本發明係關於一種導電性糊劑及導電性糊劑之製造方法。The present invention relates to a conductive paste and a method for manufacturing the conductive paste.
迄今為止，對導電性糊劑進行了各式各樣的開發。作為該種技術，例如以往已知有專利文獻1中所記載的技術。專利文獻1的段落0015等中記載有：導電性糊劑藉由向聚矽氧樹脂中添加特定量的鱗片狀銀粉並根據需要添加有機溶劑而進行混練來製造。 [先前技術文獻] [專利文獻]Various developments have been made on conductive pastes. For example, the technology described in Patent Document 1 is known. Paragraph 0015 of Patent Document 1 states that the conductive paste is produced by adding a specific amount of flaky silver powder to a polysilicone resin and, if necessary, adding an organic solvent, followed by kneading.[Prior Art Document][Patent Document]
專利文獻1：日本特開2002-150837號公報Patent Document 1: Japanese Patent Application Publication No. 2002-150837
[發明所欲解決之課題][The problem that the invention aims to solve]
然而，本發明人進行探討之結果，判斷出從抑制伸縮前後的導電性的變動的觀點考慮，在上述專利文獻1中所記載之導電性糊劑中尚有改善的餘地。 [解決課題之技術手段]However, the inventors have conducted research and determined that the conductive paste described in Patent Document 1 above still has room for improvement from the perspective of suppressing changes in conductivity before and after expansion and contraction.[Technical Means for Solving the Problem]
本發明人進而探討後發現，藉由適當控制導電性填料與彈性體組成物的初始混合條件，能夠抑制所製造出之導電性糊劑在伸縮前後的導電性的變動，從而完成了本發明。After further research, the inventors discovered that by appropriately controlling the initial mixing conditions of the conductive filler and the elastomer composition, it is possible to suppress changes in the conductivity of the produced conductive paste before and after stretching, thereby completing the present invention.
依據本發明的一態樣，提供以下導電性糊劑及導電性糊劑之製造方法。According to one aspect of the present invention, the following conductive paste and method for manufacturing the conductive paste are provided.
1.一種導電性糊劑，其含有： 彈性體組成物、 導電性填料、及 非水系溶劑； 依照JIS K5600-2-5：1999而測量之該導電性糊劑的細度計（grind gage）之值為40μm以下。 2.如1.之導電性糊劑，其中， 該導電性糊劑的前述細度計之值為5μm以上。 3.如1.或2.之導電性糊劑，其中， 在25℃條件下以20[1/s]的剪切速度測量時的該導電性糊劑的黏度為1Pa•s以上且100Pa•s以下。 4.如1.至3.中任一項之導電性糊劑，其中， 關於該導電性糊劑，在25℃條件下，將以1[1/s]的剪切速度測量時的黏度設為η1，並且將以5[1/s]的剪切速度測量時的黏度設為η5時，藉由η1/η5算出之觸變指數為1.0以上且3.0以下。 5.如1.至4.中任一項之導電性糊劑，其含有非導電性填料。 6.如1.至5.中任一項之導電性糊劑，其中， 前述彈性體組成物包含用於形成選自由聚矽氧橡膠、胺酯（urethane）橡膠、氟橡膠組成之群中之一種以上的彈性體之熱固性彈性體組成物。 7.如1.至6.中任一項之導電性糊劑，其中， 前述非水系溶劑包含沸點為100℃以上且250℃以下之高沸點非水系溶劑。 8.如1.至7.中任一項之導電性糊劑，其中， 在該導電性糊劑100質量%中，前述導電性填料的含量為30質量%以上且85質量%以下。 9.如1.至8.中任一項之導電性糊劑，其中， 前述導電性填料的BET比表面積為0.1m²/g以上且5m²/g以下。 10.一種導電性糊劑之製造方法，其包括下述混合步驟： 在攪拌槽中使用攪拌翼對含有彈性體組成物、導電性填料及非水系溶劑的原料成分進行攪拌之後，使用自轉公轉攪拌機進行混練，藉此獲得導電性糊劑。 11.如10.之導電性糊劑之製造方法，其中， 前述混合步驟中所獲得的前述導電性糊劑中依照JIS K5600-2-5：1999而測量之細度計之值為40μm以下。 12.如10.或11.之導電性糊劑之製造方法，其中， 在前述混合步驟中，前述彈性體組成物及前述非水系溶劑的混合物在25℃條件下以20[1/s]的剪切速度測量時的黏度為1Pa•s以上且100Pa•s以下。 13.如10.至12.中任一項之導電性糊劑之製造方法，其中， 前述非水系溶劑包含沸點為100℃以上且250℃以下之高沸點非水系溶劑。 14.如10.至13.中任一項之導電性糊劑之製造方法，其中， 前述導電性填料的BET比表面積為0.1m²/g以上且5m²/g以下。 [發明之效果]1. A conductive paste comprising:an elastomer composition,a conductive filler, anda non-aqueous solvent;the conductive paste having a grind gage value of 40 μm or less, as measured in accordance with JIS K5600-2-5:1999.2. The conductive paste according to 1.,wherein the grind gage value of the conductive paste is 5 μm or greater.3. The conductive paste according to 1. or 2.,wherein the conductive paste has a viscosity of 1 Pa·s or greater and 100 Pa·s or less, when measured at a shear rate of 20 [1/s] at 25°C. 4. The conductive paste according to any one of 1. to 3., wherein:Regarding the conductive paste, when the viscosity is measured at a shear rate of 1 [1/s] as η1 and the viscosity is measured at a shear rate of 5 [1/s] as η5 at 25°C, the throttling index calculated as η1/η5 is 1.0 or greater and 3.0 or less.5. The conductive paste according to any one of 1. to 4., containing a non-conductive filler.6. The conductive paste according to any one of 1. to 5., wherein:The elastomer composition comprises a thermosetting elastomer composition for forming one or more elastomers selected from the group consisting of silicone rubber, urethane rubber, and fluororubber. 7. The conductive paste according to any one of 1. to 6., wherein the non-aqueous solvent comprises a high-boiling-point non-aqueous solvent having a boiling point of 100°C to 250°C.8. The conductive paste according to any one of 1. to 7., wherein the conductive filler comprises 30% to 85% by mass of 100% by mass of the conductive paste.9. The conductive paste according to any one of 1. to 8., wherein the conductive filler has a BET specific surface area of 0.1 m²/g to 5 m²/g. 10. A method for producing a conductive paste, comprising the following mixing step:After stirring raw material components containing an elastomer composition, a conductive filler, and a non-aqueous solvent in a stirring tank using a stirring blade, kneading the mixture using a rotary stirrer to obtain a conductive paste.11. The method for producing a conductive paste according to 10.,The conductive paste obtained in the mixing step has a micrometer value of 40 μm or less as measured in accordance with JIS K5600-2-5:1999. 12. The method for producing a conductive paste according to 10 or 11, wherein:In the mixing step, the viscosity of the mixture of the elastomer composition and the non-aqueous solvent, when measured at 25°C and a shear rate of 20 [1/s], is 1 Pa·s or higher and 100 Pa·s or lower.13. The method for producing a conductive paste according to any one of 10 to 12, wherein:The non-aqueous solvent includes a high-boiling-point non-aqueous solvent having a boiling point of 100°C or higher and 250°C or lower.14. The method for producing a conductive paste according to any one of 10 to 13, wherein:The BET specific surface area of the conductive filler is 0.1 m²/g or higher and 5 m²/g or lower.[Effects of the Invention]
藉由本發明，提供一種在伸縮前後的導電性的變動抑制優異的導電性糊劑及其製造方法。The present invention provides a conductive paste that has excellent resistance to changes in conductivity before and after expansion and contraction, and a method for producing the same.
以下，使用圖式，對本發明的實施態樣進行說明。另外，在所有的圖式中，對相同的構成要素標註相同的符號，並適當省略說明。又，圖為概略圖，與實際的尺寸比率並不一致。The following drawings illustrate the embodiments of the present invention. In all drawings, identical components are denoted by identical reference numerals, and descriptions thereof are omitted where appropriate. The drawings are schematic and do not reflect actual dimensions.
對本實施態樣的導電性糊劑的概要進行說明。The outline of the conductive paste of this embodiment will be described.
本實施態樣的導電性糊劑含有彈性體組成物、導電性填料及非水系溶劑。該導電性糊劑滿足依照JIS K5600-2-5：1999而測量之細度計之值為40μm以下。The conductive paste of this embodiment contains an elastomer composition, a conductive filler, and a non-aqueous solvent. The conductive paste has a micrometer value of 40 μm or less as measured in accordance with JIS K5600-2-5:1999.
根據本發明人等的見解，明確得知，藉由在含有彈性體組成物、導電性填料及非水系溶劑之原料成分的初始混合中進行適當的攪拌，能夠提升導電性填料的分散性。亦即，即使在導電性填料的比重高於彈性體組成物且原料成分的黏度相對較高時，亦能夠藉由適當的攪拌處理來抑制導電性填料分散性的降低。作為表示該分散性之指標，使用細度計之值為較適當。 雖然詳細的機制尚不明確，但是在實施此種攪拌處理而獲得之導電性糊劑中，由於能夠抑制「從彈性體組成物中分離並懸浮在溶劑中之導電性填料的產生」，因此使用導電性糊劑形成之導電性構件在伸縮前後亦表現出導電性的變動得到抑制的特性。The inventors have discovered that proper stirring during the initial mixing of the raw materials containing an elastomer composition, a conductive filler, and a non-aqueous solvent can improve the dispersibility of the conductive filler. In other words, even when the conductive filler has a higher specific gravity than the elastomer composition and the raw materials have a relatively high viscosity, proper stirring can suppress a decrease in the dispersibility of the conductive filler. A suitable indicator of this dispersibility is the value measured on a micrometer.While the exact mechanism remains unclear, the conductive paste obtained by this stirring process suppresses the generation of conductive fillers that separate from the elastomer composition and become suspended in the solvent. Consequently, conductive components formed using this conductive paste exhibit suppressed changes in conductivity before and after stretching.
導電性糊劑的細度計之值的上限為40μm以下，較佳為35μm以下，更佳為30μm以下。藉此，能夠將伸縮前後的導電性的變動抑制得較低。 另一方面，導電性糊劑的細度計之值的下限並無特別限定，例如為5μm以上，較佳為10μm以上，更佳為15μm以上。藉此，能夠提升操作性。又，能夠抑制伸縮後的電阻值的增大。The upper limit of the conductive paste's fineness is 40 μm or less, preferably 35 μm or less, and more preferably 30 μm or less. This minimizes changes in conductivity before and after stretching.On the other hand, the lower limit of the conductive paste's fineness is not particularly limited, but is, for example, 5 μm or greater, preferably 10 μm or greater, and more preferably 15 μm or greater. This improves workability and minimizes increases in resistance after stretching.
室溫25℃條件下以剪切速度20〔1/s〕進行測量時的導電性糊劑的黏度的下限值例如為1Pa•s以上，較佳為5Pa•s以上，更佳為10Pa•s以上。藉此，能夠提升成膜性。又，即使在形成厚膜時，亦能夠提高形狀保持性。 另一方面，室溫25℃條件下的導電性糊劑的黏度的上限值例如為100Pa•s以下，較佳為90Pa•s以下，更佳為80Pa•s以下。藉此，能夠提升導電性糊劑的印刷性。The lower limit of the viscosity of the conductive paste, when measured at a shear rate of 20 [1/s] at room temperature of 25°C, is, for example, 1 Pa·s or higher, preferably 5 Pa·s or higher, and more preferably 10 Pa·s or higher. This improves film-forming properties and shape retention even when forming thick films.On the other hand, the upper limit of the viscosity of the conductive paste at room temperature of 25°C is, for example, 100 Pa·s or lower, preferably 90 Pa·s or lower, and more preferably 80 Pa·s or lower. This improves the printability of the conductive paste.
在本實施態樣的導電性糊劑中，在室溫25℃條件下，將以剪切速度1〔1/s〕進行測量時的黏度設為η1，並且將以剪切速度5〔1/s〕測量時的黏度設為η5時，根據黏度比（η1/η5）來算出觸變指數。 上述觸變指數的下限值例如為1.0以上，較佳為1.1以上，更佳為1.2以上。藉此，能夠穩定地保持藉由印刷法所獲得之配線的形狀。 另一方面，上述觸變指數的上限值例如為3.0以下，較佳為2.5以下，更佳為2.0以下。藉此，能夠提升導電性糊劑的印刷容易性。In the conductive paste of this embodiment, the tactile index is calculated from the viscosity ratio (η1/η5), where the viscosity measured at a shear rate of 1 [1/s] at room temperature of 25°C is η1, and the viscosity measured at a shear rate of 5 [1/s] is η5.The lower limit of the tactile index is, for example, 1.0 or greater, preferably 1.1 or greater, and more preferably 1.2 or greater. This ensures stable retention of the shape of the wiring obtained by printing.On the other hand, the upper limit of the tactile index is, for example, 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less. This improves the ease of printing the conductive paste.
本實施態樣的導電性糊劑對於基板的塗布性、成膜性及/或網版印刷等印刷性優異。The conductive paste of this embodiment has excellent coating properties, film-forming properties, and/or printability such as screen printing on substrates.
本實施態樣的導電性糊劑例如能夠用於形成電極、配線、感測器、發熱體、接著劑等各式各樣的導電構件。亦即，導電性糊劑的硬化物作為伸縮性導電構件，能夠在如上述的各式各樣的用途中的至少一種中使用。 作為電極，例如可以列舉生物電極或柔軟性片電極等。 作為配線，例如可以列舉伸縮性配線等。 作為感測器，例如，可以列舉位移感測器、壓力感測器、管的內層材料時的流量感測器等。 作為發熱體，可以列舉用於裝置、車輛、醫療器具等之加熱器等。 作為黏著劑，可以列舉用於電子裝置等的導電性接著劑等。 再者，在本實施態樣中，能夠提供具備此種導電構件之結構體。The conductive paste of this embodiment can be used to form a variety of conductive components, such as electrodes, wiring, sensors, heating elements, and adhesives. Specifically, the cured conductive paste can be used as a stretchable conductive component in at least one of the various applications described above.Examples of electrodes include bioelectrodes and flexible sheet electrodes.Examples of wiring include stretchable wiring.Examples of sensors include displacement sensors, pressure sensors, and flow sensors used as inner lining materials for pipes.Examples of heating elements include heaters for devices, vehicles, and medical equipment.Examples of adhesives include conductive adhesives used in electronic devices and the like.Furthermore, this embodiment can provide a structure having such a conductive component.
又，本實施態樣的導電性糊劑除了導電性填料以外還可以含有二氧化矽粒子。藉此，能夠提升使用導電性糊劑形成之導電性構件的機械強度和耐久性。Furthermore, the conductive paste of this embodiment may contain silica particles in addition to the conductive filler. This can enhance the mechanical strength and durability of the conductive member formed using the conductive paste.
此處，對本實施態樣的導電性糊劑之製造方法的一例進行說明。Here, an example of a method for producing the conductive paste according to this embodiment will be described.
