TW202045665A - Circuit-connecting adhesive film and method for manufacturing same, circuit-connecting structure manufacturing method, and adhesive film housing set - Google Patents
Circuit-connecting adhesive film and method for manufacturing same, circuit-connecting structure manufacturing method, and adhesive film housing set Download PDFInfo
- Publication number
- TW202045665A TW202045665A TW109107998A TW109107998A TW202045665A TW 202045665 A TW202045665 A TW 202045665A TW 109107998 A TW109107998 A TW 109107998A TW 109107998 A TW109107998 A TW 109107998A TW 202045665 A TW202045665 A TW 202045665A
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive layer
- adhesive film
- circuit connection
- circuit
- mass
- Prior art date
Links
Images
Classifications
-
- 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
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
- H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
Description
本發明是有關於一種電路連接用接著劑膜及其製造方法、電路連接結構體的製造方法以及接著劑膜收容組。The present invention relates to an adhesive film for circuit connection, a manufacturing method thereof, a manufacturing method of a circuit connection structure, and an adhesive film accommodating group.
先前，為了進行電路連接而使用各種接著材料。例如，作為用於液晶顯示器與帶載封裝體（tape carrier package，TCP）的連接、可撓性印刷配線基板（Flexible Printed Circuit，FPC）與TCP的連接、或FPC與印刷配線板的連接的接著材料，一直使用接著劑中分散有導電粒子且具有各向異性導電性的電路連接用接著劑膜。Previously, various adhesive materials were used for circuit connection. For example, as an adhesive for connecting a liquid crystal display and a tape carrier package (tape carrier package, TCP), connecting a flexible printed circuit board (Flexible Printed Circuit, FPC) and TCP, or connecting an FPC to a printed wiring board As a material, an adhesive film for circuit connection in which conductive particles are dispersed in the adhesive and has anisotropic conductivity has been used.
於使用具有各向異性導電性的電路連接用接著劑膜的精密電子設備的領域中，推進電路的高密度化，電極寬度及電極間隔變得極窄。因此，於微小電極上效率良好地捕捉導電粒子來獲得高連接可靠性未必容易。In the field of precision electronic equipment that uses an adhesive film for circuit connection having anisotropic conductivity, the density of circuits is advanced, and the electrode width and electrode interval have become extremely narrow. Therefore, it is not necessarily easy to efficiently capture conductive particles on the microelectrodes to obtain high connection reliability.
對此，例如專利文獻1中提出有使導電粒子偏向存在於各向異性導電性接著片的單側，將導電粒子彼此隔開的方法。
[現有技術文獻]
[專利文獻]In response to this, for example,
專利文獻1：國際公開第2005/54388號Patent Document 1: International Publication No. 2005/54388
[發明所欲解決之課題]
然而，於專利文獻1的方法中，電路連接時導電粒子流動，因此導電粒子在電極間凝聚，有可能發生短路。另外，隨著導電粒子的流動而出現的導電粒子的疏密分佈不僅使絕緣特性降低，亦有可能產生連接電阻值的偏差，尚有改良的餘地。[The problem to be solved by the invention]
However, in the method of
進而，對於電路連接用接著劑膜，要求於電路構件的連接後，即便於高溫高濕環境下（例如85℃、85%RH）長期使用電路連接結構體的情況下，亦不會自電路構件剝離。Furthermore, with regard to the adhesive film for circuit connection, it is required that after the circuit member is connected, even if the circuit connection structure is used for a long time in a high-temperature and high-humidity environment (for example, 85°C, 85% RH), it will not separate from the circuit member. Peel off.
因此，本發明的目的在於提供一種可抑制電路連接結構體的製造時發生的導電粒子的流動，且可抑制於高溫高濕環境下使用電路連接結構體時發生的電路構件與由接著劑膜所形成的電路連接部的界面處的剝離的電路連接用接著劑膜及其製造方法、使用該接著劑膜的電路連接結構體的製造方法、以及包括該接著劑膜的接著劑膜收容組。 [解決課題之手段]Therefore, the object of the present invention is to provide a circuit member that can suppress the flow of conductive particles that occurs during the manufacture of a circuit connection structure, and can suppress the occurrence of the circuit member and the adhesive film caused when the circuit connection structure is used in a high-temperature and high-humidity environment. The peeled adhesive film for circuit connection at the interface of the formed circuit connection part and its manufacturing method, the manufacturing method of the circuit connection structure body using this adhesive film, and the adhesive film accommodation group containing this adhesive film. [Means to solve the problem]
本發明的一方面的電路連接用接著劑膜包括：第一接著劑層、及積層於該第一接著劑層上的第二接著劑層，第一接著劑層包含光硬化性組成物的硬化物，第二接著劑層包含熱硬化性組成物，光硬化性組成物含有聚合性化合物、具有肟酯結構的光聚合起始劑及導電粒子，且以光硬化性組成物中的導電粒子以外的成分的合計量為基準，光聚合起始劑的含量為0.3質量%～1.2質量%。An adhesive film for circuit connection according to an aspect of the present invention includes a first adhesive layer and a second adhesive layer laminated on the first adhesive layer, and the first adhesive layer includes curing of a photocurable composition The second adhesive layer contains a thermosetting composition, the photocuring composition contains a polymerizable compound, a photopolymerization initiator having an oxime ester structure, and conductive particles, and the conductive particles in the photocuring composition The total amount of the components is the reference, and the content of the photopolymerization initiator is 0.3% by mass to 1.2% by mass.
根據所述方面的電路連接用接著劑膜，可抑制電路連接結構體的製造時發生的導電粒子的流動，且可抑制於高溫高濕環境下使用電路連接結構體時發生的電路構件與接著劑膜的界面處的剝離。根據此種電路連接用接著劑膜，可降低電路連接結構體的相向的電極間的連接電阻，進而，即便於高溫高濕環境下（例如85℃、85%RH）亦可維持低的連接電阻。即，根據該電路連接用接著劑膜，可提升電路連接結構體的連接可靠性。According to the adhesive film for circuit connection of the above aspect, the flow of conductive particles generated during the manufacture of the circuit connection structure can be suppressed, and the circuit member and the adhesive generated when the circuit connection structure is used in a high temperature and high humidity environment can be suppressed Peeling at the interface of the film. According to this adhesive film for circuit connection, the connection resistance between the opposing electrodes of the circuit connection structure can be reduced, and further, the connection resistance can be maintained low even in a high temperature and high humidity environment (for example, 85°C, 85%RH) . That is, according to the adhesive film for circuit connection, the connection reliability of the circuit connection structure can be improved.
本發明的一方面的電路連接用接著劑膜的製造方法包括：準備步驟，準備第一接著劑層；以及積層步驟，於第一接著劑層上積層包含熱硬化性組成物的第二接著劑層，準備步驟包括藉由對包含光硬化性組成物的層照射光而使光硬化性組成物硬化，獲得第一接著劑層的步驟，光硬化性組成物含有聚合性化合物、具有肟酯結構的光聚合起始劑及導電粒子，且以光硬化性組成物中的導電粒子以外的成分的合計量為基準，光聚合起始劑的含量為0.3質量%～1.2質量%。根據該方法，可獲得可抑制電路連接結構體的製造時發生的導電粒子的流動，且可抑制於高溫高濕環境下使用電路連接結構體時發生的電路構件與接著劑膜的界面處的剝離的電路連接用接著劑膜。A method of manufacturing an adhesive film for circuit connection according to one aspect of the present invention includes a preparation step of preparing a first adhesive layer; and a layering step of laminating a second adhesive containing a thermosetting composition on the first adhesive layer The preparation step includes the step of curing the photocurable composition by irradiating light to the layer containing the photocurable composition to obtain the first adhesive layer. The photocurable composition contains a polymerizable compound and has an oxime ester structure The content of the photopolymerization initiator and conductive particles is 0.3% to 1.2% by mass based on the total amount of components other than the conductive particles in the photocurable composition. According to this method, it is possible to suppress the flow of conductive particles generated during the manufacture of the circuit connection structure, and it is possible to suppress peeling at the interface between the circuit member and the adhesive film that occurs when the circuit connection structure is used in a high-temperature and high-humidity environment Adhesive film for circuit connection.
聚合性化合物可為具有自由基聚合性基的自由基聚合性化合物。The polymerizable compound may be a radical polymerizable compound having a radical polymerizable group.
熱硬化性組成物可含有具有自由基聚合性基的自由基聚合性化合物。The thermosetting composition may contain a radical polymerizable compound having a radical polymerizable group.
具有肟酯結構的光聚合起始劑可為具有下述式（VI）所表示的結構的化合物。
[化1]
第一接著劑層的厚度可為導電粒子的平均粒徑的0.1倍～0.8倍。The thickness of the first adhesive layer may be 0.1 to 0.8 times the average particle diameter of the conductive particles.
本發明的一方面的電路連接結構體的製造方法包括：使以上所述的電路連接用接著劑膜介於具有第一電極的第一電路構件、與具有第二電極的第二電路構件之間，將第一電路構件及第二電路構件熱壓接，而使第一電極及第二電極彼此電性連接的步驟。A method of manufacturing a circuit connection structure according to an aspect of the present invention includes interposing the above-mentioned adhesive film for circuit connection between a first circuit member having a first electrode and a second circuit member having a second electrode , The step of thermally compressing the first circuit member and the second circuit member to electrically connect the first electrode and the second electrode to each other.
本發明的一方面的接著劑膜收容組包括：以上所述的電路連接用接著劑膜、及收容該接著劑膜的收容構件，且收容構件具有使得能夠自外部視認收容構件的內部的視認部，視認部對波長365 nm的光的透射率為10%以下。An adhesive film accommodating set according to one aspect of the present invention includes: the above-mentioned adhesive film for circuit connection, and a housing member that houses the adhesive film, and the housing member has a visual recognition portion that allows the inside of the housing member to be visually recognized from the outside , The transmittance of the visible part to light with a wavelength of 365 nm is 10% or less.
但是，一般而言，使用電路連接用接著劑膜的環境是被稱為無塵室（clean room）且以一定水準管理室內的溫度、濕度、清潔度的房間，且當自生產現場出貨時，將電路連接用接著劑膜收容至包裝袋等收容構件中，以免直接暴露於外部氣體而因灰塵及濕氣導致品質下降。通常，於該收容構件設置有視認部，所述視認部是由透明的材料形成，以便自收容構件的外部亦可確認貼附於內部的接著劑膜上的製品名、批號、有效期等各種資訊。However, generally speaking, the environment in which the adhesive film for circuit connection is used is a room called a clean room that manages the temperature, humidity, and cleanliness of the room at a certain level, and when it is shipped from the production site , The adhesive film for circuit connection is stored in a packaging bag and other storage members to avoid direct exposure to external air and deterioration of quality due to dust and moisture. Usually, the storage member is provided with a visual recognition section, which is formed of a transparent material so that various information such as the product name, batch number, and expiration date can be confirmed from the outside of the storage member. .
然而，根據本發明者等人的研究得知，當在收容於現有的收容構件來進行保管或搬運後使用以上所述的電路連接用接著劑膜時，有時無法獲得接著劑膜的所述效果。基於此種研究結果，本發明者等人進一步進行研究，結果得知，當使用可與光硬化性組成物中的光聚合起始劑反應的化合物作為熱硬化性組成物中的聚合性化合物時，於接著劑膜的保管中及搬運中熱硬化性組成物硬化，連接電阻的降低效果減小。因此，基於藉由源自第一接著劑層中殘留的光聚合起始劑的自由基而進行熱硬化性組成物中的聚合性化合物的聚合這一推測，本發明者等人進一步進行研究，結果發現，藉由製成包括所述特定的收容構件的接著劑膜收容組，可抑制保管時或搬運時的熱硬化性組成物的硬化，可維持接著劑膜的連接電阻的降低效果。However, according to research conducted by the inventors of the present invention, when the above-mentioned adhesive film for circuit connection is used after being stored in an existing storage member for storage or transportation, sometimes the adhesive film cannot be obtained. effect. Based on the results of such research, the inventors of the present invention conducted further studies and found out that when a compound that can react with the photopolymerization initiator in the photocurable composition is used as the polymerizable compound in the thermosetting composition During storage and transportation of the adhesive film, the thermosetting composition hardens, reducing the effect of reducing the connection resistance. Therefore, based on the assumption that the polymerization of the polymerizable compound in the thermosetting composition is carried out by radicals derived from the photopolymerization initiator remaining in the first adhesive layer, the inventors of the present invention conducted further studies. As a result, it was found that by forming the adhesive film storage group including the specific storage member, hardening of the thermosetting composition during storage or transportation can be suppressed, and the effect of reducing the connection resistance of the adhesive film can be maintained.
即，根據本發明的一方面的接著劑膜收容組，當使用可與光硬化性組成物中的光聚合起始劑反應的化合物作為熱硬化性組成物中的聚合性化合物時，可抑制接著劑膜的保管時或搬運時的該熱硬化性組成物的硬化，可維持接著劑膜的連接電阻的降低效果。 [發明的效果]That is, according to the adhesive film containing set of one aspect of the present invention, when a compound capable of reacting with the photopolymerization initiator in the photocurable composition is used as the polymerizable compound in the thermosetting composition, adhesion can be suppressed. The curing of the thermosetting composition during storage or transportation of the adhesive film can maintain the effect of reducing the connection resistance of the adhesive film. [Effects of the invention]
根據本發明，可提供一種可抑制電路連接結構體的製造時發生的導電粒子的流動，且可抑制於高溫高濕環境下使用電路連接結構體時發生的電路構件與接著劑膜的界面處的剝離的電路連接用接著劑膜及其製造方法。另外，根據本發明，可提供一種使用此種接著劑膜的電路連接結構體的製造方法。另外，根據本發明，可提供一種包括此種接著劑膜的接著劑膜收容組。According to the present invention, it is possible to provide a method that can suppress the flow of conductive particles that occurs during the manufacture of the circuit connection structure, and can suppress the occurrence of the interface between the circuit member and the adhesive film when the circuit connection structure is used in a high temperature and high humidity environment. A peeled adhesive film for circuit connection and its manufacturing method. In addition, according to the present invention, a method for manufacturing a circuit connection structure using such an adhesive film can be provided. In addition, according to the present invention, it is possible to provide an adhesive film containing set including such an adhesive film.
以下，視情況參照圖式對本發明的實施形態進行詳細說明。再者，本說明書中，使用「～」所表示的數值範圍表示包含「～」的前後所記載的數值分別作為最小值及最大值的範圍。另外，個別記載的上限值及下限值能夠任意地組合。另外，本說明書中，所謂「(甲基)丙烯酸酯」是指丙烯酸酯及與其所對應的甲基丙烯酸酯的至少一者。「(甲基)丙烯醯基」等其他類似的表述亦同樣。另外，所謂「(聚)」是指詞頭「聚」存在的情況及不存在的情況兩者。Hereinafter, the embodiments of the present invention will be described in detail with reference to the drawings as appropriate. In addition, in this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as the minimum value and the maximum value, respectively. In addition, the upper limit and the lower limit described separately can be combined arbitrarily. In addition, in this specification, the "(meth)acrylate" refers to at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acryloyl". In addition, the so-called "(聚)" refers to both the presence and absence of the prefix "聚".
