TW201740392A - Conductive particles, insulated coated conductive particles, anisotropic conductive adhesive, connected structure and method for producing conductive particles - Google Patents

Conductive particles, insulated coated conductive particles, anisotropic conductive adhesive, connected structure and method for producing conductive particles Download PDF

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TW201740392A
TW201740392A TW106104324A TW106104324A TW201740392A TW 201740392 A TW201740392 A TW 201740392A TW 106104324 A TW106104324 A TW 106104324A TW 106104324 A TW106104324 A TW 106104324A TW 201740392 A TW201740392 A TW 201740392A
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particles
conductive
layer
conductive particles
inorganic particles
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TWI774656B (en
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Yoshinori Ejiri
Kunihiko Akai
Masashi Nakagawa
Yasushi Watanabe
Masahiko Noguchi
Shohei Yamazaki
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesive Tapes (AREA)

Abstract

Provided are conductive particles which enable the achievement of a good balance between excellent conduction reliability and insulation reliability in cases where the conductive particles are blended in an anisotropic conductive adhesive. Each conductive particle 100a comprises: a composite particle 103 that has a resin particle 101, which is coated with a cationic polymer, and non-conductive inorganic particles 102, which are arranged on the surface of the resin particle 101; and a metal layer that covers the composite particle 103. The non-conductive inorganic particles 102 are coated with a hydrophobilizing agent.

Description

導電粒子、絕緣被覆導電粒子、異向導電性接著劑、連接結構體及導電粒子的製造方法Conductive particles, insulating coated conductive particles, anisotropic conductive adhesive, bonded structure, and method for producing conductive particles

本發明是有關於一種導電粒子、絕緣被覆導電粒子、異向導電性接著劑、連接結構體及導電粒子的製造方法。The present invention relates to a method for producing conductive particles, insulating coated conductive particles, an anisotropic conductive adhesive, a bonded structure, and conductive particles.

於液晶顯示用玻璃面板（glass panel）上安裝液晶驅動用積體電路（Integrated Circuit，IC）的方式大致可分為玻璃上晶片（Chip-on-Glass，COG）安裝及可撓性基板上晶片（Chip-on-Flex，COF）安裝此兩種。於COG安裝中，使用含有導電粒子的異向導電性接著劑將液晶驅動用IC直接接合於玻璃面板上。另一方面，於COF安裝中，於具有金屬配線的可撓性帶（flexible tape）上接合液晶驅動用IC，使用含有導電粒子的異向導電性接著劑將該些構件接合於玻璃面板。此處所謂「異向性」，是指於加壓方向上導通，且於非加壓方向上保持絕緣性。Mounting a liquid crystal driving integrated circuit (IC) on a glass panel for liquid crystal display can be roughly classified into a chip-on-glass (COG) mounting and a wafer on a flexible substrate. (Chip-on-Flex, COF) install both. In the COG mounting, the liquid crystal driving IC is directly bonded to the glass panel using an anisotropic conductive adhesive containing conductive particles. On the other hand, in the COF mounting, the liquid crystal driving IC is bonded to a flexible tape having metal wiring, and the members are bonded to the glass panel using an anisotropic conductive adhesive containing conductive particles. Here, "anisotropy" means conduction in the pressurizing direction and insulation in the non-pressurizing direction.

先前，導電粒子一直是使用表面具有金層的導電粒子。表面具有金層的導電粒子於電阻值低的方面有利。金不易被氧化，因此即便於將表面具有金層的導電粒子長期間保存的情形時，亦可抑制該導電粒子的電阻值變高。Previously, conductive particles have been using conductive particles with a gold layer on their surface. The conductive particles having a gold layer on the surface are advantageous in terms of a low resistance value. Since gold is not easily oxidized, even when the conductive particles having a gold layer on the surface are stored for a long period of time, the electric resistance value of the conductive particles can be suppressed from becoming high.

近年來，為了應對節能化而抑制液晶驅動時的消耗電力，正在研究減少液晶驅動用IC中流通的電流量。因此，需求可達成較先前更低的電阻值的導電粒子。近年來，貴金屬的價格不斷高漲，故要求利用不使用貴金屬的導電粒子來降低電阻值。In recent years, in order to cope with energy saving and to suppress power consumption during liquid crystal driving, it has been studied to reduce the amount of current flowing through the liquid crystal driving IC. Therefore, it is required to achieve conductive particles having a lower resistance value than before. In recent years, the price of precious metals has been rising, so it is required to use conductive particles that do not use precious metals to lower the resistance value.

例如，於下述專利文獻1～專利文獻3中揭示有不使用貴金屬而僅使用鎳且具有低電阻值的導電粒子。具體而言，於專利文獻1中記載有以下方法：利用無電鍍鎳法中的鍍鎳液的自分解，於非導電粒子上同時形成鎳的微小凸起與鎳被膜，製造表面具有導電性的凸起的導電粒子。於專利文獻2中記載有以下方法：使成為芯物質的導電性物質附著於基材微粒子的表面後，對該基材微粒子進行無電鍍鎳，由此製造表面具有導電性的凸起的導電粒子。於專利文獻3中記載有以下方法：使成為芯物質的非導電性物質藉由化學鍵而吸附於基材微粒子的表面後，對該基材微粒子進行無電鍍鎳，由此製造表面具有導電性的凸起的導電粒子。 [現有技術文獻] [專利文獻]For example, Patent Literatures 1 to 3 below disclose conductive particles having a low resistance value using only a noble metal and using only nickel. Specifically, Patent Document 1 discloses a method of simultaneously forming a micro bump of a nickel and a nickel film on a non-conductive particle by self-decomposition of a nickel plating liquid in an electroless nickel plating method, and manufacturing a surface having conductivity. Raised conductive particles. Patent Document 2 describes a method in which a conductive material serving as a core material is adhered to a surface of a substrate fine particle, and then the substrate fine particles are subjected to electroless nickel plating to produce conductive conductive particles having a surface having conductivity. . Patent Document 3 describes a method in which a non-conductive material serving as a core material is adsorbed on a surface of a substrate fine particle by a chemical bond, and then the substrate fine particles are subjected to electroless nickel plating, thereby producing a surface having conductivity. Raised conductive particles. [Prior Art Document] [Patent Literature]

[專利文獻1]日本專利第5184612號公報 [專利文獻2]日本專利第4674096號公報 [專利文獻3]日本專利第4640531號公報[Patent Document 1] Japanese Patent No. 5184612 [Patent Document 2] Japanese Patent No. 4674096 (Patent Document 3) Japanese Patent No. 4640531

[發明所欲解決之課題] 於藉由異向導電性接著劑安裝晶片的情形時，必須降低所連接的電極間的導通電阻，而且充分提高晶片的鄰接電極間的絕緣電阻。近年來，電極的墊（pad）面積不斷變小，電極間所捕捉的粒子的個數不斷減少，因此要求對粒子逐一地均勻降低導通電阻。使用調配有所述專利文獻1～專利文獻3中記載的導電粒子的異向導電性接著劑的連接結構體於連接初期顯示出充分的連接電阻值。然而，於將該些連接結構體保存於高溫高濕下的情形時，有時連接電阻值上升。進而，使用調配有所述專利文獻1～專利文獻3中記載的導電粒子的異向導電性接著劑的連接結構體雖然於連接初期顯示出充分的絕緣電阻值，但於高溫高濕下進行長期間導通的遷移試驗後，有時絕緣電阻值降低。[Problem to be Solved by the Invention] When a wafer is mounted by an anisotropic conductive adhesive, it is necessary to lower the on-resistance between the electrodes to be connected, and to sufficiently increase the insulation resistance between adjacent electrodes of the wafer. In recent years, the pad area of the electrode has been continuously reduced, and the number of particles trapped between the electrodes has been continuously reduced. Therefore, it is required to uniformly reduce the on-resistance of the particles one by one. A bonded structure in which an anisotropic conductive adhesive having conductive particles described in Patent Documents 1 to 3 is used has a sufficient connection resistance value at the initial stage of connection. However, when the connection structure is stored under high temperature and high humidity, the connection resistance value may increase. Further, the bonded structure in which the anisotropic conductive adhesive agent of the conductive particles described in Patent Documents 1 to 3 is used has a sufficient insulation resistance value at the initial stage of connection, but is long under high temperature and high humidity. After the transition test during the conduction period, the insulation resistance value sometimes decreases.

本發明的一方面在於提供一種於用作調配至異向導電性接著劑中的導電粒子時可兼具優異的導通可靠性及絕緣可靠性的導電粒子及其製造方法。另外，本發明的一方面在於提供一種使用所述導電粒子的絕緣被覆導電粒子、異向導電性接著劑及連接結構體。 [用以解決課題之手段]An aspect of the present invention is to provide a conductive particle which can have excellent conduction reliability and insulation reliability when used as a conductive particle in an anisotropic conductive adhesive, and a method for producing the same. Further, an aspect of the present invention provides an insulating coated conductive particle, an anisotropic conductive adhesive, and a bonded structure using the conductive particles. [Means to solve the problem]

本發明的一態樣的導電粒子具備複合粒子及覆蓋複合粒子的金屬層，所述複合粒子具備藉由陽離子性聚合物被覆的樹脂粒子、及配置於樹脂粒子的表面的非導電性無機粒子，非導電性無機粒子是藉由疏水化處理劑而被覆。The conductive particles according to an aspect of the present invention include composite particles and a metal layer covering the composite particles, and the composite particles include resin particles coated with a cationic polymer and non-conductive inorganic particles disposed on a surface of the resin particles. The non-conductive inorganic particles are coated by a hydrophobizing agent.

根據該導電粒子，樹脂粒子是藉由陽離子性聚合物而被覆，非導電性無機粒子是藉由疏水化處理劑而被覆。非導電性無機粒子的表面的界達電位藉由疏水化而向負值（minus）偏移。藉此，靜電力於樹脂粒子與非導電性無機粒子之間發揮作用，非導電性無機粒子不易自樹脂粒子的表面脫落。因此，配置於樹脂粒子表面的非導電性無機粒子的個數的控制變容易，並且於複合粒子上形成良好的凸起。因此，即便於將使用調配有導電粒子的異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。此外，自樹脂粒子脫落的非導電性無機粒子的個數減少，故於複合粒子上不易產生異常地成長的凸起。因此，於將導電粒子調配至異向導電性接著劑中的情形等時，該導電粒子彼此不易導通，導電粒子的絕緣可靠性亦提高。因此，藉由將所述導電粒子調配至異向導電性接著劑中，可兼具優異的導通可靠性及絕緣可靠性。According to the conductive particles, the resin particles are coated with a cationic polymer, and the non-conductive inorganic particles are coated with a hydrophobizing agent. The boundary potential of the surface of the non-conductive inorganic particles is shifted to a negative value by hydrophobization. Thereby, the electrostatic force acts between the resin particles and the non-conductive inorganic particles, and the non-conductive inorganic particles are less likely to fall off from the surface of the resin particles. Therefore, the control of the number of non-conductive inorganic particles disposed on the surface of the resin particles is facilitated, and good projections are formed on the composite particles. Therefore, even when the connection structure using the anisotropic conductive adhesive prepared with the conductive particles is stored under high temperature and high humidity, the conduction reliability is also improved. Further, since the number of non-conductive inorganic particles that have fallen off from the resin particles is reduced, it is difficult to cause abnormally grown projections on the composite particles. Therefore, when the conductive particles are blended into the anisotropic conductive adhesive or the like, the conductive particles are less likely to conduct each other, and the insulating reliability of the conductive particles is also improved. Therefore, by blending the conductive particles into the anisotropic conductive adhesive, excellent conduction reliability and insulation reliability can be achieved.

疏水化處理劑亦可選自由矽氮烷系疏水化處理劑、矽氧烷系疏水化處理劑、矽烷系疏水化處理劑及鈦酸酯系疏水化處理劑所組成的群組中。The hydrophobizing agent may also be selected from the group consisting of a hydrazine-based hydrophobizing agent, a decane-based hydrophobizing agent, a decane-based hydrophobizing agent, and a titanate-based hydrophobizing agent.

疏水化處理劑亦可選自由六甲基二矽氮烷、聚二甲基矽氧烷及N,N-二甲基胺基三甲基矽烷所組成的群組中。The hydrophobizing agent may also be selected from the group consisting of hexamethyldiazepine, polydimethyloxane, and N,N-dimethylaminotrimethylnonane.

由甲醇滴定法所得的非導電性無機粒子的疏水化度亦可為30%以上。於該情形時，充分的靜電力於非導電性無機粒子與樹脂粒子之間發揮作用。The degree of hydrophobicity of the non-conductive inorganic particles obtained by the methanol titration method may be 30% or more. In this case, a sufficient electrostatic force acts between the non-conductive inorganic particles and the resin particles.

非導電性無機粒子亦可藉由靜電力而接著於樹脂粒子。The non-conductive inorganic particles may be attached to the resin particles by an electrostatic force.

樹脂粒子與非導電性無機粒子的界達電位之差亦可於pH值1以上且pH值11以下時為30 mV以上。於該情形時，樹脂粒子與非導電性無機粒子藉由靜電力而牢固地接著。因此，可於用以形成導電粒子中的金屬層的前處理步驟、金屬層的形成步驟等時，合適地抑制非導電性無機粒子自樹脂粒子脫落。The difference in the boundary potential between the resin particles and the non-conductive inorganic particles may be 30 mV or more when the pH is 1 or more and the pH is 11 or less. In this case, the resin particles and the non-conductive inorganic particles are firmly adhered by electrostatic force. Therefore, when the pretreatment step of forming the metal layer in the conductive particles, the step of forming the metal layer, or the like, the non-conductive inorganic particles are suitably prevented from falling off from the resin particles.

陽離子性聚合物亦可選自由多胺、聚亞胺、聚醯胺、聚二烯丙基二甲基氯化銨、聚乙烯基胺、聚乙烯基吡啶、聚乙烯基咪唑及聚乙烯基吡咯啶酮所組成的群組中。The cationic polymer may also be selected from polyamines, polyimines, polyamines, polydiallyldimethylammonium chloride, polyvinylamines, polyvinylpyridines, polyvinylimidazoles and polyvinylpyrroles. In a group consisting of ketones.

陽離子性聚合物亦可為聚乙烯亞胺。於該情形時，陽離子性聚合物的電荷密度變高，故可良好地抑制非導電性無機粒子的脫落。The cationic polymer may also be a polyethyleneimine. In this case, since the charge density of the cationic polymer is increased, the fall of the non-conductive inorganic particles can be satisfactorily suppressed.

非導電性無機粒子的平均粒徑亦可為25 nm以上且120 nm以下。於該情形時，導電粒子可具有多數個緻密的凸起，並且非導電性無機粒子不易自樹脂粒子脫落。The average particle diameter of the non-conductive inorganic particles may be 25 nm or more and 120 nm or less. In this case, the conductive particles may have a plurality of dense protrusions, and the non-conductive inorganic particles are not easily detached from the resin particles.

樹脂粒子的平均粒徑亦可為1 μm以上且10 μm以下。於該情形時，例如於使用含有導電粒子的異向導電性接著劑製作連接結構體時，該異向導電性接著劑的導電性等不易因該連接結構體的電極的形狀（高度）的不均一而變化。The average particle diameter of the resin particles may be 1 μm or more and 10 μm or less. In this case, for example, when a bonded structure is produced using an anisotropic conductive adhesive containing conductive particles, the conductivity of the anisotropic conductive adhesive or the like is less likely to be caused by the shape (height) of the electrode of the bonded structure. Uniform and changing.

非導電性無機粒子亦可選自由氧化矽、氧化鋯、氧化鋁及金剛石所組成的群組中。The non-conductive inorganic particles may also be selected from the group consisting of cerium oxide, zirconium oxide, aluminum oxide and diamond.

金屬層亦可具有含有鎳的第一層。於該情形時，可提高導電粒子的硬度。藉此，即便於該導電粒子經壓縮的情形時，形成於非導電性無機粒子上而成為凸起部分的第一層亦不易被壓壞。因此，導電粒子可獲得低的導通電阻。The metal layer may also have a first layer containing nickel. In this case, the hardness of the conductive particles can be increased. Thereby, even when the conductive particles are compressed, the first layer which is formed on the non-conductive inorganic particles and becomes a convex portion is not easily crushed. Therefore, the conductive particles can obtain low on-resistance.

金屬層亦可具有設於第一層上的第二層，且第二層含有選自由貴金屬及鈷所組成的群組中的金屬。於該情形時，導電粒子可獲得更低的導通電阻。The metal layer may also have a second layer disposed on the first layer, and the second layer contains a metal selected from the group consisting of noble metals and cobalt. In this case, the conductive particles can obtain a lower on-resistance.

本發明的另一態樣的絕緣被覆導電粒子具備所述導電粒子及將該導電粒子的金屬層的外表面的至少一部分被覆的絕緣性被覆部。Another aspect of the insulating coated conductive particles of the present invention includes the conductive particles and an insulating coating portion that covers at least a part of an outer surface of the metal layer of the conductive particles.

根據該絕緣被覆導電粒子，樹脂粒子是藉由陽離子性聚合物而被覆，非導電性無機粒子是藉由疏水化處理劑而被覆。非導電性無機粒子的表面的界達電位藉由疏水化而向負值偏移。藉此，靜電力於樹脂粒子與非導電性無機粒子之間發揮作用，非導電性無機粒子不易自樹脂粒子的表面脫落。因此，配置於樹脂粒子表面的非導電性無機粒子的個數的控制變容易，並且於複合粒子上形成良好的凸起。因此，即便於將使用調配有導電粒子的異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。此外，自樹脂粒子脫落的非導電性無機粒子的個數減少，故於複合粒子上不易產生異常地成長的凸起。進而，藉由設於金屬層的外表面的絕緣性被覆部，絕緣被覆導電粒子的金屬層彼此不易接觸。藉此，於將絕緣被覆導電粒子調配至異向導電性接著劑中的情形等時，絕緣被覆導電粒子彼此不易導通，使用該絕緣被覆導電粒子的連接結構體等的絕緣可靠性亦合適地提高。因此，藉由將所述導電粒子調配至異向導電性接著劑中，可兼具優異的導通可靠性及絕緣可靠性。The conductive particles are coated with the conductive particles, and the resin particles are coated with a cationic polymer, and the non-conductive inorganic particles are coated with a hydrophobizing agent. The boundary potential of the surface of the non-conductive inorganic particles is shifted to a negative value by hydrophobization. Thereby, the electrostatic force acts between the resin particles and the non-conductive inorganic particles, and the non-conductive inorganic particles are less likely to fall off from the surface of the resin particles. Therefore, the control of the number of non-conductive inorganic particles disposed on the surface of the resin particles is facilitated, and good projections are formed on the composite particles. Therefore, even when the connection structure using the anisotropic conductive adhesive prepared with the conductive particles is stored under high temperature and high humidity, the conduction reliability is also improved. Further, since the number of non-conductive inorganic particles that have fallen off from the resin particles is reduced, it is difficult to cause abnormally grown projections on the composite particles. Further, the insulating coating portion provided on the outer surface of the metal layer makes it difficult for the metal layers of the insulating coated conductive particles to be in contact with each other. When the insulating coated conductive particles are blended in the anisotropic conductive adhesive or the like, the insulating coated conductive particles are less likely to be electrically connected to each other, and the insulating reliability of the bonded structure using the insulating coated conductive particles is also suitably improved. . Therefore, by blending the conductive particles into the anisotropic conductive adhesive, excellent conduction reliability and insulation reliability can be achieved.

本發明的另一態樣的連接結構體具備具有第一電路電極的第一電路構件、與第一電路構件相對向且具有第二電路電極的第二電路構件、以及配置於第一電路構件及第二電路構件之間且含有所述導電粒子的連接部，連接部於將第一電路電極與第二電路電極以相對向的方式配置的狀態下將第一電路構件及第二電路構件相互連接，第一電路電極與第二電路電極經由變形狀態的導電粒子而相互電性連接。A connection structure according to another aspect of the present invention includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode facing the first circuit member, and being disposed on the first circuit member and a connection portion between the second circuit members and including the conductive particles, and the connection portion connects the first circuit member and the second circuit member to each other in a state in which the first circuit electrode and the second circuit electrode are disposed opposite to each other The first circuit electrode and the second circuit electrode are electrically connected to each other via the conductive particles in a deformed state.

根據該連接結構體，藉由具備含有所述導電粒子的連接部，即便於高溫高濕下保存的情形時，導通可靠性亦提高。此外，於連接部內自樹脂粒子脫落的非導電性無機粒子的個數減少，故於複合粒子上不易產生異常地成長的凸起。因此，於連接部內導電粒子彼此不易導通，絕緣可靠性亦合適地提高。因此，可提供兼具優異的導通可靠性及絕緣可靠性的連接結構體。According to the connection structure, by providing the connection portion containing the conductive particles, the conduction reliability is improved even when stored under high temperature and high humidity. Further, since the number of non-conductive inorganic particles which are detached from the resin particles in the connection portion is reduced, it is difficult to cause abnormally grown projections on the composite particles. Therefore, the conductive particles are hard to be electrically connected to each other in the connection portion, and the insulation reliability is also suitably improved. Therefore, it is possible to provide a connection structure which has excellent conduction reliability and insulation reliability.

本發明的另一態樣的連接結構體具備具有第一電路電極的第一電路構件、與第一電路構件相對向且具有第二電路電極的第二電路構件、以及配置於第一電路構件及第二電路構件之間且含有所述絕緣被覆導電粒子的連接部，連接部於將第一電路電極與第二電路電極以相對向的方式配置的狀態下將第一電路構件及第二電路構件相互連接，第一電路電極與第二電路電極經由變形狀態的絕緣被覆導電粒子而相互電性連接。A connection structure according to another aspect of the present invention includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode facing the first circuit member, and being disposed on the first circuit member and a connection portion between the second circuit members and the insulating coated conductive particles, and the connection portion connects the first circuit member and the second circuit member in a state in which the first circuit electrode and the second circuit electrode are disposed to face each other The first circuit electrode and the second circuit electrode are electrically connected to each other via the insulating coated particles in a deformed state.

根據該連接結構體，藉由具備含有所述絕緣被覆導電粒子的連接部，即便於高溫高濕下保存的情形時，導通可靠性亦提高。此外，於連接部內自樹脂粒子脫落的非導電性無機粒子的個數減少，故於複合粒子上不易產生異常地成長的凸起。進而，藉由設於金屬層的外表面的絕緣性被覆部，絕緣被覆導電粒子的金屬層彼此不易接觸。因此，於連接部內絕緣被覆導電粒子彼此不易導通，絕緣可靠性亦合適地提高。因此，可提供兼具優異的導通可靠性及絕緣可靠性的連接結構體。According to the connection structure, by providing the connection portion including the insulating-coated conductive particles, the conduction reliability is improved even when stored under high temperature and high humidity. Further, since the number of non-conductive inorganic particles which are detached from the resin particles in the connection portion is reduced, it is difficult to cause abnormally grown projections on the composite particles. Further, the insulating coating portion provided on the outer surface of the metal layer makes it difficult for the metal layers of the insulating coated conductive particles to be in contact with each other. Therefore, the insulating coated conductive particles are less likely to be electrically connected to each other in the connection portion, and the insulation reliability is also suitably improved. Therefore, it is possible to provide a connection structure which has excellent conduction reliability and insulation reliability.

本發明的另一態樣的異向導電性接著劑具備所述導電粒子及分散有導電粒子的接著劑。Another aspect of the present invention provides an anisotropic conductive adhesive comprising the conductive particles and an adhesive in which conductive particles are dispersed.

根據該異向導電性接著劑，樹脂粒子是藉由陽離子性聚合物而被覆，非導電性無機粒子是藉由疏水化處理劑而被覆。非導電性無機粒子的表面的界達電位藉由疏水化而向負值偏移。藉此，靜電力於樹脂粒子與非導電性無機粒子之間發揮作用，非導電性無機粒子不易自樹脂粒子的表面脫落。因此，配置於樹脂粒子表面的非導電性無機粒子的個數的控制變容易，並且於複合粒子上形成良好的凸起。因此，即便於將使用該異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。此外，自樹脂粒子脫落的非導電性無機粒子的個數減少，故於複合粒子上不易產生異常地成長的凸起。進而，脫落的非導電性無機粒子經金屬塗佈而形成的金屬異物不易存在於接著劑中。因此，導電粒子彼此不易良好地導通，使用該異向導電性接著劑的連接結構體等的絕緣可靠性亦合適地提高。According to the anisotropic conductive adhesive, the resin particles are coated with a cationic polymer, and the non-conductive inorganic particles are coated with a hydrophobizing agent. The boundary potential of the surface of the non-conductive inorganic particles is shifted to a negative value by hydrophobization. Thereby, the electrostatic force acts between the resin particles and the non-conductive inorganic particles, and the non-conductive inorganic particles are less likely to fall off from the surface of the resin particles. Therefore, the control of the number of non-conductive inorganic particles disposed on the surface of the resin particles is facilitated, and good projections are formed on the composite particles. Therefore, even when the connection structure using the anisotropic conductive adhesive is stored under high temperature and high humidity, the conduction reliability is improved. Further, since the number of non-conductive inorganic particles that have fallen off from the resin particles is reduced, it is difficult to cause abnormally grown projections on the composite particles. Further, the metal foreign matter formed by the metal coating of the non-conductive inorganic particles that have fallen off is less likely to be present in the adhesive. Therefore, the conductive particles are not easily electrically connected to each other, and the insulation reliability of the bonded structure or the like using the anisotropic conductive adhesive is also suitably improved.

本發明的另一態樣的異向導電性接著劑具備所述絕緣被覆導電粒子及分散有絕緣被覆導電粒子的接著劑。Another aspect of the present invention provides an anisotropic conductive adhesive comprising the insulating coated conductive particles and an adhesive in which the insulating coated conductive particles are dispersed.

根據該異向導電性接著劑，樹脂粒子是藉由陽離子性聚合物而被覆，非導電性無機粒子是藉由疏水化處理劑而被覆。非導電性無機粒子的表面的界達電位藉由疏水化而向負值偏移。藉此，靜電力於樹脂粒子與非導電性無機粒子之間發揮作用，非導電性無機粒子不易自樹脂粒子的表面脫落。因此，配置於樹脂粒子表面的非導電性無機粒子的個數的控制變容易，並且於複合粒子上形成良好的凸起。因此，即便於將使用該異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。另外，自樹脂粒子脫落的非導電性無機粒子的個數減少，故於複合粒子上不易產生異常地成長的凸起。此外，藉由設於金屬層的外表面的絕緣性被覆部，導電粒子的金屬層彼此不易接觸。進而，脫落的非導電性無機粒子經金屬塗佈而形成的金屬異物不易存在於接著劑中。因此，導電粒子彼此不易良好地導通，使用該導電粒子的連接結構體等的絕緣可靠性亦合適地提高。According to the anisotropic conductive adhesive, the resin particles are coated with a cationic polymer, and the non-conductive inorganic particles are coated with a hydrophobizing agent. The boundary potential of the surface of the non-conductive inorganic particles is shifted to a negative value by hydrophobization. Thereby, the electrostatic force acts between the resin particles and the non-conductive inorganic particles, and the non-conductive inorganic particles are less likely to fall off from the surface of the resin particles. Therefore, the control of the number of non-conductive inorganic particles disposed on the surface of the resin particles is facilitated, and good projections are formed on the composite particles. Therefore, even when the connection structure using the anisotropic conductive adhesive is stored under high temperature and high humidity, the conduction reliability is improved. Further, since the number of non-conductive inorganic particles that have fallen off from the resin particles is reduced, it is less likely to cause abnormal growth of the projections on the composite particles. Further, the metal layers of the conductive particles are less likely to contact each other by the insulating coating portion provided on the outer surface of the metal layer. Further, the metal foreign matter formed by the metal coating of the non-conductive inorganic particles that have fallen off is less likely to be present in the adhesive. Therefore, the conductive particles are not easily electrically connected to each other, and the insulation reliability of the bonded structure or the like using the conductive particles is also suitably improved.

所述異向導電性接著劑中，接著劑亦可為膜狀。In the anisotropic conductive adhesive, the adhesive may also be in the form of a film.

本發明的另一態樣的連接結構體具備具有第一電路電極的第一電路構件、與第一電路構件相對向且具有第二電路電極的第二電路構件、以及將第一電路構件及第二電路構件接著的所述異向導電性接著劑，且第一電路電極與第二電路電極彼此相對向，並且藉由異向導電性接著劑而相互電性連接。A connection structure according to another aspect of the present invention includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode facing the first circuit member, and a first circuit member and a first circuit member The two circuit members are followed by the anisotropic conductive adhesive, and the first circuit electrode and the second circuit electrode are opposed to each other and electrically connected to each other by an anisotropic conductive adhesive.

根據該連接結構體，藉由所述異向導電性接著劑將第一電路構件及第二電路構件相互電性連接，藉此可兼具優異的導通可靠性及絕緣可靠性。According to the connection structure, the first circuit member and the second circuit member are electrically connected to each other by the anisotropic conductive adhesive, whereby excellent conduction reliability and insulation reliability can be achieved.

本發明的另一態樣的導電粒子的製造方法包括：第一被覆步驟，藉由陽離子性聚合物將樹脂粒子被覆；第二被覆步驟，藉由疏水化處理劑將非導電性無機粒子被覆；粒子形成步驟，藉由靜電力將非導電性無機粒子接著於樹脂粒子的表面，形成複合粒子；以及第三被覆步驟，藉由金屬層將複合粒子被覆。A method for producing conductive particles according to another aspect of the present invention includes: a first coating step of coating the resin particles with a cationic polymer; and a second coating step of coating the non-conductive inorganic particles with a hydrophobizing agent; In the particle forming step, the non-conductive inorganic particles are attached to the surface of the resin particles by electrostatic force to form composite particles, and the third coating step is performed by coating the composite particles with the metal layer.

根據該製造方法，於第一被覆步驟中藉由陽離子性聚合物將樹脂粒子被覆，於第二被覆步驟中藉由疏水化處理劑將非導電性無機粒子被覆。非導電性無機粒子的表面的界達電位藉由疏水化而向負值偏移。藉此，於粒子形成步驟中靜電力於樹脂粒子與非導電性無機粒子之間發揮作用，故即便於進行第三被覆步驟的情形時，非導電性無機粒子亦不易自樹脂粒子的表面脫落。因此，可容易地控制配置於樹脂粒子表面的非導電性無機粒子的個數，並且可於複合粒子上形成良好的凸起。因此，即便於將使用調配有導電粒子的異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。此外，可減少自樹脂粒子脫落的非導電性無機粒子的個數，因此於複合粒子上不易產生異常地成長的凸起。因此，導電粒子彼此不易導通，使用該導電粒子的連接結構體等的絕緣可靠性亦提高。According to this production method, the resin particles are coated by the cationic polymer in the first coating step, and the non-conductive inorganic particles are coated by the hydrophobizing agent in the second coating step. The boundary potential of the surface of the non-conductive inorganic particles is shifted to a negative value by hydrophobization. Thereby, since the electrostatic force acts between the resin particles and the non-conductive inorganic particles in the particle formation step, even when the third coating step is performed, the non-conductive inorganic particles are less likely to fall off from the surface of the resin particles. Therefore, the number of non-conductive inorganic particles disposed on the surface of the resin particles can be easily controlled, and good protrusions can be formed on the composite particles. Therefore, even when the connection structure using the anisotropic conductive adhesive prepared with the conductive particles is stored under high temperature and high humidity, the conduction reliability is also improved. Further, since the number of non-conductive inorganic particles that have fallen off from the resin particles can be reduced, it is less likely to cause abnormal growth of the protrusions on the composite particles. Therefore, the conductive particles are less likely to be electrically connected to each other, and the insulation reliability of the bonded structure or the like using the conductive particles is also improved.

第三被覆步驟中，亦可藉由無電鍍敷且以含有鎳的第一層將複合粒子被覆。藉此，即便於該導電粒子經壓縮的情形時，形成於非導電性無機粒子上而成為凸起部分的第一層亦不易被壓壞。因此，導電粒子可獲得低的導通電阻。In the third coating step, the composite particles may be coated by electroless plating and with a first layer containing nickel. Thereby, even when the conductive particles are compressed, the first layer which is formed on the non-conductive inorganic particles and becomes a convex portion is not easily crushed. Therefore, the conductive particles can obtain low on-resistance.

第三被覆步驟中，亦可藉由含有選自由貴金屬及鈷所組成的群組中的金屬的第二層將經第一層覆蓋的複合粒子被覆。於該情形時，導電粒子可獲得更低的導通電阻。In the third coating step, the composite particles covered by the first layer may also be coated by a second layer containing a metal selected from the group consisting of noble metals and cobalt. In this case, the conductive particles can obtain a lower on-resistance.

樹脂粒子與非導電性無機粒子的界達電位之差亦可於pH值1以上且pH值11以下時為30 mV以上。於該情形時，樹脂粒子與非導電性無機粒子藉由靜電力而牢固地接著。因此，於第三被覆步驟時等，可合適地抑制非導電性無機粒子自樹脂粒子脫落。 [發明的效果]The difference in the boundary potential between the resin particles and the non-conductive inorganic particles may be 30 mV or more when the pH is 1 or more and the pH is 11 or less. In this case, the resin particles and the non-conductive inorganic particles are firmly adhered by electrostatic force. Therefore, in the third coating step or the like, the non-conductive inorganic particles can be suitably prevented from falling off from the resin particles. [Effects of the Invention]

根據本發明的一方面，提供一種於用作調配至異向導電性接著劑中的導電粒子時可兼具優異的導通可靠性及絕緣可靠性的導電粒子及其製造方法。另外，根據本發明的一方面，提供一種使用該導電粒子的絕緣被覆導電粒子、異向導電性接著劑及連接結構體。According to an aspect of the present invention, there is provided a conductive particle which can have both excellent conduction reliability and insulation reliability when used as a conductive particle formulated in an anisotropic conductive adhesive, and a method for producing the same. Further, according to an aspect of the present invention, an insulating coated conductive particle, an anisotropic conductive adhesive, and a bonded structure using the conductive particles are provided.

以下，一面參照圖式一面對本發明的實施形態加以詳細說明。再者，圖式中對相同部分或相當部分標註相同符號，省略重複說明。另外，上下左右等位置關係只要無特別說明，則視為基於圖式所示的位置關係。進而，圖式的尺寸比率不限於圖示的比率。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or equivalent components are designated by the same reference numerals, and the repeated description is omitted. Further, the positional relationship such as up, down, left, and right is regarded as a positional relationship based on the drawing unless otherwise specified. Further, the dimensional ratio of the drawings is not limited to the illustrated ratio.

（第一實施形態） 以下，對第一實施形態的導電粒子加以說明。(First embodiment) Hereinafter, conductive particles of the first embodiment will be described.

＜導電粒子＞ 圖1為表示第一實施形態的導電粒子的示意剖面圖。圖1所示的導電粒子100a具備複合粒子103及覆蓋複合粒子103的第一層104，所述複合粒子103具有構成導電粒子的核（core）的樹脂粒子101、及配置於該樹脂粒子101的表面的非導電性無機粒子102。反映接著於樹脂粒子101的非導電性無機粒子102的形狀而於第一層104的表面形成有凸起109。樹脂粒子101是藉由後述陽離子性聚合物而被覆。非導電性無機粒子102是藉由後述疏水性處理劑而被覆。第一層104為至少包含金屬的導電層。第一層104可為金屬層，亦可為合金層。<Electrically conductive particles> Fig. 1 is a schematic cross-sectional view showing conductive particles according to the first embodiment. The conductive particles 100a shown in FIG. 1 include composite particles 103 and a first layer 104 covering the composite particles 103. The composite particles 103 have resin particles 101 constituting a core of conductive particles, and are disposed on the resin particles 101. Non-conductive inorganic particles 102 on the surface. A protrusion 109 is formed on the surface of the first layer 104 in response to the shape of the non-conductive inorganic particles 102 following the resin particles 101. The resin particles 101 are coated by a cationic polymer described later. The non-conductive inorganic particles 102 are coated by a hydrophobic treatment agent to be described later. The first layer 104 is a conductive layer containing at least a metal. The first layer 104 can be a metal layer or an alloy layer.

導電粒子100a的平均粒徑例如可為1 μm以上，亦可為2 μm以上。導電粒子100a的平均粒徑例如可為10 μm以下，亦可為5 μm以下。即，導電粒子100a的平均粒徑例如為1 μm～10 μm。藉由導電粒子100a的平均粒徑為所述範圍內，例如於使用含有導電粒子100a的異向導電性接著劑製作連接結構體的情形時，該異向導電性接著劑的導電性等不易因該連接結構體的電極形狀（高度）的不均一而變化。導電粒子100a的平均粒徑亦可設定為藉由以下方式所得的平均值：藉由使用掃描式電子顯微鏡（Scanning Electron Microscope，以下稱為「SEM」）的觀察來進行任意300個導電粒子的粒徑測定。導電粒子100a具有凸起109，故導電粒子100a的粒徑是設定為利用SEM所拍攝的圖像中與導電粒子100a外接的圓的直徑。為了提高精度來測定導電粒子100a的平均粒徑，可使用庫爾特計數器（Coulter Counter）等市售的裝置。於該情形時，若進行50000個導電粒子的粒徑測定，則可高精度地測定平均粒徑。例如亦可藉由利用庫勒粒度分析計數儀（COULER MULTISIZER）II（貝克曼庫爾特（Beckman Coulter）股份有限公司製造，商品名）測定50000個導電粒子，而測定導電粒子100a的平均粒徑。The average particle diameter of the conductive particles 100a may be, for example, 1 μm or more, or may be 2 μm or more. The average particle diameter of the conductive particles 100a may be, for example, 10 μm or less, or may be 5 μm or less. That is, the average particle diameter of the conductive particles 100a is, for example, 1 μm to 10 μm. When the average particle diameter of the conductive particles 100a is within the above range, for example, when a bonded structure is produced using an anisotropic conductive adhesive containing conductive particles 100a, the conductivity of the anisotropic conductive adhesive is not easily caused. The electrode structure (height) of the connection structure changes unevenly. The average particle diameter of the conductive particles 100a may be set to an average value obtained by performing observation of any 300 conductive particles by observation using a scanning electron microscope (hereinafter referred to as "SEM"). Diameter measurement. Since the conductive particles 100a have the protrusions 109, the particle diameter of the conductive particles 100a is set to the diameter of a circle circumscribing the conductive particles 100a in the image taken by the SEM. In order to measure the average particle diameter of the conductive particles 100a in order to improve the accuracy, a commercially available device such as a Coulter Counter can be used. In this case, when the particle diameter of 50,000 conductive particles is measured, the average particle diameter can be measured with high precision. For example, the average particle diameter of the conductive particles 100a can be measured by measuring 50,000 conductive particles using a COULER MULTISIZER II (manufactured by Beckman Coulter Co., Ltd., trade name). .

＜樹脂粒子＞ 樹脂粒子101是由有機樹脂所構成。有機樹脂可列舉：聚甲基丙烯酸甲酯、聚丙烯酸甲酯等(甲基)丙烯酸樹脂；聚乙烯、聚丙烯等聚烯烴樹脂；聚異丁烯樹脂；聚丁二烯樹脂等。樹脂粒子101亦可使用交聯(甲基)丙烯酸粒子、交聯聚苯乙烯粒子等將有機樹脂交聯所得的粒子。樹脂粒子可由所述有機樹脂的一種構成，亦可將所述有機樹脂的兩種以上組合而構成。有機樹脂不限定於所述樹脂。<Resin Particles> The resin particles 101 are composed of an organic resin. Examples of the organic resin include (meth)acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polyolefin resins such as polyethylene and polypropylene; polyisobutylene resins; and polybutadiene resins. The resin particles 101 may be obtained by crosslinking the organic resin with crosslinked (meth)acrylic particles or crosslinked polystyrene particles. The resin particles may be composed of one type of the organic resin, or may be composed of two or more kinds of the organic resins. The organic resin is not limited to the resin.

樹脂粒子101為球狀。樹脂粒子101的平均粒徑例如可為1 μm以上且10 μm以下。樹脂粒子101的平均粒徑例如可為1 μm以上，亦可為2 μm以上。藉由樹脂粒子101的平均粒徑為1 μm以上，而充分確保導電粒子100a的變形量。樹脂粒子101的平均粒徑例如可為10 μm以下，亦可為5 μm以下。藉由樹脂粒子101的平均粒徑為10 μm以下，而抑制粒徑的不均一，從而抑制導電粒子100a的連接電阻值的不均一。樹脂粒子101的平均粒徑是設為藉由以下方式所得的平均值：藉由使用SEM的觀察來進行任意300個樹脂粒子的粒徑測定。The resin particles 101 are spherical. The average particle diameter of the resin particles 101 can be, for example, 1 μm or more and 10 μm or less. The average particle diameter of the resin particles 101 can be, for example, 1 μm or more, or 2 μm or more. The average particle diameter of the resin particles 101 is 1 μm or more, and the amount of deformation of the conductive particles 100a is sufficiently ensured. The average particle diameter of the resin particles 101 can be, for example, 10 μm or less, or 5 μm or less. When the average particle diameter of the resin particles 101 is 10 μm or less, the unevenness of the particle diameter is suppressed, and the unevenness of the connection resistance value of the conductive particles 100a is suppressed. The average particle diameter of the resin particles 101 is an average value obtained by measuring the particle diameter of arbitrary 300 resin particles by observation using SEM.

＜樹脂粒子的表面處理＞ 如上所述，對樹脂粒子101被覆陽離子性聚合物作為表面處理。該陽離子性聚合物通常可列舉多胺等般具有可帶正電的官能基的高分子化合物。陽離子性聚合物例如可選自由多胺、聚亞胺、聚醯胺、聚二烯丙基二甲基氯化銨、聚乙烯基胺、聚乙烯基吡啶、聚乙烯基咪唑及聚乙烯基吡咯啶酮所組成的群組中。就電荷密度高，與具有負電荷的表面及材料的結合力強的觀點而言，較佳為聚亞胺，更佳為聚乙烯亞胺。陽離子性聚合物亦可為可溶於水、或水與有機溶劑的混合溶液中。陽離子性聚合物的分子量視所使用的陽離子性聚合物的種類而變化，例如為500～200000左右。<Surface Treatment of Resin Particles> As described above, the resin particles 101 are coated with a cationic polymer as a surface treatment. The cationic polymer generally includes a polymer compound having a positively chargeable functional group such as a polyamine. The cationic polymer may, for example, be selected from the group consisting of polyamines, polyimines, polyamines, polydiallyldimethylammonium chloride, polyvinylamines, polyvinylpyridines, polyvinylimidazoles and polyvinylpyrroles. In a group consisting of ketones. From the viewpoint of a high charge density and a strong binding force to a surface and a material having a negative charge, a polyimine is preferred, and a polyethyleneimine is more preferred. The cationic polymer may also be soluble in water or a mixed solution of water and an organic solvent. The molecular weight of the cationic polymer varies depending on the type of the cationic polymer to be used, and is, for example, about 500 to 200,000.

