TWI703584B - Conductive particles, conductive materials, and connection structures - Google Patents

Conductive particles, conductive materials, and connection structures Download PDF

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TWI703584B
TWI703584B TW106104056A TW106104056A TWI703584B TW I703584 B TWI703584 B TW I703584B TW 106104056 A TW106104056 A TW 106104056A TW 106104056 A TW106104056 A TW 106104056A TW I703584 B TWI703584 B TW I703584B
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conductive
conductive layer
particles
nickel
particle
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TW106104056A
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TW201740390A (en
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土橋悠人
笹平昌男
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日商積水化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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

Abstract

本發明提供一種於酸及鹼之任一者之存在下，均能夠抑制包含鎳之導電層之腐蝕之導電性粒子。 本發明之導電性粒子具備基材粒子、及配置於基材粒子之表面上之包含鎳之導電層，且包含鎳之導電層係包含鎳、及錫與銦中之至少1種之合金層，包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。The present invention provides a conductive particle capable of inhibiting corrosion of a conductive layer containing nickel in the presence of either acid or alkali. The conductive particle of the present invention includes a substrate particle and a conductive layer containing nickel arranged on the surface of the substrate particle, and the conductive layer containing nickel is an alloy layer containing at least one of nickel and tin and indium. The total average content of tin and indium in 100% by weight of the area from the outer surface toward the inner side to the thickness 1/2 of the conductive layer containing nickel is less than 5% by weight.

Description

導電性粒子、導電材料及連接構造體Conductive particles, conductive materials, and connection structures

本發明係關於一種於基材粒子之表面上配置有包含鎳之導電層之導電性粒子。又，本發明係關於一種使用上述導電性粒子之導電材料及連接構造體。The present invention relates to a conductive particle in which a conductive layer containing nickel is arranged on the surface of a substrate particle. In addition, the present invention relates to a conductive material and a connection structure using the above-mentioned conductive particles.

各向異性導電膏及各向異性導電膜等各向異性導電材料廣為人知。於該等各向異性導電材料中，於黏合劑樹脂中分散有導電性粒子。 上述各向異性導電材料例如用於軟性印刷基板與玻璃基板之連接(FOG(Film on Glass))、半導體晶片與軟性印刷基板之連接(COF(Chip on Film))、半導體晶片與玻璃基板之連接(COG(Chip on Glass))、以及軟性印刷基板與環氧玻璃基板之連接(FOB(Film on Board))等，以獲得各種連接構造體。 利用上述各向異性導電材料例如將半導體晶片之電極與玻璃基板之電極電性連接時，將包含導電性粒子之各向異性導電材料配置於玻璃基板上。其次，將半導體晶片積層，並進行加熱及加壓。藉此，使各向異性導電材料硬化，經由導電性粒子將電極間電性連接而獲得連接構造體。 作為上述導電性粒子之一例，於下述專利文獻1中，揭示出具有基材粒子、及將該基材粒子之表面被覆之導電性金屬層之導電性粒子。作為構成上述導電性金屬層之金屬之具體例，可列舉：鎳、鎳合金(Ni-Au、Ni-Pd、Ni-Pd-Au、Ni-Ag、Ni-P、Ni-B、Ni-Zn、Ni-Sn、Ni-W、Ni-Co、Ni-Ti)；銅、銅合金(Cu與選自由Fe、Co、Ni、Zn、Sn、In、Ga、Tl、Zr、W、Mo、Rh、Ru、Ir、Ag、Au、Bi、Al、Mn、Mg、P、B所組成之群中之至少1種金屬元素之合金，較佳為與Ag、Ni、Sn、Zn之合金)；銀、銀合金(Ag與選自由Fe、Co、Ni、Zn、Sn、In、Ga、Tl、Zr、W、Mo、Rh、Ru、Ir、Au、Bi、Al、Mn、Mg、P、B所組成之群中之至少1種金屬元素之合金，較佳為Ag-Ni、Ag-Sn、Ag-Zn)；錫、錫合金(例如Sn-Ag、Sn-Cu、Sn-Cu-Ag、Sn-Zn、Sn-Sb、Sn-Bi-Ag、Sn-Bi-In、Sn-Au、Sn-Pb等)。 於下述專利文獻2中，揭示出於樹脂粒子之表面上形成有金屬被覆層之導電性粒子。上述金屬被覆層係藉由使用硼化合物及次磷酸化合物作為還原劑之無電解鍍鎳步驟而形成。於專利文獻2中，記載有上述金屬被覆層除鎳、硼及磷以外，亦可含有與鎳一同共析之其他金屬。作為上述與鎳一同共析之其他金屬，可列舉：鈷、銅、鋅、鐵、錳、鉻、釩、鉬、鈀、錫、銦、鎢及錸。 於下述專利文獻3中，揭示出具備基材粒子、及配置於該基材粒子之表面上之包含鎳之導電層之導電性粒子。上述導電層係包含鎳與錫之合金層。上述導電層之整體100重量%中，錫之平均含量為5重量%以上且50重量%以下。 [先前技術文獻] [技術文獻] [專利文獻1]日本專利特開2013-125649號公報 [專利文獻2]日本專利特開2008-41671號公報 [專利文獻3]日本專利特開2015-130328號公報Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In these anisotropic conductive materials, conductive particles are dispersed in the binder resin. The above-mentioned anisotropic conductive materials are, for example, used for the connection of flexible printed substrates and glass substrates (FOG (Film on Glass)), the connection of semiconductor chips and flexible printed substrates (COF (Chip on Film)), and the connection of semiconductor chips and glass substrates. (COG (Chip on Glass)), and the connection of flexible printed circuit board and epoxy glass substrate (FOB (Film on Board)), etc., to obtain various connection structures. For example, when the electrode of a semiconductor wafer and the electrode of a glass substrate are electrically connected using the above-mentioned anisotropic conductive material, an anisotropic conductive material containing conductive particles is arranged on the glass substrate. Next, the semiconductor wafers are stacked, and heated and pressurized. Thereby, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connected structure. As an example of the above-mentioned conductive particle, in the following patent document 1, the conductive particle which has a substrate particle and the conductive metal layer which coat|covers the surface of this substrate particle is disclosed. Specific examples of the metal constituting the conductive metal layer include nickel, nickel alloys (Ni-Au, Ni-Pd, Ni-Pd-Au, Ni-Ag, Ni-P, Ni-B, Ni-Zn , Ni-Sn, Ni-W, Ni-Co, Ni-Ti); copper, copper alloy (Cu and selected from Fe, Co, Ni, Zn, Sn, In, Ga, Tl, Zr, W, Mo, Rh , Ru, Ir, Ag, Au, Bi, Al, Mn, Mg, P, B is composed of at least one metal element alloy, preferably with Ag, Ni, Sn, Zn alloy); , Silver alloy (Ag and selected from Fe, Co, Ni, Zn, Sn, In, Ga, Tl, Zr, W, Mo, Rh, Ru, Ir, Au, Bi, Al, Mn, Mg, P, B The alloy of at least one metal element in the composition group, preferably Ag-Ni, Ag-Sn, Ag-Zn); tin, tin alloy (such as Sn-Ag, Sn-Cu, Sn-Cu-Ag, Sn -Zn, Sn-Sb, Sn-Bi-Ag, Sn-Bi-In, Sn-Au, Sn-Pb, etc.). Patent Document 2 below discloses conductive particles in which a metal coating layer is formed on the surface of resin particles. The metal coating layer is formed by an electroless nickel plating step using a boron compound and a hypophosphorous acid compound as a reducing agent. In Patent Document 2, it is described that the above-mentioned metal coating layer may contain other metals that eutectoid with nickel in addition to nickel, boron, and phosphorus. Examples of other metals that are eutected with nickel include cobalt, copper, zinc, iron, manganese, chromium, vanadium, molybdenum, palladium, tin, indium, tungsten, and rhenium. In the following Patent Document 3, conductive particles provided with substrate particles and a conductive layer containing nickel arranged on the surface of the substrate particles are disclosed. The conductive layer includes an alloy layer of nickel and tin. The average content of tin in the entire 100% by weight of the conductive layer is 5% by weight or more and 50% by weight or less. [Prior Art Document] [Technical Document] [Patent Document 1] Japanese Patent Laid-open No. 2013-125649 [Patent Document 2] Japanese Patent Laid-Open No. 2008-41671 [Patent Document 3] Japanese Patent Laid-Open No. 2015-130328 Bulletin

[發明所欲解決之問題] 若將如專利文獻1、2中記載之先前之導電性粒子暴露於酸之存在下，則存在產生包含鎳之導電層之腐蝕之情況。又，若將如專利文獻1～3中記載之先前之導電性粒子暴露於鹼之存在下，則存在產生包含鎳之導電層之腐蝕之情況。又，於使用先前之導電性粒子將電極間連接而獲得連接構造體之情形時，存在將連接構造體暴露於酸或鹼之存在下時，電極間之連接電阻上升之情況。進而，若包含鎳之導電層中之錫之平均含量變多，則有導電層之比電阻上升之傾向，且有導電層變脆之傾向，因此，容易因將電極間連接時之壓縮而導致產生導電層之破裂。 本發明之目的在於提供一種於酸及鹼之任一者之存在下，均能夠抑制包含鎳之導電層之腐蝕之導電性粒子。 又，本發明之目的亦在於提供一種使用上述導電性粒子之導電材料及連接構造體。 [解決問題之技術手段] 根據本發明之廣泛之態樣，提供一種導電性粒子，其具備基材粒子、及配置於上述基材粒子之表面上且包含鎳之導電層，且上述包含鎳之導電層係包含鎳、及錫與銦中之至少1種之合金層，上述包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。 於本發明之導電性粒子之某特定之態樣中，上述包含鎳之導電層之自外表面起朝向內側至厚度1/4之區域中之錫與銦之合計的平均含量較上述包含鎳之導電層之自距外表面朝向內側為厚度1/4之位置起至厚度1/2之位置之間之區域中之錫與銦之合計的平均含量多。 於本發明之導電性粒子之某特定之態樣中，上述包含鎳之導電層之自外表面起朝向內側至厚度1/4之區域的100重量%中，錫與銦之合計之含量之最大值為50重量%以下。 於本發明之導電性粒子之某特定之態樣中，上述包含鎳之導電層於外表面具有突起。 於本發明之導電性粒子之某特定之態樣中，體積電阻率為0.003 Ω・cm以下。 於本發明之導電性粒子之某特定之態樣中，上述包含鎳之導電層之自內表面起朝向外側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。 於本發明之導電性粒子之某特定之態樣中，上述導電性粒子進而具備配置於上述包含鎳之導電層之外表面上之絕緣性物質。 根據本發明之廣泛之態樣，提供一種導電材料，其包含上述導電性粒子、及黏合劑樹脂。 根據本發明之廣泛之態樣，提供一種連接構造體，其具備：第1連接對象構件；第2連接對象構件；及連接部，其將上述第1連接對象構件與上述第2連接對象構件連接；且上述連接部之材料為上述導電性粒子，或包含上述導電性粒子與黏合劑樹脂之導電材料。 [發明之效果] 於本發明之導電性粒子中，具備基材粒子、及配置於上述基材粒子之表面上且包含鎳之導電層，且上述包含鎳之導電層係包含鎳、及錫與銦中之至少1種之合金層，上述包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%，因此，於酸及鹼之任一者之存在下，均能夠抑制包含鎳之導電層之腐蝕。[Problem to be Solved by the Invention] If the previous conductive particles as described in Patent Documents 1 and 2 are exposed to the presence of acid, corrosion of the conductive layer containing nickel may occur. In addition, if the previous conductive particles described in Patent Documents 1 to 3 are exposed to the presence of alkali, corrosion of the conductive layer containing nickel may occur. In addition, in the case of obtaining a connected structure by connecting the electrodes using the conventional conductive particles, when the connecting structure is exposed to the presence of acid or alkali, the connection resistance between the electrodes may increase. Furthermore, if the average content of tin in the conductive layer containing nickel increases, the specific resistance of the conductive layer tends to increase, and the conductive layer tends to become brittle. Therefore, it is likely to be caused by compression when connecting the electrodes Cracks in the conductive layer occur. The object of the present invention is to provide a conductive particle capable of suppressing corrosion of a conductive layer containing nickel in the presence of either acid or alkali. Moreover, the object of the present invention is also to provide a conductive material and a connection structure using the above-mentioned conductive particles. [Technical Means for Solving the Problem] According to a broad aspect of the present invention, there is provided a conductive particle comprising a substrate particle and a conductive layer containing nickel disposed on the surface of the substrate particle, and the above-mentioned nickel-containing conductive layer The conductive layer includes nickel, and an alloy layer of at least one of tin and indium. The total of tin and indium in 100% by weight of the area from the outer surface toward the inner side to the thickness 1/2 of the above-mentioned conductive layer including nickel The average content is less than 5% by weight. In a specific aspect of the conductive particles of the present invention, the total average content of tin and indium in the region from the outer surface toward the inner side to the thickness of 1/4 of the conductive layer containing nickel is higher than that of the above-mentioned nickel-containing conductive layer. The conductive layer has a large average content of tin and indium in the region from the position of the thickness 1/4 to the position of the thickness 1/2 of the thickness from the outer surface toward the inner side. In a specific aspect of the conductive particles of the present invention, the total content of tin and indium is the largest in 100% by weight of the region from the outer surface to the inner side of the thickness 1/4 of the conductive layer containing nickel The value is 50% by weight or less. In a specific aspect of the conductive particles of the present invention, the conductive layer containing nickel has protrusions on the outer surface. In a specific aspect of the conductive particles of the present invention, the volume resistivity is 0.003 Ω·cm or less. In a specific aspect of the conductive particles of the present invention, the total average content of tin and indium in 100% by weight of the region from the inner surface to the outside to the thickness 1/2 of the conductive layer containing nickel is not Up to 5% by weight. In a specific aspect of the conductive particle of the present invention, the conductive particle further includes an insulating substance arranged on the outer surface of the conductive layer containing nickel. According to a broad aspect of the present invention, a conductive material is provided, which includes the above-mentioned conductive particles and a binder resin. According to a broad aspect of the present invention, there is provided a connection structure including: a first connection object member; a second connection object member; and a connecting portion that connects the first connection object member and the second connection object member ; And the material of the connecting portion is the conductive particles, or a conductive material containing the conductive particles and a binder resin. [Effects of the invention] In the conductive particles of the present invention, a substrate particle and a conductive layer containing nickel are arranged on the surface of the substrate particle, and the conductive layer containing nickel includes nickel, tin, and In an alloy layer of at least one type of indium, the total average content of tin and indium is less than 5% by weight in 100% by weight of the area from the outer surface of the conductive layer containing nickel to the inner side to the thickness 1/2. Therefore, the corrosion of the conductive layer containing nickel can be suppressed in the presence of either acid or alkali.

