TWI844506B - Rolled conductive bonding sheet, wiring board with metal reinforcement plate, and electronic equipment - Google Patents
Rolled conductive bonding sheet, wiring board with metal reinforcement plate, and electronic equipment Download PDFInfo
- Publication number
- TWI844506B TWI844506B TW113108026A TW113108026A TWI844506B TW I844506 B TWI844506 B TW I844506B TW 113108026 A TW113108026 A TW 113108026A TW 113108026 A TW113108026 A TW 113108026A TW I844506 B TWI844506 B TW I844506B
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- Taiwan
- Prior art keywords
- conductive bonding
- sheet
- conductive adhesive
- conductive
- adhesive layer
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Abstract
本公開提供一種在卷出時不產生黏連、膜厚擔保性優異、保護片的剝離性良好且層壓強度以及接著性高的卷狀導電性接合片、帶金屬增強板的配線板以及電子設備。本公開是通過如下卷狀導電性接合片來解決，即為一種將導電性接合片捲繞成卷狀而成的卷狀導電性接合片，其中，所述導電性接合片具有保護片以及導電性接合劑層，所述導電性接合劑層的探針黏性黏著力為5.0 N/cm 2以下，所述導電性接合劑層在25℃～30℃下的儲存彈性模量的最高值為1.0×10 7Pa～2.0×10 9Pa。 The present disclosure provides a roll-shaped conductive bonding sheet, a wiring board with a metal reinforcement plate, and an electronic device that do not produce adhesion when unrolling, have excellent film thickness guarantee, good peelability of the protective sheet, and high layer pressure strength and adhesion. The present disclosure solves the problem by means of the following roll-shaped conductive bonding sheet, i.e., a roll-shaped conductive bonding sheet formed by winding a conductive bonding sheet into a roll shape, wherein the conductive bonding sheet has a protective sheet and a conductive bonding agent layer, the probe tack adhesion of the conductive bonding agent layer is 5.0 N/ cm2 or less, and the maximum value of the storage elastic modulus of the conductive bonding agent layer at 25°C to 30°C is 1.0× 107Pa to 2.0× 109Pa .
Description
本公開涉及一種卷狀導電性接合片、帶金屬增強板的配線板及電子設備。The present disclosure relates to a rolled conductive bonding sheet, a wiring board with a metal reinforcement plate, and an electronic device.
搭載於電子設備的內部的撓性印刷配線板具有柔軟性，就配置電磁波遮蔽層、且連接器部等進行零件間的連接的觀點而言，已知有配置增強板來抑制變形的結構。以往，作為增強板，使用環氧玻璃等，但就賦予電磁波噪聲的抑制功能的方面而言，使用金屬板。在遮蔽層或金屬板與撓性印刷配線板的連接中使用將樹脂作為主成分的導電性接合劑。The flexible printed wiring board installed inside the electronic equipment has flexibility. From the perspective of configuring an electromagnetic wave shielding layer and connecting parts such as a connector, a structure is known to configure a reinforcing plate to suppress deformation. Conventionally, epoxy glass and the like are used as reinforcing plates, but metal plates are used from the perspective of providing a function of suppressing electromagnetic wave noise. A conductive adhesive containing resin as the main component is used to connect the shielding layer or the metal plate to the flexible printed wiring board.
例如，在國際公開2016/002780號中，作為將與接地用配線圖案（配線板）相向配置的導電性增強板（金屬板）加以接合的導電性接合劑，公開了一種具有聚胺基甲酸酯聚脲樹脂、環氧樹脂以及導電性填料的導電性接著劑組合物。另外，在國際公開2019/031394號中，公開了一種導電性接著劑，其添加有機鹽、滑石、碳黑及二氧化矽等作為損失彈性模量調整劑，從而提高了埋入性及接著性。For example, International Publication No. 2016/002780 discloses a conductive adhesive composition having a polyurethane polyurea resin, an epoxy resin, and a conductive filler as a conductive adhesive for bonding a conductive reinforcing plate (metal plate) disposed opposite to a grounding wiring pattern (wiring board). In addition, International Publication No. 2019/031394 discloses a conductive adhesive to which organic salts, talc, carbon black, and silica are added as loss modulus modifiers to improve embeddability and adhesion.
[發明所欲解決之課題][The problem that the invention wants to solve]
通常，導電性接合片於在保護片上積層有導電性接合劑層的狀態下卷取成卷狀（卷軸狀），但問題是在從卷中卷出時會發生導電性接合劑層附著於保護片的背面的現象、即發生所謂的黏連。Generally, a conductive adhesive sheet is wound into a roll (reel shape) in a state where a conductive adhesive layer is stacked on a protective sheet. However, when the conductive adhesive layer is unwound from the roll, the conductive adhesive layer adheres to the back side of the protective sheet, which is called blocking.
另外，在將樣品卷取成卷狀時，以卷不崩解的方式施加張力進行卷取，但在卷取張力強的情況下，產生如下問題：由於在導電性接合劑層受到強的壓力的狀態下長期保管，導致導電性接合劑層的厚度（膜厚）減少（膜厚擔保性）。In addition, when the sample is wound into a roll, tension is applied so that the roll does not collapse. However, if the winding tension is strong, the following problem occurs: the thickness (film thickness) of the conductive adhesive layer decreases due to long-term storage under strong pressure (film thickness guarantee).
進而，在通過熱壓接將導電性接合片臨時黏貼於金屬板等被黏物上後，在剝離保護片時保護片變形或破損，而產生無法剝離的問題（保護片的剝離性）。Furthermore, after the conductive bonding sheet is temporarily bonded to an adherend such as a metal plate by thermal compression, the protective sheet may be deformed or damaged when being peeled off, and a problem of being unable to be peeled off (peelability of the protective sheet) occurs.
另外，在所述臨時黏貼時，若導電性接合劑層的軟化不充分，則產生如下問題：導電性接合劑層對金屬板的密接力變得不充分，將導電性接合劑層與金屬板積層而成的金屬增強板加工成所期望的形狀的步驟、即所謂的沖裁加工時導電性接合劑層從金屬板剝離等（層壓強度）。In addition, if the softening of the conductive adhesive layer is insufficient during the temporary bonding, the following problems may arise: the adhesion of the conductive adhesive layer to the metal plate becomes insufficient, and the conductive adhesive layer may be peeled off from the metal plate during the process of processing the metal reinforcement plate formed by laminating the conductive adhesive layer and the metal plate into a desired shape, that is, the so-called punching process (lamination strength).
此外，在規定的溫度（例如170℃）下對金屬板/導電性接合劑層/配線板的積層體進行加熱加壓（熱壓）並接著後對保護片施加拉伸力的情況下，若常溫附近的導電性接合劑層的彈性模量非常高，則產生引起凝聚破壞而容易剝離的問題（接著性）。 [解決課題之手段] In addition, when the laminate of metal plate/conductive adhesive layer/wiring board is heated and pressed (hot pressing) at a predetermined temperature (e.g., 170°C) and then tensile force is applied to the protective sheet, if the elastic modulus of the conductive adhesive layer near room temperature is very high, cohesion failure may occur and the layer may be easily peeled off (adhesion). [Solution]
本發明人等人反覆進行了努力研究，結果發現在以下的形態中可解決本公開的課題，從而完成了本公開。 [1]：一種卷狀導電性接合片，是將導電性接合片捲繞成卷狀而成的卷狀導電性接合片，其中，所述導電性接合片具有保護片以及導電性接合劑層，所述導電性接合劑層的探針黏性黏著力為5.0 N/cm 2以下，所述導電性接合劑層在25℃～30℃下的儲存彈性模量的最高值為1.0×10 7Pa～2.0×10 9Pa。 [2]：如[1]所述的卷狀導電性接合片，其中，所述導電性接合劑層在70℃～120℃下的儲存彈性模量的最高值為3.0×10 6Pa～1.5×10 8Pa。 [3]：如[2]所述的卷狀導電性接合片，其中，所述保護片在25℃～30℃下的儲存彈性模量的最高值為1.0×10 9Pa以上。 [4]：如[1]～[3]中任一項所述的卷狀導電性接合片，其中，所述導電性接合劑層具有選自由酯鍵、醯亞胺鍵、醯胺鍵、胺基甲酸酯鍵及脲鍵所組成的群組中的一種以上。 [5]：一種帶金屬增強板的配線板，包括如[4]所述的導電性接合劑層以及金屬增強板。 [6]：一種電子設備，包括如[5]所述的帶金屬增強板的配線板。 The inventors of the present invention have repeatedly conducted diligent research and have found that the problem of the present disclosure can be solved in the following form, thereby completing the present disclosure. [1]: A roll-shaped conductive bonding sheet is a roll-shaped conductive bonding sheet formed by winding a conductive bonding sheet into a roll, wherein the conductive bonding sheet has a protective sheet and a conductive bonding agent layer, the probe tack adhesion of the conductive bonding agent layer is less than 5.0 N/ cm2 , and the maximum value of the storage elastic modulus of the conductive bonding agent layer at 25°C to 30°C is 1.0× 107Pa to 2.0× 109Pa . [2]: The rolled conductive bonding sheet as described in [1], wherein the maximum value of the storage elastic modulus of the conductive bonding agent layer at 70°C to 120°C is 3.0×10 6 Pa to 1.5×10 8 Pa. [3]: The rolled conductive bonding sheet as described in [2], wherein the maximum value of the storage elastic modulus of the protective sheet at 25°C to 30°C is 1.0×10 9 Pa or more. [4]: The rolled conductive bonding sheet as described in any one of [1] to [3], wherein the conductive bonding agent layer has one or more selected from the group consisting of ester bonds, imide bonds, amide bonds, urethane bonds, and urea bonds. [5]: A wiring board with a metal reinforcement plate, comprising the conductive adhesive layer as described in [4] and the metal reinforcement plate. [6]: An electronic device, comprising the wiring board with a metal reinforcement plate as described in [5].
[發明的效果] 通過本公開，提供一種在卷出時不產生黏連、膜厚擔保性優異、保護片的剝離性良好且層壓強度以及接著性高的卷狀導電性接合片。 [Effect of the invention] The present disclosure provides a roll-shaped conductive bonding sheet that does not cause adhesion when unrolled, has excellent film thickness assurance, good peeling property of the protective sheet, and has high lamination strength and adhesion.
以下，依次對本公開的卷狀導電性接合片、帶金屬增強板的配線板、及電子設備進行說明。此外，只要無特別記載，則表示數值範圍的「～」包含其下限值及上限值。另外，為了使說明明確，適宜簡化了附圖。另外，為了說明，附圖中的各結構的比例尺有時會大不相同。The following is a description of the coiled conductive bonding sheet, the wiring board with a metal reinforcement plate, and the electronic device disclosed in the present invention. In addition, unless otherwise specified, "~" indicating a numerical range includes its lower limit and upper limit. In addition, the attached figures are appropriately simplified for clarity. In addition, for the purpose of explanation, the scales of the various structures in the attached figures are sometimes very different.
[導電性接合片] 本公開的導電性接合片具有保護片以及導電性接合劑層，且顯示出平坦的片形狀。導電性接合劑層較佳為直接積層於保護片上的形態或者經由脫模劑層積層的形態。 [Conductive bonding sheet] The conductive bonding sheet disclosed herein has a protective sheet and a conductive bonding agent layer and has a flat sheet shape. The conductive bonding agent layer is preferably directly laminated on the protective sheet or laminated via a release agent layer.
[卷狀導電性接合片] 本公開的卷狀導電性接合片是將所述導電性接合片捲繞成卷狀而成的構件。在圖1中示出本發明的卷狀導電性接合片的示意圖及其部分放大說明圖。卷狀導電性接合片4具有卷取芯（未圖示），形成在卷取芯上纏繞有導電性接合片5的結構。導電性接合片5是以導電性接合劑層1為內側、保護片3為外側的方式纏繞的結構。 [Rolled conductive bonding sheet] The rolled conductive bonding sheet disclosed in the present invention is a component formed by winding the conductive bonding sheet into a roll shape. FIG1 shows a schematic diagram of the rolled conductive bonding sheet of the present invention and a partially enlarged explanatory diagram thereof. The rolled conductive bonding sheet 4 has a winding core (not shown), and a conductive bonding sheet 5 is wound around the winding core. The conductive bonding sheet 5 is wound in a manner such that the conductive bonding agent layer 1 is on the inner side and the protective sheet 3 is on the outer side.
