TWI540195B - A circuit connecting material and a connecting method using the same, and a connecting structure - Google Patents

A circuit connecting material and a connecting method using the same, and a connecting structure Download PDF

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TWI540195B
TWI540195B TW101134443A TW101134443A TWI540195B TW I540195 B TWI540195 B TW I540195B TW 101134443 A TW101134443 A TW 101134443A TW 101134443 A TW101134443 A TW 101134443A TW I540195 B TWI540195 B TW I540195B
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meth
circuit
acrylate
acrylate monomer
monofunctional
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TW201336956A (en
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Shinichi Hayashi
Yuta Araki
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Dexerials Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10128—Display
    • H05K2201/10136—Liquid Crystal display [LCD]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Wire Bonding (AREA)
  • Combinations Of Printed Boards (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

電路連接材料及使用其之連接方法以及連接結構體 Circuit connecting material, connecting method using same, and connecting structure

本發明係關於一種電路連接材料、及使用電路連接材料連接一對電路構件之連接方法、以及藉由該連接方法而獲得之連接結構體。 The present invention relates to a circuit connecting material, a connecting method for connecting a pair of circuit members using a circuit connecting material, and a connecting structure obtained by the connecting method.

本申請案係以2011年9月21日於日本提出申請之日本專利申請編號日本特願2011-206379為基礎而主張優先權者，該申請案係藉由參照而引用至本申請案中。 The present application claims priority on the basis of Japanese Patent Application No. 2011-206379, filed on Sep. 2011.

自先前起，於電性連接一對電路構件時，使用有使導電性粒子分散之電路連接構件。作為電路連接構件，例如可列舉異向性導電膜(ACF：Anisotropic Conductive Film)，而有經由異向性導電膜連接基板之形成有配線電極之連接面與電子零件之形成有端子電極(凸塊)之連接面的方法。於使用異向性導電膜之連接方法中，於基板之連接面上暫貼有異向性導電膜，使異向性導電膜與電子零件之連接面對向並於異向性導電膜上配置電子零件進行熱加壓。藉此，異向性導電膜中之導電性粒子被挾入至電子零件之端子電極與基板之配線電極之間並被壓碎。其結果為，電子零件之端子電極與基板之配線電極經由導電性粒子而電性連接。 From the past, when electrically connecting a pair of circuit members, a circuit connecting member that disperses conductive particles is used. Examples of the circuit connecting member include an anisotropic conductive film (ACF: Anisotropic Conductive Film), and a connection surface on which a wiring electrode is formed via an anisotropic conductive film and a terminal electrode (a bump) formed of an electronic component. ) The method of connecting the faces. In the connection method using an anisotropic conductive film, an anisotropic conductive film is temporarily attached to the connection surface of the substrate, and the connection between the anisotropic conductive film and the electronic component is faced and disposed on the anisotropic conductive film. The electronic parts are hot pressed. Thereby, the conductive particles in the anisotropic conductive film are caught between the terminal electrode of the electronic component and the wiring electrode of the substrate and are crushed. As a result, the terminal electrode of the electronic component and the wiring electrode of the substrate are electrically connected via the conductive particles.

未處於端子電極與配線電極之間之導電性粒子係存在於異向性導電膜之絕緣性接著劑組成物中，且維持電絕緣狀態。即，僅於端子電極與配線電極之間可實現電導通。 The conductive particles that are not between the terminal electrode and the wiring electrode are present in the insulating adhesive composition of the anisotropic conductive film, and are maintained in an electrically insulating state. That is, electrical conduction can be achieved only between the terminal electrode and the wiring electrode.

作為構成上述電路連接構件之接著劑組成物，先前有含有環氧樹脂等之接著劑組成物。該接著劑組成物通常含有環氧樹脂、與環氧樹脂反應之酚樹脂等硬化劑、促進環氧樹脂與硬化劑之反應之潛伏性硬化劑等。 As an adhesive composition constituting the above-described circuit connecting member, an adhesive composition containing an epoxy resin or the like has been previously included. The adhesive composition usually contains an epoxy resin, a curing agent such as a phenol resin reacted with an epoxy resin, a latent curing agent that promotes a reaction between the epoxy resin and the curing agent, and the like.

近年來，由於生產時間之縮短故而對異向性導電膜要求可於低溫短時間內進行硬化之接著劑組成物。為了滿足該要求而關注含有(甲基)丙烯酸酯衍生物及過氧化物等自由基聚合起始劑之自由基硬化型接著劑組成物。自由基硬化型之電路連接材料係藉由富有反應性之自由基而於短時間內進行硬化反應，故而對生產時間之縮短而言較為有利(參照專利文獻1、2)。 In recent years, an anisotropic conductive film has been required to be cured at a low temperature for a short time due to a shortened production time. In order to satisfy this requirement, attention has been paid to a radical-curable adhesive composition containing a radical polymerization initiator such as a (meth) acrylate derivative or a peroxide. The radically curable circuit-connecting material is hardened by a reactive radical and is hardened in a short period of time, so that it is advantageous in shortening the production time (see Patent Documents 1 and 2).

[專利文獻1]日本特開2008-291199號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-291199

[專利文獻2]日本特開2011-37953號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2011-37953

然而，(甲基)丙烯酸酯衍生物有如下傾向：與環氧樹脂等相比，聚合時之硬化收縮較大，又，硬化後之內部應力亦較大。因此，通常於使用含有自由基硬化型之接著劑組成物之電路連接材料之情形時，於其接著層與LCD面板等基板之界面產生氣泡，而有連接可靠性降低之虞。尤其是於TFT(Thin Film Transistor)方式之LCD面板中與用作面板配線上之絕緣膜的氮化矽(SiN)膜之界面，該氣泡顯著產生而密合力較差，其結果為有連接可靠性大幅降低之虞。 However, the (meth) acrylate derivative has a tendency to have a large hardening shrinkage during polymerization and a large internal stress after hardening as compared with an epoxy resin or the like. Therefore, in the case of using a circuit connecting material containing a radical curing type adhesive composition, bubbles are generated at the interface between the adhesive layer and a substrate such as an LCD panel, and the connection reliability is lowered. In particular, in an interface between a TFT panel of a TFT (Thin Film Transistor) type and a tantalum nitride (SiN) film used as an insulating film on a panel wiring, the bubble is remarkably generated and the adhesion is poor, and as a result, connection reliability is obtained. Drastically reduced.

本發明係鑒於上述先前之實際情況而提出者，其目的 在於提供一種於受到高溫高濕處理時可提高與和氮化矽膜之界面之密合性而發揮優異之連接可靠性的電路連接材料、及使用該電路連接材料連接一對電路構件之連接方法、以及藉由該連接方法而獲得之連接結構體。 The present invention has been made in view of the above-mentioned actual circumstances, and its object Provided is a circuit connecting material which can improve adhesion to an interface with a tantalum nitride film when subjected to high-temperature and high-humidity treatment, and which has excellent connection reliability, and a connection method for connecting a pair of circuit members using the circuit connecting material And a connection structure obtained by the connection method.