藉由調整陽離子性聚合物的種類及分子量，可控制非導電性無機粒子102對樹脂粒子101的被覆率。具體而言，於藉由聚乙烯亞胺等電荷密度高的陽離子性聚合物被覆樹脂粒子101的情形時，有非導電性無機粒子102的被覆率（非導電性無機粒子102被覆樹脂粒子101的比例）提高的傾向。另一方面，於藉由電荷密度低的陽離子性聚合物被覆樹脂粒子101的情形時，有非導電性無機粒子102的被覆率降低的傾向。於陽離子性聚合物的分子量大的情形時，有非導電性無機粒子102的被覆率提高的傾向，於陽離子性聚合物的分子量小的情形時，有非導電性無機粒子102的被覆率降低的傾向。By adjusting the type and molecular weight of the cationic polymer, the coverage of the resin particles 101 by the non-conductive inorganic particles 102 can be controlled. Specifically, when the resin particles 101 are coated with a cationic polymer having a high charge density such as polyethyleneimine, the coverage of the non-conductive inorganic particles 102 (the non-conductive inorganic particles 102 coated with the resin particles 101) Proportion) The tendency to increase. On the other hand, when the resin particles 101 are coated with a cationic polymer having a low charge density, the coverage of the non-conductive inorganic particles 102 tends to decrease. When the molecular weight of the cationic polymer is large, the coverage of the non-conductive inorganic particles 102 tends to increase, and when the molecular weight of the cationic polymer is small, the coverage of the non-conductive inorganic particles 102 is lowered. tendency.

陽離子性聚合物亦可實質上不含鹼金屬（Li、Na、K、Rb、Cs）離子、鹼土類金屬（Ca、Sr、Ba、Ra）離子及鹵化物離子（氟離子、氯離子、溴離子、碘離子）。於該情形時，可抑制經陽離子性聚合物被覆的樹脂粒子101的電遷移（electromigration）及腐蝕。The cationic polymer may also be substantially free of alkali metal (Li, Na, K, Rb, Cs) ions, alkaline earth metal (Ca, Sr, Ba, Ra) ions and halide ions (fluoride, chloride, bromine Ion, iodide ion). In this case, electromigration and corrosion of the resin particles 101 coated with the cationic polymer can be suppressed.

經陽離子性聚合物被覆之前的樹脂粒子101於表面具有選自羥基、羧基、烷氧基、縮水甘油基及烷氧基羰基中的官能基。藉此，陽離子性聚合物容易吸附於樹脂粒子101的表面。The resin particles 101 before being coated with the cationic polymer have a functional group selected from a hydroxyl group, a carboxyl group, an alkoxy group, a glycidyl group, and an alkoxycarbonyl group on the surface. Thereby, the cationic polymer is easily adsorbed on the surface of the resin particles 101.

關於經陽離子性聚合物被覆的樹脂粒子101的界達電位（Zeta potential），較佳為於水、有機溶劑或含有水及有機溶劑的混合溶液中均成為正值（plus）。通常pH值越低，微粒子的界達電位越成為正值。因此，較佳為將用以形成第一層104的鍍敷液、及鍍敷的前處理步驟中使用的前處理液的pH值控制於6以下。The Zeta potential of the resin particles 101 coated with the cationic polymer is preferably a positive value in water, an organic solvent or a mixed solution containing water and an organic solvent. Generally, the lower the pH value, the more the boundary potential of the microparticles becomes positive. Therefore, it is preferable to control the pH of the plating solution for forming the first layer 104 and the pretreatment liquid used in the pretreatment step of plating to 6 or less.

樹脂粒子101的界達電位例如可藉由以下方式測定：使用界達電位探針（分散技術（Dispersion Technologies）公司製造，商品名「DT300」）測定膠體振動電位，或藉由使用界他電位儀ZS（Zetasizer ZS）（馬爾文儀器（Malvern Instruments）公司製造，商品名）的雷射多普勒（laser doppler）速度測量來測定電泳遷移率。The boundary potential of the resin particles 101 can be measured, for example, by measuring the colloidal vibration potential using an exponential potential probe (Dispersion Technologies, trade name "DT300"), or by using a Ketometer Electrophoretic mobility was measured by laser doppler velocity measurement of ZS (Zetasizer ZS) (Malvern Instruments, trade name).

＜非導電性無機粒子＞ 如後述，非導電性無機粒子102藉由靜電力而牢固地接著於樹脂粒子101。非導電性無機粒子102的形狀並無特別限制，為橢圓體、球體、半球體、大致橢圓體、大致球體、大致半球體等。該些形狀中，較佳為橢圓體或球體。<Non-conductive inorganic particles> As will be described later, the non-conductive inorganic particles 102 are firmly adhered to the resin particles 101 by electrostatic force. The shape of the non-conductive inorganic particles 102 is not particularly limited, and is an ellipsoid, a sphere, a hemisphere, a substantially ellipsoid, a substantially spherical body, a substantially hemisphere, and the like. Among these shapes, an ellipsoid or a sphere is preferred.

於第一層104的形成前且第一層104形成中的前處理（詳細情況將於後述）結束後的階段中，非導電性無機粒子102對樹脂粒子101的被覆率只要成為20%～80%即可。就更可靠地獲得導電粒子100a的絕緣性及導電性的效果的觀點而言，所述被覆率可為25%以上，亦可為30%以上，且可為70%以下，亦可為60%以下。本實施形態中，「被覆率」是指樹脂粒子101的正投影面中，具有該樹脂粒子101的直徑的1/2直徑的同心圓內的非導電性無機粒子102的表面積的比例。具體而言，對藉由SEM以3萬倍觀察形成有非導電性無機粒子102的樹脂粒子101所得的圖像進行分析，算出非導電性無機粒子102於樹脂粒子101的表面中所佔的比例。In the stage after the formation of the first layer 104 and the pretreatment in the formation of the first layer 104 (details will be described later), the coverage of the non-conductive inorganic particles 102 to the resin particles 101 is 20% to 80. % can be. The coating ratio may be 25% or more, 30% or more, and may be 70% or less, or 60%, from the viewpoint of more reliably obtaining the insulating property and conductivity of the conductive particles 100a. the following. In the present embodiment, the "coverage ratio" refers to the ratio of the surface area of the non-conductive inorganic particles 102 in the concentric circles having a diameter of 1/2 of the diameter of the resin particles 101 in the front projection surface of the resin particles 101. Specifically, an image obtained by observing the resin particles 101 in which the non-conductive inorganic particles 102 are formed by SEM is analyzed by SEM, and the proportion of the non-conductive inorganic particles 102 on the surface of the resin particles 101 is calculated. .

就於第一層104的外表面形成充分個數的凸起109，進一步降低導電粒子100a連接於電極等時的導通電阻的觀點而言，非導電性無機粒子102亦可分散地配置於導電粒子100a的與直徑方向垂直的方向（表面）上。非導電性無機粒子102彼此亦可不相互接觸，而分散地配置於導電粒子100a的與直徑方向垂直的方向（表面）上。關於相互接觸的非導電性無機粒子102的個數，例如於一個導電粒子100a中可為15個以下，亦可為7個以下，亦可為0個。所謂0個，是指配置於一個導電粒子100a的表面上的非導電性無機粒子102彼此不接觸，所有非導電性無機粒子102分散地配置。The non-conductive inorganic particles 102 may be dispersedly disposed on the conductive particles from the viewpoint of forming a sufficient number of protrusions 109 on the outer surface of the first layer 104 and further reducing the on-resistance when the conductive particles 100a are connected to the electrodes or the like. 100a in the direction (surface) perpendicular to the diameter direction. The non-conductive inorganic particles 102 may be disposed in a direction (surface) perpendicular to the diameter direction of the conductive particles 100a without being in contact with each other. The number of the non-conductive inorganic particles 102 that are in contact with each other may be, for example, 15 or less in one conductive particle 100a, or may be seven or less, or may be zero. The term "zero" means that the non-conductive inorganic particles 102 disposed on the surface of one of the conductive particles 100a are not in contact with each other, and all of the non-conductive inorganic particles 102 are disposed in a dispersed manner.

形成非導電性無機粒子102的材料亦可較形成第一層104的材料更硬。藉此，導電粒子容易穿刺至電極等，導電性提高。即，想到並非使導電粒子總體變硬，而是使導電粒子的一部分變硬。例如，形成非導電性無機粒子102的材料的莫氏硬度（Mohs' hardness）大於形成第一層104的金屬的莫氏硬度。具體而言，形成非導電性無機粒子102的材料的莫氏硬度為5以上。此外，形成非導電性無機粒子102的材料的莫氏硬度與形成第一層104的金屬的莫氏硬度之差亦可為1.0以上。於第一層104含有多種金屬的情形時，非導電性無機粒子102的莫氏硬度亦可高於所有金屬的莫氏硬度。關於具體例，形成非導電性無機粒子102的材料可選自由氧化矽（二氧化矽（SiO2 ），莫氏硬度6～7）、氧化鋯（莫氏硬度8～9）、氧化鋁（莫氏硬度9）及金剛石（莫氏硬度10）所組成的群組中。於非導電性無機粒子102的表面形成有羥基（-OH），如上文所述般經疏水化處理劑被覆。所述莫氏硬度的值是參照「化學大辭典」（共立出版股份有限公司發行）。The material forming the non-conductive inorganic particles 102 may also be harder than the material forming the first layer 104. Thereby, the conductive particles are easily punctured to the electrode or the like, and the conductivity is improved. That is, it is thought that the conductive particles are not hardened as a whole, but a part of the conductive particles is hardened. For example, the Mohs' hardness of the material forming the non-conductive inorganic particles 102 is greater than the Mohs hardness of the metal forming the first layer 104. Specifically, the material forming the non-conductive inorganic particles 102 has a Mohs hardness of 5 or more. Further, the difference between the Mohs hardness of the material forming the non-conductive inorganic particles 102 and the Mohs hardness of the metal forming the first layer 104 may be 1.0 or more. In the case where the first layer 104 contains a plurality of metals, the Mohs hardness of the non-conductive inorganic particles 102 may be higher than the Mohs hardness of all metals. With regard to specific embodiments, the material forming the non-conductive inorganic particles 102 may be selected consisting of silicon oxide (silicon dioxide (SiO 2), Mohs hardness 6 to 7), zirconium oxide (Mohs' hardness 8-9), aluminum oxide (MO Hardness 9) and diamond (Mohs hardness 10) in the group. A hydroxyl group (-OH) is formed on the surface of the non-conductive inorganic particles 102, and is coated with a hydrophobizing agent as described above. The value of the Mohs hardness is referred to the "Chemical Dictionary" (issued by Kyoritsu Publishing Co., Ltd.).

非導電性無機粒子102亦可使用氧化矽粒子。氧化矽粒子的粒徑較佳為經控制。氧化矽粒子的種類並無特別限制，可列舉膠體氧化矽、煙燻氧化矽（fumed silica）、溶膠凝膠法氧化矽等。氧化矽粒子可單獨使用，亦可將兩種以上混合而使用。氧化矽粒子可使用市售品，亦可使用合成品。As the non-conductive inorganic particles 102, cerium oxide particles can also be used. The particle size of the cerium oxide particles is preferably controlled. The type of the cerium oxide particles is not particularly limited, and examples thereof include colloidal cerium oxide, fumed silica, and sol-gel cerium oxide. The cerium oxide particles may be used singly or in combination of two or more. A commercially available product can be used for the cerium oxide particles, and a synthetic product can also be used.

膠體氧化矽的製造方法可列舉公知的方法。具體可列舉：「溶膠-凝膠法的科學」（作花濟夫著，阿具根承風社（Agune Syofu Sha）發行）的第154頁～第156頁中記載的利用烷氧基矽烷的水解的方法；日本專利特開平11-60232號公報中記載的將矽酸甲酯或矽酸甲酯與甲醇的混合物滴加至包含水、甲醇、及氨或氨與銨鹽的混合溶劑中，使矽酸甲酯與水反應的方法；日本專利特開2001-48520號公報中記載的利用酸觸媒將烷基矽酸鹽（alkyl silicate）水解後，添加鹼觸媒並進行加熱，進行矽酸的聚合而使粒子成長的方法；日本專利特開2007-153732號公報中記載的於烷氧基矽烷的水解時以特定的量使用特定種類的水解觸媒的方法等。或者，亦可列舉藉由對矽酸鈉進行離子交換而進行製造的方法。水分散膠體氧化矽的市售品可列舉：斯諾特（Snowtex）、斯諾特（Snowtex）UP（均為日產化學工業股份有限公司製造，商品名），誇特龍（Quarton）PL系列（扶桑化學工業股份有限公司製造，商品名）等。A known method can be mentioned as a manufacturing method of colloidal cerium oxide. Specifically, the "Science of the Sol-Gel Method" (the use of alkoxy decane) described on pages 154 to 156 of the publication of Agune Syofu Sha a method of hydrolyzing, a mixture of methyl decanoate or methyl decanoate and methanol described in Japanese Patent Laid-Open Publication No. Hei 11-60232, which is added to a mixed solvent containing water, methanol, and ammonia or ammonia and an ammonium salt. A method of reacting methyl decanoate with water; and hydrolyzing an alkyl silicate by an acid catalyst as described in JP-A-2001-48520, adding an alkali catalyst and heating to carry out hydrazine A method of using a specific type of hydrolysis catalyst in the case of hydrolysis of alkoxydecane described in Japanese Patent Publication No. 2007-153732. Alternatively, a method of producing by sodium ion exchange with ion exchange may be mentioned. Commercially available products of water-dispersed colloidal cerium oxide include: Snowtex, Snowtex UP (all manufactured by Nissan Chemical Industries, Ltd., trade name), and Quarton PL series ( Manufactured by Fuso Chemical Industry Co., Ltd., trade name).

煙燻氧化矽的製造方法可列舉：使用將四氯化矽氣化並使其於氫氧焰中燃燒的氣相反應的公知方法。進而，煙燻氧化矽可利用公知的方法製成水分散液。製成水分散液的方法可列舉日本專利特開2004-43298號公報、日本專利特開2003-176123號公報、日本專利特開2002-309239號公報等中記載的方法。就煙燻氧化矽的絕緣可靠性的觀點而言，較佳為水分散液中的鹼金屬離子及鹼土類金屬離子的濃度為100 ppm以下。煙燻氧化矽的莫氏硬度可為5以上，亦可為6以上。A method for producing the smoked cerium oxide is a known method using a gas phase reaction in which ruthenium tetrachloride is vaporized and burned in an oxyhydrogen flame. Further, the smoked cerium oxide can be produced into an aqueous dispersion by a known method. The method of the aqueous dispersion is exemplified by the methods described in JP-A-2004-43298, JP-A-2003-176123, and JP-A-2002-309239. From the viewpoint of insulation reliability of the smoked cerium oxide, the concentration of the alkali metal ions and the alkaline earth metal ions in the aqueous dispersion is preferably 100 ppm or less. The smoked cerium oxide may have a Mohs hardness of 5 or more, and may be 6 or more.

＜疏水化處理劑＞ 被覆非導電性無機粒子102的疏水化處理劑可列舉以下記載的（1）矽氮烷系疏水化處理劑、（2）矽氧烷系疏水化處理劑、（3）矽烷系疏水化處理劑、（4）鈦酸酯系疏水化處理劑等。就反應性的觀點而言，較佳為（1）矽氮烷系疏水化處理劑。疏水化處理劑亦可含有選自由所述（1）～（4）所組成的群組中的至少一種。<Hydrogenation Treatment Agent> The hydrophobization treatment agent that coats the non-conductive inorganic particles 102 includes (1) a guanidine-based hydrophobizing agent, (2) a decane-based hydrophobizing agent, and (3) A decane-based hydrophobizing agent, (4) a titanate-based hydrophobizing agent, and the like. From the viewpoint of reactivity, (1) a guanidine-based hydrophobizing agent is preferred. The hydrophobizing agent may further contain at least one selected from the group consisting of the above (1) to (4).

（1）矽氮烷系疏水化處理劑 矽氮烷系疏水化處理劑例如可列舉有機矽氮烷系疏水化處理劑。有機矽氮烷系疏水化處理劑可列舉：六甲基二矽氮烷、三甲基二矽氮烷、四甲基二矽氮烷、六甲基環三矽氮烷、七甲基二矽氮烷、二苯基四甲基二矽氮烷、二乙烯基四甲基二矽氮烷等。有機矽氮烷系疏水化處理劑亦可為所述以外的化合物。(1) Azepine-based hydrophobization treatment agent The hydroquinone-based hydrophobization treatment agent is, for example, an organic nonazepine-based hydrophobization treatment agent. Examples of the organodazepine-based hydrophobizing agent include hexamethyldiazepine, trimethyldiazepine, tetramethyldiazepine, hexamethylcyclotriazane, heptamethyldiazine. Azane, diphenyltetramethyldiazepine, divinyltetramethyldiazepine, and the like. The organic decane-based hydrophobizing agent may also be a compound other than the above.

（2）矽氧烷系疏水化處理劑 矽氧烷系疏水化處理劑可列舉：聚二甲基矽氧烷、甲基氫二矽氧烷、二甲基二矽氧烷、六甲基二矽氧烷、1,3-二乙烯基四甲基二矽氧烷、1,3-二苯基四甲基二矽氧烷、甲基氫聚矽氧烷、二甲基聚矽氧烷、胺基改質矽氧烷等。矽氧烷系疏水化處理劑亦可為所述以外的化合物。(2) Hydroxane-based hydrophobizing agent The hydroxylating agent may be exemplified by polydimethyl methoxy oxane, methyl hydrogen dioxane, dimethyl dioxane, hexamethyl Alkane, 1,3-divinyltetramethyldioxane, 1,3-diphenyltetramethyldioxane, methylhydrogenpolyoxyalkylene, dimethylpolyoxane, Amine-based upgraded oxirane and the like. The oxirane-based hydrophobizing agent may be a compound other than the above.

（3）矽烷系疏水化處理劑 矽烷系疏水化處理劑可列舉：N,N-二甲基胺基三甲基矽烷、三甲基甲氧基矽烷、三甲基乙氧基矽烷、三甲基丙氧基矽烷、苯基二甲基甲氧基矽烷、氯丙基二甲基甲氧基矽烷、二甲基二甲氧基矽烷、甲基三甲氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷、乙基三甲氧基矽烷、二甲基二乙氧基矽烷、丙基三乙氧基矽烷、正丁基三甲氧基矽烷、正己基三甲氧基矽烷、正辛基三乙氧基矽烷、正辛基甲基二乙氧基矽烷、正十八烷基三甲氧基矽烷、苯基三甲氧基矽烷、苯基甲基二甲氧基矽烷、苯乙基三甲氧基矽烷、十二烷基三甲氧基矽烷、正十八烷基三乙氧基矽烷、苯基三甲氧基矽烷、二苯基二甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(β甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、γ-(甲基丙烯醯氧基丙基)甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、N-β(胺基乙基)γ-(胺基丙基)甲基二甲氧基矽烷、N-β(胺基乙基)γ-(胺基丙基)三甲氧基矽烷、N-β(胺基乙基)γ-(胺基丙基)三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、三氟丙基三甲氧基矽烷、十七-三氟丙基三甲氧基矽烷、正癸基三甲氧基矽烷、二甲氧基二乙氧基矽烷、雙(三乙氧基矽烷基)乙烷、六乙氧基二矽氧烷等。(3) Hydrazine Hydrophobizing Agent The decane-based hydrophobizing agent may, for example, be N,N-dimethylaminotrimethylnonane, trimethylmethoxydecane, trimethylethoxydecane or trimethyl Propyloxydecane, phenyldimethylmethoxydecane, chloropropyldimethylmethoxydecane, dimethyldimethoxydecane, methyltrimethoxydecane, tetramethoxydecane, tetra Ethoxy decane, tetrapropoxy decane, tetrabutoxy decane, ethyl trimethoxy decane, dimethyl diethoxy decane, propyl triethoxy decane, n-butyl trimethoxy decane, hexane Trimethoxy decane, n-octyltriethoxy decane, n-octylmethyldiethoxy decane, n-octadecyltrimethoxydecane, phenyltrimethoxydecane, phenylmethyldimethoxy Baseline, phenethyltrimethoxydecane, dodecyltrimethoxydecane, n-octadecyltriethoxydecane,phenyltrimethoxydecane,diphenyldimethoxydecane,vinyltrimethyl Oxy decane, vinyl triethoxy decane, vinyl tris (β methoxy ethoxy) decane, γ-methyl propylene methoxy propyl three Methoxydecane, γ-acryloxypropyltrimethoxydecane, γ-(methacryloxypropyl)methyldimethoxydecane, γ-methylpropenyloxypropylmethyl Diethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethyl Oxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, N-β(aminoethyl)γ-(aminopropyl) Methyldimethoxydecane, N-β(aminoethyl)γ-(aminopropyl)trimethoxynonane, N-β(aminoethyl)γ-(aminopropyl)triethyl Oxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxy Basear, 3-isocyanate propyl triethoxy decane, trifluoropropyltrimethoxydecane, hepta-trifluoropropyltrimethoxydecane, n-decyltrimethoxydecane, dimethoxydiethoxy Alkane, bis(triethoxydecyl)ethane, hexaethoxydioxane, and the like.

（4）鈦酸酯系疏水化處理劑 鈦酸酯系疏水化處理劑可列舉：KRTTS、KR46B、KR55、KR41B、KR38S、KR138S、KR238S、338X、KR44、KR9SA（均為味之素精密技術（Ajinomoto Fine-Tech）股份有限公司製造，商品名）等。(4) Titanate Hydrophobizing Agent The titanate hydrophobizing agent can be exemplified by KRTTS, KR46B, KR55, KR41B, KR38S, KR138S, KR238S, 338X, KR44, KR9SA (all are Ajinomoto precision technologies ( Ajinomoto Fine-Tech Co., Ltd., trade name, etc.

所述疏水化處理劑中，較佳為六甲基二矽氮烷、聚二甲基矽氧烷及N,N-二甲基胺基三甲基矽烷。因此，疏水化處理劑亦可含有選自由六甲基二矽氮烷、聚二甲基矽氧烷及N,N-二甲基胺基三甲基矽烷所組成的群組中的至少一種。非導電性無機粒子102的表面越為疏水化，非導電性無機粒子102的界達電位越向負值側增大。因此，非導電性無機粒子102與經陽離子性聚合物被覆的樹脂粒子101的電位差增大。因此，樹脂粒子101與非導電性無機粒子102藉由靜電力而牢固地接著。例如，非導電性無機粒子102的界達電位與樹脂粒子101的界達電位之差於pH值1以上且pH值11以下時可為30 mV以上，亦可為50 mV以上。Among the hydrophobizing agents, hexamethyldioxane, polydimethyloxane, and N,N-dimethylaminotrimethylnonane are preferred. Therefore, the hydrophobizing agent may further contain at least one selected from the group consisting of hexamethyldiazepine, polydimethyloxane, and N,N-dimethylaminotrimethylnonane. The surface of the non-conductive inorganic particles 102 is more hydrophobic, and the boundary potential of the non-conductive inorganic particles 102 increases toward the negative side. Therefore, the potential difference between the non-conductive inorganic particles 102 and the resin particles 101 coated with the cationic polymer increases. Therefore, the resin particles 101 and the non-conductive inorganic particles 102 are firmly adhered by the electrostatic force. For example, the difference between the boundary potential of the non-conductive inorganic particles 102 and the boundary potential of the resin particles 101 may be 30 mV or more, or 50 mV or more, when the pH is 1 or more and the pH is 11 or less.

關於經疏水化處理的非導電性無機粒子102的界達電位，較佳為於水、有機溶劑、包含水與有機溶劑的混合溶液中均成為負值（minus）。通常pH值越高，界達電位越成為負值。因此，較佳為選定樹脂粒子101與非導電性無機粒子102的界達電位之差增大的pH值。The boundary potential of the hydrophobized non-conductive inorganic particles 102 is preferably a negative value in water, an organic solvent, or a mixed solution containing water and an organic solvent. Generally, the higher the pH, the more negative the potential is. Therefore, it is preferable to select a pH value at which the difference in the boundary potential between the resin particles 101 and the non-conductive inorganic particles 102 is increased.

非導電性無機粒子102的界達電位例如可藉由以下方式測定：使用界達電位探針（分散技術（Dispersion Technologies）公司製造，商品名「DT300」）測定膠體振動電位，或藉由使用界他電位儀ZS（Zetasizer ZS）（馬爾文儀器（Malvern Instruments）公司製造，商品名）的雷射多普勒速度測量來測定電泳遷移率。The boundary potential of the non-conductive inorganic particles 102 can be measured, for example, by measuring the colloidal vibration potential using an exponential potential probe (Dispersion Technology (trade name "DT300"), or by using the boundary Electrophoretic mobility was measured by laser Doppler velocity measurement of a potentiometer ZS (Zetasizer ZS) (manufactured by Malvern Instruments, trade name).

以下，記載經陽離子性聚合物被覆的樹脂粒子101與經疏水化處理劑被覆的非導電性無機粒子102藉由靜電力而非化學鍵結力牢固地接著的原因的考察。例如，如下述化學式1般藉由六甲基二矽氮烷對賦予有羥基的氧化矽粒子進行疏水化處理。於該情形時，如下述化學式2般，氧化矽粒子經甲基被覆。藉由氧化矽粒子經甲基被覆，儘管被覆於樹脂粒子101表面的陽離子性聚合物與氧化矽粒子之間並無進行化學鍵結的部位，非導電性無機粒子102亦牢固地接著於樹脂粒子101。於使各非導電性無機粒子的粒徑相同的情形時，藉由六甲基二矽氮烷而被覆有疏水化處理劑的非導電性無機粒子102的界達電位於所述非導電性無機粒子中顯示出負值最大的電位。此時，得知非導電性無機粒子102與陽離子性聚合物之電位差變為最大。根據此種原因可想到，為了增強樹脂粒子101與非導電性無機粒子102的接著，因界達電位之差、即樹脂粒子101與非導電性無機粒子102之電位差而產生的靜電力為決定接著性的重要因素。In the following, it is considered that the resin particles 101 coated with the cationic polymer and the non-conductive inorganic particles 102 coated with the hydrophobizing agent are firmly adhered by electrostatic force rather than chemical bonding force. For example, the cerium oxide particles to which the hydroxyl group is imparted are hydrophobized by hexamethyldiazepine as in the following Chemical Formula 1. In this case, the cerium oxide particles are coated with a methyl group as in the following Chemical Formula 2. When the cerium oxide particles are coated with a methyl group, the non-conductive inorganic particles 102 are firmly adhered to the resin particles 101 even though there is no chemical bonding between the cationic polymer and the cerium oxide particles coated on the surface of the resin particles 101. . When the particle diameter of each of the non-conductive inorganic particles is the same, the boundary of the non-conductive inorganic particles 102 coated with the hydrophobization treatment agent by hexamethyldiazepine is located at the non-conductive inorganic The potential with the largest negative value is shown in the particle. At this time, it was found that the potential difference between the non-conductive inorganic particles 102 and the cationic polymer became maximum. For this reason, in order to enhance the adhesion of the resin particles 101 and the non-conductive inorganic particles 102, the electrostatic force generated by the difference in the potential between the resin particles 101 and the non-conductive inorganic particles 102 is determined. An important factor in sex.

[化1] [Chemical 1]

[化2] [Chemical 2]

關於疏水化處理劑，亦可於不妨礙非導電性無機粒子102的疏水性，將非導電性無機粒子102的界達電位保持於負值側，且不妨礙樹脂粒子101與非導電性無機粒子102的靜電接著的範圍內，具有選自由胺基、羧酸基、羥基、磺酸基、縮水甘油基及腈基所組成的群組中的至少一種。亦可除了所述疏水化處理劑以外，另行追加具有選自由胺基、羧酸基、羥基、磺酸基、縮水甘油基及腈基所組成的群組中的至少一種並且不妨礙疏水性的效果的處理劑。以下，對疏水化處理劑中具有選自由胺基、羧酸基、羥基、磺酸基、縮水甘油基及腈基所組成的群組中的至少一種，另外另行追加具有選自由胺基、羧酸基、羥基、磺酸基、縮水甘油基及腈基所組成的群組中的至少一種並且不妨礙疏水性的效果的處理劑的優點加以說明。於對複合粒子103進行後述鈀觸媒化處理作為用以形成第一層104的前處理步驟時，使用所述處理劑。於是，可促進鈀觸媒對非導電性無機粒子102表面的吸附。藉此，複合粒子103的表面的鈀吸附量增加，故可經由鈀觸媒於複合粒子103的表面均勻地形成第一層104。The hydrophobization treatment agent can maintain the boundary potential of the non-conductive inorganic particles 102 on the negative side without impeding the hydrophobicity of the non-conductive inorganic particles 102, and does not interfere with the resin particles 101 and the non-conductive inorganic particles. The electrostatic range of 102 is at least one selected from the group consisting of an amine group, a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, and a nitrile group. In addition to the hydrophobizing agent, at least one selected from the group consisting of an amine group, a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, and a nitrile group may be additionally added and does not inhibit hydrophobicity. The effect of the treatment agent. In the following, the hydrophobization treatment agent has at least one selected from the group consisting of an amine group, a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, and a nitrile group, and additionally has an alkyl group selected from the group consisting of an amine group and a carboxyl group. The advantages of the treating agent which is at least one of the group consisting of an acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, and a nitrile group and which does not impede the effect of hydrophobicity will be explained. When the palladium catalyst treatment described later is performed on the composite particles 103 as a pretreatment step for forming the first layer 104, the treatment agent is used. Thus, the adsorption of the palladium catalyst on the surface of the non-conductive inorganic particles 102 can be promoted. Thereby, the amount of palladium adsorbed on the surface of the composite particles 103 is increased, so that the first layer 104 can be uniformly formed on the surface of the composite particles 103 via the palladium catalyst.

非導電性無機粒子102的平均粒徑例如為樹脂粒子101的平均粒徑的1/300～1/10左右。於非導電性無機粒子102的平均粒徑為樹脂粒子101的平均粒徑的1/300以上的情形時，於以第一層104覆蓋複合粒子103時，容易獲得充分的高度的凸起109。另一方面，於非導電性無機粒子102的平均粒徑為樹脂粒子101的平均粒徑的1/10以下的情形時，有非導電性無機粒子102不易自樹脂粒子101脫落的傾向。為了使非導電性無機粒子102更穩定地吸附於樹脂粒子101而獲得充分的高度的凸起109，非導電性無機粒子102的平均粒徑較佳為樹脂粒子101的平均粒徑的1/200～1/10，更佳為1/120～1/25左右。如此，藉由非導電性無機粒子102的平均粒徑為所述範圍內，導電粒子100a可具有多數個緻密的凸起109，並且非導電性無機粒子102不易自樹脂粒子101脫落。The average particle diameter of the non-conductive inorganic particles 102 is, for example, about 1/300 to 1/10 of the average particle diameter of the resin particles 101. When the average particle diameter of the non-conductive inorganic particles 102 is 1/300 or more of the average particle diameter of the resin particles 101, when the composite particles 103 are covered with the first layer 104, it is easy to obtain the protrusions 109 having a sufficient height. On the other hand, when the average particle diameter of the non-conductive inorganic particles 102 is 1/10 or less of the average particle diameter of the resin particles 101, the non-conductive inorganic particles 102 tend to be less likely to fall off from the resin particles 101. In order to obtain the protrusions 109 having a sufficient height by adsorbing the non-conductive inorganic particles 102 more stably on the resin particles 101, the average particle diameter of the non-conductive inorganic particles 102 is preferably 1/200 of the average particle diameter of the resin particles 101. ～1/10, more preferably about 1/120 to 1/25. As described above, when the average particle diameter of the non-conductive inorganic particles 102 is within the above range, the conductive particles 100a may have a plurality of dense protrusions 109, and the non-conductive inorganic particles 102 are less likely to fall off from the resin particles 101.

本實施形態中，例如於樹脂粒子101的平均粒徑為3 μm的情形時，非導電性無機粒子102的較佳平均粒徑的範圍為25 nm～120 nm。另外，例如於樹脂粒子101的平均粒徑為4 μm的情形時，較佳為33 nm～160 nm，於5 μm的情形時較佳為42 nm～200 nm，於10 μm的情形時較佳為83 nm～400 nm。關於非導電性無機粒子102，例如以下示出樹脂粒子101的平均粒徑為3 μm的情形作為例子。In the present embodiment, for example, when the average particle diameter of the resin particles 101 is 3 μm, the preferred average particle diameter of the non-conductive inorganic particles 102 is in the range of 25 nm to 120 nm. Further, for example, when the average particle diameter of the resin particles 101 is 4 μm, it is preferably 33 nm to 160 nm, and in the case of 5 μm, it is preferably 42 nm to 200 nm, preferably 10 μm. It is from 83 nm to 400 nm. For the non-conductive inorganic particles 102, for example, a case where the average particle diameter of the resin particles 101 is 3 μm is exemplified below.

若非導電性無機粒子102的平均粒徑為25 nm以上（或樹脂粒子101的平均粒徑的1/120以上），則第一層104的凸起109容易成為適度的大小，有低電阻化的傾向。非導電性無機粒子102的界達電位根據粒徑而不同，發現粒徑越小界達電位越進一步向負值側偏移。因此，若非導電性無機粒子102的平均粒徑為120 nm以下（或樹脂粒子101的平均粒徑的1/25以下），則非導電性無機粒子102與樹脂粒子101的電位差變得充分，於形成第一層104時等該非導電性無機粒子102不易脫落。藉此，凸起109的個數變充分，有容易低電阻化的傾向。有時於脫落的非導電性無機粒子102凝聚而成的凝聚物上被覆第一層104的金屬而生成金屬異物。有時該金屬異物再附著於樹脂粒子101，形成過度長的凸起（例如長度超過500 nm的凸起）作為異常析出部。於該情形時，有時導致導電粒子100a的絕緣可靠性降低。進而，有時所述金屬異物本身導致絕緣可靠性降低。因此，較佳為抑制非導電性無機粒子102自樹脂粒子101脫落。非導電性無機粒子102的平均粒徑可為30 nm～110 nm，亦可為35 nm～100 nm。非導電性無機粒子102的粒徑是藉由利用布厄特（Brunauer-Emmett-Tellern，BET）法的比表面積換算法或X射線小角散射法而測定。When the average particle diameter of the non-conductive inorganic particles 102 is 25 nm or more (or 1/120 or more of the average particle diameter of the resin particles 101), the protrusions 109 of the first layer 104 are likely to have an appropriate size and have a low resistance. tendency. The boundary potential of the non-conductive inorganic particles 102 differs depending on the particle diameter, and it is found that the smaller the particle diameter is, the further the potential is shifted toward the negative side. Therefore, when the average particle diameter of the non-conductive inorganic particles 102 is 120 nm or less (or 1/25 or less of the average particle diameter of the resin particles 101), the potential difference between the non-conductive inorganic particles 102 and the resin particles 101 becomes sufficient. When the first layer 104 is formed, the non-conductive inorganic particles 102 are not easily peeled off. As a result, the number of the bumps 109 is increased, and the number of the bumps 109 tends to be low. The metal of the first layer 104 is coated on the aggregate formed by the agglomerated non-conductive inorganic particles 102 to form a metal foreign matter. In some cases, the metal foreign matter adheres to the resin particles 101 to form an excessively long projection (for example, a projection having a length of more than 500 nm) as an abnormal precipitation portion. In this case, the insulation reliability of the conductive particles 100a is sometimes lowered. Further, the metal foreign matter itself sometimes causes a decrease in insulation reliability. Therefore, it is preferable to suppress the non-conductive inorganic particles 102 from falling off from the resin particles 101. The non-conductive inorganic particles 102 may have an average particle diameter of 30 nm to 110 nm or 35 nm to 100 nm. The particle diameter of the non-conductive inorganic particles 102 is measured by a specific surface area conversion algorithm or an X-ray small angle scattering method using a Brunauer-Emmett-Tellern (BET) method.

所謂「非導電性無機粒子102的直徑」，是指於非導電性無機粒子102的正投影面中，具有與非導電性無機粒子102的面積相同的面積的正圓的直徑。具體而言，對利用SEM以10萬倍觀察非導電性無機粒子所得的圖像進行分析，劃定非導電性無機粒子的輪廓。然後，算出任意的非導電性無機粒子的面積，根據該面積而求出非導電性無機粒子102的直徑。The "diameter of the non-conductive inorganic particles 102" refers to a diameter of a perfect circle having the same area as the area of the non-conductive inorganic particles 102 in the front projection surface of the non-conductive inorganic particles 102. Specifically, an image obtained by observing non-conductive inorganic particles by SEM at 100,000 times is analyzed to define the outline of the non-conductive inorganic particles. Then, the area of any non-conductive inorganic particles is calculated, and the diameter of the non-conductive inorganic particles 102 is obtained from the area.

所謂「非導電性無機粒子102的平均粒徑」，是指於非導電性無機粒子102的正投影面中，根據具有與非導電性無機粒子102的面積相同的面積的正圓的直徑所算出的平均粒徑。具體而言，對利用SEM以10萬倍觀察非導電性無機粒子所得的圖像進行分析，劃定非導電性無機粒子的輪廓。然後，分別算出任意500個非導電性無機粒子的面積，根據將該面積換算成圓的情形的直徑而算出平均粒徑，將所算出的平均粒徑作為非導電性無機粒子102的平均粒徑。The "average particle diameter of the non-conductive inorganic particles 102" is calculated from the diameter of a perfect circle having the same area as the area of the non-conductive inorganic particles 102 in the front projection surface of the non-conductive inorganic particles 102. Average particle size. Specifically, an image obtained by observing non-conductive inorganic particles by SEM at 100,000 times is analyzed to define the outline of the non-conductive inorganic particles. Then, the area of any of the 500 non-conductive inorganic particles is calculated, and the average particle diameter is calculated from the diameter of the case where the area is converted into a circle, and the calculated average particle diameter is taken as the average particle diameter of the non-conductive inorganic particles 102. .

＜非導電性無機粒子的疏水化度＞ 由甲醇滴定法所得的非導電性無機粒子102的疏水化度例如為30%以上。於該情形時，非導電性無機粒子102可藉由靜電力而牢固地接著於樹脂粒子101。所述疏水化度可為50%以上，亦可為60%以上。疏水化度越高，非導電性無機粒子102的界達電位越進一步向負值側偏移，非導電性無機粒子102可藉由靜電力而牢固地接著於樹脂粒子101。<Hydrophilization degree of non-conductive inorganic particles> The degree of hydrophobicization of the non-conductive inorganic particles 102 obtained by the methanol titration method is, for example, 30% or more. In this case, the non-conductive inorganic particles 102 can be firmly adhered to the resin particles 101 by electrostatic force. The degree of hydrophobization may be 50% or more, or may be 60% or more. The higher the degree of hydrophobization, the more the boundary potential of the non-conductive inorganic particles 102 shifts toward the negative side, and the non-conductive inorganic particles 102 can be firmly adhered to the resin particles 101 by electrostatic force.

所謂甲醇滴定法，是使用甲醇來測定粉體的疏水化度的方法。例如首先使0.2 g需測定疏水化度的粉體漂浮於50 ml的水面上。繼而，一面輕輕攪拌水一面於水中逐次少量地添加甲醇。甲醇例如是使用滴管（burette）滴加。繼而，對水面上的粉體全部淹沒至水中的時刻的甲醇使用量進行測定。繼而，計算出甲醇體積相對於水與甲醇的合計體積之百分率，算出該值作為粉體的疏水化度。The methanol titration method is a method of measuring the degree of hydrophobicity of a powder using methanol. For example, first, 0.2 g of the powder to be measured for hydrophobization is floated on 50 ml of water. Then, methanol was added in small portions in water while gently stirring the water. Methanol is added dropwise, for example, using a burette. Then, the amount of methanol used at the time when the powder on the water surface was completely submerged in water was measured. Then, the percentage of the methanol volume with respect to the total volume of water and methanol was calculated, and this value was calculated as the degree of hydrophobicity of the powder.

＜非導電性無機粒子對樹脂粒子的接著方法＞ 非導電性無機粒子102對樹脂粒子101的接著可使用有機溶劑、或水與水溶性的有機溶劑的混合溶液來進行。可使用的水溶性的有機溶劑可列舉甲醇、乙醇、丙醇、丙酮、二甲基甲醯胺、乙腈等。於僅使用有機溶劑的情形時，有樹脂粒子101的界達電位進一步向正值側偏移，非導電性無機粒子102的界達電位進一步向負值側偏移的傾向。於僅使用有機溶劑的情形時，與使用有機溶劑與水的混合溶液的情形相比，有樹脂粒子101與非導電性無機粒子102之電位差增大的傾向。因此，於僅使用有機溶劑的情形時，有非導電性無機粒子102藉由強靜電力而牢固地接著於樹脂粒子101的傾向。結果，於形成第一層104時等非導電性無機粒子102不易自樹脂粒子101脫落。<Method of Attaching Non-Conductive Inorganic Particles to Resin Particles> The non-conductive inorganic particles 102 may be subsequently applied to the resin particles 101 using an organic solvent or a mixed solution of water and a water-soluble organic solvent. The water-soluble organic solvent which can be used may, for example, be methanol, ethanol, propanol, acetone, dimethylformamide or acetonitrile. In the case where only the organic solvent is used, the boundary potential of the resin particles 101 is further shifted toward the positive side, and the boundary potential of the non-conductive inorganic particles 102 tends to shift further toward the negative side. When only an organic solvent is used, the potential difference between the resin particles 101 and the non-conductive inorganic particles 102 tends to increase as compared with the case of using a mixed solution of an organic solvent and water. Therefore, when only an organic solvent is used, there is a tendency that the non-conductive inorganic particles 102 are firmly adhered to the resin particles 101 by a strong electrostatic force. As a result, the non-conductive inorganic particles 102 are less likely to fall off from the resin particles 101 when the first layer 104 is formed.

