KR20130006549A - Adhesive composition, adhesive for circuit connection, connected structure, and semiconductor device - Google Patents

Adhesive composition, adhesive for circuit connection, connected structure, and semiconductor device Download PDF

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Publication number
KR20130006549A
KR20130006549A KR1020127034027A KR20127034027A KR20130006549A KR 20130006549 A KR20130006549 A KR 20130006549A KR 1020127034027 A KR1020127034027 A KR 1020127034027A KR 20127034027 A KR20127034027 A KR 20127034027A KR 20130006549 A KR20130006549 A KR 20130006549A
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KR
South Korea
Prior art keywords
adhesive
weight
circuit
adhesive composition
meth
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KR1020127034027A
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Korean (ko)
Inventor
도시유끼 야나가와
도루 후지나와
다께시 호리우찌
마사또시 마쯔시따
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히다치 가세고교 가부시끼가이샤
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Publication of KR20130006549A publication Critical patent/KR20130006549A/en

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    • C—CHEMISTRY; METALLURGY
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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
    • 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
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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
    • 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
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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    • 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
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    • 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
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    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Conductive Materials (AREA)
  • Wire Bonding (AREA)

Abstract

본 발명은 저온 단시간에 경화시킨 경우에도 충분한 접착성을 나타내고, 고온 고습 조건으로 장시간 접속체를 폭로한 후에도 접속 신뢰성이 높고, 또한 저장 안정성도 우수한, (a) 열가소성 수지, (b) 1 분자 중에 2개 이상의 (메트)아크릴로일기 및 2개 이상의 우레탄 결합을 갖고, 중량 평균 분자량이 10,000 이상인 라디칼 중합성 화합물, 및 (c) 라디칼 중합 개시제를 함유하는 접착제 조성물, 및 그것을 이용한 회로 접속용 접착제, 접속체 및 반도체 장치를 제공한다. The present invention exhibits sufficient adhesiveness even when cured at a low temperature for a short time, in (a) a thermoplastic resin and (b) one molecule having high connection reliability and excellent storage stability even after exposing the connection body for a long time under high temperature and high humidity conditions. An adhesive composition comprising a radically polymerizable compound having two or more (meth) acryloyl groups and two or more urethane bonds and having a weight average molecular weight of 10,000 or more, and (c) a radical polymerization initiator, and an adhesive for circuit connection using the same, Provided are a connector and a semiconductor device.

Description

접착제 조성물, 회로 접속용 접착제, 접속체 및 반도체 장치{ADHESIVE COMPOSITION, ADHESIVE FOR CIRCUIT CONNECTION, CONNECTED STRUCTURE, AND SEMICONDUCTOR DEVICE}Adhesive composition, adhesive for circuit connection, connector, and semiconductor device {ADHESIVE COMPOSITION, ADHESIVE FOR CIRCUIT CONNECTION, CONNECTED STRUCTURE, AND SEMICONDUCTOR DEVICE}

본 발명은 접착제 조성물, 및 그것을 이용한 회로 접속용 접착제, 접속체, 반도체 장치에 관한 것이다.TECHNICAL FIELD This invention relates to an adhesive composition and the adhesive agent for circuit connections, a connection body, and a semiconductor device using the same.

반도체 소자 및 액정 표시 소자에 있어서, 소자 중의 여러가지 부재를 결합시킬 목적으로 종래부터 다양한 접착제가 사용되고 있다. 접착제에 요구되는 특성은 접착성을 비롯하여, 내열성, 고온 고습 상태에 있어서의 신뢰성 등 다방면에 걸친다. 또한, 접착에 사용되는 피착체에는 인쇄 배선판이나 폴리이미드 등의 유기 기재를 비롯하여, 구리, 알루미늄 등의 금속이나 ITO, SiN, SiO2 등의 다종다양한 표면 상태를 갖는 기재가 이용된다. 이 때문에 접착제는 각 피착체에 맞추어서 분자 설계할 필요가 있다. BACKGROUND OF THE INVENTION In a semiconductor device and a liquid crystal display device, various adhesives have been conventionally used for the purpose of bonding various members in the device. The properties required for the adhesive are multifaceted such as adhesiveness, heat resistance, reliability in high temperature and high humidity. As the adherend to be used for adhesion, substrates having various surface states such as copper, aluminum, and ITO, SiN, SiO 2 , as well as organic substrates such as printed wiring boards and polyimides, are used. For this reason, the adhesive needs to be designed molecularly in accordance with each adherend.

종래, 상기 반도체 소자나 액정 표시 소자용의 접착제로서는, 고접착성이고 또한 고신뢰성을 나타내는 에폭시 수지를 이용한 열경화성 수지가 주류로 되어 있다(예를 들면, 특허문헌 1 참조). 이러한 수지로서는, 에폭시 수지, 에폭시 수지와 반응성을 갖는 페놀 수지 등의 경화제, 및 에폭시 수지와 경화제의 반응을 촉진하는 열잠재성 촉매를 구성 성분으로서 포함하는 것이 일반적으로 이용되고 있다. 열잠재성 촉매는 경화 온도 및 경화 속도를 결정하는 중요한 인자가 되고 있고, 실온에서의 저장 안정성과 가열 시의 경화 속도 측면에서 다양한 화합물이 이용되어 왔다. 실제의 공정에서의 경화 조건은 170 내지 250℃의 온도에서 1 내지 3 시간 경화함으로써, 원하는 접착성이 얻어진다. Conventionally, as an adhesive agent for the said semiconductor element and a liquid crystal display element, the thermosetting resin using the epoxy resin which is high adhesiveness and shows high reliability has become mainstream (for example, refer patent document 1). As such resin, what contains a hardening | curing agent, such as an epoxy resin and a phenol resin which is reactive with an epoxy resin, and a heat latent catalyst which promotes reaction of an epoxy resin and a hardening | curing agent as a component is generally used. Heat latent catalysts have become important factors in determining the curing temperature and curing rate, and various compounds have been used in terms of storage stability at room temperature and curing rate upon heating. The hardening conditions in an actual process are obtained by hardening for 1 to 3 hours at the temperature of 170-250 degreeC, and desired adhesiveness is obtained.

최근 들어, 반도체 소자의 고집적화, 액정 소자의 고정밀화에 수반하여, 소자간 및 배선간 피치가 협소화하고 있다. 이 때문에, 상기한 조건으로 열 처리를 행한 경우에는, 경화 시의 가열에 의해 주변 부재에 악영향을 미칠 우려가 있다. 또한 저비용화를 위해서는 작업 처리량을 향상시킬 필요성이 있고, 저온(100 내지 170℃), 단시간(1 시간 이내, 바람직하게는 수초 이내), 바꾸어 말하면 「저온속경화」의 접착이 요구되고 있다. 이 저온속경화를 달성하기 위해서, 활성화 에너지가 낮은 열잠재성 촉매가 사용되는 경우도 있는데, 그 경우, 접착제가 실온 부근에서의 저장 안정성을 겸비하는 것이 매우 어려운 것이 알려져 있다. In recent years, with the high integration of semiconductor elements and the high precision of liquid crystal elements, the pitch between elements and wirings has narrowed. For this reason, when heat processing is performed on said conditions, there exists a possibility that it may adversely affect a peripheral member by the heating at the time of hardening. In addition, in order to reduce the cost, it is necessary to improve the throughput, and low temperature (100 to 170 ° C), short time (within 1 hour, preferably within several seconds), in other words, adhesion of "low temperature curing" is required. In order to achieve this low temperature hardening, a heat latent catalyst having a low activation energy is sometimes used. In that case, it is known that it is very difficult for the adhesive to have storage stability in the vicinity of room temperature.

최근 들어, 아크릴레이트 유도체나 메타아크릴레이트 유도체(이후, 「(메트)아크릴레이트 유도체」라 함)와 라디칼 중합 개시제인 과산화물을 병용한 라디칼 경화형 접착제가 주목받고 있다(예를 들면, 특허문헌 2 참조). In recent years, the radical curable adhesive which used the acrylate derivative and the methacrylate derivative (henceforth "(meth) acrylate derivative"), and the peroxide which is a radical polymerization initiator attracts attention (for example, refer patent document 2). ).

한편, 라디칼 경화계의 접착제는 경화 시의 경화 수축이 크기 때문에, 에폭시 수지를 이용한 경우와 비교하여 접착 강도가 떨어지는 문제가 있다. 접착 강도의 개량 방법으로서, 에테르 결합에 의해서 유연성 및 가요성을 부여한 우레탄아크릴레이트 화합물을 라디칼 중합성 화합물로서 사용하는 방법이 제안되어 있다(특허문헌 3, 4 참조). On the other hand, since the adhesive shrinkage at the time of hardening of the adhesive agent of a radical curing system is large, there exists a problem that adhesive strength falls compared with the case where an epoxy resin is used. As an improvement method of adhesive strength, the method of using the urethane acrylate compound which provided flexibility and flexibility by ether bond as a radically polymerizable compound is proposed (refer patent document 3, 4).

일본 특허 공개 (평)01-113480호 공보Japanese Patent Publication No. 01-113480 일본 특허 공개 제2002-203427호 공보Japanese Patent Laid-Open No. 2002-203427 일본 특허 제3522634호 공보Japanese Patent No. 3352634 일본 특허 공개 제2002-285128호 공보Japanese Patent Laid-Open No. 2002-285128

그러나, 특허문헌 3, 4 등에 기재된 종래의 라디칼 경화계의 접착제를 사용한 경우, 경화 후의 탄성률이나 유리 전이 온도 등의 접착제 물성이 저하되고, 또한 흡수율의 상승이나 내가수분해성이 저하된다고 하는 문제가 있다. 이 때문에, 고온 고습 조건(예를 들면 85℃/85％ RH)으로 장시간의 폭로 후에도 안정된 성능이 요구되는 반도체 소자나 액정 표시 소자에 이 접착제를 사용한 경우, 신뢰성 시험 후에 접착력이나 접속 저항 등의 특성이 악화하는 것이 문제로 되어 있다. However, when using the adhesive of the conventional radical hardening system described in patent documents 3, 4 etc., there exists a problem that adhesive physical properties, such as an elasticity modulus and glass transition temperature after hardening, fall, and a raise of water absorption rate and hydrolysis resistance fall. . For this reason, when this adhesive agent is used for the semiconductor element or liquid crystal display element which the stable performance is required even after exposure for a long time under high temperature, high humidity conditions (for example, 85 degreeC / 85% RH), it will be a characteristic, such as adhesive force or connection resistance, after a reliability test. This deterioration is a problem.

