稀二酸、反丁烯二酸、丁二酸、 2,2-—曱基丁二酸、2-乙基-2-曱基丁二酸、2,3·二曱基丁二 酸、乙二酸、丙二酸、甲基丙二酸、乙基丙’二酸、^基丙 二酸、二曱基丙二酸、戊二酸、2·曱基戊二酸、3_曱基戊 一酸、2,2-一曱基戊二酸、3,3-二甲基戊二酸、2,4_二甲基 32 戊一酸、庚二酸、辛二酸、壬二酸、癸二酸等二元酸或者 與该些二元酸對應的酸酐進行脫水縮合而獲得的脂肪族系 聚酯二醇類；或將£_己内酯等環狀酯化合物進行開環聚合 而獲得的脂肪族系聚酯系二醇類。上述二醇類及由二羧醆 所獲得的聚酯二醇類除了單獨使用以外，亦可將^種以上 的聚酯二醇類混合使用。 另外，本實施形態的黏著劑組成物中，就對ρΕΤ、、 PEN等基材的骑強度提高峨㈣言，上述胺基甲酸能 (曱基）丙烯酸酯的重量平均分子量可在8〇〇〇以上且小^ 25000的範圍内自由調整而適當使用。若上述胺基甲酸酉旨 (甲基）丙烯酸酯的重量平均分子量在上述範圍内，則可^ 知，軟性及難力兩者，與PET、pc、pEN等有機基材的 黏著強度提高’可獲得優異的連接可靠性。另外，就更充 分地獲得上述效果的難而言，上述絲甲㈣（曱基 烯酸醋的重量平均分子量更佳為1G_以上且小於 25_。此外’於該重量平均分子量小於8000的情況，存 在無，獲得充分的可撓性的傾向，若為25_以上，則存 在黏著劑組成物的流動性下降的傾向。 、上述胺基甲酸醋（曱基)丙烯酸醋_界表面張力較佳 為25 mN/m〜40 mN/m，更佳為25禮瓜〜％爾瓜。於 胺基甲_旨（甲基)㈣酸§旨_界表面張力為25福/b 4〇 mN/m的情況，與作為被黏附體的PET、PC、PEN的臨 2面張力接近’潤祕提冑，藉此黏著錢提高，可獲 知異的連接可靠性。另外，若該臨界表面張力小於^ 33 201204798 mN/m或者超過40 mN/m，則存在對pet、PC、PEN等的 潤濕性的降低或相容性惡化的顧慮。一般認為，上述胺基 甲酸醋（甲基）丙稀酸醋的臨界表面張力與胺基曱酸醋鍵當 量有關，可藉由改變二醇的數量平均分子量來調整。例如， 若增大二醇的數量平均分子量，則存在胺基曱酸酯鍵當量 減少，臨界表面張力降低的傾向。 另外，以黏著劑組成物總量為基準，上述胺基曱酸酯 (曱基)丙烯酸酯的調配量較佳為5質量％〜95質量％，更 佳為10質量％〜80質量％。於調配量小於5質量〇/。的情 況’存在对熱性容易降低的傾向，若超過95質量％，則存 在當作為膜來使用時膜形成性容易降低的傾向。 本貫施形態的黏著劑組成物中所含有的（c)自由基至 合起始劑可使用自先前以來已知的有機過氧化物或偶氮4 合物4藉由賦予來自外部的能量而產生自由基的化合物 就穩定性、反應性、相溶性的觀點而言，（c)自由基聚^ 起始劑較佳為1分鐘半衰期溫度為9〇<^〜175它，且 量為180〜1，〇〇〇的有機過氧化物。藉由卜分鐘半衰^ 在該範儲存敎性優異，自由絲合^八；^ 可以短時間硬化。 凡刀円： 、w曰网必來节、趄僻則兴髖而言可列舉： 酸1，1，3,3-四曱基丁酯、過氧化二碳酸二(4_ 基)，、過氧化二碳酸二(2_乙基己基)酷、過氧^二 丙苯基醋、過氧化新癸酸U，3,3·四甲基丁s旨、二 過氧化物、過氧化新癸酸⑽己基小甲基乙^過 34 201204798 η第一己酉曰過氧化新癸酸 三丁醋、過氧化-2-乙基己酸日過氧化特戍酸第 基_2,5-二(2-乙基己醯美過2，3,3_四曱基丁酉旨、Μ·二甲 第二己^曰、過軋化_2-乙基己酸第三丁酷、過氧化新;^ 三丁醋、過氧化-2-乙基己酸第 ：=第 甲酸二-第三丁酯、過最仆·、礼化，、虱對本一 ^ ^ ’1 —肀基丁酯、過氣化 :醯^過氧化物、二(4_甲基笨甲醯基)過氧化Γ勿過Lt =丙基早祕第二己醋、第三了基過氧化順丁烯二酸、過 氧化-3,5,5-三甲基己酸第三丁 §旨、過氧化月桂酸第三丁 醋、2,5·二甲基_2,5·二(3·甲基苯甲酿基過氧化）己烧、過氧 化-2-乙基己基單碳酸第三丁g旨、過氧化苯甲酸第三己醋、 2,5-一曱基-2,5·二(苯甲酿基過氧化)己烧、過氧化苯甲酸第 二丁i曰、過氧化二甲基己二酸二丁酯、過氧化正辛酸第三 戊酯、過氧化異壬酸第三戊酯、過氧化苯甲酸第三戊酯等 有機過氧化物；2,2’-偶氮雙-2,4-二甲基戊腈、M,_偶氮雙〇_ 乙醯氧基-1-苯基乙烷）、2,2’-偶氮雙異丁腈、2,2，偶氮雙(2_ 甲基丁腈）、二甲基-2,2’-偶氮雙異丁腈、4,4，_偶氮雙(4_氰基 戊酸）、1，1M禹氮雙(1-環己烷曱腈）等偶氮化合物等。 該些化合物除了單獨使用以外，亦可將2種以上的化 合物混合使用。 另外’（c)自由基聚合起始劑可使用藉由i5〇nm〜75〇 35 201204798 nm的光照射而產生自由基的化合物。作為如上所述的化合 物，例如 Photoinitiation， Photopolymerization and Photocuring，J.-P. Fouassier，HanserPublishers( 1995 年，pl7 〜p35)中記載的a-乙醯胺基苯酮（a-acetaminophenone) 衍生物或膦氧化物衍生物對光照射的感度高，故而更佳。 該些化合物除了單獨使用以外，亦可與上述有機過氧 化物或偶氣化合物混合使用。 相對於（a)熱塑性樹脂1〇〇質量份，上述（c)自由 基聚合起始劑的調配量較佳為0.1質量份〜5〇〇質量份， 更佳為1質量份〜300質量份’尤佳為5質量份〜5〇質量 份，特佳為10質量份〜30質量份。若（c)自由基聚合起 始劑的調配量小於0.1質量份，則存在黏著劑組成物變得 難以充分硬化的傾向，若超過500質量份，則存在儲存穩 定性惡化的傾向。 “ 本實施形態的黏著劑組成物中所含有的（d)導電性粒 子若為於其整體或者表面具有導電性的粒子即可，但於用 於具有連接端子的電路構件的連接的情況，較佳為平均粒 徑小於連接端子間距離。 ⑷導電性粒子可列舉八^八^心焊料等 塑Si:等。另外，亦可為以非導電性的玻璃、陶竟 二Φ ’且於該核上包覆有上述金屬、金屬粒子或 上包ft:二(d)導電性粒子為以塑膠為核且於該 i屬=屬由ί屬r或碳的導電性粒子或熱炫 It况由於错由加熱加壓而具有變形性，因 36 201204798 連接時與電極的接觸面 另外，將該些（d)導^ σ畀性提高，因此較佳。 脂等包覆的微 粒“制電性粒子的表面進而以高分子樹 粒子彼此的接觸引起2增加導電性教子的調配量時的由 性，因此亦可適宜:= 戈者:t極電_ 用。 ㈡者與（d)導電性粒子混合使 就刀放性、導電性的方面而古， 含=== 著劑來使用。月况，黏著劑組成物可適宜作為異向導電性黏 著劑=绿子❾使肖量衫制關，但相對於黏 ^ 01 (vol〇/〇) 〜νο β，更佳為料〇 i VGl%〜1() vg1%。若該 o.i⑽，則存在導電性變低的傾向，若超過30v〇1%，則 ，在變得容易產生電路的短路的傾向。此外，體積百分比 是基於23°C的魏前的各成分的體積而決定，各成分的體 ，可利用比重，由重量換算為體積。另外，亦可將向在量 筒等中加入有不使該成分溶解或膨潤而使該成分充分潤濕 的適當溶劑（水、醇等）者中投入該成分而增加的體積作 為該成分的體積來求出。 另外’本實施形態的黏著劑組成物中，為了控制硬化 速度或賦予儲存穩定性，可添加穩定劑。如上所述的穩定 劑並無特別限制，可使用公知的化合物，較佳為笨酉昆 (benzoquinone )或對苯二紛（hydroquinone )等酿衍生物； 37 201204798 4-甲氧基苯盼（4_methoxyphenol)或4-第三丁基鄰笨二盼 (4-t-butyl catechol)等酚衍生物；2,2,6,6-四甲基哌啶小 氧（2,2,6,6-tetramethyl piperidine-1-oxyl)或 4-經基ό 6- 四甲基D底咬氧等胺基氧（aminoxyl)衍生物；甲基丙婦 酸四甲基哌啶基酯等受阻胺衍生物等。 相對於黏著劑組成物1〇〇質量份，穩定劑的調配量較 佳為0.01質量份〜3〇質量份，更佳為〇 〇5質量份〜1〇質 量份。於調配量小於0·01質量份的情況，變得難以控制硬 化速度或賦予儲存穩定性，於超過3〇質量份的情況，變得 谷易對與其他成分的相溶性造成不良影響。 一另外，本實施形態的黏著劑組成物中，可適宜添加烷 氧基矽烷（alk〇xySilane)衍生物或矽氮烷（silazane)衍= 物所代表的偶合劑、密著提高劑及調平劑等黏著助劑。偶 合劑具體而言較佳為下述通式（R)所表示的化合物除 了單獨使用以外，亦可將2種以上的化合物混合使用。 [化 30] R27 R28-Si—^CH2^R30 ... (r> R29 t 山[式（R)中旧^及…分別獨立地表示氣原子、 石反數1〜5的烷基、碳數1〜5的烷氧基'碳數1〜5的烷氧 基幾基或者芳基，R3。表示(甲基)丙稀醯基乙婦基、異氛 38 201204798 酸醋基、。縁基、Μ基、胺基、甲基胺基、二甲基胺基、 节基胺基、苯基胺基、環己基胺基、嗎琳基、娘唉基、腺 基或者縮水甘油基，t表示1〜10的整數。] P本實施形態的黏著劑組成物亦可以應力緩和及黏著性 提高為目的而併用橡膠成分。所謂橡膠成分，是指在其原 本的狀態下表現出橡膠彈性⑽K62GG)的成分或者^由 反應而表現出橡踢彈性的成分。橡谬成分於室溫⑵。C) 下可為固形亦可為液狀，但就流動性提高的觀點而言 佳為液狀。橡膠成分較佳為具有聚了二稀骨架的化合物。 ΪΓ ί分可具有氰基、絲、雜、（甲基)丙_基或者 ::。另外’就黏著性提高的觀點而言，較佳為於側鏈 t者末端含有作為高極性基的氰基、幾基的橡膠成分。此 脑么=具有聚丁一婦骨架’亦於表現出熱塑性的情況分 H(a)熱塑性樹脂’於表現出自由基聚合性的情況分類 為（b)自由基聚合性化合物。 ，膠成分具體而言可列舉：聚異戊二烯、聚丁二稀、 =端聚丁二烯、羥基末端聚丁二烯、U-聚丁二烯、 2端=聚丁二稀、經基末端以聚丁二稀、丙稀酸 稀橡膠、雜末端苯叫丁二烯橡膠、 Α)丙橡膠，於聚合物末端含有羧基、羥基、(甲 :膠者嗎啉基的丙烯腈-丁二烯橡膠，羧基化腈 ===:=基末端， 另外上述具有馬極性基且於室溫下為液狀的橡膠成 39 201204798 νw 分具體而言可列舉：液狀丙烯腈-丁二烯橡膠，於聚合物末 端含有羧基、羥基、（甲基）丙烯醯基或者嗎啉基的液狀丙 烯腈-丁二烯橡膠、液狀羧基化腈橡膠等；作為極性基的丙 烯腈含量較佳為10質量％〜60質量％。 該些化合物除了單獨使用以外，亦可將2種以上的化 合物混合使用。 另外，本貫施形態的黏著劑組成物中，以應力緩和及 黏著性提高為目的’亦可添加有機微粒子。有機微粒子的 平均粒徑較佳為0·05 μπι〜1·〇 μιη。此外，於有機微粒子包 含上述橡膠成分的情況，分類為橡膠成分而並非有機微粒 子，於有機微粒子包含上述（a)熱塑性樹脂的情況，分類 為（a)熱塑性樹脂而並非有機微粒子。 有機微粒子具體而言可列舉包含以下化合物的有機微 粒子：聚異戊二烯、聚丁二烯、羧基末端聚丁二烯、羥基 末端聚丁二烯、1，2-聚丁二烯、羧基末端^•聚丁二烯、二 烯酸橡膠、苯乙烯-丁二烯橡膠、丙烯腈·丁二烯橡膠，於 聚合物末端含有羧基、羥基、（曱基)丙烯醯基或者^啉基 的丙烯腈-丁二烯橡膠，羧基化腈橡膠、羥基末端聚(氧丙 烯）、烷氧基矽烷基末端聚(氧丙烯）、聚(氧四亞甲基)二醇、 聚烯烴二醇（曱基）丙烯酸烷基酯_ 丁二烯_苯乙烯共聚物、 (曱基)丙烯酸烷基酯·聚矽氧共聚物或者聚矽氧（曱基)丙 酸共聚物或者複合物。 該些有機微粒子除了單獨使用以外，亦可將 的化合物個來㈣。 #UJl 201204798 本實施形態的黏著劑組成物於在常溫下為液狀的情況 可以漿料狀來使用。於在室溫下為固體的情況，除了加熱 而使用以外，亦可使用溶劑而漿料化。可使用的溶劑較;^ 為與黏著劑組成物及添加劑並無反應性且表現出充分的溶 解性的溶劑，較佳為常壓下的沸點為50°C〜150°C的溶 劑。於沸點小於50 C的情況，若於室溫下放置，則存在揮 發的顧慮增多，而變得難以於開放系統中使用的傾向。另 外，若沸點超過150。(：，則存在難以使溶劑揮發，對黏著 後的可靠性造成不良影響的情況增多的傾向。 另外，本實施形態的黏著劑組成物亦可製成膜狀而使 用。可將向黏㈣組成物巾視f要添加溶鮮而成的溶液 塗佈於氟樹脂膜、聚對苯二猶乙二賴、脫模紙等剝離 性基材上，或者使不織布等基材含浸上述溶液而載置於剝 離I1 生基材上，去除溶劑等而製成膜來使用。若以膜的形狀 使用’則就操作性等方面而言更便利。 本實施形態的黏著劑組成物可將加熱及加壓併用而黏 著。加熱溫度較佳為l〇(rc〜20(rc的溫度。壓力較佳為不 對被黏附體造成損傷的範圍，通常較佳為〇1 MPa〜i〇 MPa。該些加熱及加壓較佳為於〇 5秒〜12〇秒的範圍内進 订，於120 C〜19(TC、3 MPa、1〇秒的加熱下亦可使其黏 著。 本實施形態的黏著劑組成物可作為熱膨脹係數不同的 異種被黏附體的黏著劑來使用。具體而言，可作為異向導 電黏著劑、銀㈣、賴等所代表的電路連騎料，晶片 201204798 尺寸封裝（chip scale package，CSP)用彈性體、CSP用底 ，填充材料、引線覆蓋晶片封裝（lead on chip, L〇C)帶 等所代表的半導體元件黏著材料來使用。 本貫施形態的黏著劑組成物是作為用於將主面上具有 第一連接端子的第一電路構件、與主面上具有第二連接端 子的第一電路構件連接的黏著劑組成物來使用。此處，上 述第一電路構件及/或上述第二電路構件是由包含玻璃轉 移溫度為2GGX：以下的熱塑性樹賴基材所構成。玻璃轉 移溫度為20(TC以下的熱塑性樹脂並無特別限定，例如可 歹J牛t對曱g复乙—g旨、聚碳酸目旨及聚萘二甲酸乙二醋 等。 姐^接著’對使用上述本實施形態的黏著劑組成物的電與 ^件的連接結構體進行朗。圖丨是表示使財實施形屬 的ί者劑城物的電路構件的連接結構體的-實施形㈣ 面圖。圖2疋表不製作圖〗所示的電路構件的連為 j體^的第-電路構件、第二電路構件及黏著劑㈣ 物的不意剖面圖。 =所示的電路構件的連接結構體觸包括：於第一 路構二面3U上具有第—連接端子32的第一電 =件30、於第二電路基板41的主面化上具有第 接&子42的第二電路構件 第二連接端子42對二件4〇以及以第-連接端子32與 …與第二電路基^方式將第一電路基板31的主面 ^ 1的主面41a連接的連接構件1〇c。 第一連接W 32與第二連接端子幻是藉由相互接觸而電 42 201204798 性連接。另外，連接構件1〇c包 成物ίο的硬化物。 貫⑪形忍的點著劑組 方式來製I。的電路構件的連接結構體100例如可以如下 首先’如圖2所示，準借笛— 構件40及成形為膜狀的點著劑組成，件30三第二電路 劑組成物10載置於第二電侔 。接著，將黏著 子42的主面41aJl、隹2構件4〇的形成有第二連接端 接端子32與第二連接端子且成物1〇上以第一連 一邊絲路構件3g及第二電路構件4〇， h、4la向垂直方向加壓/於H硬化’同時對主面 路構件40之門带占、Φ & * 、 電路構件3〇及第二電 連接結構體1二〇。構件1GC，獲得圖1的電路構件的 黏英，U3是表示使用含有⑷導電性粒子的本實施形態的 意剖面ΐ成構件的連接結構體的-實施形態的示 構體之前的第一；路Π3所示的電路構件的連接結 (含有導電U r電路構件及黏著劑組成物 负等電性粒子）的示意剖面圖。 電路不的電路構件的連接結構體綱味：於第一 路構ί 30 1的ί面31a上具有第—連接端子32的第一電 接端子42 2第二電路基板41的主面化上具有第二連 第二、車垃^一電路構件务以及以第一連接端子32與 端子42相對向的方式將第—電路絲η的主面 43201204798 ^ WWW • R5—C*N-R4~ R2—R3—〇—〇C=CH2 (A) HU) towel, R2 independently represents a hydrogen atom or a ^ " a group represented by a ring-opening compound of S-hexene; or a group represented by the following formula (B), R4 represents a group represented by (B), and R5 represents a saturated aliphatic group. Or dry and lunar ring base, a represents an integer from 1 to 40.] [Chem. 29] • 0 such as 6 0 - 〇 ^ ~ C - R7 - _6 0 " 0 - ^ · 0 - R6 ^ - 〇 (B [In the formula (B), R6 and R7 each independently represent a straight or a branched alkyl group having a carbon number of 2 to 12, b represents an integer of 1 to 1 ,, and c represents an integer of 1 to 25; In the formula, R6 and R7, and b and c may be the same or different from each other.] The aliphatic diisocyanate constituting the above amino phthalate acrylate is selected from the following compounds: Mercapto diisocyanate, hexamethylene monoisocyanate, leucine diisocyanate, 2-mercaptobutyl-l,5-diisocyanate, 3-decylpentane_ι, 5-diisocyanate, 2,2,4-tridecylhexamethylene-based 1,6- Isocyanurate, 2,4,4-tridecylhexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated stupid 201204798 base diisocyanate, hydrogenated diphenylmethane diisocyanate diisocyanate, etc. Deuterated monomethyl group, in addition to the above-mentioned aminocarbazide (Azinaki_ alcohol), for example, an aliphatic system can be used. Poly s diol or fragrant surface 2, the second is to use aliphatic polyester diol. Aliphatic polyester 2 "two under the chemistry: ethylene glycol, propylene glycol, 1,2 hexane, propylene glycol, 1,3-butanediol, 1,4-butanediol, neodecanediol, 12•pentanediol, hydrazine, 4-decanediol, 1,5-pentanediol, 2,4-pentanediol, 2-mercapto-2 piperidinol, mercapto-2,4-pentanediol, 2,2,4-tridecyl-1,3-pentanediol, i2-hexanediol 1,5- Hexanediol, M-hexanediol, 2,5-hexanediol, 2-ethylhexahexanediol, 2.5-dimercapto-2,5-hexanediol, iota, 2-octanediol, Octanediol, i 7 heptanediol, 1,9-nonanediol, U-decanediol, U0·decanediol, U2 nonanediol; dodecanediol, pinacol, 1, 4-butyne a saturated low molecular weight alcohol such as an alcohol, a triethylene diethylene glycol, a dipropylene glycol or a cyclohexanol; a polycarbonate obtained by reacting at least one of the above two domains with a domain One or more kinds of monomers such as ethylene oxide, propylene oxide, and epichlorohydrin are used in a known method by using at least one of the above-mentioned diols as a starting agent. a glycol such as a polyether diol obtained by addition polymerization; adipic acid, 3-mercapto adipic acid, 2.2.5.5-tetramethyladipate, cis-succinic acid, and anti-butene Acid, succinic acid, 2,2-mercaptosuccinic acid, 2-ethyl-2-mercaptosuccinic acid, 2,3, dimercaptosuccinic acid, oxalic acid, malonic acid, A Malonic acid, ethyl propyl diacid, methacrylic acid, dimercaptomalonic acid, glutaric acid, 2, mercapto glutaric acid, 3 mercaptoic acid, 2, 2- Dibasic acids such as decyl glutaric acid, 3,3-dimethylglutaric acid, 2,4-dimethyl pentanoic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or the like An aliphatic polyester obtained by dehydration condensation of an acid anhydride corresponding to the dibasic acid An aliphatic polyester-based diol obtained by subjecting a cyclic ester compound such as £_caprolactone to ring-opening