TW202043410A - Conductive adhesive and method of using conductive adhesive - Google Patents

Conductive adhesive and method of using conductive adhesive Download PDF

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TW202043410A
TW202043410A TW109112508A TW109112508A TW202043410A TW 202043410 A TW202043410 A TW 202043410A TW 109112508 A TW109112508 A TW 109112508A TW 109112508 A TW109112508 A TW 109112508A TW 202043410 A TW202043410 A TW 202043410A
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conductive adhesive
situ polymerization
conductive
matrix resin
conductive particles
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TW109112508A
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TWI729774B (en
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堀薫夫
松永俊滋
藤田晶
岸肇
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日商化研科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

Abstract

To provide a conductive adhesive comprising micro phase separation, the conductive adhesive including more conductive particles in a base resin than in a region formed by In-Situ polymerization within the base resin, and a method for use the conductive adhesive. A conductive adhesive comprising a base resin and a region formed by In-Situ polymerization within the base resin with micro phase separation being generated therebetween, the conductive adhesive including conductive particles, wherein when the content of conductive particles included in the base resin is defined by φ1 (wt%) and that in the region formed by In-Situ polymerization within the base resin is defined by φ2 (wt%), the relationship of φ1＞φ2 is satisfied.

Description

導電性黏接劑和導電性黏接劑的使用方法Conductive adhesive and how to use conductive adhesive

本發明涉及導電性黏接劑和導電性黏接劑的使用方法。特別是涉及在固化後微相分離而成的導電性黏接劑中，與原位聚合（有時稱為In-Situ聚合）而成的區域相比，導電性粒子更容易偏向分佈於基體樹脂中的導電性黏接劑、以及使用該導電性黏接劑的導電性黏接劑使用方法。The present invention relates to a conductive adhesive and a method of using the conductive adhesive. In particular, it relates to the conductive adhesive formed by microphase separation after curing. Compared with the area formed by in-situ polymerization (sometimes called In-Situ polymerization), the conductive particles are more likely to be distributed in the matrix resin. The conductive adhesive in, and how to use the conductive adhesive using the conductive adhesive.

以往，提出了各種電絕緣性樹脂中含有規定量的導電性粒子而成的導電性黏接劑。 例如提出有兼具良好的黏接性和再加工性，並且低溫連接性等良好的導電性黏接劑（例如參照專利文獻1）。 更具體而言，一種導電性黏接劑，其特徵在於，是含有導電性填料、由熱塑性樹脂和熱固性樹脂構成的有機黏合劑而成的導電性黏接劑，導電性填料的金屬粒子具有金屬粒子表面的低熔點層和金屬粒子內部的高熔點層，多種構成金屬中不包含鉛，該構成金屬的濃度在金屬粒子表面與金屬粒子內部連續地變化，在有機黏合劑的固化溫度附近熔融。Conventionally, conductive adhesives in which a predetermined amount of conductive particles are contained in various electrical insulating resins have been proposed. For example, a conductive adhesive that has both good adhesiveness and reworkability, and good low-temperature connectivity, etc. has been proposed (for example, refer to Patent Document 1). More specifically, a conductive adhesive is characterized in that it contains a conductive filler and an organic binder composed of a thermoplastic resin and a thermosetting resin. The metal particles of the conductive filler have metal The low melting point layer on the surface of the particles and the high melting point layer inside the metal particles do not contain lead in a variety of constituent metals. The concentration of the constituent metals continuously changes on the surface of the metal particles and inside the metal particles, and melts near the solidification temperature of the organic binder.

另外，也提出了對充分的導電性和優異的塗布作業性進行控制而成的導電性黏接劑（例如參照專利文獻2）。 更具體而言，一種導電性黏接劑，是含有作為熱固性樹脂的環氧樹脂等、作為熱塑性樹脂的聚醚碸樹脂等和導電性粒子而成的導電性黏接劑，在使其固化的情況下，熱固性樹脂與熱塑性樹脂發生相分離，並且導電性粒子偏向分佈。 而且，作為導電性粒子的形狀，優選為球狀、凝聚狀、平板狀、針狀、棒狀，其平均粒徑為0.01～20μm的範圍內的值。 因此，如圖7的線A所示，含有作為熱固性樹脂的環氧樹脂等、作為熱塑性樹脂的聚醚碸樹脂等和導電性粒子而成的導電性黏接劑的情況與線B所示的不含有聚醚碸樹脂的導電性黏接劑相比，電導率良好。 現有技術文獻 專利文獻In addition, a conductive adhesive obtained by controlling sufficient conductivity and excellent coating workability has also been proposed (for example, refer to Patent Document 2). More specifically, a conductive adhesive is a conductive adhesive containing epoxy resin as a thermosetting resin and the like, polyether resin as a thermoplastic resin and conductive particles. In this case, the thermosetting resin and the thermoplastic resin are phase separated, and the conductive particles are unevenly distributed. The shape of the conductive particles is preferably spherical, agglomerated, flat, needle, or rod, and the average particle diameter is a value in the range of 0.01 to 20 μm. Therefore, as shown in line A in FIG. 7, the case of a conductive adhesive composed of epoxy resin as a thermosetting resin, polyether resin, etc., and conductive particles as a thermoplastic resin is as shown in line B Compared to conductive adhesives that do not contain polyether resin, the conductivity is better. Prior art literature Patent literature

專利文獻1：日本特開2001-172606號（申請專利範圍等）。 專利文獻2：日本特開2013-67755號（申請專利範圍等）。Patent Document 1: Japanese Patent Application Publication No. 2001-172606 (application scope, etc.). Patent Document 2: JP 2013-67755 (application scope, etc.).

然而，專利文獻1中公開的導電性黏接劑必須使用構成金屬的濃度在金屬粒子表面與金屬粒子內部連續地變化，從而具備低熔點層和高熔點層的特殊的導電性填料，存在導電性黏接劑的製造成本等容易增加的問題。 另外，存在為了得到規定導電性而要配合的導電性粒子的量很大的問題。 此外，使用苯氧基樹脂等作為熱塑性樹脂，並且使用環氧樹脂等作為熱固性樹脂，使用彼此相容性良好的樹脂，因此不會發生微相分離，無意使導電性粒子偏向分佈。However, the conductive adhesive disclosed in Patent Document 1 must use the concentration of the constituent metal to continuously change on the surface of the metal particle and the inside of the metal particle, so that it has a special conductive filler with a low melting point layer and a high melting point layer, and it is conductive. The manufacturing cost of the adhesive is likely to increase. In addition, there is a problem that the amount of conductive particles to be blended in order to obtain predetermined conductivity is large. In addition, a phenoxy resin or the like is used as a thermoplastic resin, and an epoxy resin or the like is used as a thermosetting resin. Since resins with good compatibility are used, microphase separation does not occur, and the conductive particles are unintentionally distributed.

另外，專利文獻2中公開的導電性黏接劑中，在進行熱固化的情況下，雖然熱固性樹脂與熱塑性樹脂微相分離，但導電性粒子的偏向分佈相以外的相的大小（寬度）必須小至幾nm～20nm，並且在導電性粒子的偏向分佈相中，也存在導電性粒子的偏向分佈性仍然很差。In addition, in the conductive adhesive disclosed in Patent Document 2, when thermosetting is performed, although the thermosetting resin and the thermoplastic resin are microphase separated, the size (width) of the phase other than the biased distribution phase of the conductive particles must be It is as small as several nm to 20 nm, and in the deviated distribution phase of the conductive particles, the deviated distribution of the conductive particles is still poor.

因此，本發明人等在反復進行了深入研究，結果發現通過在規定條件下，在基體樹脂中進行原位聚合，通過基體樹脂與原位聚合而成的區域相分離（微相分離），從而更多的導電性粒子偏向分佈在基體樹脂中，完成本發明。 即，本發明的目的在於提供一種利用原位聚合，即使配合較少量的導電性粒子，也使該導電性粒子大量偏向分佈在基體樹脂中而成的具有良好的導電性等的導電性黏接劑以及用於容易得到這種良好的導電性的導電性黏接劑的使用方法。Therefore, the inventors of the present invention have repeatedly conducted intensive studies, and found that by performing in-situ polymerization in the matrix resin under prescribed conditions, the matrix resin is phase separated from the in-situ polymerized domain (microphase separation). More conductive particles are eccentrically distributed in the matrix resin, and the present invention has been completed. That is, the object of the present invention is to provide a conductive adhesive having good conductivity, etc., by using in-situ polymerization, even if a small amount of conductive particles are mixed, the conductive particles are distributed in a large amount in a matrix resin. Adhesives and methods of using conductive adhesives that can easily obtain such good conductivity.

根據本發明，提供一種導電性黏接劑，其特徵在於，是基體樹脂與原位聚合而成的區域微相分離而成的導電性黏接劑，導電性黏接劑含有導電性粒子，在將基體樹脂中含有的導電性粒子的含量設為φ1（重量％）、將原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足φ1＞φ2的關係，能夠解決上述問題。 即，能夠得到一種導電性黏接劑，其基體樹脂與原位聚合而成的區域相分離（微相分離），並且基體樹脂中含有的導電性粒子大量偏向分佈而成。 因此，即使配合較少量的導電性粒子，與原位聚合而成的區域相比，相對大量地偏向分佈在基體樹脂中，因此能夠得到良好的導電性。According to the present invention, there is provided a conductive adhesive, which is characterized in that it is a conductive adhesive obtained by microphase separation of a matrix resin and a region formed by in-situ polymerization, and the conductive adhesive contains conductive particles, When the content of the conductive particles contained in the matrix resin is set to φ1 (wt%), and the content of the conductive particles contained in the in-situ polymerization area is set to φ2 (wt%), the relationship of φ1>φ2 is satisfied , Can solve the above problems. That is, it is possible to obtain a conductive adhesive in which a matrix resin is separated from a domain formed by in-situ polymerization (microphase separation), and a large amount of conductive particles contained in the matrix resin are distributed unevenly. Therefore, even if a relatively small amount of conductive particles are blended, a relatively large amount of the conductive particles are distributed in the matrix resin compared to the region formed by in-situ polymerization, and therefore, good conductivity can be obtained.

應予說明，無論加熱處理（第1加熱處理和第2加熱處理）如何，均可得到下述方式的導電性黏接劑，但這些基本上都包含於本發明的導電性黏接劑中。 類型A：第1加熱處理前／第2加熱處理前的導電性黏接劑（通常為液態） 類型B：第1加熱處理後／第2加熱處理前的導電性黏接劑（通常為液態） 類型C：第1加熱處理後／第2加熱處理後的導電性黏接劑（通常為固體狀）It should be noted that regardless of the heat treatment (first heat treatment and second heat treatment), the following conductive adhesive can be obtained, but these are basically included in the conductive adhesive of the present invention. Type A: Conductive adhesive before the first heat treatment/before the second heat treatment (usually liquid) Type B: Conductive adhesive after the first heat treatment / before the second heat treatment (usually liquid) Type C: Conductive adhesive after the first heat treatment/after the second heat treatment (usually solid)

另外，在構成本發明的導電性黏接劑時，優選將原位聚合的反應溫度設為T1（℃）、將基體樹脂的反應溫度設為T2（℃）時，ΔT（＝T2-T1）的絕對值為5～50的範圍內的值。 通過滿足這樣的溫度關係，即使含有***到進行熱固化等之前的黏度較低的基體樹脂中的狀態的丙烯酸系單體等的情況下，也能夠利用原位聚合，均勻且高精度地聚合化，使基體樹脂與原位聚合而成的區域微相分離。In addition, when constituting the conductive adhesive of the present invention, it is preferable to set the reaction temperature of the in-situ polymerization to T1 (°C) and the reaction temperature of the matrix resin to T2 (°C), ΔT (=T2-T1) The absolute value of is a value in the range of 5-50. By satisfying such a temperature relationship, even when it contains acrylic monomers that are inserted into a low-viscosity base resin before heat curing, etc., it can be polymerized uniformly and with high precision by in-situ polymerization. , Make the matrix resin and the region formed by in-situ polymerization microphase separated.

另外，在構成本發明的導電性黏接劑時，優選基體樹脂為熱固性環氧樹脂。 這樣，如果基體樹脂區域為熱固性環氧樹脂，則較容易調整作為反應溫度的T2（℃），能夠使ΔT（T2-T1）為規定範圍內的值，進一步使基體樹脂區域與原位聚合而成的區域容易且高精度地微相分離。In addition, when constituting the conductive adhesive of the present invention, the base resin is preferably a thermosetting epoxy resin. In this way, if the matrix resin region is a thermosetting epoxy resin, it is easier to adjust T2 (°C) as the reaction temperature, so that ΔT (T2-T1) can be a value within a predetermined range, and the matrix resin region can be further polymerized in situ. The formed area is microphase separated easily and with high precision.

另外，在構成本發明的導電性黏接劑時，優選原位聚合而成的區域來自於丙烯酸系單體和自由基引發劑的組合、或者封端異氰酸酯化合物和含活性氫基團的化合物的組合。 這樣，如果原位聚合而成的區域來自於丙烯酸系單體和自由基引發劑的組合等，則能夠使基體樹脂與原位聚合而成的區域更容易且高精度地微相分離。In addition, when constituting the conductive adhesive of the present invention, it is preferable that the region formed by in-situ polymerization is derived from a combination of an acrylic monomer and a radical initiator, or a blocked isocyanate compound and an active hydrogen group-containing compound. combination. In this way, if the in-situ polymerized domain is derived from a combination of an acrylic monomer and a radical initiator, etc., the matrix resin and the in-situ polymerized domain can be microphase separated more easily and with high precision.

另外，在構成本發明的導電性黏接劑時，優選使導電性粒子的含量相對於總量為25～70重量％的範圍內的值。 這樣，通過控制導電性粒子的含量，即使配合較少量的導電性粒子，也能夠通過使其偏向分佈於基體樹脂中而得到良好的導電性。 另一方面，能夠在要求導電性更低的用途、例如功率半導體的電連接部件等中，通過配合相當量的導電性粒子，提供更少發熱、更少產生裂紋的導電性黏接劑。In addition, when constituting the conductive adhesive of the present invention, the content of the conductive particles is preferably a value in the range of 25 to 70% by weight with respect to the total amount. In this way, by controlling the content of the conductive particles, even if a relatively small amount of conductive particles are blended, it is possible to obtain good conductivity by distributing them in the matrix resin. On the other hand, it is possible to provide a conductive adhesive with less heat generation and less cracking by blending a considerable amount of conductive particles in applications requiring lower conductivity, such as electrical connection parts for power semiconductors.