以下，對本發明之詳細內容進行說明。 (導電性粒子) 本發明之導電性粒子具備基材粒子、及配置於該基材粒子之表面上且包含鎳之導電層。 又，於本發明之導電性粒子中，上述包含鎳之導電層係包含鎳、及錫與銦中之至少1種之合金層。於本發明之導電性粒子中，上述包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。 導電性粒子存在因大氣中之酸性氣體或鹼性氣體、或導電材料中所包含之導電性粒子以外之酸性成分或鹼性成分等而暴露於酸或鹼之條件下的情況。 藉由採用本發明之導電性粒子中之上述構成，於酸及鹼之任一者之存在下，均能夠抑制包含鎳之導電層之腐蝕。即便將上述導電性粒子暴露於酸或鹼之存在下，亦不易產生包含鎳之導電層之腐蝕，因此能夠將作為導電性粒子之性能維持得較高。於本發明中，即便於酸之存在下，亦能夠抑制包含鎳之導電層之腐蝕，並且，進而抑制鹼之存在下之包含鎳之導電層之腐蝕。 又，由於能夠抑制包含鎳之導電層之腐蝕，故而於藉由本發明之導電性粒子將電極間電性連接而獲得連接構造體之情形時，即便將連接電極間之前之導電性粒子暴露於酸或鹼之存在下，亦能夠將連接電阻維持得較低。又，由於能夠抑制包含鎳之導電層之腐蝕，故而即便將上述連接構造體暴露於酸或鹼之存在下，亦能夠將連接電阻維持得較低。 進而，藉由採用本發明之導電性粒子中之上述構成，亦能夠提高高濕下之電極間之連接可靠性。進而，藉由採用本發明之導電性粒子中之上述構成，能夠抑制導電性粒子之凝聚。藉由抑制導電性粒子之凝聚，亦能夠有效地降低電極間之連接電阻。 進而，於本發明之導電性粒子中，由於包含鎳之導電層包含錫與銦中之至少1種，故而能夠抑制鎳之較強之磁性，獲得抑制因磁性所導致之凝聚之效果。因此，能夠效率良好地使複數個導電性粒子配置於電極上。因此，於將電極間電性連接之情形時，能夠更進一步提高電極間之連接可靠性及導通可靠性。進而，能夠防止不可連接之橫向上相鄰之電極間之電性連接，能夠更進一步提高絕緣可靠性。又，本發明之導電性粒子由於包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域之100重量%中之錫與銦之合計的平均含量未達5重量%，故而導電層不易變脆，不易產生酸或鹼之存在下之導電層之腐蝕，因此亦能夠抑制伴隨導電層之腐蝕反應之導電性粒子之凝聚。 就更進一步提高電極間之連接可靠性之觀點而言，包含鎳之導電層之整體100重量%中，錫與銦之合計之平均含量較佳為1重量%以上，更佳為2重量%以上，且較佳為5重量%以下，更佳為未達5重量%。 又，於包含鎳之導電層之整體100重量%中，錫與銦之合計之平均含量為5重量%以下之情形時，有導電層不易變脆之傾向。由此，於包含鎳之導電層之整體100重量%中，錫與銦之合計之平均含量為5重量%以下之情形時，更加不易產生酸或鹼之存在下之導電層之腐蝕，能夠更加有效地將暴露於酸或鹼之存在下之後之連接電阻維持得較低。又，於包含鎳之導電層之整體100重量%中，錫與銦之合計之平均含量為5重量%以下之情形時，有導電層之比電阻不易上升之傾向，且亦不易產生因將電極間連接時之壓縮所導致之導電層之破裂，因此能夠更加有效地將連接電阻維持得較低。 就更進一步提高基材粒子與包含鎳之導電層之密接性，並更進一步提高電極間之連接可靠性之觀點而言，包含鎳之導電層之自內表面起朝向外側至厚度1/2之區域(R1)的100重量%中，錫與銦之合計之平均含量較佳為5重量%以下，更佳為未達5重量%，進而較佳為3重量%以下，尤佳為2重量%以下。上述區域(R1)於圖4(a)中為包含鎳之導電層3之較虛線L1更內側之區域。 包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域(R2)的100重量%中，錫與銦之合計之平均含量未達5重量%。就更進一步提高電極間之連接可靠性之觀點而言，包含鎳之導電層之整體100重量%中，包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域(R2)的100重量%中，錫與銦之合計之平均含量較佳為3重量%以下，更較為2重量%以下。上述區域(R2)於圖4(a)中為包含鎳之導電層3之較虛線L1更外側之區域。 上述區域(R1)中之錫與銦之合計之平均含量可較上述區域(R2)中之錫與銦之合計的平均含量少，亦可與上述區域(R2)中之錫與銦之合計之平均含量相同，亦可較上述區域(R2)中之錫與銦之合計之平均含量多。 就更進一步提高基材粒子與包含鎳之導電層之密接性，更進一步提高電極間之連接可靠性，且更進一步抑制導電性粒子因酸或鹼所導致之腐蝕之觀點而言，較佳為上述區域(R1)中之錫與銦之合計之平均含量較上述區域(R2)中之錫與銦之合計的平均含量少。 就更進一步提高基材粒子與包含鎳之導電層之密接性，且更進一步提高電極間之連接可靠性之觀點而言，包含鎳之導電層之自外表面起朝向內側至厚度1/4之區域(R3)的100重量%中，錫與銦之合計之平均含量較佳為20重量%以下，更佳為10重量%以下。上述區域(R3)於圖4(b)中為包含鎳之導電層3之較虛線L2更外側之區域。 就更進一步提高基材粒子與包含鎳之導電層之密接性，且更進一步提高電極間之連接可靠性之觀點而言，包含鎳之導電層之自距外表面朝向內側為厚度1/4之位置起至厚度1/2之位置之間之區域(R4)的100重量%中，錫與銦之合計之平均含量較佳為10重量%以下，更佳為1重量%以下。上述區域(R4)於圖4(b)中為包含鎳之導電層3之虛線L1與虛線L2之間之區域。 就更進一步提高基材粒子與包含鎳之導電層之密接性，更進一步提高電極間之連接可靠性，且更進一步抑制導電性粒子因酸或鹼所導致之腐蝕之觀點而言，較佳為上述區域(R3)中之錫與銦之合計之平均含量較上述區域(R4)中之錫與銦之合計的平均含量多。 於上述區域(R3)中，將上述區域(R3)作為整體而觀察時，存在錫與銦不均勻地分佈之情況。存在上述區域(R3)具有錫與銦之合計之含量相對較多之部分及錫與銦之合計之含量相對較少之部分的情況。於上述區域(R3)中，存在對錫與銦之合計之含量觀察到不均之情況。就更進一步提高基材粒子與包含鎳之導電層之密接性，更進一步提高電極間之連接可靠性，且更進一步抑制導電性粒子因酸或鹼所導致之腐蝕之觀點而言，上述區域(R3)之100重量%中，錫與銦之合計之含量的最大值較佳為5重量%以上，更佳為10重量%以上，且較佳為50重量%以下，更佳為45重量%以下。上述錫與銦之合計之含量之最大值表示上述區域(R3)內之錫與銦之合計之含量最多之位置中的含量。 上述區域(R3)之100重量%中，錫與銦之合計之含量之最大值可以如下之方式進行測定。 使用聚焦離子束，製作所獲得之導電性粒子之薄膜切片。使用電場輻射型穿透式電子顯微鏡(日本電子公司製造之「JEM-2010FEF」)，利用能量分散型X射線分析裝置(EDS)對包含鎳之導電層之厚度方向上之鎳、錫及銦之含量進行測定，藉此獲得包含鎳之導電層之厚度方向上之鎳、錫及銦之含量的分佈結果。根據該結果，能夠獲得上述區域(R3)之100重量%中之錫與銦之合計之含量的最大值。 於本發明之導電性粒子中，較佳為上述包含鎳之導電層之熔點為300℃以上。熔點為300℃以上且包含鎳之導電層一般錫之平均含量較少，因此與通常稱為焊料之焊料層不同，與熔點較低之焊料層不同。上述包含鎳之導電層之熔點之上限並無特別限定。上述包含鎳之導電層之熔點可為3000℃以下，亦可為2000℃以下，亦可為1000℃以下。上述包含鎳之導電層之熔點可為400℃以上，亦可為500℃以上。 就更進一步降低連接電阻，且更進一步提高電極間之連接可靠性之觀點而言，將上述導電性粒子壓縮10%時之壓縮彈性模數(10%K值)較佳為10 N/mm2 以上，更佳為50 N/mm2 以上，且較佳為4000 N/mm2 以下，更佳為3000 N/mm2 以下。 上述導電性粒子中之上述壓縮彈性模數(10%K值)可以如下之方式進行測定。 使用微小壓縮試驗機，藉由圓柱(直徑50 μm，金剛石製)之平滑壓頭端面，於25℃，施加30秒最大試驗負載90 mN而進行負擔之條件下將導電性粒子壓縮。對此時之負載值(N)及壓縮位移(mm)進行測定。能夠藉由下述式自所得之測定值求出上述壓縮彈性模數。作為上述微小壓縮試驗機，例如使用Fischer公司製造之「Fischerscope H-100」等。 K值(N/mm2 )＝(3/21/2 )・F・S-3/2 ・R-1/2 F：導電性粒子壓縮變形10%時之負載值(N) S：導電性粒子壓縮變形10%時之壓縮位移(mm) R：導電性粒子之半徑(mm) 上述壓縮彈性模數普遍且定量地表示導電性粒子之硬度。藉由使用上述壓縮彈性模數，能夠定量且唯一地表示導電性粒子之硬度。 就更進一步抑制導電性粒子之凝聚，且更加有效地降低電極間之連接電阻之觀點而言，上述導電性粒子之體積電阻率較佳為0.003 Ω・cm以下。 以下，一面參照圖式，一面對本發明進行具體說明。 圖1係表示本發明之第1實施形態之導電性粒子之剖視圖。 圖1所示之導電性粒子1具有基材粒子2、及包含鎳之導電層3。導電層3配置於基材粒子2之表面上。於第1實施形態中，導電層3與基材粒子2之表面相接。導電性粒子1係由導電層3將基材粒子2之表面被覆之被覆粒子。 於導電性粒子1中，包含鎳之導電層3為單層之導電層。於導電性粒子1中，包含鎳之導電層3係包含鎳、及錫與銦中之至少1種之合金層。包含鎳之導電層3之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。 導電性粒子1與下述導電性粒子11、21不同，不具有芯物質。導電性粒子1於表面不具有突起。導電性粒子1為球狀。導電層3於外表面不具有突起。如此，本發明之導電性粒子可於導電性之表面不具有突起，亦可為球狀。又，導電性粒子1與下述導電性粒子11、21不同，不具有絕緣性物質。但是，導電性粒子1亦可具有配置於導電層3之外表面上之絕緣性物質。於該情形時，亦可於導電層3與絕緣性物質之間配置有不含鎳之導電層。 於導電性粒子1中，基材粒子2與包含鎳之導電層3相接。可於基材粒子與包含鎳之導電層之間配置有不含鎳之導電層，亦可於包含鎳之導電層之外表面上配置有不含鎳之導電層。 圖2表示本發明之第2實施形態之導電性粒子之剖視圖。 圖2所示之導電性粒子11具有基材粒子2、包含鎳之導電層12、複數個芯物質13、及複數個絕緣性物質14。包含鎳之導電層12係以與基材粒子2相接之方式配置於基材粒子2之表面上。 於導電性粒子11中，包含鎳之導電層12為單層之導電層。於導電性粒子11中，包含鎳之導電層12係包含鎳、及錫與銦中之至少1種之合金層。包含鎳之導電層12之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。 導電性粒子11於導電性之表面具有複數個突起11a。包含鎳之導電層12於外表面具有複數個突起12a。複數個芯物質13配置於基材粒子2之表面上。複數個芯物質13埋入於包含鎳之導電層12內。芯物質13配置於突起11a、12a之內側。包含鎳之導電層12將複數個芯物質13被覆。藉由複數個芯物質13而使包含鎳之導電層12之外表面***，從而形成突起11a、12a。 導電性粒子11具有配置於包含鎳之導電層12之外表面上之絕緣性物質14。包含鎳之導電層12之外表面之至少一部分之區域由絕緣性物質14被覆。絕緣性物質14係由具有絕緣性之材料形成，為絕緣性粒子。如此，本發明之導電性粒子亦可具有配置於導電層之外表面上之絕緣性物質。但是，本發明之導電性粒子亦可不必具有絕緣性物質。 圖3係表示本發明之第3實施形態之導電性粒子之剖視圖。 圖3所示之導電性粒子21具有基材粒子2、包含鎳之導電層22、複數個芯物質13、及複數個絕緣性物質14。包含鎳之導電層22整體上，於基材粒子2側具有第1導電層22A，於與基材粒子2側為相反側具有第2導電層22B。 於導電性粒子11與導電性粒子21中，僅導電層不同。即，於導電性粒子11中，形成有1層構造之導電層12，相對於此，於導電性粒子21中，形成有2層構造之第1導電層22A及第2導電層22B。第1導電層22A與第2導電層22B作為不同之導電層而形成。 第1導電層22A配置於基材粒子2之表面上。於基材粒子2與第2導電層22B之間配置有第1導電層22A。第1導電層22A與基材粒子2相接。第2導電層22B與第1導電層22A相接。因此，於基材粒子2之表面上配置有第1導電層22A，於第1導電層22A之表面上配置有第2導電層22B。導電性粒子21於導電性之表面具有複數個突起21a。導電層22於外表面具有複數個突起22a。第1導電層22A於外表面具有複數個突起22Aa。第2導電層22B於外表面具有複數個突起22Ba。 於導電性粒子21中，包含鎳之導電層22為2層導電層。於導電性粒子21中，包含鎳之導電層22係包含鎳、及錫與銦中之至少1種之合金層。因此，第1導電層22A及第2導電層22B分別為包含鎳、及錫與銦中之至少1種之合金層。包含鎳之導電層22之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。 以下，對導電性粒子之其他詳細內容進行說明。 (基材粒子) 作為上述基材粒子，可列舉：樹脂粒子、除金屬粒子以外之無機粒子、有機無機混成粒子及金屬粒子等。上述基材粒子較佳為除金屬粒子以外之基材粒子，更佳為樹脂粒子、除金屬粒子以外之無機粒子或有機無機混成粒子。上述基材粒子可具有核、及配置於該核之表面上之殼，亦可為核殼粒子。上述核亦可為有機核，上述殼亦可為無機殼。 上述基材粒子進而較佳為樹脂粒子或有機無機混成粒子，可為樹脂粒子，亦可為有機無機混成粒子。使用上述導電性粒子將電極間連接時，於將上述導電性粒子配置於電極間之後，藉由壓接而使上述導電性粒子壓縮。若上述基材粒子為樹脂粒子或有機無機混成粒子，則上述壓接時上述導電性粒子容易變形，導電性粒子與電極之接觸面積變大。因此，能夠更進一步提高電極間之導通可靠性。 作為用以形成上述樹脂粒子之樹脂，可適當使用各種有機物。作為用以形成上述樹脂粒子之樹脂，例如可列舉：聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚偏二氯乙烯、聚異丁烯、聚丁二烯等聚烯烴樹脂；聚甲基丙烯酸甲酯及聚丙烯酸甲酯等丙烯酸系樹脂；聚碳酸酯、聚醯胺、酚系甲醛樹脂、三聚氰胺-甲醛樹脂、苯胍胺甲醛樹脂、脲甲醛樹脂、酚系樹脂、三聚氰胺樹脂、苯胍胺樹脂、尿素樹脂、環氧樹脂、不飽和聚酯樹脂、飽和聚酯樹脂、聚對苯二甲酸乙二酯、聚碸、聚苯醚、聚縮醛、聚醯亞胺、聚醯胺醯亞胺、聚醚醚酮、聚醚碸、二乙烯苯聚合物、以及二乙烯苯系共聚物等。作為上述二乙烯苯系共聚物等，可列舉二乙烯苯-苯乙烯共聚物及二乙烯苯-(甲基)丙烯酸酯共聚物等。由於容易將上述樹脂粒子之硬度控制於適宜之範圍，故而用以形成上述樹脂粒子之樹脂較佳為使1種或2種以上之具有乙烯性不飽和基之聚合性單體聚合而成之聚合物。 於使具有乙烯性不飽和基之聚合性單體聚合而獲得上述樹脂粒子之情形時，作為上述具有乙烯性不飽和基之聚合性單體，可列舉非交聯性單體與交聯性單體。 作為上述非交聯性單體，例如可列舉：苯乙烯、α-甲基苯乙烯等苯乙烯系單體；(甲基)丙烯酸、順丁烯二酸、順丁烯二酸酐等含羧基之單體；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸異𦯉基酯等(甲基)丙烯酸烷基酯化合物；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸甘油酯、聚氧乙烯(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯等含氧原子之(甲基)丙烯酸酯化合物；(甲基)丙烯腈等含腈之單體；甲基乙烯基醚、乙基乙烯基醚、丙基乙烯基醚等乙烯醚化合物；乙酸乙烯酯、丁酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等酸乙烯酯化合物；乙烯、丙烯、異戊二烯、丁二烯等不飽和烴；(甲基)丙烯酸三氟甲酯、(甲基)丙烯酸五氟乙酯、氯乙烯、氟乙烯、氯苯乙烯等含鹵素之單體等。 作為上述交聯性單體，例如可列舉：四羥甲基甲烷四(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、(聚)伸丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯化合物；(異)氰尿酸三烯丙酯、偏苯三酸三烯丙酯、二乙烯苯、鄰苯二甲酸二烯丙酯、二烯丙基丙烯醯胺、二烯丙醚、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、三甲氧基矽烷基苯乙烯、乙烯基三甲氧基矽烷等含矽烷之單體等。 藉由利用公知之方法使上述具有乙烯性不飽和基之聚合性單體聚合能夠獲得上述樹脂粒子。作為其方法，例如可列舉：於自由基聚合起始劑之存在下進行懸浮聚合之方法、以及使用非交聯之晶種(seed-particle)使單體與自由基聚合起始劑一同膨潤而聚合之方法等。 於上述基材粒子為除金屬以外之無機粒子或有機無機混成粒子之情形時，作為用以形成基材粒子之無機物，可列舉：氧化矽、氧化鋁、鈦酸鋇、氧化鋯及碳黑等。上述無機物較佳為不為金屬。作為上述由氧化矽形成之粒子，並無特別限定，例如可列舉藉由如下方式獲得之粒子，即，於使具有2個以上之水解性之烷氧基矽烷基之矽化合物水解而形成交聯聚合物粒子後，視需要進行焙燒。作為上述有機無機混成粒子，例如可列舉由經交聯之烷氧基矽烷基聚合物與丙烯酸系樹脂所形成之有機無機混成粒子等。 上述有機無機混成粒子較佳為具有核、及配置於該核之表面上之殼之核殼型有機無機混成粒子。上述核較佳為有機核。上述殼較佳為無機殼。就有效地降低電極間之連接電阻之觀點而言，上述基材粒子較佳為具有有機核及配置於上述有機核之表面上之無機殼之有機無機混成粒子。 作為用以形成上述有機核之材料，可列舉上述用以形成樹脂粒子之樹脂等。 作為用以形成上述無機殼之材料，可列舉上述用以形成基材粒子之無機物。用以形成上述無機殼之材料較佳為氧化矽。上述無機殼較佳為藉由如下方式形成，即於上述核之表面上，利用溶膠凝膠法將金屬烷氧化物製成殼狀物，之後使該殼狀物燒結。上述金屬烷氧化物較佳為矽烷醇鹽(silane alkoxide)。上述無機殼較佳為由矽烷醇鹽形成。 上述核之粒徑較佳為0.5 μm以上，更佳為1 μm以上，且較佳為500 μm以下，更佳為100 μm以下，進而較佳為50 μm以下，尤佳為20 μm以下，最佳為10 μm以下。若上述核之粒徑為上述下限以上及上述上限以下，則能夠獲得更加適於電極間之電性連接之導電性粒子，將基材粒子較佳地用於導電性粒子之用途。例如，若上述核之粒徑為上述下限以上及上述上限以下，則於使用上述導電性粒子將電極間連接之情形時，導電性粒子與電極之接觸面積充分變大，且形成導電部時能夠不易形成凝聚之導電性粒子。又，經由導電性粒子連接之電極間之間隔不會變得過大，且能夠不易使導電部自基材粒子之表面剝離。 上述核之粒徑於上述核為真球狀之情形時，係指直徑，於上述核為真球狀以外之形狀之情形時，係指最大直徑。又，核之粒徑係指利用任意之粒徑測定裝置對核進行測定所得之平均粒徑。例如可利用使用雷射光散射、電阻值變化、拍攝後之圖像解析等原理之粒度分佈測定機。 上述殼之厚度較佳為100 nm以上，更佳為200 nm以上，且較佳為5 μm以下，更佳為3 μm以下。若上述殼之厚度為上述下限以上及上述上限以下，則能夠獲得更加適於電極間之電性連接之導電性粒子，將基材粒子較佳地用於導電性粒子之用途。上述殼之厚度係每1個基材粒子之平均厚度。藉由溶膠凝膠法之控制，能夠控制上述殼之厚度。 於上述基材粒子為金屬粒子之情形時，關於作為該金屬粒子之材料之金屬，可列舉：銀、銅、鎳、矽、金及鈦等。但是，較佳為上述基材粒子並非為金屬粒子，較佳為並非為銅粒子。 上述基材粒子之粒徑較佳為0.1 μm以上，更佳為1 μm以上，進而較佳為1.5 μm以上，尤佳為2 μm以上，且較佳為1000 μm以下，更佳為500 μm以下，進一步更佳為300 μm以下，進而較佳為50 μm以下，進而更佳為30 μm以下，尤佳為5 μm以下，最佳為3 μm以下。若上述基材粒子之粒徑為上述下限以上，則導電性粒子與電極之接觸面積變大，因此能夠更進一步提高電極間之導通可靠性，能夠更進一步降低經由導電性粒子連接之電極間之連接電阻。進而，藉由無電鍍於基材粒子之表面形成導電層時，能夠不易形成凝聚之導電性粒子。若上述基材粒子之粒徑為上述上限以下，則容易將導電性粒子充分地壓縮，能夠更進一步降低電極間之連接電阻，進而能夠使電極間之間隔變得更小。 上述基材粒子之粒徑於基材粒子為真球狀之情形時，表示直徑，於基材粒子並非為真球狀之情形時，表示最大直徑。 上述基材粒子之粒徑尤佳為2 μm以上且5 μm以下。若上述基材粒子之粒徑為2～5 μm之範圍內，則能夠使電極間之間隔變得更小，且即便使導電層之厚度變厚，亦能夠獲得較小之導電性粒子。 (導電層) 本發明之導電性粒子具備基材粒子、及配置於基材粒子之表面上之包含鎳之導電層。上述包含鎳之導電層包含鎳、及錫與銦中之至少1種。上述包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。關於該包含鎳之導電層，於以下之(導電層)之欄中，有時將包含鎳之導電層記載為導電層X。於上述導電層X中，不包含不含鎳之導電層，且不包含不含鎳之導電層部分。 就有效地提高導電性之觀點而言，上述導電層X之整體100重量%中，鎳之平均含量越多越佳。因此，上述導電層X之整體100重量%中，鎳之平均含量較佳為50重量%以上，更佳為65重量%以上，進一步更佳為70重量%以上，進而較佳為80重量%以上，進而更佳為85重量%以上，尤佳為90重量%以上，最佳為95重量%以上。上述導電層X之整體100重量%中，鎳之平均含量較佳為99重量%以下，更佳為98重量%以下，進而較佳為97重量%以下。若鎳之平均含量為上述下限以上，則能夠更進一步降低電極間之連接電阻。又，於電極或導電層之表面中之氧化覆膜較少之情形時，有鎳之平均含量越多，電極間之連接電阻越低之傾向。 上述包含鎳之導電層(導電層X)中之鎳、錫及銦之各含量之測定方法可使用已知之各種分析法，並無特別限定。可使用高頻電感耦合電漿發光分光分析裝置(堀場製作所公司製造之「ICP-AES」)、或螢光X射線分析裝置(島津製作所公司製造之「EDX-800HS」)等進行測定。 上述導電層X之厚度方向之各區域中之鎳、錫及銦之各含量可使用電場輻射型穿透式電子顯微鏡(日本電子公司製造之「JEM-2010FEF」)等進行測定。 上述導電層X整體之厚度較佳為0.005 μm以上，更佳為0.01 μm以上，進而較佳為0.05 μm以上，且較佳為1 μm以下，更佳為0.3 μm以下。若上述導電層X整體之厚度為上述下限以上及上述上限以下，則能夠獲得充分之導電性，且導電性粒子不會變得過硬，將電極間連接時導電性粒子能夠充分地變形。 上述導電層X整體之厚度尤佳為0.05 μm以上且0.3 μm以下。進而尤佳為，上述基材粒子之粒徑為2 μm以上且5 μm以下，且上述導電層X整體之厚度為0.05 μm以上且0.3 μm以下。於該情形時，能夠將導電性粒子更佳地用於流通較大之電流之用途。進而，於壓縮導電性粒子而將電極間連接之情形時，能夠更進一步抑制電極損傷。 上述導電層X之厚度例如可使用穿透式電子顯微鏡(日本電子公司製造之「JEM-2100」)等，藉由導電性粒子之剖面觀察進行測定。 上述導電層X亦可包含除鎳、錫及銦以外之金屬。作為上述導電層X中之除鎳、錫及銦以外之金屬，例如可列舉：金、銀、銅、鉑、鋅、鐵、鉛、鋁、鈷、鈀、鉻、𨭎、鈦、銻、鉍、鉈、鍺、鎘、矽、鎢及鉬等。該等金屬可僅使用1種，亦可將2種以上併用。於在上述導電層X中包含複數種金屬之情形時，複數種金屬亦可合金化。 於上述基材粒子之表面上形成上述導電層X之方法並無特別限定。作為形成導電層之方法，例如可列舉：利用無電鍍之方法、利用電鍍之方法、利用物理蒸鍍之方法、以及將金屬粉末或包含金屬粉末與黏合劑之焊膏塗佈於基材粒子或其他導電層之表面之方法等。由於導電層之形成較為簡便，故而較佳為利用無電鍍之方法。作為上述利用物理蒸鍍之方法，可列舉：真空蒸鍍、離子鍍覆及離子濺鍍等方法。 上述導電性粒子之粒徑較佳為0.5 μm以上，更佳為1 μm以上，且較佳為100 μm以下，更佳為20 μm以下，進而較佳為5 μm以下，尤佳為3 μm以下。若導電性粒子之粒徑為上述下限以上及上限以下，則於使用上述導電性粒子將電極間連接之情形時，能夠使導電性粒子與電極之接觸面積充分變大，且形成導電層時，能夠不易形成凝聚之導電性粒子。又，經由導電性粒子連接之電極間之間隔不會變得過大，且能夠不易使導電層自基材粒子之表面剝離。 上述導電性粒子之粒徑於導電性粒子為真球狀之情形時，表示直徑，於導電性粒子並非為真球狀之情形時，表示最大直徑。 上述導電層X可由1層形成，亦可由複數層形成。即，上述導電層X亦可具有2層以上之積層構造。上述導電性粒子除上述導電層X以外，亦可具備金層、鎳層、鈀層、銅層、銀層、或包含錫與銀之合金層作為最外層等。 作為控制上述導電層X之各區域中之鎳、錫及銦之各含量及各平均含量之方法，例如可列舉：藉由無電解鍍鎳形成導電層X時控制鍍鎳液之pH之方法、調整鍍鎳液中之錫及銦濃度之方法以及調整鍍鎳液中之鎳濃度之方法等。 於藉由無電鍍而形成之方法中，一般進行觸媒化步驟、及無電鍍步驟。以下，對藉由無電鍍於樹脂粒子之表面形成包含鎳之鍍覆層之方法的一例進行說明。 於上述觸媒化步驟中，使成為用以藉由無電鍍形成鍍覆層之起點之觸媒形成於樹脂粒子之表面。 作為使上述觸媒形成於樹脂粒子之表面之方法，例如可列舉如下方法等：於向包含氯化鈀與氯化錫之溶液中添加樹脂粒子後，利用酸溶液或鹼溶液使樹脂粒子之表面活化，於樹脂粒子之表面使鈀析出；以及於向含有硫酸鈀之溶液中添加樹脂粒子後，利用包含還原劑之溶液使樹脂粒子之表面活化，於樹脂粒子之表面使鈀析出。 於上述無電鍍步驟中，適宜使用包含含鎳之化合物、上述還原劑、錯合劑及含錫之化合物與含銦之化合物中之至少1種之鍍鎳浴。藉由於鍍鎳浴中浸漬樹脂粒子，能夠於在表面形成有觸媒之樹脂粒子之表面使鎳析出，從而能夠形成上述導電層X。又，使鎳析出時，使錫與銦中之至少1種共析，藉此能夠形成包含鎳、及錫與銦中之至少1種之合金鍍覆層。 作為上述含鎳之化合物，可列舉硫酸鎳及氯化鎳等。上述含鎳之化合物較佳為鎳鹽。 作為上述還原劑，可列舉：次磷酸鈉、二甲胺硼烷、氫硼化鈉、氫硼化鉀、肼一水合物、硫酸肼、及氯化鈦(III)等。 作為上述含錫之化合物，可列舉：錫酸鈉三水合物、錫酸鉀三水合物、硫酸錫(II)、氯化錫(IV)五水合物及氯化錫(II)二水合物等。 作為上述含銦之化合物，可列舉：乙酸銦(III)、硫酸銦(III)三水合物、氯化銦(III)、氫氧化銦(III)、及硝酸銦(III)等。 上述錯合劑可列舉：乙酸鈉、丙酸鈉等單羧酸系錯合劑；丙二酸二鈉等二羧酸系錯合劑；琥珀酸二鈉等三羧酸系錯合劑；乳酸、DL-蘋果酸、酒石酸鈉、檸檬酸鈉、葡萄糖酸鈉等羥酸系錯合劑；甘胺酸、EDTA(ethylenediamine tetraacetic acid，四乙酸乙二胺)等胺基酸系錯合劑；乙二胺等胺系錯合劑；順丁烯二酸等有機酸系錯合劑；以及該等之鹽等。較佳為使用選自由此處列舉之錯合劑所組成之群中之至少1種錯合劑。 (芯物質) 上述導電性粒子較佳為於導電性之表面具有突起。上述導電層較佳為於外表面具有突起。上述突起較佳為複數個。於藉由上述導電性粒子連接之電極之表面較多形成有氧化覆膜。進而，於上述導電性粒子之導電層之表面較多形成有氧化覆膜。藉由上述具有突起之導電性粒子之使用，於將導電性粒子配置於電極間之後使之壓接，藉此利用突起有效地排除氧化覆膜。因此，能夠更加確實地使電極與導電性粒子接觸，能夠降低電極間之連接電阻。進而，於上述導電性粒子於表面具有絕緣性物質之情形時，或於導電性粒子分散於黏合劑樹脂中而用作導電材料之情形時，藉由導電性粒子之突起而有效地排除導電性粒子與電極之間之絕緣性物質或黏合劑樹脂。因此，能夠提高電極間之導通可靠性。 又，若上述導電性粒子於導電層之外表面具有突起，則能夠使上述導電性粒子彼此接觸之面積變小。因此，能夠抑制複數個上述導電性粒子之凝聚。因此，能夠防止不可連接之電極間之電性連接，能夠更進一步提高絕緣可靠性。 藉由將上述芯物質埋入於上述導電層中，而容易使上述導電層於外表面具有複數個突起。但是，亦可不必使用芯物質以於上述導電性粒子及上述導電層之外表面形成突起，較佳為不使用芯物質，上述導電性粒子較佳為不具有用以使上述導電層之外表面***之芯物質。