TWI700305B - Heat-curing conductive paste for laser etching - Google Patents
Heat-curing conductive paste for laser etching Download PDFInfo
- Publication number
- TWI700305B TWI700305B TW105105352A TW105105352A TWI700305B TW I700305 B TWI700305 B TW I700305B TW 105105352 A TW105105352 A TW 105105352A TW 105105352 A TW105105352 A TW 105105352A TW I700305 B TWI700305 B TW I700305B
- Authority
- TW
- Taiwan
- Prior art keywords
- laser
- conductive
- heat
- epoxy resin
- mass
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Abstract
本發明提供一種雷射加工性優異的加熱硬化型導電性糊。根據本發明，提供一種含有導電性粉末、熱硬化性樹脂及硬化劑的雷射蝕刻用加熱硬化型導電性糊。對於所述導電性粉末而言，基於雷射繞射·光散射法的平均粒徑為0.5 μm～3 μm，平均縱橫比為1.0～1.5。於將所述導電性粉末設為100質量份時，所述熱硬化性樹脂的含有比例為35質量份以下。The present invention provides a heat-curable conductive paste with excellent laser processability. According to the present invention, there is provided a heat-curable conductive paste for laser etching containing conductive powder, thermosetting resin, and curing agent. For the conductive powder, the average particle size based on the laser diffraction and light scattering method is 0.5 μm to 3 μm, and the average aspect ratio is 1.0 to 1.5. When the conductive powder is 100 parts by mass, the content of the thermosetting resin is 35 parts by mass or less.
Description
本發明是有關於一種雷射蝕刻用的加熱硬化型導電性糊。 The present invention relates to a heat-curing conductive paste for laser etching.
對於電子設備而言，小型化或高密度化、動作速度的高速化等高性能化不斷進展。伴隨於此，對於電子設備用的電子零件，要求電極配線的進一步的高密度細線化。然而，以前用於形成電極配線的印刷法難以精度良好地形成細線狀的電極，例如難以精度良好地形成線寬與其間的空間(線與空間(line and space)：L/S)為80μm/80μm以下、進而50μm/50μm以下的電極。 For electronic devices, performance improvements such as miniaturization, higher density, and higher operating speeds are progressing. Along with this, for electronic parts for electronic devices, further high-density and thinning of electrode wiring is required. However, it is difficult to accurately form thin line-shaped electrodes with the conventional printing method used to form electrode wiring. For example, it is difficult to accurately form the line width and the space between them (line and space: L/S) of 80 μm/ An electrode of 80 μm or less, and further 50 μm/50 μm or less.
因此，近年來正在研究利用雷射蝕刻法，該雷射蝕刻法利用雷射光。 Therefore, in recent years, the use of a laser etching method that uses laser light has been studied.
該方法中，首先與以前同樣地製備導電性糊。繼而，將所製備的導電性糊印刷至所需的基板上，形成導電性的被膜(導電膜)。然後，以所形成的導電膜成為所需形狀(細線狀)的電極配線的方式遮蓋(masking)，對除此以外的(不需要的)部位照射雷射光。藉此，位於經雷射光照射的部位中的導電膜被熱分解.去除，未經雷射光照射的部位作為電極配線而殘留。 In this method, first, a conductive paste is prepared in the same manner as before. Then, the prepared conductive paste is printed on a desired substrate to form a conductive film (conductive film). Then, the formed conductive film is masked so that the electrode wiring of the desired shape (thin line shape) is formed, and laser light is irradiated to the other (unnecessary) parts. Thereby, the conductive film located in the part irradiated with the laser light is thermally decomposed and removed, and the part not irradiated with the laser light remains as the electrode wiring.
於專利文獻1、專利文獻2中揭示有可用於此種用途的雷射蝕刻用導電性糊。例如於專利文獻1中揭示有一種含有鱗片狀(薄
片狀)的導電性粉末的導電性糊。另外，於專利文獻2中揭示有一種含有熱塑性的黏合劑樹脂的導電性糊。
[專利文獻1]日本專利申請公開2014-2992號公報 [Patent Document 1] Japanese Patent Application Publication No. 2014-2992
[專利文獻2]國際公開2014/013899號公報 [Patent Document 2] International Publication No. 2014/013899
[專利文獻3]日本專利申請公開2003-147316號公報 [Patent Document 3] Japanese Patent Application Publication No. 2003-147316
[專利文獻4]日本專利申請公開2009-105361號公報 [Patent Document 4] Japanese Patent Application Publication No. 2009-105361
[專利文獻5]日本專利申請公開平11-134935號公報 [Patent Document 5] Japanese Patent Application Publication No. 11-134935
[專利文獻6]日本專利申請公開平5-36307號公報 [Patent Document 6] Japanese Patent Application Publication No. Hei 5-36307
如專利文獻1所記載般，於形成電極配線時，通常為了實現良好的導電性而使用扁平形狀的導電性粒子。即，扁平形狀的導電性粒子的堆疊(stacking)性良好，且與使用球狀導電性粒子的情形相比可減少粒子的界面。因此有提高電極的導電性或一體性的效果。然而，根據本發明者等人的研究，於使用此種扁平形狀的導電性粒子的情形時，有時於雷射加工時產生電極變細或斷線等缺陷。
As described in
一面參照圖1(C)、圖1(D)的示意圖一面對所述情況加以說明。如圖1(C)所示，總體上來看，扁平形狀的導電性粒子的一個粒子的俯視面積大。因此，扁平形狀的導電性粒子(鱗片狀粒子2)有時以橫跨作為電極配線而殘留的部位與由雷射加工去除 的部位(雷射照射部位3)的狀態而存在。若於此種狀態下照射雷射光，則如圖1(D)所示，熱亦傳至作為電極而殘留的部位的導電性粒子，有時導電膜以必要以上的程度被削去。結果，有時電極變得較既定的寬度更細、或斷線，或成為電極表面粗糙的狀態。越推進電極的細線化，所述問題越深刻。 The situation will be described while referring to the schematic diagrams of FIG. 1(C) and FIG. 1(D). As shown in FIG. 1(C), as a whole, the planar surface area of one particle of flat conductive particles is large. Therefore, the flat conductive particles (scale-like particles 2) sometimes straddle the remaining part as electrode wiring and are removed by laser processing. Exists in the state of the part (laser irradiation part 3). If laser light is irradiated in this state, as shown in FIG. 1(D), heat is also transmitted to the conductive particles remaining as the electrode, and the conductive film may be shaved off more than necessary. As a result, the electrode may become thinner than a predetermined width, or the wire may be broken, or the electrode surface may become rough. The more the electrode is made thinner, the deeper the problem.
另外，如專利文獻2所記載般，熱塑性樹脂的熱分解性良好，適於雷射加工。然而另一方面，熱塑性樹脂有耐熱性低的傾向。因此，若於圖1(C)所示的狀態下照射雷射光，則有時熱傳至作為電極而殘留的部位的樹脂而發生樹脂的劣化。結果有時導致耐久性降低。
In addition, as described in
本發明是鑒於所述方面而成，其目的在於提供一種雷射加工適性優異、且可形成具備高耐久性的電極配線的導電性糊。 The present invention is made in view of the above-mentioned aspects, and its object is to provide a conductive paste that is excellent in laser processing suitability and can form electrode wiring with high durability.
本發明者等人為了實現高耐久性的電極配線而研究了熱硬化性樹脂的使用。而且，為了提高使用熱硬化性樹脂的導電性糊(熱硬化型導電性糊)的雷射加工適性或耐久性而反覆銳意研究，以至完成了本發明。 The inventors of the present invention studied the use of thermosetting resin in order to realize highly durable electrode wiring. Furthermore, in order to improve the laser processing suitability or durability of a conductive paste using a thermosetting resin (thermosetting type conductive paste), intensive research has been conducted and the present invention has been completed.
根據本發明，提供一種含有導電性粉末、熱硬化性樹脂及硬化劑的雷射蝕刻用加熱硬化型導電性糊。對於所述導電性粉末而言，基於雷射繞射．光散射法的平均粒徑為0.5μm~3μm，平均縱橫比為1.0~1.5。於將所述導電性粉末設為100質量份時，所述熱硬化性樹脂的含有比例為35質量份以下。 According to the present invention, there is provided a heat-curable conductive paste for laser etching containing conductive powder, thermosetting resin, and curing agent. For the conductive powder, based on laser diffraction. The average particle size of the light scattering method is 0.5μm~3μm, and the average aspect ratio is 1.0~1.5. When the conductive powder is 100 parts by mass, the content of the thermosetting resin is 35 parts by mass or less.