另外，在構成本發明的導電性黏接劑時，優選使黏度為0.1～300Pa・sec.（測定溫度：25℃）的範圍內的值。 如果是這樣的導電性黏接劑的黏度，則作為液態的導電性黏接劑，使用點膠機等，能夠高精度地應用於規定位置，另外，對於導電性粒子等沉澱問題，也能夠容易地控制。In addition, when constituting the conductive adhesive of the present invention, the viscosity is preferably a value within the range of 0.1 to 300 Pa·sec. (measurement temperature: 25° C.). If it is the viscosity of such a conductive adhesive, as a liquid conductive adhesive, it can be applied to a predetermined position with high accuracy using a dispenser or the like. In addition, it can be easily applied to the problem of precipitation of conductive particles, etc.地控制。 Ground control.

另外，在構成本發明的導電性黏接劑時，優選使電阻率為1×10-4 ～1×100 Ω・cm的範圍內的值。 通過這樣限制導電性黏接劑的電阻率（電導率），從靜電屏蔽對策考慮，期待將導電性黏接劑用於功率半導體的接合部件等廣泛的用途。In addition, when constituting the conductive adhesive of the present invention, the electrical resistivity is preferably a value in the range of 1×10 -4 to 1×10 0 Ω·cm. By limiting the resistivity (conductivity) of the conductive adhesive in this way, it is expected that the conductive adhesive will be used for a wide range of applications such as bonding parts of power semiconductors from the viewpoint of electrostatic shielding measures.

另外，本發明的另一方式是如下的導電性黏接劑的使用方法，其特徵在於，是基體樹脂與原位聚合而成的區域微相分離的導電性黏接劑，包括下述工序（1）～（4）。 （1）準備含有導電性粒子，基體樹脂與原位聚合而成的區域微相分離的導電性黏接劑的工序； （2）將導電性黏接劑應用於被黏物的工序； （3）對導電性黏接劑進行加熱處理（第1加熱處理）而形成原位聚合而成的區域的工序； （4）使基體樹脂與原位聚合而成的區域微相分離，並且將基體樹脂中含有的導電性粒子的含量設為φ1（重量％）、將原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足φ1＞φ2的關係的工序。 即，通過這樣實施，能夠高效地得到使基體樹脂所具有的區域與原位聚合而成的區域高精度地相分離（微相分離），並且導電性粒子大量偏向分佈在基體樹脂中而成的導電性黏接劑。 因此，作為導電性黏接劑的使用方法，即使配合較少量的導電性粒子，也更多地偏向分佈於基體樹脂，因此能夠得到良好的導電性。In addition, another aspect of the present invention is a method of using a conductive adhesive as follows, characterized in that it is a conductive adhesive in which the matrix resin is microphase separated from the in-situ polymerized region, and includes the following steps ( 1) ~ (4). (1) The process of preparing a conductive adhesive that contains conductive particles, and the matrix resin is slightly separated from the region formed by in-situ polymerization; (2) The process of applying conductive adhesive to the adherend; (3) The process of heating the conductive adhesive (the first heating treatment) to form a zone formed by in-situ polymerization; (4) The matrix resin is microphase separated from the region formed by in-situ polymerization, and the content of conductive particles contained in the matrix resin is set to φ1 (wt%), and the conductive particles contained in the region formed by in-situ polymerization When the content of the sexual particles is φ2 (% by weight), a step that satisfies the relationship of φ1>φ2. That is, by implementing in this way, it is possible to efficiently obtain a structure in which the region of the matrix resin and the region formed by in-situ polymerization are phase separated (microphase separation) with high accuracy, and a large number of conductive particles are distributed in the matrix resin. Conductive adhesive. Therefore, as a method of using a conductive adhesive, even if a smaller amount of conductive particles are blended, they are more distributed in the matrix resin, so that good conductivity can be obtained.

［第1實施方式］ 第1實施方式是一種導電性黏接劑，其特徵在於，是基體樹脂與原位聚合而成的區域微相分離而成的導電性黏接劑，導電性黏接劑含有導電性粒子，將基體樹脂中含有的導電性粒子的含量設為φ1（重量％）、將原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足φ1＞φ2的關係。 以下，針對各個構成要件具體說明第1實施方式的導電性黏接劑。[First Embodiment] The first embodiment is a conductive adhesive characterized in that it is a conductive adhesive formed by microphase separation of a matrix resin and a region formed by in-situ polymerization, and the conductive adhesive contains conductive particles, When the content of the conductive particles contained in the matrix resin is φ1 (% by weight) and the content of the conductive particles contained in the in-situ polymerization region is φ2 (% by weight), the relationship of φ1>φ2 is satisfied. Hereinafter, the conductive adhesive of the first embodiment will be specifically described for each constituent element.

1.導電性粒子 （1）平均粒徑 導電性粒子的平均粒徑（體積平均粒徑）沒有特別限制，通常優選為0.1～30μm的範圍內的值。 該原因是因為上述導電性粒子的平均粒徑為小於0.1μm的值，則有時容易凝聚而操作性降得過低。 另一方面，若上述導電性粒子的平均粒徑為超過30μm的值，則有時使其熱固化、微相分離後的、熱固性樹脂中的導電性粒子的偏向分佈化變得困難。 因此，更優選使導電性粒子的平均粒徑為0.5～15μm的範圍內的值，進一步優選為1.5～5μm的範圍內的值。 應予說明，導電性粒子的平均粒徑可以基於JIS Z 8819-2：2001，利用雷射繞射・散射法粒度分佈測定裝置進行測定，或者可以根據電子顯微鏡照片實際測量，進而也可以根據該電子顯微鏡照片，使用圖像處理裝置進行計算。1. Conductive particles (1) Average particle size The average particle diameter (volume average particle diameter) of the conductive particles is not particularly limited, but it is usually preferably a value in the range of 0.1 to 30 μm. This is because the average particle diameter of the above-mentioned conductive particles is a value less than 0.1 μm, and they tend to aggregate and sometimes the handling properties are too low. On the other hand, when the average particle diameter of the conductive particles is a value exceeding 30 μm, it may become difficult to distribute the conductive particles in the thermosetting resin after thermal curing and microphase separation. Therefore, it is more preferable to set the average particle diameter of the conductive particles to a value in the range of 0.5 to 15 μm, and even more preferably to a value in the range of 1.5 to 5 μm. It should be noted that the average particle size of the conductive particles can be measured with a laser diffraction and scattering method particle size distribution measuring device based on JIS Z 8819-2:2001, or can be actually measured from electron micrographs, or based on the Electron micrographs, calculated using image processing equipment.

（2）形態 另外，導電性粒子的形態也沒有特別限定，通常優選為球狀、橢圓球狀、立方體狀、棒狀、毛栗狀、薄片狀、不規則形狀、或者它們的組合。 特別是導電性粒子的形態只要為毛栗狀和薄片狀，則使其熱固化、微相分離後的熱固性樹脂中的導電性粒子的偏向分佈化很容易，是更優選的形態。(2) Form In addition, the shape of the conductive particles is not particularly limited, but it is usually preferably spherical, elliptical, cubic, rod-shaped, chestnut-shaped, flake-shaped, irregular shape, or a combination thereof. In particular, as long as the shape of the conductive particles is a chestnut shape or a flake shape, the conductive particles in the thermosetting resin after the thermosetting and microphase separation can be easily distributed, which is a more preferable aspect.

另外，關於導電性粒子的形態，更優選是在內部具有晶體生長用的核材的實心銀粒子。 該原因是因為通過使用這樣的實心銀粒子，即使為毛栗狀等，也能夠調節銀粒子的晶體變化特性（銀粒子的長期形狀保持性），進而導電性黏接劑的堆積密度的調整也變得容易。In addition, with regard to the form of conductive particles, solid silver particles having a core material for crystal growth inside are more preferable. The reason is that by using such solid silver particles, even if they are chestnut-shaped, the crystal change characteristics of the silver particles (long-term shape retention of the silver particles) can be adjusted, and the bulk density of the conductive adhesive can be adjusted. It becomes easy.

另外，關於導電性粒子的形態，優選為內部具有規定空隙的中空銀粒子。 該原因是因為通過使用這樣的中空銀粒子，能夠更容易地控制導電性黏接劑中的銀粒子的偏向分佈化，並且能夠有利於導電性黏接劑的輕型化和低成本化。Moreover, about the form of electroconductive particle, it is preferable that it is a hollow silver particle which has predetermined voids inside. The reason for this is that by using such hollow silver particles, it is possible to more easily control the eccentric distribution of silver particles in the conductive adhesive, and it is possible to contribute to the reduction in weight and cost of the conductive adhesive.

（3）堆積密度 另外，優選使導電性粒子的堆積密度為0.5～5g／cm3 的範圍內的值。 該原因是因為若上述導電性粒子的堆積密度為小於0.5g／cm3 的值，則有時導電性黏接劑的黏接強度降低。 另一方面，若上述導電性粒子的堆積密度為超過5g／cm3 的值，則有時微相分離後的熱固性樹脂的偏向分佈化變得困難。 因此，更優選使導電性粒子的堆積密度為1～4g／cm3 的範圍內的值，進一步優選為1.5～3g／cm3 的範圍內的值。 應予說明，上述導電性粒子的堆積密度可以基於JIS K5101的敲擊法進行測定。(3) Bulk density In addition, it is preferable that the bulk density of conductive particles is a value within a range of 0.5 to 5 g/cm 3 . This is because if the bulk density of the conductive particles is less than 0.5 g/cm 3 , the adhesive strength of the conductive adhesive may decrease. On the other hand, if the bulk density of the conductive particles exceeds 5 g/cm 3 , it may become difficult to distribute the thermosetting resin after microphase separation. Therefore, it is more preferable to set the bulk density of conductive particles to a value in the range of 1 to 4 g/cm 3 , and even more preferably to a value in the range of 1.5 to 3 g/cm 3 . In addition, the bulk density of the said electroconductive particle can be measured based on the tapping method of JISK5101.

（4）配合量 另外，優選使導電性粒子的配合量相對於導電性黏接劑的總量為25～70重量％的範圍內的值。 該原因是因為即便配合較少量的導電性粒子或配合較大量的導電性粒子，也都能夠均勻且明顯地偏向分佈，從而能夠得到良好的導電性。 因此，更優選使導電性粒子的配合量相對於導電性黏接劑的總量為30～60重量％的範圍內的值，進一步優選為35～50重量％的範圍內的值。(4) Mixing amount Moreover, it is preferable that the compounding quantity of electroconductive particle is the value in the range of 25-70 weight% with respect to the total amount of electroconductive adhesive. The reason for this is that even if a smaller amount of conductive particles is blended or a larger amount of conductive particles are blended, the distribution can be uniformly and clearly deviated, and good conductivity can be obtained. Therefore, it is more preferable to set the compounding quantity of electroconductive particle to the value in the range of 30-60 weight% with respect to the total amount of electroconductive adhesive, and it is still more preferable to set it as the value in the range of 35-50 weight%.

（5）表面被覆層 另外，優選在導電性粒子的表面具有以有機酸、有機酸鹽、表面活性劑和偶聯劑中的至少一種為主成分的表面處理層。 該原因是因為通過具有這樣的表面處理層，能夠調節導電性粒子的晶體變化特性（例如銀粒子的長期形狀保持性）。 應予說明，如果構成表面處理層的主成分為有機酸或有機酸鹽，則還具有如下優點：調節相對於熱固性樹脂的親和性，通過熱固化處理而微相分離後的熱固性樹脂中的導電性粒子的偏向分佈化變得更容易。(5) Surface coating In addition, it is preferable to have a surface treatment layer mainly composed of at least one of an organic acid, an organic acid salt, a surfactant, and a coupling agent on the surface of the conductive particle. The reason for this is that by having such a surface treatment layer, it is possible to adjust the crystal change characteristics of conductive particles (for example, long-term shape retention of silver particles). It should be noted that if the main component constituting the surface treatment layer is an organic acid or an organic acid salt, it also has the following advantages: adjusting the affinity for the thermosetting resin, and conducting the thermosetting resin after microphase separation by the thermosetting treatment The deviated distribution of sexual particles becomes easier.

（5）-1 種類 另外，作為這種有機表面處理劑的種類，沒有特別限制，通常可舉出己酸、2-乙基己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、山嵛酸、褐煤酸、油酸、亞油酸、亞麻酸、12-羥基硬脂酸、苯甲酸、葡糖酸、肉桂酸、水楊酸、沒食子酸、十五烷酸、十七烷酸、花生酸、木質酸、蠟酸（cerotic acid）、2-戊基壬酸、2-己基癸酸、2-庚基十二烷酸、異硬脂酸、棕櫚油酸、異油酸、反油酸、蓖麻油酸、鱈油酸、芥酸、鯊油酸等一元酸；丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、蘋果酸、鄰苯二甲酸、富馬酸等二元酸等中的一種單獨或兩種以上的組合。(5)-1 Type In addition, there are no particular restrictions on the type of this organic surface treatment agent. Usually, caproic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and Acrylic acid, montanic acid, oleic acid, linoleic acid, linolenic acid, 12-hydroxystearic acid, benzoic acid, gluconic acid, cinnamic acid, salicylic acid, gallic acid, pentadecanoic acid, heptadecane Acid, arachidic acid, lignoic acid, cerotic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptyldodecanoic acid, isostearic acid, palmitoleic acid, isoleic acid, Monobasic acid such as elaidic acid, ricinoleic acid, codoleic acid, erucic acid, squalic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, apple Dibasic acids such as acid, phthalic acid, and fumaric acid are singly or in combination of two or more.

（5）-2 配合量 另外，優選使有機表面處理劑的配合量相對於導電性粒子（銀粒子等）100重量份為0.1～8重量份的範圍內的值。 該原因是因為通過這樣調整有機表面處理劑的配合量，能夠調節導電性粒子的晶體變化特性，進而能夠進一步容易控制導電性黏接劑中的導電性粒子的偏向分佈化。 即，是因為若有機表面處理劑的配合量為小於0.1重量份的值，則有時導電性粒子彼此容易凝聚。另一方面，若有機表面處理劑的配合量為超過8重量份的值，則有時得不到導電性粒子中的良好的偏向分佈化。 因此，更優選為使有機表面處理劑的配合量相對於導電性粒子100重量份為0.5～7重量份的範圍內的值，進一步優選為1～6重量份的範圍內的值。(5)-2 Mixing amount Moreover, it is preferable that the compounding quantity of an organic surface treatment agent is the value within the range of 0.1-8 weight part with respect to 100 weight part of electroconductive particles (silver particles etc.). The reason for this is that by adjusting the blending amount of the organic surface treatment agent in this way, the crystal change characteristics of the conductive particles can be adjusted, and furthermore, it is possible to further easily control the distribution of the conductive particles in the conductive adhesive. That is, if the blending amount of the organic surface treatment agent is less than 0.1 parts by weight, the conductive particles may easily aggregate. On the other hand, if the blending amount of the organic surface treatment agent exceeds 8 parts by weight, a good partial distribution in the conductive particles may not be obtained. Therefore, it is more preferable that the compounding quantity of an organic surface treatment agent is the value in the range of 0.5-7 weight part with respect to 100 weight part of electroconductive particles, and the value in the range of 1-6 weight part is still more preferable.