但是，上述導電性粒子亦可具有使上述導電層之外表面***之芯物質。於使用上述芯物質之情形時，較佳為上述芯物質配置於上述導電層之內側或內部。 作為形成上述突起之方法，可列舉：於使芯物質附著於基材粒子之表面後，藉由無電鍍形成導電層之方法；於藉由無電鍍於基材粒子之表面形成導電層後，使芯物質附著，進而藉由無電鍍而形成導電層之方法；以及於藉由無電鍍在基材粒子之表面形成導電層之中途階段添加芯物質之方法等。 作為使芯物質配置於上述基材粒子之表面上之方法，例如可列舉：向基材粒子之分散液中添加芯物質，例如藉由凡得瓦耳力使芯物質集聚並附著於基材粒子之表面之方法；以及向放入有基材粒子之容器中添加芯物質，藉由利用容器之旋轉等所產生之機械作用而使芯物質附著於基材粒子之表面的方法等。為了易於控制附著之芯物質之量，較佳為使芯物質集聚並附著於分散液中之基材粒子之表面之方法。 作為上述芯物質之材料，可列舉導電性物質及非導電性物質。作為上述導電性物質，例如可列舉：金屬、金屬之氧化物、石墨等導電性非金屬及導電性聚合物等。作為上述導電性聚合物，可列舉聚乙炔等。作為上述非導電性物質，可列舉：氧化矽、氧化鋁、鈦酸鋇及氧化鋯等。為了有效地排除氧化覆膜，芯物質較硬者較佳。金屬由於能夠提高導電性，進而能夠有效地降低連接電阻，故而較佳。上述芯物質較佳為金屬粒子。關於作為上述芯物質之材料之金屬，可適當使用上述作為導電層之材料而列舉之金屬。 作為上述芯物質之材料之具體例，可列舉：鈦酸鋇(莫氏硬度4.5)、鎳(莫氏硬度5)、氧化矽(二氧化矽，莫氏硬度6～7)、氧化鈦(莫氏硬度7)、氧化鋯(莫氏硬度8～9)、氧化鋁(莫氏硬度9)、碳化鎢(莫氏硬度9)及金剛石(莫氏硬度10)等。上述無機粒子較佳為鎳、氧化矽、氧化鈦、氧化鋯、氧化鋁、碳化鎢或金剛石，更佳為氧化矽、氧化鈦、氧化鋯、氧化鋁、碳化鎢或金剛石，進而較佳為氧化鈦、氧化鋯、氧化鋁、碳化鎢或金剛石，尤佳為氧化鋯、氧化鋁、碳化鎢或金剛石。上述芯物質之材料之莫氏硬度較佳為5以上，更佳為6以上，進而較佳為7以上，尤佳為7.5以上。 作為上述金屬，例如可列舉：金、銀、銅、鉑、鋅、鐵、鉛、錫、鋁、鈷、銦、鎳、鉻、鈦、銻、鉍、鍺及鎘等金屬；以及錫-鉛合金、錫-銅合金、錫-銀合金、錫-鉛-銀合金及碳化鎢等包含2種以上之金屬之合金等。較佳為鎳、銅、銀或金。用以形成上述芯物質之金屬可與用以形成上述導電部之金屬相同，亦可不同。用以形成上述芯物質之金屬較佳為包含用以形成上述導電部之金屬。用以形成上述芯物質之金屬較佳為包含鎳。 上述芯物質之形狀並無特別限定。上述芯物質之形狀較佳為塊狀。作為芯物質，例如可列舉粒子狀之塊、複數個微小粒子凝聚而成之凝聚塊及不定形之塊等。 上述芯物質之平均徑(平均粒徑)較佳為0.001 μm以上，更佳為0.05 μm以上，且較佳為0.9 μm以下，更佳為0.2 μm以下。若上述芯物質之平均徑為上述下限以上及上述上限以下，則能夠有效地降低電極間之連接電阻。 上述芯物質之「平均徑(平均粒徑)」表示數平均徑(數平均粒徑)。芯物質之平均徑係藉由利用電子顯微鏡或光學顯微鏡觀察任意之芯物質50個，並算出平均值而求出。 每1個上述導電性粒子之上述突起之數量較佳為3個以上，更佳為5個以上。上述突起之數量之上限並無特別限定。上述突起之數量之上限可考慮導電性粒子之粒徑等適當進行選擇。 複數個上述突起之平均高度較佳為0.001 μm以上，更佳為0.05 μm以上，且較佳為0.9 μm以下，更佳為0.2 μm以下。若上述突起之平均高度為上述下限以上及上述上限以下，則能夠有效地降低電極間之連接電阻。 (絕緣性物質) 上述導電性粒子較佳為具備配置於上述導電層之表面上之絕緣性物質。於該情形時，若將上述導電性粒子用於電極間之連接，則能夠更進一步防止相鄰之電極間之短路。具體而言，複數個導電性粒子接觸時，由於在複數個電極間存在絕緣性物質，故而能夠防止橫向相鄰之電極間而非上下之電極間之短路。再者，將電極間連接時，藉由利用2個電極對導電性粒子進行加壓，能夠容易地排除導電性粒子之導電層與電極之間之絕緣性物質。於上述導電性粒子於導電層之外表面具有複數個突起之情形時，能夠更加容易地排除上述導電性粒子之導電層與電極之間之絕緣性物質。 就壓接電極間時能夠更加容易地排除上述絕緣性物質之方面而言，上述絕緣性物質較佳為絕緣性粒子。 關於作為上述絕緣性物質之材料之絕緣性樹脂之具體例，可列舉：聚烯烴化合物、(甲基)丙烯酸酯聚合物、(甲基)丙烯酸酯共聚物、嵌段聚合物、熱塑性樹脂、熱塑性樹脂之交聯物、熱硬化性樹脂及水溶性樹脂等。 作為上述聚烯烴化合物，可列舉：聚乙烯、乙烯-乙酸乙烯酯共聚物及乙烯-丙烯酸酯共聚物等。作為上述(甲基)丙烯酸酯聚合物，可列舉：聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸乙酯及聚(甲基)丙烯酸丁酯等。作為上述嵌段聚合物，可列舉：聚苯乙烯、苯乙烯-丙烯酸酯共聚物、SB型苯乙烯-丁二烯嵌段共聚物及SBS型苯乙烯-丁二烯嵌段共聚物、以及該等之氫化物等。作為上述熱塑性樹脂，可列舉乙烯基聚合物及乙烯基共聚物等。作為上述熱硬化性樹脂，可列舉環氧樹脂、酚系樹脂及三聚氰胺樹脂等。作為上述水溶性樹脂，可列舉：聚乙烯醇、聚丙烯酸、聚丙烯醯胺、聚乙烯吡咯啶酮、聚環氧乙烷及甲基纖維素等。較佳為水溶性樹脂，更佳為聚乙烯醇。 作為將絕緣性物質配置於上述導電層之外表面上之方法，可列舉化學方法、及物理或機械方法等。作為上述化學方法，例如可列舉：界面聚合法、粒子存在下之懸浮聚合法及乳化聚合法等。作為上述物理或機械方法，可列舉利用噴霧乾燥、混成作用、靜電附著法、噴霧法、浸漬及真空蒸鍍之方法等。就絕緣性物質不易脫去之方面而言，較佳為經由化學鍵將上述絕緣性物質配置於上述導電層之表面。 上述導電層之外表面及上述絕緣性粒子之表面亦可分別由具有反應性官能基之化合物被覆。上述導電層之外表面與上述絕緣性粒子之表面可不直接化學鍵結，亦可間接地藉由具有反應性官能基之化合物而化學鍵結。於嚮導電層之外表面導入羧基後，該羧基經由聚伸乙基亞胺等高分子電解質亦可與絕緣性粒子之表面之官能基化學鍵結。 上述絕緣性物質之平均徑(平均粒徑)可根據上述導電性粒子之粒徑及用途等適當進行選擇。上述絕緣性物質之平均徑(平均粒徑)較佳為0.005 μm以上，更佳為0.01 μm以上，且較佳為1 μm以下，更佳為0.5 μm以下。若上述絕緣性物質之平均徑為上述下限以上，則將上述導電性粒子分散於黏合劑樹脂中時，能夠不易使複數個上述導電性粒子之導電層彼此接觸。若上述絕緣性粒子之平均徑為上述上限以下，則將電極間連接時，可不使壓力變得過高，亦可不加熱至高溫以排除電極與導電性粒子之間之絕緣性粒子。 上述絕緣性物質之「平均徑(平均粒徑)」表示數平均徑(數平均粒徑)。絕緣性物質之平均徑係使用粒度分佈測定裝置等求出。 (導電材料) 本發明之導電材料包含上述導電性粒子、及黏合劑樹脂。上述導電性粒子較佳為分散於黏合劑樹脂中而用作導電材料。上述導電材料較佳為各向異性導電材料。上述導電性粒子及上述導電材料較佳為分別用於電極間之電性連接。上述導電材料較佳為電路連接用材料。 上述黏合劑樹脂並無特別限定。可使用公知之絕緣性樹脂作為上述黏合劑樹脂。 作為上述黏合劑樹脂，例如可列舉：乙烯系樹脂、熱塑性樹脂、硬化性樹脂、熱塑性嵌段共聚物及彈性體等。上述黏合劑樹脂可僅使用1種，亦可將2種以上併用。 作為上述乙烯系樹脂，例如可列舉：乙酸乙烯酯樹脂、丙烯酸系樹脂及苯乙烯樹脂等。作為上述熱塑性樹脂，例如可列舉：聚烯烴樹脂、乙烯-乙酸乙烯酯共聚物及聚醯胺樹脂等。作為上述硬化性樹脂，例如可列舉：環氧樹脂、胺基甲酸酯樹脂、聚醯亞胺樹脂及不飽和聚酯樹脂等。再者，上述硬化性樹脂亦可為常溫硬化型樹脂、熱硬化型樹脂、光硬化型樹脂或濕氣硬化型樹脂。上述硬化性樹脂亦可與硬化劑併用。作為上述熱塑性嵌段共聚物，例如可列舉：苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-異戊二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物之氫化物、及苯乙烯-異戊二烯-苯乙烯嵌段共聚物之氫化物等。作為上述彈性體，例如可列舉：苯乙烯-丁二烯共聚橡膠、及丙烯腈-苯乙烯嵌段共聚橡膠等。 上述導電材料及上述黏合劑樹脂較佳為包含熱塑性成分或熱硬化性成分。上述導電材料及上述黏合劑樹脂可包含熱塑性成分，亦可包含熱硬化性成分。上述導電材料及上述黏合劑樹脂較佳為包含熱硬化性成分。上述熱硬化性成分較佳為包含可藉由加熱而硬化之硬化性化合物與熱硬化劑。上述熱硬化劑較佳為熱陽離子硬化起始劑。上述可藉由加熱而硬化之硬化性化合物與上述熱硬化劑係以上述黏合劑樹脂硬化之方式按適當之調配比而使用。若上述黏合劑樹脂包含熱陽離子硬化起始劑，則於硬化物中容易包含酸。但是，藉由使用本發明之導電性粒子，能夠將電極間之連接電阻維持得較低。 上述導電材料除上述導電性粒子及上述黏合劑樹脂以外，例如亦可包含填充劑、增量劑、軟化劑、塑化劑、聚合觸媒、硬化觸媒、著色劑、抗氧化劑、熱穩定劑、光穩定劑、紫外線吸收劑、潤滑劑、抗靜電劑及阻燃劑等各種添加劑。 上述導電材料可用作導電膏及導電膜等。於上述導電材料為導電膜之情形時，亦可將不含導電性粒子之膜積層積層於包含導電性粒子之導電膜。上述導電膏較佳為各向異性導電膏。上述導電膜較佳為各向異性導電膜。 上述導電材料100重量%中，上述黏合劑樹脂之含量較佳為10重量%以上，更佳為30重量%以上，進而較佳為50重量%以上，尤佳為70重量%以上，且較佳為99.99重量%以下，更佳為99.9重量%以下。若上述黏合劑樹脂之含量為上述下限以上及上述上限以下，則能夠有效率地將導電性粒子配置於電極間，更進一步提高利用導電材料連接之連接對象構件之連接可靠性。 上述導電材料100重量%中，上述導電性粒子之含量較佳為0.01重量%以上，更佳為0.1重量%以上，且較佳為80重量%以下，更佳為60重量%以下，進而較佳為40重量%以下，尤佳為20重量%以下，最佳為10重量%以下。若上述導電性粒子之含量為上述下限以上及上述上限以下，則能夠更進一步提高電極間之導通可靠性。 (連接構造體) 藉由使用上述導電性粒子，或使用包含上述導電性粒子與黏合劑樹脂之上述導電材料將連接對象構件連接能夠獲得連接構造體。 上述連接構造體較佳為如下連接構造體，即具備第1連接對象構件、第2連接對象構件、及將第1、第2連接對象構件連接之連接部，且該連接部之材料為本發明之導電性粒子，或包含該導電性粒子與黏合劑樹脂之本發明之導電材料。上述連接部較佳為由本發明之導電性粒子形成，或由包含該導電性粒子與黏合劑樹脂之本發明之導電材料形成。於使用導電性粒子之情形時，連接部本身為導電性粒子。即，藉由上述導電性粒子將第1、第2連接對象構件連接。 於圖5中，以正面剖視圖模式性地表示使用本發明之第1實施形態之導電性粒子之連接構造體。 圖5所示之連接構造體51具備第1連接對象構件52、第2連接對象構件53、及將第1、第2連接對象構件52、53連接之連接部54。連接部54係藉由使包含導電性粒子1之導電材料硬化而形成。再者，於圖5中，為了方便進行圖示，導電性粒子1以簡略之圖表示。亦可使用導電性粒子11、21等代替導電性粒子1。 第1連接對象構件52於表面(上表面)具有複數個第1電極52a。第2連接對象構件53於表面(下表面)具有複數個第2電極53a。第1電極52a與第2電極53a係藉由1個或複數個導電性粒子1電性連接。因此，第1、第2連接對象構件52、53係藉由導電性粒子1電性連接。 上述連接構造體之製造方法並無特別限定。作為上述連接構造體之製造方法之一例，可列舉如下方法等，即將上述導電材料配置於上述第1連接對象構件與上述第2連接對象構件之間而獲得積層體，之後對該積層體進行加熱及加壓。上述加壓之壓力為9.8×104 ～4.9×106 Pa左右。上述加熱之溫度為120～220℃左右。 作為上述連接對象構件，具體可列舉：半導體晶片、電容器及二極體等電子零件；以及印刷基板、軟性印刷基板、環氧玻璃基板及玻璃基板等電路基板。上述連接對象構件較佳為電子零件。上述導電性粒子較佳為用於電子零件中之電極之電性連接。 作為設置於上述連接對象構件之電極，可列舉：金電極、鎳電極、錫電極、鋁電極、銅電極、銀電極、SUS(Steel Use Stainless，日本不鏽鋼標準)電極、鉬電極及鎢電極等金屬電極。於上述連接對象構件為軟性印刷基板之情形時，上述電極較佳為金電極、鎳電極、錫電極或銅電極。於上述連接對象構件為玻璃基板之情形時，上述電極較佳為鋁電極、銅電極、鉬電極或鎢電極。再者，於上述電極為鋁電極之情形時，可為僅由鋁形成之電極，亦可為將鋁層積層於金屬氧化物層之表面之電極。作為上述金屬氧化物層之材料，可列舉：摻雜有三價金屬元素之氧化銦及摻雜有三價金屬元素之氧化鋅等。作為上述三價金屬元素，可列舉Sn、Al及Ga等。 以下，舉出實施例及比較例對本發明進行具體說明。本發明並非僅限定於以下之實施例。 (實施例1) 準備粒徑為3.0 μm之二乙烯苯共聚物樹脂粒子(基材粒子A，積水化學工業公司製造之「Micropearl SP-203」)。使用超音波分散器使10重量份之上述基材粒子A分散於100重量份之包含5重量%之鈀觸媒液之鹼溶液中，之後藉由過濾溶液，而取出基材粒子A。繼而，將基材粒子A添加至100重量份之二甲胺硼烷1重量%之溶液中，使基材粒子A之表面活化。於將表面經活化之基材粒子A充分水洗後，加入至500重量份之蒸餾水中，使之分散，藉此獲得分散液。其次，花費3分鐘將2 g之Ni粒子漿料(平均粒徑150 nm)添加至上述分散液中，獲得包含附著有芯物質之基材粒子之懸浮液(0)。 又，準備包含0.14 mol/L之硫酸鎳、0.46 mol/L之二甲胺硼烷及0.2 mol/L之檸檬酸鈉之鍍鎳液(1)(pH8.5)作為鍍鎳液(1)。 一面於60℃下攪拌所獲得之懸浮液(0)，一面將上述鍍鎳液(1)漸漸滴加至懸浮液中，進行無電解鍍鎳-硼合金，從而獲得懸浮液(1)。 準備包含0.14 mol/L之硫酸鎳、0.03 mol/L之錫酸鈉三水合物、0.60 mol/L之氯化鈦(III)、及0.15 mol/L之葡萄糖酸鈉之鍍鎳液(2)(pH8.0)作為鍍鎳液(2)。 將懸浮液(1)之液溫設定為70℃，將上述鍍鎳液(2)漸漸滴加至上述懸浮液(1)中，進行無電解鍍鎳-錫合金，從而獲得懸浮液(2)。 其後，藉由過濾上述懸浮液(2)而取出粒子，並進行水洗、乾燥，藉此將包含鎳之導電層(厚度0.1 μm)配置於基材粒子A之表面，從而獲得表面為導電層之導電性粒子。 (實施例2) 將鍍鎳液(2)之0.03 mol/L之錫酸鈉三水合物變更為0.04 mol/L之乙酸銦(III)，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例3) 將Ni粒子漿料變更為氧化鋁粒子漿料，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例4) 對於突起形成，不使用Ni粒子漿料，而於形成導電部時以部分地改變析出量之方式進行調整而形成突起，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例5) 將鍍鎳液(2)之0.60 mol/L之氯化鈦(III)變更為0.46 mol/L之二甲胺硼烷，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例6) 將鍍鎳液(1)之0.46 mol/L之二甲胺硼烷變更為1.40 mol/L之次磷酸鈉，並且將鍍鎳液(2)之0.60 mol/L之氯化鈦(III)變更為1.40 mol/L之次磷酸鈉，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例7) 將鍍鎳液(1)之0.46 mol/L之二甲胺硼烷變更為0.60 mol/L之氯化鈦(III)，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例8) 向鍍鎳液(1)中添加0.02 mol/L之錫酸鈉三水合物及0.10 mol/L之葡萄糖酸鈉，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例9) 向鍍鎳液(1)添加0.04 mol/L之錫酸鈉三水合物及0.20 mol/L之葡萄糖酸鈉，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例10) 將鍍鎳液(2)之錫酸鈉三水合物之添加量自0.03 mol/L變更至0.05 mol/L，並且將鍍鎳液(2)之葡萄糖酸鈉之添加量自0.15 mol/L變更至0.25 mol/L，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例11) 向鍍鎳液(1)中添加0.04 mol/L之錫酸鈉三水合物及0.20 mol/L之葡萄糖酸鈉，將鍍鎳液(2)之錫酸鈉三水合物之添加量自0.03 mol/L變更至0.05 mol/L，並且將鍍鎳液(2)之葡萄糖酸鈉之添加量自0.15 mol/L變更至0.25 mol/L，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例12) 將鍍鎳液(2)之錫酸鈉三水合物之添加量自0.03 mol/L變更至0.02 mol/L，並且向鍍鎳液(2)中添加0.02 mol/L之乙酸銦(III)，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例13) 將鍍鎳液(1)(pH8.5)之組成變更為0.18 mol/L之硫酸鎳、0.66 mol/L之二甲胺硼烷及0.25 mol/L之檸檬酸鈉，將鍍鎳液(2)(pH8.0)之組成變更為0.18 mol/L之硫酸鎳、0.04 mol/L之錫酸鈉三水合物、0.75 mol/L之氯化鈦(III)、及0.19 mol/L之葡萄糖酸鈉，並且將導電層之厚度自0.1 μm變更至0.15 μm，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例14) 將鍍鎳液(1)(pH8.5)之組成變更為0.07 mol/L之硫酸鎳、0.23 mol/L之二甲胺硼烷及0.10 mol/L之檸檬酸鈉，將鍍鎳液(2)(pH8.0)之組成變更為0.07 mol/L之硫酸鎳、0.02 mol/L之錫酸鈉三水合物、0.3 mol/L之氯化鈦(III)、及0.10 mol/L之葡萄糖酸鈉，並且將導電層之厚度自0.1 μm變更至0.06 μm，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例15) 僅粒徑與上述基材粒子A不同，準備粒徑為2.2 μm之基材粒子B。將上述基材粒子A變更為上述基材粒子B，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例16) 僅粒徑與上述基材粒子A不同，準備粒徑為10.0 μm之基材粒子C。將上述基材粒子A變更為上述基材粒子C，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例17) 向安裝有攪拌機及溫度計之500 mL之反應容器內放入300 g之0.13重量%之氨水溶液。其次，向反應容器內之氨水溶液中緩慢添加4.1 g之甲基三甲氧基矽烷、19.2 g之乙烯基三甲氧基矽烷、及0.7 g之矽酮烷氧基低聚物(信越化學工業公司製造之「X-41-1053」)之混合物。於一面攪拌，一面使之進行水解及縮合反應後，添加2.4 mL之25重量%氨水溶液，之後自氨水溶液中將粒子單離，於氧分壓10-17 atm，350℃下將所獲得之粒子焙燒2小時，從而獲得粒徑為3.0 μm之有機無機混成粒子(基材粒子D)。將上述基材粒子A變更為上述基材粒子D，除此以外，以與實施例3相同之方式獲得導電性粒子。 (實施例18) 導電部之外表面之總表面積100%中，將有突起之部分之表面積自70%變更至25%，除此以外，以與實施例1相同之方式獲得導電性粒子。 (實施例19) 於安裝有四口可分離式蓋、攪拌葉、三向旋塞、冷卻管及溫度探針之1000 mL之可分離式燒瓶中，以固形物成分率成為5重量%之方式將包含100 mmol之甲基丙烯酸甲酯、1 mmol之N,N,N-三甲基-N-2-甲基丙烯醯氧基乙基氯化銨、及1 mmol之2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽之單體組合物稱取至離子交換水中。其後，以200 rpm進行攪拌，於氮氣環境下以70℃進行聚合24小時。於反應結束後，進行冷凍乾燥，獲得於表面具有銨基，且平均粒徑為220 nm及CV值為10%之絕緣性粒子。於超音波照射下使絕緣性粒子分散於離子交換水中，從而獲得絕緣性粒子之10重量%水分散液。使10 g之於實施例1中所獲得之導電性粒子分散於500 mL之離子交換水中，並添加4 g之絕緣性粒子之水分散液，於室溫下攪拌6小時。於利用3 μm之篩網過濾器進行過濾後，進而以甲醇進行洗淨，並使其乾燥，從而獲得附著有絕緣性粒子之導電性粒子。利用掃描型電子顯微鏡(SEM)進行觀察，結果於導電性粒子之表面僅形成1層絕緣性粒子之被覆層。藉由圖像解析算出絕緣性粒子相對於自導電性粒子之中心起2.5 μm之面積(即，絕緣性粒子之粒徑之投影面積)之被覆面積，結果被覆率為30%。 (比較例1) 將鍍鎳液(2)之錫酸鈉三水合物之添加量自0.03 mol/L變更至0.10 mol/L，並且將鍍鎳液(2)之葡萄糖酸鈉之添加量自0.15 mol/L變更至0.35 mol/L，除此以外，以與實施例1相同之方式獲得導電性粒子。 (比較例2) 向鍍鎳液(1)中添加0.04 mol/L之錫酸鈉三水合物及0.20 mol/L之葡萄糖酸鈉，除此以外，以與比較例1相同之方式獲得導電性粒子。 (評價) (1)包含鎳之導電層之整體中之鎳、錫及銦之平均含量 向5 mL之60%硝酸與10 mL之37%鹽酸之混合液中加入5 g之導電性粒子，使導電層完全溶解，獲得溶液。使用所獲得之溶液，利用高頻電感耦合電漿離子源質譜分析裝置(日立製作所公司製造之「ICP-MS」)對鎳、錫及銦之含量進行分析。再者，除鎳、錫及銦以外之含量為磷或硼。 (2)包含鎳之導電層之厚度方向上之鎳、錫及銦之平均含量 對包含鎳之導電層之厚度方向上之鎳、錫及銦之含量之分佈進行測定。 使用聚焦離子束，製作所獲得之導電性粒子之薄膜切片。使用電場輻射型穿透式電子顯微鏡(日本電子公司製造之「JEM-2010FEF」)，利用能量分散型X射線分析裝置(EDS)對包含鎳之導電層之厚度方向上之鎳、錫及銦之含量進行測定。根據其結果，求出包含鎳之導電層之自內表面起朝向外側至厚度1/2之上述區域(R1)(內表面側之厚度50%的區域)、包含鎳之導電層之自外表面起朝向內側至厚度1/2之上述區域(R2)(外表面側之厚度50%的區域)、包含鎳之導電層之自外表面起朝向內側至厚度1/4之上述區域(R3)(外表面側之厚度25%的區域)、及包含鎳之導電層之自距外表面朝向內側為厚度1/4之位置起至厚度1/2位置之間的上述區域(R4)(自距外表面側為厚度25%之位置起至厚度50%之位置之間的區域)中之鎳、錫及銦之平均含量。再者，除鎳、錫及銦以外之含量為磷或硼。又，藉由上述測定，獲得包含鎳之導電層之厚度方向上之鎳、錫及銦之含量的分佈結果。根據該結果獲得上述區域(R3)中之錫與銦之合計之含量的最大值。 (3)導電性粒子之導電層之熔點 使用示差掃描熱量計(Yamato Scientific公司製造之「DSC-6300」)對所獲得之導電性粒子之導電層之熔點進行測定。其結果為，實施例中之導電層之熔點為300℃以上。 (4)導電性粒子之10%K值 使用微小壓縮試驗機(Fischer公司製造之「Fischerscope H-100」)對所獲之導電性粒子之10%K值進行測定。 (5)導電性粒子之體積電阻率 使用三菱化學公司製造之「粉體電阻率測定系統」對所獲之導電性粒子之體積電阻率進行測定。 (6)連接電阻A(初期) 連接構造體之製作： 調配20重量份之作為熱硬化性化合物之環氧化合物(Nagase chemteX Corporation.製造之「EP-3300P」)、15重量份之作為熱硬化性化合物之環氧化合物(DIC公司製造之「EPICLON HP-4032D」)、5重量份之作為熱硬化劑之熱陽離子產生劑(三新化學公司製造之San-Aid「SI-60」)、及20重量份之作為填料之氧化矽(平均粒徑0.25 μm)，進而以調配物100重量%中之含量成為10重量%之方式添加所獲得之導電性粒子，之後使用行星式攪拌機以2000 rpm攪拌5分鐘，藉此獲得各向異性導電膏。 準備於上表面具有L/S為20 μm/20 μm之Al-Ti 4%電極圖案(Al-Ti 4%電極厚度1 μm)之玻璃基板。又，準備於下表面具有L/S為20 μm/20 μm之金電極圖案(金電極厚度20 μm)之半導體晶片。 以成為厚度20 μm之方式將剛製作後之各向異性導電膏塗佈於上述玻璃基板之上表面，而形成各向異性導電材料層。其次，以電極彼此對向之方式將上述半導體晶片積層於各向異性導電材料層之上表面。其後，一面以各向異性導電材料層之溫度成為170℃之方式調整頭部之溫度，一面使加壓加熱頭載置於半導體晶片之上表面，施加2.5 MPa之壓力，於170℃下使各向異性導電材料層硬化，從而獲得連接構造體。 連接電阻之測定： 利用四端子法對所獲得之連接構造體之對向之電極間之連接電阻A進行測定。又，按照下述基準判定連接電阻A。 [連接電阻A之評價基準] 〇〇〇：連接電阻A為2.0 Ω以下 〇〇：連接電阻A超過2.0 Ω且為3.0 Ω以下 〇：連接電阻A超過3.0 Ω且為5.0 Ω以下 △：連接電阻A超過5.0 Ω且為10 Ω以下 ×：連接電阻A超過10 Ω (7)連接電阻B(酸之影響後) 將所獲得之導電性粒子浸於5%之硫酸水溶液中30分鐘。其後，藉由過濾而取出粒子，並進行水洗，進行乙醇置換放置10分鐘使粒子乾燥，藉此獲得暴露於酸之導電性粒子。使用所獲得之導電性粒子以與上述(6)相同之方式製作連接構造體，並以與連接電阻A相同之方式測定連接電阻B。又，按照下述基準判定連接電阻B。 [連接電阻B之評價基準] 〇〇〇：連接電阻B為連接電阻A之1倍以上且未達1.5倍 〇〇：連接電阻B為連接電阻A之1.5倍以上且未達2倍 〇：連接電阻B為連接電阻A之2倍以上且未達5倍 △：連接電阻B為連接電阻A之5倍以上且未達10倍 ×：連接電阻B為連接電阻A之10倍以上 (8)連接電阻C(鹼之影響後) 將所獲得之導電性粒子浸於5%之氫氧化鈉水溶液中30分鐘。其後，藉由過濾而取出粒子，並進行水洗，進行乙醇置換放置10分鐘使粒子乾燥，藉此獲得暴露於鹼之導電性粒子。使用所獲得之導電性粒子以與上述(6)相同之方式製作連接構造體，並以與連接電阻A相同之方式測定連接電阻C。又，按照下述基準判定連接電阻C。 [連接電阻C之評價基準] 〇〇〇：連接電阻C為連接電阻A之1倍以上且未達1.5倍 〇〇：連接電阻C為連接電阻A之1.5倍以上且未達2倍 〇：連接電阻C為連接電阻A之2倍以上且未達5倍 △：連接電阻C為連接電阻A之5倍以上且未達10倍 ×：連接電阻C為連接電阻A之10倍以上 (9)凝聚狀態 將10重量份之雙酚A型環氧樹脂(三菱化學公司製造之「Epikote 1009」)、40重量份之丙烯酸系橡膠(重量平均分子量約80萬)、200重量份之甲基乙基酮、50重量份之微膠囊型硬化劑(旭化成化學公司製造之「HX3941HP」)、及2重量份之矽烷偶合劑(東麗道康寧聚矽氧公司製造之「SH6040」)混合，以含量成為3重量%之方式添加導電性粒子，並使之分散，從而獲得各向異性導電材料。再者，導電性粒子使用在連接電阻A、連接電阻B、連接電阻C中使用之3個條件之粒子，製作3種各向異性導電材料。 將所獲得之3種各向異性導電材料於25℃下保管72小時。於保管後，評價於各向異性導電材料中凝聚之導電性粒子是否沈澱。按照以下之基準判定凝聚狀態。 [凝聚狀態之判定基準] 〇：於全部之3種各向異性導電材料中，凝聚之導電性粒子未沈澱 △：僅於1種各向異性導電材料中，凝聚之導電性粒子沈澱 ×：於2種以上之各向異性導電材料中，凝聚之導電性粒子沈澱 將結果示於下述表1～3。   [表1]