polymerization. The above-mentioned diols and polyester diols obtained from dicarboxy fluorene may be used alone or in combination of a plurality of polyester diols. Further, in the adhesive composition of the present embodiment, the riding strength of the base material such as ρΕΤ or PEN is improved. (IV), the weight average molecular weight of the above-mentioned amino formic acid (mercapto) acrylate may be 8 〇〇〇. It is freely adjusted in the range of the above and small ^ 25000 and is used as appropriate. When the weight average molecular weight of the above-mentioned carbamic acid methacrylate (meth) acrylate is within the above range, it is understood that both the softness and the hardness are improved with the adhesion strength to an organic substrate such as PET, pc, or pEN. Excellent connection reliability. Further, in view of the difficulty in obtaining the above effects more fully, the weight average molecular weight of the above-mentioned silk (4) (mercaptoic acid vinegar is more preferably 1 G_ or more and less than 25 mm. Further, in the case where the weight average molecular weight is less than 8,000, If there is no, sufficient flexibility is obtained, and if it is 25 or more, the fluidity of the adhesive composition tends to decrease. The above-mentioned amino formate vinegar (acrylic acid vinegar) vinegar _ 表面 surface tension is preferably 25 mN / m ~ 40 mN / m, more preferably 25 cucurbits ~ % ergua. Aminomethyl _ (methyl) (tetra) acid § _ boundary surface tension of 25 b / b 4 〇 mN / m In the case, the tension between the two sides of the PET, PC, and PEN as the adherend is close to that of the moisturizing, so that the adhesion is improved, and the reliability of the connection can be obtained. In addition, if the critical surface tension is less than ^ 33 201204798 When mN/m or more than 40 mN/m, there is a concern that the wettability of pet, PC, PEN, etc. is lowered or the compatibility is deteriorated. It is generally considered that the above-mentioned amino formate vinegar (meth) acrylate vinegar The critical surface tension is related to the amine bismuth vinegar bond equivalent, which can be changed by changing the number of diols. For example, when the number average molecular weight of the diol is increased, the amine phthalate bond equivalent decreases and the critical surface tension tends to decrease. Further, the above amine group is based on the total amount of the adhesive composition. The compounding amount of the phthalic acid ester (mercapto) acrylate is preferably from 5% by mass to 95% by mass, more preferably from 10% by mass to 80% by mass. In the case where the compounding amount is less than 5 mass%, the presence of heat is easy. When the content is more than 95% by mass, the film formability tends to be lowered when used as a film. The (c) radical-initiating agent contained in the adhesive composition of the present embodiment may be used. The use of an organic peroxide or an azo compound 4 known from the prior art to impart a radical by imparting energy from the outside, from the viewpoint of stability, reactivity, and compatibility, (c) a radical Preferably, the poly-starting agent has a one-minute half-life temperature of 9 〇<^~175, and the amount is 180 〜1, an organic peroxide of hydrazine. Excellent sex, free silk combined ^ eight; ^ can be hard for a short time Where the knife 円:, w曰 net must come to the festival, the singularity of the hip can be cited: acid 1,1,3,3-tetradecyl butyl acrylate Di(2-ethylhexyl) peroxydicarbonate, peroxydiphenylene vinegar, peroxy neodecanoic acid U, 3,3·tetramethyl butyl s, diperoxide, peroxidic neodymium Acid (10) hexyl small methyl ethyl group ^ 34 201204798 η first hexanyl peroxide neodecanoic acid tributyl vinegar, peroxy-2-ethylhexanoic acid peroxidic tetraic acid base 2,5-two ( 2-ethylhexylamine has 2,3,3_tetradecyl butyl hydrazine, Μ·dimethyl dimethyl hexene oxime, over-rolled _2-ethylhexanoic acid, third butyl, peroxidation; Tributyl vinegar, peroxy-2-ethylhexanoic acid: = = di-tert-butyl formate, the most servant, ritual, 虱, 本, ^ ^ '1 - decyl butyl acrylate, pervaporation :醯^Peroxide, bis(4_methyl benzoyl) perylene peroxide, do not pass Lt = propyl premature second vinegar, third thioperoxy acid, peroxy-3 , 5,5-trimethylhexanoic acid, third butyl, oxidized lauric acid, third vinegar, 2,5· dimethyl 2,5·bis (3·methyl benzoyl peroxide) already , tert-butyl peroxy-2-ethylhexyl monocarbonate, third hexanoic acid benzoic acid, 2,5-monodecyl-2,5·di (benzoyl peroxide) hexane, Dibutyl benzoate, dibutyl dimethyl adipate, third amyl peroxyoctanoate, third amyl peroxyisophthalate, third amyl peroxide, etc. Organic peroxide; 2,2'-azobis-2,4-dimethylvaleronitrile, M,_azobisindole_ethetoxy-1-phenylethane), 2,2'- Azobisisobutyronitrile, 2,2, azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4,-azobis(4-cyano An azo compound such as valeric acid) or 1,1 M bis (i-cyclohexane phthalonitrile). These compounds may be used alone or in combination of two or more kinds of compounds. Further, the '(c) radical polymerization initiator may be a compound which generates a radical by irradiation with light of i5〇nm~75〇 35 201204798 nm. As a compound as described above, for example, a-acetaminophenone derivative or phosphine described in Photoinitiation, Photopolymerization and Photocuring, J.-P. Fouassier, Hanser Publishers (1995, pl7 to p35) The oxide derivative is more sensitive to light irradiation, and thus is more preferable. These compounds may be used in combination with the above organic peroxide or azo compound, in addition to being used singly. The amount of the (c) radical polymerization initiator to be added is preferably from 0.1 part by mass to 5 parts by mass, more preferably from 1 part by mass to 300 parts by mass, based on 1 part by mass of the (a) thermoplastic resin. It is particularly preferably 5 parts by mass to 5 parts by mass, particularly preferably 10 parts by mass to 30 parts by mass. When the amount of the (c) radical polymerization initiator is less than 0.1 part by mass, the adhesive composition tends to be insufficiently cured. When the amount exceeds 500 parts by mass, the storage stability tends to be deteriorated. " (d) the conductive particles contained in the adhesive composition of the present embodiment may be particles having conductivity on the whole or the surface thereof, but in the case of connection for a circuit member having a connection terminal, Preferably, the average particle diameter is smaller than the distance between the connection terminals. (4) The conductive particles may be plastic Si or the like such as eight-eight-heart solder, or may be non-conductive glass or ceramics. The above-mentioned metal, metal particles or top-coated ft: two (d) conductive particles are made of plastic as the core and the conductive particles or the heat-emitting state of the genus It is deformable by heating and pressurization, and it is preferable to increase the (d) conductivity of the contact surface with the electrode at the time of connection of 201204798. The particles coated with grease or the like are "electric particles." Further, when the surface of the polymer tree particles is brought into contact with each other to cause an increase in the amount of the conductive teaching material, it is also preferable to use: = ge: t electric _. (2) The mixture with (d) conductive particles is used in terms of knife release property and electrical conductivity, and is used with === agent. In the case of the month, the adhesive composition can be suitably used as an anisotropic conductive adhesive = green ❾ ❾ 肖 肖 肖 , , , , , , , , , , , , , , , , , , , , , , , , , %~1() vg1%. When this o.i (10), the electrical conductivity tends to be low, and if it exceeds 30 v 〇 1%, the circuit tends to be short-circuited. Further, the volume percentage is determined based on the volume of each component of Wei before 23 ° C, and the body of each component can be converted into a volume by weight. In addition, a volume which is added to a measuring cylinder or the like by adding a suitable solvent (water, alcohol, or the like) which does not dissolve or swell the component to sufficiently wet the component, may be added as a volume of the component. Find out. Further, in the adhesive composition of the present embodiment, a stabilizer may be added in order to control the curing rate or to impart storage stability. The stabilizer as described above is not particularly limited, and a known compound can be used, preferably a benzoquinone or a hydroquinone-derived derivative; 37 201204798 4-methoxyphene (4_methoxyphenol) Or a phenol derivative such as 4-t-butyl catechol; 2,2,6,6-tetramethylpiperidineoxygen (2,2,6,6-tetramethyl) Piperidine-1-oxyl) or an aminoxyl derivative such as 4-carboyl 6-tetramethyl D-bottom oxygen; a hindered amine derivative such as tetramethylpiperidyl methyl propyl benzoate or the like. The amount of the stabilizer is preferably 0.01 parts by mass to 3 parts by mass, more preferably 5 parts by mass to 1 part by mass, based on 1 part by mass of the adhesive composition. When the amount is less than 0. 