根據所述構成，如圖1(A)所示，以橫跨作為電極而 殘留的部位與由雷射加工去除的部位的狀態而存在的導電性粒子(球狀粒子1)的個數減少。因此，雷射加工適性提高，如圖1(B)所示，可形成加工線寬穩定的電極。因此，可降低電極配線的變細或斷線等缺陷的產生比例。另外，可提高電極表面的平滑性。而且，例如亦可較佳地形成L/S=30μm/30μm的細線狀的電極配線。進而，藉由使用熱硬化性樹脂，與使用熱塑性樹脂的情形相比，相對不易發生樹脂成分的變質或劣化，可提高電極配線的耐久性。 According to the above configuration, as shown in Fig. 1(A), the straddle serves as the electrode and The number of conductive particles (spherical particles 1) existing in the state of the remaining part and the part removed by laser processing decreases. Therefore, the suitability of laser processing is improved, and as shown in Fig. 1(B), an electrode with stable processing line width can be formed. Therefore, it is possible to reduce the occurrence rate of defects such as thinning or disconnection of the electrode wiring. In addition, the smoothness of the electrode surface can be improved. Moreover, for example, it is also possible to preferably form a thin line-shaped electrode wiring with L/S=30 μm/30 μm. Furthermore, by using a thermosetting resin, compared with the case of using a thermoplastic resin, the resin component is relatively less likely to be changed or deteriorated, and the durability of the electrode wiring can be improved.
再者，其他與導電性糊有關的現有技術文獻可列舉專利文獻3~專利文獻6。
In addition, other prior art documents related to the conductive paste include
另外，本說明書中所謂「平均粒徑」，是指於基於雷射繞射．光散射法的體積基準的粒度分佈中，相當於自粒徑小的粒子開始累計50%的粒徑D50值(中值徑)。 In addition, the "average particle size" in this specification refers to laser diffraction. In the volume-based particle size distribution of the light scattering method, the particle size D 50 value (median diameter) corresponding to 50% of the cumulative particle size from the smaller particle size.
另外，本說明書中所謂「平均縱橫比」，是指多個導電性粒子的長徑/短徑比的平均值。例如使用電子顯微鏡觀察至少30個(例如30個~100個)導電性粒子。繼而，對各粒子圖像描畫外接的最小長方形，算出該長方形的長邊的長度A相對於短邊的長度(例如厚度)B之比(A/B)作為縱橫比。將所得的縱橫比加以算術平均，由此可求出平均縱橫比。 In addition, the "average aspect ratio" in this specification refers to the average value of the long diameter/short diameter ratio of a plurality of conductive particles. For example, at least 30 (for example, 30 to 100) conductive particles are observed using an electron microscope. Next, the smallest rectangle that circumscribes each particle image is drawn, and the ratio (A/B) of the length A of the long side of the rectangle to the length (for example, thickness) B of the short side is calculated as the aspect ratio. The arithmetic average of the obtained aspect ratios can be used to obtain the average aspect ratio.
於此處揭示的較佳一態樣中，所述導電性粉末的平均縱橫比為1.1~1.4。藉此，與使用例如平均縱橫比為1.0的(圓球狀的)導電性粉末的情形相比，雷射加工適性進一步提高。因此， 能以更高的水準發揮本申請案發明的效果。 In a preferred aspect disclosed herein, the average aspect ratio of the conductive powder is 1.1 to 1.4. Thereby, compared with the case of using (spherical) conductive powder having an average aspect ratio of 1.0, for example, the suitability for laser processing is further improved. therefore, The effect of the invention in this application can be exerted at a higher level.
於此處揭示的較佳一態樣中，所述導電性粉末不含縱橫比超過5的導電性粒子。藉此，可精度更良好地形成細線狀的電極配線。因此，能以更高的水準發揮本申請案發明的效果。 In a preferred aspect disclosed here, the conductive powder does not contain conductive particles with an aspect ratio exceeding 5. Thereby, the thin wire-shaped electrode wiring can be formed more accurately. Therefore, the effect of the invention of this application can be exerted at a higher level.
於此處揭示的較佳一態樣中，所述熱硬化性樹脂的數量平均分子量為2000以下。藉此，導電膜的熱分解性提高，雷射加工適性提高。另外，印刷糊時自製版的脫離性(脫模性)變良好，亦可提高印刷精度。 In a preferred aspect disclosed herein, the number average molecular weight of the thermosetting resin is 2000 or less. Thereby, the thermal decomposability of the conductive film is improved, and the suitability for laser processing is improved. In addition, the releasability (releasability) of the self-made plate when printing paste becomes better, and the printing accuracy can also be improved.
再者，本說明書中所謂「數量平均分子量」，是指藉由凝膠層析法(凝膠滲透層析法(Gel Permeation Chromatography，GPC))測定，並使用標準聚苯乙烯校準曲線換算所得的個數基準的平均分子量。 Furthermore, the "number average molecular weight" in this specification refers to the value measured by gel chromatography (Gel Permeation Chromatography (GPC)) and converted using a standard polystyrene calibration curve. Average molecular weight based on number.
於此處揭示的較佳一態樣中，所述熱硬化性樹脂含有環氧樹脂。藉由使用環氧樹脂，可提高雷射加工適性、接著性、耐久性、耐熱性、耐化學品性的至少一個。 In a preferred aspect disclosed here, the thermosetting resin contains epoxy resin. By using epoxy resin, at least one of laser processing suitability, adhesiveness, durability, heat resistance, and chemical resistance can be improved.
所述環氧樹脂較佳為包含具有兩個以上的環氧基的多官能環氧樹脂、與具有一個環氧基的單官能環氧樹脂。 The epoxy resin preferably includes a multifunctional epoxy resin having two or more epoxy groups and a monofunctional epoxy resin having one epoxy group.
於一較佳例中，所述多官能環氧樹脂與所述單官能環氧樹脂之質量比率為20：80~45：55。藉此，能以更高的水準實現導電性的提高。 In a preferred embodiment, the mass ratio of the multifunctional epoxy resin to the monofunctional epoxy resin is 20:80 to 45:55. With this, the conductivity can be improved at a higher level.
1:球狀粒子 1: spherical particles
2:鱗片狀粒子 2: scaly particles
3:雷射照射部位 3: Laser irradiation part
圖1(A)~圖1(D)為表示雷射蝕刻前後的導電膜的狀態的示意性剖面圖，圖1(A)、圖1(B)對本發明進行說明，圖1(C)、圖1(D)對現有技術進行說明。 Figures 1(A) to 1(D) are schematic cross-sectional views showing the state of the conductive film before and after laser etching. Figures 1(A) and 1(B) illustrate the present invention, and Figures 1(C), Figure 1(D) illustrates the prior art.
圖2為例2的電極配線的雷射顯微鏡圖像。 Fig. 2 is a laser microscope image of the electrode wiring of Example 2.
圖3為雷射加工性的評價為「×」的參考例的電極配線的雷射顯微鏡圖像。 Fig. 3 is a laser microscope image of the electrode wiring of the reference example whose laser processability is evaluated as "×".
以下，對本發明的較佳實施形態加以說明。再者，本說明書中特別提及的事項(例如雷射蝕刻用加熱硬化型導電性糊的組成)以外的且實施本發明所必需的事項(例如糊的製備方法或雷射蝕刻的方法等)可作為基於該領域的現有技術的本領域技術人員的設計事項而掌握。本發明可根據本說明書揭示的內容及該領域的技術常識來實施。 Hereinafter, a preferred embodiment of the present invention will be described. In addition, items other than the items specifically mentioned in this specification (for example, the composition of the heat-curable conductive paste for laser etching) and items necessary for the implementation of the present invention (for example, the preparation method of the paste or the method of laser etching, etc.) It can be grasped as a design matter of a person skilled in the art based on the prior art in this field. The present invention can be implemented based on the content disclosed in this specification and common technical knowledge in the field.
另外，本說明書中所謂「A~B(其中A、B為任意的值)」只要無特別說明，則視為包含A、B的值(上限值及下限值)。 In addition, the "A to B (where A and B are arbitrary values)" in this specification are considered to include the values (upper limit and lower limit) of A and B unless otherwise specified.
<雷射蝕刻用加熱硬化型導電性糊> <Heat-curing conductive paste for laser etching>
此處揭示的加熱硬化型導電性糊(以下有時簡稱為「糊」)含有(a)導電性粉末、(b)熱硬化性樹脂及(c)硬化劑作為必需構成成分。另外，典型而言不含熱塑性樹脂。而且其特徵在於：導電性粉末滿足既定的性狀，且熱硬化性樹脂的調配量為既定值以下。因此，除此以外並無特別限定，可依照各種基準任意決定。以下，對糊的構成成分等加以說明。 The heat-curable conductive paste disclosed here (hereinafter sometimes referred to as "paste") contains (a) conductive powder, (b) thermosetting resin, and (c) curing agent as essential components. In addition, no thermoplastic resin is typically contained. It is also characterized in that the conductive powder satisfies predetermined properties, and the blending amount of the thermosetting resin is not more than a predetermined value. Therefore, there is no particular limitation other than this, and it can be arbitrarily determined based on various criteria. Hereinafter, the constituent components of the paste and the like will be described.
