TWI412043B - Conductive particles, adhesive composition, circuit connection material and connection structure and circuit component connection method - Google Patents

Conductive particles, adhesive composition, circuit connection material and connection structure and circuit component connection method Download PDF

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TWI412043B
TWI412043B TW96113362A TW96113362A TWI412043B TW I412043 B TWI412043 B TW I412043B TW 96113362 A TW96113362 A TW 96113362A TW 96113362 A TW96113362 A TW 96113362A TW I412043 B TWI412043 B TW I412043B
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circuit
particles
particle
conductive
conductive particles
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TW200809879A (en
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Masaru Tanaka
Jun Taketatsu
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01044—Ruthenium [Ru]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01045—Rhodium [Rh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01046—Palladium [Pd]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01049—Indium [In]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01076—Osmium [Os]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01077—Iridium [Ir]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01078—Platinum [Pt]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/14—Integrated circuits
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19041—Component type being a capacitor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19043—Component type being a resistor

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  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide conductive particles capable of achieving for both a low enough initial resistance value of a connection part and excellent insulation property between adjacent circuit electrodes, and sufficiently restraining temporary rise of a resistance value of the connection part when circuit members with fine circuit electrodes are connected respectively, and to provide an adhesive composition and a circuit connection material using this, a connection structure with circuit members connected, as well as a connection method of the circuit members. <P>SOLUTION: This conductive particles are equipped with nuclear particles having conductivity and an insulation coating containing an organic polymer compound provided on a surface of the nuclear particles, and a coverage ratio defined in a formula (1) is in a range from 20 to 40%. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

導電粒子，黏著劑組成物，電路連接材料及連接構造及電路構件之連接方法Conductive particle, adhesive composition, circuit connecting material, connection structure and connection method of circuit member

本發明關於導電粒子、黏著劑組成物、電路連接材料及連接構造、以及電路構件的連接方法。The present invention relates to a conductive particle, an adhesive composition, a circuit connecting material, a connection structure, and a connection method of a circuit member.

作為在液晶顯示顯示器用玻璃面板上封裝液晶驅動用IC的方法，廣泛使用CHIP－ON－GLASS封裝(以下稱為「COG封裝」)或CHIP－ON－FLEX封裝(以下稱為「COF封裝」)。COG封裝係將液晶驅動用IC直接接合於玻璃面板上的方法。另一方面，COF封裝係於具有金屬配線的撓性膠帶上，接合液晶驅動用IC，使其與玻璃面板接合的方法。As a method of packaging a liquid crystal driving IC on a glass panel for a liquid crystal display, a CHIP-ON-GLASS package (hereinafter referred to as "COG package") or a CHIP-ON-FLEX package (hereinafter referred to as "COF package") is widely used. . The COG package is a method of directly bonding a liquid crystal driving IC to a glass panel. On the other hand, the COF package is a method in which a liquid crystal driving IC is bonded to a glass panel by a flexible tape having metal wiring.

於上述COG封裝及COF封裝中，作為電路連接材料，一般使用具有異方向導電性的黏著劑組成物。該黏著劑組成物係於黏著劑成分中使導電粒子分散者。In the above COG package and COF package, as the circuit connecting material, an adhesive composition having an opposite direction of conductivity is generally used. The adhesive composition is one in which the conductive particles are dispersed in the adhesive component.

近年來，隨著液晶顯示的高精細化，液晶驅動用IC的電極即凸塊或撓性膠帶的金屬配線等，係有窄間距化及小面積化的傾向。因此，就以往的黏著劑組成物而言，在應連接的電路電極間所存的導電粒子之數目係成為不足，有發生連接部分的電阻值變高等問題。In recent years, with the increase in the definition of liquid crystal display, the electrode of the liquid crystal driving IC, that is, the bump or the metal wiring of the flexible tape, tends to have a narrow pitch and a small area. Therefore, in the conventional adhesive composition, the number of conductive particles stored between the circuit electrodes to be connected is insufficient, and there is a problem that the resistance value of the connected portion becomes high.

另一方面，為了防止如此的問題，若增多黏著劑組成物的導電粒子之含量，則鄰接的電路電極間的絕緣性有變成不足之虞。On the other hand, in order to prevent such a problem, if the content of the conductive particles of the adhesive composition is increased, the insulation between the adjacent circuit electrodes becomes insufficient.

因此，作為提高連接可靠性的手段，於專利文獻1中，記載於含有導電粒子的黏著層之一面，形成具有絕緣性的黏著層。又，於專利文獻2及3中，記載使用以具有絕緣性的皮膜被覆表面的導電粒子之技術。Therefore, as a means for improving the connection reliability, Patent Document 1 describes that an insulating layer is formed on one surface of an adhesive layer containing conductive particles. Further, in Patent Documents 2 and 3, a technique of coating conductive particles on a surface with an insulating film is described.

專利文獻1：特開平08－279371號公報專利文獻2：日本發明專利第2794009號公報專利文獻3：特開2001－195921號公報Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2001-195921.

藉由專利文獻1所記載的連接構件，能得到達成連接部分之低電阻值及鄰接的電路電極間之絕緣性兩者。然而，就該連接構件而言，在凸塊面積為非常小面積(例如小於3000μm2 )時，為了充分穩定地達成上述效果，係尚有改善的餘地。According to the connecting member described in Patent Document 1, both the low resistance value of the connection portion and the insulation between the adjacent circuit electrodes can be obtained. However, in the case of the connecting member, when the bump area is a very small area (for example, less than 3000 μm 2 ), there is still room for improvement in order to achieve the above effects sufficiently stably.

如專利文獻2及3中所記載的導電粒子，若使用全表面經絕緣性皮膜所被覆的粒子，則大多可確保鄰接的電路電極間之絕緣性。然而，若使用如此的導電粒子，則無法充分降低連接部分的電阻值，該電阻值有經時上升的問題。When the conductive particles described in Patent Documents 2 and 3 are coated with particles whose entire surface is covered with an insulating film, insulation between adjacent circuit electrodes can be ensured. However, when such a conductive particle is used, the resistance value of the connection portion cannot be sufficiently lowered, and the resistance value has a problem of increasing with time.

本發明鑒於如此的實際情況，目的為提供在連接具有微細電路電極的電路構件彼此時，可達成連接部分的充分低之初期電阻值及鄰接的電路電極間之優異的絕緣性兩者，同時可充分抑制連接部分的電阻值之經時上升的導電粒子、黏著劑組成物及使用其的電路連接材料。The present invention has been made in view of such circumstances, and it is an object of the invention to provide a sufficiently low initial resistance value of a connection portion and excellent insulation between adjacent circuit electrodes when connecting circuit members having fine circuit electrodes. The conductive particles, the adhesive composition, and the circuit connecting material using the same in which the resistance value of the connection portion is increased with time is sufficiently suppressed.

又，本發明之目的為提供使用上述電路連接材料連接電路構件的連接構造、及用於得到彼的電路構件之連接方法。Further, it is an object of the present invention to provide a connection structure for connecting a circuit member using the above-described circuit connection material, and a connection method for obtaining the circuit member.

本發明的導電粒子具備具有導電性之核粒子、與設置於該核粒子表面上的含有有機高分子化合物之絕緣被覆，下述式(1)所定義之被覆率為20~40%範圍者。The conductive particles of the present invention are provided with conductive core particles and an insulating coating containing an organic polymer compound provided on the surface of the core particles, and the coverage ratio defined by the following formula (1) is in the range of 20 to 40%.

本發明的導電粒子係以被覆率成為20~40%的範圍之方式設置絕緣被覆。導電粒子的被覆率若為20~40%，為了得到低的初期電阻值，可使充分量的導電粒子含於黏著劑成分中。此係因為隨著導電粒子的含量之增大，即使導電粒子發生凝聚，但藉由設置於各導電粒子的絕緣被覆，可充分防止鄰接的電路電極彼此之電性連接。The conductive particles of the present invention are provided with an insulating coating so that the coverage ratio is in the range of 20 to 40%. When the coverage of the conductive particles is 20 to 40%, a sufficient amount of the conductive particles may be contained in the adhesive component in order to obtain a low initial resistance value. In this case, even if the conductive particles are agglomerated as the content of the conductive particles increases, the insulating layers provided on the respective conductive particles can sufficiently prevent the adjacent circuit electrodes from being electrically connected to each other.

又，於使用全表面經絕緣被覆所覆蓋的導電粒子時，絕緣被覆係存在於核粒子與電路電極表面之間，而使得絕緣被覆介於電性路徑之間存在。與其相對地，本發明的導電粒子，由於絕緣被覆係部分的，可充分減低介於電性路徑之間的絕緣被覆。因此，可充分抑制路徑上所存在的絕緣被覆之影響。因此，與全表面經絕緣被覆所覆蓋的導電粒子比較下，可降低連接部分的初期電阻值，而且可更確實地抑制電阻值的經時上升。Further, when the conductive particles covered by the insulating coating of the entire surface are used, the insulating coating is present between the core particles and the surface of the circuit electrode, so that the insulating coating exists between the electrical paths. On the other hand, in the conductive particles of the present invention, the insulating coating between the electrical paths can be sufficiently reduced due to the insulating coating portion. Therefore, the influence of the insulation coating existing on the path can be sufficiently suppressed. Therefore, compared with the conductive particles covered with the entire surface by the insulating coating, the initial resistance value of the connection portion can be lowered, and the temporal increase of the resistance value can be more reliably suppressed.

構成本發明的導電粒子之絕緣被覆的有機高分子化合物之交聯度，較佳係5~20%。有機高分子化合物的交聯度若為5~20%，則可更確實地確保鄰接的電路電極間之優異的絕緣性，同時可更確實地達成連接部分的低電阻值及該電阻值的經時上升之抑制兩者。The degree of crosslinking of the insulating coated organic polymer compound constituting the conductive particles of the present invention is preferably 5 to 20%. When the degree of crosslinking of the organic polymer compound is 5 to 20%, the excellent insulation between the adjacent circuit electrodes can be surely ensured, and the low resistance value of the connection portion and the resistance value can be more reliably achieved. The rise in time inhibits both.

具備本發明的導電粒子之絕緣被覆，係可由於設置於核粒子表面上，含有有機高分子化合物的複數絕緣性粒子所構成。於該情況下，絕緣性粒子的粒徑(D2 )與核粒子的粒徑(D1 )之比率(D2 /D1 )較佳係1/10以下。該比率若為1/10以下，則可更確實地達成連接部分的低電阻值及該電阻值的經時上升之抑制兩者。The insulating coating provided with the conductive particles of the present invention may be composed of a plurality of insulating particles containing an organic polymer compound provided on the surface of the core particles. In this case, the diameter of the insulating particle diameter (D 2) and the core particles (D 1) of the ratio (D 2 / D 1) is preferably 1/10 or less based. When the ratio is 1/10 or less, both the low resistance value of the connection portion and the suppression of the resistance value over time can be more reliably achieved.

本發明的導電粒子所具有備的絕緣被覆，係可由設置在核粒子的表面上，含有有機高分子化合物的絕緣性層所構成。於該情況下，絕緣性層的厚度(T2 )與核粒子的粒徑(D1 )之比率(T2 /D1 )較佳係1/10以下。該比率若為1/10以下，則可更確實地達成連接部分的低電阻值及該電阻值的經時上升之抑制兩者。The conductive particles of the present invention have an insulating coating, and may be composed of an insulating layer containing an organic polymer compound provided on the surface of the core particles. In this case, the ratio (T 2 /D 1 ) of the thickness (T 2 ) of the insulating layer to the particle diameter (D 1 ) of the core particles is preferably 1/10 or less. When the ratio is 1/10 or less, both the low resistance value of the connection portion and the suppression of the resistance value over time can be more reliably achieved.

本發明的黏著劑組成物具備具有黏著性的黏著劑成分、與分散於該黏著劑成分中之本發明的上述導電粒子。本發明的黏著劑組成物，由於具備上述導電粒子，即使應連接的電路電極係微細者，也可達成連接部分的充分低之初期電阻值及鄰接的電路電極間之優異的絕緣性兩者，同時可充分抑制連接部分的電阻值之經時上升。The adhesive composition of the present invention comprises an adhesive component having adhesiveness and the conductive particles of the present invention dispersed in the adhesive component. In the adhesive composition of the present invention, even if the conductive particles are provided, even if the circuit electrode to be connected is fine, a sufficiently low initial resistance value of the connection portion and excellent insulation between adjacent circuit electrodes can be achieved. At the same time, the rise in resistance of the connected portion can be sufficiently suppressed.

本發明的電路連接材料係由本發明所關於上述黏著劑組成物所構成，使用於黏著電路構件彼此的同時，以電性連接各電路構件所具有之電路電極彼此者。The circuit connecting material of the present invention is composed of the above-described adhesive composition of the present invention, and is used for electrically connecting the circuit electrodes of the respective circuit members to each other while adhering the circuit members.

本發明的連接構造具備相對配置的一對電路構件、與由本發明所關於的上述電路連接材料之硬化物所構成，介於該一對電路構件之間，欲使各電路構件所具有之電路電極彼此可經電性連接，而黏著該電路構件彼此之連接部者。The connection structure according to the present invention includes a pair of circuit members disposed opposite to each other and a cured material of the circuit connection material according to the present invention, and between the pair of circuit members, a circuit electrode to be provided for each circuit member They can be electrically connected to each other and adhere to the connection portions of the circuit members to each other.

於本發明的連接構造中，一對電路構件之至少一個可為IC晶片。又，於該連接構造中，一對電路構件所各具有的電路電極之至少一表面可由選自金、銀、錫、釕、銠、鈀、鋨、銥、鉑及銦錫氧化物之至少1種物質所構成。In the connection configuration of the present invention, at least one of the pair of circuit members may be an IC wafer. Further, in the connection structure, at least one surface of each of the circuit electrodes of the pair of circuit members may be at least one selected from the group consisting of gold, silver, tin, antimony, bismuth, palladium, iridium, iridium, platinum, and indium tin oxide. Made up of substances.

又，於本發明的連接構造中，與該連接部接觸的該一對電路構件之該接觸面的至少一面係可：具有至少一種選自氮化矽、聚矽氧烷化合物及聚醯亞胺樹脂的原料所構成之部分。Further, in the connection structure of the present invention, at least one side of the contact surface of the pair of circuit members in contact with the connection portion may have at least one selected from the group consisting of tantalum nitride, polysiloxane compound, and polyimine The part of the raw material of the resin.