01 parts by mass, it becomes difficult to control the hardening rate or to impart storage stability. When the amount is more than 3 parts by mass, it becomes difficult to adversely affect the compatibility with other components. Further, in the adhesive composition of the present embodiment, a coupling agent, a adhesion enhancer, and a leveling agent represented by an alkoxysilane (alk〇xySilane) derivative or a silazane derivative may be suitably added. Adhesive additives such as agents. In particular, the compound represented by the following formula (R) is preferably used alone or in combination of two or more kinds of compounds. R27 R28-Si—^CH2^R30 ... (r> R29 t Mountain [Formula (R) in the old ^ and ... respectively represent the gas atom, the inverse of the alkyl group 1~5, carbon Alkoxy groups of 1 to 5, alkoxy groups or aryl groups having 1 to 5 carbon atoms, and R3, which means (meth) propyl sulfanyl group, heterocyclic 38 201204798 acid vinegar group, fluorenyl group , mercapto, amine, methylamino, dimethylamino, benzylamino, phenylamino, cyclohexylamine, morphine, sulfhydryl, glandyl or glycidyl, t In the adhesive composition of the present embodiment, the rubber component may be used together for the purpose of stress relaxation and adhesion improvement. The rubber component means rubber elasticity (10) K62GG in its original state. A component or a component that exhibits rubbery elasticity by reaction. The rubber component is at room temperature (2). C) The solid form or the liquid may be liquid, but it is preferably liquid in view of improvement in fluidity. The rubber component is preferably a compound having a polydisperse skeleton. ΪΓ 分 can have cyano, silk, hetero, (meth) propyl- or ::. Further, from the viewpoint of improving the adhesion, it is preferred to contain a rubber component having a cyano group or a few groups as a highly polar group at the terminal of the side chain t. In the case where the polymer exhibits thermoplasticity, the H(a) thermoplastic resin is classified as (b) a radically polymerizable compound in the case of exhibiting radical polymerizability. Specific examples of the gum component include polyisoprene, polybutadiene, = terminal polybutadiene, hydroxyl terminated polybutadiene, U-polybutadiene, 2 terminal = polybutadiene, and The base end is made of polybutylene dilute, acrylic acid dilute rubber, hetero-terminal benzene is called butadiene rubber, Α) propylene rubber, and contains carboxyl group, hydroxyl group at the end of the polymer, (A: acrylonitrile-butyl group of morpholinyl group) Diene rubber, carboxylated nitrile ===:= base end, in addition to the above-mentioned rubber having a polar group and liquid at room temperature, 39 201204798 νw, specifically, liquid acrylonitrile-butadiene Rubber, liquid acrylonitrile-butadiene rubber containing a carboxyl group, a hydroxyl group, a (meth)acrylonyl group or a morpholinyl group at the polymer terminal, a liquid carboxylated nitrile rubber, etc.; a acrylonitrile content as a polar group is preferred The compound is used in an amount of from 10% by mass to 60% by mass. In addition, the two or more compounds may be used in combination, and the adhesive composition of the present embodiment is intended to improve stress relaxation and adhesion. 'Also can add organic microparticles. The average particle size of organic microparticles is better than In the case where the organic fine particles include the rubber component, the rubber component is classified as a rubber component and is not an organic fine particle, and when the organic fine particle contains the (a) thermoplastic resin, it is classified as (a). The thermoplastic resin is not an organic fine particle. Specific examples of the organic fine particles include organic fine particles containing polyisoprene, polybutadiene, carboxyl terminal polybutadiene, hydroxyl terminal polybutadiene, 1,2- Polybutadiene, carboxy terminal ^• polybutadiene, dienoic rubber, styrene-butadiene rubber, acrylonitrile butadiene rubber, containing carboxyl, hydroxyl, (mercapto) acrylonitrile at the end of the polymer Acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl terminated poly(oxypropylene), alkoxyalkyl end poly(oxypropylene), poly(oxytetramethylene) glycol, Polyolefin diol (mercapto) alkyl acrylate _ butadiene _ styrene copolymer, alkyl (meth) acrylate, poly aroxy copolymer or poly fluorene (mercapto) propionic acid copolymer or composite The organic micro In addition to the use of the compound, it is also possible to use the compound (IV). #UJl 201204798 The adhesive composition of the present embodiment can be used in the form of a slurry when it is liquid at normal temperature. It is solid at room temperature. In other cases, it may be slurried by using a solvent in addition to heating. The solvent which can be used is a solvent which is not reactive with the adhesive composition and the additive and exhibits sufficient solubility, and is preferably a solvent. The solvent having a boiling point of 50 ° C to 150 ° C. When the boiling point is less than 50 C, if it is left at room temperature, there is a concern that volatilization may increase, and it becomes difficult to use it in an open system. When the boiling point exceeds 150. (:, there is a tendency that it is difficult to volatilize the solvent, and the reliability after adhesion is increased. Further, the adhesive composition of the present embodiment can also be used in the form of a film. The solution to be added to the adhesive (four) composition can be applied to a release substrate such as a fluororesin film, a polyethylene terephthalate or a release paper, or a substrate such as a nonwoven fabric. The solution is impregnated and placed on a release I1 substrate, and a solvent or the like is removed to form a film. If it is used in the shape of a film, it is more convenient in terms of operability and the like. The adhesive composition of the present embodiment can be adhered by heating and pressurization. The heating temperature is preferably 〇1 (rc~20 (the temperature of rc. The pressure is preferably a range which does not cause damage to the adherend, and is usually preferably 〇1 MPa to i〇MPa. The heating and pressurization are preferably It can be ordered in the range of 5 seconds to 12 seconds, and can be adhered to it under heating of 120 C to 19 (TC, 3 MPa, and 1 sec. The adhesive composition of the present embodiment can be used as a coefficient of thermal expansion. The heterogeneous type is used as an adhesive for the adhesive body. Specifically, it can be used as an electrical circuit for anisotropic conductive adhesive, silver (four), Lai, etc., wafer 201204798 elastomer for chip scale package (CSP) The CSP has a bottom, a filling material, a lead-on-chip (L〇C) tape, and the like, and is used as a semiconductor element adhesive material. The adhesive composition of the present embodiment is used as a main surface. a first circuit member having a first connection terminal and an adhesive composition connected to a first circuit member having a second connection terminal on the main surface. Here, the first circuit member and/or the second circuit member Is the temperature of the glass containing the transfer The degree is 2GGX: the following thermoplastic tree base material is formed. The glass transition temperature is 20 (the thermoplastic resin of TC or less is not particularly limited, and for example, it can be 牛J 牛 曱 曱 复 复 — — 、 、 、 聚 聚 聚 聚 聚 聚 聚Ethyl diacetate or the like. Sister ^ then 'to the connection structure of the electric and the component using the adhesive composition of the above-described embodiment, the figure is a representation of the property of the invention. The fourth embodiment of the connection structure of the circuit member is shown in Fig. 2. The second circuit member, the second circuit member, and the adhesive (four) of the circuit member shown in Fig. 2 are not formed. The cross-sectional view of the connecting structure of the circuit member shown includes: the first electric component 30 having the first connection terminal 32 on the first surface 3U of the first path, and the main surface of the second circuit substrate 41 The second circuit member second connection terminal 42 having the first & sub-42 has two pairs of 4 〇 and the main surface of the first circuit substrate 31 by the first connection terminal 32 and the second circuit substrate The connecting member 1〇c connected to the main surface 41a. The first connection W 32 and the second connection terminal The connection member 1〇c is formed into a cured product by the contact with each other. In addition, the connection structure 100 of the circuit member can be manufactured by the method of the 11-shaped tolerant point group. First, as shown in Fig. 2, the quasi-float-member 40 and the dot-forming agent formed into a film are formed, and the third circuit composition 10 of the member 30 is placed on the second electric cymbal. Next, the adhesive 42 is placed. The main surface 41aJ1 and the 隹2 member 4 are formed with the second connection terminal 32 and the second connection terminal, and the first connection side wire member 3g and the second circuit member 4 are formed on the object 1 〇, h, 4la is pressed in the vertical direction/hardened by H' while the gate of the main surface member 40 is occupied, Φ & *, the circuit member 3A and the second electrical connection structure 1 are two turns. The member 1GC obtains the viscosity of the circuit member of Fig. 1, and U3 is the first before the display structure using the connection structure of the intentional cross-section forming member of the present embodiment containing the (4) conductive particles; A schematic cross-sectional view of the connection of the circuit member shown in FIG. 3 (containing the conductive U r circuit member and the negatively-charged particles of the adhesive composition). The connection structure of the circuit member in which the circuit is not provided: the first electrical connection terminal 42 having the first connection terminal 32 on the ί face 31a of the first path structure 30 2 has the main surface of the second circuit substrate 41 The second connecting second, the second circuit member, and the main surface 43 of the first circuit wire η in such a manner that the first connecting terminal 32 faces the terminal 42

