JP2010004067A - Circuit connection material - Google Patents

Circuit connection material Download PDF

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JP2010004067A
JP2010004067A JP2009214664A JP2009214664A JP2010004067A JP 2010004067 A JP2010004067 A JP 2010004067A JP 2009214664 A JP2009214664 A JP 2009214664A JP 2009214664 A JP2009214664 A JP 2009214664A JP 2010004067 A JP2010004067 A JP 2010004067A
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connection
connection terminal
circuit
heating
resin
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Mitsugi Fujinawa
貢 藤縄
Masami Yusa
正己 湯佐
Akira Nagai
朗 永井
Kenzo Takemura
賢三 竹村
Seiji Tai
誠司 田井
Hidehiro Nakamura
英博 中村
Tetsuya Enomoto
哲也 榎本
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrical/electronic circuit connection material more excellent in low-temperature fast curability than in that of a conventional epoxy resin and also having a pot life. <P>SOLUTION: In a connection material for use in a connection method for electrically connecting a first circuit member having a first connection terminal and a second circuit member having a second connection terminal by heating pressurization and ultrasonic impression with the first connection terminal and the second connection terminal oppositely disposed, and the oppositely disposed first connection terminal and second connection terminal superposed by interposing the circuit connection material, the circuit connection material essentially includes the following components (1) to (4): (1) a curing agent generating a free radical by heating, (2) a hydroxyl group-containing resin having a molecular weight of 10,000 or larger, (3) a radically polymerizable substance and (4) a conductive particle having an insulating resin as an external layer and whose thickness of the insulating resin is 20% or less of a particle diameter. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、回路接続材料に関する。   The present invention relates to a circuit connecting material.

エポキシ樹脂系接着剤は、高い接着強さが得られ、耐水性や耐熱性に優れること等から、電気・電子・建築・自動車・航空機等の各種用途に多用されている。中でも一液型エポキシ樹脂系接着剤は、主剤と硬化剤との混合が不必要であり使用が簡便なことから、フィルム状・ペースト状・粉体状の形態で使用されている。この場合、エポキシ樹脂と硬化剤及び変性剤との多様な組み合わせにより、特定の性能を得ることが一般的である。(例えば、特開昭62−141083号公報)。   Epoxy resin adhesives are widely used in various applications such as electricity, electronics, architecture, automobiles, and aircraft because of their high adhesive strength and excellent water resistance and heat resistance. Among them, one-pack type epoxy resin adhesives are used in the form of films, pastes, and powders because they do not require mixing of the main agent and the curing agent and are easy to use. In this case, it is common to obtain specific performance by various combinations of an epoxy resin, a curing agent, and a modifier. (For example, JP-A-62-141083).

特開昭62−141083号公報JP-A-62-141083

しかしながら、上記特開昭62−141083号公報に示されるフィルム状接着剤は、作業性に優れるものの、20秒程度の接続時間とするには、140〜180℃程度の加熱、10秒程度の接続時間とするには、180〜210℃程度の加熱が必要であった。これは、短時間硬化性(速硬化性)と貯蔵安定性(保存性)のバランスをとるため、常温で不活性な触媒型硬化剤を用いているので、硬化に際して十分な反応が得られないためである。近年、精密電子機器の分野では、回路の高密度化が進んでおり、電極幅、電極間隔が極めて狭くなっている。このため、従来のエポキシ樹脂系を用いた回路接続材料の接続条件では、配線の脱落、剥離や位置ずれが生じる問題、電極上に十分な導電性粒子を存在させるために導電性粒子の含有量を増加すると、隣接する電極間に過剰の導電性粒子が存在して短絡を引き起こすなどの問題があった。また、生産効率向上のために10秒以下で接続できる接続時間の短縮化が求められており、低温速硬化性が必要不可欠となっている。本発明は、従来のエポキシ樹脂系よりも低温速硬化性に優れ、かつ、可使時間を有する電気・電子用の回路接続材料を提供することにある。   However, although the film adhesive shown in the above-mentioned JP-A-62-141083 is excellent in workability, heating to about 140 to 180 ° C. and connection for about 10 seconds are required for a connection time of about 20 seconds. In order to make time, heating at about 180 to 210 ° C. was necessary. In order to balance short-time curability (fast curability) and storage stability (preservability), a catalyst-type curing agent that is inert at room temperature is used, so that a sufficient reaction cannot be obtained during curing. Because. In recent years, in the field of precision electronic equipment, the density of circuits has been increasing, and the electrode width and electrode interval have become extremely narrow. For this reason, under the connection conditions of circuit connection materials using conventional epoxy resin systems, there is a problem that the wiring is dropped, peeled off or misaligned, and the content of conductive particles in order to have sufficient conductive particles on the electrodes When there is an increase, excessive conductive particles exist between adjacent electrodes, causing a short circuit. In addition, in order to improve production efficiency, shortening of the connection time that can be connected in 10 seconds or less is required, and low temperature fast curing is indispensable. An object of the present invention is to provide a circuit connection material for electric and electronic use which is superior in low-temperature fast curing property and has a usable time as compared with conventional epoxy resin systems.

本発明は、第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、対向配置した第一の接続端子と第二の接続端子を、回路接続材料を介在させて重ね合わせた状態で加熱加圧及び超音波印加によって、電気的に接続する接続方法に用いる接続材料であって、下記(1)〜(4)の成分を必須とする回路接続材料である。
(1)加熱により遊離ラジカルを発生する硬化剤
(2)分子量10000以上の水酸基含有樹脂
(3)ラジカル重合性物質
(4)最外層として絶縁性樹脂を有し、絶縁性樹脂の厚みが粒子径の20%以下である導電性粒子
According to the present invention, a first circuit member having a first connection terminal and a second circuit member having a second connection terminal are disposed so that the first connection terminal and the second connection terminal are opposed to each other. A connection material used for a connection method in which the first connection terminal and the second connection terminal arranged opposite to each other are electrically connected to each other by heating and pressurization and ultrasonic application in a state where the circuit connection material is interposed therebetween. And it is a circuit connection material which makes the component of following (1)-(4) essential.
(1) Curing agent that generates free radicals upon heating (2) Hydroxyl-containing resin having a molecular weight of 10,000 or more (3) Radical polymerizable material (4) Insulating resin as outermost layer, and the thickness of the insulating resin is the particle size Conductive particles that are 20% or less of

さらに、ラジカル重合性物質が、式(I)で示されるラジカル重合性物質を含有することが好ましい。   Furthermore, the radical polymerizable substance preferably contains a radical polymerizable substance represented by the formula (I).