＜第一層＞ 第一層104為含有鎳作為主成分的導電層。第一層104的厚度例如為40 nm～200 nm。若第一層104的厚度為所述範圍內，則即便於導電粒子100a經壓縮的情形時，亦可抑制第一層104的破裂。另外，可藉由第一層104將複合粒子103的表面充分地被覆。藉此，可使非導電性無機粒子102固著於樹脂粒子101，抑制非導電性無機粒子102的脫落。結果，可於所得的導電粒子100a上逐一高密度地形成均勻形狀的凸起109。第一層104的厚度亦可為60 nm以上。第一層104的厚度可為150 nm以下，亦可為120 nm以下。第一層104可為單層結構，亦可為積層結構。本實施形態中，第一層104具有兩層結構。<First Layer> The first layer 104 is a conductive layer containing nickel as a main component. The thickness of the first layer 104 is, for example, 40 nm to 200 nm. If the thickness of the first layer 104 is within the above range, cracking of the first layer 104 can be suppressed even when the conductive particles 100a are compressed. Further, the surface of the composite particles 103 can be sufficiently covered by the first layer 104. Thereby, the non-conductive inorganic particles 102 can be fixed to the resin particles 101, and the non-conductive inorganic particles 102 can be prevented from falling off. As a result, a uniform shape of the protrusions 109 can be formed at a high density one by one on the obtained conductive particles 100a. The thickness of the first layer 104 can also be 60 nm or more. The thickness of the first layer 104 may be 150 nm or less, or may be 120 nm or less. The first layer 104 may be a single layer structure or a laminate structure. In the present embodiment, the first layer 104 has a two-layer structure.

第一層104的厚度是使用藉由穿透式電子顯微鏡（Transmission Electron Microscope，以下稱為「TEM」）所拍攝的照片而算出。作為具體例，首先以通過導電粒子100a的中心附近的方式利用超薄切片法（Ultramicrotome method）切出該導電粒子100a的剖面。繼而，使用TEM以25萬倍的倍率觀察所切出的剖面而獲得圖像。繼而，可由根據所得的圖像估算的第一層104（圖2）的剖面積而算出第一層104的厚度。此時，於難以區分第一層104、樹脂粒子101及非導電性無機粒子102的情形時，藉由TEM所附帶的能量分散型X射線檢測器（Energy Dispersive X-Ray detector，以下稱為「EDX」）進行成分分析。藉此，明確區分第一層104、樹脂粒子101及非導電性無機粒子102，算出僅第一層104的厚度。第一層104的厚度是設為10個導電粒子的厚度的平均值。The thickness of the first layer 104 was calculated using a photograph taken by a transmission electron microscope (hereinafter referred to as "TEM"). As a specific example, first, the cross section of the conductive particle 100a is cut by an ultramicrotome method so as to pass near the center of the conductive particle 100a. Then, an image was obtained by observing the cut cross section at a magnification of 250,000 times using a TEM. The thickness of the first layer 104 can then be calculated from the cross-sectional area of the first layer 104 (FIG. 2) estimated from the resulting image. In this case, when it is difficult to distinguish the first layer 104, the resin particles 101, and the non-conductive inorganic particles 102, an energy dispersive X-ray detector (hereinafter referred to as "Energy Dispersive X-ray detector" (hereinafter referred to as " EDX") Performs component analysis. Thereby, the first layer 104, the resin particles 101, and the non-conductive inorganic particles 102 are clearly distinguished, and only the thickness of the first layer 104 is calculated. The thickness of the first layer 104 is an average value of the thickness of 10 conductive particles.

第一層104亦可除了以鎳作為主成分的金屬以外，含有選自由磷及硼所組成的群組中的至少一種。藉此，可提高含有鎳的第一層104的硬度，可容易地將導電粒子經壓縮時的導通電阻保持得低。第一層104亦可含有與磷或硼一併共析的金屬。第一層104所含有的金屬例如為鈷、銅、鋅、鐵、錳、鉻、釩、鉬、鈀、錫、鎢及錸。藉由第一層104含有鎳及所述金屬，可提高第一層104的硬度。藉此，即便於導電粒子100a經壓縮的情形時，亦可抑制形成於非導電性無機粒子102上部的部分（凸起109）被壓壞。所述金屬亦可含有具有高硬度的鎢。第一層104的構成材料例如較佳為鎳（Ni）及磷（P）的組合、鎳（Ni）及硼（B）的組合、鎳（Ni）及鎢（W）及硼（B）的組合、以及鎳（Ni）及鈀（Pd）的組合。The first layer 104 may contain at least one selected from the group consisting of phosphorus and boron, in addition to the metal containing nickel as a main component. Thereby, the hardness of the first layer 104 containing nickel can be increased, and the on-resistance when the conductive particles are compressed can be easily kept low. The first layer 104 may also contain a metal that is co-eprogressed with phosphorus or boron. The metal contained in the first layer 104 is, for example, cobalt, copper, zinc, iron, manganese, chromium, vanadium, molybdenum, palladium, tin, tungsten, and rhenium. The hardness of the first layer 104 can be increased by the first layer 104 containing nickel and the metal. Thereby, even when the conductive particles 100a are compressed, it is possible to suppress the portion (protrusion 109) formed on the upper portion of the non-conductive inorganic particles 102 from being crushed. The metal may also contain tungsten having a high hardness. The constituent material of the first layer 104 is preferably, for example, a combination of nickel (Ni) and phosphorus (P), a combination of nickel (Ni) and boron (B), nickel (Ni), and tungsten (W) and boron (B). Combination, and a combination of nickel (Ni) and palladium (Pd).

於藉由後述無電鍍鎳來形成第一層104的情形時，例如亦可使用次亞磷酸鈉等含磷化合物作為還原劑。於該情形時，可使磷共析，可形成含有鎳-磷合金的第一層104。亦可使用例如二甲基胺硼烷、硼氫化鈉、硼氫化鉀等含硼化合物作為還原劑。於該情形時，可使硼共析，可形成含有鎳-硼合金的第一層104。鎳-硼合金的硬度高於鎳-磷合金。因此，於使用含硼化合物作為還原劑的情形時，即便於導電粒子100a經壓縮的情形時，亦可良好地抑制形成於非導電性無機粒子102上部的凸起109被壓壞。In the case where the first layer 104 is formed by electroless nickel described later, for example, a phosphorus-containing compound such as sodium hypophosphite may be used as the reducing agent. In this case, the phosphorus can be eutectoidally formed to form the first layer 104 containing the nickel-phosphorus alloy. A boron-containing compound such as dimethylamine borane, sodium borohydride or potassium borohydride may also be used as the reducing agent. In this case, boron can be eutectoidally formed to form a first layer 104 containing a nickel-boron alloy. The hardness of the nickel-boron alloy is higher than that of the nickel-phosphorus alloy. Therefore, when a boron-containing compound is used as the reducing agent, even when the conductive particles 100a are compressed, the protrusions 109 formed on the upper portion of the non-conductive inorganic particles 102 can be satisfactorily suppressed from being crushed.

第一層104亦可具有鎳的濃度（含量）隨著遠離複合粒子103的表面而增高的濃度梯度。藉由此種構成，即便於導電粒子100a經壓縮的情形時，亦可保持低的導通電阻。該濃度梯度可為連續性，亦可為非連續性。於鎳的濃度梯度為非連續性的情形時，亦可於複合粒子103的表面設置鎳的含量不同的多個層作為第一層104。於該情形時，設置於遠離複合粒子103之側的層的鎳的濃度增高。The first layer 104 may also have a concentration gradient in which the concentration (content) of nickel increases as it moves away from the surface of the composite particles 103. With such a configuration, even when the conductive particles 100a are compressed, a low on-resistance can be maintained. The concentration gradient can be continuous or discontinuous. When the concentration gradient of nickel is discontinuous, a plurality of layers having different contents of nickel may be provided on the surface of the composite particles 103 as the first layer 104. In this case, the concentration of nickel provided on the layer away from the side of the composite particles 103 is increased.

第一層104中的鎳的含量於第一層104的厚度方向上隨著接近表面而增高。第一層104的表面側的層中的鎳的含量例如成為99質量%～97質量%。所述表面側的層的厚度例如為5 nm～60 nm。該層的厚度亦可為10 nm～50 nm，亦可為15 nm～40 nm。於所述表面側的層的厚度為5 nm以上的情形時，有第一層104的連接電阻值降低的傾向。另一方面，於表面側的層的厚度為60 nm以下的情形時，有導電粒子100a的單分散率進一步提高的傾向。因此，於第一層104的表面側的層中的鎳的含量成為99質量%～97質量%，且所述表面側的層的厚度為5 nm～60 nm的情形時，容易使第一層104更為低電阻化。此外，進一步抑制導電粒子100a彼此的凝聚，容易獲得高的絕緣可靠性。The content of nickel in the first layer 104 is increased as it approaches the surface in the thickness direction of the first layer 104. The content of nickel in the layer on the surface side of the first layer 104 is, for example, 99% by mass to 97% by mass. The thickness of the layer on the surface side is, for example, 5 nm to 60 nm. The thickness of the layer may also be from 10 nm to 50 nm, and may also be from 15 nm to 40 nm. When the thickness of the layer on the surface side is 5 nm or more, the connection resistance value of the first layer 104 tends to decrease. On the other hand, when the thickness of the layer on the surface side is 60 nm or less, the monodispersion ratio of the conductive particles 100a tends to be further improved. Therefore, when the content of nickel in the layer on the surface side of the first layer 104 is 99% by mass to 97% by mass, and the thickness of the layer on the surface side is 5 nm to 60 nm, the first layer is easily formed. 104 is more low resistance. Further, aggregation of the conductive particles 100a with each other is further suppressed, and high insulation reliability is easily obtained.

亦可於第一層104的厚度方向上，於複合粒子103側形成鎳的含量為97質量%以下的層。該複合粒子103側的層的鎳的含量亦可為95質量%以下，亦可為94質量%以下。複合粒子103側的層的厚度可為20 nm以上，亦可為40 nm以上，亦可為50 nm以上。尤其若於第一層104的複合粒子103側形成20 nm以上的94質量%以下的層，則導電粒子100a彼此不易受到磁性的影響，有抑制該導電粒子100a彼此的凝聚的傾向。A layer having a nickel content of 97% by mass or less may be formed on the side of the composite particles 103 in the thickness direction of the first layer 104. The content of nickel in the layer on the side of the composite particles 103 may be 95% by mass or less, or may be 94% by mass or less. The thickness of the layer on the side of the composite particle 103 may be 20 nm or more, 40 nm or more, or 50 nm or more. In particular, when a layer of 94% by mass or more of 20 nm or more is formed on the side of the composite particles 103 of the first layer 104, the conductive particles 100a are less likely to be affected by magnetic properties, and the aggregation of the conductive particles 100a tends to be suppressed.

第一層104中的元素的種類及該元素的含量例如可藉由利用超薄切片法切出導電粒子的剖面後，藉由TEM所附帶的EDX進行成分分析而測定。The type of the element in the first layer 104 and the content of the element can be measured, for example, by cutting out the cross section of the conductive particle by the ultrathin sectioning method, and then performing component analysis by EDX attached to the TEM.

＜無電鍍鎳＞ 本實施形態中，第一層104是藉由無電鍍鎳而形成。於該情形時，無電鍍鎳液含有水溶性鎳化合物。無電鍍鎳液亦可更含有選自由穩定劑（例如硝酸鉍）、錯合劑、還原劑、pH調整劑及界面活性劑所組成的群組中的至少一種化合物。<Electroless Nickel Plating> In the present embodiment, the first layer 104 is formed by electroless nickel plating. In this case, the electroless nickel solution contains a water-soluble nickel compound. The electroless nickel plating solution may further contain at least one compound selected from the group consisting of a stabilizer (for example, cerium nitrate), a binder, a reducing agent, a pH adjuster, and a surfactant.

水溶性鎳化合物可使用：硫酸鎳、氯化鎳、次亞磷酸鎳等水溶性鎳無機鹽；乙酸鎳、蘋果酸鎳等水溶性鎳有機鹽等。水溶性鎳化合物可單獨使用一種或組合使用兩種以上。As the water-soluble nickel compound, a water-soluble nickel inorganic salt such as nickel sulfate, nickel chloride or nickel hypophosphite; a water-soluble nickel organic salt such as nickel acetate or nickel malate; and the like can be used. The water-soluble nickel compounds may be used alone or in combination of two or more.

無電鍍鎳液中的水溶性鎳化合物的濃度較佳為0.001 mol/L～1 mol/L，更佳為0.01 mol/L～0.3 mol/L。藉由水溶性鎳化合物的濃度為所述範圍內，可充分獲得鍍敷被膜的析出速度，並且可抑制鍍敷液的黏度變得過高而提高鎳析出的均勻性。The concentration of the water-soluble nickel compound in the electroless nickel plating solution is preferably from 0.001 mol/L to 1 mol/L, more preferably from 0.01 mol/L to 0.3 mol/L. When the concentration of the water-soluble nickel compound is within the above range, the deposition rate of the plating film can be sufficiently obtained, and the viscosity of the plating solution can be prevented from becoming excessively high to improve the uniformity of nickel deposition.

錯合劑只要為作為錯合劑而發揮功能的化合物即可，具體可列舉：乙二胺四乙酸；乙二胺四乙酸的鈉鹽（例如1-鈉鹽、2-鈉鹽、3-鈉鹽及4-鈉鹽）；乙二胺三乙酸；硝基四乙酸、其鹼鹽；醛醣酸（glyconic acid）、酒石酸、葡萄糖酸鹽（gluconate）、檸檬酸、葡萄糖酸（gluconic acid）、琥珀酸、焦磷酸、甘醇酸、乳酸、蘋果酸、丙二酸、該些酸的鹼鹽（例如鈉鹽）；三乙醇胺葡萄糖酸(γ)-內酯等。錯合劑亦可使用所述以外的材料。錯合劑可單獨使用一種或組合使用兩種以上。The compounding agent may be a compound that functions as a blocking agent, and specific examples thereof include ethylenediaminetetraacetic acid; sodium salt of ethylenediaminetetraacetic acid (for example, 1-sodium salt, 2-sodium salt, 3-sodium salt, and 4-sodium salt); ethylenediamine triacetic acid; nitrotetraacetic acid, its alkali salt; glycolic acid, tartaric acid, gluconate, citric acid, gluconic acid, succinic acid , pyrophosphoric acid, glycolic acid, lactic acid, malic acid, malonic acid, alkali salts of such acids (for example, sodium salts); triethanolamine gluconic acid (γ)-lactones, and the like. Materials other than the above may also be used as the wrong agent. The complexing agents may be used alone or in combination of two or more.

無電鍍鎳液中的錯合劑的濃度通常較佳為0.001 mol/L～2 mol/L，更佳為0.002 mol/L～1 mol/L。藉由錯合劑的濃度為所述範圍內，可抑制鍍敷液中的氫氧化鎳的沈澱及鍍敷液的分解並且獲得鍍敷被膜的充分的析出速度，並且可抑制鍍敷液的黏度變得過高而提高鎳析出的均勻性。錯合劑的濃度亦可根據種類而不同。The concentration of the complexing agent in the electroless nickel plating solution is usually preferably from 0.001 mol/L to 2 mol/L, more preferably from 0.002 mol/L to 1 mol/L. When the concentration of the binder is within the above range, precipitation of nickel hydroxide in the plating solution and decomposition of the plating solution can be suppressed, a sufficient deposition rate of the plating film can be obtained, and viscosity of the plating solution can be suppressed. It is too high to increase the uniformity of nickel precipitation. The concentration of the wrong agent may also vary depending on the type.

還原劑可使用無電鍍鎳液中所用的公知的還原劑。還原劑可列舉：次亞磷酸鈉、次亞磷酸鉀等次亞磷酸化合物；硼氫化鈉、硼氫化鉀、二甲基胺硼烷等硼氫化合物；肼類等。As the reducing agent, a known reducing agent used in the electroless nickel plating solution can be used. Examples of the reducing agent include hypophosphorous compounds such as sodium hypophosphite and potassium hypophosphite; borohydrides such as sodium borohydride, potassium borohydride and dimethylamine borane; and hydrazines.

無電鍍鎳液中的還原劑的濃度通常較佳為0.001 mol/L～1 mol/L，更佳為0.002 mol/L～0.5 mol/L。若還原劑的濃度為所述範圍內，則可充分獲得鍍敷液中的鎳離子的還原速度，並且抑制鍍敷液的分解。關於還原劑的濃度，亦可根據還原劑的種類而不同。The concentration of the reducing agent in the electroless nickel plating solution is usually preferably from 0.001 mol/L to 1 mol/L, more preferably from 0.002 mol/L to 0.5 mol/L. When the concentration of the reducing agent is within the above range, the reduction rate of nickel ions in the plating solution can be sufficiently obtained, and decomposition of the plating solution can be suppressed. The concentration of the reducing agent may vary depending on the type of the reducing agent.

pH調整劑例如可列舉酸性的pH調整劑及鹼性的pH調整劑。酸性的pH調整劑可列舉：鹽酸；硫酸；硝酸；磷酸；乙酸；甲酸；氯化銅；硫酸鐵等鐵化合物；鹼金屬氯化物；過硫酸銨；含有該些化合物的一種以上的水溶液；鉻酸、鉻酸-硫酸、鉻酸-氫氟酸、重鉻酸、重鉻酸-氟硼酸等酸性的含有六價鉻的水溶液等。鹼性的pH調整劑可列舉：氫氧化鈉、氫氧化鉀、碳酸鈉等鹼金屬的氫氧化物；鹼土類金屬的氫氧化物；乙二胺、甲胺、2-胺基乙醇等含有胺基的化合物；含有該些化合物的一種以上的溶液等。Examples of the pH adjuster include an acidic pH adjuster and an alkaline pH adjuster. The acidic pH adjusting agent may, for example, be hydrochloric acid; sulfuric acid; nitric acid; phosphoric acid; acetic acid; formic acid; copper chloride; iron compound such as iron sulfate; alkali metal chloride; ammonium persulfate; more than one aqueous solution containing the compounds; An acidic aqueous solution containing hexavalent chromium such as acid, chromic acid-sulfuric acid, chromic acid-hydrofluoric acid, dichromic acid or dichromic acid-fluoroboric acid. Examples of the alkaline pH adjuster include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, and sodium carbonate; hydroxides of alkaline earth metals; and amines such as ethylenediamine, methylamine, and 2-aminoethanol. a compound of the group; one or more solutions containing the compounds, and the like.

界面活性劑可使用陽離子界面活性劑、陰離子界面活性劑、兩性界面活性劑、非離子界面活性劑、該些界面活性劑的混合物等。As the surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a mixture of these surfactants, or the like can be used.

＜無電鍍鎳的前處理＞ 於藉由上文所述的無電鍍鎳來形成第一層104的情形時，亦可對複合粒子103預先進行鈀觸媒化處理作為前處理。鈀觸媒化處理可利用公知的方法來進行。該方法並無特別限定，例如可列舉使用被稱為鹼性種液（seeder）或酸性種液的觸媒化處理液的觸媒化處理方法。<Pretreatment of Electroless Nickel Plating> When the first layer 104 is formed by electroless nickel described above, the composite particles 103 may be subjected to palladium catalyst treatment in advance as a pretreatment. The palladium photocatalytic treatment can be carried out by a known method. The method is not particularly limited, and examples thereof include a catalyst treatment method using a catalytic treatment liquid called a seed seed or an acid seed liquid.

使用鹼性種液的觸媒化處理方法例如可列舉以下方法。首先使樹脂粒子浸漬於含有經2-胺基吡啶配位的鈀離子的溶液中，由此使鈀離子吸附於樹脂粒子表面。水洗後，使吸附有鈀離子的樹脂粒子分散於含有次亞磷酸鈉、硼氫化鈉、二甲基胺硼烷、肼、福馬林等還原劑的溶液中而進行還原處理。藉此，將吸附於樹脂粒子表面的鈀離子還原成金屬鈀。The following method can be mentioned, for example, the catalytic treatment method using an alkaline seed liquid. First, the resin particles are immersed in a solution containing palladium ions coordinated by 2-aminopyridine, whereby palladium ions are adsorbed on the surface of the resin particles. After washing with water, the resin particles having palladium ions adsorbed thereon are dispersed in a solution containing a reducing agent such as sodium hypophosphite, sodium borohydride, dimethylamine borane, hydrazine or formalin to carry out a reduction treatment. Thereby, palladium ions adsorbed on the surface of the resin particles are reduced to metal palladium.

使用酸性種液的觸媒化處理方法例如可列舉以下方法。首先使樹脂粒子分散於氯化亞錫溶液中，進行使錫離子吸附於樹脂粒子表面的感受性化處理之後，進行水洗。然後，使其分散於含有氯化鈀的溶液中，進行使樹脂粒子表面捕捉鈀離子的活化處理。水洗後，使其分散於含有次亞磷酸鈉、硼氫化鈉、二甲基胺硼烷、肼、福馬林等還原劑的溶液中而進行還原處理。藉此，將吸附於樹脂粒子表面的鈀離子還原成金屬鈀。The following method can be mentioned, for example, the catalytic treatment method using an acidic seed liquid. First, the resin particles are dispersed in a stannous chloride solution, and the tin ions are adsorbed on the surface of the resin particles to be subjected to a sensitization treatment, followed by washing with water. Then, it is dispersed in a solution containing palladium chloride to carry out an activation treatment for capturing palladium ions on the surface of the resin particles. After washing with water, it is dispersed in a solution containing a reducing agent such as sodium hypophosphite, sodium borohydride, dimethylamine borane, hydrazine or formalin to carry out a reduction treatment. Thereby, palladium ions adsorbed on the surface of the resin particles are reduced to metal palladium.

若將鹼性種液與酸性種液比較，則就溶液的pH值的觀點而言，較佳為酸性種液。如上所述，pH值越低，樹脂粒子101本身的界達電位越向正值偏移，故較佳為使用酸性種液。另一方面，pH值越高，非導電性無機粒子102的界達電位越向負值偏移，故較佳為使用鹼性種液。此處，若考慮到樹脂粒子101與非導電性無機粒子102的界達電位之差，則有pH值越低而界達電位之差越增大的傾向。藉由使用酸性種液，有可維持藉由靜電力使非導電性無機粒子102牢固地接著於樹脂粒子101的狀態的傾向。When the alkaline seed solution is compared with the acid seed solution, the acid seed solution is preferred from the viewpoint of the pH of the solution. As described above, the lower the pH value, the more the boundary potential of the resin particles 101 itself shifts to a positive value, so it is preferred to use an acidic seed solution. On the other hand, the higher the pH value, the more the boundary potential of the non-conductive inorganic particles 102 shifts to a negative value, so it is preferable to use an alkaline seed liquid. When the difference between the boundary potentials of the resin particles 101 and the non-conductive inorganic particles 102 is considered, the difference in the pH value tends to increase as the difference in the potential is increased. By using an acidic seed liquid, there is a tendency that the non-conductive inorganic particles 102 are firmly adhered to the resin particles 101 by electrostatic force.

於使用鹼性種液的情形時，較佳為於疏水化處理劑中具有選自由胺基、羧酸基、羥基、磺酸基、縮水甘油基及腈基所組成的群組中的至少一種。例如羧酸基及羥基的H+ 於pH值7以上時解離，非導電性無機粒子102的界達電位進一步向負值側偏移。然而，樹脂粒子101的界達電位亦根據pH值而變動，故較佳為以可保持樹脂粒子101與非導電性無機粒子102的界達電位之差大的方式選擇種液的種類。In the case of using an alkaline seed solution, it is preferred to have at least one selected from the group consisting of an amine group, a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, and a nitrile group in the hydrophobizing treatment agent. . For example, when the H + of the carboxylic acid group and the hydroxyl group is dissociated at a pH of 7 or more, the boundary potential of the non-conductive inorganic particles 102 is further shifted to the negative side. However, since the boundary potential of the resin particles 101 also varies depending on the pH value, it is preferable to select the type of the seed liquid so that the difference between the boundary potentials of the resin particles 101 and the non-conductive inorganic particles 102 can be kept large.

該些鈀觸媒化處理方法中，使鈀離子吸附於表面後進行水洗，進而分散於含有還原劑的溶液中。藉此，將吸附於複合粒子103的表面的鈀離子還原，藉此可形成原子水準的大小的鈀析出核。In the palladium catalytic treatment method, palladium ions are adsorbed on the surface, washed with water, and further dispersed in a solution containing a reducing agent. Thereby, the palladium ions adsorbed on the surface of the composite particles 103 are reduced, whereby a palladium precipitation nucleus having an atomic level can be formed.

＜凸起＞ 導電粒子100a的凸起109的面積是指導電粒子100a的正投影面中，具有導電粒子100a的直徑的1/2直徑的同心圓內的凸起109的面積、或由鄰接的凸起109彼此之間的凹部所劃分的各凸起109的輪廓的面積。凸起109的直徑（外徑）是指對導電粒子100a的正投影面中具有導電粒子100a的直徑的1/2直徑的同心圓內所存在的凸起109而算出，具有與該凸起109的面積相同的面積的正圓的直徑。具體而言，對藉由SEM以3萬倍觀察導電粒子100a所得的圖像進行分析，劃定凸起109的輪廓，藉此求出各凸起的面積。然後根據該面積而算出直徑。<Bump> The area of the protrusion 109 of the conductive particle 100a is the area of the protrusion 109 in the concentric circle having the diameter of the conductive particle 100a in the orthographic projection plane of the electric particle 100a, or by the adjacent The area of the outline of each of the projections 109 in which the projections 109 are recessed from each other. The diameter (outer diameter) of the protrusion 109 is calculated by expressing the protrusion 109 existing in a concentric circle having a diameter of 1/2 of the diameter of the conductive particle 100a in the orthographic projection surface of the conductive particle 100a, and having the protrusion 109 The area of the same area of the diameter of the perfect circle. Specifically, the image obtained by observing the conductive particles 100a by SEM at 30,000 times is analyzed, and the outline of the protrusions 109 is defined, thereby obtaining the area of each of the protrusions. Then, the diameter is calculated from the area.

關於凸起109的面積的比例（被覆率），可將導電粒子100a的正投影面中具有導電粒子100a的直徑的1/2直徑的同心圓的總面積作為分母，將具有導電粒子100a的直徑的1/2直徑的同心圓內的凸起109的面積的總和作為分子，以除算的百分率來表示。凸起109的面積的比例（被覆率）可為50%以上，亦可為65%以上，亦可為80%以上。若凸起109的被覆率為所述範圍內，則即便於將導電粒子100a置於高濕下的情形時，其導通電阻亦不易增加。Regarding the ratio (coverage ratio) of the area of the protrusions 109, the total area of the concentric circles having the diameter of the 1/2 diameter of the diameter of the conductive particles 100a in the orthographic projection surface of the conductive particles 100a can be used as the denominator, and the diameter of the conductive particles 100a can be made. The sum of the areas of the protrusions 109 in the 1/2 diameter concentric circles is taken as a numerator, expressed as a percentage of division. The ratio (coverage ratio) of the area of the protrusions 109 may be 50% or more, may be 65% or more, or may be 80% or more. When the coverage of the bumps 109 is within the above range, even when the conductive particles 100a are placed under high humidity, the on-resistance does not easily increase.

凸起109的最適的直徑（外徑）的大小、及凸起109的被覆率的最適比例是根據樹脂粒子101及非導電性無機粒子102的直徑的大小而不同。無論使用哪種非導電性無機粒子102，均可藉由將非導電性無機粒子102對樹脂粒子101的被覆率設為20%～80%，而將凸起109的被覆率設為50%以上。The optimum diameter (outer diameter) of the projections 109 and the optimum ratio of the coverage of the projections 109 are different depending on the diameters of the resin particles 101 and the non-conductive inorganic particles 102. When the non-conductive inorganic particles 102 are used, the coverage of the non-conductive inorganic particles 102 to the resin particles 101 can be set to 20% to 80%, and the coverage of the projections 109 can be made 50% or more. .

於非導電性無機粒子102的平均粒徑小於50 nm的情形時，於每一個導電粒子100a中，直徑（外徑）小於100 nm的凸起109相對於總凸起數的比例亦可小於80%，直徑為100 nm以上且小於200 nm的凸起109相對於總凸起數的比例亦可為20%～80%，直徑為200 nm以上的凸起109相對於總凸起數的比例亦可小於20%。於每一個導電粒子100a中，直徑小於100 nm的凸起109相對於總凸起數的比例亦可小於70%，直徑為100 nm以上且小於200 nm的凸起109相對於總凸起數的比例亦可為30%～70%，直徑為200 nm以上的凸起109相對於總凸起數的比例亦可小於15%。於每一個導電粒子100a中，直徑（外徑）小於100 nm的凸起109的個數可為50個以上，亦可為80個以上。於每一個導電粒子100a中，直徑為100 nm以上且小於200 nm的凸起109的個數可為30個以上，亦可為50個以上。於每一個導電粒子100a中，直徑為200 nm以上且350 nm以下的凸起109的個數可為15個以內，亦可為2個～13個以內，亦可為2個～10個以內。In the case where the average particle diameter of the non-conductive inorganic particles 102 is less than 50 nm, the ratio of the protrusions 109 having a diameter (outer diameter) of less than 100 nm to the total number of protrusions may be less than 80 in each of the conductive particles 100a. %, the ratio of the protrusions 109 having a diameter of 100 nm or more and less than 200 nm to the total number of protrusions may be 20% to 80%, and the ratio of the protrusions 109 having a diameter of 200 nm or more to the total number of protrusions is also Can be less than 20%. In each of the conductive particles 100a, the ratio of the protrusions 109 having a diameter of less than 100 nm to the total number of protrusions may be less than 70%, and the protrusions 109 having a diameter of 100 nm or more and less than 200 nm with respect to the total number of protrusions The ratio may also be 30% to 70%, and the ratio of the protrusions 109 having a diameter of 200 nm or more to the total number of protrusions may be less than 15%. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter (outer diameter) of less than 100 nm may be 50 or more, or may be 80 or more. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter of 100 nm or more and less than 200 nm may be 30 or more, or may be 50 or more. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter of 200 nm or more and 350 nm or less may be 15 or less, or may be 2 to 13 or less, or may be 2 to 10 or less.

於非導電性無機粒子102的平均粒徑為50 nm以上且小於90 nm的情形時，於每一個導電粒子100a中，直徑（外徑）小於100 nm的凸起109相對於總凸起數的比例亦可小於70%，直徑為100 nm以上且小於200 nm的凸起109相對於總凸起數的比例亦可為20%～80%，直徑為200 nm以上的凸起109相對於總凸起數的比例亦可小於20%。於每一個導電粒子100a中，直徑小於100 nm的凸起109相對於總凸起數的比例亦可小於60%，直徑為100 nm以上且小於200 nm的凸起109相對於總凸起數的比例亦可為30%～70%，直徑為200 nm以上的凸起109相對於總凸起數的比例亦可小於15%。於每一個導電粒子100a中，直徑（外徑）小於100 nm的凸起109的個數可為30個以上，亦可為50個以上。於每一個導電粒子100a中，直徑為100 nm以上且小於200 nm的凸起109的個數可為30個以上，亦可為50個以上。於每一個導電粒子100a中，直徑為200 nm以上且350 nm以下的凸起109的個數可為15個以內，亦可為2個～13個以內，亦可為2個～10個以內。In the case where the average particle diameter of the non-conductive inorganic particles 102 is 50 nm or more and less than 90 nm, in each of the conductive particles 100a, the protrusions 109 having a diameter (outer diameter) of less than 100 nm with respect to the total number of protrusions The ratio may be less than 70%, the ratio of the protrusions 109 having a diameter of 100 nm or more and less than 200 nm to the total number of protrusions may be 20% to 80%, and the protrusions 109 having a diameter of 200 nm or more with respect to the total protrusion. The proportion of the number can also be less than 20%. In each of the conductive particles 100a, the ratio of the protrusions 109 having a diameter of less than 100 nm to the total number of protrusions may be less than 60%, and the protrusions 109 having a diameter of 100 nm or more and less than 200 nm with respect to the total number of protrusions The ratio may also be 30% to 70%, and the ratio of the protrusions 109 having a diameter of 200 nm or more to the total number of protrusions may be less than 15%. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter (outer diameter) of less than 100 nm may be 30 or more, or may be 50 or more. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter of 100 nm or more and less than 200 nm may be 30 or more, or may be 50 or more. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter of 200 nm or more and 350 nm or less may be 15 or less, or may be 2 to 13 or less, or may be 2 to 10 or less.

於非導電性無機粒子102的平均粒徑為90 nm以上且小於130 nm的情形時，於每一個導電粒子100a中，直徑（外徑）小於100 nm的凸起109相對於總凸起數的比例亦可小於70%，直徑為100 nm以上且小於200 nm的凸起109相對於總凸起數的比例亦可為20%～90%，直徑為200 nm以上的凸起109相對於總凸起數的比例亦可小於70%。進而，於每一個導電粒子100a中，直徑小於100 nm的凸起109相對於總凸起數的比例亦可小於60%，直徑為100 nm以上且小於200 nm的凸起109相對於總凸起數的比例亦可為30%～80%，直徑為200 nm以上的凸起109相對於總凸起數的比例亦可小於50%。於每一個導電粒子100a中，直徑（外徑）小於100 nm的凸起109的個數可為30個以上，亦可為50個以上。於每一個導電粒子100a中，直徑為100 nm以上且小於200 nm的凸起109的個數可為30個以上，亦可為50個以上。於每一個導電粒子100a中，直徑為200 nm以上且350 nm以下的凸起109的個數可為15個以內，亦可為2個～13個以內，亦可為2個～10個以內。In the case where the average particle diameter of the non-conductive inorganic particles 102 is 90 nm or more and less than 130 nm, in each of the conductive particles 100a, the protrusions 109 having a diameter (outer diameter) of less than 100 nm with respect to the total number of protrusions The ratio may be less than 70%, the ratio of the protrusions 109 having a diameter of 100 nm or more and less than 200 nm to the total number of protrusions may be 20% to 90%, and the protrusions 109 having a diameter of 200 nm or more with respect to the total protrusion. The proportion of the number can also be less than 70%. Further, in each of the conductive particles 100a, the ratio of the protrusion 109 having a diameter of less than 100 nm to the total number of protrusions may be less than 60%, and the protrusion 109 having a diameter of 100 nm or more and less than 200 nm with respect to the total protrusion The ratio of the number may also be 30% to 80%, and the ratio of the protrusions 109 having a diameter of 200 nm or more to the total number of protrusions may be less than 50%. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter (outer diameter) of less than 100 nm may be 30 or more, or may be 50 or more. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter of 100 nm or more and less than 200 nm may be 30 or more, or may be 50 or more. In each of the conductive particles 100a, the number of the protrusions 109 having a diameter of 200 nm or more and 350 nm or less may be 15 or less, or may be 2 to 13 or less, or may be 2 to 10 or less.

於與非導電性無機粒子102的平均粒徑相對應的凸起的個數為所述範圍內的情形時，例如於使導電粒子100a介於相對向的電極間而將電極彼此壓接連接時，可獲得充分低的導通電阻。When the number of the protrusions corresponding to the average particle diameter of the non-conductive inorganic particles 102 is within the above range, for example, when the conductive particles 100a are interposed between the opposing electrodes, the electrodes are pressure-bonded to each other. A sufficiently low on-resistance can be obtained.

＜導電粒子的單分散率＞ 導電粒子100a的單分散率可為96.0%以上，亦可為98.0%以上。藉由導電粒子100a的單分散率為所述範圍內，例如可於吸濕試驗後獲得高的絕緣可靠性。導電粒子100a的單分散率例如可使用50,000個導電粒子藉由庫勒粒度分析計數儀（COULER MULTISIZER）II（貝克曼庫爾特（Beckman Coulter）股份有限公司製造，商品名）而測定。<Monogen Dispersion Rate of Conductive Particles> The monodispersion ratio of the conductive particles 100a may be 96.0% or more, or may be 98.0% or more. By the monodispersity of the conductive particles 100a being within the above range, for example, high insulation reliability can be obtained after the moisture absorption test. The monodispersity of the conductive particles 100a can be measured, for example, by using 50,000 conductive particles by a COULER MULTISIZER II (manufactured by Beckman Coulter Co., Ltd., trade name).

＜導電粒子的製造方法＞ 繼而，對第一實施形態的導電粒子100a的製造方法加以說明。首先，作為第一步驟，藉由陽離子性聚合物將樹脂粒子101被覆（第一被覆步驟）。於第一步驟中，將表面上具有羥基等的樹脂粒子101分散於陽離子性聚合物溶液中，利用陽離子性聚合物將該樹脂粒子101被覆。<Method for Producing Conductive Particles> Next, a method for producing the conductive particles 100a of the first embodiment will be described. First, as a first step, the resin particles 101 are coated by a cationic polymer (first covering step). In the first step, the resin particles 101 having a hydroxyl group or the like on the surface are dispersed in the cationic polymer solution, and the resin particles 101 are coated with the cationic polymer.

其次，作為第二步驟，藉由疏水化處理劑將非導電性無機粒子102的表面被覆（第二被覆步驟）。疏水化處理劑對非導電性無機粒子102的被覆是於水、有機溶劑、或水與水溶性的有機溶劑的混合溶液中或者氣相中進行。可使用的水溶性的有機溶劑例如可列舉甲醇、乙醇、丙醇、丙酮、二甲基甲醯胺及乙腈。亦可購入預先經疏水化處理劑被覆的非導電性無機粒子，用作非導電性無機粒子102。Next, as a second step, the surface of the non-conductive inorganic particles 102 is covered by a hydrophobizing agent (second covering step). The coating of the non-conductive inorganic particles 102 by the hydrophobization treatment agent is carried out in water, an organic solvent, or a mixed solution of water and a water-soluble organic solvent or in a gas phase. Examples of the water-soluble organic solvent that can be used include methanol, ethanol, propanol, acetone, dimethylformamide, and acetonitrile. Non-conductive inorganic particles coated with a hydrophobizing agent in advance may be purchased and used as the non-conductive inorganic particles 102.

然後，作為第三步驟，將非導電性無機粒子102接著於樹脂粒子101的表面，形成複合粒子103（粒子形成步驟）。關於非導電性無機粒子102對樹脂粒子101的接著，例如藉由有機溶劑、或水與水溶性的有機溶劑的混合溶液來進行處理。較佳為僅使用有機溶劑使非導電性無機粒子102接著於樹脂粒子101。若考慮到樹脂粒子101與非導電性無機粒子102的界達電位之差，則相較於使用含有水的有機溶劑的情形，於僅使用有機溶劑的情形時，非導電性無機粒子102與樹脂粒子101的界達電位之差增大。若更強的靜電力於非導電性無機粒子102與樹脂粒子101之間發揮作用，則可將非導電性無機粒子102牢固地接著於樹脂粒子101。結果，於用以進行無電鍍鎳的前處理步驟、及無電鍍鎳步驟中，非導電性無機粒子102不易脫落。Then, as a third step, the non-conductive inorganic particles 102 are attached to the surface of the resin particles 101 to form composite particles 103 (particle formation step). The subsequent treatment of the resin particles 101 by the non-conductive inorganic particles 102 is carried out, for example, by an organic solvent or a mixed solution of water and a water-soluble organic solvent. It is preferred that the non-conductive inorganic particles 102 are adhered to the resin particles 101 using only an organic solvent. When the difference between the boundary potentials of the resin particles 101 and the non-conductive inorganic particles 102 is taken into consideration, the non-conductive inorganic particles 102 and the resin are used in the case where only an organic solvent is used as compared with the case of using an organic solvent containing water. The difference in the boundary potential of the particles 101 increases. When a stronger electrostatic force acts between the non-conductive inorganic particles 102 and the resin particles 101, the non-conductive inorganic particles 102 can be firmly adhered to the resin particles 101. As a result, the non-conductive inorganic particles 102 are less likely to fall off in the pretreatment step for performing electroless nickel plating and the electroless nickel plating step.

繼而，作為第四步驟，藉由無電鍍敷且以金屬層被覆複合粒子103（第三被覆步驟）。於第四步驟中，將含有鎳的第一層104設為金屬層，藉由該第一層104被覆複合粒子103的整個表面（即，樹脂粒子101及非導電性無機粒子102的露出的整個面）。於該情形時，亦可對複合粒子103進行鈀觸媒化處理來作為用以藉由無電鍍鎳形成第一層104的前處理步驟。鈀觸媒化處理可利用公知的方法進行，例如利用上文所述的使用被稱為鹼性種液或酸性種液的觸媒化處理液的觸媒化處理方法來進行。即便預先於樹脂粒子101的表面配置非導電性無機粒子102，樹脂粒子101與非導電性無機粒子102的界達電位亦受到周圍的pH值的影響而變化。Then, as a fourth step, the composite particles 103 are coated with a metal layer by electroless plating (third coating step). In the fourth step, the first layer 104 containing nickel is used as a metal layer, and the entire surface of the composite particles 103 is covered by the first layer 104 (that is, the entire exposed portion of the resin particles 101 and the non-conductive inorganic particles 102) surface). In this case, the composite particles 103 may be subjected to palladium-catalytic treatment as a pretreatment step for forming the first layer 104 by electroless nickel plating. The palladium catalytic treatment can be carried out by a known method, for example, by the above-described catalytic treatment method using a catalytic treatment liquid called an alkaline seed solution or an acid seed solution. Even if the non-conductive inorganic particles 102 are placed on the surface of the resin particles 101 in advance, the boundary potential between the resin particles 101 and the non-conductive inorganic particles 102 is changed by the influence of the surrounding pH.

於使用酸性種液的情形時，觸媒化處理液的pH值成為1左右。於該情形時，樹脂粒子101的界達電位的測定值、與非導電性無機粒子102的界達電位的測定值之差的絕對值成為50 mV以上。因此，經疏水化處理劑被覆的非導電性無機粒子102不易脫落。另一方面，於使用通常所用的鹼性種液的情形時，觸媒化處理液的pH值成為10～11。於該情形時，樹脂粒子101的界達電位的測定值、與非導電性無機粒子102的界達電位的測定值之差的絕對值成為30 mV～50 mV左右。因此，於所述前處理步驟中，非導電性無機粒子102容易自樹脂粒子101脫落。When an acidic seed solution is used, the pH of the catalytic treatment liquid is about 1. In this case, the absolute value of the difference between the measured value of the boundary potential of the resin particles 101 and the measured value of the boundary potential of the non-conductive inorganic particles 102 is 50 mV or more. Therefore, the non-conductive inorganic particles 102 coated with the hydrophobizing agent are less likely to fall off. On the other hand, when using an alkaline seed liquid which is generally used, the pH of the catalytic treatment liquid is 10 to 11. In this case, the absolute value of the difference between the measured value of the boundary potential of the resin particle 101 and the measured value of the boundary potential of the non-conductive inorganic particle 102 is about 30 mV to 50 mV. Therefore, in the pretreatment step, the non-conductive inorganic particles 102 are easily peeled off from the resin particles 101.