201204798 ^ L 31a與第二電路基板41的主面仏連接的連 此外，連接構件20C是於黏著劑組成物的導電性 的成㈣中分散有導電性粒子22_著劑組成物的硬 化物（即’於㈣劑、喊躺導電性粒子以 化物21C中分散有導電性粒子22的硬化物），於== 一連接鈿子32與第二連接端子42之間，導電性粒子η 與兩連接端子接觸，藉此經由導電性粒子22而使 子電性連接。 圖3所示的電路構件的連接結構體2〇〇例如可如圖4 所示，準備第一電路構件30、第二電路構件4〇及成形為 膜狀的黏著劑組成物20,利用與獲得上述電路構件的連接 結構體100的方法相同的方法來製造。 此處，第一電路構件30及第二電路構件4〇中的至少 一者是由含有玻璃轉移溫度為200°C以下的熱塑性樹脂的 基材所構成。即，第一電路基板31及第二電路基板41中 的至少一者含有玻璃轉移溫度為200。(：以下的熱塑性樹 月曰。此處’玻璃轉移溫度為200°C以下的熱塑性樹脂較佳 為選自由聚對笨二曱酸乙二酯、聚碳酸酯及聚萘二曱酸乙 二酯所組成組群中的至少1種。若第一電路構件30及第二 電路構件40中的至少一者為由含有選自由聚對苯二甲酸 乙二酯、聚碳酸酯及聚萘二曱酸乙二酯所組成組群中的至 少1種的基材所構成的電路構件，則與黏著劑組成物的潤 濕性提尚，黏著強度進一步提高。因此，此種電路構件的 連接結構體可獲得更優異的連接可靠性。 44 201204798 ----·χ·-Ι 此外，第一電路構件30及第二電路構件40中的一者 可由不含選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二 曱酸乙二酯所組成組群中的至少1種的基材所構成。形成 此種電路構件的基材可使用：半導體、玻璃、陶竟等包含 無機物的基材，聚醢亞胺等包含有機物的基材，玻璃/環氧 等組合有無機物與有機物的基材等。 另外，第一連接端子32及第二連接端子42中的至少 一者較佳為由選自由ΙΤΟ及ΙΖΟ所組成組群中的至少1種 所構成。ΙΤΟ及ΙΖΟ由於容易進行蝕刻，圖案加工性優異， 故而適宜作為連接端子。並且，藉由使用本實施形態的黏 著劑組成物，可充分抑制由ΙΤ0及/或ΙΖ〇構成的連接端 子的腐蝕。 此外，第一連接端子32及第二連接端子42中的一者 或=者可由ΙΤΟ及ΙΖΟ以外的材料所構成。如上所述的連 接端子可使用包含銅、銀、铭、金、纪、錄及該些金屬的 合金等金屬的連接端子。 此外，作為連接構件來使用的本實施形態的黏著劑組 成物無需完全硬化（於規定硬化條件下可達成的最高度的 硬化），只要產生上述特性，則亦可為部分硬化的狀態。 實例 以下，基於貧例對本實施形態進行具體說明，但本實 施形態並不限定於此。 〈熱塑性樹脂〉 (苯氧基樹脂的調整） 45 201204798201204798 ^ L 31a is connected to the main surface of the second circuit board 41. The connecting member 20C is a cured product in which the conductive particles 22_the composition of the composition are dispersed in the conductivity (4) of the adhesive composition. That is, 'the (four) agent, the cured material in which the conductive particles 22 are dispersed in the conductive particles 21C), and the conductive particles η and the two are connected between == one of the connection pairs 32 and the second connection terminal 42. The terminals are in contact with each other, whereby the sub-electrodes are electrically connected via the conductive particles 22 . The connection structure 2 of the circuit member shown in FIG. 3 can be prepared, for example, as shown in FIG. 4, by preparing the first circuit member 30, the second circuit member 4, and the adhesive composition 20 formed into a film shape. The above-described circuit member is connected to the structural body 100 by the same method. Here, at least one of the first circuit member 30 and the second circuit member 4 is made of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C or less. That is, at least one of the first circuit board 31 and the second circuit board 41 contains a glass transition temperature of 200. (: The following thermoplastic tree 曰. Here, the thermoplastic resin having a glass transition temperature of 200 ° C or less is preferably selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. At least one of the group consisting of at least one of the first circuit member 30 and the second circuit member 40 is selected from the group consisting of polyethylene terephthalate, polycarbonate, and polynaphthalene The circuit member comprising at least one of the substrates of the ethylene glycol group is improved in wettability with the adhesive composition, and the adhesion strength is further improved. Therefore, the connection structure of the circuit member can be Further excellent connection reliability is obtained. 44 201204798 ----·χ·-Ι In addition, one of the first circuit member 30 and the second circuit member 40 may be selected from the group consisting of polyethylene terephthalate, A substrate comprising at least one of a group consisting of polycarbonate and polyethylene naphthalate. The substrate on which the circuit member is formed may be a substrate containing an inorganic material such as a semiconductor, a glass or a ceramic. , organic substrate, polyimide, etc., glass/epoxy Further, at least one of the first connection terminal 32 and the second connection terminal 42 is preferably composed of at least one selected from the group consisting of ruthenium and iridium. Further, since it is easy to perform etching and has excellent pattern workability, it is suitable as a connection terminal. Further, by using the adhesive composition of the present embodiment, corrosion of the connection terminal made of ΙΤ0 and/or ΙΖ〇 can be sufficiently suppressed. One or the other of the first connection terminal 32 and the second connection terminal 42 may be made of materials other than ΙΤΟ and 。. The connection terminals as described above may be used including copper, silver, Ming, Jin, Ji, and In addition, the adhesive composition of the present embodiment used as the connecting member does not need to be completely cured (the highest degree of hardening which can be achieved under predetermined curing conditions), and as long as the above characteristics are produced, The embodiment may be partially hardened. EXAMPLES Hereinafter, the present embodiment will be specifically described based on a poor example, but the embodiment is not limited thereto. Thereto. <Thermoplastic Resin> (adjustment of phenoxy resin) 45 201 204 798

L f苯氧基樹脂（東都化成股份有限公司製造，YP-50 (商品名））40 f量份溶解於甲基乙基則 中製 成固體成分為40質量％的溶液。 (聚酯胺基甲酸酯樹脂的準備） 聚醋胺基甲_旨樹脂（東洋紡股份有限公司製造， UR 1400 (商品名））是使用樹脂成分為％質量％的甲基 乙基酮與甲笨的1 : 1混合溶劑溶解品。 (胺基甲酸酯樹脂的合成） 、、=具㈣拌機、溫度計、絲有氣化㉟乾燥管的 回流 V部s、氮氣導A管的反應容时，將重量平均分子量為 2000的聚己二酸丁二醋二醇45〇質量份、重量平均分子量 為2000的聚氧四亞甲基二醇45〇質量份、及丨，4 丁二醇 綱質量份於甲基乙基酮4_質量份中均勻混合，添加二 苯基曱烷二異氰酸酯390質量份，於7〇。(：下反應，獲得重 量平均分子量為35萬的胺基甲酸酯樹脂。 〈自由基聚合性化合物〉 (胺基甲酸酯丙烯酸酯（L-1600S)的準備） 準備重：£平均分子3:為15000且臨界表面張力為a mN/m的胺基甲酸酯丙烯酸酯（Mitsui Polyurethane股份有 限公司製造’ L-1600S (商品名））。另外，l_16〇〇s為使用 醚系二醇的化合物，並不滿足上述通式（A)。 (胺基曱酸酯丙烯酸酯（PE-UA1)的合成） 於具備攪拌機、溫度計、安裝有氣化鈣乾燥管的回流 冷卻管、氮氣導入管的反應容器中，投入數量平均分子量 46 201204798 為2000的聚(3_曱基戊烷己二酸酯）二醇（脂肪族聚酯二 醇’ Kuraray股份有限公司製造，Kurap〇i p_2〇 1 〇 (商品名）） 2000質量份（1.00莫耳）、二月桂酸二丁基錫（Aldrich股 份有限公司製造）5.53質量份。充分導入氮氣後，加熱至 70°C〜75°C ’然後以3小時均勻滴加二環己基曱烷4,4，-二 異氧酸Sa (脂肪族二異氰酸醋，Evonik Degussa公司製造’ VESTANATH12DMI (商品名））787 質量份（3.00 莫耳）’ 使其反應。滴加完畢後繼續反應約1〇小時。接著向其中投 入丙烯酸2-羥基乙酯（Aldrich股份有限公司製造）238質 量份（2.05莫耳）、對苯二酚單曱醚（Aldrich股份有限公 司製造）0.53質量份，進而反應10小時，藉由紅外線 (infrared，IR)測定來確認異氰酸酯消失而結束反應，獲 得胺基曱酸酯丙烯酸酯。所得的胺基曱酸酯丙浠酸酯 (PE-UA1)的臨界表面張力為3〇mN/m，重量平均分子量 為15300。另外，PE-UA1是使用聚酯二醇的化合物，滿足 上述通式（A)。 (胺基甲酸酯丙烯酸酯（PE-UA2)的合成） 於具備攪拌機、溫度計、安裝有氣化鈣乾燥管的回流 冷卻管、氮氣導入管的反應容器中，投入數量平均分子量 為2000的聚己内酯二醇（脂肪族聚酯二醇，商品名：piaccei 220EB，Daicel化學工業股份有限公司製造）2000質量份 (1.00莫耳）、二月桂酸二丁基錫（Aldrich股份有限公司 製造）5.53質量份。充分導入氮氣後，加熱至7〇。(：〜75°C， 然後以3小時均勻滴加異佛爾酮二異氰酸酯（脂肪族二異 201204798 氰酸酯，Aldrich股份有限公司製造）666質量份（3·00莫 耳），使其反應。滴加完畢後繼續反應約10小時。接著向 其中投入丙烯酸2-羥基乙酯（Aldrich股份有限公司製造） 238質量份（2.05莫耳）、對苯二酚單曱醚（Aldrich股份 有限公司製造）0.53質量份’進而反應1〇小時，藉由IR 測定來確認異氰酸酯消失而結束反應’獲得胺基甲酸酯丙 烯酸酯。所得的胺基曱酸酯丙烯酸酯（PE-UA2)的臨界表 面張力為25 mN/m，重量平均分子量為13500。另外， PE-UA2是使用聚酯二醇的化合物’滿足上述通式（A)。 (胺基甲酸酯丙烯酸酯（PE-UA3)的合成） 於具備攪拌機、溫度計、安裝有氣化鈣乾燥管的回流 冷卻管、氮氣導入管的反應容器中，投入丙烯酸2-羥基乙 酯（Aldrich股份有限公司製造）238質量份（2.05莫耳）、 對笨二酚單甲醚（Aldrich股份有限公司製造）0.53質量 份、數量平均分子量為1000的聚己内酯二醇（脂肪族聚酯 二醇’商品名：Placcel210N，Daicel化學工業股份有限公 句製造）2000質量份（2.00莫耳）、二月桂酸二丁基錫 (Aldrich股份有限公司製造）5·53質量份。充分導入氮氣 後，加熱至70°C〜75t，然後以3小時均勻滴加異佛爾酮 二·異氰酸酯（脂肪族二異氰酸酯，Aldrich股份有限公司製 造）666質量份（3.00莫耳），使其反應。滴加完畢後繼續 反應約10小時，藉由IR測定來確認異氰酸酯消失而結束 反應，獲得胺基甲酸酯丙烯酸酯。所得的胺基曱酸酯丙烯 酿S旨（PE-UA3 )的臨界表面張力為28 mN/m，重量平均分 48 201204798 子量為14500。另外，PE-UA3是使用聚酯二醇的化合物， 滿足上述通式（A)。 (胺基甲酸酯丙烯酸酯（PE-UA4)的合成） 於具備攪拌機、溫度計、安裝有氣化鈣乾燥管的回流 冷卻管 '氮氣導入管的反應容器中’加入3-曱基_1，5_戊二 醇1650質量份（14莫耳）及間苯二曱酸166〇質量份（1〇 莫耳於常壓下充分導入氮氣後，一邊將在約170°C下生 成的水蒸顧去除至系統外，一邊進行酯化反應。於聚酯的 酸值成為0.3 mgKOH/g以下的時刻利用真空泵緩緩提高真 空度，使反應完結。以上述方式獲得的芳香族聚醋二醇 (ED-1)的數量平均分子量為2〇〇〇。 進而，於具備攪拌機、溫度計、安裝有氣化鈣乾燥管 的回流冷卻管、氮氣導入管的反應容器中，投入所得的芳 香族聚酯二醇（ED-1) 2000質量份（1.00莫耳）、二月桂 酸二丁基錫（Aldrich股份有限公司製造）5.53質量份。充 分導入氮氣後，加熱至70°C〜75°C，然後以3小時均句滴 加異佛爾酮二異氰酸酯（脂肪族二異氰酸酯，Aldrich股份 有限公司製造）666質量份（3.00莫耳），使其反應。滴力^ 完畢後，繼續反應約15小時。接著向其中投入丙稀酸 經基乙酯（Aldrich股份有限公司製造）238質量份（2〇5 莫耳）、對苯二酚單曱醚（Aldrich股份有限公司製造）〇 ^ 質量份’進而反應7小時，藉由IR測定來確認異氰酸自旨消 失而結束反應，獲得胺基甲酸酯丙烯酸酯。所得的胺義甲 酸酯丙烯酸酯（PE-UA4)的臨界表面張力為42mN/m，重 49 201204798t 量平均分子量為11500。另外’ PE-UA4是使用聚酯二醇的 化合物，滿足上述通式（A)。 (胺基曱酸酯丙烯酸酯（PE-UA5)的合成） 於具備授拌機、溫度計、安裝有氣化弼乾燥管的回流 冷卻管、氮氣導入管的反應容器中，投入數量平均分子量 為2000的聚（l，6-己二醇碳酸酯)二醇（脂肪族聚碳酸酯二 醇，旭化成化學股份有限公司製造，PCDL T5652(商品名）) 4000質量份（2.00莫耳）、二月桂酸二丁基錫（Aldrich股 份有限公司製造）5.53質量份。充分導入氮氣後，加熱至 70°C〜75°C，然後以3小時均勻滴加異佛爾酮二異氰酸酯 (脂肪族二異氰酸酯’ Aldrich股份有限公司製造）666質 量份（3.00莫耳）’使其反應。滴加完畢後，繼續反應約 Μ小時。接著向其中投入丙烯酸2-羥基乙酯（Aldrich股 份有限公司製造）238質量份（2.05莫耳）、對苯二酚單甲 喊（Aldrich股份有限公司製造）0.53質量份，進而反應 W小時，藉由IR測定來確認異氰酸酯消失而結束反應， 獲得胺基曱酸酯丙烯酸酯。所得的胺基曱酸酯丙烯酸酯 (PE_UA5)的臨界表面張力為21 mN/m，重量平均分子量 為30000。另外’ PE_UA5為使用聚碳酸酯二醇的化合物， 並不滿足上述通式（A)。 (異三聚氰酸改質2官能丙烯酸酯（M-215)的準備） 準備異三聚氰酸改質2官能丙烯酸酯（東亞合成股份 有限公司製造，M-215 (商品名）。 (具有磷酸基的乙烯基化合物（P-2M)的準備） 50 201204798Lf phenoxy resin (manufactured by Tohto Kasei Co., Ltd., YP-50 (trade name)) was dissolved in methyl ethyl group to prepare a solution having a solid content of 40% by mass. (Preparation of polyester urethane resin) Polyacetate-based resin (manufactured by Toyobo Co., Ltd., UR 1400 (trade name)) is a methyl ethyl ketone and a resin using a resin component of % by mass. Stupid 1: 1 mixed solvent solution. (Synthesis of urethane resin), == (4) Mixer, thermometer, wire with gasification 35, dry tube V portion s, nitrogen gas tube A tube reaction volume, a weight average molecular weight of 2000 45 parts by mass of butyl diacetate adipate, 45 parts by mass of polyoxytetramethylene glycol having a weight average molecular weight of 2,000, and hydrazine, 4 parts by mass of tetrabutyl diol in methyl ethyl ketone 4_ The mixture was uniformly mixed, and 390 parts by mass of diphenyldecane diisocyanate was added at 7 Torr. (: The next reaction was carried out to obtain a urethane resin having a weight average molecular weight of 350,000. <Free radical polymerizable compound> (Preparation of urethane acrylate (L-1600S)) Preparation weight: £ average molecule 3 : a urethane acrylate having a critical surface tension of a mN/m (manufactured by Mitsui Polyurethane Co., Ltd. 'L-1600S (trade name)). In addition, l_16〇〇s is an ether diol. The compound does not satisfy the above formula (A). (Synthesis of amino phthalate acrylate (PE-UA1)) It is provided with a stirrer, a thermometer, a reflux cooling tube equipped with a vaporized calcium drying tube, and a nitrogen introduction tube. In the reaction vessel, poly(3-decylpentane adipate) diol (aliphatic polyester diol) manufactured by Kuraray Co., Ltd., Kurap〇i p_2〇1 〇 (manufactured by Kuraray Co., Ltd.) having an average molecular weight of 46 201204798 of 2000 was charged. Trade name)) 2000 parts by mass (1.00 mol), dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.) 