<(a)導電性粉末> <(a) Conductive powder>
導電性粉末為用以對電極配線賦予導電性的成分。導電性粉末並無特別限定，可根據用途等而適當使用具備所需的導電性或其他物性的各種金屬、合金等。一較佳例可列舉：金(Au)、銀(Ag)、銅(Cu)、鉑(Pt)、鈀(Pd)、釕(Ru)、銠(Rh)、銥(Ir)、鋨(Os)、鎳(Ni)、鋁(Al)等金屬及該些金屬的包覆混合物或合金等。其中，較佳為銀(Ag)、鉑(Pt)、鈀(Pd)等貴金屬的單質及該些貴金屬的混合物(塗銀銅、塗銀銅-鋅合金、塗銀鎳)或合金(銀-鈀(Ag-Pd)、銀-鉑(Ag-Pt)、銀-銅(Ag-Cu)等)。尤其就成本相對較低且導電性亦優異的方面而言，較佳為銀及塗銀品、以及銀的合金。 The conductive powder is a component for imparting conductivity to the electrode wiring. The conductive powder is not particularly limited, and various metals, alloys, etc. having required conductivity or other physical properties can be appropriately used according to the application and the like. A preferred example can include: gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir), osmium (Os) ), nickel (Ni), aluminum (Al) and other metals and coating mixtures or alloys of these metals. Among them, the simple substance of precious metals such as silver (Ag), platinum (Pt), palladium (Pd) and the mixture of these precious metals (silver-coated copper, silver-coated copper-zinc alloy, silver-nickel) or alloys (silver- Palladium (Ag-Pd), silver-platinum (Ag-Pt), silver-copper (Ag-Cu), etc.). Especially in terms of relatively low cost and excellent conductivity, silver, silver-coated products, and silver alloys are preferred.
此處揭示的糊的導電性粉末的平均縱橫比為1.0~1.5，例如為1.0~1.4。藉此，構成導電性粉末的導電性粒子的俯視面積變小。結果，可有效地減少成為橫跨作為電極配線而殘留的部位、與由雷射加工進行熱分解去除的部位的狀態的導電性粒子。因此，可顯著地改善電極變細或斷線。即，雷射加工適性飛躍性地提高，能以穩定的加工線寬形成細線狀的電極。 The conductive powder of the paste disclosed here has an average aspect ratio of 1.0 to 1.5, for example, 1.0 to 1.4. Thereby, the planar surface area of the electroconductive particle which comprises electroconductive powder becomes small. As a result, it is possible to effectively reduce conductive particles in a state that straddles the part remaining as the electrode wiring and the part thermally decomposed and removed by laser processing. Therefore, the thinning or disconnection of the electrode can be significantly improved. That is, the suitability of laser processing is greatly improved, and it is possible to form thin wire electrodes with a stable processing line width.
再者，於使用圓球狀或大致球狀(亦包含球狀、橢圓狀、多角體狀等。以下相同)的導電性粒子的情形時，例如與使用鱗片狀等的縱橫比更大的導電性粒子的情形相比，粒子彼此的接觸面積變小。因此，通常擔心電極配線的電阻變高。然而，根據此處揭示的技術，可精度良好地形成細線狀電極的效果、與高度地 取得糊構成成分的平衡的效果相互作用，可抑制電極配線總體的電阻增大。結果，與使用鱗片狀般的縱橫比大的導電性粒子的現有的糊相比，能以毫不遜色的程度實現高的體積電阻率。 In addition, in the case of using spherical or substantially spherical (including spherical, elliptical, polygonal, etc.) conductive particles, for example, conductive particles with a larger aspect ratio such as scales are used. Compared with the case of sexual particles, the contact area between particles becomes smaller. Therefore, there is usually a concern that the resistance of the electrode wiring will increase. However, according to the technology disclosed here, it is possible to accurately form the effect of thin wire-shaped electrodes and to achieve a high degree of The effects of achieving a balance of the constituent components of the paste interact with each other to suppress the increase in the resistance of the entire electrode wiring. As a result, compared to the conventional paste using scaly-like conductive particles with a large aspect ratio, it is possible to achieve a high volume resistivity not inferior to that.
於較佳的一態樣中，導電性粉末的縱橫比為1.1~1.4。根據所述構成，雷射加工性可進一步提高。即，縱橫比更接近1.00的圓球狀的導電性粒子的摩擦少，滑動性或移動性高。因此，在雷射加工時，有時未對導電性粒子有效率地照射雷射。若導電性粒子相較於圓球而言稍微為扁平狀，則該形狀可發揮「止滑」的功能。即，摩擦變大，滑動性或移動性降低。結果，與使用圓球狀的導電性粒子的情形相比，對導電性粉末準確地照射雷射光。因此，可減少雷射加工時的能量或加工時間。 In a preferred aspect, the aspect ratio of the conductive powder is 1.1 to 1.4. According to the above configuration, the laser processability can be further improved. That is, spherical conductive particles with an aspect ratio closer to 1.00 have less friction, and have high sliding properties or mobility. Therefore, during laser processing, the conductive particles may not be irradiated with the laser efficiently. If the conductive particles have a slightly flat shape compared to a sphere, the shape can exhibit the function of "anti-slip". That is, friction increases, and sliding properties or mobility are reduced. As a result, compared with the case of using spherical conductive particles, the conductive powder is accurately irradiated with laser light. Therefore, the energy or processing time during laser processing can be reduced.
於較佳的另一態樣中，導電性粉末不含鱗片狀或樹枝狀的導電性粒子。即，導電性粉末理想的是不含縱橫比超過10(較佳為超過5、更佳為超過3、例如超過2)的導電性粒子。換言之，導電性粉末可包含圓球狀或大致球狀的(例如縱橫比為1.0~2.0、較佳為縱橫比為1.1~1.4的)導電性粒子。藉此，能以更高的水準穩定地獲得本發明的效果。 In another preferred aspect, the conductive powder does not contain scaly or dendritic conductive particles. That is, it is desirable that the conductive powder does not contain conductive particles having an aspect ratio of more than 10 (preferably more than 5, more preferably more than 3, for example, more than 2). In other words, the conductive powder may include spherical or substantially spherical (for example, an aspect ratio of 1.0 to 2.0, preferably an aspect ratio of 1.1 to 1.4) conductive particles. Thereby, the effect of the present invention can be stably obtained at a higher level.
此處揭示的糊的導電性粉末的平均粒徑為3μm以下，例如為2.5μm以下。藉此，導電性粒子的俯視面積變小，可有效地減少成為橫跨作為電極而殘留的部位與由雷射熱分解的部位的狀態的導電性粒子。因此，雷射加工適性進一步提高，可穩定地形成細線狀的電極。 The conductive powder of the paste disclosed here has an average particle size of 3 μm or less, for example, 2.5 μm or less. Thereby, the area of the conductive particles in plan view is reduced, and the conductive particles in a state of straddling the remaining part as an electrode and the part decomposed by laser heat can be effectively reduced. Therefore, the suitability for laser processing is further improved, and thin wire-shaped electrodes can be formed stably.
此處揭示的糊的導電性粉末的平均粒徑為0.5μm以上，例如為1.0μm以上。藉此，電極配線內的粒子彼此的接觸點減少，內部電阻降低。因此，可實現更高的導電性。另外，可使糊具有較佳的流動性(黏度)，亦可提高糊的操作性、或於基板上賦予糊時的作業性。 The conductive powder of the paste disclosed here has an average particle size of 0.5 μm or more, for example, 1.0 μm or more. Thereby, the contact points of the particles in the electrode wiring are reduced, and the internal resistance is reduced. Therefore, higher conductivity can be achieved. In addition, the paste can have better fluidity (viscosity), and the workability of the paste can also be improved, or the workability when applying the paste on the substrate.
再者，通常於使用圓球狀或大致球狀的導電性粒子的情形時，與使用例如鱗片狀等的縱橫比更大的導電性粒子的情形相比，導電性粒子彼此的接觸面積容易變小。結果，有電極配線的體積電阻增大的傾向。因此，為了形成導電性優異的電極配線，將導電性粉末的平均粒徑設為既定值以上而減少粒子間的接觸極為重要。 Furthermore, when generally spherical or substantially spherical conductive particles are used, the contact area between the conductive particles tends to change compared to the case of using conductive particles with a larger aspect ratio such as scales. small. As a result, the volume resistance of the electrode wiring tends to increase. Therefore, in order to form an electrode wiring with excellent conductivity, it is extremely important to reduce the contact between particles by setting the average particle size of the conductive powder to a predetermined value or more.
於較佳的一態樣中，構成導電性粉末的導電性粒子為了防止凝聚，於其表面上具備含有脂肪酸的被膜。該脂肪酸例如可為癸酸、棕櫚酸、硬脂酸等碳原子數為10以上的飽和高級脂肪酸；油酸、亞麻油酸等不飽和脂肪酸。藉由導電性粒子具備含有脂肪酸的被膜，於粒子表面上羥基增加而可有效地提高親水性。熱硬化性樹脂典型而言為疏水性。因此，根據該態樣，導電性粒子與熱硬化性樹脂的濡濕性降低。結果有導電性粒子彼此容易形成接點的效果。 In a preferred aspect, the conductive particles constituting the conductive powder are provided with a film containing fatty acid on the surface in order to prevent aggregation. The fatty acid may be, for example, saturated higher fatty acids having 10 or more carbon atoms such as capric acid, palmitic acid, and stearic acid; unsaturated fatty acids such as oleic acid and linoleic acid. When the conductive particles are provided with a fatty acid-containing film, the hydroxyl groups on the surface of the particles increase and the hydrophilicity can be effectively improved. Thermosetting resins are typically hydrophobic. Therefore, according to this aspect, the wettability between the conductive particles and the thermosetting resin decreases. As a result, there is an effect that conductive particles can easily form contact points.