본 발명은 저온 단시간에 경화시킨 경우에도 충분한 접착성을 나타내고, 고온 고습 조건(예를 들면 85℃/85％ RH)으로 장시간 접속체를 폭로한 후에도 접속 신뢰성이 높고, 또한 저장 안정성도 우수한 접착제 조성물, 및 그것을 이용한 회로 접속용 접착제, 접속체 및 반도체 장치를 제공하는 것을 목적으로 한다. The present invention exhibits sufficient adhesiveness even when cured at a low temperature for a short time, and has high connection reliability and excellent storage stability even after exposing the connection body for a long time under high temperature and high humidity conditions (for example, 85 ° C / 85% RH). And an adhesive for connecting circuits, a connecting body and a semiconductor device using the same.

상기 사정을 감안하여 본 발명은 (a) 열가소성 수지, (b) 1 분자 중에 2개 이상의 (메트)아크릴로일기 및 2개 이상의 우레탄 결합을 갖고, 중량 평균 분자량이 10,000 이상인 라디칼 중합성 화합물(이하, 간단히 「(b) 라디칼 중합성 화합물」이라고도 함), 및 (c) 라디칼 중합 개시제를 함유하는 접착제 조성물을 제공한다.In view of the above circumstances, the present invention provides a radically polymerizable compound having (a) a thermoplastic resin, (b) two or more (meth) acryloyl groups and two or more urethane bonds in one molecule, and having a weight average molecular weight of 10,000 or more (hereinafter, , "(B) radically polymerizable compound", and (c) radical polymerization initiator are provided.

이러한 접착제 조성물에 따르면, 저온 단시간에 경화시킨 경우에도 충분한 접착성을 나타내고, 고온 고습 조건으로 장시간 접속체를 폭로한 후에도 접속 신뢰성이 높고, 또한 저장 안정성도 우수하다. According to such an adhesive composition, even when it hardens at low temperature for a short time, sufficient adhesiveness is exhibited, connection reliability is high and storage stability is also excellent even after exposing a connection body for a long time on high temperature, high humidity conditions.

본 발명의 접착제 조성물은 (a) 열가소성 수지 100 중량부에 대하여, (b) 라디칼 중합성 화합물을 10 내지 250 중량부, (c) 라디칼 중합 개시제를 0.05 내지 30 중량부 함유하는 것이 바람직하다. It is preferable that the adhesive composition of this invention contains 10-250 weight part of (b) radically polymerizable compounds and 0.05-30 weight part of (c) radical polymerization initiators with respect to 100 weight part of (a) thermoplastic resins.

본 발명의 접착제 조성물은 (d) 분자 내에 적어도 1개 이상의 인산기를 갖는 비닐 화합물을 (a) 열가소성 수지 100 중량부에 대하여 0.1 내지 20 중량부 더 함유하는 것이 바람직하다. It is preferable that the adhesive composition of this invention contains 0.1-20 weight part of (d) vinyl compounds which have at least 1 or more phosphoric acid group in a molecule with respect to 100 weight part of (a) thermoplastic resins.

본 발명의 접착제 조성물은 (e) 도전성 입자를 더 함유하는 것이 바람직하다. It is preferable that the adhesive composition of this invention contains (e) electroconductive particle further.

본 발명은 또한 서로 대향하는 회로 전극을 갖는 기판 사이에 개재시켜, 서로 대향하는 회로 전극끼리가 전기적으로 접속되도록 기판 끼리를 접착하기 위해서 이용되는 회로 접속용 접착제로서, 상기 본 발명의 접착제 조성물로 이루어지는 회로 접속용 접착제를 제공한다. The present invention is also an adhesive for circuit connection which is interposed between substrates having circuit electrodes opposed to each other, and is used to bond the substrates so that the circuit electrodes facing each other are electrically connected, comprising the adhesive composition of the present invention. An adhesive for circuit connection is provided.

이러한 회로 접속용 접착제는 본 발명의 접착제 조성물을 이용하고 있기 때문에, 저온 단시간에 경화시킨 경우에도 충분한 접착성을 나타내고, 고온 고습 조건으로 장시간 접속체를 폭로한 후에도 접속 신뢰성이 높고, 또한 저장 안정성도 우수하다. Since the adhesive agent for circuit connection uses the adhesive composition of this invention, even when it hardens in low temperature and short time, it shows sufficient adhesiveness, high connection reliability, and storage stability also after exposing a connection body for a long time on high temperature, high humidity conditions. great.

본 발명은 또한 제1 회로 전극을 갖는 제1 기판과, 제2 회로 전극을 갖는 제2 기판을, 제1 회로 전극과 제2 회로 전극이 서로 대향하도록 배치하고, 대향 배치한 제1 기판과 제2 기판 사이에 상기 본 발명의 회로 접속용 접착제를 개재시키고, 가열 가압하여 제1 회로 전극과 제2 회로 전극을 전기적으로 접속시켜 이루어지는 접속체를 제공한다. The present invention further provides a first substrate having a first circuit electrode and a second substrate having a second circuit electrode, wherein the first circuit electrode and the second circuit electrode are disposed so as to face each other, and the first substrate and the second substrate are disposed to face each other. Provided is a connecting body formed by interposing an adhesive for a circuit connection of the present invention between two substrates and heating and pressing to electrically connect the first circuit electrode and the second circuit electrode.

본 발명은 또한, 대향 배치한 반도체 소자와 반도체 탑재용 기판 사이에 상기 본 발명의 회로 접속용 접착제를 개재시키고, 가열 가압하여 반도체 소자와 반도체 탑재용 기판을 전기적으로 접속시켜 이루어지는 반도체 장치를 제공한다. The present invention also provides a semiconductor device in which the circuit connecting adhesive of the present invention is interposed between the semiconductor element and the semiconductor mounting substrate, which are disposed opposite each other, and are heated and pressurized to electrically connect the semiconductor element and the semiconductor mounting substrate. .

이러한 접속체 및 반도체 장치는 본 발명의 회로 접속용 접착제를 이용하고 있기 때문에, 충분히 접착성이 높고, 고온 고습 조건으로 장시간 폭로한 후에도 접속 신뢰성이 높다. Since such a connection body and a semiconductor device use the adhesive agent for circuit connections of this invention, adhesiveness is high enough and connection reliability is high, even after exposing for a long time on high temperature, high humidity conditions.

본 발명에 따르면, 저온 단시간에 경화시킨 경우에도 충분한 접착성 및 접속 신뢰성을 얻는 것을 가능하게 하고, 또한 저장 안정성도 우수한 접착제 조성물, 및 그것을 이용한 회로 접속용 접착제, 접속체 및 반도체 장치를 제공할 수 있다. ADVANTAGE OF THE INVENTION According to this invention, even when it hardens in low temperature and short time, it is possible to provide sufficient adhesiveness and connection reliability, and also the adhesive composition excellent in storage stability, and the adhesive agent for circuit connection, a connection body, and a semiconductor device using the same can be provided. have.

이하, 본 발명에 대해서 상세히 설명하는데, 본 발명은 이것에 한정되는 것은 아니다. 또한, 본 명세서 중, (메트)아크릴이란 아크릴 및 그것에 대응하는 메타크릴을 의미하며, (메트)아크릴레이트란 아크릴레이트 및 그것에 대응하는 메타크릴레이트를 의미하며, (메트)아크릴로일기란 아크릴로일기 및 그것에 대응하는 메타크릴로일기를 의미한다. EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail, this invention is not limited to this. In addition, in this specification, (meth) acryl means an acryl and methacryl corresponding to it, (meth) acrylate means an acrylate and a methacrylate corresponding to it, and a (meth) acryloyl group is acryl Diary and the corresponding methacryloyl group.

또한, 본 명세서 중, 「중량 평균 분자량」이란 이하의 조건으로 겔 투과 크로마토그래피법(GPC)에 의해 표준 폴리스티렌에 의한 검량선을 이용하여 측정한 것을 말한다. In addition, in this specification, a "weight average molecular weight" means the thing measured using the analytical curve by standard polystyrene by the gel permeation chromatography method (GPC) on the following conditions.

〈GPC 조건〉 ≪ GPC condition >

사용 기기: 히다치 L-6000형〔가부시끼가이샤 히다치 세이사꾸쇼〕Equipment used: Hitachi L-6000 type (Kabushikishaisha Hitachi Seisakusho)

칼럼: 겔팩 GL-R420+겔팩 GL-R430+겔팩 GL-R440(계 3개)〔히다치 가세이 고교 가부시끼가이샤 제조의 상품명〕Column: Gel Pack GL-R420 + Gel Pack GL-R430 + Gel Pack GL-R440 (three in total) (trade name of Hitachi Kasei Kogyo Co., Ltd.)

용리액: 테트라히드로푸란 Eluent: tetrahydrofuran

측정 온도: 40℃ Measuring temperature: 40 ° C

유량: 1.75 ml/분 Flow rate: 1.75 ml / min

검출기: L-3300RI〔가부시끼가이샤 히다치 세이사꾸쇼〕Detector: L-3300RI [Kabushikisha Hitachi Seisakusho]

본 발명의 접착제 조성물은 (a) 열가소성 수지, (b) 라디칼 중합성 화합물, 및 (c) 라디칼 중합 개시제를 함유한다. The adhesive composition of this invention contains (a) a thermoplastic resin, (b) radically polymerizable compound, and (c) radical polymerization initiator.

(a) 열가소성 수지로서는 특별히 제한 없이 공지된 것을 사용할 수 있다. 이러한 수지로서는, 폴리이미드, 폴리아미드, 페녹시 수지류, 폴리(메트)아크릴레이트류, 폴리이미드류, 폴리우레탄류(우레탄 수지류), 폴리에스테르류, 폴리비닐부티랄류, 폴리우레탄에스테르류 등을 사용할 수 있다. 이들은 단독 또는 2종 이상을 혼합하여 사용할 수 있고, 특히 페녹시 수지와 우레탄 수지를 병용하는 것이 바람직하다. (a) As a thermoplastic resin, a well-known thing can be used without a restriction | limiting in particular. Examples of such resins include polyimide, polyamide, phenoxy resins, poly (meth) acrylates, polyimides, polyurethanes (urethane resins), polyesters, polyvinyl butyrals, polyurethane esters, and the like. Can be used. These can be used individually or in mixture of 2 or more types, It is preferable to use together a phenoxy resin and a urethane resin especially.