5.53 parts by mass. After introducing nitrogen gas sufficiently, it is heated to 70 ° C to 75 ° C ' and then uniformly dropped in 3 hours. Dicyclohexyldecane 4 , 4,-diisooxy acid Sa (aliphatic diisocyanate, manufactured by Evonik Degussa, 'VESTANATH12DMI (trade name)) 787 parts by mass (3.00 mole)' to react. Continue the reaction after the addition is completed. Then, 238 parts by mass (2.05 mol) of hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and hydroquinone monoterpene ether (manufactured by Aldrich Co., Ltd.) were added in an amount of 0.53 parts by mass, and further reacted 10 In an hour, the disappearance of the isocyanate was confirmed by infrared (IR) measurement to terminate the reaction, and an amino phthalate acrylate was obtained. The obtained amino phthalate propionate (PE-UA1) had a critical surface tension of 3 〇mN/m, weight average molecular weight is 15300. In addition, PE-UA1 is a compound using a polyester diol, which satisfies the above formula (A). (Synthesis of urethane acrylate (PE-UA2)) A polycaprolactone diol (aliphatic polyester diol having a number average molecular weight of 2000) was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube equipped with a vaporized calcium drying tube, and a nitrogen introduction tube (trade name: piaccei) twenty two 0 EB, manufactured by Daicel Chemical Industry Co., Ltd., 2000 parts by mass (1.00 mol), and dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.), 5.53 parts by mass. After introducing nitrogen gas sufficiently, it was heated to 7 Torr. (: ~75°) C, 666 parts by mass (3.000 mol) of isophorone diisocyanate (aliphatic diiso 201204798 cyanate ester, manufactured by Aldrich Co., Ltd.) was uniformly added dropwise over 3 hours to cause a reaction. After the completion of the dropwise addition, the reaction was continued for about 10 hours. Then, 238 parts by mass of hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and 0.53 parts by mass of hydroquinone monoterpene ether (manufactured by Aldrich Co., Ltd.) were further introduced thereto, and further reacted for 1 hour. The disappearance of the isocyanate was confirmed by an IR measurement to terminate the reaction to obtain a urethane acrylate. The obtained amino phthalate acrylate (PE-UA2) had a critical surface tension of 25 mN/m and a weight average molecular weight of 13,500. Further, PE-UA2 is a compound using a polyester diol, which satisfies the above formula (A). (Synthesis of urethane acrylate (PE-UA3)) 2-hydroxyethyl acrylate was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube equipped with a vaporized calcium drying tube, and a nitrogen introduction tube. 238 parts by mass (2.05 mol) manufactured by Aldrich Co., Ltd., 0.53 parts by mass of a stilbene monomethyl ether (manufactured by Aldrich Co., Ltd.), and a polycaprolactone diol (aliphatic polyester having a number average molecular weight of 1,000) Diol 'trade name: Placcel 210N, manufactured by Daicel Chemical Industry Co., Ltd.) 2000 parts by mass (2.00 mol), dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.) 5.53 parts by mass. After introducing nitrogen gas sufficiently, it was heated to 70 ° C to 75 t, and then 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) was uniformly added dropwise over 3 hours. reaction. After completion of the dropwise addition, the reaction was continued for about 10 hours, and it was confirmed by IR measurement that the isocyanate disappeared, and the reaction was terminated to obtain a urethane acrylate. The obtained amino phthalate acrylate was designed to have a critical surface tension of 28 mN/m and a weight average of 48 201204798 by 14500. Further, PE-UA3 is a compound using a polyester diol, and satisfies the above formula (A). (Synthesis of urethane acrylate (PE-UA4)) Add 3-mercapto-1 to a reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube 'nitrogen inlet tube equipped with a vaporized calcium drying tube. 5_ pentanediol 1650 parts by mass (14 moles) and 166 parts by mass of m-benzoic acid (1 〇 mol is fully introduced into the atmosphere under normal pressure, and the water formed at about 170 ° C is distilled. The esterification reaction is carried out while removing the system. When the acid value of the polyester is 0.3 mgKOH/g or less, the vacuum degree is gradually increased by a vacuum pump to complete the reaction. The aromatic polyglycol (ED) obtained in the above manner is obtained. -1) The number average molecular weight is 2 〇〇〇. Further, the obtained aromatic polyester diol is charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube to which a vaporized calcium drying tube is attached, and a nitrogen gas introduction tube. (ED-1) 2000 parts by mass (1.00 mol), and 2.5 parts by mass of dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.). After sufficiently introducing nitrogen gas, heating to 70 ° C to 75 ° C, and then for 3 hours Sentence plus isophorone diisocyanate (fat Group II isocyanate, manufactured by Aldrich Co., Ltd., 666 parts by mass (3.00 mole), and reacted. After the completion of the dropping force, the reaction was continued for about 15 hours, and then the ethyl acrylate was added thereto (Aldrich Co., Ltd.) Manufactured by the company, 238 parts by mass (2〇5 mol), hydroquinone monoterpene ether (manufactured by Aldrich Co., Ltd.) 〇^ parts by mass and further reacted for 7 hours, confirmed by IR measurement that isocyanic acid disappeared The reaction was terminated to obtain a urethane acrylate. The obtained amine phthalate acrylate (PE-UA4) had a critical surface tension of 42 mN/m and a weight of 49 201204798t. The average molecular weight was 11500. In addition, 'PE-UA4 It is a compound using a polyester diol, and it satisfies the above formula (A). (Synthesis of amino phthalate acrylate (PE-UA5)) Having a remixer equipped with a mixer, a thermometer, and a gasification 弼 drying tube In a reaction vessel of a cooling pipe and a nitrogen gas introduction pipe, a poly(l,6-hexanediol carbonate) diol having an average molecular weight of 2000 (aliphatic polycarbonate diol, manufactured by Asahi Kasei Chemicals Co., Ltd., PCDL T5652) was charged. Business Name)) 4000 parts by mass (2.00 mol), dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.) 5.53 parts by mass. After introducing nitrogen gas sufficiently, it is heated to 70 ° C to 75 ° C, and then uniformly added dropwise over 3 hours. 666 parts by mass (3.00 mole) of isophorone diisocyanate (manufactured by Aldrich Co., Ltd.) was allowed to react. After the completion of the dropwise addition, the reaction was continued for about several hours, and then 2-hydroxyacrylic acid was introduced thereto. Ethyl acetate (manufactured by Aldrich Co., Ltd.), 238 parts by mass (2.05 mol), hydroquinone monomethyl shim (manufactured by Aldrich Co., Ltd.), 0.53 parts by mass, and further reacted for an hour, and the disappearance of the isocyanate was confirmed by IR measurement. The reaction was terminated to obtain an amino phthalate acrylate. The obtained amino phthalate acrylate (PE_UA5) had a critical surface tension of 21 mN/m and a weight average molecular weight of 30,000. Further, 'PE_UA5 is a compound using a polycarbonate diol, and does not satisfy the above formula (A). (Preparation of iso-cyanuric acid-modified difunctional acrylate (M-215)) Preparation of an iso-cyanuric acid-modified 2-functional acrylate (manufactured by Toagosei Co., Ltd., M-215 (trade name). Preparation of a phosphate-based vinyl compound (P-2M) 50 201204798

A 準備磷酸2-(曱基）丙烯醯氧基乙酯（商品名：Ught Ester P-2M’共榮社化學股份有限公司製造）。 〈自由基聚合起始劑〉 準備過氧化二笨曱醯（商品名：NyperBW，日油股份 有限公司製造）作為自由基聚合起始劑。 〈導電性粒子〉 (導電性粒子的製作） 於以聚苯乙烯為核的粒子的表面設置厚度〇·2 的 鎳層，且於該鎳層的外側設置厚度0 02 μιη的金層，製作 平均粒徑為10 μιη、比重為2.5的導電性粒子。 [實例1〜實例10及比較例1〜比較例5] 以固體重量比計如表2所示來調配熱塑性樹脂、自由 基聚合性化合物及自由基聚合起始劑，進而調配分散15 νοί的導電性粒子，獲得黏著劑組成物。使用塗佈裝置， 將所得的黏著劑組成物塗佈於厚度8〇 μιη的氟樹脂膜上， 藉由70°C、10分鐘的熱風乾燥而獲得黏著劑層的厚度為 20 μηι的膜狀黏著劑組成物。 51 201204798 ▲ ι [表2] 調配劑 實 例 1 實 例 2 實 例 3 實 例 4 實 例 5 實 例 6 實 例 7 實 例 8 實 例 9 實 例 10 比 較 例 1 比 較 例 2 比 較 例 3 比 較 例 4 比 較 例 5 熱塑性樹脂 YP-50 50 50 • _ 50 - - 50 - - 50 50 - - - UR-1400 • • 50 50 - 50 45 50 4ί&gt; - - 50 50 45 胺基甲酸酯樹脂 _ • _ - - 5 - - 5 - - *· - 5 自由基聚合 性化合物 PE-UA1 (30 mN/m) 30 - 30 - - - - - - - - - - - PE-UA2 (25 mN/m ) - 30 30 - - - - - - - - - - - PE-UA3 (28 mN/m) - - 30 30 50 - - - - - - - PE-UA4 (42 mN/m ) _ _ - - - - 30 30 50 - - - - - L-1600S (15 mN/m) - - - - - - - - - 30 - 30 - PE-UA5 (21 mN/m) 響 _ - - - - - - - - 30 - 30 50 M-215 20 20 20 20 20 20 - 20 20 - 20 20 20 20 - P-2M 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 自由基聚合 起始劑 Nyper BW 4 4 4 4 4 — 〜 4 4 4 4 4 4 4 4 4 4 [連接電阻、黏著強度的測定] 使實例1〜實例10以及比較例1〜比較例5的膜狀黏 著劑組成物，介隔存在於在聚醯亞胺膜（Tg為350。(：）上 具有80根線寬為150 μιη、間距為300 μπι、厚度為8 μηι 的銅電路的可撓性電路板（flexible printed circuit，FPC) 與形成有厚度5 μηι的Ag漿料薄層的PET基板（厚度為 0.1 mm)之間。另外，使實例1〜實例1〇以及比較例1〜 比較例5的膜狀黏著劑組成物’介隔存在於在聚醯亞胺膜 52 201204798 上具有80根線寬為150μπ1、間距為3〇〇μηι、厚度為18μιη 的銅電路的FPC與在PET (厚度為0.1 mm)膜上形成有 線寬為150μπι、間距為300 μιη、厚度為1〇μπ^々Ag漿料 電路的基板之間。對該些分別使用熱壓接裝置（加熱方式： 悝溫型，Toray Engineering 公司製造），於 150°c、2 Mpa 下加熱加壓10秒，遍及寬度2 mm而連接，製作連接體。 於剛黏著後及在85°C、85%RH的高溫高濕射保持24〇 小時後（5式驗後）’利用萬用表來測定該些連接體的鄰接電 路間的電阻值。電阻值是以鄰接電路間的電阻37點的平均 值表示。 另外’依據JIS-Z0237，利用90度剝離法來測定各個 連接體_著強度，進行。此處’姆強度的測定裝 置是使用Toyo Baldwin股份有限公司製造的τ_〇η UTM-4 (剝離速度為50mm/min，25。〇。將以上述方式進 行的膜狀黏著_成物鱗接電阻及輯強度的測定的结 果示於下述表3。 53 20120479^ [表3] 附有Ag薄膜的PET 附有Ag電路的PET 連接電阻（Ω) 黏著強度（N/m) 黏著強度（（N/m) 剛黏著後 240 h 後 剛黏著後 240 h 後 剛黏著後 240 h 後 實例1 0.6 1.0 830 710 730 700 實例2 0.8 1.1 750 690 680 650 實例3 0.5 0.7 780 730 760 710 實例4 0.7 1.1 730 700 700 680 實例5 0.9 1.2 750 730 720 690 實例6 0.7 0.9 770 750 780 720 實例7 0.6 0.8 800 780 810 760 實例8 0.6 1.2 650 520 480 360 實例9 0.6 0.9 680 540 500 400 實例10 0.7 1.0 520 480 590 450 比較例1 0.9 1.3 500 450 300 250 比較例2 2.4 9.5 630 450 530 450 比較例3 0.7 1.2 580 460 280 260 比較例4 2.1 8.4 650 500 550 500 比較例5 3.0 9.5 630 620 610 580 實例1〜實例7的黏著劑組成物於加熱溫度150°C下， 於剛黏著後及在85°C、85%RH的高溫高濕槽中保持240 小時後（試驗後），表現出約1.2 Ω以下的良好連接電阻及 600 N/m以上的良好黏著強度。 