本發明的電路構件之連接方法，係使相對配置的一對電路構件之間介著與本發明有關的上述電路連接材料，將全體加熱及加壓，形成由電路連接材料的硬化物構成，介於一對電路構件之間，欲使各電路構件所具有之電路電極彼此可經電性連接，而黏著該電路構件彼此之連接部，可得到具備一對電路構件及連接部之連接結構。In the method of connecting the circuit members of the present invention, the circuit connecting materials according to the present invention are interposed between a pair of circuit members disposed oppositely, and the entire circuit is heated and pressurized to form a cured material of the circuit connecting material. Between the pair of circuit members, a connection structure including a pair of circuit members and a connection portion can be obtained by electrically connecting the circuit electrodes of the respective circuit members to each other and adhering the connection portions of the circuit members.

依照本發明，可提供於連接具有微細電路電極的電路構件彼此時，可達成連接部分的充分低之初期電阻值及鄰接的電路電極間之優異的絕緣性兩者，同時可充分抑制連接部分的電阻值之經時上升的導電粒子、黏著劑組成物及使用其的電路連接材料。又，可提供使用上述電路連接材料所連接的電路構件之連接構造，以及用於得到彼的電路構件之連接方法。According to the present invention, when the circuit members having the fine circuit electrodes are connected to each other, both the sufficiently low initial resistance value of the connection portion and the excellent insulation between the adjacent circuit electrodes can be achieved, and the connection portion can be sufficiently suppressed. Conductive particles having an increased resistance value over time, an adhesive composition, and a circuit connecting material using the same. Further, a connection structure of a circuit member to which the above-described circuit connection material is connected, and a connection method for obtaining the circuit member of the same can be provided.

實施發明的最佳形態Best form for implementing the invention

以下邊參照所附的圖面邊詳細說明本發明的較佳實施形態。再者，於圖面的說明中，同一要素給予同一符號，省略重複的說明。又，圖面在方便上，圖面的尺寸比率係未必與說明者一致。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and the description thereof will not be repeated. Moreover, the drawing is convenient, and the dimensional ratio of the drawing is not necessarily consistent with the explanation.

又，於本說明書中，「(甲基)丙烯酸」係意味「丙烯酸」及對應於其的「甲基丙烯酸」，「(甲基)丙烯酸酯」係意味「丙烯酸酯」及對應於其的「甲基丙烯酸酯」。In addition, in the present specification, "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" corresponding thereto, and "(meth)acrylate" means "acrylic acid ester" and "corresponding to it" Methacrylate."

圖1係顯示使用具備與本發明有關的導電粒子之黏著劑組成物當作電路連接材料，連接電路電極彼此的連接構造之示意截面圖。圖1所示的連接構造100，係具有相互對向的第1電路構件30及第2電路構件40，於第1電路構件30與第2電路構件40之間，設有用於連接此等的連接部50a。Fig. 1 is a schematic cross-sectional view showing a connection structure of connecting circuit electrodes to each other using an adhesive composition having conductive particles related to the present invention as a circuit connecting material. The connection structure 100 shown in FIG. 1 has a first circuit member 30 and a second circuit member 40 that face each other, and a connection for connecting these is provided between the first circuit member 30 and the second circuit member 40. Part 50a.

第1電路構件30係具備電路基板(第1電路基板)31、與形成在電路基板31的主面31a上之電路電極(第1電路電極)32。第2電路構件40係具備電路基板(第2電路基板)41、與形成在電路基板41的主面41a上之電路電極(第2電路電極)42。於電路基板31、41中，電路電極32、42的表面係成為平坦。再者，此處所言的「電路電極的表面係平坦」係意味電路電極的表面之凹凸係20nm以下。The first circuit member 30 includes a circuit board (first circuit board) 31 and a circuit electrode (first circuit electrode) 32 formed on the main surface 31a of the circuit board 31. The second circuit member 40 includes a circuit board (second circuit board) 41 and a circuit electrode (second circuit electrode) 42 formed on the main surface 41a of the circuit board 41. In the circuit boards 31 and 41, the surfaces of the circuit electrodes 32 and 42 are flat. In addition, "the surface of the circuit electrode is flat" as used herein means that the unevenness of the surface of the circuit electrode is 20 nm or less.

作為電路構件的具體例子，IC晶片(半導體晶片)、電阻晶片、電容晶片等的晶片零件等。此等電路構件具備電路電極，一般為具備多數的電路電極者。作為上述電路構件所連接的另一方之電路構件的具體例子，可舉出具有金屬配線的撓性膠帶、撓性印刷電路板、經銦錫氧化物(ITO)所蒸鍍的玻璃基板等之電路基板。依照本發明，可有效率地且以高的連接可靠性來連接此等電路構件彼此。然而，與本發明有關的導電粒子係適合於對具備多數微細連接端子(電路電極)的晶片零件之電路基板上的COG封裝或COF封裝。Specific examples of the circuit member include a wafer wafer of an IC wafer (semiconductor wafer), a resistor wafer, a capacitor wafer, and the like. These circuit members have circuit electrodes and are generally provided with a large number of circuit electrodes. Specific examples of the other circuit member to which the circuit member is connected include a flexible tape having metal wiring, a flexible printed circuit board, and a circuit such as a glass substrate vapor-deposited with indium tin oxide (ITO). Substrate. According to the present invention, the circuit members can be connected to each other efficiently and with high connection reliability. However, the conductive particles according to the present invention are suitable for a COG package or a COF package on a circuit board of a wafer component having a plurality of fine connection terminals (circuit electrodes).

主面31a及/或主面41a亦可被氮化矽、聚矽氧烷化合物及聚矽氧烷樹脂、以及感光性或非感光性的聚醯亞胺樹脂等之有機絕緣物質所塗覆。又，主面31a及/或主面41a也可部分地具有由上述材質所構成的區域。再者，電路基板31及/或電路基板41本身亦可由上述材質所構成。主面31a、41a可由1種上述材質所構成，也可由2種以上所構成。藉由適宜地選擇黏著劑成分，亦可較佳地連接具有由上述材質所構成的部分之電路基板彼此。The main surface 31a and/or the main surface 41a may be coated with an organic insulating material such as a tantalum nitride, a polyoxyalkylene compound, a polyoxyalkylene resin, or a photosensitive or non-photosensitive polyimide resin. Further, the main surface 31a and/or the main surface 41a may partially have a region composed of the above materials. Furthermore, the circuit board 31 and/or the circuit board 41 itself may be composed of the above materials. The main surfaces 31a and 41a may be composed of one type of the above materials, or may be composed of two or more types. It is also possible to preferably connect the circuit boards having the portions made of the above materials to each other by appropriately selecting the adhesive component.

各電路電極32、42之表面可由選自金、銀、錫、釕、銠、鈀、鋨、銥、鉑及銦錫氧化物(ITO)之至少1種物質所構成，也可由2種以上的物質所構成。又，電路電極32、42的表面材質，在全部電路電極中可為相同，也可不同。The surface of each of the circuit electrodes 32 and 42 may be composed of at least one selected from the group consisting of gold, silver, tin, antimony, bismuth, palladium, iridium, iridium, platinum, and indium tin oxide (ITO), or two or more kinds thereof. Composition of matter. Further, the surface materials of the circuit electrodes 32 and 42 may be the same or different in all the circuit electrodes.

連接部50a具備含於電路連接材料的黏著劑成分之硬化物20a、與分散於其中的導電粒子10A。因此，於連接構造100中，相對的電路電極32與電路電極42，係經由導電粒子10A而電性連接。即，導電粒子10A係直接接觸電路電極32、42雙方。The connecting portion 50a includes a cured product 20a containing an adhesive component of the circuit connecting material, and conductive particles 10A dispersed therein. Therefore, in the connection structure 100, the opposing circuit electrode 32 and the circuit electrode 42 are electrically connected via the conductive particles 10A. That is, the conductive particles 10A directly contact both of the circuit electrodes 32 and 42.

因此，電路電極32、42間的連接電阻係被充分減低，電路電極32、42間的良好電性連接係成為可能。另一方面，硬化物20a係具有電絕緣性，可確保鄰接的電路電極彼此之絕緣性。因此，可使電路電極32、42間的電流之流動成為圓滑，可充分發揮電路所具有的機能。Therefore, the connection resistance between the circuit electrodes 32 and 42 is sufficiently reduced, and a good electrical connection between the circuit electrodes 32 and 42 is possible. On the other hand, the cured product 20a is electrically insulating, and the insulation of the adjacent circuit electrodes can be ensured. Therefore, the flow of the current between the circuit electrodes 32 and 42 can be made smooth, and the function of the circuit can be fully utilized.

其次，詳細說明黏著劑成分硬化以前的狀態下之黏著劑組成物。圖2係顯示使用與本發明有關的黏著劑組成物當作電路連接材料時，較佳的實施形態之示意截面圖。圖2所示的電路連接材料50之形狀係片狀。電路連接材料50具有黏著劑成分20、與分散於黏著劑成分20中的導電粒子10A。黏著劑組成物亦可以為糊狀，但於使用在IC晶片等的COG封裝或COF封裝時，從操作性的觀點來看，較佳為將電路連接材料形成片狀。Next, the adhesive composition in the state before the adhesive component is hardened will be described in detail. Fig. 2 is a schematic cross-sectional view showing a preferred embodiment when an adhesive composition relating to the present invention is used as a circuit connecting material. The shape of the circuit connecting material 50 shown in Fig. 2 is in the form of a sheet. The circuit connecting material 50 has an adhesive component 20 and conductive particles 10A dispersed in the adhesive component 20. The adhesive composition may be in the form of a paste. However, when it is used in a COG package or a COF package such as an IC chip, it is preferable to form the circuit connecting material into a sheet shape from the viewpoint of workability.

電路連接材料50係藉由使用塗佈裝置，將含有黏著劑成分及導電粒子的黏著劑組成物塗佈在薄膜狀的支持體上，進行指定時間的熱風乾燥而製作。The circuit connecting material 50 is produced by applying an adhesive composition containing an adhesive component and conductive particles to a film-shaped support using a coating device, and drying it by hot air for a predetermined period of time.

關於導電粒子10A的構成，邊參照圖3邊說明。圖3係顯示與本發明有關的導電粒子之較佳實施形態的截面圖。圖3所示的導電粒子10A係由具有導電性的核粒子1及設置於該核粒子1之表面上的複數絕緣性粒子2A所構成。The configuration of the conductive particles 10A will be described with reference to Fig. 3 . Fig. 3 is a cross-sectional view showing a preferred embodiment of conductive particles related to the present invention. The conductive particles 10A shown in FIG. 3 are composed of core particles 1 having conductivity and a plurality of insulating particles 2A provided on the surface of the core particles 1.

核粒子1係由構成中心部分的基材粒子1a及設置於該基材粒子1a之表面上的導電層1b所構成。The core particle 1 is composed of a substrate particle 1a constituting a central portion and a conductive layer 1b provided on the surface of the substrate particle 1a.

作為基材粒子1a的材質，可舉出玻璃、陶瓷、有機高分子化合物等。於此等材質之中，較佳為經由加熱及/或加壓而變形者(例如玻璃、有機高分子化合物)。基材粒子1a若為變形者，於導電粒子10A被電路電極32、42所推壓時，會增加與電路電極的接觸面積。又，可以吸收電路電極32、42的表面之凹凸。因此，提高電路電極間的連接可靠性。Examples of the material of the substrate particles 1a include glass, ceramics, and organic polymer compounds. Among these materials, those which are deformed by heating and/or pressurization (for example, glass or an organic polymer compound) are preferred. When the substrate particles 1a are deformed, when the conductive particles 10A are pressed by the circuit electrodes 32 and 42, the contact area with the circuit electrodes is increased. Further, the unevenness of the surface of the circuit electrodes 32, 42 can be absorbed. Therefore, the connection reliability between the circuit electrodes is improved.

根據上述般的觀點，作為適合構成基材粒子1a的材質者，例如丙烯酸樹脂、苯乙烯樹脂、苯并胍胺樹脂、聚矽氧烷樹脂、聚丁二烯樹脂或此等的共聚物、以及交聯此等者。基材粒子1a在粒子間係可為同一種類或不同種類的材質，同一粒子可單獨使用1種材質，或混合2種以上的材質來使用。From the above-mentioned viewpoint, as a material suitable for constituting the substrate particles 1a, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyalkylene resin, a polybutadiene resin, or the like, and Crosslink these people. The substrate particles 1a may be of the same type or different types of materials between the particles, and the same particles may be used alone or in combination of two or more materials.

基材粒子1a的平均粒徑，可按照用途等來適宜設計，但較佳為0.5~20μ m，尤佳為1~10μ m，更佳為2~5μ m。若使用平均粒徑低於0.5μ m的基材粒子於製作導電粒子，則粒子發生二次凝聚，鄰接的電路電極間之絕緣性有變不充分的傾向，而若使用超過20μ m的基材粒子於製作導電粒子，則起因於其大小，鄰接的電路電極間之絕緣性有變不充分的傾向。The average particle diameter of the substrate particles 1a can be appropriately designed according to the use, etc., but is preferably 0.5 to 20 μm , particularly preferably 1 to 10 μm , and more preferably 2 to 5 μm . When the conductive particles are produced by using the substrate particles having an average particle diameter of less than 0.5 μm , the particles are secondarily aggregated, and the insulation between the adjacent circuit electrodes tends to be insufficient, and if more than 20 μm is used, When the conductive particles are produced by the material particles, the insulation between the adjacent circuit electrodes tends to be insufficient due to the size thereof.

導電層1b係由為了覆蓋基材粒子1a的表面而設置的具有導電性之材質所構成之層。從充分確保導電性的觀點來看，導電層1b較佳係被覆基材粒子1a的全表面。The conductive layer 1b is a layer composed of a conductive material provided to cover the surface of the substrate particle 1a. The conductive layer 1b preferably covers the entire surface of the substrate particle 1a from the viewpoint of sufficiently ensuring conductivity.

作為導電層1b的材質，例如可舉出金、銀、鉑、鎳、銅及此等的合金、含錫的焊料等之合金、以及碳等的具有導電性的非金屬。由於對於基材粒子1a，可以藉由無電解鍍敷來被覆，故導電層1b的材質較佳為金屬。又，為了得到充分的適用期，較佳為金、銀、鉑或此等的合金，更佳為金。再者，此等可被單獨1種使用，或可組合2種以上來使用。Examples of the material of the conductive layer 1b include gold, silver, platinum, nickel, copper, alloys thereof, alloys such as tin-containing solder, and non-metals having conductivity such as carbon. Since the substrate particles 1a can be coated by electroless plating, the material of the conductive layer 1b is preferably metal. Further, in order to obtain a sufficient pot life, it is preferably gold, silver, platinum or an alloy thereof, and more preferably gold. Further, these may be used alone or in combination of two or more.