Figure 106104056-A0304-0001
[表2]
Figure 106104056-A0304-0002
 [表3]
Figure 106104056-A0304-0003
 Hereinafter, the details of the present invention will be described. (Electroconductive particle) The electroconductive particle of this invention is equipped with the electrically conductive layer which arrange|positions on the surface of this substrate particle and nickel which is a substrate particle. In addition, in the conductive particles of the present invention, the conductive layer containing nickel includes nickel and an alloy layer of at least one of tin and indium. In the conductive particles of the present invention, the total average content of tin and indium is less than 5% by weight in 100% by weight of the region from the outer surface toward the inner side to the thickness 1/2 of the conductive layer containing nickel. The conductive particles may be exposed to acid or alkali conditions due to acidic gas or alkaline gas in the atmosphere, or acidic or alkaline components other than the conductive particles contained in the conductive material. By adopting the above-mentioned structure in the conductive particles of the present invention, corrosion of the conductive layer containing nickel can be suppressed in the presence of either acid or alkali. Even if the above-mentioned conductive particles are exposed to the presence of acid or alkali, corrosion of the conductive layer containing nickel is not likely to occur, so the performance as conductive particles can be maintained high. In the present invention, even in the presence of acid, corrosion of the conductive layer containing nickel can be suppressed, and further, the corrosion of the conductive layer containing nickel in the presence of alkali can be suppressed. In addition, since the corrosion of the conductive layer containing nickel can be suppressed, when the conductive particles of the present invention are used to electrically connect the electrodes to obtain a connected structure, even if the conductive particles before connecting the electrodes are exposed to acid Or in the presence of alkali, the connection resistance can be kept low. In addition, since corrosion of the conductive layer containing nickel can be suppressed, even if the connection structure is exposed to the presence of acid or alkali, the connection resistance can be maintained low. Furthermore, by adopting the above-mentioned structure in the conductive particles of the present invention, the connection reliability between electrodes under high humidity can also be improved. Furthermore, by adopting the above-mentioned constitution in the conductive particles of the present invention, it is possible to suppress aggregation of the conductive particles. By suppressing aggregation of conductive particles, the connection resistance between electrodes can also be effectively reduced. Furthermore, in the conductive particles of the present invention, since the conductive layer containing nickel contains at least one of tin and indium, the strong magnetic properties of nickel can be suppressed, and the effect of suppressing aggregation due to magnetism can be obtained. Therefore, a plurality of conductive particles can be efficiently arranged on the electrode. Therefore, when the electrodes are electrically connected, the connection reliability and conduction reliability between the electrodes can be further improved. Furthermore, it is possible to prevent electrical connection between electrodes adjacent to each other in the lateral direction that cannot be connected, and to further improve insulation reliability. In addition, the conductive particles of the present invention are conductive because the total average content of tin and indium in 100% by weight of the region from the outer surface toward the inner side to the thickness 1/2 of the conductive layer containing nickel is less than 5% by weight. The layer is not easy to become brittle, and it is not easy to cause corrosion of the conductive layer in the presence of acid or alkali, so it can also inhibit the aggregation of conductive particles accompanying the corrosion reaction of the conductive layer. From the viewpoint of further improving the reliability of the connection between the electrodes, the total average content of tin and indium in 100% by weight of the entire conductive layer containing nickel is preferably 1% by weight or more, more preferably 2% by weight or more , And preferably less than 5% by weight, more preferably less than 5% by weight. In addition, when the total average content of tin and indium is less than 5% by weight in the total 100% by weight of the conductive layer containing nickel, the conductive layer tends to be less brittle. Therefore, when the total average content of tin and indium in the total 100% by weight of the conductive layer containing nickel is less than 5% by weight, the corrosion of the conductive layer in the presence of acid or alkali is less likely to occur, and the conductive layer can be more Effectively maintain low connection resistance after exposure to acid or alkali. In addition, when the total average content of tin and indium is less than 5% by weight in the total 100% by weight of the conductive layer containing nickel, the specific resistance of the conductive layer tends not to rise easily, and it is not easy to cause The rupture of the conductive layer caused by the compression during the indirect connection can effectively keep the connection resistance low. From the viewpoint of further improving the adhesion between the substrate particles and the conductive layer containing nickel, and further improving the connection reliability between the electrodes, the conductive layer containing nickel is from the inner surface toward the outside to the thickness of 1/2 In 100% by weight of the region (R1), the total average content of tin and indium is preferably 5% by weight or less, more preferably less than 5% by weight, still more preferably 3% by weight or less, and particularly preferably 2% by weight the following. The above-mentioned area (R1) is the area on the inner side of the conductive layer 3 containing nickel than the dotted line L1 in FIG. 4(a). In 100% by weight of the area (R2) from the outer surface to the inner side of the thickness 1/2 of the conductive layer containing nickel, the total average content of tin and indium is less than 5% by weight. From the viewpoint of further improving the reliability of the connection between the electrodes, in the total 100% by weight of the conductive layer containing nickel, the conductive layer containing nickel extends from the outer surface toward the inner side to the region (R2) of thickness 1/2 In 100% by weight, the total average content of tin and indium is preferably 3% by weight or less, more preferably 2% by weight or less. The above-mentioned area (R2) is the area outside the dotted line L1 of the conductive layer 3 containing nickel in FIG. 4(a). The total average content of tin and indium in the above-mentioned region (R1) may be less than the total average content of tin and indium in the above-mentioned region (R2), or it may be equal to the total of tin and indium in the above-mentioned region (R2) The average content is the same, and may be more than the total average content of tin and indium in the above-mentioned region (R2). From the viewpoint of further improving the adhesion between the substrate particles and the conductive layer containing nickel, further improving the connection reliability between the electrodes, and further suppressing the corrosion of the conductive particles due to acid or alkali, it is preferably The total average content of tin and indium in the above region (R1) is less than the total average content of tin and indium in the above region (R2). From the viewpoint of further improving the adhesion between the substrate particles and the conductive layer containing nickel, and further improving the connection reliability between the electrodes, the conductive layer containing nickel is from the outer surface toward the inner side to a thickness of 1/4 In 100% by weight of the region (R3), the total average content of tin and indium is preferably 20% by weight or less, more preferably 10% by weight or less. The above-mentioned area (R3) is an area outside the dotted line L2 of the conductive layer 3 containing nickel in FIG. 4(b). From the viewpoint of further improving the adhesion between the substrate particles and the conductive layer containing nickel, and further improving the connection reliability between the electrodes, the conductive layer containing nickel is 1/4 of the thickness from the outer surface toward the inner side The total average content of tin and indium in 100% by weight of the region (R4) between the position and the thickness 1/2 position is preferably 10% by weight or less, more preferably 1% by weight or less. The above-mentioned area (R4) is the area between the dotted line L1 and the dotted line L2 of the conductive layer 3 containing nickel in FIG. 4(b). From the viewpoint of further improving the adhesion between the substrate particles and the conductive layer containing nickel, further improving the connection reliability between the electrodes, and further suppressing the corrosion of the conductive particles due to acid or alkali, it is preferably The total average content of tin and indium in the aforementioned region (R3) is greater than the total average content of tin and indium in the aforementioned region (R4). In the region (R3), when the region (R3) is viewed as a whole, tin and indium may be unevenly distributed. The above-mentioned region (R3) may have a portion where the total content of tin and indium is relatively large and a portion where the total content of tin and indium is relatively small. In the aforementioned region (R3), unevenness may be observed in the total content of tin and indium. In terms of further improving the adhesion between the substrate particles and the conductive layer containing nickel, further improving the connection reliability between the electrodes, and further suppressing the corrosion of the conductive particles due to acid or alkali, the above-mentioned area ( In R3) 100% by weight, the maximum of the total content of tin and indium is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 50% by weight or less, and more preferably 45% by weight or less . The maximum value of the total content of tin and indium indicates the content in the position where the total content of tin and indium in the region (R3) is the largest. The maximum value of the total content of tin and indium in 100% by weight of the above region (R3) can be measured as follows. Using a focused ion beam, a thin film slice of the obtained conductive particles is made. Using an electric field radiation type transmission electron microscope ("JEM-2010FEF" manufactured by JEOL Ltd.), using an energy dispersive X-ray analyzer (EDS) to analyze the thickness of nickel, tin and indium of the conductive layer containing nickel The content is measured to obtain the distribution result of the content of nickel, tin, and indium in the thickness direction of the conductive layer containing nickel. According to this result, the maximum value of the total content of tin and indium in 100% by weight of the region (R3) can be obtained. In the conductive particles of the present invention, it is preferable that the melting point of the conductive layer containing nickel is 300°C or higher. The conductive layer with a melting point of 300°C or higher and containing nickel generally has a lower average content of tin, so it is different from the solder layer that is usually called solder, and is different from the solder layer with a lower melting point. The upper limit of the melting point of the conductive layer containing nickel is not particularly limited. The melting point of the conductive layer containing nickel may be 3000°C or lower, 2000°C or lower, or 1000°C or lower. The melting point of the conductive layer containing nickel may be 400°C or higher, or 500°C or higher. From the viewpoint of further reducing the connection resistance and further improving the connection reliability between the electrodes, the compressive elastic modulus (10% K value) when the conductive particles are compressed by 10% is preferably 10 N/mm 2 Above, it is more preferably 50 N/mm 2 or more, and more preferably 4000 N/mm 2 or less, and more preferably 3000 N/mm 2 or less. The compression modulus (10% K value) in the conductive particles can be measured as follows. Using a micro-compression tester, the conductive particles are compressed with a cylindrical (50 μm diameter, diamond-made) smooth indenter end surface at 25°C and a maximum test load of 90 mN for 30 seconds. Measure the load value (N) and compression displacement (mm) at this time. The compressive elastic modulus can be obtained from the obtained measured value by the following formula. As the aforementioned micro-compression tester, for example, "Fischerscope H-100" manufactured by Fischer, etc. is used. K value (N/mm 2 )=(3/2 1/2 )・F・S -3/2・R -1/2 F: Load value when conductive particles compress and deform 10% (N) S: Conductive Compression displacement (mm) when the conductive particle is compressed and deformed by 10% R: the radius of the conductive particle (mm) The above-mentioned compression elastic modulus generally and quantitatively indicates the hardness of the conductive particle. By using the above-mentioned compression elastic modulus, it is possible to quantitatively and uniquely express the hardness of the conductive particles. From the viewpoint of further suppressing aggregation of conductive particles and reducing the connection resistance between electrodes more effectively, the volume resistivity of the conductive particles is preferably 0.003 Ω·cm or less. Hereinafter, the present invention will be described in detail while referring to the drawings. Fig. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. The conductive particle 1 shown in FIG. 1 has the base particle 2 and the conductive layer 3 containing nickel. The conductive layer 3 is disposed on the surface of the substrate particle 2. In the first embodiment, the conductive layer 3 is in contact with the surface of the substrate particle 2. The conductive particle 1 is a coating particle in which the surface of the substrate particle 2 is coated with the conductive layer 3. In the conductive particle 1, the conductive layer 3 containing nickel is a single-layer conductive layer. In the conductive particles 1, the conductive layer 3 containing nickel is an alloy layer containing at least one of nickel and tin and indium. The total average content of tin and indium in the 100% by weight of the area from the outer surface toward the inner side to the thickness 1/2 of the conductive layer 3 containing nickel is less than 5% by weight. The conductive particle 1 is different from the following conductive particles 11 and 21 and does not have a core material. The conductive particle 1 does not have protrusions on the surface. The conductive particles 1 are spherical. The conductive layer 3 has no protrusions on the outer surface. In this way, the conductive particles of the present invention may not have protrusions on the conductive surface, or may be spherical. In addition, the conductive particle 1 is different from the following conductive particles 11 and 21 in that it does not have an insulating substance. However, the conductive particles 1 may have an insulating substance arranged on the outer surface of the conductive layer 3. In this case, a conductive layer containing no nickel may be arranged between the conductive layer 3 and the insulating material. In the conductive particle 1, the base particle 2 is in contact with the conductive layer 3 containing nickel. A conductive layer containing no nickel can be arranged between the substrate particles and the conductive layer containing nickel, or a conductive layer containing no nickel can be arranged on the outer surface of the conductive layer containing nickel. Fig. 2 shows a cross-sectional view of conductive particles according to a second embodiment of the present invention. The conductive particle 11 shown in FIG. 2 has a base particle 2, a conductive layer 12 containing nickel, a plurality of core materials 13, and a plurality of insulating materials 14. The conductive layer 12 containing nickel is arranged on the surface of the substrate particle 2 in a manner in contact with the substrate particle 2. In the conductive particles 11, the conductive layer 12 containing nickel is a single-layer conductive layer. In the conductive particles 11, the conductive layer 12 containing nickel is an alloy layer containing at least one of nickel and tin and indium. The total average content of tin and indium in 100% by weight of the area from the outer surface toward the inner side to the thickness 1/2 of the conductive layer 12 containing nickel is less than 5% by weight. The conductive particle 11 has a plurality of protrusions 11a on the conductive surface. The conductive layer 12 containing nickel has a plurality of protrusions 12a on the outer surface. A plurality of core materials 13 are arranged on the surface of the substrate particle 2. A plurality of core materials 13 are embedded in the conductive layer 12 containing nickel. The core material 13 is arranged inside the protrusions 11a and 12a. The conductive layer 12 containing nickel coats a plurality of core materials 13. The outer surface of the conductive layer 12 containing nickel is raised by a plurality of core materials 13, thereby forming protrusions 11a and 12a. The conductive particles 11 have an insulating substance 14 arranged on the outer surface of the conductive layer 12 containing nickel. At least a part of the area of the outer surface of the conductive layer 12 containing nickel is covered by the insulating material 14. The insulating substance 14 is formed of an insulating material and is an insulating particle. In this way, the conductive particle of the present invention may have an insulating substance arranged on the outer surface of the conductive layer. However, the conductive particles of the present invention may not necessarily have an insulating substance. Fig. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention. The conductive particle 21 shown in FIG. 3 has a base particle 2, a conductive layer 22 containing nickel, a plurality of core materials 13, and a plurality of insulating materials 14. As a whole, the conductive layer 22 containing nickel has a first conductive layer 22A on the side of the substrate particle 2 and a second conductive layer 22B on the side opposite to the side of the substrate particle 2. In the conductive particles 11 and the conductive particles 21, only the conductive layer is different. That is, in the conductive particle 11, the conductive layer 12 of a one-layer structure is formed, and in contrast to this, in the conductive particle 21, the 1st conductive layer 22A and the 2nd conductive layer 22B of a two-layer structure are formed. The first conductive layer 22A and the second conductive layer 22B are formed as different conductive layers. The first conductive layer 22A is arranged on the surface of the substrate particle 2. The first conductive layer 22A is arranged between the substrate particles 2 and the second conductive layer 22B. The first conductive layer 22A is in contact with the substrate particles 2. The second conductive layer 22B is in contact with the first conductive layer 22A. Therefore, the first conductive layer 22A is arranged on the surface of the substrate particle 2, and the second conductive layer 22B is arranged on the surface of the first conductive layer 22A. The conductive particle 21 has a plurality of protrusions 21a on the conductive surface. The conductive layer 22 has a plurality of protrusions 22a on the outer surface. The first conductive layer 22A has a plurality of protrusions 22Aa on the outer surface. The second conductive layer 22B has a plurality of protrusions 22Ba on the outer surface. In the conductive particles 21, the conductive layer 22 containing nickel is a two-layer conductive layer. In the conductive particles 21, the conductive layer 22 containing nickel is an alloy layer containing at least one of nickel and tin and indium. Therefore, each of the first conductive layer 22A and the second conductive layer 22B is an alloy layer containing at least one of nickel and tin and indium. The total average content of tin and indium in 100% by weight of the area from the outer surface toward the inner side to the thickness 1/2 of the conductive layer 22 containing nickel is less than 5% by weight. Hereinafter, other details of the conductive particles will be described. (Substrate particles) Examples of the above-mentioned substrate particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles, metal particles, and the like. The substrate particles are preferably substrate particles other than metal particles, and more preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles. The aforementioned substrate particles may have a core and a shell arranged on the surface of the core, or may be core-shell particles. The core may be an organic core, and the shell may be an inorganic shell. The aforementioned substrate particles are more preferably resin particles or organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles. When connecting the electrodes using the conductive particles, after the conductive particles are arranged between the electrodes, the conductive particles are compressed by pressure bonding. If the substrate particles are resin particles or organic-inorganic mixed particles, the conductive particles are easily deformed during the pressure bonding, and the contact area between the conductive particles and the electrode becomes larger. Therefore, the reliability of conduction between the electrodes can be further improved. As the resin for forming the above-mentioned resin particles, various organic substances can be suitably used. Examples of resins used to form the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; polymethacrylic acid Acrylic resins such as methyl and polymethyl acrylate; polycarbonate, polyamide, phenolic formaldehyde resin, melamine-formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenolic resin, melamine resin, benzoguanamine Resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polyether, polyphenylene ether, polyacetal, polyimide, polyamide Amine, polyether ether ketone, polyether agglomerate, divinylbenzene polymer, and divinylbenzene copolymer, etc. As said divinylbenzene copolymer etc., a divinylbenzene-styrene copolymer, a divinylbenzene-(meth)acrylate copolymer, etc. are mentioned. Since it is easy to control the hardness of the resin particles in an appropriate range, the resin used to form the resin particles is preferably polymerized by polymerizing one or more polymerizable monomers with ethylenically unsaturated groups Things. When polymerizing a polymerizable monomer having an ethylenically unsaturated group to obtain the resin particles, examples of the polymerizable monomer having an ethylenically unsaturated group include non-crosslinkable monomers and crosslinkable monomers. body. Examples of the above-mentioned non-crosslinkable monomers include: styrene-based monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride. Monomers; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) ) Lauryl acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, iso-(meth)acrylate, etc. (meth) ) Alkyl acrylate compounds; 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, glycidyl (meth)acrylate and other oxygen atoms ( Meth)acrylate compounds; (meth)acrylonitrile and other nitrile-containing monomers; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acetate, vinyl butyrate , Vinyl laurate, vinyl stearate and other acid vinyl ester compounds; ethylene, propylene, isoprene, butadiene and other unsaturated hydrocarbons; (meth)acrylic acid trifluoromethyl, (meth)acrylic acid five Halogen-containing monomers such as ethyl fluoride, vinyl chloride, vinyl fluoride, chlorostyrene, etc. Examples of the above-mentioned crosslinkable monomers include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and tetramethylolmethane di(meth)acrylate. , Trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol tri(meth)acrylate Meth) acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)butylene glycol di(meth)acrylate, 1,4 -Multifunctional (meth)acrylate compounds such as butanediol di(meth)acrylate; triallyl (iso)cyanurate, triallyl trimellitate, divinylbenzene, diphthalate Allyl ester, diallyl acrylamide, diallyl ether, γ-(meth) acryloxypropyl trimethoxysilane, trimethoxysilyl styrene, vinyl trimethoxysilane, etc. The monomer of silane, etc. The above-mentioned resin particles can be obtained by polymerizing the above-mentioned polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of the method include: suspension polymerization in the presence of a radical polymerization initiator, and the use of non-crosslinked seed particles to swell the monomer and the radical polymerization initiator together. Methods of aggregation, etc. When the above-mentioned substrate particles are inorganic particles or organic-inorganic mixed particles other than metals, examples of the inorganic substances used to form the substrate particles include: silica, alumina, barium titanate, zirconia, carbon black, etc. . The above-mentioned inorganic substance is preferably not a metal. The above-mentioned particles formed of silicon oxide are not particularly limited. Examples include particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinks. After polymer particles are fired as necessary. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin. The aforementioned organic-inorganic hybrid particles are preferably core-shell organic-inorganic hybrid particles having a core and a shell arranged on the surface of the core. The aforementioned core is preferably an organic core. The aforementioned shell is preferably an inorganic shell. From the viewpoint of effectively reducing the connection resistance between the electrodes, the substrate particle is preferably an organic-inorganic hybrid particle having an organic core and an inorganic shell arranged on the surface of the organic core. Examples of the material used to form the organic core include the resin used to form the resin particles described above. Examples of the material for forming the above-mentioned inorganic shell include the above-mentioned inorganic substances for forming the substrate particles. The material used to form the above-mentioned inorganic shell is preferably silicon oxide. The inorganic shell is preferably formed by forming a metal alkoxide on the surface of the core by a sol-gel method into a shell, and then sintering the shell. The aforementioned metal alkoxide is preferably silane alkoxide. The above-mentioned inorganic shell is preferably formed of a silanate. The particle diameter of the above-mentioned core is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, particularly preferably 20 μm or less, most preferably It is preferably 10 μm or less. If the particle diameter of the above-mentioned core is more than the above-mentioned lower limit and below the above-mentioned upper limit, conductive particles more suitable for electrical connection between electrodes can be obtained, and the substrate particles can be preferably used for the purpose of conductive particles. For example, if the particle size of the core is more than the lower limit and less than the upper limit, when the conductive particles are used to connect the electrodes, the contact area between the conductive particles and the electrode is sufficiently increased, and the conductive portion can be formed It is not easy to form agglomerated conductive particles. In addition, the gap between the electrodes connected via conductive particles does not become too large, and it is possible to make it difficult to peel off the conductive portion from the surface of the substrate particle. The particle size of the nucleus refers to the diameter when the nucleus is a true spherical shape, and refers to the maximum diameter when the nucleus is a shape other than the true spherical shape. In addition, the particle diameter of the core refers to the average particle diameter obtained by measuring the core with any particle diameter measuring device. For example, a particle size distribution measuring machine using the principles of laser light scattering, resistance change, image analysis after shooting, etc. can be used. The thickness of the above-mentioned shell is preferably 100 nm or more, more preferably 200 nm or more, and preferably 5 μm or less, and more preferably 3 μm or less. If the thickness of the shell is at least the above lower limit and below the above upper limit, conductive particles more suitable for electrical connection between electrodes can be obtained, and the substrate particles can be preferably used for the purpose of conductive particles. The thickness of the aforementioned shell is the average thickness per one substrate particle. Through the control of the sol-gel method, the thickness of the shell can be controlled. In the case where the aforementioned substrate particles are metal particles, the metal used as the material of the metal particles includes silver, copper, nickel, silicon, gold, and titanium. However, it is preferable that the aforementioned substrate particles are not metal particles, and it is preferable that they are not copper particles. The particle size of the substrate particles is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more, particularly preferably 2 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less , Further more preferably 300 μm or less, still more preferably 50 μm or less, still more preferably 30 μm or less, particularly preferably 5 μm or less, and most preferably 3 μm or less. If the particle size of the substrate particles is greater than or equal to the above lower limit, the contact area between the conductive particles and the electrode becomes larger. Therefore, the reliability of conduction between the electrodes can be further improved, and the gap between the electrodes connected via the conductive particles can be further reduced. Connect resistance. Furthermore, when a conductive layer is formed on the surface of the substrate particle by electroless plating, it is possible to hardly form agglomerated conductive particles. If the particle size of the substrate particles is equal to or less than the above upper limit, the conductive particles can be easily compressed sufficiently, the connection resistance between the electrodes can be further reduced, and the interval between the electrodes can be made smaller. The particle diameter of the aforementioned substrate particle indicates the diameter when the substrate particle is a true spherical shape, and indicates the maximum diameter when the substrate particle is not a true spherical shape. The particle diameter of the substrate particles is particularly preferably 2 μm or more and 5 μm or less. If the particle size of the substrate particles is in the range of 2 to 5 μm, the gap between the electrodes can be made smaller, and even if the thickness of the conductive layer is thickened, smaller conductive particles can be obtained. (Conductive layer) The conductive particle of the present invention includes a substrate particle and a conductive layer containing nickel arranged on the surface of the substrate particle. The conductive layer containing nickel contains at least one of nickel, and tin and indium. The total average content of tin and indium in the 100% by weight of the region from the outer surface toward the inner side to the thickness 1/2 of the conductive layer containing nickel is less than 5% by weight. Regarding the conductive layer containing nickel, the conductive layer containing nickel may be described as the conductive layer X in the column of (conductive layer) below. In the above-mentioned conductive layer X, the conductive layer not containing nickel is not included, and the conductive layer portion not containing nickel is not included. From the viewpoint of effectively improving the conductivity, in 100% by weight of the entire conductive layer X, the higher the average content of nickel, the better. Therefore, in the entire 100% by weight of the conductive layer X, the average content of nickel is preferably 50% by weight or more, more preferably 65% by weight or more, still more preferably 70% by weight or more, and still more preferably 80% by weight or more , And more preferably 85% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more. In 100% by weight of the entire conductive layer X, the average content of nickel is preferably 99% by weight or less, more preferably 98% by weight or less, and still more preferably 97% by weight or less. If the average content of nickel is more than the above lower limit, the connection resistance between the electrodes can be further reduced. In addition, when there is less oxide film on the surface of the electrode or the conductive layer, the higher the average content of nickel, the lower the connection resistance between the electrodes. The method for measuring the contents of nickel, tin, and indium in the conductive layer containing nickel (conductive layer X) can use various known analysis methods, and is not particularly limited. It can be measured using a high-frequency inductively coupled plasma emission spectrometer ("ICP-AES" manufactured by Horiba), or a fluorescent X-ray analyzer ("EDX-800HS" manufactured by Shimadzu). The contents of nickel, tin, and indium in each region in the thickness direction of the conductive layer X can be measured using an electric field radiation type transmission electron microscope ("JEM-2010FEF" manufactured by JEOL Ltd.). The thickness of the entire conductive layer X is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and preferably 1 μm or less, and more preferably 0.3 μm or less. If the thickness of the entire conductive layer X is greater than or equal to the aforementioned lower limit and less than or equal to the aforementioned upper limit, sufficient conductivity can be obtained, the conductive particles will not become too hard, and the conductive particles can be sufficiently deformed when the electrodes are connected. The thickness of the entire conductive layer X is particularly preferably 0.05 μm or more and 0.3 μm or less. More preferably, the particle size of the substrate particles is 2 μm or more and 5 μm or less, and the thickness of the entire conductive layer X is 0.05 μm or more and 0.3 μm or less. In this case, the conductive particles can be better used for the purpose of flowing a larger current. Furthermore, when the conductive particles are compressed and the electrodes are connected, damage to the electrodes can be further suppressed. The thickness of the conductive layer X can be measured by observation of the cross-section of the conductive particles, for example, using a transmission electron microscope ("JEM-2100" manufactured by JEOL Ltd.). The conductive layer X may also include metals other than nickel, tin, and indium. Examples of metals other than nickel, tin, and indium in the conductive layer X include gold, silver, copper, platinum, zinc, iron, lead, aluminum, cobalt, palladium, chromium, titanium, antimony, and bismuth. , Thallium, germanium, cadmium, silicon, tungsten and molybdenum. These metals may use only 1 type, and may use 2 or more types together. In the case where multiple metals are included in the conductive layer X, multiple metals may also be alloyed. The method of forming the conductive layer X on the surface of the substrate particle is not particularly limited. As a method of forming a conductive layer, for example, a method using electroless plating, a method using electroplating, a method using physical vapor deposition, and coating metal powder or solder paste containing metal powder and a binder on the substrate particles or Other surface methods of conductive layer, etc. Since the formation of the conductive layer is relatively simple, it is preferable to use an electroless plating method. Examples of the method using physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. The particle size of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 100 μm or less, more preferably 20 μm or less, still more preferably 5 μm or less, and particularly preferably 3 μm or less . If the particle size of the conductive particles is more than the above lower limit and below the upper limit, when the above conductive particles are used to connect the electrodes, the contact area between the conductive particles and the electrode can be sufficiently increased, and when the conductive layer is formed, Can not easily form agglomerated conductive particles. In addition, the gap between the electrodes connected via the conductive particles does not become too large, and it is possible to prevent the conductive layer from peeling off the surface of the substrate particles. The particle diameter of the above-mentioned conductive particle represents the diameter when the conductive particle is a true spherical shape, and represents the maximum diameter when the conductive particle is not a true spherical shape. The conductive layer X may be formed of one layer, or may be formed of a plurality of layers. That is, the said conductive layer X may have a laminated structure of 2 or more layers. In addition to the conductive layer X, the conductive particles may include a gold layer, a nickel layer, a palladium layer, a copper layer, a silver layer, or an alloy layer containing tin and silver as the outermost layer. As a method of controlling the contents and average contents of nickel, tin, and indium in each region of the conductive layer X, for example, a method of controlling the pH of the nickel plating solution when the conductive layer X is formed by electroless nickel plating, The method of adjusting the concentration of tin and indium in the nickel plating solution and the method of adjusting the concentration of nickel in the nickel plating solution, etc. In the method of forming by electroless plating, a catalytic step and an electroless plating step are generally performed. Hereinafter, an example of a method of forming a plating layer containing nickel on the surface of a resin particle by electroless plating will be described. In the above-mentioned catalystization step, a catalyst used as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles. As a method of forming the above-mentioned catalyst on the surface of the resin particle, for example, the following method can be cited: after adding the resin particle to a solution containing palladium chloride and tin chloride, the surface of the resin particle is treated with an acid solution or an alkali solution. Activation is to precipitate palladium on the surface of the resin particles; and after adding the resin particles to the solution containing palladium sulfate, the surface of the resin particles is activated by the solution containing a reducing agent to precipitate palladium on the surface of the resin particles. In the above electroless plating step, a nickel plating bath containing at least one of a compound containing nickel, the reducing agent, a complexing agent, and a compound containing tin and a compound containing indium is suitably used. By impregnating the resin particles in the nickel plating bath, nickel can be deposited on the surface of the resin particles on which the catalyst is formed, and the above-mentioned conductive layer X can be formed. In addition, when nickel is deposited, at least one of tin and indium is made to eutectoid, thereby forming an alloy plating layer containing nickel and at least one of tin and indium. Examples of the nickel-containing compound include nickel sulfate and nickel chloride. The above-mentioned nickel-containing compound is preferably a nickel salt. As said reducing agent, sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, hydrazine monohydrate, hydrazine sulfate, titanium (III) chloride, etc. are mentioned. Examples of the tin-containing compounds include sodium stannate trihydrate, potassium stannate trihydrate, tin sulfate (II), tin chloride (IV) pentahydrate, tin chloride (II) dihydrate, etc. . Examples of the above-mentioned indium-containing compounds include indium acetate (III), indium sulfate (III) trihydrate, indium chloride (III), indium hydroxide (III), and indium nitrate (III). The above-mentioned complexing agents include: monocarboxylic acid complexing agents such as sodium acetate and sodium propionate; dicarboxylic acid complexing agents such as disodium malonate; tricarboxylic acid complexing agents such as disodium succinate; lactic acid, DL-apple Acid, sodium tartrate, sodium citrate, sodium gluconate and other hydroxy acid complexing agents; glycine, EDTA (ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid) and other amino acid complexing agents; ethylenediamine and other amine complexing agents Mixtures; organic acid complexing agents such as maleic acid; and salts of these. It is preferable to use at least one complexing agent selected from the group consisting of the complexing agents listed here. (Core material) The above-mentioned conductive particles preferably have protrusions on the conductive surface. The aforementioned conductive layer preferably has protrusions on the outer surface. The above-mentioned protrusions are preferably plural. Many oxide films are formed on the surfaces of the electrodes connected by the above-mentioned conductive particles. Furthermore, many oxide films are formed on the surface of the conductive layer of the said electroconductive particle. By using the above-mentioned conductive particles having protrusions, after the conductive particles are arranged between the electrodes, they are pressure-bonded, thereby effectively removing the oxide film by the protrusions. Therefore, the electrode and the conductive particle can be brought into contact with each other more reliably, and the connection resistance between the electrodes can be reduced. Furthermore, when the conductive particles have an insulating substance on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the protrusions of the conductive particles effectively eliminate the conductivity Insulating material or binder resin between particles and electrodes. Therefore, the reliability of conduction between the electrodes can be improved. In addition, if the conductive particles have protrusions on the outer surface of the conductive layer, the area where the conductive particles contact each other can be reduced. Therefore, aggregation of a plurality of the above-mentioned conductive particles can be suppressed. Therefore, it is possible to prevent electrical connection between unconnectable electrodes, and to further improve insulation reliability. By embedding the core material in the conductive layer, it is easy to make the conductive layer have a plurality of protrusions on the outer surface. However, it is not necessary to use a core material to form protrusions on the outer surface of the conductive particles and the conductive layer. It is preferable not to use a core material. The conductive particles preferably do not have an outer surface for forming the conductive layer. The core material of the uplift. However, the said electroconductive particle may have a core substance which bulges the outer surface of the said electroconductive layer. When the above-mentioned core material is used, it is preferable that the above-mentioned core material is disposed inside or inside the conductive layer. As a method of forming the above-mentioned protrusions, a method of forming a conductive layer by electroless plating after the core material is attached to the surface of the substrate particle; after forming a conductive layer on the surface of the substrate particle by electroless plating, using A method of attaching a core material to form a conductive layer by electroless plating; and a method of adding a core material in the middle of forming a conductive layer on the surface of the substrate particle by electroless plating. As a method of disposing the core material on the surface of the substrate particles, for example, adding the core material to the dispersion of the substrate particles, for example, the core material is gathered and attached to the substrate particles by Van der Waals force. Surface method; and a method of adding a core material to a container with a substrate particle, and attaching the core material to the surface of the substrate particle by using the mechanical action generated by the rotation of the container. In order to easily control the amount of the core material attached, a method of accumulating and attaching the core material to the surface of the substrate particles in the dispersion is preferred. Examples of the material of the aforementioned core material include conductive materials and non-conductive materials. Examples of the above-mentioned conductive substance include conductive non-metals and conductive polymers such as metals, metal oxides, and graphite. As said conductive polymer, polyacetylene etc. are mentioned. Examples of the above-mentioned non-conductive material include silicon oxide, aluminum oxide, barium titanate, and zirconium oxide. In order to effectively remove the oxide film, the core material is preferably harder. Metals are preferred because they can improve conductivity and can effectively reduce connection resistance. The aforementioned core material is preferably metal particles. Regarding the metal as the material of the above-mentioned core substance, the metals listed above as the material of the conductive layer can be suitably used. Specific examples of the material of the aforementioned core material include: barium titanate (Mohs hardness 4.5), nickel (Mohs hardness 5), silicon oxide (silica dioxide, Mohs hardness 6-7), titanium oxide (Mohs hardness 6-7) Hardness 7), zirconia (Mohs hardness 8-9), alumina (Mohs hardness 9), tungsten carbide (Mohs hardness 9), diamond (Mohs hardness 10), etc. The above-mentioned inorganic particles are preferably nickel, silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, tungsten carbide or diamond, more preferably silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, tungsten carbide or diamond, and more preferably oxide Titanium, zirconia, alumina, tungsten carbide or diamond, particularly preferably zirconia, alumina, tungsten carbide or diamond. The Mohs hardness of the material of the core material is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, and particularly preferably 7.5 or more. Examples of the above metal include: gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium; and tin-lead Alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys and tungsten carbide alloys containing two or more metals. Preferably, it is nickel, copper, silver or gold. The metal used to form the core substance may be the same as or different from the metal used to form the conductive portion. The metal used to form the core material preferably includes a metal used to form the conductive portion. The metal used to form the aforementioned core material preferably contains nickel. The shape of the aforementioned core material is not particularly limited. The shape of the aforementioned core material is preferably a block shape. As the core material, for example, a granular block, agglomerate formed by agglomerating a plurality of fine particles, and an amorphous block are mentioned. The average diameter (average particle diameter) of the above-mentioned core material is preferably 0.001 μm or more, more preferably 0.05 μm or more, and preferably 0.9 μm or less, and more preferably 0.2 μm or less. If the average diameter of the core material is greater than or equal to the lower limit and less than the upper limit, the connection resistance between the electrodes can be effectively reduced. The "average diameter (average particle diameter)" of the above-mentioned core material means the number average diameter (number average particle diameter). The average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope, and calculating the average value. The number of the protrusions per one of the conductive particles is preferably 3 or more, more preferably 5 or more. The upper limit of the number of the aforementioned protrusions is not particularly limited. The upper limit of the number of the above-mentioned protrusions can be appropriately selected in consideration of the particle size of the conductive particles, etc. The average height of the plurality of the protrusions is preferably 0.001 μm or more, more preferably 0.05 μm or more, and preferably 0.9 μm or less, and more preferably 0.2 μm or less. If the average height of the protrusions is more than the lower limit and less than the upper limit, the connection resistance between the electrodes can be effectively reduced. (Insulating material) The conductive particles preferably include an insulating material arranged on the surface of the conductive layer. In this case, if the above-mentioned conductive particles are used for the connection between electrodes, it is possible to further prevent short circuits between adjacent electrodes. Specifically, when a plurality of conductive particles are in contact, since an insulating material exists between the plurality of electrodes, it is possible to prevent short circuits between the electrodes adjacent in the lateral direction instead of between the upper and lower electrodes. In addition, when connecting the electrodes, by pressing the conductive particles with two electrodes, the insulating material between the conductive layer of the conductive particles and the electrodes can be easily removed. When the conductive particle has a plurality of protrusions on the outer surface of the conductive layer, the insulating material between the conductive layer and the electrode of the conductive particle can be eliminated more easily. In terms of making it easier to remove the insulating material when crimping between electrodes, the insulating material is preferably insulating particles. Specific examples of the insulating resin as the material of the above-mentioned insulating substance include: polyolefin compounds, (meth)acrylate polymers, (meth)acrylate copolymers, block polymers, thermoplastic resins, and thermoplastics Cross-linked resins, thermosetting resins, water-soluble resins, etc. As said polyolefin compound, polyethylene, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, etc. are mentioned. As said (meth)acrylate polymer, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, etc. are mentioned. As the above-mentioned block polymer, polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and the Hydride and so on. As said thermoplastic resin, a vinyl polymer, a vinyl copolymer, etc. are mentioned. As said thermosetting resin, epoxy resin, phenol resin, melamine resin, etc. are mentioned. As said water-soluble resin, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, methyl cellulose, etc. are mentioned. Preferably, it is a water-soluble resin, and more preferably is polyvinyl alcohol. As a method of disposing an insulating substance on the outer surface of the conductive layer, a chemical method, a physical or mechanical method, etc. can be cited. Examples of the above-mentioned chemical methods include interfacial polymerization, suspension polymerization in the presence of particles, and emulsion polymerization. Examples of the above-mentioned physical or mechanical methods include methods using spray drying, mixing, electrostatic adhesion, spraying, dipping, and vacuum deposition. As far as the insulating material is not easily removed, it is preferable to arrange the insulating material on the surface of the conductive layer via a chemical bond. The outer surface of the conductive layer and the surface of the insulating particles may be respectively coated with a compound having a reactive functional group. The outer surface of the conductive layer and the surface of the insulating particle may not be directly chemically bonded, or may be chemically bonded indirectly by a compound having a reactive functional group. After introducing the carboxyl group to the outer surface of the conductive layer, the carboxyl group can also be chemically bonded to the functional group on the surface of the insulating particle via a polymer electrolyte such as polyethyleneimine. The average diameter (average particle diameter) of the insulating material can be appropriately selected according to the particle diameter and use of the conductive particles. The average diameter (average particle diameter) of the insulating material is preferably 0.005 μm or more, more preferably 0.01 μm or more, and preferably 1 μm or less, and more preferably 0.5 μm or less. If the average diameter of the insulating material is greater than or equal to the lower limit, when the conductive particles are dispersed in the binder resin, it is difficult to make the conductive layers of the conductive particles contact each other. If the average diameter of the insulating particles is equal to or less than the above upper limit, the pressure may not be too high when the electrodes are connected, and the insulating particles between the electrodes and the conductive particles may not be heated to a high temperature. The "average diameter (average particle diameter)" of the above-mentioned insulating material means the number average diameter (number average particle diameter). The average diameter of the insulating material is determined using a particle size distribution measuring device or the like. (Conductive material) The conductive material of the present invention contains the aforementioned conductive particles and a binder resin. The above-mentioned conductive particles are preferably dispersed in a binder resin and used as a conductive material. The aforementioned conductive material is preferably an anisotropic conductive material. The conductive particles and the conductive material are preferably used for electrical connection between electrodes, respectively. The aforementioned conductive material is preferably a material for circuit connection. The above-mentioned binder resin is not particularly limited. A well-known insulating resin can be used as the above-mentioned binder resin. Examples of the above-mentioned binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. The said binder resin may use only 1 type, and may use 2 or more types together. As said vinyl resin, vinyl acetate resin, acrylic resin, styrene resin, etc. are mentioned, for example. As said thermoplastic resin, polyolefin resin, an ethylene-vinyl acetate copolymer, a polyamide resin, etc. are