導電性糊劑之製造方法例如能夠包括下述混合步驟：在攪拌槽中使用攪拌翼對含有彈性體組成物、導電性填料及非水系溶劑的原料成分進行攪拌之後（攪拌處理），使用自轉公轉攪拌機進行混練（混練處理），藉此獲得導電性糊劑（混合物）。 藉由使用攪拌翼進行攪拌處理，能夠進一步提高導電性糊劑中的導電性填料的分散性。 又，對於使用了攪拌翼的攪拌，較佳為使用含有彈性體組成物及非水系溶劑之原料成分（混合物）的黏度為1Pa•s以上且100Pa•s以下者。藉此，在使用施加有高剪切力的攪拌翼進行攪拌時，能夠實現穩定的攪拌操作。 此處，在25℃的條件下，以20[1/s]的剪切速度測量黏度。再者，成為黏度測量的對象的原料成分（混合物）中亦可以不含有導電性填料。A method for producing a conductive paste may include, for example, a mixing step comprising stirring a raw material component containing an elastomer composition, a conductive filler, and a non-aqueous solvent in a stirring tank using a stirring blade (stirring process), followed by kneading using a rotary stirrer (kneading process) to obtain a conductive paste (mixture).Stirring with a stirring blade can further improve the dispersibility of the conductive filler in the conductive paste.For stirring with a stirring blade, it is preferred that the raw material component (mixture) containing the elastomer composition and the non-aqueous solvent has a viscosity of 1 Pa·s or higher and 100 Pa·s or lower. This enables stable stirring when using a stirring blade that applies high shear force.Here, viscosity was measured at a shear rate of 20 [1/s] at 25°C. Furthermore, the raw material components (mixture) used for viscosity measurement do not necessarily contain conductive fillers.
攪拌槽的容量或攪拌槽的底部形狀能夠依據原料成分的黏度或容量等而適當選擇。 又，攪拌翼的轉速、旋轉時間亦能夠依據原料成分的黏度或容量等適當選擇。The capacity and bottom shape of the agitator can be appropriately selected based on the viscosity and volume of the raw materials.Also, the speed and rotation time of the agitator blade can be appropriately selected based on the viscosity and volume of the raw materials.
攪拌翼可以為螺旋翼、渦輪翼、槳（paddle）翼、3片後掠翼等低黏度用攪拌翼，亦可以為錨（anchor）翼、螺帶翼等高黏度用攪拌翼。其中，就抑制攪拌中的導電性填料的沉降之方面而言，較佳為能夠均勻且有效率地攪拌導電性糊劑整體之攪拌翼。The stirring blades can be propellers, turbines, paddles, or triple-swept blades for low viscosity applications, or anchors or ribbons for high viscosity applications. To prevent sedimentation of the conductive filler during stirring, a stirring blade that can uniformly and efficiently stir the entire conductive paste is preferred.
在本實施態樣中，例如藉由適當選擇導電性糊劑中所含之各成分的種類和摻合量、導電性糊劑之製備方法等，能夠控制上述細度計之值。該等中，例如，可以列舉「實施攪拌翼等的適當的攪拌處理」、「適當地控制供於攪拌之原料成分的黏度、金屬粉的BET比表面積」等來作為用於將上述細度計之值設為所期望的數值範圍的因素。In this embodiment, the value of the fineness gauge can be controlled by, for example, appropriately selecting the type and amount of each component contained in the conductive paste, the preparation method of the conductive paste, etc. Examples of factors for setting the fineness gauge value within the desired numerical range include "proper stirring using a stirring blade, etc." and "properly controlling the viscosity of the raw material components used for stirring and the BET specific surface area of the metal powder."
在本實施態樣之製造方法中，較佳為混合步驟中不使用三輥研磨機。若在三輥研磨機中溶劑進行揮發，則可能會產生研磨後的糊劑黏度上升之情形、因在三輥研磨機上乾固而回收率下降之情形等，製造穩定性降低。In the production method of this embodiment, it is preferred not to use a three-roll mill during the mixing step. If the solvent volatilizes in a three-roll mill, the viscosity of the milled paste may increase, the recovery rate may decrease due to drying in the three-roll mill, and other factors may reduce production stability.
又，本實施態樣之製造方法可以包括對在混合步驟中所獲得之混合物進行過濾處理的過濾步驟。 又，本實施態樣之製造方法可以包括對在混練步驟中所獲得之混合物進行脫泡處理的脫泡步驟。 可以實施上述過濾步驟及脫泡步驟中的至少一者或兩者。實施的順序並無特別限定，但是可以在過濾步驟之後實施脫泡步驟。亦可以實施其他公知的處理。Furthermore, the production method of this embodiment may include a filtration step of filtering the mixture obtained in the mixing step.Furthermore, the production method of this embodiment may include a defoaming step of defoaming the mixture obtained in the kneading step.At least one or both of the filtration and defoaming steps may be performed. The order of performance is not particularly limited, but the defoaming step may be performed after the filtration step. Other known treatments may also be performed.
又，本實施態樣之製造方法可以包括：評價步驟，對在混合步驟中所獲得之混合物進行「選自由黏度、固形物成分濃度及膠化時間組成之群中之一個或兩個以上的特性是否滿足特定條件」的判斷。藉此，能夠提高導電性糊劑的製造穩定性。評價步驟可以在上述各步驟之間實施，亦可以在最後的步驟之後實施。Furthermore, the manufacturing method of this embodiment may include an evaluation step to determine whether the mixture obtained in the mixing step satisfies specific requirements for one or more properties selected from the group consisting of viscosity, solids content concentration, and gelation time. This can improve the manufacturing stability of the conductive paste. The evaluation step can be performed between the aforementioned steps or after the final step.
以下，對導電性糊劑的各成分進行詳細說明。The following describes the components of the conductive paste in detail.
本實施態樣的導電性糊劑含有彈性體組成物、導電性填料及非水系溶劑。The conductive paste of this embodiment contains an elastomer composition, a conductive filler, and a non-aqueous solvent.
（彈性體組成物） 彈性體組成物可以使用聚矽氧橡膠、胺酯橡膠、氟橡膠、腈橡膠、丙烯酸橡膠、苯乙烯橡膠、氯丁二烯橡膠、乙烯丙烯橡膠等。其中，彈性體組成物為用於形成選自由聚矽氧橡膠、胺酯橡膠、氟橡膠組成之群中之至少一種彈性體之組成物。 其中，彈性體組成物可以是含有熱固性彈性體組成物或熱塑性彈性體的組成物，較佳為熱固性彈性體組成物，進而較佳為聚矽氧橡膠組成物。(Elastomer Composition)The elastomer composition may include silicone rubber, urethane rubber, fluororubber, nitrile rubber, acrylic rubber, styrene rubber, chloroprene rubber, ethylene propylene rubber, and the like. The elastomer composition is a composition that forms at least one elastomer selected from the group consisting of silicone rubber, urethane rubber, and fluororubber.The elastomer composition may include a thermosetting elastomer composition or a thermoplastic elastomer, preferably a thermosetting elastomer composition, and more preferably a silicone rubber composition.
上述的聚矽氧橡膠組成物例如較佳為含有聚矽氧複合物（compound）、交聯劑及觸媒之聚矽氧橡膠系硬化性組成物。 此處，對聚矽氧橡膠系硬化性組成物的一例進行說明。 在聚矽氧橡膠系硬化性組成物的一例中，聚矽氧複合物為含有後述的含乙烯基之有機聚矽氧烷（A）、二氧化矽粒子（C）及矽烷偶合劑（D）者，交聯劑為含有有機氫聚矽氧烷（B）者，觸媒可以含有鉑或鉑化合物（E）。The silicone rubber composition described above is preferably a silicone rubber curable composition comprising a silicone compound, a crosslinking agent, and a catalyst.Herein, an example of a silicone rubber curable composition is described.In this example of a silicone rubber curable composition, the silicone compound comprises a vinyl group-containing organopolysiloxane (A), silica particles (C), and a silane coupling agent (D), as described below; the crosslinking agent comprises an organohydropolysiloxane (B); and the catalyst may comprise platinum or a platinum compound (E).
在導電性糊劑100質量%中，導電性糊劑中的彈性體組成物或聚矽氧橡膠系硬化性組成物的含量的下限例如較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上。 另一方面，在導電性糊劑100質量%中，導電性糊劑中的彈性體組成物或聚矽氧橡膠系硬化性組成物的含量的上限例如較佳為25質量%以下，更佳為20質量%以下，進而較佳為15質量%以下。 藉由將彈性體組成物或聚矽氧橡膠系硬化性組成物的含量設為上述下限值以上，能夠使導電性糊劑的彈性體具有適當的柔軟性。又，藉由將彈性體組成物或聚矽氧橡膠系硬化性組成物的含量設為上述上限值以下，能夠謀求彈性體的機械強度的提升。The lower limit of the content of the elastomer composition or silicone rubber curable composition in the conductive paste is, for example, preferably 1% by mass or greater, more preferably 3% by mass or greater, and even more preferably 5% by mass or greater, based on 100% by mass of the conductive paste.On the other hand, the upper limit of the content of the elastomer composition or silicone rubber curable composition in the conductive paste is, for example, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on 100% by mass of the conductive paste.By setting the content of the elastomer composition or silicone rubber curable composition to or above the above lower limit, the elastomer in the conductive paste can be given appropriate flexibility. Furthermore, by setting the content of the elastomer composition or the silicone rubber curable composition below the above upper limit, the mechanical strength of the elastomer can be improved.
在導電性糊劑100質量%中，導電性糊劑中的導電性填料或金屬粉末（G）的含量的下限例如較佳為30質量%以上，更佳為40質量%以上，進而較佳為50質量%以上。 另一方面，在導電性糊劑100質量%中，導電性糊劑中的導電性填料或金屬粉末（G）的含量的上限例如較佳為85質量%以下，更佳為75質量%以下，進而較佳為65質量%以下。 藉由將導電性填料或金屬粉末（G）的含量設為上述下限值以上，能夠使導電性糊劑的彈性體具有適當的導電性。又，藉由將導電性填料或金屬粉末（G）的含量設為上述上限值以下，能夠使彈性體具有適當的柔軟性。The lower limit of the content of the conductive filler or metal powder (G) in the conductive paste is, for example, preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on 100% by mass of the conductive paste.On the other hand, the upper limit of the content of the conductive filler or metal powder (G) in the conductive paste is, for example, preferably 85% by mass or less, more preferably 75% by mass or less, and even more preferably 65% by mass or less, based on 100% by mass of the conductive paste.By setting the content of the conductive filler or metal powder (G) to or above the lower limit, the elastomer in the conductive paste can have appropriate conductivity. Furthermore, by setting the content of the conductive filler or metal powder (G) below the above upper limit, the elastomer can be given appropriate flexibility.
依需要，導電性糊劑能夠含有二氧化矽粒子（C）等非導電性填料。 此時，在導電性糊劑100質量%中，導電性糊劑中的二氧化矽粒子（C）的含量的下限例如較佳為1質量%以上，更佳為2質量%以上，進而較佳為3質量%以上。 另一方面，在導電性糊劑100質量%中，導電性糊劑中的二氧化矽粒子（C）的含量的上限例如較佳為15質量%以下，更佳為12質量%以下，進而較佳為10質量%以下。 藉由將二氧化矽粒子（C）或非導電性填料的含量設為上述下限值以上，能夠使導電性糊劑的彈性體具有適當的機械強度。又，藉由將二氧化矽粒子（C）或非導電性填料的含量設為上述上限值以下，能夠使彈性體具有適當的導電性。The conductive paste may optionally contain non-conductive fillers such as silica particles (C).In this case, the lower limit of the content of the silica particles (C) in the conductive paste is, for example, preferably 1% by mass or greater, more preferably 2% by mass or greater, and even more preferably 3% by mass or greater, based on 100% by mass of the conductive paste.On the other hand, the upper limit of the content of the silica particles (C) in the conductive paste is, for example, preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the conductive paste.By setting the content of the silica particles (C) or non-conductive filler to or above the above lower limit, the elastomer in the conductive paste can have appropriate mechanical strength. Furthermore, by setting the content of the silica particles (C) or the non-conductive filler below the above upper limit, the elastomer can have appropriate conductivity.
又，相對於二氧化矽粒子（C）及導電性填料的合計量100質量%，導電性糊劑中的二氧化矽粒子（C）的含量的下限值例如能夠設為1質量%以上，較佳為3質量%以上，更佳為5質量%以上。藉此，能夠提升導電性糊劑的彈性體的機械強度。另一方面，相對於二氧化矽粒子（C）及導電性填料的合計量100質量%，上述導電性糊劑中的上述二氧化矽粒子（C）的含量的上限值例如為20質量%以下，較佳為15質量%以下，更佳為10質量%以下。藉此，能夠謀求導電性糊劑的彈性體中的伸縮電特性與機械強度的平衡。Furthermore, the lower limit of the content of the silica particles (C) in the conductive paste can be set to, for example, 1 mass% or more, preferably 3 mass% or more, and more preferably 5 mass% or more, relative to 100 mass% of the total amount of the silica particles (C) and the conductive filler. This can enhance the mechanical strength of the elastomer of the conductive paste. Meanwhile, the upper limit of the content of the silica particles (C) in the conductive paste can be set to, for example, 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less, relative to 100 mass% of the total amount of the silica particles (C) and the conductive filler. This can achieve a balance between the dielastic properties and the mechanical strength of the elastomer of the conductive paste.
相對於含乙烯基之有機聚矽氧烷（A）的合計量100質量%，導電性糊劑中的矽烷偶合劑（D）的含量下限較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上。 另一方面，相對於含乙烯基之有機聚矽氧烷（A）的合計量100質量%，矽烷偶合劑（D）的含量的上限較佳為100質量%以下，更佳為80質量%以下，進而較佳為40質量%以下。 藉由將導電性糊劑中的矽烷偶合劑（D）的含量設為上述下限值以上，使導電性糊劑的彈性體具有與基板的適當的密接性，又，在使用二氧化矽粒子（C）的情況下，能夠有助於提升彈性體整體的機械強度。又，藉由將矽烷偶合劑（D）的含量設為上述上限值以下，能夠使彈性體具有適當的機械特性。The lower limit of the content of the silane coupling agent (D) in the conductive paste is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more, relative to 100 mass% of the total amount of the vinyl group-containing organopolysiloxane (A).On the other hand, the upper limit of the content of the silane coupling agent (D) is preferably 100 mass% or less, more preferably 80 mass% or less, and even more preferably 40 mass% or less, relative to 100 mass% of the total amount of the vinyl group-containing organopolysiloxane (A). By setting the content of the silane coupling agent (D) in the conductive paste to above the lower limit, the elastomer in the conductive paste can have suitable adhesion to the substrate. Furthermore, when silica particles (C) are used, the mechanical strength of the elastomer as a whole can be improved. Furthermore, by setting the content of the silane coupling agent (D) to below the upper limit, the elastomer can have suitable mechanical properties.