Figure 2010004067

(式中、Rは、水素、メチル基を示し、nは、1〜3の整数を示す。)
上述の回路接続材料によって、第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、対向配置した第一の接続端子と第二の接続端子を、下記(1)〜(4)の成分を必須とする回路接続材料を用いて電気的に接続する接続方法において、回路接続材料を介在させて重ね合わせた状態で加熱加圧及び超音波印加によって、上記相対向する電極端子部を電気的および機械的接続を行うことを特徴とする回路板の製造方法を提供できる。
(1)加熱により遊離ラジカルを発生する硬化剤
(2)分子量10000以上の水酸基含有樹脂
(3)ラジカル重合性物質
(4)最外層として絶縁性樹脂を有し、絶縁性樹脂の厚みが粒子径の20%以下である導電性粒子
Figure 2010004067

(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 1 to 3.)
With the above circuit connection material, the first circuit member having the first connection terminal and the second circuit member having the second connection terminal are opposed to each other. In the connection method of electrically connecting the first connection terminal and the second connection terminal, which are disposed opposite to each other, using a circuit connection material that essentially includes the following components (1) to (4): It is possible to provide a method of manufacturing a circuit board characterized in that the electrode terminal portions facing each other are electrically and mechanically connected by heating and pressurizing and applying ultrasonic waves in a state where the connecting materials are overlapped.
(1) Curing agent that generates free radicals upon heating (2) Hydroxyl-containing resin having a molecular weight of 10,000 or more (3) Radical polymerizable material (4) Insulating resin as outermost layer, and the thickness of the insulating resin is the particle size Conductive particles that are 20% or less of

さらに、ラジカル重合性物質が、式(I)で示されるラジカル重合性物質を含有することが好ましい。   Furthermore, the radical polymerizable substance preferably contains a radical polymerizable substance represented by the formula (I).

また、本発明は、第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、前記対向配置した第一の接続端子と第二の接続端子を、回路接続材料を介在させて重ね合わせた状態で加熱加圧及び超音波印加によって、電気的に接続する接続方法において、下記(1)〜(3)の成分を必須とする回路接続材料も提供する。
(1)加熱により遊離ラジカルを発生する硬化剤、
(2)分子量10000以上の水酸基含有樹脂、
(3)ラジカル重合性物質
The present invention also provides a first circuit member having a first connection terminal and a second circuit member having a second connection terminal, with the first connection terminal and the second connection terminal facing each other. In the connection method of arranging and electrically connecting the first connection terminal and the second connection terminal arranged opposite to each other by heating and pressing and applying ultrasonic waves in a state where the circuit connection material is interposed therebetween, The circuit connection material which makes the following (1)-(3) component essential is also provided.
(1) a curing agent that generates free radicals upon heating;
(2) a hydroxyl group-containing resin having a molecular weight of 10,000 or more,
(3) Radical polymerizable substance

本回路接続材料は、上記(1)〜(3)の成分とさらに導電性粒子を必須成分とすることが好ましい。また、導電性粒子の表面が絶縁性樹脂により被覆されており、導電性粒子の表面を被覆する絶縁性樹脂の厚みが導電性粒子の粒子径の20%以下であると好ましい。さらに、ラジカル重合性物質が、式(I)で示されるラジカル重合性物質を含有することが好ましい。   It is preferable that this circuit connection material has the above components (1) to (3) and further conductive particles as essential components. Moreover, it is preferable that the surface of the conductive particles is covered with an insulating resin, and the thickness of the insulating resin covering the surface of the conductive particles is 20% or less of the particle diameter of the conductive particles. Furthermore, the radical polymerizable substance preferably contains a radical polymerizable substance represented by the formula (I).

本発明によれば、回路接続材料による電極端子部と例えばFPC基板との接続の際に加熱や加圧と同時に超音波印加をすることにより、低い加熱温度での接続及び接続抵抗の低抵抗化が可能となり、接続部と周囲(ガラスや液晶等)へのダメージを低減することができる。   According to the present invention, by applying ultrasonic waves simultaneously with heating and pressurization when connecting an electrode terminal portion made of a circuit connecting material and, for example, an FPC board, connection at a low heating temperature and reduction in connection resistance are achieved. It is possible to reduce damage to the connection portion and the surroundings (glass, liquid crystal, etc.).

従来の回路板の製造方法を示す断面図である。It is sectional drawing which shows the manufacturing method of the conventional circuit board. 本発明の回路接続材料を用いた、回路板の製造方法を示す断面図である。It is sectional drawing which shows the manufacturing method of a circuit board using the circuit connection material of this invention. 本発明の回路接続材料を用いた、回路板の製造方法を示す断面図である。It is sectional drawing which shows the manufacturing method of a circuit board using the circuit connection material of this invention. 本発明の回路接続材料を用いた、回路板の製造方法を示す断面図である。It is sectional drawing which shows the manufacturing method of a circuit board using the circuit connection material of this invention.