關於以上所說明的第一實施形態的導電粒子100a的作用效果，一面與所述專利文獻1～專利文獻3比較一面進行說明。於依照所述專利文獻1、專利文獻2中記載的方法形成導電粒子的情形時，難以控制該導電粒子的凸起的個數、大小及形狀，有使用該些導電粒子的接著劑等的電阻值變高的傾向。因此，於欲提高所述專利文獻1、專利文獻2中記載的導電粒子的導電性的情形時，有於該導電粒子的表面形成長度超過500 nm的異常大小的凸起（異常凸起）的傾向。使用此種具有異常凸起（異常析出部）的導電粒子的接著劑有絕緣可靠性降低的傾向。尤其於依照專利文獻2中記載的方法形成導電粒子的情形時，為了降低導電粒子的電阻值，必須使充分量的芯物質附著於成為基材的微粒子的表面。然而，若增加該芯物質的附著量，則有芯物質自身於微粒子的表面凝聚，容易形成異常凸起的傾向。The effects of the conductive particles 100a of the first embodiment described above will be described in comparison with Patent Documents 1 to 3. When the conductive particles are formed by the method described in Patent Document 1 and Patent Document 2, it is difficult to control the number, size, and shape of the protrusions of the conductive particles, and there is a resistor such as an adhesive using the conductive particles. The tendency to get higher. Therefore, when the conductivity of the conductive particles described in Patent Document 1 and Patent Document 2 is to be improved, an abnormally large number of protrusions (abnormal protrusions) having a length exceeding 500 nm are formed on the surface of the conductive particles. tendency. The use of such an adhesive having conductive particles having abnormal protrusions (abnormal precipitation portions) tends to lower the insulation reliability. In particular, when the conductive particles are formed by the method described in Patent Document 2, in order to reduce the electric resistance value of the conductive particles, it is necessary to adhere a sufficient amount of the core material to the surface of the fine particles serving as the base material. However, when the amount of adhesion of the core material is increased, the core material itself aggregates on the surface of the fine particles, and tends to form abnormal protrusions.

專利文獻3中記載的方法中，使成為芯物質的非導電性物質藉由化學鍵吸附於樹脂粒子的表面而形成複合粒子。若為了於該複合粒子上被覆金屬層而進行用以進行無電鍍鎳的前處理步驟、或無電鍍鎳步驟，則非導電性物質自樹脂粒子脫落。因此，難以控制複合粒子的凸起的個數、大小及形狀，有使用該些導電粒子的接著劑等的電阻值變高的傾向。進而，若於無電鍍鎳步驟時，已析出鎳的非導電性物質脫落，則成為金屬異物的產生源。於該金屬異物再附著於複合粒子的情形時，有時形成異常凸起（異常析出部）。進而，有時所述金屬異物本身含有於接著劑中，由此導致絕緣可靠性降低。In the method described in Patent Document 3, the non-conductive substance serving as the core material is adsorbed on the surface of the resin particle by a chemical bond to form a composite particle. When a pretreatment step for performing electroless nickel or a step of electroless nickel plating is performed to coat the metal layer on the composite particles, the non-conductive material is detached from the resin particles. Therefore, it is difficult to control the number, size, and shape of the bumps of the composite particles, and the electric resistance value of the adhesive or the like using the conductive particles tends to be high. Further, when the non-electroconductive material having precipitated nickel falls off during the electroless nickel plating step, it becomes a source of metal foreign matter. When the metal foreign matter adheres to the composite particles, an abnormal protrusion (abnormal precipitation portion) may be formed. Further, sometimes the metal foreign matter itself is contained in the adhesive, thereby causing a decrease in insulation reliability.

相對於該些專利文獻1～專利文獻3，根據藉由第一實施形態的製造方法所形成的導電粒子100a，樹脂粒子101是藉由陽離子性聚合物而被覆，非導電性無機粒子102是藉由疏水化處理劑而被覆。非導電性無機粒子102的表面的界達電位藉由疏水化而向負值偏移。藉此，靜電力於樹脂粒子101與非導電性無機粒子102之間發揮作用，非導電性無機粒子102不易自樹脂粒子101的表面脫落。因此，配置於樹脂粒子101的表面的非導電性無機粒子102的個數的控制變容易，並且於複合粒子103上形成良好的凸起109。因此，即便於將使用調配有導電粒子100a的異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。此外，自樹脂粒子101脫落的非導電性無機粒子102的個數減少，故於複合粒子103上不易產生異常地成長的凸起。因此，於將導電粒子100a調配至異向導電性接著劑中的情形等時導電粒子100a彼此不易導通，導電粒子100a的絕緣可靠性亦提高。因此，藉由將所述導電粒子調配至異向導電性接著劑中，可兼具優異的導通可靠性及絕緣可靠性。With respect to the conductive particles 100a formed by the manufacturing method of the first embodiment, the resin particles 101 are coated with a cationic polymer, and the non-conductive inorganic particles 102 are borrowed from the above-mentioned Patent Documents 1 to 3. It is covered by a hydrophobizing agent. The boundary potential of the surface of the non-conductive inorganic particles 102 is shifted to a negative value by hydrophobization. Thereby, the electrostatic force acts between the resin particles 101 and the non-conductive inorganic particles 102, and the non-conductive inorganic particles 102 are less likely to fall off from the surface of the resin particles 101. Therefore, the control of the number of the non-conductive inorganic particles 102 disposed on the surface of the resin particles 101 is facilitated, and a good protrusion 109 is formed on the composite particles 103. Therefore, even when the bonded structure using the anisotropic conductive adhesive in which the conductive particles 100a are disposed is stored under high temperature and high humidity, the conduction reliability is improved. Further, since the number of the non-conductive inorganic particles 102 that have fallen off from the resin particles 101 is reduced, it is less likely that the composite particles 103 are abnormally grown. Therefore, when the conductive particles 100a are blended into the anisotropic conductive adhesive or the like, the conductive particles 100a are not easily electrically connected to each other, and the insulation reliability of the conductive particles 100a is also improved. Therefore, by blending the conductive particles into the anisotropic conductive adhesive, excellent conduction reliability and insulation reliability can be achieved.

導電粒子100a中，非導電性無機粒子102不易自樹脂粒子101脫落，故抑制異常析出部的產生，於製作導電粒子時可減少金屬異物的產生。In the conductive particles 100a, the non-conductive inorganic particles 102 are less likely to fall off from the resin particles 101, so that generation of abnormal precipitation portions is suppressed, and generation of metallic foreign matter can be reduced when the conductive particles are produced.

疏水化處理劑是選自由矽氮烷系疏水化處理劑、矽氧烷系疏水化處理劑、矽烷系疏水化處理劑及鈦酸酯系疏水化處理劑所組成的群組中。The hydrophobization treatment agent is selected from the group consisting of a guanidine-based hydrophobizing agent, a decane-based hydrophobizing agent, a decane-based hydrophobizing agent, and a titanate hydrophobizing agent.

疏水化處理劑亦可選自由六甲基二矽氮烷、聚二甲基矽氧烷及N,N-二甲基胺基三甲基矽烷所組成的群組中。The hydrophobizing agent may also be selected from the group consisting of hexamethyldiazepine, polydimethyloxane, and N,N-dimethylaminotrimethylnonane.

由甲醇滴定法所得的非導電性無機粒子102的疏水化度例如為30%以上。於該情形時，充分的靜電力於非導電性無機粒子102與樹脂粒子101之間發揮作用。The degree of hydrophobicization of the non-conductive inorganic particles 102 obtained by the methanol titration method is, for example, 30% or more. In this case, a sufficient electrostatic force acts between the non-conductive inorganic particles 102 and the resin particles 101.

樹脂粒子101與非導電性無機粒子102的界達電位之差例如於pH值1以上且pH值11以下時為30 mV以上。於該情形時，樹脂粒子101與非導電性無機粒子102藉由靜電力而牢固地接著。因此，可於用以形成導電粒子100a中的第一層104的前處理步驟、第一層104的形成步驟等時，合適地抑制非導電性無機粒子102自樹脂粒子101脫落。The difference in the boundary potential between the resin particles 101 and the non-conductive inorganic particles 102 is, for example, 30 mV or more when the pH is 1 or more and the pH is 11 or less. In this case, the resin particles 101 and the non-conductive inorganic particles 102 are firmly adhered by an electrostatic force. Therefore, when the pre-processing step of forming the first layer 104 in the conductive particles 100a, the forming step of the first layer 104, and the like, the non-conductive inorganic particles 102 are suitably prevented from falling off from the resin particles 101.

陽離子性聚合物是選自由多胺、聚亞胺、聚醯胺、聚二烯丙基二甲基氯化銨、聚乙烯基胺、聚乙烯基吡啶、聚乙烯基咪唑及聚乙烯基吡咯啶酮所組成的群組中。The cationic polymer is selected from the group consisting of polyamines, polyimines, polyamines, polydiallyldimethylammonium chloride, polyvinylamines, polyvinylpyridines, polyvinylimidazoles, and polyvinylpyrrolidines. In the group consisting of ketones.

陽離子性聚合物亦可為聚乙烯亞胺。於該情形時，陽離子性聚合物的電荷密度提高，故可良好地抑制非導電性無機粒子102的脫落。The cationic polymer may also be a polyethyleneimine. In this case, since the charge density of the cationic polymer is increased, the fall of the non-conductive inorganic particles 102 can be satisfactorily suppressed.

非導電性無機粒子102的平均粒徑例如為25 nm以上且120 nm以下。於該情形時，導電粒子100a具有多數個緻密的凸起109，並且非導電性無機粒子102不易自樹脂粒子101脫落。The average particle diameter of the non-conductive inorganic particles 102 is, for example, 25 nm or more and 120 nm or less. In this case, the conductive particles 100a have a plurality of dense protrusions 109, and the non-conductive inorganic particles 102 are less likely to fall off from the resin particles 101.

樹脂粒子的平均粒徑例如為1 μm以上且10 μm以下。例如於使用含有導電粒子100a的異向導電性接著劑製作連接結構體時，該異向導電性接著劑的導電性等不易因該連接結構體的電極的形狀（高度）的不均一而變化。The average particle diameter of the resin particles is, for example, 1 μm or more and 10 μm or less. For example, when a bonded structure is produced using an anisotropic conductive adhesive containing conductive particles 100a, the conductivity of the anisotropic conductive adhesive or the like is less likely to change due to the unevenness of the shape (height) of the electrode of the bonded structure.

非導電性無機粒子102是選自由氧化矽、氧化鋯、氧化鋁及金剛石所組成的群組中。The non-conductive inorganic particles 102 are selected from the group consisting of cerium oxide, zirconium oxide, aluminum oxide, and diamond.

金屬層具有含有鎳的第一層104。此外，該第一層104為藉由無電鍍敷而被覆複合粒子103的層。於該情形時，可提高導電粒子100a的硬度。藉此，即便於該導電粒子100a經壓縮的情形時，形成於非導電性無機粒子102上而成為凸起部分的第一層104亦不易被壓壞。因此，導電粒子100a可獲得低的導通電阻。The metal layer has a first layer 104 containing nickel. Further, the first layer 104 is a layer in which the composite particles 103 are coated by electroless plating. In this case, the hardness of the conductive particles 100a can be increased. Thereby, even when the conductive particles 100a are compressed, the first layer 104 which is formed on the non-conductive inorganic particles 102 and becomes a convex portion is not easily crushed. Therefore, the conductive particles 100a can obtain a low on-resistance.

金屬層的第一層104亦可具有多個導電層。該些導電層的厚度、組成、形狀的至少一者亦可互不相同。例如，第一層104中成為主成分的金屬的含量亦可於第一層104的厚度方向上隨著接近表面而增高。為了形成此種具有多個導電層的第一層104，亦可使用多種鍍敷液。例如藉由使用析出的金屬濃度不同的鍍敷液，可容易地形成具有多個導電層的第一層104。The first layer 104 of the metal layer can also have a plurality of conductive layers. At least one of the thickness, composition, and shape of the conductive layers may be different from each other. For example, the content of the metal which is the main component in the first layer 104 may also increase as it approaches the surface in the thickness direction of the first layer 104. In order to form such a first layer 104 having a plurality of conductive layers, a plurality of plating solutions can also be used. The first layer 104 having a plurality of conductive layers can be easily formed, for example, by using a plating solution having different concentrations of precipitated metals.

第一層104例如亦可藉由以下方式而形成：於第一鍍敷液的投入之後，或第一鍍敷液的投入結束之前，開始投入析出的金屬濃度不同於（高於）該第一鍍敷液的第二鍍敷液。於該情形時，可形成厚度方向上的金屬濃度朝向表面而逐漸變化（增高）的第一層104。另外，因無需分別形成不同組成的多個導電層的步驟，故可於短時間內形成第一層104。The first layer 104 may be formed, for example, by the fact that after the input of the first plating solution or before the end of the input of the first plating solution, the concentration of the metal that starts to be deposited is different from (higher than) the first The second plating solution of the plating solution. In this case, the first layer 104 whose metal concentration in the thickness direction is gradually changed (increased) toward the surface can be formed. In addition, since it is not necessary to separately form a plurality of conductive layers having different compositions, the first layer 104 can be formed in a short time.

（第二實施形態） 以下，對第二實施形態的導電粒子加以說明。第二實施形態的說明中，省略與第一實施形態重複的記載，而記載與第一實施形態不同的部分。即，亦可於技術上可能的範圍內，於第二實施形態中適當使用第一實施形態的記載。(Second embodiment) Hereinafter, the conductive particles of the second embodiment will be described. In the description of the second embodiment, the description overlapping the first embodiment will be omitted, and the portion different from the first embodiment will be described. That is, the description of the first embodiment can be appropriately used in the second embodiment within the technically possible range.

圖3為表示第二實施形態的導電粒子的示意剖面圖。圖3所示的導電粒子100b除了具有設於第一層104上的第二層105的方面以外，具有與圖1所示的導電粒子100a相同的構成。第二層105可為金屬層，亦可為合金層。Fig. 3 is a schematic cross-sectional view showing conductive particles according to a second embodiment. The conductive particles 100b shown in FIG. 3 have the same configuration as the conductive particles 100a shown in FIG. 1 except for the second layer 105 provided on the first layer 104. The second layer 105 may be a metal layer or an alloy layer.

＜第二層＞ 第二層105為被覆第一層104而設置的導電層。第二層105的厚度例如為5 nm～100 nm。第二層105的厚度可為5 nm以上，亦可為10 nm以上。第二層105的厚度亦可為30 nm以下。於第二層105的厚度為所述範圍內的情形時，於形成第二層105的情形時可使該第二層105的厚度均勻，藉此可良好地防止第一層104所含有的元素（例如鎳）向與第二層105為相反側的表面擴散。<Second Layer> The second layer 105 is a conductive layer provided to cover the first layer 104. The thickness of the second layer 105 is, for example, 5 nm to 100 nm. The thickness of the second layer 105 may be 5 nm or more, or may be 10 nm or more. The thickness of the second layer 105 may also be 30 nm or less. When the thickness of the second layer 105 is within the above range, the thickness of the second layer 105 can be made uniform in the case of forming the second layer 105, whereby the elements contained in the first layer 104 can be well prevented. (for example, nickel) diffuses to the surface on the opposite side to the second layer 105.

第二層105的厚度是使用藉由TEM所拍攝的照片而算出。作為具體例，首先以通過導電粒子100b的中心附近的方式利用超薄切片法切出導電粒子100b的剖面。繼而，使用TEM以25萬倍的倍率觀察所切出的剖面而獲得圖像。然後，可由根據所得的圖像估算的第二層105（圖4）的剖面積而算出第二層105的厚度。此時，於難以區分第二層105、第一層104、樹脂粒子101及非導電性無機粒子102的情形時，藉由TEM所附帶的EDX進行成分分析。藉此，明確區分第二層105、第一層104、樹脂粒子101及非導電性無機粒子102，算出僅第二層105的厚度。第二層105的厚度是設為10個導電粒子的厚度的平均值。The thickness of the second layer 105 was calculated using a photograph taken by TEM. As a specific example, first, the cross section of the conductive particles 100b is cut by an ultrathin section method so as to pass through the vicinity of the center of the conductive particles 100b. Then, an image was obtained by observing the cut cross section at a magnification of 250,000 times using a TEM. Then, the thickness of the second layer 105 can be calculated from the cross-sectional area of the second layer 105 (Fig. 4) estimated from the obtained image. At this time, when it is difficult to distinguish the second layer 105, the first layer 104, the resin particles 101, and the non-conductive inorganic particles 102, component analysis is performed by EDX attached to the TEM. Thereby, the second layer 105, the first layer 104, the resin particles 101, and the non-conductive inorganic particles 102 are clearly distinguished, and only the thickness of the second layer 105 is calculated. The thickness of the second layer 105 is an average value of the thickness of 10 conductive particles.

第二層105含有選自由貴金屬及鈷所組成的群組中的至少一種。貴金屬為鈀、銠、銥、釕、鉑、銀或金。於第二層105含有金的情形時，可降低導電粒子100b的表面的導通電阻，提高導電粒子100b的導電特性。於該情形時，第二層105作為含有鎳的第一層104的抗氧化層而發揮功能。因此，第二層105是形成於第一層104上。含有金的情形的第二層105的厚度亦可為30 nm以下。於該情形時，導電粒子100b的表面的導通電阻的降低效果與製造成本的平衡優異。然而，含有金的情形的第二層105的厚度亦可超過30 nm。The second layer 105 contains at least one selected from the group consisting of noble metals and cobalt. The noble metal is palladium, rhodium, ruthenium, iridium, platinum, silver or gold. When the second layer 105 contains gold, the on-resistance of the surface of the conductive particles 100b can be lowered, and the conductive characteristics of the conductive particles 100b can be improved. In this case, the second layer 105 functions as an oxidation resistant layer of the first layer 104 containing nickel. Therefore, the second layer 105 is formed on the first layer 104. The thickness of the second layer 105 in the case of containing gold may also be 30 nm or less. In this case, the effect of reducing the on-resistance of the surface of the conductive particles 100b is excellent in balance with the manufacturing cost. However, the thickness of the second layer 105 in the case of gold may also exceed 30 nm.

第二層105較佳為由選自由鈀、銠、銥、釕及鉑所組成的群組中的至少一種所構成。於該情形時，可抑制導電粒子100b的表面的氧化，且提高導電粒子100b的絕緣可靠性。第二層105更佳為由選自由鈀、銠、銥及釕所組成的群組中的至少一種所構成。於該情形時，即便於導電粒子100b經壓縮的情形時，亦抑制形成於非導電性無機粒子102上的成為凸起109的第一層104被壓壞，抑制經壓縮的導電粒子100b的電阻增加。第二層105例如是於第一實施形態的第四步驟中形成第一層104後，藉由無電鍍敷而形成於由該第一層104所覆蓋的複合粒子103上。The second layer 105 is preferably composed of at least one selected from the group consisting of palladium, rhodium, iridium, iridium, and platinum. In this case, oxidation of the surface of the conductive particles 100b can be suppressed, and insulation reliability of the conductive particles 100b can be improved. The second layer 105 is more preferably composed of at least one selected from the group consisting of palladium, rhodium, ruthenium and iridium. In this case, even when the conductive particles 100b are compressed, the first layer 104 which becomes the protrusion 109 formed on the non-conductive inorganic particles 102 is suppressed from being crushed, and the resistance of the compressed conductive particles 100b is suppressed. increase. The second layer 105 is formed on the composite particles 103 covered by the first layer 104 by electroless plating, for example, after the first layer 104 is formed in the fourth step of the first embodiment.

＜鈀＞ 於第二層105含有鈀的情形時，該第二層105例如可藉由無電鍍鈀而形成。無電鍍鈀可利用不使用還原劑的置換型、及使用還原劑的還原型的任一種。關於此種無電鍍鈀液，置換型可列舉MCA（世界金屬（World Metal）股份有限公司製造，商品名）等。還原型可列舉APP（石原化學股份有限公司製造，商品名）等。於將置換型與還原型相比較的情形時，就所產生的孔隙（void）少，容易確保被覆面積的觀點而言，較佳為還原型。<Palladium> When the second layer 105 contains palladium, the second layer 105 can be formed, for example, by electroless palladium plating. The electroless palladium may be any of a substitution type in which no reducing agent is used and a reduced type in which a reducing agent is used. Examples of such an electroless plating palladium liquid include MCA (trade name, manufactured by World Metal Co., Ltd.). Examples of the reduction type include APP (manufactured by Ishihara Chemical Co., Ltd., trade name). When the substitution type is compared with the reduction type, the number of voids generated is small, and from the viewpoint of easily securing the coated area, the reduction type is preferable.

於第二層105含有鈀的情形時，以第二層105的總量為基準，第二層105中的鈀的含量的下限可為90質量%以上，亦可為93質量%以上，亦可為94質量%以上。以第二層105的總量為基準，第二層105中的鈀的含量的上限可為99質量%以下，亦可為98質量%以下。於第二層105中的鈀的含量為所述範圍內的情形時，第二層105的硬度提高。因此，即便於導電粒子100b經壓縮的情形時，亦抑制凸起109被壓壞。When the second layer 105 contains palladium, the lower limit of the content of palladium in the second layer 105 may be 90% by mass or more, or may be 93% by mass or more, based on the total amount of the second layer 105. It is 94% by mass or more. The upper limit of the content of palladium in the second layer 105 may be 99% by mass or less, or may be 98% by mass or less based on the total amount of the second layer 105. When the content of palladium in the second layer 105 is within the above range, the hardness of the second layer 105 is increased. Therefore, even when the conductive particles 100b are compressed, the projections 109 are suppressed from being crushed.

為了調整第二層105中的鈀的含量（例如為了調整為93質量%～99質量%），無電鍍鈀液中所用的還原劑並無特別限制，可使用：次亞磷酸、亞磷酸、該些酸的鹼鹽等含磷化合物；含硼化合物等。於該情形時，所得的第二層105含有鈀-磷合金或鈀-硼合金。因此，較佳為以第二層105中的鈀含量成為所需範圍的方式，調整還原劑的濃度、pH值、鍍敷液的溫度等。In order to adjust the content of palladium in the second layer 105 (for example, to adjust it to 93% by mass to 99% by mass), the reducing agent used in the electroless palladium plating liquid is not particularly limited, and: hypophosphorous acid, phosphorous acid, A phosphorus-containing compound such as an alkali salt of an acid; a boron-containing compound or the like. In this case, the resulting second layer 105 contains a palladium-phosphorus alloy or a palladium-boron alloy. Therefore, it is preferred to adjust the concentration of the reducing agent, the pH, the temperature of the plating solution, and the like so that the palladium content in the second layer 105 is within a desired range.

＜銠＞ 於第二層105含有銠的情形時，該第二層105例如可藉由無電鍍銠而形成。無電鍍銠液中所用的銠的供給源例如可列舉：氫氧化氨合銠、硝酸氨合銠、乙酸氨合銠、硫酸氨合銠、亞硫酸氨合銠、溴化氨合銠及氨合銠化合物。<铑> When the second layer 105 contains germanium, the second layer 105 can be formed, for example, by electroless plating. Examples of the supply source of ruthenium used in the electroless ruthenium plating solution include ruthenium hydroxide, ruthenium nitrate, ruthenium acetate, ruthenium sulphate, ruthenium sulfite, ruthenium bromide, and ammonia.铑 compound.

無電鍍銠液中所用的還原劑例如可列舉：肼、次亞磷酸鈉、硼酸二甲基胺、硼酸二乙基胺及硼氫化鈉。還原劑較佳為肼。亦可於無電鍍銠液中添加穩定劑或錯合劑（氫氧化銨、羥基胺鹽、二氯化肼等）。Examples of the reducing agent used in the electroless plating bath include hydrazine, sodium hypophosphite, dimethylamine borate, diethylamine borate, and sodium borohydride. The reducing agent is preferably hydrazine. Stabilizers or complexing agents (ammonium hydroxide, hydroxylamine salts, cerium dichloride, etc.) may also be added to the electroless plating mash.

就獲得充分的鍍敷速度的觀點而言，無電鍍銠液的溫度（浴溫）可為40℃以上，亦可為50℃以上。就穩定地保持無電鍍銠液的觀點而言，鍍敷液的溫度可為90℃以下，亦可為80℃以下。From the viewpoint of obtaining a sufficient plating speed, the temperature (bath temperature) of the electroless plating sputum may be 40 ° C or higher, or may be 50 ° C or higher. The temperature of the plating solution may be 90 ° C or lower or 80 ° C or lower from the viewpoint of stably maintaining the electroless plating sputum.

＜銥＞ 於第二層105含有銥的情形時，該第二層105例如可藉由無電鍍銥而形成。無電鍍銥液中所用的銥的供給源例如可列舉：三氯化銥、四氯化銥、三溴化銥、四溴化銥、六氯化銥三鉀、六氯化銥二鉀、六氯化銥三鈉、六氯化銥二鈉、六溴化銥三鉀、六溴化銥二鉀、六碘化銥三鉀、三硫酸二銥及雙硫酸銥。<铱> When the second layer 105 contains germanium, the second layer 105 can be formed, for example, by electroless plating. Examples of the supply source of ruthenium used in the electroless plating sputum include ruthenium trichloride, ruthenium tetrachloride, ruthenium tribromide, ruthenium tetrabromide, ruthenium hexachloride, dipotassium hexachloride, and six. Trisodium sulphate, disodium hexachloride, tripotassium hexabromide, dipotassium hexabromide, tripotassium hexacylate, bismuth trisulfate and bismuth sulphate.

無電鍍銥液中所用的還原劑例如可列舉：肼、次亞磷酸鈉、硼酸二甲基胺、硼酸二乙基胺及硼氫化鈉。還原劑較佳為肼。亦可於無電鍍銥液中添加穩定劑或錯合劑。Examples of the reducing agent used in the electroless plating bath include hydrazine, sodium hypophosphite, dimethylamine borate, diethylamine borate, and sodium borohydride. The reducing agent is preferably hydrazine. Stabilizers or complexing agents may also be added to the electroless plating mash.

穩定劑或錯合劑亦可添加選自由單羧酸、二羧酸及該些酸的鹽所組成的群組中的至少一種。單羧酸的具體例可列舉甲酸、乙酸、丙酸、丁酸、乳酸等。二羧酸的具體例可列舉草酸、丙二酸、琥珀酸、戊二酸、己二酸、富馬酸、馬來酸、蘋果酸等。所述鹽例如可列舉鈉、鉀、鋰等作為抗衡離子鍵結於所述羧酸而成的化合物。穩定劑或錯合劑可單獨使用一種或組合使用兩種以上。The stabilizer or the complexing agent may also be added with at least one selected from the group consisting of monocarboxylic acids, dicarboxylic acids, and salts of the acids. Specific examples of the monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, and lactic acid. Specific examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, and malic acid. Examples of the salt include a compound in which sodium, potassium, lithium or the like is bonded to the carboxylic acid as a counter ion. The stabilizer or the complexing agent may be used alone or in combination of two or more.

就抑制鍍敷對象物的腐蝕，並且獲得充分的鍍敷速度的觀點而言，無電鍍銥液的pH值可為1以上，亦可為2以上。就容易抑制鍍敷反應受阻的觀點而言，無電鍍銥液的pH值可為6以下，亦可為5以下。The pH of the electroless plating mash may be 1 or more, or 2 or more, from the viewpoint of suppressing corrosion of the object to be plated and obtaining a sufficient plating speed. From the viewpoint of easily suppressing the inhibition of the plating reaction, the pH of the electroless plating mash may be 6 or less, or may be 5 or less.

就獲得充分的鍍敷速度的觀點而言，無電鍍銥液的溫度（浴溫）可為40℃以上，亦可為50℃以上。就穩定地保持無電鍍銥液的觀點而言，無電鍍銥液的溫度（浴溫）可為90℃以下，亦可為80℃以下。From the viewpoint of obtaining a sufficient plating speed, the temperature (bath temperature) of the electroless plating sputum may be 40 ° C or higher, or may be 50 ° C or higher. From the viewpoint of stably maintaining the electroless plating sputum, the temperature (bath temperature) of the electroless plating sputum may be 90 ° C or lower, or may be 80 ° C or lower.

＜釕＞ 於第二層105含有釕的情形時，該第二層105例如可藉由無電鍍釕而形成。無電鍍釕液例如可使用市售的鍍敷液，可使用無電釕Ru（奧野製藥工業股份有限公司製造，商品名）。<钌> When the second layer 105 contains germanium, the second layer 105 can be formed, for example, by electroless plating. As the electroless plating sputum, for example, a commercially available plating solution can be used, and an electroless Ru (manufactured by Okuno Pharmaceutical Co., Ltd., trade name) can be used.

＜鉑＞ 於第二層105含有鉑的情形時，該第二層105例如可藉由無電鍍鉑而形成。無電鍍鉑液中所用的鉑的供給源例如可列舉：Pt(NH3 )4 (NO3 )2 、Pt(NH3 )4 (OH)2 、PtCl2 (NH3 )2 、Pt(NH3 )2 (OH)2 、(NH4 )2 PtCl6 、(NH4 )2 PtCl4 、Pt(NH3 )2 Cl4 、H2 PtCl6 及PtCl2 。<Platinum> When the second layer 105 contains platinum, the second layer 105 can be formed, for example, by electroless platinum plating. Examples of the supply source of platinum used in the electroless platinum plating solution include Pt(NH 3 ) 4 (NO 3 ) 2 , Pt(NH 3 ) 4 (OH) 2 , PtCl 2 (NH 3 ) 2 , and Pt (NH 3 ). 2 (OH) 2 , (NH 4 ) 2 PtCl 6 , (NH 4 ) 2 PtCl 4 , Pt(NH 3 ) 2 Cl 4 , H 2 PtCl 6 and PtCl 2 .

無電鍍鉑液中所用的還原劑例如可列舉：肼、次亞磷酸鈉、硼酸二甲基胺、硼酸二乙基胺及硼氫化鈉。還原劑較佳為肼。亦可於無電鍍鉑液中添加穩定劑或錯合劑（氯化羥基胺、二氯化肼、氫氧化銨、乙二胺四乙酸（Ethylene Diamine Tetraacetic Acid，EDTA）等）。Examples of the reducing agent used in the electroless platinum plating solution include hydrazine, sodium hypophosphite, dimethylamine borate, diethylamine borate, and sodium borohydride. The reducing agent is preferably hydrazine. A stabilizer or a binder (chlorinated hydroxylamine, ruthenium dichloride, ammonium hydroxide, Ethylene Diamine Tetraacetic Acid, EDTA, etc.) may also be added to the electroless platinum solution.

就獲得充分的鍍敷速度的觀點而言，無電鍍鉑液的溫度（浴溫）可為40℃以上，亦可為50℃以上。就穩定地保持無電鍍鉑液的觀點而言，無電鍍鉑液的溫度（浴溫）可為90℃以下，亦可為80℃以下。The temperature (bath temperature) of the electroless platinum plating solution may be 40° C. or higher or 50° C. or higher from the viewpoint of obtaining a sufficient plating speed. From the viewpoint of stably maintaining the electroless platinum plating solution, the temperature (bath temperature) of the electroless platinum plating solution may be 90 ° C or lower, or may be 80 ° C or lower.

於使用無電鍍鉑液進行鍍鉑時，無電鍍鉑液的pH值只要為8～12即可。若pH值為8以上，則鉑容易充分析出。若pH值為12以下，則可容易地確保良好的操作環境。When platinization is performed using an electroless platinum solution, the pH of the electroless platinum solution may be 8 to 12. If the pH is 8 or more, the platinum is easily analyzed. If the pH is 12 or less, a good operating environment can be easily ensured.

＜銀＞ 於第二層105含有銀的情形時，該第二層105例如可藉由無電鍍銀而形成。無電鍍銀液中所用的銀的供給源只要可溶於鍍敷液中，則並無特別限定。例如可使用：硝酸銀、氧化銀、硫酸銀、氯化銀、亞硫酸銀、碳酸銀、乙酸銀、乳酸銀、磺基琥珀酸銀、磺酸銀、胺基磺酸銀及草酸銀。水溶性銀化合物可單獨使用一種或組合使用兩種以上。<Silver> When the second layer 105 contains silver, the second layer 105 can be formed, for example, by electroless silver plating. The supply source of silver used in the electroless silver plating solution is not particularly limited as long as it is soluble in the plating solution. For example, silver nitrate, silver oxide, silver sulfate, silver chloride, silver sulfite, silver carbonate, silver acetate, silver lactate, silver sulfosuccinate, silver sulfonate, silver sulfonate and silver oxalate can be used. The water-soluble silver compound may be used alone or in combination of two or more.

無電鍍銀液中所用的還原劑只要具有將無電鍍銀液中的水溶性銀化合物還原成金屬銀的能力且為水溶性的化合物，則並無特別限定。例如可使用：肼衍生物、甲醛化合物、羥基胺類、糖類、羅雪鹽（Rochelle salt）、硼氫化合物、次亞磷酸鹽、二甲基胺硼烷（Dimethylamine borane，DMAB）及抗壞血酸。還原劑可單獨使用一種或組合使用兩種以上。The reducing agent used in the electroless silver plating solution is not particularly limited as long as it has a capability of reducing the water-soluble silver compound in the electroless silver plating solution to metal silver and is water-soluble. For example, an anthracene derivative, a formaldehyde compound, a hydroxylamine, a saccharide, a Rochelle salt, a borohydride, a hypophosphite, a dimethylamine borane (DMAB), and ascorbic acid can be used. The reducing agents may be used alone or in combination of two or more.

亦可於無電鍍銀液中添加穩定劑或錯合劑。穩定劑或錯合劑例如可使用：亞硫酸鹽、琥珀醯亞胺、乙內醯脲衍生物、乙二胺及乙二胺四乙酸（EDTA）。穩定劑或錯合劑可單獨使用一種或組合使用兩種以上。Stabilizers or complexing agents may also be added to the electroless silver plating solution. For stabilizers or complexing agents, for example, sulfites, amber imines, intramethylene urea derivatives, ethylenediamine and ethylenediaminetetraacetic acid (EDTA) can be used. The stabilizer or the complexing agent may be used alone or in combination of two or more.

無電鍍銀液中，除了所述成分以外，亦可添加公知的界面活性劑、pH調整劑、緩衝劑、平滑劑、應力緩和劑等添加劑。In the electroless silver plating solution, additives such as a known surfactant, a pH adjuster, a buffering agent, a smoothing agent, and a stress relieving agent may be added in addition to the above components.

無電鍍銀液的液溫只要為0℃～80℃的範圍即可。若無電鍍銀液的溫度為0℃以上，則銀的析出速度充分快，可縮短用以獲得既定的銀析出量的時間。若無電鍍銀液的溫度為80℃以下，則可抑制由自分解反應所致的還原劑的損耗、及無電鍍銀液的穩定性的降低。若設為10℃～60℃左右，則可使無電鍍銀液的穩定性更良好。The liquid temperature of the electroless silver plating solution may be in the range of 0 ° C to 80 ° C. When the temperature of the electroless silver plating solution is 0 ° C or more, the deposition rate of silver is sufficiently fast, and the time for obtaining a predetermined amount of silver deposition can be shortened. When the temperature of the electroless silver plating solution is 80 ° C or lower, the loss of the reducing agent due to the self-decomposition reaction and the decrease in the stability of the electroless silver plating solution can be suppressed. When the temperature is set to about 10 ° C to 60 ° C, the stability of the electroless silver plating solution can be further improved.

無電鍍銀液（例如還原型無電鍍銀液）的pH值例如為1～14。藉由鍍敷液的pH值為6～13左右，可使鍍敷液的穩定性更良好。關於鍍敷液的pH值調整，通常於降低pH值的情形時，可使用具有與水溶性銀鹽的陰離子部分為同種的陰離子部分的酸（例如於使用硫酸銀作為水溶性銀鹽的情形時為硫酸，於使用硝酸銀作為水溶性銀鹽的情形時為硝酸）。於提高無電鍍銀液的pH值的情形時，可使用鹼金屬氫氧化物、氨等。The pH of the electroless silver plating solution (for example, reduced electroless silver plating solution) is, for example, 1 to 14. The stability of the plating solution can be further improved by the pH of the plating solution being about 6 to 13. Regarding the pH adjustment of the plating solution, generally in the case of lowering the pH, an acid having an anion portion which is the same as the anion portion of the water-soluble silver salt can be used (for example, when silver sulfate is used as the water-soluble silver salt) It is sulfuric acid, and it is nitric acid when silver nitrate is used as a water-soluble silver salt. In the case of increasing the pH of the electroless silver plating solution, an alkali metal hydroxide, ammonia or the like can be used.

＜金＞ 於第二層105含有金的情形時，該第二層105例如可藉由無電鍍金而形成。無電鍍金液可使用置換型鍍金液（例如日立化成股份有限公司製造，商品名「HGS-100」）、還原型鍍金液（例如日立化成股份有限公司製造，商品名「HGS-2000」）等。於將置換型與還原型相比較的情形時，就孔隙少，容易確保被覆面積的觀點而言，較佳為使用還原型。<Gold> When the second layer 105 contains gold, the second layer 105 can be formed, for example, by electroless gold plating. For the electroless gold plating liquid, a replacement gold plating liquid (for example, manufactured by Hitachi Chemical Co., Ltd., trade name "HGS-100"), a reduced gold plating liquid (for example, manufactured by Hitachi Chemical Co., Ltd., trade name "HGS-2000"), etc., may be used. . In the case of comparing the substitution type with the reduction type, it is preferable to use a reduction type from the viewpoint of having a small number of pores and easily securing the coated area.

＜鈷＞ 於第二層105含有鈷的情形時，該第二層105例如可藉由無電鍍鈷而形成。無電鍍鈷液中所用的鈷的供給源例如可列舉：硫酸鈷、氯化鈷、硝酸鈷、乙酸鈷及碳酸鈷。<Cobalt> When the second layer 105 contains cobalt, the second layer 105 can be formed, for example, by electroless cobalt plating. Examples of the supply source of cobalt used in the electroless cobalt plating solution include cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, and cobalt carbonate.

無電鍍鈷液中所用的還原劑例如可使用：次亞磷酸鈉、次亞磷酸銨、次亞磷酸鎳等次亞磷酸鹽及次亞磷酸。亦可於無電鍍鈷液中添加穩定劑或錯合劑（脂肪族羧酸等）。穩定劑或錯合劑可單獨使用一種或組合使用兩種以上。As the reducing agent used in the electroless cobalt plating solution, for example, hypophosphites such as sodium hypophosphite, ammonium hypophosphite, and nickel hypophosphite, and hypophosphorous acid can be used. Stabilizers or complexing agents (aliphatic carboxylic acids, etc.) may also be added to the electroless cobalt plating solution. The stabilizer or the complexing agent may be used alone or in combination of two or more.

就獲得充分的鍍敷速度的觀點而言，無電鍍鈷液的溫度（浴溫）可為40℃以上，亦可為50℃以上。就穩定地保持無電鍍鈷液的觀點而言，無電鍍鈷液的溫度（浴溫）可為90℃以下，亦可為80℃以下。The temperature (bath temperature) of the electroless cobalt plating solution may be 40° C. or higher or 50° C. or higher from the viewpoint of obtaining a sufficient plating speed. From the viewpoint of stably maintaining the electroless cobalt plating solution, the temperature (bath temperature) of the electroless cobalt plating solution may be 90 ° C or lower, or may be 80 ° C or lower.

以上所說明的第二實施形態的導電粒子100b亦與第一實施形態的導電粒子100a同樣地，非導電性無機粒子102不易自樹脂粒子101的表面脫落。因此，配置於樹脂粒子101的表面的非導電性無機粒子102的個數的控制變容易，並且於複合粒子103上形成良好的凸起109。因此，即便於將使用調配有導電粒子100b的異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。此外，自樹脂粒子101脫落的非導電性無機粒子102的個數減少，故於複合粒子103上不易產生異常地成長的凸起。因此，於將導電粒子100a調配至異向導電性接著劑中的情形等時，導電粒子100b彼此不易導通，導電粒子100b的絕緣可靠性亦提高。Also in the conductive particles 100b of the second embodiment described above, the non-conductive inorganic particles 102 are less likely to fall off from the surface of the resin particles 101, similarly to the conductive particles 100a of the first embodiment. Therefore, the control of the number of the non-conductive inorganic particles 102 disposed on the surface of the resin particles 101 is facilitated, and a good protrusion 109 is formed on the composite particles 103. Therefore, even when the bonded structure using the anisotropic conductive adhesive in which the conductive particles 100b are blended is stored under high temperature and high humidity, the conduction reliability is also improved. Further, since the number of the non-conductive inorganic particles 102 that have fallen off from the resin particles 101 is reduced, it is less likely that the composite particles 103 are abnormally grown. Therefore, when the conductive particles 100a are blended into the anisotropic conductive adhesive or the like, the conductive particles 100b are not easily electrically connected to each other, and the insulation reliability of the conductive particles 100b is also improved.

於第一實施形態中，第一層104成為導電粒子100a的最外層。該導電粒子100a例如於分散於異向導電性接著劑內時，有時第一層104內所含有的鎳溶出至接著劑中而發生遷移。有時由該遷移的鎳導致異向導電性接著劑的絕緣可靠性降低。相對於此，第二實施形態的金屬層具有設於第一層104上的第二層105，第二層105含有選自由貴金屬及鈷所組成的群組中的金屬。於該情形時，導電粒子100b的最外層成為第二層105。該第二層105具有防止鎳自第一層104中溶出的功能，故可抑制該鎳的遷移的發生。此外，該第二層105相對較不易被氧化，故導電粒子100b的導電性能不易劣化。藉由導電粒子100b具有第二層105，可高度地控制凸起109的個數、大小及形狀。In the first embodiment, the first layer 104 serves as the outermost layer of the conductive particles 100a. When the conductive particles 100a are dispersed in the anisotropic conductive adhesive, for example, nickel contained in the first layer 104 may be eluted into the adhesive to cause migration. The insulation reliability of the anisotropic conductive adhesive is sometimes lowered by the migrated nickel. In contrast, the metal layer of the second embodiment has the second layer 105 provided on the first layer 104, and the second layer 105 contains a metal selected from the group consisting of noble metals and cobalt. In this case, the outermost layer of the conductive particles 100b becomes the second layer 105. The second layer 105 has a function of preventing nickel from eluting from the first layer 104, so that the occurrence of migration of the nickel can be suppressed. Further, the second layer 105 is relatively less susceptible to oxidation, so that the conductive properties of the conductive particles 100b are not easily deteriorated. By having the second layer 105 of the conductive particles 100b, the number, size, and shape of the protrusions 109 can be highly controlled.