相對於該些實例，比較例1及比較例3的黏著劑組成 物於剛黏著後及在85°C、85%RH的高溫高濕槽中保持240 小時後（試驗後），雖表現出良好的連接電阻，但黏著強度 變低。另外，比較例2、比較例4及比較例5的黏著劑組 成物於剛連接後及在85°C、85%RH的高溫高濕槽中保持 240小時後（試驗後）的連接電阻高，黏著強度亦與實例1 〜實例7相比較而變低。 54 201204798 4 j 面實例8〜實例10 —黏著劑組成物於剛黏著 t在 85%RH的高溫高濕槽中保持240小時後(試 現出約以下的良好連接電阻，且與比較例 1及比較例3相比，黏著強度優異。 [貫例11貫例13以及比較例6及比較例7] ϋ二卜，實例3、實例4及實例7以及比較例3及比 ==狀黏著劑組成物，分別介隔存在於在聚醯亞胺 ㈣^ Ϊ根線寬為150 μΐΏ、間距為300 μΠ1、厚度為8㈣ 的銅電路的可撓性魏板（肌）與PET膜（厚度為αι 及PEN膜（厚度為αι mm，Tg為16〇。〇之間。對嗜些 分別使用熱壓接裝置（加熱方式：怪溫型，T〇ra—y Engineering公司製造），於15〇t、2 Mpa下加熱加壓ι〇 秒，遍及寬度2 mm而壓接，製作連接體。 另外’各個連接體的黏著強度是以與上述方法相同的 方式測定。將m方式崎賴綠著敝絲的 強度的測定結果示於下述表4。 ’ 55A Preparation of 2-(indenyl) propylene methoxyethyl phosphate (trade name: Ught Ester P-2M', manufactured by Kyoeisha Chemical Co., Ltd.). <Radical Polymerization Initiator> A second abbreviated peroxide (trade name: Nyper BW, manufactured by Nippon Oil Co., Ltd.) was prepared as a radical polymerization initiator. <Electrically conductive particles> (Preparation of conductive particles) A nickel layer having a thickness of 〇·2 is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0 2 μm is provided outside the nickel layer to prepare an average Conductive particles having a particle size of 10 μηη and a specific gravity of 2.5. [Example 1 to Example 10 and Comparative Example 1 to Comparative Example 5] A thermoplastic resin, a radically polymerizable compound, and a radical polymerization initiator were blended as shown in Table 2 in terms of solid weight ratio, and further, a conductive dispersion of 15 νοί was prepared. Sex particles, obtaining an adhesive composition. Using the coating device, the obtained adhesive composition was applied onto a fluororesin film having a thickness of 8 μm, and dried by hot air at 70 ° C for 10 minutes to obtain a film-like adhesive having a thickness of the adhesive layer of 20 μm. Agent composition. 51 201204798 ▲ ι [Table 2] Formulation Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Thermoplastic Resin YP-50 50 50 • _ 50 - - 50 - - 50 50 - - - UR-1400 • • 50 50 - 50 45 50 4ί&gt; - - 50 50 45 Urethane Resin _ • _ - - 5 - - 5 - - *· - 5 Radical polymerizable compound PE-UA1 (30 mN/m) 30 - 30 - - - - - - - - - - - PE-UA2 (25 mN/m ) - 30 30 - - - - - - - - - - - PE-UA3 (28 mN/m) - - 30 30 50 - - - - - - - PE-UA4 (42 mN/m ) _ _ - - - - 30 30 50 - - - - - L -1600S (15 mN/m) - - - - - - - - - 30 - 30 - PE-UA5 (21 mN/m) _ - - - - - - - - 30 - 30 50 M-215 20 20 20 20 20 20 - 20 20 - 20 20 20 20 - P-2M 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Radical polymerization initiator Nyper BW 4 4 4 4 4 — ~ 4 4 4 4 4 4 4 4 4 4 [Measurement of connection resistance and adhesion strength] The film-like adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 were interspersed. Flexible printed circuit (FPC) on a polymethylene imide film (Tg of 350. (:) with 80 copper lines with a line width of 150 μηη, a pitch of 300 μπι, and a thickness of 8 μηι) Between the PET substrate (thickness: 0.1 mm) in which a thin layer of Ag paste having a thickness of 5 μm was formed. Further, the film-like adhesive compositions of Examples 1 to 1 and Comparative Examples 1 to 5 were introduced. Between the FPC having a copper circuit having a line width of 150 μπ1, a pitch of 3 μm, and a thickness of 18 μm on the polyimide film 52 201204798 and the formation of a line width on the PET (thickness 0.1 mm) film 150 μm, a pitch of 300 μm, and a thickness of 1 μμπ^々 between the substrates of the Ag paste circuit. Each of these was heated and pressurized at 150 ° C and 2 Mpa for 10 seconds using a thermocompression bonding apparatus (heating method: heating type, manufactured by Toray Engineering Co., Ltd.), and connected to each other to form a joined body. After the adhesion and after holding at a high temperature and high humidity of 85 ° C and 85% RH for 24 hours (5 test), the resistance between the adjacent circuits of the connectors was measured using a multimeter. The resistance value is expressed as an average value of 37 points of resistance between adjacent circuits. Further, according to JIS-Z0237, the strength of each of the connectors was measured by a 90-degree peeling method. Here, the apparatus for measuring the strength of the strength is τ_〇η UTM-4 manufactured by Toyo Baldwin Co., Ltd. (the peeling speed is 50 mm/min, 25. 〇. The film-like adhesion in the above manner is squashed The results of the measurement of the resistance and the intensity are shown in Table 3. 53 20120479^ [Table 3] PET with Ag film PET connection resistance with Ag circuit (Ω) Adhesion strength (N/m) Adhesion strength (( N/m) 240 h after adhesion just after 240 h after adhesion just after 240 h after adhesion Example 1 0.6 1.0 830 710 730 700 Example 2 0.8 1.1 750 690 680 650 Example 3 0.5 0.7 780 730 760 710 Example 4 0.7 1.1 730 700 700 680 Example 5 0.9 1.2 750 730 720 690 Example 6 0.7 0.9 770 750 780 720 Example 7 0.6 0.8 800 780 810 760 Example 8 0.6 1.2 650 520 480 360 Example 9 0.6 0.9 680 540 500 400 Example 10 0.7 1.0 520 480 590 450 Comparative Example 1 0.9 1.3 500 450 300 250 Comparative Example 2 2.4 9.5 630 450 530 450 Comparative Example 3 0.7 1.2 580 460 280 260 Comparative Example 4 2.1 8.4 650 500 550 500 Comparative Example 5 3.0 9.5 630 620 610 580 Example 1~ The adhesive composition of Example 7 was heated At 150 ° C, after standing for 24 hours in the high temperature and high humidity bath at 85 ° C and 85% RH (after the test), it shows a good connection resistance of about 1.2 Ω or less and 600 N/m or more. Good adhesion strength. Relative to these examples, the adhesive compositions of Comparative Example 1 and Comparative Example 3 were held for 24 hours after the adhesion and in the high temperature and high humidity tank at 85 ° C and 85% RH (after the test). Although the adhesion resistance was good, the adhesive strength was low. Moreover, the adhesive compositions of Comparative Example 2, Comparative Example 4, and Comparative Example 5 were high-temperature and high-temperature after the connection and at 85 ° C and 85% RH. After 24 hours in the tank (after the test), the connection resistance was high, and the adhesion strength was also lower than that of Examples 1 to 7. 54 201204798 4 j Surface Example 8 to Example 10 - Adhesive composition was adhered to t After maintaining for 240 hours in a high-temperature and high-humidity bath of 85% RH (the following good connection resistance was exhibited, and the adhesion strength was excellent compared with the comparative example 1 and the comparative example 3. [Example 11 and Comparative Example 6 and Comparative Example 7] ϋ二卜, Example 3, Example 4 and Example 7 and Comparative Example 3 and ratio == adhesive composition, respectively, present in the 醯Imine (IV) ^ Flexible core plate (muscle) and PET film of copper circuit with a line width of 150 μΐΏ, a spacing of 300 μΠ1 and a thickness of 8 (4) (thickness of αι and PEN film (thickness of αι mm, Tg is 16〇.Between the 〇. Use a thermo-compression device (heating method: strange temperature type, manufactured by T〇ra-y Engineering Co., Ltd.) for heating The connection body was produced by crimping to a width of 2 mm. The adhesion strength of each of the connectors was measured in the same manner as the above method. The measurement results of the strength of the m-mode green wire were shown in Table 4 below. ' 55

201204798 L201204798 L

[表4] 項目 基材 黏著強度（N/m) 剛黏著後 240 h 後 實例11 (黏著劑組成物：實例3) PET 690 600 PC 650 610 PEN 680 620 實例12 (黏著劑組成物：實例4) PET 720 690 PC 700 670 PEN 690 650 實例13 (黏著劑組成物：實例7) PET 710 690 PC 710 680 PEN 690 650 比較例6 (黏著劑組成物：比較例3) PET 440 400 PC 420 380 PEN 380 300 比較例7 (黏著劑組成物：比較例4) peth 430 360 PC 450 380 PEN 420 320 實例11〜實例13中使用的黏著劑組成物對於任一種 基材，均於加熱溫度150°C下，於剛黏著後及在85°C、 85%RH的高溫高濕槽中保持240小時後（試驗後），表現 出600 N/m以上的良好黏著強度。相對於該些實例，比較 例6及比較例7中使用的黏著劑組成物於剛黏著後及在 85°C、85%RH的高溫高濕槽中保持240小時後（試驗後）， 黏著強度變低。 [參考例1〜參考例6] 作為參考例，使實例3、實例4、實例6及實例7以及 比較例1及比較例3的膜狀黏著劑組成物，介隔存在於在 聚醯亞胺膜上具有500根線寬為25 μιη、間距為50 μιη、 厚度為8 μιη的銅電路的可撓性電路板（FPC)與形成有 56 201204798 0.2 μιη的ITO薄層的玻璃（厚度為丨1 mm，表面電阻為 20 Ω/口）之間。對其使用熱壓接裝置（加熱方式：恆溫型， Toray Engineering 公司製造），於 150。〇、2 MPa 下加熱加 壓10秒，遍及寬度2 mm而連接，製作連接體。於剛黏著 後及在85°C、85%RH的高溫高濕槽中保持240小時後（試 驗後）’利用萬用表來測定該連接體的鄰接電路間的電阻 值。電阻值是以鄰接電路間的電阻37點的平均值表示。 另外，依據JIS-Z0237，利用90度剝離法來測定該連 接體的黏著強度’進行評價。此處，黏著強度的測定裝置 是使用Toyo Baldwin股份有限公司製造的Tensilon UTM-4 (剝離速度為50mm/min，25°C )。將以上述方式進行的膜 狀黏著劑組成物的連接電阻及黏著強度的測定的結果示於 下述表5。 [表5] 附有ITO的玻璃 連接電阻（Ω) 黏著強度（N/m) 剛黏著德 240 h 後 剛黏著後 240 h 後 參考例1 (實例3) 1.3 1.8 880 730 參考例2 (實例4) 1.4 1.9 830 700 參考例3 (實例6) 1.6 2.1 850 730 參考例4 (實例7) 1.3 2.2 870 750 參考例5 (比較例1) 1.7 2.4 700 680 參考例6 (比較例3 ) 1.5 2.3 720 700 57 201204798 如上所示，比較例的黏著劑組成物於被黏附體為ΡΕτ 膜、PC膜及PEN膜的情況，連接電阻或黏著強度差。但 是，如表5所示，於被黏附體為附有IT0的玻璃的情況， 包括使用比較例的黏著劑組成物的情況的參考例丨〜參考 例6的所有例子中，於剛黏著後及在幻艺、85%RH的高 溫高濕槽中保持240小時後（試驗後），確認獲得2 5 Ω以 下的良好連接電阻及680 N/m以上的良好黏著強度。 [產業上之可利用性] 依據本實施形態，可提供一種對於聚對苯二甲酸乙二 酯、聚碳酸酯、聚萘二曱酸乙二酯等有機基材，即便於低 溫2硬:匕條件下亦可獲得優異的黏著強度，且於長時間的 p性試驗（高溫高濕試驗）後亦可維持穩定的性能（黏 者強度或連接電阻）的黏著劑組成物，使用該黏著劑 物，電路構件的連接結構體，連接結構體的製造方法以 霉占著劑組成物的應用。 【圖式簡單說明】 “I1是表示使用本實施形態的黏著劑組成物的電路構 件的連接結構體的-實施形態的示意剖面圖。