本発明の回路接続材料を用いた、回路板の製造方法において、超音波印加は例えば、接続開始から所定時間経過後に印加を開始するといったように、本接続時に任意のタイミングで印加することができる。また、印加方向は、第一の接続端子と第二の接続端子を対向して配置し、対向配置した第一の接続端子と第二の接続端子の接続物と垂直方向または水平方向に超音波振動を与える方法が利用できる。接続部へのダメージを低減できることから、水平方向に超音波振動を与えるのが好ましい。しかし、接続初期では垂直方向に超音波振動を与えた後、水平方向に超音波振動与えるといった印加方法も利用でき、さらに上下からの超音波印加等の組み合わせも利用できる。また、回路板にあらかじめ回路接続材料を仮接続するときに、超音波を印可することも可能であり、この場合は仮圧着に要する加熱温度の低下が図れると共に、基材との密着性が向上するといった点から好ましい。さらに、仮接続及び本接続において超音波を印可することも可能である。超音波の印可は、超音波の印加または接続部の加熱が可能な押圧ツールからの印可や、支持台からの超音波の印加または接続部の加熱によって行われ、加熱加圧及び超音波の印可が可能な範囲で組み合わせて使用することができる。本発明の回路板の製造方法における電極端子部を有する回路板としては、TFT基板、FPC、TCP等、さらには電極端子部として、例えばリードボール、バンプによる電極端子部をもつ素子とこの素子をマウントする基板等が挙げられる。電極端子表面はITOなどの導電性薄膜、金、スズ等が利用可能である。   In the method for manufacturing a circuit board using the circuit connection material of the present invention, the ultrasonic wave can be applied at an arbitrary timing during the main connection, for example, the application is started after a predetermined time has elapsed from the start of the connection. . In addition, the first connection terminal and the second connection terminal are arranged to face each other, and the ultrasonic wave is applied in the vertical direction or the horizontal direction with the connection object of the first connection terminal and the second connection terminal arranged to face each other. A method of applying vibration can be used. Since damage to the connection portion can be reduced, it is preferable to apply ultrasonic vibration in the horizontal direction. However, an application method in which ultrasonic vibration is applied in the vertical direction and then ultrasonic vibration is applied in the horizontal direction at the initial stage of connection can be used, and a combination of ultrasonic application from above and below can also be used. In addition, when the circuit connection material is temporarily connected to the circuit board in advance, it is also possible to apply ultrasonic waves. In this case, the heating temperature required for temporary pressure bonding can be reduced and the adhesion to the substrate is improved. It is preferable from the point of doing. Furthermore, it is possible to apply ultrasonic waves in the temporary connection and the main connection. The application of ultrasonic waves is performed by applying from a pressing tool that can apply ultrasonic waves or heating the connection part, or by applying ultrasonic waves from a support base or heating the connection part. Can be used in combination within the possible range. As a circuit board having an electrode terminal part in the method for producing a circuit board of the present invention, a TFT substrate, FPC, TCP, etc., and further, as an electrode terminal part, for example, an element having an electrode terminal part by a lead ball or a bump and this element are used. Examples include a substrate to be mounted. For the electrode terminal surface, a conductive thin film such as ITO, gold, tin or the like can be used.

本発明に用いる回路接続材料に必須成分として含有される加熱により遊離ラジカルを発生する硬化剤としては、過酸化化合物、アゾ系化合物などの加熱により分解して遊離ラジカルを発生するものであり、目的とする接続温度、接続時間、ポットライフ等により適宜選定されるが、高反応性とポットライフの点から、半減期10時間の温度が40℃以上かつ、半減期1分の温度が180℃以下の有機過酸化物が好ましく、半減期10時間の温度が60℃以上かつ、半減期1分の温度が170℃以下の有機過酸化物が好ましい。接続時間を10秒以下とした場合、硬化剤の配合量は十分な反応率を得るためには2〜10重量%程度とするのが好ましく4〜8重量%がより好ましい。具体的には、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル、パーオキシケタール、ジアルキルパーオキサイド、ハイドロパーオキサイド、シリルパーオキサイドなどから選定できる。また、回路部材の接続端子の腐食を抑えるために、硬化剤中に含有される塩素イオンや有機酸は5000ppm以下であることが好ましく、さらに、加熱分解後に発生する有機酸が少ないものがより好ましい。具体的には、パーオキシエステル、ジアルキルパーオキサイド、ハイドロパーオキサイド、シリルパーオキサイドから選定され、高反応性が得られるパーオキシエステルから選定されることがより好ましい。これらは、適宜混合して用いることができる。   The curing agent that generates free radicals by heating, which is contained as an essential component in the circuit connection material used in the present invention, generates free radicals by being decomposed by heating of peroxide compounds, azo compounds, etc. The connection temperature, connection time, pot life, etc. are appropriately selected. From the viewpoint of high reactivity and pot life, the half-life time of 10 hours is 40 ° C or higher and the half-life temperature of 1 minute is 180 ° C or lower. An organic peroxide having a half-life of 10 hours at a temperature of 60 ° C. or more and a half-life of 1 minute at a temperature of 170 ° C. or less is preferred. When the connection time is 10 seconds or less, the amount of the curing agent is preferably about 2 to 10% by weight and more preferably 4 to 8% by weight in order to obtain a sufficient reaction rate. Specifically, it can be selected from diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide, and the like. Further, in order to suppress corrosion of the connection terminals of the circuit member, the chlorine ions and organic acids contained in the curing agent are preferably 5000 ppm or less, and more preferably less organic acids generated after the thermal decomposition. . Specifically, it is more preferably selected from peroxyesters, dialkyl peroxides, hydroperoxides, silyl peroxides, and peroxyesters that provide high reactivity. These can be mixed and used as appropriate.

パーオキシエステル類としては、クミルパーオキシネオデカノエート、1,1,3,3−テトラメチルブチルパーオキシネオデカノエート、1−シクロヘキシル−1−メチルエチルパーオキシノエデカノエート、t−ヘキシルパーオキシネオデカノエート、t−ブチルパーオキシピバレート、1,1,3,3−テトラメチルブチルパーオキシ−2−エチルヘキサノネート、2,5−ジメチル−2,5−ジ(2−エチルヘキサノイルパーオキシ)ヘキサン、1−シクロヘキシル−1−メチルエチルパーオキシ−2−エチルヘキサノネート、t−ヘキシルパーオキシ−2−エチルヘキサノネート、t−ブチルパーオキシ−2−エチルヘキサノネート、t−ブチルパーオキシイソブチレート、1、1−ビス(t−ブチルパーオキシ)シクロヘキサン、t−ヘキシルパーオキシイソプロピルモノカーボネート、t−ブチルパーオキシ−3,5,5−トリメチルヘキサノネート、t−ブチルパーオキシラウレート、2,5−ジメチル−2,5−ジ(m−トルオイルパーオキシ)ヘキサン、t−ブチルパーオキシイソプロピルモノカーボネート、t−ブチルパーオキシ−2−エチルヘキシルモノカーボネート、t−ヘキシルパーオキシベンゾエート、t−ブチルパーオキシアセテート等が挙げられる。   Peroxyesters include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t- Hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (2 -Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexa Nonate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoyl) Peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate and the like.