（第三實施形態） 以下，對第三實施形態的絕緣被覆導電粒子加以說明。於第三實施形態的說明中，省略與第一實施形態及第二實施形態重複的記載，而記載與第一實施形態及第二實施形態不同的部分。即，亦可於技術上可能的範圍內，於第三實施形態中適當使用第一實施形態及第二實施形態的記載。(Third embodiment) Hereinafter, the insulating coated conductive particles of the third embodiment will be described. In the description of the third embodiment, the descriptions overlapping with the first embodiment and the second embodiment are omitted, and portions different from the first embodiment and the second embodiment are described. That is, the descriptions of the first embodiment and the second embodiment can be appropriately used in the third embodiment within the technically possible range.

＜絕緣被覆導電粒子＞ 圖5為表示本實施形態的絕緣被覆導電粒子的示意剖面圖。圖5所示的絕緣被覆導電粒子200具備第一實施形態的導電粒子100a、及將第一層104的表面的至少一部分被覆的絕緣性粒子（絕緣性被覆部）210。<Insulation-coated conductive particles> Fig. 5 is a schematic cross-sectional view showing the insulating-coated conductive particles of the present embodiment. The insulating-coated conductive particles 200 shown in FIG. 5 include the conductive particles 100a of the first embodiment and insulating particles (insulating covering portions) 210 that cover at least a part of the surface of the first layer 104.

絕緣性粒子210的平均粒徑是指根據絕緣性粒子210的正投影面中具有與絕緣性粒子210的面積相同的面積的正圓的直徑所算出的平均粒徑。絕緣性粒子210的平均粒徑例如為20 nm～500 nm。於絕緣性粒子210的平均粒徑為所述範圍內的情形時，例如吸附於導電粒子100a上的絕緣性粒子210容易作為絕緣膜而有效地發揮作用。另外，連接的加壓方向的導電性容易變良好。絕緣性粒子210的平均粒徑例如亦可藉由利用BET法的比表面積換算法、或X射線小角散射法來測定。The average particle diameter of the insulating particles 210 is an average particle diameter calculated from the diameter of a perfect circle having the same area as the area of the insulating particles 210 in the front projection surface of the insulating particles 210. The average particle diameter of the insulating particles 210 is, for example, 20 nm to 500 nm. When the average particle diameter of the insulating particles 210 is within the above range, for example, the insulating particles 210 adsorbed on the conductive particles 100a easily function as an insulating film. Further, the conductivity in the pressurizing direction of the connection tends to be good. The average particle diameter of the insulating particles 210 can be measured, for example, by a specific surface area conversion algorithm by the BET method or an X-ray small angle scattering method.

就容易降低電阻，且容易抑制電阻的經時上升的觀點而言，相對於導電粒子100a的平均粒徑，絕緣性粒子210的平均粒徑可為1/10以下，亦可為1/15以下。就獲得更良好的絕緣可靠性的觀點而言，相對於導電粒子100a的平均粒徑，絕緣性粒子210的平均粒徑亦可為1/20以上。The average particle diameter of the insulating particles 210 may be 1/10 or less, or 1/15 or less, with respect to the average particle diameter of the conductive particles 100a, from the viewpoint of easily reducing the electric resistance and easily suppressing the increase in resistance over time. . From the viewpoint of obtaining more excellent insulation reliability, the average particle diameter of the insulating particles 210 may be 1/20 or more with respect to the average particle diameter of the conductive particles 100a.

絕緣性粒子210以絕緣性粒子210對導電粒子100a的被覆率成為例如20%～70%的方式而被覆導電粒子100a的表面。就更可靠地獲得絕緣性及導電性的效果的觀點而言，被覆率亦可為20%～60%，亦可為25%～60%，亦可為28%～55%。「被覆率」是指絕緣被覆導電粒子200的正投影面中，具有絕緣被覆導電粒子200的直徑的1/2直徑的同心圓內的絕緣性粒子210的表面積的比例。具體而言，對藉由SEM以3萬倍觀察形成有絕緣性粒子210的絕緣被覆導電粒子200所得的圖像進行分析，算出絕緣性粒子210於絕緣被覆導電粒子200的表面中所佔的比例。The insulating particles 210 are coated on the surface of the conductive particles 100a so that the coverage of the conductive particles 210 to the conductive particles 100a is, for example, 20% to 70%. The coating ratio may be 20% to 60%, 25% to 60%, or 28% to 55%, from the viewpoint of more reliably obtaining the effects of insulation and conductivity. The "coverage ratio" refers to a ratio of the surface area of the insulating particles 210 in the concentric circles having a diameter of 1/2 of the diameter of the insulating coated conductive particles 200 in the front projection plane of the insulating coated conductive particles 200. Specifically, an image obtained by observing the insulating coated conductive particles 200 in which the insulating particles 210 are formed by SEM is analyzed by SEM, and the proportion of the insulating particles 210 on the surface of the insulating coated conductive particles 200 is calculated. .

被覆導電粒子100a的絕緣性粒子210可列舉有機高分子化合物微粒子、無機氧化物微粒子等。於使用無機氧化物微粒子作為絕緣性粒子210的情形時，容易提高絕緣可靠性，於使用有機高分子化合物微粒子的情形時，可容易地降低導通電阻。Examples of the insulating particles 210 covering the conductive particles 100a include organic polymer compound fine particles and inorganic oxide fine particles. When the inorganic oxide fine particles are used as the insulating particles 210, the insulation reliability is easily improved, and when the organic polymer compound fine particles are used, the on-resistance can be easily lowered.

有機高分子化合物只要為具有熱軟化性的化合物即可，具體可使用：聚乙烯、乙烯-乙酸乙烯酯共聚物、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、聚胺基甲酸酯、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、固態環氧樹脂等。有機高分子化合物可單獨使用一種或組合使用兩種以上。The organic polymer compound may be a compound having thermal softening property, and specifically: polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer , polyester, polyamide, polyurethane, polystyrene, styrene-divinylbenzene copolymer, styrene-isobutylene copolymer, styrene-butadiene copolymer, styrene-(A Acrylic acid copolymer, ethylene-propylene copolymer, (meth)acrylate rubber, styrene-ethylene-butene copolymer, phenoxy resin, solid epoxy resin, and the like. The organic polymer compound may be used alone or in combination of two or more.

無機氧化物例如可列舉：含有選自由矽、鋁、鋯、鈦、鈮、鋅、錫、鈰及鎂所組成的群組中的至少一種元素的氧化物。無機氧化物可單獨使用一種或組合使用兩種以上。無機氧化物中，亦較佳為氧化矽。氧化矽中，水分散膠體氧化矽（SiO2 ）於表面具有羥基，故與導電粒子的結合性優異，並且容易使粒徑一致且價廉，故特別合適。此種無機氧化物的微粒子的市售品例如可列舉：斯諾特（Snowtex）、斯諾特（Snowtex）UP（日產化學工業股份有限公司製造，商品名）及誇特龍（Quarton）PL系列（扶桑化學工業股份有限公司製造，商品名）。The inorganic oxide may, for example, be an oxide containing at least one element selected from the group consisting of ruthenium, aluminum, zirconium, titanium, lanthanum, zinc, tin, antimony, and magnesium. The inorganic oxides may be used alone or in combination of two or more. Among the inorganic oxides, cerium oxide is also preferred. Among the cerium oxide, the water-dispersed colloidal cerium oxide (SiO 2 ) has a hydroxyl group on the surface, so that it is excellent in the binding property to the conductive particles, and it is easy to make the particle diameter uniform and inexpensive, and therefore it is particularly suitable. Commercial products of such inorganic oxide fine particles include, for example, Snowtex, Snowtex UP (manufactured by Nissan Chemical Industries, Ltd., trade name), and Quarton PL series. (Manufactured by Fusang Chemical Industry Co., Ltd., trade name).

於無機氧化物微粒子於表面具有羥基的情形時，可利用矽烷偶合劑等將羥基改質成胺基、羧基、環氧基等。然而，於無機氧化物微粒子的平均粒徑為500 nm以下的情形時，有時難以改質。於該情形時，亦可不進行改質而被覆導電粒子100a。When the inorganic oxide fine particles have a hydroxyl group on the surface, the hydroxyl group can be modified into an amine group, a carboxyl group, an epoxy group or the like by a decane coupling agent or the like. However, when the average particle diameter of the inorganic oxide fine particles is 500 nm or less, it may be difficult to reform. In this case, the conductive particles 100a may be coated without modification.

通常無機氧化物微粒子的表面具有羥基，藉此可與矽烷偶合劑等表面處理劑的羥基、羧基、烷氧基、烷氧基羰基等鍵結。鍵結形態例如可列舉脫水縮合的共價鍵、氫鍵及配位鍵。Usually, the surface of the inorganic oxide fine particles has a hydroxyl group, whereby it can be bonded to a hydroxyl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group or the like of a surface treatment agent such as a decane coupling agent. Examples of the bond form include a covalent bond, a hydrogen bond, and a coordinate bond of dehydration condensation.

於導電粒子100a的外表面包含金或鈀的情形時，亦可使用分子內具有與該些金屬形成配位鍵的巰基、硫醚基、二硫醚基等的化合物於無機氧化物微粒子的表面形成羥基、羧基、烷氧基、烷氧基羰基等官能基。所述化合物例如可列舉巰基乙酸、2-巰基乙醇、巰基乙酸甲酯、巰基琥珀酸、硫甘油及半胱胺酸。When the outer surface of the conductive particle 100a contains gold or palladium, a compound having a sulfhydryl group, a thioether group, a disulfide group or the like having a coordinate bond with the metal in the molecule may be used on the surface of the inorganic oxide fine particle. A functional group such as a hydroxyl group, a carboxyl group, an alkoxy group or an alkoxycarbonyl group is formed. Examples of the compound include mercaptoacetic acid, 2-mercaptoethanol, methyl thioglycolate, mercapto succinic acid, thioglycerol, and cysteine.

金、鈀等貴金屬、銅等容易與硫醇反應。鎳等卑金屬難以與硫醇反應。因此，於導電粒子100a的最外層包含貴金屬、銅等的情形時，與導電粒子100a的最外層包含卑金屬的情形相比，更容易與硫醇反應。Precious metals such as gold and palladium, copper and the like are easily reacted with a thiol. It is difficult to react with thiols such as nickel. Therefore, when the outermost layer of the conductive particles 100a contains a noble metal, copper, or the like, it is more likely to react with the thiol than when the outermost layer of the conductive particles 100a contains a base metal.

例如對金表面進行所述化合物的處理的方法並無特別限定，可使巰基乙酸等所述化合物以10 mmol/L～100 mmol/L左右分散於甲醇、乙醇等有機溶劑中，使最外層為金的導電粒子100a分散於其中。For example, the method of treating the compound on the gold surface is not particularly limited, and the compound such as thioglycolic acid may be dispersed in an organic solvent such as methanol or ethanol at a ratio of 10 mmol/L to 100 mmol/L to make the outermost layer The gold conductive particles 100a are dispersed therein.

繼而，對由第一實施形態的導電粒子100a來製造第三實施形態的絕緣被覆導電粒子200的方法的一例加以說明。以絕緣性粒子210被覆導電粒子100a的表面的方法例如可列舉將高分子電解質與絕緣性粒子交替積層的方法。Next, an example of a method of manufacturing the insulating coated conductive particles 200 of the third embodiment from the conductive particles 100a of the first embodiment will be described. A method of coating the surface of the conductive particles 100a with the insulating particles 210 is, for example, a method in which a polymer electrolyte and insulating particles are alternately laminated.

首先，進行（1）將導電粒子100a分散於高分子電解質溶液中，使高分子電解質吸附於該導電粒子100a的表面後，進行淋洗的步驟。繼而，進行（2）將導電粒子100a分散於絕緣性粒子的分散溶液中，使絕緣性粒子吸附於該導電粒子100a的表面後，進行淋洗的步驟。經由該些步驟，可製造表面經將高分子電解質與絕緣性粒子積層而成的絕緣性粒子210被覆的絕緣被覆導電粒子200。（1）步驟及（2）步驟可為（1）、（2）的順序，亦可為（2）、（1）的順序。（1）步驟、（2）步驟亦可交替反覆進行。First, (1) a step of dispersing the conductive particles 100a in the polymer electrolyte solution, adsorbing the polymer electrolyte on the surface of the conductive particles 100a, and then performing rinsing. Then, (2) a step of dispersing the conductive particles 100a in the dispersion solution of the insulating particles and adsorbing the insulating particles on the surface of the conductive particles 100a, followed by rinsing. Through these steps, the insulating coated conductive particles 200 whose surface is covered with the insulating particles 210 in which the polymer electrolyte and the insulating particles are laminated can be produced. The steps (1) and (2) may be in the order of (1) and (2), or may be in the order of (2) and (1). (1) Steps and (2) steps may also be performed alternately and repeatedly.

高分子電解質例如可使用：於水溶液中電離，於主鏈或側鏈中具有帶電的官能基的高分子。例如可使用多胺類等般具有可帶正電的官能基的高分子化合物，亦可使用與樹脂粒子101的表面處理中所用的上文所述的陽離子性聚合物相同的化合物。具體可使用：聚乙烯亞胺（PEI）、聚烯丙基胺鹽酸鹽（PAH）、聚二烯丙基二甲基氯化銨（PDDA）、聚乙烯基吡啶（PVP）、聚離胺酸、聚丙烯醯胺、將形成該些聚合物的一種以上的單體聚合所得的共聚物等。就電荷密度高，與具有負電荷的表面及材料的結合力強的觀點而言，較佳為使用聚乙烯亞胺。As the polymer electrolyte, for example, a polymer having a charged functional group in a main chain or a side chain which is ionized in an aqueous solution can be used. For example, a polymer compound having a positively chargeable functional group such as a polyamine may be used, and the same compound as the above-described cationic polymer used in the surface treatment of the resin particle 101 may be used. Specifically used: polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethylammonium chloride (PDDA), polyvinylpyridine (PVP), polyamine An acid, a polypropylene decylamine, a copolymer obtained by polymerizing one or more monomers forming these polymers, and the like. From the viewpoint of a high charge density and a strong binding force to a surface and a material having a negative charge, polyethyleneimine is preferably used.

反覆進行所述（1）步驟、（2）步驟的方法被稱為交替積層法（Layer-by-Layer assembly）。交替積層法是由G.德謝爾（G.Decher）等人於1992年發表的形成有機薄膜的方法（《固體薄膜（Thin Solid Films）》，210/211，p831（1992））。根據由G.德謝爾（G.Decher）等人所發表的方法，將基材（基板等）交替浸漬於帶正電荷的聚合物電解質（聚陽離子）、及帶負電荷的聚合物電解質（聚陰離子）的水溶液中，藉由靜電引力而吸附於基材上的聚陽離子與聚陰離子的組積層，由此可獲得複合膜（交替積層膜）。The method of repeatedly performing the steps (1) and (2) is called a Layer-by-Layer assembly. The alternate layering method is a method of forming an organic film published by G. Decher et al. in 1992 (Thin Solid Films, 210/211, p831 (1992)). The substrate (substrate, etc.) is alternately immersed in a positively charged polymer electrolyte (polycation) and a negatively charged polymer electrolyte according to a method published by G. Decher et al. In the aqueous solution of the polyanion), a composite layer (alternating laminated film) can be obtained by a combination of a polycation and a polyanion adsorbed on the substrate by electrostatic attraction.

交替積層法中，藉由靜電引力，已形成於基材上的材料的電荷、與溶液中的帶相反電荷的材料相互吸引，由此進行膜成長。因此，若吸附進行而引起電荷的中和，則不發生進一步的吸附。因此，只要達到某一飽和點，則膜厚不會進一步增加。利沃夫（Lvov）等人報告了以下方法：將交替積層法應用於微粒子，使用氧化矽、氧化鈦、氧化鈰等的各微粒子分散液，利用交替積層法來積層帶有與微粒子的表面電荷為相反電荷的高分子電解質（《郎繆爾（Langmuir）》，Vol.13，（1997）p6195-6203）。若使用利沃夫（Lvov）所報告的方法，則藉由將帶有負表面電荷的氧化矽的微粒子、與作為帶有其相反電荷的聚陽離子的聚二烯丙基二甲基氯化銨（PDDA）、聚乙烯亞胺（PEI）等交替積層，可形成將氧化矽微粒子與高分子電解質交替積層而成的微粒子積層薄膜。In the alternating layering method, the charge of the material formed on the substrate and the oppositely charged material in the solution are attracted to each other by electrostatic attraction, thereby performing film growth. Therefore, if the adsorption proceeds to cause neutralization of the charge, no further adsorption occurs. Therefore, as long as a certain saturation point is reached, the film thickness does not increase further. Lvov et al. reported the following method: applying an alternating layering method to microparticles, using a microparticle dispersion of cerium oxide, titanium oxide, cerium oxide, etc., using an alternate layering method to laminate surface charges with microparticles. A polymer electrolyte of opposite charge (Langmuir, Vol. 13, (1997) p6195-6203). If the method reported by Lvov is used, by using microparticles with a negative surface charge of cerium oxide and polydiallyldimethylammonium chloride as a polycation with its opposite charge An alternate layer of (PDDA) or polyethyleneimine (PEI) is formed to form a fine particle laminated film in which cerium oxide fine particles and a polymer electrolyte are alternately laminated.

以上所說明的第三實施形態的絕緣被覆導電粒子200亦與第一實施形態同樣地，即便於將使用調配有該絕緣被覆導電粒子200的異向導電性接著劑的連接結構體於高溫高濕下保存的情形時，導通可靠性亦提高。此外，藉由設於第一層104的外表面的絕緣性粒子210，導電粒子100a的第一層104彼此不易接觸。進而，脫落的非導電性無機粒子102經金屬塗佈而形成的金屬異物不易存在於接著劑中。因此，絕緣被覆導電粒子200彼此不易良好地導通，使用該絕緣被覆導電粒子200的連接結構體等的絕緣可靠性亦合適地提高。In the same manner as in the first embodiment, the insulating-coated conductive particles 200 of the third embodiment described above are used in a high-temperature and high-humidity connection structure using an anisotropic conductive adhesive in which the insulating-coated conductive particles 200 are blended. When the case is saved, the continuity reliability is also improved. Further, the first layer 104 of the conductive particles 100a is not easily contacted with each other by the insulating particles 210 provided on the outer surface of the first layer 104. Further, the metal foreign matter formed by the metal coating of the non-conductive inorganic particles 102 that have fallen off is less likely to be present in the adhesive. Therefore, the insulating coated conductive particles 200 are not easily electrically connected to each other, and the insulation reliability of the bonded structure or the like using the insulating coated conductive particles 200 is also suitably improved.

尤其近年來，對COG安裝用的異向導電性接著劑等要求約10 μm的窄間距的絕緣可靠性。藉由使用第三實施形態的絕緣被覆導電粒子200，可實現此種絕緣可靠性。In particular, in recent years, an insulating reliability of a narrow pitch of about 10 μm is required for an anisotropic conductive adhesive for COG mounting. Such insulation reliability can be achieved by using the insulating coated conductive particles 200 of the third embodiment.

關於第三實施形態的絕緣被覆導電粒子200中的導電粒子，例如可使用第二實施形態的導電粒子100b等代替導電粒子100a。於該情形時，絕緣被覆導電粒子200除了所述作用效果以外，可發揮第二實施形態的導電粒子100b的作用效果。For the conductive particles in the insulating-coated conductive particles 200 of the third embodiment, for example, the conductive particles 100b of the second embodiment or the like can be used instead of the conductive particles 100a. In this case, the insulating coated conductive particles 200 can exhibit the effects of the conductive particles 100b of the second embodiment in addition to the above-described effects.

（第四實施形態） 以下，對第四實施形態的異向導電性接著劑加以說明。第四實施形態的說明中，省略與第一實施形態～第三實施形態重複的記載，而記載與第一實施形態～第三實施形態不同的部分。即，亦可於技術上可能的範圍內，於第四實施形態中適當使用第一實施形態～第三實施形態的記載。(Fourth embodiment) Hereinafter, an anisotropic conductive adhesive of a fourth embodiment will be described. In the description of the fourth embodiment, the descriptions overlapping with the first embodiment to the third embodiment are omitted, and portions different from the first embodiment to the third embodiment are described. In other words, the description of the first embodiment to the third embodiment can be appropriately used in the fourth embodiment within the technically possible range.

＜異向導電性接著劑＞ 第四實施形態的異向導電性接著劑含有第一實施形態的導電粒子100a、及分散有該導電粒子100a的接著劑。<Anisotropic Conductive Adhesive> The anisotropic conductive adhesive of the fourth embodiment contains the conductive particles 100a of the first embodiment and an adhesive in which the conductive particles 100a are dispersed.

接著劑例如可使用熱反應性樹脂與硬化劑的混合物。接著劑例如可列舉環氧樹脂與潛伏性硬化劑的混合物、及自由基聚合性化合物與有機過氧化物的混合物。As the subsequent agent, for example, a mixture of a thermally reactive resin and a hardener can be used. Examples of the subsequent agent include a mixture of an epoxy resin and a latent curing agent, and a mixture of a radical polymerizable compound and an organic peroxide.

接著劑可使用膏狀或膜狀的接著劑。為了將異向導電性接著劑成形為膜狀，亦可於接著劑中調配苯氧樹脂、聚酯樹脂、聚醯胺樹脂、聚酯樹脂、聚胺基甲酸酯樹脂、(甲基)丙烯酸樹脂、聚酯胺基甲酸酯樹脂等熱塑性樹脂。A paste or film-like adhesive can be used as the adhesive. In order to form the anisotropic conductive adhesive into a film shape, a phenoxy resin, a polyester resin, a polyamide resin, a polyester resin, a polyurethane resin, or a (meth)acrylic acid may be blended in the adhesive. A thermoplastic resin such as a resin or a polyester urethane resin.

以上所說明的第四實施形態的異向導電性接著劑亦與第一實施形態同樣地，導通可靠性提高。此外，自樹脂粒子101脫落的非導電性無機粒子102的個數減少，故於複合粒子103上不易產生異常地成長的凸起。另外，因脫落至接著劑中的非導電性無機粒子102而生成的金屬異物的個數減少。因此，分散於異向導電性接著劑中的導電粒子100a彼此不易導通，異向導電性接著劑的絕緣可靠性亦提高。The anisotropic conductive adhesive of the fourth embodiment described above also has improved conduction reliability as in the first embodiment. Further, since the number of the non-conductive inorganic particles 102 that have fallen off from the resin particles 101 is reduced, it is less likely that the composite particles 103 are abnormally grown. Further, the number of metal foreign matters generated by the non-conductive inorganic particles 102 falling off from the adhesive is reduced. Therefore, the conductive particles 100a dispersed in the anisotropic conductive adhesive are less likely to be electrically connected to each other, and the insulation reliability of the anisotropic conductive adhesive is also improved.

關於第四實施形態的異向導電性接著劑中的導電粒子，例如可使用第二實施形態的導電粒子100b等代替導電粒子100a。於該情形時，異向導電性接著劑可發揮第二實施形態的導電粒子100b的作用效果。亦可使用絕緣被覆導電粒子200代替導電粒子100a。於該情形時，異向導電性接著劑可發揮第三實施形態的導電粒子100b的作用效果。For the conductive particles in the anisotropic conductive adhesive of the fourth embodiment, for example, the conductive particles 100b of the second embodiment or the like can be used instead of the conductive particles 100a. In this case, the anisotropic conductive adhesive can exhibit the effect of the conductive particles 100b of the second embodiment. Insulation-coated conductive particles 200 may be used instead of the conductive particles 100a. In this case, the anisotropic conductive adhesive can exhibit the effect of the conductive particles 100b of the third embodiment.

（第五實施形態） 以下，對第五實施形態的連接結構體加以說明。第五實施形態的說明中，省略與第一實施形態～第四實施形態重複的記載，而記載與第一實施形態～第四實施形態不同的部分。即，亦可於技術上可能的範圍內，於第五實施形態中適當使用第一實施形態～第四實施形態的記載。(Fifth Embodiment) Hereinafter, a connection structure of a fifth embodiment will be described. In the description of the fifth embodiment, the descriptions overlapping with the first to fourth embodiments are omitted, and portions different from the first to fourth embodiments are described. In other words, the description of the first embodiment to the fourth embodiment can be appropriately used in the fifth embodiment within the technically possible range.

＜連接結構體＞ 對第五實施形態的連接結構體加以說明。本實施形態的連接結構體具備：具有第一電路電極的第一電路構件、具有第二電路電極的第二電路構件、以及配置於第一電路構件與第二電路構件之間且含有所述導電粒子及所述絕緣被覆導電粒子的至少一者的連接部。連接部於將第一電路電極與第二電路電極以相對向的方式配置的狀態下將第一電路構件及第二電路構件彼此連接。第一電路電極及第二電路電極經由變形狀態的導電粒子或絕緣被覆導電粒子而相互電性連接。<Connection Structure> The connection structure of the fifth embodiment will be described. The connection structure of the present embodiment includes: a first circuit member having a first circuit electrode; a second circuit member having a second circuit electrode; and a first circuit member and a second circuit member disposed between the first circuit member and the second circuit member A connecting portion of at least one of the particles and the insulating coated conductive particles. The connection portion connects the first circuit member and the second circuit member to each other in a state in which the first circuit electrode and the second circuit electrode are disposed to face each other. The first circuit electrode and the second circuit electrode are electrically connected to each other via the conductive particles in the deformed state or the insulating coated conductive particles.

繼而，一面參照圖6，一面對第五實施形態的連接結構體進一步進行說明。圖6為表示第五實施形態的連接結構體的示意剖面圖。圖6所示的連接結構體300具備彼此相對向的第一電路構件310及第二電路構件320、以及配置於第一電路構件310與第二電路構件320之間的連接部330。連接結構體300可列舉液晶顯示器、個人電腦、行動電話、智慧型手機、平板等可攜式產品。Next, a connection structure body according to the fifth embodiment will be further described with reference to Fig. 6 . Fig. 6 is a schematic cross-sectional view showing a connection structure according to a fifth embodiment. The connection structure 300 shown in FIG. 6 includes a first circuit member 310 and a second circuit member 320 that face each other, and a connection portion 330 that is disposed between the first circuit member 310 and the second circuit member 320. The connection structure 300 can be exemplified by a portable product such as a liquid crystal display, a personal computer, a mobile phone, a smart phone, or a tablet.

第一電路構件310具備電路基板（第一電路基板）311、及配置於電路基板311的主面311a上的電路電極（第一電路電極）312。第二電路構件320具備電路基板（第二電路基板）321、及配置於電路基板321的主面321a上的電路電極（第二電路電極）322。The first circuit member 310 includes a circuit board (first circuit board) 311 and a circuit electrode (first circuit electrode) 312 disposed on the main surface 311 a of the circuit board 311 . The second circuit member 320 includes a circuit board (second circuit board) 321 and a circuit electrode (second circuit electrode) 322 disposed on the main surface 321a of the circuit board 321 .

電路構件310、電路構件320中的一者的具體例可列舉：積體電路（Integrated Circuit，IC）晶片（半導體晶片）、電阻器晶片、電容器晶片、驅動IC等晶片零件；硬質（rigid）型的封裝基板等。該些電路構件具備電路電極，通常具備多數個電路電極。電路構件310、電路構件320中的另一者（與所述一個電路構件連接的電路構件）的具體例可列舉：具有金屬配線的可撓性帶基板、可撓性印刷配線板、蒸鍍有銦錫氧化物（Indium Tin Oxide，ITO）的玻璃基板等配線基板等。例如藉由使用膜狀的異向導電性接著劑，可有效率地且以高連接可靠性將該些電路構件彼此連接。例如第四實施形態的異向導電性接著劑適於具備多數個微細的電路電極的晶片零件向配線基板上的COG安裝或COF安裝。Specific examples of one of the circuit member 310 and the circuit member 320 include an integrated circuit (IC) wafer (semiconductor wafer), a resistor chip, a capacitor chip, a driver IC, and the like; and a rigid type Package substrate, etc. These circuit members are provided with circuit electrodes and usually have a plurality of circuit electrodes. Specific examples of the other of the circuit member 310 and the circuit member 320 (the circuit member connected to the one circuit member) include a flexible tape substrate having metal wiring, a flexible printed wiring board, and vapor deposition. A wiring board such as a glass substrate of Indium Tin Oxide (ITO). For example, by using a film-shaped anisotropic conductive adhesive, the circuit members can be connected to each other efficiently and with high connection reliability. For example, the anisotropic conductive adhesive of the fourth embodiment is suitable for COG mounting or COF mounting on a wiring board with a wafer component including a plurality of fine circuit electrodes.

連接部330具備接著劑的硬化物332、及分散於該硬化物332中的絕緣被覆導電粒子200。連接部330例如可使用所述第四實施形態中記載的膜狀的異向導電性接著劑。連接結構體300中，相對向的電路電極312與電路電極322經由絕緣被覆導電粒子200而電性連接。更具體而言，如圖6所示，絕緣被覆導電粒子200中的導電粒子100a因壓縮而變形，電性連接於電路電極312、電路電極322兩者。另一方面，導電粒子100a於與壓縮方向交叉的方向上，絕緣性粒子210介於導電粒子100a間，藉此維持絕緣被覆導電粒子200彼此的絕緣性。因此，可進一步提高窄間距（例如10 μm水準的間距）的絕緣可靠性。視用途不同，亦可使用未經絕緣被覆的導電粒子100a、導電粒子100b代替絕緣被覆導電粒子200。The connection portion 330 includes a cured product 332 of an adhesive and insulating covered conductive particles 200 dispersed in the cured product 332. As the connecting portion 330, for example, the film-shaped anisotropic conductive adhesive described in the fourth embodiment can be used. In the connection structure 300, the opposing circuit electrodes 312 and the circuit electrodes 322 are electrically connected via the insulating coated conductive particles 200. More specifically, as shown in FIG. 6, the conductive particles 100a in the insulating coated conductive particles 200 are deformed by compression, and are electrically connected to both the circuit electrode 312 and the circuit electrode 322. On the other hand, in the direction in which the conductive particles 100a intersect the compression direction, the insulating particles 210 are interposed between the conductive particles 100a, thereby maintaining the insulation properties of the insulating coated conductive particles 200. Therefore, the insulation reliability of a narrow pitch (for example, a pitch of 10 μm level) can be further improved. Instead of the insulating coated conductive particles 200, the conductive particles 100a and the conductive particles 100b which are not covered with insulation may be used depending on the application.

連接結構體300是藉由以下方式獲得：將具有電路電極312的第一電路構件310與具有電路電極322的第二電路構件320以電路電極312與電路電極322相對向的方式配置，使異向導電性接著劑介於第一電路構件310與第二電路構件320之間，對該等進行加熱及加壓而使電路電極312與電路電極322電性連接。第一電路構件310及第二電路構件320是藉由接著劑的硬化物332而接著。The connection structure 300 is obtained by arranging the first circuit member 310 having the circuit electrode 312 and the second circuit member 320 having the circuit electrode 322 in such a manner that the circuit electrode 312 and the circuit electrode 322 face each other, causing an anisotropy The conductive adhesive is interposed between the first circuit member 310 and the second circuit member 320, and is heated and pressurized to electrically connect the circuit electrode 312 and the circuit electrode 322. The first circuit member 310 and the second circuit member 320 are followed by a cured product 332 of an adhesive.

＜連接結構體的製造方法＞ 一面參照圖7（a）〜圖7（c）一面對第五實施形態的連接結構體的製造方法加以說明。圖7（a）〜圖7（c）為用以說明圖6所示的連接結構體的製造方法的一例的示意剖面圖。第五實施形態中，使異向導電性接著劑熱硬化而製造連接結構體。<Manufacturing Method of Connection Structure> A method of manufacturing the connection structure according to the fifth embodiment will be described with reference to FIGS. 7(a) to 7(c). 7(a) to 7(c) are schematic cross-sectional views for explaining an example of a method of manufacturing the connection structure shown in Fig. 6. In the fifth embodiment, the anisotropic conductive adhesive is thermally cured to produce a bonded structure.

首先，準備第一電路構件310及異向導電性接著劑330a。本實施形態中，使用成形為膜狀而成的接著劑膜（異向導電性接著劑膜）作為異向導電性接著劑330a。異向導電性接著劑330a含有絕緣被覆導電粒子200及絕緣性的接著劑332a。First, the first circuit member 310 and the anisotropic conductive adhesive 330a are prepared. In the present embodiment, an adhesive film (isotropic conductive adhesive film) formed into a film shape is used as the anisotropic conductive adhesive 330a. The anisotropic conductive adhesive 330a contains the insulating coated conductive particles 200 and an insulating adhesive 332a.

繼而，將異向導電性接著劑330a載置於第一電路構件310的主面311a（形成有電路電極312的面）上。然後，如圖7（a）所示，沿著方向A及方向B對異向導電性接著劑330a進行加壓。藉此，如圖7（b）所示，將異向導電性接著劑330a積層於第一電路構件310上。Then, the anisotropic conductive adhesive 330a is placed on the main surface 311a (the surface on which the circuit electrode 312 is formed) of the first circuit member 310. Then, as shown in FIG. 7(a), the anisotropic conductive adhesive 330a is pressurized in the direction A and the direction B. Thereby, as shown in FIG. 7(b), the anisotropic conductive adhesive 330a is laminated on the first circuit member 310.

繼而，如圖7（c）所示，以電路電極312與電路電極322相對向的方式，將第二電路構件320載置於異向導電性接著劑330a上。然後，一面將異向導電性接著劑330a加熱，一面沿著圖7（c）所示的方向A及方向B對總體（第一電路構件310及第二電路構件320）進行加壓。Then, as shown in FIG. 7(c), the second circuit member 320 is placed on the anisotropic conductive adhesive 330a so that the circuit electrode 312 faces the circuit electrode 322. Then, while the anisotropic conductive adhesive 330a is heated, the entire body (the first circuit member 310 and the second circuit member 320) is pressurized in the direction A and the direction B shown in FIG. 7(c).

藉由加熱，異向導電性接著劑330a硬化而形成連接部330，獲得圖6所示般的連接結構體300。異向導電性接著劑亦可為膏狀。By heating, the anisotropic conductive adhesive 330a is cured to form the connection portion 330, and the connection structure 300 as shown in FIG. 6 is obtained. The anisotropic conductive adhesive may also be in the form of a paste.

以上所說明的第五實施形態的連接結構體300中，於連接部330內含有第三實施形態的絕緣被覆導電粒子200。根據所述連接結構體300，經由絕緣被覆導電粒子200而將電路電極312與電路電極322良好地電性連接。因此，即便於電路電極312及電路電極322的面積小，且電路電極312、電路電極322之間捕捉的絕緣被覆導電粒子200的個數少的情形時，亦長期間發揮優異的導通可靠性。此外，藉由絕緣被覆導電粒子200具有絕緣性粒子210，連接部330內的絕緣被覆導電粒子200的第一層104彼此不易接觸。因此，例如即便於設於電路電極312內（電路電極322內）的電極彼此的間距為例如10 μm以下的情形時，連接部330內的絕緣被覆導電粒子200彼此亦不易導通，連接結構體300的絕緣可靠性亦合適地提高。In the connection structure 300 of the fifth embodiment described above, the insulating coated conductive particles 200 of the third embodiment are contained in the connection portion 330. According to the connection structure 300, the circuit electrode 312 and the circuit electrode 322 are electrically connected to each other via the insulating coated conductive particles 200. Therefore, even when the area of the circuit electrode 312 and the circuit electrode 322 is small and the number of the insulating coated conductive particles 200 captured between the circuit electrode 312 and the circuit electrode 322 is small, excellent conduction reliability is exhibited for a long period of time. Further, since the insulating coated conductive particles 200 have the insulating particles 210, the first layers 104 of the insulating coated conductive particles 200 in the connecting portion 330 are less likely to contact each other. Therefore, for example, even when the pitch between the electrodes provided in the circuit electrode 312 (in the circuit electrode 322) is, for example, 10 μm or less, the insulating coated conductive particles 200 in the connecting portion 330 are not easily electrically connected to each other, and the connection structure 300 is connected. The insulation reliability is also suitably increased.

以上，對本發明的實施形態進行了說明，但本發明並非僅限定於所述實施形態。例如，所述實施形態中非導電性無機粒子的平均粒徑為25 nm～120 nm，但本發明不限定於此。同樣地，樹脂粒子的平均粒徑亦可未必為1 μm～10 μm。 [實施例]Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. For example, in the above embodiment, the average particle diameter of the non-conductive inorganic particles is from 25 nm to 120 nm, but the present invention is not limited thereto. Similarly, the average particle diameter of the resin particles may not necessarily be 1 μm to 10 μm. [Examples]

以下，列舉實施例及比較例對本發明的內容加以更具體說明。再者，本發明不限定於下述實施例。Hereinafter, the contents of the present invention will be more specifically described by way of examples and comparative examples. Furthermore, the present invention is not limited to the following examples.

＜實施例1＞ [導電粒子的製作] （步驟a）陽離子性聚合物對樹脂粒子表面的被覆 將2 g平均粒徑3.0 μm的交聯聚苯乙烯粒子（日本觸媒股份有限公司製造，商品名「所里奧斯達（Soliostar）」）添加至將3 g平均分子量7萬（M.W.為7萬）的30質量%聚乙烯亞胺水溶液（和光純藥工業股份有限公司製造）溶解於100 ml純水中所得的水溶液中，於室溫下攪拌15分鐘。繼而，藉由使用f3 μm的薄膜過濾器（membrane filter）（默克密理博（Merck Millipore）公司製造）的過濾而取出樹脂粒子。以200 g的超純水將薄膜過濾器上的樹脂粒子清洗2次，將未吸附的聚乙烯亞胺去除，獲得經聚乙烯亞胺吸附的樹脂粒子。<Example 1> [Preparation of conductive particles] (Step a) Coating of the surface of the resin particles by the cationic polymer 2 g of crosslinked polystyrene particles having an average particle diameter of 3.0 μm (manufactured by Nippon Shokubai Co., Ltd., product) The name "Soliostar" was added to a 30% by mass aqueous solution of polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd.) with an average molecular weight of 70,000 (MW of 70,000) dissolved in 100 ml. The aqueous solution obtained in pure water was stirred at room temperature for 15 minutes. Then, the resin particles were taken out by filtration using a f3 μm membrane filter (manufactured by Merck Millipore Co., Ltd.). The resin particles on the membrane filter were washed twice with 200 g of ultrapure water, and the unadsorbed polyethyleneimine was removed to obtain polyethyleneimine-adsorbed resin particles.

（步驟b）疏水化處理劑對非導電性無機粒子表面的被覆 使用平均粒徑60 nm的氣相法親水性球狀氧化矽粉末作為非導電性無機粒子。將100 g該球狀氧化矽粉末收容於振動流化床裝置（中央化工機股份有限公司製造，商品名「振動流化床裝置VUA-15型」）中。繼而，一面利用藉由抽吸風機而循環的空氣使球狀氧化矽流動一面噴霧1.5 g水而流動混合5分鐘。繼而，噴霧2.5 g六甲基二矽氮烷（Hexamethyl disilazane，HMDS）（日本邁圖高新材料（Momentive Performance Materials Japan）合同公司製造，商品名「TSL-8802」），流動混合30分鐘。藉由甲醇滴定法對所得的疏水性球狀氧化矽微粉體的疏水化度進行測定。疏水化度是利用以下的方法測定，非導電性無機粒子的疏水化度為70%。(Step b) Coating of the surface of the non-conductive inorganic particles by the hydrophobization treatment agent A vapor-phase hydrophilic spherical cerium oxide powder having an average particle diameter of 60 nm is used as the non-conductive inorganic particles. 100 g of the spherical cerium oxide powder was placed in a vibrating fluidized bed apparatus (manufactured by Central Chemical Machinery Co., Ltd., trade name "Vibrating fluidized bed apparatus VUA-15 type"). Then, while circulating the spherical cerium oxide by using the air circulated by the suction fan, 1.5 g of water was sprayed and mixed for 5 minutes. Then, 2.5 g of Hexamethyl disilazane (HMDS) (manufactured by Momentive Performance Materials Japan Co., Ltd., trade name "TSL-8802") was sprayed and mixed for 30 minutes. The degree of hydrophobicity of the obtained hydrophobic spherical cerium oxide fine powder was measured by a methanol titration method. The degree of hydrophobization was measured by the following method, and the degree of hydrophobicity of the non-conductive inorganic particles was 70%.

（步驟c）非導電性無機粒子對樹脂粒子表面的靜電接著步驟 將2 g經聚乙烯亞胺吸附的樹脂粒子添加至甲醇中，一面照射共振頻率28 kHz、輸出100 W的超音波一面於室溫下攪拌5分鐘。其後，將0.05 g經HMDS疏水化的球狀氧化矽粉末添加至所述甲醇中，一面照射共振頻率28 kHz、輸出100 W的超音波一面進一步於室溫下攪拌5分鐘。藉此，獲得藉由靜電而吸附有氧化矽的樹脂粒子（粒子A）。藉由靜電而吸附有氧化矽的粒子A為2.05 g。(Step c) Electrostatic discharge of non-conductive inorganic particles on the surface of the resin particles Next step 2 g of polyethyleneimine-adsorbed resin particles were added to methanol, and a resonance frequency of 28 kHz was applied to output a supersonic wave of 100 W. Stir for 5 minutes at warm. Thereafter, 0.05 g of spherical cerium oxide powder hydrophobized by HMDS was added to the methanol, and the mixture was irradiated with a resonance frequency of 28 kHz and an ultrasonic wave of 100 W was output, and further stirred at room temperature for 5 minutes. Thereby, resin particles (particles A) to which cerium oxide is adsorbed by static electricity are obtained. The particle A in which cerium oxide was adsorbed by static electricity was 2.05 g.