＜電路連接用接著劑膜＞
圖1是表示一實施形態的電路連接用接著劑膜的示意剖面圖。如圖1所示，電路連接用接著劑膜1（以下亦簡稱為「接著劑膜1」）包括第一接著劑層2、及積層於第一接著劑層2上的第二接著劑層3。＜Adhesive film for circuit connection＞
Fig. 1 is a schematic cross-sectional view showing an adhesive film for circuit connection according to an embodiment. As shown in FIG. 1, the
（第一接著劑層）
第一接著劑層2包含光硬化性組成物的硬化物（光硬化物）。光硬化性組成物含有（A）聚合性化合物（以下亦稱為「（A）成分」）、（B）具有肟酯結構的光聚合起始劑（以下亦稱為「（B）成分」）及（C）導電粒子4（以下亦稱為「（C）成分」）。光硬化性組成物亦可更含有（D）熱硬化性樹脂（以下亦稱為「（D）成分」）及/或（E）熱聚合起始劑（以下亦稱為「（E）成分」）。即，光硬化性組成物可為光及熱硬化性組成物。(The first adhesive layer)
The first
第一接著劑層2例如可藉由以下方式獲得：藉由對包含光硬化性組成物的層照射光能量而使（A）成分聚合，使光硬化性組成物硬化。即，第一接著劑層2包含導電粒子4、及使光硬化性組成物光硬化而成的接著劑成分5。接著劑成分5中至少包含（A）成分的聚合物。接著劑成分5可含有未反應的（A）成分及（B）成分，亦可不含。The first
[（A）成分：聚合性化合物] （A）成分例如為藉由光聚合起始劑因光（例如紫外光）的照射產生的自由基、陽離子或陰離子而聚合的化合物。（A）成分可為單體、寡聚物或聚合物的任一者。作為（A）成分，可單獨使用一種化合物，亦可組合使用多種化合物。[(A) component: polymerizable compound] The (A) component is, for example, a compound polymerized by radicals, cations, or anions generated by a photopolymerization initiator by irradiation of light (for example, ultraviolet light). (A) The component may be any of monomers, oligomers, and polymers. As the (A) component, one compound may be used alone, or multiple compounds may be used in combination.
（A）成分具有至少一個聚合性基。就連接電阻的降低效果進一步提升、連接可靠性更優異的觀點而言，聚合性基較佳為藉由自由基而進行反應的自由基聚合性基。即，（A）成分較佳為自由基聚合性化合物。作為自由基聚合性基，例如可列舉：乙烯基、烯丙基、苯乙烯基、烯基、伸烯基、(甲基)丙烯醯基、馬來醯亞胺基等。關於（A）成分所具有的聚合性基的數量，就聚合後容易獲得用以降低連接電阻而所需的物性及交聯密度的觀點而言，可為兩個以上，就抑制聚合時的硬化收縮的觀點而言，可為10個以下。就該些觀點而言，（A）成分所具有的聚合性基的數量可為2個～10個。就光照射後可獲得均勻且穩定的膜（第一接著劑層）的方面而言，較佳為抑制聚合時的硬化收縮。於本實施形態中，為了取得交聯密度與硬化收縮的平衡，除使用聚合性基的數量為所述範圍內的聚合性化合物之外，亦可追加使用聚合性基的數量為所述範圍外的聚合性化合物。(A) The component has at least one polymerizable group. From the viewpoint that the effect of reducing the connection resistance is further improved and the connection reliability is more excellent, the polymerizable group is preferably a radical polymerizable group that reacts by radicals. That is, it is preferable that (A) component is a radically polymerizable compound. As a radical polymerizable group, a vinyl group, an allyl group, a styryl group, an alkenyl group, an alkenylene group, a (meth)acryloyl group, a maleimide group etc. are mentioned, for example. Regarding the number of polymerizable groups contained in the component (A), from the viewpoint of easily obtaining physical properties and crosslinking density required to reduce connection resistance after polymerization, it may be two or more, in order to suppress curing during polymerization From the viewpoint of shrinkage, it may be 10 or less. From these viewpoints, the number of polymerizable groups which the (A) component has may be 2-10. In terms of obtaining a uniform and stable film (first adhesive layer) after light irradiation, it is preferable to suppress curing shrinkage during polymerization. In this embodiment, in order to achieve a balance between crosslink density and curing shrinkage, in addition to using a polymerizable compound whose number of polymerizable groups is within the above range, it is also possible to additionally use the number of polymerizable groups outside the above range. The polymerizable compound.
作為（A）成分的具體例，可列舉：(甲基)丙烯酸酯化合物、馬來醯亞胺化合物、乙烯基醚化合物、烯丙基化合物、苯乙烯衍生物、丙烯醯胺衍生物、納迪克醯亞胺（nadiimide）衍生物、天然橡膠、異戊二烯橡膠、丁基橡膠、腈橡膠、丁二烯橡膠、苯乙烯-丁二烯橡膠、丙烯腈-丁二烯橡膠、羧基化腈橡膠等。Specific examples of (A) component include: (meth)acrylate compounds, maleimide compounds, vinyl ether compounds, allyl compounds, styrene derivatives, acrylamide derivatives, and Nadic Nadiimide derivatives, natural rubber, isoprene rubber, butyl rubber, nitrile rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber Wait.
作為(甲基)丙烯酸酯化合物，可列舉：環氧(甲基)丙烯酸酯、(聚)胺基甲酸酯(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、聚醚(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚丁二烯(甲基)丙烯酸酯、矽酮丙烯酸酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸2-氰基乙酯、2-(2-乙氧基乙氧基)(甲基)丙烯酸乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正月桂基酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸四氫糠酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚烷二醇二(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、異三聚氰酸改質二官能(甲基)丙烯酸酯、異三聚氰酸改質三官能(甲基)丙烯酸酯、三環癸基丙烯酸酯、二羥甲基-三環癸烷二丙烯酸酯、2-羥基-1,3-二丙烯醯氧基丙烷、2,2-雙[4-(丙烯醯氧基甲氧基)苯基]丙烷、2,2-雙[4-(丙烯醯氧基聚乙氧基)苯基]丙烷、2,2-二(甲基)丙烯醯氧基二乙基磷酸酯、2-(甲基)丙烯醯氧基乙基酸式磷酸酯等。Examples of the (meth)acrylate compound include epoxy (meth)acrylate, (poly)urethane (meth)acrylate, methyl (meth)acrylate, and polyether (meth) Acrylate, polyester (meth)acrylate, polybutadiene (meth)acrylate, silicone acrylate, ethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 2- (2-Ethoxyethoxy) ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-hexyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, isopropyl (meth)acrylate, hydroxypropyl (meth)acrylate, isobutyl (meth)acrylate, isobornyl (meth)acrylate, (former Base) isodecyl acrylate, isooctyl (meth)acrylate, n-lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate Ester, tetrahydrofurfuryl (meth)acrylate, 2-(meth)acryloyloxyethyl phosphate, N,N-dimethylaminoethyl (meth)acrylate, N (meth)acrylate, N-dimethylaminopropyl ester, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate , Polyethylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Dicyclopentenoxy ethyl ester, neopentyl glycol di(meth)acrylate, pentaerythritol (meth)acrylate, dipentaerythritol hexa(meth)acrylate, isocyanuric acid modified difunctional (meth)acrylate Base) acrylate, isocyanuric acid modified trifunctional (meth)acrylate, tricyclodecyl acrylate, dimethylol-tricyclodecane diacrylate, 2-hydroxy-1,3-di Propyleneoxypropane, 2,2-bis[4-(acryloxymethoxy)phenyl]propane, 2,2-bis[4-(acryloxypolyethoxy)phenyl]propane , 2,2-Di(meth)acryloyloxy diethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, etc.
作為馬來醯亞胺化合物，可列舉：1-甲基-2,4-雙馬來醯亞胺苯、N,N'-間苯雙馬來醯亞胺、N,N'-對苯雙馬來醯亞胺、N,N'-間甲苯雙馬來醯亞胺、N,N'-4,4-聯苯雙馬來醯亞胺、N,N'-4,4-(3,3'-二甲基-聯苯)雙馬來醯亞胺、N,N'-4,4-(3,3'-二甲基二苯基甲烷)雙馬來醯亞胺、N,N'-4,4-(3,3'-二乙基二苯基甲烷)雙馬來醯亞胺、N,N'-4,4-二苯基甲烷雙馬來醯亞胺、N,N'-4,4-二苯基丙烷雙馬來醯亞胺、N,N'-4,4-二苯基醚雙馬來醯亞胺、N,N'-3,3-二苯基碸雙馬來醯亞胺、2,2-雙(4-(4-馬來醯亞胺苯氧基)苯基)丙烷、2,2-雙(3-第二丁基-4-8(4-馬來醯亞胺苯氧基)苯基)丙烷、1,1-雙(4-(4-馬來醯亞胺苯氧基)苯基)癸烷、4,4'-亞環己基-雙(1-(4-馬來醯亞胺苯氧基)-2-環己基)苯、2,2'-雙(4-(4-馬來醯亞胺苯氧基)苯基)六氟丙烷等。Examples of maleimide compounds include: 1-methyl-2,4-bismaleimide benzene, N,N'-m-phenylenedimaleimide, and N,N'-p-phenylenediimide Maleimide, N,N'-m-toluene bismaleimide, N,N'-4,4-biphenyl bismaleimide, N,N'-4,4-(3, 3'-Dimethyl-biphenyl)bismaleimide, N,N'-4,4-(3,3'-dimethyldiphenylmethane)bismaleimide, N,N '-4,4-(3,3'-Diethyldiphenylmethane) bismaleimide, N,N'-4,4-Diphenylmethane bismaleimide, N,N '-4,4-Diphenylpropane bismaleimide, N,N'-4,4-diphenyl ether bismaleimide, N,N'-3,3-diphenylene Bismaleimide, 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis(3-secondbutyl-4-8(4 -Maleimidephenoxy)phenyl)propane, 1,1-bis(4-(4-maleimidephenoxy)phenyl)decane, 4,4'-cyclohexylene- Bis(1-(4-maleimidphenoxy)-2-cyclohexyl)benzene, 2,2'-bis(4-(4-maleimidphenoxy)phenyl)hexafluoro Propane etc.
作為乙烯基醚化合物，可列舉：二乙二醇二乙烯基醚、二丙二醇二乙烯基醚、環己烷二甲醇二乙烯基醚、三羥甲基丙烷三乙烯基醚等。As a vinyl ether compound, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylol propane trivinyl ether, etc. are mentioned.
作為烯丙基化合物，可列舉1,3-二烯丙基鄰苯二甲酸酯、1,2-二烯丙基鄰苯二甲酸酯、三烯丙基異氰脲酸酯等。Examples of the allyl compound include 1,3-diallyl phthalate, 1,2-diallyl phthalate, triallyl isocyanurate, and the like.
就硬化反應速度與硬化後的物性的平衡優異的觀點而言，（A）成分較佳為(甲基)丙烯酸酯化合物。就兼具用以降低連接電阻的凝聚力與用以提升接著力的伸長率、獲得更優異的接著特性的觀點而言，（A）成分可為(聚)胺基甲酸酯(甲基)丙烯酸酯化合物。另外，就提升凝聚力、進一步降低連接電阻的觀點而言，（A）成分可為具有二環戊二烯骨架等高Tg骨架的(甲基)丙烯酸酯化合物。From the viewpoint that the curing reaction rate and the physical properties after curing are excellent in the balance, the (A) component is preferably a (meth)acrylate compound. From the viewpoint of having both the cohesive force to reduce the connection resistance and the elongation to increase the adhesive force, and to obtain more excellent adhesive properties, the (A) component may be (poly)urethane (meth)acrylic acid Ester compound. In addition, from the viewpoint of enhancing the cohesive force and further reducing the connection resistance, the (A) component may be a (meth)acrylate compound having a high Tg skeleton such as a dicyclopentadiene skeleton.
就取得交聯密度與硬化收縮的平衡、進一步降低連接電阻、提升連接可靠性的觀點而言，（A）成分可為於丙烯酸樹脂、苯氧基樹脂、聚胺基甲酸酯樹脂等熱塑性樹脂的末端或側鏈導入有乙烯基、烯丙基、(甲基)丙烯醯基等聚合性基的化合物（例如聚胺基甲酸酯(甲基)丙烯酸酯）。該情況下，就交聯密度與硬化收縮的平衡優異的觀點而言，（A）成分的重量平均分子量可為3000以上，可為5000以上，可為1萬以上。另外，就與其他成分的相容性優異的觀點而言，（A）成分的重量平均分子量可為100萬以下，可為50萬以下，可為25萬以下。就該些觀點而言，（A）成分的重量平均分子量可為3000～100萬，可為5000～50萬，可為1萬～25萬。再者，重量平均分子量是指依照實施例中記載的條件，藉由凝膠滲透層析儀（gel-permeation chromatograph，GPC），且使用由標準聚苯乙烯所得的校準曲線而測定出的值。From the viewpoint of achieving a balance between crosslink density and hardening shrinkage, further reducing connection resistance, and improving connection reliability, component (A) can be a thermoplastic resin such as acrylic resin, phenoxy resin, polyurethane resin, etc. A compound (for example, polyurethane (meth)acrylate) in which a polymerizable group such as a vinyl group, an allyl group, and a (meth)acryloyl group is introduced into the terminal or side chain of. In this case, the weight average molecular weight of the component (A) may be 3000 or more, 5000 or more, or 10,000 or more from the viewpoint of excellent balance between crosslink density and curing shrinkage. In addition, from the viewpoint of excellent compatibility with other components, the weight average molecular weight of the component (A) may be 1 million or less, 500,000 or less, or 250,000 or less. From these viewpoints, the weight average molecular weight of the component (A) may be 3,000 to 1 million, 5,000 to 500,000, or 10,000 to 250,000. In addition, the weight average molecular weight refers to a value measured by a gel-permeation chromatograph (GPC) under the conditions described in the examples and using a calibration curve obtained from standard polystyrene.
作為(甲基)丙烯酸酯化合物，（A）成分較佳為包含具有下述式（1）所表示的磷酸酯結構的自由基聚合性化合物。該情況下，對於無機物（金屬等）的表面的接著強度提升，因此適於電極彼此（例如電路電極彼此）的接著。
[化2]
式（1）中，n表示1～3的整數，R表示氫原子或甲基。In formula (1), n represents an integer of 1 to 3, and R represents a hydrogen atom or a methyl group.
所述具有磷酸酯結構的自由基聚合性化合物例如可藉由使無水磷酸與(甲基)丙烯酸-2-羥基乙酯反應而獲得。作為具有磷酸酯結構的自由基聚合性化合物的具體例，可列舉單(2-(甲基)丙烯醯氧基乙基)酸式磷酸酯、二(2-(甲基)丙烯醯氧基乙基)酸式磷酸酯等。The radically polymerizable compound having a phosphate structure can be obtained, for example, by reacting anhydrous phosphoric acid with 2-hydroxyethyl (meth)acrylate. Specific examples of the radically polymerizable compound having a phosphate structure include mono(2-(meth)acryloyloxyethyl) acid phosphate, di(2-(meth)acryloyloxyethyl) Base) acid phosphate, etc.