ジアルキルパーオキサイド類では、α,α’ビス(t−ブチルパーオキシ)ジイソプロピルベンゼン、ジクミルパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、t−ブチルクミルパーオキサイド等が挙げられる。   Dialkyl peroxides include α, α ′ bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and t-butyl cumi. Examples include ruperoxide.

ハイドロパーオキサイド類では、ジイソプロピルベンゼンハイドロパーオキサイド、クメンハイドロパーオキサイド等が挙げられる。ジアシルパーオキサイド類としては、イソブチルパーオキサイド、2,4−ジクロロベンゾイルパーオキサイド、3,5,5−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、スクシニックパーオキサイド、ベンゾイルパーオキシトルエン、ベンゾイルパーオキサイド等が挙げられる。   Examples of hydroperoxides include diisopropylbenzene hydroperoxide and cumene hydroperoxide. Examples of diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, Examples include benzoyl peroxytoluene and benzoyl peroxide.

パーオキシジカーボネート類としては、ジ−n−プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ビス(4−t−ブチルシクロヘキシル)パーオキシジカーボネト、ジ−2−エトキシメトキシパーオキシジカーボネート、ジ(2−エチルヘキシルパーオキシ)ジカーボネート、ジメトキシブチルパーオキシジカーボネート、ジ(3−メチル−3−メトキシブチルパーオキシ)ジカーボネート等がある。   Peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, Examples include di (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, and the like.

パーオキシケタール類では、1,1−ビス(t−ヘキシルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−ビス(t−ヘキシルパーオキシ)シクロヘキサン、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−(t−ブチルパーオキシ)シクロドデカン、2,2−ビス(t−ブチルパーオキシ)デカン等が挙げられる。   In peroxyketals, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butyl peroxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like.

シリルパーオキサイド類としては、t−ブチルトリメチルシリルパーオキサイド、ビス(t−ブチル)ジメチルシリルパーオキサイド、t−ブチルトリビニルシリルパーオキサイド、ビス(t−ブチル)ジビニルシリルパーオキサイド、トリス(t−ブチル)ビニルシリルパーオキサイド、t−ブチルトリアリルシリルパーオキサイド、ビス(t−ブチル)ジアリルシリルパーオキサイド、トリス(t−ブチル)アリルシリルパーオキサイド等が挙げられる。   Examples of silyl peroxides include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, and tris (t-butyl). ) Vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide, tris (t-butyl) allylsilyl peroxide, and the like.

前記したように、回路部材の接続端子の腐食を抑えるために、硬化剤中に含有される塩素イオンや有機酸は5000ppm以下であることが好ましく、さらに、加熱分解後に発生する有機酸が少ないものがより好ましい。具体的には、前記した有機化酸化物のなかでパーオキシエステル類、ジアルキルパーオキサイド類、ハイドロパーオキサイド類、シリルパ−オキサイド類から選定され、なかでも高反応性で速硬化性が得られるパーオキシエステル類から選定されることが好ましい。これらのは適宜混合して使用することができる。これらの遊離ラジカル発生剤は単独または混合して使用することができ、分解促進剤、抑制剤等を混合して用いても良い。また、これらの硬化剤をポリウレタン系、ポリエステル系の高分子物質等で被覆してマイクロカプセル化したものは、可使時間が延長されるために好ましい。   As described above, in order to suppress the corrosion of the connection terminals of the circuit members, the chlorine ions and organic acids contained in the curing agent are preferably 5000 ppm or less, and further, those that generate less organic acids after thermal decomposition. Is more preferable. Specifically, peroxyesters, dialkyl peroxides, hydroperoxides, and silyl peroxides among the above-mentioned organic oxides are selected, and among them, a highly reactive and quick curing property is obtained. It is preferably selected from oxyesters. These can be mixed and used as appropriate. These free radical generators can be used alone or in combination, and a decomposition accelerator, an inhibitor and the like may be used in combination. In addition, those encapsulating these curing agents with polyurethane-based or polyester-based polymeric substances and the like and microencapsulated are preferable because the pot life is extended.

本発明で用いる回路接続材料に必須成分として含有される分子量10000以上の水酸基含有樹脂は、分子内に水酸基を有する分子量10000以上の樹脂でありポリビニルホルマール、ポリビニルブチラール、ポリエステル、ポリアミド、キシレン樹脂、フェノキシ樹脂、ポリウレタン等が挙げられ、硬化時の応力緩和に優れ、極性を有するため接着性が向上する。分子量10000以上の水酸基含有樹脂は、ラジカル重合性の官能基などによって変性されていても良く、ラジカル重合性の官能基で変性したものは耐熱性が向上するため好ましい。分子量は10000以上が好ましいが10000000以上になると混合性、流動性が悪くなる。分子量10000以上の水酸基含有樹脂の配合量は、2〜80重量%が適用可能な範囲であり、5〜70重量%が好ましく、10〜60重量%がより好ましい。2重量%未満では、回路接続材料の硬化時、熱負荷等の応力緩和の効果に乏しく、接着強度が低下する。また、80重量%を超えると流動性が低下する恐れがある。   The hydroxyl group-containing resin having a molecular weight of 10,000 or more, which is contained as an essential component in the circuit connecting material used in the present invention, is a resin having a molecular weight of 10,000 or more having a hydroxyl group in the molecule, such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, xylene resin, Resin, polyurethane, etc. are mentioned, and it is excellent in stress relaxation at the time of curing, and has adhesiveness because it has polarity. The hydroxyl group-containing resin having a molecular weight of 10,000 or more may be modified with a radical polymerizable functional group or the like, and a resin modified with a radical polymerizable functional group is preferable because heat resistance is improved. The molecular weight is preferably 10,000 or more, but if it is 10,000,000 or more, the mixing property and fluidity deteriorate. The blending amount of the hydroxyl group-containing resin having a molecular weight of 10,000 or more is within a range where 2 to 80% by weight is applicable, preferably 5 to 70% by weight, and more preferably 10 to 60% by weight. If it is less than 2% by weight, the effect of relieving stress such as heat load is insufficient when the circuit connecting material is cured, and the adhesive strength is lowered. Moreover, when it exceeds 80 weight%, there exists a possibility that fluidity | liquidity may fall.