更佳為脂肪酸為二元以上的多元不飽和脂肪酸。二元以上的多元不飽和脂肪酸例如可列舉烷基琥珀酸或烯基琥珀酸。 More preferably, the fatty acid is a polyunsaturated fatty acid having a valence of two or more. Examples of the polyunsaturated fatty acids having two or more valences include alkyl succinic acid or alkenyl succinic acid.
導電性粉末於糊的必需構成成分的總質量(即(a)+(b) +(c))中所佔的比例並無特別限定，通常可為50質量%以上、典型而言為60質量%~95質量%、較佳為70質量%~95質量%、例如80質量%~90質量%。藉由滿足所述範圍，能以更高的水準兼顧導電性高的電極配線的形成、與優異的作業性或操作性。 The total mass of the necessary constituents of the conductive powder in the paste (i.e. (a) + (b) The proportion of +(c)) is not particularly limited, and it can usually be 50% by mass or more, typically 60% to 95% by mass, preferably 70% to 95% by mass, for example 80% by mass ~90% by mass. By satisfying the above-mentioned range, it is possible to achieve both the formation of highly conductive electrode wiring and the excellent workability and operability at a higher level.
<(b)熱硬化性樹脂> <(b) Thermosetting resin>
熱硬化性樹脂為用以對電極配線賦予接著性或耐久性的成分。熱硬化性樹脂於添加硬化劑並進行加熱時，於分子間形成網狀的交聯結構而硬化。一旦硬化後亦難以溶解於溶媒中，即便加熱亦不表現出塑化性(不變形)。因此，藉由使用熱硬化性樹脂，與使用熱塑性樹脂的現有品相比，可實現耐熱性、耐化學品性、機械強度及耐久性優異的電極配線。 The thermosetting resin is a component for imparting adhesiveness or durability to the electrode wiring. When a thermosetting resin is added with a curing agent and heated, a network-like cross-linked structure is formed between molecules to be cured. Once hardened, it is difficult to dissolve in the solvent, and does not show plasticization (no deformation) even if heated. Therefore, by using a thermosetting resin, it is possible to realize electrode wiring with excellent heat resistance, chemical resistance, mechanical strength, and durability compared to conventional products using thermoplastic resin.
熱硬化性樹脂並無特別限定，可根據用途等而適當使用以前已知的熱硬化性樹脂。一較佳例可列舉：環氧樹脂、酚醛清漆樹脂、甲階酚醛樹脂、烷基苯酚樹脂等酚樹脂、脲樹脂、三聚氰胺樹脂、醇酸樹脂、矽樹脂、胺基甲酸酯樹脂。該些熱硬化性樹脂可單獨使用一種，亦可併用兩種以上。其中，就雷射加工性(熱分解性)或接著性的觀點而言，較佳為環氧樹脂或酚樹脂。另外，就耐熱性或耐久性的觀點而言，熱分解溫度(藉由熱重分析(Thermogravimetric analysis，TGA)法於空氣環境中以10℃/分鐘的升溫速度升溫時，重量減少5%的溫度)大致可為200℃以上、例如240℃以上、尤其300℃以上。 The thermosetting resin is not particularly limited, and conventionally known thermosetting resins can be suitably used according to the application and the like. A preferred example includes epoxy resin, novolak resin, phenol resin such as resol phenol resin, alkylphenol resin, urea resin, melamine resin, alkyd resin, silicone resin, and urethane resin. These thermosetting resins may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of laser processability (thermal decomposition property) or adhesiveness, epoxy resin or phenol resin is preferred. In addition, from the viewpoint of heat resistance or durability, the thermal decomposition temperature (the temperature at which the weight is reduced by 5% when the temperature is increased by the thermogravimetric analysis (TGA) method in an air environment at a temperature increase rate of 10°C/min) ) May be approximately 200°C or higher, for example 240°C or higher, especially 300°C or higher.
於較佳的一態樣中，熱硬化性樹脂含有環氧樹脂。此處 所謂的環氧樹脂，是指作為三員環醚的於分子中具有一個以上的環氧基的所有化合物。於熱硬化性樹脂中，環氧樹脂的接著性、耐熱性、耐化學品性、耐久性優異。因此，藉由使用環氧樹脂，可獲得形狀保持性或穩定性更優異的電極配線。環氧樹脂可佔熱硬化性樹脂總體的大致95質量%以上。 In a preferred aspect, the thermosetting resin contains epoxy resin. Here The so-called epoxy resin refers to all compounds having one or more epoxy groups in the molecule as three-membered cyclic ethers. Among thermosetting resins, epoxy resins are excellent in adhesiveness, heat resistance, chemical resistance, and durability. Therefore, by using epoxy resin, electrode wiring with more excellent shape retention and stability can be obtained. The epoxy resin can account for approximately 95% by mass or more of the entire thermosetting resin.
環氧樹脂的環氧當量並無特別限定，為了以高水準發揮所述特性(特別是接著性)，大致可為100g/eq~1000g/eq、典型而言為100g/eq~500g/eq、例如150g/eq~450g/eq左右。再者，環氧當量可依據日本工業標準(Japanese Industrial Standards，JIS)K7236(2009)而求出。 The epoxy equivalent of the epoxy resin is not particularly limited. In order to exhibit the characteristics (especially adhesiveness) at a high level, it can be roughly 100g/eq~1000g/eq, typically 100g/eq~500g/eq, For example, around 150g/eq~450g/eq. In addition, the epoxy equivalent can be calculated based on Japanese Industrial Standards (JIS) K7236 (2009).
於較佳的一態樣中，環氧樹脂為包含於分子內具有兩個以上的環氧基的多官能環氧樹脂、與於分子內具有一個環氧基的單官能環氧樹脂的混合物。藉此，能以更高的水準發揮本申請案發明的效果。 In a preferred aspect, the epoxy resin is a mixture of a multifunctional epoxy resin having two or more epoxy groups in the molecule and a monofunctional epoxy resin having one epoxy group in the molecule. Thereby, the effect of the invention of this application can be exerted at a higher level.
即，藉由使用多官能環氧樹脂，電極配線的機械強度或形狀穩定性提高，可實現更優異的耐久性。另一方面，多官能環氧樹脂因其剛直的骨架結構而硬，流動性或移動性低。因此，難以經雷射削去，有雷射加工性降低的傾向。另外，即便於加熱硬化後，於導電性粒子彼此的接點亦大量殘存樹脂，有體積電阻增加的傾向。根據本發明者等人的研究，於使用此處揭示般的圓球狀或大致球狀的導電性粉末的情形時，此種體積電阻增加的傾向可能尤其變明顯。 That is, by using a multifunctional epoxy resin, the mechanical strength or shape stability of the electrode wiring is improved, and more excellent durability can be achieved. On the other hand, multifunctional epoxy resins are hard due to their rigid skeleton structure and have low fluidity or mobility. Therefore, it is difficult to remove by laser, and the laser processability tends to decrease. In addition, even after heating and curing, a large amount of resin remains at the contact points between the conductive particles, and the volume resistance tends to increase. According to the research conducted by the inventors of the present invention, when the spherical or substantially spherical conductive powder as disclosed herein is used, such a tendency to increase the volume resistance may be particularly noticeable.
因此，較佳為於多官能環氧樹脂中混合單官能環氧樹脂。藉此，可對樹脂賦予適度的柔軟性，可提高雷射加工性。另外，根據本發明者等人的研究，藉由減少環氧樹脂的交聯點而提高柔軟性或軟質性，可獲得如下效果：存在於導電性粒子彼此的接點的樹脂於加熱硬化時被排斥(被排除)。因此，導電性粒子彼此的接觸面積增加，可將體積電阻抑制得更低。 Therefore, it is preferable to mix a monofunctional epoxy resin with a multifunctional epoxy resin. Thereby, moderate flexibility can be imparted to the resin, and the laser processability can be improved. In addition, according to the research of the inventors, by reducing the crosslinking point of epoxy resin to improve flexibility or softness, the following effect can be obtained: the resin existing at the contact point of conductive particles is cured by heating. Repel (to be excluded). Therefore, the contact area of conductive particles increases, and the volume resistance can be suppressed lower.
多官能環氧樹脂可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、多官能酚型環氧樹脂、聯苯型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂及該些樹脂的改質型等。該些樹脂可單獨使用一種，亦可併用兩種以上。其中，就接著性或疏水性、獲取容易性的觀點等而言，較佳為雙酚型環氧樹脂、酚醛清漆型環氧樹脂。尤其就以更高的水準降低體積電阻的觀點等而言，較佳為雙酚型環氧樹脂。 Examples of multifunctional epoxy resins include: bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, and dicyclopentane Diene epoxy resins, multifunctional phenol epoxy resins, biphenyl epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, and modified types of these resins. These resins may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoints of adhesiveness, hydrophobicity, and ease of availability, etc., bisphenol-type epoxy resins and novolak-type epoxy resins are preferred. In particular, from the viewpoint of lowering volume resistance at a higher level, etc., a bisphenol-type epoxy resin is preferable.