[保護片] 保護片在導電性接合片中成為導電性接合劑層的支撐體。另外，在卷狀導電性接合片中位於卷的最表面，承擔保護導電性接合劑層不破損、不污染的功能。 [Protective sheet] The protective sheet is a support for the conductive adhesive layer in the conductive adhesive sheet. In addition, in the case of a rolled conductive adhesive sheet, it is located on the outermost surface of the roll and has the function of protecting the conductive adhesive layer from damage and contamination.
作為保護片的一例，可列舉：聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚氟乙烯、聚偏二氟乙烯、硬質聚氯乙烯、聚偏二氯乙烯、尼龍、聚醯亞胺、聚苯乙烯、聚乙烯醇、乙烯-乙烯醇共聚物、聚碳酸酯、聚丙烯腈、聚丁烯、軟質聚氯乙烯、聚乙烯、聚丙烯、聚胺基甲酸酯、乙烯乙酸乙烯酯共聚物、聚乙酸乙烯酯等塑膠片等、玻璃紙、道林紙（woodfree paper）、牛皮紙、塗布紙等紙類、各種無紡布、合成紙、金屬箔或將它們組合而成的複合膜等。這些中，就通過調配材料成分而容易調整儲存彈性模量的觀點而言，較佳為塑膠片，其中，更佳為兼具剛性以及柔軟性的聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯。Examples of the protective sheet include polyethylene terephthalate, polyethylene naphthalate, polyvinyl fluoride, polyvinylidene fluoride, rigid polyvinyl chloride, polyvinylidene chloride, nylon, polyimide, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate, polyacrylonitrile, polybutylene, soft polyvinyl chloride, polyethylene, polypropylene, polyurethane, ethylene vinyl acetate copolymer, polyvinyl acetate and other plastic sheets, cellophane, woodfree paper, kraft paper, coated paper and other papers, various nonwoven fabrics, synthetic paper, metal foil or composite films of these. Among these, plastic sheets are preferred from the viewpoint of easily adjusting the storage elastic modulus by adjusting the material components, and polyethylene terephthalate and polyethylene naphthalate, which have both rigidity and flexibility, are more preferred.
保護片的表面也可視需要進行消光處理。消光處理的方法可列舉：砂消光、蝕刻消光、塗布消光、化學消光、混煉消光等。就提高保護片的剝離性的觀點而言，導電性接合片中的與導電性接合劑層積層的面的保護片的表面粗糙度Ra較佳為0.01 μm～1 μm。就提高耐黏連性的觀點而言，和與導電性接合劑層積層的面相反的保護片的表面粗糙度Ra較佳為0.01 μm～5 μm。The surface of the protective sheet may also be matte treated as needed. The methods of matte treatment include: sand matte, etching matte, coating matte, chemical matte, mixing matte, etc. From the perspective of improving the releasability of the protective sheet, the surface roughness Ra of the protective sheet on the surface of the conductive adhesive sheet on which the conductive adhesive layer is layered is preferably 0.01 μm to 1 μm. From the perspective of improving the adhesion resistance, the surface roughness Ra of the protective sheet opposite to the surface on which the conductive adhesive layer is layered is preferably 0.01 μm to 5 μm.
就提高保護片的剝離性的觀點而言，保護片較佳為在表面具有脫模劑層的形態。脫模劑層較佳為塗布脫模劑而形成。作為脫模劑，可選擇：聚乙烯、聚丙烯等烴系樹脂、高級脂肪酸及其金屬鹽、高級脂肪酸皂、蠟、動植物油脂、雲母、滑石、矽酮系表面活性劑、矽油、矽酮樹脂、醇酸系樹脂、氟系表面活性劑、氟樹脂、含氟的矽酮樹脂、三聚氰胺系樹脂、丙烯酸系樹脂，較佳為醇酸系樹脂。作為脫模劑的塗布方法，可通過以往公知的方式，例如凹版塗布方式、吻合式塗布方式、模塗方式、唇口塗布方式、缺角輪塗布方式、刮板塗布方式、輥塗方式、刀片塗布方式、噴塗方式、棒塗方式、旋塗方式、浸漬塗布方式等進行。脫模劑層較佳為形成於保護片的單面，更佳為形成於兩面。From the viewpoint of improving the peeling property of the protective sheet, the protective sheet is preferably in a form having a release agent layer on the surface. The release agent layer is preferably formed by coating the release agent. As the release agent, hydrocarbon resins such as polyethylene and polypropylene, higher fatty acids and their metal salts, higher fatty acid soaps, wax, animal and plant oils and fats, mica, talc, silicone surfactants, silicone oils, silicone resins, alkyd resins, fluorine surfactants, fluorine resins, fluorine-containing silicone resins, melamine resins, and acrylic resins can be selected, and alkyd resins are preferred. The release agent can be applied by any known method, such as gravure coating, kiss coating, die coating, lip coating, notch wheel coating, scraper coating, roll coating, blade coating, spray coating, rod coating, spin coating, dip coating, etc. The release agent layer is preferably formed on one side of the protective sheet, and more preferably on both sides.
保護片的厚度並無特別限制，但由於在剝離時在保護片具有韌性以及強度時保護片不易發生破損，因此較佳為38 μm以上，就防止臨時黏貼時熱不易穿過導電性接合劑層或臨時黏貼性降低的觀點而言，較佳為100 μm以下。The thickness of the protective sheet is not particularly limited, but is preferably 38 μm or more because the protective sheet has toughness and strength and is not easily damaged during peeling. From the perspective of preventing heat from penetrating the conductive adhesive layer during temporary bonding or preventing temporary adhesion from decreasing, it is preferably 100 μm or less.
[保護片的儲存彈性模量] 本公開的保護片在25℃～30℃下的儲存彈性模量的最高值較佳為1.0×10 9Pa以上且1.5×10 10Pa以下，更佳為1.5×10 9Pa以上且1.0×10 10Pa以下。另外，通過保護片在25℃～30℃下的儲存彈性模量的最高值處於1.0×10 9Pa以上且1.5×10 10Pa以下，在熱層壓後也可充分提高保護片的剛性（韌性），可防止從導電性接合劑層剝離保護片時的保護片的破損，從而實現優異的剝離性。另外，可防止卷取時的折疊皺褶等卷取不良。保護片的儲存彈性模量可通過材質或聚合物的主鏈骨架、交聯密度、取向性進行調節。 [Storage elastic modulus of the protective sheet] The maximum value of the storage elastic modulus of the protective sheet disclosed herein at 25°C to 30°C is preferably 1.0×10 9 Pa or more and 1.5×10 10 Pa or less, and more preferably 1.5×10 9 Pa or more and 1.0×10 10 Pa or less. In addition, since the maximum value of the storage elastic modulus of the protective sheet at 25°C to 30°C is 1.0×10 9 Pa or more and 1.5×10 10 Pa or less, the rigidity (toughness) of the protective sheet can be sufficiently improved even after hot lamination, and damage to the protective sheet when the protective sheet is peeled off from the conductive adhesive layer can be prevented, thereby achieving excellent peeling properties. In addition, it can prevent winding defects such as folds and wrinkles during winding. The storage elastic modulus of the protective sheet can be adjusted by the main chain skeleton, crosslinking density, and orientation of the material or polymer.
[導電性接合劑層] 本公開的導電性接合劑層是通過將導電性組合物塗敷於保護片上並進行乾燥而獲得，在25℃下為非流動性的固體物質，且形成一定厚度的層狀。 就使薄膜性以及導電性並存的觀點而言，導電性接合片中的導電性接合劑層的厚度較佳為5 μm～200 μm，更佳為10 μm～100 μm，進而較佳為30 μm～70 μm。 [Conductive adhesive layer] The conductive adhesive layer disclosed in the present invention is obtained by applying a conductive composition on a protective sheet and drying it. It is a non-flowing solid substance at 25°C and forms a layer of a certain thickness. From the perspective of achieving both thin film properties and conductivity, the thickness of the conductive adhesive layer in the conductive adhesive sheet is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm, and further preferably 30 μm to 70 μm.
[導電性接合劑層的探針黏性黏著力] 導電性接合劑層的探針黏性黏著力為5.0 N/cm 2以下。通過導電性接合劑層的探針黏性黏著力為5.0 N/cm 2以下，而使黏著性降低，從而在卷成卷狀時可抑制向保護層的黏附，從而可提高耐黏連性。導電性接合劑層的探針黏性黏著力更佳為3.5 N/cm 2以下。此外，所述探針黏性黏著力的下限值較佳為0 N/cm 2。 [Probe tack adhesion of the conductive adhesive layer] The probe tack adhesion of the conductive adhesive layer is 5.0 N/cm 2 or less. By making the probe tack adhesion of the conductive adhesive layer 5.0 N/cm 2 or less, the tackiness is reduced, and thus adhesion to the protective layer can be suppressed when the film is rolled into a roll, thereby improving the anti-sticking property. The probe tack adhesion of the conductive adhesive layer is more preferably 3.5 N/cm 2 or less. In addition, the lower limit of the probe tack adhesion is preferably 0 N/cm 2 .
本公開中的導電性接合劑層的探針黏性黏著力例如可通過萜烯樹脂等黏著賦予樹脂的添加量調節、或後述的黏合劑（A）中所含的樹脂（a-1）的主鏈骨架及側鏈的變更、或基於硬化劑的添加量調節的交聯密度的調節、金屬粒子及其他填料的種類或添加量進行控制。對導電性接合劑層的探針黏性黏著力進行控制的方法只要是可實現所期望的探針黏性黏著力的方法，則可並不限定於之前所述的方法而使用。The probe tack adhesion of the conductive adhesive layer in the present disclosure can be controlled by, for example, adjusting the amount of tack-imparting resin such as terpene resin added, changing the main chain skeleton and side chain of the resin (a-1) contained in the adhesive (A) described later, adjusting the crosslinking density by adjusting the amount of hardener added, or the type or amount of metal particles and other fillers added. The method for controlling the probe tack adhesion of the conductive adhesive layer is not limited to the method described above as long as it is a method that can achieve the desired probe tack adhesion.
[導電性接合劑層的儲存彈性模量] 導電性接合劑層在25℃～30℃下的儲存彈性模量的最高值為1.0×10 7Pa～2.0×10 9Pa。通過將導電性接合劑層在25℃～30℃下的彈性模量設為1.0×10 7Pa以上，在針對導電性接合片而將樣品卷取成卷狀時，即使卷取張力強，而對導電性接合劑層施加壓力，進而以卷狀態長期保管，也可抑制導電性接合劑層的厚度變化。另外，通過將導電性接合劑層在25℃～30℃下的彈性模量設為2.0×10 9Pa以下，可防止導電性接合劑層的凝聚破壞，從而可維持高接著力。 [Storage elastic modulus of the conductive adhesive layer] The maximum value of the storage elastic modulus of the conductive adhesive layer at 25°C to 30°C is 1.0×10 7 Pa to 2.0×10 9 Pa. By setting the elastic modulus of the conductive adhesive layer at 25°C to 30°C to 1.0×10 7 Pa or more, when the conductive adhesive sheet is wound into a roll, even if a strong winding tension is applied to the conductive adhesive layer and the rolled sample is stored for a long period of time, the thickness change of the conductive adhesive layer can be suppressed. Furthermore, by setting the elastic modulus of the conductive adhesive layer at 25°C to 30°C to 2.0×10 9 Pa or less, cohesive destruction of the conductive adhesive layer can be prevented, thereby maintaining high adhesion.
導電性接合劑層在25℃～30℃下的儲存彈性模量的最高值較佳為1.0×10 7Pa～1.7×10 9Pa，更佳為1.0×10 8Pa～1.3×10 9Pa。 導電性接合劑層在70℃～120℃下的儲存彈性模量的最高值較佳為3.0×10 6Pa～1.5×10 8Pa，更佳為7.0×10 6Pa～1.0×10 8Pa，進而較佳為1.0×10 7Pa～8.0×10 7Pa。通過使導電性接合劑層在70℃～120℃下的儲存彈性模量的最高值為3.0×10 6Pa～1.5×10 8Pa，例如在通過110℃的熱層壓進行臨時黏貼時產生導電性接合劑層的流動性，可提高在保護片上的層壓強度。 The maximum value of the storage elastic modulus of the conductive adhesive layer at 25°C to 30°C is preferably 1.0×10 7 Pa to 1.7×10 9 Pa, more preferably 1.0×10 8 Pa to 1.3×10 9 Pa. The maximum value of the storage elastic modulus of the conductive adhesive layer at 70°C to 120°C is preferably 3.0×10 6 Pa to 1.5×10 8 Pa, more preferably 7.0×10 6 Pa to 1.0×10 8 Pa, further preferably 1.0×10 7 Pa to 8.0×10 7 Pa. By setting the maximum value of the storage elastic modulus of the conductive adhesive layer at 70°C to 120°C to 3.0×10 6 Pa to 1.5×10 8 Pa, the fluidity of the conductive adhesive layer is generated during temporary bonding by hot lamination at 110°C, for example, and the lamination strength on the protective sheet can be increased.
對於本公開中的導電性接合劑層的儲存彈性模量的最高值的控制，例如可採用如下等的方法：變更樹脂的主鏈骨架及側鏈、或通過硬化劑添加量調節來調節交聯密度、添加黏著賦予樹脂並調節添加量、通過金屬粒子及其他填料的種類或添加量進行調節。作為黏著賦予樹脂，例如較佳為萜烯樹脂或萜烯酚樹脂、松香或松香衍生物等。The maximum value of the storage elastic modulus of the conductive adhesive layer in the present disclosure can be controlled by, for example, changing the main chain skeleton and side chain of the resin, or adjusting the crosslinking density by adjusting the amount of hardener added, adding an adhesion-imparting resin and adjusting the amount of addition, or adjusting by the type or amount of metal particles and other fillers. As the adhesion-imparting resin, for example, terpene resins or terpene phenol resins, rosin or rosin derivatives are preferred.
[導電性組合物] 導電性組合物包含黏合劑（A）以及金屬粒子（B）。 [Conductive composition] The conductive composition includes a binder (A) and metal particles (B).
[黏合劑（A）] 黏合劑（A）成為導電性組合物的基體，具有分散擔載金屬粒子（B）或其他添加填料的功能。黏合劑（A）只要具有所述功能，則組成等並無特別限制，較佳為包含樹脂（a-1）。本公開中的樹脂（a-1）被定義為通常（常溫）為固體、半固體或凝固體、且具有軟化或熔融範圍的重量平均分子量（Mw）為5,000以上的有機材料。 [Binder (A)] The binder (A) serves as the matrix of the conductive composition and has the function of dispersing and supporting the metal particles (B) or other added fillers. The composition of the binder (A) is not particularly limited as long as it has the above-mentioned function, but it preferably contains a resin (a-1). The resin (a-1) in this disclosure is defined as an organic material that is usually (at room temperature) solid, semi-solid or solidified and has a softening or melting range and a weight average molecular weight (Mw) of 5,000 or more.
[樹脂（a-1）] 樹脂（a-1）除了所述重量平均分子量（Mw）以外，組成、分子結構等並無特別限制，這些中，較佳為具有選自由酯鍵、醯亞胺鍵、醯胺鍵、胺基甲酸酯鍵及脲鍵所組成的群組中的一種以上的化學鍵的樹脂。醯亞胺鍵、醯胺鍵、胺基甲酸酯鍵及脲鍵可通過鍵中所含的氮原子的非共價電子對與被黏物相互作用來實現牢固的接著力。作為具有所述化學鍵群的樹脂，例如可列舉：聚酯樹脂、聚胺基甲酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、脲樹脂、聚胺基甲酸酯脲樹脂。 [Resin (a-1)] The composition, molecular structure, etc. of the resin (a-1) are not particularly limited except for the weight average molecular weight (Mw). Among these, a resin having one or more chemical bonds selected from the group consisting of ester bonds, imide bonds, amide bonds, urethane bonds, and urea bonds is preferred. Imidide bonds, amide bonds, urethane bonds, and urea bonds can achieve strong adhesion by interacting with the adherend through the non-covalent electron pairs of the nitrogen atoms contained in the bonds. Examples of the resin having the chemical bond group include polyester resin, polyurethane resin, polyamide resin, polyimide resin, polyamideimide resin, urea resin, and polyurethane urea resin.
另外，樹脂（a-1）更佳為具有選自由酯鍵、醯亞胺鍵、醯胺鍵、胺基甲酸酯鍵及脲鍵所組成的群組中的兩種以上。通過黏合劑（A）具有選自由酯鍵、醯亞胺鍵、醯胺鍵、胺基甲酸酯鍵及脲鍵所組成的群組中的兩種以上，與被黏物的相互作用多重化，能夠表現出更牢固的密接力。所謂具有選自由酯鍵、醯亞胺鍵、醯胺鍵、胺基甲酸酯鍵及脲鍵所組成的群組中的兩種以上的樹脂，例如為聚酯醯胺、聚醯胺醯亞胺樹脂、聚胺基甲酸酯脲樹脂等。In addition, the resin (a-1) preferably has two or more selected from the group consisting of ester bonds, imide bonds, amide bonds, urethane bonds, and urea bonds. Since the adhesive (A) has two or more selected from the group consisting of ester bonds, imide bonds, amide bonds, urethane bonds, and urea bonds, the interaction with the adherend is multiplexed, and a stronger adhesion can be exhibited. The resin having two or more selected from the group consisting of ester bonds, imide bonds, amide bonds, urethane bonds, and urea bonds is, for example, polyesteramide, polyamideimide resin, polyurethaneurea resin, etc.
黏合劑（A）較佳為包含選自由環氧基、氧雜環丁烷基、環硫基、及氮丙啶基所組成的群組中的至少一個官能基。在樹脂（a-1）具有酸性基等反應性官能基的情況下，所述官能基群組在其反應性官能基或者所述官能基彼此引起硬化反應，可表現出高接著性。作為使黏合劑（A）含有所述官能基群組的方法，例如可採取如下等的方法：將具有所述官能基群組的樹脂（a-1）添加至黏合劑（A），或者將後述的硬化劑（C）中的具有所述官能基群組的硬化劑添加至黏合劑（A）。The adhesive (A) preferably contains at least one functional group selected from the group consisting of an epoxy group, an oxacyclobutane group, a cyclothio group, and an aziridine group. When the resin (a-1) has a reactive functional group such as an acidic group, the functional group group can exhibit high adhesion by causing a curing reaction between the reactive functional groups or between the functional groups. As a method for making the adhesive (A) contain the functional group group, for example, the following method can be adopted: adding the resin (a-1) having the functional group group to the adhesive (A), or adding the curing agent having the functional group group in the curing agent (C) described later to the adhesive (A).
如上所述，就組成、分子結構的觀點而言，樹脂（a-1）能夠適宜選擇，但也能夠根據樹脂的性質選擇適當的樹脂。就對導電性組合物施加熱刺激而使其顯現接著性的觀點而言，樹脂（a-1）較佳為熱硬化性樹脂（a-2）或熱塑性樹脂（a-3）。As described above, the resin (a-1) can be appropriately selected from the viewpoint of composition and molecular structure, but an appropriate resin can also be selected according to the properties of the resin. From the viewpoint of applying a thermal stimulus to the conductive composition to make it adherent, the resin (a-1) is preferably a thermosetting resin (a-2) or a thermoplastic resin (a-3).
[熱硬化性樹脂（a-2）] 熱硬化性樹脂（a-2）是樹脂（a-1）中具有熱硬化性的樹脂。所謂熱硬化性，被定義為「在通過加熱或放射線、催化劑等之類的其他手段進行硬化時，可變化為實質上不融性且不溶性製品」。 [Thermosetting resin (a-2)] Thermosetting resin (a-2) is a thermosetting resin among resins (a-1). Thermosetting is defined as "a resin that can be transformed into a substantially infusible and insoluble product when hardened by heating or other means such as radiation or a catalyst."
所述熱硬化性在熱硬化性樹脂（a-2）具有酸性基等反應性官能基的情況下，可通過反應性官能基彼此反應來表現，另外，也可通過熱硬化性樹脂（a-2）與組入至後述的硬化劑（C）各者的反應性官能基反應來表現。在導電性接合劑層中使用熱硬化性樹脂（a-2）的情況下，所述導電性接合劑層的探針黏性黏著力、25℃～30℃下的儲存彈性模量、及70℃～120℃下的儲存彈性模量為熱硬化反應前的值。The thermosetting property can be exhibited by the reaction of the reactive functional groups when the thermosetting resin (a-2) has a reactive functional group such as an acidic group, or can be exhibited by the reaction of the thermosetting resin (a-2) with the reactive functional groups incorporated into each of the curing agents (C) described later. When the thermosetting resin (a-2) is used in the conductive adhesive layer, the probe tack adhesion, storage elastic modulus at 25°C to 30°C, and storage elastic modulus at 70°C to 120°C of the conductive adhesive layer are values before the thermosetting reaction.
熱硬化性樹脂（a-2）的酸值較佳為5 mgKOH/g～40 mgKOH/g。通過酸值為所述範圍內，交聯結構的密度成為適當的範圍，能夠使柔軟性以及強韌性並存。酸值更佳為10 mgKOH/g～20 mgKOH/g。The acid value of the thermosetting resin (a-2) is preferably 5 mgKOH/g to 40 mgKOH/g. When the acid value is within the above range, the density of the cross-linked structure is within an appropriate range, and flexibility and toughness can be achieved. The acid value is more preferably 10 mgKOH/g to 20 mgKOH/g.
[熱塑性樹脂（a-3）] 熱塑性樹脂（a-3）是樹脂（a-1）中具有熱塑性的樹脂。所謂熱塑性，定義為「可在塑膠特有的溫度範圍內反覆進行利用加熱的軟化及利用冷卻的硬化，且在軟化狀態下可通過反覆進行利用流動使形狀一致地成形、擠出或成形，而形成為物品的狀態」。 [Thermoplastic resin (a-3)] Thermoplastic resin (a-3) is a thermoplastic resin among resins (a-1). Thermoplasticity is defined as "a state in which a plastic can be repeatedly softened by heating and hardened by cooling within a temperature range unique to plastics, and can be formed, extruded or molded into a uniform shape by repeatedly flowing in a softened state to form an article."
[硬化劑（C）] 本公開中的硬化劑（C）是促進或調節硬化反應的物質，定義為分子量或重量平均分子量（Mw）小於5,000的物質。所謂硬化反應，定義為「通過加熱或放射線、催化劑等之類的其他手段使預聚物或聚合組合物聚合和/或交聯，使彈性模量不可逆地上升」。在黏合劑（A）中，就通過熱等刺激而形成聚合和/或交聯，使導電性組合物顯現出牢固的接著性的觀點而言，本公開的黏合劑（A）較佳為包含硬化劑（C）。 [Hardener (C)] The hardener (C) in the present disclosure is a substance that promotes or regulates the hardening reaction, and is defined as a substance having a molecular weight or weight average molecular weight (Mw) of less than 5,000. The so-called hardening reaction is defined as "polymerization and/or crosslinking of a prepolymer or a polymer composition by heating or other means such as radiation, a catalyst, etc., so that the elastic modulus increases irreversibly." In the adhesive (A), from the perspective of forming polymerization and/or crosslinking by stimulation such as heat, so that the conductive composition exhibits strong adhesion, the adhesive (A) of the present disclosure preferably contains a hardener (C).
關於所述硬化反應，可為硬化劑（C）彼此進行自身反應的反應，例如也可與樹脂（a-1）等黏合劑（A）中的其他成分反應。在樹脂（a-1）與硬化劑（C）進行硬化反應的情況下，就效率良好地進行反應的觀點而言，樹脂（a-1）較佳為熱硬化性樹脂（a-2）。The curing reaction may be a reaction in which the curing agent (C) reacts with itself, or may react with other components in the binder (A) such as the resin (a-1). When the resin (a-1) and the curing agent (C) undergo a curing reaction, the resin (a-1) is preferably a thermosetting resin (a-2) from the viewpoint of efficiently reacting.
就在保管時不進行硬化反應、僅在加熱時產生硬化反應的觀點而言，作為所述熱硬化性樹脂（a-2）與硬化劑（C）的組合，較佳為選擇在50°C下不進行交聯反應、在150°C下促進硬化反應的組合。 另外，通過適宜組合硬化反應的開始溫度不同的兩種以上的硬化劑，也可對各溫度帶中的導電性組合物的交聯密度進行控制。 硬化劑（C）可列舉：環氧硬化劑、氧雜環丁烷硬化劑、環硫硬化劑、氮丙啶硬化劑、胺硬化劑、異氰酸酯硬化劑、及咪唑硬化劑。其中，環氧硬化劑、氧雜環丁烷硬化劑、環硫硬化劑、及氮丙啶硬化劑與熱硬化性樹脂（a-2）有效率地進行硬化反應，可表現出高接著性，因此較佳。 From the viewpoint that the curing reaction does not proceed during storage and only occurs when heated, the combination of the thermosetting resin (a-2) and the curing agent (C) is preferably a combination that does not undergo a crosslinking reaction at 50°C and promotes a curing reaction at 150°C. In addition, by appropriately combining two or more curing agents having different starting temperatures for the curing reaction, the crosslinking density of the conductive composition in each temperature zone can also be controlled. The curing agent (C) can be exemplified by epoxy curing agent, cyclohexane curing agent, cyclosulfide curing agent, aziridine curing agent, amine curing agent, isocyanate curing agent, and imidazole curing agent. Among them, epoxy curing agent, cyclohexane curing agent, cyclosulfide curing agent, and aziridine curing agent are preferred because they can efficiently undergo curing reaction with the thermosetting resin (a-2) and exhibit high adhesion.
作為環氧硬化劑，例如較佳為縮水甘油醚型環氧化合物、縮水甘油胺型環氧化合物、縮水甘油酯型環氧化合物、環狀脂肪族（脂環型）環氧化合物等。As the epoxy curing agent, for example, glycidyl ether type epoxy compounds, glycidyl amine type epoxy compounds, glycidyl ester type epoxy compounds, cycloaliphatic (alicyclic) epoxy compounds, etc. are preferred.
作為所述縮水甘油醚型環氧化合物，例如可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、雙酚AD型環氧化合物、甲酚酚醛清漆型環氧化合物、苯酚酚醛清漆型環氧化合物、a-1-萘酚酚醛清漆型環氧化合物、雙酚A型酚醛清漆型環氧化合物、二環戊二烯型環氧化合物、四溴雙酚A型環氧化合物、溴化苯酚酚醛清漆型環氧化合物、三(縮水甘油氧基苯基)甲烷、四(縮水甘油氧基苯基)乙烷等。Examples of the glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol AD type epoxy compounds, cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, α-1-naphthol novolac type epoxy compounds, bisphenol A type novolac type epoxy compounds, dicyclopentadiene type epoxy compounds, tetrabromobisphenol A type epoxy compounds, brominated phenol novolac type epoxy compounds, tris(glycidyloxyphenyl)methane, tetrakis(glycidyloxyphenyl)ethane, and the like.
作為所述縮水甘油胺型環氧化合物，例如可列舉：四縮水甘油基二胺基二苯基甲烷、三縮水甘油基對胺基苯酚、三縮水甘油基間胺基苯酚、四縮水甘油基間苯二甲胺等。Examples of the glycidylamine type epoxy compound include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, tetraglycidylmeta-xylylenediamine, and the like.
作為所述縮水甘油酯型環氧化合物，例如可列舉：鄰苯二甲酸二縮水甘油酯、六氫鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯等。Examples of the glycidyl ester type epoxy compound include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.
作為所述環狀脂肪族（脂環型）環氧化合物，例如可列舉：環氧環己基甲基-環氧環己烷羧酸酯、雙(環氧環己基)己二酸酯等。Examples of the cyclic aliphatic (alicyclic) epoxy compound include epoxyethylene methyl-epoxyethylene hexane carboxylate and bis(epoxyethylene hexyl) adipate.
氧雜環丁烷硬化劑例如可列舉：1,4-雙{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}苯、3-乙基-3-{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷、1,3-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、4,4'-雙[(3-乙基-3-氧雜環丁基)甲氧基甲基]聯苯、(2-乙基-2-氧雜環丁基)乙醇與對苯二甲酸的酯化物、(2-乙基-2-氧雜環丁基)乙醇與苯酚酚醛清漆樹脂的醚化物、(2-乙基-2-氧雜環丁基)乙醇與多元羧酸化合物的酯化物等。Examples of cyclohexane curing agents include: 1,4-bis{[(3-ethylcyclohexane-3-yl)methoxy]methyl}benzene, 3-ethyl-3-{[(3-ethylcyclohexane-3-yl)methoxy]methyl}cyclohexane, 1,3-bis[(3-ethylcyclohexane-3-yl)methoxy]benzene, 4,4' -bis[(3-ethyl-3-oxocyclobutyl)methoxymethyl]biphenyl, esters of (2-ethyl-2-oxocyclobutyl)ethanol and terephthalic acid, ethers of (2-ethyl-2-oxocyclobutyl)ethanol and phenol novolac resin, esters of (2-ethyl-2-oxocyclobutyl)ethanol and polycarboxylic acid compounds, etc.
環硫硬化劑例如可列舉：雙(1,2-環硫乙基)硫化物、雙(1,2-環硫乙基)二硫化物、雙(2,3-環硫丙基)硫化物、雙(2,3-環硫丙基硫代)甲烷、雙(2,3-環硫丙基)二硫化物、雙(2,3-環硫丙基二硫代)甲烷、雙(2,3-環硫丙基二硫代)乙烷、雙(6,7-環硫-3,4-二硫代庚基)硫化物、雙(6,7-環硫-3,4-二硫代庚基)二硫化物、1,4-二噻烷-2,5-雙(2,3-環硫丙基二硫代甲基)、1,3-雙(2,3-環硫丙基二硫代甲基)苯、1,6-雙(2,3-環硫丙基二硫代甲基)-2-(2,3-環硫丙基二硫代乙基硫代)-4-硫代己烷、1,2,3-三(2,3-環硫丙基二硫代)丙烷等。Examples of cyclosulfide curing agents include bis(1,2-cyclothioethyl) sulfide, bis(1,2-cyclothioethyl) disulfide, bis(2,3-cyclothiopropyl) sulfide, bis(2,3-cyclothiopropylthio) methane, bis(2,3-cyclothiopropyl) disulfide, bis(2,3-cyclothiopropyl disulfide) methane, bis(2,3-cyclothiopropyl disulfide) ethane, bis(6,7-cyclothio-3,4-dithioheptyl) sulfide, Bis(6,7-cyclothio-3,4-dithioheptyl) disulfide, 1,4-dithiane-2,5-bis(2,3-cyclothiopropyldithiomethyl), 1,3-bis(2,3-cyclothiopropyldithiomethyl)benzene, 1,6-bis(2,3-cyclothiopropyldithiomethyl)-2-(2,3-cyclothiopropyldithioethylthio)-4-thiohexane, 1,2,3-tris(2,3-cyclothiopropyldithio)propane, etc.
氮丙啶硬化劑例如可列舉：三羥甲基丙烷-三-a-2-氮丙啶基丙酸酯、四羥甲基甲烷-三-a-2-氮丙啶基丙酸酯、N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶羧基醯胺)、N,N'-六亞甲基-1,6-雙(1-氮丙啶羧基醯胺)等。Examples of aziridine hardeners include trihydroxymethylpropane-tri-a-2-aziridine propionate, tetrahydroxymethylmethane-tri-a-2-aziridine propionate, N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxyamide), and N,N'-hexamethylene-1,6-bis(1-aziridine carboxyamide).
胺硬化劑例如可列舉：二亞乙基三胺、三亞乙基四胺、亞甲基雙(2-氯苯胺)、亞甲基雙(2-甲基-6-甲基苯胺)、1,5-萘二異氰酸酯、鄰苯二甲酸正丁基苄基酯等。Examples of the amine hardener include diethylenetriamine, triethylenetetramine, methylenebis(2-chloroaniline), methylenebis(2-methyl-6-methylaniline), 1,5-naphthalene diisocyanate, and n-butylbenzyl phthalate.
異氰酸酯硬化劑例如可列舉：甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、亞二甲苯基二異氰酸酯、二環己基甲烷二異氰酸酯、1,5-萘二異氰酸酯、四甲基亞二甲苯基二異氰酸酯、三甲基六亞甲基二異氰酸酯等。Examples of the isocyanate curing agent include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, 1,5-naphthalene diisocyanate, tetramethylxylylene diisocyanate, and trimethylhexamethylene diisocyanate.
咪唑硬化劑例如可列舉：2-甲基咪唑、2-十七烷基咪唑、2-苯基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸酯等。Examples of the imidazole hardener include 2-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-cyanoethyl-2-undecylimidazolium trimellitate.
硬化劑（C）可單獨使用一種或組合使用兩種以上。就對導電性組合物的儲存彈性模量或玻璃化轉變溫度進行調整的方面而言，所述硬化劑（C）較佳為使用分子量或重量平均分子量為100以上的硬化劑。The hardener (C) may be used alone or in combination of two or more. In order to adjust the storage elastic modulus or glass transition temperature of the conductive composition, the hardener (C) preferably has a molecular weight or a weight average molecular weight of 100 or more.
相對於熱硬化性樹脂（a-2）100質量份，硬化劑（C）較佳為調配0.1質量份～70質量份，更佳為0.1質量份～50質量份。通過將硬化劑（C）的添加量設為0.1質量份以上，可使導電性組合物的交聯結構的密度為最佳，提高接著性，並且能夠提高膜厚擔保性。通過將硬化劑（C）的添加量設為70質量份以下，可防止導電性組合物過度地變硬，提高接著性與衝壓加工性。The curing agent (C) is preferably blended in an amount of 0.1 to 70 parts by mass, more preferably 0.1 to 50 parts by mass, relative to 100 parts by mass of the thermosetting resin (a-2). By setting the added amount of the curing agent (C) to 0.1 parts by mass or more, the density of the cross-linked structure of the conductive composition can be optimized, the adhesiveness can be improved, and the film thickness guarantee can be improved. By setting the added amount of the curing agent (C) to 70 parts by mass or less, the conductive composition can be prevented from being excessively hardened, and the adhesiveness and punching processability can be improved.
[金屬粒子（B）] 金屬粒子（B）較佳為金、鉑、銀、銅及鎳等導電性金屬、及其合金。另外，對於成為核體的金屬而非單一組成的微粒子，就降低成本的觀點而言，較佳為由導電性比核體高的原材料形成被覆所述核體的表面的被覆層的複合微粒子。 核體較佳為選自鎳、二氧化矽、銅及它們的合金。被覆層例如可列舉：金、鉑、銀、錫、錳、及銦等、以及其合金。其中，就導電性與材料成本的觀點而言，較佳為使用銀。 [Metal particles (B)] Metal particles (B) are preferably conductive metals such as gold, platinum, silver, copper and nickel, and alloys thereof. In addition, for the metal that becomes the core body rather than the microparticles of a single composition, from the viewpoint of reducing costs, it is preferred to use a composite microparticle in which a coating layer covering the surface of the core body is formed from a raw material having a higher conductivity than the core body. The core body is preferably selected from nickel, silicon dioxide, copper and their alloys. Examples of the coating layer include: gold, platinum, silver, tin, manganese, indium, etc., and alloys thereof. Among them, from the viewpoint of conductivity and material cost, it is preferred to use silver.
複合微粒子較佳為相對於核體100質量份，以1質量份～40質量份的比例具有被覆層，更佳為5質量份～30質量份。若以1質量份～40質量份進行被覆，則可一面維持導電性，一面進一步降低成本。此外，複合微粒子較佳為被覆層完全地覆蓋核體。但是，實際上存在核體的一部分露出的情況。在此種情況下，若導電性物質覆蓋核體表面面積的70%以上，則容易維持導電性。The composite microparticles preferably have a coating layer in a ratio of 1 to 40 parts by mass relative to 100 parts by mass of the core, and more preferably 5 to 30 parts by mass. If the coating is performed in a ratio of 1 to 40 parts by mass, the conductivity can be maintained while further reducing the cost. In addition, the composite microparticles preferably have a coating layer that completely covers the core. However, there is actually a situation where a portion of the core is exposed. In this case, if the conductive material covers more than 70% of the surface area of the core, it is easy to maintain conductivity.
金屬粒子（B）可單獨使用一種，也可並用兩種以上。The metal particles (B) may be used alone or in combination of two or more.
金屬粒子（B）的形狀只要可獲得所期望的導電性即可，並無限定。例如可列舉：球狀、薄片狀、葉狀、樹枝狀、板狀、針狀、棒狀、葡萄狀、不定形塊狀。此外，就提高導電性的觀點而言，更佳為球狀、薄片狀、葉狀、樹枝狀、板狀。The shape of the metal particles (B) is not limited as long as the desired conductivity can be obtained. For example, spherical, flake, leaf, branch, plate, needle, rod, grape, and amorphous block shapes can be listed. In addition, from the viewpoint of improving the conductivity, spherical, flake, leaf, branch, and plate shapes are more preferred.
關於金屬粒子（B）的平均粒徑，平均粒徑D 50較佳為1 μm～50 μm，更佳為3 μm～30 μm，進而較佳為5 μm～20 μm。通過平均粒徑D 50處於1 μm～50 μm，可形成適當的導通通路，可提高導電性。此外，平均粒徑D 50可通過雷射衍射-散射法粒度分佈測定裝置而求出。 The average particle size of the metal particles (B) is preferably 1 μm to 50 μm, more preferably 3 μm to 30 μm, and further preferably 5 μm to 20 μm. When the average particle size D 50 is 1 μm to 50 μm, a suitable conductive path can be formed, and the conductivity can be improved. The average particle size D 50 can be obtained by a laser diffraction-scattering method particle size distribution measuring device.
關於金屬粒子（B）的平均粒徑，平均粒徑D 90較佳為1 μm～120 μm，更佳為5 μm～70 μm。通過平均粒徑D 90處於1 μm～120 μm，可抑制引起黏連的情況。 The average particle size of the metal particles (B) is preferably 1 μm to 120 μm, more preferably 5 μm to 70 μm. When the average particle size D 90 is 1 μm to 120 μm, the occurrence of sticking can be suppressed.
導電性接合劑層的厚度除以金屬粒子（B）的平均粒徑D 50而得的值X較佳為1～35。通過X為35以下，在導電性接合劑層內有效果地形成金屬粒子（B）的導電通路，導電性提高。就提高導電性的觀點而言，X更佳為18以下。另外，通過X為1以上，被黏物與金屬粒子（B）的接觸點不會過度地增加，被黏物與黏合劑（A）的接觸面積增大，因此接著性提高。X更佳為5以上。 The value X obtained by dividing the thickness of the conductive adhesive layer by the average particle size D50 of the metal particles (B) is preferably 1 to 35. When X is 35 or less, a conductive path of the metal particles (B) is effectively formed in the conductive adhesive layer, and the conductivity is improved. From the viewpoint of improving the conductivity, X is more preferably 18 or less. In addition, when X is 1 or more, the contact points between the adherend and the metal particles (B) are not excessively increased, and the contact area between the adherend and the adhesive (A) is increased, thereby improving the adhesion. X is more preferably 5 or more.
金屬粒子（B）較佳為在導電性組合物的全部固體成分中包含40質量%～90質量%。通過設為所述含量，可使耐黏連性、膜厚擔保性、接著性並存。金屬粒子（B）的含量更佳為45質量%～80質量%，進而較佳為50質量%～70質量%。The metal particles (B) are preferably contained in an amount of 40% to 90% by mass in the total solid content of the conductive composition. By setting the content to this level, anti-blocking properties, film thickness guarantee, and adhesion can be achieved simultaneously. The content of the metal particles (B) is more preferably 45% to 80% by mass, and further preferably 50% to 70% by mass.
本實施形態中的導電性組合物也可調配耐熱穩定劑、無機填料、有機填料、顏料、染料、黏著賦予樹脂、塑化劑、矽烷偶合劑、紫外線吸收劑、消泡劑、流平調整劑等作為其他任意成分。The conductive composition in this embodiment may also contain heat-resistant stabilizers, inorganic fillers, organic fillers, pigments, dyes, adhesive imparting resins, plasticizers, silane coupling agents, ultraviolet absorbers, defoamers, leveling agents, etc. as other optional components.
作為無機填料，例如可列舉：二氧化矽、氧化鋁、氫氧化鋁、氫氧化鎂、硫酸鋇、碳酸鈣、氧化鈦、氧化鋅、三氧化銻、氧化鎂、滑石、蒙脫石、高嶺土、膨潤土等。通過所述導電性組合物含有無機填料，可對探針黏性的抑制進行控制，進而可對儲存彈性模量進行控制，並對膜厚擔保性進行控制。Examples of the inorganic filler include silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorillonite, kaolin, bentonite, etc. By including the inorganic filler in the conductive composition, the viscosity of the probe can be suppressed, and the storage elastic modulus can be controlled, thereby controlling the film thickness guarantee.
作為有機填料，例如可列舉：胺基甲酸酯樹脂粒子、丙烯酸樹脂粒子、酚樹脂粒子、尼龍粒子等。通過所述導電性組合物含有有機填料，可在確保臨時黏貼性的同時，進而對儲存彈性模量進行控制，並對膜厚擔保性進行控制。Examples of the organic filler include urethane resin particles, acrylic resin particles, phenol resin particles, and nylon particles. When the conductive composition contains an organic filler, temporary adhesion can be ensured while controlling the storage elastic modulus and controlling the film thickness guarantee.
[導電性接合片的製造方法] 本公開的導電性接合片例如可通過將導電性組合物塗敷於保護片上，並進行乾燥，進而根據需要進行B階段硬化而獲得。將所述乾燥後的導電性組合物稱為導電性接合劑層。塗敷方法只要從公知的方法中，考慮導電性接合劑層的膜厚等適宜選擇即可。作為塗敷方法的具體例，可列舉：凹版塗布方式、吻合塗布方式、模塗方式、唇式塗布方式、缺角輪塗布方式、刀片塗布方式、輥塗方式、刀塗方式、噴塗方式、棒塗方式、旋塗方式、浸塗方式等。 [Method for manufacturing conductive bonding sheet] The conductive bonding sheet disclosed in the present invention can be obtained, for example, by applying a conductive composition on a protective sheet, drying it, and then performing B-stage hardening as needed. The conductive composition after drying is referred to as a conductive bonding agent layer. The coating method can be appropriately selected from known methods, taking into account the film thickness of the conductive bonding agent layer. Specific examples of coating methods include: gravure coating method, matching coating method, die coating method, lip coating method, notch wheel coating method, blade coating method, roller coating method, knife coating method, spray coating method, rod coating method, spin coating method, dip coating method, etc.
所謂B階段硬化，是通過以規定的溫度、時間對導電性接合劑層進行加熱而部分地產生硬化反應的方法。通過進行B階段硬化，可在維持導電性接合劑層的接著力的同時提高強度。B-stage curing is a method of partially causing a curing reaction by heating the conductive adhesive layer at a specified temperature and time. By performing B-stage curing, the strength of the conductive adhesive layer can be improved while maintaining its adhesion.
[卷狀導電性接合片的製造方法] 導電性接合片通過將其前端部按壓於卷取芯材上並卷取，可獲得卷狀導電性接合片。 [Manufacturing method of rolled conductive bonding sheet] The conductive bonding sheet is rolled by pressing the front end thereof onto a winding core material, thereby obtaining a rolled conductive bonding sheet.
本公開的卷取芯材並無特別限定，例如可例示紙管、金屬管、塑膠管。一般而言為在附隨於印刷機、塗敷機、成型機、撚紗機等的製造裝置的卷取裝置中所使用的橫寬方向上長的管。關於所述卷取芯材，一般而言較佳為直徑1 cm～40 cm左右。另外，關於卷取芯材的橫寬，只要為可設置於卷取裝置的寬度即可而並無特別限定。一般而言為2 mm～6 m左右。The winding core material disclosed in the present invention is not particularly limited, and examples thereof include paper tubes, metal tubes, and plastic tubes. Generally speaking, it is a tube that is long in the transverse direction and is used in a winding device attached to a manufacturing device such as a printing machine, a coating machine, a molding machine, or a twisting machine. The winding core material is generally preferably about 1 cm to 40 cm in diameter. In addition, the transverse width of the winding core material is not particularly limited as long as it is a width that can be installed in the winding device. Generally speaking, it is about 2 mm to 6 m.
作為導電性接合片的其他卷取方法，也可例示：使用接著性構件將導電性接合片的前端部固定於卷取芯材上進行卷取的方法。接著性構件有雙面黏著帶、澆鑄黏著帶、單面黏著帶。作為第一方法，可例示：使用雙面黏著帶將導電性接合片的前端部的導電性接合劑層面固定於卷取芯材上的方法。另外，作為第二方法，可例示使用雙面黏著帶將導電性接合片的前端部的保護片面與卷取芯材進行固定的方法。利用所述第一方法或第二方法將導電性接合片固定於卷取芯材上後，開始卷取。As another method for winding up the conductive bonding sheet, there can also be exemplified a method of using an adhesive member to fix the front end portion of the conductive bonding sheet to a winding core material for winding up. Adhesive members include double-sided adhesive tape, cast adhesive tape, and single-sided adhesive tape. As a first method, there can be exemplified a method of using a double-sided adhesive tape to fix the conductive adhesive layer at the front end portion of the conductive bonding sheet to the winding core material. In addition, as a second method, there can be exemplified a method of using a double-sided adhesive tape to fix the protective sheet surface of the front end portion of the conductive bonding sheet to the winding core material. After the conductive bonding sheet is fixed to the winding core material using the first method or the second method, winding up begins.
導電性接合片的卷取時的張力因保護片的材質等而異，因此並無特別限定，但需要設定為保護片不變形的張力且不使保護片鬆弛的張力。例如，在將聚對苯二甲酸乙二酯（polyethylene terephthalate，PET）作為保護片時較佳為0.5 N/cm～2.5 N/cm。The tension when winding the conductive adhesive sheet varies depending on the material of the protective sheet, etc., so there is no particular limitation, but it needs to be set to a tension that does not deform the protective sheet and does not make the protective sheet loose. For example, when polyethylene terephthalate (PET) is used as the protective sheet, it is preferably 0.5 N/cm to 2.5 N/cm.