本発明で用いる回路接続材料に必須成分として含有されるラジカル重合性物質としては、ラジカルにより重合する官能基を有する物質であり、アクリレート、メタクリレート、マレイミド化合物等が挙げられる。ラジカル重合性物質はモノマー、オリゴマーいずれの状態で用いることが可能であり、モノマーとオリゴマーを併用することも可能である。アクリレート(メタクリレート)の具体例としては、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、イソブチルアクリレート、エチレングリコールジアクリレート、ジエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、2−ヒドロキシ−1,3−ジアクリロキシプロパン、2,2−ビス〔4−(アクリロキシメトキシ)フェニル〕プロパン、2,2−ビス〔4−(アクリロキシポリエトキシ)フェニル〕プロパン、ジシクロペンテニルアクリレート、トリシクロデカニルアクリレート、トリス(アクリロイロキシエチル)イソシアヌレート等が挙げられる。これらは単独または併用して用いることができ、必要によっては、ハイドロキノン、メチルエーテルハイドロキノン類などの重合禁止剤を適宜用いてもよい。また、ジシクロペンタニル基またはトリシクロデカニル基またはトリアジン環を有する場合は、耐熱性が向上するので好ましい。   The radical polymerizable substance contained as an essential component in the circuit connecting material used in the present invention is a substance having a functional group that is polymerized by radicals, and examples thereof include acrylates, methacrylates, maleimide compounds, and the like. The radical polymerizable substance can be used in either a monomer or oligomer state, and the monomer and oligomer can be used in combination. Specific examples of the acrylate (methacrylate) include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, 2-hydroxy-1,3. -Diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodecanyl Examples thereof include acrylate and tris (acryloyloxyethyl) isocyanurate. These can be used alone or in combination. If necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be appropriately used. In addition, a dicyclopentanyl group, a tricyclodecanyl group, or a triazine ring is preferable because heat resistance is improved.

また、式(I)で示されるリン酸エステル構造を有するラジカル重合性物質を0.1〜10重量部用いた場合、金属等の無機物表面での接着強度が向上するので好ましく、0.5〜5重量部がより好ましい。リン酸エステル構造を有するラジカル重合性物質は、無水リン酸と2−ヒドロキシエチル(メタ)アクリレートの反応物として得られる。具体的には、モノ(2−メタクリロイルオキシエチル)アッシドホスフェート、ジ(2−メタクリロイルオキシエチル)アッシドホスフェート等がある。これらは単独でもまた組み合わせても使用できる。   Further, when 0.1 to 10 parts by weight of the radical polymerizable substance having a phosphate ester structure represented by the formula (I) is used, the adhesive strength on the surface of an inorganic material such as a metal is preferably improved, and 0.5 to 5 parts by weight is more preferred. The radically polymerizable substance having a phosphoric ester structure is obtained as a reaction product of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate. Specific examples include mono (2-methacryloyloxyethyl) acid phosphate and di (2-methacryloyloxyethyl) acid phosphate. These can be used alone or in combination.

Figure 2010004067

(式中、Rは、水素、メチル基を示し、nは、1〜3の整数を示す。)
Figure 2010004067

(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 1 to 3.)

マレイミド化合物としては、分子中にマレイミド基を少なくとも2個以上含有するもので、例えば、1−メチル−2,4−ビスマレイミドベンゼン、N,N’−m−フェニレンビスマレイミド、N,N’−p−フェニレンビスマレイミド、N,N’−m−トルイレンビスマレイミド、N,N’−4,4−ビフェニレンビスマレイミド、N,N’−4,4−−(3,3’−ジメチルビフェニレン)ビスマレイミド、N,N’−4,4−(3,3’−ジメチルジフェニルメタン)ビスマレイミド、N,N’−4,4−(3,3’−ジエチルジフェニルメタン)ビスマレイミド、N,N’−4,4−ジフェニルメタンビスマレイミド、N,N’−4,4−ジフェニルプロパンビスマレイミド、N,N’−4,4−ジフェニルエーテルビスマレイミド、N,N’−3,3’−ジフェニルスルホンビスマレイミド、2,2−ビス(4−(4−マレイミドフェノキシ)フェニル)プロパン、2,2−ビス(3−s−ブチル−3,4−(4−マレイミドフェノキシ)フェニル)プロパン、1,1−ビス(4−(4−マレイミドフェノキシ)フェニル)デカン、4,4’−シクロヘキシリデン−ビス(1−(4マレイミドフェノキシ)−2−シクロヘキシルベンゼン、2,2−ビス(4−(4−マレイミドフェノキシ)フェニル)ヘキサフルオロプロパン、などを挙げることができる。   The maleimide compound contains at least two maleimide groups in the molecule. For example, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N, N′— p-phenylene bismaleimide, N, N'-m-toluylene bismaleimide, N, N'-4,4-biphenylene bismaleimide, N, N'-4,4-(3,3'-dimethylbiphenylene) Bismaleimide, N, N′-4,4- (3,3′-dimethyldiphenylmethane) bismaleimide, N, N′-4,4- (3,3′-diethyldiphenylmethane) bismaleimide, N, N′- 4,4-diphenylmethane bismaleimide, N, N′-4,4-diphenylpropane bismaleimide, N, N′-4,4-diphenyl ether bismaleimide N, N′-3,3′-diphenylsulfone bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- ( 4-maleimidophenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene-bis (1- (4maleimidophenoxy) -2-cyclohexylbenzene 2,2-bis (4- (4-maleimidophenoxy) phenyl) hexafluoropropane, and the like.