單官能環氧樹脂例如可列舉：碳數為6~36(典型而言為6~26、例如6~18)的烷基縮水甘油醚、烷基苯基縮水甘油醚、烯基縮水甘油醚、炔基縮水甘油醚、苯基縮水甘油醚等縮水甘油醚系環氧樹脂；碳數為6~36(典型而言為6~26、例如6~18)的烷基縮水甘油酯、烯基縮水甘油酯、苯基縮水甘油酯等縮水甘油酯系環氧樹脂等。該些樹脂可單獨使用一種，亦可併用兩種以上。其中，較佳為烷基縮水甘油醚、苯基縮水甘油醚、烷基縮水甘油酯、苯基縮水甘油酯。尤其較佳為苯基縮水甘油醚。 Examples of monofunctional epoxy resins include alkyl glycidyl ethers, alkylphenyl glycidyl ethers, alkenyl glycidyl ethers, carbon numbers of 6 to 36 (typically 6 to 26, such as 6 to 18). Glycidyl ether epoxy resins such as alkynyl glycidyl ether and phenyl glycidyl ether; alkyl glycidyl esters and alkenyl glycidyl esters with carbon numbers of 6 to 36 (typically 6 to 26, such as 6 to 18) Glycidyl ester-based epoxy resins such as glycerides and phenyl glycidyl esters. These resins may be used individually by 1 type, and may use 2 or more types together. Among them, alkyl glycidyl ether, phenyl glycidyl ether, alkyl glycidyl ester, and phenyl glycidyl ester are preferred. Especially preferred is phenyl glycidyl ether.
多官能環氧樹脂與單官能環氧樹脂之質量比率並無特別限定，作為大致標準，較佳為單官能環氧樹脂佔環氧樹脂總體的一半以上。於一較佳例中，多官能環氧樹脂與單官能環氧樹脂之質量比率大致為20：80~45：55、例如20：80~30：70。藉此，可較佳地獲得適於雷射加工的相對較薄的(例如10μm以下的)導電膜。另外，可獲得以更高的水準兼具導電性與耐久性的電極配線。 The mass ratio of the multifunctional epoxy resin and the monofunctional epoxy resin is not particularly limited. As a rough guideline, it is preferable that the monofunctional epoxy resin accounts for more than half of the total epoxy resin. In a preferred example, the mass ratio of the multifunctional epoxy resin to the monofunctional epoxy resin is approximately 20:80~45:55, for example 20:80~30:70. Thereby, a relatively thin (for example, 10 μm or less) conductive film suitable for laser processing can be obtained. In addition, it is possible to obtain electrode wiring that has both conductivity and durability at a higher level.
熱硬化性樹脂的性狀並無特別限定，數量平均分子量Mc大致可為5000以下、較佳為2000以下、例如100~1000。若數量平均分子量Mc為既定值以下，則熱硬化性樹脂的熱分解性提高，雷射加工性可進一步提高。另外，印刷糊時自製版的脫離性(脫模性)變良好，印刷精度可提高。進而，若數量平均分子量Mc為既定值以上，則與基材的接著性或配線電極的形狀一體性可提高。 The properties of the thermosetting resin are not particularly limited, and the number average molecular weight Mc may be approximately 5000 or less, preferably 2000 or less, for example, 100 to 1000. If the number average molecular weight Mc is equal to or less than a predetermined value, the thermal decomposition property of the thermosetting resin is improved, and the laser processability can be further improved. In addition, the releasability (releasability) of the self-made plate when printing paste becomes better, and the printing accuracy can be improved. Furthermore, if the number average molecular weight Mc is more than a predetermined value, the adhesiveness with a base material and the shape integration of a wiring electrode can improve.
於將導電性粉末設為100質量份時，糊中的熱硬化性樹脂的含有比例為35質量份以下。於一較佳例中，熱硬化性樹脂的含有比例為25質量份以下，更佳為20質量份以下。藉此，可實現導電性優異的電極配線。 When the conductive powder is 100 parts by mass, the content of the thermosetting resin in the paste is 35 parts by mass or less. In a preferred example, the content ratio of the thermosetting resin is 25 parts by mass or less, more preferably 20 parts by mass or less. Thereby, electrode wiring with excellent conductivity can be realized.
熱硬化性樹脂的含有比例的下限值並無特別限定，大致可為2質量份以上、較佳為5質量份以上、例如8質量份以上。藉此可實現接著性或耐久性、可靠性更優異的電極配線。 The lower limit of the content of the thermosetting resin is not particularly limited, and it may be approximately 2 parts by mass or more, preferably 5 parts by mass or more, for example, 8 parts by mass or more. As a result, electrode wiring with more excellent adhesiveness, durability, and reliability can be realized.
熱硬化性樹脂於糊的必需構成成分的總質量(即(a)+ (b)+(c))中所佔的比例大致可為3質量%以上、較佳為5質量%以上、例如8質量%以上，且典型而言可為30質量%以下、較佳為25質量%以下、例如20質量%以下。若熱硬化性樹脂的比例為既定值以上，則可適度提高糊的黏性，獲得良好的印刷性。另外，若熱硬化性樹脂的比例為既定值以下，則印刷糊時自製版的脫離變良好，可抑制拉絲等不良狀況。因此，可獲得精度高的細線狀的電極配線，能以更高的水準發揮本發明的效果。 The total mass of the necessary components of the thermosetting resin in the paste (i.e. (a) + (b)+(c)) can be approximately 3% by mass or more, preferably 5% by mass or more, for example, 8% by mass or more, and typically can be 30% by mass or less, preferably 25 Mass% or less, for example, 20 mass% or less. If the ratio of the thermosetting resin is more than a predetermined value, the viscosity of the paste can be appropriately increased, and good printability can be obtained. In addition, if the ratio of the thermosetting resin is equal to or less than a predetermined value, the self-made plate will be better released when printing paste, and defects such as wire drawing can be suppressed. Therefore, it is possible to obtain fine wire-shaped electrode wiring with high accuracy, and the effect of the present invention can be exhibited at a higher level.
<(c)硬化劑> <(c) Hardener>
硬化劑為用以於所述熱硬化性樹脂的分子間形成交聯結構而使其硬化的成分。硬化劑並無特別限定，可根據熱硬化性樹脂的種類等而適當使用。例如於使用環氧樹脂作為熱硬化性樹脂的情形時，可使用能與該環氧樹脂的環氧基反應而形成交聯結構的化合物。一較佳例可列舉：咪唑系硬化劑、酸酐系硬化劑、酚系硬化劑、胺系硬化劑、醯胺系硬化劑、異氰酸酯系硬化劑、有機膦類及該些化合物的衍生物等。該些化合物可單獨使用一種，亦可併用兩種以上。 The curing agent is a component for forming a cross-linked structure between molecules of the thermosetting resin and curing it. The curing agent is not particularly limited, and can be appropriately used according to the type of thermosetting resin and the like. For example, when an epoxy resin is used as the thermosetting resin, a compound that can react with the epoxy group of the epoxy resin to form a crosslinked structure can be used. A preferred example includes imidazole-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, amine-based curing agents, amide-based curing agents, isocyanate-based curing agents, organic phosphines, and derivatives of these compounds. These compounds may be used alone or in combination of two or more.
糊中的硬化劑的含有比例並無特別限定，於將導電性粉末設為100質量份時，通常可為0.5質量份以上、較佳為1質量份以上、例如2質量份以上，且典型而言可為7質量份以下、例如5質量份以下。藉此，可防止發生硬化不良而使硬化反應順暢地進行。另外，可防止未反應的硬化劑殘留而將體積電阻抑制得更低。 The content ratio of the curing agent in the paste is not particularly limited. When the conductive powder is 100 parts by mass, it can usually be 0.5 parts by mass or more, preferably 1 part by mass or more, for example, 2 parts by mass or more, and typically It may be 7 parts by mass or less, for example, 5 parts by mass or less. Thereby, it is possible to prevent the occurrence of poor curing and allow the curing reaction to proceed smoothly. In addition, the unreacted hardener can be prevented from remaining and the volume resistance can be suppressed lower.
硬化劑於糊的必需構成成分的總質量(即(a)+(b)+ (c))中所佔的比例並無特別限定，大致可為0.1質量%以上、較佳為0.5質量%以上、例如1質量%以上，且典型而言可為5質量%以下、較佳為3質量%以下、例如2.5質量%以下。藉由滿足所述範圍，可穩定地形成體積電阻得以降低的電極配線。 The total mass of the necessary components of the hardener in the paste (i.e. (a) + (b) + The proportion in (c)) is not particularly limited, and it can be generally 0.1% by mass or more, preferably 0.5% by mass or more, for example, 1% by mass or more, and typically can be 5% by mass or less, preferably 3% by mass or less, for example, 2.5% by mass or less. By satisfying the above range, it is possible to stably form electrode wiring with reduced volume resistance.