（步驟d）鈀觸媒賦予步驟 將2.05 g粒子A添加至100 mL的經調整為pH值1.0且含有20質量%的鈀觸媒（日立化成股份有限公司製造，商品名「HS201」）的鈀觸媒化液中。其後，一面照射共振頻率28 kHz、輸出100 W的超音波一面於30℃下攪拌30分鐘。繼而，利用f3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）過濾後，進行水洗，由此使鈀觸媒吸附於粒子A的表面。其後，將粒子A添加至經調整為pH值6.0的0.5質量%二甲基胺硼烷液中，一面照射共振頻率28 kHz、輸出100 W的超音波一面於60℃下攪拌5分鐘，獲得2.05 g固著有鈀觸媒的粒子B。然後，將2.05 g固著有鈀觸媒的粒子B浸漬於20 mL的蒸餾水中後，對粒子B進行超音波分散，由此獲得樹脂粒子分散液。(Step d) Palladium Catalyst Supply Step: 2.05 g of the particle A was added to 100 mL of palladium adjusted to a pH of 1.0 and containing 20% by mass of a palladium catalyst (manufactured by Hitachi Chemical Co., Ltd., trade name "HS201") In the catalyst solution. Thereafter, the ultrasonic wave was irradiated at a resonance frequency of 28 kHz and output at 100 W while stirring at 30 ° C for 30 minutes. Then, it was filtered with a f3 μm membrane filter (manufactured by Merck Millipore Co., Ltd.), and then washed with water to adsorb the palladium catalyst on the surface of the particles A. Thereafter, the particles A were added to a 0.5 mass% dimethylamine borane solution adjusted to a pH of 6.0, and the ultrasonic wave was output at a resonance frequency of 28 kHz while outputting 100 W while stirring at 60 ° C for 5 minutes. 2.05 g of particles B with palladium catalyst immobilized. Then, 2.05 g of the particles B to which the palladium catalyst was immobilized was immersed in 20 mL of distilled water, and then the particles B were ultrasonically dispersed to obtain a resin particle dispersion.

（步驟e）第一層的a層的形成 利用1000 mL經加溫至80℃的水將步驟d中所得的粒子B分散液稀釋後，添加1 mL作為鍍敷穩定劑的1 g/L的硝酸鉍水溶液。繼而，於粒子B分散液中以5 mL/min的滴加速度滴加80 mL下述組成（含有下述成分的水溶液，每1 L鍍敷液添加1 mL的1 g/L的硝酸鉍水溶液。以下相同）的a層形成用的無電鍍鎳液。滴加結束後，經過10分鐘後，將添加有鍍敷液的分散液過濾。以水清洗過濾物後，利用80℃的真空乾燥機進行乾燥。如此而形成粒子C，該粒子C具有表1-1所示的包含膜厚80 nm的鎳-磷合金被膜的a層。藉由形成a層所得的粒子C為4.05 g。第一層的a層形成用的無電鍍鎳液的組成如下。 硫酸鎳·············400 g/L 次亞磷酸鈉·········150 g/L 檸檬酸鈉···········120 g/L 硝酸鉍水溶液（1 g/L）···1 mL/L(Step e) Formation of the a layer of the first layer After diluting the particle B dispersion obtained in the step d with 1000 mL of water heated to 80 ° C, 1 mL of 1 g/L as a plating stabilizer was added. An aqueous solution of cerium nitrate. Then, 80 mL of the following composition (the aqueous solution containing the following components) was added dropwise to the particle B dispersion at a dropping rate of 5 mL/min, and 1 mL of a 1 g/L aqueous solution of lanthanum nitrate was added per 1 L of the plating solution. The following electroless nickel plating solution for the formation of the a layer is the same. After the completion of the dropwise addition, after 10 minutes passed, the dispersion to which the plating solution was added was filtered. After washing the filtrate with water, it was dried by a vacuum dryer at 80 °C. Particles C having the a layer including the nickel-phosphorus alloy film having a film thickness of 80 nm shown in Table 1-1 were formed in this manner. The particle C obtained by forming the a layer was 4.05 g. The composition of the electroless nickel plating solution for forming the a layer of the first layer is as follows. Nickel Sulfate································································································· 120 g/L aqueous solution of lanthanum nitrate (1 g/L)···1 mL/L

（步驟f）第一層的b層的形成 將4.05 g步驟e中所得的粒子C水洗及過濾後，使其分散於1000 mL經加溫至70℃的水中。於該分散液中添加1 mL的作為鍍敷穩定劑的1 g/L的硝酸鉍水溶液。繼而，以5 mL/min的滴加速度滴加20 mL下述組成的b層形成用的無電鍍鎳液。滴加結束後，經過10分鐘後，將添加有鍍敷液的分散液過濾。以水清洗過濾物後，利用80℃的真空乾燥機進行乾燥。如此而形成粒子D（導電粒子），該粒子D（導電粒子）具有表1-1所示的包含膜厚20 nm的鎳-磷合金被膜的b層。藉由形成b層所得的粒子D為4.55 g。第一層的b層形成用的無電鍍鎳液的組成如下。 硫酸鎳············400 g/L 次亞磷酸鈉········150 g/L 酒石酸鈉二水合物·····60 g/L 硝酸鉍水溶液（1 g/L）···1 mL/L(Step f) Formation of b layer of the first layer The particles C obtained in 4.05 g of the step e were washed with water and filtered, and then dispersed in 1000 mL of water heated to 70 °C. To the dispersion was added 1 mL of a 1 g/L aqueous solution of lanthanum nitrate as a plating stabilizer. Then, 20 mL of an electroless nickel plating liquid for forming a b layer having the following composition was dropped at a dropping rate of 5 mL/min. After the completion of the dropwise addition, after 10 minutes passed, the dispersion to which the plating solution was added was filtered. After washing the filtrate with water, it was dried by a vacuum dryer at 80 °C. Particles D (conductive particles) having the b layer including the nickel-phosphorus alloy film having a thickness of 20 nm shown in Table 1-1 were formed in this manner. The particle D obtained by forming the b layer was 4.55 g. The composition of the electroless nickel plating solution for forming the b layer of the first layer is as follows. Nickel Sulfate······································································································· Aqueous solution (1 g/L)···1 mL/L

[導電粒子的評價] 根據下述項目來評價導電粒子、或導電粒子所含的樹脂粒子及非導電性無機粒子。將結果示於表1-1及表1-2中。[Evaluation of Conductive Particles] The conductive particles or the resin particles and the non-conductive inorganic particles contained in the conductive particles were evaluated according to the following items. The results are shown in Table 1-1 and Table 1-2.

（疏水化度（%）） 藉由以下的方法來測定導電粒子的疏水化度。首先，將50 ml離子交換水、0.2 g試樣（導電粒子）加入至燒杯中，一面利用磁力攪拌器進行攪拌一面自滴管滴加甲醇。隨著燒杯內的甲醇濃度增加而粉體逐漸沈降，將其總量沈澱的終點時的甲醇-水混合溶液中的甲醇的質量分率作為導電粒子的疏水化度（%）。(Hydrophilization degree (%)) The degree of hydrophobicization of the conductive particles was measured by the following method. First, 50 ml of ion-exchanged water and 0.2 g of a sample (conductive particles) were placed in a beaker, and methanol was dropped from a dropper while stirring using a magnetic stirrer. As the concentration of methanol in the beaker increases, the powder gradually settles, and the mass fraction of methanol in the methanol-water mixed solution at the end of the total amount of precipitation is taken as the degree of hydrophobicity (%) of the conductive particles.

（非導電性無機粒子的平均粒徑） 關於非導電性無機粒子的粒徑，首先對藉由SEM（日立高新技術（Hitachi High-technologies）股份有限公司製造，商品名「S-4800」）以10萬倍觀察所得的圖像進行分析，測定500個粒子各自的面積。繼而，算出將粒子換算成圓的情形的直徑作為非導電性無機粒子的平均粒徑。另外，以百分率來算出粒徑的標準偏差相對於所得的平均粒徑之比，作為CV。(Average particle diameter of the non-conductive inorganic particles) The particle size of the non-conductive inorganic particles is first determined by SEM (Hitachi High-technologies Co., Ltd., trade name "S-4800"). The image obtained by observation at 100,000 times was analyzed, and the area of each of 500 particles was measured. Then, the diameter of the case where the particles were converted into a circle was calculated as the average particle diameter of the non-conductive inorganic particles. Further, the ratio of the standard deviation of the particle diameter to the obtained average particle diameter was calculated as a percentage of CV.

（界達電位的測定） 成為測定對象的各種粒子的界達電位是藉由以下的方法來測定。測定界達電位時，使用界他電位儀ZS（Zetasizer ZS）（馬爾文儀器（Malvern Instruments）公司製造，商品名）。首先，以成為測定對象的各種粒子成為約0.02質量%的方式將分散體稀釋。繼而，測定僅甲醇、pH值1、ph值7及pH值10.5的甲醇與離子交換水的混合溶劑合計四個條件下的界達電位。於甲醇與離子交換水的混合溶劑中，將甲醇的比例設為10質量%，pH值是藉由硫酸或氫氧化鉀來調整。所述界達電位的測定是對成為測定對象的各粒子進行。(Measurement of the boundary potential) The boundary potential of various particles to be measured is measured by the following method. For the determination of the Zeta potential, a Zetastat ZS (Zalsizer ZS) (trade name, manufactured by Malvern Instruments) was used. First, the dispersion is diluted so that the various particles to be measured become about 0.02% by mass. Then, the boundary potential of four conditions in which methanol, pH value 1, pH value 7, and a mixed solvent of methanol and ion-exchanged water having a pH of 10.5 were measured in total was measured. In the mixed solvent of methanol and ion-exchanged water, the ratio of methanol was set to 10% by mass, and the pH was adjusted by sulfuric acid or potassium hydroxide. The measurement of the boundary potential is performed on each particle to be measured.

（膜厚及成分的評價） 以通過所得的導電粒子的中心附近的方式利用超薄切片法切出剖面。使用TEM（日本電子股份有限公司製造，商品名「JEM-2100F」）以25萬倍的倍率觀察該剖面。根據所得的圖像估算第一層的a層、b層及第二層的剖面積，根據該剖面積算出第一層的a層、b層及第二層的膜厚（實施例1中，由於未形成第二層，故僅將第一層的a層、b層的膜厚作為測定的對象）。根據剖面積算出各層的膜厚時，藉由圖像分析來讀取寬度500 nm的剖面中的各層的剖面積，算出換算成寬度500 nm的長方形的情形的高度作為各層的膜厚。表1-1中示出對10個導電粒子算出的膜厚的平均值。此時，於難以區分第一層的a層、b層的情形時，藉由利用TEM所附帶的EDX（日本電子股份有限公司製造，商品名「JED-2300」）的成分分析來明確區分第一層的a層、b層，由此估算各自的剖面積，測量膜厚。根據EDX匹配資料算出第一層的a層、b層中的元素的含量（純度）。薄膜切片狀的樣本（導電粒子的剖面試樣）的製作方法的詳細情況、利用EDX的匹配的方法的詳細情況及各層中的元素的含量的算出方法的詳細情況將於後述。(Evaluation of Film Thickness and Composition) The cross section was cut by an ultrathin section method so as to pass the vicinity of the center of the obtained conductive particles. This cross section was observed at a magnification of 250,000 times using TEM (manufactured by JEOL Ltd., trade name "JEM-2100F"). Calculating a sectional area of the a layer, the b layer, and the second layer of the first layer from the obtained image, and calculating a film thickness of the a layer, the b layer, and the second layer of the first layer according to the sectional area (in the first embodiment, Since the second layer is not formed, only the film thicknesses of the a layer and the b layer of the first layer are measured. When the film thickness of each layer was calculated from the cross-sectional area, the cross-sectional area of each layer in the cross section having a width of 500 nm was read by image analysis, and the height in the case of converting into a rectangular shape having a width of 500 nm was calculated as the film thickness of each layer. Table 1-1 shows the average value of the film thicknesses calculated for the ten conductive particles. In this case, when it is difficult to distinguish between the a layer and the b layer of the first layer, the component analysis of EDX (manufactured by JEOL Ltd., trade name "JED-2300") attached to the TEM is used to clearly distinguish the The a layer and the b layer of one layer were used to estimate the respective sectional areas, and the film thickness was measured. The content (purity) of the elements in the a layer and the b layer of the first layer was calculated from the EDX matching data. The details of the method of producing the film-shaped sample (cross-sectional sample of the conductive particles), the details of the method of matching by EDX, and the method of calculating the content of the elements in each layer will be described later.

（吸附於樹脂粒子表面的非導電性無機粒子的評價） ｛非導電性無機粒子的被覆率｝ 於步驟c與步驟d之後所得的粒子A及粒子B的正投影面中，分別算出具有粒子A及粒子B的直徑的1/2直徑的同心圓內所存在的非導電性無機粒子的被覆率。具體而言，於粒子A及粒子B的正投影面中的具有粒子A、粒子B的直徑的1/2直徑的同心圓內，藉由圖像分析來區分非導電性無機粒子與樹脂粒子。繼而，算出同心圓內所存在的非導電性無機粒子的面積的比例，將該比例作為非導電性無機粒子的被覆率。分別算出粒子A及粒子B中的氧化矽粒子的被覆率，由此評價步驟d（鈀觸媒賦予步驟）對非導電性無機粒子向樹脂粒子表面的吸附性所造成的影響。(Evaluation of Non-Electroconductive Inorganic Particles Adsorbed on the Surface of Resin Particles) {Relay Ratio of Non-Conducting Inorganic Particles} The particle A was calculated in the orthographic projection surfaces of the particles A and B obtained after the steps c and d And the coverage of the non-conductive inorganic particles present in the concentric circles of the diameter of 1/2 of the diameter of the particles B. Specifically, in the concentric circles having the diameters of 1/2 diameter of the diameters of the particles A and B in the orthographic projection surfaces of the particles A and B, the non-conductive inorganic particles and the resin particles are distinguished by image analysis. Then, the ratio of the area of the non-conductive inorganic particles existing in the concentric circles is calculated, and this ratio is defined as the coverage of the non-conductive inorganic particles. The coating ratio of the cerium oxide particles in the particles A and B was calculated, and the influence of the step d (palladium catalyst supplying step) on the adsorptivity of the non-conductive inorganic particles to the surface of the resin particles was evaluated.

具體而言，非導電性無機粒子的被覆率是根據分別藉由SEM以3萬倍觀察粒子A及粒子B所得的圖像來評價。圖8中示出對實施例1的步驟d之後的粒子B進行觀察的SEM圖像。Specifically, the coverage of the non-conductive inorganic particles was evaluated based on an image obtained by observing the particles A and B at 30,000 times by SEM, respectively. An SEM image of the observation of the particles B after the step d of Example 1 is shown in FIG.

｛非導電性無機粒子的直徑及個數｝ 於步驟c與步驟d之後所得的粒子A及粒子B的正投影面中，分別算出具有粒子A及粒子B的直徑的1/2直徑的同心圓內所存在的非導電性無機粒子的直徑及個數。藉由分別算出粒子A及粒子B中的非導電性無機粒子的個數，而評價步驟d（鈀觸媒賦予步驟）對非導電性無機粒子向樹脂粒子表面的吸附性所造成的影響。{diameter and number of non-conductive inorganic particles} In the orthographic projection surfaces of the particles A and B obtained after the step c and the step d, a concentric circle having a diameter of 1/2 of the diameter of the particles A and B is calculated. The diameter and number of non-conductive inorganic particles present therein. By calculating the number of non-conductive inorganic particles in the particles A and B, respectively, the influence of the step d (palladium catalyst application step) on the adsorption of the non-conductive inorganic particles on the surface of the resin particles was evaluated.

具體而言，氧化矽粒子的個數是根據藉由SEM以10萬倍觀察粒子A及粒子B所得的圖像來評價。測定各非導電性無機粒子的面積，算出具有與該面積相同的面積的正圓的直徑作為非導電性無機粒子的直徑。根據表1-2所示的直徑的範圍將非導電性無機粒子分類，求出各範圍的非導電性無機粒子的個數。圖9中示出對實施例1的步驟d之後的粒子B進行觀察的SEM圖像。圖9為具有粒子B的直徑的1/2直徑的同心圓內的一部分。Specifically, the number of cerium oxide particles was evaluated based on an image obtained by observing particles A and B at 100,000 times by SEM. The area of each of the non-conductive inorganic particles was measured, and the diameter of a perfect circle having the same area as the area was calculated as the diameter of the non-conductive inorganic particles. The non-conductive inorganic particles were classified according to the range of diameters shown in Table 1-2, and the number of non-conductive inorganic particles in each range was determined. An SEM image of the particles B after the step d of Example 1 is shown in FIG. Figure 9 is a portion of a concentric circle having a diameter of 1/2 of the diameter of the particle B.

（形成於導電粒子表面的凸起的評價） ｛凸起的被覆率｝ 根據藉由SEM以3萬倍觀察導電粒子所得的SEM圖像，算出導電粒子表面的凸起的被覆率（面積的比例）。具體而言，於導電粒子的正投影面中的具有導電粒子的直徑的1/2直徑的同心圓內，藉由圖像分析來區分凸起形成部與平坦部。繼而，算出同心圓內所存在的凸起形成部的面積的比例，將該比例作為凸起的被覆率。圖10中示出藉由SEM對實施例1中的粒子D進行觀察的結果。(Evaluation of the protrusion formed on the surface of the conductive particle) {Cladding ratio of the protrusion} The coverage ratio of the surface of the conductive particle was calculated from the SEM image obtained by observing the conductive particle at 30,000 times by SEM. ). Specifically, the convex portion and the flat portion are distinguished by image analysis in a concentric circle having a diameter of 1/2 of the diameter of the conductive particles in the orthographic projection surface of the conductive particles. Then, the ratio of the area of the convex portion formed in the concentric circle is calculated, and this ratio is used as the coverage ratio of the convex. The result of observing the particle D in Example 1 by SEM is shown in FIG.

｛凸起的直徑及個數｝ 於導電粒子的正投影面中，算出具有導電粒子的直徑的1/2直徑的同心圓內所存在的凸起的直徑及個數。{Drilled Diameter and Number} The diameter and number of the protrusions present in the concentric circles having the diameter of the 1/2 diameter of the diameter of the conductive particles were calculated on the orthographic projection surface of the conductive particles.

具體而言，對藉由SEM以10萬倍觀察導電粒子所得的圖像進行分析，劃定凸起的輪廓。繼而，測定凸起的面積（由凸起間的凹部所劃分的凸起的輪廓的面積），算出具有與該面積相同的面積的正圓的直徑作為凸起的直徑（外徑）。圖11中示出藉由SEM觀察實施例1中的粒子D的結果。Specifically, the image obtained by observing the conductive particles by SEM at 100,000 times was analyzed to define the outline of the protrusion. Then, the area of the protrusion (the area of the outline of the protrusion divided by the concave portion between the protrusions) was measured, and the diameter of the perfect circle having the same area as the area was calculated as the diameter (outer diameter) of the protrusion. The result of observing the particles D in Example 1 by SEM is shown in FIG.

根據表1-2所示的直徑的範圍將凸起分類，求出各範圍的凸起的個數。圖11為具有粒子D的直徑的1/2直徑的同心圓內的一部分。The projections were classified according to the range of diameters shown in Table 1-2, and the number of projections in each range was obtained. Figure 11 is a portion of a concentric circle having a diameter of 1/2 of the diameter of the particle D.

（導電粒子的剖面試樣的製作方法） 對導電粒子的剖面試樣的製作方法的詳細情況加以說明。使用超薄切片法，如下述般由導電粒子的剖面來製作用以進行TEM分析及掃描穿透式電子顯微鏡（scanning transmission electron microscope，STEM）/EDX分析的具有60 nm±20 nm的厚度的剖面試樣（以下稱為「TEM測定用的薄膜切片」）。(Method for Producing Cross-Section Sample of Conductive Particles) The details of the method for producing the cross-sectional sample of the conductive particles will be described. Using the ultrathin sectioning method, a profile having a thickness of 60 nm ± 20 nm for performing TEM analysis and scanning transmission electron microscope (STEM)/EDX analysis was prepared from the cross section of the conductive particles as follows. Sample (hereinafter referred to as "film slice for TEM measurement").

為了穩定地進行薄膜化加工，使導電粒子分散於注模樹脂中。具體而言，於雙酚A型液狀環氧樹脂、丁基縮水甘油醚及其他環氧樹脂的10 g混合物（瑞泛泰（Refine Tec）股份有限公司製造，商品名「愛博馬特（Epomount）主劑27-771」）中混合1.0 g二乙三胺（瑞泛泰（Refine Tec）股份有限公司製造，商品名「愛博馬特（Epomount）硬化劑27-772」）。使用刮勺（spatula）進行攪拌，目測確認經均勻地混合。於3 g該混合物中添加0.5 g經乾燥的導電粒子後，使用刮勺進行攪拌直至變均勻。將含有導電粒子的混合物流入至樹脂注模用的模具（D.S.K 堂阪EM（Dosaka-EM）股份有限公司製造，商品名「矽酮包埋板II型」）中，於常溫（室溫）下靜置24小時。確認注模樹脂固化，獲得導電粒子的樹脂注模物。In order to stably carry out the film forming process, the conductive particles are dispersed in the injection resin. Specifically, a 10 g mixture of bisphenol A type liquid epoxy resin, butyl glycidyl ether and other epoxy resins (manufactured by Refine Tec Co., Ltd., trade name "Aibomat ( Epomount) The main ingredient 27-771") was mixed with 1.0 g of diethylenetriamine (manufactured by Refin Tec Co., Ltd., trade name "Epomount hardener 27-772"). Stirring was carried out using a spatula, and it was confirmed by visual observation that the mixture was uniformly mixed. After adding 0.5 g of the dried conductive particles to 3 g of the mixture, stirring was carried out using a spatula until uniform. The mixture containing the conductive particles is poured into a mold for resin injection molding (manufactured by Dosaka-EM Co., Ltd., trade name "anthrone-embedded plate type II") at room temperature (room temperature). Allow to stand for 24 hours. It was confirmed that the injection molded resin was cured, and a resin injection molded article of the conductive particles was obtained.

使用超薄切片機（徠卡微系統（Leica Microsystems）股份有限公司製造，商品名「EM-UC6」），由含有導電粒子的樹脂注模物來製作TEM測定用的薄膜切片。於製作TEM測定用的薄膜切片時，首先使用固定於超薄切片機的裝置本體上的玻璃製刀（knife），如圖12（a）所示，對樹脂注模物的前端進行修整（trimming）加工直至成為能切出TEM測定用的薄膜切片的形狀。A film slice for TEM measurement was prepared from a resin injection molded article containing conductive particles using an ultramicrotome (manufactured by Leica Microsystems, Inc., trade name "EM-UC6"). When making a film slice for TEM measurement, first, a glass knife fixed to the apparatus body of the ultramicrotome is used to trim the front end of the resin injection molded body as shown in Fig. 12 (a). The processing is performed until the shape of the film slice for TEM measurement can be cut out.

更詳細而言，如圖12（b）所示，以樹脂注模物的前端的剖面形狀成為具有縱向200 μm～400 μm及橫向100 μm～200 μm的長度的大致長方體狀的方式進行修整加工。將剖面的橫向長度設為100 μm～200 μm的原因在於：於自樹脂注模物切出TEM測定用的薄膜切片時，減少金剛石刀與試樣之間所產生的摩擦。藉此，容易防止TEM測定用的薄膜切片的皺褶及彎折，容易製作TEM測定用的薄膜切片。More specifically, as shown in FIG. 12( b ), the cross-sectional shape of the tip end of the resin injection molded article is trimmed in a substantially rectangular parallelepiped shape having a length of 200 μm to 400 μm in the longitudinal direction and a length of 100 μm to 200 μm in the lateral direction. . The reason why the lateral length of the cross section is set to 100 μm to 200 μm is to reduce the friction generated between the diamond blade and the sample when the film slice for TEM measurement is cut out from the resin injection molded article. Thereby, it is easy to prevent wrinkles and bending of the film slice for TEM measurement, and it is easy to produce a film slice for TEM measurement.

繼而，將帶有舟皿（boat）的金剛石刀（大通（DIATONE）公司製造，商品名「克洛維（Cryo Wet）」，刀寬2.0 mm，刀角度35°）固定於超薄切片機裝置本體的既定部位。然後，以離子交換水充滿舟皿，調整刀的設置角度並以離子交換水濡濕刀尖。Then, a diamond knife with a boat (manufactured by DIATONE Co., Ltd., trade name "Cryo Wet", knife width 2.0 mm, knife angle 35°) was fixed to the ultra-thin slicer device. The established part of the body. Then, fill the boat with ion-exchanged water, adjust the setting angle of the knife, and wet the tip with ion-exchanged water.

此處，使用圖13對刀的設置角度的調整加以說明。於調整刀的設置角度時，可調整上下方向的角度、左右方向的角度及間隙角。所謂「上下方向的角度的調整」，如圖13所示，是指以試樣表面與刀的行進方向成平行的方式調整試樣固持器的上下方向的角度。所謂「左右方向的角度的調整」，如圖13所示，是指以刀的刀尖與試樣表面成平行的方式調整刀的左右方向的角度。所謂「間隙角的調整」，如圖13所示，是指調整刀的刀尖的試樣側之面與刀的行進方向所成的最小角度。間隙角較佳為5°～10°。若間隙角為所述範圍，則可減少刀的刀尖與試樣表面的摩擦，並且防止自試樣切出薄膜切片後刀摩擦試樣表面。Here, the adjustment of the setting angle of the blade will be described using FIG. When adjusting the setting angle of the knife, the angle in the up and down direction, the angle in the left and right direction, and the clearance angle can be adjusted. As shown in FIG. 13, the "adjustment of the angle in the up-and-down direction" means that the angle of the sample holder in the vertical direction is adjusted such that the surface of the sample is parallel to the traveling direction of the blade. As shown in FIG. 13, the "adjustment of the angle in the left-right direction" means that the angle of the left-right direction of the blade is adjusted so that the blade edge of the blade is parallel to the surface of the sample. As shown in FIG. 13, the "adjustment of the clearance angle" means the minimum angle formed by the surface of the blade side of the blade of the adjustment blade and the traveling direction of the blade. The gap angle is preferably from 5 to 10 degrees. If the clearance angle is in the range, the friction between the blade tip of the blade and the surface of the sample can be reduced, and the blade can be prevented from rubbing against the surface of the sample after the film slice is cut out from the sample.

一面對超薄切片機裝置本體所附帶的光學顯微鏡進行確認，一面使試樣與金剛石刀的距離接近，以刀速度0.3 mm/s、薄膜的切出厚度成為60 nm±20 nm的方式設定切片機裝置的設定值，自樹脂注模物切出薄膜切片。繼而，使TEM測定用的薄膜切片漂浮於離子交換水的水面上。自漂浮於水面上的TEM測定用的薄膜切片的上表面按壓TEM測定用的銅網（帶有微細網眼（microgrid）的銅網），使TEM測定用的薄膜切片吸附於銅網，製成TEM試樣。利用切片機所得的TEM測定用的薄膜切片並非與切片機的切出厚度的設定值準確地一致，故預先求出可獲得所需厚度的設定值。As soon as the optical microscope attached to the main body of the ultra-thin microtome is confirmed, the distance between the sample and the diamond knife is close, and the knife speed is 0.3 mm/s, and the cut thickness of the film is 60 nm±20 nm. The set value of the microtome device was cut out from the resin injection molded material. Then, the film slice for TEM measurement was floated on the water surface of the ion-exchanged water. A copper mesh (a copper mesh with a microgrid) for TEM measurement was pressed from the upper surface of a film slice for TEM measurement floating on a water surface, and a film slice for TEM measurement was adsorbed on a copper mesh to prepare a film. TEM sample. The film slice for TEM measurement obtained by the microtome does not exactly match the set value of the cut thickness of the microtome, so that the set value of the desired thickness can be obtained in advance.

（利用EDX的匹配的方法） 對利用EDX的匹配的方法的詳細情況加以說明。將TEM測定用的薄膜切片連同銅網固定於試樣固持器（日本電子股份有限公司製造，商品名「鈹試樣雙軸傾斜固持器，EM-31640」），***至TEM內部。以加速電壓200 kV開始對試樣的電子束照射後，將電子束的照射系統切換為STEM模式。(Method of matching by EDX) The details of the method of matching by EDX will be described. The film slice for TEM measurement was attached to a sample holder (manufactured by JEOL Ltd., trade name "铍 sample biaxial tilt holder, EM-31640"), and inserted into the inside of the TEM. After the electron beam irradiation of the sample was started at an acceleration voltage of 200 kV, the irradiation system of the electron beam was switched to the STEM mode.

將掃描像觀察裝置***至STEM觀察時的位置，啟動STEM觀察用的軟體「JEOL圖片查看器（JEOL Simple Image Viewer）（版本（Version）1.3.5）」（日本電子股份有限公司製造）後，觀察TEM測定用的薄膜切片。於其中所觀察到的導電粒子的剖面中，搜索適於EDX測定的部位並進行拍攝。此處所謂「適於測定的部位」，是指於導電粒子的中心附近切斷而可觀察金屬層的剖面的部位。將剖面傾斜的部位、及於偏離導電粒子的中心附近的位置切斷的部位從測定對象中除外。拍攝時，觀察倍率為25萬倍，將STEM觀察像的畫素數設為縱向512點、橫向512點。若於該條件下觀察，則可獲得視角600 nm的觀察像，但若改變裝置則即便為相同倍率有時視角亦改變，故必須注意。When the scanning image observation device is inserted at the position of the STEM observation, the software "JEOL Simple Image Viewer (Version 1.3.5)" (manufactured by JEOL Ltd.) for STEM observation is activated. Film sections for TEM measurement were observed. In the cross section of the conductive particles observed therein, a portion suitable for EDX measurement was searched for and photographed. Here, the "portion suitable for measurement" means a portion which is cut near the center of the conductive particles to observe the cross section of the metal layer. The portion where the cross section is inclined and the portion cut at a position deviated from the center of the conductive particle are excluded from the measurement target. At the time of shooting, the observation magnification was 250,000 times, and the number of pixels of the STEM observation image was 512 dots in the vertical direction and 512 dots in the horizontal direction. If observed under these conditions, an observation image with a viewing angle of 600 nm can be obtained. However, if the device is changed, the viewing angle changes even if the magnification is the same, so care must be taken.

STEM/EDX分析時，若對TEM測定用的薄膜切片照射電子束，則導電粒子的樹脂粒子及注模樹脂發生收縮及熱膨脹，於測定中試樣變形或移動。為了抑制此種EDX測定中的試樣變形及試樣移動，預先對測定部位照射電子束30分鐘～1小時左右，確認變形及移動經控制後進行分析。In the STEM/EDX analysis, when the electron beam is irradiated to the film slice for TEM measurement, the resin particles and the injection resin of the conductive particles are shrunk and thermally expanded, and the sample is deformed or moved during the measurement. In order to suppress the deformation of the sample and the movement of the sample in the EDX measurement, the electron beam is irradiated to the measurement site for about 30 minutes to one hour in advance, and it is confirmed that the deformation and the movement are controlled and analyzed.

為了進行STEM/EDX分析，使EDX移動至測定位置，啟動EDX測定用的軟體「分析站（Analysis Station）」（日本電子股份有限公司製造）。於利用EDX的匹配時，需要於匹配時獲得充分的解析度，故使用用以使電子束聚焦於目標部位的聚焦裝置。In order to carry out the STEM/EDX analysis, the EDX was moved to the measurement position, and the software "Analysis Station" (manufactured by JEOL Ltd.) for EDX measurement was started. In the case of matching with EDX, it is necessary to obtain sufficient resolution at the time of matching, so that a focusing device for focusing the electron beam on the target portion is used.

於STEM/EDX分析時，以所檢測的特性X射線的計數（每秒計數（Counts Per Second，CPS））成為10,000 CPS以上的方式，於0.5 nm～1.0 nm的範圍內調整電子束的點徑。測定後，於與匹配測定同時獲得的EDX光譜中，確認到源自鎳的Kα射線的峰值的高度至少成為5,000 Counts以上。於取得資料時，以與所述STEM觀察時相同的視角，將畫素數設為縱向256點、橫向256點。將每一點的累計時間設為20毫秒，以累計次數1次進行測定。In the STEM/EDX analysis, the spot diameter of the electron beam is adjusted in the range of 0.5 nm to 1.0 nm in such a manner that the measured characteristic X-ray count (Counts Per Second (CPS)) becomes 10,000 CPS or more. . After the measurement, it was confirmed that the height of the peak of the Kα ray derived from nickel was at least 5,000 Counts or more in the EDX spectrum obtained simultaneously with the matching measurement. When the data is acquired, the number of pixels is 256 dots in the vertical direction and 256 dots in the horizontal direction at the same viewing angle as that in the STEM observation. The cumulative time of each point was set to 20 milliseconds, and the measurement was performed once in the cumulative number of times.

從所得的EDX匹配資料中視需要提取第一層、無電鍍鎳析出核、第二層的EDX光譜，算出各部分的元素存在比。其中，於算出定量值時，將貴金屬、鎳及磷的合計比例設為100質量%，算出各元素的質量%濃度。From the obtained EDX matching data, the EDX spectrum of the first layer, the electroless nickel precipitation nucleus, and the second layer were extracted as needed, and the element existence ratio of each part was calculated. In the calculation of the quantitative value, the total ratio of the noble metal, nickel, and phosphorus was set to 100% by mass, and the mass% concentration of each element was calculated.

關於所述以外的元素，由於下述原因而比例容易變動，故於算出定量值時除外。碳的比例因TEM測定用的網所使用的碳支持膜、或電子束照射時吸附於試樣表面的雜質的影響而增減。氧的比例可能因製作TEM試樣後直至測定為止的期間中進行空氣氧化而增加。銅會從TEM測定用所用的銅網中檢測到。The elements other than the above are easily changed in proportion due to the following reasons, and are excluded when the quantitative value is calculated. The ratio of carbon is increased or decreased by the influence of the carbon supporting film used for the mesh for TEM measurement or the impurities adsorbed on the surface of the sample during electron beam irradiation. The ratio of oxygen may increase due to air oxidation during the period from the preparation of the TEM sample to the measurement. Copper is detected from the copper mesh used for TEM measurement.

｛外徑1 μm以上的金屬異物｝ 關於外徑1 μm以上的金屬異物的個數的測定，藉由SEM以5千倍觀察1000個導電粒子，對觀察1000個導電粒子的過程中所發現的外徑1 μm以上的金屬異物的個數進行計數。{Metal foreign matter having an outer diameter of 1 μm or more} For the measurement of the number of metal foreign matters having an outer diameter of 1 μm or more, 1000 conductive particles were observed by SEM at 5,000 times, and found in the process of observing 1000 conductive particles. The number of metal foreign matters having an outer diameter of 1 μm or more was counted.

｛異常析出部的有無｝ 長度超過500 nm的凸起（異常析出部）的有無是藉由圖14（a）〜圖14（b）中示意性地示出的方法來判別。具體而言，藉由SEM以3萬倍觀察1000個導電粒子400，測量將異常析出部401的基端的直徑方向兩端連結的直線（將異常析出部401兩側的凹部與凹部連結的直線）至垂直方向上的異常析出部401的頂點的距離，藉此獲得異常析出部401的長度402。繼而，對具有長度超過500 nm的異常析出部的導電粒子數進行計數。{Presence or absence of abnormal precipitation portion} The presence or absence of a projection (abnormal precipitation portion) having a length exceeding 500 nm is determined by the method schematically shown in Figs. 14(a) to 14(b). Specifically, by observing 1000 conductive particles 400 at 30,000 times by SEM, a straight line connecting the both ends in the radial direction of the proximal end of the abnormal deposition portion 401 (a straight line connecting the concave portion on both sides of the abnormal deposition portion 401 and the concave portion) is measured. The length 402 of the abnormal precipitation unit 401 is obtained by the distance to the apex of the abnormal deposition unit 401 in the vertical direction. Then, the number of conductive particles having an abnormal precipitation portion having a length exceeding 500 nm was counted.

（單分散率的測定） 使0.05 g導電粒子分散於電解水中，添加界面活性劑，進行5分鐘超音波分散（亞速旺（AS-One）股份有限公司製造，商品名「US-4R」，高頻輸出：160 W，振盪頻率：40 kHz單頻）。將導電粒子的分散液注入至庫勒粒度分析計數儀（COULER MULTISIZER）II（貝克曼庫爾特（Beckman Coulter）股份有限公司製造，商品名）的試樣杯中，測定50000個導電粒子的單分散率。單分散率是藉由下述式而算出，根據其值按照下述基準來判定水溶劑中的粒子的凝聚性。 單分散率（%）＝｛第一峰（first peak）粒子數（個）/總粒子數（個）｝×100(Measurement of monodispersity ratio) 0.05 g of conductive particles were dispersed in electrolyzed water, and a surfactant was added thereto, and ultrasonic dispersion was performed for 5 minutes (manufactured by AS-One Co., Ltd., trade name "US-4R", High frequency output: 160 W, oscillation frequency: 40 kHz single frequency). The dispersion of the conductive particles was injected into a sample cup of a COULER MULTISIZER II (manufactured by Beckman Coulter Co., Ltd., trade name), and a single of 50,000 conductive particles was measured. Dispersion rate. The monodispersity ratio is calculated by the following formula, and the cohesiveness of the particles in the aqueous solvent is determined based on the following values according to the following criteria. Monodispersity ratio (%) = {first peak number of particles (number) / total number of particles (pieces)} × 100

[絕緣性粒子的製作] 按照以下所示的絕緣性粒子的調配莫耳比將單體添加至經加入至500 ml燒瓶中的400 g純水中。以所有單體的總量相對於純水而成為10質量%的方式調配。氮氣置換後，一面於70℃下攪拌一面進行6小時加熱。攪拌速度為300 min-1 （300 rpm）。KBM-503（信越化學股份有限公司製造，商品名）為3-甲基丙烯醯氧基丙基三甲氧基矽烷。[Production of Insulating Particles] The monomer was added to 400 g of pure water which was added to a 500 ml flask in accordance with the blending molar ratio of the insulating particles shown below. The total amount of all the monomers was adjusted so as to be 10% by mass based on the pure water. After nitrogen substitution, heating was carried out for 6 hours while stirring at 70 °C. Stirring speed is 300 min -1 (300 rpm). KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) is 3-methylpropenyloxypropyltrimethoxydecane.

（絕緣性粒子的調配莫耳比） 成分 莫耳比 苯乙烯 600 過氧二硫酸鉀 6 甲基丙烯酸鈉 5.4 苯乙烯磺酸鈉 0.32 二乙烯基苯 16.8 KBM-503 4.2(Morch ratio of insulating particles) Component Mobibi Styrene 600 Potassium peroxodisulfate 6 Sodium methacrylate 5.4 Sodium styrene sulfonate 0.32 Divinylbenzene 16.8 KBM-503 4.2

對藉由SEM所拍攝的圖像進行分析而測定所合成的絕緣性粒子的平均粒徑。絕緣性粒子的平均粒徑為315 nm。The average particle diameter of the synthesized insulating particles was measured by analyzing an image taken by SEM. The average particle diameter of the insulating particles was 315 nm.

使用示差掃描熱析儀（Differential Scanning Calorimeter，DSC）（帕金艾爾瑪（Perkin Elmer）公司製造，商品名「DSC-7」），於樣本量為10 mg、升溫速度為5℃/min、測定環境為空氣的條件下測定所合成的絕緣性粒子的Tg（玻璃轉移點）。A Differential Scanning Calorimeter (DSC) (manufactured by Perkin Elmer, trade name "DSC-7") was used, and the sample amount was 10 mg, and the temperature increase rate was 5 ° C/min. The Tg (glass transition point) of the synthesized insulating particles was measured under the condition that the measurement environment was air.

（矽酮寡聚物的製備） 於具備攪拌裝置、冷凝器及溫度計的玻璃燒瓶中，添加將118 g的3-縮水甘油氧基丙基三甲氧基矽烷與5.9 g甲醇調配而成的溶液。進而添加5 g活性白土及4.8 g蒸餾水，於75℃下攪拌一定時間後，獲得重量平均分子量1300的矽酮寡聚物。所得的矽酮寡聚物具有甲氧基或矽醇基作為與羥基反應的末端官能基。於所得的矽酮寡聚物溶液中添加甲醇，製備固體成分為20質量%的處理液。(Preparation of an fluorenone oligomer) To a glass flask equipped with a stirring device, a condenser, and a thermometer, a solution prepared by mixing 118 g of 3-glycidoxypropyltrimethoxydecane with 5.9 g of methanol was added. Further, 5 g of activated clay and 4.8 g of distilled water were added, and after stirring at 75 ° C for a certain period of time, an anthrone oligopolymer having a weight average molecular weight of 1300 was obtained. The resulting indolone oligomer has a methoxy or decyl group as a terminal functional group reactive with a hydroxyl group. Methanol was added to the obtained fluorenone oligomer solution to prepare a treatment liquid having a solid content of 20% by mass.

矽酮寡聚物的重量平均分子量是藉由利用凝膠滲透層析（Gel Permeation Chromatography，GPC）法進行測定，並使用標準聚苯乙烯的校準曲線進行換算而算出。於測定矽酮寡聚物的重量平均分子量時，使用泵（日立製作所股份有限公司製造，商品名「L-6000」）、管柱（吉爾帕（Gelpack）GL-R420、吉爾帕（Gelpack）GL-R430、吉爾帕（Gelpack）GL-R440（以上為日立化成股份有限公司製造，商品名））、檢測器（日立製作所股份有限公司製造，商品名「L-3300型RI」）。使用四氫呋喃（THF）作為溶離液，將測定溫度設為40℃，將流量設為2.05 mL/min進行測定。The weight average molecular weight of the fluorenone oligomer was measured by a gel permeation chromatography (GPC) method and converted using a calibration curve of standard polystyrene. For the measurement of the weight average molecular weight of the fluorenone oligomer, a pump (manufactured by Hitachi, Ltd., trade name "L-6000"), a column (Gelpack GL-R420, Gilpack GL) was used. -R430, Gilpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd., trade name), and detector (manufactured by Hitachi, Ltd., trade name "L-3300 type RI"). Tetrahydrofuran (THF) was used as the elution solution, and the measurement temperature was 40 ° C, and the flow rate was 2.05 mL / min.

[絕緣被覆導電粒子的製作] 使8 mmol巰基乙酸溶解於200 ml甲醇中而製備反應液。繼而將導電粒子（實施例1中為粒子D）添加至2 g所述反應液中，利用三一馬達（Three-One Motor）及直徑45 mm的攪拌翼於室溫下攪拌2小時。利用甲醇清洗後，使用孔徑3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）進行過濾，由此獲得2 g表面具有羧基的導電粒子。[Preparation of Insulating Coated Conductive Particles] A reaction liquid was prepared by dissolving 8 mmol of thioglycolic acid in 200 ml of methanol. Then, conductive particles (particle D in Example 1) were added to 2 g of the reaction liquid, and stirred at room temperature for 2 hours using a Three-One Motor and a stirring blade having a diameter of 45 mm. After washing with methanol, filtration was carried out using a membrane filter having a pore size of 3 μm (manufactured by Merck Millipore Co., Ltd.), thereby obtaining 2 g of conductive particles having a carboxyl group on the surface.