電路構 =2是表讀侧丨所_魏構件的連接結構 電路構件、第二電路構件及黏著劑組成物的示意 電性使用本實施形態的勘著劑組成物(含有導 =子)的電路構件的連接結構體的-實施形態的4 58[Table 4] Item substrate adhesion strength (N/m) Immediately after adhesion for 240 h Example 11 (Adhesive composition: Example 3) PET 690 600 PC 650 610 PEN 680 620 Example 12 (Adhesive composition: Example 4 PET 720 690 PC 700 670 PEN 690 650 Example 13 (Adhesive Composition: Example 7) PET 710 690 PC 710 680 PEN 690 650 Comparative Example 6 (Adhesive Composition: Comparative Example 3) PET 440 400 PC 420 380 PEN 380 300 Comparative Example 7 (Adhesive Composition: Comparative Example 4) peth 430 360 PC 450 380 PEN 420 320 The adhesive compositions used in Examples 11 to 13 were heated at a temperature of 150 ° C for any of the substrates. After standing for 24 hours (after the test) in the high-temperature and high-humidity bath at 85 ° C and 85% RH, it showed good adhesion strength of 600 N/m or more. With respect to these examples, the adhesive compositions used in Comparative Example 6 and Comparative Example 7 were held for 24 hours after the adhesion and in the high-temperature and high-humidity bath at 85 ° C and 85% RH (after the test), the adhesion strength. Go low. [Reference Example 1 to Reference Example 6] As a reference example, the film-like adhesive compositions of Example 3, Example 4, Example 6 and Example 7 and Comparative Example 1 and Comparative Example 3 were interspersed in polyimine. A flexible circuit board (FPC) having a copper circuit with a line width of 25 μm, a pitch of 50 μm, and a thickness of 8 μm, and a thin glass of ITO formed with 56 201204798 0.2 μm on the film (thickness 丨1) Mm, surface resistance is between 20 Ω / port). A thermocompression bonding apparatus (heating method: constant temperature type, manufactured by Toray Engineering Co., Ltd.) was used at 150. 〇, heating at 2 MPa for 10 seconds, and connecting them over a width of 2 mm to make a joint. After the adhesion and after holding for 240 hours in a high-temperature and high-humidity bath at 85 ° C and 85% RH (after the test), the resistance between the adjacent circuits of the connected body was measured by a multimeter. The resistance value is expressed as the average value of the resistance 37 points between adjacent circuits. Further, according to JIS-Z0237, the adhesion strength of the joined body was measured by a 90-degree peeling method. Here, the measuring device for the adhesion strength was Tensilon UTM-4 (peeling speed: 50 mm/min, 25 ° C) manufactured by Toyo Baldwin Co., Ltd. The results of measurement of the connection resistance and the adhesion strength of the film-like adhesive composition which was carried out in the above manner are shown in Table 5 below. [Table 5] Glass connection resistance (Ω) with ITO Adhesive strength (N/m) Just after adhesion for 240 h immediately after 240 h, reference example 1 (Example 3) 1.3 1.8 880 730 Reference Example 2 (Example 4 1.4 1.9 830 700 Reference Example 3 (Example 6) 1.6 2.1 850 730 Reference Example 4 (Example 7) 1.3 2.2 870 750 Reference Example 5 (Comparative Example 1) 1.7 2.4 700 680 Reference Example 6 (Comparative Example 3) 1.5 2.3 720 700 57 201204798 As shown above, in the case where the adhesive composition of the comparative example is a ΡΕτ film, a PC film, and a PEN film, the connection resistance or the adhesion strength is poor. However, as shown in Table 5, in the case where the adherend is a glass to which IT0 is attached, the reference example of the case where the adhesive composition of the comparative example is used, in all the examples of Reference Example 6, after the adhesion and After 240 hours in the high-temperature and high-humidity tank of 85% RH (after the test), it was confirmed that a good connection resistance of 25 Ω or less and a good adhesion strength of 680 N/m or more were obtained. [Industrial Applicability] According to the present embodiment, it is possible to provide an organic substrate such as polyethylene terephthalate, polycarbonate or polyethylene naphthalate, even at a low temperature of 2: 匕An adhesive composition which can also obtain excellent adhesive strength and maintain stable performance (adhesive strength or joint resistance) after a prolonged p-test (high temperature and high humidity test), using the adhesive The connection structure of the circuit member and the method of manufacturing the connection structure are used as a composition of the mold. BRIEF DESCRIPTION OF THE DRAWINGS "I1 is a schematic cross-sectional view showing an embodiment of a connection structure using a circuit member of the adhesive composition of the present embodiment. The circuit configuration = 2 is a connection of the reading side member The electrically conductive structure of the structural circuit member, the second circuit member, and the adhesive composition is used as the connection structure of the circuit member of the present embodiment (including the conductor).

201204798 L 圖4是表示製作圖3所示的電路構件的連接 前的第一電路構件、第二電路構件及黏著劑組成物（含有 導電性粒子）的示意剖面圖。 a 【主要元件符號說明】 10、20 :黏著劑組成物 10C、20C :連接構件 21 :不含導電性粒子的黏著劑組成物 22 :導電性粒子 21C .不含導電性粒子的黏著劑組成物的硬化物 30 :第一電路構件 31 :第一電路基板 31a :主面 32 :第一連接端子 40 :第二電路構件 41 :第二電路基板 41a :主面 42 :第二連接端子 100、200 :電路構件的連接結構體 59201204798 L Fig. 4 is a schematic cross-sectional view showing a first circuit member, a second circuit member, and an adhesive composition (containing conductive particles) before the connection of the circuit member shown in Fig. 3 is produced. a [Description of main component symbols] 10, 20: Adhesive composition 10C, 20C: Connecting member 21: Adhesive composition 22 containing no conductive particles: Conductive particles 21C. Adhesive composition containing no conductive particles Hardened material 30: first circuit member 31: first circuit substrate 31a: main surface 32: first connection terminal 40: second circuit member 41: second circuit substrate 41a: main surface 42: second connection terminal 100, 200 : Connection structure of circuit member 59

Claims (1)

201204798 L 、申請專利範圍： 子的第· 路構件連接 種黏著劑組成物，用於將主面上具有第一連接端 與主面上具有第一連接端子的第 電 上述第一電路構件及/或上述第二電路構件是由包含 破璃轉移溫度為2GGt以下的熱塑性樹脂的基材所構成， 上述黏著劑組成物含有（a)熱塑性樹脂、（b)自由美 聚合性化合物及（〇自由基聚合起始劑，且上述⑻= 由基聚合性彳b合她含具有^嶋〜⑼爾㈤的臨界表 面張力的胺基甲酸酯（甲基）丙烯酸酯。 2.如申請專利範圍帛丄項所述之黏著劑組成物，盆中 上述胺基甲酸醋（甲基)丙烯酸酿是下述通式⑷所表示 胺基甲酸酯（甲基)丙烯酸酯： [化1] CHZ=C-C—O-R3—O-c-N-R*-0 5 Η ί- -RS— ΤΓ o—rs—o—c*c= ·&lt;Α) [式⑷t，R及R2分別獨立地表示氫原子或者甲 基’ H3表不伸乙基' 伸丙基、由ε•己内賴開環化合物所 衍生的基團或者下述通式⑻所表示的·，r4表示下 述通式⑻所表示的基團’ R5表示飽和脂肪絲或者飽 和脂環基，a表示1〜40的整數] [化2] 201204798201204798 L. Patent application scope: The first component of the sub-component is connected to the adhesive composition for electrically connecting the first circuit member having the first connection end on the main surface and the first connection terminal on the main surface and/or Or the second circuit member is made of a base material comprising a thermoplastic resin having a glass transition temperature of 2 GGt or less, and the adhesive composition contains (a) a thermoplastic resin, (b) a freely polymerizable compound, and (an free radical) a polymerization initiator, and the above (8) = base-polymerizable 彳b, which contains a urethane (meth) acrylate having a critical surface tension of 嶋 ( (9) er (f). The above-mentioned adhesive composition, wherein the above-mentioned amino carboxylic acid (meth)acrylic acid in the pot is a urethane (meth) acrylate represented by the following formula (4): [Chemical Formula 1] CHZ=CC- O-R3—OcNR*-0 5 Η ί- -RS— ΤΓ o—rs—o—c*c= ·&lt;Α) [Formula (4) t, R and R2 independently represent a hydrogen atom or a methyl group. Does not extend ethyl 'propyl group, a group derived from a ε•hexene lysine ring-opening compound or · ⑻ represented by the following formula, r4 represents a group of the general formula represented ⑻ 'R5 represents a saturated or unsaturated aliphatic wire alicyclic group, a represents an integer of 1~40] [Chemical Formula 2] 201 204 798 •“（B) 吉^ )中’ R&amp;R&gt;_立地表示碳數2〜12的 直鏈或者分支鏈的伸絲，b表示丨〜 2^ 〜25的整數；此外，式中，R6彼此、R7J b % c彼此分別可相同，亦可不同]。 彼此以及 + ^ 著劑組成物，用於將主面上具有第—連接端 路構件連接， 连接細子的第一電 上述第一電路構件及/或上述第二電路構件是由包含 鴻轉移溫度為2〇〇t：以下的熱塑性樹脂的基材所構成， 上述黏著劑組成物含有（a)熱塑性樹脂、（b)自由基 聚合性化合物及（Ο自由基聚合起始劑，且上述⑻自 由基聚合性化合物包含下述通式（A)所表示的胺基甲酸 酯（曱基)丙烯酸酯： [化3] R1 0• "(B) 吉^) in 'R&amp;R&gt;_standground means a straight or branched chain of carbon number 2~12, b means an integer of 丨~2^~25; in addition, in the formula, R6 is mutually R7J b % c may be the same or different from each other. The mutual and the + ^ composition are used to connect the first connecting end member on the main surface, and connect the first electric circuit of the first electric circuit. The member and/or the second circuit member are made of a base material comprising a thermoplastic resin having a heat transfer temperature of 2 〇〇 t or less, and the adhesive composition contains (a) a thermoplastic resin and (b) a radical polymerizable property. a compound and a ruthenium radical polymerization initiator, and the (8) radically polymerizable compound contains a urethane (mercapto) acrylate represented by the following formula (A): [Chemical 3] R1 0 -H-R4—N-c-Λ I II Η HO ••(A) ·〇 一 r3 一 II ο [，（^)中’ R1及R2分別獨立地表示氫原子或者曱 基R表示伸乙基、伸丙基、由ε_己内酯的開環化合物所 何生的基團或者下述通式（Β)所表示的基團，R4表示下 201204798 述通式（B)所表示的基團，R5表示飽和脂肪族基或者飽 和脂環基’ a表示1〜40的整數] [化4]-H-R4—Nc-Λ I II Η HO ••(A) ·〇一r3一II ο [,(^)中' R1 and R2 each independently represent a hydrogen atom or a sulfhydryl group R represents an ethyl group and a stretch a propyl group, a group derived from a ring-opening compound of ε_caprolactone or a group represented by the following formula (Β), and R4 represents a group represented by the formula (B) in the following 201204798, R5 Indicates a saturated aliphatic group or a saturated alicyclic group 'a represents an integer of 1 to 40] [Chemical 4] » (日&gt; [式（B)中，R6及r7分別獨立地表示碳數2〜12的 直鍵或者分支鏈的伸烷基，b表示1〜10的整數，c表示1 〜25的整數；此外’式中，R6彼此、R7彼此、b彼此以及 c彼此分別可相同，亦可不同]。 4·如申請專利範圍第1項至第3項中任一項所述之黏 著劑組成物，其中上述胺基曱酸酯（曱基）丙烯酸酯是使用 脂肪族聚酯二醇而獲得。 5.如申請專利範圍第1項至第4項中任一項所述之黏 著劑組成物，其中上述胺基曱酸酯（曱基）丙烯酸酯的重量 平均分子量為8000以上且小於25000。 —6.如申請專利範圍第1項至第5項中任一項所述之黏 著劑組成物，其中上述（b)自由基聚合性化合物含有i 種以上的具有磷酸基的乙烯基化合物、及丨種以上的上述 具有鱗Si基的乙烯基化合物以外的自由基聚合性化合物。 _ 7.如申請專利範圍第i項至第6項中任一項所述之黏 著劑組成物，其中上述（a)熱塑性樹脂含有選自由苯氧基 樹脂、聚胺基甲酸酯樹脂、聚酯胺基曱酸酯樹脂、丁醛樹 62 201204798 脂、丙烯酸樹脂及聚醯亞胺樹脂所組成組群中的至少 —8.如申請專利範圍第工項至第7項中任一項所: 者劑組成物，其中更含有⑷導電性粒子。 1 9· -種電路構件的連接結構體，包括··主面上 式二 子 =Γ利範圍第1項至第8項中任一項所述之黏著二 上述連接構件介於上述第一電路構件與 電 路構件之間，而且上述第-連接端子及上述第二連ί:: 電性連接，危 上述第一電路構件及/或上述第二電路構件是由含有 玻璃轉移*度為2〇〇t以下的熱塑性獅旨的基材所構成。 10. 如申請專利範圍第9項所述之電路構件的連接結 ，體，其中上述玻璃轉移溫度為200°c以下的熱塑性樹脂 是選自由聚對苯二曱酸乙二酯、聚碳酸酯及聚萘二曱酸乙 二酯所組成組群中的至少1種。 