<(d)其他成分> <(d) Other ingredients>
此處揭示的糊除了所述(a)成分~(c)成分(即，導電性粉末、熱硬化性樹脂及硬化劑)以外，視需要可含有各種添加成分。此種添加成分的一例可列舉：反應促進劑(助觸媒)、雷射光吸收劑、無機填料、界面活性劑、分散劑、增黏劑、消泡劑、塑化劑、穩定劑、抗氧化劑、顏料、稀釋溶媒等。該些添加成分可適當使用已知可用於通常的導電性糊中的成分。 The paste disclosed here may contain various additional components as needed in addition to the above-mentioned (a) component to (c) component (that is, conductive powder, thermosetting resin, and curing agent). Examples of such additives include: reaction accelerators (catalysts), laser light absorbers, inorganic fillers, surfactants, dispersants, tackifiers, defoamers, plasticizers, stabilizers, and antioxidants , Pigments, dilution solvents, etc. As these additional components, those known to be used in general conductive pastes can be suitably used.
反應促進劑(助觸媒)例如可列舉：含有鋯(Zr)、鈦(Ti)、鋁(Al)、錫(Sn)等金屬元素的醇鹽、螯合物(錯合物)、醯化物。該些化合物可單獨使用一種，亦可併用兩種以上。其中，較佳為含有有機鋯化合物。 Examples of reaction accelerators (co-catalysts) include alkoxides, chelate (complex), and acyl compounds containing metal elements such as zirconium (Zr), titanium (Ti), aluminum (Al), and tin (Sn) . These compounds may be used alone or in combination of two or more. Among them, it is preferable to contain an organic zirconium compound.
另外，稀釋溶媒例如可列舉二醇系溶劑、二醇醚系溶劑、酯系溶劑、醇系溶劑、烴系溶劑等有機溶劑。 In addition, examples of the dilution solvent include organic solvents such as glycol solvents, glycol ether solvents, ester solvents, alcohol solvents, and hydrocarbon solvents.
添加成分的含有比例並無特別限定，於將導電性粉末設為100質量份時，例如可為10質量份以下、較佳為5質量份以下、更佳為3質量份以下。 The content ratio of the additive component is not particularly limited, and when the conductive powder is 100 parts by mass, for example, it may be 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.
<糊的製備> <Preparation of Paste>
此種糊可藉由以下方式製備：以成為既定的含有率(質量比 率)的方式秤量所述材料，均質地攪拌混合。材料的攪拌混合可使用以前公知的各種攪拌混合裝置、例如輥磨機、磁力攪拌機、行星式混合機、分散機等來進行。 This paste can be prepared by the following method: to become a predetermined content rate (mass ratio Weigh the materials by means of rate), stir and mix homogeneously. Stirring and mixing of materials can be performed using various known stirring and mixing devices, such as roller mills, magnetic stirrers, planetary mixers, and dispersers.
<糊的使用方法> <How to use paste>
於糊的一使用例中，首先準備基板。基板並無特別限定，例如可考慮塑膠基板、玻璃基板、非晶矽基板等。尤其於採用包含耐熱性低的材料的基板的情形時，可較佳地採用本發明。 In an example of use of the paste, a substrate is first prepared. The substrate is not particularly limited. For example, a plastic substrate, a glass substrate, an amorphous silicon substrate, etc. can be considered. Especially when a substrate containing a material with low heat resistance is used, the present invention can be preferably adopted.
繼而，於該基板上以成為所需厚度(例如1μm~50μm、較佳為1μm~10μm)的方式賦予(典型而言為印刷)糊。此時，較所需的電極配線的尺寸稍大(寬廣)地賦予糊。糊的賦予例如可使用網版印刷、棒塗機、狹縫塗佈機、凹版塗佈機、浸漬塗佈機、噴霧塗佈機等進行。 Then, the paste is applied (typically, printed) on the substrate so as to have a desired thickness (for example, 1 μm to 50 μm, preferably 1 μm to 10 μm). At this time, the paste is applied slightly larger (wider) than the size of the required electrode wiring. The application of the paste can be performed using screen printing, bar coater, slit coater, gravure coater, dip coater, spray coater, etc., for example.
繼而，對賦予至基板上的糊進行加熱乾燥。加熱溫度例如可設定為(b)熱硬化性樹脂的玻璃轉移點以上的溫度。藉此，使所賦予的糊硬化，於基板上形成膜狀的導電體(導電膜)。 Then, the paste applied on the substrate is heated and dried. The heating temperature can be set to a temperature higher than the glass transition point of (b) thermosetting resin, for example. Thereby, the applied paste is cured, and a film-like conductor (conductive film) is formed on the substrate.
繼而，以導電膜成為所需形狀(例如細線狀)的電極的方式實施遮蓋，對除此以外的部位照射雷射光。 Then, masking is performed so that the conductive film becomes an electrode of a desired shape (for example, a thin line shape), and laser light is irradiated to other parts.
雷射的種類並無特別限定，可適當使用已知可用於此種用途中的雷射。一較佳例可列舉紅外線(Infrared，IR)雷射、纖維雷射、CO2雷射、準分子雷射、釔鋁石榴石(Yttrium Aluminum Garnet，YAG)雷射、半導體雷射等。例如可使用產生750nm~1500nm的波長範圍、進而900nm~1100nm的波長範圍的近紅外 雷射光的雷射。 The type of laser is not particularly limited, and known lasers that can be used for such applications can be appropriately used. A preferred example includes infrared (IR) lasers, fiber lasers, CO 2 lasers, excimer lasers, Yttrium Aluminum Garnet (YAG) lasers, semiconductor lasers, and the like. For example, a laser that generates near-infrared laser light in a wavelength range of 750 nm to 1500 nm, and further a wavelength range of 900 nm to 1100 nm can be used.
於一較佳例中，以雷射光的基本波長與基材的吸收波長範圍不一致方式選擇雷射的種類。例如以雷射光的基本波長成為基材的吸收波長範圍的倍波(2倍波、3倍波等)的方式選擇雷射的種類。藉此可將對基材的損傷抑制為最小限度。 In a preferred embodiment, the type of laser is selected in such a way that the basic wavelength of the laser light is inconsistent with the absorption wavelength range of the substrate. For example, the type of laser is selected so that the basic wavelength of the laser light becomes a double (double wave, triple wave, etc.) in the absorption wavelength range of the substrate. This can minimize damage to the substrate.
於另一較佳例中，以雷射光的基本波長與構成導電膜的成分的吸收波長範圍一致的方式選擇雷射種類。藉此，導電膜對雷射光的波長具有吸收帶，由此可提高雷射加工時的作業性或生產性。例如於構成導電膜的硬化膜(具體而言利用(c)硬化劑使所述(b)熱硬化性樹脂硬化而成的硬化物)的吸收波長範圍在大致9000cm-1~10000cm-1、例如9300cm-1~9900cm-1的範圍內的情形時，可較佳地使用基本波長1064nm的IR雷射。 In another preferred embodiment, the type of laser is selected in such a way that the fundamental wavelength of the laser light coincides with the absorption wavelength range of the components constituting the conductive film. Thereby, the conductive film has an absorption band with respect to the wavelength of the laser light, thereby improving the workability and productivity during laser processing. For example, the absorption wavelength range of the cured film (specifically, the cured product formed by curing the (b) thermosetting resin with the (c) curing agent) of the conductive film is approximately 9000 cm -1 to 10000 cm -1 , for example When it is in the range of 9300 cm -1 to 9900 cm -1 , an IR laser with a fundamental wavelength of 1064 nm can be preferably used.
雷射光的照射條件並無特別限定。例如雷射輸出亦取決於導電膜的厚度等，就避免對基材的損傷並且將導電膜的不需要的部位適當地去除的觀點而言，大致可為0.5W~100W。例如於使用IR雷射對厚度為1μm~10μm左右的導電膜進行加工的情形時，可將雷射輸出設為1W~10W左右。 The irradiation conditions of the laser light are not particularly limited. For example, the laser output also depends on the thickness of the conductive film, etc. From the viewpoint of avoiding damage to the base material and appropriately removing unnecessary parts of the conductive film, it can be approximately 0.5W-100W. For example, when using an IR laser to process a conductive film with a thickness of about 1 μm to 10 μm, the laser output can be set to about 1W to 10W.
另外，就維持生產性高並且將導電膜的不需要的部位適當地去除的觀點而言，雷射的掃描速度大致可為1000mm/s~10000mm/s、例如1500mm/s~5000mm/s。 In addition, from the viewpoint of maintaining high productivity and appropriately removing unnecessary parts of the conductive film, the scanning speed of the laser may be approximately 1000 mm/s to 10000 mm/s, for example, 1500 mm/s to 5000 mm/s.
另外，雷射光的照射環境可設為大氣環境、惰性環境、還原性環境等。 In addition, the laser light irradiation environment can be an atmospheric environment, an inert environment, a reducing environment, etc.
雷射的光能被轉換成熱能，到達導電膜。藉此，於雷射光的照射部位中將導電膜熱分解並加以熔融、去除。而且，僅於未經雷射光照射的部位中殘存導電膜，而形成電極配線。 The light energy of the laser is converted into heat energy and reaches the conductive film. Thereby, the conductive film is thermally decomposed, melted, and removed in the area irradiated by the laser light. In addition, the conductive film remains only in the portion not irradiated with the laser light, and the electrode wiring is formed.
如以上般，可獲得於基板上具備既定圖案的電極配線的結構體(配線基板)。 As described above, a structure (wiring board) provided with electrode wiring of a predetermined pattern on the substrate can be obtained.