さらに、充填材、軟化剤、促進剤、老化防止剤、着色剤、難燃化剤、チキソトロピック剤、カップリング剤及びフェノール樹脂やメラミン樹脂、イソシアネート類等を含有することもできる。充填材を含有した場合、接続信頼性等の向上が得られるので好ましい。充填材の最大径が導電粒子の粒径未満であれば使用でき、5〜60体積%の範囲が好ましい。60体積%以上では信頼性向上の効果が飽和する。カップリング剤としては、ビニル基、アクリル基、アミノ基、エポキシ基、またはイソシアネート基含有物が、接着性の向上の点から好ましい。また、回路接続材料を2層以上に分割し、遊離ラジカルを発生する硬化剤を含有する層と導電粒子を含有する層に分離して用いることもできる。   Furthermore, a filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, a melamine resin, isocyanates, and the like can also be contained. The inclusion of a filler is preferable because it improves connection reliability and the like. If the maximum diameter of the filler is less than the particle diameter of the conductive particles, it can be used, and the range of 5 to 60% by volume is preferable. If it is 60% by volume or more, the effect of improving the reliability is saturated. As a coupling agent, a vinyl group, an acrylic group, an amino group, an epoxy group, or an isocyanate group-containing material is preferable from the viewpoint of improving adhesiveness. Further, the circuit connecting material can be divided into two or more layers and separated into a layer containing a curing agent that generates free radicals and a layer containing conductive particles.

本発明で用いる回路接続材料は導電性粒子がなくても、接続時に相対向する接続端子の直接接触により接続が得られるが、導電粒子を含有した場合、より安定した接続が得られる。導電性粒子としては、Au、Ag、Ni、Cu、はんだ等の金属粒子やカーボン等があり、十分なポットライフを得るためには、表層はNi、Cuなどの遷移金属類ではなくAu、Ag、白金族の貴金属類が好ましくAuがより好ましい。また、Niなどの遷移金属類の表面をAu等の貴金属類で被覆したものでもよい。また、非導電性のガラス、セラミック、プラスチック等に前記した導通層を被覆等により形成し最外層に貴金属類を被覆したしたものでもよい。プラスチックを核とした場合や熱溶融金属粒子の場合、加熱加圧により変形性を有するので接続時に電極との接触面積が増加し信頼性が向上するので好ましい。貴金族類の被覆層の厚みは良好な抵抗を得るためには、100Å以上が好ましい。しかし、Ni等の遷移金属の上に貴金属類の層を設ける場合では、貴金属類層の欠損や導電粒子の混合分散時に生じる貴金属類層の欠損等により生じる酸化還元作用で遊離ラジカルが発生しポットライフの低下を引き起こすため、300Å以上が好ましい。また、上記導電性粒子を絶縁性樹脂により被覆したものを用いることもでき、この場合は超音波印可により加熱加圧のみでは達成できなかった端子と導電性粒子間の絶縁樹脂の排除が達成され低抵抗化が可能となるばかりでなく隣接端子間の絶縁性が向上する。導電性粒子の表面を被覆する絶縁性樹脂の厚みが導電性粒子の粒子径の20%以下であることが、上記の効果をより達成できるので好ましい。導電性粒子は、回路接続材料である接着剤成分100体積に対して0.1〜30体積%の範囲で用途により使い分ける。過剰な導電性粒子による隣接回路の短絡等を防止するためには0.1〜10体積%とするのがより好ましい。本発明においては、従来のエポキシ樹脂系よりも低温速硬化性に優れかつ可使時間(使用できる保存期間が長い)を有する電気・電子用の回路板の製造方法及び回路接続材料を提供が可能となる。   Even if the circuit connection material used in the present invention has no conductive particles, the connection can be obtained by direct contact of the connection terminals facing each other at the time of connection. However, when the conductive particles are contained, a more stable connection can be obtained. Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, carbon, and the like. In order to obtain a sufficient pot life, the surface layer is not a transition metal such as Ni or Cu, but Au, Ag. Platinum group noble metals are preferred, and Au is more preferred. Alternatively, the surface of a transition metal such as Ni may be coated with a noble metal such as Au. Further, the conductive layer described above may be formed by coating or the like on non-conductive glass, ceramic, plastic or the like, and the outermost layer may be coated with a noble metal. In the case of using plastic as a core or hot-melt metal particles, it is preferable because it has deformability by heating and pressurization, so that the contact area with the electrode is increased at the time of connection and reliability is improved. The thickness of the noble metal coating layer is preferably 100 mm or more in order to obtain good resistance. However, in the case where a noble metal layer is provided on a transition metal such as Ni, a free radical is generated due to the redox effect caused by the noble metal layer deficiency or the noble metal layer deficiency generated when the conductive particles are mixed and dispersed. In order to cause a decrease in life, 300 mm or more is preferable. Also, the conductive particles coated with an insulating resin can be used. In this case, the application of ultrasonic waves can eliminate the insulating resin between the terminal and the conductive particles, which cannot be achieved only by heating and pressing. Not only can resistance be reduced, but also insulation between adjacent terminals is improved. It is preferable that the thickness of the insulating resin covering the surface of the conductive particles is 20% or less of the particle diameter of the conductive particles because the above effect can be further achieved. The conductive particles are properly used depending on the application within a range of 0.1 to 30% by volume with respect to 100 volumes of the adhesive component which is a circuit connecting material. In order to prevent an adjacent circuit from being short-circuited by excessive conductive particles, the content is more preferably 0.1 to 10% by volume. In the present invention, it is possible to provide a circuit board manufacturing method and circuit connection material that are superior to conventional epoxy resin systems in terms of low-temperature fast-curing properties and have a usable time (longer usable storage period). It becomes.