就容易獲得用以降低連接電阻、提升連接可靠性而所需的交聯密度的觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，（A）成分的含量可為5質量%以上，可為10質量%以上，可為20質量%以上。就抑制聚合時的硬化收縮的觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，（A）成分的含量可為90質量%以下，可為80質量%以下，可為70質量%以下。就該些觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，（A）成分的含量可為5質量%～90質量%，可為10質量%～80質量%，可為20質量%～70質量%。From the viewpoint of easily obtaining the crosslink density required to reduce the connection resistance and improve the connection reliability, the content of the component (A) is based on the total amount of the components other than the conductive particles in the photocurable composition It may be 5 mass% or more, 10 mass% or more, or 20 mass% or more. From the viewpoint of suppressing curing shrinkage during polymerization, based on the total amount of components other than the conductive particles in the photocurable composition, the content of component (A) may be 90% by mass or less, and 80% by mass or less , Can be 70% by mass or less. From these viewpoints, based on the total amount of the components other than the conductive particles in the photocurable composition, the content of component (A) may be 5 mass% to 90 mass%, or 10 mass% to 80 mass%. %, which can be 20% to 70% by mass.
[（B）成分：光聚合起始劑] 光硬化性組成物含有具有肟酯結構的光聚合起始劑作為（B）成分。[Component (B): photopolymerization initiator] The photocurable composition contains a photopolymerization initiator having an oxime ester structure as the (B) component.
光聚合起始劑可包括多個具有肟酯結構的光聚合起始劑。作為（B）成分，可單獨使用一種化合物，亦可組合使用多種化合物。The photopolymerization initiator may include a plurality of photopolymerization initiators having an oxime ester structure. As the (B) component, one compound may be used alone, or multiple compounds may be used in combination.
作為具有肟酯結構的化合物，較佳為使用具有下述式（VI）所表示的結構的化合物。
[化3]
式（VI）中，R11 、R12 及R13 分別獨立地表示氫原子、碳數1～20的烷基、或包含芳香族系烴基的有機基。In formula (VI), R 11 , R 12, and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an organic group containing an aromatic hydrocarbon group.
作為具有肟酯結構的化合物的具體例，可列舉：1-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-鄰苯甲醯基肟、1,3-二苯基丙三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(鄰苯甲醯基)肟、1,2-辛二酮,1-[4-(苯硫基)苯基-,2-(鄰苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)等。Specific examples of compounds having an oxime ester structure include: 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione -2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2 -O-Benzyl oxime, 1,3-Diphenylglycerin-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxyglycerin-2-(o-benzyl) Aceto) oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(o-benzyl oxime)], ethyl ketone, 1-(9-ethyl- 6-(2-Methylbenzyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) and the like.
就導電粒子的流動抑制效果進一步提升的觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，具有肟酯結構的光聚合起始劑的含量為0.3質量%以上，較佳為0.45質量%以上，更佳為0.55質量%以上，進而佳為0.85質量%以上。就剝離的抑制效果進一步提升的觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，具有肟酯結構的光聚合起始劑的含量為1.2質量%以下，較佳為0.9質量%以下，更佳為0.6質量%以下。就該些觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，具有肟酯結構的光聚合起始劑的含量為0.3質量%～1.2質量%，較佳為0.45質量%～0.9質量%，更佳為0.45質量%～0.6質量%。From the viewpoint of further improving the flow suppression effect of the conductive particles, the content of the photopolymerization initiator having an oxime ester structure is 0.3% by mass or more based on the total amount of the components other than the conductive particles in the photocurable composition , Preferably 0.45 mass% or more, more preferably 0.55 mass% or more, and still more preferably 0.85 mass% or more. From the viewpoint of further enhancing the effect of inhibiting peeling, the content of the photopolymerization initiator having an oxime ester structure is 1.2% by mass or less based on the total amount of the components other than the conductive particles in the photocurable composition. It is preferably 0.9% by mass or less, and more preferably 0.6% by mass or less. From these viewpoints, the content of the photopolymerization initiator having an oxime ester structure is 0.3% by mass to 1.2% by mass based on the total amount of components other than the conductive particles in the photocurable composition, preferably 0.45 mass% to 0.9 mass%, more preferably 0.45 mass% to 0.6 mass%.
除具有肟酯結構的光聚合起始劑以外，光硬化性組成物亦可更含有具有α-胺基苯烷基酮結構、胺基二苯甲酮結構、N-苯基甘胺酸結構、醯基氧化膦結構、苯偶醯二甲基縮酮結構、α-羥基苯烷基酮結構等結構的光聚合起始劑。In addition to the photopolymerization initiator having an oxime ester structure, the photocurable composition may further contain an α-aminophenalkylketone structure, an aminobenzophenone structure, an N-phenylglycine structure, A photopolymerization initiator with a structure such as phosphine oxide structure, benzil dimethyl ketal structure, and α-hydroxyphenalkyl ketone structure.
就導電粒子的流動抑制效果進一步提升的觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，光聚合起始劑的含量的合計為0.3質量%以上，較佳為0.45質量%以上，更佳為0.55質量%以上，進而佳為0.85質量%以上。就剝離的抑制效果進一步提升的觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，（B）成分的含量較佳為1.2質量%以下，更佳為0.9質量%以下，進而佳為0.6質量%以下。就該些觀點而言，以光硬化性組成物中的導電粒子以外的成分的合計量為基準，（B）成分的含量較佳為0.3質量%～1.2質量%，更佳為0.45質量%～0.9質量%，進而佳為0.45質量%～0.6質量%。From the viewpoint of further enhancing the effect of suppressing the flow of conductive particles, the total content of the photopolymerization initiator is preferably 0.3% by mass or more based on the total amount of components other than the conductive particles in the photocurable composition. It is 0.45 mass% or more, more preferably 0.55 mass% or more, and still more preferably 0.85 mass% or more. From the viewpoint of further enhancing the effect of inhibiting peeling, the content of component (B) is preferably 1.2% by mass or less, more preferably 0.9% by mass based on the total amount of components other than the conductive particles in the photocurable composition % Or less, more preferably 0.6% by mass or less. From these viewpoints, based on the total amount of the components other than the conductive particles in the photocurable composition, the content of the component (B) is preferably 0.3% by mass to 1.2% by mass, more preferably 0.45% by mass to 0.9% by mass, more preferably 0.45% by mass to 0.6% by mass.
[（C）成分：導電粒子] （C）成分若為具有導電性的粒子則並無特別限制，可為包含Au、Ag、Ni、Cu、焊料等金屬的金屬粒子；包含導電性碳的導電性碳粒子等。（C）成分亦可為包括核及被覆核的被覆層的被覆導電粒子，所述核包含非導電性的玻璃、陶瓷、塑膠（聚苯乙烯等）等，所述被覆層包含所述金屬或導電性碳。該些中，可較佳地使用包括如下核及被覆核的被覆層的被覆導電粒子，所述核包含由熱熔融性金屬形成的金屬粒子或塑膠，所述被覆層包含金屬或導電性碳。該情況下，容易藉由加熱或加壓而使光硬化性組成物的硬化物變形，因此當將電極彼此電性連接時，可增加電極與（C）成分的接觸面積，而使電極間的導電性進一步提升。[Component (C): Conductive particles] (C) The component is not particularly limited as long as it is conductive particles, and may be metal particles containing metals such as Au, Ag, Ni, Cu, and solder; conductive carbon particles containing conductive carbon, and the like. The component (C) may also be a coated conductive particle including a core and a coating layer covering the core. The core includes non-conductive glass, ceramic, plastic (polystyrene, etc.), etc., and the coating layer includes the metal or Conductive carbon. Among these, it is preferable to use coated conductive particles including a core containing a metal particle or plastic formed of a hot-melt metal and a coating layer covering the core, and the coating layer contains metal or conductive carbon. In this case, it is easy to deform the cured product of the photocurable composition by heating or pressing. Therefore, when the electrodes are electrically connected to each other, the contact area between the electrode and the (C) component can be increased, and the The conductivity is further improved.
（C）成分可為包括所述金屬粒子、導電性碳粒子或被覆導電粒子以及絕緣層的絕緣被覆導電粒子，所述絕緣層包含樹脂等絕緣材料，且被覆該粒子的表面。若（C）成分為絕緣被覆導電粒子，則即便於（C）成分的含量多的情況下，亦會因粒子的表面被樹脂被覆而可抑制由（C）成分彼此的接觸引發短路，另外，亦可提升相鄰電極電路間的絕緣性。（C）成分可單獨使用以上所述的各種導電粒子的一種或組合使用兩種以上。The component (C) may be insulating coated conductive particles including the metal particles, conductive carbon particles, or coated conductive particles, and an insulating layer, the insulating layer containing an insulating material such as resin and covering the surface of the particles. If the component (C) is an insulating-coated conductive particle, even when the content of the component (C) is large, the surface of the particle is coated with resin, so that the contact between the components (C) can be prevented from causing a short circuit. In addition, It can also improve the insulation between adjacent electrode circuits. (C) The component can be used alone or in combination of two or more of the various conductive particles described above.
（C）成分的最大粒徑需要較電極的最小間隔（相鄰電極間的最短距離）更小。就分散性及導電性優異的觀點而言，（C）成分的最大粒徑可為1.0 μm以上，可為2.0 μm以上，可為2.5 μm以上。就分散性及導電性優異的觀點而言，（C）成分的最大粒徑可為50 μm以下，可為30 μm以下，可為20 μm以下。就該些觀點而言，（C）成分的最大粒徑可為1.0 μm～50 μm，可為2.0 μm～30 μm，可為2.5 μm～20 μm。本說明書中，對任意的300個（pcs）導電粒子，藉由使用掃描式電子顯微鏡（Scanning Electron Microscope，SEM）的觀察進行粒徑的測定，將所獲得的最大值設為（C）成分的最大粒徑。再者，於（C）成分具有突起等並非球形的情況下，（C）成分的粒徑設為與SEM的圖像中的導電粒子外切的圓的直徑。(C) The maximum particle size of the component needs to be smaller than the minimum distance between electrodes (the shortest distance between adjacent electrodes). From the viewpoint of excellent dispersibility and conductivity, the maximum particle size of the component (C) may be 1.0 μm or more, may be 2.0 μm or more, or may be 2.5 μm or more. From the viewpoint of excellent dispersibility and conductivity, the maximum particle size of the component (C) may be 50 μm or less, 30 μm or less, or 20 μm or less. From these viewpoints, the maximum particle size of the component (C) may be 1.0 μm to 50 μm, may be 2.0 μm to 30 μm, and may be 2.5 μm to 20 μm. In this manual, for arbitrary 300 pcs conductive particles, the particle size is measured by observation with a scanning electron microscope (Scanning Electron Microscope, SEM), and the maximum value obtained is set as the value of (C) component Maximum particle size. In addition, when the (C) component has protrusions etc. and is not spherical, the particle size of the (C) component shall be the diameter of the circle circumscribed to the conductive particle in the SEM image.
就分散性及導電性優異的觀點而言，（C）成分的平均粒徑可為1.0 μm以上，可為2.0 μm以上，可為2.5 μm以上。就分散性及導電性優異的觀點而言，（C）成分的平均粒徑可為50 μm以下，可為30 μm以下，可為20 μm以下。就該些觀點而言，（C）成分的平均粒徑可為1.0 μm～50 μm，可為2.0 μm～30 μm，可為2.5 μm～20 μm。本說明書中，對任意的300個（pcs）導電粒子，藉由使用掃描式電子顯微鏡（SEM）的觀察進行粒徑的測定，將所獲得的粒徑的平均值設為平均粒徑。From the viewpoint of excellent dispersibility and conductivity, the average particle size of the component (C) may be 1.0 μm or more, 2.0 μm or more, or 2.5 μm or more. From the viewpoint of excellent dispersibility and conductivity, the average particle diameter of the component (C) may be 50 μm or less, 30 μm or less, or 20 μm or less. From these viewpoints, the average particle size of the component (C) may be 1.0 μm to 50 μm, may be 2.0 μm to 30 μm, or may be 2.5 μm to 20 μm. In this specification, the particle size of arbitrary 300 (pcs) conductive particles is measured by observation with a scanning electron microscope (SEM), and the average value of the obtained particle size is the average particle size.
第一接著劑層2中，較佳為（C）成分均勻地分散。就容易獲得穩定的連接電阻的觀點而言，第一接著劑層2中的（C）成分的粒子密度可為100 pcs/mm2
以上，可為1000 pcs/mm2
以上，可為2000 pcs/mm2
以上。就提升相鄰電極間的絕緣性的觀點而言，第一接著劑層2中的（C）成分的粒子密度可為100000 pcs/mm2
以下，可為50000 pcs/mm2
以下，可為10000 pcs/mm2
以下。就該些觀點而言，第一接著劑層2中的（C）成分的粒子密度可為100 pcs/mm2
～100000 pcs/mm2
，可為1000 pcs/mm2
～50000 pcs/mm2
，可為2000 pcs/mm2
～10000 pcs/mm2
。In the first
就可進一步提升導電性的觀點而言，以第一接著劑層中的總體積基準計，（C）成分的含量可為0.1體積%以上，可為1體積%以上，可為5體積%以上。就容易抑制短路的觀點而言，以第一接著劑層中的總體積基準計，（C）成分的含量可為50體積%以下，可為30體積%以下，可為20體積%以下。就該些觀點而言，以第一接著劑層中的總體積基準計，（C）成分的含量可為0.1體積%～50體積%，可為1體積%～30體積%，可為5體積%～20體積%。再者，以光硬化性組成物的總體積為基準的（C）成分的含量可與所述範圍相同。From the viewpoint of further improving conductivity, based on the total volume in the first adhesive layer, the content of component (C) may be 0.1% by volume or more, 1% by volume or more, or 5% by volume or more . From the viewpoint of easily suppressing short circuits, the content of the component (C) may be 50% by volume or less, 30% by volume or less, or 20% by volume based on the total volume in the first adhesive layer. From these viewpoints, based on the total volume in the first adhesive layer, the content of component (C) can be 0.1% to 50% by volume, 1% to 30% by volume, and 5% by volume. %～20% by volume. In addition, the content of the component (C) based on the total volume of the photocurable composition may be the same as the aforementioned range.
[（D）成分：熱硬化性樹脂] （D）成分為藉由熱而硬化的樹脂，具有至少一個熱硬化性基。（D）成分例如為藉由熱而與硬化劑反應並因此而進行交聯的化合物。作為（D）成分，可單獨使用一種化合物，亦可組合使用多種化合物。[Component (D): Thermosetting resin] The component (D) is a resin that is cured by heat and has at least one thermosetting group. The (D) component is, for example, a compound that reacts with the hardener by heat and thereby undergoes crosslinking. As the (D) component, one compound may be used alone, or multiple compounds may be used in combination.
就連接電阻的降低效果進一步提升、連接可靠性更優異的觀點而言，熱硬化性基例如可為環氧基、氧雜環丁烷基等。From the viewpoints that the connection resistance reduction effect is further improved and the connection reliability is more excellent, the thermosetting group may be, for example, an epoxy group, an oxetanyl group, or the like.
作為（D）成分的具體例，可列舉作為表氯醇與雙酚A、雙酚F、雙酚AD等的反應產物的雙酚型環氧樹脂；作為表氯醇與苯酚酚醛清漆、甲酚酚醛清漆等的反應產物的環氧酚醛清漆樹脂；具有含萘環的骨架的萘系環氧樹脂；縮水甘油胺、縮水甘油醚等一分子內具有兩個以上的縮水甘油基的各種環氧化合物等環氧樹脂。Specific examples of (D) component include bisphenol-type epoxy resins as reaction products of epichlorohydrin and bisphenol A, bisphenol F, bisphenol AD, etc.; as epichlorohydrin and phenol novolac, cresol Epoxy novolac resins, which are reaction products of novolacs, etc.; naphthalene-based epoxy resins with a naphthalene ring-containing skeleton; various epoxy compounds having two or more glycidyl groups in one molecule, such as glycidylamine and glycidyl ether Wait for epoxy resin.