또한, 이들 수지 중에는, 실록산 결합이나 불소 치환기가 포함되어 있을 수도 있다. 이들은 혼합하는 수지끼리가 완전히 상용하거나, 또는 마이크로 상분리가 생겨 백탁하는 상태이면 바람직하게 사용할 수 있다. In addition, these resin may contain a siloxane bond and a fluorine substituent. These resins can be suitably used as long as the resins to be mixed are completely compatible or have a microphase separation.

상기 열가소성 수지의 분자량은 클수록 필름 형성성이 용이하게 얻어지고, 또한 접착제로서의 유동성에 영향을 주는 용융 점도를 광범위하게 설정할 수 있다. 분자량은 특별히 제한을 받는 것이 아니지만, 일반적인 중량 평균 분자량으로서는 5,000 내지 150,000이 바람직하고, 10,000 내지 80,000이 특히 바람직하다. 이 값이 5,000 미만이면 필름 형성성이 떨어지는 경향이 있고, 또한 150,000을 초과하면 다른 성분과의 상용성이 나빠지는 경향이 있다. The larger the molecular weight of the thermoplastic resin is, the more easily the film formability can be obtained, and the melt viscosity that affects the fluidity as the adhesive can be set in a wide range. Although molecular weight is not specifically limited, As a general weight average molecular weight, 5,000-150,000 are preferable and 10,000-80,000 are especially preferable. When this value is less than 5,000, there exists a tendency for film formability to fall and when it exceeds 150,000, there exists a tendency for compatibility with other components to worsen.

(b) 라디칼 중합성 화합물은 1 분자 중에 2개 이상의 (메트)아크릴로일기 및 2개 이상의 우레탄 결합을 갖고, 중량 평균 분자량이 10,000 이상인 것인데, 내열성, 유동성, 접착성 측면에서, 하기 화학식 (A), 하기 화학식 (B)로부터 선택되는 적어도 하나 이상의 구조를 포함하는 화합물인 것이 바람직하다. (b) The radically polymerizable compound has two or more (meth) acryloyl groups and two or more urethane bonds in one molecule, and has a weight average molecular weight of 10,000 or more, in terms of heat resistance, fluidity, and adhesion, the formula (A) And a compound containing at least one structure selected from the following general formula (B).

Figure pat00001
Figure pat00001

Figure pat00002
Figure pat00002

(b) 라디칼 중합성 화합물의 중량 평균 분자량(Mw)은 10,000 내지 60,000이면 바람직하고, 30,000보다 크고 50,000 이하이면 특히 바람직하다. (b) The weight average molecular weight (Mw) of a radically polymerizable compound is preferable in it being 10,000-60,000, and especially preferable in it being larger than 30,000 and 50,000 or less.

Mw가 10,000 미만이면 경화 수축에 의해 접착력이 저하되고, 60,000을 초과한 경우에는 가교 밀도가 저하되어, 접속 신뢰성이 저하될 우려가 있다. When Mw is less than 10,000, adhesive force will fall by hardening shrinkage, and when it exceeds 60,000, crosslinking density will fall and connection reliability may fall.

Mw가 10,000 이상인 (b) 라디칼 중합성 화합물은 고분자량체이기 때문에, 반응성 성분임과 동시에 (a) 열가소성 수지와 동등 또는 그것에 유사한 특성을 발현할 것을 기대할 수 있어, 필름 형성성, 유동성이나 접착력의 향상과 같은 필름의 설계 여유도가 넓어지기 때문에 바람직하다. Since the (b) radically polymerizable compound having a Mw of 10,000 or more is a high molecular weight body, it can be expected to exhibit a characteristic equivalent to or similar to that of the reactive component and (a) a thermoplastic resin, thereby improving film formability, fluidity and adhesion. Since the design margin of such a film becomes wider, it is preferable.

(b) 라디칼 중합성 화합물의 함유량은 (a) 열가소성 수지 100 중량부에 대하여 바람직하게는 10 내지 250 중량부이고, 보다 바람직하게는 30 내지 150 중량부이다. The content of the (b) radically polymerizable compound is preferably 10 to 250 parts by weight, more preferably 30 to 150 parts by weight based on 100 parts by weight of the (a) thermoplastic resin.

(b) 라디칼 중합성 화합물의 함유량이 10 중량부 미만인 경우에는, 경화 후의 내열성 저하가 우려되고, 또한 250 중량부 이상인 경우에는, 필름으로서 사용하는 경우에 필름 형성성이 저하될 우려가 있다. (b) When content of a radically polymerizable compound is less than 10 weight part, the heat resistance fall after hardening may be concerned, and when it is 250 weight part or more, there exists a possibility that film formability may fall when using as a film.

(c) 라디칼 중합 개시제로서는, 종래부터 알려져 있는 과산화물이나 아조 화합물 등의 공지된 화합물을 사용할 수 있는데, 안정성, 반응성, 상용성 측면에서, 1분간 반감기 온도가 90 내지 175℃이고, 또한 분자량이 180 내지 1,000인 퍼옥시에스테르 유도체가 바람직하다. As the (c) radical polymerization initiator, conventionally known compounds such as peroxides and azo compounds can be used. In terms of stability, reactivity and compatibility, the half-life temperature is 90 to 175 ° C for 1 minute, and the molecular weight is 180. Preference is given to peroxyester derivatives having from 1 to 1,000.

그 구체예로서는, 쿠밀퍼옥시네오데카노에이트, 1,1,3,3-테트라메틸부틸퍼옥시네오데카노에이트, 1-시클로헥실-1-메틸에틸퍼옥시네오데카노에이트, t-헥실퍼옥시네오데카노에이트, t-부틸퍼옥시네오데카노에이트, t-부틸퍼옥시피발레이트, 1,1,3,3-테트라메틸부틸퍼옥시-2-에틸헥사노에이트, 2,5-디메틸-2,5-디(2-에틸헥사노일퍼옥시)헥산, t-헥실퍼옥시-2-에틸헥사노에이트, t-부틸퍼옥시-2-에틸헥사노에이트, t-부틸퍼옥시네오헵타노에이트, t-아밀퍼옥시-2-에틸헥사노에이트, 디-t-부틸퍼옥시헥사히드로테레프탈레이트, t-아밀퍼옥시-3,5,5-트리메틸헥사노에이트, 3-히드록시-1,1-디메틸부틸퍼옥시네오데카노에이트, 1,1,3,3-테트라메틸부틸퍼옥시-2-에틸헥사노에이트, t-아밀퍼옥시네오데카노에이트, t-아밀퍼옥시-2-에틸헥사노에이트, 2,2'-아조비스-2,4-디메틸발레로니트릴, 1,1'-아조비스(1-아세톡시-1-페닐에탄), 2,2'-아조비스이소부티로니트릴, 2,2'-아조비스(2-메틸부티로니트릴), 디메틸-2,2'-아조비스이소부티로니트릴, 4,4'-아조비스(4-시아노발레르산), 1,1'-아조비스(1-시클로헥산카르보니트릴), t-헥실퍼옥시이소프로필모노카보네이트, t-부틸퍼옥시말레산, t-부틸퍼옥시-3,5,5-트리메틸헥사노에이트, t-부틸퍼옥시라우레이트, 2,5-디메틸-2,5-디(3-메틸벤조일퍼옥시)헥산, t-부틸퍼옥시-2-에틸헥실모노카보네이트, t-헥실퍼옥시벤조에이트, 2,5-디메틸-2,5-디(벤조일퍼옥시)헥산, t-부틸퍼옥시벤조에이트, 디부틸퍼옥시트리메틸아디페이트, t-아밀퍼옥시노르말옥토에이트, t-아밀퍼옥시이소노나노에이트, t-아밀퍼옥시벤조에이트 등을 들 수 있다. 이들 화합물은 단독으로 이용하거나, 2종 이상의 화합물을 혼합하여 이용할 수도 있다.Specific examples thereof include cumylperoxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, 1-cyclohexyl-1-methylethylperoxy neodecanoate, t-hexyl fur Oxyneodecanoate, t-butylperoxy neodecanoate, t-butylperoxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl -2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy neohep Tanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy- 1,1-dimethylbutyl peroxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy neodecanoate, t-amylperoxy- 2-ethylhexanoate, 2,2'-azobis-2,4-dimethylval Ronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), Dimethyl-2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (1-cyclohexanecarbonitrile), t-hexylper Oxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t -Butyl peroxy benzoate, dibutyl peroxy trimethyl adipate, t-amyl peroxy normal mal octoate, t- amyl peroxy isononanoate, t- amyl peroxy benzoate, etc. are mentioned. These compounds may be used alone or in combination of two or more compounds.

(c) 라디칼 중합 개시제의 함유량은 (a) 열가소성 수지 100 중량부에 대하여 바람직하게는 0.05 내지 30 중량부이고, 보다 바람직하게는 0.1 내지 20 중량부이다.The content of the (c) radical polymerization initiator is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the (a) thermoplastic resin.

함유량이 0.05 중량부 미만인 경우, 경화 부족이 우려되고, 또한 30 중량부를 초과하는 경우에는, 방치 안정성이 저하될 우려가 있다. When content is less than 0.05 weight part, there exists a possibility that hardening deficiency may be exceeded, and when it exceeds 30 weight part, it will be left to stand stability.

본 발명의 접착제 조성물은 (d) 분자 내에 적어도 1개 이상의 인산기를 갖는 비닐 화합물을 함유하는 것이 바람직하다. (d) 분자 내에 적어도 1개 이상의 인산기를 갖는 비닐 화합물로서는, 특별히 제한 없이 공지된 것을 사용할 수가 있지만, 하기 화학식 (1) 내지 (3)으로 표시되는 화합물이 바람직하다. It is preferable that the adhesive composition of this invention contains the vinyl compound which has at least 1 or more phosphoric acid group in (d) molecule | numerator. (d) As a vinyl compound which has at least 1 or more phosphoric acid group in a molecule | numerator, a well-known thing can be used without a restriction | limiting in particular, The compound represented by following General formula (1)-(3) is preferable.

Figure pat00003
Figure pat00003

(화학식 1 중, R1은 아크릴로일기 또는 메타크릴로일기이고, R2는 수소 또는 메틸기이며, m, n은 각각 독립적으로 1 내지 8의 정수를 나타냄)(In Formula 1, R 1 is acryloyl group or methacryloyl group, R 2 is hydrogen or methyl group, m, n each independently represent an integer of 1 to 8)

Figure pat00004
Figure pat00004

(화학식 2 중, R3은 아크릴로일기 또는 메타크릴로일기이고, l은 1 내지 8의 정수이며, m, n은 각각 독립적으로 1 내지 8의 정수를 나타냄)(In Formula 2, R <3> is acryloyl group or methacryloyl group, l is an integer of 1-8, m and n represent the integer of 1-8 each independently.)