在導電性糊劑100質量%中，導電性糊劑中的鉑或鉑化合物（E）的含量的下限例如為較佳為0.0001質量%以上，更佳為0.0002質量%以上，進而較佳為0.0003質量%以上。 另一方面，相對於導電性糊劑的整體，導電性糊劑中的鉑或鉑化合物（E）的含量的上限較佳為1質量%以下，更佳為0.5質量%以下，進而較佳為0.1質量%以下。 藉由將鉑或鉑化合物（E）的含量設為上述下限值以上，能夠使導電性糊劑以適當的速度硬化。又，將鉑或鉑化合物（E）的含量設為上述上限值以下，能夠有助於降低製作導電性糊劑時的成本。The lower limit of the content of platinum or the platinum compound (E) in the conductive paste is, for example, preferably 0.0001 mass% or more, more preferably 0.0002 mass% or more, and even more preferably 0.0003 mass% or more, based on 100 mass% of the conductive paste.On the other hand, the upper limit of the content of platinum or the platinum compound (E) in the conductive paste is preferably 1 mass% or less, more preferably 0.5 mass% or less, and even more preferably 0.1 mass% or less, relative to the entire conductive paste.By setting the content of platinum or the platinum compound (E) to or above the above lower limit, the conductive paste can be cured at an appropriate rate. Furthermore, setting the content of platinum or a platinum compound (E) below the upper limit can contribute to reducing the cost of producing the conductive paste.
＜＜含乙烯基之有機聚矽氧烷（A）＞＞ 聚矽氧橡膠系硬化性組成物可以含有含乙烯基之有機聚矽氧烷（A）。含乙烯基之有機聚矽氧烷（A）可以為聚矽氧橡膠系硬化性組成物中的主要成分。<<Vinyl-containing organopolysiloxane (A)>>The silicone rubber curable composition may contain a vinyl-containing organopolysiloxane (A). The vinyl-containing organopolysiloxane (A) may be the main component of the silicone rubber curable composition.
上述含乙烯基之有機聚矽氧烷（A）能夠包含具有直鏈結構之含乙烯基之直鏈狀有機聚矽氧烷（A1）。The vinyl group-containing organopolysiloxane (A) may include a vinyl group-containing linear organopolysiloxane (A1) having a linear structure.
上述含乙烯基之直鏈狀有機聚矽氧烷（A1）具有直鏈結構且含有乙烯基，該乙烯基成為硬化時的交聯點。The vinyl group-containing linear organic polysiloxane (A1) has a linear structure and contains vinyl groups, and the vinyl groups serve as crosslinking points during curing.
含乙烯基之直鏈狀有機聚矽氧烷（A1）的乙烯基含量並無特別限定，例如，分子內具有2個以上的乙烯基且較佳為15莫耳%以下，更佳為0.01～12莫耳%。藉此，使含乙烯基之直鏈狀有機聚矽氧烷（A1）中之乙烯基的量最佳化，能夠確實地形成與後述各成分的網路。The vinyl content of the vinyl-containing linear organopolysiloxane (A1) is not particularly limited. For example, the molecule may contain two or more vinyl groups and the vinyl content is preferably 15 mol% or less, more preferably 0.01 to 12 mol%. This allows the amount of vinyl groups in the vinyl-containing linear organopolysiloxane (A1) to be optimized, enabling reliable formation of a network with the components described below.
再者，在本說明書中，乙烯基含量是指，在將構成含乙烯基之直鏈狀有機聚矽氧烷（A1）之所有單元設為100莫耳%時的含乙烯基之矽氧烷單元的莫耳%。但是，認為相對於1個含乙烯基之矽氧烷單元，乙烯基為1個。In this specification, the vinyl content refers to the molar percentage of vinyl-containing siloxane units when all units constituting the vinyl-containing linear organopolysiloxane (A1) are taken as 100 molar percentage. However, it is assumed that one vinyl group is present for each vinyl-containing siloxane unit.
又，含乙烯基之直鏈狀有機聚矽氧烷（A1）的聚合度並無特別限定，例如在較佳為1000～10000左右、更佳為2000～5000左右的範圍內。再者，關於聚合度，例如能夠作為「將氯仿設為展開溶劑之GPC（凝膠滲透層析法）中之聚苯乙烯換算的數量平均聚合度（或數量平均分子量）」等求出。The degree of polymerization of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, but is preferably within the range of approximately 1,000 to 10,000, more preferably approximately 2,000 to 5,000. The degree of polymerization can be determined, for example, as the polystyrene-equivalent number average degree of polymerization (or number average molecular weight) measured by GPC (gel permeation chromatography) using chloroform as the developing solvent.
在本說明書中，只要沒有特別說明，則「～」表示包含上限值和下限值。In this specification, “～” means that the upper limit and the lower limit are included unless otherwise specified.
進而，含乙烯基之直鏈狀有機聚矽氧烷（A1）的比重並無特別限定，較佳為在0.9～1.1左右的範圍內。Furthermore, the specific gravity of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, but is preferably in the range of approximately 0.9 to 1.1.
藉由使用具有如上所述的範圍內的聚合度及比重者作為含乙烯基之直鏈狀有機聚矽氧烷（A1），能夠謀求所獲得之聚矽氧橡膠的耐熱性、阻燃性、化學穩定性等的提升。By using a linear organopolysiloxane (A1) having a degree of polymerization and a specific gravity within the above ranges, it is possible to improve the heat resistance, flame retardancy, chemical stability, etc. of the resulting silicone rubber.
作為含乙烯基之直鏈狀有機聚矽氧烷（A1），尤其較佳為具有由下述式（1）表示之結構者。As the vinyl group-containing linear organopolysiloxane (A1), one having a structure represented by the following formula (1) is particularly preferred.
式（1）中，R1為碳數1～10的經取代或未經取代的烷基、烯基、芳基或者將該等組合而獲得之烴基。作為碳數1～10的烷基，例如可以列舉甲基、乙基、丙基等，其中，較佳為甲基。作為碳數1～10的烯基，例如可以列舉乙烯基、烯丙基、丁烯基等，其中，較佳為乙烯基。作為碳數1～10的芳基，例如可以列舉苯基等。In formula (1),R1 is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, or alkyl group obtained by combining these groups having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of the alkenyl group having 1 to 10 carbon atoms include vinyl, allyl, and butenyl groups, with vinyl being preferred. Examples of the aryl group having 1 to 10 carbon atoms include phenyl groups.
又，R2為碳數1～10的經取代或未經取代的烷基、烯基、芳基或者將該等組合而獲得之烴基。作為碳數1～10的烷基，例如可以列舉甲基、乙基、丙基等，其中，較佳為甲基。作為碳數1～10的烯基，例如可以列舉乙烯基、烯丙基、丁烯基。作為碳數1～10的芳基，例如可以列舉苯基。Furthermore,R2 is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, or alkyl group derived from a combination of 1 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of alkenyl groups having 1 to 10 carbon atoms include vinyl, allyl, and butenyl groups. Examples of aryl groups having 1 to 10 carbon atoms include phenyl groups.
又，R3為碳數1～8的經取代或未經取代的烷基、芳基或者將該等組合而獲得之烴基。作為碳數1～8的烷基，例如可以列舉甲基、乙基、丙基等，其中，較佳為甲基。作為碳數1～8的芳基，例如可以列舉苯基。Furthermore, R<3> is a substituted or unsubstituted alkyl group, an aryl group, or a alkyl group obtained by combining these groups having 1 to 8 carbon atoms. Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of aryl groups having 1 to 8 carbon atoms include phenyl groups.
進而，作為式（1）中的R1及R2的取代基，例如可以列舉甲基、乙烯基等，作為R3的取代基，例如可以列舉甲基等。Furthermore, examples of substituents for R1 and R2 in formula (1) include methyl and vinyl groups, and examples of substituents for R3 include methyl and the like.
再者，式（1）中，複數個R1為彼此獨立者，可以彼此不同，亦可以相同。進而，關於R2及R3亦同樣如此。Furthermore, in formula (1), the plurality of R1's are independent of each other and may be different or the same. The same applies to R2 and R3 .
進而，m、n為構成由式（1）表示之含乙烯基之直鏈狀有機聚矽氧烷（A1）之重複單元的數量，m為0～2000的整數，n為1000～10000的整數。m較佳為0～1000，n較佳為2000～5000。Furthermore, m and n are the numbers of repeating units constituting the vinyl group-containing linear organopolysiloxane (A1) represented by formula (1), m is an integer from 0 to 2000, and n is an integer from 1000 to 10000. m is preferably from 0 to 1000, and n is preferably from 2000 to 5000.
又，作為由式（1）表示之含乙烯基之直鏈狀有機聚矽氧烷（A1）的具體的結構，例如可以列舉由下述式（1-1）表示者。Furthermore, as a specific structure of the vinyl group-containing linear organopolysiloxane (A1) represented by the formula (1), for example, there can be cited the structure represented by the following formula (1-1).
式（1-1）中，R1及R2分別獨立地為甲基或乙烯基，至少一者為乙烯基。In formula (1-1), R1 and R2 are each independently a methyl group or a vinyl group, and at least one of them is a vinyl group.
進而，作為含乙烯基之直鏈狀有機聚矽氧烷（A1），較佳為含有「分子內具有2個以上乙烯基且乙烯基含量為0.4莫耳%以下的第1含乙烯基之直鏈狀有機聚矽氧烷（A1-1）」、及「乙烯基含量為0.5～15莫耳%的第2含乙烯基之直鏈狀有機聚矽氧烷（A1-2）」者。作為聚矽氧橡膠的原料之生橡膠，藉由組合「具有一般乙烯基含量的第1含乙烯基之直鏈狀有機聚矽氧烷（A1-1）」和「乙烯基含量高的第2含乙烯基之直鏈狀有機聚矽氧烷（A1-2）」，能夠使乙烯基偏在化，並且能夠在聚矽氧橡膠的交聯網路中更有效地形成交聯密度的疏密。其結果，能夠更有效地提高聚矽氧橡膠的撕裂強度。Furthermore, the vinyl-containing linear organopolysiloxane (A1) preferably contains a "first vinyl-containing linear organopolysiloxane (A1-1) having two or more vinyl groups in the molecule and a vinyl content of 0.4 mol% or less" and a "second vinyl-containing linear organopolysiloxane (A1-2) having a vinyl content of 0.5 to 15 mol%." By combining the "first vinyl-containing linear organopolysiloxane (A1-1) having a normal vinyl content" with the "second vinyl-containing linear organopolysiloxane (A1-2) having a high vinyl content" in the raw rubber used as the silicone rubber raw material, the vinyl groups can be localized, and the crosslinking density within the silicone rubber's crosslinking network can be more effectively varied. As a result, the tear strength of silicone rubber can be more effectively improved.
具體而言，作為含有乙烯基之直鏈狀有機聚矽氧烷（A1），例如，較佳為使用：在上述式（1-1）中，在分子內具有2個以上R1為乙烯基之單元及/或R2為乙烯基之單元並且包含0.4莫耳%以下的該等單元之第1含有乙烯基之直鏈狀有機聚矽氧烷（A1-1）、及包含0.5～15莫耳%的R1為乙烯基之單元及/或R2為乙烯基之單元之第2含有乙烯基之直鏈狀有機聚矽氧烷（A1-2）。Specifically, as the vinyl group-containing linear organic polysiloxane (A1), for example, preferably used are: in the above formula (1-1), a first vinyl group-containing linear organic polysiloxane (A1-1) having two or more units in whichR1 is a vinyl group and/or units in whichR2 is a vinyl group in the molecule, wherein the units comprise not more than 0.4 mol% of these units; and a second vinyl group-containing linear organic polysiloxane (A1-2) comprising 0.5 to 15 mol% of units in whichR1 is a vinyl group and/or units in whichR2 is a vinyl group.
又，較佳為第1含乙烯基之直鏈狀有機聚矽氧烷（A1-1）的乙烯基含量為0.01～0.2莫耳%。又，較佳為第2含乙烯基之直鏈狀有機聚矽氧烷（A1-2）的乙烯基含量為0.8～12莫耳%。The first vinyl group-containing linear organopolysiloxane (A1-1) preferably has a vinyl content of 0.01 to 0.2 mol %. The second vinyl group-containing linear organopolysiloxane (A1-2) preferably has a vinyl content of 0.8 to 12 mol %.
進而，在將第1含乙烯基之直鏈狀有機聚矽氧烷（A1-1）和第2含乙烯基之直鏈狀有機聚矽氧烷（A1-2）組合而摻合之情況下，（A1-1）與（A1-2）的比例並無特別限定，例如較佳為以重量比計（A1-1）:（A1-2）為50:50～95:5，更佳為80:20～90:10。Furthermore, when the first vinyl group-containing linear organopolysiloxane (A1-1) and the second vinyl group-containing linear organopolysiloxane (A1-2) are combined and blended, the ratio of (A1-1) to (A1-2) is not particularly limited. For example, the weight ratio of (A1-1):(A1-2) is preferably 50:50 to 95:5, and more preferably 80:20 to 90:10.
再者，第1含乙烯基之直鏈狀有機聚矽氧烷（A1-1）及第2含乙烯基之直鏈狀有機聚矽氧烷（A1-2）可以分別僅使用1種，亦可以組合使用2種以上。The first vinyl group-containing linear organopolysiloxane (A1-1) and the second vinyl group-containing linear organopolysiloxane (A1-2) may be used alone or in combination of two or more.
又，含乙烯基之有機聚矽氧烷（A）可以包含具有支鏈結構之含乙烯基之支鏈狀有機聚矽氧烷（A2）。Furthermore, the vinyl group-containing organopolysiloxane (A) may include a vinyl group-containing branched organopolysiloxane (A2) having a branched structure.
＜＜有機氫聚矽氧烷（B）＞＞ 聚矽氧橡膠系硬化性組成物可以含有有機氫聚矽氧烷（B）。 有機氫聚矽氧烷（B）分類為具有直鏈結構之直鏈狀有機氫聚矽氧烷（B1）和具有支鏈結構之支鏈狀有機氫聚矽氧烷（B2），並且能夠包含該等之中的任一者或兩者。<<Organohydropolysiloxane (B)>>The silicone rubber curable composition may contain an organohydropolysiloxane (B).Organohydropolysiloxane (B) is classified into linear organohydropolysiloxanes (B1) having a linear structure and branched organohydropolysiloxanes (B2) having a branched structure, and may contain either or both of these.
直鏈狀有機氫聚矽氧烷（B1）具有直鏈結構，並且為如下聚合物：具有氫與Si直接鍵結之結構（≡Si-H），除了含乙烯基之有機聚矽氧烷（A）的乙烯基以外，與摻合於聚矽氧橡膠系硬化性組成物中之成分所具有之乙烯基進行矽氫化反應，以使該等成分交聯。The linear organohydropolysiloxane (B1) has a linear structure and is a polymer having a structure in which hydrogen and Si are directly bonded (≡Si-H). In addition to the vinyl groups of the vinyl-containing organopolysiloxane (A), the linear organohydropolysiloxane undergoes a silylation reaction with the vinyl groups of the components incorporated into the silicone rubber curable composition, thereby crosslinking these components.
直鏈狀有機氫聚矽氧烷（B1）的分子量並無特別限定，例如重量平均分子量較佳為20000以下，更佳為1000以上且10000以下。The molecular weight of the linear organohydropolysiloxane (B1) is not particularly limited. For example, the weight average molecular weight is preferably 20,000 or less, and more preferably 1,000 or more and 10,000 or less.