導電層1b的厚度係可按照使用於其材質或用途等來適宜設計，較佳為50~200nm，更佳為80~150nm。厚度若小於50nm，則在連接部分有得不到充分低的電阻值之傾向。另一方面，厚度超過200nm的導電層1b，係製造效率有降低的傾向。The thickness of the conductive layer 1b can be appropriately designed according to the material or use thereof, and is preferably 50 to 200 nm, more preferably 80 to 150 nm. When the thickness is less than 50 nm, a sufficiently low resistance value may not be obtained in the joint portion. On the other hand, the conductive layer 1b having a thickness of more than 200 nm tends to have a low production efficiency.

導電層1b可以由一層或二層以上所構成。於任一情況中，從使用其所製作的黏著劑組成物之保存性的觀點來看，核粒子1的表面層較佳由金、銀、鉑或此等的合金所構成，更佳由金所構成。於導電層1b由金、銀、鉑或此等的合金(以下稱為「金等的金屬」)所成的一層所構成時，為了在連接部分得到充分低的電阻值，其厚度較佳為10~200nm。The conductive layer 1b may be composed of one layer or more. In either case, the surface layer of the core particle 1 is preferably composed of gold, silver, platinum or the like from the viewpoint of the preservability of the adhesive composition produced therefrom, more preferably by gold. Composition. When the conductive layer 1b is made of a layer of gold, silver, platinum or the like (hereinafter referred to as "metal such as gold"), the thickness is preferably a thickness in order to obtain a sufficiently low resistance value at the joint portion. 10~200nm.

另一方面，於導電層1b由二層以上所構成時，導電層1b的最外層較佳係由金等的金屬所構成，最外層與基材粒子1a之間的層，例如亦可由含有鎳、銅、錫或此等的合金之金屬層所構成。於該情況下，構成導電層1b的最外層之金等的金屬所成的金屬層之厚度，從黏著劑組成物的保存性之觀點來看，較佳為30~200nm。鎳、銅、錫或此等的合金，會由於氧化還原作用而發生游離自由基。因此，金等的金屬所成的最外層之厚度若小於30nm，、則於併用具有自由基聚合性的黏著劑成分時，充分防止游離自由基的影響係有變困難的傾向。On the other hand, when the conductive layer 1b is composed of two or more layers, the outermost layer of the conductive layer 1b is preferably made of a metal such as gold, and the layer between the outermost layer and the substrate particles 1a may be, for example, nickel. , copper, tin or a metal layer of these alloys. In this case, the thickness of the metal layer formed of the metal such as gold which constitutes the outermost layer of the conductive layer 1b is preferably 30 to 200 nm from the viewpoint of storage stability of the adhesive composition. Nickel, copper, tin or these alloys will generate free radicals due to redox. Therefore, when the thickness of the outermost layer formed of the metal such as gold is less than 30 nm, when the adhesive component having a radical polymerizable property is used in combination, it is difficult to sufficiently prevent the influence of free radicals.

作為基材粒子1a表面上形成導電層1b方法，可舉出無電解鍍敷處理或物理的塗覆處理。從導電層1b的形成容易性之觀點來看，較佳為藉由無電解鍍敷處理，使金屬所成的導電層1b形成在基材粒子1a的表面上。The method of forming the conductive layer 1b on the surface of the substrate particle 1a may be an electroless plating treatment or a physical coating treatment. From the viewpoint of easiness of formation of the conductive layer 1b, it is preferable to form the conductive layer 1b made of a metal on the surface of the substrate particle 1a by electroless plating treatment.

絕緣性粒子2A係由有機高分子化合物所構成。作為有機高分子化合物，較佳為具有熱軟化性者。絕緣性粒子的合適原料，例如為聚乙烯、乙烯－醋酸共聚物、乙烯－(甲基)丙烯酸共聚物、乙烯－(甲基)丙烯酸共聚物、乙烯－(甲基)丙烯酸酯共聚物、聚酯、聚醯胺、聚胺甲酸酯、聚苯乙烯、苯乙烯－二乙烯基苯共聚物、苯乙烯－異丁烯共聚物、苯乙烯－丁二烯共聚物、苯乙烯－(甲基)丙烯酸共聚物、乙烯－丙烯共聚物、(甲基)丙烯酸酯系橡膠、苯乙烯－乙烯－丁烯共聚物、苯氧樹脂、固形環氧樹脂等。此等可被單獨1種使用，亦可組合2種以上來使用。再者，從粒度分佈的分散度、耐溶劑性及耐熱性的觀點來看，特佳為苯乙烯－(甲基)丙烯酸共聚物。作為絕緣性粒子2A的製造方法，可舉出種子聚合法等。The insulating particles 2A are composed of an organic polymer compound. The organic polymer compound is preferably one having thermal softening properties. Suitable starting materials for the insulating particles are, for example, polyethylene, ethylene-acetic acid copolymer, ethylene-(meth)acrylic copolymer, ethylene-(meth)acrylic copolymer, ethylene-(meth)acrylate copolymer, poly Ester, polyamide, polyurethane, polystyrene, styrene-divinylbenzene copolymer, styrene-isobutylene copolymer, styrene-butadiene copolymer, styrene-(meth)acrylic acid Copolymer, ethylene-propylene copolymer, (meth)acrylate rubber, styrene-ethylene-butene copolymer, phenoxy resin, solid epoxy resin, and the like. These may be used alone or in combination of two or more. Further, from the viewpoint of dispersity of the particle size distribution, solvent resistance and heat resistance, a styrene-(meth)acrylic acid copolymer is particularly preferred. A method of producing the insulating particles 2A includes a seed polymerization method and the like.

構成絕緣性粒子2A的有機高分子化合物之軟化點，較佳為電路構件彼此之連接時的加熱溫度以上。軟化點若低於連接時的加熱溫度，則連接時起因於絕緣性粒子2A的過度變形，有無法得到良好的電性連接之傾向。The softening point of the organic polymer compound constituting the insulating particles 2A is preferably at least the heating temperature when the circuit members are connected to each other. When the softening point is lower than the heating temperature at the time of connection, the insulating particles 2A are excessively deformed at the time of connection, and there is a tendency that a good electrical connection cannot be obtained.

構成絕緣性粒子2A的有機高分子化合物之交聯度，較佳為5~20%，尤佳為5~15%，更佳為8~13%。交聯度在上述範圍內的有機高分子化合物，與範圍外的有機高分子化合物比較下，具有連接可靠性及絕緣性兩者皆優異的特性。因此，交聯度若低於5%，則鄰接的電極電路間之絕緣性有變不充分的傾向。另一方面，交聯度若超過20%，則有難以達成連接部分的充分低之初期電阻值及電阻值的經時上升之抑制兩者的傾向。The degree of crosslinking of the organic polymer compound constituting the insulating particles 2A is preferably 5 to 20%, particularly preferably 5 to 15%, more preferably 8 to 13%. The organic polymer compound having a crosslinking degree within the above range is superior in both connection reliability and insulation properties to the organic polymer compound outside the range. Therefore, if the degree of crosslinking is less than 5%, the insulation between adjacent electrode circuits tends to be insufficient. On the other hand, when the degree of crosslinking exceeds 20%, it is difficult to achieve both a sufficiently low initial resistance value of the joined portion and a suppression of the temporal increase in the resistance value.

有機高分子化合物的交聯度，係可藉由交聯性單體與非交聯性單體的組成比來調整。本發明中所言的交聯度，係意味交聯性單體與非交聯性單體的組成比(投入重量比)之理論計算值。即，由合成有機高分子化合物時所混合的交聯性單體之投入重量除以交聯性及非交聯性單體的合計投入重量比而算出的值。The degree of crosslinking of the organic polymer compound can be adjusted by the composition ratio of the crosslinkable monomer to the non-crosslinkable monomer. The degree of crosslinking as used in the present invention means a theoretically calculated value of the composition ratio (input weight ratio) of the crosslinkable monomer to the non-crosslinkable monomer. In other words, the input weight of the crosslinkable monomer mixed in the synthesis of the organic polymer compound is divided by the total input weight ratio of the crosslinkable and non-crosslinkable monomers.

構成絕緣性粒子2A的有機高分子化合物之凝膠分率較佳為90%以上，更佳為95%以上。凝膠分率若低於90%，則於使導電粒子10A分散於黏著劑成分中以製作黏著劑組成物時，黏著劑成分的絕緣電阻有經時降低的傾向。The gel fraction of the organic polymer compound constituting the insulating particles 2A is preferably 90% or more, and more preferably 95% or more. When the gel fraction is less than 90%, when the conductive particles 10A are dispersed in the adhesive component to form an adhesive composition, the insulation resistance of the adhesive component tends to decrease with time.

此處所言的凝膠分率，係對於有機高分子化合物的溶劑而言，表示耐性的指標，以下說明其測定方法。測定應該測定凝膠分率的有機高分子化合物(被測定試料)之質量(質量A)。將被測定試料收納於容器內，於其中加入溶劑。在溫度23℃，將被測定試料在溶劑中攪拌浸漬24小時。然後，使溶劑揮發等而被去除，測定攪拌浸漬後的被測定試料之質量(質量B)。凝膠分率(%)係由(質量B/質量A×100)的式所算出之值。The gel fraction referred to herein is an index indicating the resistance to the solvent of the organic polymer compound, and the measurement method will be described below. The mass (mass A) of the organic polymer compound (measured sample) to which the gel fraction was to be measured was measured. The sample to be measured was placed in a container, and a solvent was added thereto. The sample to be measured was immersed in a solvent for 24 hours at a temperature of 23 °C. Then, the solvent was removed by volatilization or the like, and the mass (mass B) of the sample to be measured after the stirring and immersion was measured. The gel fraction (%) is a value calculated from the formula of (mass B / mass A × 100).

凝膠分率之測定時所用的溶劑係甲苯。再者，黏著劑組成物的溶液之調製，一般使用甲苯、二甲苯、醋酸乙酯、醋酸丁酯、甲基乙基酮、甲基異丁基酮、四氫呋喃。可以使用此等之中的單獨1種，或混合2種以上來使用。The solvent used in the measurement of the gel fraction is toluene. Further, in the preparation of the solution of the adhesive composition, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone or tetrahydrofuran is generally used. One of these may be used alone or two or more of them may be used in combination.

絕緣性粒子2A的平均粒徑係可按照用途等來適宜設計，較佳為50~500nm，尤佳為50~400nm，更佳為100~300nm。平均粒徑若小於50nm，則鄰接的電極電路間之絕緣性有變不充分的傾向，另一方面，若超過500nm，則有難以達成連接部分的充分低之初期電阻值及電阻值的經時上升之抑制兩者的傾向。The average particle diameter of the insulating particles 2A can be appropriately designed according to the use, etc., and is preferably 50 to 500 nm, more preferably 50 to 400 nm, still more preferably 100 to 300 nm. When the average particle diameter is less than 50 nm, the insulation between the adjacent electrode circuits tends to be insufficient. On the other hand, when the average particle diameter exceeds 500 nm, it is difficult to achieve a sufficiently low initial resistance value and resistance value of the connection portion. The tendency to suppress both rises.

絕緣性粒子2A係以達成上述式(1)所定義的被覆率為20~40%的方式，形成在核粒子1的表面上。從更確實地得到本發明的效果之觀點來看，被覆率較佳為25~35%，更佳為28~32%。被覆率若小於20%，則鄰接的電路電極間之絕緣性有變不充分的傾向，另一方面，若超過40%，則有難以達成連接部分的充分低之初期電阻值及電阻值的經時上升之抑制兩者的傾向。再者，被覆核粒子1的複數絕緣性粒子2A，在核粒子1的表面上，較佳係充分分散者。The insulating particles 2A are formed on the surface of the core particle 1 so as to have a coverage ratio defined by the above formula (1) of 20 to 40%. From the viewpoint of more reliably obtaining the effect of the present invention, the coverage ratio is preferably from 25 to 35%, more preferably from 28 to 32%. When the coverage is less than 20%, the insulation between adjacent circuit electrodes tends to be insufficient. On the other hand, if it exceeds 40%, it is difficult to achieve a sufficiently low initial resistance value and resistance value of the connection portion. The tendency to suppress both rises. Further, the plurality of insulating particles 2A covering the core particles 1 are preferably sufficiently dispersed on the surface of the core particles 1.

本發明中所言的被覆率係指藉由微差掃描電子顯微鏡(倍率8000倍)所觀察而得之以下述測定值為基礎者。即，被覆率係以核粒子及絕緣性粒子的各自粒徑、以及附著於1個核粒子的絕緣性粒子之個數為基礎，所算出的值。對任意選擇的50個粒子，如上述地作測定，算出其平均值。The coverage ratio as used in the present invention is based on a differential scanning electron microscope (magnification: 8000 times) and is based on the following measurement values. In other words, the coverage ratio is a value calculated based on the respective particle diameters of the core particles and the insulating particles and the number of the insulating particles attached to one core particle. The arbitrarily selected 50 particles were measured as described above, and the average value was calculated.

核粒子1的粒徑係如以下地測定。即，任意選擇1個核粒子，用微差掃描電子顯微鏡來觀察它，測定其最大直徑及最小直徑。以該最大直徑及最小直徑的積之平方根當作該粒子的粒徑。對任意選擇出的50個核粒子，如上述地測定粒徑，以其平均值當作核粒子1的粒徑(D1 )。關於絕緣性粒子2A的粒徑，與其同樣地作，對任意的50個絕緣性粒子，測定粒徑，以其平均值當作絕緣性粒子2A的粒徑(D2 )。The particle diameter of the core particle 1 was measured as follows. That is, one nuclear particle was arbitrarily selected, and it was observed by a differential scanning electron microscope, and its maximum diameter and minimum diameter were measured. The square root of the product of the largest diameter and the smallest diameter is taken as the particle diameter of the particle. The particle diameter of 50 core particles arbitrarily selected was measured as described above, and the average value thereof was taken as the particle diameter (D 1 ) of the core particle 1. The particle diameter of the insulating particles 2A was measured in the same manner as in any of the 50 insulating particles, and the average value thereof was used as the particle diameter (D 2 ) of the insulating particles 2A.

具備1個導電粒子絕緣性粒子之個數係如以下地測定。即，任意選擇1個由複數絕緣性粒子2A所被覆表面的一部分之導電粒子。然後，用微差掃描電子顯微鏡來拍攝它，於能觀察的核粒子表面上，計數所附著的絕緣性粒子之數。使由此所得到的計數成為2倍，算出附著於1個核粒子的絕緣性粒子之數。對任意選擇出的50個導電粒子，如上述地測定絕緣性粒子的數，以其平均值當作1個導電粒子所具備的絕緣性粒子之個數。The number of one conductive particle insulating particles is measured as follows. In other words, one conductive particle of a part of the surface covered by the plurality of insulating particles 2A is arbitrarily selected. Then, it was photographed by a differential scanning electron microscope, and the number of attached insulating particles was counted on the surface of the nuclear particles that could be observed. The number of the thus obtained counts was doubled, and the number of insulating particles adhering to one core particle was calculated. The number of the insulating particles was measured as described above for the 50 conductive particles which were arbitrarily selected, and the average value thereof was taken as the number of insulating particles included in one conductive particle.