Figure pat00005
Figure pat00005

(화학식 3 중, R4는 아크릴로일기 또는 메타크릴로일기이고, R5는 수소 또는 메틸기이며, p, q는 각각 독립적으로 1 내지 8의 정수를 나타냄)(In Formula 3, R <4> is an acryloyl group or a methacryloyl group, R <5> is a hydrogen or a methyl group, and p and q each independently represent the integer of 1-8.)

이들의 구체예로서는 애시드포스포옥시에틸메타크릴레이트, 애시드포스포옥시에틸아크릴레이트, 애시드포스포옥시프로필메타크릴레이트, 애시드포스포옥시폴리옥시에틸렌글리콜모노메타크릴레이트, 애시드포스포옥시폴리옥시프로필렌글리콜모노메타크릴레이트, 2,2'-디(메트)아크릴로일옥시디에틸포스페이트, EO(에틸렌옥사이드) 변성 인산디메타크릴레이트, 인산 변성 에폭시아크릴레이트 등을 들 수 있다.Specific examples thereof include acid phospho oxyethyl methacrylate, acid phospho oxyethyl acrylate, acid phospho oxypropyl methacrylate, acid phospho oxy polyoxyethylene glycol monomethacrylate, and acid phospho oxy poly oxypropylene. Glycol monomethacrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO (ethylene oxide) modified phosphate dimethacrylate, phosphoric acid modified epoxy acrylate, etc. are mentioned.

(d) 분자 내에 적어도 1개 이상의 인산기를 갖는 비닐 화합물의 함유량은 (a) 열가소성 수지 100 중량부에 대하여 바람직하게는 0.1 내지 20 중량부이고, 보다 바람직하게는 0.5 내지 10 중량부이다. (d) Content of the vinyl compound which has at least 1 or more phosphoric acid group in a molecule | numerator becomes like this. Preferably it is 0.1-20 weight part with respect to 100 weight part of (a) thermoplastic resin, More preferably, it is 0.5-10 weight part.

함유량이 0.1 중량부 미만인 경우, 접착 강도 향상 효과가 낮은 경향이 있고, 또한 20 중량부를 초과하는 경우에는, 경화 후의 접착제의 물성이 저하되어, 접속 신뢰성이 저하될 우려가 있다. When content is less than 0.1 weight part, there exists a tendency for the adhesive strength improvement effect to be low, and when it exceeds 20 weight part, the physical property of the adhesive agent after hardening may fall, and connection reliability may fall.

본 발명의 접착제 조성물은 (e) 도전성 입자를 함유하는 것이 바람직하다. (e) 도전성 입자로서는, Au, Ag, Ni, Cu, 땜납 등의 금속 입자나 카본 등을 들 수 있다. It is preferable that the adhesive composition of this invention contains (e) electroconductive particle. (e) As electroconductive particle, metal particles, such as Au, Ag, Ni, Cu, solder, carbon etc. are mentioned.

또한, 비도전성의 유리, 세라믹, 플라스틱 등을 핵으로 하고, 이 핵에 상기 금속, 금속 입자나 카본을 피복한 것일 수도 있다. It is also possible to use a non-conductive glass, ceramic, plastic, or the like as a nucleus and coating the nucleus with the metal, metal particles, or carbon.

도전성 입자가 플라스틱을 핵으로 하고, 이 핵에 상기 금속, 금속 입자나 카본을 피복한 것이나 땜납 같은 열용융 금속 입자의 경우, 가열 가압에 의해 변형성을 가지기 때문에 접속 시에 전극과의 접촉 면적이 증가하여 전극의 두께 변동을 흡수하여, 접속 신뢰성이 향상하기 때문에 바람직하다. In the case where the conductive particles are made of plastic as a nucleus, and the nucleus is coated with the metal, metal particles or carbon, or hot melt metal particles such as solder, they are deformable by heating and pressurization, so that the contact area with the electrode increases during connection. This is preferable because it absorbs the thickness variation of the electrode and improves the connection reliability.

또한 이들 도전성 입자의 표면을 고분자 수지, 미립자 등으로 더 피복한 도전성 입자는 도전성 입자의 배합량을 증가한 경우의 입자끼리의 접촉에 의한 단락을 억제하여, 전극 회로 사이의 절연성을 향상할 수 있기 때문에, 적절하게 이것을 단독 또는 도전성 입자와 혼합하여 이용할 수도 있다. Moreover, since the electroconductive particle which further coat | covered the surface of these electroconductive particle with a polymer resin, microparticles | fine-particles, etc. can suppress the short circuit by the contact of the particles when the compounding quantity of electroconductive particle is increased, and the insulation between electrode circuits can be improved, You may use this suitably individually or in mixture with electroconductive particle.

이 도전성 입자의 평균 입경은 분산성, 도전성 면에서 1 내지 18 ㎛인 것이 바람직하다. 도전성 입자의 함유량은 특별히 제한은 받지 않지만, 접착제 조성물전량을 기준으로 하여 0.1 내지 30 부피％로 하는 것이 바람직하고, 0.1 내지 10 부피％로 하는 것이 보다 바람직하다. It is preferable that the average particle diameter of this electroconductive particle is 1-18 micrometers from a dispersibility and electroconductivity. Although content in particular of electroconductive particle is not restrict | limited, It is preferable to set it as 0.1-30 volume% on the basis of the adhesive composition whole quantity, and it is more preferable to set it as 0.1-10 volume%.

이 값이 0.1 부피％ 미만이면 도전성이 떨어지는 경향이 있고, 30 부피％를 초과하면 회로의 단락이 발생하기 쉬운 경향이 있다. If this value is less than 0.1 volume%, there exists a tendency for electroconductivity to fall, and when it exceeds 30 volume%, there exists a tendency for a short circuit to occur easily.

또한, 「부피％」는 23℃의 경화 전의 각 성분의 부피를 바탕으로 결정되는데, 각 성분의 부피는 비중을 이용하여 중량으로부터 부피로 환산할 수 있다. 또한, 메스실린더 등에 그 성분을 용해하거나 팽윤시키거나 하지 않고, 그 성분을 잘 적시는 적당한 용매(물, 알코올 등)를 넣은 것에, 그 성분을 투입하여 증가한 부피를 그 부피로서 구할 수도 있다. In addition, although "vol%" is determined based on the volume of each component before hardening at 23 degreeC, the volume of each component can be converted from volume to volume using specific gravity. In addition, the volume increased by injecting the component into an appropriate solvent (water, alcohol, etc.) that wets the component well without dissolving or swelling the component in a measuring cylinder or the like may be obtained as the volume.

본 발명의 접착제 조성물에는 전술한 (b) 라디칼 중합성 화합물과 병용하고, (b) 성분 이외의 라디칼 중합성 화합물을 사용할 수 있다. 이러한 라디칼 중합성 화합물로서는 스티렌 유도체나 말레이미드 유도체와 같이 라디칼에 의해서 중합하는 화합물이면 특별히 제한 없이 공지된 것을 사용할 수 있다. In combination with the (b) radically polymerizable compound mentioned above, radical adhesive polymers other than (b) component can be used for the adhesive composition of this invention. As such a radically polymerizable compound, if it is a compound which superpose | polymerizes with a radical like a styrene derivative and a maleimide derivative, a well-known thing can be used without a restriction | limiting in particular.

그 구체예로서는, 에폭시(메트)아크릴레이트올리고머, 폴리에테르(메트)아크릴레이트올리고머, 폴리에스테르(메트)아크릴레이트올리고머 등의 올리고머, 트리 메틸올프로판트리(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 폴리알킬렌글리콜디(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜테닐옥시에틸(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트, 이소시아누르산 변성 2관능 (메트)아크릴레이트, 이소시아누르산 변성 3관능 (메트)아크릴레이트 등의 다관능 (메트)아크릴레이트 화합물을 들 수 있고, 특히 3관능 이상의 (메트)아크릴레이트를 (b) 라디칼 중합성 화합물과 병용하는 것이 바람직하다. Specific examples thereof include oligomers such as epoxy (meth) acrylate oligomers, polyether (meth) acrylate oligomers, and polyester (meth) acrylate oligomers, trimethylolpropane tri (meth) acrylate, and polyethylene glycol di (meth). Acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol Polyfunctional (meth) acrylate compounds, such as hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, and isocyanuric acid modified trifunctional (meth) acrylate, are especially trifunctional It is preferable to use the above (meth) acrylate together with (b) radically polymerizable compound.

또한, 유동성의 조절을 목적으로 단관능 (메트)아크릴레이트를 사용할 수도 있다. 그 구체예로서는 펜타에리트리톨(메트)아크릴레이트, 2-시아노에틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜테닐옥시에틸(메트)아크릴레이트, 2-(2-에톡시에톡시)에틸(메트)아크릴레이트, 2-에톡시에틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, n-헥실(메트)아크릴레이트, 2-히드록시에틸(메트)아크릴레이트, 히드록시프로필(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, n-라우릴(메트)아크릴레이트, 2-메톡시에틸(메트)아크릴레이트, 2-페녹시에틸(메트)아크릴레이트, 테트라히드로푸르푸릴(메트)아크릴레이트, 2-(메트)아크릴로일옥시에틸포스페이트, N,N-디메틸아미노에틸(메트)아크릴레이트, N,N-디메틸아미노에틸(메트)아크릴레이트, N,N-디메틸아미노프로필(메트)아크릴레이트, N,N-디메틸아미노프로필(메트)아크릴레이트, (메트)아크릴로일모르폴린 등을 들 수 있다. 이들 화합물은 단독으로 이용하거나, 필요에 따라서 복수의 화합물을 혼합하여 이용할 수도 있다. Moreover, monofunctional (meth) acrylate can also be used for the purpose of adjusting fluidity. Specific examples thereof include pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth). Acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl ( Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, N , N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth T) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth) acryloyl morpholine, etc. are mentioned. These compounds may be used alone, or may be used by mixing a plurality of compounds as necessary.