再者，關於直鏈狀有機氫聚矽氧烷（B1）的重量平均分子量，例如能夠藉由將氯仿設為展開溶劑之GPC（凝膠滲透層析法）中之聚苯乙烯換算進行測量。The weight average molecular weight of the linear organohydropolysiloxane (B1) can be measured, for example, by polystyrene conversion using GPC (gel permeation chromatography) using chloroform as a developing solvent.
又，較佳為直鏈狀有機氫聚矽氧烷（B1）一般不具有乙烯基。藉此，能夠確實地防止在直鏈狀有機氫聚矽氧烷（B1）的分子內進行交聯反應。Furthermore, it is generally preferred that the linear organohydropolysiloxane (B1) does not have a vinyl group. This ensures that crosslinking reactions within the molecules of the linear organohydropolysiloxane (B1) can be prevented.
作為如上所述的直鏈狀有機氫聚矽氧烷（B1），例如可以較佳地使用具有由下述式（2）表示之結構者。As the linear organohydropolysiloxane (B1), for example, one having a structure represented by the following formula (2) can be preferably used.
式（2）中，R4為碳數1～10的經取代或未經取代的烷基、烯基、芳基、將該等組合而獲得之烴基或者氫化物基。作為碳數1～10的烷基，例如可以列舉甲基、乙基、丙基等，其中，較佳為甲基。作為碳數1～10的烯基，例如可以列舉乙烯基、烯丙基、丁烯基等。作為碳數1～10的芳基，例如可以列舉苯基。In formula (2),R₄ represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkyl group obtained by combining these groups, or hydride group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of the alkenyl group having 1 to 10 carbon atoms include vinyl, allyl, and butenyl groups. Examples of the aryl group having 1 to 10 carbon atoms include phenyl groups.
又，R5為碳數1～10的經取代或未經取代的烷基、烯基、芳基、將該等組合而獲得之烴基或者氫化物基。作為碳數1～10的烷基，例如可以列舉甲基、乙基、丙基，其中，較佳為甲基。作為碳數1～10的烯基，例如可以列舉乙烯基、烯丙基、丁烯基等。作為碳數1～10的芳基，例如可以列舉苯基。Furthermore,R₅ is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkyl group obtained by combining these groups, or hydride group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of the alkenyl group having 1 to 10 carbon atoms include vinyl, allyl, and butenyl groups. Examples of the aryl group having 1 to 10 carbon atoms include phenyl groups.
再者，式（2）中，複數個R4為彼此獨立者，可以彼此不同，亦可以相同。關於R5亦同樣如此。但是，複數個R4及R5中的至少2個以上為氫化物基。Furthermore, in formula (2), the plurality of R4's are independent of each other and may be different or the same. The same applies to R5's . However, at least two of the plurality of R4's and R5 's are hydride groups.
又，R6為碳數1～8的經取代或未經取代的烷基、芳基或者將該等組合而獲得之烴基。作為碳數1～8的烷基，例如可以列舉甲基、乙基、丙基等，其中，較佳為甲基。作為碳數1～8的芳基，例如可以列舉苯基。複數個R6為彼此獨立者，可以彼此不同，亦可以相同。Furthermore,R₆ is a substituted or unsubstituted alkyl group, an aryl group, or a alkyl group derived from a combination of these groups having 1 to 8 carbon atoms. Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of aryl groups having 1 to 8 carbon atoms include phenyl. MultipleR₆ groups are independent of each other and may be different or the same.
再者，作為式（2）中的R4、R5、R6的取代基，例如可以列舉甲基、乙烯基等，就防止分子內的交聯反應之方面而言，較佳為甲基。Furthermore, examples of substituents for R4 , R5 , and R6 in formula (2) include methyl and vinyl groups. From the perspective of preventing intramolecular cross-linking reactions, methyl groups are preferred.
進而，m、n為構成由式（2）表示之直鏈狀有機氫聚矽氧烷（B1）之重複單元的數量，m為2～150的整數，n為2～150的整數。較佳為，m為2～100的整數，n為2～100的整數。Furthermore, m and n are the numbers of repeating units constituting the linear organohydropolysiloxane (B1) represented by formula (2), m is an integer of 2 to 150, and n is an integer of 2 to 150. Preferably, m is an integer of 2 to 100, and n is an integer of 2 to 100.
再者，直鏈狀有機氫聚矽氧烷（B1）可以僅單獨使用1種，亦可以組合使用2種以上。The linear organohydropolysiloxane (B1) may be used alone or in combination of two or more.
支鏈狀有機氫聚矽氧烷（B2）具有支鏈結構，因此為如下成分：形成交聯密度高的區域，對聚矽氧橡膠系中的交聯密度的疏密結構形成有很大貢獻。又，與上述直鏈狀有機氫聚矽氧烷（B1）同樣地，為如下聚合物：具有氫與Si直接鍵結之結構（≡Si-H），除了含乙烯基之有機聚矽氧烷（A）的乙烯基以外，與摻合於聚矽氧橡膠系硬化性組成物中之成分的乙烯基進行矽氫化反應，以使該等成分交聯。The branched organohydropolysiloxane (B2) has a branched structure and is a component that forms regions of high crosslink density, significantly contributing to the formation of a coarse and fine crosslinking structure within the silicone rubber system. Similar to the linear organohydropolysiloxane (B1), it is a polymer that has a structure in which hydrogen and Si are directly bonded (≡Si-H). In addition to the vinyl groups in the vinyl-containing organohydropolysiloxane (A), it undergoes a silylation reaction with the vinyl groups of components incorporated into the silicone rubber curable composition, thereby crosslinking these components.
又，支鏈狀有機氫聚矽氧烷（B2）的比重在0.9～0.95的範圍內。Furthermore, the specific gravity of the branched organohydropolysiloxane (B2) is in the range of 0.9 to 0.95.
進而，較佳為支鏈狀有機氫聚矽氧烷（B2）一般不具有乙烯基。藉此，能夠確實地防止在支鏈狀有機氫聚矽氧烷（B2）的分子內進行交聯反應。Furthermore, it is generally preferred that the branched organohydropolysiloxane (B2) does not have a vinyl group. This ensures that crosslinking reactions within the branched organohydropolysiloxane (B2) molecule can be prevented.
又，作為支鏈狀有機氫聚矽氧烷（B2），較佳為由下述平均組成式（c）表示者。Furthermore, the branched organohydropolysiloxane (B2) is preferably represented by the following average composition formula (c).
平均組成式（c） （Ha（R7）3-aSiO1/2）m（SiO4/2）n（在式（c）中，R7為一價的有機基，a為1～3的範圍的整數，m為Ha（R7）3-aSiO1/2單元的數量，n為SiO4/2單元的數量）Average composition formula (c) (Ha (R7 )3-a SiO1/2 )m (SiO4/2 )n (In formula (c), R7 is a monovalent organic group, a is an integer ranging from 1 to 3, m is the number of Ha (R7 )3-a SiO1/2 units, and n is the number of SiO4/2 units)
在式（c）中，R7為一價的有機基，較佳為碳數1～10的經取代或未經取代的烷基、芳基或者將該等組合而獲得之烴基。作為碳數1～10的烷基，例如可以列舉甲基、乙基、丙基等，其中，較佳為甲基。作為碳數1～10的芳基，例如可以列舉苯基。In formula (c),R⁷ is a monovalent organic group, preferably a substituted or unsubstituted alkyl group, an aryl group, or a alkyl group obtained by combining these groups having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of the aryl group having 1 to 10 carbon atoms include phenyl.
在式（c）中，a為氫化物基（與Si直接鍵結之氫原子）的數量，並且為1～3的範圍的整數，較佳為1。In formula (c), a represents the number of hydride groups (hydrogen atoms directly bonded to Si) and is an integer in the range of 1 to 3, preferably 1.
又，在式（c）中，m為Ha（R7）3-aSiO1/2單元的數量，n為SiO4/2單元的數量。In formula (c), m is the number ofHa (R7 )3- aSiO1/2 units, and n is the number of SiO4/2 units.
支鏈狀有機氫聚矽氧烷（B2）具有支鏈狀結構。直鏈狀有機氫聚矽氧烷（B1）和支鏈狀有機氫聚矽氧烷（B2）於其結構是直鏈狀還是支鏈狀這一方面不同，在將Si的數量設為1個時與Si鍵結之烷基R的數量（R/Si）在直鏈狀有機氫聚矽氧烷（B1）中為1.8～2.1而在支鏈狀有機氫聚矽氧烷（B2）中為0.8～1.7的範圍內。Branched organohydropolysiloxane (B2) has a branched structure. Linear organohydropolysiloxane (B1) and branched organohydropolysiloxane (B2) differ in whether their structures are linear or branched. When the number of Si atoms is set to 1, the number of alkyl groups R bonded to Si (R/Si) is 1.8 to 2.1 in the linear organohydropolysiloxane (B1) and 0.8 to 1.7 in the branched organohydropolysiloxane (B2).
再者，支鏈狀有機氫聚矽氧烷（B2）具有支鏈結構，因此例如在氮氣環境下，以升溫速度10℃/分鐘加熱至1000℃時的殘渣量成為5%以上。相對於此，直鏈狀有機氫聚矽氧烷（B1）為直鏈狀，因此在上述條件下進行加熱之後的殘渣量幾乎為零。Furthermore, because the branched organohydropolysiloxane (B2) has a branched structure, for example, when heated to 1000°C at a heating rate of 10°C/minute in a nitrogen atmosphere, the amount of residue becomes 5% or more. In contrast, because the linear organohydropolysiloxane (B1) is linear, the amount of residue after heating under the above conditions is almost zero.
又，作為支鏈狀有機氫聚矽氧烷（B2）的具體例，可以列舉具有由下述式（3）表示之結構者。Specific examples of the branched organohydropolysiloxane (B2) include those having a structure represented by the following formula (3).
式（3）中，R7為碳數1～8的經取代或未經取代的烷基、芳基或者將該等組合而獲得之烴基、或者氫原子。作為碳數1～8的烷基，例如可以列舉甲基、乙基、丙基等，其中，較佳為甲基。作為碳數1～8的芳基，例如可以列舉苯基。作為R7的取代基，例如可以列舉甲基等。In formula (3),R₇ is a substituted or unsubstituted alkyl group, an aryl group, or a alkyl group obtained by combining these groups, having 1 to 8 carbon atoms, or a hydrogen atom. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of the aryl group having 1 to 8 carbon atoms include phenyl groups. Examples of substituents forR₇ include methyl groups.
再者，式（3）中，複數個R7為彼此獨立者，可以彼此不同，亦可以相同。Furthermore, in formula (3), the plurality of R7 are independent of each other and may be different from each other or the same.
又，式（3）中，「-O-Si≡」表示Si具有三維擴展之支鏈結構。In formula (3), “-O-Si≡” indicates that Si has a three-dimensional extended branched chain structure.
再者，支鏈狀有機氫聚矽氧烷（B2）可以僅單獨使用1種，亦可以組合使用2種以上。The branched organohydropolysiloxane (B2) may be used alone or in combination of two or more.
又，在直鏈狀有機氫聚矽氧烷（B1）和支鏈狀有機氫聚矽氧烷（B2）中，與Si直接鍵結之氫原子（氫化物基）的量各自並無特別限定。但是，在聚矽氧橡膠系硬化性組成物中，相對於含乙烯基之直鏈狀有機聚矽氧烷（A1）中的乙烯基1莫耳，直鏈狀有機氫聚矽氧烷（B1）和支鏈狀有機氫聚矽氧烷（B2）的合計的氫化物基量較佳為成為0.5～5莫耳之量，更佳為成為1～3.5莫耳之量。藉此，能夠在直鏈狀有機氫聚矽氧烷（B1）及支鏈狀有機氫聚矽氧烷（B2）與含乙烯基之直鏈狀有機聚矽氧烷（A1）之間確實地形成交聯網路。The amount of hydrogen atoms (hydride groups) directly bonded to Si in the linear organohydropolysiloxane (B1) and the branched organohydropolysiloxane (B2) is not particularly limited. However, in the silicone rubber curable composition, the total amount of hydride groups in the linear organohydropolysiloxane (B1) and the branched organohydropolysiloxane (B2) is preferably 0.5 to 5 mol, more preferably 1 to 3.5 mol, per 1 mol of vinyl groups in the vinyl-containing linear organohydropolysiloxane (A1). Thereby, a cross-linking network can be reliably formed between the linear organohydropolysiloxane (B1), the branched organohydropolysiloxane (B2), and the vinyl group-containing linear organopolysiloxane (A1).
＜＜二氧化矽粒子（C）＞＞ 依需要，聚矽氧橡膠系硬化性組成物可以含有二氧化矽粒子（C）作為非導電性填料。並不限於二氧化矽粒子（C），亦可以含有其他非導電性填料。藉此，能夠謀求由導電性糊劑形成之彈性體的硬度和機械強度的提升。 作為非導電性填料，能夠使用公知的材料，例如可以使用二氧化矽粒子、聚矽氧橡膠粒子、滑石等。可以將該等單獨使用，亦可以組合2種以上來使用。<<Silica Particles (C)>>Optionally, the silicone rubber curable composition may contain silica particles (C) as a non-conductive filler. This is not limited to silica particles (C); other non-conductive fillers may also be included. This can enhance the hardness and mechanical strength of the elastomer formed from the conductive paste.Non-conductive fillers can be made from known materials, such as silica particles, silicone rubber particles, and talc. These materials may be used alone or in combination.
作為二氧化矽粒子（C），並無特別限定，例如使用氣相二氧化矽（fumed silica）、燒成二氧化矽、沉降二氧化矽等。可以將該等單獨使用，亦可以組合2種以上來使用。The silica particles (C) are not particularly limited, and for example, fumed silica, calcined silica, precipitated silica, etc. can be used. These can be used alone or in combination of two or more.
二氧化矽粒子（C）例如藉由BET法測得之比表面積例如較佳為50～400m²/g，更佳為100～400m²/g，進而較佳為200～400m²/g。 又，二氧化矽粒子（C）的平均一次粒徑例如較佳為1～100nm，更佳為5～20nm左右。The specific surface area of the silica particles (C), as measured by the BET method, is preferably 50 to 400 m²/g, more preferably 100 to 400 m²/g, and even more preferably 200 to 400 m²/g.The average primary particle size of the silica particles (C) is preferably 1 to 100 nm, more preferably 5 to 20 nm, for example.
藉由使用在該比表面積及平均粒徑的範圍內者作為二氧化矽粒子（C），能夠提升所形成之聚矽氧橡膠的硬度和機械強度，尤其能夠提升拉伸強度。By using silica particles (C) within the above-specified specific surface area and average particle size ranges, the hardness and mechanical strength of the resulting silicone rubber can be increased, particularly the tensile strength.