2.基體樹脂 在構成本發明的導電性黏接劑時，作為基體樹脂，優選使用熱固性樹脂和熱塑性樹脂、或者其中任一方的樹脂。 而且，通過第1加熱處理，在基體樹脂中，進行規定單體成分的原位聚合，形成規定區域（熱固化區域和／或熱塑性區域），接著，利用第2加熱處理，能夠發揮作為規定的導電性黏接劑的功能。 此時，優選使導電性黏接劑最終熱固化等時，配合與原位聚合得到的區域相互微相分離的基體樹脂。 該原因是因為通過作為與原位聚合而成的區域相互相分離的基體樹脂而配合，即使配合較少量的導電性粒子，也能夠基本上使導電性粒子向基體樹脂中集中地偏向分佈，例如能夠得到圖1的線A所示的良好的電阻率（導電性）。 但是，另外發現通過對基體樹脂的種類、原位聚合而成的區域的種類、以及導電性粒子的表面處理劑、表面處理等分別適當地控制，也能夠與基體樹脂相比，使導電性粒子集中地偏向分佈在原位聚合而成的區域。2. Matrix resin When constituting the conductive adhesive of the present invention, as the matrix resin, it is preferable to use a thermosetting resin, a thermoplastic resin, or any one of them. In addition, through the first heat treatment, in the matrix resin, the predetermined monomer components are polymerized in situ to form a predetermined area (thermosetting area and/or thermoplastic area). Then, the second heat treatment can be used as a predetermined area. Function of conductive adhesive. At this time, it is preferable to blend a matrix resin that is microphase separated from the region obtained by in-situ polymerization when the conductive adhesive is finally thermally cured or the like. The reason for this is that by blending as a matrix resin separated from the regions formed by in-situ polymerization, even if a small amount of conductive particles are blended, the conductive particles can be basically concentrated and distributed in the matrix resin. For example, good resistivity (conductivity) as shown by the line A in FIG. 1 can be obtained. However, it has also been found that by appropriately controlling the type of matrix resin, the type of regions formed by in-situ polymerization, and the surface treatment agent and surface treatment of the conductive particles, it is also possible to make the conductive particles comparable to the matrix resin. Concentrated and biased in the area formed by in-situ aggregation.

這裡，圖1中，線A相當於利用由本發明的原位聚合得到的相分離狀態的導電性黏接劑，線B相偏向以往的非相分離狀態的導電性黏接劑即、未利用原位聚合的導電性黏接劑。 而且，如線A所示，可理解若與線B相比是相同的銀添加量（例如為40重量％～60重量％的範圍），則利用由原位聚合得到的相分離狀態的導電性黏接劑的電阻率的值要低3個數量級左右。Here, in FIG. 1, line A corresponds to the conductive adhesive in a phase-separated state obtained by the in-situ polymerization of the present invention, and the line B phase is biased toward the conventional non-phase-separated conductive adhesive, that is, the unused original Position-polymerized conductive adhesive. Moreover, as shown by line A, it can be understood that if the silver addition amount is the same as that of line B (for example, the range of 40% to 60% by weight), the conductivity in the phase separated state obtained by in-situ polymerization is used. The electrical resistivity of the adhesive is about 3 orders of magnitude lower.

（1）種類1 對於用於基體樹脂的樹脂的種類，沒有特別限制，例如作為熱固性樹脂，可舉出環氧系樹脂（包含固化劑）、酚醛系樹脂、聚醯亞胺系樹脂、丙烯酸系樹脂（交聯丙烯酸系樹脂）、氨基甲酸酯系樹脂（交聯氨基甲酸酯系樹脂）、有機矽系樹脂、不飽和聚酯系樹脂、乙烯基酯系樹脂、三聚氰胺系樹脂、脲系樹脂等中中的一種單獨或兩種以上的組合。 並且可以說這些物質中作為用於基體樹脂的樹脂，更優選為含有固化劑的環氧系樹脂。 該原因是因為通過使用這樣的含有固化劑的環氧系樹脂，容易控制與原位聚合而成的區域的相互極性，進而容易發生相分離，導電性粒子在基體樹脂中的偏向分佈變得更容易。 另外，是因為如果基體樹脂為環氧系樹脂，則作為導電性黏接劑，對各種被黏物顯示出良好的黏接性，進一步得到適度的機械強度。(1) Category 1 There are no particular restrictions on the type of resin used in the matrix resin. For example, as thermosetting resins, epoxy resins (including curing agents), phenolic resins, polyimide resins, acrylic resins (crosslinked acrylic resins) Resin), urethane resin (crosslinked urethane resin), silicone resin, unsaturated polyester resin, vinyl ester resin, melamine resin, urea resin, etc. One kind alone or a combination of two or more kinds. In addition, it can be said that among these substances, the resin used for the matrix resin is more preferably an epoxy resin containing a curing agent. The reason is that by using such epoxy resin containing curing agent, it is easy to control the mutual polarity with the in-situ polymerized area, and furthermore, the phase separation is likely to occur, and the deviated distribution of conductive particles in the matrix resin becomes more easy. In addition, the reason is that if the base resin is an epoxy-based resin, as a conductive adhesive, it exhibits good adhesion to various adherends and further obtains appropriate mechanical strength.

（2）種類2 另一方面，作為用於基體樹脂的熱塑性樹脂，例如可舉出苯氧基系樹脂、丙烯酸系樹脂（非交聯丙烯酸系樹脂）、氨基甲酸酯系樹脂（非交聯氨基甲酸酯系樹脂）、聚酯系樹脂（非交聯聚酯系樹脂）、有機矽系樹脂等中的一種單獨或兩種以上的組合。 並且，這些物質中非交聯氨基甲酸酯系樹脂是作為更優選的基體樹脂的熱塑性樹脂。 該原因是因為通過使用這樣的基體樹脂所含有的熱塑性樹脂，容易控制與原位聚合而形成的區域的相互極性，進而容易發生相分離，基體樹脂所具有的熱塑性樹脂中的導電性粒子的偏向分佈變得更容易。 另外，如果基體樹脂為熱塑性的非交聯氨基甲酸酯系樹脂，則作為導電性黏接劑，重複耐久性較優異，進一步可得到適度的硬度，因而優選。(2) Category 2 On the other hand, as the thermoplastic resin used for the base resin, for example, phenoxy resin, acrylic resin (non-crosslinked acrylic resin), urethane resin (non-crosslinked urethane resin) Resin), polyester resin (non-crosslinked polyester resin), silicone resin, etc., alone or in combination of two or more. In addition, among these, non-crosslinked urethane-based resins are thermoplastic resins that are more preferable matrix resins. The reason for this is that by using the thermoplastic resin contained in the matrix resin, it is easy to control the mutual polarity of the regions formed by in-situ polymerization, and furthermore, the phase separation is likely to occur, and the conductive particles in the thermoplastic resin of the matrix resin are biased. Distribution becomes easier. In addition, if the base resin is a thermoplastic non-crosslinked urethane-based resin, it is preferable as a conductive adhesive because it has excellent repetitive durability and can obtain appropriate hardness.

（3）配合量 另外，優選使基體樹脂的配合量相對於導電性粒子（銀粒子等）100重量份為15～225重量份的範圍內的值。 該原因是因為通過如此調整基體樹脂的配合量，基體樹脂所具有的熱固化區域和／或熱塑性樹脂中的導電性粒子的偏向分佈化變得更容易，可得到良好的電特性，並且相對於各種被黏物的黏接性等變得更良好。 即是因為若基體樹脂的配合量為小於15重量份的值，則熱處理後，無法穩定地微相分離，有時導電性粒子的偏向分佈化變得不充分。 另一方面，若基體樹脂的配合量為超過225重量份的值，則有時電導率降低，反之電阻率過度增加。 因此，更優選使基體樹脂的配合量相對於導電性粒子100重量份為17～210重量份的範圍內的值，進一步優選為21～195重量份的範圍內的值。(3) Mixing amount In addition, it is preferable that the blending amount of the matrix resin is a value in the range of 15 to 225 parts by weight with respect to 100 parts by weight of conductive particles (silver particles, etc.). This is because by adjusting the blending amount of the matrix resin in this way, the thermosetting region of the matrix resin and/or the distribution of the conductive particles in the thermoplastic resin becomes easier, and good electrical characteristics can be obtained. The adhesion of various adherends etc. becomes better. That is, if the blending amount of the base resin is less than 15 parts by weight, after the heat treatment, the microphase separation cannot be stably performed, and the uneven distribution of the conductive particles may become insufficient. On the other hand, if the blending amount of the base resin exceeds 225 parts by weight, the electrical conductivity may decrease, and conversely, the electrical resistivity may increase excessively. Therefore, it is more preferable that the blending amount of the matrix resin is a value in the range of 17 to 210 parts by weight with respect to 100 parts by weight of the conductive particles, and a value in the range of 21 to 195 parts by weight is still more preferable.

3.原位聚合用成分 （1）種類 作為原位聚合用成分的種類，只要以規定量混合存在於基體樹脂中，在原位能夠產生規定的聚合反應的單體成分、化合物等，就沒有特別限制，例如優選為丙烯酸系單體和自由基引發劑的組合、封端異氰酸酯化合物和含活性氫基團的化合物的組合（例如氨基甲酸酯預聚物的封端化物和聚胺的組合）、環氧樹脂和離子聚合催化劑中的至少一個。 特別是如果原位聚合用成分是丙烯酸系單體和自由基引發劑的組合、或封端異氰酸酯化合物和含活性氫基團的化合物的組合，則在各種基體樹脂中均以較低的溫度迅速且均勻地進行原位聚合，因而可以說是優選的。3. Ingredients for in-situ polymerization (1) Type There are no particular restrictions on the types of components for in-situ polymerization as long as they are mixed in a predetermined amount in the matrix resin and can produce a predetermined polymerization reaction in situ, such as monomer components, compounds, etc., and for example, acrylic monomers and Combinations of free radical initiators, combinations of blocked isocyanate compounds and compounds containing active hydrogen groups (for example, combinations of blocked urethane prepolymers and polyamines), epoxy resins and ion polymerization catalysts at least one. Especially if the in-situ polymerization component is a combination of acrylic monomers and free radical initiators, or a combination of blocked isocyanate compounds and active hydrogen group-containing compounds, it will be rapid in various matrix resins at lower temperatures. In addition, the in-situ polymerization is performed uniformly, which can be said to be preferable.

（2）配合量 另外，優選使原位聚合用成分的配合量相對於基體樹脂100重量份為30～200重量份的範圍內的值。 該原因是因為若該原位聚合用成分的配合量過少，為小於30重量份，則有時難以在各種基體樹脂中以比較低的溫度迅速且均勻地進行原位聚合。 另一方面，若該原位聚合用成分的配合量超過200重量份，則有時反而容易殘留未反應的原位聚合。 因此，更優選使原位聚合用成分的配合量相對於基體樹脂100重量份為40～150重量份的範圍內的值，進一步優選為50～100重量份的範圍內的值。(2) Mixing amount Moreover, it is preferable that the compounding quantity of the component for in-situ polymerization is a value in the range of 30-200 weight part with respect to 100 weight part of matrix resins. This is because if the blending amount of the component for in-situ polymerization is too small, less than 30 parts by weight, it may sometimes be difficult to perform in-situ polymerization quickly and uniformly in various matrix resins at a relatively low temperature. On the other hand, if the blending amount of the component for in-situ polymerization exceeds 200 parts by weight, unreacted in-situ polymerization tends to remain instead. Therefore, it is more preferable that the compounding amount of the component for in-situ polymerization is a value in the range of 40 to 150 parts by weight with respect to 100 parts by weight of the matrix resin, and a value in the range of 50 to 100 parts by weight is still more preferable.

4.其它配合成分 （1）黏度調節劑 另外，優選在導電性黏接劑中，配合芳香族烴類、酯類、酮類、二元醇醚等中的至少一種作為黏度調節劑（稀釋劑、相分離調節劑等）。 作為芳香族烴類的種類，更優選為甲苯、二甲苯等，作為酯類，更優選為乙酸乙酯、乙酸戊酯等，作為酮類，更優選為甲基乙基酮、甲基異丁基酮等，作為二元醇醚，更優選為乙二醇單丁基醚、乙二醇二甲基醚等。4. Other ingredients (1) Viscosity regulator In addition, it is preferable to blend at least one of aromatic hydrocarbons, esters, ketones, glycol ethers, etc. as a viscosity modifier (diluent, phase separation modifier, etc.) in the conductive adhesive. As the type of aromatic hydrocarbons, toluene, xylene, etc. are more preferred, as esters, ethyl acetate, amyl acetate, etc. are more preferred, and as ketones, methyl ethyl ketone and methyl isobutyl are more preferred. The base ketones, etc., as glycol ethers are more preferably ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, and the like.

而且，導電性黏接劑中的黏度調節劑的配合量根據導電性黏接劑的用途等確定，但通常優選相對於基體樹脂100重量份為0.1～2000重量份的範圍內的值。 該原因是因為若該黏度調節劑的配合量過少，小於0.1重量份，則有時無法表現出配合的添加效果，反之若黏度調節劑的配合量超過2000重量份，則有時無法適當地實施原位聚合。 因此，更優選為使黏度調節劑的配合量相對於基體樹脂100重量份為1～200重量份的範圍內的值，進一步優選為10～100重量份的範圍內的值。In addition, the compounding amount of the viscosity modifier in the conductive adhesive is determined according to the use of the conductive adhesive and the like, but it is usually preferably a value in the range of 0.1 to 2000 parts by weight with respect to 100 parts by weight of the base resin. The reason is that if the blending amount of the viscosity modifier is too small, less than 0.1 parts by weight, the added effect of the blending may not sometimes be exhibited. On the contrary, if the blending amount of the viscosity modifier exceeds 2000 parts by weight, it may not be properly implemented. In-situ polymerization. Therefore, it is more preferable that the compounding quantity of a viscosity adjuster is the value in the range of 1-200 weight part with respect to 100 weight part of matrix resins, and the value in the range of 10-100 weight part is still more preferable.