式(1)之核粒子的全表面積，係意味以上述D1 當作直徑的球之表面積。另一方面，核粒子表面被絕緣被覆所覆蓋的部分之面積，係意味以上述D2 當作直徑的圓之面積值乘以1個導電粒子所具備的絕緣性粒子之個數，所得之值。The total surface area of the core particles of the formula (1) means the surface area of the sphere having the above D 1 as the diameter. On the other hand, the area of the portion of the surface of the core particle covered with the insulating coating means that the area value of the circle having the diameter D 2 is multiplied by the number of the insulating particles of one conductive particle, and the obtained value is obtained. .

絕緣性粒子2A的平均粒徑D2 與核粒子1的平均粒徑D1 之比率(D2 /D1 )較佳為1/10以下，更佳為1/15以下。再者，該比率(D2 /D1 )的下限較佳為1/20。D2 /D1 若超過1/10，則有難以達成連接部分的充分低之初期電阻值及電阻值的經時上升之抑制兩者的傾向。另一方面，若低於1/20，則鄰接的電路間之絕緣性有變不充分的傾向。Insulating particles 2A average particle diameter D 2 and D average particle diameter of the core particles 1 ratio (D 2 / D 1) is preferably 1/10 or less of 1, more preferably 1/15 or less. Further, the lower limit of the ratio (D 2 /D 1 ) is preferably 1/20. When D 2 /D 1 exceeds 1/10, it is difficult to achieve both a sufficiently low initial resistance value of the connection portion and a suppression of the resistance value over time. On the other hand, when it is less than 1/20, the insulation between adjacent circuits tends to be insufficient.

再者，核粒子1的表面上所形成的絕緣被覆，係不限定於如絕緣性粒子2A的球狀者。絕緣被覆亦可為由與絕緣性粒子2A同樣的材質所成的絕緣性層。例如，圖4中所示的導電粒子10B具備部分地設置於核粒子1的表面上之絕緣性層2B。Further, the insulating coating formed on the surface of the core particle 1 is not limited to a spherical shape such as the insulating particles 2A. The insulating coating may be an insulating layer made of the same material as the insulating particles 2A. For example, the conductive particles 10B shown in FIG. 4 include the insulating layer 2B partially provided on the surface of the core particle 1.

絕緣性層2B係以成為上述式(1)所定義的被覆率為20~40%的方式，形成在核粒子1的表面上。從更確實地得到本發明的效果之觀點來看，被覆率較佳為25~35%，更佳為28~32%。被覆率若小於20%，則鄰接的電路電極間之絕緣性有變不充分的傾向，另一方面，若超過40%，則有難以達成連接部分的充分低之初期電阻值及電阻值的經時上升之抑制兩者的傾向。再者，被覆核粒子1的絕緣性層2B之各被覆區域，在核粒子1的表面上，較佳係充分分散。各被覆區域亦可為各自孤立的，也可為連續的。The insulating layer 2B is formed on the surface of the core particle 1 so that the coverage ratio defined by the above formula (1) is 20 to 40%. From the viewpoint of more reliably obtaining the effect of the present invention, the coverage ratio is preferably from 25 to 35%, more preferably from 28 to 32%. When the coverage is less than 20%, the insulation between adjacent circuit electrodes tends to be insufficient. On the other hand, if it exceeds 40%, it is difficult to achieve a sufficiently low initial resistance value and resistance value of the connection portion. The tendency to suppress both rises. Further, each of the covering regions of the insulating layer 2B covering the core particles 1 is preferably sufficiently dispersed on the surface of the core particles 1. Each of the covered regions may also be isolated or continuous.

絕緣性層2B的厚度T2 與核粒子1的平均粒徑D1 之比率(T2 /D1 )，較佳係1/10以下，更佳係1/15以下。再者，該比率(T2 /D1 )的下限較佳為1/20。T2 /D1 若超過1/10，則有難以達成連接部分的充分低之初期電阻值及電阻值的經時上升之抑制兩者的傾向。另一方面，若小於1/20，則鄰接的電極電路間之絕緣性有變不充分的傾向。The ratio (T 2 /D 1 ) of the thickness T 2 of the insulating layer 2B to the average particle diameter D 1 of the core particles 1 is preferably 1/10 or less, more preferably 1/15 or less. Further, the lower limit of the ratio (T 2 /D 1 ) is preferably 1/20. When T 2 /D 1 exceeds 1/10, it is difficult to achieve both a sufficiently low initial resistance value of the connected portion and a suppression of the temporal increase in the resistance value. On the other hand, when it is less than 1/20, the insulation between adjacent electrode circuits tends to be insufficient.

於絕緣被覆由絕緣性層2B所構成時，被覆率係可藉由以下的手續來算出。即，用微差掃描電子顯微鏡來分別拍攝經任意選擇的50個導電粒子，對能觀察的核粒子表面上所附著的絕緣性層之面積的測定值作相加平均，藉此而得。又，關於絕緣性層2B的厚度T2 ，亦可用微差掃描電子顯微鏡來分別拍攝經任意選擇的50個導電粒子，將各導電粒子的表面上之絕緣性層2B的厚度之測定值作相加平均而得。When the insulating coating is composed of the insulating layer 2B, the coverage ratio can be calculated by the following procedure. That is, each of the 50 conductive particles which are arbitrarily selected is imaged by a differential scanning electron microscope, and the measured values of the area of the insulating layer adhered on the surface of the observed nuclear particles are added and averaged. Further, regarding the thickness T 2 of the insulating layer 2B, it is also possible to separately photograph 50 randomly selected conductive particles by a differential scanning electron microscope, and to measure the thickness of the insulating layer 2B on the surface of each conductive particle. Plus average.

作為於核粒子1的表面上形成絕緣被覆(絕緣性粒子2A或絕緣性層2B)的方法，可以使用眾所周知的手法，例如利用有機溶劑或分散劑所致的化學變化之濕式方式及利用機械能量所致的物理化學變化之乾式方式。例如，可舉出噴霧法、高速攪拌法、噴霧乾燥法等。As a method of forming an insulating coating (insulating particle 2A or insulating layer 2B) on the surface of the core particle 1, a well-known method such as a wet method using chemical changes by an organic solvent or a dispersing agent, and a mechanical utilization method can be used. A dry way of physicochemical changes caused by energy. For example, a spray method, a high-speed stirring method, a spray drying method, and the like can be given.

為了更確實地得到本發明的效果，較佳為將粒徑充分均一化的複數絕緣性粒子2A設置在核粒子1的表面上，由此構成絕緣被覆。又，與溶劑或分散劑的完全去除為困難的濕式方式比較下，較佳為採用不使用溶劑的乾式方式。In order to obtain the effect of the present invention more reliably, it is preferable that the plurality of insulating particles 2A having a sufficiently uniform particle diameter are provided on the surface of the core particle 1 to constitute an insulating coating. Further, in comparison with the wet method in which the complete removal of the solvent or the dispersant is difficult, it is preferred to use a dry method in which no solvent is used.

作為於乾式方式中在核粒子1的表面上可形成絕緣被覆的裝置，例如可舉出Mechanomill(商品名，股份有限公司德壽工作所製)、Hybridizer(股份有限公司奈良機械製作所製，商品名：NHS系列)等。其中，於粒子1的表面上形成絕緣被覆時，由於可將核粒子1的表面改質成為較合適的狀態，較佳為使用Hybridizer。藉由該裝置，可進行粒子水平的精密被覆，可在核粒子1的表面上形成粒徑充分均一化的絕緣性粒子2A。In the dry type, the insulating coating can be formed on the surface of the core particle 1. For example, Mechanomill (trade name, manufactured by Deshou Co., Ltd.) and Hybridizer (manufactured by Nara Machinery Co., Ltd., trade name) : NHS series) and so on. In the case where an insulating coating is formed on the surface of the particle 1, the surface of the core particle 1 can be modified to a suitable state, and a Hybridizer is preferably used. According to this apparatus, precise coating of the particle level can be performed, and the insulating particles 2A having a sufficiently uniform particle diameter can be formed on the surface of the core particle 1.

絕緣被覆的形狀控制，例如可藉由調整被覆處理的條件來進行。被覆處理的條件，例如為溫度、回轉速度。又，絕緣性粒子2A的粒徑或絕緣性層2B的厚度，係藉由調整被覆處理的條件或供該處理的核粒子1與有機高分子化合物(絕緣被覆的材質)的混合比率來進行。The shape control of the insulating coating can be performed, for example, by adjusting the conditions of the coating treatment. The conditions of the coating treatment are, for example, temperature and speed of rotation. Further, the particle diameter of the insulating particles 2A or the thickness of the insulating layer 2B is adjusted by adjusting the conditions of the coating treatment or the mixing ratio of the core particles 1 to be treated and the organic polymer compound (material for insulating coating).

被覆處理(乾式方式)的溫度較佳為30~90℃，更佳為50~70℃。又，被覆處理(乾式方式)的回轉速度較佳為6000~20000/分鐘，更佳為10000~17000/分鐘。The temperature of the coating treatment (dry mode) is preferably from 30 to 90 ° C, more preferably from 50 to 70 ° C. Further, the turning speed of the coating treatment (dry method) is preferably from 6,000 to 20,000 per minute, more preferably from 10,000 to 17,000 per minute.

其次，說明使導電粒子分散的黏著劑成分。作為黏著劑成分20，較佳為含有(a)熱硬化性樹脂與(b)熱硬化性樹脂用硬化劑所成的黏著劑之組成物，含有(c)藉由加熱或光產生游離自由基的硬化劑與(d)自由基聚合性物質所成的黏著劑之組成物，或(a)、(b)、(c)及(d)的混合組成物。Next, an adhesive component which disperses the conductive particles will be described. The adhesive component 20 preferably contains a composition of an adhesive composed of (a) a thermosetting resin and (b) a curing agent for a thermosetting resin, and contains (c) free radicals generated by heating or light. A composition of an adhesive of (d) a radically polymerizable substance, or a mixed composition of (a), (b), (c), and (d).

再者，作為黏著劑成分，亦可以為聚乙烯、聚丙烯等的熱塑性樹脂。但是，從耐熱性、耐濕性及機械的特性的觀點來看，較佳為環氧樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、丙烯酸樹脂等的硬化性樹脂。以下詳細說明、黏著劑成分。Further, as the adhesive component, a thermoplastic resin such as polyethylene or polypropylene may be used. However, from the viewpoint of heat resistance, moisture resistance, and mechanical properties, a curable resin such as an epoxy resin, a polyimide resin, a polyamide amide resin, or an acrylic resin is preferable. The adhesive composition will be described in detail below.

作為(a)熱硬化性樹脂，只要是在任意的溫度範圍中可硬化處理的熱硬化性樹脂即可，而沒有特別的限定，較佳為環氧樹脂。作為環氧樹脂，可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚－酚醛清漆型環氧樹脂、甲酚－酚醛清漆型環氧樹脂、雙酚A－酚醛清漆型環氧樹脂、雙酚F－酚醛清漆型環氧樹脂、脂環式環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油基胺型環氧樹脂、內醯脲型環氧樹脂、異氰尿酸酯型環氧樹脂、脂肪族鎖狀環氧樹脂等。此等環氧樹脂可被鹵化，也可被加氫。此等環氧樹脂可被單獨1種使用，或組合2種以上來使用。The (a) thermosetting resin is not particularly limited as long as it is a thermosetting resin which can be cured in any temperature range, and is preferably an epoxy resin. Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, and cresol novolac epoxy resin. , bisphenol A-novolak type epoxy resin, bisphenol F-novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, carbamide Type epoxy resin, isocyanurate type epoxy resin, aliphatic lock epoxy resin, and the like. These epoxy resins can be halogenated or hydrogenated. These epoxy resins may be used alone or in combination of two or more.

作為(b)熱硬化性樹脂用硬化劑，可舉出胺系、苯酚系、酸酐系、咪唑系、醯肼系、氰胍、三氟化硼－胺錯合物、鋶鹽、碘鎓鹽、胺醯亞胺等。此等可單獨地或混合2種以上來使用，亦可混合分解促進劑、抑制劑等而使用。又，此等硬化劑經聚胺甲酸酯系、聚酯系的高分子物質等所被覆而成為微膠囊者，由於延長可使用時間，故係較宜的。Examples of the hardening agent for thermosetting resin (b) include an amine system, a phenol type, an acid anhydride type, an imidazole type, an anthraquinone type, a cyanogenic group, a boron trifluoride-amine complex, a phosphonium salt, and an iodonium salt. , amine imine and the like. These may be used singly or in combination of two or more kinds, and may be used by mixing a decomposition accelerator, an inhibitor, or the like. Moreover, since these hardeners are covered with a polyurethane material, a polyester-based polymer material or the like to form a microcapsule, it is preferable because the usable time is prolonged.

(b)熱硬化性樹脂用硬化劑的配合量，以黏著劑成分的總質量為基準，較佳係0.1~60.0質量%左右，更佳係1.0~20.0質量%。熱硬化性樹脂用硬化劑的配合量若低於0.1質量%，則硬化反應的進行變成不充分，有難以得到良好的黏著強度或連接電阻值之傾向。另一方面，若超過60質量%，則黏著劑成分的流動性降低下，或適用期有變短的傾向。又，連接部分的連接電阻值有變高的傾向。(b) The amount of the curing agent for the thermosetting resin is preferably from about 0.1 to 60.0% by mass, more preferably from 1.0 to 20.0% by mass, based on the total mass of the adhesive component. When the amount of the curing agent for the thermosetting resin is less than 0.1% by mass, the progress of the curing reaction is insufficient, and it is difficult to obtain a good adhesion strength or a connection resistance value. On the other hand, when it exceeds 60% by mass, the fluidity of the adhesive component is lowered, or the pot life is shortened. Further, the connection resistance value of the connection portion tends to be high.

作為(c)藉由加熱或光產生游離自由基的硬化劑，可舉出過氧化化合物、偶氟系化合物等之藉由加熱或光所致的分解而產生游離自由基者。可依照目的之連接溫度、連接時間、適用期等來適宜選定。從高反應性與適用期之點來看，較佳係半衰期10小時的溫度為40℃以上，且半衰期1分鐘的溫度為180℃以下的有機過氧化物。於此情況下，(c)藉由加熱或光產生游離自由基的硬化劑之配合量，以黏著劑成分的總質量為基準，較佳係0.05~10質量%，更佳係0.1~5質量%。(c) A curing agent which generates free radicals by heating or light, and examples of the generation of free radicals by decomposition by heating or light, such as a peroxy compound or a fluorochemical compound, may be mentioned. It can be suitably selected according to the connection temperature, connection time, pot life, etc. of the purpose. From the viewpoint of high reactivity and pot life, an organic peroxide having a half-life of 10 hours and a temperature of 40 ° C or more and a half-life of 1 minute is preferably 180 ° C or less. In this case, (c) the amount of the curing agent which generates free radicals by heating or light is preferably 0.05 to 10% by mass, more preferably 0.1 to 5 by mass based on the total mass of the adhesive component. %.