[金屬增強板] 本公開的金屬增強板中，在金屬板上貼合有導電性接合劑層。所述金屬板例如可列舉金、銀、銅、鐵及不銹鋼等導電性金屬。這些中，就作為金屬板的強度、成本及化學穩定性的方面而言，較佳為不銹鋼。金屬板的厚度一般而言為0.04 mm～1 mm左右。金屬板較佳為鎳層形成於金屬板的整個表面。鎳層較佳為利用電解鍍鎳法形成。鎳層的厚度為0.5 μm～5 μm左右，更佳為1 μm～4 μm。此外，金屬增強板所包括的導電性接合劑層在25℃下為非流動性的固體物質，且呈一定厚度的層狀。 [Metal reinforcement plate] In the metal reinforcement plate disclosed herein, a conductive adhesive layer is bonded to the metal plate. The metal plate may be, for example, conductive metals such as gold, silver, copper, iron and stainless steel. Among these, stainless steel is preferred in terms of strength, cost and chemical stability as a metal plate. The thickness of the metal plate is generally about 0.04 mm to 1 mm. The metal plate is preferably a nickel layer formed on the entire surface of the metal plate. The nickel layer is preferably formed by electrolytic nickel plating. The thickness of the nickel layer is about 0.5 μm to 5 μm, more preferably 1 μm to 4 μm. In addition, the conductive adhesive layer included in the metal reinforcement plate is a non-flowing solid substance at 25°C and is in the form of a layer with a certain thickness.
[帶金屬增強板的配線板] 本實施形態的帶金屬增強板的配線板100（參照圖2）配置有：配線板20，在絕緣性膜21上配置有接地電路22，覆蓋層23被覆所述接地電路22，所述接地電路22的一部分經由開口部30露出；以及金屬增強板10，位於所述配線板20上。金屬增強板10的導電性接合劑層1呈層狀，將配線板20與金屬板2接合。本實施形態的配線板20中，通過將導電性接合劑層1的一部分填充至開口部30，接地電路22與金屬板2經由導電性接合劑層1而電連接。在配線板20上進而還可設置信號配線。 [Wiring board with metal reinforcement plate] The wiring board with metal reinforcement plate 100 of the present embodiment (see FIG. 2 ) is configured with: a wiring board 20, a grounding circuit 22 is configured on an insulating film 21, a covering layer 23 covers the grounding circuit 22, and a part of the grounding circuit 22 is exposed through an opening 30; and a metal reinforcement plate 10, which is located on the wiring board 20. The conductive adhesive layer 1 of the metal reinforcement plate 10 is in a layered state, and the wiring board 20 is bonded to the metal plate 2. In the wiring board 20 of the present embodiment, the grounding circuit 22 and the metal plate 2 are electrically connected through the conductive adhesive layer 1 by filling a part of the conductive adhesive layer 1 into the opening 30. Signal wiring can also be provided on the wiring board 20.
配線板20的開口部30的面積可設為0.16 mm 2以上且0.81 mm 2以下。通過將開口部30的面積設為0.16 mm 2以上，可使導電性接合劑層向開口部30的填充性良好。另外，通過將開口部30的面積設為0.81 mm 2以下，可減小開口部30在配線板20中所占的面積。開口部30的面積較佳為設為0.25 mm 2以上且0.64 mm 2以下，進而較佳為設為0.36 mm 2以上且0.49 mm 2以下。在開口部30的面積為0.16 mm 2以上且0.81 mm 2以下的情況下，可使導電性接合劑層向開口部30的填充性良好，可降低導電性接合劑層與接地電路22的接觸電阻。 The area of the opening 30 of the wiring board 20 can be set to be greater than or equal to 0.16 mm 2 and less than or equal to 0.81 mm 2. By setting the area of the opening 30 to be greater than or equal to 0.16 mm 2 , the filling property of the conductive adhesive layer into the opening 30 can be improved. In addition, by setting the area of the opening 30 to be less than or equal to 0.81 mm 2 , the area occupied by the opening 30 in the wiring board 20 can be reduced. The area of the opening 30 is preferably set to be greater than or equal to 0.25 mm 2 and less than or equal to 0.64 mm 2 , and more preferably set to be greater than or equal to 0.36 mm 2 and less than or equal to 0.49 mm 2 . When the area of the opening 30 is not less than 0.16 mm 2 and not more than 0.81 mm 2 , the conductive adhesive layer can be filled into the opening 30 well, and the contact resistance between the conductive adhesive layer and the ground circuit 22 can be reduced.
俯視時的開口部30的形狀可為矩形形狀，也可為圓形形狀。在開口部30的形狀為矩形形狀的情況下，在矩形形狀的開口部的四角填充導電性接合劑層變得特別困難，容易在四角形成間隙。然而，通過使用將樹脂流動控制在適當的範圍內的本實施形態的導電性接合劑層，即使是矩形形狀的開口部，也可將導電性接合劑層良好地填充至開口部內。The shape of the opening 30 when viewed from above may be a rectangle or a circle. When the opening 30 is a rectangle, it becomes particularly difficult to fill the four corners of the rectangular opening with the conductive adhesive layer, and gaps are easily formed at the four corners. However, by using the conductive adhesive layer of the present embodiment that controls the resin flow within an appropriate range, the conductive adhesive layer can be well filled into the opening even in a rectangular opening.
[電子設備] 此種帶金屬增強板的配線板例如可搭載於移動電話、智能手機、筆記型個人計算機（personal computer，PC）、數字照相機、液晶顯示器等電子設備。另外，也可適當地搭載於汽車、電車、船舶、飛機等輸送設備。 [Electronic equipment] This type of wiring board with a metal reinforcement plate can be installed in electronic equipment such as mobile phones, smart phones, personal computers (PCs), digital cameras, and liquid crystal displays. In addition, it can also be appropriately installed in transportation equipment such as cars, trains, ships, and airplanes.
[實施例] 以下，列舉實施例、比較例對本公開更具體地進行說明，但本公開並不僅限定於以下的實施例。此外，以下的「份」及「%」分別為基於「質量份」及「質量%」的值。另外，樹脂（a-1）的酸值與重量平均分子量（Mw）、及金屬粒子（B）的D 50平均粒徑的測定利用以下方法進行。 [Examples] The present disclosure is described in more detail below with reference to Examples and Comparative Examples, but the present disclosure is not limited to the following Examples. In addition, the following "parts" and "%" are values based on "parts by mass" and "% by mass", respectively. In addition, the acid value and weight average molecular weight (Mw) of the resin (a-1) and the D50 average particle size of the metal particles (B) were measured by the following method.
[樹脂（a-1）的酸值] 依據日本工業標準（Japanese Industrial Standards，JIS）K 0070的中和滴定法，通過對測定的酸值（mgKOH/g）進行固體成分換算來求出。在共栓三角燒瓶中精確地量取試樣約1 g，加入四氫呋喃/乙醇（容量比：四氫呋喃/乙醇=2/1）混合液100 mL並進行溶解。向其中加入酚酞試液作為指示劑，利用0.1 N醇性氫氧化鉀溶液滴定，以指示劑保持淡紅色30秒時為終點。酸值通過下式求出（單位：mgKOH/g）。 酸值（mgKOH/g）=（5.611×a×F）/S 其中， S：試樣的採集量（g） a：0.1 N醇性氫氧化鉀溶液的消耗量（mL） F：0.1 N醇性氫氧化鉀溶液的力值 [Acid value of resin (a-1)] According to the neutralization titration method of Japanese Industrial Standards (JIS) K 0070, the acid value (mgKOH/g) is converted to solid content. Accurately weigh about 1 g of the sample in a co-corked Erlenmeyer flask, add 100 mL of a tetrahydrofuran/ethanol (volume ratio: tetrahydrofuran/ethanol = 2/1) mixed solution and dissolve it. Add phenolphthalein test solution as an indicator, and titrate with 0.1 N alcoholic potassium hydroxide solution until the indicator remains light red for 30 seconds. The acid value is calculated by the following formula (unit: mgKOH/g). Acid value (mgKOH/g) = (5.611×a×F)/S Where, S: sample collection amount (g) a: consumption of 0.1 N alcoholic potassium hydroxide solution (mL) F: force value of 0.1 N alcoholic potassium hydroxide solution
[樹脂（a-1）的重量平均分子量（Mw）] Mw的測定通過凝膠滲透層析儀（Gel Permeation Chromatograph，GPC）「HPC-8020」（東曹公司製造）進行。GPC是將溶解於溶媒（THF：四氫呋喃）中的物質根據其分子尺寸的差異進行分離定量的液相層析儀。本測定是在管柱上串聯連接並使用2根「LF-604」（昭和電工公司製造：快速分析用GPC管柱：6 mmID×150 mm尺寸），在流量0.6 mL/min、管柱溫度40℃的條件下進行。Mw的確定利用聚苯乙烯換算進行。 [Weight average molecular weight (Mw) of resin (a-1)] Mw was measured using a gel permeation chromatograph (GPC) "HPC-8020" (manufactured by Tosoh Corporation). GPC is a liquid chromatograph that quantitatively separates substances dissolved in a solvent (THF: tetrahydrofuran) based on the difference in their molecular size. This measurement was performed using two "LF-604" (manufactured by Showa Denko: GPC column for rapid analysis: 6 mmID×150 mm size) connected in series on the column at a flow rate of 0.6 mL/min and a column temperature of 40°C. Mw was determined using polystyrene conversion.
[金屬粒子（B）的D 50平均粒徑] 關於D 50平均粒徑，使用雷射衍射-散射法粒度分佈測定裝置LS13320（貝克曼-庫爾特（Beckman-coulter）公司製造）。為通過旋風乾燥粉體樣品模塊對金屬粒子（B）進行測定而獲得的數值，且為粒子徑累計分佈中的累計值為50%的粒徑。此外，關於折射率的設定，設為1.6。 [ D50 average particle size of metal particles (B)] The D50 average particle size was measured using a laser diffraction-scattering particle size distribution measuring device LS13320 (manufactured by Beckman-Coulter). The value is obtained by measuring the metal particles (B) using a cyclone-dried powder sample module, and is the particle size at which the cumulative value in the cumulative distribution of particle sizes is 50%. In addition, the refractive index was set to 1.6.