（2）二氧化矽粒子 另外，優選在導電性黏接劑中，添加二氧化矽粒子作為無機填料。 該原因是因為若在導電性黏接劑中存在二氧化矽粒子，則容易調整基體樹脂與原位聚合而成的區域之間的極性，進一步容易相分離。 另外是因為若在導電性黏接劑中存在二氧化矽粒子，則導熱係數、耐久性、以及黏接性也提高。(2) Silicon dioxide particles In addition, it is preferable to add silica particles as an inorganic filler to the conductive adhesive. This is because if silica particles are present in the conductive adhesive, it is easier to adjust the polarity between the matrix resin and the region formed by in-situ polymerization, and the phase separation is further facilitated. In addition, if silica particles are present in the conductive adhesive, the thermal conductivity, durability, and adhesiveness are also improved.

這裡，作為二氧化矽粒子，疏水性二氧化矽或親水性二氧化矽都可以適宜地配合。 另外，也可以為凝聚二氧化矽粒子或非凝聚二氧化矽粒子。 而且，優選使該二氧化矽粒子的添加量相對於總量為0.1～5重量％的範圍內的值。 該原因是因為若該二氧化矽粒子的添加量為小於0.1重量％的值，則有時不顯示添加效果。 另一方面，若該二氧化矽粒子的添加量為超過5重量％的值，則有時導電性和導熱性過度降低。 因此，更優選為使該二氧化矽粒子的添加量相對於總量為0.2～3重量％的範圍內的值，進一步優選為0.5～2重量％的範圍內的值。Here, as the silica particles, either hydrophobic silica or hydrophilic silica can be suitably blended. In addition, it may be aggregated silica particles or non-aggregated silica particles. Furthermore, it is preferable that the addition amount of the silica particles is a value in the range of 0.1 to 5% by weight with respect to the total amount. The reason is that if the addition amount of the silica particles is less than 0.1% by weight, the addition effect may not be shown. On the other hand, if the addition amount of the silica particles exceeds 5% by weight, the electrical conductivity and thermal conductivity may be excessively reduced. Therefore, it is more preferable that the addition amount of the silica particles is a value in the range of 0.2 to 3% by weight relative to the total amount, and a value in the range of 0.5 to 2% by weight is still more preferable.

（3）其它添加劑 另外，也優選在導電性黏接劑中，添加其它的各種添加劑，例如抗氧化劑、紫外線吸收劑、金屬離子捕獲劑、黏度調節劑、二氧化矽粒子以外的無機填料、有機填料、碳纖維、著色劑以及偶聯劑等。 此時，也根據所配合的添加劑的種類、配合目的而不同，通常優選相對於導電性黏接劑的總量為0.01～10重量％的範圍內，更優選為0.1～5重量％的範圍內。 另外，導電性黏接劑有時因添加導電性粒子而導致氧化劣化加速，因此作為抗氧化劑，優選使胺系抗氧化劑、酚醛系抗氧化劑或磷酸酯系抗氧化劑等相對於總量以0.1～10重量％的範圍內添加。(3) Other additives In addition, it is also preferable to add other various additives to the conductive adhesive, such as antioxidants, ultraviolet absorbers, metal ion traps, viscosity modifiers, inorganic fillers other than silica particles, organic fillers, carbon fibers, coloring Agents and coupling agents. At this time, it also differs according to the type of additives to be blended and the purpose of blending. It is usually preferably in the range of 0.01 to 10% by weight, and more preferably in the range of 0.1 to 5% by weight based on the total amount of the conductive adhesive. . In addition, the addition of conductive particles may accelerate the oxidative degradation of the conductive adhesive. Therefore, as the antioxidant, it is preferable to use an amine antioxidant, a phenolic antioxidant, or a phosphoric ester antioxidant in a ratio of 0.1 to the total amount. Add in the range of 10% by weight.

5.黏度 另外，導電性黏接劑的黏度（測定溫度：25℃，以下相同）可以根據用途等適當地變更，通常優選為0.1～300Pa・sec.的範圍內的值。 該原因是因為若該導電性黏接劑的黏度為小於0.1Pa・sec的值，則有時導電性粒子容易沉澱，或導電性和導熱性顯著降低。 另一方面，若該導電性黏接劑的黏度超過300Pa・sec，則有時操作變得困難，或即使使用點膠機也難以均勻地塗布。 因此，更優選使導電性黏接劑的黏度為1～150Pa・sec的範圍內的值，進一步優選為5～40Pa・sec的範圍內的值。 應予說明，上述導電性黏接劑的黏度可以使用後述的實施例1的E型黏度計，按照規定條件進行測定。5. Viscosity In addition, the viscosity of the conductive adhesive (measurement temperature: 25° C., the same below) can be appropriately changed according to the use and the like, but it is usually preferably a value in the range of 0.1 to 300 Pa·sec. This is because when the viscosity of the conductive adhesive is less than 0.1 Pa·sec, the conductive particles may easily precipitate, or the electrical conductivity and thermal conductivity may be significantly reduced. On the other hand, if the viscosity of the conductive adhesive exceeds 300 Pa·sec, handling may become difficult, or even if a dispenser is used, it may be difficult to apply uniformly. Therefore, the viscosity of the conductive adhesive is more preferably a value in the range of 1 to 150 Pa·sec, and even more preferably a value in the range of 5 to 40 Pa·sec. In addition, the viscosity of the said conductive adhesive can be measured using the E-type viscometer of Example 1 mentioned later under predetermined conditions.

6.密度 另外，優選使導電性黏接劑的密度通常為1.3～3.5g／cm3 的範圍內的值。 該原因是因為若該導電性黏接劑的密度為小於1.3g／cm3 的值，則有時導電性和導熱性顯著降低。 另一方面，若該導電性黏接劑的密度超過3.5g／cm3 ，則有時即使在基體樹脂與原位聚合而成的區域之間相分離，導電性粒子也難以偏向分佈。 另外，若該導電性黏接劑的密度超過3.5g／cm3 ，則有時操作性降低，或黏接性降低，容易從被黏物剝離。 因此，更優選使導電性黏接劑的密度為1.5～3g／cm3 的範圍內的值，進一步優選為1.6～2.5g／cm3 的範圍內的值。6. Density In addition, it is preferable that the density of the conductive adhesive is usually a value in the range of 1.3 to 3.5 g/cm 3 . This is because if the density of the conductive adhesive is less than 1.3 g/cm 3 , the electrical conductivity and thermal conductivity may be significantly reduced. On the other hand, if the density of the conductive adhesive exceeds 3.5 g/cm 3 , even if the matrix resin is separated from the region formed by in-situ polymerization, the conductive particles may be difficult to be distributed unevenly. In addition, if the density of the conductive adhesive exceeds 3.5 g/cm 3 , the workability may be reduced, or the adhesiveness may be reduced, and it may be easily peeled from the adherend. Therefore, it is more preferable to set the density of the conductive adhesive to a value in the range of 1.5 to 3 g/cm 3 , and even more preferably to a value in the range of 1.6 to 2.5 g/cm 3 .

7.製造方法 以下，參照圖2（a）～（c）和圖3～圖4等，對由導電性粒子10、原位聚合用的單體成分12、基體樹脂用單體成分14等製造導電性黏接劑20的方法進行說明。7. Manufacturing method Hereinafter, referring to Figs. 2(a) to (c) and Figs. 3 to 4, etc., a conductive adhesive is made from conductive particles 10, monomer components 12 for in-situ polymerization, and monomer components 14 for matrix resin. The method of agent 20 will be described.

（1）導電性黏接劑的原液的準備 如圖2的（a）所示，由導電性粒子10、原位聚合用的單體成分12、和基體樹脂用單體成分14等製造導電性黏接劑20的原液。 例如，利用螺旋槳式混合機、行星式混合機、三輥機、捏合機、刮刀等，在基體樹脂用單體成分14中混合分散規定量的導電性粒子10、原位聚合用的單體成分12等，製造均勻的導電性黏接劑的原液20a。(1) Preparation of the stock solution of conductive adhesive As shown in FIG. 2( a ), a stock solution of the conductive adhesive 20 is produced from the conductive particles 10, the monomer component 12 for in-situ polymerization, and the monomer component 14 for matrix resin. For example, using a propeller mixer, a planetary mixer, a three-roller, a kneader, a doctor blade, etc., a predetermined amount of conductive particles 10 and a monomer component for in-situ polymerization are mixed and dispersed in the monomer component 14 for matrix resin. 12, etc., to manufacture a uniform conductive adhesive stock solution 20a.

（2）前處理 接著，雖然沒有圖示，但優選對得到的導電性黏接劑的原液，使用過濾器等對導電性粒子的凝聚物、廢物等進行過濾處理而除去。 該原因是因為通過對導電性粒子的凝聚物等進行過濾處理，能夠在使用點膠機等塗布導電性黏接劑的情況下，有效地防止堵塞。 應予說明，如果是導電性粒子（銀粒子等），則通過在內部具有空洞，並且實施規定的表面處理，具有凝聚物的產生少，例如使用孔徑20～200μm的篩網過濾器等能夠容易地進行過濾處理的優點。(2) Pre-treatment Next, although not shown in the drawings, it is preferable to filter and remove the agglomerates of conductive particles, wastes, etc., using a filter or the like to remove the resulting stock solution of the conductive adhesive. The reason for this is that by filtering agglomerates of conductive particles, etc., clogging can be effectively prevented when the conductive adhesive is applied using a dispenser or the like. It should be noted that if it is conductive particles (silver particles, etc.), there are cavities inside and a predetermined surface treatment is performed to reduce the generation of aggregates. For example, it is easy to use a mesh filter with a pore size of 20 to 200 μm. Advantages of filtering treatment locally.

（3）原位聚合 接著，如圖2的（b）所示，通過加熱處理等（有時稱為第1加熱處理等），在基體樹脂用單體成分14中對原位聚合用的單體成分12進行原位聚合。 即，在基體樹脂用單體成分14中，對單體成分12進行原位聚合而形成規定區域12a，它們與基體樹脂用單體成分14相分離，隨之，導電性粒子10稍微偏向分佈，由此製成相分離前的導電性黏接劑（有時稱為原位聚合後的導電性黏接劑）20b。(3) In-situ polymerization Next, as shown in FIG. 2(b), the monomer component 12 for in-situ polymerization is performed in-situ in the monomer component 14 for matrix resin by heat treatment or the like (sometimes referred to as the first heat treatment or the like). polymerization. That is, in the monomer component 14 for matrix resin, the monomer component 12 is polymerized in situ to form a predetermined area 12a, which is separated from the monomer component 14 for matrix resin, and accordingly, the conductive particles 10 are distributed slightly. In this way, a conductive adhesive before phase separation (sometimes referred to as a conductive adhesive after in-situ polymerization) 20b is prepared.

應予說明，如圖3所示，進行第1加熱處理等時，作為原位聚合用單體成分，可使用丙烯酸系單體，因此可以說原位聚合基本上是丙烯酸自由基聚合。 接著，通過加熱處理，進行原位聚合，相分離前的導電性黏接劑的黏度例如在60～80℃再次上升。 應予說明，為圖3所示的本發明的導電性黏接劑的情況下，可理解為例如50～70℃的黏度為1×10-1 Pa・sec.左右，是相當低的值。In addition, as shown in FIG. 3, when the first heat treatment or the like is performed, an acrylic monomer can be used as a monomer component for in-situ polymerization. Therefore, it can be said that in-situ polymerization is basically acrylic radical polymerization. Next, heat treatment is performed to perform in-situ polymerization, and the viscosity of the conductive adhesive before phase separation rises again, for example, at 60 to 80°C. In addition, in the case of the conductive adhesive of the present invention shown in FIG. 3, it can be understood that the viscosity at 50 to 70°C is about 1×10 −1 Pa·sec., which is a relatively low value.

與此相對，不利用圖4所示的現有的原位聚合的導電性黏接劑的情況下，例如在50～70℃為1×102 Pa・sec.左右，黏度是相當高的值。 因此，可理解為本發明的導電性黏接劑在黏度低且黏度的值穩定方面與現有的導電性黏接劑相比，操作性也優異，具有相當大的優勢。 應予說明，如圖2的（c）所示，本發明的導電性黏接劑的情況下，通過加熱處理等（有時稱為第2加熱處理等），使基體樹脂用單體成分14聚合，含有大量的導電性粒子10，與原位聚合而成的區域12a完全相分離，製成本發明的導電性黏接劑20。In contrast, when the conventional in-situ polymerized conductive adhesive shown in FIG. 4 is not used, for example, the viscosity is about 1×10 2 Pa·sec. at 50 to 70° C., and the viscosity is a relatively high value. Therefore, it can be understood that the conductive adhesive of the present invention has a low viscosity and a stable value of viscosity, compared with the existing conductive adhesive, and has excellent operability and has considerable advantages. In addition, as shown in FIG. 2(c), in the case of the conductive adhesive of the present invention, the monomer component 14 for matrix resin is made by heat treatment or the like (sometimes referred to as second heat treatment or the like) After polymerization, a large number of conductive particles 10 are contained, and they are completely separated from the region 12a formed by in-situ polymerization to form the conductive adhesive 20 of the present invention.

然後，優選檢查得到的導電性黏接劑的黏度、外觀等，並且，實際上使用點膠機等而應用於被黏物，評價黏接性、電導率、導電性粒子的偏向分佈性等，確認是本發明中規定的導電性黏接劑。 例如，根據圖5的（a）的照片，可理解在本發明中規定的導電性黏接劑中，主要在基體樹脂中偏向分佈存在有大量導電性粒子。 對此，如圖5的（b）的照片，可理解僅利用環氧系樹脂而不利用相分離的導電性黏接劑時，導電性粒子不會偏向分佈，作為整體相當均勻地存在。Then, it is preferable to inspect the viscosity, appearance, etc. of the obtained conductive adhesive, and actually use a dispenser or the like to apply it to the adherend to evaluate the adhesiveness, electrical conductivity, and distribution of conductive particles. It was confirmed that it is a conductive adhesive specified in the present invention. For example, from the photograph of FIG. 5(a), it can be understood that in the conductive adhesive specified in the present invention, a large number of conductive particles are mainly distributed in a biased manner in the matrix resin. In this regard, as shown in the photograph of Fig. 5(b), it can be understood that when only the epoxy resin is used and the phase-separated conductive adhesive is not used, the conductive particles are not distributed unevenly and exist fairly uniformly as a whole.