(c)藉由加熱或光產生游離自由基的硬化劑，具體地可從二醯基過氧化物、過氧二碳酸酯、過氧酯、過氧縮酮、二烷基過氧化物、過氧化氫等中來選定。為了抑制電路構件的電路電極之腐蝕，較佳為從過氧酯、二烷基過氧化物、過氧化氫中來選定，更佳為從能得到高反應性的過氧酯來選定。(c) a hardener which generates free radicals by heating or light, in particular from dimercapto peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, It is selected from hydrogen peroxide and the like. In order to suppress corrosion of the circuit electrode of the circuit member, it is preferably selected from peroxyester, dialkyl peroxide and hydrogen peroxide, and more preferably from a peroxyester which can obtain high reactivity.

作二醯基過氧化物類，例如可舉出異丁基過氧化物、2,4－二氯苯甲醯基過氧化物、3,5,5－三甲基己醯基過氧化物、辛醯基過氧化物、月桂醯基過氧化物、硬脂醯基過氧化物、琥珀醯基過氧化物、苯甲醯基過氧甲苯、苯甲醯基過氧化物等。Examples of the dithiol peroxide include isobutyl peroxide, 2,4-dichlorobenzhydryl peroxide, and 3,5,5-trimethylhexyl peroxide. Octyl peroxide, lauryl peroxide, stearyl peroxide, amber-based peroxide, benzamidine peroxytoluene, benzammonium peroxide, and the like.

作為過氧二碳酸酯類，例如可舉出二正丙基過氧二碳酸酯、二異丙基過氧二碳酸酯、雙(4－第三丁基環己基)過氧二碳酸酯、二－2－乙氧基甲氧基過氧二碳酸酯、二(2－乙基己基過氧)二碳酸酯、二甲氧基丁基過氧二碳酸酯、二(3－甲基－3－甲氧基丁基過氧)二碳酸酯等。Examples of the peroxydicarbonate include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, and 2-ethoxymethoxy peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, di(3-methyl-3- Methoxybutyl peroxy) dicarbonate and the like.

作為過氧酯類，例如可舉出枯基過氧新癸酸酯、1,1,3,3－四甲基丁基過氧新癸酸酯、1－環己基－1－甲基乙基過氧新癸酸酯、第三己基過氧新癸酸酯、第三丁基過氧三甲基乙酸酯、1,1,3,3－四甲基丁基過氧－2－乙基己酸酯、2,5－二甲基－2,5－雙(2－乙基己醯基過氧)己烷、1－環己基－1－甲基乙基過氧－2－乙基己酸酯、第三己基過氧－2－乙基己酸酯、第三丁基過氧－2－乙基己酸酯、第三丁基過氧異丁酸酯、1,1－雙(第三丁基過氧)環己烷、第三己基過氧異丙基單碳酸酯、第三丁基過氧－3,5,5－三甲基己酸酯、第三丁基過氧月酸酯、2,5－二甲基－2,5－雙(間甲苯醯基過氧)己烷、第三丁基過氧異丙基單碳酸酯、第三丁基過氧－2－乙基己基單碳酸酯、第三己基過氧苯甲酸酯、第三丁基過氧醋酸酯等。Examples of the peroxyesters include cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, and 1-cyclohexyl-1-methylethyl. Peroxy neodecanoate, third hexyl peroxy neodecanoate, tert-butylperoxytrimethyl acetate, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexyl Acid ester, third hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy isobutyrate, 1,1-double (first Tributylperoxy)cyclohexane, third hexylperoxyisopropylmonocarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylic acid Ester, 2,5-dimethyl-2,5-bis(m-tolylperoxy)hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethyl Hexyl monocarbonate, third hexyl peroxybenzoate, t-butyl peroxyacetate, and the like.

作為過氧縮酮類，例如可舉出1,1－雙(第三己基過氧)－3,5,5－三甲基環己烷、1,1－雙(第三己基過氧)環己烷、1,1－雙(第三丁基過氧)－3,5,5－三甲基環己烷、1,1－(第三丁基過氧)環十二烷、2,2－雙(第三丁基過氧)癸烷等。Examples of the peroxyketals include 1,1-bis(Third-hexylperoxy)-3,5,5-trimethylcyclohexane and 1,1-bis(trihexylperoxy) rings. Hexane, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane, 2,2 - bis(t-butylperoxy)decane, and the like.

作為二烷基過氧化物類，例如可舉出α,α’－雙(第三丁基過氧)二異丙基苯、二枯基過氧化物、2,5－二甲基－2,5－二(第三丁基過氧)己烷、第三丁基枯基過氧化物等。Examples of the dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, and 2,5-dimethyl-2. 5-bis(t-butylperoxy)hexane, tert-butylcumyl peroxide, and the like.

作為過氧化氫類，例如可舉出二異丙基苯過氧化氫、異丙苯氫過氧化物等。Examples of the hydrogen peroxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

此等(c)藉由加熱或光產生游離自由基的硬化劑，可被單獨1種地或混合2種以上來使用，亦可混合分解促進劑、抑制劑等而使用。(c) The curing agent which generates a free radical by heat or light may be used alone or in combination of two or more kinds thereof, or may be used by mixing a decomposition accelerator, an inhibitor or the like.

(d)自由基聚合性物質係具有藉由自由基聚合的官能基之物質，例如可舉出(甲基)丙烯酸酯、馬來醯亞胺化合物等。(d) The radical polymerizable substance is a substance having a functional group polymerized by radical polymerization, and examples thereof include a (meth) acrylate and a maleimide compound.

作為(甲基)丙烯酸酯，例如可舉出胺甲酸酯(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、2－羥基－1,3－二(甲基)丙烯醯氧基丙烷、2,2－雙[4－((甲基)丙烯醯氧基甲氧基)苯基]丙烷、2,2－雙[4－((甲基)丙烯醯氧基聚乙氧基)苯基]丙烷、(甲基)丙烯酸二環戊烯酯、三環癸基(甲基)丙烯酸酯、雙((甲基)丙烯醯氧基乙基)異氰尿酸酯、ε－己內酯改性三((甲基)丙烯醯氧基乙基)異氰尿酸酯三((甲基)丙烯醯氧基乙基)異氰尿酸酯等。Examples of the (meth) acrylate include urethane (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and isopropyl (meth) acrylate. Isobutyl acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tris(A) Acrylate, tetramethylol methane tetra(meth)acrylate, 2-hydroxy-1,3-bis(methyl)propenyloxypropane, 2,2-bis[4-((methyl)) Propylene methoxymethoxy)phenyl]propane, 2,2-bis[4-((meth)propenyloxypolyethoxy)phenyl]propane, dicyclopentenyl (meth)acrylate , tricyclodecyl (meth) acrylate, bis((meth) propylene methoxyethyl) isocyanurate, ε-caprolactone modified tris((meth) propylene methoxyethyl Isocyanurate tris((meth)acryloxyethyl)isocyanurate or the like.

如此的自由基聚合性物質可被單獨1種地使用，或組合2種以上來使用。黏著劑成分特佳為至少含25℃的黏度為100000~1000000mPa．s的自由基聚合性物質，尤佳為含有具100000~500000mPa．s的黏度(25℃)之自由基聚合性物質。自由基聚合性物質的黏度之測定，係可使用市售的E型黏度計來測定。Such a radically polymerizable substance may be used alone or in combination of two or more. Adhesive component is particularly good at a viscosity of at least 25 ° C is 100000 ~ 1000000mPa. The radical polymerizable substance of s, particularly preferably containing 100000~500000mPa. A free radical polymerizable substance of s viscosity (25 ° C). The measurement of the viscosity of the radically polymerizable substance can be measured using a commercially available E-type viscometer.

於自由基聚合性物質之中，從黏著性的觀點來看，較佳為胺甲酸酯(甲基)丙烯酸酯，又，於與用於提高耐熱性的有機過氧化物交聯後，特佳為單獨地併用能顯示100℃以上的Tg之自由基聚合性物質來使用。作為如此的自由基聚合性物質，可以使用分子內具有二環戊烯基、三環癸基及/或三肟環者。特佳為使用分子內具有三環癸基或三肟環的自由基聚合性物質。Among the radically polymerizable substances, from the viewpoint of adhesion, a urethane (meth) acrylate is preferable, and after crosslinking with an organic peroxide for improving heat resistance, It is preferred to use a radically polymerizable substance capable of exhibiting Tg of 100 ° C or more in combination. As such a radically polymerizable substance, those having a dicyclopentenyl group, a tricyclodecanyl group, and/or a triterpene ring in the molecule can be used. It is particularly preferable to use a radically polymerizable substance having a tricyclic indenyl group or a triterpene ring in the molecule.

作為馬來醯亞胺化合物，較佳為分子中具有至少2個以上的馬來醯亞胺基者，例如可舉出1－甲基－2,4－雙馬來醯亞胺苯、N,N’－間伸苯基雙馬來醯亞胺、N,N’－對伸苯基雙馬來醯亞胺、N,N’－間伸甲苯基雙馬來醯亞胺、N,N’－4,4－伸聯苯基雙馬來醯亞胺、N,N’－4,4－(3,3’－二甲基－伸聯苯基)雙馬來醯亞胺、N,N’－4,4－(3,3’－二甲基二苯基甲烷)雙馬來醯亞胺、N,N’,4,4－(3,3’－二乙基二苯基甲烷)雙馬來醯亞胺、N,N’－4,4－二苯基甲烷雙馬來醯亞胺、N,N’－4,4－二苯基丙烷雙馬來醯亞胺、N,N’－4,4－二苯基醚雙馬來醯亞胺、N,N’－3,3’－二苯基碸雙馬來醯亞胺、2,2－雙[4－(4－馬來醯亞胺苯氧基)苯基]丙烷、2,2－雙[3－s－丁基－4,8－(4－馬來醯亞胺苯氧基)苯基]丙烷、1,1－雙[4－(4－馬來醯亞胺苯氧基)苯基]癸烷、4,4’－亞環己基－雙[1－(4－馬來醯亞胺苯氧基)－2－環己基]苯、2,2－雙[4－(4－馬來醯亞胺苯氧基)苯基]六氟丙烷等。此等可被單獨1種使用，或併用2種以上來使用，亦可與烯丙基苯酚、烯丙基苯基醚、苯甲酸烯丙酯等的烯丙基化合物併用而使用。The maleimide compound is preferably one having at least two or more maleimine groups in the molecule, and examples thereof include 1-methyl-2,4-bismamidine benzene and N. N'-meta-phenyl-p-maleimide, N,N'-p-phenyl-p-maleimide, N,N'-m-tolyl-m-maleimide, N,N' -4,4-Exbiphenyl dimaleimide, N,N'-4,4-(3,3'-dimethyl-extended biphenyl) 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'-diphenylfluorene bismaleimide, 2,2-bis[4-(4-horse醯iminophenoxy)phenyl]propane, 2,2-bis[3-s-butyl-4,8-(4-maleimidophenoxy)phenyl]propane, 1,1 - bis[4-(4-maleimidophenoxy)phenyl]decane, 4,4'-cyclohexylene-bis[1-(4-maleimide) Oxy) -2-cyclohexyl] benzene, 2,2-bis [4- (4-maleic (PEI) phenoxy) phenyl] hexafluoropropane. These may be used alone or in combination of two or more kinds thereof, or may be used in combination with an allyl compound such as allylphenol, allylphenyl ether or allyl benzoate.

又，視需要，亦可適宜使用氫醌、甲基醚氫醌類等的聚合抑制劑。Further, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be suitably used as needed.

黏著劑成分20亦可含有膜形成性高分子。以黏著劑成分20的總質量當作基準，膜形成性高分子的含量較佳係2~80質量%，尤佳係5~70質量%，更佳係10~60質量%。作為膜形成性高分子，可以使用聚苯乙烯、聚乙烯、聚乙烯縮丁醛、聚乙烯縮甲醛、聚醯亞胺、聚醯胺、聚酯、聚氯乙烯、聚苯醚、尿素樹脂、蜜胺樹脂、苯酚樹脂、二甲苯樹脂、聚異氰酸酯樹脂、苯氧樹脂、聚醯亞胺樹脂、聚酯胺甲酸酯樹脂。The adhesive component 20 may also contain a film-forming polymer. The content of the film-forming polymer is preferably from 2 to 80% by mass, particularly preferably from 5 to 70% by mass, more preferably from 10 to 60% by mass, based on the total mass of the adhesive component 20. As the film-forming polymer, polystyrene, polyethylene, polyvinyl butyral, polyvinyl formal, polyimide, polyamine, polyester, polyvinyl chloride, polyphenylene ether, urea resin, or the like can be used. A melamine resin, a phenol resin, a xylene resin, a polyisocyanate resin, a phenoxy resin, a polyimide resin, a polyester urethane resin.

於上述膜形成性高分子之中，更佳為具有羥基等的官能基之樹脂，因為其可提高黏著性。又，亦可使用此等高分子經自由基聚合性官能基所改性者。Among the above film-forming polymers, a resin having a functional group such as a hydroxyl group is more preferable because it can improve adhesion. Further, those in which the polymer is modified by a radical polymerizable functional group can also be used.

再者，電路連接材料50亦可含有填料、軟化劑、促進劑、防老化劑、著色劑、難燃化劑、搖變劑、偶合劑、苯酚樹脂、蜜胺樹脂、異氰酸酯類等。Furthermore, the circuit connecting material 50 may also contain a filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a shaker, a coupling agent, a phenol resin, a melamine resin, an isocyanate or the like.

於含有填料時，由於得到連接可靠性等的提高，故係較宜的。填料係可使用最大直徑小於導電粒子的粒徑者，較佳為5~60體積%的範圍。若超過60體積%，則可靠性的提高效果係飽和了。When the filler is contained, it is preferable because the connection reliability and the like are improved. The filler may be used in a range in which the maximum diameter is smaller than the particle diameter of the conductive particles, and preferably in the range of 5 to 60% by volume. If it exceeds 60% by volume, the effect of improving the reliability is saturated.

作為偶合劑，從黏著性的提高之點來看，較佳為含有選自乙烯基、丙烯醯基、胺基、環氧基及異氰酸基所組族群的1種以上之基的化合物。The coupling agent is preferably a compound containing one or more groups selected from the group consisting of a vinyl group, an acryl group, an amine group, an epoxy group, and an isocyanate group, from the viewpoint of improving the adhesion.

於電路連接材料50中，導電粒子10A的含量，以電路連接材料50的全體積當作100體積份，其較佳為0.1~30體積份，其含量係依照用途而靈活運用。再者，為了達成高的連接可靠性，其含量更佳為0.1~10體積份。In the circuit connecting material 50, the content of the conductive particles 10A is taken as 100 parts by volume based on the entire volume of the circuit connecting material 50, and it is preferably 0.1 to 30 parts by volume, and the content thereof is flexibly used according to the use. Further, in order to achieve high connection reliability, the content is more preferably 0.1 to 10 parts by volume.

圖5係顯示與本發明有關的電路連接材料50設置在薄膜狀的支持體60上之狀態的截面圖。作為支持體60，例如可以使用聚對苯二甲酸乙二酯薄膜(PET薄膜)、聚對萘二甲酸乙二酯薄膜、聚間苯二甲酸乙二酯薄膜、對苯二甲酸丁二酯薄膜、聚烯烴系薄膜、聚醋酸酯薄膜、聚碳酸酯薄膜、聚苯硫醚薄膜、聚醯胺薄膜、乙烯一醋酸乙烯酯共聚物薄膜、聚氯乙烯薄膜、聚偏二氯乙烯薄膜、合成橡膠系薄膜、液晶聚合物薄膜等的各種薄膜。對於上述薄膜的表面，亦可以使用視需要施有電暈放電處理、增黏塗覆處理、抗靜電處理等的支持體。Fig. 5 is a cross-sectional view showing a state in which the circuit connecting material 50 according to the present invention is placed on the film-like support 60. As the support 60, for example, a polyethylene terephthalate film (PET film), a polyethylene naphthalate film, a polyethylene isophthalate film, a butylene terephthalate film can be used. , polyolefin film, polyacetate film, polycarbonate film, polyphenylene sulfide film, polyamide film, ethylene-vinyl acetate copolymer film, polyvinyl chloride film, polyvinylidene chloride film, synthetic rubber It is a film of various films, such as a film and a liquid crystal polymer film. For the surface of the above film, a support such as a corona discharge treatment, a tackifying coating treatment, an antistatic treatment, or the like may be used as needed.

於使用電路連接材料50時，亦可以能容易從電路連接材料50剝離支持體60的方式，視需要在支持體60的表面上塗覆剝離處理劑而使用。作為剝離處理劑，可以使用聚矽氧烷樹脂、聚矽氧烷與有機系樹脂的共聚物、醇酸樹脂、胺基醇酸樹脂、具長鏈烷基的樹脂、具氟烷基的樹脂、蟲膠樹脂等的各種剝離處理劑。When the circuit connecting material 50 is used, the support 60 can be easily peeled off from the circuit connecting material 50, and a peeling treatment agent can be applied to the surface of the support 60 as needed. As the release treatment agent, a polydecane resin, a copolymer of a polysiloxane and an organic resin, an alkyd resin, an amino alkyd resin, a resin having a long-chain alkyl group, a resin having a fluoroalkyl group, or a resin having a fluoroalkyl group can be used. Various release treatment agents such as shellac resin.

支持體60的膜厚係沒有特別的限制，但考慮所製作的電路連接材料50之保管、使用時的便利性等，較佳為4~200μ m，若再考慮材料成本或生產性，更佳為15~75μ m。The film thickness of the support 60 is not particularly limited, but it is preferably 4 to 200 μm in consideration of storage and use of the circuit connecting material 50 to be produced, and further consideration of material cost or productivity. Good is 15~75 μ m.

(連接方法)(connection method)

圖6係藉由示意截面圖來顯示與本發明有關的電路構件之連接方法的一實施形態之步驟圖。Fig. 6 is a flow chart showing an embodiment of a method of connecting circuit members according to the present invention by a schematic cross-sectional view.

首先，準備上述第1電路構件30及片狀的電路連接材料50。電路連接材料50係由含有導電粒子10A的黏著劑組成物所成。First, the first circuit member 30 and the sheet-shaped circuit connecting material 50 are prepared. The circuit connecting material 50 is formed of an adhesive composition containing the conductive particles 10A.

電路連接材料50的厚度較佳為5~50μ m。電路連接材料50的厚度若小於5μ m，則在第1及第2電路電極32、42間，電路連接材料50有填充不足的傾向。另一方面，若超過50μ m，則有難以確保第1及第2電路電極32、42間的導通之傾向。The thickness of the circuit connecting material 50 is preferably 5 to 50 μm . When the thickness of the circuit connecting material 50 is less than 5 μm , the circuit connecting material 50 tends to be insufficiently filled between the first and second circuit electrodes 32 and 42. On the other hand, when it exceeds 50 μm , it tends to be difficult to ensure conduction between the first and second circuit electrodes 32 and 42.

其次，將電路連接材料50載置第1電路構件30的電路電極32之形成面上。然後，將電路連接材料50在圖5(a)的箭號A及B方向中作加壓，以使電路連接材料50臨時連接第1電路構件30(圖5(b))。Next, the circuit connecting material 50 is placed on the surface on which the circuit electrode 32 of the first circuit member 30 is formed. Then, the circuit connecting material 50 is pressurized in the arrows A and B directions of Fig. 5 (a) to temporarily connect the circuit connecting material 50 to the first circuit member 30 (Fig. 5 (b)).

此時的壓力只要在不對電路構件造成損傷的範圍內即可，而沒有特別的限制，一般較佳為0.1~30.0MPa。又，亦可邊加熱邊加壓，加熱溫度係電路連接材料50不實質硬化的溫度。加熱溫度一般較佳為50~190℃。此等加熱及加壓在0.5~120秒間的範圍內進行。The pressure at this time may be within a range that does not cause damage to the circuit member, and is not particularly limited, and is generally preferably 0.1 to 30.0 MPa. Further, it is also possible to pressurize while heating, and to heat the temperature at which the circuit connecting material 50 does not substantially harden. The heating temperature is generally preferably from 50 to 190 °C. These heating and pressurization are carried out in the range of 0.5 to 120 seconds.

接著，如圖5(c)所示地，以第2電路電極42朝向第1電路構件30之側的方式，將第2電路構件40載置於電路連接材料50。然後，邊加熱片狀的電路連接材料50，邊在圖5(c)的箭號A及B方向中將全體加壓。Next, as shown in FIG. 5(c), the second circuit member 40 is placed on the circuit connecting material 50 so that the second circuit electrode 42 faces the side of the first circuit member 30. Then, while heating the sheet-like circuit connecting material 50, the whole is pressurized in the arrows A and B directions of Fig. 5 (c).

此時的加熱溫度係電路連接材料50能硬化的溫度。加熱溫度較佳係60~180℃，尤佳係70~170℃，更佳係80~160℃。加熱溫度若低於60℃，則硬化速度有變慢的傾向，而若超過180℃，則有容易進行不宜的副反應之傾向。加熱時間較佳係0.1~180秒，尤佳係0.5~180秒，更佳係1~180秒。The heating temperature at this time is the temperature at which the circuit connecting material 50 can harden. The heating temperature is preferably 60 to 180 ° C, particularly preferably 70 to 170 ° C, more preferably 80 to 160 ° C. When the heating temperature is lower than 60 ° C, the curing rate tends to be slow, and when it exceeds 180 ° C, undesired side reactions tend to occur. The heating time is preferably 0.1 to 180 seconds, particularly preferably 0.5 to 180 seconds, and more preferably 1 to 180 seconds.

藉由電路連接材料50的硬化而形成黏著部50a，得到如圖1所示的連接構造100。連接的條件係依照所使用的用途、黏著劑組成物、電路構件來適宜選擇。再者，作為電路連接材料50的黏著劑成分，於使用藉由光硬化者時，對電路連接材料50可適宜照射活性光線或能量線。作為活性光線，可舉出紫外線、可見光、紅外線等。The adhesive portion 50a is formed by hardening of the circuit connecting material 50, and the connection structure 100 as shown in FIG. 1 is obtained. The conditions of the connection are appropriately selected depending on the use, the adhesive composition, and the circuit member. Further, as the adhesive component of the circuit connecting material 50, when the light is cured by light, the circuit connecting material 50 can be suitably irradiated with active light rays or energy rays. Examples of the active light include ultraviolet light, visible light, infrared light, and the like.

作為能量線，可舉出電子線、X射線、γ射線、微波等。Examples of the energy line include an electron beam, X-rays, γ-rays, and microwaves.

以上說明本發明較合適之實施形態，惟本發明不受上述實施形態所限定。本發明在不脫離其要旨的範圍內，可有各式各樣的變形。例如，於上述實施形態中，例示由基材粒子1a及導電層1b所構成的核粒子1，但是核粒子亦可由具有導電性的材質(例如與導電層1b同樣的材質)所構成者。又，亦可使用由熱熔融金屬所成的粒子當作核粒子。於該情況下，可藉由加熱及加壓使核粒子充分變形。The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments. The present invention can be variously modified without departing from the spirit and scope of the invention. For example, in the above embodiment, the core particles 1 composed of the substrate particles 1a and the conductive layer 1b are exemplified, but the core particles may be composed of a conductive material (for example, the same material as the conductive layer 1b). Further, particles made of a hot molten metal may be used as the core particles. In this case, the core particles can be sufficiently deformed by heating and pressurization.

又，導電粒子亦可為使作為絕緣被覆的絕緣性粒子2A及絕緣性層2B兩方設置在核粒子1的表面上者。In addition, the conductive particles may be provided on both surfaces of the core particle 1 such that the insulating particles 2A and the insulating layer 2B which are insulated are provided.

片狀的電路連接材料可為單層構造，亦可為複數層所積層的多層構造。多層構造的電路連接材料係可藉由積層複數的黏著劑成分及導電粒子的種類或彼等含量不同的層來製造。例如，電路連接材料亦可具備含有導電粒子的含導電粒子層、與在該含導電粒子層的至少一面上所設置的不含有導電粒子的不含導電粒子層。The sheet-like circuit connecting material may be a single layer structure or a multilayer structure in which a plurality of layers are laminated. The circuit connecting material of the multilayer structure can be manufactured by laminating a plurality of adhesive components and layers of conductive particles or layers having different contents. For example, the circuit connecting material may further include a conductive particle-containing layer containing conductive particles and a conductive particle-free layer provided on at least one surface of the conductive particle-containing layer and containing no conductive particles.

圖7係顯示二層構造電路連接材料被支持體所支撐的狀態之截面圖。圖7所示的電路連接材料70係由含有導電粒子的含導電粒子層70a及不含有導電粒子的不導電粒子層70b所構成。於電路連接材料70的兩最外面，設置各自的支持體60a、60b。電路連接材料70係可藉由在支持體60a的表面上形成含導電粒子層70a，另一方面，在支持體60b的表面上形成不含導電粒子層70b，使用習知的層壓機等貼合此等而製作。於使用電路連接材料70時，適宜地剝離支持體60a、60b而使用。Fig. 7 is a cross-sectional view showing a state in which a two-layer construction circuit connecting material is supported by a support. The circuit connecting material 70 shown in FIG. 7 is composed of a conductive particle-containing layer 70a containing conductive particles and a non-conductive particle layer 70b containing no conductive particles. On the outermost surfaces of the circuit connecting material 70, respective support bodies 60a, 60b are provided. The circuit connecting material 70 can form a conductive particle-containing layer 70a on the surface of the support 60a, and on the other hand, a conductive particle-free layer 70b can be formed on the surface of the support 60b, and can be attached using a conventional laminator or the like. Produced in conjunction with this. When the circuit connecting material 70 is used, the supports 60a and 60b are suitably peeled off and used.

於藉由電路連接材料70來接合電路構件彼此時，可充分抑制起因於黏著劑成分的流動所導致的電路電極上的導電粒子個數之減少。例如，於藉由COG封裝或COF封裝將IC晶片連接於基板上時，可充分確保IC晶片的金屬凸塊上之導電粒子個數。於該情況下，具備IC晶片之金屬凸塊的面與不含導電粒子層70b，或應封裝IC晶片的基板與含導電粒子層70a，較佳係以各自對接的方式配置電路連接材料70。When the circuit members are joined to each other by the circuit connecting material 70, the decrease in the number of conductive particles on the circuit electrodes due to the flow of the adhesive component can be sufficiently suppressed. For example, when an IC wafer is connected to a substrate by a COG package or a COF package, the number of conductive particles on the metal bumps of the IC wafer can be sufficiently ensured. In this case, the surface of the metal bump of the IC wafer and the substrate 16 that does not contain the conductive particle layer 70b, or the substrate on which the IC wafer is to be packaged, and the conductive particle-containing layer 70a are preferably disposed so as to be butted to each other.

實施例Example (實施例1)(Example 1)

如以下地製造具有導電性的核粒子。即，準備交聯聚苯乙烯粒子(總研化學製，商品名：SX系列，平均粒徑：4μ m)當作基材粒子，於該粒子的表面上，藉由無電解鍍敷處理來設置Ni層(厚度0.08μ m)。再者，於該Ni層的外側，藉由無電解鍍敷處理來設置Au層(厚度0.03μ m)，得到由Ni層及Au層所成的具有導電層的核粒子。Conductive core particles are produced as follows. In other words, crosslinked polystyrene particles (manufactured by Konica Chemical Co., Ltd., trade name: SX series, average particle diameter: 4 μm ) were prepared as substrate particles, and electroless plating treatment was applied to the surface of the particles. Set the Ni layer (thickness 0.08 μm ). Further, on the outer side of the Ni layer, an Au layer (thickness: 0.03 μm ) was provided by electroless plating treatment to obtain core particles having a conductive layer made of a Ni layer and an Au layer.

作為用於被覆核粒子表面的有機高分子化合物(絕緣被覆)，準備交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：20%，凝膠分率：18%)。將4克該交聯丙烯酸樹脂及20克核粒子導入Hybridizer(股份有限公司奈良機械製作所製，商品名：NHS系列)中，製作導電粒子。再者，Hybridizer的處理條件係回轉速度16000/分鐘，反應槽溫度為60℃。藉此，得到如圖3所示構成的導電粒子。微差掃描電子顯微鏡(倍率8000倍)的觀察結果為該導電粒子的被覆率係25%。As an organic polymer compound (insulating coating) for coating the surface of the core particle, a crosslinked acrylic resin (trade name: MP series, degree of crosslinking: 20%, gel fraction: 18%) was prepared. 4 g of the crosslinked acrylic resin and 20 g of the core particles were introduced into a Hybridizer (manufactured by Nara Machinery Co., Ltd., trade name: NHS series) to prepare conductive particles. Further, the processing conditions of the Hybridizer were a spinning speed of 16,000 /min and a reaction tank temperature of 60 °C. Thereby, conductive particles configured as shown in FIG. 3 were obtained. The observation result of the differential scanning electron microscope (magnification: 8000 times) showed that the coverage of the conductive particles was 25%.