<糊的用途> <Use of Paste>
此處揭示的雷射蝕刻用加熱硬化型導電性糊可形成高耐久的電極。另外，此處揭示的雷射蝕刻用加熱硬化型導電性糊由於雷射加工性優異，故尤其可較佳地用於形成L/S=80μm/80μm以下、進而L/S=50μm/50μm以下的細線狀的電極配線。 The heat-curable conductive paste for laser etching disclosed here can form highly durable electrodes. In addition, the heat-curing conductive paste for laser etching disclosed here is excellent in laser processability, so it can be particularly preferably used for forming L/S=80μm/80μm or less, and further L/S=50μm/50μm or less The thin wire-shaped electrode wiring.
具代表性的一使用用途可列舉：各種電子零件的電極形成，或具有柔性基板的觸控面板或液晶顯示器、電子紙等柔性元件的導體電路的形成。柔性基板例如可例示：包含聚丙烯(polypropylene，PP)、聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)、聚萘二甲酸乙二酯(polyethylene naphthalate，PEN)、聚碳酸酯(polycarbonate，PC)、聚醯胺等樹脂的膜狀的塑膠基板，或玻璃基板等。再者，亦可為於柔性基板上成膜有氧化銦錫(Indium Tin Oxide，ITO)膜等包含氧化物的導電膜的狀態。 A representative application can include the formation of electrodes of various electronic parts, or the formation of conductor circuits of flexible elements such as touch panels with flexible substrates, liquid crystal displays, and electronic paper. Examples of flexible substrates include polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polycarbonate (polycarbonate, PC), polyamide and other resin film-like plastic substrates, or glass substrates. Furthermore, it may be a state in which a conductive film containing an oxide, such as an indium tin oxide (ITO) film, is formed on the flexible substrate.
以下，對與本發明有關的若干實施例加以說明，但其意並非將本發明限定於該實施例所示的內容。 Hereinafter, some embodiments related to the present invention will be described, but the intention is not to limit the present invention to the content shown in the embodiments.
首先，準備成為雷射蝕刻用加熱硬化型導電性糊的構成成分的以下材料。 First, the following materials are prepared as constituent components of the heat-curable conductive paste for laser etching.
<導電性粉末> <Conductive powder>
．導電性粉末1：球狀銀粉末 . Conductive powder 1: spherical silver powder
(同和電子(DOWA ELECTRONICS)股份有限公司製造，D50=0.5μm，平均縱橫比為1.0) (Manufactured by DOWA ELECTRONICS Co., Ltd., D 50 =0.5μm, average aspect ratio is 1.0)
．導電性粉末2：球狀銀粉末 . Conductive powder 2: spherical silver powder
(同和電子(DOWA ELECTRONICS)股份有限公司製造，D50=1.0μm，平均縱橫比為1.1) (Manufactured by DOWA ELECTRONICS Co., Ltd., D 50 =1.0μm, average aspect ratio is 1.1)
．導電性粉末3：球狀銀粉末 . Conductive powder 3: spherical silver powder
(同和電子(DOWA ELECTRONICS)股份有限公司製造，D50=3.0μm，平均縱橫比為1.1) (Manufactured by DOWA ELECTRONICS Co., Ltd., D 50 =3.0μm, average aspect ratio is 1.1)
．導電性粉末4：球狀塗銀銅粉末 . Conductive powder 4: spherical silver-coated copper powder
(同和電子(DOWA ELECTRONICS)股份有限公司製造，D50=2.2μm，平均縱橫比為1.1) (Manufactured by DOWA ELECTRONICS Co., Ltd., D 50 =2.2μm, average aspect ratio is 1.1)
．導電性粉末5：塗銀銅-鋅合金粉末 . Conductive powder 5: silver-coated copper-zinc alloy powder
(同和電子(DOWA ELECTRONICS)股份有限公司製造，D50=2.2μm，平均縱橫比為1.1) (Manufactured by DOWA ELECTRONICS Co., Ltd., D 50 =2.2μm, average aspect ratio is 1.1)
．導電性粉末6：球狀銀粉末 . Conductive powder 6: spherical silver powder
(福田金屬箔股份有限公司製造，D50=2.5μm，平均縱橫比為1.4) (Manufactured by Futian Metal Foil Co., Ltd., D 50 =2.5μm, average aspect ratio is 1.4)
．導電性粉末7：鱗片狀銀粉末 . Conductive powder 7: scaly silver powder
(同和電子(DOWA ELECTRONICS)股份有限公司製造，D50=15μm，平均縱橫比為16.7) (Manufactured by DOWA ELECTRONICS Co., Ltd., D 50 =15μm, average aspect ratio is 16.7)
<多官能環氧樹脂> <Multifunctional epoxy resin>
．多官能環氧樹脂A：酚醛清漆型環氧樹脂 . Multifunctional epoxy resin A: Novolac type epoxy resin
(日本化藥股份有限公司製造，環氧當量為193g/eq，數量平均分子量Mc為1100) (Manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is 193g/eq, number average molecular weight Mc is 1100)
．多官能環氧樹脂B：雙酚改質型環氧樹脂 . Multifunctional epoxy resin B: Bisphenol modified epoxy resin
(迪愛生(DIC)股份有限公司製造，環氧當量為403g/eq，數量平均分子量Mc為800) (Manufactured by DIC Co., Ltd., epoxy equivalent is 403g/eq, number average molecular weight Mc is 800)
<單官能環氧樹脂> <Monofunctional epoxy resin>
．苯基縮水甘油醚型環氧樹脂 . Phenyl glycidyl ether type epoxy resin
(艾迪科(ADEKA)股份有限公司製造，環氧當量為206g/eq，數量平均分子量Mc為210) (Manufactured by ADEKA Co., Ltd., epoxy equivalent is 206g/eq, number average molecular weight Mc is 210)
<硬化劑> <hardener>
．咪唑系硬化劑 . Imidazole hardener
(味之素精密技術(Ajinomoto Fine-techno)股份有限公司製造，環氧咪唑加合物) (Manufactured by Ajinomoto Fine-techno Co., Ltd., epoxy imidazole adduct)
<添加劑(觸媒)> <Additive (catalyst)>
．有機鋯化合物 . Organic Zirconium Compound
(松本精化(Matsumoto Fine Chemical)股份有限公司製造，四乙醯丙酮鋯) (Manufactured by Matsumoto Fine Chemical Co., Ltd., zirconium tetraacetone)
[導電膜的形成] [Formation of conductive film]
將所述準備的材料以成為表1所示的質量比率的方式秤量、混合，製備加熱硬化型導電性糊(例1~例9、參考例1~參考例 3)。 The prepared materials were weighed and mixed so as to become the mass ratio shown in Table 1 to prepare heat-curing conductive pastes (Example 1 to Example 9, Reference Example 1 to Reference Example 3).
將所述製備的糊以5μm左右的厚度以□10cm×10cm的正方形形狀網版印刷(全面塗佈)於玻璃基板的表面上，於150℃下進行30分鐘加熱乾燥。藉此，於玻璃基板上形成導電膜(硬化膜)。 The prepared paste was screen-printed on the surface of the glass substrate in a square shape of □10cm×10cm with a thickness of about 5 μm (overall coating), and heated and dried at 150°C for 30 minutes. Thereby, a conductive film (cured film) is formed on the glass substrate.
[雷射加工性的評價] [Evaluation of Laser Processability]
以如下條件對所述形成的導電膜照射雷射，嘗試形成L/S=30μm/30μm的細線。 The conductive film formed as described above was irradiated with a laser under the following conditions, and an attempt was made to form a thin line of L/S=30 μm/30 μm.
<雷射加工條件> <Laser processing conditions>
．雷射種類：IR雷射(基本波長：1064nm) . Laser type: IR laser (basic wavelength: 1064nm)
．雷射輸出：5W . Laser output: 5W
．掃描速度：2000mm/s . Scanning speed: 2000mm/s
利用雷射顯微鏡對藉由所述雷射加工形成的細線進行觀察，評價雷射加工性。顯微鏡觀察時，以倍率10來確認三個視場。將結果示於表1的「雷射加工性」的欄中。表1中，「◎」表示並無斷線或切削殘餘，且殘留線寬為20μm以上且30μm以下，「○」表示並無斷線或切削殘餘，且殘留線寬為10μm以上且小於20μm，「△」表示並無斷線或切削殘餘，但殘留線寬小於10μm，「×」表示於雷射照射部中有斷線或切削殘餘。將例2的觀察圖像示於圖2中。另外，將評價為「×」的參考例的觀察圖像示於圖3中。 The thin lines formed by the laser processing were observed with a laser microscope to evaluate the laser processing properties. During microscope observation, three fields of view are confirmed at a magnification of 10. The results are shown in the "laser processability" column of Table 1. In Table 1, "◎" means that there is no wire breakage or cutting residue, and the residual line width is 20μm or more and 30μm or less, "○" means that there is no wire breakage or cutting residue, and the residual line width is 10μm or more and less than 20μm, "△" means that there is no broken wire or cutting residue, but the residual line width is less than 10μm, "×" means that there is broken wire or cutting residue in the laser irradiation part. The observation image of Example 2 is shown in FIG. 2. In addition, the observation image of the reference example evaluated as "×" is shown in FIG. 3.