以下に、本発明を実施例により具体的に説明する。
(実施例1)
(回路接続材料)回路接続材料(絶縁性接着剤成分)は、(1)加熱により遊離ラジカルを発生する硬化剤としてt−ヘキシルパーオキシ−2−エチルヘキサノネートを、(2)分子量10000以上の水酸基含有樹脂としてフェノキシ樹脂(PKHC;ユニオンカーバイド社製商品名、重量平均分子量45000)を、(3)ラジカル重合性物質としてウレタンアクリレートとリン酸エステル型アクリレート(共栄社油脂株式会社製、商品名P2M)を用いた。導電性粒子として、ポリスチレンを核とする粒子の表面に、厚み0.2μmのニッケル層を設けこのニッケル層の外側に、厚み0.04μmの金層を設け、さらに最外層を絶縁性樹脂で被覆した平均粒径5μmとした導電性粒子を用い、固形重量比でフェノキシ樹脂50g、ウレタンアクリレート49g、リン酸エステル型アクリレート(共栄社油脂株式会社製、商品名P2M)1g、t−ヘキシルパーオキシ−2−エチルヘキサノネート5g、メチルエチルケトン100gとなるように配合し、これに、導電性粒子を3体積%分散させた分散溶液を、片面を表面処理した厚み80μmのPETフィルムに塗工装置を用いて塗布乾燥し、接着剤層の厚みが20μmのフィルム状の回路接続材料を作製した。
Hereinafter, the present invention will be specifically described by way of examples.
Example 1
(Circuit connection material) The circuit connection material (insulating adhesive component) includes (1) t-hexylperoxy-2-ethylhexanate as a curing agent that generates free radicals upon heating, and (2) a molecular weight of 10,000 or more. Phenoxy resin (PKHC; trade name made by Union Carbide, weight average molecular weight 45000) is used as the hydroxyl group-containing resin, and (3) urethane acrylate and phosphate ester acrylate (trade name P2M, manufactured by Kyoeisha Yushi Co., Ltd.) as the radical polymerizable substance. ) Was used. As the conductive particles, a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, a gold layer having a thickness of 0.04 μm is provided outside the nickel layer, and the outermost layer is covered with an insulating resin. The conductive particles having an average particle diameter of 5 μm were used, and the solid weight ratio was 50 g of phenoxy resin, 49 g of urethane acrylate, 1 g of phosphate ester acrylate (trade name P2M, manufactured by Kyoeisha Yushi Co., Ltd.), t-hexylperoxy-2 -5 g of ethyl hexanonate and 100 g of methyl ethyl ketone were blended, and a dispersion solution in which 3% by volume of conductive particles were dispersed in this was applied to a PET film having a thickness of 80 μm on one side using a coating apparatus. Coating and drying were performed to produce a film-like circuit connection material having an adhesive layer thickness of 20 μm.

(回路の接続)上記の回路接続材料を用いて、ポリイミドとポリイミドと銅箔を接着する接着材及び厚み18μmの銅箔からなる3層構成の銅箔付きポリイミドフィルムを用い、レジストにより銅箔をライン幅30μm、ピッチ70μmにパターンニングした後、銅箔表面にSnメッキを施し、電極端子部(11)を有するFPC(10)を作製した。このFPCと厚み0.7mmのガラス上にアルミ薄膜を形成し表面にITOベタ電極端子部(2)をスパッタリング法により形成したITOベタガラスを上記回路接続材料を用いて、超音波印可及び加熱可能な押圧ツール(6)で140℃、3MPaで10秒間加熱加圧及び超音波印可して幅2mmにわたり接続して、回路接続材料(3)中の絶縁性樹脂(5)により被覆された導電性粒子(4)の絶縁性樹脂(5)を加熱加圧及び超音波印可によって効果的に排除することで導電性粒子(4)による電極端子部(2)と電極端子部(11)の電気的接続を確実にするとともに回路接続材料(3)中の熱硬化型の絶縁性樹脂(5)を硬化させて機械的接続を行なった。この時、ITOベタガラス上に、回路接続材料の接着面を貼り付けた後、60℃、1MPa、3秒で加熱加圧を行うとともに超音波を印加して仮接続し、その後、セパレータ(8)を剥離してもう一方のFPCと接続した。 (Circuit connection) Using the above circuit connection material, a polyimide film with a copper foil having a three-layer structure composed of an adhesive for bonding polyimide, polyimide and copper foil and a copper foil having a thickness of 18 μm is used. After patterning to a line width of 30 μm and a pitch of 70 μm, Sn plating was applied to the copper foil surface to produce an FPC (10) having electrode terminal portions (11). This FPC and ITO solid glass in which an aluminum thin film is formed on a glass having a thickness of 0.7 mm and an ITO solid electrode terminal portion (2) is formed on the surface by sputtering can be ultrasonically applied and heated using the above circuit connecting material. Conductive particles coated with insulating resin (5) in circuit connecting material (3), connected with pressure tool (6) at 140 ° C., 3 MPa for 10 seconds, heated and pressurized and ultrasonically applied for 2 mm width Electrical connection between the electrode terminal part (2) and the electrode terminal part (11) by the conductive particles (4) by effectively removing the insulating resin (5) of (4) by heating and pressing and applying ultrasonic waves The thermosetting insulating resin (5) in the circuit connecting material (3) was cured and mechanical connection was made. At this time, after adhering the adhesive surface of the circuit connection material on the ITO solid glass, heating and pressurizing at 60 ° C., 1 MPa, 3 seconds and applying ultrasonic waves for temporary connection, and then the separator (8) Was peeled off and connected to the other FPC.

(接着力の測定)上述で得られた回路の接続体を、90度剥離、剥離速度50mm/minで、初期と、85℃、85%RHの高温高湿槽中に500時間保持した後の接着力測定を行った。 (Measurement of Adhesive Force) The connection body of the circuit obtained above was peeled at 90 °, peeled off at a speed of 50 mm / min, and initially held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 500 hours. Adhesion was measured.

(接続抵抗の測定)上述の回路接続材料を用いて、隣接回路間の抵抗値を、初期と、85℃、85%RHの高温高湿槽中に500時間保持した後にマルチメータで、隣接回路間の抵抗50点の平均値を測定した。 (Measurement of connection resistance) Using the above-mentioned circuit connection material, the resistance value between adjacent circuits is initially maintained in a high-temperature and high-humidity tank of 85 ° C. and 85% RH for 500 hours, and then the adjacent circuit The average value of 50 points in between was measured.

(比較例1)実施例1において、超音波印可をすることなく、押圧ツールの加熱加圧のみによって実施例1と同様にして接続を行った。 (Comparative Example 1) In Example 1, the connection was made in the same manner as in Example 1 only by heating and pressing the pressing tool without applying ultrasonic waves.