본 발명의 접착제 조성물에는 가교율의 향상을 목적으로 하여, 상기 (메트)아크릴로일기를 갖는 화합물 외에, 알릴기, 말레이미드기, 비닐기 등의 활성 라디칼에 의해서 중합하는 관능기를 갖는 화합물을 적절하게 첨가할 수도 있다. In addition to the compound which has the said (meth) acryloyl group, the compound which has a functional group superposed | polymerized by active radicals, such as an allyl group, a maleimide group, and a vinyl group, is suitable for the adhesive composition of this invention for the purpose of the improvement of a crosslinking rate. May be added.

그 구체예로서는, N-비닐이미다졸, N-비닐피리딘, N-비닐피롤리돈, N-비닐포름아미드, N-비닐카프로락탐, 4,4'-비닐리덴비스(N,N-디메틸아닐린), N-비닐아세트아미드, N,N-디메틸아크릴아미드, N-이소프로필아크릴아미드, N,N-디에틸아크릴아미드, 아크릴아미드 등을 들 수 있다. Specific examples thereof include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4'-vinylidenebis (N, N-dimethylaniline ), N-vinylacetamide, N, N-dimethyl acrylamide, N-isopropyl acrylamide, N, N-diethyl acrylamide, acrylamide and the like.

본 발명의 접착제 조성물에는 경화 속도의 제어나 저장 안정성을 부여하기 위해서 안정화제를 첨가할 수도 있다.Stabilizers can also be added to the adhesive composition of this invention in order to provide control of a cure rate, or to provide storage stability.

이러한 안정화제로서는 특별히 제한 없이 공지된 화합물을 사용할 수가 있지만, 벤조퀴논이나 히드로퀴논 등의 퀴논 유도체, 4-메톡시페놀이나 4-t-부틸카테콜 등의 페놀 유도체, 2,2,6,6-테트라메틸피페리딘-1-옥실이나 4-히드록시-2,2,6,6-테트라메틸피페리딘-1-옥실 등의 아미녹실 유도체, 테트라메틸피페리딜메타크릴레이트 등의 힌더드 아민 유도체가 바람직하다. As such stabilizers, known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, and 2,2,6,6- Aminoxyl derivatives, such as tetramethyl piperidine-1-oxyl, 4-hydroxy-2,2,6,6- tetramethyl piperidine-1-oxyl, and hinders, such as tetramethyl piperidyl methacrylate Amine derivatives are preferred.

안정화제를 첨가하는 경우의 그 첨가량은 (a) 열가소성 수지 100 중량부에 대하여 바람직하게는 0.01 내지 30 중량부이고, 보다 바람직하게는 0.05 내지 10 중량부이다. 함유량이 0.01 중량부 미만인 경우, 첨가 효과가 현저히 저하될 것이 우려되고, 또한 30 중량부 이상인 경우에는, 다른 성분과의 상용성이 저하될 우려가 있다. The addition amount in the case of adding a stabilizer becomes like this. Preferably it is 0.01-30 weight part with respect to 100 weight part of (a) thermoplastic resins, More preferably, it is 0.05-10 weight part. When content is less than 0.01 weight part, there exists a possibility that a remarkable effect may fall remarkably, and when it is 30 weight part or more, there exists a possibility that compatibility with another component may fall.

본 발명의 접착제 조성물에는 알콕시실란 유도체나 실라잔 유도체로 대표되는 커플링제 및 밀착 향상제, 레벨링제 등의 접착 보조제를 적절하게 첨가할 수도 있다.In the adhesive composition of the present invention, an adhesive aid such as a coupling agent typified by an alkoxysilane derivative or a silazane derivative, an adhesion improving agent, a leveling agent or the like may be appropriately added.

본 발명의 접착제 조성물에는 응력 완화 및 접착성 향상을 목적으로 고무 성분을 첨가할 수도 있다. The rubber component may be added to the adhesive composition of the present invention for the purpose of stress relaxation and adhesion improvement.

그 구체예로서는, 폴리이소프렌, 폴리부타디엔, 카르복실기 말단 폴리부타디엔, 수산기 말단 폴리부타디엔, 1,2-폴리부타디엔, 카르복실기 말단 1,2-폴리부타디엔, 수산기 말단 1,2-폴리부타디엔, 아크릴 고무, 스티렌-부타디엔 고무, 수산기 말단 스티렌-부타디엔 고무, 아크릴로니트릴-부타디엔 고무, 카르복실기, 수산기, (메트)아크릴로일기 또는 모르폴린기를 중합체 말단에 함유하는 아크릴로니트릴-부타디엔 고무, 카르복실화니트릴 고무, 수산기 말단 폴리(옥시프로필렌), 알콕시실릴기 말단 폴리(옥시프로필렌), 폴리(옥시테트라메틸렌)글리콜, 폴리올레핀글리콜, 폴리-ε-카프로락톤 등을 들 수 있다. Specific examples thereof include polyisoprene, polybutadiene, carboxyl terminal polybutadiene, hydroxyl terminal polybutadiene, 1,2-polybutadiene, carboxyl terminal 1,2-polybutadiene, hydroxyl terminal 1,2-polybutadiene, acrylic rubber, styrene- Butadiene rubber, hydroxyl terminal styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, acrylonitrile-butadiene rubber containing (meth) acryloyl group or morpholine group at the polymer terminal, carboxylated nitrile rubber, hydroxyl group Terminal poly (oxypropylene), alkoxysilyl group terminal poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, poly-ε-caprolactone and the like.

상기 고무 성분으로서는, 접착성 향상 측면에서, 고극성기인 시아노기, 카르복실기를 측쇄 또는 말단에 포함하는 고무 성분이 바람직하고, 또한 유동성 향상 측면에서 액상 고무가 보다 바람직하다. 그 구체예로서는, 액상 아크릴로니트릴-부타디엔 고무, 카르복실기, 수산기, (메트)아크릴로일기 또는 모르폴린기를 중합체 말단에 함유하는 액상 아크릴로니트릴-부타디엔 고무, 액상 카르복실화니트릴 고무를 들 수 있고, 극성기인 아크릴로니트릴 함유량이 10 내지 60 중량％가 바람직하다. 이들 화합물은 단독으로 이용하거나, 2종 이상의 화합물을 혼합하여 이용할 수도 있다. As said rubber component, the rubber component which contains the cyano group which is a high polar group, and a carboxyl group in a side chain or the terminal from a viewpoint of adhesive improvement is preferable, and a liquid rubber is more preferable from a viewpoint of fluidity improvement. As the specific example, the liquid acrylonitrile- butadiene rubber which contains a liquid acrylonitrile- butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group at a polymer terminal, and a liquid carboxylated nitrile rubber are mentioned, As for an acrylonitrile content which is a polar group, 10 to 60 weight% is preferable. These compounds may be used alone or in combination of two or more compounds.

본 발명의 접착제 조성물은 상온(25℃)에서 액상인 경우에는 페이스트상 접착제로서 사용할 수 있다. 실온(25℃)에서 고체인 경우에는, 가열하여 사용하는 외에, 용제를 사용하여 페이스트화하여, 페이스트상 접착제로서 사용할 수도 있다.The adhesive composition of the present invention can be used as a paste adhesive when it is liquid at room temperature (25 ° C). In the case of a solid at room temperature (25 ° C), in addition to heating, it may be pasted using a solvent and used as a paste adhesive.

사용할 수 있는 용제로서는 접착제 조성물 및 첨가제와 반응성이 충분히 작고, 또한 충분한 용해성을 나타내는 것이면 특별히 제한은 받지 않지만, 상압에서의 비점이 50 내지 150℃인 것이 바람직하다. 비점이 50℃ 이하인 경우, 실온에서 방치하면 휘발할 우려가 있어, 개방계에서의 사용이 제한된다. 또한, 비점이 150℃ 이상이면, 용제를 휘발시키는 것이 어려워, 접착 후의 신뢰성에 악영향을 미칠 우려가 있다. The solvent that can be used is not particularly limited as long as the reactivity is sufficiently small with the adhesive composition and the additive and exhibits sufficient solubility, but the boiling point at normal pressure is preferably 50 to 150 ° C. When boiling point is 50 degrees C or less, when left at room temperature, it may volatilize and use in an open system is restrict | limited. Moreover, when a boiling point is 150 degreeC or more, it is difficult to volatilize a solvent and it may have a bad influence on the reliability after adhesion.

본 발명의 접착제 조성물은 필름상 접착제로서 이용할 수도 있다. 필름상 접착제는, 예를 들면 접착제 조성물에 필요에 따라 용제 등을 가하는 등을 한 용액을, 불소 수지 필름, 폴리에틸렌테레프탈레이트 필름, 이형지 등의 박리성 기재 상에 도포하거나, 또는 부직포 등의 기재에 상기 용액을 함침시켜 박리성 기재 상에 얹어 놓고, 용제 등을 제거함으로써 제작할 수 있다. 필름의 형상으로 사용하면 취급성 등 면에서 한층 편리하다. The adhesive composition of this invention can also be used as a film adhesive. The film adhesive is, for example, applied a solution obtained by adding a solvent or the like to the adhesive composition on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, a release paper, or a substrate such as a nonwoven fabric. The solution can be impregnated and placed on a peelable base material, and produced by removing a solvent or the like. When used in the shape of a film, it is more convenient in terms of handling properties.

상술한 페이스트상 접착제 및 필름상 접착제는 특히 회로 접속용 접착제로서 바람직하게 사용할 수 있다. The paste adhesive and film adhesive mentioned above can be used especially suitably as an adhesive agent for circuit connections.

본 발명의 회로 접속용 접착제는 가열 및 가압을 병용하여 접착시킬 수 있다. 가열 온도는 특별히 제한은 받지 않지만, 100 내지 210℃인 것이 바람직하다. 압력은 피착체에 손상을 제공하지 않는 범위이면 특별히 제한은 받지 않지만, 일반적으로는 0.1 내지 10 MPa가 바람직하다. 이들 가열 및 가압은 0.5 내지 120초간의 범위에서 행하는 것이 바람직하고, 140 내지 170℃, 3 MPa, 10초의 가열에서도 접착시키는 것이 가능하다. The adhesive for circuit connection of this invention can be bonded together using heating and pressurization. Although heating temperature in particular is not restrict | limited, It is preferable that it is 100-210 degreeC. The pressure is not particularly limited as long as it does not damage the adherend, but generally 0.1 to 10 MPa is preferred. It is preferable to perform these heatings and pressurization in the range for 0.5 to 120 second, and it is possible to make it adhere | attach even at the heating of 140-170 degreeC, 3 MPa, and 10 second.