＜原料＞ [黏合劑（A）] （a-1）-1：聚酯樹脂：酸值36 mgKOH/g、Mw＝27,000（東洋化工（TOYO CHEM）製造） （a-1）-2：聚醯亞胺樹脂：酸值18 mgKOH/g、Mw＝55,000（東洋化工（TOYO CHEM）製造） （a-1）-3：聚醯胺樹脂：酸值22 mgKOH/g、Mw＝49,000（東洋化工（TOYO CHEM）製造） （a-1）-4：聚胺基甲酸酯樹脂：酸值16 mgKOH/g、Mw＝98,000（東洋化工（TOYO CHEM）製造） （a-1）-5：聚胺基甲酸酯脲樹脂：酸值15 mgKOH/g、Mw＝100,000（東洋化工（TOYO CHEM）製造） （a-1）-6：苯乙烯彈性體：酸值55 mgKOH/g、Mw＝120,000（東洋化工（TOYO CHEM）製造） [金屬粒子（B）] B1：銀被覆銅粉：D 50＝5.7 μm、樹枝狀（三井金屬礦業製造） B2：銀被覆銅粉：D 50＝31.2 μm、樹枝狀（三井金屬礦業製造） B3：銀被覆銅粉：D 50＝10.8 μm、球狀（力森諾科（Resonac）製造） B4：銀被覆銅粉：D 50＝7.5 μm、球狀（力森諾科（Resonac）製造） B5：銀被覆銅粉：D 50＝11.3 μm、薄片狀（同和控股（DOWA holdings）製造） [硬化劑（C）] C1：Ti螯合物（TC100、分子量=364、松本精細化工（Matsumoto Fine Chemical）） C2：雙酚A型環氧化合物（jER（注冊商標）828、分子量=370、三菱化學製造） C3：間苯二甲酸型氧雜環丁烷化合物（艾塔納科（ETERNACOLL）（注冊商標）OXIPA、分子量＝362、宇部興產製造） C4：氫化雙酚A型環硫化合物（TBIS（注冊商標）-AHS、分子量＝384、田岡化學工業製造） C5：多官能型氮丙啶化合物（凱米泰特（Chemitite）（注冊商標）PZ-33、分子量＝425、日本催化劑製造） C6：聚碳二醯亞胺化合物（卡保迪萊（Carbodilite）V-05、分子量＝1200、日清紡化學製造） [黏著賦予樹脂] 萜烯樹脂（YS樹脂PX300N，安原化學（Yasuhara Chemical）製造） [保護片（D）] D1：PET制膜（賽拉皮爾（Cerapeel）PJ271、膜厚50 μm、表面處理：單面醇酸系脫模劑處理、東麗（Toray）製造） D2：紙制膜（G62白AA（N7-82）、膜厚58 μm、表面處理：雙面矽系脫模劑處理、琳得科（Lnteci）製造） D3：聚丙烯制膜（陶來芬（Trefin）#30-2500H、膜厚50 μm、表面處理：雙面醇酸系脫模劑處理、東麗（Toray）製造） D4：聚乙烯制膜（宇部波利片（UBEPOLYSHEET）、膜厚70 μm、表面處理：雙面醇酸系脫模劑處理、宇部膜製造） D5：聚氯乙烯制膜（一般用聚氯乙烯（Polyvinylchloride，PVC）膜、膜厚120 μm、表面處理：雙面醇酸系脫模劑處理、岡本（Okamoto）製造） <Raw materials> [Binder (A)] (a-1)-1: Polyester resin: acid value 36 mgKOH/g, Mw = 27,000 (manufactured by Toyo Chemical Industry) (a-1)-2: Polyimide resin: acid value 18 mgKOH/g, Mw = 55,000 (manufactured by Toyo Chemical Industry) (a-1)-3: Polyamide resin: acid value 22 mgKOH/g, Mw = 49,000 (manufactured by Toyo Chemical Industry) (a-1)-4: Polyurethane resin: acid value 16 mgKOH/g, Mw = 98,000 (manufactured by Toyo Chemical Industry) (a-1)-5: Polyurethane urea resin: acid value 15 mgKOH/g, Mw=100,000 (manufactured by Toyo Chemical Industries, Ltd.) (a-1)-6: Styrene elastomer: acid value 55 mgKOH/g, Mw=120,000 (manufactured by Toyo Chemical Industries, Ltd.) [Metal particles (B)] B1: Silver-coated copper powder: D 50 = 5.7 μm, dendrite shape (manufactured by Mitsui Metal Mining Co., Ltd.) B2: Silver-coated copper powder: D 50 = 31.2 μm, dendrite shape (manufactured by Mitsui Metal Mining Co., Ltd.) B3: Silver-coated copper powder: D 50 = 10.8 μm, spherical shape (manufactured by Resonac) B4: Silver-coated copper powder: D 50 = 7.5 μm, spherical (manufactured by Resonac) B5: Silver-coated copper powder: D 50 = 11.3 μm, flake (manufactured by DOWA Holdings) [Hardener (C)] C1: Ti chelate (TC100, molecular weight = 364, Matsumoto Fine Chemical) C2: Bisphenol A type epoxy compound (jER (registered trademark) 828, molecular weight = 370, manufactured by Mitsubishi Chemical) C3: Isophthalic acid type cyclohexane compound (ETERNACOLL (registered trademark) OXIPA, molecular weight = 362, manufactured by Ube Industries) C4: Hydrogenated bisphenol A type cyclic sulfide compound (TBIS (registered trademark)-AHS, molecular weight = 384, manufactured by TAOKA Chemical Industry Co., Ltd.) C5: Polyfunctional aziridine compound (Chemitite (registered trademark) PZ-33, molecular weight = 425, manufactured by Nippon Catalyst Co., Ltd.) C6: Polycarbodiimide compound (Carbodilite V-05, molecular weight = 1200, manufactured by Nisshinbo Chemical Co., Ltd.) [Adhesion-imparting resin] Terpene resin (YS resin PX300N, manufactured by Yasuhara Chemical) [Protective sheet (D)] D1: PET film (Cerapeel PJ271, film thickness 50 μm, surface treatment: one-sided alkyd release agent treatment, manufactured by Toray) D2: Paper film (G62 White AA (N7-82), film thickness 58 μm, surface treatment: double-sided silicone release agent treatment, manufactured by Lnteci) D3: Polypropylene film (Trefin #30-2500H, film thickness 50 μm, surface treatment: double-sided alkyd release agent treatment, manufactured by Toray) D4: Polyethylene film (UBEPOLYSHEET), film thickness 70 μm, surface treatment: double-sided alkyd release agent treatment, manufactured by Ube Film) D5: Polyvinyl chloride film (generally used polyvinyl chloride (PVC) film, film thickness 120 μm, Surface treatment: Double-sided alkyd release agent treatment, manufactured by Okamoto)
＜導電性組合物及導電性接合片的製作＞ [實施例1] 加入作為樹脂（a-1）的（（a-1）-1）100質量份、作為金屬粒子（B）的（B1）167質量份、作為黏著賦予樹脂的萜烯樹脂（YS樹脂 PX300N）10質量份，以不揮發成分濃度成為40質量%的方式加入作為溶媒的甲基乙基酮並加以混合。繼而，加入作為硬化劑（C）的（C1）1.5質量份，利用攪拌機攪拌10分鐘而製備導電性組合物溶液。 接著，使用線速度2 m/min的逗式塗佈機（comma head coater），將所述所製備的導電性組合物溶液以乾燥後的厚度成為60 μm的方式塗敷於300 mm寬的作為保護片 （D）的D1（脫模劑：醇酸系脫模劑）的經剝離處理的其中一個面上，經由設定為100℃的2 m的電烘箱A以及設定為120℃的2 m的 電烘箱B進行乾燥，由此在保護片上形成導電性接合劑層。繼而，以所述導電性接合片的導電性接合劑層位於內側的方式卷取於直徑8.8 cm的塑膠制的卷芯上，從而獲得卷狀導電性接合片。 <Preparation of conductive composition and conductive bonding sheet> [Example 1] 100 parts by mass of ((a-1)-1) as resin (a-1), 167 parts by mass of (B1) as metal particles (B), and 10 parts by mass of terpene resin (YS resin PX300N) as adhesion-imparting resin were added, and methyl ethyl ketone as solvent was added and mixed so that the non-volatile component concentration became 40% by mass. Then, 1.5 parts by mass of (C1) as hardener (C) was added, and stirred for 10 minutes using a stirrer to prepare a conductive composition solution. Next, the prepared conductive composition solution was applied to one of the peeled surfaces of D1 (release agent: alkyd release agent) as a protective sheet (D) with a width of 300 mm using a comma head coater with a line speed of 2 m/min to a thickness of 60 μm after drying, and dried in an electric oven A set at 100°C for 2 m and an electric oven B set at 120°C for 2 m, thereby forming a conductive adhesive layer on the protective sheet. Then, the conductive adhesive layer of the conductive adhesive sheet was wound up on a plastic core with a diameter of 8.8 cm so that the conductive adhesive layer of the conductive adhesive sheet was located on the inside, thereby obtaining a rolled conductive adhesive sheet.
[實施例2～實施例36、比較例1～比較例4] 除了將調配的各成分的種類及調配量設為表1～表6所記載的那樣以外，與實施例1同樣地進行操作，獲得各實施例2～實施例36及比較例1～比較例4的卷狀導電性接合片。 [Example 2 to Example 36, Comparative Example 1 to Comparative Example 4] Except that the types and amounts of each component to be prepared are set as described in Tables 1 to 6, the same operation as in Example 1 is performed to obtain roll-shaped conductive bonding sheets of each of Examples 2 to Example 36 and Comparative Examples 1 to Comparative Examples 4.
[探針黏性黏著力的測定] 從所獲得的各卷狀導電性接合片卷出導電性接合片，按照「第十七修正日本藥典 一般試驗法 6.製劑試驗法 6.12黏著力試驗法 3.4探針黏性試驗法」實施探針黏性測定。將導電性接合片切成2 cm見方，獲得樣品。將樣品貼於重量環，在其上載置合計200 g的重物，從而施加載荷，使用探針黏性測試儀（TE-6001探針黏性測試儀、測試儀產業股份有限公司製造）對探針黏性黏著力（單位N/cm 2）進行測定。 [Measurement of probe tack] Conductive adhesive sheets were unrolled from each of the obtained roll-shaped conductive adhesive sheets, and probe tack was measured in accordance with "Seventeenth Revised Japanese Pharmacopoeia General Testing Methods 6. Preparation Testing Methods 6.12 Adhesion Test Method 3.4 Probe Tack Test Method". The conductive adhesive sheet was cut into 2 cm squares to obtain a sample. The sample was attached to a weight ring, and a total of 200 g of weight was placed on it to apply a load, and the probe tack (unit N/ cm2 ) was measured using a probe tack tester (TE-6001 probe tack tester, manufactured by Tester Industry Co., Ltd.).
[儲存彈性模量的測定] 對於各導電性接合劑層及保護片，使用動態黏彈性測定裝置（DVA-200，IT測量控制股份有限公司製造）實施儲存彈性模量測定。 將導電性接合劑層及保護片切成寬度5 mm×長度5 cm，獲得樣品。將裝置設定為恒速升溫（10℃/min），在-50℃～300℃為止的溫度帶以測定頻率10 Hz的拉伸模式實施測定，由此對各溫度下的儲存彈性模量（單位Pa）進行測定，從而求出25℃～30℃及70℃～120℃下的最高值。 [Storage modulus measurement] For each conductive adhesive layer and protective sheet, the storage modulus was measured using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Measurement & Control Co., Ltd.). The conductive adhesive layer and protective sheet were cut into 5 mm wide x 5 cm long samples. The device was set to a constant temperature increase (10°C/min) and the measurement was performed in a tensile mode with a measurement frequency of 10 Hz in a temperature range of -50°C to 300°C. The storage modulus (unit: Pa) at each temperature was measured, and the highest values at 25°C to 30°C and 70°C to 120°C were obtained.
＜評價＞ 對於所獲得的各卷狀導電性接合片，按照下述方法對耐黏連性、膜厚擔保性、保護片的剝離性、層壓強度、接著性進行評價。將評價結果示於表1～表5。 <Evaluation> For each of the obtained roll-shaped conductive bonding sheets, the anti-blocking property, film thickness guarantee, protective sheet peeling property, lamination strength, and adhesion were evaluated according to the following method. The evaluation results are shown in Tables 1 to 5.
[耐黏連性] 將如下卷樣品、即將各實施例及比較例中製作的卷狀導電性接合片切割成寬度249 mm、長度10 m且以卷取張力1.6 N/cm按照導電性接合劑層位於內側的方式卷取於直徑8.8 cm的塑膠管而得的卷樣品在50℃的環境下放置24小時。其後，從卷中卷出導電性接合片，按照以下的基準對黏連性進行評價。 +++：導電性接合劑層未貼附於保護片面（非常優異）。 ++：導電性接合劑層的一部分貼附於保護片面，但導電性接合劑層不會發生浮起（優異）。 +：導電性接合劑層的一部分貼附於保護片面，導電性接合劑層的一部分發生浮起（能夠實用）。 不可（NG）：導電性接合劑層貼附於保護片面，導電性接合劑層的一部分斷裂（不能實用）。 [Anti-adhesion] The following roll samples, i.e., the roll-shaped conductive adhesive sheets prepared in each embodiment and comparative example were cut into a width of 249 mm and a length of 10 m and wound on a plastic tube with a diameter of 8.8 cm at a winding tension of 1.6 N/cm so that the conductive adhesive layer was located inside, were placed in an environment of 50°C for 24 hours. Thereafter, the conductive adhesive sheet was unrolled from the roll, and the adhesion was evaluated according to the following criteria. +++: The conductive adhesive layer was not attached to the protective sheet surface (very good). ++: A portion of the conductive adhesive layer was attached to the protective sheet surface, but the conductive adhesive layer did not float (good). +: Part of the conductive adhesive layer adheres to the protective sheet surface, and part of the conductive adhesive layer floats (can be used practically). Not acceptable (NG): The conductive adhesive layer adheres to the protective sheet surface, and part of the conductive adhesive layer is broken (cannot be used practically).