其次，使用雙酚A型環氧樹脂和9,9’－雙(4－羥苯基)茀，合成玻璃轉移溫度為80℃的苯氧樹脂。將50克苯氧樹脂溶解在溶劑中，調製固體成分40質量%的溶液。再者，作為溶劑，使用甲苯與醋酸乙酯的混合溶劑(兩者的混合質量比＝1：1)。Next, a phenoxy resin having a glass transition temperature of 80 ° C was synthesized using a bisphenol A type epoxy resin and 9,9'-bis(4-hydroxyphenyl) fluorene. 50 g of phenoxy resin was dissolved in a solvent to prepare a solution having a solid content of 40% by mass. Further, as a solvent, a mixed solvent of toluene and ethyl acetate (mixed mass ratio of the two = 1:1) was used.

為了摻合40克苯氧樹脂(固體成分)與60克(固體成分)含有微膠囊型潛在性硬化劑的液狀環氧樹脂，將上述溶液與環氧樹脂混合。對於100體積份的由此所得到的黏著劑成分之溶液，摻合5體積份的上述導電粒子，在溫度23℃攪拌分散，以調製黏著劑組成物的溶液。In order to blend 40 g of a phenoxy resin (solid content) with 60 g (solid content) of a liquid epoxy resin containing a microcapsule-type latent hardener, the above solution was mixed with an epoxy resin. To 100 parts by volume of the solution of the thus obtained adhesive component, 5 parts by volume of the above-mentioned conductive particles were blended and stirred and dispersed at a temperature of 23 ° C to prepare a solution of the adhesive composition.

於經剝離處理劑(聚矽氧烷樹脂)施有表面處理的PET薄膜(帝人杜邦薄膜股份有限公司，商品名：Purex,厚度：50μ m)之面上，塗佈黏著劑組成物的溶液。然後，對其進行熱風乾燥(在80℃ 5分鐘)，以得到被PET薄膜所支持的厚度10μ m之含導電粒子層。A solution of an adhesive composition is applied to a surface of a PET film (People DuPont Film Co., Ltd., trade name: Purex, thickness: 50 μm ) to which a surface treatment is applied by a release treatment agent (polysiloxane). . Then, it was subjected to hot air drying (at 80 ° C for 5 minutes) to obtain a conductive particle-containing layer having a thickness of 10 μm supported by the PET film.

再者，代替黏著劑組成物的溶液，將與上述同樣地作所調製的黏著劑成分之溶液，塗佈到PET薄膜上。然後，對其進行熱風乾燥(在80℃ 5分鐘)，以得到被PET薄膜所支持的厚度10μ m之不含導電粒子層。Further, in place of the solution of the adhesive composition, a solution of the prepared adhesive component was applied to the PET film in the same manner as described above. Then, it was subjected to hot air drying (at 80 ° C for 5 minutes) to obtain a conductive particle-free layer having a thickness of 10 μm supported by the PET film.

使用習知的層壓機來貼合此等黏著膜彼此。藉此，得到圖7所示狀態的二層構成之電路連接材料。A conventional laminating machine is used to fit the adhesive films to each other. Thereby, a circuit connecting material of a two-layer structure in the state shown in Fig. 7 was obtained.

(連接構造的製作)(production of connection structure)

使用如上述所製造的電路連接材料，連接ITO基板(表面電阻<20Ω/□)與IC晶片，而形成連接構造。IC晶片係使用具有面積2500μm2 (50μm×50μm)、間距100μ m、高度20μ m的金凸塊者。ITO基板係使用在厚度1.1mm的玻璃板的表面上蒸鍍ITO而形成者。The ITO substrate (surface resistance <20 Ω/□) and the IC wafer were connected using the circuit connecting material manufactured as described above to form a connection structure. The IC wafer used was a gold bump having an area of 2500 μm 2 (50 μm × 50 μm), a pitch of 100 μm , and a height of 20 μm . The ITO substrate was formed by vapor-depositing ITO on the surface of a glass plate having a thickness of 1.1 mm.

於IC晶片與ITO基板之間，介著電路連接材料，使用壓接裝置(東麗工程株式會社製，商品名：FC－1200)進行連接。具體地，首先剝離含導電粒子層側的PET薄膜，以含導電粒子層與ITO基板成接觸的方式，將電路連接材料配置在ITO基板上置。然後，使用壓接裝置，進行臨時壓接(在溫度75℃、壓力1.0MPa進行2秒)。然後，剝離不含導電粒子側的PET薄膜後，以金凸塊與不含導電粒子層成接觸的方式，載置IC晶片。使用石英玻璃於底座，在溫度210℃、壓力80MPa下作5秒的加熱加壓，以得到具備連接部的連接構造。The connection between the IC wafer and the ITO substrate was carried out using a pressure bonding device (manufactured by Toray Engineering Co., Ltd., trade name: FC-1200) via a circuit connecting material. Specifically, the PET film containing the conductive particle layer side is first peeled off, and the circuit connecting material is placed on the ITO substrate so that the conductive particle layer is brought into contact with the ITO substrate. Then, temporary crimping was carried out using a pressure bonding device (for 2 seconds at a temperature of 75 ° C and a pressure of 1.0 MPa). Then, after peeling off the PET film containing no conductive particle side, the IC bump was placed so that the gold bump was in contact with the conductive particle-free layer. Quartz glass was used for the base and heated and pressurized for 5 seconds at a temperature of 210 ° C and a pressure of 80 MPa to obtain a connection structure having a connection portion.

(初期連接電阻的測定)(Measurement of initial connection resistance)

使用電阻測定機(股份有限公司ADVANTEST製,商品名：Digitalmulimeter)來測定如上述所製作的連接構造之連接部的初期電阻。再者，測定係在電極間流動1mA的電流而進行。The initial resistance of the connection portion of the connection structure produced as described above was measured using a resistance measuring machine (manufactured by ADVANTEST Co., Ltd., trade name: Digital mulimeter). Further, the measurement was carried out by flowing a current of 1 mA between the electrodes.

(鄰接電極間的絕緣性之評價)(Evaluation of insulation between adjacent electrodes)

鄰接的電極間之絕緣電阻係使用電阻測定機(股份有限公司ADVANTEST製、商品名：Digitalmulimeter)，藉由以下手續來測定。首先，在連接構造的連接部施加1分鐘的直流(DC)50V之電壓。然後，絕緣電阻的測定係對於電壓施加後的連接部，以2端子測定法來進行。再者，於上述電壓的施加中，使用電壓計(股份有限公司ADVANTEST製，商品名：ULTRA HIGH RESISTANCE METER)。The insulation resistance between the adjacent electrodes was measured by the following procedure using a resistance measuring machine (manufactured by ADVANTEST Co., Ltd., trade name: Digital mulimeter). First, a voltage of direct current (DC) of 50 V was applied for 1 minute at the connection portion of the connection structure. Then, the measurement of the insulation resistance was performed by a two-terminal measurement method for the connection portion after the voltage application. Further, in the application of the above voltage, a voltmeter (manufactured by ADVANTEST Co., Ltd., trade name: ULTRA HIGH RESISTANCE METER) was used.

(連接電阻的經時變化之評價)(Evaluation of the change in the resistance of the connection resistance)

其次，就連接部的電阻值之經時上升而言，藉由進行溫度循環試驗來作評價。溫度循環試驗係藉由將連接構造收納於溫度循環槽(ETAC製，商品名：NT1020)內，重複500次從室溫降溫到－40℃降溫、從－40℃升溫到100℃、及從100℃降溫到室溫的溫度循環而進行。在－40℃及100℃的保持時間皆為30分鐘。溫度循環試驗後的連接部分之電阻的測定，係與初期電阻的測定同樣地進行。Next, the temperature rise test of the connection portion was evaluated by a temperature cycle test. The temperature cycle test was carried out by storing the connection structure in a temperature cycle tank (manufactured by ETAC, trade name: NT1020), and repeating 500 times from room temperature to -40 ° C to cool down, from -40 ° C to 100 ° C, and from 100 °C is carried out by cooling the temperature to room temperature. The hold time at -40 ° C and 100 ° C was 30 minutes. The measurement of the electrical resistance of the connected portion after the temperature cycle test was carried out in the same manner as the measurement of the initial resistance.

表1中彙總顯示導電粒子的被覆率及構成絕緣被覆的有機高分子化合物之交聯度、以及所得到的結果。Table 1 shows collectively the coverage of the conductive particles and the degree of crosslinking of the organic polymer compound constituting the insulating coating, and the results obtained.

(實施例2)(Example 2)

除了代替交聯度20%的交聯丙烯酸樹脂，使用交聯度10%的交聯丙烯酸樹脂(總研化學製，商品名：MP系列，凝膠分率：8%)以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。導電粒子的被覆率係25%。In addition to the crosslinked acrylic resin having a crosslinking degree of 20%, a crosslinked acrylic resin having a degree of crosslinking of 10% (manufactured by Konica Chemical Co., Ltd., trade name: MP series, gel fraction: 8%) was used, and Example 1 was used. The same procedure was carried out to produce conductive particles, a circuit connecting material, and a connection structure. The coverage of the conductive particles was 25%.

(實施例3)(Example 3)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：10%，凝膠分率：8%)導入Hybridizer，製作如圖3所示構成的導電粒子。再者，Hybridizer的處理條件係回轉速度16000/分鐘、反應槽溫度60℃的條件。該導電粒子的被覆率係30%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 10%, gel fraction: 8%) which were produced in the same manner as in the example 1 were introduced into the Hybridizer. Conductive particles constructed as shown in Fig. 3 were produced. Further, the processing conditions of the Hybridizer were conditions of a revolution speed of 16,000/min and a reaction tank temperature of 60 °C. The coverage of the conductive particles was 30%.

(實施例4)(Example 4)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：13%，凝膠分率：10%)導入Hybridizer，製作如圖3所示構成的導電粒子。再者，Hybridizer的處理條件係回轉速度16000/分鐘、反應槽溫度60℃的條件。該導電粒子的被覆率係35%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 13%, gel fraction: 10%) which were produced in the same manner as in the example 1 were introduced into the Hybridizer. Conductive particles constructed as shown in Fig. 3 were produced. Further, the processing conditions of the Hybridizer were conditions of a revolution speed of 16,000/min and a reaction tank temperature of 60 °C. The coverage of the conductive particles was 35%.

(實施例5)(Example 5)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子及交聯丙烯酸樹脂導入Hybridizer，製作導電粒子。適宜地調整核粒子及導電粒子的投入重量、Hybridizer的回轉速度、反應槽溫度，得到如圖4所示構成的導電粒子。該導電粒子的被覆率係25%。Specifically, the core particles and the crosslinked acrylic resin similar to those produced in Example 1 were introduced into a Hybridizer to prepare conductive particles. The input weight of the core particles and the conductive particles, the rotation speed of the Hybridizer, and the temperature of the reaction vessel were appropriately adjusted to obtain conductive particles having the composition shown in FIG. The coverage of the conductive particles was 25%.

(實施例6)(Example 6)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：10%，凝膠分率：8%)導入Hybridizer，製作導電粒子。適宜地調整核粒子及導電粒子的投入重量、Hybridizer的回轉速度、反應槽溫度，得到如圖4所示構成的導電粒子。該導電粒子的被覆率係25%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 10%, gel fraction: 8%) which were produced in the same manner as in the example 1 were introduced into the Hybridizer. Make conductive particles. The input weight of the core particles and the conductive particles, the rotation speed of the Hybridizer, and the temperature of the reaction vessel were appropriately adjusted to obtain conductive particles having the composition shown in FIG. The coverage of the conductive particles was 25%.

(實施例7)(Example 7)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：13%，凝膠分率：10%)導入Hybridizer，製作導電粒子。適宜地調整核粒子及導電粒子的投入重量、Hybridizer的回轉速度、反應槽溫度，得到如圖4所示構成的導電粒子。該導電粒子的被覆率係25%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 13%, gel fraction: 10%) which were produced in the same manner as in the example 1 were introduced into the Hybridizer. Make conductive particles. The input weight of the core particles and the conductive particles, the rotation speed of the Hybridizer, and the temperature of the reaction vessel were appropriately adjusted to obtain conductive particles having the composition shown in FIG. The coverage of the conductive particles was 25%.

(比較例1)(Comparative Example 1)

除了不在核粒子的表面上形成絕緣被覆，使用該核粒子代替使用具備絕緣被覆的導電粒子以外，與實施例1同樣地進行，以製作電路連接材料及連接構造。An insulating coating was not formed on the surface of the core particles, and the core particles were used in the same manner as in Example 1 except that the conductive particles having the insulating coating were used, and a circuit connecting material and a connection structure were produced.

(比較例2)(Comparative Example 2)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：10%，凝膠分率：8%)導入Hybridizer，製作如圖3所示構成的導電粒子。再者，Hybridizer的處理條件係回轉速度16000/分鐘、反應槽溫度60℃的條件。該導電粒子的被覆率係10%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 10%, gel fraction: 8%) which were produced in the same manner as in the example 1 were introduced into the Hybridizer. Conductive particles constructed as shown in Fig. 3 were produced. Further, the processing conditions of the Hybridizer were conditions of a revolution speed of 16,000/min and a reaction tank temperature of 60 °C. The coverage of the conductive particles was 10%.

(比較例3)(Comparative Example 3)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：10%，凝膠分率：8%)導入Hybridizer，製作如圖3所示構成的導電粒子。再者，Hybridizer的處理條件係回轉速度16000/分鐘、反應槽溫度60℃的條件。該導電粒子的被覆率係50%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 10%, gel fraction: 8%) which were produced in the same manner as in the example 1 were introduced into the Hybridizer. Conductive particles constructed as shown in Fig. 3 were produced. Further, the processing conditions of the Hybridizer were conditions of a revolution speed of 16,000/min and a reaction tank temperature of 60 °C. The coverage of the conductive particles was 50%.

(比較例4)(Comparative Example 4)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：3%，凝膠分率：2%)導入Hybridizer，製作如圖3所示構成的導電粒子。再者，Hybridizer的處理條件係回轉速度16000/分鐘、反應槽溫度60℃的條件。該導電粒子的被覆率係50%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 3%, gel fraction: 2%) similar to those produced in Example 1 were introduced into Hybridizer. Conductive particles constructed as shown in Fig. 3 were produced. Further, the processing conditions of the Hybridizer were conditions of a revolution speed of 16,000/min and a reaction tank temperature of 60 °C. The coverage of the conductive particles was 50%.