mentioned, for example. As said curable resin, epoxy resin, urethane resin, polyimide resin, unsaturated polyester resin, etc. are mentioned, for example. In addition, the above-mentioned curable resin may be a room temperature curable resin, a thermosetting resin, a light curable resin, or a moisture curable resin. The above-mentioned curable resin may be used in combination with a curing agent. Examples of the above-mentioned thermoplastic block copolymers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and styrene-butadiene-styrene block copolymers. The hydrogenated product of block copolymer, and the hydrogenated product of styrene-isoprene-styrene block copolymer, etc. As said elastomer, a styrene-butadiene copolymer rubber, an acrylonitrile-styrene block copolymer rubber, etc. are mentioned, for example. The conductive material and the binder resin preferably contain a thermoplastic component or a thermosetting component. The conductive material and the binder resin may include a thermoplastic component or a thermosetting component. The conductive material and the binder resin preferably contain a thermosetting component. The above-mentioned thermosetting component preferably contains a curable compound that can be hardened by heating and a thermosetting agent. The thermal hardening agent is preferably a thermal cationic hardening initiator. The above-mentioned curable compound which can be hardened by heating and the above-mentioned thermosetting agent are used in an appropriate mixing ratio in such a way that the above-mentioned binder resin is hardened. If the above-mentioned binder resin contains a thermal cationic curing initiator, it is easy to contain an acid in the cured product. However, by using the conductive particles of the present invention, the connection resistance between the electrodes can be maintained low. In addition to the conductive particles and the binder resin, the conductive material may also include fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, and heat stabilizers. , Light stabilizers, UV absorbers, lubricants, antistatic agents and flame retardants and other additives. The aforementioned conductive materials can be used as conductive pastes, conductive films, and the like. When the above-mentioned conductive material is a conductive film, a film containing no conductive particles may be laminated on the conductive film containing conductive particles. The aforementioned conductive paste is preferably an anisotropic conductive paste. The above-mentioned conductive film is preferably an anisotropic conductive film. In 100% by weight of the conductive material, the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, and more preferably It is 99.99% by weight or less, more preferably 99.9% by weight or less. If the content of the binder resin is greater than or equal to the aforementioned lower limit and less than or equal to the aforementioned upper limit, the conductive particles can be efficiently arranged between the electrodes, and the connection reliability of the connection object members connected by the conductive material can be further improved. In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 80% by weight or less, more preferably 60% by weight or less, and more preferably It is 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less. If the content of the conductive particles is greater than or equal to the aforementioned lower limit and less than or equal to the aforementioned upper limit, the reliability of conduction between electrodes can be further improved. (Connection structure) A connection structure can be obtained by connecting the connection object member using the said electroconductive particle, or the said electroconductive material containing the said electroconductive particle and a binder resin. The above-mentioned connection structure is preferably a connection structure comprising a first connection object member, a second connection object member, and a connecting portion connecting the first and second connection object members, and the material of the connection portion is the present invention Or the conductive material of the present invention comprising the conductive particles and a binder resin. The above-mentioned connection part is preferably formed of the conductive particles of the present invention or formed of the conductive material of the present invention containing the conductive particles and a binder resin. In the case of using conductive particles, the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the above-mentioned conductive particles. In Fig. 5, a front cross-sectional view schematically shows a connected structure using conductive particles according to the first embodiment of the present invention. The connection structure 51 shown in FIG. 5 includes a first connection object member 52, a second connection object member 53, and a connection portion 54 that connects the first and second connection object members 52 and 53. The connection portion 54 is formed by curing a conductive material containing the conductive particles 1. In addition, in FIG. 5, the electroconductive particle 1 is shown as a schematic diagram for the convenience of illustration. Instead of the conductive particles 1, the conductive particles 11, 21, etc. may be used. The first connection object member 52 has a plurality of first electrodes 52a on the surface (upper surface). The second connection object member 53 has a plurality of second electrodes 53a on the surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected by one or more conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1. The manufacturing method of the said connection structure is not specifically limited. As an example of a method of manufacturing the above-mentioned connection structure, a method of disposing the conductive material between the first connection object member and the second connection object member to obtain a laminate, and then heating the laminate And pressurization. The above-mentioned pressurization pressure is about 9.8×10 4 to 4.9×10 6 Pa. The above heating temperature is about 120-220°C. Specific examples of the connection target member include electronic components such as semiconductor wafers, capacitors, and diodes; and circuit boards such as printed circuit boards, flexible printed circuit boards, epoxy glass substrates, and glass substrates. The connection target member is preferably an electronic component. The above-mentioned conductive particles are preferably used for electrical connection of electrodes in electronic parts. Examples of the electrodes provided on the above-mentioned connection target member include metals such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, silver electrodes, SUS (Steel Use Stainless, Japanese stainless steel standards) electrodes, molybdenum electrodes, and tungsten electrodes. electrode. When the connection object member is a flexible printed circuit board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection object member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. Furthermore, when the above-mentioned electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or may be an electrode in which aluminum is laminated on the surface of a metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with trivalent metal elements, zinc oxide doped with trivalent metal elements, and the like. As said trivalent metal element, Sn, Al, Ga, etc. are mentioned. Hereinafter, examples and comparative examples are given to specifically describe the present invention. The present invention is not limited to the following examples. (Example 1) Divinylbenzene copolymer resin particles (base material particle A, "Micropearl SP-203" manufactured by Sekisui Chemical Industry Co., Ltd.) having a particle diameter of 3.0 μm were prepared. An ultrasonic disperser was used to disperse 10 parts by weight of the above-mentioned substrate particles A in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution, and then the substrate particles A were taken out by filtering the solution. Then, the substrate particle A was added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the substrate particle A. After the substrate particle A whose surface has been activated is sufficiently washed with water, it is added to 500 parts by weight of distilled water to disperse it, thereby obtaining a dispersion. Next, it took 3 minutes to add 2 g of Ni particle slurry (average particle size 150 nm) to the above dispersion to obtain a suspension (0) containing substrate particles with attached core material. Also, prepare a nickel plating solution (1) (pH 8.5) containing 0.14 mol/L of nickel sulfate, 0.46 mol/L of dimethylamine borane and 0.2 mol/L of sodium citrate as the nickel plating solution (1) . While stirring the obtained suspension (0) at 60°C, the above-mentioned nickel plating solution (1) was gradually added dropwise to the suspension to perform electroless nickel-boron alloy plating, thereby obtaining a suspension (1). Prepare a nickel plating solution containing 0.14 mol/L nickel sulfate, 0.03 mol/L sodium stannate trihydrate, 0.60 mol/L titanium chloride (III), and 0.15 mol/L sodium gluconate (2) (pH8.0) as the nickel plating solution (2). The temperature of the suspension (1) was set to 70°C, and the nickel plating solution (2) was gradually added dropwise to the suspension (1) to perform electroless nickel-tin alloy plating to obtain a suspension (2) . After that, the particles were taken out by filtering the suspension (2), washed with water, and dried, thereby disposing a conductive layer (thickness 0.1 μm) containing nickel on the surface of the substrate particle A, thereby obtaining a conductive layer on the surface The conductive particles. (Example 2) The 0.03 mol/L sodium stannate trihydrate of the nickel plating solution (2) was changed to 0.04 mol/L indium (III) acetate, except that it was obtained in the same manner as in Example 1 Conductive particles. (Example 3) Except having changed the Ni particle slurry to the alumina particle slurry, it carried out similarly to Example 1, and obtained electroconductive particle. (Example 4) For the formation of protrusions, the Ni particle paste was not used, and adjustments were made by partially changing the precipitation amount when forming the conductive part to form protrusions. Except for this, the conductivity was obtained in the same manner as in Example 1. Sex particles. (Example 5) The 0.60 mol/L titanium chloride (III) of the nickel plating solution (2) was changed to 0.46 mol/L dimethylamine borane, except that it was obtained in the same manner as in Example 1 Conductive particles. (Example 6) The 0.46 mol/L dimethylamine borane of the nickel plating solution (1) was changed to 1.40 mol/L sodium hypophosphite, and the nickel plating solution (2) was chlorinated at 0.60 mol/L Except that titanium (III) was changed to 1.40 mol/L sodium hypophosphite, conductive particles were obtained in the same manner as in Example 1. (Example 7) The 0.46 mol/L dimethylamine borane of the nickel plating solution (1) was changed to 0.60 mol/L titanium(III) chloride, except that it was obtained in the same manner as in Example 1 Conductive particles. (Example 8) To the nickel plating solution (1), 0.02 mol/L of sodium stannate trihydrate and 0.10 mol/L of sodium gluconate were added, except that the conductivity was obtained in the same manner as in Example 1 particle. (Example 9) To the nickel plating solution (1), 0.04 mol/L of sodium stannate trihydrate and 0.20 mol/L of sodium gluconate were added, except that conductive particles were obtained in the same manner as in Example 1. . (Example 10) The addition amount of sodium stannate trihydrate in the nickel plating solution (2) was changed from 0.03 mol/L to 0.05 mol/L, and the addition amount of sodium gluconate in the nickel plating solution (2) was changed from Except for changing 0.15 mol/L to 0.25 mol/L, conductive particles were obtained in the same manner as in Example 1. (Example 11) Add 0.04 mol/L of sodium stannate trihydrate and 0.20 mol/L of sodium gluconate to nickel plating solution (1), and combine the sodium stannate trihydrate of nickel plating solution (2) The addition amount was changed from 0.03 mol/L to 0.05 mol/L, and the addition amount of sodium gluconate in the nickel plating solution (2) was changed from 0.15 mol/L to 0.25 mol/L. Otherwise, the same as in Example 1. In the same way, conductive particles are obtained. (Example 12) The addition amount of sodium stannate trihydrate in the nickel plating solution (2) was changed from 0.03 mol/L to 0.02 mol/L, and 0.02 mol/L of acetic acid was added to the nickel plating solution (2) Except for indium (III), conductive particles were obtained in the same manner as in Example 1. (Example 13) The composition of the nickel plating solution (1) (pH 8.5) was changed to 0.18 mol/L nickel sulfate, 0.66 mol/L dimethylamine borane, and 0.25 mol/L sodium citrate. The composition of the nickel plating bath (2) (pH 8.0) is changed to 0.18 mol/L nickel sulfate, 0.04 mol/L sodium stannate trihydrate, 0.75 mol/L titanium(III) chloride, and 0.19 mol /L of sodium gluconate, and the thickness of the conductive layer was changed from 0.1 μm to 0.15 μm, except that the conductive particles were obtained in the same manner as in Example 1. (Example 14) The composition of the nickel plating solution (1) (pH 8.5) was changed to 0.07 mol/L nickel sulfate, 0.23 mol/L dimethylamine borane, and 0.10 mol/L sodium citrate. The composition of the nickel plating bath (2) (pH 8.0) was changed to 0.07 mol/L nickel sulfate, 0.02 mol/L sodium stannate trihydrate, 0.3 mol/L titanium(III) chloride, and 0.10 mol /L of sodium gluconate, and the thickness of the conductive layer was changed from 0.1 μm to 0.06 μm, except that the conductive particles were obtained in the same manner as in Example 1. (Example 15) Only the particle diameter is different from the above-mentioned substrate particle A, and the substrate particle B having a particle diameter of 2.2 μm was prepared. Except having changed the said substrate particle A into the said substrate particle B, it carried out similarly to Example 1, and obtained electroconductive particle. (Example 16) Only the particle diameter is different from the above-mentioned substrate particle A, and the substrate particle C having a particle diameter of 10.0 μm was prepared. Except having changed the said substrate particle A into the said substrate particle C, it carried out similarly to Example 1, and obtained electroconductive particle. (Example 17) Into a 500 mL reaction vessel equipped with a stirrer and a thermometer, 300 g of 0.13 wt% ammonia solution was placed. Secondly, slowly add 4.1 g of methyl trimethoxysilane, 19.2 g of vinyl trimethoxysilane, and 0.7 g of silicone alkoxy oligomer (manufactured by Shin-Etsu Chemical Co., Ltd.) to the ammonia solution in the reaction vessel. "X-41-1053") mixture. After stirring on one side, hydrolysis and condensation reaction on the other side, add 2.4 mL of 25 wt% ammonia solution, and then separate the particles from the ammonia solution. The obtained oxygen partial pressure is 10 -17 atm and 350℃. The particles were calcined for 2 hours to obtain organic-inorganic mixed particles (base material particles D) with a particle diameter of 3.0 μm. Except having changed the said substrate particle A into the said substrate particle D, it carried out similarly to Example 3, and obtained electroconductive particle. (Example 18) In 100% of the total surface area of the outer surface of the conductive part, the surface area of the part with protrusions was changed from 70% to 25%, except that the conductive particles were obtained in the same manner as in Example 1. (Example 19) In a 1000 mL separable flask equipped with a four-port separable cap, a stirring blade, a three-way stopcock, a cooling tube, and a temperature probe, the solid content ratio became 5 wt%. Contains 100 mmol of methyl methacrylate, 1 mmol of N,N,N-trimethyl-N-2-methacryloxyethyl ammonium chloride, and 1 mmol of 2,2'-azo The monomer composition of bis(2-amidinopropane) dihydrochloride is weighed into ion exchange water. Thereafter, stirring was carried out at 200 rpm, and polymerization was carried out at 70°C for 24 hours in a nitrogen atmosphere. After the reaction is completed, freeze-drying is performed to obtain insulating particles with an ammonium group on the surface, an average particle diameter of 220 nm and a CV value of 10%. Disperse the insulating particles in ion-exchanged water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of insulating particles. Disperse 10 g of the conductive particles obtained in Example 1 in 500 mL of ion-exchange water, and add 4 g of an aqueous dispersion of insulating particles, and stir at room temperature for 6 hours. After filtering with a 3 μm mesh filter, it was further washed with methanol and dried to obtain conductive particles with insulating particles attached. Observation using a scanning electron microscope (SEM) showed that only one coating layer of insulating particles was formed on the surface of the conductive particles. The coverage area of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles (that is, the projected area of the particle diameter of the insulating particles) was calculated by image analysis. As a result, the coverage rate was 30%. (Comparative Example 1) The addition amount of sodium stannate trihydrate in the nickel plating solution (2) was changed from 0.03 mol/L to 0.10 mol/L, and the addition amount of sodium gluconate in the nickel plating solution (2) was changed from Except for changing 0.15 mol/L to 0.35 mol/L, in the same manner as in Example 1, conductive particles were obtained. (Comparative Example 2) Add 0.04 mol/L of sodium stannate trihydrate and 0.20 mol/L of sodium gluconate to the nickel plating solution (1), except that the conductivity was obtained in the same manner as in Comparative Example 1 particle. (Evaluation) (1) The average content of nickel, tin, and indium in the entire conductive layer containing nickel Add 5 g of conductive particles to a mixture of 5 mL of 60% nitric acid and 10 mL of 37% hydrochloric acid to make The conductive layer is completely dissolved and a solution is obtained. Using the obtained solution, a high-frequency inductively coupled plasma ion source mass spectrometer (“ICP-MS” manufactured by Hitachi, Ltd.) was used to analyze the contents of nickel, tin, and indium. Furthermore, the content other than nickel, tin and indium is phosphorus or boron. (2) The average content of nickel, tin, and indium in the thickness direction of the conductive layer containing nickel is measured for the distribution of the content of nickel, tin, and indium in the thickness direction of the conductive layer containing nickel. Using a focused ion beam, a thin film slice of the obtained conductive particles is made. Using an electric field radiation type transmission electron microscope ("JEM-2010FEF" manufactured by JEOL Ltd.), using an energy dispersive X-ray analyzer (EDS) to analyze the thickness of nickel, tin and indium of the conductive layer containing nickel The content is determined. Based on the results, the above-mentioned region (R1) of the thickness of 1/2 from the inner surface of the conductive layer containing nickel to the outside (the region of thickness 50% on the inner surface side), and the outer surface of the conductive layer containing nickel The above-mentioned region (R2) from the inner side to the thickness of 1/2 (the region of 50% thickness on the outer surface side), and the above-mentioned region (R3) from the outer surface to the inner side of the thickness 1/4 of the conductive layer containing nickel ( The area of 25% thickness on the outer surface side), and the above-mentioned area (R4) between the position of the thickness 1/4 from the outer surface to the inner side of the conductive layer containing nickel and the position of the thickness 1/2 (from the outer The surface side is the average content of nickel, tin, and indium in the area from the position of 25% thickness to the position of 50% thickness. Furthermore, the content other than nickel, tin and indium is phosphorus or boron. In addition, by the above measurement, the distribution results of the contents of nickel, tin, and indium in the thickness direction of the conductive layer containing nickel are obtained. Based on this result, the maximum value of the total content of tin and indium in the above region (R3) is obtained. (3) The melting point of the conductive layer of the conductive particles was measured using a differential scanning calorimeter ("DSC-6300" manufactured by Yamato Scientific). As a result, the melting point of the conductive layer in the example was 300°C or higher. (4) 10% K value of conductive particles The 10% K value of the obtained conductive particles was measured using a micro compression tester ("Fischerscope H-100" manufactured by Fischer). (5) The volume resistivity of the conductive particles was measured using the "Powder Resistivity Measurement System" manufactured by Mitsubishi Chemical Corporation to measure the volume resistivity of the obtained conductive particles. (6) Connection resistance A (initial stage) Connection structure production: 20 parts by weight of epoxy compound ("EP-3300P" manufactured by Nagase chemteX Corporation.) as a thermosetting compound, and 15 parts by weight as thermosetting Epoxy compound ("EPICLON HP-4032D" manufactured by DIC), 5 parts by weight of thermal cation generator (San-Aid "SI-60" manufactured by Sanshin Chemical Company) as a thermal hardening agent, and 20 parts by weight of silica as filler (average particle size 0.25 μm), and then add the obtained conductive particles so that the content in 100% by weight of the formulation becomes 10% by weight, and then stir at 2000 rpm with a planetary mixer 5 minutes, thereby obtaining an anisotropic conductive paste. Prepare a glass substrate with an Al-Ti 4% electrode pattern (Al-Ti 4% electrode thickness of 1 μm) with L/S of 20 μm/20 μm on the upper surface. In addition, a semiconductor wafer having a gold electrode pattern (gold electrode thickness 20 μm) with L/S of 20 μm/20 μm on the lower surface was prepared. The anisotropic conductive paste immediately after production was applied to the upper surface of the glass substrate to form a thickness of 20 μm to form an anisotropic conductive material layer. Next, the above-mentioned semiconductor wafer is laminated on the upper surface of the anisotropic conductive material layer with the electrodes facing each other. After that, while adjusting the temperature of the head so that the temperature of the anisotropic conductive material layer becomes 170°C, the pressure heating head is placed on the upper surface of the semiconductor wafer, and a pressure of 2.5 MPa is applied at 170°C. The anisotropic conductive material layer is hardened to obtain a connection structure. Measurement of connection resistance: Use the four-terminal method to measure the connection resistance A between the opposite electrodes of the obtained connection structure. In addition, the connection resistance A was determined based on the following criteria. [Evaluation criteria for connection resistance A] 〇〇〇: Connection resistance A is 2.0 Ω or less 〇〇〇: Connection resistance A exceeds 2.0 Ω and is 3.0 Ω or less 〇: Connection resistance A exceeds 3.0 Ω and is 5.0 Ω or less △: Connection resistance A exceeds 5.0 Ω and is 10 Ω or less ×: Connection resistance A exceeds 10 Ω (7) Connection resistance B (after the influence of acid) Immerse the obtained conductive particles in a 5% sulfuric acid aqueous solution for 30 minutes. After that, the particles were taken out by filtration, washed with water, and replaced with ethanol, and allowed to stand for 10 minutes to dry the particles, thereby obtaining conductive particles exposed to acid. Using the obtained conductive particles, a connection structure was produced in the same manner as in (6) above, and the connection resistance B was measured in the same manner as the connection resistance A. In addition, the connection resistance B was determined based on the following criteria. [Evaluation criteria for connection resistance B] 〇〇〇: Connection resistance B is more than 1 time and less than 1.5 times the connection resistance A 〇〇: Connection resistance B is more than 1.5 times and less than 2 times the connection resistance A 〇: Connection Resistance B is more than 2 times and less than 5 times the connecting resistance A △: Connecting resistance B is more than 5 times and less than 10 times the connecting resistance A ×: Connecting resistance B is more than 10 times the connecting resistance A (8) Connection Resistance C (after the influence of alkali) The obtained conductive particles are immersed in a 5% sodium hydroxide aqueous solution for 30 minutes. After that, the particles were taken out by filtration, washed with water, and replaced with ethanol and allowed to stand for 10 minutes to dry the particles, thereby obtaining conductive particles exposed to alkali. Using the obtained conductive particles, a connection structure was produced in the same manner as in (6) above, and the connection resistance C was measured in the same manner as the connection resistance A. In addition, the connection resistance C was determined based on the following criteria. [Evaluation criteria for connection resistance C] 〇〇〇: Connection resistance C is more than 1 time and less than 1.5 times the connection resistance A 〇〇: Connection resistance C is more than 1.5 times and less than 2 times the connection resistance A 〇: Connection Resistance C is more than 2 times and less than 5 times the connection resistance A △: Connection resistance C is more than 5 times and less than 10 times the connection resistance A ×: Connection resistance C is more than 10 times the connection resistance A (9) Condensation State: 10 parts by weight of bisphenol A epoxy resin ("Epikote 1009" manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight approximately 800,000), and 200 parts by weight of methyl ethyl ketone , 50 parts by weight of microcapsule hardener ("HX3941HP" manufactured by Asahi Kasei Chemical Co., Ltd.), and 2 parts by weight of silane coupling agent ("SH6040" manufactured by Toray Dow Corning Polysiloxane) are mixed, and the content becomes 3 weight Add conductive particles and disperse them to obtain an anisotropic conductive material. In addition, as the conductive particles, particles of the three conditions used in connection resistance A, connection resistance B, and connection resistance C were used to produce three types of anisotropic conductive materials. The three anisotropic conductive materials obtained were stored at 25°C for 72 hours. After storage, it was evaluated whether or not the conductive particles aggregated in the anisotropic conductive material had precipitated. Determine the aggregation state according to the following criteria. [Criteria for determination of aggregation state] ○: In all three anisotropic conductive materials, the aggregated conductive particles are not precipitated △: Only in one anisotropic conductive material, the aggregated conductive particles are precipitated ×: In In two or more anisotropic conductive materials, the aggregated conductive particles precipitated. The results are shown in Tables 1 to 3 below. [Table 1]
Figure 106104056-A0304-0001
 [Table 2]
Figure 106104056-A0304-0002
 [table 3]
Figure 106104056-A0304-0003

1‧‧‧導電性粒子2‧‧‧基材粒子3‧‧‧包含鎳之導電層11‧‧‧導電性粒子11a‧‧‧突起12‧‧‧包含鎳之導電層12a‧‧‧突起13‧‧‧芯物質14‧‧‧絕緣性物質21‧‧‧導電性粒子21a‧‧‧突起22‧‧‧包含鎳之導電層22a‧‧‧突起22A‧‧‧第1導電層22Aa‧‧‧突起22B‧‧‧第2導電層22Ba‧‧‧突起51‧‧‧連接構造體52‧‧‧第1連接對象構件52a‧‧‧第1電極53‧‧‧第2連接對象構件53a‧‧‧第2電極54‧‧‧連接部L1‧‧‧虛線L2‧‧‧虛線R1‧‧‧區域R2‧‧‧區域R3‧‧‧區域R4‧‧‧區域1‧‧‧Conductive particles 2‧‧‧Substrate particles 3‧‧‧Conductive layer containing nickel 11‧‧‧Conductive particles 11a‧‧‧Protrusion 12‧‧‧Conductive layer containing nickel 12a‧‧‧Protrusion 13 ‧‧‧Core material 14‧‧‧Insulating material 21‧‧‧Conductive particle 21a‧‧‧Protrusion 22‧‧‧Conductive layer 22a‧‧‧Containing nickel 22A‧‧‧Protrusion 22A‧‧‧First conductive layer 22Aa‧‧‧ Protrusion 22B‧‧‧Second conductive layer 22Ba‧‧‧Protrusion 51‧‧‧Connection structure 52‧‧‧First connection object member 52a‧‧‧First electrode 53‧‧‧Second connection object member 53a‧‧‧ The second electrode 54‧‧‧Connecting part L1‧‧‧Dotted line L2‧‧‧Dotted line R1‧‧‧Region R2‧‧‧Region R3‧‧‧Region R4‧‧‧Region