본 발명의 회로 접속용 접착제는 열팽창 계수가 서로 다른 이종의 피착체의 접착제로서 사용할 수 있다. 구체적으로는, 이방 도전 접착제, 은 페이스트, 은 필름 등으로 대표되는 회로 접속 재료, CSP용 엘라스토머, CSP용 언더필재, LOC 테이프 등으로 대표되는 반도체 소자 접착 재료로서 사용할 수 있다. The adhesive for circuit connection of this invention can be used as an adhesive agent of the heterogeneous to-be-adhered body from which a thermal expansion coefficient differs. Specifically, it can be used as a semiconductor element adhesive material represented by a circuit connection material represented by an anisotropic conductive adhesive, a silver paste, a silver film, etc., an elastomer for CSP, an underfill material for CSP, a LOC tape, and the like.

본 발명의 접속체는, 제1 회로 전극을 갖는 제1 기판과, 제2 회로 전극을 갖는 제2 기판을, 제1 회로 전극과 제2 회로 전극이 서로 대향하도록 배치하고, 대향 배치한 제1 기판과 제2 기판 사이에 상기 본 발명의 회로 접속용 접착제를 개재시키고, 가열 가압하여 제1 회로 전극과 제2 회로 전극을 전기적으로 접속시켜 이루어지는 것이다. The connection body of this invention arrange | positions the 1st board | substrate which has a 1st circuit electrode, and the 2nd board | substrate which has a 2nd circuit electrode so that a 1st circuit electrode and a 2nd circuit electrode may mutually oppose, and 1st arrange | positioned facing It interposes between a board | substrate and a 2nd board | substrate, and heat-pressurizes the circuit connection adhesive agent of the said invention, and electrically connects a 1st circuit electrode and a 2nd circuit electrode.

회로 전극을 형성하는 기판으로서는, 반도체, 유리, 세라믹 등의 무기질, 폴리이미드 수지, 폴리카보네이트 수지, 폴리에스테르 수지, 폴리에테르술폰 수지 등의 유기물, 유리 섬유/에폭시 수지 등의 복합 재료의 각 조합을 적용할 수 있다. As a board | substrate which forms a circuit electrode, each combination of organic materials, such as inorganic materials, such as a semiconductor, glass, ceramic, a polyimide resin, a polycarbonate resin, a polyester resin, and a polyether sulfone resin, and a composite material, such as glass fiber / epoxy resin, Applicable

[실시예][Example]

이하에, 본 발명을 실시예에 기초하여 구체적으로 설명하는데, 본 발명은 이것에 한정되는 것은 아니다. EMBODIMENT OF THE INVENTION Although this invention is demonstrated concretely based on an Example below, this invention is not limited to this.

(우레탄아크릴레이트 (U-1)의 합성)(Synthesis of urethane acrylate (U-1))

교반기, 온도계, 냉각관 및 공기 가스 도입관을 구비한 반응 용기에 공기 가스를 도입한 후, 2-히드록시에틸아크릴레이트 238 중량부(2.05몰), 수 평균 분자량 2,000의 폴리(헥사메틸렌카보네이트)디올(알드리치사 제조) 4000 중량부(2몰), 히드로퀴논모노메틸에테르 0.49 중량부, 디부틸주석디라우레이트 6.35 중량부를 투입하고, 90 내지 100℃로 가열하고, 이소포론 디이소시아네이트 666 중량부(3몰)을 3시간에 균일하게 적하하여 반응시켰다. After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and an air gas introduction tube, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate and a poly (hexamethylene carbonate) having a number average molecular weight of 2,000 4000 parts by weight (2 mol) of diol (manufactured by Aldrich), 0.49 parts by weight of hydroquinone monomethyl ether, 6.35 parts by weight of dibutyltin dilaurate were added, heated to 90 to 100 ° C, and 666 parts by weight of isophorone diisocyanate ( 3 mol) was uniformly added dropwise for 3 hours to react.

적하 완료 후 약 24시간 반응을 계속하고, IR 측정에 의해 이소시아네이트가 소실한 것을 확인하여 반응을 종료하여, 중량 평균 분자량 45,000의 우레탄아크릴레이트 (U-1)를 얻었다. After completion of the dropwise addition, the reaction was continued for about 24 hours, confirmed that the isocyanate disappeared by IR measurement, and the reaction was terminated to obtain a urethane acrylate (U-1) having a weight average molecular weight of 45,000.

(우레탄아크릴레이트 (U-2)의 합성)(Synthesis of urethane acrylate (U-2))

교반기, 온도계, 냉각관 및 공기 가스 도입관을 구비한 반응 용기에 공기 가스를 도입한 후, 2-히드록시에틸아크릴레이트 238 중량부(2.05몰), 수 평균 분자량 900의 폴리(에틸렌글리콜)디올(알드리치사 제조) 1,800 중량부(2몰), 히드로퀴논모노메틸에테르 0.27 중량부, 디부틸주석디라우레이트 2.70 중량부를 투입하고, 70 내지 75℃로 가열하고, 이소포론 디이소시아네이트 666 중량부(3몰)을 3시간에 균일하게 적하하여 반응시켰다. After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and an air gas introduction tube, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate and a poly (ethylene glycol) diol having a number average molecular weight of 900 (Manufactured by Aldrich) 1,800 parts by weight (2 moles), 0.27 parts by weight of hydroquinone monomethyl ether, 2.70 parts by weight of dibutyltin dilaurate, and heated to 70 to 75 ℃, 666 parts by weight of isophorone diisocyanate (3 Mole) was uniformly added dropwise for 3 hours to react.

적하 완료 후, 약 15시간 반응을 계속하고, IR 측정에 의해 이소시아네이트가 소실한 것을 확인하여 반응을 종료하여, 중량 평균 분자량 4,800의 우레탄아크릴레이트 (U-2)를 얻었다. After completion of the dropwise addition, the reaction was continued for about 15 hours, confirmed that the isocyanate disappeared by IR measurement, and the reaction was terminated to obtain a urethane acrylate (U-2) having a weight average molecular weight of 4,800.

(실시예 1, 비교예 1)(Example 1, Comparative Example 1)

(a) 열가소성 수지로서 페녹시 수지 및 우레탄 수지를 사용하였다. (a) A phenoxy resin and urethane resin were used as a thermoplastic resin.

페녹시 수지로서는 페녹시 수지(PKHC, 유니온카바이트사 제조의 상품명, 평균 분자량 45,000) 40 g을 메틸에틸케톤 60 g에 용해하여, 고형분 40 중량％의 용액으로 한 것을 이용하였다. As the phenoxy resin, 40 g of phenoxy resin (PKHC, trade name manufactured by Union Carbide Co., Ltd., average molecular weight 45,000) was dissolved in 60 g of methyl ethyl ketone to prepare a solution having a solid content of 40% by weight.

또한 우레탄 수지로서는 평균 분자량 2,000의 폴리부틸렌아디페이트디올 450 중량부와 평균 분자량 2,000의 폴리옥시테트라메틸렌글리콜 450 중량부, 1,4-부틸렌글리콜 100 중량부를 메틸에틸케톤 4000 중량부 중에서 균일하게 혼합하고, 디페닐메탄디이소시아네이트 390 중량부를 가하고 70℃에서 반응시켜 얻어진 중량 평균 분자량 35만의 우레탄 수지를 사용하였다. As the urethane resin, 450 parts by weight of polybutylene adipatediol having an average molecular weight of 2,000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, and 100 parts by weight of 1,4-butylene glycol are uniformly contained in 4000 parts by weight of methyl ethyl ketone. A urethane resin having a weight average molecular weight of 350,000 obtained by mixing and adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C was used.

(b) 라디칼 중합성 화합물로서는, 상술한 U-1(중량 평균 분자량 45,000) 또는 U-2(중량 평균 분자량 4,800) 50 g을, 각각 메틸에틸케톤 50 g에 용해하여 고형분 50 중량％의 용액으로 한 것을 사용하였다. (b) As a radically polymerizable compound, 50 g of U-1 (weight average molecular weight 45,000) or U-2 (weight average molecular weight 4,800) mentioned above is melt | dissolved in 50 g of methyl ethyl ketone, respectively, and it is made into the solution of 50 weight% of solid content. One was used.

또한 (b) 성분 이외의 라디칼 중합성 화합물로서, 펜타에리트리톨트리아크릴레이트(NK 에스테르 A-TMM-3L, 신나카무라 가가꾸 고교 가부시끼가이샤 제조의 상품명)을 이용하였다. As radically polymerizable compounds other than the component (b), pentaerythritol triacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Industries, Ltd.) was used.

(c) 라디칼 중합 개시제로서, t-헥실퍼옥시-2-에틸헥사노에이트(퍼헥실 O, 닛본 유시 가부시끼가이샤 제조의 상품명)을 이용하였다. (c) As a radical polymerization initiator, t-hexyl peroxy-2-ethylhexanoate (perhexyl O, the Nippon Yushi Chemical Co., Ltd. brand name) was used.

(d) 분자 내에 적어도 1개 이상의 인산기를 갖는 비닐 화합물로서, 2-(메트)아크릴로일옥시에틸포스페이트(라이트에스테르 P-2M, 교에이샤 가가꾸 가부시끼가이샤 제조의 상품명)을 이용하였다. (d) As a vinyl compound which has at least 1 or more phosphoric acid group in a molecule | numerator, 2- (meth) acryloyloxyethyl phosphate (light ester P-2M, the brand name of Kyogisha Chemical Co., Ltd. product) was used.

(e) 도전성 입자로서는, 폴리스티렌을 핵으로 하는 입자의 표면에 두께 0.2 ㎛의 니켈층을 설치하고, 이 니켈층의 외측에 두께 0.02 ㎛의 금층을 설치하여 제작한 평균 입경 4 ㎛, 비중 2.5의 도전성 입자를 이용하였다. (e) As electroconductive particle, the nickel particle of thickness 0.2micrometer was provided in the surface of the particle which uses polystyrene as a nucleus, and the gold particle of 0.02micrometer thickness was provided on the outer side of this nickel layer, and the average particle diameter of 4 micrometers and specific gravity 2.5 of Electroconductive particle was used.

상술한 성분을 표 1에 나타내는 고형 중량비로 배합하고, 또한 (e) 도전성 입자를 1.5 부피％ 배합 분산시켰다. 얻어진 분산액을 두께 80 ㎛의 불소 수지 필름에 도공 장치를 이용하여 도포하고, 70℃, 10분의 열풍 건조에 의해서 접착제층의 두께가 15 ㎛인 필름상 접착제를 얻었다.
The above-mentioned component was mix | blended in the solid weight ratio shown in Table 1, and (e) 1.5 volume% mixture dispersion | distribution of electroconductive particle were carried out. The obtained dispersion liquid was apply | coated to the 80-micrometer-thick fluororesin film using a coating apparatus, and the film adhesive whose thickness of an adhesive bond layer was 15 micrometers was obtained by 70 degreeC and hot air drying for 10 minutes.