＜＜矽烷偶合劑（D）＞＞ 聚矽氧橡膠系硬化性組成物可以含有矽烷偶合劑（D）。 矽烷偶合劑（D）能夠具有水解性基。水解性基被水水解而成為羥基，該羥基與二氧化矽粒子（C）表面的羥基進行脫水縮合反應，從而能夠進行二氧化矽粒子（C）的表面改質。<<Silane Coupling Agent (D)>>The silicone rubber curable composition may contain a silane coupling agent (D).The silane coupling agent (D) may have a hydrolyzable group. These hydrolyzable groups are hydrolyzed by water to form hydroxyl groups. These hydroxyl groups undergo a dehydration condensation reaction with hydroxyl groups on the surface of the silica particles (C), thereby modifying the surface of the silica particles (C).
又，該矽烷偶合劑（D）能夠包含具有疏水基之矽烷偶合劑。藉此，推測為如下：在二氧化矽粒子（C）的表面賦予該疏水基，因此在聚矽氧橡膠系硬化性組成物中進而在聚矽氧橡膠中，二氧化矽粒子（C）的凝集力降低（基於由矽醇基進行之氫鍵之凝集變少），其結果，聚矽氧橡膠系硬化性組成物中的二氧化矽粒子的分散性提升。藉此，二氧化矽粒子與橡膠基質的界面增加，二氧化矽粒子的加強效果增加。進而，推測為如下：在橡膠的基質變形時，在基質內的二氧化矽粒子的潤滑性提升。然後，藉由二氧化矽粒子（C）的分散性的提升及潤滑性的提升，基於二氧化矽粒子（C）之聚矽氧橡膠的機械強度（例如，拉伸強度或撕裂強度等）提升。Furthermore, the silane coupling agent (D) can include a silane coupling agent having a hydrophobic group. This is presumed to impart the hydrophobic group to the surface of the silica particles (C), thereby reducing the cohesion of the silica particles (C) within the silicone rubber curable composition and, in turn, within the silicone rubber itself (due to reduced aggregation via hydrogen bonds via silanol groups). This results in improved dispersibility of the silica particles within the silicone rubber curable composition. This increases the interface between the silica particles and the rubber matrix, enhancing the reinforcing effect of the silica particles. Furthermore, it is presumed that, when the rubber matrix deforms, the lubricity of the silica particles within the matrix is enhanced. Then, due to the improved dispersibility and lubricity of the silica particles (C), the mechanical strength (e.g., tensile strength or tear strength) of the silicone rubber based on the silica particles (C) is improved.
進而，矽烷偶合劑（D）能夠包含具有乙烯基之矽烷偶合劑。藉此，在二氧化矽粒子（C）的表面導入乙烯基。因此，在使聚矽氧橡膠系硬化性組成物硬化時，亦即在「含乙烯基之有機聚矽氧烷（A）所具有之乙烯基與有機氫聚矽氧烷（B）所具有之氫化物基進行矽氫化反應而形成基於該等之網路（交聯結構）」時，二氧化矽粒子（C）所具有之乙烯基亦參與和有機氫聚矽氧烷（B）所具有之氫化物基的矽氫化反應，因此二氧化矽粒子（C）亦納入網路中。藉此，能夠謀求所形成之聚矽氧橡膠的低硬度化及高模數化。Furthermore, the silane coupling agent (D) can include a silane coupling agent having vinyl groups. This introduces vinyl groups onto the surface of the silica particles (C). Therefore, when the silicone rubber curable composition is cured, i.e., when the vinyl groups of the vinyl-containing organopolysiloxane (A) undergo a silylation reaction with the hydride groups of the organohydropolysiloxane (B) to form a network (crosslinked structure) based thereon, the vinyl groups of the silica particles (C) also participate in the silylation reaction with the hydride groups of the organohydropolysiloxane (B), thereby incorporating the silica particles (C) into the network. This can achieve lower hardness and higher modulus for the resulting silicone rubber.
作為矽烷偶合劑（D），能夠併用具有疏水基之矽烷偶合劑及具有乙烯基之矽烷偶合劑。As the silane coupling agent (D), a silane coupling agent having a hydrophobic group and a silane coupling agent having a vinyl group can be used in combination.
作為矽烷偶合劑（D），例如可以列舉由下述式（4）表示者。Examples of the silane coupling agent (D) include those represented by the following formula (4).
Yn-Si-（X）4-n……（4） 上述式（4）中，n表示1～3的整數。Y表示具有疏水基、親水基或乙烯基者中的任一個官能基，在n為1時為疏水基，在n為2或3時其中至少1個為疏水基。X表示水解性基。Yn -Si-(X)4-n ……(4) In the above formula (4), n represents an integer of 1 to 3. Y represents any functional group having a hydrophobic group, a hydrophilic group, or a vinyl group. When n is 1, it is a hydrophobic group. When n is 2 or 3, at least one of them is a hydrophobic group. X represents a hydrolyzable group.
疏水基為碳數1～6的烷基、芳基或者將該等組合而獲得之烴基，例如可以列舉甲基、乙基、丙基、苯基等，其中，尤其較佳為甲基。The hydrophobic group is an alkyl group or an aryl group having 1 to 6 carbon atoms, or a alkyl group obtained by combining these groups, for example, methyl group, ethyl group, propyl group, phenyl group, etc. Among them, methyl group is particularly preferred.
又，作為親水基，例如可以列舉羥基、磺酸基、羧基或羰基等，其中，尤其較佳為羥基。再者，親水基可以作為官能基而被包含，但是就對矽烷偶合劑（D）賦予疏水性等方面而言，較佳為不包含。Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, a carboxyl group, and a carbonyl group. Among these, a hydroxyl group is particularly preferred. Furthermore, a hydrophilic group may be included as a functional group, but is preferably not included from the perspective of imparting hydrophobicity to the silane coupling agent (D).
進而，作為水解性基，可以列舉如甲氧基、乙氧基的烷氧基、氯基或矽氮烷基等，其中，由於與二氧化矽粒子（C）的反應性高，因此較佳為矽氮烷基。再者，由於其結構上的特性，具有矽氮烷基作為水解性基者具有2個上述式（4）中的（Yn-Si-）的結構。Examples of hydrolyzable groups include methoxy, ethoxy, alkoxy, chlorine, and silazane groups. Among these, silazane groups are preferred due to their high reactivity with the silica particles (C). Furthermore, due to their structural characteristics, a silazane group having a hydrolyzable group has two (Yn -Si-) structures in the above formula (4).
關於由上述式（4）表示之矽烷偶合劑（D）的具體例，例如關於具有疏水基作為官能基者，可以列舉如「甲基三甲氧基矽烷、二甲基二甲氧基矽烷、苯基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、苯基三乙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、己基三甲氧基矽烷、己基三乙氧基矽烷、癸基三甲氧基矽烷」的烷氧基矽烷；如「甲基三氯矽烷、二甲基二氯矽烷、三甲基氯矽烷、苯基三氯矽烷」的氯矽烷；六甲基二矽氮烷，作為具有乙烯基作為官能基者，可以列舉如「甲基丙烯醯氧基丙基三乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷、甲基丙烯醯氧基丙基甲基二乙氧基矽烷、甲基丙烯醯氧基丙基甲基二甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基甲基二甲氧基矽烷」的烷氧基矽烷；如乙烯基三氯矽烷、乙烯基甲基二氯矽烷的氯矽烷；二乙烯基四甲基二矽氮烷，其中，若考慮上述記載，則作為具有疏水基者，尤其較佳為六甲基二矽氮烷，作為具有乙烯基者，尤其較佳為二乙烯基四甲基二矽氮烷。Specific examples of the silane coupling agent (D) represented by the above formula (4) include, for example, alkoxysilanes such as "methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane"; chlorosilanes such as "methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane"; hexamethyldisilazane as a silane having a vinyl group as an functional group; Examples of the silane having a hydrophobic group include alkoxysilanes such as "methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinylmethyldimethoxysilane"; chlorosilanes such as vinyltrichlorosilane and vinylmethyldichlorosilane; and divinyltetramethyldisilazane. Among these, considering the above description, hexamethyldisilazane is particularly preferred as the silane having a hydrophobic group, and divinyltetramethyldisilazane is particularly preferred as the silane having a vinyl group.
＜＜鉑或鉑化合物（E）＞＞ 本實施態樣的聚矽氧橡膠系硬化性組成物能夠含有鉑或鉑化合物（E）。 鉑或鉑化合物（E）為作為硬化時的觸媒而發揮作用之觸媒成分。鉑或鉑化合物（E）的添加量為觸媒量。<<Platinum or Platinum Compound (E)>>The silicone rubber curable composition of this embodiment may contain platinum or a platinum compound (E).The platinum or platinum compound (E) is a catalytic component that acts as a catalyst during curing. The amount of platinum or platinum compound (E) added is the catalytic amount.
作為鉑或鉑化合物（E），能夠使用公知者，例如可以列舉將鉑黑、鉑承載於二氧化矽或碳黑等中者、氯鉑酸或氯鉑酸的醇溶液、氯鉑酸與烯烴的錯鹽、氯鉑酸與乙烯基矽氧烷的錯鹽等。 再者，鉑或鉑化合物（E）可以僅單獨使用1種，亦可以組合使用2種以上。Known platinum or platinum compounds (E) can be used, including platinum black, platinum supported on silica or carbon black, chloroplatinic acid or an alcoholic solution of chloroplatinic acid, chloroplatinic acid and an alkene salt, and chloroplatinic acid and a vinylsiloxane salt.Platinum or platinum compounds (E) may be used alone or in combination of two or more.
又，可以代替鉑或鉑化合物（E）或與其併用而使用成分（E）以外的觸媒。作為成分（E）以外的觸媒，例如，可以列舉酮過氧化物類、二醯基過氧化物類、氫過氧化物類、二烷基過氧化物類、過氧縮酮類、烷基過氧酯類、過氧酯類及過氧二碳酸酯類等有機過氧化物等。Alternatively, a catalyst other than component (E) may be used in place of or in combination with platinum or a platinum compound (E). Examples of catalysts other than component (E) include organic peroxides such as ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxyesters, peroxyesters, and peroxydicarbonates.
＜＜水（F）＞＞ 再者，在本實施態樣的聚矽氧橡膠系硬化性組成物中，除了上述成分（A）～（E）以外，還可以含有水（F）。<<Water (F)>>The silicone rubber curable composition of this embodiment may contain water (F) in addition to the above-mentioned components (A) to (E).
水（F）為如下成分：作為使聚矽氧橡膠系硬化性組成物中所含之各成分分散之分散介質而發揮作用，並且對二氧化矽粒子（C）與矽烷偶合劑（D）的反應有貢獻。因此，在聚矽氧橡膠中，能夠使二氧化矽粒子（C）和矽烷偶合劑（D）更確實地彼此連結，從而能夠發揮整體上均勻的特性。Water (F) acts as a dispersion medium for dispersing the various components contained in the silicone rubber curable composition and contributes to the reaction between the silica particles (C) and the silane coupling agent (D). This ensures that the silica particles (C) and the silane coupling agent (D) are more securely bonded to each other within the silicone rubber, enabling uniform properties throughout the entire composition.
＜＜其他成分＞＞ 進而，本實施態樣的聚矽氧橡膠系硬化性組成物除了上述（A）～（F）成分以外，還能夠含有其他成分。作為該其他成分，例如可以列舉「矽藻土、氧化鐵、氧化鋅、氧化鈦、氧化鋇、氧化鎂、氧化鈰、碳酸鈣、碳酸鎂、碳酸鋅、玻璃棉、雲母」等二氧化矽粒子（C）以外的無機填料、反應抑制劑、分散劑、顏料、染料、抗靜電劑、抗氧化劑、阻燃劑、導熱性改良劑等添加劑。 作為二氧化矽粒子（C）以外的無機填充材料，例如，可以列舉矽藻土、氧化鐵、氧化鋅、氧化鈦、氧化鋇、氧化鎂、氧化鈰、碳酸鈣、碳酸鎂、碳酸鋅、玻璃棉、雲母等。<<Other Ingredients>>The silicone rubber curable composition of this embodiment may further contain other ingredients in addition to the above-mentioned components (A) to (F). Examples of such other ingredients include inorganic fillers other than the silica particles (C) such as diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, sulphur oxide, calcium carbonate, magnesium carbonate, zinc carbonate, glass wool, and mica, reaction inhibitors, dispersants, pigments, dyes, antistatic agents, antioxidants, flame retardants, and thermal conductivity improvers, among other additives.Examples of inorganic fillers other than silica particles (C) include diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, baic acid oxide, calcium carbonate, magnesium carbonate, zinc carbonate, glass wool, and mica.
此處，對聚矽氧橡膠系硬化性組成物之製造方法的一例進行說明。Here, an example of a method for producing a silicone rubber-based curable composition is described.
首先，藉由任意的混練裝置，將聚矽氧橡膠系硬化性組成物的各成分均勻地混合，從而製備聚矽氧橡膠系硬化性組成物。First, the various components of the silicone rubber curable composition are uniformly mixed using an arbitrary kneading device to prepare the silicone rubber curable composition.
[1]例如，稱量特定量的含乙烯基之有機聚矽氧烷（A）、二氧化矽粒子（C）及矽烷偶合劑（D），其後，藉由任意的混練裝置進行混練，從而獲得含有該等各成分（A）、（C）及（D）之混練物。[1] For example, a specific amount of vinyl group-containing organopolysiloxane (A), silica particles (C) and a silane coupling agent (D) are weighed and then kneaded using an arbitrary kneading device to obtain a mixture containing the components (A), (C) and (D).
再者，關於該混練物，較佳為預先將含乙烯基之有機聚矽氧烷（A）和矽烷偶合劑（D）進行混練，其後，將二氧化矽粒子（C）進行混練而獲得。藉此，更加提升含乙烯基之有機聚矽氧烷（A）中之二氧化矽粒子（C）的分散性。Furthermore, it is preferred that the mixture be obtained by pre-kneading the vinyl group-containing organopolysiloxane (A) and the silane coupling agent (D) and then kneading the silica particles (C). This further improves the dispersibility of the silica particles (C) in the vinyl group-containing organopolysiloxane (A).
又，可以設為如下：在獲得該混練物時，依據需要，將水（F）添加到各成分（A）、（C）及（D）的混練物中。藉此，能夠更確實地進行矽烷偶合劑（D）與二氧化矽粒子（C）的反應。Alternatively, water (F) may be added to the kneaded mixture of components (A), (C), and (D) as needed. This allows the reaction between the silane coupling agent (D) and the silica particles (C) to proceed more reliably.
進而，在含有水（F）之情況下，其含量能夠適當設定，具體而言，相對於矽烷偶合劑（D）100重量份例如較佳為在10～100重量份的範圍內，更佳為在30～70重量份的範圍內。藉此，能夠更確實地進行矽烷偶合劑（D）與二氧化矽粒子（C）的反應。Furthermore, when water (F) is present, its content can be appropriately adjusted. Specifically, it is preferably within the range of 10 to 100 parts by weight, and more preferably within the range of 30 to 70 parts by weight, relative to 100 parts by weight of the silane coupling agent (D). This ensures a more reliable reaction between the silane coupling agent (D) and the silica particles (C).
進而，各成分（A）、（C）及（D）的混練較佳為經過在第1溫度進行加熱之第1步驟和在第2溫度下進行加熱之第2步驟。藉此，在第1步驟中，能夠用矽烷偶合劑（D）對二氧化矽粒子（C）的表面進行表面處理，並且在第2步驟中，能夠從混練物中確實地去除在二氧化矽粒子（C）與矽烷偶合劑（D）的反應中所生成之副產物。其後，可以依據需要，在所獲得之混練物中添加成分（A），進而進行混練。藉此，能夠提升混練物的成分的親和性。Furthermore, kneading of components (A), (C), and (D) is preferably performed through a first step of heating at a first temperature and a second step of heating at a second temperature. This allows the surface of the silica particles (C) to be treated with the silane coupling agent (D) in the first step, and byproducts generated by the reaction between the silica particles (C) and the silane coupling agent (D) to be reliably removed from the kneaded mixture in the second step. Component (A) can then be added to the resulting kneaded mixture as needed and further kneaded. This improves the compatibility of the components in the kneaded mixture.
第1溫度例如較佳為40～120℃左右，例如更佳為60～90℃左右。第2溫度例如較佳為130～210℃左右，例如更佳為160～180℃左右。The first temperature is preferably about 40 to 120° C., for example, more preferably about 60 to 90° C. The second temperature is preferably about 130 to 210° C., for example, more preferably about 160 to 180° C., for example.
又，第1步驟中之環境較佳為如氮氣環境下的非活性環境下，第2步驟中之環境較佳為減壓環境下。Furthermore, the environment in step 1 is preferably an inert environment such as a nitrogen environment, and the environment in step 2 is preferably a reduced pressure environment.
進而，第1步驟的時間例如較佳為0.3～1.5小時左右，更佳為0.5～1.2小時左右。第2步驟的時間例如較佳為0.7～3.0小時左右，更佳為1.0～2.0小時左右。Furthermore, the time for the first step is preferably about 0.3 to 1.5 hours, more preferably about 0.5 to 1.2 hours, and the time for the second step is preferably about 0.7 to 3.0 hours, more preferably about 1.0 to 2.0 hours.
藉由將第1步驟及第2步驟設為如上所述的條件，能夠更顯著地獲得前述效果。By setting the conditions in steps 1 and 2 as described above, the aforementioned effects can be more significantly achieved.
[2]接著，稱量特定量的有機氫聚矽氧烷（B）和鉑或鉑化合物（E），其後，使用任意的混練裝置，在上述步驟[1]中所製備之混練物中混練各成分（B）、（E），從而獲得聚矽氧橡膠系硬化性組成物（彈性體組成物）。[2] Next, a specific amount of organohydropolysiloxane (B) and platinum or a platinum compound (E) is weighed, and then, using any mixing device, the components (B) and (E) are mixed with the mixture prepared in the above step [1] to obtain a silicone rubber-based curable composition (elastomer composition).
再者，在混練該各成分（B）、（E）時，較佳為預先將在上述步驟[1]中所製備之混練物和有機氫聚矽氧烷（B）進行混練，並將在上述步驟[1]中所製備之混練物和鉑或鉑化合物（E）進行混練，其後，將各自的混練物進行混練。藉此，能夠在不進行含乙烯基之有機聚矽氧烷（A）與有機氫聚矽氧烷（B）的反應的情況下，使各成分（A）～（E）確實地分散於聚矽氧橡膠系硬化性組成物中。Furthermore, when kneading the components (B) and (E), it is preferred to knead the mixture prepared in step [1] and the organohydropolysiloxane (B) in advance, and to knead the mixture prepared in step [1] and the platinum or platinum compound (E) in advance, and then knead the respective mixtures. In this way, the components (A) to (E) can be reliably dispersed in the silicone rubber curable composition without causing the reaction between the vinyl group-containing organopolysiloxane (A) and the organohydropolysiloxane (B).
關於混練各成分（B）、（E）時的溫度，作為輥設定溫度，例如較佳為10～70℃左右，更佳為25～30℃左右。The temperature during kneading of the components (B) and (E) is preferably about 10 to 70°C, more preferably about 25 to 30°C, as the roll setting temperature.
進而，混練時間例如較佳為5分鐘～1小時左右，更佳為10～40分鐘左右。Furthermore, the kneading time is preferably about 5 minutes to 1 hour, more preferably about 10 to 40 minutes.
在上述步驟[1]及上述步驟[2]中，藉由將溫度設在上述範圍內，能夠更確實地防止或抑制含乙烯基之有機聚矽氧烷（A）與有機氫聚矽氧烷（B）的反應的進行。又，在上述步驟[1]及上述步驟[2]中，藉由將混練時間設在上述範圍內，能夠使各成分（A）～（E）更確實地分散於聚矽氧橡膠系硬化性組成物中。In the above steps [1] and [2], by setting the temperature within the above range, the reaction between the vinyl group-containing organopolysiloxane (A) and the organohydropolysiloxane (B) can be more reliably prevented or suppressed. In addition, in the above steps [1] and [2], by setting the kneading time within the above range, the components (A) to (E) can be more reliably dispersed in the silicone rubber curable composition.
再者，作為在各步驟[1]、[2]中所使用之混練裝置，並無特別限定，例如能夠使用捏合機、2輥研磨機、班布里混合機（連續捏合機）、加壓捏合機等。Furthermore, the kneading apparatus used in each step [1] and [2] is not particularly limited, and for example, a kneader, a two-roll mill, a Banbury mixer (continuous kneader), a pressure kneader, etc. can be used.
又，可以設為如下：在本步驟[2]中，在混練物中添加如1-乙炔基環己醇的反應抑制劑。藉此，即使將混練物的溫度設定為相對高的溫度，亦能夠更確實地防止或抑制含乙烯基之有機聚矽氧烷（A）與有機氫聚矽氧烷（B）的反應的進行。 藉由以上步驟[2]，作為彈性體組成物，獲得聚矽氧橡膠系硬化性組成物。Alternatively, a reaction inhibitor such as 1-ethynylcyclohexanol may be added to the mixture in this step [2]. This allows the reaction between the vinyl group-containing organopolysiloxane (A) and the organohydropolysiloxane (B) to be more reliably prevented or inhibited even when the temperature of the mixture is set to a relatively high temperature. By performing the above step [2], a silicone rubber curable composition is obtained as an elastomer composition.
（導電性填料） 導電性填料可以使用公知的導電材料，例如可以包含選自由粉末狀或纖維狀的金屬系填料、碳系填料（導電性碳材料）、金屬氧化物填料及鍍金屬填料組成之群中的一個或兩個以上。其中，可以是金屬系填料，亦可以是如以下的金屬粉末（G）。(Conductive Filler)The conductive filler can be a known conductive material. For example, it can include one or more selected from the group consisting of powdered or fibrous metal fillers, carbon fillers (conductive carbon materials), metal oxide fillers, and plated metal fillers. The metal filler can be either a metal filler or a metal powder (G) as described below.
構成金屬粉末（G）之金屬並無特別限定，例如能夠包含銅、銀、金、鎳、錫、鉛、鋅、鉍、銻或使該等合金化之金屬粉末中的至少一種或者該等之中的兩種以上。 該等之中，作為金屬粉末（G），就導電性高和獲得容易性高的方面而言，較佳為包含銀或銅、亦即包含銀粉或銅粉。 再者，該等金屬粉末（G）亦能夠使用由其他種類的金屬塗布者。The metal constituting the metal powder (G) is not particularly limited. For example, the metal powder (G) may include at least one of copper, silver, gold, nickel, tin, lead, zinc, bismuth, antimony, or alloyed metal powders thereof, or two or more of these metal powders.Among these metal powders, the metal powder (G) preferably includes silver or copper, i.e., silver powder or copper powder, due to its high electrical conductivity and ease of availability.Furthermore, the metal powder (G) may also be coated with other types of metals.
金屬粉末（G）的形狀並無特別限制，但是能夠使用樹枝狀、球狀、鱗片狀等以往使用者。其中，可以使用鱗片狀的金屬粉末（G）。The shape of the metal powder (G) is not particularly limited, but conventional shapes such as branch-shaped, spherical, and scaly shapes can be used. Among them, scaly-shaped metal powder (G) can be used.
又，金屬粉末（G）或磷片狀的金屬粉末（G）的粒徑的下限並無特別限制，但是以平均粒徑D50計，例如為0.001μm以上，較佳為0.01μm以上，更佳為0.1μm以上，進而較佳為1μm以上。 關於金屬粉末（G）或磷片狀的金屬粉末（G）的粒徑的上限，以平均粒徑D50計，例如為1,000μm以下，較佳為100μm以下，更佳為50μm以下，進而較佳為20μm以下。 藉由將平均粒徑D50設定在此種範圍內，能夠作為導電性糊劑的彈性體發揮適當的導電性。 又，導電性填料或金屬粉末（G）的BET比表面積的下限例如為0.1m²/g以上，較佳為0.5m²/g以上，更佳為1.0m²/g以上。藉此，能夠提高伸長時的導電性。 另一方面，導電性填料或金屬粉末（G）的BET比表面積的上限例如為5m²/g以下，較佳為3m²/g以下，更佳為2m²/g。藉此，能夠將糊劑黏度抑制的較低。 再者，金屬粉末（G）的粒徑能夠定義為如下：在用穿透型電子顯微鏡等觀察導電性糊劑或該彈性體之後，進行影像分析，並獲取任意選擇之金屬粉末200個的平均值。The lower limit of the particle size of the metal powder (G) or the flaky metal powder (G) is not particularly limited, but the average particle sizeD50 is, for example, 0.001 μm or greater, preferably 0.01 μm or greater, more preferably 0.1 μm or greater, and further preferably 1 μm or greater. The upper limit of the particle size of the metal powder (G) or the flaky metal powder (G) is, for example, 1,000 μm or less, preferably 100 μm or less, more preferably 50 μm or less, and further preferably 20 μm or less, as measured by the average particle sizeD50 . By setting the average particle sizeD50 within this range, the elastomer in the conductive paste can exhibit appropriate conductivity. The lower limit of the BET specific surface area of the conductive filler or metal powder (G) is, for example, 0.1 m²/g or greater, preferably 0.5 m²/g or greater, and more preferably 1.0 m²/g or greater. This improves conductivity during elongation. On the other hand, the upper limit of the BET specific surface area of the conductive filler or metal powder (G) is, for example, 5 m²/g or less, preferably 3 m²/g or less, and more preferably 2 m²/g. This helps to keep the paste viscosity low. Furthermore, the particle size of the metal powder (G) can be defined as follows: after observing the conductive paste or the elastomer using a transmission electron microscope, for example, and then performing image analysis, the average value of 200 randomly selected metal powders is obtained.
（非水系溶劑） 作為非水系溶劑，能夠使用公知的各種非水系溶劑，例如，能夠包含高沸點非水系溶劑。可以將該等單獨使用，亦可以組合2種以上來使用。(Non-aqueous Solvent)Various known non-aqueous solvents can be used as the non-aqueous solvent, including, for example, high-boiling-point non-aqueous solvents. These solvents may be used alone or in combination of two or more.
上述高沸點非水系溶劑的沸點的下限值例如為100℃以上，較佳為130℃以上，更佳為150℃以上。藉此，能夠提升網版印刷等的印刷穩定性。另一方面，上述高沸點非水系溶劑的沸點的上限值並無特別限定，例如可以為300℃以下，亦可以為290℃以下，亦可以為280℃以下。藉此，能夠抑制形成配線時的過度的熱歷程，因此能夠防止對基底基板的損壞，並且良好地維持由導電性糊劑形成之配線的形狀。 又，高沸點非水系溶劑的沸點的上限可以為250℃以下，亦可以為240℃以下，亦可以為200℃以下。藉此，能夠抑制導電性糊劑硬化時硬化物中的溶劑的殘留。The lower limit of the boiling point of the high-boiling-point non-aqueous solvent is, for example, 100°C or higher, preferably 130°C or higher, and more preferably 150°C or higher. This improves printing stability during screen printing and other processes. Meanwhile, the upper limit of the boiling point of the high-boiling-point non-aqueous solvent is not particularly limited and can be, for example, 300°C or lower, 290°C or lower, or 280°C or lower. This can suppress excessive thermal history during wiring formation, thereby preventing damage to the base substrate and maintaining the shape of the wiring formed with the conductive paste.The upper limit of the boiling point of the high-boiling-point non-aqueous solvent can be 250°C or lower, 240°C or lower, or even 200°C or lower. This can prevent residual solvent from remaining in the cured product during the curing of the conductive paste.
又，作為非水系溶劑，就彈性體組成物的溶解性或沸點的方面而言，能夠適當選擇，但是例如能夠包含碳數5以上且20以下的脂肪族烴、較佳為碳數8以上且18以下的脂肪族烴、更佳為碳數10以上且15以下的脂肪族烴。The non-aqueous solvent can be appropriately selected from the perspective of the solubility or boiling point of the elastomer composition, and may contain, for example, an aliphatic hydrocarbon having 5 to 20 carbon atoms, preferably an aliphatic hydrocarbon having 8 to 18 carbon atoms, and more preferably an aliphatic hydrocarbon having 10 to 15 carbon atoms.
又，作為非水系溶劑的一例，例如可以例示戊烷、己烷、環己烷、庚烷、甲基環己烷、乙基環己烷、辛烷、癸烷、十二烷、十四烷等脂肪族烴類；苯、甲苯、乙苯、二甲苯、對稱三甲苯、三氟甲苯（trifluoromethyl benzene）、苯并三氟（benzotrifluoride）等芳香族烴類；二乙醚、二異丙醚、二丁醚、環戊基甲醚、環戊基乙醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇單丁醚、二丙二醇二甲醚、二丙二醇甲基-正丙醚、1,4-二㗁烷、1,3-二㗁烷、四氫呋喃等醚類；二氯甲烷、氯仿、1,1-二氯乙烷、1,2-二氯乙烷、1,1,1-三氯乙烷、1,1,2-三氯乙烷等鹵烷類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等羧酸醯胺類；二甲基亞碸、二乙基亞碸等亞碸類；碳酸二乙酯等酯類等。可以將該等單獨使用，亦可以組合2種以上來使用。 在此使用之溶劑只要從能夠使上述導電性糊劑中的組成成分均勻地溶解並分散之溶劑中適當選擇即可。Examples of non-aqueous solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, methylcyclohexane, ethylcyclohexane, octane, decane, dodecane, and tetradecane; benzene, toluene, ethylbenzene, xylene, trimethylbenzene, and trifluoromethylbenzene. Aromatic hydrocarbons such as benzene), benzotrifluoride; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, 1,4-dioxane, 1,3-dioxane, and tetrahydrofuran; halides such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, and 1,1,2-trichloroethane; carboxylic acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; esters such as diethyl carbonate, etc. These can be used individually or in combination.The solvent used here can be appropriately selected from solvents that can uniformly dissolve and disperse the components of the conductive paste.
又，非水系溶劑能夠包含第1非水系溶劑，該第1非水系溶劑的漢森溶解度參數（Hansen solubility parameter）的極性項（δp）的上限值例如為10MPa1/2以下，較佳為7MPa1/2以下，更佳為5.5MPa1/2以下。藉此，能夠使聚矽氧橡膠系硬化性樹脂組成物等彈性體組成物在導電性糊劑中的分散性和溶解性良好。該第1非水系溶劑的上述極性項（δp）的下限值並無特別限定，例如可以為0Pa1/2以上。Furthermore, the non-aqueous solvent can include a first non-aqueous solvent, wherein the upper limit of the polarity term (δp ) of the Hansen solubility parameter of the first non-aqueous solvent is, for example, 10 MPa1/2 or less, preferably 7 MPa1/2 or less, and more preferably 5.5 MPa1/2 or less. This improves the dispersibility and solubility of an elastomer composition, such as a silicone rubber-based curable resin composition, in the conductive paste. The lower limit of the polarity term (δp ) of the first non-aqueous solvent is not particularly limited and can be, for example, 0 Pa1/2 or greater.
上述第1非水系溶劑中之漢森溶解度參數的氫鍵項（δh）的上限值例如為20MPa1/2以下，較佳為10MPa1/2以下，更佳為7MPa1/2以下。藉此，能夠使聚矽氧橡膠系硬化性樹脂組成物等彈性體組成物在導電性糊劑中的分散性和溶解性良好。該第1非水系溶劑的上述氫鍵項（δh）的下限值並無特別限定，例如可以為0Pa1/2以上。The upper limit of the hydrogen bonding term (δh ) of the Hansen solubility parameter in the first non-aqueous solvent is, for example, 20 MPa1/2 or less, preferably 10 MPa1/2 or less, and even more preferably 7 MPa1/2 or less. This improves the dispersibility and solubility of elastomer compositions, such as silicone rubber-based curable resin compositions, in the conductive paste. The lower limit of the hydrogen bonding term (δh ) in the first non-aqueous solvent is not particularly limited and can be, for example, 0 Pa1/2 or greater.
漢森溶解度參數（HSP）為表示某種物質在另一某種物質中溶解多少的溶解性之指標。HSP由三維向量表示溶解性。典型地，該三維向量能夠由分散項（δd）、極性項（δp）、氫鍵項（δh）表示。然後，向量相似者彼此能夠判斷為溶解性高。能夠由漢森溶解度參數的距離（HSP距離）來判斷向量的相似度。The Hansen Solubility Parameter (HSP) is a solubility indicator that indicates how well one substance dissolves in another. The HSP represents solubility as a three-dimensional vector. Typically, this three-dimensional vector is represented by a dispersion term (δd ), a polar term (δp ), and a hydrogen bonding term (δh ). Similar vectors can be considered highly soluble. The similarity of vectors can be determined by the distance between their Hansen Solubility Parameters (HSP distance).
關於在本說明書中所使用之漢森溶解度參數（HSP值），能夠使用HSPiP（Hansen Solubility Parameters in Practice）等軟體來算出。在此，在由Hansen和Abbott開發之電腦軟體HSPiP中包含計算HSP距離之功能及記載了各式各樣的樹脂和非水系溶劑或水系溶劑的漢森參數之數據庫。 調查各樹脂對於「純非水系溶劑」及「良非水系溶劑與不良非水系溶劑的混合非水系溶劑」之溶解性，將其結果輸入至HSPiP軟體，並算出D：分散項、P：極性項、H：氫鍵項、R0：溶解球半徑。The Hansen Solubility Parameters (HSP values) used in this manual can be calculated using software such as HSPiP (Hansen Solubility Parameters in Practice). HSPiP, a computer software developed by Hansen and Abbott, includes functionality for calculating HSP distances and a database of Hansen parameters for various resins and non-aqueous and aqueous solvents.The solubility of each resin in pure non-aqueous solvents and mixtures of good and poor non-aqueous solvents is investigated and input into HSPiP to calculate D (dispersion term), P (polar term), H (hydrogen bond term), and R0 (solvation sphere radius).
作為非水系溶劑，例如能夠選擇彈性體或構成彈性體之構成單元與非水系溶劑的HSP距離、極性項或氫鍵項的差分較小者。As the non-aqueous solvent, for example, an elastomer or a constituent unit of the elastomer can be selected in which the difference between the HSP distance, polarity term, or hydrogen bonding term of the non-aqueous solvent is small.
以上，對本發明的實施態樣進行了敘述，但是該等為本發明的示例，能夠採用上述以外的各式各樣的構成。又，本發明並不限定於上述實施態樣，並且能夠達成本發明的目的之範圍內的變形、改良等包含在本發明中。 以下，附記參考態樣的例子。 1.一種導電性糊劑，其含有： 彈性體組成物、 導電性填料、及 非水系溶劑； 依照JIS K5600-2-5：1999，並使用細度計測量之該導電性糊劑的分散度為40μm以下。 2.如1.之導電性糊劑，其中， 在25℃條件下以20[1/s]的剪切速度測量時的該導電性糊劑的黏度為1Pa•s以上且100Pa•s以下。 3.如1.或2.之導電性糊劑，其中， 關於該導電性糊劑，在25℃條件下，將以1[1/s]的剪切速度測量時的黏度設為η1，並且將以5[1/s]的剪切速度測量時的黏度設為η5時，藉由η1/η5算出之觸變指數為1.0以上且3.0以下。 4.如1.至3.中任一項之導電性糊劑，其含有非導電性填料。 5.如1.至4.中任一項之導電性糊劑，其中， 前述彈性體組成物包含用於形成選自由聚矽氧橡膠、胺酯橡膠、氟橡膠組成之群中之一種以上的彈性體之熱固性彈性體組成物。 6.如1.至5.中任一項之導電性糊劑，其中， 前述非水系溶劑包含沸點為100℃以上且300℃以下之高沸點非水系溶劑。 7.如1.至6.中任一項之導電性糊劑，其中， 在該導電性糊劑100質量%中，前述導電性填料的含量為30質量%以上且85質量%以下。 8.一種導電性糊劑之製造方法，其包括下述混合步驟： 在攪拌槽中使用攪拌翼對含有彈性體組成物、導電性填料及非水系溶劑的原料成分進行攪拌之後，使用自轉公轉攪拌機進行混練，藉此獲得導電性糊劑。 [實施例]The above descriptions describe embodiments of the present invention. However, these are merely examples of the present invention, and various configurations other than those described above may be employed. Furthermore, the present invention is not limited to the above embodiments, and modifications and improvements that achieve the objectives of the present invention are encompassed by the present invention.Examples of reference embodiments are provided below.1. A conductive paste comprising:an elastomer composition,a conductive filler, anda non-aqueous solvent;the conductive paste having a dispersion of 40 μm or less, as measured using a micrometer in accordance with JIS K5600-2-5:1999.2. The conductive paste according to 1., wherein:The viscosity of the conductive paste, when measured at a shear rate of 20 [1/s] at 25°C, is 1 Pa·s or greater and 100 Pa·s or less.3. The conductive paste according to 1. or 2., wherein:Regarding the conductive paste, when measured at a shear rate of 1 [1/s] at 25°C, η1 is defined as the viscosity thereof, and when measured at a shear rate of 5 [1/s] is defined as η5, the throttling index calculated as η1/η5 is 1.0 or greater and 3.0 or less.4. The conductive paste according to any one of 1. to 3., containing a non-conductive filler.5. The conductive paste according to any one of 1. to 4., wherein the elastomer composition comprises a thermosetting elastomer composition for forming an elastomer selected from the group consisting of silicone rubber, urethane rubber, and fluororubber.6. The conductive paste according to any one of 1. to 5., wherein the non-aqueous solvent comprises a high-boiling-point non-aqueous solvent having a boiling point of 100°C to 300°C.7. The conductive paste according to any one of 1. to 6., wherein the content of the conductive filler is 30% to 85% by mass based on 100% by mass of the conductive paste. 8. A method for producing a conductive paste, comprising the following mixing step:After stirring raw materials containing an elastomer composition, a conductive filler, and a non-aqueous solvent in a stirring tank using a stirring blade, the mixture is kneaded using a rotary stirrer to obtain a conductive paste.[Example]
以下，參閱實施例對本發明進行詳細說明，但本發明並不受該等實施例的記載的任何限定。Hereinafter, the present invention will be described in detail with reference to the embodiments, but the present invention is not limited in any way by the description of these embodiments.
＜彈性體組成物＞ 以特定比例混合含乙烯基之有機聚矽氧烷（A）、矽烷偶合劑（D）及水（F），並添加特定量的二氧化矽粒子（C）進而進行混合，從而獲得了聚矽氧橡膠複合物。 對於聚矽氧橡膠複合物，添加特定量的作為交聯劑的有機氫聚矽氧烷（B）、作為觸媒的鉑或鉑化合物（E）、及反應抑制劑並進行混合，從而獲得了彈性體組成物（聚矽氧橡膠系硬化性組成物）。<Elastomer Composition>A vinyl group-containing organopolysiloxane (A), a silane coupling agent (D), and water (F) are mixed in specific proportions, and a specific amount of silica particles (C) are added and mixed to obtain a silicone rubber compound.Specific amounts of an organohydropolysiloxane (B) as a crosslinking agent, platinum or a platinum compound (E) as a catalyst, and a reaction inhibitor are added and mixed to the silicone rubber compound to obtain an elastomer composition (silicone rubber curing composition).
＜導電性糊劑的製造＞ [實施例1] 將特定量的癸烷（非水系溶劑，沸點174℃）添加至所獲得之彈性體組成物中並進行混合，獲得了混合物。在25℃、剪切速度20〔1/s〕的條件下，使用E型黏度計（東機產業公司（TOKI SANGYO CO., LTD.）製造，TPE-100H）測量而得之混合物的黏度為15Pa•s。 對所獲得之混合物進而混合了銀粉A（導電性填料，BET比表面積：1.5m²/g）之後，在轉速15rpm、10分鐘的攪拌條件下，使用附錨翼之攪拌機（Three One Motor（註冊商標），新東科學公司（SHINTO Scientific Co., Ltd.）製造）進行了攪拌。其後，使用自轉/公轉攪拌機（Awatori Rentaro（註冊商標），THINKY公司製造）進行充分混練，從而獲得了實施例1的導電性糊劑。 [實施例2] 將特定量的十四烷（非水系溶劑，沸點253℃）添加至所獲得之彈性體組成物中並進行混合，獲得了混合物。在25℃、剪切速度20〔1/s〕的條件下，使用E型黏度計（東機產業公司（TOKI SANGYO CO., LTD.）製造，TPE-100H）測量而得之混合物的黏度為20Pa•s。 對所獲得之混合物進而混合了銀粉A（導電性填料，BET比表面積：1.5m²/g）之後，在轉速15rpm、10分鐘的攪拌條件下，使用附錨翼之攪拌機（Three One Motor（註冊商標），新東科學公司（SHINTO Scientific Co., Ltd.）製造）進行了攪拌。其後，使用自轉/公轉攪拌機（Awatori Rentaro（註冊商標），THINKY公司製造）進行充分混練。藉由進而使用三輥研磨機進行追加混練，獲得了實施例2的導電性糊劑。 [實施例3] 將特定量的癸烷（非水系溶劑，沸點174℃）添加至所獲得之彈性體組成物中並進行混合，獲得了混合物。在25℃、剪切速度20〔1/s〕的條件下，使用E型黏度計（東機產業公司（TOKI SANGYO CO., LTD.）製造，TPE-100H）測量而得之混合物的黏度為12Pa•s。 對所獲得之混合物進而混合了銀粉B（導電性填料，BET比表面積：0.7m²/g）之後，在轉速15rpm、10分鐘的攪拌條件下，使用附錨翼之攪拌機（Three One Motor（註冊商標），新東科學公司（SHINTO Scientific Co., Ltd.）製造）進行了攪拌。其後，使用自轉/公轉攪拌機（Awatori Rentaro（註冊商標），THINKY公司製造）進行充分混練，從而獲得了實施例3的導電性糊劑。<Production of Conductive Paste>[Example 1]A specific amount of decane (non-aqueous solvent, boiling point 174°C) was added to the obtained elastomer composition and mixed to obtain a mixture. The viscosity of the mixture, measured at 25°C and a shear rate of 20 [1/s] using an E-type viscometer (TPE-100H, manufactured by Toki Sangyo Co., Ltd.), was 15 Pa·s. The resulting mixture was further mixed with silver powder A (conductive filler, BET specific surface area: 1.5 m²/g) and stirred at 15 rpm for 10 minutes using a stirrer with anchor blades (Three One Motor (registered trademark), manufactured by Shinto Scientific Co., Ltd.). The mixture was then thoroughly kneaded using a rotary/orbital stirrer (Awatori Rentaro (registered trademark), manufactured by Thinky Co., Ltd.) to obtain the conductive paste of Example 1.[Example 2]A specific amount of tetradecane (non-aqueous solvent, boiling point 253°C) was added to the resulting elastomer composition and mixed to obtain a mixture. The viscosity of the mixture, measured at 25°C and a shear rate of 20 [1/s] using an E-type viscometer (TPE-100H, manufactured by Toki Sangyo Co., Ltd.), was 20 Pa·s.The resulting mixture was further mixed with silver powder A (conductive filler, BET specific surface area: 1.5 m²/g) and stirred at 15 rpm for 10 minutes using an anchor stirrer (Three One Motor (registered trademark), manufactured by Shinto Scientific Co., Ltd.). The mixture was then thoroughly kneaded using a rotary/revolving stirrer (Awatori Rentaro (registered trademark), manufactured by Thinky). Additional kneading was performed using a three-roll mill to obtain the conductive paste of Example 2.[Example 3]A specific amount of decane (non-aqueous solvent, boiling point 174°C) was added to the obtained elastomer composition and mixed to obtain a mixture. The viscosity of the mixture, measured at 25°C and a shear rate of 20 [1/s] using an E-type viscometer (TPE-100H, manufactured by TOKI SANGYO CO., LTD.), was 12 Pa·s. The resulting mixture was further mixed with silver powder B (a conductive filler with a BET specific surface area of 0.7 m²/g) and stirred at 15 rpm for 10 minutes using a stirrer with anchor blades (Three One Motor (registered trademark), manufactured by SHINTO Scientific Co., Ltd.). The mixture was then thoroughly kneaded using a rotary/revolving stirrer (Awatori Rentaro (registered trademark), manufactured by THINKY Co., Ltd.) to obtain the conductive paste of Example 3.
[比較例1] 未使用上述攪拌機及自轉/公轉攪拌機而藉由使用人手的手工攪拌進行攪拌、混練，除此之外，以與實施例1相同的方式，獲得了比較例1的導電性糊劑。 在比較例1中，在所獲得之導電性糊劑中各處看見塊（結塊）。推測該塊為源自彈性體組成物之塊。再者，在實施例1～3中，未確認到攪拌後的混合物中存在上述塊。 [比較例2] 將混合物中所含之癸烷的添加量調整得較少，獲得黏度成為130Pa•s之混合物，將銀粉A添加到該混合物中之後，使用附錨翼之攪拌機進行了攪拌，除此之外，設為與實施例1相同的條件。 在比較例2中，使用了附錨翼之攪拌機開始攪拌，但在途中無法繼續攪拌上述混合物。在攪拌無法進行的時間點，結束了製程。[Comparative Example 1]A conductive paste according to Comparative Example 1 was obtained in the same manner as in Example 1, except that the aforementioned stirrer and rotary/revolutionary stirrer were not used, and manual stirring was used for mixing and kneading.In Comparative Example 1, lumps (agglomerates) were observed in various locations in the resulting conductive paste. These lumps are presumably derived from the elastomer composition. Furthermore, no such lumps were observed in the stirred mixtures of Examples 1-3.[Comparative Example 2]The same conditions as in Example 1 were used, except that the amount of decane added to the mixture was adjusted to a smaller amount, resulting in a mixture with a viscosity of 130 Pa·s. Silver powder A was added to the mixture and then stirred using an anchored stirrer.In Comparative Example 2, stirring was initiated using the anchored stirrer, but the mixture became unstable midway through. The process was terminated at this point.
[導電性糊劑的評價] 根據以下項目對所獲得之導電性糊劑進行了評價。[Evaluation of Conductive Paste]The obtained conductive paste was evaluated based on the following criteria.
＜細度計之值的測量＞ 如下，依照JIS K5600-2-5：1999，測量了所獲得之導電性糊劑中之細度計之值。 首先，將乾淨且乾燥的細度計置於平滑且水平且不滑動的表面上。 接著，在25℃的室溫條件下，使用刮刀將試樣充分攪拌混合後，將足夠量的試樣（導電性糊劑）流入溝槽的較深側的前端，使其稍微溢出溝。 接著，用雙手的拇指和其他手指之間夾住刮刀，使刮刀的長邊與量規的寬度方向平行，並且使刃尖接觸量規的溝槽的較深的前端。一邊使刮刀垂直地保持於量規的表面，一邊以相對於溝槽的長邊方向成直角的方式並以均等的速度經1～2秒鐘將量規的表面拉引到溝槽的深度0的位置。對刮刀施加足夠的力，以使溝槽被試樣填滿，並去除多餘的部分。 其後，在拉引結束後的3秒鐘內，以相對於溝槽的長邊成直角並以相對於量規的表面成20°以上30°以下的角度的觀察方向，照射光並進行觀察，以使容易看到試樣的圖案。 在上述觀察中，讀取出現於溝槽中之複數個斑點中最初出現之斑點的位置的量規刻度，並將其設為細度計之值（μm）。<Measurement of Fineness Gauge Value>The fineness gauge value of the obtained conductive paste was measured as follows in accordance with JIS K5600-2-5:1999.First, place a clean, dry fineness gauge on a smooth, level, non-slip surface.Next, at room temperature of 25°C, thoroughly mix the sample with a spatula. Then, pour a sufficient amount of the sample (conductive paste) into the deep end of the groove, slightly overflowing the groove.Next, hold the spatula between your thumb and fingers, aligning the long side of the spatula parallel to the width of the gauge, with the tip of the blade touching the deep end of the groove of the gauge. While holding the scraper perpendicular to the gauge surface, pull the gauge surface at a constant speed, perpendicular to the long side of the groove, over 1-2 seconds until the groove depth reaches zero. Apply sufficient force to the scraper to completely fill the groove with the sample, removing any excess.Then, within 3 seconds of completion of the pull, illuminate the surface with light, observing it at an angle of 20° to 30° relative to the long side of the groove and perpendicular to the gauge surface, ensuring that the sample pattern is easily visible.During this observation, read the gauge scale at the location of the first spot to appear among the multiple spots appearing in the groove, and use this value as the micrometer reading (μm).
（上述測量中使用之細度計） 材質：不銹鋼製 尺寸：長度約165mm，寬度35mm，厚度13mm 溝槽：2條，長度約125mm，寬度12mm 溝槽的最大深度：100μm 刻度間隔：10μm 測量範圍：0～100μm(Gage used in the above measurements)Material: Stainless steelDimensions: Approximately 165mm long, 35mm wide, 13mm thickGrooves: 2, approximately 125mm long, 12mm wideMaximum groove depth: 100μmScale interval: 10μmMeasuring range: 0-100μm
（上述測量中使用之刮刀） 材質：不銹鋼製 刃尖：兩側、長邊為直線，R：約0.25 尺寸：長度約50mm，寬度約38mm，厚度約5mm(Scraper used in the above measurements)Material: Stainless steelTip: Both sides and the long side are straight, R: approximately 0.25Dimensions: Length approximately 50mm, Width approximately 38mm, Thickness approximately 5mm
實施3次上述細度計之值的測量，並計算出其平均值。 其結果，細度計之值為如下： 實施例1為21μm， 實施例2為8μm， 實施例3為32μm， 比較例1為超過40μm。The above-mentioned gage values were measured three times, and the average value was calculated.The gage values were as follows:Example 1: 21 μm,Example 2: 8 μm,Example 3: 32 μm,Comparative Example 1: over 40 μm.
＜黏度＞ 關於所獲得之導電性糊劑，使用東機產業公司製造的TPE-100H（E型黏度計），在導電性糊劑的製作後立即測量25℃條件下的剪切速度20〔1/s〕時的黏度。黏度的單位為Pa•s。 在實施例1中，25℃條件下的黏度為20Pa•s。<Viscosity>The viscosity of the resulting conductive paste was measured immediately after preparation at a shear rate of 20 [1/s] at 25°C using a TPE-100H (E-type viscometer) manufactured by Toki Sangyo Co., Ltd. The unit of viscosity is Pa·s.In Example 1, the viscosity at 25°C was 20 Pa·s.
＜觸變指數＞ 關於所獲得之導電性糊劑，在25℃的條件下，將以剪切速度1〔1/s〕測量時之黏度設為η1，並且將以剪切速度5〔1/s〕測量時之黏度設為η5，使用東機產業公司製造的TPE-100H（E型黏度計），在導電性糊劑的製作後立即測量各自的黏度。黏度的單位為Pa•s。藉由η1/η5黏度比求出了觸變指數。 在實施例1中，觸變指數為1.7。<Trigger Index>The viscosity of the resulting conductive paste was measured immediately after preparation at 25°C using a TPE-100H (E-type viscometer) manufactured by Toki Sangyo Co., Ltd., with the viscosity measured at a shear rate of 1 [1/s] as η1 and the viscosity measured at a shear rate of 5 [1/s] as η5. The unit of viscosity is Pa·s. The trigger index was calculated from the viscosity ratio η1/η5.In Example 1, the trigger index was 1.7.
＜伸縮前後的電阻值的測量＞ 將所獲得之彈性體組成物在170℃的條件下硬化120分鐘，並將其成形為片狀，從而製作出由聚矽氧橡膠形成之寬度5cm×高度500μm×長度5cm的基板。 接著，使用所獲得之導電性糊劑，在所獲得之基板上繪製四邊形的配線圖案，並以170℃、120分鐘的條件將其硬化，形成了寬度30mm×長度30mm×厚度70μm的配線圖案。 重複100次「沿四角形的配線圖案的對角線方向伸長50%之後釋放伸長狀態之伸長操作」。此時，在伸長操作前和進行100次伸長操作後立即測量未伸長時的對角線方向的配線圖案的電阻值。 在實施例1中，伸長操作前的電阻值為0.4Ω，伸長操作後的電阻值為0.6Ω， 在實施例2中，伸長操作前的電阻值為0.3Ω，伸長操作後的電阻值為0.5Ω， 在實施例3中，伸長操作前的電阻值為0.4Ω，伸長操作後的電阻值為0.7Ω， 在比較例1中，伸長操作前的電阻值為3.2Ω，伸長操作後的電阻值為27Ω。 [參考例1] 除了使用了一次粒徑為0.4μm（BET比表面積為4m²/g）的銀粉C以外，獲得了細度計之值為3μm的參考例1的導電性糊劑。 確認到，基於上述＜伸縮前後的電阻值的測量＞而測量之參考例1的伸長操作後的電阻值低於比較例1的值，但高於實施例1～3的值。<Resistance Measurement Before and After Stretching>The resulting elastomer composition was cured at 170°C for 120 minutes and formed into a sheet, creating a silicone rubber substrate measuring 5 cm wide, 500 μm high, and 5 cm long.Next, a rectangular wiring pattern was drawn on the substrate using the resulting conductive paste and cured at 170°C for 120 minutes, resulting in a 30 mm wide, 30 mm long, and 70 μm thick wiring pattern.The stretching operation of stretching the rectangular wiring pattern 50% along its diagonal direction and then releasing the stretch was repeated 100 times. At this time, the resistance of the unstretched diagonal wiring pattern was measured before and immediately after the 100 stretching cycles.In Example 1, the resistance before the stretching cycle was 0.4Ω, and the resistance after the stretching cycle was 0.6Ω.In Example 2, the resistance before the stretching cycle was 0.3Ω, and the resistance after the stretching cycle was 0.5Ω.In Example 3, the resistance before the stretching cycle was 0.4Ω, and the resistance after the stretching cycle was 0.7Ω.In Comparative Example 1, the resistance before the stretching cycle was 3.2Ω, and the resistance after the stretching cycle was 27Ω. [Reference Example 1]In addition to using silver powder C with a primary particle size of 0.4 μm (BET specific surface area of 4 m²/g), a conductive paste of Reference Example 1 with a micrometer value of 3 μm was obtained.The resistance value of Reference Example 1 after the stretching operation, measured according to the above-mentioned "Measurement of Resistance Values Before and After Stretching," was confirmed to be lower than that of Comparative Example 1 but higher than that of Examples 1 to 3.
實施例1～3的導電性糊劑顯示出與比較例1相比，初始的電阻值與伸長操作後的電阻值之間的差分較小的結果。可知此種實施例的導電性糊劑能夠抑制伸縮前後的導電性的變動。The conductive pastes of Examples 1 to 3 showed a smaller difference between the initial resistance value and the resistance value after the stretching operation than that of Comparative Example 1. This indicates that the conductive pastes of these examples can suppress the change in conductivity before and after stretching.
採用了將彈性體組成物、銀粉及非水系溶劑中的非水系溶劑的含有比率設為相同之條件，除此之外，藉由與實施例1～3中的各自相同的原料成分、混合及混練條件，獲得了實施例1’～3’的導電性糊劑。 使用所獲得之實施例1'～3'，以170℃，120分鐘的條件實施硬化處理，並對所獲得之硬化物進行溶劑殘留程度的評價。確認到，實施例1’及3’的導電性糊劑與「使用沸點超過250℃的非水系溶劑之實施例2’的導電性糊劑的情形」相比，硬化物中的溶劑的殘留程度較低。Conductive pastes of Examples 1'-3' were obtained using the same raw material ingredients, mixing, and kneading conditions as in Examples 1-3, except that the elastomer composition, silver powder, and non-aqueous solvent content ratios were kept constant.The resulting pastes of Examples 1'-3' were cured at 170°C for 120 minutes, and the resulting cured products were evaluated for residual solvent. The conductive pastes of Examples 1' and 3' were found to have lower residual solvent content than the conductive paste of Example 2', which used a non-aqueous solvent with a boiling point exceeding 250°C.
本申請主張基於2023年9月6日申請之日本申請特願2023-144192號之優先權，並將其揭示的全部內容援用於此。This application claims priority based on Japanese patent application No. 2023-144192 filed on September 6, 2023, and incorporates herein the entire contents disclosed therein.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023144192 | 2023-09-06 | ||
| JP2023-144192 | 2023-09-06 |
| Publication Number | Publication Date |
|---|---|
| TW202512227A TW202512227A (en) | 2025-03-16 |
| TWI891416Btrue TWI891416B (en) | 2025-07-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW113123795ATWI891416B (en) | 2023-09-06 | 2024-06-26 | Conductive paste and method of manufacturing conductive paste |
| Country | Link |
|---|---|
| JP (1) | JP7740576B2 (en) |
| TW (1) | TWI891416B (en) |
| WO (1) | WO2025052759A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033379A (en)* | 2006-03-10 | 2007-09-12 | 国家淀粉及化学投资控股公司 | Anisotropic conductive adhesive |
| CN103468159A (en)* | 2013-03-11 | 2013-12-25 | 苏州牛剑新材料有限公司 | Silver coated nickel powder conductive adhesive and preparation method thereof |
| TW201612918A (en)* | 2014-08-07 | 2016-04-01 | Denki Kagaku Kogyo Kk | Conductive polymer material and molded article using same |
| CN105632587A (en)* | 2016-02-22 | 2016-06-01 | 昆山海斯电子有限公司 | Epoxy resin conductive silver paste and preparation method thereof |
| WO2018047597A1 (en)* | 2016-09-06 | 2018-03-15 | 株式会社スリーボンド | Thermosetting electrically conductive adhesive |
| CN113635534A (en)* | 2021-08-10 | 2021-11-12 | 芜湖佳宏新材料股份有限公司 | Process method for reducing contact resistance of conductive polymer and metal conductor |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4276063B2 (en)* | 2003-12-26 | 2009-06-10 | Ｔｄｋ株式会社 | Electrode capacitor electrode manufacturing method and electrochemical capacitor manufacturing method |
| JP2009062523A (en) | 2007-08-10 | 2009-03-26 | Think Laboratory Co Ltd | Electroconductive ink composition |
| JP6673322B2 (en) | 2017-12-20 | 2020-03-25 | 住友ベークライト株式会社 | Conductive paste and stretchable wiring board |
| CN109686473B (en) | 2019-01-29 | 2020-06-30 | 大连海外华昇电子科技有限公司 | A kind of soft terminal electrode copper paste for multilayer ceramic capacitor and its application |
| JP7301089B2 (en) | 2021-04-07 | 2023-06-30 | 住友ベークライト株式会社 | Flexible sheet electrodes, wearable bioelectrodes and biosensors |
| WO2023058523A1 (en) | 2021-10-04 | 2023-04-13 | デンカ株式会社 | Thermoelectric conversion module and manufacturing method therefor |
| JP2023091380A (en) | 2021-12-20 | 2023-06-30 | 太陽インキ製造株式会社 | Conductive composition and conductor, laminated structure and electronic component using the same |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033379A (en)* | 2006-03-10 | 2007-09-12 | 国家淀粉及化学投资控股公司 | Anisotropic conductive adhesive |
| CN103468159A (en)* | 2013-03-11 | 2013-12-25 | 苏州牛剑新材料有限公司 | Silver coated nickel powder conductive adhesive and preparation method thereof |
| TW201612918A (en)* | 2014-08-07 | 2016-04-01 | Denki Kagaku Kogyo Kk | Conductive polymer material and molded article using same |
| CN105632587A (en)* | 2016-02-22 | 2016-06-01 | 昆山海斯电子有限公司 | Epoxy resin conductive silver paste and preparation method thereof |
| WO2018047597A1 (en)* | 2016-09-06 | 2018-03-15 | 株式会社スリーボンド | Thermosetting electrically conductive adhesive |
| CN113635534A (en)* | 2021-08-10 | 2021-11-12 | 芜湖佳宏新材料股份有限公司 | Process method for reducing contact resistance of conductive polymer and metal conductor |
| Publication number | Publication date |
|---|---|
| JP7740576B2 (en) | 2025-09-17 |
| JPWO2025052759A1 (en) | 2025-03-13 |
| WO2025052759A1 (en) | 2025-03-13 |
| TW202512227A (en) | 2025-03-16 |
| Publication | Publication Date | Title |
|---|---|---|
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