[膜厚擔保性] 將各實施例及比較例中製作的卷狀導電性接合片切割成寬度249 mm、長度10 m，以卷取張力1.9 N/cm按照導電性接合劑層位於內側的方式卷取於直徑8.8 cm的塑膠管，製作卷樣品，在50℃的環境下放置240小時。 [Film thickness guarantee] The rolled conductive bonding sheet prepared in each embodiment and comparative example was cut into a width of 249 mm and a length of 10 m, and rolled onto a plastic tube with a diameter of 8.8 cm at a winding tension of 1.9 N/cm with the conductive bonding agent layer located on the inside to prepare a roll sample, which was placed in an environment of 50°C for 240 hours.
接著，從卷樣品的外卷卷出10 m，採集5 cm見方的樣品，利用接觸式膜厚計對導電性接合劑層的厚度（H1）進行測定。將導電性接合片的導電性接合劑層的初始厚度60 μm設為H2，求出各實施例及比較例的ΔH=H1/H2，按照下述評價基準進行評價。 +++：ΔH為0.6以上（非常優異）。 ++：ΔH為0.5以上且小於0.6（優異）。 +：ΔH為0.4以上且小於0.5（能夠實用）。 NG：ΔH小於0.4（不能實用）。 Next, 10 m of the outer roll of the roll sample was unwound, and a 5 cm square sample was collected, and the thickness (H1) of the conductive adhesive layer was measured using a contact film thickness meter. The initial thickness of the conductive adhesive layer of the conductive adhesive sheet, 60 μm, was set as H2, and ΔH=H1/H2 was calculated for each embodiment and comparative example, and the evaluation was performed according to the following evaluation criteria. +++: ΔH is 0.6 or more (very good). ++: ΔH is 0.5 or more and less than 0.6 (excellent). +: ΔH is 0.4 or more and less than 0.5 (practical). NG: ΔH is less than 0.4 (not practical).
[保護片的剝離性] 從各實施例及比較例中製作的卷狀導電性接合片切斷採集寬度25 mm、長度100 mm的導電性接合片，以導電性接合劑層與寬度30 mm、長度150 mm的不銹鋼（stainless steel，SUS）板（在厚度0.2 mm的市售的SUS304板的表面形成厚度為2 μm的鎳層的物質）的方式將導電性接合片重疊。繼而，使用輥層壓機，在130℃、3 kgf/cm 2、0.5 m/min的條件下，將導電性接合片與SUS板加以層壓後，從導電性接合劑層剝離保護片。其後，對殘存於導電性接合劑層上的保護片的殘存面積進行測定，根據下述式求出保護片的殘存率，按照下述的評價基準進行評價。 保護片的殘存率=保護片的殘存面積/導電性接合劑層的面積×100 +++：保護片的殘存率為0%（非常優異）。 ++：保護片的殘存率大於0%且小於1%（優異）。 +：保護片的殘存率為1%以上且小於2%（能夠實用）。 NG：保護片的殘存率為2%以上（不能實用）。 [Releasability of protective sheet] A conductive bonding sheet with a width of 25 mm and a length of 100 mm was cut from the roll-shaped conductive bonding sheet produced in each of the examples and comparative examples, and the conductive bonding sheet was superimposed on a stainless steel (SUS) plate with a width of 30 mm and a length of 150 mm (a nickel layer with a thickness of 2 μm was formed on the surface of a commercially available SUS304 plate with a thickness of 0.2 mm). Then, the conductive bonding sheet and the SUS plate were laminated using a roll press at 130°C, 3 kgf/ cm2 , and 0.5 m/min, and the protective sheet was peeled off from the conductive bonding layer. Thereafter, the remaining area of the protective sheet remaining on the conductive adhesive layer was measured, and the residual rate of the protective sheet was calculated according to the following formula, and the evaluation was performed according to the following evaluation criteria. Residual rate of protective sheet = residual area of protective sheet / area of conductive adhesive layer × 100 +++: The residual rate of the protective sheet is 0% (very excellent). ++: The residual rate of the protective sheet is greater than 0% and less than 1% (excellent). +: The residual rate of the protective sheet is greater than 1% and less than 2% (practical). NG: The residual rate of the protective sheet is greater than 2% (not practical).
[層壓強度] 從各實施例及比較例中製作的卷狀導電性接合片切斷採集寬度25 mm、長度100 mm的導電性接合片，以導電性接合劑層與寬度30 mm、長度150 mm的SUS板（在厚度0.2 mm的市售的SUS304板的表面形成厚度2 μm的鎳層的物質）的方式將導電性接合片重疊。繼而，使用輥層壓機，在130℃、3 kgf/cm 2、0.5 m/min的條件下將所述導電性接合片與所述SUS板加以輥層壓後，從導電性接合劑層剝離保護片，在導電性接合劑層露出的面上重疊銅箔（厚度25 μm），使用輥層壓機，在130℃、3 kgf/cm 2、0.5 m/min的條件下將導電性接合劑層與銅箔加以輥層壓，從而獲得評價用試樣。 [Laminar Compression Strength] A conductive bonding sheet with a width of 25 mm and a length of 100 mm was cut from the roll of conductive bonding sheets produced in each embodiment and comparative example, and the conductive bonding sheet was overlapped in the form of a conductive bonding agent layer and a SUS plate with a width of 30 mm and a length of 150 mm (a material in which a 2 μm thick nickel layer was formed on the surface of a commercially available SUS304 plate with a thickness of 0.2 mm). Next, the conductive adhesive sheet and the SUS plate were roll-pressed at 130°C, 3 kgf/ cm2 , and 0.5 m/min using a roll press, and then the protective sheet was peeled off from the conductive adhesive layer. A copper foil (thickness 25 μm) was superimposed on the exposed surface of the conductive adhesive layer, and the conductive adhesive layer and the copper foil were roll-pressed at 130°C, 3 kgf/ cm2 , and 0.5 m/min using a roll press to obtain an evaluation sample.
繼而，使用拉伸試驗機（小型桌上試驗機EZ-TEST，島津製作所製造），在拉伸速度50 mm/min的條件下，以90°剝離試驗中的評價用試樣的導電性接合劑層相對於SUS板的接著強度為指標，按照下述評價基準對臨時黏貼性進行評價。 +++：接著強度為3 N/cm以上（非常優異）。 ++：接著強度為2 N/cm以上且小於3 N/cm（優異）。 +：接著強度為1 N/cm以上且小於2 N/cm（能夠實用）。 NG：接著強度小於1 N/cm（不能實用）。 Next, using a tensile tester (small tabletop tester EZ-TEST, manufactured by Shimadzu Corporation), the temporary adhesion was evaluated according to the following evaluation criteria, using the bonding strength of the conductive adhesive layer of the evaluation sample to the SUS plate in the 90° peel test as an indicator under the condition of a tensile speed of 50 mm/min. +++: Bonding strength is 3 N/cm or more (very good). ++: Bonding strength is 2 N/cm or more and less than 3 N/cm (excellent). +: Bonding strength is 1 N/cm or more and less than 2 N/cm (practical). NG: Bonding strength is less than 1 N/cm (not practical).
[接著性] 從各實施例及比較例中製作的卷狀導電性接合片切斷採集寬度25 mm、長度100 mm的導電性接合片，以導電性接合劑層與寬度30 mm、長度150 mm的金屬板（在厚度0.2 mm的市售的SUS304板的表面形成厚度2 μm的鎳層的物質）的方式將導電性接合片重疊。繼而，使用輥層壓機，在130℃、3 kgf/cm 2、0.5 m/min的條件下將所述導電性接合片與所述金屬板加以輥層壓後，從所述導電性接合劑層剝離保護片，在導電性接合劑層露出的面上重疊銅箔（厚度25 μm），使用輥層壓機，在130℃、3 kgf/cm 2、0.5 m/min的條件下將導電性接合劑層與銅箔加以輥層壓，從而獲得積層體。在170℃、2 MPa、3分鐘的條件下對所述積層體進行壓接處理，利用160℃的電烘箱進行60分鐘的加熱處理，從而獲得評價用試樣。 [Adhesion] A conductive bonding sheet with a width of 25 mm and a length of 100 mm was cut from the roll of conductive bonding sheets produced in each embodiment and comparative example, and the conductive bonding sheet was overlapped in the form of a conductive bonding agent layer and a metal plate with a width of 30 mm and a length of 150 mm (a material in which a 2 μm thick nickel layer was formed on the surface of a commercially available SUS304 plate with a thickness of 0.2 mm). Next, the conductive adhesive sheet and the metal plate were roll-pressed at 130°C, 3 kgf/ cm2 , and 0.5 m/min using a roll press, and then the protective sheet was peeled off from the conductive adhesive layer. A copper foil (thickness 25 μm) was superimposed on the exposed surface of the conductive adhesive layer, and the conductive adhesive layer and the copper foil were roll-pressed at 130°C, 3 kgf/ cm2 , and 0.5 m/min using a roll press to obtain a laminate. The laminate was subjected to a compression treatment at 170°C and 2 MPa for 3 minutes, and then subjected to a heat treatment in an electric oven at 160°C for 60 minutes, thereby obtaining an evaluation sample.
繼而，使用拉伸試驗機（小型桌上試驗機EZ-TEST，島津製作所製造），在拉伸速度50 mm/min的條件下，以90°剝離試驗中的評價用試樣的導電性組合物相對於金屬板的接著強度為指標，按照下述評價基準對接著性進行評價。 +++：接著強度為4 N/cm以上（非常優異）。 ++：接著強度為3 N/cm以上且小於4 N/cm（優異）。 +：接著強度為1 N/cm以上且小於3 N/cm（能夠實用）。 NG：接著強度小於1 N/cm（不能實用）。 Next, using a tensile tester (small tabletop tester EZ-TEST, manufactured by Shimadzu Corporation), the adhesion of the conductive composition of the evaluation sample to the metal plate in the 90° peel test was evaluated according to the following evaluation criteria at a tensile speed of 50 mm/min. +++: Adhesion strength is 4 N/cm or more (very good). ++: Adhesion strength is 3 N/cm or more and less than 4 N/cm (excellent). +: Adhesion strength is 1 N/cm or more and less than 3 N/cm (practical). NG: Adhesion strength is less than 1 N/cm (not practical).
[表1]
表1
[表2]
表2
[表3]
表3
[表4]
表4
[表5]
表5
[表6]
表6
1:導電性接合劑層1: Conductive adhesive layer
2:金屬板2:Metal plate
3:保護片3: Protective film
4:卷狀導電性接合片4: Roll-shaped conductive bonding sheet
5:導電性接合片5: Conductive bonding sheet
10:金屬增強板10:Metal reinforcement plate
20:配線板20: Distribution board
21:絕緣性膜21: Insulation film
22:接地電路22: Ground circuit
23:覆蓋層23: Covering layer
30:開口部30: Opening
100:帶金屬增強板的配線板100: Patch panel with metal reinforcement plate
圖1是表示本公開的卷狀導電性接合片的示意圖。 圖2是表示本公開的帶金屬增強板的配線板的剖面的示意圖。 FIG. 1 is a schematic diagram showing a rolled conductive bonding sheet of the present disclosure. FIG. 2 is a schematic diagram showing a cross section of a wiring board with a metal reinforcement plate of the present disclosure.
1:導電性接合劑層 1: Conductive bonding agent layer
3:保護片 3: Protective film
4:卷狀導電性接合片 4: Rolled conductive bonding sheet
5:導電性接合片 5: Conductive bonding sheet
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023-061598 | 2023-04-05 | ||
| JP2023-073962 | 2023-04-28 |
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| Publication Number | Publication Date |
|---|---|
| TWI844506B true TWI844506B (en) | 2024-06-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW201910466A (en) | 2017-08-07 | 2019-03-16 | 日商拓自達電線股份有限公司 | Conductive adhesive |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201910466A (en) | 2017-08-07 | 2019-03-16 | 日商拓自達電線股份有限公司 | Conductive adhesive |
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