11. 如申請專利範圍第9項或第1〇項所述之電路構件 的連接結構體，其中上述第—電路構件或者上述第二電路 構=中的—方的電路構件是由含有選自由聚對苯二甲酸乙 一酉曰、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少 1種的基材所構成，並且 上述第一電路構件或第二電路構件中的另一方的電路 63 201204798 酉旨 構件是由含有選自由聚醯亞胺樹脂及聚對苯二甲酸乙 所組成組群中的至少丨種的基材所構成。 下步t一種電路構件的連接結構體的製造方法，包括以 上且面ΐί有第一連接端子的第一電路構件、與主面 ，、有第一連接鈿子的第二電路構件，以 端子及上述第二連接端子對向的方式配置， 項至第8項中任一項所述之黏著劑;: 上述第一電路構件與上述第二電路構件之間，·以及 ㈣ft述㈣齡成物加熱，使其硬化㈣上述第一電 路構件與上述第二電路構件連接。 13. —種黏著劑組成物的應用，用 及第二電路構件連接， Μ電路構件 上述黏著劑組成物含有⑷熱塑性樹脂、㈤自由美 合物及(c)自由基聚合起始劑，且上述(心 =二性化合物包含具有25 mN/m〜4〇 mN/m的臨界表 面張力的胺基甲酸酯（甲基)丙烯酸酯， 第- 電路構件於主面上具有第—連接端子，上述 第-電路構件於主面上具有第二連接端子且至少 包含玻璃轉移溫度2贼町的熱塑性樹脂 二，專利範圍第13項所述之_組成物的應 用八中述胺基甲酸醋（甲基)丙烯酸醋是由下述通式⑷ 所表示的胺基甲酸酯（甲基)丙烯酸酯： 64 201204798 [化5] Ο δ H HO R5一O-N^R4 Ο Η» (Day &gt; [In the formula (B), R6 and r7 each independently represent a straight bond of a carbon number of 2 to 12 or an alkyl group of a branched chain, b represents an integer of 1 to 10, and c represents an integer of 1 to 25 Further, in the formula, R6, R7, b, and c, respectively, may be the same or different from each other. 4. The adhesive composition according to any one of claims 1 to 3 The above-mentioned amino phthalic acid ester (mercapto) acrylate is obtained by using an aliphatic polyester diol. 5. The adhesive composition according to any one of claims 1 to 4, The weight average molecular weight of the above-mentioned amino phthalic acid ester (mercapto) acrylate is 8000 or more and less than 25,000. The adhesive composition according to any one of the items 1 to 5, The (b) radically polymerizable compound contains at least one vinyl compound having a phosphoric acid group and a radical polymerizable compound other than the above-described vinyl compound having a scaly Si group. Adhesive composition according to any one of items 1 to 6 of the patent scope Wherein the above (a) thermoplastic resin comprises a resin selected from the group consisting of a phenoxy resin, a polyurethane resin, a polyester amine phthalate resin, a butyraldehyde tree 62 201204798 grease, an acrylic resin, and a polyimide resin. At least - 8. The method according to any one of the claims to the seventh aspect of the invention, wherein the composition of the composition further comprises (4) conductive particles. 1 9 - a connecting structure of a circuit member, The bonding member according to any one of the items 1 to 8, wherein the connecting member is interposed between the first circuit member and the circuit member, and the first connecting terminal And the second connection: the electrical connection, the first circuit member and/or the second circuit member are made of a substrate containing a thermoplastic ray having a glass transition degree of 2 〇〇t or less. The connection structure of the circuit member according to claim 9, wherein the thermoplastic resin having a glass transition temperature of 200 ° C or less is selected from the group consisting of polyethylene terephthalate, polycarbonate, and poly Group consisting of ethylene naphthalate The connection structure of the circuit member according to claim 9 or the first aspect, wherein the first circuit member or the second circuit structure = the circuit component Is composed of a substrate containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and the first circuit member or the second circuit The other circuit of the member 63 201204798 is composed of a substrate containing at least a seed selected from the group consisting of a polyimide resin and a polyethylene terephthalate. The manufacturing method of the connection structure includes the first circuit member having the first connection terminal and the main surface, the second circuit member having the first connection port, and the terminal and the second connection terminal pair The adhesive according to any one of the preceding claims, wherein: the first circuit member and the second circuit member are heated between the first circuit member and the second circuit member, and the (four) age object is heated to harden (4) the first The circuit member is coupled to the second circuit member. 13. The use of an adhesive composition for connection to a second circuit member, the above-mentioned adhesive composition comprising (4) a thermoplastic resin, (5) a free-form composition, and (c) a radical polymerization initiator, and Heart = the amphoteric compound comprises a urethane (meth) acrylate having a critical surface tension of 25 mN/m to 4 〇 mN/m, and the first circuit member has a first connection terminal on the main surface, the above - the circuit member has a second connection terminal on the main surface and at least comprises a thermoplastic resin 2 of a glass transition temperature of 2 thims, and the application of the composition described in the thirteenth patent of the patent range is described in the urethane (meth) Acrylic vinegar is a urethane (meth) acrylate represented by the following formula (4): 64 201204798 [Chemical 5] Ο δ H HO R5-ON^R4 Ο Η 0-R3—Ο—C&quot;C=CH2 ---(A) δ ψ [式（Α)中，R1及R2分別獨立地表示氫原子或者甲 基’ R3表示伸乙基、伸丙基、由ε_己内S旨的開環化合物所 衍生的基團或者下述通式（Β)所表示的基團’R4表示下 述通式（Β)所表示的基團，R5表示飽和脂肪族基或者飽 和脂環基，a表示1〜40的整數] [化6]0-R3—Ο—C&quot;C=CH2 ---(A) δ ψ [In the formula (R), R1 and R2 each independently represent a hydrogen atom or a methyl group, and R3 represents an exoethyl group, a propyl group, and A group derived from a ring-opening compound of ε_本内 or a group represented by the following formula (Β) represents a group represented by the following formula (Β), and R5 represents a saturated aliphatic group. Or a saturated alicyclic group, a represents an integer of 1 to 40] [Chemical 6] • * « (B) [式（B)中，R6及R7分別獨立地表示碳數2〜12的 直鏈或者分支鏈的伸烷基，b表示1〜10的整數，C表示1 〜25的整數，此外’式中’ r6彼此、r7彼此、b彼此以及 c彼此分別可相同，亦可不同]。 15· —種黏著劑組成物的應用，用於將第一電路構件 及第二電路構件連接， 上述黏著劑組成物含有（a)熱塑性樹脂、（b)自由基 聚合性化合物及（c)自由基聚合起始劑，且上述（b)自 由基聚合性化合物包含下述通式（A)所表示的胺基曱酸 65 201204798. 酯（曱基）丙烯酸酯，並且 上述第一電路構件於主面上具有第一連接端子，上述 第二電路構件於主面上具有第二連接端子，且至少一方的 電路構件是由包含玻璃轉移溫度200°C以下的熱塑性樹脂 的基材所構成， [化7] R1 CH2—C_CwO—R3&quot;—〇»C—C-〇 δ Λ ή δ 'R5—C-N-R4一N-C-〇Η Η Ο …CA) [式（Α)中’ R1及R2分別獨立地表示氫原子或者甲 基’ R3表示伸乙基、伸丙基、由ε-己内酯的開環化合物所 衍生的基團或者下述通式（Β)所表示的基團，R4表示下 述通式（Β)所表示的基團，R5表示飽和脂肪族基或者飽 和脂環基，a表示1〜40的整數] [化8] 0 O&quot;^R6--〇^-C-R7 - C-+0-R6^—〇— ·，·(Β) [式（Β)中，R6及R7分別獨立地表示碳數2〜12的 直鏈或者分支鏈的伸烧基，b表示1〜10的整數，c表示1 〜25的整數；此外，式中，R6彼此、R7彼此、b彼此以及 c彼此分別可相同，亦可不同]。 66 201204798 16.如申請專利範圍第13項至第15項中任一項所述 之黏著劑組成物的應用，其中上述胺基甲酸酿（曱基）丙烯 酸酯是使用脂肪族聚醋二醇而獲得。 Π.如申請專利範圍第13項至第16項中任一項所述 之黏著劑組成物的應用，其中上述胺基曱酸酯（曱基）丙烯 酸酯的重量平均分子量為8000以上且小於25000。 18·如申請專利範圍第13項至第17項中任一項所述 之黏著劑組成物的應用，其中上述（b)自由基聚合性化合 物含有1種以上的具有磷酸基的乙烯基化合物、及1種以 上的上述具有填酸基的乙細基化合物以外的自由基聚合性 化合物。 19. 如申請專利範圍第13項至第18項中任一項所述 之黏著劑組成物的應用，其中上述（a)熱塑性樹脂含有選 自由笨氧基樹脂、聚胺基甲酸酯樹脂、聚酯胺基曱酸酯樹 脂、丁醛樹脂、丙烯酸樹脂及聚醯亞胺樹脂所組成組群中 的至少1種。 20. 如申請專利範圍第13項至第19項中任一項所述 之黏著劑組成物的應用’其中上述黏著劑組成物更含有（d) 導電性粒子。 67• * « (B) [In the formula (B), R6 and R7 each independently represent a straight or branched alkyl group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and C represents 1 to 25; Integer, in addition, 'in the formula' r6, r7, b, and c, respectively, may be the same or different. 15. An application of an adhesive composition for joining a first circuit member and a second circuit member, wherein the adhesive composition comprises (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) free And the (b) radically polymerizable compound comprises an amino phthalic acid 65 201204798. ester (mercapto) acrylate represented by the following formula (A), and the first circuit member is mainly a first connection terminal on the surface, the second circuit member has a second connection terminal on the main surface, and at least one of the circuit members is made of a base material comprising a thermoplastic resin having a glass transition temperature of 200 ° C or less. 7] R1 CH2—C_CwO—R3&quot;—〇»C—C—〇δ Λ δ δ 'R5—CN-R4—NC-〇Η Η Ο ...CA) [Formula (Α) in 'R1 and R2 are independently The hydrogen atom or the methyl group 'R3' represents an ethyl group, a propyl group, a group derived from a ring-opening compound of ε-caprolactone or a group represented by the following formula (Β), and R4 represents the following a group represented by the formula (Β), R5 represents a saturated aliphatic group or saturated Ring group, a represents an integer of 1 to 40] [Chemical 8] 0 O&quot;^R6--〇^-C-R7 - C-+0-R6^-〇- ·,·(Β) [Formula (Β) In the above, R6 and R7 each independently represent a linear or branched chain of a carbon number of 2 to 12, b represents an integer of 1 to 10, and c represents an integer of 1 to 25; further, in the formula, R6 and R7 The mutuals, b, and c may be the same or different from each other. The use of the adhesive composition according to any one of claims 13 to 15, wherein the above-mentioned amino formic acid thiol acrylate is an aliphatic polyester diol. obtain. The use of the adhesive composition according to any one of claims 13 to 16, wherein the amino phthalate acrylate has a weight average molecular weight of 8,000 or more and less than 25,000. . The application of the adhesive composition according to any one of the items of the present invention, wherein the (b) radically polymerizable compound contains one or more vinyl compounds having a phosphate group, And one or more kinds of radical polymerizable compounds other than the above-mentioned ethyl group-containing compound having an acid group. The use of the adhesive composition according to any one of claims 13 to 18, wherein the (a) thermoplastic resin contains a resin selected from the group consisting of an epoxy resin, a polyurethane resin, At least one of a group consisting of a polyester amine phthalate resin, a butyral resin, an acrylic resin, and a polyimide resin. The application of the adhesive composition according to any one of claims 13 to 19 wherein the above adhesive composition further contains (d) conductive particles. 67
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