應予說明，為本發明的導電性黏接劑的情況下，即使相分離，如圖6中其表面（照片）所示也極其平滑化。 因此，為本發明的導電性黏接劑的情況下，即使加工為膜狀等的形態，也可理解為沒有特別問題。In addition, in the case of the conductive adhesive of the present invention, even if the phases are separated, the surface (photograph) is extremely smooth as shown in FIG. 6. Therefore, in the case of the conductive adhesive of the present invention, even if it is processed into a form such as a film, it can be understood that there is no particular problem.

［第2實施方式］ 第2實施方式是使基體樹脂與原位聚合而成的區域微相分離而成的導電性黏接劑的使用方法，其特徵在於，包括下述工序（1）～（4）。 （1）作為導電性黏接劑，準備包含導電性粒子，基體樹脂與原位聚合而成的區域微相分離的導電性黏接劑的工序； （2）將導電性黏接劑應用於被黏物的工序； （3）對導電性黏接劑進行加熱處理而形成原位聚合而成的區域的工序； （4）通過熱處理形成原位聚合而成的區域和基體樹脂，使它們微相分離，並且將基體樹脂中含有的導電性粒子的含量設為φ1（重量％）、將原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足φ1＞φ2的關係的工序。[Second Embodiment] The second embodiment is a method of using a conductive adhesive obtained by microphase separation of a matrix resin and a domain formed by in-situ polymerization, and is characterized by including the following steps (1) to (4). (1) As a conductive adhesive, a process of preparing a conductive adhesive that contains conductive particles, and the matrix resin is microphase separated from the region formed by in-situ polymerization; (2) The process of applying conductive adhesive to the adherend; (3) The process of heating the conductive adhesive to form a region formed by in-situ polymerization; (4) The in-situ polymerized region and the matrix resin are formed by heat treatment, and they are microphase separated, and the content of the conductive particles contained in the matrix resin is set to φ1 (weight%), and the in-situ polymerization is made When the content of the conductive particles contained in the region is φ2 (weight%), a step that satisfies the relationship of φ1>φ2.

1.工序（1） 工序（1）是作為導電性黏接劑，準備包含導電性粒子進行加熱處理的情況下，使基體樹脂與原位聚合而成的區域微相分離的導電性黏接劑的工序。 而且，優選在準備導電性黏接劑時，將原位聚合的反應溫度設為T1（℃）、將基體樹脂的反應溫度設為T2（℃）時，將ΔT＝絕對值（T2-T1）設為5～50的範圍內的值。 該原因是因為通過滿足這樣的溫度關係，在熱固化等前的較低黏度的基體樹脂區域中，通過原位聚合即便丙烯酸系單體等也能夠均勻且高精度地聚合化而微相分離。 因此，更優選將ΔT＝絕對值（T2-T1）設為10～45的範圍內的值，進一步優選將ΔT＝絕對值（T2-T1）設為15～40的範圍內的值。 應予說明，在工序（1）的導電性黏接劑的準備工序中，第1實施方式中說明的導電性黏接劑的配合成分、製造方法等可以是相同的內容，因此省略再次說明。1. Process (1) Step (1) is a step of preparing, as a conductive adhesive, a conductive adhesive that microphase separates the matrix resin from the region formed by in-situ polymerization when the conductive particles are included in the heat treatment. Furthermore, it is preferable to set the reaction temperature of the in-situ polymerization to T1 (°C) and the reaction temperature of the matrix resin to T2 (°C) when preparing the conductive adhesive, and set ΔT = absolute value (T2-T1) Set to a value in the range of 5-50. The reason for this is that by satisfying such a temperature relationship, in the low-viscosity matrix resin region before thermal curing or the like, even acrylic monomers and the like can be polymerized uniformly and highly accurately and microphase separated by in-situ polymerization. Therefore, it is more preferable to set ΔT=absolute value (T2-T1) to a value in the range of 10 to 45, and it is still more preferable to set ΔT=absolute value (T2-T1) to a value in the range of 15 to 40. In addition, in the preparation process of the conductive adhesive of the step (1), the compounding components, the manufacturing method, and the like of the conductive adhesive described in the first embodiment may be the same, and therefore the description is omitted again.

2.工序（2） 工序（2）是用於將導電性黏接劑針對被黏物使用點膠機等塗布裝置而應用於各種被黏物，發生原位聚合的準備工序。 因此，由於使用點膠機等塗布裝置，因此優選將導電性黏接劑的黏度設為規定範圍內的值。2. Process (2) Step (2) is a preparation step for applying the conductive adhesive to the adherend using a coating device such as a dispenser and applying it to various adherends to cause in-situ polymerization. Therefore, since a coating device such as a dispenser is used, it is preferable to set the viscosity of the conductive adhesive to a value within a predetermined range.

3.工序（3） 對應用於被黏物的導電性黏接劑進行加熱處理（有時稱為第1加熱處理），使其原位聚合而形成熱可塑區域的工序。 此時，對第1加熱處理的加熱方法、加熱條件根據原位聚合的單體成分的種類等適當地進行變更，但作為一個例子優選為50～100℃、1～60分鐘。3. Process (3) The process of heating the conductive adhesive applied to the adherend (sometimes called the first heating treatment) to polymerize it in situ to form a thermoplastic region. At this time, the heating method and heating conditions of the first heat treatment are appropriately changed according to the types of monomer components to be polymerized in situ, etc. However, as an example, it is preferably 50 to 100° C. for 1 to 60 minutes.

4.工序（4） 工序（4）是如下的工序：將原位聚合而成的區域和基體樹脂通過加熱處理（有時稱為第2加熱處理）形成而微相分離，並且將基體樹脂中含有的導電性粒子的含量設為φ1（重量％）、將原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足φ1＞φ2的關係。 應予說明，是否滿足φ1＞φ2的關係可以根據SEM圖像（SEM照片）充分推定。 進而，根據該SEM圖像，分別由面積計算導電性粒子的含量φ1、φ2，以此為基礎，進一步考慮導電性粒子、樹脂成分的比重等的規定條件，也可以分別換算為重量％，由此能夠容易地確認滿足規定大小關係。 實施例 以下，參照實施例，進一步詳細說明本發明的導電性黏接劑等。4. Process (4) Step (4) is the following step: the region formed by in-situ polymerization and the matrix resin are formed by heat treatment (sometimes referred to as the second heat treatment) to be microphase separated, and the conductive particles contained in the matrix resin are separated When the content is set to φ1 (% by weight) and the content of the conductive particles contained in the region formed by in-situ polymerization is set to φ2 (% by weight), the relationship of φ1>φ2 is satisfied. It should be noted that whether the relationship of φ1>φ2 is satisfied can be fully estimated from the SEM image (SEM photograph). Furthermore, based on the SEM image, the contents φ1 and φ2 of the conductive particles are calculated from the area, and based on this, and further considering predetermined conditions such as the specific gravity of the conductive particles and the resin component, they can also be converted into weight %, respectively. This can easily confirm that the prescribed size relationship is satisfied. Example Hereinafter, referring to Examples, the conductive adhesive and the like of the present invention will be described in further detail.

［實施例1］ 1.導電性粒子（銀粒子）的製造 （1）毛栗狀銀粉（A-1）的製備 首先，準備包含硝酸銀和離子交換水的第1水溶液。 即，在帶有攪拌裝置的容器（容器A）內收容硝酸銀4g和離子交換水24g，使用磁力攪拌器攪拌直到均勻溶解。 接著，準備包含還原劑和離子交換水的第2水溶液。 即，在其它帶有攪拌裝置的容器（容器B）內收容作為還原劑的L-抗壞血酸4g、離子交換水24g，使用磁力攪拌器攪拌直到均勻溶解，形成L-抗壞血酸水溶液。[Example 1] 1. Manufacturing of conductive particles (silver particles) (1) Preparation of hair chestnut-shaped silver powder (A-1) First, a first aqueous solution containing silver nitrate and ion exchange water is prepared. That is, 4 g of silver nitrate and 24 g of ion-exchange water were contained in a container with a stirring device (container A), and stirred with a magnetic stirrer until uniformly dissolved. Next, a second aqueous solution containing a reducing agent and ion exchange water is prepared. That is, 4 g of L-ascorbic acid as a reducing agent and 24 g of ion-exchanged water were contained in another container with a stirring device (container B), and stirred with a magnetic stirrer until uniformly dissolved to form an L-ascorbic acid aqueous solution.

在得到的L-抗壞血酸水溶液中投入用於生成核物質的液體2.5g，製成第2水溶液。即，該用於生成核物質的液體在其總量中，混合97.4重量％的水、明膠0.1重量％和硝酸銀1重量％之後，在80℃加熱溶解。然後，冷卻至25℃後，將濃度28重量％的氨水1.5重量％和硝酸銀1重量％在室溫均勻地混合攪拌而構成。 接著，以各自的液溫成為25℃的方式保持溫度後，向容器A中的第1水溶液添加容器B的第2水溶液，保持原狀繼續攪拌，使毛栗狀銀粉析出生成。In the obtained L-ascorbic acid aqueous solution, 2.5 g of a liquid for generating nuclear substances was added to prepare a second aqueous solution. That is, in the total amount of the liquid for generating nuclear materials, 97.4% by weight of water, 0.1% by weight of gelatin, and 1% by weight of silver nitrate were mixed, and then heated and dissolved at 80°C. Then, after cooling to 25°C, ammonia water 1.5% by weight and 1% by weight of silver nitrate having a concentration of 28% by weight were uniformly mixed and stirred at room temperature to form a structure. Next, after maintaining the temperature so that the respective liquid temperatures became 25° C., the second aqueous solution of the container B was added to the first aqueous solution in the container A, and stirring was continued as it was to precipitate and produce chestnut-like silver powder.

接著，利用離子交換水將析出生成的毛栗狀銀粉水洗後，將肉豆蔻酸銨水溶液（濃度：0.5重量％）1g添加到混合液中，利用有機酸進行表面處理。 之後，將進行了表面處理的毛栗狀銀粉通過過濾排乾，並且使用真空烘箱，以100℃在3小時的條件下進行乾燥，得到毛栗狀銀粉（A-1，平均粒徑（D50）：3μm）。Next, after washing the deposited and produced chestnut-like silver powder with ion exchange water, 1 g of an ammonium myristate aqueous solution (concentration: 0.5% by weight) was added to the mixed solution, and the surface treatment was performed with an organic acid. After that, the surface-treated chestnut-shaped silver powder was drained by filtration, and dried using a vacuum oven at 100°C for 3 hours to obtain a chestnut-shaped silver powder (A-1, average particle size (D50)) : 3μm).

（2）封端異氰酸酯化合物（c1）的製備 在帶有攪拌裝置的容器內收容SANPRENE P-663L（氨基甲酸酯預聚物溶液，異氰酸酯含量2.9％，三洋化成工業（株）製）94.0g，在40℃溫浴加熱升溫後，收容6.0g甲基乙基酮肟（東京化成工業（株）製），混合30分鐘。放熱平緩後，在70℃的溫浴中混合3小時。 此時，利用紅外分光計確認表示2200cm-1 異氰酸酯基的峰消失，得到封端氨基甲酸酯溶液（c1）。(2) Preparation of blocked isocyanate compound (c1): 94.0 g of SANPRENE P-663L (urethane prepolymer solution, isocyanate content 2.9%, manufactured by Sanyo Chemical Industry Co., Ltd.) is contained in a container with a stirring device , After heating in a 40°C warm bath, containing 6.0 g of methyl ethyl ketoxime (manufactured by Tokyo Chemical Industry Co., Ltd.) and mixing for 30 minutes. After the exotherm was gentle, the mixture was mixed in a warm bath at 70°C for 3 hours. At this time, it was confirmed with an infrared spectrometer that the peak indicating the isocyanate group at 2200 cm -1 disappeared, and a blocked urethane solution (c1) was obtained.

（3）導電性黏接劑的製作 在行星混合器容器內收容23.3g的YL-983U（雙酚F型環氧樹脂，三菱化學（株）製）、7.4g的ADEKA GLYCIROL ED-509S（丁基苯基縮水甘油醚，ADEKA製）、3.5g的CUREZOL C-11Z（咪唑，四國化成工業製），混合15分鐘，得到熱固化樹脂成分（B-1）。 接著，收容上述（2）中得到的封端異氰酸酯化合物（c1）13.3g、ADEKA HARDENER EH-5030S（聚胺化合物，ADEKA製）2.5g的混合物（C-1）後，混合15分鐘。 接著，收容毛栗狀銀粉（A-1）50.0g，攪拌混合60分鐘直到配合成分變得均勻。 接著，使混合物通過三輥機（輥間隔30～40μm，轉速20rpm）2次後，再次返回到行星混合器容器。 接著，在-0.1MPa・G的減壓條件下，脫泡30分鐘後，使用具備孔徑63μm的篩網過濾器的過濾裝置，進行過濾處理，得到利用原位聚合的導電性黏接劑，實施下述的評價。(3) Production of conductive adhesive 23.3g of YL-983U (bisphenol F epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.) and 7.4g of ADEKA GLYCIROL ED-509S (butylphenyl glycidyl ether, manufactured by ADEKA) are contained in the planetary mixer container , 3.5 g of CUREZOL C-11Z (imidazole, manufactured by Shikoku Chemical Industry Co., Ltd.), mixed for 15 minutes to obtain a thermosetting resin component (B-1). Next, a mixture (C-1) of 13.3 g of the blocked isocyanate compound (c1) obtained in (2) above and 2.5 g of ADEKA HARDENER EH-5030S (polyamine compound, manufactured by ADEKA) was accommodated, and then mixed for 15 minutes. Next, 50.0 g of hair chestnut-shaped silver powder (A-1) was contained, and the mixture was stirred and mixed for 60 minutes until the blended ingredients became uniform. Next, the mixture was passed through a three-roller (roll interval 30-40 μm, rotation speed 20 rpm) twice, and then returned to the planetary mixer container again. Next, after defoaming for 30 minutes under reduced pressure of -0.1MPa·G, a filter device equipped with a mesh filter with a pore size of 63μm is used for filtration treatment to obtain a conductive adhesive by in-situ polymerization. The following evaluation.