繼而，以超純水將重量平均分子量70,000的30%聚乙烯亞胺水溶液（和光純藥工業股份有限公司製造）稀釋，獲得0.3質量%聚乙烯亞胺水溶液。將2 g所述表面具有羧基的導電粒子添加至0.3質量%聚乙烯亞胺水溶液中，於室溫下攪拌15分鐘。其後，使用孔徑3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）將導電粒子過濾，將經過濾的導電粒子加入至200 g超純水中，於室溫下攪拌5分鐘。進而使用孔徑3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）將導電粒子過濾，於所述薄膜過濾器上以200 g的超純水進行2次清洗。藉由進行該些操作，將未吸附的聚乙烯亞胺去除，獲得表面經含胺基聚合物被覆的導電粒子。Then, a 30% aqueous solution of polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd.) having a weight average molecular weight of 70,000 was diluted with ultrapure water to obtain a 0.3 mass% aqueous solution of polyethyleneimine. 2 g of the conductive particles having a carboxyl group on the surface were added to a 0.3% by mass aqueous solution of polyethyleneimine, and stirred at room temperature for 15 minutes. Thereafter, the conductive particles were filtered using a membrane filter having a pore size of 3 μm (manufactured by Merck Millipore Co., Ltd.), and the filtered conductive particles were added to 200 g of ultrapure water and stirred at room temperature for 5 minutes. . Further, the conductive particles were filtered using a membrane filter having a pore size of 3 μm (manufactured by Merck Millipore Co., Ltd.), and the membrane filter was washed twice with 200 g of ultrapure water. By performing these operations, the unadsorbed polyethyleneimine is removed to obtain conductive particles whose surface is coated with the amine group-containing polymer.

繼而，利用矽酮寡聚物對絕緣性粒子進行處理，製備表面具有含縮水甘油基寡聚物的絕緣性粒子的甲醇分散介質（絕緣性粒子的甲醇分散介質）。Then, the insulating particles were treated with an anthrone oligo polymer to prepare a methanol dispersion medium (methanol dispersion medium of insulating particles) having insulating particles containing a glycidyl group-containing oligomer on the surface.

將所述表面經含胺基聚合物被覆的導電粒子浸漬於甲醇中，於該甲醇中滴加絕緣性粒子的甲醇分散介質，由此製作絕緣被覆導電粒子。利用縮合劑及十八烷基胺對所得的絕緣被覆導電粒子進行處理，清洗並進行表面的疏水化。其後以80℃、1小時的條件加熱乾燥而製作絕緣被覆導電粒子。對藉由SEM所拍攝的圖像進行分析，由此測定絕緣性粒子對導電粒子的平均被覆率，結果為約30%。The conductive particles coated with the amine group-containing polymer were immersed in methanol, and a methanol dispersion medium of insulating particles was dropped on the methanol to prepare insulating coated conductive particles. The obtained insulating coated conductive particles are treated with a condensing agent and octadecylamine, and washed and hydrophobized on the surface. Thereafter, the film was dried by heating at 80 ° C for 1 hour to prepare insulating coated conductive particles. The average particle coverage of the conductive particles with respect to the conductive particles was measured by analyzing the image taken by the SEM, and it was about 30%.

[異向導電性接著膜及連接結構體的製作] 將100 g苯氧樹脂（聯合碳化物（Union Carbide）公司製造，商品名「PKHC」）、75 g丙烯酸橡膠（40質量份丙烯酸丁酯、30質量份丙烯酸乙酯、30質量份丙烯腈、3質量份甲基丙烯酸縮水甘油酯的共聚物，分子量：85萬）溶解於400 g乙酸乙酯中而獲得溶液。於該溶液中添加300 g含有微膠囊型潛伏性硬化劑的液狀環氧樹脂（旭化成環氧股份有限公司製造，商品名「諾瓦固（Novacure）HX-3941」，環氧當量185），攪拌而獲得接著劑溶液。[Production of an anisotropic conductive adhesive film and a bonded structure] 100 g of phenoxy resin (manufactured by Union Carbide, trade name "PKHC"), 75 g of acryl rubber (40 parts by mass of butyl acrylate, 30 parts by mass of ethyl acrylate, 30 parts by mass of acrylonitrile, and 3 parts by mass of a copolymer of glycidyl methacrylate, molecular weight: 850,000) were dissolved in 400 g of ethyl acetate to obtain a solution. 300 g of a liquid epoxy resin containing a microcapsule type latent curing agent (manufactured by Asahi Kasei Epoxy Co., Ltd., trade name "Novacure HX-3941", epoxy equivalent 185) was added to the solution. Stirring to obtain an adhesive solution.

於該接著劑溶液中，以接著劑溶液的總量為基準而使所述絕緣被覆導電粒子以成為9體積%的方式分散，獲得分散液。使用輥塗機將所得的分散液塗佈於隔離膜（經矽酮處理的聚對苯二甲酸乙二酯膜，厚度40 μm）上，於90℃下進行10分鐘加熱，藉此進行乾燥，於隔離膜上製作厚度25 μm的異向導電性接著膜。In the adhesive solution, the insulating-coated conductive particles were dispersed so as to be 9 vol% based on the total amount of the adhesive solution to obtain a dispersion. The obtained dispersion liquid was applied onto a separator (an anthraquinone-treated polyethylene terephthalate film having a thickness of 40 μm) using a roll coater, and heated at 90 ° C for 10 minutes to dry. An anisotropic conductive adhesive film having a thickness of 25 μm was formed on the separator.

繼而，使用所製作的異向導電性接著膜，按照以下所示的i）～iii）的順序，進行分別設有362個的金凸塊（1）（面積：約20 μm×約40 μm，高度：15 μm）、金凸塊（2）（面積：約30 μm×約40 μm，高度：15 μm）及金凸塊（3）（面積：約40 μm×約40 μm，高度：15 μm）的晶片（1.7 mm×20 mm，厚度：0.5 μm）與帶有氧化銦鋅（Indium Zinc Oxide，IZO）電路的玻璃基板（厚度：0.7 mm）的連接，獲得連接結構體。將金凸塊（1）的間隙設為6 μm，將金凸塊（2）的間隙設為8 μm，將金凸塊（3）的間隙設為10 μm。所謂間隙相當於金凸塊彼此的距離。 i）以80℃、0.98 MPa（10 kgf/cm2 ）將異向導電性接著膜（2 mm×24 mm）貼附於帶有IZO電路的玻璃基板上。 ii）將隔離膜剝離，進行晶片的凸塊與帶有IZO電路的玻璃基板的對位。 iii）以190℃、40 gf/凸塊、10秒的條件從晶片上方進行加熱及加壓，進行晶片與玻璃基板的接著，並且進行晶片的凸塊與IZO電路的電性連接。Then, using the produced anisotropic conductive adhesive film, 362 gold bumps (1) were respectively provided in the order of i) to iii) (area: about 20 μm × about 40 μm, Height: 15 μm), gold bumps (2) (area: approx. 30 μm x approx. 40 μm, height: 15 μm) and gold bumps (3) (area: approx. 40 μm x approx. 40 μm, height: 15 μm The wafer (1.7 mm × 20 mm, thickness: 0.5 μm) was connected to a glass substrate (thickness: 0.7 mm) with an Indium Zinc Oxide (IZO) circuit to obtain a bonded structure. The gap between the gold bumps (1) was set to 6 μm, the gap of the gold bumps (2) was set to 8 μm, and the gap of the gold bumps (3) was set to 10 μm. The gap corresponds to the distance between the gold bumps. i) at 80 ℃, 0.98 MPa (10 kgf / cm 2) followed by the anisotropic conductive film (2 mm × 24 mm) attached on a glass substrate with IZO circuit. Ii) The separator is peeled off to align the bumps of the wafer with the glass substrate with the IZO circuit. Iii) Heating and pressurizing from above the wafer at 190 ° C, 40 gf / bump, and 10 seconds, the wafer and the glass substrate were bonded, and the bumps of the wafer were electrically connected to the IZO circuit.

[連接結構體的評價] 如以下般進行所得的連接結構體的導通電阻試驗及絕緣電阻試驗。[Evaluation of Connection Structure] The on-resistance test and the insulation resistance test of the obtained bonded structure were carried out as follows.

（導通電阻試驗） 於晶片電極（凸塊）與IZO電路的連接時，測定導通電阻的初期值、及吸濕耐熱試驗（於溫度85℃、濕度85%的條件下放置100小時、300小時、500小時、1000小時、2000小時）後的導通電阻的值。晶片電極（凸塊）與IZO電路的連接區域是設為約20 μm×約40 μm、約30 μm×約40 μm及約40 μm×約40 μm。於約20 μm×約40 μm的連接區域中，以晶片電極與IZO電路經3個導電粒子（捕捉導電粒子）連接的方式設定。於約30 μm×約40 μm的連接區域中，以晶片電極與IZO電路經6個導電粒子連接的方式設定。於約40 μm×約40 μm的連接區域中，以晶片電極與IZO電路經10個導電粒子連接的方式設定。再者，對20個樣本進行測定，算出該些樣本的平均值。根據所得的平均值按照下述基準評價導通電阻，將評價的結果示於表6-1中。於凸塊數6個的情況下於吸濕耐熱試驗500小時後滿足下述A或B基準的情形時，評價為導通電阻良好。 A：導通電阻的平均值小於2 Ω B：導通電阻的平均值為2 Ω以上且小於5 Ω C：導通電阻的平均值為5 Ω以上且小於10 Ω D：導通電阻的平均值為10 Ω以上且小於20 Ω E：導通電阻的平均值為20 Ω以上(On-resistance test) When the wafer electrode (bump) is connected to the IZO circuit, the initial value of the on-resistance and the moisture absorption heat resistance test are measured (the temperature is 85 ° C and the humidity is 85%, and it is allowed to stand for 100 hours, 300 hours, The value of the on-resistance after 500 hours, 1000 hours, and 2000 hours). The connection area of the wafer electrode (bump) and the IZO circuit is set to be about 20 μm × about 40 μm, about 30 μm × about 40 μm, and about 40 μm × about 40 μm. In a connection region of about 20 μm × about 40 μm, the wafer electrode and the IZO circuit are connected via three conductive particles (capture conductive particles). In a connection region of about 30 μm × about 40 μm, the wafer electrode and the IZO circuit are connected via six conductive particles. In a connection region of about 40 μm × about 40 μm, the wafer electrode and the IZO circuit are connected via 10 conductive particles. Furthermore, 20 samples were measured, and the average value of the samples was calculated. The on-resistance was evaluated based on the obtained average value according to the following criteria, and the results of the evaluation are shown in Table 6-1. When the number of the bumps was six, the following A or B criteria were satisfied after 500 hours of the moisture absorption heat resistance test, and it was evaluated that the on-resistance was good. A: The average value of the on-resistance is less than 2 Ω. B: The average value of the on-resistance is 2 Ω or more and less than 5 Ω. C: The average value of the on-resistance is 5 Ω or more and less than 10 Ω. D: The average value of the on-resistance is 10 Ω. Above and less than 20 Ω E: The average value of the on-resistance is 20 Ω or more

（絕緣電阻試驗） 作為晶片電極（凸塊）間的絕緣電阻，測定絕緣電阻的初期值、及遷移試驗（於溫度60℃、濕度90%、施加20 V的條件下放置100小時、300小時、1000小時、2000小時）後的絕緣電阻的值。對20個樣本進行測定，算出所有20個樣本中絕緣電阻值成為109 Ω以上的樣本的比例。測定是對金凸塊（1）～金凸塊（3）分別進行。即，對金凸塊的間隙為6 μm、8 μm、10 μm的情況分別進行絕緣電阻試驗。根據所得的比例按照下述基準評價絕緣電阻。將結果示於表6-1中。於間隙為8 μm的情況下於吸濕耐熱試驗1000小時後滿足下述A或B基準的情形時，評價為絕緣電阻良好。 A：絕緣電阻值109 Ω以上的比例為100% B：絕緣電阻值109 Ω以上的比例為90%以上且小於100% C：絕緣電阻值109 Ω以上的比例為80%以上且小於90% D：絕緣電阻值109 Ω以上的比例為50%以上且小於80% E：絕緣電阻值109 Ω以上的比例小於50%(Insulation resistance test) As the insulation resistance between the wafer electrodes (bumps), the initial value of the insulation resistance and the migration test were measured (the temperature was 60 ° C, the humidity was 90%, and 20 V was applied for 100 hours, 300 hours, The value of the insulation resistance after 1000 hours and 2000 hours). Twenty samples were measured, and the ratio of samples in which the insulation resistance value became 10 9 Ω or more in all 20 samples was calculated. The measurement was performed on each of the gold bumps (1) to the gold bumps (3). That is, the insulation resistance test was performed for the case where the gap of the gold bumps was 6 μm, 8 μm, or 10 μm. The insulation resistance was evaluated in accordance with the following criteria in accordance with the obtained ratio. The results are shown in Table 6-1. When the gap was 8 μm, the following A or B criteria were satisfied after 1000 hours of the moisture absorption heat resistance test, and the insulation resistance was evaluated to be good. A: ratio above 10 9 Ω insulation resistance value was 100% B: ratio above 10 9 Ω insulation resistance value of less than 90% and less than 100% C: the ratio above 10 9 Ω insulation resistance value of less than 80% and less than 90% D: The ratio of the insulation resistance value of 10 9 Ω or more is 50% or more and less than 80%. E: The ratio of the insulation resistance value of 10 9 Ω or more is less than 50%.

＜實施例2＞ 於實施例1的（步驟b）中，將平均粒徑60 nm的氣相法親水性球狀氧化矽粉末變更為平均粒徑25 nm的氣相法親水性球狀氧化矽粉末，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表1-1、表1-2及表6-1中。<Example 2> In the step (1) of Example 1, a vapor-phase hydrophilic spherical cerium oxide powder having an average particle diameter of 60 nm was changed into a vapor phase hydrophilic spherical cerium oxide having an average particle diameter of 25 nm. In the same manner as in Example 1, the production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in Example 1. The results are shown in Table 1-1, Table 1-2, and Table 6-1.

＜實施例3＞ 於實施例1的（步驟b）中，將平均粒徑60 nm的氣相法親水性球狀氧化矽粉末變更為平均粒徑40 nm的氣相法親水性球狀氧化矽粉末，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表1-1、表1-2及表6-1中。<Example 3> In the step (1) of Example 1, a vapor-phase hydrophilic spherical cerium oxide powder having an average particle diameter of 60 nm was changed to a gas phase hydrophilic spherical cerium oxide having an average particle diameter of 40 nm. In the same manner as in Example 1, the production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in Example 1. The results are shown in Table 1-1, Table 1-2, and Table 6-1.

＜實施例4＞ 於實施例1的（步驟b）中，將平均粒徑60 nm的氣相法親水性球狀氧化矽粉末變更為平均粒徑80 nm的氣相法親水性球狀氧化矽粉末，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表1-1、表1-2及表6-1中。<Example 4> In the step (1) of Example 1, a vapor-phase hydrophilic spherical cerium oxide powder having an average particle diameter of 60 nm was changed to a gas phase hydrophilic spherical cerium oxide having an average particle diameter of 80 nm. In the same manner as in Example 1, the production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in Example 1. The results are shown in Table 1-1, Table 1-2, and Table 6-1.

＜實施例5＞ 於實施例1的（步驟b）中，將平均粒徑60 nm的氣相法親水性球狀氧化矽粉末變更為平均粒徑100 nm的氣相法親水性球狀氧化矽粉末，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表1-3、表1-4及表6-1中。<Example 5> In the step (1) of Example 1, a vapor-phase hydrophilic spherical cerium oxide powder having an average particle diameter of 60 nm was changed to a vapor-phase hydrophilic spherical cerium oxide having an average particle diameter of 100 nm. In the same manner as in Example 1, the production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in Example 1. The results are shown in Tables 1-3, 1-4 and 6-1.

＜實施例6＞ 於實施例1的（步驟b）中，將平均粒徑60 nm的氣相法親水性球狀氧化矽粉末變更為平均粒徑120 nm的氣相法親水性球狀氧化矽粉末，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表1-3、表1-4及表6-2中。<Example 6> In the step (1) of Example 1, a vapor-phase hydrophilic spherical cerium oxide powder having an average particle diameter of 60 nm was changed to a vapor-phase hydrophilic spherical cerium oxide having an average particle diameter of 120 nm. In the same manner as in Example 1, the production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in Example 1. The results are shown in Tables 1-3, 1-4 and 6-2.

＜實施例7＞ 於實施例1的（步驟d）中，使用100 mL的經調整為pH值10.5且含有8質量%的鈀觸媒（日本安美特（Atotech Japan）股份有限公司製造，商品名「安美特尼奧加特（Atotech Neoganth）834」）的鈀觸媒化液作為鈀觸媒化液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表1-3、表1-4及表6-2中。<Example 7> In (Step d) of Example 1, 100 mL of a palladium catalyst adjusted to a pH of 10.5 and containing 8 mass% (manufactured by Atotech Japan Co., Ltd., trade name) was used. In the same manner as in Example 1, the conductive particles, the insulating coated conductive particles, and the anisotropic conductivity were carried out in the same manner as in Example 1 except that the palladium-catalyzed liquid of the "Atotech Neoganth 834" was used as the palladium-catalyzed liquid. Next, the production of the film and the bonded structure, and evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Tables 1-3, 1-4 and 6-2.

＜實施例8＞ 於實施例1的（步驟b）中，使用平均粒徑25nm的氣相法親水性球狀氧化矽粉末作為氧化矽粉末，及於實施例1的（步驟d）中，使用100 mL的經調整為pH值10.5且含有8質量%的安美特尼奧加特（Atotech Neoganth）834的鈀觸媒化液作為鈀觸媒化液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表2-1、表2-2及表6-2中。<Example 8> In the step (1) of Example 1, a vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 25 nm was used as the cerium oxide powder, and in the step (1) of Example 1, The same procedure as in Example 1 was carried out except that 100 g of a palladium-catalyzed liquid having a pH of 10.5 and containing 8 mass% of Atotech Neoganth 834 was used as the palladium-catalyzed liquid. Preparation of conductive particles, insulating coated conductive particles, anisotropic conductive adhesive film and bonded structure, and evaluation of conductive particles and bonded structures. The results are shown in Table 2-1, Table 2-2, and Table 6-2.

＜實施例9＞ 於實施例1的（步驟b）中，使用平均粒徑40 nm的氣相法親水性球狀氧化矽粉末作為氧化矽粉末，及於實施例1的（步驟d）中，使用100 mL的經調整為pH值10.5且含有8質量%的安美特尼奧加特（Atotech Neoganth）834的鈀觸媒化液代替100 mL鈀觸媒化液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表2-1、表2-2及表6-2中。<Example 9> In the step (1) of Example 1, a vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 40 nm was used as the cerium oxide powder, and in (Step d) of Example 1, Using 100 mL of a palladium catalyst solution adjusted to pH 10.5 and containing 8 mass% of Atotech Neoganth 834 instead of 100 mL of palladium catalyst solution, except Example 1 In the same manner, the conductive particles, the insulating coated conductive particles, the production of the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Table 2-1, Table 2-2, and Table 6-2.

＜實施例10＞ 於實施例1的（步驟b）中，使用平均粒徑80 nm的氣相法親水性球狀氧化矽粉末作為氧化矽粉末，及於實施例1的（步驟d）中，使用100 mL的經調整為pH值10.5且含有8質量%的安美特尼奧加特（Atotech Neoganth）834的鈀觸媒化液作為鈀觸媒化液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表2-1、表2-2及表7-1中。<Example 10> In the step (1) of Example 1, a vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 80 nm was used as the cerium oxide powder, and in (Step d) of Example 1, In the same manner as in Example 1, except that 100 g of a palladium-catalyzed liquid having a pH of 10.5 and a 8% by mass of Atotech Neoganth 834 was used as the palladium-catalyzed liquid. The conductive particles, the insulating coated conductive particles, the production of the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Table 2-1, Table 2-2, and Table 7-1.

＜實施例11＞ 於實施例1的（步驟b）中，使用平均粒徑100 nm的氣相法親水性球狀氧化矽粉末作為氧化矽粉末，及於實施例1的（步驟d）中，使用100 mL的經調整為pH值10.5且含有8質量%的安美特尼奧加特（Atotech Neoganth）834的鈀觸媒化液作為鈀觸媒化液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表2-1、表2-2及表7-1中。<Example 11> In the step (1) of Example 1, a vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 100 nm was used as the cerium oxide powder, and in (Step d) of Example 1, In the same manner as in Example 1, except that 100 g of a palladium-catalyzed liquid having a pH of 10.5 and a 8% by mass of Atotech Neoganth 834 was used as the palladium-catalyzed liquid. The conductive particles, the insulating coated conductive particles, the production of the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Table 2-1, Table 2-2, and Table 7-1.

＜實施例12＞ 於實施例1的（步驟b）中，使用平均粒徑120 nm的氣相法親水性球狀氧化矽粉末作為氧化矽粉末，及於實施例1的（步驟d）中，使用100 mL的經調整為pH值10.5且含有8質量%的安美特尼奧加特（Atotech Neoganth）834的鈀觸媒化液作為鈀觸媒化液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表2-3、表2-4及表7-1中。<Example 12> In the step (1) of Example 1, a vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 120 nm was used as the cerium oxide powder, and in (Step d) of Example 1, In the same manner as in Example 1, except that 100 g of a palladium-catalyzed liquid having a pH of 10.5 and a 8% by mass of Atotech Neoganth 834 was used as the palladium-catalyzed liquid. The conductive particles, the insulating coated conductive particles, the production of the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Table 2-3, Table 2-4, and Table 7-1.

＜實施例13＞ 藉由以下所示的方法來代替實施例1的（步驟b）而製造非導電性無機粒子，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表2-3、表2-4及表7-1中。<Example 13> Conductive particles, insulating coated conductive particles, and the like were produced in the same manner as in Example 1 except that the non-conductive inorganic particles were produced in place of (Step b) of Example 1 by the method described below. Preparation of a conductive adhesive film and a bonded structure, and evaluation of conductive particles and a bonded structure. The results are shown in Table 2-3, Table 2-4, and Table 7-1.

於實施例13中，首先使用平均粒徑100 nm的氣相法親水性球狀氧化矽粉末，將100 g球狀氧化矽粉末收容於振動流化床裝置（中央化工機股份有限公司製造，商品名「振動流化床裝置VUA-15型」）中。繼而，不使用循環氣體，於將裝置上部開放的狀態下藉由壓縮機（compressor）的壓縮空氣使球狀氧化矽流動，噴霧3.0 g水而流動混合5分鐘。繼而，噴霧5.0 g的HMDS（六甲基二矽氮烷）（日本邁圖高新材料（Momentive Performance Materials Japan）合同公司製造，商品名「TSL-8802」），流動混合30分鐘。藉由甲醇滴定法對所得的疏水性球狀氧化矽微粉體的疏水化度進行測定。實施例13的非導電性無機粒子的疏水化度為30%。In Example 13, first, a gas phase hydrophilic spherical cerium oxide powder having an average particle diameter of 100 nm was used, and 100 g of spherical cerium oxide powder was placed in a vibrating fluidized bed apparatus (manufactured by Central Chemical Machinery Co., Ltd., Named "Vibrating fluidized bed unit VUA-15 type"). Then, without using the circulating gas, the spherical cerium oxide was flowed by the compressed air of a compressor while the upper portion of the apparatus was opened, and 3.0 g of water was sprayed and mixed for 5 minutes. Then, 5.0 g of HMDS (hexamethyldioxane) (manufactured by Momentive Performance Materials Japan Co., Ltd., trade name "TSL-8802") was sprayed and mixed for 30 minutes. The degree of hydrophobicity of the obtained hydrophobic spherical cerium oxide fine powder was measured by a methanol titration method. The degree of hydrophobicization of the non-conductive inorganic particles of Example 13 was 30%.

＜實施例14＞ 藉由以下所示的方法來代替實施例1的（步驟b）而製造非導電性無機粒子，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表2-3、表2-4及表7-1中。(Example 14) Conductive particles, insulating coated conductive particles, and the like were produced in the same manner as in Example 1 except that the non-conductive inorganic particles were produced in place of the above-described method (Step b). Preparation of a conductive adhesive film and a bonded structure, and evaluation of conductive particles and a bonded structure. The results are shown in Table 2-3, Table 2-4, and Table 7-1.

於實施例14中，首先使用平均粒徑100 nm的氣相法親水性球狀氧化矽粉末，將100 g球狀氧化矽粉末收容於振動流化床裝置（中央化工機股份有限公司製造，商品名「振動流化床裝置VUA-15型」）中。繼而，一面利用藉由抽吸風機而循環的空氣使球狀氧化矽流動一面噴霧3.5 g水，流動混合5分鐘。繼而，噴霧2.5 g的HMDS（六甲基二矽氮烷）（日本邁圖高新材料（Momentive Performance Materials Japan）合同公司製造，商品名「TSL-8802」），流動混合30分鐘。藉由甲醇滴定法對所得的疏水性球狀氧化矽微粉體的疏水化度進行測定。實施例14的非導電性無機粒子的疏水化度為50%。In Example 14, first, a gas phase hydrophilic spherical cerium oxide powder having an average particle diameter of 100 nm was used, and 100 g of spherical cerium oxide powder was placed in a vibrating fluidized bed apparatus (manufactured by Central Chemical Machinery Co., Ltd., a product Named "Vibrating fluidized bed unit VUA-15 type"). Then, while circulating the spherical cerium oxide by using the air circulated by the suction fan, 3.5 g of water was sprayed and mixed by flow for 5 minutes. Then, 2.5 g of HMDS (hexamethyldioxane) (manufactured by Momentive Performance Materials Japan Co., Ltd., trade name "TSL-8802") was sprayed and mixed for 30 minutes. The degree of hydrophobicity of the obtained hydrophobic spherical cerium oxide fine powder was measured by a methanol titration method. The degree of hydrophobicization of the non-conductive inorganic particles of Example 14 was 50%.

＜實施例15＞ 藉由以下所示的方法來代替實施例1的（步驟b）而製造非導電性無機粒子，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表3-1、表3-2及表7-2中。(Example 15) Conductive particles, insulating coated conductive particles, and the like were produced in the same manner as in Example 1 except that the non-conductive inorganic particles were produced in place of the above-described method (Step b). Preparation of a conductive adhesive film and a bonded structure, and evaluation of conductive particles and a bonded structure. The results are shown in Table 3-1, Table 3-2, and Table 7-2.

於實施例15中，首先使用平均粒徑100 nm的氣相法親水性球狀氧化矽粉末，將100 g球狀氧化矽粉末收容於振動流化床裝置（中央化工機股份有限公司製造，商品名「振動流化床裝置VUA-15型」）中。繼而，一面利用藉由抽吸風機而循環的空氣使球狀氧化矽流動一面噴霧3.0 g水，流動混合5分鐘。繼而，噴霧5.0 g的HMDS（六甲基二矽氮烷）（日本邁圖高新材料（Momentive Performance Materials Japan）合同公司製造，商品名「TSL-8802」），流動混合30分鐘。藉由甲醇滴定法對所得的疏水性球狀氧化矽微粉體的疏水化度進行測定。實施例15的非導電性無機粒子的疏水化度為80%。In Example 15, first, a gas phase hydrophilic spherical cerium oxide powder having an average particle diameter of 100 nm was used, and 100 g of spherical cerium oxide powder was placed in a vibrating fluidized bed apparatus (manufactured by Central Chemical Machinery Co., Ltd., a product Named "Vibrating fluidized bed unit VUA-15 type"). Then, 3.0 g of water was sprayed while flowing the spherical cerium oxide by the air circulated by the suction fan, and the mixture was flow-mixed for 5 minutes. Then, 5.0 g of HMDS (hexamethyldioxane) (manufactured by Momentive Performance Materials Japan Co., Ltd., trade name "TSL-8802") was sprayed and mixed for 30 minutes. The degree of hydrophobicity of the obtained hydrophobic spherical cerium oxide fine powder was measured by a methanol titration method. The degree of hydrophobicization of the non-conductive inorganic particles of Example 15 was 80%.

＜實施例16＞ 藉由以下所示的方法來代替實施例1的（步驟b）而製造非導電性無機粒子，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表3-1、表3-2及表7-2中。(Example 16) Conductive particles, insulating coated conductive particles, and the like were produced in the same manner as in Example 1 except that the non-conductive inorganic particles were produced in place of the above-described method (Step b). Preparation of a conductive adhesive film and a bonded structure, and evaluation of conductive particles and a bonded structure. The results are shown in Table 3-1, Table 3-2, and Table 7-2.

於實施例16中，首先使用平均粒徑100 nm的氣相法親水性球狀氧化矽粉末，將100 g球狀氧化矽粉末收容於振動流化床裝置（中央化工機股份有限公司製造，商品名「振動流化床裝置VUA-15型」）中。繼而，一面利用藉由抽吸風機而循環的空氣使球狀氧化矽流動一面噴霧3.0 g水，流動混合5分鐘。繼而，噴霧6.0 g的HMDS（六甲基二矽氮烷）（日本邁圖高新材料（Momentive Performance Materials Japan）合同公司製造，商品名「TSL-8802」），流動混合30分鐘。藉由甲醇滴定法對所得的疏水性球狀氧化矽微粉體的疏水化度進行測定。實施例16的非導電性無機粒子的疏水化度為90%。In Example 16, first, a gas phase hydrophilic spherical cerium oxide powder having an average particle diameter of 100 nm was used, and 100 g of spherical cerium oxide powder was placed in a vibrating fluidized bed apparatus (manufactured by Central Chemical Machinery Co., Ltd., a product Named "Vibrating fluidized bed unit VUA-15 type"). Then, 3.0 g of water was sprayed while flowing the spherical cerium oxide by the air circulated by the suction fan, and the mixture was flow-mixed for 5 minutes. Then, 6.0 g of HMDS (hexamethyldioxane) (manufactured by Momentive Performance Materials Japan Co., Ltd., trade name "TSL-8802") was sprayed and mixed for 30 minutes. The degree of hydrophobicity of the obtained hydrophobic spherical cerium oxide fine powder was measured by a methanol titration method. The degree of hydrophobicization of the non-conductive inorganic particles of Example 16 was 90%.

＜實施例17＞ 於實施例1的（步驟c）中，將經HMDS疏水化的球狀氧化矽粉末設為0.04 g來代替0.05 g，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表3-1、表3-2及表7-2中。(Example 17) Conductive particles were produced in the same manner as in Example 1 except that the spherical cerium oxide powder hydrophobized by HMDS was changed to 0.04 g in place of 0.05 g in the first step. The production of the insulating coated conductive particles, the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure. The results are shown in Table 3-1, Table 3-2, and Table 7-2.

＜實施例18＞ 於實施例1的（步驟c）中，將經HMDS疏水化的球狀氧化矽粉末設為0.03 g來代替0.05 g，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表3-1、表3-2及表7-2中。(Example 18) Conductive particles were carried out in the same manner as in Example 1 except that the spherical cerium oxide powder hydrophobized by HMDS was changed to 0.03 g in the same manner as in Example 1 (Step c). The production of the insulating coated conductive particles, the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure. The results are shown in Table 3-1, Table 3-2, and Table 7-2.

＜實施例19＞ 於實施例1的（步驟a）中，變更為3 g平均分子量600的30質量%聚乙烯亞胺水溶液（和光純藥工業股份有限公司製造）來代替3 g聚乙烯亞胺水溶液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表3-3、表3-4及表8-1中。<Example 19> In the (Step a) of Example 1, a 30% by mass aqueous solution of polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd.) of 3 g of an average molecular weight of 600 was changed to replace 3 g of polyethyleneimine. In the same manner as in Example 1, except for the aqueous solution, the production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Tables 3-3, 3-4 and Table 8-1.

＜實施例20＞ 於實施例1的（步驟a）中，變更為3 g平均分子量1萬的30質量%聚乙烯亞胺水溶液（和光純藥工業股份有限公司製造）來代替3 g聚乙烯亞胺水溶液，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表3-3、表3-4及表8-1中。<Example 20> In the (Step a) of Example 1, it was changed to 3 g of a 30 mass% polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having an average molecular weight of 10,000 instead of 3 g of polyethylene. In the same manner as in Example 1, except that the conductive liquid particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure were produced, and the conductive particles and the bonded structure were evaluated. The results are shown in Tables 3-3, 3-4 and Table 8-1.

＜實施例21＞ 於實施例1的（步驟b）中，變更為2.5 g聚二甲基矽氧烷（PDMS）（和光純藥工業股份有限公司製造）來代替2.5 g的HMDS，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表3-3、表3-4及表8-1中。<Example 21> In (Step b) of Example 1, it was changed to 2.5 g of polydimethyl methoxy oxane (PDMS) (manufactured by Wako Pure Chemical Industries, Ltd.) instead of 2.5 g of HMDS. In the same manner as in the first embodiment, the production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Tables 3-3, 3-4 and Table 8-1.

＜實施例22＞ 於實施例1的（步驟b）中，變更為2.5 g的N,N-二甲基胺基三甲基矽烷（N,N-dimethylamino trimethylsilane，DMATMS）（和光純藥工業股份有限公司製造）來代替2.5 g的HMDS，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表4-1、表4-2及表8-1中。<Example 22> In the (Step b) of Example 1, it was changed to 2.5 g of N,N-dimethylamino trimethylsilane (DMATMS) (Wako Pure Chemical Industries Co., Ltd.) In the same manner as in the first embodiment, the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the conductive particles and the bonded structure were produced in the same manner as in the first embodiment. Evaluation. The results are shown in Table 4-1, Table 4-2 and Table 8-1.

＜實施例23＞ 省略實施例1的（步驟e），及藉由以下所示的方法來代替實施例1的（步驟f）而形成第一層的b層，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表4-1、表4-2及表8-2中。<Example 23> The (step e) of the first embodiment was omitted, and the b layer of the first layer was formed instead of the (step f) of the first embodiment by the method shown below, and the example 1 was In the same manner, the conductive particles, the insulating coated conductive particles, the production of the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out. The results are shown in Table 4-1, Table 4-2 and Table 8-2.

於實施例23中，首先將第一層的b層形成用的無電鍍鎳液的液量設為100 ml，形成包含膜厚100 nm的鎳-磷合金被膜的第一層的b層。藉由形成第一層的b層所得的粒子D為4.55 g。In Example 23, first, the liquid amount of the electroless nickel plating liquid for forming the b layer of the first layer was set to 100 ml, and a p layer of the first layer including the nickel-phosphorus alloy coating film having a thickness of 100 nm was formed. The particle D obtained by forming the b layer of the first layer was 4.55 g.

＜實施例24＞ 藉由以下所示的方法來代替實施例1的（步驟e）、（步驟f）而形成第一層的a層、b層，除此以外，與實施例1同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表4-1、表4-2及表8-2中。<Example 24> The same procedure as in Example 1 was carried out except that the a layer and the b layer of the first layer were formed instead of (step e) and (step f) of the first embodiment. Preparation of conductive particles, insulating coated conductive particles, anisotropic conductive adhesive film and bonded structure, and evaluation of conductive particles and bonded structures. The results are shown in Table 4-1, Table 4-2 and Table 8-2.

首先，利用1000 mL經加溫至80℃的水將步驟d中所得的粒子B分散液稀釋後，添加1 mL作為鍍敷穩定劑的1 g/L的硝酸鉍水溶液。繼而，於粒子B分散液中以5 mL/min的滴加速度滴加20 mL下述組成的a層形成用的無電鍍鎳液。第一層的a層形成用的無電鍍鎳液的組成如下。 硫酸鎳············400 g/L 次亞磷酸鈉········150 g/L 乙酸················120 g/L 硝酸鉍水溶液（1 g/L）···1 mL/LFirst, the particle B dispersion obtained in the step d was diluted with 1000 mL of water heated to 80 ° C, and then 1 mL of a 1 g/L aqueous solution of lanthanum nitrate as a plating stabilizer was added. Then, 20 mL of an electroless nickel plating solution for forming a layer having the following composition was dropped into the particle B dispersion at a dropping rate of 5 mL/min. The composition of the electroless nickel plating solution for forming the a layer of the first layer is as follows. Nickel Sulfate································································································· ·120 g / L aqueous solution of lanthanum nitrate (1 g / L) · · · 1 mL / L

第一層的a層的鍍敷液的滴加結束後，於3分鐘後以5 mL/min的滴加速度滴加80 mL的下述組成的b層形成用的鍍敷液。滴加結束後，經過10分鐘後，將添加有鍍敷液的分散液過濾。以水清洗過濾物後，利用80℃的真空乾燥機進行乾燥。如此而形成第一層，該第一層包含表4-1所示的第一層的a層為20 nm、第一層的b層為80 nm的膜厚的鎳-磷合金被膜。藉由形成第一層的a層及b層所得的粒子D為4.55 g。 （b層形成用的無電鍍鎳液） 硫酸鎳············400 g/L 次亞磷酸鈉········150 g/L 酒石酸鈉二水合物·····60 g/L 硝酸鉍水溶液（1 g/L）···1 mL/LAfter the completion of the dropwise addition of the plating solution of the layer a of the first layer, 80 mL of a plating solution for forming a layer b of the following composition was dropped at a dropping rate of 5 mL/min after 3 minutes. After the completion of the dropwise addition, after 10 minutes passed, the dispersion to which the plating solution was added was filtered. After washing the filtrate with water, it was dried by a vacuum dryer at 80 °C. Thus, the first layer was formed, and the first layer contained a nickel-phosphorus alloy film having a thickness of 20 nm in the first layer shown in Table 4-1 and a thickness of 80 nm in the b layer of the first layer. The particles D obtained by forming the a layer and the b layer of the first layer were 4.55 g. (electroless nickel plating solution for layer b formation) nickel sulfate ···························································································· ·····60 g/L aqueous solution of lanthanum nitrate (1 g/L)···1 mL/L

於實施例24中，a層的鎳的濃度為93.0質量%（剩餘部分為磷），b層的鎳的濃度朝向導電粒子的表面而逐漸增高。b層的表面的鎳的濃度為97.5質量%（剩餘部分為磷）。如此，藉由將b層形成用的無電鍍鎳液直接添加至a層形成用的無電鍍鎳液中，可獲得鎳濃度逐漸增高的層。而且，藉由在形成無電鍍鎳皮膜時的初期形成20 nm以上的94質量%以下的層，導電粒子彼此幾乎不受到磁性的影響，故可抑制該導電粒子彼此的凝聚。另外，無需如實施例1般分兩次形成不同組成的鎳-磷合金被膜，故可於短時間內製作導電粒子。In Example 24, the concentration of nickel in the a layer was 93.0% by mass (the remainder was phosphorus), and the concentration of nickel in the b layer gradually increased toward the surface of the conductive particles. The concentration of nickel on the surface of the b layer was 97.5% by mass (the remainder was phosphorus). As described above, by directly adding the electroless nickel plating liquid for forming the p layer to the electroless nickel plating solution for forming the a layer, a layer having a gradually increased nickel concentration can be obtained. In addition, when a layer of 94% by mass or more of 20 nm or more is formed in the initial stage when the electroless nickel plating film is formed, the conductive particles are hardly affected by the magnetic properties, and aggregation of the conductive particles can be suppressed. Further, it is not necessary to form a nickel-phosphorus alloy coating film having a different composition twice as in the first embodiment, so that conductive particles can be produced in a short time.

＜實施例25＞ 將4.55 g經過實施例1的（步驟a）～（步驟f）所製作的粒子D浸漬於1 L下述組成的無電鍍鈀液（pH值：6），形成第二層。於反應時間為10分鐘、溫度為50℃的條件下進行處理。第二層的平均厚度為10 nm，第二層的鈀含量為100質量%。除了使用該導電粒子以外，與實施例1同樣地進行絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表4-3、表4-4及表8-2中。無電鍍鈀液的組成如下。 氯化鈀·······0.07 g/L EDTA二鈉···1 g/L 檸檬酸二鈉···1 g/L 甲酸鈉·······0.2 g/L<Example 25> 4.55 g of the particles D prepared in (Step a) to (Step f) of Example 1 were immersed in 1 L of an electroless palladium liquid of the following composition (pH: 6) to form a second layer. . The treatment was carried out under the conditions of a reaction time of 10 minutes and a temperature of 50 °C. The second layer has an average thickness of 10 nm and the second layer has a palladium content of 100% by mass. The production of the insulating-coated conductive particles, the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in Example 1 except that the conductive particles were used. The results are shown in Table 4-3, Table 4-4 and Table 8-2. The composition of the electroless palladium liquid is as follows. Palladium chloride········0.07 g/L EDTA disodium···1 g/L disodium citrate···1 g/L sodium formate·····················

＜實施例26＞ 將4.55 g經過實施例1的（步驟a～步驟f）所製作的粒子D於1 L置換鍍金液（日立化成股份有限公司製造，商品名「HGS-100」）100 mL/L的溶液中於85℃下浸漬2分鐘，進而水洗2分鐘，形成第二層。於反應時間為10分鐘、溫度為60℃的條件下進行處理。第二層的平均厚度為10 nm，第二層中的金含量為大致100質量%。除了使用該導電粒子以外，與實施例1同樣地進行絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表4-3、表4-4及表8-2中。<Example 26> 4.55 g of the particles D produced in the first step (step a to step f) of Example 1 were replaced with a gold plating solution (manufactured by Hitachi Chemical Co., Ltd., trade name "HGS-100") 100 mL/ The solution of L was immersed at 85 ° C for 2 minutes and further washed with water for 2 minutes to form a second layer. The treatment was carried out under the conditions of a reaction time of 10 minutes and a temperature of 60 °C. The second layer has an average thickness of 10 nm and the second layer has a gold content of approximately 100% by mass. The production of the insulating-coated conductive particles, the anisotropic conductive adhesive film and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in Example 1 except that the conductive particles were used. The results are shown in Table 4-3, Table 4-4 and Table 8-2.