(比較例5)(Comparative Example 5)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：20%，凝膠分率：18%)導入Hybridizer，製作如圖3所示構成的導電粒子。再者，Hybridizer的處理條件係回轉速度16000/分鐘、反應槽溫度60℃的條件。該導電粒子的被覆率係25%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 20%, gel fraction: 18%) which were produced in the same manner as in the example 1 were introduced into the Hybridizer. Conductive particles constructed as shown in Fig. 3 were produced. Further, the processing conditions of the Hybridizer were conditions of a revolution speed of 16,000/min and a reaction tank temperature of 60 °C. The coverage of the conductive particles was 25%.

(比較例6)(Comparative Example 6)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：10%，凝膠分率：8%)導入Hybridizer。適宜地調整核粒子及導電粒子的投入重量、Hybridizer的回轉速度、反應槽溫度，得到如圖4所示構成的導電粒子。該導電粒子的被覆率係10%。In other words, the core particles and the crosslinked acrylic resin (product name: MP series, degree of crosslinking: 10%, gel fraction: 8%) which were produced in the same manner as in Example 1 were introduced into a Hybridizer. The input weight of the core particles and the conductive particles, the rotation speed of the Hybridizer, and the temperature of the reaction vessel were appropriately adjusted to obtain conductive particles having the composition shown in FIG. The coverage of the conductive particles was 10%.

(比較例7)(Comparative Example 7)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：3%，凝膠分率：2%)導入Hybridizer。適宜地調整核粒子及導電粒子的投入重量、Hybridizer的回轉速度、反應槽溫度，得到如圖4所示構成的導電粒子。該導電粒子的被覆率係50%。Specifically, the same nuclear particles as those produced in Example 1 and a crosslinked acrylic resin (manufactured by Konica Chemical Co., Ltd., trade name: MP series, degree of crosslinking: 3%, gel fraction: 2%) were introduced into a Hybridizer. The input weight of the core particles and the conductive particles, the rotation speed of the Hybridizer, and the temperature of the reaction vessel were appropriately adjusted to obtain conductive particles having the composition shown in FIG. The coverage of the conductive particles was 50%.

(比較例8)(Comparative Example 8)

除了於核粒子的表面上如下述地形成絕緣被覆以外，與實施例1同樣地進行，以製作導電粒子、電路連接材料及連接構造。A conductive particle, a circuit connecting material, and a connection structure were produced in the same manner as in Example 1 except that an insulating coating was formed on the surface of the core particle as follows.

即，將與實施例1所製作者同樣的核粒子、及交聯丙烯酸樹脂(總研化學製，商品名：MP系列，交聯度：20%，凝膠分率：18%)導入Hybridizer。適宜地調整核粒子及導電粒子的投入重量、Hybridizer的回轉速度、反應槽溫度，得到如圖4所示構成的導電粒子。該導電粒子的被覆率係25%。Specifically, the same nuclear particles as those produced in Example 1 and a crosslinked acrylic resin (manufactured by Konica Chemical Co., Ltd., product name: MP series, degree of crosslinking: 20%, gel fraction: 18%) were introduced into a Hybridizer. The input weight of the core particles and the conductive particles, the rotation speed of the Hybridizer, and the temperature of the reaction vessel were appropriately adjusted to obtain conductive particles having the composition shown in FIG. The coverage of the conductive particles was 25%.

表1~4中顯示與實施例2~7及比較例1~8所製作的導電粒子有關的參數。又，亦合併與實施例1同樣進行的各種測定之結果，示於表1~4中。The parameters relating to the conductive particles produced in Examples 2 to 7 and Comparative Examples 1 to 8 are shown in Tables 1 to 4. Further, the results of various measurements performed in the same manner as in Example 1 are shown in Tables 1 to 4.

產業上的利用可能性Industrial utilization possibility

依照本發明，可提供於連接具有微細電路電極的電路構件彼此時，可達成連接部分的充分低之初期電阻值及鄰接的電路電極間之優異的絕緣性兩者，同時可充分抑制連接部分的電阻值之經時上升的導電粒子、黏著劑組成物及使用其的電路連接材料。又，可提供使用上述電路連接材料所連接的電路構件之連接構造，以及用於得到彼的電路構件之連接方法。According to the present invention, when the circuit members having the fine circuit electrodes are connected to each other, both the sufficiently low initial resistance value of the connection portion and the excellent insulation between the adjacent circuit electrodes can be achieved, and the connection portion can be sufficiently suppressed. Conductive particles having an increased resistance value over time, an adhesive composition, and a circuit connecting material using the same. Further, a connection structure of a circuit member to which the above-described circuit connection material is connected, and a connection method for obtaining the circuit member of the same can be provided.

1．．．核粒子1. . . Nuclear particle

1a．．．基材粒子1a. . . Substrate particle

1b．．．導電層1b. . . Conductive layer

2A．．．絕緣性粒子(絕緣被覆)2A. . . Insulating particles (insulation coating)

2B．．．絕緣性層(絕緣被覆)2B. . . Insulating layer (insulation coating)

10A、10B．．．導電粒子10A, 10B. . . Conductive particle

20．．．黏著劑成分20. . . Adhesive composition

30．．．第1電路構件30. . . First circuit component

31．．．電路基板(第1電路基板)31. . . Circuit board (first circuit board)

32．．．電路電極(第1電路電極)32. . . Circuit electrode (first circuit electrode)

40．．．第2電路構件40. . . Second circuit component

41．．．電路基板(第2電路基板)41. . . Circuit board (second circuit board)

42．．．電路電極(第2電路電極)42. . . Circuit electrode (second circuit electrode)

50、70．．．電路連接材料50, 70. . . Circuit connection material

60、60a、60b．．．支持體60, 60a, 60b. . . Support

70a．．．含導電粒子層70a. . . Conductive particle layer

70b．．．不含導電粒子層70b. . . No conductive particle layer

100．．．連接構造100. . . Connection structure

圖1係顯示與本發明有關的具有導電粒子的電路連接材料使用於電路電極間，連接電路電極彼此的狀態之截面圖。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a state in which circuit connecting materials having conductive particles according to the present invention are used between circuit electrodes to connect circuit electrodes to each other.

圖2係顯示與本發明有關的電路連接材料的一實施形態之截面圖。Fig. 2 is a cross-sectional view showing an embodiment of a circuit connecting material relating to the present invention.

圖3係顯示與本發明有關的導電粒子的一實施形態之截面圖。Fig. 3 is a cross-sectional view showing an embodiment of conductive particles related to the present invention.

圖4係顯示與本發明有關的本發明的導電粒子的另一實施形態之截面圖。Fig. 4 is a cross-sectional view showing another embodiment of the electroconductive particle of the present invention relating to the present invention.

圖5係顯示與本發明有關的電路連接材料設置在支持體上的狀態之截面圖。Fig. 5 is a cross-sectional view showing a state in which a circuit connecting material relating to the present invention is disposed on a support.

圖6係藉由示意截面圖來顯示與本發明有關的電路構件之連接方法的一實施形態之步驟圖。Fig. 6 is a flow chart showing an embodiment of a method of connecting circuit members according to the present invention by a schematic cross-sectional view.

圖7係顯示與本發明有關的電路連接材料被支持體所支撐的狀態之截面圖。Fig. 7 is a cross-sectional view showing a state in which a circuit connecting material relating to the present invention is supported by a support.

1．．．核粒子1. . . Nuclear particle

1a．．．基材粒子1a. . . Substrate particle

1b．．．導電層1b. . . Conductive layer

2A．．．絕緣性粒子(絕緣被覆)2A. . . Insulating particles (insulation coating)

10A．．．導電粒子10A. . . Conductive particle

Claims (15)

一種導電粒子，其特徵為具備具有導電性之核粒子、與設置於該核粒子表面上的含有交聯度8~20%的有機高分子化合物之絕緣被覆，下述式(1)所定義之被覆率為20~40%範圍者，前述核粒子係由構成中心部分的基材粒子及設置於前述基材粒子之表面上的導電層所構成者，前述絕緣被覆為設置於前述核粒子的表面上，含有前述有機高分子化合物的複數絕緣性粒子所構成者，前述絕緣性粒子的粒徑(D2 )與前述核粒子的粒徑(D1 )之比率(D2 /D1 )為1/20以上，1/10以下者； A conductive particle characterized by comprising a conductive core particle and an insulating coating containing an organic polymer compound having a crosslinking degree of 8 to 20% provided on the surface of the core particle, and is defined by the following formula (1) When the coverage is in the range of 20 to 40%, the core particles are composed of a substrate particle constituting a central portion and a conductive layer provided on a surface of the substrate particle, and the insulating coating is provided on the surface of the core particle. In the case where the plurality of insulating particles containing the organic polymer compound are formed, the ratio (D 2 /D 1 ) of the particle diameter (D 2 ) of the insulating particles to the particle diameter (D 1 ) of the core particles is 1 /20 or more, less than 1/10; 一種導電粒子，其特徵為具備具有導電性之核粒子、與設置於該核粒子表面上的含有交聯度8~20%的有機高分子化合物之絕緣被覆，下述式(1)所定義之被覆率為20~40%範圍者，前述核粒子係由構成中心部分的基材粒子及設置於前述基材粒子之表面上的導電層所構成者，前述絕緣被覆為設置於前述核粒子的表面上，含有前述有 機高分子化合物的複數絕緣性粒子所構成者，前述絕緣性層的厚度(T2 )與前述核粒子的粒徑(D1 )之比率(T2 /D1 )為1/20以上，1/10以下者； A conductive particle characterized by comprising a conductive core particle and an insulating coating containing an organic polymer compound having a crosslinking degree of 8 to 20% provided on the surface of the core particle, and is defined by the following formula (1) When the coverage is in the range of 20 to 40%, the core particles are composed of a substrate particle constituting a central portion and a conductive layer provided on a surface of the substrate particle, and the insulating coating is provided on the surface of the core particle. In the case where the plurality of insulating particles containing the organic polymer compound are formed, the ratio (T 2 /D 1 ) of the thickness (T 2 ) of the insulating layer to the particle diameter (D 1 ) of the core particle is 1/ 20 or more, less than 1/10; 如申請專利範圍第1項或第2項之導電粒子，其中前述有機高分子化合物的交聯度為8~15%。 The conductive particles according to claim 1 or 2, wherein the crosslinking degree of the organic polymer compound is 8 to 15%. 如申請專利範圍第1項或第2項之導電粒子，其中前述有機高分子化合物的交聯度為8~13%。 The conductive particles according to claim 1 or 2, wherein the crosslinking degree of the organic polymer compound is 8 to 13%. 如申請專利範圍第1項或第2項之導電粒子，其中前述被覆率為25~35%的範圍。 The conductive particles according to claim 1 or 2, wherein the coverage ratio is in the range of 25 to 35%. 如申請專利範圍第1項或第2項之導電粒子，其中前述被覆率為28~32%的範圍。 The conductive particles according to claim 1 or 2, wherein the coverage ratio is in the range of 28 to 32%. 一種黏著劑組成物，其特徵為具備具有黏著性的黏著劑成分、與分散於該黏著劑成分中之如申請專利範圍第1項或第2項之導電粒子者。 An adhesive composition characterized by having an adhesive component having adhesiveness and conductive particles dispersed in the adhesive component as in the first or second aspect of the patent application. 一種電路連接材料，其特徵為由如申請專利範圍第7項之黏著劑組成物所構成，使用於黏著電路構件彼此的同時，以電性連接各電路構件所具有之電路電極彼此者。 A circuit connecting material comprising the adhesive composition according to claim 7 of the patent application, wherein the circuit members are electrically connected to each other and the circuit electrodes of the circuit members are electrically connected to each other. 如申請專利範圍第8項之電路連接材料，其中必須以電氣性連接的一對電路構件中，至少一方的電路構件為具有凸塊面積為未達3000μm2 的凸塊之IC晶片。The circuit connecting material of claim 8, wherein at least one of the pair of circuit members that must be electrically connected is an IC chip having bumps having a bump area of less than 3000 μm 2 . 一種連接結構，其特徵為具備 相對配置的一對電路構件、與由如申請專利範圍第8項之電路連接材料的硬化物所構成，介於該一對電路構件之間，欲使各電路構件所具有之電路電極彼此可經電性連接，而黏著該電路構件彼此之連接部者。 a connection structure characterized by having a pair of circuit members disposed opposite to each other, and a cured material of a circuit connecting material according to claim 8 of the patent application, between the pair of circuit members, wherein the circuit electrodes of the circuit members are allowed to pass each other Electrically connected to the connection of the circuit members to each other. 如申請專利範圍第10項之連接結構，其中該一對電路構件之至少一個為IC晶片。 The connection structure of claim 10, wherein at least one of the pair of circuit members is an IC wafer. 如申請專利範圍第11項之連接結構，其中前述IC晶片為具有凸塊面積未達3000μm2 的凸塊者。The connection structure of claim 11, wherein the IC chip is a bump having a bump area of less than 3000 μm 2 . 如申請專利範圍第10項之連接結構，其中該一對電路構件各具有的電路電極之至少一表面係由選自金、銀、錫、釕、銠、鈀、鋨、銥、鉑及銦錫氧化物之至少1種物質所構成。 The connection structure of claim 10, wherein the pair of circuit members each have at least one surface of the circuit electrode selected from the group consisting of gold, silver, tin, antimony, bismuth, palladium, iridium, iridium, platinum, and indium tin. It is composed of at least one substance of an oxide. 如申請專利範圍第10項之連接結構，其中與該連接部接觸的該一對電路構件之該接觸面的至少一面為，具有至少一種選自氮化矽、聚矽氧烷化合物及聚醯亞胺樹脂的原料所構成之部分。 The connection structure of claim 10, wherein at least one side of the contact surface of the pair of circuit members in contact with the connection portion has at least one selected from the group consisting of tantalum nitride, polysiloxane compound, and poly A part of the raw material of the amine resin. 一種電路構件的連接方法，其特徵為使相對配置的一對電路構件之間介著如申請專利範圍第8項之電路連接材料，將全體進行加熱及加壓，形成由該電路連接材料的硬化物構成，介於該一對電路構件之間，欲使各電路構件所具有之電路電極彼此可經電性連接，而黏著該電路構件彼此之連接部，可得到具備該一對電路構件及該連接部之連接結構。 A method for connecting circuit members, characterized in that between a pair of circuit members disposed oppositely, a circuit connecting material according to item 8 of the patent application scope is applied, and the whole is heated and pressurized to form a hardening of the connecting material of the circuit. Between the pair of circuit members, the circuit electrodes of the circuit members are electrically connected to each other, and the connection portions of the circuit members are adhered to each other, thereby providing the pair of circuit members and the Connection structure of the connection portion.
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