2.導電性黏接劑的評價 （1）黏度 使用E型黏度計VISCOMETER TV22（東洋工業（株）製）對得到的導電性黏接劑（導電性糊劑）的黏度（測定溫度：25℃）進行測定，按照下述基準評價。 ◎：40Pa・sec.以下。 〇：超過40Pa・sec.且為150Pa・sec.以下。 △：超過150Pa・sec.且為300Pa・sec.以下。 ×：超過300Pa・sec.。2. Evaluation of conductive adhesive (1) Viscosity The viscosity (measurement temperature: 25°C) of the obtained conductive adhesive (conductive paste) was measured using an E-type viscometer VISCOMETER TV22 (manufactured by Toyo Kogyo Co., Ltd.), and evaluated according to the following criteria. ◎: Below 40Pa·sec. ○: More than 40 Pa·sec. and less than 150 Pa·sec. △: More than 150Pa·sec. and less than 300Pa·sec. ×: More than 300Pa·sec.

（2）相分離性 評價得到的導電性黏接劑的相分離性。 即，利用點膠機將得到的導電性黏接劑塗布在厚度1mm的玻璃板上1cm3 後，在微風烘箱中，在溫度120℃、1小時的條件下進行加熱處理，使導電性黏接劑熱固化，進一步實施表面研磨，得到測定樣品。 接著，對測定樣品的研磨表面進行SEM觀察，按照下述基準評價基體樹脂與原位聚合而成的區域的相分離性。 ◎：觀察到微相分離為雙連續結構。 ○：觀察到微相分離為海島結構。 △：觀察到微相分離為反向海島結構。 ×：沒有觀察到相分離。(2) Phase separability The phase separability of the conductive adhesive obtained by evaluation. That is, after applying the obtained conductive adhesive on a glass plate with a thickness of 1mm by a dispenser for 1 cm 3 , it is heated in a breeze oven at a temperature of 120°C for 1 hour to make the conductive adhesive bond. The agent is thermally cured, and the surface is further polished to obtain a measurement sample. Next, the polished surface of the measurement sample was observed by SEM, and the phase separation between the matrix resin and the in-situ polymerized region was evaluated according to the following criteria. ⊚: Microphase separation into a bicontinuous structure is observed. ○: Microphase separation into a sea-island structure is observed. △: Microphase separation into a reverse sea-island structure is observed. ×: No phase separation is observed.

（3）導電性粒子的偏向分佈性 基於評價相分離性的SEM圖像，求出相分離的各相中的導電性粒子的面積，還同時考慮比重等，由此換算為導電性粒子的相分離的各相中的重量比例。 即，根據換算的基體樹脂區域的、導電性粒子的存在比例（φ1）與原位聚合而成的區域的導電性粒子的存在比例（φ2），按照下述基準，評價導電性粒子的偏向分佈性。 ◎：滿足φ1＞φ2×10。 〇：φ1＞φ2×5且滿足φ1≤φ2×10。 △：φ1＞φ2且滿足φ1≤φ2×5。 ×：φ1≤φ2或在評價對象之外。(3) Partial distribution of conductive particles Based on the SEM image for evaluating the phase separation properties, the area of the conductive particles in each phase of the phase separation is obtained, and the specific gravity is also taken into consideration, and this is converted into the weight ratio of each phase of the phase separation of the conductive particles. That is, based on the ratio of the presence of conductive particles in the matrix resin region (φ1) and the ratio of the presence of conductive particles in the in-situ polymerization region (φ2), the deviated distribution of conductive particles was evaluated based on the following criteria Sex. ◎: Satisfies φ1>φ2×10. ○: φ1>φ2×5 and φ1≤φ2×10 are satisfied. △: φ1>φ2 and satisfy φ1≤φ2×5. ×: φ1≦φ2 or outside the evaluation target.

（4）電阻率 對得到的導電性黏接劑的電阻率（其倒數為導電率）進行評價。 即，利用金屬掩模將得到的導電性黏接劑在厚度1mm的玻璃板上印刷成長度50mm×寬度1mm×厚度0.1mm的線狀。 接著，在微風烘箱中，在溫度120℃、1小時的條件下進行加熱處理，使導電性黏接劑熱固化，製成測定樣品。 接著，使用四端子法（測定電流：0.1mA）測定測定樣品中的線狀的熱固化的導電性黏接劑的2點間（20mm）的電導率（測常量：3），計算其平均值，並且按照下述基準進行評價。 ◎：電阻率的平均值為1×10-2 Ω／cm以下的值。 ○：電阻率的平均值為1×10-1 Ω／cm以下且為上述範圍外的值。 △：電阻率的平均值為1×100 Ω／cm以下且為上述範圍外的值。 ×：電阻率的平均值超過1×101 Ω／cm或無法確認導通的狀態。(4) Electrical resistivity The electrical resistivity (the reciprocal of which is the electrical conductivity) of the obtained conductive adhesive was evaluated. That is, the obtained conductive adhesive was printed on a glass plate having a thickness of 1 mm in a line shape of 50 mm in length × 1 mm in width × 0.1 mm in thickness using a metal mask. Next, in a breeze oven, heat treatment was performed under the conditions of a temperature of 120°C for 1 hour to thermally cure the conductive adhesive to prepare a measurement sample. Next, use the four-terminal method (measurement current: 0.1 mA) to measure the conductivity (measurement constant: 3) between two points (20 mm) of the linear heat-cured conductive adhesive in the measurement sample, and calculate the average value , And evaluated in accordance with the following criteria. ◎: The average value of the resistivity is 1×10 -2 Ω/cm or less. ○: The average value of resistivity is 1×10 -1 Ω/cm or less and is a value outside the above range. △: The average value of resistivity is 1×10 0 Ω/cm or less and is a value outside the above range. ×: The average value of the resistivity exceeds 1×10 1 Ω/cm or the conduction state cannot be confirmed.

（5）黏接性 對得到的導電性黏接劑的黏接性進行評價。 即，使用點膠機將得到的導電性黏接劑的規定量塗布在作為一個被黏物的經鍍銀處理的銅板上。 接著，將作為另一個被黏物的經銀濺射處理的2mm見方Si晶片（Si/Ti/Ag處理）重疊在規定位置。 接著，在微風烘箱中，在溫度120℃、1小時的條件下進行加熱處理，製成測定樣品。 接著，使用拉伸試驗機，測定測定樣品中的剪切黏接強度（測定次數：3），計算其平均值，並且按照下述基準進行評價。 ◎：黏接強度的平均值為20MPa以上的值。 ○：黏接強度的平均值為10MPa以上的值。 △：黏接強度的平均值為5MPa以上的值。 ×：黏接強度的平均值為小於5MPa的值。(5) Adhesion The adhesiveness of the obtained conductive adhesive was evaluated. That is, a predetermined amount of the obtained conductive adhesive is coated on a silver-plated copper plate as an adherend using a dispenser. Next, a 2 mm square Si wafer (Si/Ti/Ag processing) that was subjected to silver sputtering treatment as another adherend was superimposed on a predetermined position. Then, in a breeze oven, heat treatment was performed under the conditions of a temperature of 120°C for 1 hour to prepare a measurement sample. Next, using a tensile tester, the shear bonding strength in the measurement sample was measured (number of measurements: 3), the average value was calculated, and the evaluation was performed according to the following criteria. ⊚: The average value of the adhesive strength is a value of 20 MPa or more. ○: The average value of the adhesive strength is a value of 10 MPa or more. △: The average value of the adhesive strength is a value of 5 MPa or more. ×: The average value of adhesive strength is a value less than 5 MPa.

[實施例2] 實施例2中，作為A成分，將毛栗狀銀粉（A-1）的配合量設為55.0g，作為B成分，使用18.6g的YL-983U、10.9g的ADEKA GLYCIROL ED-509S、2.8g的CUREZOL C-11Z的混合物（B-3），作為C成分，使用10.6g的封端異氰酸酯化合物（c1）和2.0g的ADEKA HARDENER EH-509S的混合物（C-4），除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑，進行評價。[Example 2] In Example 2, as the A component, the blending amount of the hair chestnut-shaped silver powder (A-1) was 55.0 g, and as the B component, 18.6 g of YL-983U, 10.9 g of ADEKA GLYCIROL ED-509S, 2.8 g were used A mixture of CUREZOL C-11Z (B-3), as component C, a mixture of 10.6 g of blocked isocyanate compound (c1) and 2.0 g of ADEKA HARDENER EH-509S (C-4), in addition, In the same manner as in Example 1, a conductive adhesive using in-situ polymerization was obtained and evaluated.

[實施例3] 實施例3中，作為A成分，將毛栗狀銀粉（A-1）的配合量設為60.0g，作為B成分，使用16.7g的YL-983U、9.4g的ADEKA GLYCIROL ED-509S和2.5g的CUREZOL C-11Z的混合物（B-4），作為C成分，使用9.6g的封端異氰酸酯化合物（c1）和1.8g的ADEKA HARDENER EH-509S的混合物（C-5），除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑，進行評價。[Example 3] In Example 3, as the A component, the blending amount of the hair chestnut-shaped silver powder (A-1) was 60.0 g, and as the B component, 16.7 g of YL-983U, 9.4 g of ADEKA GLYCIROL ED-509S, and 2.5 g were used A mixture of CUREZOL C-11Z (B-4), as component C, a mixture (C-5) of 9.6 g of blocked isocyanate compound (c1) and 1.8 g of ADEKA HARDENER EH-509S is used, in addition, In the same manner as in Example 1, a conductive adhesive using in-situ polymerization was obtained and evaluated.

[實施例4] 實施例4中，作為A成分，將薄片狀銀粉（A-2）的配合量設為50.0g，作為B成分，使用20.9g的YL-983U、11.7g的ADEKA GLYCIROL ED-509S和3.1g的CUREZOL C-11Z的混合物（B-5），作為C成分，使用12.0g的封端異氰酸酯化合物（c1）和2.3g的ADEKA HARDENER EH-509S的混合物（C-6），除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑，進行評價。[Example 4] In Example 4, as component A, the blending amount of flaky silver powder (A-2) was 50.0 g, and as component B, 20.9 g of YL-983U, 11.7 g of ADEKA GLYCIROL ED-509S and 3.1 g of CUREZOL C-11Z mixture (B-5), as C component, use 12.0 g of blocked isocyanate compound (c1) and 2.3 g of ADEKA HARDENER EH-509S mixture (C-6), in addition to In Example 1, a conductive adhesive using in-situ polymerization was similarly obtained and evaluated.

應予說明，薄片狀銀粉（A-2）如下進行製造。 首先，準備含有硝酸銀、離子交換水、有機酸和硝酸的第1水溶液。 即，在帶有攪拌裝置的容器（容器A）內收容硝酸銀4g、離子交換水24g、硝酸（濃度：60重量％）0.225g和氨水（濃度：28重量％）0.25g，使用磁力攪拌器攪拌至均勻溶解。 接著，準備含有還原劑和離子交換水的第2水溶液。 即，在另一個帶有攪拌裝置的容器（容器B）內收容作為還原劑的L-抗壞血酸4g、離子交換水24g、檸檬酸（檸檬酸一水合物）0.008g和硝酸（濃度：60重量％）2g，使用磁力攪拌器攪拌至均勻溶解。In addition, the flaky silver powder (A-2) is produced as follows. First, prepare a first aqueous solution containing silver nitrate, ion-exchanged water, organic acid, and nitric acid. That is, 4 g of silver nitrate, 24 g of ion-exchange water, 0.225 g of nitric acid (concentration: 60% by weight), and 0.25 g of ammonia (concentration: 28% by weight) are contained in a container with a stirring device (container A), and stirred with a magnetic stirrer To dissolve evenly. Next, a second aqueous solution containing a reducing agent and ion exchange water is prepared. That is, 4 g of L-ascorbic acid as a reducing agent, 24 g of ion-exchanged water, 0.008 g of citric acid (citric acid monohydrate), and nitric acid (concentration: 60% by weight) are contained in another container with a stirring device (container B) ) 2g, use a magnetic stirrer to stir until uniformly dissolved.

然後，以各自液溫成為25℃的方式保持溫度後，向容器A中的第1水溶液添加容器B中的第2水溶液後，保持原狀繼續攪拌，使薄片狀銀粉析出生成。 接著，利用離子交換水將析出生成的薄片狀銀粉水洗後，在混合液中添加肉豆蔻酸銨水溶液（0.5重量％）1g，利用有機酸進行表面處理。 之後，將進行了表面處理的薄片狀銀粉過濾排乾，並使用真空烘箱，在100℃、3小時的條件下進行乾燥，得到薄片狀銀粉（A-2，平均粒徑（D50）：5μm）。Then, after maintaining the temperature so that the respective liquid temperatures become 25°C, the second aqueous solution in the container B is added to the first aqueous solution in the container A, and stirring is continued as it is to precipitate flaky silver powder. Next, after washing the precipitated flaky silver powder with ion-exchange water, 1 g of an ammonium myristate aqueous solution (0.5% by weight) was added to the mixed solution, and the surface treatment was performed with an organic acid. After that, the surface-treated flaky silver powder was filtered and drained, and dried using a vacuum oven at 100°C for 3 hours to obtain flaky silver powder (A-2, average particle size (D50): 5μm) .

[實施例5] 實施例5中，作為A成分，將薄片狀銀粉（A-2）的配合量設為45.0g，作為B成分，使用23.3g的YL-983U、12.4g的ADEKA GLYCIROL ED-509S、和3.5g的CUREZOL C-11Z的混合物（B-6），作為C成分，使用13.3g的封端異氰酸酯化合物（c1）和2.5g的ADEKA HARDENER EH-509S的混合物（C-7），除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑，進行評價。[Example 5] In Example 5, as component A, the blending amount of flaky silver powder (A-2) was 45.0 g, and as component B, 23.3 g YL-983U, 12.4 g ADEKA GLYCIROL ED-509S, and 3.5 g were used CUREZOL C-11Z mixture (B-6), as the C component, use 13.3g of blocked isocyanate compound (c1) and 2.5g of ADEKA HARDENER EH-509S mixture (C-7), in addition, In the same manner as in Example 1, a conductive adhesive using in-situ polymerization was obtained and evaluated.

[實施例6] 實施例6中，作為A成分，將薄片狀銀粉（A-2）的配合量設為40.0g，作為B成分，使用25.6g的YL-983U、13.2g的ADEKA GLYCIROL ED-509S和3.8g的CUREZOL C-11Z的混合物（B-7），作為C成分，使用14.6g的封端異氰酸酯化合物（c1）和2.8g的ADEKA HARDENER EH-509S的混合物（C-8），除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑，進行評價。[Example 6] In Example 6, as the A component, the blending amount of flaky silver powder (A-2) was 40.0 g, and as the B component, 25.6 g of YL-983U, 13.2 g of ADEKA GLYCIROL ED-509S, and 3.8 g of CUREZOL C-11Z mixture (B-7), as the C component, a mixture of 14.6 g of blocked isocyanate compound (c1) and 2.8 g of ADEKA HARDENER EH-509S (C-8), in addition to In Example 1, a conductive adhesive using in-situ polymerization was similarly obtained and evaluated.