圖1係表示本發明之第1實施形態之導電性粒子之剖視圖。 圖2係表示本發明之第2實施形態之導電性粒子之剖視圖。 圖3係表示本發明之第3實施形態之導電性粒子之剖視圖。 圖4(a)及圖(b)係用以說明於包含鎳之導電層中求出錫與銦之合計之平均含量之各區域的模式圖。 圖5係模式性地表示使用本發明之第1實施形態之導電性粒子之連接構造體的正面剖視圖。Fig. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. Fig. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention. Fig. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention. 4(a) and (b) are schematic diagrams for explaining each area where the total average content of tin and indium in a conductive layer containing nickel is obtained. Fig. 5 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.

1‧‧‧導電性粒子 1‧‧‧Conductive particles

2‧‧‧基材粒子 2‧‧‧Substrate particles

3‧‧‧包含鎳之導電層 3‧‧‧Conducting layer containing nickel

Claims (9)

一種導電性粒子，其具備 基材粒子、及配置於上述基材粒子之表面上且包含鎳之導電層，且 上述包含鎳之導電層係包含鎳、及錫與銦中之至少1種之合金層， 上述包含鎳之導電層之自外表面起朝向內側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。A conductive particle comprising a substrate particle and a conductive layer containing nickel arranged on the surface of the substrate particle, and the conductive layer containing nickel is an alloy containing at least one of nickel and tin and indium Layer, in 100% by weight of the area from the outer surface of the conductive layer containing nickel to the inner side to the thickness 1/2, the total average content of tin and indium is less than 5% by weight. 如請求項1之導電性粒子，其中上述包含鎳之導電層之自外表面起朝向內側至厚度1/4之區域中之錫與銦之合計的平均含量較上述包含鎳之導電層之自距外表面朝向內側為厚度1/4之位置起至厚度1/2之位置之間之區域中之錫與銦之合計的平均含量多。The conductive particle of claim 1, wherein the total average content of tin and indium in the region from the outer surface of the conductive layer containing nickel to the inner side to the thickness of 1/4 is greater than the distance of the conductive layer containing nickel The total average content of tin and indium in the region from the position where the thickness is 1/4 to the position where the thickness is 1/2 toward the inner surface is large. 如請求項1或2之導電性粒子，其中上述包含鎳之導電層之自外表面起朝向內側至厚度1/4之區域的100重量%中，錫與銦之合計之含量之最大值為50重量%以下。The conductive particles according to claim 1 or 2, wherein the maximum value of the total content of tin and indium in 100% by weight of the area from the outer surface to the inner side of the thickness 1/4 of the thickness of the conductive layer containing nickel is 50 Weight% or less. 如請求項1或2之導電性粒子，其中上述包含鎳之導電層於外表面具有突起。The conductive particle of claim 1 or 2, wherein the conductive layer containing nickel has protrusions on the outer surface. 如請求項1或2之導電性粒子，其體積電阻率為0.003 Ω・cm以下。For example, the conductive particles of claim 1 or 2 have a volume resistivity of 0.003 Ω·cm or less. 如請求項1或2之導電性粒子，其中上述包含鎳之導電層之自內表面起朝向外側至厚度1/2之區域的100重量%中，錫與銦之合計之平均含量未達5重量%。The conductive particles of claim 1 or 2, wherein the total average content of tin and indium in 100% by weight of the area from the inner surface to the outside of the thickness 1/2 of the conductive layer containing nickel is less than 5 weight %. 如請求項1或2之導電性粒子，其進而具備配置於上述包含鎳之導電層之外表面上之絕緣性物質。The conductive particles according to claim 1 or 2, further comprising an insulating substance arranged on the outer surface of the conductive layer containing nickel. 一種導電材料，其包含如請求項1至7中任一項之導電性粒子、及黏合劑樹脂。A conductive material comprising the conductive particles according to any one of claims 1 to 7 and a binder resin. 一種連接構造體，其具備： 第1連接對象構件； 第2連接對象構件；及 連接部，其將上述第1連接對象構件與上述第2連接對象構件連接；且 上述連接部之材料為如請求項1至7中任一項之導電性粒子，或包含上述導電性粒子與黏合劑樹脂之導電材料。A connection structure comprising: a first connection object member; a second connection object member; and a connecting portion that connects the first connection object member and the second connection object member; and the material of the connection portion is as requested The conductive particles of any one of items 1 to 7, or a conductive material containing the conductive particles and a binder resin.
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