(比較例2)回路接続材料(絶縁性接着剤)として、フェノキシ樹脂(PKHC)、ビスフェノールA型エポキシ樹脂(YL980、油化シェルエポキシ株式会社製商品名)、イミダゾール系マイクロカプセル型硬化剤(3941HP、旭化成工業株式会社製商品名)を用いて、フェノキシ樹脂/ビスフェノールA型エポキシ樹脂/イミダゾール系マイクロカプセル型硬化剤の固形重量比を40g/20g/40gとした他は、実施例1と同様にして回路接続材料を作製した。実施例、比較例1、2で得られた接着強度、接続抵抗を表1に示した。 (Comparative Example 2) As a circuit connecting material (insulating adhesive), phenoxy resin (PKHC), bisphenol A type epoxy resin (YL980, product name manufactured by Yuka Shell Epoxy Co., Ltd.), imidazole microcapsule type curing agent (3941HP) In the same manner as in Example 1, except that the solid weight ratio of phenoxy resin / bisphenol A type epoxy resin / imidazole microcapsule type curing agent was 40 g / 20 g / 40 g. Thus, a circuit connection material was produced. Table 1 shows the adhesive strength and connection resistance obtained in Examples and Comparative Examples 1 and 2.

Figure 2010004067
Figure 2010004067

比較例2は、従来のエポキシ樹脂系の回路接続部材の例であるが、接着強度が弱い。また、比較例1は、超音波印可をしない場合であり、超音波印可を加え接続した実施例に比べ初期接着強度、500時間後の接着強度に劣っている。これに対し、本発明の回路接続材料は、比較例2の従来のエポキシ樹脂系に比べ、低温短時間での接着強度が高く、また高温での耐湿性に優れる。さらに、回路板の製造方法において、超音波印可により、初期接着強度、500時間後の接着強度が改善される。尚、上述の実施例は本発明の一例であり、本発明の要旨を逸脱しない範囲でその他様々な構成が取り得る。上記の各実施例における加熱は、一定の加熱を連続して行う連続ヒートでも、一定時間ごとに周期的に加熱を行うパルスヒートでも行うことができる。   Comparative Example 2 is an example of a conventional epoxy resin circuit connecting member, but the adhesive strength is weak. Moreover, the comparative example 1 is a case where ultrasonic application is not performed, and is inferior to the initial adhesive strength and the adhesive strength after 500 hours compared with the example which added ultrasonic connection and was connected. On the other hand, the circuit connection material of the present invention has high adhesive strength at a low temperature in a short time and excellent moisture resistance at a high temperature as compared with the conventional epoxy resin system of Comparative Example 2. Furthermore, in the circuit board manufacturing method, the initial adhesive strength and the adhesive strength after 500 hours are improved by applying ultrasonic waves. The above-described embodiment is an example of the present invention, and various other configurations can be taken without departing from the gist of the present invention. The heating in each of the above embodiments can be performed by continuous heating in which constant heating is continuously performed or pulse heat in which heating is periodically performed at regular intervals.

1・・・TFT基板、2・・・電極端子部、3・・・回路接続材料、4・・・導電性粒子、5・・・絶縁性樹脂(接着剤)、6・・・押圧ツール、7・・・支持台(超音波印加がなされる支持台)、8・・・セパレータ、10・・・FPC(フレキシブルプリント基板)、11・・・電極端子部   DESCRIPTION OF SYMBOLS 1 ... TFT substrate, 2 ... Electrode terminal part, 3 ... Circuit connection material, 4 ... Conductive particle, 5 ... Insulating resin (adhesive), 6 ... Press tool, 7: Support base (support base to which ultrasonic waves are applied), 8 ... Separator, 10 ... FPC (flexible printed circuit board), 11 ... Electrode terminal part

Claims (2)

第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、対向配置した前記第一の接続端子と前記第二の接続端子を、回路接続材料を介在させて重ね合わせた状態で加熱加圧及び超音波印加によって、電気的に接続する接続方法に用いる接続材料であって、下記(1)〜(4)の成分を必須とする回路接続材料。
(1)加熱により遊離ラジカルを発生する硬化剤
(2)分子量10000以上の水酸基含有樹脂
(3)ラジカル重合性物質
(4)最外層として絶縁性樹脂を有し、前記絶縁性樹脂の厚みが粒子径の20%以下である導電性粒子。
The first circuit member having the first connection terminal and the second circuit member having the second connection terminal are disposed so as to face each other, with the first connection terminal and the second connection terminal facing each other. A connection material used in a connection method in which the first connection terminal and the second connection terminal are electrically connected to each other by heating and pressing and applying an ultrasonic wave in a state where the circuit connection material is interposed therebetween. A circuit connecting material essentially comprising the following components (1) to (4).
(1) Curing agent that generates free radicals upon heating (2) Hydroxyl-containing resin having a molecular weight of 10,000 or more (3) Radical polymerizable material (4) Insulating resin as outermost layer, and the thickness of the insulating resin is a particle Conductive particles having a diameter of 20% or less.
ラジカル重合性物質が、式(I)で示されるラジカル重合性物質を含有することを特徴とする請求項1に記載の回路接続材料。
Figure 2010004067

(式中、Rは、水素、メチル基を示し、nは、1〜3の整数を示す。)

The circuit connecting material according to claim 1, wherein the radical polymerizable substance contains a radical polymerizable substance represented by the formula (I).
Figure 2010004067

(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 1 to 3.)

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WO1998044067A1 (en) * 1997-03-31 1998-10-08 Hitachi Chemical Company, Ltd. Circuit connecting material, and structure and method of connecting circuit terminal
JPH1126922A (en) * 1997-07-02 1999-01-29 Matsushita Electric Ind Co Ltd Method for mounting chip
JPH11163501A (en) * 1997-12-02 1999-06-18 Rohm Co Ltd Method for mounting electronic part, and electronic circuit device manufactured there by
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JPH0329207A (en) * 1988-12-05 1991-02-07 Hitachi Chem Co Ltd Composition for circuit connection and connection method and connection structure of semiconductor chip using the composition
JPH04184887A (en) * 1990-11-16 1992-07-01 Citizen Watch Co Ltd Connecting method and its device
WO1998044067A1 (en) * 1997-03-31 1998-10-08 Hitachi Chemical Company, Ltd. Circuit connecting material, and structure and method of connecting circuit terminal
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017033956A1 (en) * 2015-08-26 2017-03-02 日本化薬株式会社 Dimer-containing polyamide resin and resin composition of same
CN107709462A (en) * 2015-08-26 2018-02-16 日本化药株式会社 Polyamide and its resin combination containing dimer

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