[實施例7] 實施例7中，作為B成分，使用28.6g的YL-983U和1.4g的CUREZOL C-11Z的混合物（B-2），作為C成分，使用下述製造方法中得到的丙烯酸系熱固性樹脂化合物（C-3）代替熱固性樹脂化合物（C-1）並將其配合量設為20.0g，除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑進行評價。 應予說明，丙烯酸系熱固性樹脂化合物（C-3）如下製造。 即，在帶有攪拌裝置的容器內收容甲基丙烯酸二環戊烯氧基乙基酯（SIGMA-ALDRICH公司製）99.0g和2,2’-偶氮雙（2,4-二甲基戊腈）（東京化成工業（株）製）1.0g，接著，混合攪拌30分鐘直到變得均勻，得到丙烯酸系熱固性樹脂化合物（C-3）。[Example 7] In Example 7, as the B component, a mixture (B-2) of 28.6 g of YL-983U and 1.4 g of CUREZOL C-11Z was used, and as the C component, the acrylic thermosetting resin compound obtained in the following production method was used ( C-3) Except that the thermosetting resin compound (C-1) was replaced with 20.0 g and the blending amount was set to 20.0 g, in the same manner as in Example 1, a conductive adhesive using in-situ polymerization was obtained and evaluated. In addition, the acrylic thermosetting resin compound (C-3) is produced as follows. That is, 99.0 g of dicyclopentenoxyethyl methacrylate (manufactured by SIGMA-ALDRICH) and 2,2'-azobis(2,4-dimethylpentane) are contained in a container with a stirring device. Nitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.0 g, and then mixed and stirred for 30 minutes until it became uniform to obtain an acrylic thermosetting resin compound (C-3).

[實施例8] 實施例8中，作為A成分，將薄片狀銀粉（A-2）的配合量設為50g，作為B成分，使用28.6g的YL-983U和1.4g的CUREZOL C-11Z的混合物（B-2），作為C成分，將丙烯酸系熱固性樹脂化合物（C-3）的配合量設為20.0g，除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑，進行評價。[Example 8] In Example 8, as the A component, the blending amount of the flaky silver powder (A-2) was 50 g, and as the B component, a mixture of 28.6 g of YL-983U and 1.4 g of CUREZOL C-11Z (B-2 ), as the C component, except that the blending amount of the acrylic thermosetting resin compound (C-3) was set to 20.0 g, in the same manner as in Example 1, a conductive adhesive using in-situ polymerization was obtained, and Evaluation.

[實施例9] 實施例9中，作為A成分，使用薄片狀銀粉（A-3）並將其配合量設為50g，作為B成分，使用28.6g的YL-983U和1.4g的CUREZOL C-11Z的混合物（B-2），作為C成分，將丙烯酸系熱固性樹脂化合物（C-3）設為20.0g，除此之外，與實施例1同樣地得到利用了原位聚合的導電性黏接劑進行評價。[Example 9] In Example 9, as component A, flaky silver powder (A-3) was used and the blending amount was 50 g, and as component B, a mixture of 28.6 g of YL-983U and 1.4 g of CUREZOL C-11Z (B -2) Except that the acrylic thermosetting resin compound (C-3) was set to 20.0 g as the component C, in the same manner as in Example 1, a conductive adhesive using in-situ polymerization was obtained and evaluated.

應予說明，薄片狀銀粉（A-3）如下進行製造。 首先，準備含有硝酸銀、離子交換水、有機酸和硝酸的第1水溶液。 即，在帶有攪拌裝置的容器（容器A）內，收容硝酸銀4g、離子交換水24g、硝酸（濃度：60重量％）0.225g和氨水（濃度：28重量％）0.25g，使用磁力攪拌器而攪拌至均勻地溶解。 接著，準備含有還原劑和離子交換水的第2水溶液。 即，在其它帶有攪拌裝置的容器（容器B）內，收容作為還原劑的L-抗壞血酸4g、離子交換水24g、檸檬酸（檸檬酸一水合物）0.008g和硝酸（濃度：60重量％）2g，使用磁力攪拌器攪拌至均勻地溶解。 而且，以各自液溫成為25℃的方式保持溫度後，向容器A中的第1水溶液添加容器B中的第2水溶液後，保持這樣持續攪拌，使薄片狀銀粉析出生成。In addition, the flaky silver powder (A-3) is produced as follows. First, prepare a first aqueous solution containing silver nitrate, ion-exchanged water, organic acid, and nitric acid. That is, in a container with a stirring device (container A), 4 g of silver nitrate, 24 g of ion-exchange water, 0.225 g of nitric acid (concentration: 60% by weight), and 0.25 g of ammonia (concentration: 28% by weight) are stored, and a magnetic stirrer is used And stir to dissolve evenly. Next, a second aqueous solution containing a reducing agent and ion exchange water is prepared. That is, in another container with a stirring device (container B), 4 g of L-ascorbic acid as a reducing agent, 24 g of ion exchange water, 0.008 g of citric acid (citric acid monohydrate), and nitric acid (concentration: 60% by weight) ) 2g, use a magnetic stirrer to stir until uniformly dissolved. Then, after maintaining the temperature so that the respective liquid temperatures become 25°C, the second aqueous solution in the container B is added to the first aqueous solution in the container A, and stirring is continued in this manner to precipitate and generate flaky silver powder.

接著，利用離子交換水將析出生成的薄片狀銀粉水洗後，將DL蘋果酸銨水溶液（0.5重量％）1g添加到混合液中，利用機酸進行表面處理。 其後，將進行了表面處理的薄片狀銀粉過濾而排乾，並且使用真空烘箱，在100℃、3小時的條件下進行乾燥，得到薄片狀銀粉（A-3，平均粒徑（D50）：5μm）。Next, after washing the deposited flaky silver powder with ion-exchange water, 1 g of a DL ammonium malate aqueous solution (0.5% by weight) was added to the mixed solution, and the surface treatment was performed with organic acid. After that, the surface-treated flaky silver powder was filtered and drained, and dried using a vacuum oven at 100°C for 3 hours to obtain flaky silver powder (A-3, average particle size (D50): 5μm).

[比較例1] 比較例1中，在行星混合器容器內，收容29.3g的YL-983U（雙酚F型環氧樹脂，三菱化學（株）製）、6.2g的ADEKA GLYCIROL ED-509S（丁基苯基縮水甘油醚，ADEKA製）和4.5g的CUREZOL C-11Z（咪唑，四國化成工業製）後，混合15分鐘，得到熱固化樹脂成分（B-8）。 接著，收容毛栗狀銀粉（A-1）60.0g，攪拌混合60分鐘直到導電性糊劑的配合成分變成均勻。 接著，使混合物通過三輥機（輥間隔30～40μm，轉速20rpm）2次後，再次返回到行星混合器容器。 接著，在-0.1MPa・G的減壓條件下脫泡30分鐘後，使用具備孔徑63μm的網狀過濾器的過濾裝置，進行過濾處理，得到未利用原位聚合的導電性黏接劑，與實施例1同樣地進行評價。[Comparative Example 1] In Comparative Example 1, 29.3 g of YL-983U (bisphenol F epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.) and 6.2 g of ADEKA GLYCIROL ED-509S (butyl phenyl shrinkage) were contained in a planetary mixer container. Glyceryl ether, manufactured by ADEKA) and 4.5 g of CUREZOL C-11Z (imidazole, manufactured by Shikoku Kasei Kogyo) were mixed for 15 minutes to obtain a thermosetting resin component (B-8). Next, 60.0 g of hair chestnut-shaped silver powder (A-1) was contained, and stirred and mixed for 60 minutes until the compounding components of the conductive paste became uniform. Next, the mixture was passed through a three-roller (roll interval 30-40 μm, rotation speed 20 rpm) twice, and then returned to the planetary mixer container again. Then, after degassing for 30 minutes under reduced pressure of -0.1 MPa·G, a filter device with a mesh filter with a pore size of 63 μm is used for filtration treatment to obtain a conductive adhesive that does not utilize in-situ polymerization. Example 1 was evaluated in the same manner.

[比較例2] 比較例2中，作為A成分，將毛栗狀銀粉（A-1）的配合量設為65.0g，作為B成分，使用25.6g的YL-983U、5.5g的ADEKA GLYCIROL ED-509S和3.9g的CUREZOL C-11Z的混合物（B-9），除此之外，與比較例1同樣地得到未利用原位聚合的導電性黏接劑進行評價。[Comparative Example 2] In Comparative Example 2, as the A component, the blending amount of the hair chestnut-shaped silver powder (A-1) was 65.0 g, and as the B component, 25.6 g of YL-983U, 5.5 g of ADEKA GLYCIROL ED-509S and 3.9 g were used Except for the mixture (B-9) of CUREZOL C-11Z, in the same manner as in Comparative Example 1, a conductive adhesive without in-situ polymerization was obtained and evaluated.

[比較例3] 比較例3中，作為A成分，將毛栗狀銀粉（A-1）的配合量設為57.0g，作為B成分，使用31.5g的YL-983U、6.7g的ADEKA GLYCIROL ED-509S、和4.8g的CUREZOL C-11Z的混合物（B-10），除此之外，與比較例1同樣地得到未利用原位聚合的導電性黏接劑進行評價。[Comparative Example 3] In Comparative Example 3, as the A component, the blending amount of the chestnut-shaped silver powder (A-1) was 57.0 g, and as the B component, 31.5 g of YL-983U, 6.7 g of ADEKA GLYCIROL ED-509S, and 4.8 were used. Except for the mixture (B-10) of g CUREZOL C-11Z, in the same manner as in Comparative Example 1, a conductive adhesive that did not use in-situ polymerization was obtained and evaluated.

[比較例4] 比較例4中，作為A成分，將毛栗狀銀粉（A-1）的配合量設為52.0g，作為B成分，使用35.2g的YL-983U、7.5g的ADEKA GLYCIROL ED-509S和5.4g的CUREZOL C-11Z的混合物（B-11），除此之外，與比較例1同樣地得到未利用原位聚合的導電性黏接劑進行評價。[Comparative Example 4] In Comparative Example 4, as the A component, the blending amount of the hair chestnut-shaped silver powder (A-1) was 52.0 g, and as the B component, 35.2 g of YL-983U, 7.5 g of ADEKA GLYCIROL ED-509S and 5.4 g were used Except for the mixture (B-11) of CUREZOL C-11Z, in the same manner as in Comparative Example 1, a conductive adhesive without in-situ polymerization was obtained and evaluated.

[比較例5] 比較例5中，作為A成分，將毛栗狀銀粉（A-1）的配合量設為57.0g，作為C成分，使用37.4g的封端異氰酸酯化合物（c2）和5.6g的ADEKA HARDENER EH-509S的混合物（C-2），除此之外，與比較例1同樣地得到未利用原位聚合的導電性黏接劑進行評價。 應予說明，用作C成分的一部分的封端異氰酸酯化合物（c2）如下進行製造。 首先，在帶有攪拌裝置的容器內，收容SANPRENE P-663L（氨基甲酸酯預聚物溶液，異氰酸酯含量2.9％，三洋化成工業（株）製）75.3g和SANNIX PP-200（聚丙二醇，三洋化成工業製）20.0g，混合攪拌30分鐘。 接著，收容4.7g甲基乙基酮肟（東京化成工業（株）製），混合30分鐘。進一步在70℃的溫浴中混合3小時。並且，利用紅外分光計確認表示2200cm-1異氰酸酯基的峰消失，得到封端異氰酸酯化合物（c2）。[Comparative Example 5] In Comparative Example 5, as the A component, the blending amount of the chestnut-shaped silver powder (A-1) was 57.0 g, and as the C component, 37.4 g of the blocked isocyanate compound (c2) and 5.6 g of ADEKA HARDENER EH- Except for the mixture (C-2) of 509S, in the same manner as in Comparative Example 1, a conductive adhesive that was not polymerized in situ was obtained and evaluated. In addition, the blocked isocyanate compound (c2) used as a part of C component is manufactured as follows. First, in a container with a stirring device, 75.3 g of SANPRENE P-663L (urethane prepolymer solution, isocyanate content 2.9%, manufactured by Sanyo Chemical Co., Ltd.) and SANNIX PP-200 (polypropylene glycol, Sanyo Chemical Industry Co., Ltd.) 20.0g, mixed and stirred for 30 minutes. Next, 4.7 g of methyl ethyl ketoxime (manufactured by Tokyo Chemical Industry Co., Ltd.) was contained and mixed for 30 minutes. It was further mixed in a warm bath at 70°C for 3 hours. In addition, it was confirmed with an infrared spectrometer that the peak indicating the isocyanate group at 2200 cm-1 disappeared, and a blocked isocyanate compound (c2) was obtained.

[比較例6] 比較例6中，作為A成分，將薄片狀銀粉（A-2）的配合量設為50.0g，作為B成分，使用36.6g的YL-983U、7.8g的ADEKA GLYCIROL ED-509S和5.6g的CUREZOL C-11Z的混合物（B-12），除此之外，與比較例1同樣地得到未利用原位聚合的導電性黏接劑進行評價。[Comparative Example 6] In Comparative Example 6, as component A, the blending amount of flaky silver powder (A-2) was 50.0g, and as component B, 36.6g YL-983U, 7.8g ADEKA GLYCIROL ED-509S and 5.6g were used. Except for the mixture (B-12) of CUREZOL C-11Z, in the same manner as in Comparative Example 1, a conductive adhesive that was not polymerized in situ was obtained and evaluated.

[比較例7] 比較例7中，作為A成分，將薄片狀銀粉（A-2）的配合量設為45.0g，作為B成分，使用40.3g的YL-983U、8.6g的ADEKA GLYCIROL ED-509S和6.1g的CUREZOL C-11Z的混合物（B-13），除此之外，與比較例1同樣地得到未利用原位聚合的導電性黏接劑進行評價。[Comparative Example 7] In Comparative Example 7, as component A, the blending amount of flaky silver powder (A-2) was 45.0g, and as component B, 40.3g of YL-983U, 8.6g of ADEKA GLYCIROL ED-509S and 6.1g of Except for the mixture (B-13) of CUREZOL C-11Z, in the same manner as in Comparative Example 1, a conductive adhesive that was not polymerized in situ was obtained and evaluated.