為了解決上述課題，本發明之電路連接材料之特徵在於：含有：(1)多官能(甲基)丙烯酸酯單體、(2)藉由熱或光而產生游離自由基之自由基聚合起始劑、及(3)單官能(甲基)丙烯酸酯單體，單官能(甲基)丙烯酸酯單體係以化學式(1)表示，於化學式(1)中，R為聯苯基或伸萘基，R與鍵結於其之氧原子之鍵結位置為鄰位、間位、或對位，n為1~10。 In order to solve the above problems, the circuit connecting material of the present invention is characterized by comprising: (1) a polyfunctional (meth) acrylate monomer, and (2) a radical polymerization initiation which generates free radicals by heat or light. And (3) a monofunctional (meth) acrylate monomer, the monofunctional (meth) acrylate single system is represented by the chemical formula (1), and in the chemical formula (1), R is a biphenyl group or a naphthene The bond between R and the oxygen atom bonded to it is ortho, meta or para, and n is 1 to 10.

又，為了解決上述課題，本發明之連接結構體係於配置成電路電極彼此對向之一對電路構件之間，隔著電路連接材料電性且機械性地連接對向之電路構件而成者，其特徵在於：電路構件之一者其表面被氮化矽膜所覆蓋，且電路連接材料含有：(1)多官能(甲基)丙烯酸酯單體、(2)藉由熱或光而產生游離自由基之自由基聚合起始劑、及(3)單官能(甲基)丙烯酸酯單體，且單官能(甲基)丙烯酸酯單體係以化學式(1)所表示，於化學式(1)中，R為聯苯基或伸萘基，R與鍵結於其之氧原子之鍵結位置為鄰位、間位、或對位，n為1~10。 Further, in order to solve the above problems, the connection structure system of the present invention is configured such that a pair of circuit members are disposed between the pair of circuit members, and the circuit members are electrically and mechanically connected to each other via the circuit connection material. The method is characterized in that: one of the circuit members has a surface covered by a tantalum nitride film, and the circuit connecting material comprises: (1) a polyfunctional (meth) acrylate monomer, and (2) free by heat or light. a free radical radical polymerization initiator, and (3) a monofunctional (meth) acrylate monomer, and the monofunctional (meth) acrylate single system is represented by the chemical formula (1), in the chemical formula (1) Wherein R is a biphenyl group or a naphthyl group, and the bonding position of R to the oxygen atom bonded thereto is an ortho, meta or para position, and n is 1 to 10.

又，為了解決上述課題，本發明之連接方法使電路連接材料介於配置成電路電極彼此對向之一對電路構件之間，藉由熱加壓使對向之該電路構件電性且機械性地連接，其特徵在於：電路構件之一者其表面係由氮化矽膜所覆蓋，電路連接材料含有：(1)多官能(甲基)丙烯酸酯單體、(2)藉由熱或光而產生游離自由基之自由基聚合起始劑、及(3)單官能(甲基)丙烯酸酯單體，且單官能(甲基)丙烯酸酯單體係以化學式(1)所表示，於化學式(1)中，R為聯苯基或伸萘基，R與鍵結於其之氧原子之鍵結位置為鄰位、間位、或對位，n為1~10。 Further, in order to solve the above problems, the connection method of the present invention has a circuit connecting material interposed between a pair of circuit members arranged such that circuit electrodes are opposed to each other, and the circuit member is electrically and mechanically opposed by thermal pressurization. Ground connection, characterized in that one of the circuit members has a surface covered by a tantalum nitride film, and the circuit connection material comprises: (1) a polyfunctional (meth) acrylate monomer, and (2) by heat or light. a radical polymerization initiator which generates free radicals, and (3) a monofunctional (meth) acrylate monomer, and the monofunctional (meth) acrylate single system is represented by the chemical formula (1), in the chemical formula In (1), R is a biphenyl group or a naphthyl group, and the bonding position of R to the oxygen atom bonded thereto is an ortho, meta or para position, and n is 1 to 10.

根據本發明，可提供一種於受到高溫高濕處理時能夠提高與和氮化矽膜之界面之密合性而發揮優異之連接可靠性的電路連接材料、及使用該電路連接材料連接一對電路構件之連接方法、以及藉由該連接方法而獲得之連接結構體。 According to the present invention, it is possible to provide a circuit connecting material which can improve adhesion to an interface with a tantalum nitride film when subjected to high-temperature and high-humidity treatment, and which exhibits excellent connection reliability, and a pair of circuits connected using the circuit connecting material a joining method of the member, and a joined structure obtained by the joining method.

以下，一面參照圖式一面按下述順序對本發明之具體之實施形態(以下簡稱為「本實施形態」)進行詳細說明。 Hereinafter, a specific embodiment (hereinafter simply referred to as "this embodiment") of the present invention will be described in detail with reference to the drawings in the following order.

<1.電路連接材料> <1. Circuit connection material>

<2.連接方法> <2. Connection method>

<3.實施例> <3. Example>

<1.電路連接材料> <1. Circuit connection material>

本實施形態中之電路連接材料係介於配置成電路電極彼此對向之一對電路構件之間並電性且機械性地連接對向之該電路構件者。本實施形態中之電路連接材料係應用於在絕緣性接著劑組成物中分散有複數個導電性粒子並形成為膜狀之異向性導電膜。 The circuit connecting material in the present embodiment is a circuit member that is disposed between the pair of circuit members facing each other and electrically and mechanically connected to the circuit member. The circuit connecting material in the present embodiment is applied to an anisotropic conductive film in which a plurality of conductive particles are dispersed in an insulating adhesive composition and formed into a film shape.

絕緣性接著劑組成物含有多官能(甲基)丙烯酸酯化合物、單官能(甲基)丙烯酸酯單體、藉由熱或光而產生游離自由基之自由基聚合起始劑、及膜形成樹脂。此處，(甲基)丙烯酸酯包含丙烯酸酯與甲基丙烯酸酯。 The insulating adhesive composition contains a polyfunctional (meth) acrylate compound, a monofunctional (meth) acrylate monomer, a radical polymerization initiator which generates free radicals by heat or light, and a film-forming resin . Here, the (meth) acrylate contains an acrylate and a methacrylate.

多官能(甲基)丙烯酸酯化合物、單官能(甲基)丙烯酸酯單體均為自由基聚合性樹脂，於對異向性導電膜進行加熱時於絕緣性接著劑組成物內形成交聯結構，藉此，使接著劑組成物硬化。 The polyfunctional (meth) acrylate compound and the monofunctional (meth) acrylate monomer are all radical polymerizable resins, and form a crosslinked structure in the insulating adhesive composition when the anisotropic conductive film is heated. Thereby, the adhesive composition is hardened.

單官能(甲基)丙烯酸酯單體係以化學式(1)所表示。 The monofunctional (meth) acrylate single system is represented by the chemical formula (1).

於化學式(1)中，R為聯苯基或伸萘基。R與鍵結於其之氧原子O之鍵結位置為鄰位、間位、或對位。n為1~10，尤佳為1~3。若n過大，則交聯結構變鬆，會使異向 性導電膜對氮化矽膜之密合性(接著性)降低。 In the chemical formula (1), R is a biphenyl group or a naphthyl group. The bonding position between R and the oxygen atom O bonded thereto is an ortho, meta or para position. n is 1~10, especially 1~3. If n is too large, the crosslinked structure becomes loose, which will cause an anomaly The adhesion (adhesion) of the conductive film to the tantalum nitride film is lowered.

如此，單官能(甲基)丙烯酸酯單體根據由龐大之R、適當長度之(CH2CH20)n、及進行自由基聚合之-COCH=CH2所構成之結構而於聚合時硬化收縮變小，又，硬化後之內部應力亦變小，因此，可抑制於連接時於接著層與基板之氮化矽膜之界面產生氣泡，從而藉由較高之密合力而連接。即，藉由於異向性導電膜中含有此種單官能(甲基)丙烯酸酯單體，而可於使用該異向性導電膜連接而成之連接結構體中，獲得較高之連接可靠性。 Thus, the monofunctional (meth) acrylate monomer hardens and shrinks during polymerization according to a structure composed of a bulky R, an appropriate length of (CH 2 CH 20 ) n , and a radical polymerization-COCH=CH 2 . When the thickness is small, the internal stress after hardening is also reduced. Therefore, it is possible to suppress the generation of bubbles at the interface between the adhesive layer and the tantalum nitride film of the substrate during the connection, thereby connecting by a high adhesion force. In other words, since the monofunctional (meth) acrylate monomer is contained in the anisotropic conductive film, high connection reliability can be obtained in the bonded structure in which the anisotropic conductive film is connected. .

作為單官能(甲基)丙烯酸酯單體，例如可列舉以化學式(2)所表示之乙氧化鄰苯基苯酚丙烯酸酯。 Examples of the monofunctional (meth) acrylate monomer include ethoxylated o-phenylphenol acrylate represented by the chemical formula (2).

再者，聯苯基與鍵結於其之氧原子之鍵結位置並不如化學式(2)所示限定於鄰位，亦可為間位(乙氧化間苯基苯酚丙烯酸酯)或對位(乙氧化對苯基苯酚丙烯酸酯)。 Further, the bonding position of the biphenyl group and the oxygen atom bonded thereto is not limited to the ortho position as shown in the chemical formula (2), and may be a meta position (oxyphenyl phenol phenol acrylate) or a para position ( Ethoxylated p-phenylphenol acrylate).

又，於R為伸萘基之情形時亦相同，伸萘基與鍵結於其之氧原子之鍵結位置亦可為鄰位、間位、對位中之任一者。 Further, in the case where R is a naphthyl group, the bonding position of the stretching naphthyl group and the oxygen atom bonded thereto may be any of an ortho, meta or para position.

絕緣性之接著劑組成物中之單官能(甲基)丙烯酸酯單體之摻合量較佳為3~20質量%(相對於絕緣性接著劑組成物100質量份為3~20質量份)。若未達3質量%，則不易 獲得單官能(甲基)丙烯酸酯單體之效果，接著強度變弱。另一方面，若超過20質量%，則成為耐熱性較差之硬化物，導通電阻值變高。 The blending amount of the monofunctional (meth) acrylate monomer in the insulating adhesive composition is preferably from 3 to 20% by mass (3 to 20 parts by mass based on 100 parts by mass of the insulating adhesive composition) . If it is less than 3% by mass, it is not easy The effect of obtaining a monofunctional (meth) acrylate monomer is followed by weakening of the strength. On the other hand, when it exceeds 20% by mass, it becomes a cured product which is inferior in heat resistance, and the on-resistance value becomes high.

藉由含有上述單官能(甲基)丙烯酸酯單體，可一面抑制受到高溫高濕處理時之電路電極間之電阻值之變動，一面提高與和氮化矽膜之界面之密合性而發揮優異之連接可靠性。 By containing the monofunctional (meth) acrylate monomer, it is possible to improve the adhesion to the interface with the tantalum nitride film while suppressing the variation in the resistance value between the circuit electrodes during the high-temperature and high-humidity treatment. Excellent connection reliability.

作為多官能(甲基)丙烯酸酯化合物，可列舉：多官能(甲基)丙烯酸酯單體、多官能(甲基)丙烯酸酯低聚物、多官能(甲基)丙烯酸酯聚合物等。 Examples of the polyfunctional (meth) acrylate compound include a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate oligomer, and a polyfunctional (meth) acrylate polymer.

作為二官能(甲基)丙烯酸酯，可列舉：雙酚F-EO改質二(甲基)丙烯酸酯、雙酚A-EO改質二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯、二氫芳樟醇二(甲基)丙烯酸酯、二環戊二烯(甲基)丙烯酸酯等。 Examples of the difunctional (meth) acrylate include bisphenol F-EO modified di(meth)acrylate, bisphenol A-EO modified di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Acrylate, polyethylene glycol (meth) acrylate, dihydro linalool di(meth) acrylate, dicyclopentadiene (meth) acrylate, and the like.

作為三官能(甲基)丙烯酸酯，可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷PO改質(甲基)丙烯酸酯、異三聚氰酸EO改質三(甲基)丙烯酸酯等。 Examples of the trifunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate, trimethylolpropane PO modified (meth) acrylate, and isomeric cyanuric acid EO modified three. (Meth) acrylate, etc.

作為四官能以上之(甲基)丙烯酸酯，可列舉：二新戊四醇五(甲基)丙烯酸酯、新戊四醇六(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二(三羥甲基)丙烷四丙烯酸酯等。此外，亦可使用多官能(甲基)丙烯酸胺酯。 Examples of the tetrafunctional or higher (meth) acrylate include dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Ester, bis(trimethylol)propane tetraacrylate, and the like. Further, a polyfunctional (meth) acrylate can also be used.

自由基聚合起始劑係藉由熱或光而分解並產生游離自由基之硬化劑，可選擇公知之自由基聚合起始劑。例如可列舉：過氧化雙乙醯基、過氧化二碳酸酯、過氧酯、過氧 縮酮、過氧化二烷基、過氧化氫等過氧化物系聚合起始劑；偶氮二丁腈等偶氮系聚合起始劑；氧化還原系聚合起始劑等。 The radical polymerization initiator is a hardener which decomposes by heat or light and generates free radicals, and a known radical polymerization initiator can be selected. For example, peroxydiethyl hydrazine, peroxydicarbonate, peroxyester, peroxygen a peroxide-based polymerization initiator such as a ketal, a dialkyl peroxide or a hydrogen peroxide; an azo polymerization initiator such as azobisbutyronitrile; a redox polymerization initiator;

絕緣性之接著劑組成物中之自由基聚合起始劑之摻合量若過少則硬化不充分，若過多則異向性導電膜之凝集力降低，故而相對於(甲基)丙烯酸酯化合物100質量份，較佳為1~10質量份、更佳為3~7質量份。 When the amount of the radical polymerization initiator in the insulating adhesive composition is too small, the curing is insufficient. If the amount is too large, the cohesive force of the anisotropic conductive film is lowered, so that the (meth) acrylate compound 100 is reduced. The mass part is preferably from 1 to 10 parts by mass, more preferably from 3 to 7 parts by mass.

作為膜形成樹脂，例如可使用環氧樹脂、聚酯樹脂、聚胺酯樹脂、苯氧樹脂、聚醯胺、EVA等熱塑性彈性體等。其中，為了耐熱性、接著性而可列舉：聚酯樹脂、聚胺酯樹脂、苯氧樹脂，尤其是苯氧樹脂，例如雙A型環氧樹脂、具有茀骨架之苯氧樹脂。 As the film-forming resin, for example, a thermoplastic elastomer such as an epoxy resin, a polyester resin, a polyurethane resin, a phenoxy resin, a polyamide or EVA can be used. Among them, examples of the heat resistance and the adhesion include a polyester resin, a polyurethane resin, a phenoxy resin, and particularly a phenoxy resin, for example, a double A type epoxy resin and a phenoxy resin having an anthracene skeleton.

膜形成樹脂若過少則不形成膜，若過多則有用以獲得電連接之樹脂之排斥性變低之傾向，因此，相對於樹脂固形物成分(由聚合性丙烯酸系化合物與膜形成樹脂所構成之接著劑組成物)100質量份，為80~30質量份、更佳為70~40質量份。 When the film-forming resin is too small, no film is formed, and if it is too large, the repellent property of the resin for obtaining electrical connection tends to be low. Therefore, the resin solid component (composed of a polymerizable acrylic compound and a film-forming resin) is formed. The amount of the composition of the second component is from 80 to 30 parts by mass, more preferably from 70 to 40 parts by mass, per 100 parts by mass.

作為導電性粒子，可使用先前之異向性導電膜中所使用之導電性粒子，例如可列舉：金粒子、銀粒子、鎳粒子等金屬粒子；以金、鎳、鋅等金屬將苯代三聚氰胺樹脂(benzoguanamine resin)或苯乙烯樹脂等樹脂粒子之表面被覆之金屬被覆樹脂粒子等。作為導電性粒子之平均粒徑，就連接可靠性之觀點而言較佳為1~20 μm，更佳為2~10 μm。 As the conductive particles, conductive particles used in the conventional anisotropic conductive film can be used, and examples thereof include metal particles such as gold particles, silver particles, and nickel particles; and benzene melamine is used as a metal such as gold, nickel, or zinc. A metal-coated resin particle coated with a surface of a resin particle such as a benzoguanamine resin or a styrene resin. The average particle diameter of the conductive particles is preferably from 1 to 20 μm, more preferably from 2 to 10 μm, from the viewpoint of connection reliability.

絕緣性之接著劑組成物中之導電性粒子之平均粒子密度，就連接可靠性及絕緣可靠性之觀點而言，較佳為500~50000個/mm2，更佳為1000~30000個/mm2。 The average particle density of the conductive particles in the insulating adhesive composition is preferably from 500 to 50,000/mm 2 , more preferably from 1,000 to 30,000/mm, from the viewpoint of connection reliability and insulation reliability. 2 .

於絕緣性之接著劑組成物中，為了提高對金屬之接著性，可含有磷酸丙烯酸酯。 In the insulating adhesive composition, phosphoric acid acrylate may be contained in order to improve the adhesion to the metal.

進而，於絕緣性之接著劑組成物中可含有其他添加組成物，例如各種丙烯酸單體等稀釋用單體、填充劑、軟化劑、著色劑、難燃劑、觸變劑、矽烷偶合劑、二氧化矽微粒子等。 Further, the insulating adhesive composition may contain other additive components, for example, various monomers such as various acrylic monomers, a filler, a softener, a colorant, a flame retardant, a thixotropic agent, a decane coupling agent, Antimony dioxide particles and the like.

藉由含有矽烷偶合劑而提高有機材料與無機材料之界面之接著性。藉由含有二氧化矽微粒子而可調整儲存彈性模數、線膨脹係數等，從而使連接可靠性提高。 The adhesion of the interface between the organic material and the inorganic material is improved by containing a decane coupling agent. The storage elastic modulus, the linear expansion coefficient, and the like can be adjusted by containing the cerium oxide fine particles, thereby improving the connection reliability.

本實施形態之異向性導電膜可藉由利用棒式塗佈機等公知之塗佈方法以乾燥厚度成為10~50 μm之方式將下述混合物塗佈於聚矽氧剝離處理聚酯膜等剝離膜，並投入至例如50~90℃之恆溫槽中進行乾燥而製造，上述混合物係利用公知之分散方法使導電性粒子均勻地分散混合於含有作為自由基聚合性樹脂之多官能(甲基)丙烯酸酯化合物及以化學式(1)所表示之單官能(甲基)丙烯酸酯單體、(甲基)丙烯酸酯化合物、自由基聚合起始劑、以及膜形成樹脂的絕緣性接著劑組成物中而獲得。當於該異向性導電膜上積層絕緣性接著膜之情形時，可藉由將絕緣性接著劑組成物塗佈於異向性導電膜上並進行乾燥而獲得。 The anisotropic conductive film of the present embodiment can be applied to a polyfluorinated release-treated polyester film or the like by a known coating method such as a bar coater so that the dry thickness is 10 to 50 μm. The film is released and dried by, for example, drying in a thermostatic chamber at 50 to 90 ° C, and the mixture is uniformly dispersed and mixed with a polyfunctional (methyl group) as a radical polymerizable resin by a known dispersion method. An acrylate compound and an insulating adhesive composition of a monofunctional (meth) acrylate monomer, a (meth) acrylate compound, a radical polymerization initiator, and a film-forming resin represented by the chemical formula (1) Obtained in the middle. When an insulating adhesive film is laminated on the anisotropic conductive film, it can be obtained by applying an insulating adhesive composition onto an anisotropic conductive film and drying it.

作為剝離膜，例如，於PET(Poly Ethylene Terephthalate)、OPP(Oriented Polypropylene)、PMP(Poly-4-methlpentene-1)、PTFE(Polytetrafluoroethylene)等塗佈聚矽氧等剝離劑而成，防止異向性導電膜之乾燥並且維持異向性導電膜之形狀。 As a release film, for example, in PET (Poly Ethylene) Terephthalate), OPP (Oriented Polypropylene), PMP (Poly-4-methlpentene-1), PTFE (Polytetrafluoroethylene), etc. are coated with a stripping agent such as polyfluorene to prevent drying of the anisotropic conductive film and maintain anisotropic conductivity. The shape of the film.

根據本實施形態之異向性導電膜，藉由含有以化學式(1)所表示之結構之單官能(甲基)丙烯酸酯單體，而可一面抑制受到高溫高濕處理時之電路電極間之電阻值之變動，一面提高與和氮化矽膜之界面之密合性而發揮優異之連接可靠性。 According to the anisotropic conductive film of the present embodiment, by containing the monofunctional (meth) acrylate monomer having the structure represented by the chemical formula (1), it is possible to suppress the circuit electrodes between the high temperature and high humidity treatments. The change in the resistance value improves the adhesion to the interface with the tantalum nitride film and exhibits excellent connection reliability.

<2.連接方法> <2. Connection method>

提供一種經由本實施形態之異向性導電膜將構成LCD(Liquid Crystal Display)面板之玻璃基板與作為配線材之COF(Chip On Film)壓著連接之連接方法。於玻璃基板細間距地形成有配線電極。又，於COF，根據配線電極之配線圖案形成有端子電極。而且，藉由利用該連接方法對玻璃基板之配線電極與COF之端子電極進行異向性導電連接，而獲得連接結構體。 Provided is a connection method in which a glass substrate constituting an LCD (Liquid Crystal Display) panel and a COF (Chip On Film) as a wiring member are pressure-bonded via the anisotropic conductive film of the present embodiment. A wiring electrode is formed at a fine pitch on the glass substrate. Further, in the COF, terminal electrodes are formed in accordance with the wiring pattern of the wiring electrodes. Further, the connection structure is obtained by anisotropic conductive connection between the wiring electrode of the glass substrate and the terminal electrode of the COF by the connection method.

以下，對經由異向性導電膜壓著連接玻璃基板與COF之連接方法進行具體說明。首先，於玻璃基板上之形成有配線電極之面上，將異向性導電膜暫貼於玻璃基板(暫貼步驟)。於該暫貼中，將加壓接合機之加熱至低溫之頭部之加壓面輕輕抵壓於含導電性粒子之層上面並以低壓進行加壓。加熱溫度係絕緣性接著劑組成物雖流動但不會硬化之程度之低溫(例如60~80℃中之特定之值)。又，暫貼步驟 中之加壓壓力例如為0.5 MPa~2 MPa中之特定之值。又，暫貼步驟中之熱加壓時間例如為1~3秒(sec)中之特定之時間。 Hereinafter, a method of connecting the glass substrate and the COF by pressure bonding via an anisotropic conductive film will be specifically described. First, the anisotropic conductive film is temporarily attached to the glass substrate on the surface on which the wiring electrode is formed on the glass substrate (temporary step). In this temporary application, the pressing surface of the head of the press bonding machine heated to a low temperature is gently pressed against the layer containing the conductive particles and pressurized at a low pressure. The heating temperature is a low temperature (for example, a specific value in 60 to 80 ° C) in which the insulating adhesive composition flows but does not harden. Also, the temporary step The pressing pressure in the middle is, for example, a specific value of 0.5 MPa to 2 MPa. Further, the hot pressurization time in the temporary attaching step is, for example, a specific time of 1 to 3 seconds (sec).

於暫貼步驟中暫貼異向性導電膜之後，確認異向性導電膜之對位狀態，於產生位置偏移等不良狀況之情形時，於該暫貼步驟之後，進行剝離異向性導電膜並再次將異向性導電膜暫貼於正確位置上之修復處理(修復步驟)。 After temporarily attaching the anisotropic conductive film to the temporary bonding step, the alignment state of the anisotropic conductive film is confirmed, and when a problem such as a positional deviation occurs, the exfoliation anisotropic conduction is performed after the temporary bonding step. The film is again subjected to a repair process (repair step) in which the anisotropic conductive film is temporarily attached to the correct position.

繼而，以使凸塊與配線電極對向之方式將COF配置於異向性導電膜上(配置步驟)。 Then, the COF is placed on the anisotropic conductive film so that the bumps face the wiring electrodes (arrangement step).

然後，將加壓接合機之經加熱之頭部之加壓面(未圖示)抵壓於COF之上面而使玻璃基板與COF壓著連接(連接步驟)。 Then, the pressurized surface (not shown) of the heated head of the press bonding machine is pressed against the upper surface of the COF to press-bond the glass substrate to the COF (connection step).

連接步驟中之加壓壓力例如為1 MPa~5 MPa中之特定之值。又，連接步驟中之加熱溫度係使絕緣性粒子熔融並且使絕緣性之接著劑組成物硬化之溫度(例如溫度160~210℃中之特定之值)。又，連接步驟中之熱加壓時間例如為3~10秒中之特定之時間。 The pressing pressure in the joining step is, for example, a specific value of 1 MPa to 5 MPa. Further, the heating temperature in the joining step is a temperature at which the insulating particles are melted and the insulating adhesive composition is cured (for example, a specific value in a temperature of 160 to 210 ° C). Further, the heat pressurization time in the joining step is, for example, a specific time of 3 to 10 seconds.

以上述方式，使導電性粒子挾持於配線電極與凸塊之間，使接著劑組成物硬化。藉此，電性及機械性地連接玻璃基板與COF。而且，獲得異向性導電連接有玻璃基板與COF而成之連接結構體。所獲得之連接結構體如上所述，可一面良好地維持絕緣可靠性，一面發揮優異之連接可靠性及導通可靠性。 In the above manner, the conductive particles are held between the wiring electrode and the bump to harden the adhesive composition. Thereby, the glass substrate and the COF are electrically and mechanically connected. Further, a connection structure in which a glass substrate and a COF are electrically connected to each other is obtained. As described above, the obtained connection structure can exhibit excellent connection reliability and conduction reliability while maintaining insulation reliability.

以上，已對本實施形態進行說明，但不言而喻，本發 明並非限定於上述實施形態，於不脫離本發明之要旨之範圍內可進行各種變更。 The embodiment has been described above, but it goes without saying that the present invention The present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit and scope of the invention.

於上述實施形態中，使用異向性導電膜作為異向性導電接著構件。然而，異向性導電接著構件之結構並不限定於此，例如，亦可製成進而積層有絕緣性接著劑層之雙層結構的異向性導電膜。又，例如，亦可藉由將下述接著劑漿料重疊進行塗佈而製成雙層之接著劑層，上述接著劑漿料係由於絕緣性之接著劑組成物中含有導電性粒子而成之導電性接著劑漿料，及由絕緣性之接著劑組成物所構成之絕緣性接著劑漿料而構成。 In the above embodiment, an anisotropic conductive film is used as the anisotropic conductive member. However, the structure of the anisotropic conductive member is not limited thereto, and for example, an anisotropic conductive film having a two-layer structure in which an insulating adhesive layer is laminated may be used. Further, for example, a double-layer adhesive layer may be formed by laminating the following adhesive paste, and the adhesive slurry is formed by containing conductive particles in an insulating adhesive composition. The conductive adhesive paste is composed of an insulating adhesive paste composed of an insulating adhesive composition.

又，於上述實施形態中，已對使用構成LCD(Liquid Crystal Display)面板之玻璃基板作為玻璃基板之情形進行說明，但玻璃基板並不限定於此，例如亦可為構成PDP基板(PDP面板)、有機EL基板(有機EL面板)等之玻璃基板。 Further, in the above-described embodiment, a case where a glass substrate constituting an LCD (Liquid Crystal Display) panel is used as the glass substrate has been described. However, the glass substrate is not limited thereto, and may be, for example, a PDP substrate (PDP panel). A glass substrate such as an organic EL substrate (organic EL panel).

又，於上述實施形態中，已對使用玻璃基板作為基板之情形進行說明，但亦可為硬質基板、軟性基板等其他基板。又，於上述實施形態中，已對使用COF作為電子零件之情形進行說明，但亦可為IC晶片、TAB等其他電子零件。 Further, in the above embodiment, the case where the glass substrate is used as the substrate has been described, but it may be another substrate such as a hard substrate or a flexible substrate. Further, in the above embodiment, the case of using COF as an electronic component has been described, but it may be another electronic component such as an IC chip or a TAB.

又，於上述實施形態中，已對將本發明應用於FOG(Film On Glass)之情形進行說明，但本發明亦可應用於COG(Chip On Glass)、FOR(Film On Board)等其他安裝方法。 Further, in the above embodiment, the case where the present invention is applied to FOG (Film On Glass) has been described, but the present invention is also applicable to other mounting methods such as COG (Chip On Glass) and FOR (Film On Board). .

[實施例] [Examples]

以下，基於實驗結果對本發明之具體實施例進行說明。 Hereinafter, specific embodiments of the present invention will be described based on experimental results.

<實施例1> <Example 1>

於含有作為膜形成樹脂之以固形物成分換算計為60質量份(相對於絕緣性接著劑組成物為60質量%)之聚酯胺酯樹脂(商品名：UR8200，東洋紡織股份有限公司製造，以甲基乙基酮/甲苯=50：50之混合溶劑溶解成20質量%者)、自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)33質量份(33質量%)及乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)1質量份(1質量%)、矽烷偶合劑(商品名：KBM-503，信越化學股份有限公司製造)1質量份(1質量%)、磷酸丙烯酸酯(商品名：P-1M，共榮化學股份有限公司製造)1質量份(1質量%)、自由基聚合起始劑(商品名：Perhexa C，日本油脂股份有限公司製造)4質量份(4質量%)的絕緣性接著劑組成物中，以粒子密度成為10000個/mm2之方式使導電性粒子(商品名：AUL704，積水化學工業股份有限公司製造)均勻地分散，利用棒式塗佈機將含導電性粒子之組成物塗佈於剝離膜上並進行乾燥，製作厚度15μm之電路連接材料。 A polyester urethane resin (trade name: UR8200, manufactured by Toyobo Co., Ltd.) containing 60 parts by mass (60% by mass of the insulating adhesive composition) in terms of the solid content of the film-forming resin. 33 parts by mass of a radically polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) dissolved in a mixed solvent of methyl ethyl ketone/toluene = 50:50 (manufactured by Daicel-Cytec Co., Ltd.) (33 mass) %) and ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1 part by mass (1% by mass), decane coupling agent (trade name: KBM-503, 1 part by mass (1% by mass), phosphoric acid acrylate (trade name: P-1M, manufactured by Kyoei Chemical Co., Ltd.), 1 part by mass (1% by mass), radical polymerization initiator (trade name: Perhexa C, manufactured by Nippon Oil & Fat Co., Ltd.) 4 parts by mass (4% by mass) of the insulating adhesive composition, the conductive particles were obtained so that the particle density was 10,000/mm 2 (trade name: AUL704, manufactured by Sekisui Chemical Industry Co., Ltd.) is evenly dispersed, Using a bar coater composition containing conductive particles is applied to the release film and dried to a thickness of 15μm of the circuit-connecting material.

繼而，進行經由製作而成之異向性導電膜連接玻璃基板與COF(50μmP、Cu8μmt-鍍Sn、38μmt-S'perflex基材)之處理。此處，作為玻璃基板，使用IZO塗層玻璃基板(整個表面為IZO塗層，玻璃厚度為0.7mm)作為之後之導通電阻值測定用，使用SiN塗層玻璃基板(整個表面為SiN塗層)用作連接強度測定用。首先，於玻璃基板 上之形成有配線電極之面上，將異向性導電膜切割成1.5 mm寬度並暫貼於玻璃基板上(暫貼步驟)。於該暫貼中，將加壓接合機之加熱至低溫之頭部的加壓面輕輕抵壓於含導電性粒子之層上面並以低壓進行加壓。加熱溫度設為絕緣性粒子不會熔解且絕緣性接著劑組成物雖流動但不會硬化之程度之低溫即70℃。又，暫貼步驟中之加壓壓力設為1 MPa。又，暫貼步驟中之熱加壓時間設為2秒。 Then, a treatment of connecting the glass substrate and COF (50 μmP, Cu 8 μmt-plated Sn, 38 μm-S'perflex substrate) through the produced anisotropic conductive film was performed. Here, as the glass substrate, an IZO coated glass substrate (the entire surface is an IZO coating, the glass thickness is 0.7 mm) is used as the subsequent on-resistance value measurement, and a SiN-coated glass substrate (the entire surface is SiN-coated) is used. ) Used for connection strength measurement. First, on the glass substrate On the surface on which the wiring electrode was formed, the anisotropic conductive film was cut into a width of 1.5 mm and temporarily attached to the glass substrate (temporary step). In this temporary application, the pressing surface of the head of the press bonding machine heated to a low temperature is gently pressed against the layer containing the conductive particles and pressurized at a low pressure. The heating temperature is 70 ° C which is a low temperature at which the insulating particles do not melt and the insulating adhesive composition flows but does not harden. Further, the pressurizing pressure in the temporary attaching step was set to 1 MPa. Further, the hot pressurization time in the temporary attaching step was set to 2 seconds.

繼而，以使COF之端子電極與玻璃基板之配線電極對向之方式將COF配置於異向性導電膜(配置步驟)。 Then, the COF is placed on the anisotropic conductive film so that the terminal electrode of the COF and the wiring electrode of the glass substrate face each other (arrangement step).

然後，經由緩衝材(100μmt鐵氟龍(註冊商標))將加壓接合機之經加熱之頭部之加壓面(1.5mm寬度)抵壓於COF之上面而使玻璃基板與COF壓著連接(連接步驟)。 Then, the pressure surface (1.5 mm width) of the heated head of the press bonding machine is pressed against the COF via a buffer material (100 μmt Teflon (registered trademark)) to press the glass substrate and the COF. (Connection step).

連接步驟中之加壓壓力設為4 MPa。又，連接步驟中之加熱溫度設為190℃。又，連接步驟中之熱加壓時間設為5秒。 The pressing pressure in the joining step was set to 4 MPa. Further, the heating temperature in the joining step was set to 190 °C. Further, the hot pressurization time in the joining step was set to 5 seconds.

以上述方式，使導電性粒子挾持於配線電極與凸塊之間，使接著劑組成物硬化並電性及機械性地連接玻璃基板與COF，從而獲得連接結構體。 In the above manner, the conductive particles are held between the wiring electrode and the bump, and the adhesive composition is cured to electrically and mechanically bond the glass substrate and the COF to obtain a bonded structure.

<實施例2> <Example 2>

將自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)設為32質量份、乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)設為2質量份，除此以外，藉由與實施例1相同之條件製作電路連接材料。 A radically polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was used as 32 parts by mass of ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, Shin-Nakamura Chemical Industry Co., Ltd.) A circuit connecting material was produced under the same conditions as in Example 1 except that the amount of the product was changed to 2 parts by mass.

<實施例3> <Example 3>

將自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)設為31質量份、乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)設為3質量份，除此以外，藉由與實施例1相同之條件製作電路連接材料。 The radically polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was used as 31 parts by mass of ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, Shin-Nakamura Chemical Industry Co., Ltd.) A circuit connecting material was produced under the same conditions as in Example 1 except that the amount of the product was changed to 3 parts by mass.

<實施例4> <Example 4>

將自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)設為30質量份、乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)設為4質量份，除此以外，藉由與實施例1相同之條件製作電路連接材料。 The radical polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was used as 30 parts by mass of ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, Shin-Nakamura Chemical Industry Co., Ltd.) A circuit connecting material was produced under the same conditions as in Example 1 except that the amount of the product was changed to 4 parts by mass.

<實施例5> <Example 5>

將自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)設為29質量份、乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)設為5質量份，除此以外，藉由與實施例1相同之條件製作電路連接材料。 The radically polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was used as 29 parts by mass of ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, Shin-Nakamura Chemical Industry Co., Ltd.) A circuit connecting material was produced under the same conditions as in Example 1 except that the amount of the product was changed to 5 parts by mass.

<實施例6> <Example 6>

將自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)設為19質量份、乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)設為15質量份，除此以外，藉由與實施例1相同之條件製作電路連接材料。 The radical polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was used as 19 parts by mass of ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, Shin-Nakamura Chemical Industry Co., Ltd.) A circuit connecting material was produced under the same conditions as in Example 1 except that the amount of the product was changed to 15 parts by mass.

<實施例7> <Example 7>

將自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)設為14質量份、乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)設為20質量份，除此以外，藉由與實施例1相同之條件製作電路連接材料。 The radically polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was used as 14 parts by mass of ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, Shin-Nakamura Chemical Industry Co., Ltd.) A circuit connecting material was produced under the same conditions as in Example 1 except that the amount of the product was changed to 20 parts by mass.

<實施例8> <Example 8>

將自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)設為9質量份、乙氧化鄰苯基苯酚丙烯酸酯(商品名：A-LEN-10，新中村化學工業股份有限公司製造)設為25質量份，除此以外，藉由與實施例1相同之條件製作電路連接材料。 The radically polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was set to 9 parts by mass, and ethoxylated o-phenylphenol acrylate (trade name: A-LEN-10, Shin-Nakamura Chemical Industry Co., Ltd.) A circuit connecting material was produced under the same conditions as in Example 1 except that the amount of the product was changed to 25 parts by mass.

<比較例1> <Comparative Example 1>

使自由基聚合性樹脂(商品名：EB-600，Daicel-Cytec股份有限公司製造)含有34質量份且不含有乙氧化鄰苯基苯酚丙烯酸酯，除此以外，藉由與實施例1相同之條件製作電路連接材料。 In the same manner as in Example 1, except that the radical polymerizable resin (trade name: EB-600, manufactured by Daicel-Cytec Co., Ltd.) was contained in an amount of 34 parts by mass and did not contain ethoxylated o-phenylphenol acrylate. Condition the circuit to connect the material.

[導通電阻值之測定] [Measurement of On-resistance value]

對於實施例1~8、比較例1中製得之連接結構體，測定初始(Initial)之電阻，及溫度85℃、濕度85%RH、500小時之TH試驗(Thermal Humidity Test)後之電阻。測定係使用數位萬用表(數位萬用表7561，橫河電機公司製造)並利用4端子法測定流通1 mA之電流時之連接電阻。 With respect to the bonded structures obtained in Examples 1 to 8 and Comparative Example 1, the resistance of the initial (Initial) and the resistance after the temperature of 85 ° C, the humidity of 85% RH, and the TH hour test (Thermal Humidity Test) were measured. In the measurement, a digital multimeter (a digital multimeter 7561, manufactured by Yokogawa Electric Co., Ltd.) was used, and the connection resistance at the time of flowing a current of 1 mA was measured by a 4-terminal method.

[接著強度之測定] [Measurement of strength]

對於實施例1~8、比較例1之連接結構體，使用拉伸試驗機(Tensilon，Orientec公司製造)以剝離速度50 mm/分鐘於90度(Y軸方向)提拉，測定接著強度(N/cm)。 The bonded structures of Examples 1 to 8 and Comparative Example 1 were pulled at a peeling speed of 50 mm/min at 90 degrees (Y-axis direction) using a tensile tester (Tensilon, manufactured by Orientec Co., Ltd.) to measure the strength (N). /cm).

將匯總實施例1~8及比較例1之條件、導通電阻值及連接強度之測定結果者示於[表1]。 The results of measuring the conditions, on-resistance values, and connection strength of Examples 1 to 8 and Comparative Example 1 are shown in [Table 1].

實施例1~8之異向性導電膜含有乙氧化鄰苯基苯酚丙烯酸酯，因此，可認為根據由龐大之聯苯基、(CH2CH20)n(n=1)、及進行自由基聚合之-COCH=CH2所構成之結構而於聚合時硬化收縮變小，又，硬化後之內部應力亦變小。藉此可認為，可抑制於連接時於接著層與基板之氮化矽膜之界面上產生氣泡，從而藉由優異之密合力而獲得較高之接著強度(連接可靠性)。 The anisotropic conductive films of Examples 1 to 8 contain ethoxylated o-phenylphenol acrylate, and therefore, it can be considered that the radical is based on a large amount of biphenyl, (CH 2 CH 20 ) n (n=1), and radical. The structure of the polymerization-COCH=CH 2 is small, and the hardening shrinkage at the time of polymerization becomes small, and the internal stress after hardening also becomes small. From this, it is considered that generation of bubbles at the interface between the adhesive layer and the tantalum nitride film of the substrate at the time of connection can be suppressed, and a high adhesive strength (connection reliability) can be obtained by excellent adhesion.

其中，於含有乙氧化鄰苯基苯酚丙烯酸酯3~20重量%之實施例3~7中，於導通電阻值及接著強度上可獲得良好之值。 Among them, in Examples 3 to 7 containing 3 to 20% by weight of ethoxylated o-phenylphenol acrylate, good values were obtained in terms of on-resistance value and adhesion strength.

另一方面，於比較例1中，由於不含有乙氧化鄰苯基 苯酚丙烯酸酯，故而於聚合時硬化收縮變大，並且硬化後之內部應力亦變大，藉此可認為，於連接時於接著層與基板之氮化矽膜之界面產生氣泡，作為結果，接著強度變低。 On the other hand, in Comparative Example 1, since ethoxylated o-phenyl group was not contained Since phenol acrylate has a large hardening shrinkage during polymerization and an internal stress after hardening, it is considered that bubbles are generated at the interface between the adhesive layer and the tantalum nitride film of the substrate at the time of connection, and as a result, The intensity is low.

Claims (4)

一種電路連接材料，含有：(1)多官能(甲基)丙烯酸酯單體、(2)自由基聚合起始劑，其係藉由熱或光而產生游離自由基、及(3)單官能(甲基)丙烯酸酯單體，其於絕緣性之接著劑組成物中之摻合量為3~20質量%；該單官能(甲基)丙烯酸酯單體係以化學式(1)表示， 於該化學式(1)中，R為聯苯基或伸萘基，R與鍵結於其之氧原子的鍵結位置為鄰位、間位、或對位，n為1~10。 A circuit connecting material comprising: (1) a polyfunctional (meth) acrylate monomer, (2) a radical polymerization initiator, which generates free radicals by heat or light, and (3) monofunctional a (meth) acrylate monomer having a blending amount of 3 to 20% by mass in the insulating adhesive composition; the monofunctional (meth) acrylate single system is represented by the chemical formula (1), In the chemical formula (1), R is a biphenyl group or a naphthyl group, and the bonding position of R to the oxygen atom bonded thereto is an ortho, meta or para position, and n is 1 to 10. 如申請專利範圍第1項之電路連接材料，其中，該單官能(甲基)丙烯酸酯單體為乙氧化鄰苯基苯酚丙烯酸酯。 The circuit connecting material of claim 1, wherein the monofunctional (meth) acrylate monomer is ethoxylated o-phenylphenol acrylate. 一種連接結構體，其係於配置成電路電極彼此對向之一對電路構件之間，隔著電路連接材料電性且機械性地連接對向之該電路構件而成者，該電路構件之一者其表面被氮化矽膜覆蓋，該電路連接材料含有：(1)多官能(甲基)丙烯酸酯單體、(2)自由基聚合起始劑，其係藉由熱或光而產生游離自由基、及 (3)單官能(甲基)丙烯酸酯單體，其於絕緣性之接著劑組成物中之摻合量為3~20質量%；該單官能(甲基)丙烯酸酯單體係以下述化學式(1)表示， 於該化學式(1)中，R為聯苯基或伸萘基，R與鍵結於其之氧原子的鍵結位置為鄰位、間位、或對位，n為1~10。 A connection structure formed by electrically and mechanically connecting a pair of circuit members between a pair of circuit members disposed opposite to each other with a circuit connecting material, one of the circuit members The surface of the circuit is covered by a tantalum nitride film, and the circuit connecting material comprises: (1) a polyfunctional (meth) acrylate monomer, and (2) a radical polymerization initiator, which is free by heat or light. a free radical, and (3) a monofunctional (meth) acrylate monomer, which is incorporated in the insulating adhesive composition in an amount of from 3 to 20% by mass; the monofunctional (meth) acrylate monomer It is represented by the following chemical formula (1). In the chemical formula (1), R is a biphenyl group or a naphthyl group, and the bonding position of R to the oxygen atom bonded thereto is an ortho, meta or para position, and n is 1 to 10. 一種連接方法，使電路連接材料介於配置成電路電極彼此對向之一對電路構件之間，藉由熱加壓使對向之該電路構件電性且機械性地連接，該電路構件之一者其表面被氮化矽膜覆蓋，該電路連接材料含有：(1)多官能(甲基)丙烯酸酯單體、(2)自由基聚合起始劑，其係藉由熱或光而產生游離自由基、及(3)單官能(甲基)丙烯酸酯單體，其於絕緣性之接著劑組成物中之摻合量為3~20質量%；該單官能(甲基)丙烯酸酯單體係以下述化學式(1)表示， 於該化學式(1)中，R為聯苯基或伸萘基，R與鍵結於其之氧原子的鍵結位置為鄰位、間位、或對位，n為1~10。 A connection method for electrically connecting a circuit connecting material between a pair of circuit members disposed opposite to each other, and electrically and mechanically connecting the opposite circuit member by thermal pressurization, one of the circuit members The surface of the circuit is covered by a tantalum nitride film, and the circuit connecting material comprises: (1) a polyfunctional (meth) acrylate monomer, and (2) a radical polymerization initiator, which is free by heat or light. a free radical, and (3) a monofunctional (meth) acrylate monomer, which is incorporated in the insulating adhesive composition in an amount of from 3 to 20% by mass; the monofunctional (meth) acrylate monomer It is represented by the following chemical formula (1). In the chemical formula (1), R is a biphenyl group or a naphthyl group, and the bonding position of R to the oxygen atom bonded thereto is an ortho, meta or para position, and n is 1 to 10.
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CN103797078B (en) 2016-08-31
KR20140064967A (en) 2014-05-28
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JP5844589B2 (en) 2016-01-20
JP2012041541A (en) 2012-03-01

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