以第一接著劑層中的導電粒子以外的成分的合計量為基準，（D）成分的含量可為30質量%以上，且可為70質量%以下，可為30質量%～70質量%。Based on the total amount of the components other than the conductive particles in the first adhesive layer, the content of the component (D) may be 30% by mass or more, 70% by mass or less, or 30% to 70% by mass.
於第一接著劑層包含熱硬化性樹脂的情況下，第一接著劑層可更含有用於使熱硬化性樹脂硬化的硬化劑。作為硬化劑，只要為藉由熱而產生陽離子種的硬化劑，則並無特別限制，可根據目的而適當選擇。作為硬化劑，例如可列舉鋶鹽、錪鹽等。關於硬化劑的含量，例如相對於熱硬化性樹脂100質量份，可為0.1質量份以上，且可為50質量份以下，可為0.1質量份～50質量份。When the first adhesive layer contains a thermosetting resin, the first adhesive layer may further contain a curing agent for curing the thermosetting resin. The curing agent is not particularly limited as long as it is a curing agent that generates cationic species by heat, and can be appropriately selected according to the purpose. As the hardening agent, for example, sulphur salt, sulphur salt, etc. are mentioned. Regarding the content of the curing agent, for example, relative to 100 parts by mass of the thermosetting resin, it may be 0.1 parts by mass or more, and may be 50 parts by mass or less, and may be 0.1 to 50 parts by mass.
[（E）成分：熱聚合起始劑] （E）成分可為藉由熱而產生自由基、陽離子或陰離子的熱聚合起始劑（熱自由基聚合起始劑、熱陽離子聚合起始劑或熱陰離子聚合起始劑），就連接電阻的降低效果進一步提升、連接可靠性更優異的觀點而言，較佳為熱自由基聚合起始劑。作為（E）成分，可單獨使用一種化合物，亦可組合使用多種化合物。[Component (E): Thermal polymerization initiator] (E) Component can be a thermal polymerization initiator (thermal radical polymerization initiator, thermal cationic polymerization initiator or thermal anionic polymerization initiator) that generates free radicals, cations or anions by heat, just connect the resistance From the viewpoint of further enhancing the effect of reducing the amount and having more excellent connection reliability, a thermal radical polymerization initiator is preferred. As the (E) component, one compound may be used alone, or multiple compounds may be used in combination.
熱自由基聚合起始劑藉由熱而分解，從而產生游離自由基。即，熱自由基聚合起始劑為藉由賦予來自外部的熱能量而產生自由基的化合物。作為熱自由基聚合起始劑，可自現有已知的有機過氧化物及偶氮化合物中任意地選擇。作為熱自由基聚合起始劑，就導電粒子的流動抑制效果及剝離的抑制效果進一步提升的觀點而言，較佳為有機過氧化物，就穩定性、反應性及相容性的觀點而言，更佳為一分鐘半衰期溫度為90℃～175℃且重量平均分子量為180～1000的有機過氧化物。藉由一分鐘半衰期溫度處於該範圍，儲存穩定性更優異，自由基聚合性亦足夠高，可於短時間內硬化。The thermal radical polymerization initiator is decomposed by heat to generate free radicals. That is, the thermal radical polymerization initiator is a compound that generates radicals by imparting thermal energy from the outside. As the thermal radical polymerization initiator, it can be arbitrarily selected from conventionally known organic peroxides and azo compounds. As the thermal radical polymerization initiator, an organic peroxide is preferred from the viewpoint of further enhancing the flow inhibition effect and peeling inhibition effect of the conductive particles, and from the viewpoint of stability, reactivity, and compatibility More preferably, it is an organic peroxide with a one-minute half-life temperature of 90°C to 175°C and a weight average molecular weight of 180 to 1000. With the one-minute half-life temperature in this range, the storage stability is better, and the radical polymerizability is high enough to harden in a short time.
作為（E）成分的具體例，可列舉：過氧化新癸酸-1,1,3,3-四甲基丁酯、過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二(2-乙基己基)酯、過氧化新癸酸枯基酯、過氧化二月桂醯、過氧化新癸酸-1-環己基-1-甲基乙酯、過氧化新癸酸第三己酯、過氧化新癸酸第三丁酯、過氧化三甲基乙酸第三丁酯、過氧化-2-乙基己酸-1,1,3,3-四甲基丁酯、2,5-二甲基-2,5-二(2-乙基己醯基過氧化)己烷、過氧化-2-乙基己酸-第三己酯、過氧化-2-乙基己酸第三丁酯、過氧化新庚酸第三丁酯、過氧化-2-乙基己酸第三戊酯、過氧化六氫鄰苯二甲酸二-第三丁酯、過氧化-3,5,5-三甲基己酸第三戊酯、過氧化新癸酸-3-羥基-1,1-二甲基丁基酯、過氧化新癸酸第三戊酯、過氧化二(3-甲基苯甲醯)、過氧化二苯甲醯、過氧化二(4-甲基苯甲醯)、過氧化異丙基單碳酸第三己酯、過氧化馬來酸第三丁酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、2,5-二甲基-2,5-二(3-甲基苯甲醯基過氧化)己烷、過氧化-2-乙基己基單碳酸第三丁酯、過氧化苯甲酸第三己酯、2,5-二甲基-2,5-二(苯甲醯基過氧化)己烷、過氧化苯甲酸第三丁酯、過氧化三甲基己二酸二丁酯、過氧化正辛酸第三戊酯、過氧化異壬酸第三戊酯、過氧化苯甲酸第三戊酯等有機過氧化物；2,2'-偶氮雙-2,4-二甲基戊腈、1,1'-偶氮雙(1-乙醯氧基-1-苯基乙烷)、2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、4,4'-偶氮雙(4-氰基戊酸)、1,1'-偶氮雙(1-環己烷甲腈)等偶氮化合物等。Specific examples of the component (E) include: 1,1,3,3-tetramethylbutyl peroxyneodecanoate, bis(4-tertiarybutylcyclohexyl) peroxydicarbonate, and Di(2-ethylhexyl) oxydicarbonate, cumyl peroxide neodecanoate, dilauric peroxide, 1-cyclohexyl-1-methyl ethyl peroxide, neodecyl peroxide Tertiary hexyl acid, tertiary butyl peroxyneodecanoate, tertiary butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate , 2,5-Dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, peroxy-2-ethylhexanoic acid-third hexyl ester, peroxy-2-ethyl Tertiary butyl caproate, tertiary butyl peroxyneoheptanoate, tertiary pentyl peroxide-2-ethylhexanoate, di-tertiary butyl peroxide hexahydrophthalate, peroxy-3 , 5,5-Trimethylhexanoic acid tertiary amyl ester, Peroxyneodecanoic acid-3-hydroxy-1,1-dimethylbutyl ester, Peroxyneodecanoic acid tertiary amyl ester, Diperoxide ( 3-methylbenzyl), dibenzyl peroxide, bis(4-methylbenzyl) peroxide, tertiary hexyl peroxide isopropyl monocarbonate, tertiary butyl peroxide maleate , Tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-bis(3-methylbenzamide Peroxy)hexane, tert-butyl peroxy-2-ethylhexyl monocarbonate, tertiary hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzyl peroxy) Oxidation) hexane, tertiary butyl peroxybenzoate, dibutyl peroxytrimethyladipate, tertiary amyl peroxide n-octanoate, tertiary amyl peroxide isononanoate, tertiary peroxybenzoic acid Organic peroxides such as tripentyl ester; 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane) ), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 1, Azo compounds such as 1'-azobis(1-cyclohexanecarbonitrile), etc.
就快速硬化性優異的觀點、以及導電粒子的流動抑制效果及剝離的抑制效果進一步提升的觀點而言，以第一接著劑層中的導電粒子以外的成分的合計量為基準，（E）成分的含量可為0.1質量%以上，可為0.5質量%以上，可為1質量%以上。就適用期（pot life）的觀點而言，以第一接著劑層中的導電粒子以外的成分的合計量為基準，（E）成分的含量可為20質量%以下，可為10質量%以下，可為5質量%以下。就該些觀點而言，以第一接著劑層中的導電粒子以外的成分的合計量為基準，（E）成分的含量可為0.1質量%～20質量%，可為0.5質量%～10質量%，可為1質量%～5質量%。第一接著劑層2亦可不含有（E）成分。再者，以光硬化性組成物中的導電粒子以外的成分的合計量為基準的（E）成分的含量可與所述範圍相同。From the viewpoint of excellent rapid curing and the viewpoint that the effect of suppressing the flow of conductive particles and the effect of suppressing peeling are further improved, the total amount of the components other than the conductive particles in the first adhesive layer is used as the reference, (E) component The content can be 0.1% by mass or more, can be 0.5% by mass or more, and can be 1% by mass or more. From the point of view of pot life, based on the total amount of components other than conductive particles in the first adhesive layer, the content of component (E) may be 20% by mass or less, or 10% by mass or less , Can be 5 mass% or less. From these viewpoints, based on the total amount of the components other than the conductive particles in the first adhesive layer, the content of the (E) component may be 0.1% by mass to 20% by mass, and may be 0.5% by mass to 10% by mass. % Can be 1% to 5% by mass. The first
[其他成分]
光硬化性組成物可更含有（A）成分、（B）成分、（C）成分、（D）成分及（E）成分以外的其他成分。作為其他成分，例如可列舉熱塑性樹脂、偶合劑、填充材及以上所述的硬化劑。該些成分亦可含有於第一接著劑層2中。[Other ingredients]
The photocurable composition may further contain components other than the (A) component, (B) component, (C) component, (D) component, and (E) component. Examples of other components include thermoplastic resins, coupling agents, fillers, and the above-mentioned curing agents. These components may also be contained in the first
作為熱塑性樹脂，例如可列舉：苯氧基樹脂、聚酯樹脂、聚醯胺樹脂、聚胺基甲酸酯樹脂、聚酯胺基甲酸酯樹脂、丙烯酸橡膠等。於光硬化性組成物含有熱塑性樹脂的情況下，可容易地形成第一接著劑層。另外，於光硬化性組成物含有熱塑性樹脂的情況下，可緩和光硬化性組成物的硬化時產生的第一接著劑層的應力。另外，於熱塑性樹脂具有羥基等官能基的情況下，第一接著劑層的接著性容易提升。關於熱塑性樹脂的含量，例如以光硬化性組成物中的導電粒子以外的成分的合計量為基準，可為5質量%以上，且可為80質量%以下，可為5質量%～80質量%。Examples of thermoplastic resins include phenoxy resins, polyester resins, polyamide resins, polyurethane resins, polyester urethane resins, and acrylic rubbers. When the photocurable composition contains a thermoplastic resin, the first adhesive layer can be easily formed. In addition, when the photocurable composition contains a thermoplastic resin, the stress of the first adhesive layer generated when the photocurable composition is cured can be alleviated. In addition, when the thermoplastic resin has a functional group such as a hydroxyl group, the adhesiveness of the first adhesive layer is easily improved. Regarding the content of the thermoplastic resin, for example, based on the total amount of the components other than the conductive particles in the photocurable composition, it may be 5% by mass or more, 80% by mass or less, and 5% by mass to 80% by mass. .
作為偶合劑，可列舉具有(甲基)丙烯醯基、巰基、胺基、咪唑基、環氧基等有機官能基的矽烷偶合劑；四烷氧基矽烷等矽烷化合物；四烷氧基鈦酸酯衍生物、聚二烷基鈦酸酯衍生物等。於光硬化性組成物含有偶合劑的情況下，可進一步提升接著性。關於偶合劑的含量，例如以光硬化性組成物中的導電粒子以外的成分的合計量為基準，可為0.1質量%以上，且可為20質量%以下，可為0.1質量%～20質量%。Examples of the coupling agent include silane coupling agents having organic functional groups such as (meth)acrylic acid groups, mercapto groups, amino groups, imidazole groups, and epoxy groups; silane compounds such as tetraalkoxysilanes; tetraalkoxy titanic acid Ester derivatives, polydialkyl titanate derivatives, etc. When the photocurable composition contains a coupling agent, the adhesiveness can be further improved. Regarding the content of the coupling agent, for example, based on the total amount of the components other than the conductive particles in the photocurable composition, it can be 0.1% by mass or more, 20% by mass or less, and can be 0.1% by mass to 20% by mass. .
作為填充材，例如可列舉非導電性的填料（例如非導電粒子）。於光硬化性組成物含有填充材的情況下，可進一步期待連接可靠性的提升。填充材可為無機填料及有機填料的任一者。作為無機填料，例如可列舉二氧化矽微粒子、氧化鋁微粒子、二氧化矽-氧化鋁微粒子、二氧化鈦微粒子、氧化鋯微粒子等金屬氧化物微粒子；氮化物微粒子等無機微粒子。作為有機填料，例如可列舉矽酮微粒子、甲基丙烯酸酯-丁二烯-苯乙烯微粒子、丙烯酸-矽酮微粒子、聚醯胺微粒子、聚醯亞胺微粒子等有機微粒子。該些微粒子可具有均勻的結構，亦可具有核-殼型結構。填充材的最大直徑較佳為小於導電粒子4的最小粒徑。關於填充材的含量，例如以光硬化性組成物的總體積為基準，可為1體積%以上，且可為30體積%以下，可為1體積%～30體積%。Examples of fillers include non-conductive fillers (for example, non-conductive particles). When the photocurable composition contains a filler, further improvement in connection reliability can be expected. The filler may be any one of inorganic filler and organic filler. Examples of the inorganic filler include metal oxide fine particles such as silica fine particles, alumina fine particles, silica-alumina fine particles, titanium dioxide fine particles, and zirconia fine particles; and inorganic fine particles such as nitride fine particles. Examples of the organic filler include organic fine particles such as silicone fine particles, methacrylate-butadiene-styrene fine particles, acrylic-silicone fine particles, polyamide fine particles, and polyimide fine particles. The particles can have a uniform structure or a core-shell structure. The maximum diameter of the filler is preferably smaller than the minimum particle diameter of the
光硬化性組成物亦可含有軟化劑、促進劑、劣化抑制劑、著色劑、阻燃劑、觸變劑等其他添加劑。以光硬化性組成物中的導電粒子以外的成分的合計量為基準，該些添加劑的含量例如可為0.1質量%～10質量%。該些添加劑亦可含有於第一接著劑層2中。The photocurable composition may also contain other additives such as softeners, accelerators, deterioration inhibitors, colorants, flame retardants, and thixotropic agents. Based on the total amount of the components other than the conductive particles in the photocurable composition, the content of these additives may be, for example, 0.1% by mass to 10% by mass. These additives may also be contained in the first
第一接著劑層2亦可包含未反應的（B）成分。推測：當將本實施形態的接著劑膜1收容於現有的收容構件來進行保管及搬運時，於第一接著劑層2中殘留未反應的（B）成分，因而於保管中及搬運中，第二接著劑層3中的熱硬化性組成物的一部分硬化，接著劑膜1的連接電阻的降低效果減小。因此，於第一接著劑層2包含（B）成分的情況下，藉由將接著劑膜1收容於後述的收容構件，可防止連接電阻的降低效果的減小。The first
就容易在相向的電極間捕捉導電粒子4、可進一步降低連接電阻的觀點而言，第一接著劑層2的厚度d1可為導電粒子4的平均粒徑的0.1倍以上，可為0.2倍以上，可為0.3倍以上。就於熱壓接時導電粒子夾於相向的電極間時，導電粒子更容易壓壞，可進一步降低連接電阻的觀點而言，第一接著劑層2的厚度d1可為導電粒子4的平均粒徑的0.8倍以下，可為0.7倍以下。就該些觀點而言，第一接著劑層2的厚度d1可為導電粒子4的平均粒徑的0.1倍～0.8倍，可為0.2倍～0.8倍，可為0.3倍～0.7倍。再者，第一接著劑層2的厚度d1是指位於相鄰的導電粒子4、導電粒子4的隔開部分的第一接著劑層的厚度。From the viewpoint of easily trapping the
於第一接著劑層2的厚度d1與導電粒子4的平均粒徑滿足如上所述的關係的情況下，例如，如圖1所示，第一接著劑層2中的導電粒子4的一部分可自第一接著劑層2突出至第二接著劑層3側。該情況下，第一接著劑層2與第二接著劑層3的邊界S位於相鄰的導電粒子4、導電粒子4的隔開部分。亦可藉由以沿著導電粒子的表面的方式於導電粒子上存在邊界S，而在第一接著劑層2中的導電粒子4不自第一接著劑層2突出至第二接著劑層3側的情況下，滿足所述關係。導電粒子4可不在第一接著劑層2的與第二接著劑層3側為相反側的表面2a露出，相反側的表面2a為平坦面。第一接著劑層2的厚度d1與導電粒子4的最大粒徑的關係可與所述相同。例如，第一接著劑層2的厚度d1可為導電粒子4的最大粒徑的0.1倍～0.8倍，可為0.2倍～0.8倍，可為0.3倍～0.7倍。In the case where the thickness d1 of the first
第一接著劑層2的厚度d1可根據所接著的電路構件的電極高度等而適當設定。第一接著劑層2的厚度d1例如可為0.5 μm以上，且可為20 μm以下，可為0.5 μm～20 μm。再者，於導電粒子4的一部分自第一接著劑層2的表面露出（例如突出至第二接著劑層3側）的情況下，自第一接著劑層2的與第二接著劑層3側為相反側的表面2a至位於相鄰的導電粒子4、導電粒子4的隔開部分的第一接著劑層2與第二接著劑層3的邊界S為止的最短距離（圖1中以d1表示的距離）為第一接著劑層2的厚度，導電粒子4的露出部分不包含於第一接著劑層2的厚度中。導電粒子4的露出部分的長度例如可為0.1 μm以上，且可為20 μm以下，可為0.1 μm～20 μm。The thickness d1 of the first
接著劑層的厚度可藉由以下方法進行測定。首先，利用兩片玻璃（厚度：1 mm左右）夾入接著劑膜。繼而，利用包含雙酚A型環氧樹脂（商品名：JER811，三菱化學股份有限公司製造）100 g及硬化劑（商品名：艾波忙特（Epomount）硬化劑，立發科技（Refine Tec）股份有限公司製造）10 g的樹脂組成物進行澆鑄。然後，使用研磨機進行剖面研磨，使用掃描式電子顯微鏡（SEM，商品名：SE-8020，日立高科技（Hitachi High-tech science）股份有限公司製造）測定各接著劑層的厚度。The thickness of the adhesive layer can be measured by the following method. First, use two pieces of glass (thickness: about 1 mm) to sandwich the adhesive film. Then, using 100 g containing bisphenol A epoxy resin (trade name: JER811, manufactured by Mitsubishi Chemical Co., Ltd.) and hardener (trade name: Epomount hardener, Refine Tec) Co., Ltd.) 10 g of resin composition was cast. Then, the cross section was polished using a grinder, and the thickness of each adhesive layer was measured using a scanning electron microscope (SEM, trade name: SE-8020, manufactured by Hitachi High-tech Science Co., Ltd.).
（第二接著劑層）
第二接著劑層3例如包含含有（a）聚合性化合物（以下亦稱為（a）成分）及（b）熱聚合起始劑（以下亦稱為（b）成分）的熱硬化性組成物。構成第二接著劑層3的熱硬化性組成物為電路連接時能夠流動的熱硬化性組成物，例如為未硬化的熱硬化性組成物。(Second adhesive layer)
The second
[（a）成分：聚合性化合物] （a）成分例如為藉由熱聚合起始劑因熱產生的自由基、陽離子或陰離子而聚合的化合物。作為（a）成分，可使用作為（A）成分而例示的化合物。就低溫短時間下的連接容易、連接電阻的降低效果進一步提升、連接可靠性更優異的觀點而言，（a）成分較佳為具有藉由自由基而反應的自由基聚合性基的自由基聚合性化合物。（a）成分中的較佳自由基聚合性化合物的例子及較佳自由基聚合性化合物的組合與（A）成分相同。於（a）成分為自由基聚合性化合物且第一接著劑層中的（B）成分為光自由基聚合起始劑的情況下，藉由將接著劑膜收容於後述的收容構件，而有顯著抑制接著劑膜的保管時或搬運時的熱硬化性組成物的硬化的傾向。[(A) component: polymerizable compound] The component (a) is, for example, a compound polymerized by radicals, cations, or anions generated by heat by a thermal polymerization initiator. As (a) component, the compound illustrated as (A) component can be used. In terms of easy connection at low temperature and short time, the effect of reducing the connection resistance is further improved, and the connection reliability is more excellent, the component (a) is preferably a radical having a radical polymerizable group that reacts by a radical Polymeric compound. The examples of the preferable radical polymerizable compound in the component (a) and the combination of the preferable radical polymerizable compound are the same as those of the component (A). In the case where the component (a) is a radical polymerizable compound and the component (B) in the first adhesive layer is a photo-radical polymerization initiator, the adhesive film is housed in a receiving member described later, and there is The tendency of hardening of the thermosetting composition during storage or transportation of the adhesive film is significantly suppressed.
（a）成分可為單體、寡聚物或聚合物的任一者。作為（a）成分，可單獨使用一種化合物，亦可組合使用多種化合物。（a）成分可與（A）成分相同亦可不同。(A) The component may be any of monomers, oligomers, and polymers. As the (a) component, one compound may be used alone, or multiple compounds may be used in combination. The component (a) may be the same as or different from the component (A).
就容易獲得用以降低連接電阻、提升連接可靠性而所需的交聯密度的觀點而言，以熱硬化性組成物的總質量基準計，（a）成分的含量可為10質量%以上，可為20質量%以上，可為30質量%以上。就可抑制聚合時的硬化收縮，可獲得良好的可靠性的觀點而言，以熱硬化性組成物的總質量基準計，（a）成分的含量可為90質量%以下，可為80質量%以下，可為70質量%以下。就該些觀點而言，以熱硬化性組成物的總質量基準計，（a）成分的含量可為10質量%～90質量%，可為20質量%～80質量%，可為30質量%～70質量%。From the viewpoint of easily obtaining the crosslink density required to reduce connection resistance and improve connection reliability, the content of component (a) may be 10% by mass or more based on the total mass of the thermosetting composition. It may be 20% by mass or more, and it may be 30% by mass or more. From the viewpoint of suppressing curing shrinkage during polymerization and obtaining good reliability, based on the total mass of the thermosetting composition, the content of component (a) may be 90% by mass or less, and 80% by mass Below, it may be 70% by mass or less. From these viewpoints, based on the total mass of the thermosetting composition, the content of (a) component may be 10% by mass to 90% by mass, 20% by mass to 80% by mass, or 30% by mass. ～70% by mass.
[（b）成分：熱聚合起始劑] 作為（b）成分，可使用與（E）成分相同的熱聚合起始劑。作為（b）成分，可單獨使用一種化合物，亦可組合使用多種化合物。（b）成分較佳為熱自由基聚合起始劑。（b）成分中較佳的熱自由基聚合起始劑的例子與（E）成分相同。[Component (b): Thermal polymerization initiator] As the (b) component, the same thermal polymerization initiator as the (E) component can be used. As the (b) component, one compound may be used alone, or multiple compounds may be used in combination. (B) The component is preferably a thermal radical polymerization initiator. Examples of preferable thermal radical polymerization initiators among the components (b) are the same as those of the component (E).
就連接電阻的降低效果進一步提升、連接可靠性更優異的觀點而言，以熱硬化性組成物的總質量基準計，（b）成分的含量可為0.1質量%以上，可為0.5質量%以上，可為1質量%以上。就適用期的觀點而言，以熱硬化性組成物的總質量基準計，（b）成分的含量可為30質量%以下，可為20質量%以下，可為10質量%以下。就該些觀點而言，以熱硬化性組成物的總質量基準計，（b）成分的含量可為0.1質量%～30質量%，可為0.5質量%～20質量%，可為1質量%～10質量%。From the viewpoint of further improvement of the connection resistance reduction effect and better connection reliability, based on the total mass of the thermosetting composition, the content of component (b) may be 0.1% by mass or more and 0.5% by mass or more , It can be 1% by mass or more. From the viewpoint of pot life, based on the total mass of the thermosetting composition, the content of component (b) may be 30% by mass or less, 20% by mass or less, or 10% by mass or less. From these viewpoints, based on the total mass of the thermosetting composition, the content of component (b) may be 0.1% by mass to 30% by mass, 0.5% by mass to 20% by mass, or 1% by mass. ～10% by mass.
[其他成分]
熱硬化性組成物可更含有（a）成分及（b）成分以外的其他成分。作為其他成分，例如可列舉熱塑性樹脂、偶合劑、填充材、軟化劑、促進劑、劣化抑制劑、著色劑、阻燃劑、觸變劑等。其他成分的詳細情況與第一接著劑層2中的其他成分的詳細情況相同。[Other ingredients]
The thermosetting composition may further contain components other than the (a) component and (b) component. Examples of other components include thermoplastic resins, coupling agents, fillers, softeners, accelerators, deterioration inhibitors, colorants, flame retardants, and thixotropic agents. The details of the other components are the same as those of the other components in the first
熱硬化性組成物亦可含有與以上所述的（D）成分同樣的熱硬化性樹脂來代替（a）成分及（b）成分，或者在（a）成分及（b）成分之外含有與以上所述的（D）成分同樣的熱硬化性樹脂。該情況下，熱硬化性組成物亦可含有用於將以上所述的熱硬化性樹脂硬化的硬化劑。於使用熱硬化性樹脂來代替（a）成分及（b）成分的情況下，關於熱硬化性組成物中的熱硬化性樹脂的含量，例如以熱硬化性組成物的總質量為基準，可為20質量%以上，且可為80質量%以下，可為20質量%～80質量%。於在（a）成分及（b）成分之外使用熱硬化性樹脂的情況下，關於熱硬化性組成物中的熱硬化性樹脂的含量，例如以熱硬化性組成物的總質量為基準，可為20質量%以上，且可為80質量%以下，可為20質量%～80質量%。硬化劑的含量可與作為光硬化性組成物中的硬化劑的含量所記載的範圍相同。The thermosetting composition may contain the same thermosetting resin as the above-mentioned (D) component instead of (a) component and (b) component, or in addition to (a) component and (b) component and The above-mentioned (D) component is the same thermosetting resin. In this case, the thermosetting composition may contain a curing agent for curing the above-mentioned thermosetting resin. In the case of using a thermosetting resin instead of the (a) component and (b) component, the content of the thermosetting resin in the thermosetting composition may be based on the total mass of the thermosetting composition, for example. It is 20% by mass or more, and may be 80% by mass or less, and may be 20% by mass to 80% by mass. When a thermosetting resin is used in addition to the (a) component and (b) component, the content of the thermosetting resin in the thermosetting composition is based on the total mass of the thermosetting composition, for example, It can be 20% by mass or more, and it can be 80% by mass or less, and it can be 20% by mass to 80% by mass. The content of the curing agent may be the same as the range described as the content of the curing agent in the photocurable composition.
關於第二接著劑層3中的導電粒子4的含量，例如以第二接著劑層的總質量基準計，可為1質量%以下，亦可為0質量%。第二接著劑層3較佳為不含導電粒子4。Regarding the content of the
第二接著劑層3的厚度d2可根據所接著的電路構件的電極高度等而適當設定。就可充分填充電極間的空間而將電極密封，獲得更良好的連接可靠性的觀點而言，第二接著劑層3的厚度d2可為5 μm以上，且可為200 μm以下，可為5 μm～200 μm。再者，於導電粒子4的一部分自第一接著劑層2的表面露出（例如突出至第二接著劑層3側）的情況下，自第二接著劑層3的與第一接著劑層2側為相反側的表面3a至位於相鄰的導電粒子4、導電粒子4的隔開部分的第一接著劑層2與第二接著劑層3的邊界S為止的距離（圖1中以d2表示的距離）為第二接著劑層3的厚度。The thickness d2 of the second
就可充分填充電極間的空間而將電極密封，獲得更良好的可靠性的觀點而言，第一接著劑層2的厚度d1相對於第二接著劑層3的厚度d2的比（第一接著劑層2的厚度d1/第二接著劑層3的厚度d2）可為1以上，且可為100以下。From the viewpoint of sufficiently filling the space between the electrodes to seal the electrodes and obtain better reliability, the ratio of the thickness d1 of the first
接著劑膜1的厚度（構成接著劑膜1的所有層的厚度的合計；圖1中，第一接著劑層2的厚度d1及第二接著劑層3的厚度d2的合計）例如可為5 μm以上，且可為200 μm以下，可為5 μm～200 μm。The thickness of the adhesive film 1 (the total thickness of all the layers constituting the
接著劑膜1中，導電粒子4分散於第一接著劑層2中。因此，接著劑膜1為具有各向異性導電性的各向異性導電性接著劑膜。接著劑膜1用於介於具有第一電極的第一電路構件、與具有第二電極的第二電路構件之間，將第一電路構件及第二電路構件熱壓接，而使第一電極及第二電極彼此電性連接。In the
根據接著劑膜1，可抑制於電路連接結構體的製造時發生的導電粒子的流動，且可抑制於高溫高濕環境下使用電路連接結構體時發生的電路構件與由接著劑膜所形成的電路連接部的界面處的剝離。According to the
以上，對本實施形態的電路連接用接著劑膜進行了說明，但本發明並不限定於所述實施形態。As mentioned above, although the adhesive film for circuit connection of this embodiment was demonstrated, this invention is not limited to the said embodiment.
例如，電路連接用接著劑膜可為包含第一接著劑層及第二接著劑層的兩層者，亦可為包括第一接著劑層及第二接著劑層以外的層（例如第三接著劑層）的包含三層以上的層者。第三接著劑層可為具有與以上關於第一接著劑層或第二接著劑層而所述的組成相同的組成的層，可為具有與以上關於第一接著劑層或第二接著劑層而所述的厚度相同的厚度的層。電路連接用接著劑膜例如可於第一接著劑層的與第二接著劑層為相反側的表面上更包括第三接著劑層。即，電路連接用接著劑膜例如是以第二接著劑層、第一接著劑層及第三接著劑層的順序積層而成。該情況下，第三接著劑層例如與第二接著劑層同樣地包含熱硬化性組成物。For example, the adhesive film for circuit connection may be two layers including a first adhesive layer and a second adhesive layer, or may include a layer other than the first adhesive layer and the second adhesive layer (for example, the third adhesive layer). The agent layer) contains three or more layers. The third adhesive layer may be a layer having the same composition as that described above with respect to the first adhesive layer or the second adhesive layer, and may be a layer having the same composition as the above regarding the first adhesive layer or the second adhesive layer. And the thickness is the same as the thickness of the layer. The adhesive film for circuit connection may further include a third adhesive layer on the surface of the first adhesive layer opposite to the second adhesive layer. That is, the adhesive film for circuit connection is laminated|stacked in this order of a 2nd adhesive layer, a 1st adhesive layer, and a 3rd adhesive layer, for example. In this case, the third adhesive layer contains a thermosetting composition like the second adhesive layer, for example.
另外，所述實施形態的電路連接用接著劑膜為具有各向異性導電性的各向異性導電性接著劑膜，但電路連接用接著劑膜亦可為不具有各向異性導電性的導電性接著劑膜。In addition, the adhesive film for circuit connection of the above embodiment is an anisotropic conductive adhesive film having anisotropic conductivity, but the adhesive film for circuit connection may be conductive without anisotropic conductivity. Adhesive film.
＜電路連接用接著劑膜的製造方法＞
本實施形態的電路連接用接著劑膜1的製造方法例如包括：準備以上所述的第一接著劑層2的準備步驟（第一準備步驟）；以及於第一接著劑層2上積層以上所述的第二接著劑層3的積層步驟。電路連接用接著劑膜1的製造方法亦可更包括：準備第二接著劑層3的準備步驟（第二準備步驟）。<Method of manufacturing adhesive film for circuit connection>
The method of manufacturing the
於第一準備步驟中，例如，於基材上形成第一接著劑層2而獲得第一接著劑膜，藉此準備第一接著劑層2。具體而言，首先將（A）成分、（B）成分及（C）成分、以及視需要而添加的（D）成分及（E）成分等其他成分加入有機溶媒中，藉由攪拌混合、混煉等進行溶解或分散而製備清漆組成物（光硬化性組成物的清漆）。然後，於實施了脫模處理的基材上，使用刮刀塗佈機、輥塗機、敷料器、缺角輪塗佈機、模塗機等來塗佈清漆組成物後，藉由加熱而使有機溶媒揮發，從而於基材上形成包含光硬化性組成物的層。繼而，藉由對包含光硬化性組成物的層照射光而使光硬化性組成物硬化，從而於基材上形成第一接著劑層2（硬化步驟）。藉此，獲得第一接著劑膜。In the first preparation step, for example, the first
作為清漆組成物的製備中使用的有機溶媒，較佳為具有可將各成分均勻地溶解或分散的特性者，例如可列舉甲苯、丙酮、甲基乙基酮、甲基異丁基酮、乙酸乙酯、乙酸丙酯、乙酸丁酯等。該些有機溶媒可單獨使用或將兩種以上組合而使用。製備清漆組成物時的攪拌混合及混煉例如可使用攪拌機、磨碎機、三輥、球磨機、珠磨機或均質機來進行。The organic solvent used in the preparation of the varnish composition is preferably one having the property of uniformly dissolving or dispersing each component, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetic acid Ethyl acetate, propyl acetate, butyl acetate, etc. These organic solvents can be used alone or in combination of two or more. The stirring, mixing and kneading at the time of preparing the varnish composition can be performed using, for example, a mixer, an attritor, a three-roller, a ball mill, a bead mill, or a homogenizer.
作為基材，只要為具有可耐受使有機溶媒揮發時的加熱條件的耐熱性者則並無特別限制，例如可使用包含延伸聚丙烯（oriented polypropylene，OPP）、聚對苯二甲酸乙二酯（polyethylene terephthalate，PET）、聚萘二甲酸乙二酯、聚間苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚烯烴、聚乙酸酯、聚碳酸酯、聚苯硫醚、聚醯胺、聚醯亞胺、纖維素、乙烯-乙酸乙烯酯共聚物、聚氯乙烯、聚偏二氯乙烯、合成橡膠系、液晶聚合物等的基材（例如膜）。The substrate is not particularly limited as long as it has heat resistance that can withstand the heating conditions when the organic solvent is volatilized. For example, oriented polypropylene (OPP) and polyethylene terephthalate can be used. (Polyethylene terephthalate, PET), polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, polyolefin, polyacetate, polycarbonate, polyphenylene sulfide, Base materials (for example, films) of polyamide, polyimide, cellulose, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, synthetic rubber, liquid crystal polymer, etc.
使有機溶媒自塗佈於基材的清漆組成物揮發時的加熱條件較佳為設為有機溶媒充分揮發的條件。加熱條件例如可為40℃以上且120℃以下、0.1分鐘以上且10分鐘以下。The heating conditions when the organic solvent is volatilized from the varnish composition applied to the substrate are preferably set to conditions under which the organic solvent is sufficiently volatilized. The heating conditions can be, for example, 40° C. or higher and 120° C. or lower, 0.1 minute or longer and 10 minutes or shorter.
硬化步驟中的光的照射中，較佳為使用波長150 nm～750 nm的範圍內的照射光（例如紫外光）。光的照射例如可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、金屬鹵化物燈、發光二極體（light-emitting diode，LED）光源等來進行。光的照射量並無特別限定，例如以波長365 nm的光的累計光量計可為100 mJ/cm2 以上，可為200 mJ/cm2 以上，可為300 mJ/cm2 以上。光的照射量例如以波長365 nm的光的累計光量計可為10000 mJ/cm2 以下，可為5000 mJ/cm2 以下，可為3000 mJ/cm2 以下。In the irradiation of light in the curing step, it is preferable to use irradiation light (for example, ultraviolet light) within a wavelength range of 150 nm to 750 nm. The light irradiation can be performed using, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a light-emitting diode (LED) light source, or the like. The amount of light irradiation is not particularly limited. For example, the cumulative light amount of light with a wavelength of 365 nm may be 100 mJ/cm 2 or more, 200 mJ/cm 2 or more, or 300 mJ/cm 2 or more. The irradiation amount of light may be 10000 mJ/cm 2 or less, 5000 mJ/cm 2 or less, or 3000 mJ/cm 2 or less in terms of the cumulative light amount of light having a wavelength of 365 nm, for example.
於第二準備步驟中，除使用（a）成分及（b）成分以及視需要而添加的其他成分、及不進行光照射以外，與第一準備步驟同樣地於基材上形成第二接著劑層3而獲得第二接著劑膜，藉此準備第二接著劑層3。In the second preparation step, the second adhesive is formed on the substrate in the same manner as in the first preparation step, except that the components (a) and (b) and other components added as necessary are used and light irradiation is not performed.
於積層步驟中，可藉由將第一接著劑膜與第二接著劑膜貼合而於第一接著劑層2上積層第二接著劑層3，亦可藉由於第一接著劑層2上塗佈使用（a）成分及（b）成分以及視需要而添加的其他成分而獲得的清漆組成物（熱硬化性組成物的清漆），使有機溶媒揮發而於第一接著劑層2上積層第二接著劑層3。積層步驟亦可於第一準備步驟的中途進行。例如，亦可於形成包含光硬化性組成物的層後，進行積層步驟，獲得包括包含光硬化性組成物的層（第一接著劑層2的前驅物）及包含熱硬化性組成物的層（第二接著劑層3）的積層體。該情況下，可藉由對所獲得的積層體照射光而使包含光硬化性組成物的層硬化，完成第一準備步驟。In the laminating step, the second
作為使第一接著劑膜與第二接著劑膜貼合的方法，例如可列舉加熱壓製、輥層壓、真空層壓等方法。層壓例如可於0℃～80℃的溫度條件下進行。As a method of bonding the first adhesive film and the second adhesive film, for example, methods such as heat pressing, roll lamination, and vacuum lamination can be cited. Lamination can be performed under temperature conditions of 0°C to 80°C, for example.
＜電路連接結構體及其製造方法＞
以下，對使用以上所述的電路連接用接著劑膜1作為電路連接材料的電路連接結構體及其製造方法進行說明。＜Circuit connection structure and its manufacturing method＞
Hereinafter, a circuit connection structure using the above-mentioned
圖2是表示一實施形態的電路連接結構體的示意剖面圖。如圖2所示，電路連接結構體10包括：具有第一電路基板11及形成於第一電路基板11的主面11a上的第一電極12的第一電路構件13；具有第二電路基板14及形成於第二電路基板14的主面14a上的第二電極15的第二電路構件16；以及配置於第一電路構件13及第二電路構件16之間，將第一電極12及第二電極15彼此電性連接的電路連接部17。Fig. 2 is a schematic cross-sectional view showing a circuit connection structure according to an embodiment. As shown in FIG. 2, the
第一電路構件13及第二電路構件16彼此可相同亦可不同。第一電路構件13及第二電路構件16可為形成有電極的玻璃基板或塑膠基板、印刷配線板、陶瓷配線板、可撓性配線板、半導體矽積體電路（integrated circuit，IC）晶片等。第一電路基板11及第二電路基板14可由半導體、玻璃、陶瓷等無機物，聚醯亞胺、聚碳酸酯等有機物，玻璃/環氧等複合物等形成。第一電極12及第二電極15可由金、銀、錫、釕、銠、鈀、鋨、銥、鉑、銅、鋁、鉬、鈦、銦錫氧化物（Indium Tin Oxide，ITO）、銦鋅氧化物（Indium Zinc Oxide，IZO）、銦鎵鋅氧化物（Indium Gallium Zinc Oxide，IGZO）等形成。第一電極12及第二電極15可為電路電極，亦可為凸塊（bump）電極。可為第一電極12及第二電極15的至少一者為凸塊電極。圖2中，第二電極15為凸塊電極。The
電路連接部17包含以上所述的接著劑膜1的硬化物。電路連接部17例如包括：第一區域18，位於第一電路構件13與第二電路構件16彼此相向的方向（以下「相向方向」）上的第一電路構件13側，包含以上所述的光硬化性組成物的導電粒子4以外的（A）成分、（B）成分等成分的硬化物；第二區域19，位於相向方向上的第二電路構件16側，包含含有（a）成分、（b）成分等的以上所述的熱硬化性組成物的硬化物；以及導電粒子4，至少介於第一電極12及第二電極15之間來將第一電極12及第二電極15彼此電性連接。電路連接部亦可並非如第一區域18及第二區域19般具有兩個區域，例如亦可包含以上所述的光硬化性組成物的導電粒子4以外的成分的硬化物與以上所述的熱硬化性組成物的硬化物混合存在的硬化物。The
圖3是表示電路連接結構體10的製造方法的示意剖面圖。如圖3所示，電路連接結構體10的製造方法例如包括以下步驟：使以上所述的接著劑膜1介於具有第一電極12的第一電路構件13、與具有第二電極15的第二電路構件16之間，將第一電路構件13及第二電路構件16熱壓接，而使第一電極12及第二電極15彼此電性連接。FIG. 3 is a schematic cross-sectional view showing a method of manufacturing the
具體而言，如圖3的（a）所示，首先，準備具有第一電路基板11及形成於第一電路基板11的主面11a上的第一電極12的第一電路構件13、以及具有第二電路基板14及形成於第二電路基板14的主面14a上的第二電極15的第二電路構件16。Specifically, as shown in FIG. 3(a), first, a
其次，以第一電極12與第二電極15彼此相向的方式配置第一電路構件13與第二電路構件16，於第一電路構件13與第二電路構件16之間配置接著劑膜1。例如，如圖3的（a）所示，以第一接著劑層2側與第一電路構件13的安裝面11a相向的方式，將接著劑膜1層壓於第一電路構件13上。其次，以第一電路基板11上的第一電極12與第二電路基板14上的第二電極15彼此相向的方式，於層壓有接著劑膜1的第一電路構件13上配置第二電路構件16。Next, the
並且，如圖3的（b）所示，一邊將第一電路構件13、接著劑膜1及第二電路構件16加熱一邊於厚度方向上對第一電路構件13與第二電路構件16進行加壓，藉此而將第一電路構件13與第二電路構件16彼此熱壓接。此時，如圖3的（b）中箭頭所示，第二接著劑層3由於包含能夠流動的未硬化的熱硬化性組成物，而以填埋第二電極15、第二電極15間的空隙的方式流動，並且藉由所述加熱而硬化。藉此，第一電極12及第二電極15介隔導電粒子4而彼此電性連接，另外，第一電路構件13及第二電路構件16彼此接著，獲得圖2所示的電路連接結構體10。於本實施形態的電路連接結構體10的製造方法中，由於第一接著劑層2為預先硬化的層，因此將導電粒子4固定於第一接著劑層2中，另外，第一接著劑層2於所述熱壓接時幾乎不流動，而在相向的電極間有效率地捕捉導電粒子，因此相向的電極12及電極15間的連接電阻降低。因此，獲得連接可靠性優異的電路連接結構體。And, as shown in FIG. 3(b), the
＜接著劑膜收容組＞
圖4是表示一實施形態的接著劑膜收容組的立體圖。如圖4所示，接著劑膜收容組20包括：電路連接用接著劑膜1、捲繞有該接著劑膜1的卷軸21、及收容接著劑膜1及卷軸21的收容構件22。＜Adhesive film storage group＞
Fig. 4 is a perspective view showing an adhesive film storage group according to an embodiment. As shown in FIG. 4, the adhesive
如圖4所示，接著劑膜1例如為帶狀。帶狀的接著劑膜1例如是藉由將片狀的整幅片材以根據用途的寬度裁斷為長條狀而製作。可於接著劑膜1的其中一個面上設置基材。作為基材，可使用以上所述的PET膜等基材。As shown in FIG. 4, the
卷軸21包括：具有用來捲繞接著劑膜1的卷芯23的第一側板24、以及以夾隔卷芯23而與第一側板24相向的方式配置的第二側板25。The
第一側板24例如是包含塑膠的圓板，於第一側板24的中央部分設置有剖面圓形的開口部。The
第一側板24具有的卷芯23為捲繞接著劑膜1的部分。卷芯23例如包含塑膠，形成為厚度與接著劑膜1的寬度相同的圓環狀。卷芯23以包圍第一側板24的開口部的方式固定於第一側板24的內側面。另外，於卷軸21的中央部設置有作為供捲繞裝置或輸出裝置（未圖示）的旋轉軸***的部分的軸孔26。當於該軸孔26中塞入捲繞裝置或輸出裝置的旋轉軸的狀態下驅動旋轉軸時，卷軸21便會旋轉而不會空轉。亦可於軸孔26中嵌入收容乾燥劑的乾燥劑收容容器。The winding
第二側板25與第一側板24同樣地，例如是包含塑膠的圓板，於第二側板25的中央部分設置有與第一側板24的開口部直徑相同的剖面圓形的開口部。The
收容構件22例如呈袋狀，收容接著劑膜1及卷軸21。收容構件22具有用於將接著劑膜1及卷軸21收容（***）至收容構件22的內部的***口27。The
收容構件22具有使得能夠自外部視認收容構件22的內部的視認部28。圖4所示的收容構件22是以收容構件22的整體成為視認部28的方式構成。The accommodating
視認部28具有對可見光的透射性。例如，當以波長450 nm～750 nm的範圍測定視認部28對光的透射率時，於波長450 nm～750 nm之間存在至少一個光的透射率的平均值為30%以上且波長寬度為50 nm的區域。視認部28對光的透射率可藉由製作將視認部28截取為規定大小的試樣，並利用紫外可見分光光度計測定試樣對光的透射率而獲得。收容構件22具有此種視認部28，因而自收容構件22的外部亦可確認到收容構件22內部的例如貼附於卷軸21的製品名、批號、有效期等各種資訊。藉此，可期待防止混入錯誤的製品、及分類作業變得效率良好。The
視認部28對波長365 nm的光的透射率為10%以下。視認部28對波長365 nm的光的透過為10%以下，因此可抑制由自收容構件22的外部入射至內部的光及第一接著劑層2中殘留的光聚合起始劑所引起的熱硬化性組成物的硬化。結果，可維持接著劑膜1的連接電阻的降低效果，於將接著劑膜1用於電路構件彼此的連接時，可降低相向的電極間的連接電阻。就進一步抑制自光聚合起始劑產生自由基的觀點而言，視認部28對波長365 nm的光的透射率較佳為10%以下，更佳為5%以下，進而佳為1%以下，特佳為0.1%以下。The transmittance of the
就同樣的觀點而言，視認部28對能夠自所述光聚合起始劑（（B）成分）產生自由基、陽離子或陰離子的波長區域下的光的透射率的最大值較佳為10%以下，更佳為5%以下，進而佳為1%以下，特佳為0.1%以下。具體而言，視認部28對波長254 nm～405 nm的光的透射率的最大值較佳為10%以下，更佳為5%以下，進而佳為1%以下，特佳為0.1%以下。From the same viewpoint, the maximum value of the light transmittance of the
視認部28（收容構件22）例如是由厚度10 μm～5000 μm的片材所形成。該片材包括視認部28對波長365 nm的光的透射率為10%以下的材料。此種材料可包含一種成分，亦可包含多種成分。作為該材料，例如可列舉低密度聚乙烯、直鏈狀低密度聚乙烯、聚碳酸酯、聚酯、聚丙烯酸酯、聚醯胺、玻璃等。該些材料亦可包含紫外線吸收劑。視認部28亦可具有藉由積層透光性不同的多個層而形成的積層結構。該情況下，構成視認部28的各層可包含以上所述的材料。The visual recognition part 28 (housing member 22) is formed of, for example, a sheet with a thickness of 10 μm to 5000 μm. This sheet material includes a material whose transmittance of the
為了防止收容時空氣自外部侵入，例如可藉由利用密封機等進行封口而將***口27密閉。該情況下，較佳為於封閉***口27前預先將收容構件22內的空氣抽吸去除。可期待自收容的初始階段起收容構件22內的濕氣變少，且防止空氣自外部進入。另外，藉由收容構件22的內表面與卷軸21密接，可防止因搬運時的振動使收容構件22的內表面與卷軸21的表面摩擦而產生異物，並且可防止對卷軸21的側板24、側板25的外側面的刮傷。In order to prevent the intrusion of air from the outside during storage, for example, the
所述實施形態中，收容構件是以收容構件的整體成為視認部的方式構成，於另一實施形態中，收容構件亦可於收容構件的一部分具有視認部。例如，收容構件可於收容構件的側面的大致中央具有矩形形狀的視認部。該情況下，收容構件的視認部以外的部分例如可呈黑色，以便不透射紫外光及可見光。In the said embodiment, the storage member is comprised so that the whole of the storage member may become a visual recognition part, In another embodiment, the storage member may have a visual recognition part in a part of a storage member. For example, the accommodating member may have a rectangular-shaped visible part in the approximate center of the side surface of the accommodating member. In this case, the portion other than the visible portion of the storage member may be black, for example, so as not to transmit ultraviolet light and visible light.
另外，所述實施形態中，收容構件的形狀為袋狀，收容構件例如亦可為箱狀。收容構件較佳為帶有用於開封的切痕。該情況下，使用時的開封作業變容易。 [實施例]In addition, in the above embodiment, the shape of the storage member is a bag shape, and the storage member may be, for example, a box shape. The receiving member preferably has cut marks for unsealing. In this case, the opening operation at the time of use becomes easy. [Example]
以下，藉由實施例來更具體地說明本發明，但本發明並不限定於實施例。Hereinafter, the present invention will be explained more specifically with examples, but the present invention is not limited to the examples.
＜聚胺基甲酸酯丙烯酸酯（UA1）的合成＞ 於具備攪拌機、溫度計、具有氯化鈣乾燥管的回流冷卻管、及氮氣導入管的反應容器中，歷時3小時均勻地滴加聚(1,6-己二醇碳酸酯)（商品名：杜南醇（Duranol）T5652，旭化成化學（Asahi Kasei Chemicals）股份有限公司製造，數量平均分子量為1000）2500質量份（2.50 mol）、及異佛爾酮二異氰酸酯（西格瑪奧德里奇（Sigma-Aldrich）公司製造）666質量份（3.00 mol）。繼而，向反應容器中充分地導入氮氣後，將反應容器內加熱至70℃～75℃來進行反應。其次，向反應容器中添加對苯二酚單甲基醚（西格瑪奧德里奇公司製造）0.53質量份（4.3 mmol）、及二月桂酸二丁基錫（西格瑪奧德里公司製造）5.53質量份（8.8 mmol）後，加入丙烯酸2-羥基乙酯（西格瑪奧德里奇公司製造）238質量份（2.05 mol），於空氣環境下以70℃反應6小時。藉此而獲得聚胺基甲酸酯丙烯酸酯（UA1）。聚胺基甲酸酯丙烯酸酯（UA1）的重量平均分子量為15000。再者，重量平均分子量是依照下述條件，藉由凝膠滲透層析儀（GPC），且使用由標準聚苯乙烯所得的校準曲線而測定。 （測定條件） 裝置：東曹（Tosoh）股份有限公司製造的GPC-8020 檢測器：東曹股份有限公司製造的RI-8020 管柱：日立化成股份有限公司製造的Gelpack GLA160S+GLA150S 試樣濃度：120 mg/3 mL 溶媒：四氫呋喃 注入量：60 μL 壓力：2.94×106 Pa（30 kgf/cm2 ） 流量：1.00 mL/min<Synthesis of polyurethane acrylate (UA1)> In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube with a calcium chloride drying tube, and a nitrogen inlet tube, the poly( 1,6-hexanediol carbonate) (trade name: Duranol (Duranol) T5652, manufactured by Asahi Kasei Chemicals Co., Ltd., with a number average molecular weight of 1000) 2500 parts by mass (2.50 mol), and Folone diisocyanate (manufactured by Sigma-Aldrich) 666 parts by mass (3.00 mol). Then, after fully introducing nitrogen gas into the reaction vessel, the inside of the reaction vessel is heated to 70°C to 75°C to perform the reaction. Next, 0.53 parts by mass (4.3 mmol) of hydroquinone monomethyl ether (manufactured by Sigma-Aldrich) and 5.53 parts by mass (8.8 mmol) of dibutyltin dilaurate (manufactured by Sigma-Aldrich) were added to the reaction vessel. ), 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Sigma-Aldrich) was added, and reacted at 70° C. for 6 hours in an air environment. Thus, polyurethane acrylate (UA1) was obtained. The weight average molecular weight of polyurethane acrylate (UA1) is 15,000. In addition, the weight average molecular weight is measured by a gel permeation chromatography (GPC) using a calibration curve obtained from standard polystyrene in accordance with the following conditions. (Measurement conditions) Device: GPC-8020 manufactured by Tosoh Co., Ltd. Detector: RI-8020 manufactured by Tosoh Co., Ltd. Column: Gelpack GLA160S+GLA150S manufactured by Hitachi Chemical Co., Ltd. Sample concentration: 120 mg/3 mL solvent: tetrahydrofuran injection volume: 60 μL pressure: 2.94×10 6 Pa (30 kgf/cm 2 ) flow: 1.00 mL/min
＜導電粒子的製作＞ 於聚苯乙烯粒子的表面上，以層的厚度為0.2 μm的方式形成包含鎳的層。以所述方式獲得平均粒徑為4 μm、最大粒徑為4.5 μm、比重為2.5的導電粒子。＜Production of conductive particles＞ On the surface of the polystyrene particles, a layer containing nickel was formed so that the thickness of the layer was 0.2 μm. In the manner described, conductive particles having an average particle diameter of 4 μm, a maximum particle diameter of 4.5 μm, and a specific gravity of 2.5 were obtained.
＜聚酯胺基甲酸酯樹脂的製備方法＞ 於具備攪拌機、溫度計、冷凝器、真空發生裝置及氮氣導入管的帶有加熱器的不鏽鋼製高壓釜中，投入間苯二甲酸48質量份及新戊二醇37質量份，進而，投入作為觸媒的四丁氧基鈦酸酯0.02質量份。繼而，於氮氣流下升溫至220℃，直接攪拌8小時。然後，減壓至大氣壓（760 mmHg），冷卻至室溫。藉此，析出白色的沈澱物。繼而，取出白色的沈澱物，水洗後，藉由進行真空乾燥而獲得聚酯多元醇。將所獲得的聚酯多元醇充分乾燥後，溶解於甲基乙基酮（methyl ethyl ketone，MEK）中，投入至安裝有攪拌機、滴液漏斗、回流冷卻機及氮氣導入管的四口燒瓶中。另外，投入相對於聚酯多元醇100質量份成為0.05質量份的量的月桂酸二丁基錫作為觸媒，將相對於聚酯多元醇100質量份成為50質量份的量的4,4'-二苯基甲烷二異氰酸酯溶解於MEK中並利用滴液漏斗進行投入，於80℃下攪拌4小時，藉此獲得作為目標的聚酯胺基甲酸酯樹脂。＜Preparation method of polyester urethane resin＞ Into a stainless steel autoclave with a heater equipped with a stirrer, a thermometer, a condenser, a vacuum generator, and a nitrogen inlet pipe, 48 parts by mass of isophthalic acid and 37 parts by mass of neopentyl glycol were charged, and then charged as a contact 0.02 parts by mass of tetrabutoxy titanate. Then, the temperature was raised to 220°C under a nitrogen stream, and the mixture was directly stirred for 8 hours. Then, reduce pressure to atmospheric pressure (760 mmHg) and cool to room temperature. Thereby, a white precipitate is deposited. Then, a white precipitate was taken out, washed with water, and vacuum dried to obtain a polyester polyol. After the obtained polyester polyol is sufficiently dried, it is dissolved in methyl ethyl ketone (MEK) and put into a four-necked flask equipped with a stirrer, a dropping funnel, a reflux cooler and a nitrogen introduction tube . In addition, dibutyltin laurate in an amount of 0.05 parts by mass relative to 100 parts by mass of the polyester polyol was added as a catalyst, and 4,4'-dibutyltin in an amount of 50 parts by mass relative to 100 parts by mass of the polyester polyol was added. Phenylmethane diisocyanate was dissolved in MEK and charged in a dropping funnel, and stirred at 80°C for 4 hours, thereby obtaining the target polyester urethane resin.
＜光硬化性組成物的清漆（清漆組成物）的製備＞
將以下所示的成分以表1所示的調配量（質量份）混合，製備光硬化性組成物1～光硬化性組成物8的清漆。<Preparation of varnish (varnish composition) of photocurable composition>
The components shown below were mixed in the blending amounts (parts by mass) shown in Table 1 to prepare varnishes of the
（聚合性化合物） A1：二環戊二烯型二丙烯酸酯（商品名：DCP-A，東亞合成股份有限公司製造） A2：如上所述般合成的聚胺基甲酸酯丙烯酸酯（UA1） A3：2-甲基丙烯醯氧基乙基酸式磷酸酯（商品名：萊特酯（Light Ester）P-2M，共榮社化學股份有限公司製造） （光聚合起始劑） B1：1,2-辛二酮,1-[4-(苯硫基)苯基-,2-(O-苯甲醯基肟)]（商品名：豔佳固（Irgacure）（註冊商標）OXE01，巴斯夫（BASF）公司製造） B2：乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)（商品名：豔佳固（Irgacure）（註冊商標）OXE02，巴斯夫（BASF）公司製造） （導電粒子） C1：如上所述般製作的導電粒子 （熱聚合起始劑） E1：過氧化苯甲醯（商品名：耐帕（NYPER）BMT-K40，日油股份有限公司製造） （熱塑性樹脂） F1：如上所述般合成的聚酯胺基甲酸酯樹脂 （偶合劑） G1：3-甲基丙烯醯氧基丙基三甲氧基矽烷（商品名：KBM503，信越化學工業股份有限公司製造） （填充材） H1：二氧化矽微粒子（商品名：R104，日本艾羅技（AEROSIL）股份有限公司製造，平均粒徑（一次粒徑）：12 nm） （溶劑） I1：甲基乙基酮(Polymerizable compound) A1: Dicyclopentadiene type diacrylate (trade name: DCP-A, manufactured by Toagosei Co., Ltd.) A2: Polyurethane acrylate (UA1) synthesized as described above A3: 2-Methacryloxy ethyl acid phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) (Photopolymerization initiator) B1: 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzyloxime)] (trade name: Irgacure (registered trademark) OXE01, manufactured by BASF Corporation) B2: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (trade name: Irgacure (registered trademark) OXE02, manufactured by BASF Corporation) (Conductive particles) C1: Conductive particles made as described above (Thermal polymerization initiator) E1: Benzoyl peroxide (trade name: NYPER BMT-K40, manufactured by NOF Corporation) (Thermoplastic resin) F1: Polyester urethane resin synthesized as described above (Coupling agent) G1: 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) (Filling material) H1: Silica particles (trade name: R104, manufactured by AEROSIL Co., Ltd., average particle size (primary particle size): 12 nm) (Solvent) I1: Methyl ethyl ketone
[表1]
＜熱硬化性組成物的清漆（清漆組成物）的製備＞
作為聚合性化合物a1～聚合性化合物a3、熱聚合起始劑b1、偶合劑g1、填充材h1及溶劑i1，使用與光硬化性組成物中的聚合性化合物A1～聚合性化合物A3、熱聚合起始劑E1、偶合劑G1、填充材H1及溶劑I1相同者，熱塑性樹脂f1使用以下所示的成分，將該些成分以表2所示的調配量（質量份）混合，製備熱硬化性組成物1的清漆。
（熱塑性樹脂）
f1：苯氧基樹脂（商品名：PKHC，聯合碳化物（Union Carbide）公司製造）<Preparation of varnish of thermosetting composition (varnish composition)>
As polymerizable compound a1 to polymerizable compound a3, thermal polymerization initiator b1, coupling agent g1, filler h1, and solvent i1, use polymerizable compound A1 to polymerizable compound A3 and thermal polymerization in the photocurable composition If the initiator E1, the coupling agent G1, the filler H1, and the solvent I1 are the same, the following components are used for the thermoplastic resin f1, and the components are mixed in the blending amounts (parts by mass) shown in Table 2 to prepare thermosetting Varnish of
[表2]
（實施例1）
[第一接著劑膜的製作]
使用塗敷裝置將光硬化性組成物1的清漆塗佈於厚度50 μm的PET膜上。繼而，進行70℃、3分鐘的熱風乾燥，於PET膜上形成包含厚度（乾燥後的厚度）為4 μm的光硬化性組成物1的層。此處的厚度使用接觸式厚度計進行測定。再者，若使用接觸式厚度計則反映導電粒子的大小，測定存在導電粒子的區域的厚度。因此，於積層第二接著劑層，製作兩層構成的電路連接用接著劑膜之後，藉由後述的方法，測定位於相鄰的導電粒子的隔開部分的第一接著劑層的厚度。(Example 1)
[Production of the first adhesive film]
The varnish of the
其次，對包含光硬化性組成物1的層，使用金屬鹵化物燈以累計光量為1500 mJ/cm2
的方式進行光照射，使聚合性化合物聚合。藉此，使光硬化性組成物1硬化，形成第一接著劑層。藉由以上操作，獲得於PET膜上具備第一接著劑層的第一接著劑膜（存在導電粒子的區域的厚度：4 μm）。此時的導電粒子密度約為7000 pcs/mm2
。Next, the layer containing the
[第二接著劑膜的製作]
使用塗敷裝置將熱硬化性組成物1的清漆塗佈於厚度50 μm的PET膜上。繼而，進行70℃、3分鐘的熱風乾燥，於PET膜上形成厚度為8 μm的第二接著劑層（包含熱硬化性組成物1的層）。藉由以上操作，獲得於PET膜上具備第二接著劑層的第二接著劑膜。[Production of the second adhesive film]
The varnish of the
[電路連接用接著劑膜的製作] 將第一接著劑膜與第二接著劑膜以各自的接著劑層相向的方式配置，與作為基材的PET膜一併於40℃下進行加熱，同時利用輥層壓機進行層壓。藉此，製作第一接著劑層與第二接著劑層積層而成的兩層構成的電路連接用接著劑膜。[Production of adhesive film for circuit connection] The first adhesive film and the second adhesive film were arranged such that the respective adhesive layers face each other, and were heated at 40° C. together with the PET film as the base material, and were laminated with a roll laminator. Thereby, the adhesive film for circuit connection of the two-layer structure which laminated|stacked the 1st adhesive layer and the 2nd adhesive layer was produced.
藉由以下方法來測定所製作的電路連接用接著劑膜的第一接著劑層的厚度。首先，利用兩片玻璃（厚度：1 mm左右）夾入電路連接用接著劑膜，利用包含雙酚A型環氧樹脂（商品名：JER811，三菱化學股份有限公司製造）100 g及硬化劑（商品名：艾波忙特（Epomount）硬化劑、立發科技（Refine Tec）股份有限公司製造）10 g的樹脂組成物進行澆鑄。然後，使用研磨機進行剖面研磨，使用掃描式電子顯微鏡（SEM，商品名：SE-8020，日立高科技（Hitachi High-tech science）股份有限公司製造）測定位於相鄰的導電粒子的隔開部分的第一接著劑層的厚度。第一接著劑層的厚度為2 μm。The thickness of the first adhesive layer of the produced adhesive film for circuit connection was measured by the following method. First, two pieces of glass (thickness: about 1 mm) are used to sandwich the adhesive film for circuit connection, using 100 g containing bisphenol A epoxy resin (trade name: JER811, manufactured by Mitsubishi Chemical Co., Ltd.) and hardener ( Trade name: Epomount hardener, made by Refine Tec Co., Ltd. 10 g of resin composition was cast. Then, the cross-section is polished using a grinder, and the separation between adjacent conductive particles is measured using a scanning electron microscope (SEM, trade name: SE-8020, manufactured by Hitachi High-tech Science Co., Ltd.) The thickness of the first adhesive layer. The thickness of the first adhesive layer is 2 μm.
[電路連接結構體的製作] 介隔所製作的電路連接用接著劑膜，對間距25 μm的COF（弗萊克斯得（FLEXSEED）公司製造）、及玻璃基板上具備包含非晶氧化銦錫（ITO）的薄膜電極（高度：1200 Å）的帶有薄膜電極的玻璃基板（吉奧馬（Geomatec）公司製造），使用熱壓接裝置（加熱方式：接觸加熱（contact heat）型，太陽機械製作所股份有限公司製造），以170℃、6 MPa下4秒鐘的條件進行加熱加壓，跨及寬度1 mm進行連接，製作電路連接結構體（連接結構體）。再者，於連接時，以電路連接用接著劑膜中的第一接著劑層側的表面與玻璃基板相向的方式將電路連接用接著劑膜配置於玻璃基板上。[Production of circuit connection structure] Adhesive film for circuit connection made by the interlayer for COF (manufactured by FLEXSEED) with a pitch of 25 μm, and thin film electrodes containing amorphous indium tin oxide (ITO) on a glass substrate (height: 1200 Å) glass substrate with thin-film electrodes (manufactured by Geomatec), using a thermocompression bonding device (heating method: contact heat type, manufactured by Taiyo Machinery Co., Ltd.) at 170°C , Heat and press under the condition of 6 MPa for 4 seconds, and connect with a width of 1 mm to make a circuit connection structure (connection structure). Furthermore, at the time of connection, the adhesive film for circuit connection was arrange|positioned on the glass substrate so that the surface on the side of the 1st adhesive layer of the adhesive film for circuit connection faced the glass substrate.
＜電路連接結構體的評價＞ [粒子流動性評價] 對於所獲得的電路連接結構體，使用顯微鏡（商品名：伊克利普斯（ECLIPSE）L200，尼康股份有限公司製造）來評價電路連接用接著劑膜的樹脂滲出部分的粒子流動狀態。具體而言，利用顯微鏡自玻璃基板側觀察所製作的電路連接結構體，分三個階段來評價較電路連接用接著劑膜的寬度更向外側滲出的部分的粒子狀態。將粒子幾乎不移動，滲出部分沒有粒子的狀態評價為1，將粒子稍微移動但未觀察到粒子彼此的連結的狀態評價為2，將粒子流動且觀察到粒子彼此的連結的狀態評價為3。＜Evaluation of circuit connection structure＞ [Particle fluidity evaluation] With respect to the obtained circuit connection structure, a microscope (trade name: ECLIPSE L200, manufactured by Nikon Co., Ltd.) was used to evaluate the particle flow state of the resin oozing portion of the adhesive film for circuit connection. Specifically, the produced circuit connection structure was observed from the glass substrate side with a microscope, and the particle state of the part oozing out to the outside of the width of the adhesive film for circuit connection was evaluated in three stages. The state where the particles hardly moved and no particles in the exuded portion was evaluated as 1, the state where the particles moved slightly but no connection between the particles was observed was evaluated as 2, and the state where the particles flowed and the connection between the particles was observed was evaluated as 3.
[連接電阻值評價] 對於所獲得的電路連接結構體，藉由萬用電表來測定剛剛連接後以及高溫高濕試驗後的相向的電極間的連接電阻值。高溫高濕試驗是藉由於85℃、85%RH的恆溫恆濕槽中放置200小時來進行。連接電阻值是作為16處的相向的電極間的電阻的平均值而求出。[Evaluation of Connection Resistance Value] For the obtained circuit connection structure, the connection resistance value between the facing electrodes immediately after the connection and after the high-temperature and high-humidity test was measured by a multimeter. The high-temperature and high-humidity test is performed by placing it in a constant temperature and humidity bath at 85°C and 85%RH for 200 hours. The connection resistance value was calculated as the average value of the resistance between the 16 opposing electrodes.
[剝離評價] 使用顯微鏡（商品名：伊克利普斯（ECLIPSE）L200，尼康股份有限公司製造）來評價高溫高濕試驗後的電路連接結構體的電路連接部有無剝離。具體而言，利用顯微鏡自玻璃基板側觀察如上所述般製作的電路連接結構體，分三個階段來評價玻璃基板與電路連接用接著劑膜的剝離狀態。求出電路連接用接著劑膜整體的面積中，自玻璃基板剝離的比例，將幾乎沒有發生剝離（剝離部分的比例小於整體的5%以下）者評價為A，將發生少量剝離（剝離部分的比例為整體的5%以上且小於20%）者評價為B，將發生剝離（剝離部分的比例為整體的20%以上）者評價為C。[Peeling Evaluation] A microscope (trade name: ECLIPSE L200, manufactured by Nikon Co., Ltd.) was used to evaluate whether the circuit connection part of the circuit connection structure after the high temperature and high humidity test was peeled off. Specifically, the circuit connection structure produced as described above was observed from the glass substrate side with a microscope, and the peeling state of the glass substrate and the adhesive film for circuit connection was evaluated in three stages. The ratio of peeling from the glass substrate in the area of the entire area of the adhesive film for circuit connection was determined, and the one with almost no peeling (the proportion of the peeled portion is less than 5% of the total) was evaluated as A, and a small amount of peeling (the peeling portion was Those with a ratio of 5% or more and less than 20% of the total) were evaluated as B, and those with peeling (the ratio of the peeled portion was 20% or more of the entire) was evaluated as C.
（實施例2～實施例6及比較例1～比較例2）
作為光硬化性組成物，使用光硬化性組成物2～光硬化性組成物8，除此以外，以與實施例1相同的方式製作電路連接用接著劑膜及電路連接結構體，且以與實施例1相同的方式進行電路連接結構體的評價。將結果示於表3及表4中。(Example 2 to Example 6 and Comparative Example 1 to Comparative Example 2)
As the photocurable composition, the
[表3]
[表4]
1:電路連接用接著劑膜
2:第一接著劑層
2a:第一接著劑層的與第二接著劑層側為相反側的表面
3:第二接著劑層
3a:第二接著劑層的與第一接著劑層側為相反側的表面
4:導電粒子
5:接著劑成分
10:電路連接結構體
11:第一電路基板
11a:第一電路基板的主面（安裝面）
12:電路電極（第一電極）
13:第一電路構件
14:第二電路基板
14a:第二電路基板的主面
15:凸塊電極（第二電極）
16:第二電路構件
17:電路連接部
18:第一區域
19:第二區域
20:接著劑膜收容組
21:卷軸
22:收容構件
23:卷芯
24:第一側板
25:第二側板
26:軸孔
27:***口
28:視認部
d1:第一接著劑層的厚度（距離）
d2:第二接著劑層的厚度（距離）
S:第一接著劑層與第二接著劑層的邊界1: Adhesive film for circuit connection
2: The first
圖1是表示本發明的一實施形態的電路連接用接著劑膜的示意剖面圖。 圖2是表示本發明的一實施形態的電路連接結構體的示意剖面圖。 圖3是表示本發明的一實施形態的電路連接結構體的製造步驟的示意剖面圖。 圖4是表示本發明的一實施形態的接著劑膜收容組的立體圖。Fig. 1 is a schematic cross-sectional view showing an adhesive film for circuit connection according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a circuit connection structure according to an embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing a manufacturing process of a circuit connection structure according to an embodiment of the present invention. Fig. 4 is a perspective view showing an adhesive film storage group according to an embodiment of the present invention.
1:電路連接用接著劑膜 1: Adhesive film for circuit connection
2:第一接著劑層 2: The first adhesive layer
2a:第一接著劑層的與第二接著劑層側為相反側的表面 2a: The surface on the opposite side of the first adhesive layer and the second adhesive layer side
3:第二接著劑層 3: The second adhesive layer
3a:第二接著劑層的與第一接著劑層側為相反側的表面 3a: The surface of the second adhesive layer opposite to the first adhesive layer side
4:導電粒子 4: conductive particles
5:接著劑成分 5: Adhesive ingredients
d1:第一接著劑層的厚度(距離) d1: Thickness (distance) of the first adhesive layer
d2:第二接著劑層的厚度(距離) d2: The thickness (distance) of the second adhesive layer
S:第一接著劑層與第二接著劑層的邊界 S: The boundary between the first adhesive layer and the second adhesive layer
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019046431 | 2019-03-13 | ||
| JP2019-046431 | 2019-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW202045665A true TW202045665A (en) | 2020-12-16 |
Family
ID=72426624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW109107998A TW202045665A (en) | 2019-03-13 | 2020-03-11 | Circuit-connecting adhesive film and method for manufacturing same, circuit-connecting structure manufacturing method, and adhesive film housing set |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7480772B2 (en) |
| KR (1) | KR20210141954A (en) |
| CN (1) | CN113557273B (en) |
| TW (1) | TW202045665A (en) |
| WO (1) | WO2020184584A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4907840B2 (en) * | 2003-11-12 | 2012-04-04 | 日立化成工業株式会社 | Anisotropic conductive film and circuit board using the same |
| WO2005054388A1 (en) | 2003-12-04 | 2005-06-16 | Asahi Kasei Emd Corporation | Anisotropic conductive adhesive sheet and coupling structure |
| CN104508064B (en) * | 2012-08-03 | 2016-10-12 | 迪睿合电子材料有限公司 | Anisotropic conductive film and manufacture method thereof |
| JP6185742B2 (en) * | 2013-04-19 | 2017-08-23 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, and joined body |
| JP2017171472A (en) | 2016-03-24 | 2017-09-28 | デクセリアルズ株式会社 | Reel member and film wound body |
| JP7013649B2 (en) | 2017-01-27 | 2022-02-01 | 昭和電工マテリアルズ株式会社 | Adhesive composition, film-like adhesive, connection structure and its manufacturing method |
| KR102631317B1 (en) * | 2017-09-11 | 2024-02-01 | 가부시끼가이샤 레조낙 | Adhesive film for circuit connection and manufacturing method thereof, manufacturing method of circuit connection structure, and adhesive film accommodation set |
-
2020
- 2020-03-10 KR KR1020217031909A patent/KR20210141954A/en unknown
- 2020-03-10 CN CN202080019861.8A patent/CN113557273B/en active Active
- 2020-03-10 WO PCT/JP2020/010387 patent/WO2020184584A1/en active Application Filing
- 2020-03-10 JP JP2021505093A patent/JP7480772B2/en active Active
- 2020-03-11 TW TW109107998A patent/TW202045665A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP7480772B2 (en) | 2024-05-10 |
| KR20210141954A (en) | 2021-11-23 |
| JPWO2020184584A1 (en) | 2020-09-17 |
| WO2020184584A1 (en) | 2020-09-17 |
| CN113557273A (en) | 2021-10-26 |
| CN113557273B (en) | 2023-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111052881B (en) | Adhesive film for circuit connection, method for producing same, method for producing circuit connection structure, and adhesive film housing assembly | |
| TW202045650A (en) | Adhesive film for circuit connection, manufacturing method thereof, manufacturing method of circuit connection structure, and adhesive film accommodating set | |
| KR102533475B1 (en) | Adhesive film for circuit connection and manufacturing method thereof, manufacturing method for circuit connection structure, and adhesive film accommodating set | |
| TWI805614B (en) | Adhesive film storage kit and manufacturing method thereof | |
| TWI808990B (en) | Adhesive film for circuit connection, manufacturing method thereof, method of manufacturing circuit connection structure, and adhesive film storage set | |
| WO2022059647A1 (en) | Adhesive film for circuit connection and manufacturing method thereof, and circuit connection structure manufacturing | |
| JP2022020338A (en) | Adhesive film for circuit connection and production method of the same, and method of producing circuit connection structure | |
| TW202045665A (en) | Circuit-connecting adhesive film and method for manufacturing same, circuit-connecting structure manufacturing method, and adhesive film housing set | |
| TW202045664A (en) | Adhesive film for circuit connection and method for producing same, method for producing circuit connected structure, and adhesive film housing set | |
| TW202039764A (en) | Adhesive film for circuit connection, method for producing circuit connected structure, and adhesive film housing set | |
| JP2022098985A (en) | Adhesive film for circuit connection and method for producing the same, and method for producing circuit connection structure | |
| JP2022039384A (en) | Adhesive film for circuit connection and method for producing the same, and method for producing circuit connection structure | |
| JP2022048791A (en) | Circuit connection adhesive film, as well as, circuit connection structure and manufacturing method thereof | |
| JP2023134038A (en) | Adhesive film for connecting circuits, and circuit connection structure and method for manufacturing the same |