*(실시예 2, 비교예 2)* (Example 2, Comparative Example 2)

(a) 열가소성 수지로서 페녹시 수지 및 우레탄 수지를 사용하였다. (a) A phenoxy resin and urethane resin were used as a thermoplastic resin.

페녹시 수지로서는 페녹시 수지(PKHC, 유니온카바이트사 제조의 상품명, 평균 분자량 45,000) 40 g을 메틸에틸케톤 60 g에 용해하여 고형분 40 중량％의 용액으로 한 것을 이용하였다. As the phenoxy resin, 40 g of phenoxy resin (PKHC, trade name manufactured by Union Carbide Co., Ltd., average molecular weight 45,000) was dissolved in 60 g of methyl ethyl ketone to prepare a solution having a solid content of 40% by weight.

또한 우레탄 수지로서는 평균 분자량 2,000의 폴리부틸렌아디페이트디올 450 중량부와 평균 분자량 2,000의 폴리옥시테트라메틸렌글리콜 450 중량부, 1,4-부틸렌글리콜 100 중량부를 메틸에틸케톤 4000 중량부 중에서 균일하게 혼합하고, 디페닐메탄디이소시아네이트 390 중량부를 가하고 70℃에서 반응시켜 얻어진 중량 평균 분자량 35만의 우레탄 수지를 사용하였다. As the urethane resin, 450 parts by weight of polybutylene adipatediol having an average molecular weight of 2,000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, and 100 parts by weight of 1,4-butylene glycol are uniformly contained in 4000 parts by weight of methyl ethyl ketone. A urethane resin having a weight average molecular weight of 350,000 obtained by mixing and adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C was used.

(b) 라디칼 중합성 화합물로서는, 상술한 U-1(중량 평균 분자량 45,000) 또는 U-250 g을, 각각 메틸에틸케톤 50 g에 용해하여, 고형분 50 중량％의 용액으로 한 것을 사용하였다. (b) As a radically polymerizable compound, what dissolved U-1 (weight average molecular weight 45,000) or U-250g mentioned above in 50 g of methyl ethyl ketone, respectively, was used as the solution of 50 weight% of solid content.

또한 (b) 성분 이외의 라디칼 중합성 화합물로서, 펜타에리트리톨트리아크릴레이트(NK 에스테르 A-TMM-3L, 신나카무라 가가꾸 고교 가부시끼가이샤 제조의 상품명)을 이용하였다. As radically polymerizable compounds other than the component (b), pentaerythritol triacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Industries, Ltd.) was used.

(c) 라디칼 중합 개시제로서, t-헥실퍼옥시-2-에틸헥사노에이트(퍼헥실 O, 닛본 유시 가부시끼가이샤 제조의 상품명)을 이용하였다. (c) As a radical polymerization initiator, t-hexyl peroxy-2-ethylhexanoate (perhexyl O, the Nippon Yushi Chemical Co., Ltd. brand name) was used.

(d) 분자 내에 적어도 1개 이상의 인산기를 갖는 비닐 화합물로서, 2-(메트)아크릴로일옥시에틸포스페이트(라이트에스테르 P-2M, 교에이샤 가가꾸 가부시끼가이샤 제조의 상품명)을 이용하였다. (d) As a vinyl compound which has at least 1 or more phosphoric acid group in a molecule | numerator, 2- (meth) acryloyloxyethyl phosphate (light ester P-2M, the brand name of Kyogisha Chemical Co., Ltd. product) was used.

상술한 성분을 표 1에 나타내는 고형 중량비로 배합하고, 또한 (e) 도전성 입자로서의 Ni 입자를 1.5 부피％ 배합 분산시켰다. 얻어진 분산액을, 두께 80 ㎛의 불소 수지 필름에 도공 장치를 이용하여 도포하고, 70℃, 10분의 열풍 건조에 의해서 접착제층의 두께가 40 ㎛인 필름상 접착제를 얻었다. The above-mentioned component was mix | blended in the solid weight ratio shown in Table 1, and (e) 1.5 volume% mixture dispersion | distribution of Ni particle as electroconductive particle were carried out. The obtained dispersion liquid was apply | coated to the 80-micrometer-thick fluororesin film using a coating apparatus, and the film adhesive whose thickness of an adhesive bond layer is 40 micrometers was obtained by 70 degreeC and hot air drying for 10 minutes.

Figure pat00006
Figure pat00006

〔접착 강도, 접속 저항의 측정〕[Measurement of Adhesive Strength and Connection Resistance]

(실시예 1, 비교예 1)(Example 1, Comparative Example 1)

상기 제조 방법에 의해서 얻은 필름상 접착제를 이용하여 라인폭 25 ㎛, 피치 50 ㎛, 두께 8 ㎛의 구리 회로를 500개 갖는 플렉시블 회로판(FPC)과, 0.2 ㎛의 산화인듐(ITO)의 박층을 형성한 유리(두께 1.1 mm, 표면 저항 20Ω/□)를, 열압착 장치(가열 방식: 콘스탄트히트형, 도레이 엔지니어링 가부시끼가이샤 제조)를 이용하고, 160℃의 온도, 3 MPa의 압력으로 10초간의 가열 가압을 행하여 폭 2 mm에 걸쳐서 접속하여 접속체를 제작하였다. Using a film adhesive obtained by the above production method, a flexible circuit board (FPC) having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 8 μm, and a thin layer of 0.2 μm of indium oxide (ITO) were formed. One glass (thickness 1.1mm, surface resistance 20Ω / square) using thermocompression bonding apparatus (heating method: constant heat type, Toray Engineering Co., Ltd.) for 10 seconds at temperature of 160 degreeC, pressure of 3MPa It heated and pressurized and connected over 2 mm width, and produced the connector.

이 접속체의 인접 회로 사이의 저항값을 접착 직후와, 85℃, 85％ RH의 고온 고습조 중에 250시간 유지한 후에 멀티미터로 측정하였다. 저항값은 인접 회로 사이의 저항 37점의 평균으로 나타내었다. The resistance value between adjacent circuits of this connection body was measured by a multimeter immediately after adhesion | attachment, after hold | maintaining for 250 hours in 85 degreeC and the high temperature high humidity tank of 85% RH. The resistance value was represented by the average of 37 resistance points between adjacent circuits.

〔접착 강도, 접속 저항의 측정〕[Measurement of Adhesive Strength and Connection Resistance]

(실시예 2, 비교예 2)(Example 2, Comparative Example 2)

상기 제조 방법에 의해서 얻은 필름상 접착제를 이용하여, 라인폭 100 ㎛, 피치 200 ㎛, 두께 18 ㎛의 구리 회로를 500개 갖는 플렉시블 회로판(FPC)과, 라인폭 100 ㎛, 피치 200 ㎛, 두께 35 ㎛의 구리 회로를 500개 갖는 인쇄 기판(PCB)(두께 1.1 mm)을, 열압착 장치(가열 방식: 콘스탄트히트형, 도레이 엔지니어링 가부시끼가이샤 제조)를 이용하여, 160℃의 온도, 3 MPa의 압력으로 10초간의 가열 가압을 행하여 폭 2 mm에 걸쳐서 접속하여 접속체를 제작하였다. Using the film adhesive obtained by the said manufacturing method, the flexible circuit board (FPC) which has 500 copper lines of 100 micrometers in width, 200 micrometers in pitch, and 18 micrometers in thickness, 100 micrometers in line width, 200 micrometers in pitch, and thickness 35 A printed circuit board (PCB) having a thickness of 500 μm (PCB) (thickness: 1.1 mm) was heated at a temperature of 160 ° C. and 3 MPa using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). 10 seconds of heating and pressure were performed under pressure, and the connection body was produced by connecting over 2 mm in width.

이 접속체의 인접 회로 사이의 저항값을, 접착 직후와, 85℃, 85％ RH의 고온 고습조 중에 250시간 유지한 후에 멀티미터로 측정하였다. 저항값은 인접 회로 사이의 저항 37점의 평균으로 나타내었다. The resistance value between adjacent circuits of this connection body was measured by a multimeter immediately after adhesion | attachment, after hold | maintaining for 250 hours in 85 degreeC and the high temperature high humidity tank of 85% RH. The resistance value was represented by the average of 37 resistance points between adjacent circuits.

또한, 이 접속체의 접착 강도를 JIS-Z0237에 준하여 90도 박리법으로 측정하고, 평가하였다. 여기서, 접착 강도의 측정 장치는 도요 볼드윈 가부시끼가이샤 제조의 텐실론 UTM-4(박리 속도 50 mm/분, 25℃)를 사용하였다. In addition, the adhesive strength of this connector was measured and evaluated by the 90 degree peeling method according to JIS-Z0237. Here, Tensilon UTM-4 (peel rate 50 mm / min, 25 degreeC) by Toyo Baldwin Co., Ltd. was used for the measurement apparatus of adhesive strength.

이상과 같이 하여 행한 접속체의 접착 강도, 접속 저항의 측정의 결과를 표 2에 나타내었다. Table 2 shows the results of the measurement of the adhesive strength and the connection resistance of the connectors carried out as described above.

Figure pat00007
Figure pat00007

중량 평균 분자량이 10,000 이상인 우레탄(메트)아크릴레이트 화합물을 조성 중에 포함하는, 실시예 1 내지 2에서 얻어진 필름상 접착제는, 접착 직후 및 85℃, 85％ RH의 고온 고습조 중에 250시간 유지한 후에, 양호한 접속 저항 및 접착 강도를 나타내어, 양호한 특성을 나타내는 것을 알 수 있었다. The film adhesives obtained in Examples 1-2 containing the urethane (meth) acrylate compound which has a weight average molecular weight of 10,000 or more in a composition immediately after adhesion and after hold | maintaining for 250 hours in 85 degreeC, 85% RH high temperature high-humidity tank. It showed that favorable connection resistance and adhesive strength were shown and favorable characteristic was shown.