＜比較例1＞ 首先，進行實施例1的（步驟a）。繼而，利用超純水將平均粒徑100 nm的膠體氧化矽分散液稀釋，獲得0.33質量%氧化矽粒子分散液（氧化矽總量0.05 g）。於該分散液中添加（步驟a）中製作的經聚乙烯亞胺吸附的樹脂粒子，於室溫下攪拌15分鐘。其後藉由使用f3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）的過濾而取出樹脂粒子。自濾液中未萃取出氧化矽，故確認到實質上所有的氧化矽粒子吸附於樹脂粒子。將經氧化矽粒子吸附的樹脂粒子加入至200 g超純水中並於室溫下攪拌5分鐘。其後，藉由使用f3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）的過濾而取出樹脂粒子，以200 g的超純水將薄膜過濾器上的樹脂粒子清洗2次。將清洗後的樹脂粒子以80℃下30分鐘、120℃下1小時的順序加熱，藉此進行乾燥，獲得2.05 g於表面吸附有氧化矽粒子的樹脂粒子。<Comparative Example 1> First, (Step a) of Example 1 was carried out. Then, the colloidal cerium oxide dispersion having an average particle diameter of 100 nm was diluted with ultrapure water to obtain a 0.33 mass% cerium oxide particle dispersion (the total amount of cerium oxide was 0.05 g). The polyethyleneimine-adsorbed resin particles produced in the step (a) were added to the dispersion, and stirred at room temperature for 15 minutes. Thereafter, the resin particles were taken out by filtration using a f3 μm membrane filter (manufactured by Merck Millipore Co., Ltd.). Since cerium oxide was not extracted from the filtrate, it was confirmed that substantially all of the cerium oxide particles were adsorbed to the resin particles. The resin particles adsorbed by the cerium oxide particles were added to 200 g of ultrapure water and stirred at room temperature for 5 minutes. Thereafter, the resin particles were taken out by filtration using a f3 μm membrane filter (manufactured by Merck Millipore Co., Ltd.), and the resin particles on the membrane filter were washed twice with 200 g of ultrapure water. The washed resin particles were heated at 80 ° C for 30 minutes and at 120 ° C for 1 hour, and dried to obtain 2.05 g of resin particles having cerium oxide particles adsorbed on the surface.

對2.05 g所述樹脂粒子照射共振頻率28 kHz、輸出100 W的超音波15分鐘後，添加至100 mL的含有8質量%的鈀觸媒（日本安美特（Atotech Japan）股份有限公司製造，商品名「安美特尼奧加特（Atotech Neoganth）834」）的鈀觸媒化液中，一面照射超音波一面於30℃下攪拌30分鐘。其後，藉由使用f3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）的過濾而取出樹脂粒子，將所取出的樹脂粒子水洗。將水洗後的樹脂粒子添加至經調整為pH值6.0的0.5質量%二甲基胺硼烷液中，獲得2.01 g固著有鈀觸媒的樹脂粒子。繼而，將2.01 g固著有鈀觸媒的樹脂粒子浸漬於20 mL的蒸餾水中後，進行超音波分散，由此獲得樹脂粒子分散液。將藉由SEM對超音波分散後的粒子進行觀察的結果示於圖15中。2.05 g of the resin particles were irradiated with a resonance frequency of 28 kHz, and an ultrasonic wave of 100 W was output for 15 minutes, and then added to 100 mL of a palladium catalyst containing 8 mass% (manufactured by Atotech Japan Co., Ltd., a product). The palladium catalyst solution of the name "Atotech Neoganth 834" was stirred at 30 ° C for 30 minutes while being irradiated with ultrasonic waves. Thereafter, the resin particles were taken out by filtration using a f3 μm membrane filter (manufactured by Merck Millipore Co., Ltd.), and the taken-out resin particles were washed with water. The water-washed resin particles were added to a 0.5 mass% dimethylamine borane solution adjusted to pH 6.0 to obtain 2.01 g of resin particles to which a palladium catalyst was immobilized. Then, 2.01 g of the resin particles to which the palladium catalyst was immobilized was immersed in 20 mL of distilled water, and then ultrasonically dispersed to obtain a resin particle dispersion. The result of observing the ultrasonically dispersed particles by SEM is shown in Fig. 15 .

以後與實施例1的（步驟e）以後同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表5-1、表5-2及表9-1中。將藉由SEM對比較例1中的（步驟f）之後的導電粒子進行觀察的結果示於圖16中。The production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in the case of (Step e) of Example 1. The results are shown in Table 5-1, Table 5-2 and Table 9-1. The results of observing the conductive particles after (step f) in Comparative Example 1 by SEM are shown in Fig. 16 .

＜比較例2＞ 首先，進行實施例1的（步驟a）。繼而，將2 g經聚乙烯亞胺吸附的樹脂粒子加入至甲醇中，一面照射共振頻率28 kHz、輸出100 W的超音波一面於室溫下攪拌5分鐘。其後，加入0.05 g與實施例5相同的平均粒徑100 nm的氣相法親水性球狀氧化矽粉末，一面照射共振頻率28 kHz、輸出100 W的超音波一面進一步於室溫下攪拌5分鐘，由此獲得吸附有氧化矽的樹脂粒子。吸附有氧化矽的樹脂粒子為2.05 g。<Comparative Example 2> First, (Step a) of Example 1 was carried out. Then, 2 g of polyethyleneimine-adsorbed resin particles were added to methanol, and the mixture was stirred at room temperature for 5 minutes while irradiating a resonance frequency of 28 kHz and outputting 100 W of ultrasonic waves. Thereafter, 0.05 g of the vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 100 nm as in Example 5 was added, and the ultrasonic wave was irradiated at a resonance frequency of 28 kHz while outputting 100 W while further stirring at room temperature. In minutes, resin particles having cerium oxide adsorbed thereon were obtained. The resin particles adsorbed with cerium oxide were 2.05 g.

對2.05 g所述樹脂粒子照射共振頻率28 kHz、輸出100 W的超音波15分鐘後，添加至100 mL的含有8質量%的鈀觸媒（日本安美特（Atotech Japan）股份有限公司製造，商品名「安美特尼奧加特（Atotech Neoganth）834」）的鈀觸媒化液中，一面照射超音波一面於30℃下攪拌30分鐘。其後，藉由使用f3 μm的薄膜過濾器（默克密理博（Merck Millipore）公司製造）的過濾而取出樹脂粒子，將所取出的樹脂粒子水洗。將水洗後的樹脂粒子添加至經調整為pH值6.0的0.5質量%二甲基胺硼烷液中，獲得2.01 g固著有鈀觸媒的樹脂粒子。繼而，將2.01 g固著有鈀觸媒的樹脂粒子浸漬於20 mL的蒸餾水中後，進行超音波分散，由此獲得樹脂粒子分散液。2.05 g of the resin particles were irradiated with a resonance frequency of 28 kHz, and an ultrasonic wave of 100 W was output for 15 minutes, and then added to 100 mL of a palladium catalyst containing 8 mass% (manufactured by Atotech Japan Co., Ltd., a product). The palladium catalyst solution of the name "Atotech Neoganth 834" was stirred at 30 ° C for 30 minutes while being irradiated with ultrasonic waves. Thereafter, the resin particles were taken out by filtration using a f3 μm membrane filter (manufactured by Merck Millipore Co., Ltd.), and the taken-out resin particles were washed with water. The water-washed resin particles were added to a 0.5 mass% dimethylamine borane solution adjusted to pH 6.0 to obtain 2.01 g of resin particles to which a palladium catalyst was immobilized. Then, 2.01 g of the resin particles to which the palladium catalyst was immobilized was immersed in 20 mL of distilled water, and then ultrasonically dispersed to obtain a resin particle dispersion.

以後與實施例1的（步驟e）以後同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表5-1、表5-2及表9-1中。The production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in the case of (Step e) of Example 1. The results are shown in Table 5-1, Table 5-2 and Table 9-1.

＜比較例3＞ 首先，進行實施例1的（步驟a）。繼而，將2 g經聚乙烯亞胺吸附的樹脂粒子加入至甲醇中，一面照射共振頻率28 kHz、輸出100 W的超音波一面於室溫下攪拌5分鐘。其後，加入0.05 g與實施例2相同的平均粒徑25 nm的氣相法親水性球狀氧化矽粉末，一面照射共振頻率28 kHz、輸出100 W的超音波一面進一步於室溫下攪拌5分鐘，由此獲得吸附有氧化矽的樹脂粒子。吸附有氧化矽的樹脂粒子為2.05 g。<Comparative Example 3> First, (Step a) of Example 1 was carried out. Then, 2 g of polyethyleneimine-adsorbed resin particles were added to methanol, and the mixture was stirred at room temperature for 5 minutes while irradiating a resonance frequency of 28 kHz and outputting 100 W of ultrasonic waves. Thereafter, 0.05 g of the vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 25 nm as in Example 2 was added, and the ultrasonic wave was irradiated at a resonance frequency of 28 kHz while outputting 100 W while further stirring at room temperature. In minutes, resin particles having cerium oxide adsorbed thereon were obtained. The resin particles adsorbed with cerium oxide were 2.05 g.

以後與實施例1的（步驟d）以後同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表5-1、表5-2及表9-1中。The production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in the case of (Step d) of Example 1. The results are shown in Table 5-1, Table 5-2 and Table 9-1.

＜比較例4＞ 首先，進行實施例1的（步驟a）。繼而，將2 g經聚乙烯亞胺吸附的樹脂粒子加入至甲醇中，一面照射共振頻率28 kHz、輸出100 W的超音波一面於室溫下攪拌5分鐘。其後，加入0.05 g與實施例1相同的平均粒徑60 nm的氣相法親水性球狀氧化矽粉末，一面照射共振頻率28 kHz、輸出100 W的超音波一面進一步於室溫下攪拌5分鐘，由此獲得吸附有氧化矽的樹脂粒子。吸附有氧化矽的樹脂粒子為2.05 g。<Comparative Example 4> First, (Step a) of Example 1 was carried out. Then, 2 g of polyethyleneimine-adsorbed resin particles were added to methanol, and the mixture was stirred at room temperature for 5 minutes while irradiating a resonance frequency of 28 kHz and outputting 100 W of ultrasonic waves. Thereafter, 0.05 g of the vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 60 nm as in Example 1 was added, and the ultrasonic wave was irradiated at a resonance frequency of 28 kHz while outputting 100 W while further stirring at room temperature. In minutes, resin particles having cerium oxide adsorbed thereon were obtained. The resin particles adsorbed with cerium oxide were 2.05 g.

以後與實施例1的（步驟d）以後同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表5-1、表5-2及表9-1中。The production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in the case of (Step d) of Example 1. The results are shown in Table 5-1, Table 5-2 and Table 9-1.

＜比較例5＞ 首先，進行實施例1的（步驟a）。繼而，將2 g經聚乙烯亞胺吸附的樹脂粒子加入至甲醇中，一面照射共振頻率28 kHz、輸出100 W的超音波一面於室溫下攪拌5分鐘。其後，加入0.05 g與實施例5相同的平均粒徑100 nm的氣相法親水性球狀氧化矽粉末，一面照射共振頻率28 kHz、輸出100 W的超音波一面進一步於室溫下攪拌5分鐘，由此獲得吸附有氧化矽的樹脂粒子。吸附有氧化矽的樹脂粒子為2.05 g。<Comparative Example 5> First, (Step a) of Example 1 was carried out. Then, 2 g of polyethyleneimine-adsorbed resin particles were added to methanol, and the mixture was stirred at room temperature for 5 minutes while irradiating a resonance frequency of 28 kHz and outputting 100 W of ultrasonic waves. Thereafter, 0.05 g of the vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 100 nm as in Example 5 was added, and the ultrasonic wave was irradiated at a resonance frequency of 28 kHz while outputting 100 W while further stirring at room temperature. In minutes, resin particles having cerium oxide adsorbed thereon were obtained. The resin particles adsorbed with cerium oxide were 2.05 g.

以後與實施例1的（步驟d）以後同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表5-3、表5-4及表9-2中。The production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in the case of (Step d) of Example 1. The results are shown in Table 5-3, Table 5-4 and Table 9-2.

＜比較例6＞ 首先，進行實施例1的（步驟a）。繼而，將2 g經聚乙烯亞胺吸附的樹脂粒子加入至甲醇中，一面照射共振頻率28 kHz、輸出100 W的超音波一面於室溫下攪拌5分鐘。其後，加入0.05 g與實施例6相同的平均粒徑120 nm的氣相法親水性球狀氧化矽粉末，一面照射共振頻率28 kHz、輸出100 W的超音波一面進一步於室溫下攪拌5分鐘，由此獲得吸附有氧化矽的樹脂粒子。吸附有氧化矽的樹脂粒子為2.05 g。<Comparative Example 6> First, (Step a) of Example 1 was carried out. Then, 2 g of polyethyleneimine-adsorbed resin particles were added to methanol, and the mixture was stirred at room temperature for 5 minutes while irradiating a resonance frequency of 28 kHz and outputting 100 W of ultrasonic waves. Thereafter, 0.05 g of the vapor phase hydrophilic spherical cerium oxide powder having an average particle diameter of 120 nm as in Example 6 was added, and the ultrasonic wave was irradiated at a resonance frequency of 28 kHz and output at 100 W while further stirring at room temperature. In minutes, resin particles having cerium oxide adsorbed thereon were obtained. The resin particles adsorbed with cerium oxide were 2.05 g.

以後與實施例1的（步驟d）以後同樣地進行導電粒子、絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及導電粒子及連接結構體的評價。將結果示於表5-3、表5-4及表9-2中。The production of the conductive particles, the insulating coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the conductive particles and the bonded structure were carried out in the same manner as in the case of (Step d) of Example 1. The results are shown in Table 5-3, Table 5-4 and Table 9-2.

＜比較例7＞ 使用平均粒徑3.0 μm的交聯聚苯乙烯粒子（日本觸媒股份有限公司製造，商品名「所里奧斯達（Soliostar）」）作為樹脂粒子。一面攪拌400 mL的清潔調整劑（cleaner conditioner）231水溶液（羅門哈斯（Rohm and Haas）電子材料股份有限公司製造，濃度40 mL/L），一面於其中投入30 g樹脂粒子。繼而，將水溶液加溫至60℃，一面施加超音波一面攪拌30分鐘，進行樹脂粒子的表面改質及分散處理。<Comparative Example 7> Crosslinked polystyrene particles (manufactured by Nippon Shokubai Co., Ltd., trade name "Soliostar") having an average particle diameter of 3.0 μm were used as the resin particles. While stirring 400 mL of a clean conditioner 231 aqueous solution (manufactured by Rohm and Haas Electronic Materials Co., Ltd., concentration: 40 mL/L), 30 g of resin particles were placed therein. Then, the aqueous solution was heated to 60 ° C, and while stirring, the surface of the resin particles was subjected to surface modification and dispersion treatment while applying ultrasonic waves for 30 minutes.

將所述水溶液過濾，將所得的粒子水洗1次後，使30 g粒子分散於水中而獲得200 mL的漿料。於該漿料中添加200 mL氯化亞錫水溶液（濃度為1.5 g/L），於常溫下攪拌5分鐘，進行使錫離子吸附於粒子表面的感受性化處理。繼而，將水溶液過濾，將所得的粒子水洗1次。然後，使30 g粒子分散於水中而製備400 mL的漿料後，加溫至60℃。一面併用超音波攪拌漿料，一面添加2 mL的10 g/L的氯化鈀水溶液。保持該狀態而攪拌5分鐘，由此進行使粒子的表面捕捉鈀離子的活化處理。繼而，將水溶液過濾，將所得的粒子水洗1次。The aqueous solution was filtered, and the obtained particles were washed with water once, and then 30 g of the particles were dispersed in water to obtain 200 mL of a slurry. 200 mL of a stannous chloride aqueous solution (concentration: 1.5 g/L) was added to the slurry, and the mixture was stirred at normal temperature for 5 minutes to carry out a sensitization treatment for adsorbing tin ions on the surface of the particles. Then, the aqueous solution was filtered, and the obtained particles were washed with water once. Then, 30 g of the particles were dispersed in water to prepare a slurry of 400 mL, and then the temperature was raised to 60 °C. While stirring the slurry with ultrasonic waves, 2 mL of a 10 g/L palladium chloride aqueous solution was added. While maintaining this state, the mixture was stirred for 5 minutes to carry out an activation treatment for capturing palladium ions on the surface of the particles. Then, the aqueous solution was filtered, and the obtained particles were washed with water once.

繼而，將包含溶解有20 g/L的酒石酸鈉、10 g/L的硫酸鎳及0.5 g/L的次亞磷酸鈉的水溶液的3 L無電鍍敷液升溫至60℃。於該無電鍍敷液中投入10 g所述粒子。將其攪拌5分鐘，確認到氫的發泡停止。Then, a 3 L electroless plating solution containing an aqueous solution in which 20 g/L of sodium tartrate, 10 g/L of nickel sulfate, and 0.5 g/L of sodium hypophosphite was dissolved was heated to 60 °C. 10 g of the particles were placed in the electroless plating solution. This was stirred for 5 minutes, and it was confirmed that the foaming of hydrogen was stopped.

其後，分別同時藉由定量泵將400 mL的200 g/L的硫酸鎳水溶液、與400 mL的200 g/L的次亞磷酸鈉及90 g/L的氫氧化鈉混合水溶液連續地添加至含有粒子的鍍敷液中。添加速度均設為3 mL/min。繼而，一面將該溶液保持於60℃一面攪拌5分鐘後，將溶液過濾。將過濾物清洗3次後，利用100℃的真空乾燥機進行乾燥，獲得具有鎳-磷合金被膜的導電粒子。對所得的導電粒子以通過粒子的中心附近的方式藉由超薄切片法切出剖面，使用TEM以25萬倍的倍率進行觀察。根據所得的剖面的圖像，由剖面積的平均值算出膜厚，結果鎳-磷合金被膜的平均膜厚為105 nm。Thereafter, 400 mL of a 200 g/L aqueous solution of nickel sulfate, and 400 mL of a mixed aqueous solution of 200 g/L of sodium hypophosphite and 90 g/L of sodium hydroxide were successively added to each other by a metering pump. In the plating solution containing particles. The addition speed was set to 3 mL/min. Then, while stirring the solution at 60 ° C for 5 minutes, the solution was filtered. After the filtrate was washed three times, it was dried by a vacuum dryer at 100 ° C to obtain conductive particles having a nickel-phosphorus alloy coating. The obtained conductive particles were cut out by ultrathin sectioning so as to pass through the vicinity of the center of the particles, and observed at a magnification of 250,000 times using TEM. From the image of the obtained cross section, the film thickness was calculated from the average value of the cross-sectional areas, and as a result, the average film thickness of the nickel-phosphorus alloy film was 105 nm.

除了使用該導電粒子以外，與實施例1同樣地進行絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及連接結構體的評價。關於導電粒子的評價，與實施例1同樣地進行一部分評價。將結果示於表5-3、表5-4及表9-2中。The production of the insulating-coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the bonded structure were carried out in the same manner as in Example 1 except that the conductive particles were used. Regarding the evaluation of the conductive particles, a part of the evaluation was performed in the same manner as in Example 1. The results are shown in Table 5-3, Table 5-4 and Table 9-2.

＜比較例8＞ 使用平均粒徑3.0 μm的交聯聚苯乙烯粒子（日本觸媒股份有限公司製造，商品名「所里奧斯達（Soliostar）」）作為樹脂粒子。一面攪拌400 mL的清潔調整劑231水溶液（羅門哈斯（Rohm and Haas）電子材料股份有限公司製造，濃度40 mL/L），一面於其中投入7 g樹脂粒子。繼而，將水溶液加溫至60℃，一面施加超音波一面攪拌30分鐘，進行樹脂粒子的表面改質及分散處理。<Comparative Example 8> Crosslinked polystyrene particles (manufactured by Nippon Shokubai Co., Ltd., trade name "Soliostar") having an average particle diameter of 3.0 μm were used as the resin particles. While stirring 400 mL of an aqueous solution of cleaning conditioner 231 (manufactured by Rohm and Haas Electronic Materials Co., Ltd., concentration: 40 mL/L), 7 g of resin particles were placed therein. Then, the aqueous solution was heated to 60 ° C, and while stirring, the surface of the resin particles was subjected to surface modification and dispersion treatment while applying ultrasonic waves for 30 minutes.

將所述水溶液過濾，將所得的粒子水洗1次後，使7 g粒子分散於純水中而獲得200 mL的漿料。於該漿料中添加200 mL氯化亞錫水溶液（濃度1.5 g/L），於常溫下攪拌5分鐘，進行使錫離子吸附於粒子表面的感受性化處理。繼而，將水溶液過濾，將所得的粒子水洗1次。然後，使7 g粒子分散於水中而製備400 mL的漿料後，加溫至60℃。一面併用超音波攪拌漿料，一面添加2 mL的10 g/L的氯化鈀水溶液。保持該狀態攪拌5分鐘，由此進行使粒子的表面捕捉鈀離子的活化處理。繼而，將水溶液過濾，將所得的粒子水洗1次。The aqueous solution was filtered, and the obtained particles were washed with water once, and then 7 g of the particles were dispersed in pure water to obtain 200 mL of a slurry. 200 mL of a stannous chloride aqueous solution (concentration: 1.5 g/L) was added to the slurry, and the mixture was stirred at normal temperature for 5 minutes to carry out a sensitization treatment for adsorbing tin ions on the surface of the particles. Then, the aqueous solution was filtered, and the obtained particles were washed with water once. Then, after dissolving 7 g of the particles in water to prepare 400 mL of the slurry, the mixture was heated to 60 °C. While stirring the slurry with ultrasonic waves, 2 mL of a 10 g/L palladium chloride aqueous solution was added. The state was stirred for 5 minutes while maintaining the activation treatment of capturing palladium ions on the surface of the particles. Then, the aqueous solution was filtered, and the obtained particles were washed with water once.

將7 g所得的粒子添加至300 mL純水中，攪拌3分鐘而使其分散。繼而，於該分散液中添加2.25 g鎳粒子（三井金屬礦業股份有限公司製造，商品名「2007SUS」，平均粒徑50 nm）作為芯物質，獲得附著有芯物質的粒子。7 g of the obtained particles were added to 300 mL of pure water and stirred for 3 minutes to be dispersed. Then, 2.25 g of nickel particles (manufactured by Mitsui Mining & Mining Co., Ltd., trade name "2007SUS", average particle diameter: 50 nm) was added as a core material to the dispersion, and particles having a core substance adhered thereto were obtained.

進一步以1200 mL水將所述分散液稀釋，添加4 mL作為鍍敷穩定劑的硝酸鉍水溶液（濃度1 g/L）。其次，於該分散液中通過定量泵以81 mL/min的添加速度添加450 g/L硫酸鎳、150 g/L次亞磷酸鈉、116 g/L檸檬酸鈉及6 mL鍍敷穩定劑（硝酸鉍水溶液（濃度1 g/L））的120 mL混合溶液。其後，進行攪拌直至pH值穩定，確認到氫的發泡停止。The dispersion was further diluted with 1200 mL of water, and 4 mL of an aqueous solution of cerium nitrate (concentration 1 g/L) as a plating stabilizer was added. Next, 450 g/L of nickel sulfate, 150 g/L of sodium phosphite, 116 g/L of sodium citrate and 6 mL of plating stabilizer were added to the dispersion by a metering pump at an addition rate of 81 mL/min ( A 120 mL mixed solution of an aqueous solution of cerium nitrate (concentration 1 g/L). Thereafter, stirring was carried out until the pH was stabilized, and it was confirmed that the foaming of hydrogen was stopped.

繼而，通過定量泵以27 mL/min的添加速度添加450 g/L硫酸鎳、150 g/L次亞磷酸鈉、116 g/L檸檬酸鈉、35 mL鍍敷穩定劑（硝酸鉍水溶液（濃度1 g/L））的650 mL混合溶液。其後，進行攪拌直至pH值穩定，確認到氫的發泡停止。Then, 450 g/L nickel sulfate, 150 g/L sodium phosphite, 116 g/L sodium citrate, and 35 mL plating stabilizer (aqueous solution of lanthanum nitrate (concentration) were added by a dosing pump at an addition rate of 27 mL/min. 1 g/L)) 650 mL of mixed solution. Thereafter, stirring was carried out until the pH was stabilized, and it was confirmed that the foaming of hydrogen was stopped.

然後，將鍍敷液過濾，以水將過濾物清洗。其後，利用80℃的真空乾燥機進行乾燥而獲得具有鎳-磷合金被膜的導電粒子。對所得的導電粒子以通過粒子的中心附近的方式利用超薄切片法切出剖面，使用TEM以25萬倍的倍率進行觀察。根據所得的剖面的圖像，由剖面積的平均值算出膜厚，結果鎳-磷合金被膜的平均膜厚為101 nm。Then, the plating solution was filtered, and the filtrate was washed with water. Thereafter, it was dried by a vacuum dryer at 80 ° C to obtain conductive particles having a nickel-phosphorus alloy coating. The obtained conductive particles were cut out by ultrathin sectioning so as to pass through the vicinity of the center of the particles, and observed at a magnification of 250,000 times using TEM. From the image of the obtained cross section, the film thickness was calculated from the average value of the cross-sectional areas, and as a result, the average film thickness of the nickel-phosphorus alloy film was 101 nm.

除了使用所述導電粒子以外，與實施例1同樣地進行絕緣被覆導電粒子、異向導電性接著膜及連接結構體的製作以及連接結構體的評價。關於導電粒子的評價，與實施例1同樣地進行一部分評價。將結果示於表5-3、表5-4及表9-2中。The production of the insulating-coated conductive particles, the anisotropic conductive adhesive film, and the bonded structure, and the evaluation of the bonded structure were carried out in the same manner as in Example 1 except that the conductive particles were used. Regarding the evaluation of the conductive particles, a part of the evaluation was performed in the same manner as in Example 1. The results are shown in Table 5-3, Table 5-4 and Table 9-2.

比較例1對應於所述專利文獻3的導電粒子。比較例7的導電粒子對應於所述專利文獻1的導電粒子。比較例8的導電粒子對應於所述專利文獻2的導電粒子。Comparative Example 1 corresponds to the conductive particles of Patent Document 3. The conductive particles of Comparative Example 7 correspond to the conductive particles of Patent Document 1. The conductive particles of Comparative Example 8 correspond to the conductive particles of Patent Document 2.

[表1-1] [Table 1-1]

[表1-2] [Table 1-2]

[表1-3] [Table 1-3]

[表1-4] [Table 1-4]

[表2-1] [table 2-1]

[表2-2] [Table 2-2]

[表2-3] [Table 2-3]

[表2-4] [Table 2-4]

[表3-1] [Table 3-1]

[表3-2] [Table 3-2]

[表3-3] [Table 3-3]

[表3-4] [Table 3-4]

[表4-1] [Table 4-1]

[表4-2] [Table 4-2]

[表4-3] [Table 4-3]

[表4-4] [Table 4-4]

[表5-1] [Table 5-1]

[表5-2] [Table 5-2]

[表5-3] [Table 5-3]

[表5-4] [Table 5-4]

[表6-1] [Table 6-1]

[表6-2] [Table 6-2]

[表7-1] [Table 7-1]

[表7-2] [Table 7-2]

[表8-1] [Table 8-1]

[表8-2] [Table 8-2]

[表9-1] [Table 9-1]

[表9-2] [Table 9-2]

100a、100b、400‧‧‧導電粒子
101‧‧‧樹脂粒子
102‧‧‧非導電性無機粒子
103‧‧‧複合粒子
104‧‧‧第一層
105‧‧‧第二層
109‧‧‧凸起
200‧‧‧絕緣被覆導電粒子
210‧‧‧絕緣性粒子（絕緣性被覆部）
300‧‧‧連接結構體
310‧‧‧第一電路構件
311、321‧‧‧電路基板
311a、321a‧‧‧主面
312、322‧‧‧電路電極
320‧‧‧第二電路構件
330‧‧‧連接部
330a‧‧‧異向導電性接著劑
332‧‧‧硬化物
332a‧‧‧接著劑
401‧‧‧異常析出部
402‧‧‧長度
A、B‧‧‧方向100a, 100b, 400‧‧‧ conductive particles
101‧‧‧ resin particles
102‧‧‧ Non-conductive inorganic particles
103‧‧‧Composite particles
104‧‧‧ first floor
105‧‧‧ second floor
109‧‧‧ bumps
200‧‧‧Insulated coated conductive particles
210‧‧‧Insulating particles (insulating coating)
300‧‧‧Connected structure
310‧‧‧First circuit component
311, 321‧‧‧ circuit board
311a, 321a‧‧‧ main faces
312, 322‧‧‧ circuit electrodes
320‧‧‧Second circuit components
330‧‧‧Connecting Department
330a‧‧‧Anisotropic conductive adhesive
332‧‧‧ hardened material
332a‧‧‧Binder
401‧‧‧ abnormal precipitation department
402‧‧‧ Length
A, B‧‧ direction

圖1為表示第一實施形態的導電粒子的示意剖面圖。 圖2為表示第一實施形態的導電粒子的示意放大剖面圖。 圖3為表示第二實施形態的導電粒子的示意剖面圖。 圖4為表示第二實施形態的導電粒子的示意放大剖面圖。 圖5為表示第三實施形態的絕緣被覆導電粒子的示意剖面圖。 圖6為表示第五實施形態的連接結構體的示意剖面圖。 圖7（a）〜圖7（c）為用以說明第五實施形態的連接結構體的製造方法的一例的示意剖面圖。 圖8為對實施例1的導電粒子的製作中的步驟d中所得的粒子進行觀察的SEM圖像。 圖9為對實施例1的導電粒子的製作中的步驟d中所得的粒子的表面進行觀察的SEM圖像。 圖10為對實施例1的導電粒子的製作中的步驟f中所得的粒子進行觀察的SEM圖像。 圖11為對實施例1的導電粒子的製作中的步驟f中所得的粒子的表面進行觀察的SEM圖像。 圖12（a）〜圖12（b）為用以說明修整加工的示意圖。 圖13為用以說明製作TEM測定用的薄膜切片的方法的示意圖。 圖14（a）〜圖14（b）為用以說明異常析出部的示意圖。 圖15為對比較例1中藉由將固著有鈀觸媒的樹脂粒子浸漬後進行超音波分散所得的粒子進行觀察的SEM圖像。 圖16為對比較例1中形成第一層的b層後的導電粒子進行觀察的SEM圖像。Fig. 1 is a schematic cross-sectional view showing conductive particles according to a first embodiment. Fig. 2 is a schematic enlarged cross-sectional view showing conductive particles of the first embodiment. Fig. 3 is a schematic cross-sectional view showing conductive particles according to a second embodiment. Fig. 4 is a schematic enlarged cross-sectional view showing conductive particles according to a second embodiment. Fig. 5 is a schematic cross-sectional view showing the insulating coated conductive particles of the third embodiment. Fig. 6 is a schematic cross-sectional view showing a connection structure according to a fifth embodiment. 7(a) to 7(c) are schematic cross-sectional views for explaining an example of a method of manufacturing the bonded structure of the fifth embodiment. 8 is an SEM image of the particles obtained in the step d in the production of the conductive particles of Example 1. FIG. 9 is an SEM image of the surface of the particles obtained in the step d in the production of the conductive particles of Example 1. FIG. FIG. 10 is an SEM image of the particles obtained in the step f in the production of the conductive particles of Example 1. FIG. FIG. 11 is an SEM image of the surface of the particles obtained in the step f in the production of the conductive particles of Example 1. FIG. 12(a) to 12(b) are schematic views for explaining the trimming process. Fig. 13 is a schematic view for explaining a method of producing a film slice for TEM measurement. 14(a) to 14(b) are schematic views for explaining the abnormal precipitation unit. 15 is an SEM image of the particles obtained by impregnating the resin particles to which the palladium catalyst is immersed in Comparative Example 1 and performing ultrasonic dispersion. Fig. 16 is an SEM image of the conductive particles after the formation of the b layer of the first layer in Comparative Example 1.

100a‧‧‧導電粒子 100a‧‧‧ conductive particles

101‧‧‧樹脂粒子 101‧‧‧ resin particles

102‧‧‧非導電性無機粒子 102‧‧‧ Non-conductive inorganic particles

103‧‧‧複合粒子 103‧‧‧Composite particles

104‧‧‧第一層 104‧‧‧ first floor

109‧‧‧凸起 109‧‧‧ bumps

Claims (24)

一種導電粒子，具備： 複合粒子，具有藉由陽離子性聚合物而被覆的樹脂粒子、及配置於所述樹脂粒子的表面的非導電性無機粒子；以及 金屬層，覆蓋所述複合粒子；並且 所述非導電性無機粒子是藉由疏水化處理劑而被覆。A conductive particle comprising: composite particles having resin particles coated with a cationic polymer; and non-conductive inorganic particles disposed on a surface of the resin particles; and a metal layer covering the composite particles; The non-conductive inorganic particles are coated with a hydrophobizing agent. 如申請專利範圍第1項所述的導電粒子，其中所述疏水化處理劑是選自由矽氮烷系疏水化處理劑、矽氧烷系疏水化處理劑、矽烷系疏水化處理劑及鈦酸酯系疏水化處理劑所組成的群組中。The conductive particle according to claim 1, wherein the hydrophobization treatment agent is selected from the group consisting of a hydroxylation treatment agent, a hydroxylation treatment agent, a decane hydrophobizing agent, and a titanic acid. A group consisting of ester hydrophobizing agents. 如申請專利範圍第1項或第2項所述的導電粒子，其中所述疏水化處理劑是選自由六甲基二矽氮烷、聚二甲基矽氧烷及N,N-二甲基胺基三甲基矽烷所組成的群組中。The conductive particle according to claim 1 or 2, wherein the hydrophobizing agent is selected from the group consisting of hexamethyldiazepine, polydimethyloxane, and N,N-dimethyl In the group consisting of aminotrimethylnonane. 如申請專利範圍第1項至第3項中任一項所述的導電粒子，其中由甲醇滴定法所得的所述非導電性無機粒子的疏水化度為30%以上。The conductive particles according to any one of claims 1 to 3, wherein the non-conductive inorganic particles obtained by the methanol titration method have a degree of hydrophobicity of 30% or more. 如申請專利範圍第1項至第4項中任一項所述的導電粒子，其中所述非導電性無機粒子藉由靜電力而接著於所述樹脂粒子。The conductive particles according to any one of claims 1 to 4, wherein the non-conductive inorganic particles are attached to the resin particles by an electrostatic force. 如申請專利範圍第1項至第5項中任一項所述的導電粒子，其中所述樹脂粒子與所述非導電性無機粒子的界達電位之差於pH值1以上且pH值11以下時為30 mV以上。The conductive particle according to any one of the first to fifth aspect, wherein the difference between the boundary potential of the resin particle and the non-conductive inorganic particle is greater than or equal to pH 1 and below pH 11 The time is 30 mV or more. 如申請專利範圍第1項至第6項中任一項所述的導電粒子，其中所述陽離子性聚合物是選自由多胺、聚亞胺、聚醯胺、聚二烯丙基二甲基氯化銨、聚乙烯基胺、聚乙烯基吡啶、聚乙烯基咪唑及聚乙烯基吡咯啶酮所組成的群組中。The conductive particle according to any one of claims 1 to 6, wherein the cationic polymer is selected from the group consisting of polyamines, polyimines, polyamines, polydiallyldimethyl groups. A group consisting of ammonium chloride, polyvinylamine, polyvinylpyridine, polyvinylimidazole and polyvinylpyrrolidone. 如申請專利範圍第1項至第6項中任一項所述的導電粒子，其中所述陽離子性聚合物為聚乙烯亞胺。The conductive particle according to any one of the preceding claims, wherein the cationic polymer is polyethyleneimine. 如申請專利範圍第1項至第8項中任一項所述的導電粒子，其中所述非導電性無機粒子的平均粒徑為25 nm以上且120 nm以下。The conductive particles according to any one of claims 1 to 8, wherein the non-conductive inorganic particles have an average particle diameter of 25 nm or more and 120 nm or less. 如申請專利範圍第1項至第9項中任一項所述的導電粒子，其中所述樹脂粒子的平均粒徑為1 μm以上且10 μm以下。The conductive particles according to any one of the items 1 to 9, wherein the resin particles have an average particle diameter of 1 μm or more and 10 μm or less. 如申請專利範圍第1項至第10項中任一項所述的導電粒子，其中所述非導電性無機粒子是選自由氧化矽、氧化鋯、氧化鋁及金剛石所組成的群組中。The conductive particles according to any one of claims 1 to 10, wherein the non-conductive inorganic particles are selected from the group consisting of cerium oxide, zirconium oxide, aluminum oxide, and diamond. 如申請專利範圍第1項至第11項中任一項所述的導電粒子，其中所述金屬層具有含有鎳的第一層。The conductive particle according to any one of the items 1 to 11, wherein the metal layer has a first layer containing nickel. 如申請專利範圍第12項所述的導電粒子，其中所述金屬層具有設於所述第一層上的第二層， 所述第二層含有選自由貴金屬及鈷所組成的群組中的金屬。The conductive particle according to claim 12, wherein the metal layer has a second layer disposed on the first layer, and the second layer contains a group selected from the group consisting of a noble metal and cobalt. metal. 一種連接結構體，具備： 第一電路構件，具有第一電路電極； 第二電路構件，與所述第一電路構件相對向，且具有第二電路電極；以及 連接部，配置於所述第一電路構件及所述第二電路構件之間，含有如申請專利範圍第1項至第13項中任一項所述的導電粒子；並且 所述連接部於將所述第一電路電極與所述第二電路電極以相對向的方式配置的狀態下，將所述第一電路構件及所述第二電路構件相互連接， 所述第一電路電極與所述第二電路電極經由變形狀態的所述導電粒子而相互電性連接。A connection structure comprising: a first circuit member having a first circuit electrode; a second circuit member facing the first circuit member and having a second circuit electrode; and a connection portion disposed at the first Between the circuit member and the second circuit member, the conductive particles according to any one of claims 1 to 13; and the connecting portion is configured to connect the first circuit electrode with the The first circuit member and the second circuit member are connected to each other in a state in which the second circuit electrodes are arranged in an opposing manner, and the first circuit electrode and the second circuit electrode are in a state of being deformed Conductive particles are electrically connected to each other. 一種絕緣被覆導電粒子，具備： 如申請專利範圍第1項至第13項中任一項所述的導電粒子；以及 將所述導電粒子的所述金屬層的外表面的至少一部分被覆的絕緣性被覆部。An insulating coated conductive particle, comprising: the conductive particles according to any one of claims 1 to 13; and an insulating layer covering at least a portion of an outer surface of the metal layer of the conductive particle Covered part. 一種連接結構體，具備： 第一電路構件，具有第一電路電極； 第二電路構件，與所述第一電路構件相對向，且具有第二電路電極；以及 連接部，配置於所述第一電路構件及所述第二電路構件之間，含有如申請專利範圍第15項所述的絕緣被覆導電粒子；並且 所述連接部於將所述第一電路電極與所述第二電路電極以相對向的方式配置的狀態下，將所述第一電路構件及所述第二電路構件相互連接， 所述第一電路電極與所述第二電路電極經由變形狀態的所述絕緣被覆導電粒子而相互電性連接。A connection structure comprising: a first circuit member having a first circuit electrode; a second circuit member facing the first circuit member and having a second circuit electrode; and a connection portion disposed at the first Between the circuit member and the second circuit member, the insulating coated conductive particles according to claim 15; and the connecting portion is opposite to the first circuit electrode and the second circuit electrode In a state in which the first circuit member and the second circuit member are connected to each other, the first circuit electrode and the second circuit electrode are coated with conductive particles via the insulating state in a deformed state. Electrical connection. 一種異向導電性接著劑，具備： 如申請專利範圍第1項至第13項中任一項所述的導電粒子；以及 分散有所述導電粒子的接著劑。An anisotropic conductive adhesive comprising: the conductive particles according to any one of claims 1 to 13; and an adhesive in which the conductive particles are dispersed. 一種異向導電性接著劑，具備： 如申請專利範圍第15項所述的絕緣被覆導電粒子；以及 分散有所述絕緣被覆導電粒子的接著劑。An anisotropic conductive adhesive comprising: the insulating coated conductive particles according to claim 15; and an adhesive in which the insulating coated conductive particles are dispersed. 如申請專利範圍第17項或第18項所述的異向導電性接著劑，其中所述接著劑為膜狀。The anisotropic conductive adhesive according to claim 17 or claim 18, wherein the adhesive is in the form of a film. 一種連接結構體，具備： 第一電路構件，具有第一電路電極； 第二電路構件，與所述第一電路構件相對向，且具有第二電路電極；以及 將所述第一電路構件及所述第二電路構件接著的如申請專利範圍第17項至第19項中任一項所述的異向導電性接著劑；並且 所述第一電路電極與所述第二電路電極彼此相對向，並且藉由所述異向導電性接著劑而相互電性連接。A connection structure comprising: a first circuit member having a first circuit electrode; a second circuit member opposite the first circuit member and having a second circuit electrode; and the first circuit member and the The second circuit member is the anisotropic conductive adhesive according to any one of claims 17 to 19; and the first circuit electrode and the second circuit electrode are opposed to each other, And electrically connected to each other by the anisotropic conductive adhesive. 一種導電粒子的製造方法，包括： 第一被覆步驟，藉由陽離子性聚合物將樹脂粒子被覆； 第二被覆步驟，藉由疏水化處理劑將非導電性無機粒子被覆； 粒子形成步驟，藉由靜電力將所述非導電性無機粒子接著於所述樹脂粒子的表面，形成複合粒子；以及 第三被覆步驟，藉由金屬層將所述複合粒子被覆。A method for producing conductive particles, comprising: a first coating step of coating resin particles with a cationic polymer; a second coating step of coating non-conductive inorganic particles with a hydrophobizing agent; and a particle forming step by The electrostatic force binds the non-conductive inorganic particles to the surface of the resin particles to form composite particles, and the third coating step covers the composite particles with a metal layer. 如申請專利範圍第21項所述的導電粒子的製造方法，其中於所述第三被覆步驟中，藉由無電鍍敷且以含有鎳的第一層將所述複合粒子被覆。The method for producing conductive particles according to claim 21, wherein in the third coating step, the composite particles are coated by electroless plating and a first layer containing nickel. 如申請專利範圍第22項所述的導電粒子的製造方法，其中於所述第三被覆步驟中，藉由含有選自由貴金屬及鈷所組成的群組中的金屬的第二層，將經所述第一層覆蓋的所述複合粒子被覆。The method for producing a conductive particle according to claim 22, wherein in the third coating step, the second layer is made of a metal selected from the group consisting of a noble metal and cobalt. The composite particles covered by the first layer are coated. 如申請專利範圍第21項至第23項中任一項所述的導電粒子的製造方法，其中所述樹脂粒子與所述非導電性無機粒子的界達電位之差於pH值1以上且pH值11以下時為30 mV以上。The method for producing conductive particles according to any one of the preceding claims, wherein the difference between the boundary potential of the resin particles and the non-conductive inorganic particles is pH 1 or higher and pH When the value is 11 or less, it is 30 mV or more.
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