[表1]   A成分 B成分 C成分 評價1 評價2 評價3 評價4 評價5 實施例1 A-1 50 B-1 34.2 C-1 15.8 ○ ○ ◎ ○ ○ 實施例2 A-1 55 B-3 32.3 C-4 12.7 ◎ ○ ◎ ○ ◎ 實施例3 A-1 60 B-4 28.6 C-5 11.4 ○ ○ ◎ ◎ ○ 實施例4 A-2 50 B-5 35.8 C-6 14.3 ○ ○ ◎ ◎ ○ 實施例5 A-2 45 B-6 39.2 C-7 15.8 ◎ ○ ◎ ○ ◎ 實施例6 A-2 40 B-7 42.6 C-8 17.4 ◎ ○ ◎ ○ ◎ 實施例7 A-1 50 B-2 30 C-3 20 ◎ ◎ ◎ ○ ○ 實施例8 A-2 50 B-2 30 C-3 20 ◎ ◎ ◎ ○ ○ 實施例9 A-3 50 B-2 30 C-3 20 ◎ ◎ ◎ ○ ○ 評價1：黏度 評價2：相分離性 評價3：導電性例子的偏向分布性 評價4：電阻率 評價5：黏接性[Table 1] A component B component C component Evaluation 1 Evaluation 2 Evaluation 3 Evaluation 4 Evaluation 5 Example 1 A-1 50 B-1 34.2 C-1 15.8 ○ ○ ◎ ○ ○ Example 2 A-1 55 B-3 32.3 C-4 12.7 ◎ ○ ◎ ○ ◎ Example 3 A-1 60 B-4 28.6 C-5 11.4 ○ ○ ◎ ◎ ○ Example 4 A-2 50 B-5 35.8 C-6 14.3 ○ ○ ◎ ◎ ○ Example 5 A-2 45 B-6 39.2 C-7 15.8 ◎ ○ ◎ ○ ◎ Example 6 A-2 40 B-7 42.6 C-8 17.4 ◎ ○ ◎ ○ ◎ Example 7 A-1 50 B-2 30 C-3 20 ◎ ◎ ◎ ○ ○ Example 8 A-2 50 B-2 30 C-3 20 ◎ ◎ ◎ ○ ○ Example 9 A-3 50 B-2 30 C-3 20 ◎ ◎ ◎ ○ ○ Evaluation 1: Evaluation of viscosity 2: Evaluation of phase separation 3: Evaluation of eccentricity distribution of conductivity examples 4: Evaluation of electrical resistivity 5: Adhesion

[表2]   A成分 B成分 C成分 評價1 評價2 評價3 評價4 評價5 比較例1 A-1 60 B-8 40   △ × × ○ ○ 比較例2 A-1 65 B-9 35   △ × × ○ ○ 比較例3 A-1 57 B-10 43   ○ × × △ ○ 比較例4 A-1 52 B-11 48   ○ × × × ○ 比較例5 A-2 57   C-2 43 × × × △ △ 比較例6 A-2 50 B-12 50   ◎ × × △ ○ 比較例7 A-1 45 B-13 55   ◎ × × × ○ 評價1：黏度 評價2：相分離性 評價3：導電性例子的偏向分布性 評價4：電阻率 評價5：黏接性 產業上的利用可能性[Table 2] A component B component C component Evaluation 1 Evaluation 2 Evaluation 3 Evaluation 4 Evaluation 5 Comparative example 1 A-1 60 B-8 40 △ × × ○ ○ Comparative example 2 A-1 65 B-9 35 △ × × ○ ○ Comparative example 3 A-1 57 B-10 43 ○ × × △ ○ Comparative example 4 A-1 52 B-11 48 ○ × × × ○ Comparative example 5 A-2 57 C-2 43 × × × △ △ Comparative example 6 A-2 50 B-12 50 ◎ × × △ ○ Comparative example 7 A-1 45 B-13 55 ◎ × × × ○ Evaluation 1: Evaluation of viscosity 2: Evaluation of phase separation 3: Evaluation of eccentricity distribution of conductivity examples 4: Evaluation of electrical resistivity 5: Industrial application potential of adhesive

如以上說明，根據本發明，提供一種基體樹脂與原位聚合而成的區域微相分離而成的導電性黏接劑及其使用方法。 並且特徵在於，導電性黏接劑含有規定量的導電性粒子，並且將基體樹脂區域中含有的導電性粒子的含量設為φ1（重量％），將原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足規定的大小關係（φ1＞φ2等）。As explained above, according to the present invention, there is provided a conductive adhesive obtained by microphase separation of a matrix resin and a region formed by in-situ polymerization, and a method of use thereof. And it is characterized in that the conductive adhesive contains a predetermined amount of conductive particles, and the content of the conductive particles contained in the matrix resin region is set to φ1 (weight%), and the conductive particles contained in the region formed by in-situ polymerization When the content of the sexual particles is set to φ2 (weight%), the predetermined size relationship (φ1>φ2, etc.) is satisfied.

因此，在使用導電性黏接劑時，推測熱處理等時的基體樹脂與原位聚合而成的區域穩定地微相分離，導電性粒子容易穩定地偏向分佈在基體樹脂中。Therefore, when a conductive adhesive is used, it is presumed that the matrix resin during heat treatment or the like is stably microphase separated from the region formed by in-situ polymerization, and the conductive particles are likely to be stably distributed in the matrix resin.

因此，根據本發明的導電性黏接劑等，由於偏向分佈在基體樹脂中，因此即使配置較少量的導電性粒子，也可得到良好的導電性、黏接強度，進而可期待這種導電性黏接劑在各種領域中廣泛使用。Therefore, according to the conductive adhesive etc. of the present invention, since it is distributed in the matrix resin, even if a small amount of conductive particles are arranged, good conductivity and bonding strength can be obtained, and this conductivity can be expected Adhesives are widely used in various fields.

其中，還另外發現通過對導電性黏接劑中的基體樹脂的種類、原位聚合而成的區域的種類、以及導電性粒子的表面處理劑/表面處理等分別適當地控制，從而提高導電性粒子與原位聚合而成的區域的親和性，由此與基體樹脂相比，使導電性粒子向原位聚合而成的區域集中地偏向分佈。 因此，根據用途，對於該導電性黏接劑也可以優選地使用。Among them, it has also been found that the conductivity is improved by appropriately controlling the type of matrix resin in the conductive adhesive, the type of in-situ polymerized area, and the surface treatment agent/surface treatment of conductive particles. The affinity between the particles and the region formed by the in-situ polymerization allows the conductive particles to be concentrated and distributed in the region formed by the in-situ polymerization compared with the matrix resin. Therefore, depending on the application, the conductive adhesive can also be preferably used.

10:導電性粒子 12:原位聚合用單體 12a:原位聚合後的區域 14:基體樹脂用單體 14a:熱聚合後的基體樹脂 20:導電性黏接劑 20a:相分離前的導電性黏接劑（導電性黏接劑原液） 20b:原位聚合後的導電性黏接劑10: Conductive particles 12: Monomers for in-situ polymerization 12a: Area after in-situ polymerization 14: Monomer for matrix resin 14a: Matrix resin after thermal polymerization 20: Conductive adhesive 20a: Conductive adhesive before phase separation (conducting adhesive stock solution) 20b: Conductive adhesive after in-situ polymerization

圖1是分別對利用原位聚合而成的導電性黏接劑中的銀添加量（重量％）與導電性黏接劑的電阻率（Ω・cm）的關係、以及不利用原位聚合的導電性黏接劑中的銀添加（重量％）與導電性黏接劑的電阻率（Ω・cm）的關係進行說明的圖。 圖2的（a）～（c）是用於說明包含本發明的基體樹脂和由原位聚合得到的區域的微相分離的圖。 圖3是用於說明本發明的導電性黏接劑（導電性粒子／熱固化系環氧樹脂／由原位聚合得到的丙烯酸樹脂）的反應溫度與黏度的關係的圖。 圖4是用於說明以往的導電性黏接劑（導電性粒子／熱固化系環氧樹脂／聚醚碸樹脂）的反應溫度與黏度的關係的圖。 圖5的（a）是用於說明已相分離的導電性黏接劑中的導電性粒子的狀態的圖（照片，倍率2000），圖5的（b）是用於說明未相分離的導電性黏接劑中的銀狀態的圖（照片，倍率2000）。 圖6是用於說明將已相分離的導電性黏接劑製成片狀時的表面狀態的圖（照片，倍率1000）。 圖7是分別對含有聚醚碸（PES）的導電性黏接劑中的銀添加量（vol.％）與導電性黏接劑的電導率（S／cm）的關係（線A）、以及不含聚醚碸（PES）的導電性黏接劑中的銀添加量（vol.％）與導電性黏接劑的電導率（S／cm）的關係（線B）進行說明的圖。Figure 1 shows the relationship between the amount of silver added (wt%) in a conductive adhesive formed by in-situ polymerization and the electrical resistivity (Ω·cm) of the conductive adhesive, and the relationship between in-situ polymerization A diagram illustrating the relationship between the silver addition (wt%) in the conductive adhesive and the electrical resistivity (Ω·cm) of the conductive adhesive. Fig. 2 (a) to (c) are diagrams for explaining the microphase separation between the matrix resin of the present invention and the region obtained by in-situ polymerization. 3 is a graph for explaining the relationship between the reaction temperature and viscosity of the conductive adhesive (conductive particles/thermosetting epoxy resin/acrylic resin obtained by in-situ polymerization) of the present invention. 4 is a graph for explaining the relationship between the reaction temperature and viscosity of a conventional conductive adhesive (conductive particles/thermosetting epoxy resin/polyether resin). Fig. 5(a) is a diagram (photograph, magnification 2000) for explaining the state of conductive particles in the conductive adhesive that has been phase separated, and Fig. 5(b) is for explaining the conduction without phase separation Picture of the state of silver in the adhesive (photograph, 2000 magnification). Fig. 6 is a diagram for explaining the surface state when the phase-separated conductive adhesive is made into a sheet shape (photograph, magnification: 1000). Figure 7 shows the relationship between the amount of silver added (vol.%) and the conductivity (S/cm) of the conductive adhesive (line A) in the conductive adhesive containing PES (line A), and A graph illustrating the relationship (line B) between the amount of silver added (vol.%) in a conductive adhesive that does not contain polyether sulfite (PES) and the conductivity (S/cm) of the conductive adhesive.

Claims (8)

一種導電性黏接劑，其特徵在於，是基體樹脂與原位聚合而成的區域微相分離而成的導電性黏接劑， 所述導電性黏接劑含有導電性粒子， 將所述基體樹脂中含有的導電性粒子的含量設為φ1（重量％）、將原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足φ1＞φ2的關係。A conductive adhesive characterized in that it is a conductive adhesive formed by microphase separation of a matrix resin and a region formed by in-situ polymerization, The conductive adhesive contains conductive particles, When the content of the conductive particles contained in the matrix resin is set to φ1 (wt%), and the content of the conductive particles contained in the region formed by in-situ polymerization is set to φ2 (wt%), φ1>φ2 is satisfied Relationship. 如請求項1所述的導電性黏接劑，其特徵在於，將所述原位聚合的反應溫度設為T1（℃）、將所述基體樹脂的反應溫度設為T2（℃）時，ΔT（＝T2-T1）的絕對值為5～50的範圍內的值。The conductive adhesive according to claim 1, wherein when the reaction temperature of the in-situ polymerization is set to T1 (°C) and the reaction temperature of the matrix resin is set to T2 (°C), ΔT The absolute value of (=T2-T1) is a value in the range of 5-50. 如請求項1所述的導電性黏接劑，其特徵在於，所述基體樹脂為熱固性環氧樹脂。The conductive adhesive according to claim 1, wherein the matrix resin is a thermosetting epoxy resin. 如請求項1所述的導電性黏接劑，其特徵在於，所述原位聚合而成的區域來自於丙烯酸系單體和自由基引發劑的組合、或者封端異氰酸酯化合物和含活性氫基團的化合物的組合。The conductive adhesive according to claim 1, wherein the region formed by in-situ polymerization is derived from a combination of an acrylic monomer and a radical initiator, or a blocked isocyanate compound and an active hydrogen-containing group The combination of the compound of the group. 如請求項1所述的導電性黏接劑，其特徵在於，使所述導電性粒子的含量相對於總量為25～70重量％的範圍內的值。The conductive adhesive according to claim 1, wherein the content of the conductive particles is a value in the range of 25 to 70% by weight with respect to the total amount. 如請求項1所述的導電性黏接劑，其特徵在於，使黏度為0.1～300Pa・sec.（測定溫度：25℃）的範圍內的值。The conductive adhesive according to claim 1, wherein the viscosity is a value in the range of 0.1 to 300 Pa·sec. (measurement temperature: 25°C). 如請求項1所述的導電性黏接劑，其特徵在於，使電阻率為1×10-4 ～1×100 Ω・cm的範圍內的值。The conductive adhesive according to claim 1, wherein the electrical resistivity has a value in the range of 1×10 -4 to 1×10 0 Ω·cm. 一種導電性黏接劑的使用方法，其特徵在於，是一基體樹脂與一原位聚合而成的區域微相分離而成的導電性黏接劑的使用方法，包括下述工序（1）～（4）， （1）準備含有一導電性粒子、且所述基體樹脂與所述原位聚合而成的區域微相分離的導電性黏接劑的工序； （2）將所述導電性黏接劑應用於一被黏物的工序； （3）對所述導電性黏接劑進行加熱而形成所述原位聚合而成的區域的工序；及 （4）使所述基體樹脂與所述原位聚合而成的區域微相分離，並且將所述基體樹脂中含有的導電性粒子的含量設為φ1（重量％）、將所述原位聚合而成的區域中含有的導電性粒子的含量設為φ2（重量％）時，滿足φ1＞φ2的關係的工序。A method of using a conductive adhesive, characterized in that it is a method of using a conductive adhesive formed by microphase separation of a matrix resin and a region formed by in-situ polymerization, including the following steps (1) to (4), (1) A step of preparing a conductive adhesive containing a conductive particle and the matrix resin is slightly separated from the region formed by in-situ polymerization; (2) The process of applying the conductive adhesive to an adherend; (3) A step of heating the conductive adhesive to form the region formed by the in-situ polymerization; and (4) The matrix resin is microphase separated from the domain formed by the in-situ polymerization, and the content of the conductive particles contained in the matrix resin is set to φ1 (wt%), and the in-situ polymerization When the content of the conductive particles contained in the resulting region is φ2 (% by weight), a step that satisfies the relationship of φ1>φ2.
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