한편, 중량 평균 분자량이 10,000 이상인 우레탄(메트)아크릴레이트 화합물을 조성 중에 포함하지 않는 비교예 1 내지 2에서는, 접착 직후의 접속 저항값은 양호하지만, 85℃, 85％ RH의 고온 고습조 중에 250시간 유지한 후(신뢰성 시험 후)에는 접속 저항값이 상승하였다. 또한, 접착력에 대해서도, 실시예 1 내지 2와 비교하여 접착 직후의 접착력은 높지만, 신뢰성 시험 후의 접착력 저하가 현저하였다.On the other hand, in Comparative Examples 1-2 which do not contain the urethane (meth) acrylate compound whose weight average molecular weight is 10,000 or more in a composition, although the connection resistance value immediately after adhesion | attachment is favorable, it is 250 in 85 degreeC and the high temperature high humidity tank of 85% RH. After hold | maintaining for time (after reliability test), connection resistance value rose. Moreover, also about adhesive force, although the adhesive force immediately after adhesion | attachment is high compared with Examples 1-2, the fall of the adhesive force after a reliability test was remarkable.

이상의 결과로부터, 본 발명의 (b) 라디칼 중합성 화합물을 이용함으로써 양호한 접속 저항과 접착력을 양립할 수 있는 것이 분명해졌다. From the above result, it became clear that favorable connection resistance and adhesive force can be made compatible by using the (b) radically polymerizable compound of this invention.

(실시예 3) (Example 3)

실시예 1에서 얻어진 필름상 접착제를, 진공 포장을 실시하고, 40℃에서 3일간 방치한 후, 실시예 1과 동일하게 FPC와 ITO를 160℃, 3 MPa, 10초로 가열 압착을 행하였다. 이상과 같이 하여 행한 접속체의 접착 강도, 접속 저항을 측정한 바, 접착 강도는 840 내지 880 N/m, 접속 저항은 1.0 내지 1.3 Ω을 나타내어, 처리 전인 실시예 1과 값에 변화가 거의 없기 때문에, 방치 안정성이 우수한 것을 알 수 있었다. After vacuum-packing the film adhesive obtained in Example 1 and leaving it to stand at 40 degreeC for 3 days, FPC and ITO were heat-compression-bonded at 160 degreeC, 3 MPa, and 10 second similarly to Example 1. When the adhesive strength and the connection resistance of the connection body made as described above were measured, the adhesive strength was 840 to 880 N / m, and the connection resistance was 1.0 to 1.3 Ω, so that there was little change in the value of Example 1 before the treatment. Therefore, it turned out that the standing stability is excellent.

(실시예 4) (Example 4)

반도체칩(3×10 mm, 높이 0.5 mm, 주요면의 4변 주위에 범프라고 불리는 각변 100 ㎛, 높이 20 ㎛의 돌기한 금 전극이 존재)의 범프 배치와 대응한 접속 단자를 갖는 두께 1 mm의 유리 에폭시 기판(회로는 동박으로 두께 18 ㎛)으로부터 제작한 반도체 탑재용 기판을 준비하였다. 1 mm thick with connection terminals corresponding to the bump arrangement of the semiconductor chip (3 x 10 mm, height 0.5 mm, protruding gold electrodes with bumps of 100 μm and 20 μm in height around the four sides of the main face) The board | substrate for semiconductor mountings produced from the glass epoxy board | substrate (the circuit is 18 micrometers in thickness with copper foil) was prepared.

반도체 탑재용 기판의 회로 표면에는 니켈/금 도금을 실시하였다. 반도체칩의 돌기 전극과 반도체 탑재용 기판을 상기 실시예 1의 필름상 접착제를 이용하여 다음과 같이 하여 접속하였다. Nickel / gold plating was performed on the circuit surface of the semiconductor mounting substrate. The protrusion electrode of the semiconductor chip and the board | substrate for semiconductor mounting were connected as follows using the film adhesive of the said Example 1.

반도체 탑재용 기판의 회로면에 필름상 접착재를 80℃, 1 MPa, 3초로 가압착하고, 박리성 불소 수지 필름을 박리한 후, 반도체칩의 돌기 전극과 반도체 탑재용 기판과의 위치 정렬을 행하고, 180℃, 10 kgf/칩의 온도 및 압력으로 20초간 가열압착하였다. After pressing the film adhesive on the circuit surface of a semiconductor mounting board | substrate at 80 degreeC, 1 MPa, and 3 second, peeling a peelable fluororesin film, and performing position alignment of the protrusion electrode of a semiconductor chip, and a semiconductor mounting board | substrate, Heat compression was performed for 20 seconds at a temperature and pressure of 180 ° C., 10 kgf / chip.

이것에 의해서 필름상 접착제를 통해 반도체칩의 돌기 전극과 반도체 탑재용 기판의 회로를 전기적으로 접속함과 동시에 반도체칩과 반도체 탑재용 기판의 전극은 필름상 접착제의 경화에 의해서 이 접속 상태를 유지하였다. 이와 같이 하여 얻은 반도체칩과 반도체 탑재용 기판을 접속한 반도체 장치를(-55℃, 30분)/(125℃, 30분)의 조건으로 반복하는 냉열 사이클 시험에 처하였다. As a result, the projection electrode of the semiconductor chip and the circuit of the semiconductor mounting substrate were electrically connected to each other through the film adhesive, and the electrode of the semiconductor chip and the semiconductor mounting substrate was kept in this connection state by curing the film adhesive. . The semiconductor device which connected the semiconductor chip obtained in this way and the board | substrate for semiconductor mounting was subjected to the cold heat cycle test which repeats on conditions of (-55 degreeC, 30 minutes) / (125 degreeC, 30 minutes).

이 냉열 사이클 시험 1,000회 후의 반도체칩의 돌기 전극과 기판 회로의 접속 저항을 측정한 바 접속 저항의 상승이 없어, 양호한 접속 신뢰성을 나타내었다.
When the connection resistance of the protruding electrode of the semiconductor chip and the board | substrate circuit was measured 1,000 times after this cold-heat cycle test, there was no increase in connection resistance, and favorable connection reliability was shown.

Claims (9)

(a) 열가소성 수지, (b) 1 분자 중에 2개 이상의 (메트)아크릴로일기 및 2개 이상의 우레탄 결합을 갖고, 중량 평균 분자량이 30,000보다 크고 50,000 이하인 라디칼 중합성 화합물, 및 (c) 라디칼 중합 개시제를 함유하는 접착제 조성물. (a) a thermoplastic resin, (b) a radically polymerizable compound having two or more (meth) acryloyl groups and two or more urethane bonds in one molecule, and having a weight average molecular weight of greater than 30,000 and 50,000 or less, and (c) radical polymerization Adhesive composition containing an initiator. 제1항에 있어서, 상기 (a) 열가소성 수지 100 중량부에 대하여, 상기 (b) 라디칼 중합성 화합물을 10 내지 250 중량부, 상기 (c) 라디칼 중합 개시제를 0.05 내지 30 중량부 함유하는 접착제 조성물. The adhesive composition according to claim 1, comprising 10 to 250 parts by weight of the (b) radical polymerizable compound and 0.05 to 30 parts by weight of the (c) radical polymerization initiator with respect to 100 parts by weight of the (a) thermoplastic resin. . 제1항에 있어서, 상기 (c) 라디칼 중합 개시제가 과산화물 또는 아조 화합물인 접착제 조성물.The adhesive composition according to claim 1, wherein the (c) radical polymerization initiator is a peroxide or an azo compound. 제1항에 있어서, 상기 (b) 라디칼 중합성 화합물이, 하기 화학식 (A) 및 하기 화학식 (B)로부터 선택되는 적어도 하나 이상의 구조를 포함하는 화합물인 접착제 조성물.
Figure pat00008

Figure pat00009
The adhesive composition of Claim 1 whose said (b) radically polymerizable compound is a compound containing at least 1 or more structure chosen from following General formula (A) and following General formula (B).
Figure pat00008

Figure pat00009
 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 (a) 열가소성 수지 100 중량부에 대하여, (d) 분자 내에 적어도 1개 이상의 인산기를 갖는 비닐 화합물을 0.1 내지 20 중량부 더 함유하는 접착제 조성물. The adhesive according to any one of claims 1 to 4, further comprising 0.1 to 20 parts by weight of a vinyl compound having at least one or more phosphoric acid groups in the molecule (d), based on 100 parts by weight of the (a) thermoplastic resin. Composition. 제1항 내지 제4항 중 어느 한 항에 있어서, (e) 도전성 입자를 더 함유하는 접착제 조성물. The adhesive composition according to any one of claims 1 to 4, further comprising (e) conductive particles. 서로 대향하는 회로 전극을 갖는 기판 사이에 개재시켜, 상기 서로 대향하는 회로 전극끼리가 전기적으로 접속되도록 상기 기판 끼리를 접착하기 위해서 이용되는 회로 접속용 접착제로서,
제1항 내지 제4항 중 어느 한 항에 기재된 접착제 조성물로 이루어지는 회로 접속용 접착제. An adhesive for circuit connection interposed between substrates having circuit electrodes opposing each other, and used to bond the substrates so that the circuit electrodes opposing each other are electrically connected.
Adhesive for circuit connection which consists of an adhesive composition in any one of Claims 1-4. 제1 회로 전극을 갖는 제1 기판과,
제2 회로 전극을 갖는 제2 기판을,
상기 제1 회로 전극과 상기 제2 회로 전극이 서로 대향하도록 배치하고,
대향 배치한 상기 제1 기판과 제2 기판 사이에 제7항에 기재된 회로 접속용 접착제를 개재시키고, 가열 가압하여 상기 제1 회로 전극과 상기 제2 회로 전극을 전기적으로 접속시켜 이루어지는 접속체. A first substrate having a first circuit electrode,
A second substrate having a second circuit electrode,
The first circuit electrode and the second circuit electrode are disposed to face each other,
A connecting body formed by electrically pressurizing the first circuit electrode and the second circuit electrode by interposing the adhesive for a circuit connection according to claim 7 between the first substrate and the second substrate that are disposed opposite each other. 대향 배치한 반도체 소자와 반도체 탑재용 기판 사이에 제7항에 기재된 회로 접속용 접착제를 개재시키고, 가열 가압하여 상기 반도체 소자와 상기 반도체 탑재용 기판을 전기적으로 접속시켜 이루어지는 반도체 장치. The semiconductor device which electrically connects the said semiconductor element and the said semiconductor mounting board | substrate between the opposingly arrange | positioned semiconductor element and the semiconductor mounting board | substrate through the adhesive for circuit connection of Claim 7, and pressing.
KR1020127034027A 2008-04-17 2009-04-17 Adhesive composition, adhesive for circuit connection, connected structure, and semiconductor device KR20130006549A (en)

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