[吸收波長的測定] [Measurement of absorption wavelength]
使用紫外可見近紅外分光光度計測定所述製備的糊的吸收波長。將結果示於表1的「吸收波長」的欄中。 The absorption wavelength of the prepared paste was measured using an ultraviolet-visible-near infrared spectrophotometer. The results are shown in the column of "absorption wavelength" in Table 1.
[接著性的評價] [Subsequent evaluation]
於所述形成的細線上貼附賽珞凡膠帶(Cellophane tape)，自其上按壓橡皮而充分密接後，以45°的角度將賽珞凡膠帶一下子剝離，評價接著性。將結果示於表1的「接著性」的欄中。表1中，「○」表示未確認到細線的剝離(導電膜對賽珞凡膠帶的附著)，「×」表示確認到細線的剝離。 A cellophane tape was attached to the thin thread formed, and the rubber was pressed from it to fully adhere the cellophane tape, and then the cellophane tape was peeled off at an angle of 45° to evaluate the adhesion. The results are shown in the column of "Adhesion" in Table 1. In Table 1, "○" indicates that the peeling of the thin line (adhesion of the conductive film to the Cyrofan tape) was not confirmed, and "×" indicates that the peeling of the thin line was confirmed.
[體積電阻的測定] [Measurement of volume resistance]
使用電阻率計(三菱化學分析儀器(Mitsubishi Chemical Analytech)股份有限公司製造，型號：低阻計(Loresta)GP MCP-T610)測定所述形成的細線的體積電阻率。具體而言，使端子與細線的一個端部和另一端部接觸，利用二端子法測定電阻。另外，利用雷射顯微鏡來觀察細線的剖面，測定細線的剖面積。根據所得的電阻及剖面積算出體積電阻率。將結果示於表1的「體積電阻率」的欄中。 A resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., model: Loresta GP MCP-T610) was used to measure the volume resistivity of the thin wire formed. Specifically, the terminal is brought into contact with one end and the other end of the thin wire, and the resistance is measured by the two-terminal method. In addition, a laser microscope was used to observe the cross section of the thin line to measure the cross-sectional area of the thin line. Calculate the volume resistivity from the obtained resistance and cross-sectional area. The results are shown in the column of "Volume Resistivity" in Table 1.
如表1及圖2所示，例1~例9的雷射加工性優異。另外，例1~例9與基材的接著性高，體積電阻率亦可抑制於200μΩ．cm以下(較佳為150μΩ．cm以下、尤其100μΩ．cm以下)。 As shown in Table 1 and Figure 2, the laser processability of Examples 1 to 9 is excellent. In addition, the adhesion of Examples 1 to 9 to the substrate is high, and the volume resistivity can be suppressed to 200μΩ. cm or less (preferably 150 μΩ·cm or less, especially 100 μΩ·cm or less).
相對於此，於使用平均粒徑超過3μm及/或縱橫比超過1.5的導電性粉末的參考例1、參考例2中，雷射加工性降低。另外，於樹脂的含有比例超過40質量份的參考例3中，雷射加工性降低，進而體積電阻率亦大幅度地劣化。 In contrast, in Reference Example 1 and Reference Example 2 in which conductive powder having an average particle diameter of more than 3 μm and/or an aspect ratio of more than 1.5 was used, the laser processability was reduced. In addition, in Reference Example 3 in which the resin content ratio exceeded 40 parts by mass, the laser processability was reduced, and the volume resistivity was also greatly deteriorated.
例1~例9中，例1~例3、例7的雷射加工性尤其優異。其原因雖不確定，但可推測：導電性粉末包含銀，或縱橫比小於1.4，故雷射加工適性提高(即，電極配線被多餘地削去的情況少)等。 Among Examples 1 to 9, the laser processability of Examples 1 to 3 and 7 is particularly excellent. Although the reason is not certain, it can be presumed that the conductive powder contains silver or the aspect ratio is less than 1.4, so the suitability for laser processing is improved (that is, the electrode wiring is less likely to be scraped off).
另外，例1~例6中，例1、例2、例3、例6可將體積電阻率抑制於100μΩ．cm以下。關於其原因，可推測：導電性粉末的材質不同，即，銀粉末的導電性較塗銀銅粉末更優異。尤其於使用導電性粉末2的例2中，體積電阻率被抑制得最低，為55μΩ．cm以下。其原因雖不確定，但可想到平均粒徑與樹脂量的平衡。即，關於例3~例6，平均粒徑大於(換言之比表面積小於)例2，每比表面積的樹脂量變多。因此可推測，存在於導電性粒子間的界面的樹脂量變多，體積電阻率較例2增加等。另外，關於例1，可推測由於平均粒徑小於例2，因而導電性粒子彼此的接觸點增加而界面電阻增大，體積電阻率較例2增加等。
In addition, among Examples 1 to 6, Examples 1, 2, 3, and 6 can suppress the volume resistivity to 100μΩ. cm below. As for the reason, it can be presumed that the material of the conductive powder is different, that is, the conductivity of the silver powder is better than that of the silver-coated copper powder. Especially in Example 2 where
該些結果示出規定導電性粉末的性狀、及導電性粉末與熱硬化性樹脂之調配比的本申請案發明的技術意義。 These results show the technical significance of the invention of the present application that defines the properties of the conductive powder and the blending ratio of the conductive powder and the thermosetting resin.
以上，對本發明進行了詳細說明，但這些說明僅為例示，本發明可於不偏離其主旨的範圍內加以各種變更。 The present invention has been described in detail above, but these descriptions are only examples, and various changes can be made to the present invention within a range that does not deviate from the gist.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015068364 | 2015-03-30 | ||
| JP2015-068364 | 2015-03-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201634517A TW201634517A (en) | 2016-10-01 |
| TWI700305B true TWI700305B (en) | 2020-08-01 |
Family
ID=57081063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW105105352A TWI700305B (en) | 2015-03-30 | 2016-02-24 | Heat-curing conductive paste for laser etching |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6242418B2 (en) |
| CN (1) | CN106024097B (en) |
| TW (1) | TWI700305B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500278A (en) * | 2001-03-28 | 2004-05-26 | E・I・内穆尔杜帮公司 | Compsn. for filling through-holes in printed wiring boards |
| JP2014216432A (en) * | 2013-04-24 | 2014-11-17 | 東洋インキＳｃホールディングス株式会社 | Composition for forming capacitor electrode, capacitor electrode, and capacitor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001236827A (en) * | 2000-02-23 | 2001-08-31 | Hitachi Chem Co Ltd | Conductive paste |
| JP2005317491A (en) * | 2004-04-01 | 2005-11-10 | Hitachi Chem Co Ltd | Conductive paste and electronic component mounting substrate using it |
| CN104488040B (en) * | 2012-07-20 | 2018-08-03 | 东洋纺株式会社 | Use circuit wiring, circuit and touch panel made of laser ablation processing conductive paste |
| JP2014107533A (en) * | 2012-11-29 | 2014-06-09 | Pelnox Ltd | Conductive paste composition for laser etching |
| JP6049606B2 (en) * | 2013-12-25 | 2016-12-21 | 株式会社ノリタケカンパニーリミテド | Heat-curing conductive paste |
-
2016
- 2016-02-24 TW TW105105352A patent/TWI700305B/en not_active IP Right Cessation
- 2016-03-16 JP JP2016052317A patent/JP6242418B2/en active Active
- 2016-03-30 CN CN201610190728.4A patent/CN106024097B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500278A (en) * | 2001-03-28 | 2004-05-26 | E・I・内穆尔杜帮公司 | Compsn. for filling through-holes in printed wiring boards |
| JP2014216432A (en) * | 2013-04-24 | 2014-11-17 | 東洋インキＳｃホールディングス株式会社 | Composition for forming capacitor electrode, capacitor electrode, and capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6242418B2 (en) | 2017-12-06 |
| CN106024097B (en) | 2019-06-28 |
| CN106024097A (en) | 2016-10-12 |
| TW201634517A (en) | 2016-10-01 |
| JP2016191042A (en) | 2016-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6174106B2 (en) | Conductive paste and method for producing conductive film | |
| TWI645421B (en) | Thermosetting conductive paste | |
| TWI733657B (en) | Heat-curing conductive paste | |
| TWI622998B (en) | Conductive composition and hardened product using the same | |
| US11479686B2 (en) | Conductive composition and wiring board using the same | |
| TW201833940A (en) | Conductive composition | |
| TWI708821B (en) | Heat-curing conductive paste | |
| TWI695657B (en) | Flexible wiring board and its utilization | |
| JP6373293B2 (en) | Heat-curing conductive paste | |
| TWI700305B (en) | Heat-curing conductive paste for laser etching | |
| KR20150060683A (en) | Anisotropic conductive film, connection method, and connected body | |
| US20210243893A1 (en) | Printed circuit board and method of manufacturing printed circuit board | |
| JP2013112807A (en) | Conductive ink composition and method of producing conductive pattern | |
| TWI690556B (en) | Heat-curable conductive paste and conductive coating | |
| US20210238442A1 (en) | Printed wiring board, printed circuit board, and method of manufacturing printed wiring board | |
| WO2019058727A1 (en) | Conductive composition and wiring board using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |