TWI783947B - Conductive film composite and production method thereof - Google Patents

Abstract

A conductive film composite and a production method thereof are provided. The conductive film composite includes a substrate and a conductive film. Even though a substrate with low thermal resistance or glass substrate is used, the conductive film composite still has good adhesiveness of the conductive film with respect to the substrate and excellent conductivity and thermal resistance of the conductive film. The invention relates to a conductive film composite, including: a substrate; a resin layer formed on at least one portion of the substrate; and a conductive film formed on at least one portion of the resin layer, and the conductive film is a sintered body of fine silver particles, and the resin layer has a layer thickness of 1 μm or less.

Description

導電性塗層複合體及其製造方法 Conductive coating composite and method of manufacturing the same

本發明是有關於一種可較佳地用於半導體積體電路等的配線、印刷配線板的配線、透明電極及相對於有機薄膜電晶體基板的配線或電極的導電性塗層複合體及其製造方法，所述導電性塗層複合體具有基材與導電性塗層。 The present invention relates to a conductive coating complex that can be preferably used for wiring of semiconductor integrated circuits, wiring of printed wiring boards, transparent electrodes, wiring or electrodes for organic thin film transistor substrates, and its manufacture In the method, the conductive coating composite has a substrate and a conductive coating.

先前已知如下方法：藉由濺鍍或蒸鍍等，於基板的整個面上形成金屬薄膜後，利用光微影法對不需要的部分進行蝕刻而形成所需的導電膜圖案。然而，該方法除了步驟繁雜以外，還需要使用高價的真空裝置。 Conventionally, a method is known in which a metal thin film is formed on the entire surface of a substrate by sputtering or vapor deposition, and then an unnecessary portion is etched by photolithography to form a desired conductive film pattern. However, in addition to complicated steps, this method also requires the use of an expensive vacuum device.

因此，要求更簡便且廉價的導電膜圖案的形成方法，近年來，提出了使用凸版印刷法、凹版印刷法、網版印刷法、噴墨印刷法等印刷法的方法。進而，作為能夠形成更高精細的圖案的印刷方法，提出了使用反轉印刷法或微接觸印刷法等的方法，正在開發適合於該些印刷法的導電性油墨、絕緣性油墨及電阻油墨等各種油墨。此處，特別關注的是利用銀微粒子的低溫燒結性的導電性油墨。 Therefore, a simpler and less expensive method of forming a conductive film pattern is required, and in recent years, methods using printing methods such as letterpress printing, gravure printing, screen printing, and inkjet printing have been proposed. Furthermore, as a printing method capable of forming higher-definition patterns, methods using reverse printing or microcontact printing have been proposed, and conductive inks, insulating inks, and resistive inks suitable for these printing methods are being developed. Various inks. Here, a low-temperature sinterable conductive ink utilizing silver microparticles is of particular interest.

例如，於專利文獻1(日本專利特開2012-162767號公 報)中揭示有一種被覆金屬微粒子的製造方法，其特徵在於包括：第一步驟，將胺混合液與包含金屬原子的金屬化合物混合而生成包含該金屬化合物與胺的錯化合物，所述胺混合液包含碳數為6以上的烷基胺與碳數為5以下的烷基胺；及第2步驟，藉由對該錯化合物進行加熱而使其分解，從而生成金屬微粒子。 For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2012-162767 Newspaper) discloses a method for producing coated metal microparticles, which is characterized in that it includes: a first step, mixing the amine mixture solution with a metal compound containing metal atoms to generate an aluminum compound containing the metal compound and amine, and the amine is mixed The solution includes alkylamines with 6 or more carbon atoms and alkylamines with 5 or less carbon atoms; and the second step is to decompose the aluminum compound by heating to generate metal fine particles.

於所述專利文獻1中，於藉由金屬胺錯合物分解法來製造被覆金屬微粒子的過程中，可順暢地生成胺與金屬化合物的錯化合物，可縮短製造所需的時間。另外，根據被覆金屬微粒子的用途等，可使用各種胺，因此可提供於例如100℃以下的溫度下亦可順暢地進行燒結的被覆金屬微粒子，且於如聚對苯二甲酸乙二酯(Polyethylene terephthalate，PET)及聚丙烯般的耐熱性低的塑膠基板上亦可形成導電膜、導電配線。 In the above-mentioned Patent Document 1, in the process of producing coated metal microparticles by the metal amine complex decomposition method, the complex compound of amine and metal compound can be smoothly generated, and the time required for production can be shortened. In addition, various amines can be used depending on the application of the coated metal microparticles. Therefore, it is possible to provide coated metal microparticles that can be sintered smoothly even at a temperature of 100° C. or lower. terephthalate, PET) and polypropylene-like plastic substrates with low heat resistance can also form conductive films and conductive wiring.

另外，於專利文獻2(日本專利特開2013-142173號公報)中揭示有一種銀奈米粒子的製造方法，其包括：製備胺混合液，將包含脂肪族烴基及一個胺基、且該脂肪族烴基的碳總數為6以上的脂肪族烴單胺(A)，與包含脂肪族烴基及一個胺基、且該脂肪族烴基的碳總數為5以下的脂肪族烴單胺(B)，以胺(A)與胺(B)的合計為基準，以胺(A)5莫耳%以上且小於20莫耳%、及胺(B)超過80莫耳%且95莫耳%以下的比例包含；將銀化合物與所述胺混合液混合，而生成包含銀化合物及胺的錯化合物；對錯化合物進行加熱使其熱分解，而形成銀奈米粒子。 In addition, in Patent Document 2 (Japanese Patent Application Laid-Open No. 2013-142173), a method for producing silver nanoparticles is disclosed, which includes: preparing an amine mixed solution, which contains an aliphatic hydrocarbon group and an amine group, and the aliphatic an aliphatic hydrocarbon monoamine (A) having an aliphatic hydrocarbon group having a total carbon number of 6 or more, and an aliphatic hydrocarbon monoamine (B) comprising an aliphatic hydrocarbon group and an amine group and having a total carbon number of the aliphatic hydrocarbon group being 5 or less, and Based on the total of the amine (A) and the amine (B), the amine (A) is included in a ratio of 5 mol% to less than 20 mol%, and the amine (B) is contained in a ratio of more than 80 mol% to 95 mol% ; The silver compound is mixed with the amine mixture to generate an aluminum compound including the silver compound and the amine; the aluminum compound is heated to thermally decompose it to form silver nanoparticles.

於所述專利文獻2中，藉由使用包含碳總數6以上的脂 肪族烴單胺(A)與碳總數5以下的脂肪族烴單胺(B)的胺混合液，可獲得銀奈米粒子的適當的穩定化。 In the above-mentioned patent document 2, by using a fat containing a total number of carbons of 6 or more The amine mixture liquid of the aliphatic hydrocarbon monoamine (A) and the aliphatic hydrocarbon monoamine (B) whose total number of carbon atoms is 5 or less can obtain appropriate stabilization of the silver nanoparticles.

進而，亦提出有多種具有與基材的密接性優異的導電性塗層的導電性基材，例如，於專利文獻3(日本專利特開2008-149681號公報)中揭示有一種透光性導電性基材，其特徵在於：於支撐體上具有細線圖案與透明導電性層，所述細線圖案包含含有顯影銀的導電性金屬，且於支撐體與該細線圖案之間具有相對於水的膨潤率小於60%的易接著層。 Furthermore, various conductive substrates having conductive coatings with excellent adhesion to substrates have also been proposed. For example, a light-transmitting conductive A conductive base material, characterized in that: a thin line pattern and a transparent conductive layer are provided on a support, the thin line pattern includes a conductive metal containing developed silver, and there is swelling between the support body and the thin line pattern relative to water An easy-to-adhesive layer with a rate of less than 60%.

於所述專利文獻3中，於支撐體與細線圖案層之間設置易接著層，並將該層相對於水的膨潤率控制為小於60%，藉此高溫高濕環境下的耐久性或密接性顯著提高，並容易調整細線形狀(薄度與寬廣度)與導電性的併存性或細線形狀(薄度與寬廣度)與透光性的併存性。 In the above-mentioned Patent Document 3, an easy-adhesive layer is provided between the support body and the fine-line pattern layer, and the swelling rate of this layer with respect to water is controlled to be less than 60%, so that the durability or adhesion in high-temperature and high-humidity environments can be improved. The performance is significantly improved, and it is easy to adjust the coexistence of thin line shape (thinness and width) and conductivity or the coexistence of thin line shape (thinness and width) and light transmission.

另外，於專利文獻4(日本專利特開2014-196556號公報)中揭示有一種導電性材料的製造方法，其包括：(1)將樹脂層形成用組成物(b)塗佈於絕緣性基材(A)上而形成樹脂層(B)的步驟；(2)將分散液(C)塗佈於(1)中所獲得的樹脂層(B)上而形成非導電性層(D)的步驟，所述分散液(C)含有0.5質量%以上的由具有氮原子、硫原子、磷原子及氧原子的化合物(c1)保護而成的選自由金、銀、銅及鉑所組成的群組中的一種以上的金屬微粒子(c2)；及(3)對具有(2)中所獲得的非導電性層(D)的基材進行無電解鍍敷而形成導電層(E)的步驟，所述導電性材 料的製造方法的特徵在於：樹脂層形成用組成物(b)為含有胺基甲酸酯樹脂(b1)、乙烯基聚合物(b2)及水性介質(b3)的樹脂層形成用組成物。 In addition, Patent Document 4 (Japanese Patent Laid-Open No. 2014-196556) discloses a method for producing a conductive material, which includes: (1) applying the resin layer-forming composition (b) to an insulating substrate; the step of forming the resin layer (B) on the material (A); (2) applying the dispersion (C) on the resin layer (B) obtained in (1) to form the non-conductive layer (D) step, the dispersion (C) contains more than 0.5% by mass of a compound (c1) protected by a nitrogen atom, a sulfur atom, a phosphorus atom, and an oxygen atom selected from the group consisting of gold, silver, copper, and platinum. one or more metal microparticles (c2) in the group; and (3) a step of electrolessly plating the substrate having the non-conductive layer (D) obtained in (2) to form a conductive layer (E), The conductive material The method for producing a material is characterized in that the resin layer-forming composition (b) is a resin layer-forming composition containing a urethane resin (b1), a vinyl polymer (b2), and an aqueous medium (b3).

於所述專利文獻4中，藉由將樹脂層形成於各種絕緣性基材上，包含由特定的化合物保護而成的含有金、銀、銅、鉑的金屬微粒子的非導電性層可藉由塗佈法而容易獲得，另外，非導電性層顯示出優異的無電解鍍敷的觸媒活性且作為引起強密接性的鍍敷膜的立足點發揮功能，因此可無需真空設備而以低成本製造可於高密度安裝領域中使用的高性能導電性材料、印刷配線基板用基板、印刷配線板。 In the above-mentioned Patent Document 4, by forming a resin layer on various insulating substrates, a non-conductive layer containing metal fine particles containing gold, silver, copper, and platinum protected by a specific compound can be formed by It is easy to obtain by the coating method. In addition, the non-conductive layer exhibits excellent catalytic activity of electroless plating and functions as a foothold for a plated film that causes strong adhesion, so it can be produced at low cost without vacuum equipment. Manufactures high-performance conductive materials, substrates for printed wiring boards, and printed wiring boards that can be used in the field of high-density packaging.

[現有技術文獻] [Prior art literature]

[專利文獻] [Patent Document]

[專利文獻1]日本專利特開2012-162767號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2012-162767

[專利文獻2]日本專利特開2013-142173號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2013-142173

[專利文獻3]日本專利特開2008-149681號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2008-149681

[專利文獻4]日本專利特開2014-196556號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2014-196556

然而，於使用所述專利文獻1及專利文獻2中記載的銀奈米粒子的情況下，於低溫下進行煅燒而獲得的導電性塗層具有優異的導電性，但例如於將導電性塗層形成於聚對苯二甲酸乙二酯(Polyethylene terephthalate，PET)及聚萘二甲酸乙二酯 (Polyethylene naphthalate，PEN)等非耐熱性基材或玻璃基材上的情況下，難以確保對於基材的密接性。 However, in the case of using the silver nanoparticles described in Patent Document 1 and Patent Document 2, the conductive coating obtained by firing at a low temperature has excellent conductivity, but for example, the conductive coating Formed in polyethylene terephthalate (PET) and polyethylene naphthalate (Polyethylene naphthalate, PEN) and other non-heat-resistant substrates or glass substrates, it is difficult to ensure the adhesion to the substrate.

另外，於所述專利文獻3及專利文獻4中記載的導電性材料中，導電性塗層相對於基材的密接性良好，但有導電性塗層的導電性受損的情況。 In addition, in the conductive materials described in Patent Document 3 and Patent Document 4, the adhesiveness of the conductive coating to the base material is good, but the conductivity of the conductive coating may be impaired.

進而，於安裝時亦對導電性塗層要求耐熱性(例如於180℃環境下保持1分鐘)，結果極其難以形成除了該耐熱性以外，還全部兼具對於基材的密接性及導電性的導電性塗層。 Furthermore, heat resistance is also required for the conductive coating at the time of mounting (for example, holding at 180°C for 1 minute), and as a result, it is extremely difficult to form a coating that has both adhesion to the base material and conductivity in addition to the heat resistance. Conductive coating.

因此，本發明的目的在於提供一種即便於使用耐熱性低的基材或玻璃基材的情況下，亦兼具導電性塗層相對於基材的良好的密接性與導電性塗層的優異的導電性及耐熱性的導電性塗層複合體及其製造方法，所述導電性塗層複合體具有基材與導電性塗層。 Therefore, an object of the present invention is to provide a substrate having both good adhesion of the conductive coating to the substrate and excellent performance of the conductive coating even when using a substrate with low heat resistance or a glass substrate. A conductive and heat-resistant conductive coating composite and a manufacturing method thereof. The conductive coating composite has a base material and a conductive coating.

本發明者為了達成所述目的而反覆進行努力研究，結果發現如下情況於達成所述目的的方面極其有效，從而完成本發明，所述情況：為了獲得具有相對於基材的優異的密接性，且相對於耐熱性低的基材或玻璃基材，亦表現出良好導電性且耐熱性亦優異的導電性塗層複合體，而將具有特定的厚度的樹脂以密接層的形式形成於基材與導電性塗層之間，並使用特定的銀奈米粒子分散體來形成導電性塗層。 The inventors of the present invention have diligently studied to achieve the object, and as a result, found that the following is extremely effective in achieving the object, and thus completed the present invention. In order to obtain excellent adhesion to the base material, And compared to the base material or glass base material with low heat resistance, it also exhibits a conductive coating composite with good conductivity and excellent heat resistance, and a resin with a specific thickness is formed on the base material in the form of an adhesive layer Between the conductive coating and the use of a specific dispersion of silver nanoparticles to form a conductive coating.

即，本發明提供一種導電性塗層複合體，其特徵在於包 括：基材；樹脂層，形成於所述基材的至少一部分上；及導電性塗層，形成於所述樹脂層的至少一部分上，所述導電性塗層是由銀微粒子形成，所述樹脂層的膜厚為1μm以下。 That is, the present invention provides a conductive coating composite, characterized in that Comprising: a substrate; a resin layer formed on at least a part of the substrate; and a conductive coating formed on at least a part of the resin layer, the conductive coating is formed of silver particles, the The film thickness of the resin layer is 1 μm or less.

於本發明的導電性塗層複合體中，樹脂層作為基材與導電性塗層的密接層發揮功能，因此基材與導電性塗層具有良好的密接性。另外，藉由將樹脂層的膜厚設為1μm以下，樹脂層的膨潤、收縮的影響變小，可對導電性塗層賦予優異的耐熱性。 In the conductive coating composite of the present invention, since the resin layer functions as an adhesive layer between the base material and the conductive coating layer, the base material and the conductive coating layer have good adhesion. In addition, by setting the film thickness of the resin layer to 1 μm or less, the influence of swelling and shrinkage of the resin layer is reduced, and excellent heat resistance can be imparted to the conductive coating layer.

另外，若樹脂層厚於1μm，則有時產生由樹脂層的特性所引起的問題。具體而言，藉由樹脂層的柔軟性而導電性塗層過剩地膨脹收縮，結果於導電性塗層中形成缺陷(斷線)。另外，有時產生由厚的樹脂層所引起的透明性的惡化、由吸濕等所引起的白化、由熱所引起的黃化等。此處，藉由將樹脂層的膜厚設為1μm以下，可最小限度地抑制該些不良影響。除此之外，藉由將樹脂層的膜厚設為1μm以下，而不存在使用所需以上的材料的情況，因此於成本方面變得有利。 In addition, when the resin layer is thicker than 1 μm, problems may arise due to the properties of the resin layer. Specifically, the conductive coating excessively expands and shrinks due to the flexibility of the resin layer, and as a result, defects (disconnections) are formed in the conductive coating. In addition, deterioration of transparency due to a thick resin layer, whitening due to moisture absorption, etc., yellowing due to heat, etc. may occur. Here, by setting the film thickness of the resin layer to be 1 μm or less, these adverse effects can be minimized. In addition, by setting the film thickness of the resin layer to 1 μm or less, there is no need to use more than necessary materials, which is advantageous in terms of cost.

再者，樹脂層的更佳的膜厚為0.05μm~0.8μm，最佳的膜厚為0.1μm~0.5μm。若小於0.05μm，則有無法充分發揮樹脂層的效果而密接性差的情況。 Furthermore, the more preferable film thickness of the resin layer is 0.05 μm to 0.8 μm, and the most preferable film thickness is 0.1 μm to 0.5 μm. If it is less than 0.05 μm, the effect of the resin layer cannot be fully exhibited, and the adhesiveness may be poor.

於本發明的導電性塗層複合體中，所述樹脂層若為與基 材表現出良好的密接性的樹脂，則並無特別限定，但為了發揮與基材的優異的密接性，較佳為具有羧基或羥基等官能基，例如可使用聚乙烯醇系樹脂(包含聚乙烯丁醛)或聚乙烯吡咯啶酮等，此外，較佳為：所述樹脂層的主成分為聚胺基甲酸酯樹脂，於所述聚胺基甲酸酯樹脂中添加異氰酸酯基由封端劑保護的聚合物及/或包含噁唑啉基的聚合物作為交聯劑。藉由在聚胺基甲酸酯樹脂中添加所述交聯劑，可控制樹脂層的柔軟性。 In the conductive coating composite of the present invention, if the resin layer is There are no particular limitations on the resin that exhibits good adhesion to the substrate, but in order to exert excellent adhesion to the substrate, it is preferable to have a functional group such as a carboxyl group or a hydroxyl group. For example, a polyvinyl alcohol-based resin (including polyvinyl alcohol) can be used Vinyl butyraldehyde) or polyvinylpyrrolidone, etc. In addition, it is preferable that the main component of the resin layer is polyurethane resin, and isocyanate groups are added to the polyurethane resin to seal End agent protected polymers and/or polymers containing oxazoline groups are used as crosslinking agents. By adding the crosslinking agent to the polyurethane resin, the flexibility of the resin layer can be controlled.

另外，於本發明的導電性塗層複合體中，較佳為：所述交聯劑相對於所述聚胺基甲酸酯樹脂的固體成分的固體成分量為10重量%以內。若交聯劑相對於聚胺基甲酸酯樹脂的固體成分的固體成分量多於10重量%，則聚胺基甲酸酯樹脂中所含的特定的官能基與交聯劑過剩地過反應，因此除了樹脂層的柔軟性受損以外，還有樹脂層與基材及導電性塗層的密接性受損的傾向。 In addition, in the conductive coating composite of the present invention, it is preferable that the solid content of the crosslinking agent is within 10% by weight relative to the solid content of the polyurethane resin. When the solid content of the crosslinking agent is more than 10% by weight relative to the solid content of the polyurethane resin, the specific functional group contained in the polyurethane resin and the crosslinking agent are excessively overreacted Therefore, in addition to the impairment of the flexibility of the resin layer, there is also a tendency that the adhesiveness of the resin layer, the base material, and the conductive coating layer is impaired.

另外，詳細的理由並不明確，但認為理由在於：用作密接層的聚胺基甲酸酯樹脂具有-COO-H、-COOR、-COO^-NH⁺R₂及-COO^-NH₄ ⁺(其中，R、R₂分別獨立地表示直鏈或分支的可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的伸烷基、可具有取代基的氧伸烷基、可具有取代基的芳基、可具有取代基的芳烷基、可具有取代基的雜環基、可具有取代基的烷氧基、可具有取代基的烷氧基羰基、可具有取代基的醯基)中的任一種官能基，藉此樹脂層與基材及樹脂層與導電性塗層的密接性提高。另外，只要使用所述聚胺基甲酸酯樹脂，則高溫高濕環境下的耐 久性變得良好，就該方面而言亦較佳。 In addition, the detailed reason is not clear, but the reason is considered to be that the polyurethane resin used as the adhesive layer has -COO-H, -COOR, -COO ^- NH ⁺ R ₂ and -COO ^- NH ₄ ⁺ ( _Wherein , R and R independently represent a linear or branched alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkylene group that may have a substituent, or an oxyalkylene group that may have a substituent , Aryl group which may have substituent, Aralkyl group which may have substituent, Heterocyclic group which may have substituent, Alkoxy group which may have substituent, Alkoxycarbonyl group which may have substituent, Optional substituent Any functional group in the acyl group), thereby improving the adhesion between the resin layer and the substrate and the resin layer and the conductive coating. Moreover, as long as the above-mentioned polyurethane resin is used, the durability in a high-temperature, high-humidity environment becomes favorable, and it is also preferable in this point.

另外，於本發明的導電性塗層複合體中，導電性塗層是由銀微粒子形成，進而藉由外部加熱等而使其燒結，藉此具有與銀微粒子本來所具有的導電性相同程度的良好導電性。表現出該良好導電性的理由並不明確，但認為是起因於用作密接層的樹脂層的優異的變形性能。 In addition, in the conductive coating composite of the present invention, the conductive coating layer is formed of silver microparticles, and then sintered by external heating or the like, thereby having the same degree of conductivity as the silver microparticles originally have. Good electrical conductivity. The reason why this good conductivity is exhibited is not clear, but it is considered to be caused by the excellent deformability of the resin layer used as the adhesion layer.

樹脂層較佳為斷裂伸長率為600%以上，藉由該柔軟性及收縮膨脹性，於使銀微粒子燒結的製程中，可緩和基材與導電性塗層的熱膨脹係數差。其結果，銀微粒子的燒結順暢地進行，從而可獲得具有優異的導電性的導電性塗層。 The resin layer preferably has an elongation at break of 600% or more. Due to the flexibility and shrinkage and expansion properties, the difference in thermal expansion coefficient between the base material and the conductive coating can be alleviated during the process of sintering the silver particles. As a result, the sintering of the silver fine particles proceeds smoothly, and a conductive coating having excellent conductivity can be obtained.

另外，於本發明的導電性塗層複合體中，較佳為：所述聚胺基甲酸酯樹脂為水系聚胺基甲酸酯樹脂。水系聚胺基甲酸酯樹脂的臭味低，可實現作業環境的惡化防止及環境負荷的減低。 In addition, in the conductive coating composite of the present invention, preferably: the polyurethane resin is a water-based polyurethane resin. The water-based polyurethane resin has low odor, which can prevent the deterioration of the working environment and reduce the environmental load.

另外，於本發明的導電性塗層複合體中，較佳為：所述樹脂層是將溶解於溶劑中的所述水系聚胺基甲酸酯樹脂塗佈於所述基材上而形成。通常，水系聚胺基甲酸酯樹脂以分散於水中的狀態(乳膠)存在，並進行溶媒的揮發而成膜，但有根據成膜條件而受乳膠的粒子徑的影響地形成膜的情況。 In addition, in the conductive coating composite of the present invention, preferably, the resin layer is formed by coating the water-based polyurethane resin dissolved in a solvent on the substrate. Usually, water-based polyurethane resin exists in a dispersed state (emulsion) in water, and volatilizes the solvent to form a film. However, depending on the film-forming conditions, a film may be formed depending on the particle size of the latex.

此處，於欲形成薄的樹脂層的情況下，有表面粗糙度變大的問題。相對於此，藉由將水系聚胺基甲酸酯樹脂溶於溶媒(例如乙醇或丙酮等)中，乳膠破泡而成為均勻溶液，因此成膜形成性能(特別是薄膜中的膜質均勻性)提高。 Here, when attempting to form a thin resin layer, there is a problem that the surface roughness becomes large. In contrast, by dissolving the water-based polyurethane resin in a solvent (such as ethanol or acetone, etc.), the latex foam is broken and becomes a uniform solution, so the film forming performance (especially the uniformity of film quality in the film) improve.

另外，於本發明的導電性塗層複合體中，較佳為：所述導電性塗層是由銀微粒子分散體形成，所述銀微粒子分散體包含：所述銀微粒子；短鏈胺；溶媒；及用以使所述銀微粒子分散的分散劑。 In addition, in the conductive coating composite of the present invention, preferably: the conductive coating is formed from a dispersion of silver particles, and the dispersion of silver particles includes: the silver particles; short-chain amine; solvent and a dispersant for dispersing the silver microparticles.

另外，於本發明的導電性塗層複合體中，所述短鏈胺的碳數較佳為5以下，所述溶媒較佳為高極性溶媒，所述分散劑較佳為具有酸價，所述短鏈胺的分配係數logP較佳為-1.0~1.4。 In addition, in the conductive coating composite of the present invention, the carbon number of the short-chain amine is preferably less than 5, the solvent is preferably a highly polar solvent, and the dispersant preferably has an acid value, so The distribution coefficient logP of the short-chain amine is preferably -1.0 to 1.4.

所述銀微粒子分散體是於多種溶媒(特別是高極性溶媒)中均勻分散有銀微粒子的具有低溫燒結性的銀微粒子分散體，藉由該銀微粒子複合體的燒結而形成導電性塗層，藉此可於低溫下形成具有良好導電性的導電性塗層。 The silver microparticle dispersion is a low-temperature sinterable silver microparticle dispersion uniformly dispersed with silver microparticles in various solvents (especially highly polar solvents), and a conductive coating is formed by sintering the silver microparticle composite, Accordingly, a conductive coating with good conductivity can be formed at low temperature.

胺的一分子內的胺基具有相對較高的極性，容易產生氫鍵的相互作用，該些官能基以外的部分具有相對較低的極性。進而，胺基分別容易顯示出鹼性的性質。因此，胺若局部存在(附著)於銀微粒子的表面的至少一部分(即，若被覆銀微粒子的表面的至少一部分)上，則可使有機成分與無機粒子充分親和，可防止銀微粒子彼此的凝聚(提高分散性)。即，胺的官能基以適度的強度吸附於銀微粒子的表面，防止銀微粒子彼此的相互接觸，因此有助於保管狀態下的銀微粒子的穩定性。另外認為，藉由加熱而自銀微粒子的表面移動及/或揮發，藉此促進銀微粒子彼此的 熔著。 The amine group in one molecule of the amine has relatively high polarity and is prone to hydrogen bond interaction, and the parts other than these functional groups have relatively low polarity. Furthermore, each of the amine groups tends to exhibit basic properties. Therefore, if the amine is partially present (attached) on at least a part of the surface of the silver microparticles (that is, if at least a part of the surface of the silver microparticles is coated), the organic component and the inorganic particles can be sufficiently compatible, and the aggregation of the silver microparticles can be prevented. (improves dispersion). That is, the functional group of the amine is adsorbed on the surface of the silver microparticles with moderate strength, and prevents the mutual contact of the silver microparticles, thereby contributing to the stability of the silver microparticles in a storage state. In addition, it is believed that by heating, the surface of the silver particles moves and/or volatilizes, thereby promoting the mutual interaction of the silver particles. melted.

另外，藉由將構成銀微粒子分散體的胺設為碳數為5以下的短鏈胺，能夠容易地去除藉由加熱而附著於銀微粒子的表面的至少一部分上的胺，可確保銀微粒子的良好的低溫燒結性(例如100℃~350℃下的燒結性)。 In addition, by setting the amine constituting the silver microparticle dispersion as a short-chain amine having a carbon number of 5 or less, the amine attached to at least a part of the surface of the silver microparticles by heating can be easily removed, and the silver microparticles can be secured. Good low-temperature sinterability (such as sinterability at 100°C~350°C).

另外，將短鏈胺的分配係數logP設為-1.0~1.4的原因在於：若分配係數logP小於-1.0，則短鏈胺的極性過高，因此銀的還原急速進行，變得難以控制銀微粒子生成，若分配係數logP超過1.4，則與銀配位的胺的極性低，因此變得難以分散於高極性溶媒中。 In addition, the reason why the distribution coefficient logP of the short-chain amine is set to -1.0 to 1.4 is that if the distribution coefficient logP is less than -1.0, the polarity of the short-chain amine is too high, so the reduction of silver proceeds rapidly, and it becomes difficult to control the silver particles. Formation, if the distribution coefficient logP exceeds 1.4, the polarity of the amine coordinated with silver becomes low, so it becomes difficult to disperse in a highly polar solvent.

分配係數logP是指使用正辛醇與水作為溶媒的辛醇/水分配係數，分別求出辛醇中的濃度Co與水中的濃度Cw，算出濃度比P=Co/Cw的常用對數logP來作為分配係數。因此，分配係數logP是指表示銀微粒子能否藉由某一範圍的極性溶媒分散的一個指標。分配係數logP的測定方法並無特別限定，例如可藉由使用燒瓶振盪法、高效液相層析(High Performance Liquid Chromatography，HPLC)法及定量結構活性關係演算法(quantitative structure-activity relationship algorithm)的計算等來求出，亦可使用美國國家生物技術資訊中心(National Center for Biotechnology Information)等網站上公布的文獻值。 The partition coefficient logP refers to the octanol/water partition coefficient using n-octanol and water as the solvent. The concentration Co in octanol and the concentration Cw in water are obtained respectively, and the common logarithm logP of the concentration ratio P=Co/Cw is calculated as Partition coefficient. Therefore, the distribution coefficient logP is an index indicating whether silver particles can be dispersed by a certain range of polar solvents. The method for determining the partition coefficient logP is not particularly limited, for example, by using flask shaking method, high performance liquid chromatography (High Performance Liquid Chromatography, HPLC) method and quantitative structure-activity relationship algorithm (quantitative structure-activity relationship algorithm) It can be obtained by calculation or the like, and the literature value published on the website of the National Center for Biotechnology Information (National Center for Biotechnology Information) or the like can be used.

進而，銀微粒子分散體的特徵在於包含在銀微粒子合成後添加的具有酸價的分散劑(即，用以使銀微粒子分散的具有酸 價的分散劑)。此處所謂的「具有酸價的分散劑」包含作為吸附基或官能基而不具有胺基或羥基等的全部分散劑。藉由使用所述分散劑，可提高溶媒中的銀微粒子的分散穩定性。該分散劑的酸價較佳為5~200，另外，該分散劑較佳為具有由磷酸而來的官能基。「具有酸價的分散劑」較佳的原因未必明確，但本發明者們認為，不僅藉由對金屬的吸附作用，還藉由與短鏈胺相互作用，而能夠以更密的形態來吸附，不僅具有低溫燒結性，而且表現出高的分散性。 Furthermore, the silver microparticle dispersion is characterized in that it contains a dispersant with an acid value (that is, a dispersant with an acid value in order to disperse the silver microparticles) added after the silver microparticles are synthesized. Valuable dispersants). The term "a dispersant having an acid value" here includes all dispersants that do not have an amino group, a hydroxyl group, or the like as an adsorption group or a functional group. By using such a dispersant, the dispersion stability of silver fine particles in a solvent can be improved. The acid value of the dispersant is preferably 5-200, and the dispersant preferably has a functional group derived from phosphoric acid. The reason why "a dispersant with an acid value" is better is not necessarily clear, but the inventors believe that not only through the adsorption of metals, but also through the interaction with short-chain amines, it can be adsorbed in a denser form. , not only has low-temperature sinterability, but also exhibits high dispersion.

於欲使銀微粒子分散於後述高極性溶劑中的情況下，通常有效的是使用極性高的分散劑。例如雖考慮使用logP更小的短鏈胺，但短鏈胺通常發揮還原性而存在無法將反應速度保持為適當的情況。具體而言，存在過度提高反應速度而無法形成分散性優異的銀微粒子的情況。因此，藉由在銀微粒子合成後添加更高極性的分散劑，銀微粒子可維持原狀態而僅提高對分散介質的相容性(表面改質)。 When it is intended to disperse silver fine particles in a highly polar solvent described later, it is generally effective to use a highly polar dispersant. For example, use of a short-chain amine with a smaller logP may be considered, but the short-chain amine generally exhibits reducing properties, and the reaction rate may not be maintained at an appropriate level. Specifically, silver microparticles excellent in dispersibility may not be formed by increasing the reaction rate too much. Therefore, by adding a more polar dispersant after the synthesis of silver particles, the silver particles can be maintained in their original state and only improve the compatibility with the dispersion medium (surface modification).

若分散劑的酸價為5以上，則與胺配位，粒子表面開始產生對於成為鹼性的金屬物的酸鹼相互作用下的吸附，若為200以下，則由於不具有過度吸附的部位，故而以適當的形態吸附，因此較佳。另外，藉由分散劑具有由磷酸而來的官能基，磷P經由氧O而與金屬M相互作用、互相牽引，故而對於與金屬或金屬化合物的吸附最有效果，能夠以必要最小限度的吸附量來獲得適當的分散性，因此較佳。此處所謂「酸價」，是由為了將1g試樣 中所含的酸性成分加以中和而需要的氫氧化鉀的mg數所表示。酸價的測定法可列舉指示劑法(對萘酚苯甲醇(p-naphtholbenzein)指示劑)或電位差滴定法。 If the acid value of the dispersant is 5 or more, it will coordinate with the amine, and the surface of the particles will start to adsorb under the acid-base interaction with respect to the metal substance that becomes basic. If it is 200 or less, there will be no excessive adsorption sites, Therefore, it is preferable to adsorb in an appropriate form. In addition, since the dispersant has a functional group derived from phosphoric acid, phosphorus P interacts with metal M through oxygen O and is attracted to each other. Therefore, it is most effective for adsorption to metals or metal compounds, and can be adsorbed with the necessary minimum. Amount to obtain proper dispersibility is therefore preferred. The so-called "acid value" here is for 1g sample It is expressed by the mg of potassium hydroxide required to neutralize the acidic components contained in it. The method for measuring the acid value includes an indicator method (p-naphtholbenzin indicator) and a potentiometric titration method.

．ISO6618-1997：與利用指示劑滴定法的中和值試驗法→指示劑滴定法(酸價)對應 ． ISO6618-1997: Corresponds to neutralization value test method using indicator titration method → indicator titration method (acid value)

．ISO6619-1988：與電位差滴定法(酸價)→電位差滴定法(酸價)對應 ． ISO6619-1988: Corresponding to potentiometric titration (acid value) → potentiometric titration (acid value)

銀微粒子分散體亦可更包含於銀微粒子合成前添加的作為保護劑的具有酸價的分散劑(保護分散劑)。此處所謂的「保護分散劑」可與所述的銀微粒子合成後添加的「具有酸價的分散劑」相同。 The silver microparticle dispersion may further include a dispersant having an acid value (protective dispersant) added as a protective agent before the synthesis of the silver microparticles. The so-called "protective dispersant" here may be the same as the "dispersant with acid value" added after the synthesis of the silver particles.

另外，銀微粒子分散體中，溶媒可使用多種溶媒、特別是高極性溶媒。所謂高極性溶媒，是指與己烷或甲苯之類的低極性溶劑難以相容者，通常為水或碳數少的醇等，本發明中，更佳為使用碳數1~6的醇。藉由設碳數1~6的醇作為高極性溶媒，可避免使用低極性溶媒時的異常，例如可避免當於樹脂上積層銀微粒子分散體時，溶媒侵入基底的樹脂層。此處，胺中較佳為使用烷氧基胺。藉由將胺設為烷氧基胺，可使銀微粒子良好地分散於高極性溶媒中。 In addition, in the silver fine particle dispersion, various solvents can be used as the solvent, especially a highly polar solvent. The so-called highly polar solvent refers to those that are difficult to be compatible with low-polarity solvents such as hexane or toluene, and are usually water or alcohols with a small number of carbon atoms. In the present invention, alcohols with 1 to 6 carbon atoms are more preferably used. By setting the alcohol with carbon number 1-6 as the high polarity solvent, the abnormality when using the low polarity solvent can be avoided, for example, when the silver microparticle dispersion is laminated on the resin, the solvent can be prevented from invading the resin layer of the substrate. Here, among amines, alkoxyamines are preferably used. By using the amine as an alkoxyamine, silver fine particles can be favorably dispersed in a highly polar solvent.

構成銀微粒子分散體的銀微粒子的粒徑較佳為如產生熔點下降的奈米尺寸，理想為1nm~200nm，視需要亦可包含微米尺寸的粒子。 The particle diameter of the silver microparticles constituting the silver microparticle dispersion is preferably nanometer-sized such as to cause melting point depression, ideally 1 nm to 200 nm, and micron-sized particles may be included as needed.

另外，本發明亦提供一種導電性塗層複合體的製造方法，其特徵在於包括：第一步驟，將樹脂塗佈於基材的至少一部分上而形成樹脂層；第二步驟，將銀微粒子分散體塗佈於所述樹脂層的至少一部分上；及第三步驟，藉由外部加熱而使所述銀微粒子分散體中所含的銀微粒子燒結，從而形成導電性塗層。 In addition, the present invention also provides a method for manufacturing a conductive coating composite, which is characterized in that it includes: a first step of coating resin on at least a part of the substrate to form a resin layer; a second step of dispersing silver particles body coating on at least a part of the resin layer; and a third step of sintering the silver microparticles contained in the silver microparticle dispersion by external heating, thereby forming a conductive coating.

藉由銀微粒子分散體的塗佈及外部加熱來形成導電性塗層，藉此可於低溫下形成導電性優異的導電性塗層，可獲得相對於耐熱性低的基板亦表現出良好導電性的導電性塗層複合體。 Conductive coating is formed by coating silver microparticle dispersion and external heating, thereby forming a conductive coating with excellent conductivity at low temperature, and can obtain a substrate with low heat resistance that exhibits good conductivity conductive coating composites.

另外，於本發明的導電性塗層複合體的製造方法中，藉由使用樹脂層作為密接層，可提高樹脂層與基材及樹脂層與導電性塗層的密接性。 Moreover, in the manufacturing method of the electroconductive coating composite of this invention, by using a resin layer as an adhesive layer, the adhesiveness of a resin layer and a base material, and a resin layer and an electroconductive coating can be improved.

另外，於本發明的導電性塗層複合體的製造方法中，較佳為：將樹脂層的主成分設為聚胺基甲酸酯樹脂，於該聚胺基甲酸酯樹脂中添加異氰酸酯基由封端劑保護的聚合物及/或包含噁唑啉基的聚合物作為交聯劑。藉由將所述交聯劑添加於聚胺基甲酸酯樹脂中，可控制樹脂層的柔軟性。即，較佳為使用包含聚胺基甲酸酯樹脂及交聯劑的聚胺基甲酸酯樹脂組成物。 In addition, in the manufacturing method of the conductive coating composite of the present invention, it is preferable that the main component of the resin layer is polyurethane resin, and isocyanate groups are added to the polyurethane resin. Polymers protected by capping agents and/or polymers containing oxazoline groups serve as crosslinkers. By adding the crosslinking agent to the polyurethane resin, the flexibility of the resin layer can be controlled. That is, it is preferable to use a polyurethane resin composition containing a polyurethane resin and a crosslinking agent.

所述交聯劑相對於聚胺基甲酸酯樹脂的固體成分的固體成分量較佳為設為10重量%以內。若交聯劑相對於聚胺基甲酸酯樹脂的固體成分的固體成分量多於10重量%，則聚胺基甲酸酯 樹脂中所含的特定的官能基與交聯劑過剩地過反應，因此除了樹脂層的柔軟性受損以外，還有樹脂層與基材及導電性塗層的密接性受損的傾向。 The solid content of the crosslinking agent is preferably within 10% by weight relative to the solid content of the polyurethane resin. If the solid content of the crosslinking agent relative to the solid content of the polyurethane resin is more than 10% by weight, the polyurethane Specific functional groups contained in the resin overreact excessively with the crosslinking agent, and therefore, not only the flexibility of the resin layer is impaired, but also the adhesion between the resin layer, the base material, and the conductive coating layer tends to be impaired.

藉由將例如斷裂伸長率600%以上的聚胺基甲酸酯樹脂用於樹脂層中，於使銀微粒子燒結的第三步驟中，可充分緩和基材與導電性塗層的熱膨脹係數差。其結果，銀微粒子的燒結順暢地進行，從而可獲得具有優異的導電性的導電性塗層。 By using, for example, a polyurethane resin having an elongation at break of 600% or more for the resin layer, the difference in thermal expansion coefficient between the base material and the conductive coating layer can be sufficiently alleviated in the third step of sintering the silver particles. As a result, the sintering of the silver fine particles proceeds smoothly, and a conductive coating having excellent conductivity can be obtained.

另外，於本發明的導電性塗層複合體的製造方法中，較佳為使用水系聚胺基甲酸酯樹脂作為所述聚胺基甲酸酯樹脂。水系聚胺基甲酸酯樹脂的臭味低，可實現作業環境的惡化防止及環境負荷的減低。 Moreover, in the manufacturing method of the electroconductive coating composite of this invention, it is preferable to use a water-based polyurethane resin as said polyurethane resin. The water-based polyurethane resin has low odor, which can prevent the deterioration of the working environment and reduce the environmental load.

另外，於本發明的導電性塗層複合體的製造方法中，較佳為將所述樹脂層的膜厚設為1μm以下。藉由將樹脂層的膜厚設為1μm以下，樹脂層的膨潤、收縮的影響變小，可對導電性塗層賦予優異的耐熱性。再者，樹脂層的膜厚可根據旋轉塗佈的轉速或稀釋液量等來適宜控制。 Moreover, in the manufacturing method of the electroconductive coating composite of this invention, it is preferable to make the film thickness of the said resin layer into 1 micrometer or less. By setting the film thickness of the resin layer to 1 μm or less, the influence of swelling and shrinkage of the resin layer becomes small, and excellent heat resistance can be imparted to the conductive coating layer. In addition, the film thickness of a resin layer can be suitably controlled according to the rotational speed of spin coating, the amount of diluent, etc.

另外，於本發明的導電性塗層複合體的製造方法中，較佳為：於第一步驟中，將溶解於溶劑中的所述水系聚胺基甲酸酯樹脂塗佈於所述基材上而形成所述樹脂層。通常，水系聚胺基甲酸酯樹脂以分散於水中的狀態(乳膠)存在，並進行溶媒的揮發而成膜，但有根據成膜條件而受乳膠的粒子徑的影響地形成膜的情況。 In addition, in the method for producing the conductive coating composite of the present invention, it is preferred that in the first step, the water-based polyurethane resin dissolved in a solvent is applied to the base material to form the resin layer. Usually, water-based polyurethane resin exists in a dispersed state (emulsion) in water, and volatilizes the solvent to form a film. However, depending on the film-forming conditions, a film may be formed depending on the particle size of the latex.

此處，於欲形成薄的樹脂層的情況下，有時引起表面粗糙度變大的問題。相對於此，藉由將水系聚胺基甲酸酯樹脂溶於溶媒(例如乙醇或丙酮等)中，乳膠破泡而成為均勻溶液，因此成膜形成性能(特別是薄膜中的膜質均勻性)提高。 Here, when trying to form a thin resin layer, the problem that surface roughness becomes large may arise. In contrast, by dissolving the water-based polyurethane resin in a solvent (such as ethanol or acetone, etc.), the latex foam is broken and becomes a uniform solution, so the film forming performance (especially the uniformity of film quality in the film) improve.

另外，於本發明的導電性塗層複合體的製造方法中，較佳為：作為所述銀微粒子分散體，使用如下銀微粒子分散體，其包含：所述銀微粒子；碳數為5以下的短鏈胺；高極性溶媒；及用以使所述銀微粒子分散的具有酸價的分散劑，且所述短鏈胺的分配係數logP為-1.0~1.4。 In addition, in the method for producing the conductive coating composite of the present invention, it is preferable to use, as the silver microparticle dispersion, a silver microparticle dispersion comprising: the silver microparticles; short-chain amine; highly polar solvent; and a dispersant with acid value for dispersing the silver particles, and the distribution coefficient logP of the short-chain amine is -1.0-1.4.

如上所述，所述銀微粒子分散體是於多種溶媒(特別是高極性溶媒)中均勻分散有銀微粒子的具有低溫燒結性的銀微粒子分散體，因此對於基材的塗佈容易(第二步驟)，藉由該銀微粒子複合體的燒結(第三步驟)而形成導電性塗層，藉此可於低溫下形成具有良好導電性的導電性塗層。 As mentioned above, the silver microparticle dispersion is a silver microparticle dispersion with low-temperature sintering properties in which silver microparticles are uniformly dispersed in various solvents (especially highly polar solvents), so it is easy to coat the substrate (the second step ), a conductive coating is formed by sintering the silver particle composite (the third step), whereby a conductive coating with good conductivity can be formed at a low temperature.

依據本發明的導電性塗層複合體及其製造方法，可提供一種即便於使用耐熱性低的基材或玻璃基材的情況下，亦兼具導電性塗層相對於基材的良好的密接性與導電性塗層的優異的導電性，此外，耐熱性亦優異的導電性塗層複合體及其製造方法，所 述導電性塗層複合體具有基材與導電性塗層。 According to the conductive coating composite and its production method of the present invention, even when using a substrate with low heat resistance or a glass substrate, it is possible to provide a composite material having good adhesion of the conductive coating to the substrate. The excellent conductivity of the conductive coating and the conductive coating, in addition, the conductive coating composite with excellent heat resistance and its manufacturing method, so The conductive coating composite has a substrate and a conductive coating.

1:導電性塗層複合體 1: Conductive coating complex

2:基材 2: Substrate

4:樹脂層 4: resin layer

6:導電性塗層 6: Conductive coating

S01~S03:步驟 S01~S03: Steps

圖1是本發明的導電性塗層複合體的概略剖面圖。 Fig. 1 is a schematic sectional view of the conductive coating composite of the present invention.

圖2是本發明的導電性塗層複合體的製造方法的步驟圖。 Fig. 2 is a step diagram of the method of manufacturing the conductive coating composite of the present invention.

以下，對本發明的導電性塗層複合體的較佳的一實施形態及其製造方法進行詳細說明。再者，以下的說明中有時省略重覆的說明。 Hereinafter, a preferred embodiment of the conductive coating composite of the present invention and its manufacturing method will be described in detail. In addition, in the following description, overlapping description may be omitted.

(1)導電性塗層複合體 (1) Conductive coating complex

圖1中示出本實施形態的導電性塗層複合體的概略剖面圖。本發明的導電性塗層複合體1包括：基材2；樹脂層4，形成於基材2的至少一部分上；及導電性塗層6，形成於樹脂層4的至少一部分上。 FIG. 1 shows a schematic cross-sectional view of the conductive coating composite of the present embodiment. The conductive coating composite 1 of the present invention includes: a substrate 2 ; a resin layer 4 formed on at least a part of the substrate 2 ; and a conductive coating 6 formed on at least a part of the resin layer 4 .

於基材2與導電性塗層6之間形成樹脂層4作為密接層，因此導電性塗層6與基材2具有良好的密接性。 The resin layer 4 is formed between the substrate 2 and the conductive coating 6 as an adhesive layer, so the conductive coating 6 and the substrate 2 have good adhesion.

(1-1)基材 (1-1) Substrate

基材2只要不損及本發明的效果，則並無特別限定，可使用現有公知的多種基材。作為可用於基材2中的材料，例如可列舉：聚醯胺(Polyamide，PA)、聚醯亞胺(Polyimide，PI)、聚醯胺醯亞胺(Polyamide imide，PAI)、聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(Polybutylene terephthalate，PBT)、聚萘二甲 酸乙二酯(PEN)等聚酯，聚碳酸酯(Polycarbonate，PC)、聚醚碸(Polyether sulfone，PES)、乙烯樹脂、氟樹脂、液晶聚合物、陶瓷或玻璃等。 The substrate 2 is not particularly limited unless the effect of the present invention is impaired, and various conventionally known substrates can be used. As materials that can be used in the base material 2, for example, polyamide (Polyamide, PA), polyamide imide (Polyimide, PI), polyamide imide (Polyamide imide, PAI), polyterephthalamide Ethylene formate (PET), polybutylene terephthalate (Polybutylene terephthalate, PBT), polyethylene naphthalate Polyester such as ethylene glycol ester (PEN), polycarbonate (PC), polyether sulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramic or glass, etc.

(1-2)樹脂層 (1-2) Resin layer

樹脂層4的膜厚為1μm以下。藉由將樹脂層4的膜厚設為1μm以下，樹脂層的膨潤、收縮的影響變小，可對導電性塗層6賦予優異的耐熱性。再者，樹脂層4的更佳的膜厚為0.05μm~0.8μm，最佳的膜厚為0.1μm~0.5μm。 The film thickness of the resin layer 4 is 1 micrometer or less. By setting the film thickness of the resin layer 4 to 1 μm or less, the influence of swelling and shrinkage of the resin layer is reduced, and excellent heat resistance can be imparted to the conductive coating layer 6 . Furthermore, the more preferable film thickness of the resin layer 4 is 0.05 μm-0.8 μm, and the most preferable film thickness is 0.1 μm-0.5 μm.

若樹脂層4厚於1μm，則有時產生由樹脂層4的特性所引起的問題。具體而言，藉由樹脂層4的柔軟性而導電性塗層6過剩地膨脹收縮，結果於導電性塗層6中形成缺陷(斷線)。另外，有時產生由厚的樹脂層4所引起的透明性的惡化、由吸濕等所引起的白化、由熱所引起的黃化等。此處，藉由將樹脂層4的膜厚設為1μm以下，可最小限度地抑制該些不良影響。除此之外，藉由將樹脂層4的膜厚設為1μm以下，而不存在使用所需以上的材料的情況，因此於成本方面變得有利。 When the resin layer 4 is thicker than 1 μm, problems may arise due to the properties of the resin layer 4 . Specifically, the conductive coating 6 expands and contracts excessively due to the flexibility of the resin layer 4 , and as a result, defects (disconnections) are formed in the conductive coating 6 . In addition, deterioration of transparency due to the thick resin layer 4 , whitening due to moisture absorption or the like, yellowing due to heat, and the like may occur. Here, by setting the film thickness of the resin layer 4 to 1 μm or less, these adverse effects can be minimized. In addition, by setting the film thickness of the resin layer 4 to 1 μm or less, there is no need to use more than necessary materials, which is advantageous in terms of cost.

樹脂層4只要不損及本發明的效果，則並無特別限定，可使用現有公知的多種樹脂，但較佳為：主成分為聚胺基甲酸酯樹脂，且於聚胺基甲酸酯樹脂中添加異氰酸酯基由封端劑保護的聚合物及/或包含噁唑啉基的聚合物作為交聯劑。藉由於聚胺基甲酸酯樹脂中添加所述交聯劑，可控制樹脂層4的柔軟性。 The resin layer 4 is not particularly limited as long as it does not impair the effect of the present invention, and various known resins can be used, but it is preferable that the main component is a polyurethane resin, and the polyurethane A polymer whose isocyanate group is protected by a blocking agent and/or a polymer containing an oxazoline group is added to the resin as a crosslinking agent. By adding the crosslinking agent to the polyurethane resin, the flexibility of the resin layer 4 can be controlled.

另外，交聯劑相對於聚胺基甲酸酯樹脂的固體成分的固 體成分量較佳為10重量%以內。若交聯劑相對於聚胺基甲酸酯樹脂的固體成分的固體成分量多於10重量%，則聚胺基甲酸酯樹脂中所含的特定的官能基與交聯劑過剩地過反應，因此除了樹脂層4的柔軟性受損以外，還有樹脂層4與基材2及導電性塗層6的密接性受損的傾向。 In addition, the solid content of the crosslinking agent relative to the solid content of the polyurethane resin The body composition is preferably within 10% by weight. When the solid content of the crosslinking agent is more than 10% by weight relative to the solid content of the polyurethane resin, the specific functional group contained in the polyurethane resin and the crosslinking agent are excessively overreacted Therefore, in addition to the impairment of the flexibility of the resin layer 4, there is a tendency that the adhesion between the resin layer 4, the base material 2, and the conductive coating layer 6 is impaired.

另外，樹脂層4的主成分更佳為斷裂伸長率為600%以上的聚胺基甲酸酯樹脂，該聚胺基甲酸酯樹脂較佳為具有-COO-H、-COOR、-COO^-NH⁺R₂及-COO^-NH₄ ⁺(其中，R、R₂分別獨立地表示直鏈或分支的可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的伸烷基、可具有取代基的氧伸烷基、可具有取代基的芳基、可具有取代基的芳烷基、可具有取代基的雜環基、可具有取代基的烷氧基、可具有取代基的烷氧基羰基、可具有取代基的醯基)中的任一種官能基。 In addition, the main component of the resin layer 4 is more preferably a polyurethane resin having an elongation at break of 600% or more, and the polyurethane resin preferably has -COO ^- H, -COOR, -COO- NH ⁺ R ₂ and -COO ^- NH ₄ ⁺ (wherein, R and R ₂ independently represent a linear or branched alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or an alkyl group that may have a substituent An alkyl group, an optionally substituted oxyalkylene group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted Any functional group in an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent).

於導電性塗層複合體1中，樹脂層4作為基材2與導電性塗層6的密接層發揮功能，因此基材2與導電性塗層6具有良好的密接性。另外，詳細的理由並不明確，但藉由用作密接層的聚胺基甲酸酯樹脂具有所述特定的官能基，樹脂層4與基材2及樹脂層4與導電性塗層6的密接性提高。 In the conductive coating composite 1 , since the resin layer 4 functions as an adhesive layer between the base material 2 and the conductive coating layer 6 , the base material 2 and the conductive coating layer 6 have good adhesion. In addition, the detailed reason is not clear, but since the polyurethane resin used as the adhesion layer has the above-mentioned specific functional group, the relationship between the resin layer 4 and the base material 2 and the resin layer 4 and the conductive coating layer 6 Adhesiveness is improved.

另外，於作為樹脂層4的主成分的聚胺基甲酸酯樹脂具有斷裂伸長率600%以上的特徵的情況下，富有柔軟性及收縮膨脹性，因此於使銀微粒子燒結而形成導電性塗層6的製程中，可緩和基材2與導電性塗層6的熱膨脹係數差。其結果認為，銀微粒 子的燒結順暢地進行，從而可獲得具有優異的導電性的導電性塗層6。 In addition, when the polyurethane resin, which is the main component of the resin layer 4, has the characteristics of a breaking elongation of 600% or more, it is rich in flexibility and shrinkage and expansion, so it is suitable for sintering silver particles to form a conductive coating. During the manufacturing process of the layer 6 , the thermal expansion coefficient difference between the substrate 2 and the conductive coating 6 can be alleviated. As a result, silver particles The sintering of the substructure proceeds smoothly, so that the conductive coating 6 having excellent conductivity can be obtained.

聚胺基甲酸酯樹脂較佳為水系聚胺基甲酸酯樹脂。水系聚胺基甲酸酯樹脂的臭味低，可實現作業環境的惡化防止及環境負荷的減低。 The polyurethane resin is preferably a water-based polyurethane resin. The water-based polyurethane resin has low odor, which can prevent the deterioration of the working environment and reduce the environmental load.

作為聚胺基甲酸酯樹脂，亦可使用酯系、醚系、聚碳酸酯系的任一種聚胺基甲酸酯樹脂，但較佳為使用耐水解性優異的醚系或聚碳酸酯系的聚胺基甲酸酯樹脂。 Any of ester-based, ether-based, and polycarbonate-based polyurethane resins can be used as the polyurethane resin, but it is preferable to use ether-based or polycarbonate-based resins that are excellent in hydrolysis resistance. of polyurethane resin.

更具體而言，作為聚胺基甲酸酯樹脂，可較佳地使用第一工業製藥製造的超級弗萊克斯(Superflex)系列：300、460、470、500M、740、E-2000、E-4800，或迪愛生(DIC)股份有限公司的海德朗(Hydran)系列：HW-312B、HW-311、AP-10、AP-70，三洋化成製造的胺基甲酸酯樹脂乳膠：帕瑪琳(Parmalin)UA-200、尤普倫(Uprene)UXA-307等。 More specifically, as the polyurethane resin, the Superflex series manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: 300, 460, 470, 500M, 740, E-2000, E- 4800, or Hydran series of DIC Co., Ltd.: HW-312B, HW-311, AP-10, AP-70, urethane resin latex manufactured by Sanyo Chemical: Parmarin (Parmalin) UA-200, Uprene (Uprene) UXA-307, etc.

另外，作為樹脂層4的主成分而使用的聚胺基甲酸酯樹脂具有特定的官能基，因此藉由添加與該官能基進行反應的交聯劑，亦可控制樹脂層4的柔軟性。作為可適用的官能基，可列舉：胺基或異氰酸酯基、噁唑啉基、碳二醯亞胺基等。此處，官能基與交聯劑的反應理想的是於成膜時進行，因此較佳為使用於常溫下難以進行反應的封端異氰酸酯基或噁唑啉基等。 In addition, since the polyurethane resin used as the main component of the resin layer 4 has a specific functional group, the flexibility of the resin layer 4 can also be controlled by adding a crosslinking agent that reacts with the functional group. As an applicable functional group, an amine group, an isocyanate group, an oxazoline group, a carbodiimide group, etc. are mentioned. Here, since the reaction between the functional group and the crosslinking agent is ideally carried out during film formation, it is preferable to use a blocked isocyanate group, an oxazoline group, etc. which are difficult to react at normal temperature.

然而，若過添加交聯劑，則聚胺基甲酸酯樹脂中所含的特定的官能基與交聯劑過剩地過反應，因此樹脂層4的柔軟性受 損。除此之外，有樹脂層4與基材2及導電性塗層6的密接性受損的傾向。因此，較佳為將交聯劑相對於聚胺基甲酸酯樹脂的固體成分的固體成分量設為10重量%以內。 However, if the crosslinking agent is added too much, the specific functional group contained in the polyurethane resin and the crosslinking agent will react excessively, so the flexibility of the resin layer 4 will be affected. damage. In addition, there exists a tendency for the adhesiveness of the resin layer 4, the base material 2, and the conductive coating layer 6 to be impaired. Therefore, it is preferable to set the solid content amount of a crosslinking agent within 10 weight% with respect to the solid content of a polyurethane resin.

交聯劑只要不損及本發明的效果，則並無特別限定，可使用現有公知的多種交聯劑，例如可使用第一工業製藥製造的艾拉斯特隆(Elastron)系列的BN-69、BN-77，或日本觸媒製造的艾坡酷勞斯(Epocros)系列的WS-300、WS-500、WS-700等。 The cross-linking agent is not particularly limited as long as it does not impair the effect of the present invention, and various known cross-linking agents can be used, for example, BN-69 of the Elastron series manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. can be used. , BN-77, or WS-300, WS-500, WS-700 of the Epocros series manufactured by Nippon Shokubai.

樹脂層4的成膜方法並無特別限定，例如可使用浸漬、噴霧式、棒塗佈式、旋轉塗佈、縫模塗佈式、氣刀式、逆輥塗佈式、凹版塗佈式、幕塗流動式等。 The film-forming method of the resin layer 4 is not particularly limited, and for example, dipping, spraying, bar coating, spin coating, slot die coating, air knife, reverse roll coating, gravure coating, Curtain coating flow type, etc.

另外，成膜溫度亦無特別限定，只要使用作為樹脂層4的原料而使用的組成物的最低成膜溫度以上的溫度即可。進而，視需要亦可於基材2的耐熱溫度以下的溫度下實施加熱處理。 In addition, the film-forming temperature is not particularly limited, as long as it is at least the minimum film-forming temperature of the composition used as the raw material of the resin layer 4 . Furthermore, heat processing may be performed at the temperature below the heat-resistant temperature of the base material 2 as needed.

(1-3)導電性塗層 (1-3) Conductive coating

導電性塗層6是由銀微粒子形成，是藉由對其進行外部加熱而形成的燒結體，且具有與銀微粒子本來所具有的導電性相同程度的良好導電性。導電性塗層6的厚度較佳為0.1μm~2μm。若小於0.1μm，則有厚度過薄而無法獲得充分的導電性的情況。即便超過2μm，於導電性方面亦無問題，但使用量變多，因此成本高而欠佳。 The conductive coating layer 6 is formed of silver fine particles, is a sintered body formed by external heating, and has good electrical conductivity to the same extent as the silver fine particles originally have. The thickness of the conductive coating 6 is preferably 0.1 μm˜2 μm. If it is less than 0.1 μm, the thickness may be too thin and sufficient conductivity may not be obtained. Even if it exceeds 2 μm, there is no problem in terms of conductivity, but since the amount of use increases, the cost is high and it is not preferable.

用於形成導電性塗層6的銀微粒子分散體只要不損及本發明的效果，則並無特別限定，可使用現有公知的多種銀微粒子 分散體，較佳為使用如下銀微粒子分散體，其包含銀微粒子、碳數為5以下的短鏈胺、高極性溶媒及用以使銀微粒子分散的具有酸價的分散劑，且短鏈胺的分配係數logP為-1.0~1.4。 The silver particle dispersion used to form the conductive coating 6 is not particularly limited as long as it does not impair the effect of the present invention, and various conventionally known silver particles can be used. Dispersion, preferably using the following silver microparticle dispersion, which contains silver microparticles, short-chain amines with a carbon number of 5 or less, a highly polar solvent, and a dispersant with an acid value for dispersing the silver microparticles, and the short-chain amines The distribution coefficient logP is -1.0~1.4.

所述銀微粒子分散體是於多種溶媒(特別是高極性溶媒)中均勻分散有銀微粒子的具有低溫燒結性的銀微粒子分散體，藉由該銀微粒子複合體的燒結而形成導電性塗層6，藉此可於低溫下形成具有良好導電性的導電性塗層6。 The silver microparticle dispersion is a low-temperature sinterable silver microparticle dispersion uniformly dispersed with silver microparticles in various solvents (especially highly polar solvents), and a conductive coating is formed by sintering the silver microparticle composite. , so that the conductive coating 6 with good conductivity can be formed at low temperature.

進而，銀微粒子中所含的短鏈胺與作為樹脂層4的主成分而使用的聚胺基甲酸酯樹脂的特定的官能基相互作用，可發揮良好的密接性。 Furthermore, the short-chain amine contained in the silver microparticles interacts with a specific functional group of the polyurethane resin used as the main component of the resin layer 4 to exhibit good adhesion.

(1-3-1)銀微粒子分散體 (1-3-1) Silver particle dispersion

本實施形態的銀微粒子分散體包含銀微粒子、碳數為5以下的短鏈胺及高極性溶媒。以下，對該些各成分等進行說明。 The silver microparticle dispersion of this embodiment contains silver microparticles, a short-chain amine having 5 or less carbon atoms, and a highly polar solvent. Hereinafter, these respective components and the like will be described.

(A)銀微粒子 (A) Silver particles

本實施形態的銀微粒子分散體中的銀微粒子的平均粒徑若為不損及本發明的效果的範圍，則並無特別限制，較佳為具有如產生熔點下降的平均粒徑者，例如若為1nm~200nm即可。尤佳為2nm~100nm。若銀微粒子的平均粒徑為1nm以上，則不僅銀微粒子具備良好的低溫燒結性，而且銀微粒子製造不會成為高成本，故而實用。另外，若為200nm以下，則銀微粒子的分散性難以經時性變化，故而較佳。 The average particle size of the silver particles in the silver particle dispersion of the present embodiment is not particularly limited as long as it is within the range that does not impair the effects of the present invention, but it is preferably one that has an average particle size that causes a decrease in the melting point, for example, if It can be 1nm~200nm. Preferably, it is 2nm~100nm. When the average particle size of the silver fine particles is 1 nm or more, not only the silver fine particles have good low-temperature sinterability, but also the production of the silver fine particles does not become expensive, so it is practical. Moreover, when it is 200 nm or less, since the dispersibility of silver microparticles is hard to change with time, it is preferable.

對於銀微粒子分散體，例如考慮到遷移的問題，亦可添 加離子化序列貴於氫的金屬，即金、銅、鉑、鈀等的粒子。 For the dispersion of silver particles, for example, considering the problem of migration, you can also add Add metals whose ionization sequence is more expensive than hydrogen, that is, particles of gold, copper, platinum, palladium, etc.

再者，本實施形態的銀微粒子分散體中的銀微粒子的粒徑亦可不固定。另外，於銀微粒子分散體包含後述的分散劑等作為任意成分的情況下，存在包含平均粒徑超過200nm的金屬粒子成分的情況，但若為不會產生凝聚，不會顯著損及本發明的效果的成分，則亦可包含所述具有超過200nm的平均粒徑的金屬粒子成分。 In addition, the particle size of the silver fine particle in the silver fine particle dispersion of this embodiment does not need to be constant. In addition, when the silver microparticle dispersion contains a dispersant described later as an optional component, there may be a metal particle component with an average particle diameter exceeding 200 nm, but if aggregation does not occur, the scope of the present invention will not be significantly impaired. The effective component may also contain the above-mentioned metal particle component having an average particle diameter exceeding 200 nm.

此處，本實施形態的銀微粒子分散體中的銀微粒子的粒徑可利用動態光散射法、小角X射線散射法、廣角X射線繞射法來測定。為了顯示出奈米尺寸的銀微粒子的熔點下降，較佳為利用廣角X射線繞射法來求出的微晶直徑。例如廣角X射線繞射法中，更具體而言，可使用理學電機(股)製造的RINT-UltimaIII，利用繞射法於2θ為30°~80°的範圍內測定。該情況下，以試樣於在中央部具有深度為0.1mm~1mm左右的凹坑的玻璃板上，表面變得平坦的方式拉薄來測定即可。另外，若將使用理學電機(股)製造的嘉德(JADE)，將所獲得的繞射光譜的半值寬代入下述的謝樂方程式(Scherrer equation)中而算出的微晶直徑(D)作為粒徑即可。 Here, the particle size of the silver fine particles in the silver fine particle dispersion of this embodiment can be measured by a dynamic light scattering method, a small-angle X-ray scattering method, or a wide-angle X-ray diffraction method. In order to show the melting point depression of nanometer-sized silver microparticles, the crystallite diameter obtained by the wide-angle X-ray diffraction method is preferable. For example, in the wide-angle X-ray diffraction method, more specifically, RINT-Ultima III manufactured by Rigaku Denki Co., Ltd. can be used to measure in the range of 2θ of 30° to 80° by the diffraction method. In this case, what is necessary is just to measure by stretching a sample so that the surface becomes flat on the glass plate which has the pit with a depth of about 0.1 mm - 1 mm in the center part. In addition, when using JADE manufactured by Rigaku Electric Co., Ltd., the crystallite diameter (D) calculated by substituting the half-value width of the obtained diffraction spectrum into the following Scherrer equation (Scherrer equation) is taken as particle size.

D=Kλ/Bcosθ D=Kλ/Bcosθ

此處，K：謝樂常數(0.9)，λ：X射線的波長，B：繞射線的 半值寬，θ：布拉格角。 Here, K: Scherrer constant (0.9), λ: the wavelength of X-rays, B: the Width at half value, θ: Bragg angle.

(B)碳數為5以下的短鏈胺 (B) Short-chain amines with 5 or less carbon atoms

本實施形態的銀微粒子分散體中，於銀微粒子的表面的至少一部分上附著有碳數為5以下的短鏈胺。再者，於銀微粒子的表面，亦可如原料中最初作為雜質而包含的微量有機物、於後述製造過程中混入的微量有機物、於洗滌過程中未徹底去除的殘留還原劑、殘留分散劑等般，附著有微量的有機物。 In the silver fine particle dispersion of the present embodiment, a short-chain amine having 5 or less carbon atoms adheres to at least a part of the surface of the silver fine particles. Furthermore, on the surface of the silver particles, trace organic matter initially included as impurities in the raw material, trace organic matter mixed in the manufacturing process described later, residual reducing agent and residual dispersant not completely removed in the washing process, etc. , with a small amount of organic matter attached.

碳數為5以下的短鏈胺若分配係數logP為-1.0~1.4，則並無特別限定，可為直鏈狀，亦可為分支鏈狀，另外，亦可具有側鏈。作為該短鏈胺，例如可列舉：乙胺(-0.3)、丙胺(0.5)、丁胺(1.0)、N-(3-甲氧基丙基)丙烷-1,3-二胺(-0.6)、1,2-乙二胺、N-(3-甲氧基丙基)甲醯胺(-0.2)、2-甲氧基乙胺(-0.9)、3-甲氧基丙胺(-0.5)、3-乙氧基丙胺(-0.1)、1,4-丁二胺(-0.9)、1,5-戊二胺(-0.6)、戊醇胺(-0.3)、胺基異丁醇(-0.8)等，其中較佳為使用烷氧基胺。 The short-chain amine having 5 or less carbon atoms is not particularly limited as long as the distribution coefficient logP is -1.0 to 1.4, and may be linear or branched, and may have a side chain. Examples of such short-chain amines include ethylamine (-0.3), propylamine (0.5), butylamine (1.0), N-(3-methoxypropyl)propane-1,3-diamine (-0.6 ), 1,2-ethylenediamine, N-(3-methoxypropyl) formamide (-0.2), 2-methoxyethylamine (-0.9), 3-methoxypropylamine (-0.5 ), 3-ethoxypropylamine (-0.1), 1,4-butanediamine (-0.9), 1,5-pentanediamine (-0.6), pentanolamine (-0.3), aminoisobutanol (-0.8), among others, it is preferable to use alkoxyamine.

所述短鏈胺例如亦可為包含羥基、羧基、烷氧基、羰基、酯基、巰基等胺以外的官能基的化合物。另外，所述胺可分別單獨使用，亦可併用兩種以上。除此之外，常壓下的沸點較佳為300℃以下，尤佳為250℃以下。 The short-chain amine may be, for example, a compound containing a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group, or a mercapto group. In addition, these amines may be used alone, respectively, or two or more kinds may be used in combination. In addition, the boiling point under normal pressure is preferably at most 300°C, particularly preferably at most 250°C.

若為不損及本發明的效果的範圍，則本實施形態的銀粒子分散體除了包含所述碳數為5以下的短鏈胺以外，亦可包含羧酸。羧酸的一分子內的羧基具有相對較高的極性，容易產生利用 氫鍵的相互作用，但該些官能基以外的部分具有相對較低的極性。進而，羧基容易顯示出酸性的性質。另外，羧酸若於本實施形態的銀粒子分散體中，局部存在(附著)於銀微粒子的表面的至少一部分(即，被覆銀微粒子的表面的至少一部分)，則可使溶媒與銀微粒子充分親和，可防止銀微粒子彼此的凝聚(提高分散性)。 The silver particle dispersion of this embodiment may contain carboxylic acid other than the short-chain amine whose carbon number is 5 or less as long as it is the range which does not impair the effect of this invention. The carboxyl group in one molecule of carboxylic acid has a relatively high polarity and is easy to produce and utilize Hydrogen bond interactions, but the parts other than these functional groups have relatively low polarity. Furthermore, a carboxyl group tends to exhibit acidic properties. In addition, if the carboxylic acid locally exists (attaches) on at least a part of the surface of the silver particle (that is, at least a part of the surface of the coated silver particle) in the silver particle dispersion of the present embodiment, the solvent and the silver particle can be sufficiently formed. Affinity prevents aggregation of silver particles (improves dispersibility).

作為羧酸，可廣泛使用具有至少1個羧基的化合物，例如可列舉：甲酸、乙二酸、乙酸、己酸、丙烯酸、辛酸、油酸等。羧酸的一部分的羧基亦可與金屬離子形成鹽。再者，關於該金屬離子，亦可包含兩種以上的金屬離子。 As the carboxylic acid, compounds having at least one carboxyl group can be widely used, for example, formic acid, oxalic acid, acetic acid, hexanoic acid, acrylic acid, caprylic acid, oleic acid and the like are mentioned. A part of the carboxyl groups of the carboxylic acid can also form a salt with a metal ion. In addition, two or more kinds of metal ions may be contained about this metal ion.

所述羧酸例如亦可為包含胺基、羥基、烷氧基、羰基、酯基、巰基等羧基以外的官能基的化合物。該情況下，羧基的數量較佳為羧基以外的官能基的數量以上。另外，所述羧酸可分別單獨使用，亦可併用兩種以上。除此之外，常壓下的沸點較佳為300℃以下，尤佳為250℃以下。另外，胺與羧酸形成醯胺。該醯胺基亦適度地吸附於銀微粒子表面，因此於銀微粒子表面亦可附著有醯胺基。 The carboxylic acid may be, for example, a compound containing a functional group other than a carboxyl group such as an amine group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group, or a mercapto group. In this case, the number of carboxyl groups is preferably more than the number of functional groups other than carboxyl groups. Moreover, these carboxylic acids may be used individually, respectively, and may use 2 or more types together. In addition, the boiling point under normal pressure is preferably at most 300°C, particularly preferably at most 250°C. Additionally, amines form amides with carboxylic acids. The amide group is also moderately adsorbed on the surface of the silver microparticles, so the amide group may also be attached to the surface of the silver microparticles.

於由銀微粒子與附著於該銀微粒子的表面的有機物(所述碳數為5以下的短鏈胺等)來構成膠體的情況下，該膠體中的有機成分的含量較佳為0.5質量%~50質量%。若有機成分含量為0.5質量%以上，則存在所獲得的銀微粒子分散體的儲存穩定性變得良好的傾向，若為50質量%以下，則存在對銀微粒子分散體進 行加熱而獲得的煅燒體的導電性良好的傾向。有機成分的更佳含量為1%~30質量%，尤佳含量為2%~15質量%。 When the colloid is composed of silver particles and organic matter (short-chain amines with 5 or less carbon number, etc.) attached to the surface of the silver particles, the content of the organic components in the colloid is preferably 0.5% by mass to 0.5% by mass. 50% by mass. If the organic component content is 0.5% by mass or more, there is a tendency that the storage stability of the obtained silver particle dispersion becomes good, and if it is 50% by mass or less, there is a tendency for the silver particle dispersion to be further improved. The conductivity of the calcined body obtained by heating tends to be good. The more preferable content of the organic component is 1% to 30% by mass, and the most preferable content is 2% to 15% by mass.

(C)高極性溶媒 (C) highly polar solvent

本實施形態的銀微粒子分散體是於多種高極性溶媒中分散有銀微粒子者。 The silver fine particle dispersion of this embodiment is what dispersed the silver fine particle in several types of highly polar solvents.

作為所述溶媒，可於不損及本發明的效果的範圍內，使用多種高極性溶媒。作為高極性溶媒，可例示：甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、2-丁醇、戊醇、己醇、異戊醇、糠醇、硝基甲烷、乙腈、吡啶、丙酮甲酚、二甲基甲醯胺、二噁烷、乙二醇、甘油、苯酚、對甲酚、乙酸丙酯、乙酸異丙酯、第三丁醇、1-戊醇、2-戊醇、4-甲基-2-戊醇、3-甲基-1-戊醇、3-甲基-2-戊醇、2-丁醇、1-己醇、2-己醇2-戊酮、2-庚酮、乙酸2-(2-乙氧基乙氧基)乙酯、乙酸-2-丁氧基乙酯、乙酸2-(2-丁氧基乙氧基)乙酯、乙酸-2-甲氧基乙酯、2-己氧基乙醇等，但本發明中由於與所述碳數為5以下的短鏈胺的相容性良好，故而較佳為使用碳數1~6的醇。再者，該些溶媒可分別單獨使用，亦可併用兩種以上。 As the solvent, various highly polar solvents can be used within the range not impairing the effect of the present invention. Examples of highly polar solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, pentanol, hexanol, isoamyl alcohol, furfuryl alcohol, nitromethane, acetonitrile, and pyridine. , acetone cresol, dimethylformamide, dioxane, ethylene glycol, glycerin, phenol, p-cresol, propyl acetate, isopropyl acetate, tertiary butanol, 1-pentanol, 2-pentanol Alcohol, 4-methyl-2-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 2-butanol, 1-hexanol, 2-hexanol 2-pentanone , 2-heptanone, 2-(2-ethoxyethoxy) ethyl acetate, 2-butoxyethyl acetate, 2-(2-butoxyethoxy) ethyl acetate, acetic acid- 2-methoxyethyl ester, 2-hexyloxyethanol, etc., but in the present invention, because the compatibility with the short-chain amines with the carbon number of 5 or less is good, it is preferable to use the short-chain amines with the carbon number of 1 to 6 alcohol. In addition, these solvents may be used individually, respectively, and may use 2 or more types together.

(D)分散劑 (D) Dispersant

本實施形態的銀粒子分散體中，更包含為了使銀微粒子分散而於銀微粒子合成後添加的「具有酸價的分散劑」。藉由使用所述分散劑，可提高溶媒中的銀微粒子的分散穩定性。此處，該分散劑的酸價更佳為5~200，另外，尤佳為該分散劑具有由磷酸而來的官能基。 The silver particle dispersion of the present embodiment further includes a "dispersant having an acid value" added after the synthesis of the silver fine particles in order to disperse the silver fine particles. By using such a dispersant, the dispersion stability of silver fine particles in a solvent can be improved. Here, the acid value of the dispersant is more preferably 5 to 200, and it is more preferable that the dispersant has a functional group derived from phosphoric acid.

其原因在於，若分散劑的酸價為5以上，則與胺配位，粒子表面開始產生對於成為鹼性的金屬物的酸鹼相互作用下的吸附；且原因在於，若為200以下，則不具有過度吸附的部位，故而以較佳形態來吸附。另外，藉由分散劑具有由磷酸而來的官能基，磷P經由氧O而與金屬M相互作用來牽引，故而對於與金屬或金屬化合物的吸附最有效果，能夠以必要最小限的吸附量來獲得較佳的分散性。 The reason is that if the acid value of the dispersant is 5 or more, it will coordinate with the amine, and the surface of the particle will start to adsorb under the acid-base interaction for the metal substance that becomes basic; and the reason is that if it is 200 or less, then There are no excessively adsorbed parts, so it is adsorbed in a better form. In addition, because the dispersant has a functional group derived from phosphoric acid, phosphorus P interacts with metal M through oxygen O to attract it, so it is most effective for the adsorption of metals or metal compounds, and can be adsorbed with the necessary minimum amount. for better dispersion.

再者，作為酸價為5~200的高分子分散劑，例如，路博潤(Lubrizol)公司的索爾斯帕斯(SOLSPERSE)系列中可列舉索爾斯帕斯(SOLSPERSE)-16000、21000、41000、41090、43000、44000、46000、54000等，畢克化學(BYK-Chemie)公司的迪斯帕畢克(DISPERBYK)系列中可列舉：迪斯帕畢克(DISPERBYK)-102、110、111、170、190、194N、2015、2090、2096等，贏創(Evonik)公司的迪高迪斯帕(TEGO Dispers)系列中可列舉：610、610S、630、651、655、750W、755W等，楠本化成(股)製造的帝司巴隆(Disparlon)系列中可列舉DA-375、DA-1200等，共榮化學工業(股)製造的弗洛蘭(Flowlen)系列中可例示：WK-13E、G-700、G-900、GW-1500、GW-1640、WK-13E。 Furthermore, as a polymer dispersant with an acid value of 5 to 200, for example, Solsperse (SOLSPERSE)-16000, 21000, etc. . 111, 170, 190, 194N, 2015, 2090, 2096, etc. Evonik's TEGO Dispers series can include: 610, 610S, 630, 651, 655, 750W, 755W, etc. , DA-375, DA-1200, etc. can be listed in the Disparlon series manufactured by Kusumoto Chemical Co., Ltd., and the Flowlen series manufactured by Kyoei Chemical Industry Co., Ltd. can be exemplified: WK- 13E, G-700, G-900, GW-1500, GW-1640, WK-13E.

於本實施形態的銀微粒子分散體中含有分散劑的情況下的含量若根據黏度等所需的特性來調整即可，例如於將銀微粒子分散體用作銀油墨的情況下，較佳為將分散劑的含量設為0.5質量%~20質量%，於用作銀漿的情況下，較佳為將分散劑的含量 設為0.1質量%~10質量%。 When the silver microparticle dispersion of the present embodiment contains a dispersant, the content may be adjusted according to desired properties such as viscosity. For example, when the silver microparticle dispersion is used as a silver ink, it is preferable to use The content of the dispersant is set to 0.5% by mass to 20% by mass. When used as a silver paste, it is preferable to make the content of the dispersant It is set at 0.1 mass % - 10 mass %.

高分子分散劑的含量較佳為0.1質量%~15質量%。若高分子分散劑的含量為0.1%以上，則所獲得的銀微粒子分散體的分散穩定性變得良好，於含量過多的情況下，低溫燒結性會下降。就所述觀點而言，高分子分散劑的更佳含量為0.3質量%~10質量%，尤佳含量為0.5質量%~8質量%。 The content of the polymer dispersant is preferably 0.1% by mass to 15% by mass. When the content of the polymer dispersant is 0.1% or more, the dispersion stability of the obtained silver microparticle dispersion becomes good, but when the content is too large, the low-temperature sinterability will decrease. From this point of view, the more preferable content of the polymer dispersant is 0.3% by mass to 10% by mass, and the most preferable content is 0.5% by mass to 8% by mass.

本實施形態的分散體尤佳為：藉由熱分析，自室溫加熱至200℃時的重量減少率為20質量%以下，且自200℃加熱至500℃時的重量減少率為10質量%以下。此處，至200℃的重量減少率主要表示有助於低溫燒結性的低溫成分即短鏈胺的含量，200℃~500℃的高溫成分的重量減少率主要表示有助於分散穩定性的酸價的分散劑的含量。若短鏈胺或高溫成分過剩，則低溫燒結性受損。即，若自室溫加熱至200℃時的重量減少率為20質量%以下，且自200℃加熱至500℃時的重量減少率為10質量%以下，則低溫燒結性更優異。 In the dispersion of this embodiment, it is preferable that the weight loss rate when heated from room temperature to 200° C. is 20% by mass or less, and the weight loss rate when heated from 200° C. to 500° C. is 10% by mass or less by thermal analysis. . Here, the weight loss rate up to 200°C mainly indicates the content of short-chain amines, which are low-temperature components that contribute to low-temperature sinterability, and the weight loss rate of high-temperature components from 200°C to 500°C mainly indicates the acid that contributes to dispersion stability. content of dispersant. If the short-chain amine or the high-temperature component is excessive, the low-temperature sinterability will be impaired. That is, if the weight loss rate when heated from room temperature to 200°C is 20% by mass or less, and the weight loss rate when heated from 200°C to 500°C is 10% by mass or less, the low-temperature sinterability is more excellent.

(E)保護劑(保護分散劑) (E) Protective agent (protective dispersant)

本實施形態的銀微粒子分散體可更包含作為於銀微粒子合成前添加的保護劑的具有酸價的分散劑(保護分散劑)。此處所謂的「保護分散劑」，可與所述銀微粒子合成後添加的「具有酸價的分散劑」為相同種類者，亦可為不同種類者。 The silver fine particle dispersion of this embodiment may further contain a dispersant having an acid value (protective dispersant) as a protective agent added before silver fine particle synthesis. The "protective dispersant" here may be of the same type as the "dispersant having an acid value" added after the synthesis of the silver microparticles, or may be of a different type.

(F)其他成分 (F) Other ingredients

本實施形態的銀微粒子分散體中，除了所述成分以外，亦可 於不損及本發明的效果的範圍內，為了賦予與使用目的對應的適度的黏性、密合性、乾燥性或者印刷性等功能，而添加例如發揮作為黏合劑的作用的寡聚物成分、樹脂成分、有機溶劑(可將固體成分的一部分溶解或者分散)、界面活性劑、增黏劑或者表面張力調整劑等任意成分。作為所述任意成分，並無特別限定。 In the silver microparticle dispersion of the present embodiment, in addition to the above-mentioned components, Within the range that does not impair the effect of the present invention, in order to impart appropriate functions such as viscosity, adhesiveness, dryness, or printability corresponding to the purpose of use, for example, an oligomer component that functions as a binder is added. , a resin component, an organic solvent (which can dissolve or disperse a part of the solid content), a surfactant, a thickener, or a surface tension regulator and other optional components. It does not specifically limit as said arbitrary component.

作為樹脂成分，例如可列舉：聚酯系樹脂、封端異氰酸酯等聚胺基甲酸酯系樹脂、聚丙烯酸酯系樹脂、聚丙烯醯胺系樹脂、聚醚系樹脂、三聚氰胺系樹脂或者萜烯系樹脂等，該些樹脂成分可分別單獨使用，亦可併用兩種以上。 Examples of the resin component include polyester resins, polyurethane resins such as blocked isocyanate, polyacrylate resins, polyacrylamide resins, polyether resins, melamine resins, or terpene resins. These resin components may be used alone or two or more of them may be used in combination.

作為增黏劑，例如可列舉：黏土(clay)、膨土(bentonite)或者鋰膨潤石(hectorite)等黏土礦物，例如聚酯系乳膠樹脂、丙烯酸系乳膠樹脂、聚胺基甲酸酯系乳膠樹脂或者封端異氰酸酯等乳膠，甲基纖維素、羧基甲基纖維素、羥基乙基纖維素、羥基丙基纖維素、羥基丙基甲基纖維素等纖維素衍生物、三仙膠(xanthan gum)或者瓜爾膠(guar gum)等多糖類等，該些增黏劑可分別單獨使用，亦可併用兩種以上。 Examples of tackifiers include clay minerals such as clay, bentonite, and hectorite, polyester-based latex resins, acrylic latex resins, and polyurethane-based latex resins. Latex such as resin or blocked isocyanate, cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, xanthan gum ) or polysaccharides such as guar gum, these thickeners may be used alone or in combination of two or more.

亦可添加與所述有機成分不同的界面活性劑。多成分溶媒系的無機膠體分散液中，容易產生由乾燥時的揮發速度不同所引起的塗層表面的粗糙以及固體成分的偏移。藉由在本實施形態的銀微粒子分散體中添加界面活性劑來抑制該些不利，可獲得能夠形成均勻的導電性塗層的銀微粒子分散體。 A surfactant different from the organic component may also be added. In the inorganic colloid dispersion liquid of the multi-component solvent system, the roughness of the coating surface and the deviation of the solid content easily occur due to the difference in the volatilization rate during drying. These disadvantages are suppressed by adding a surfactant to the silver fine particle dispersion of this embodiment, and a silver fine particle dispersion capable of forming a uniform conductive coating layer can be obtained.

作為本實施形態中可使用的界面活性劑，並無特別限 定，可使用陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑的任一者，例如可列舉：烷基苯磺酸鹽、四級銨鹽等。其中，由於以少量的添加量來獲得效果，故而較佳為氟系界面活性劑、矽酮系界面活性劑。 The surfactant usable in this embodiment is not particularly limited Certainly, any one of anionic surfactant, cationic surfactant, and nonionic surfactant can be used, for example, alkylbenzenesulfonate, quaternary ammonium salt, etc. are mentioned. Among these, fluorine-based surfactants and silicone-based surfactants are preferable because effects are obtained with a small amount of addition.

(1-3-2)銀微粒子 (1-3-2) Silver particles

本實施形態的銀微粒子分散體中所含的銀微粒子為於表面的至少一部分上附著有分配係數logP為-1.0~1.4且碳數為5以下的烷氧基胺的銀微粒子。 The silver fine particles contained in the silver fine particle dispersion of the present embodiment are silver fine particles having a distribution coefficient logP of −1.0 to 1.4 and an alkoxyamine having 5 or less carbon atoms adhered to at least a part of the surface.

藉由使銀微粒子的表面的至少一部分上附著分配係數logP為-1.0~1.4且碳數為5以下的烷氧基胺，可對銀微粒子賦予對於多種溶媒(特別是高極性溶媒)而言的優異分散性及低溫燒結性。 By making at least a part of the surface of the silver microparticles attach a partition coefficient logP of -1.0 to 1.4 and an alkoxyamine having a carbon number of 5 or less, the silver microparticles can be given a variety of solvents (especially highly polar solvents). Excellent dispersibility and low temperature sinterability.

作為所述溶媒，可於不損及本發明的效果的範圍內使用多種溶媒，可使用SP值(溶解參數(solubility parameter))為7.0~15.0的溶媒。此處，於高極性溶媒中亦均勻分散有銀微粒子是本發明的銀微粒子分散體的特徵之一，本發明中由於與所述碳數為5以下的短鏈胺的相容性良好，故而較佳為使用碳數1~6的醇。再者，該些溶媒可分別單獨使用，亦可併用兩種以上。 As the solvent, various solvents can be used within the range not impairing the effect of the present invention, and a solvent having an SP value (solubility parameter) of 7.0 to 15.0 can be used. Here, it is one of the characteristics of the silver particle dispersion of the present invention that silver particles are also uniformly dispersed in the highly polar solvent. In the present invention, due to the good compatibility with the short-chain amine with the carbon number of 5 or less, it is Preferably, an alcohol having 1 to 6 carbon atoms is used. In addition, these solvents may be used individually, respectively, and may use 2 or more types together.

作為SP值(溶解參數)為7.0~15.0的溶媒，例如可例示：己烷(7.2)、三乙胺(7.3)、***(7.7)、正辛烷(7.8)、環己烷(8.3)、乙酸正戊酯(8.3)、乙酸異丁酯(8.3)、甲基異丙基酮(8.4)、戊基苯(8.5)、乙酸丁酯(8.5)、四氯化碳(8.6)、乙 基苯(8.7)、對二甲苯(8.8)、甲苯(8.9)、甲基丙基酮(8.9)、乙酸乙酯(8.9)、四氫呋喃(9.2)、甲基乙基酮(9.3)、氯仿(9.4)、丙酮(9.8)、二噁烷(10.1)、吡啶(10.8)、異丁醇(11.0)、正丁醇(11.1)、硝基乙烷(11.1)、異丙醇(11.2)、間甲酚(11.4)、乙腈(11.9)、正丙醇(12.1)、糠醇(12.5)、硝基甲烷(12.7)、乙醇(12.8)、甲酚(13.3)、乙二醇(14.2)、甲醇(14.8)、苯酚、對甲酚、乙酸丙酯、乙酸異丙酯、第三丁醇、1-戊醇、2-戊醇、4-甲基-2-戊醇、3-甲基-1-戊醇、3-甲基-2-戊醇、2-丁醇、1-己醇、2-己醇、2-戊酮、2-庚酮、乙酸2-(2-乙氧基乙氧基)乙酯、乙酸-2-丁氧基乙酯、乙酸2-(2-丁氧基乙氧基)乙酯、乙酸-2-甲氧基乙酯、2-己氧基乙醇等。 As a solvent with an SP value (dissolution parameter) of 7.0 to 15.0, for example, hexane (7.2), triethylamine (7.3), diethyl ether (7.7), n-octane (7.8), cyclohexane (8.3), N-pentyl acetate (8.3), isobutyl acetate (8.3), methyl isopropyl ketone (8.4), amylbenzene (8.5), butyl acetate (8.5), carbon tetrachloride (8.6), ethyl Benzene (8.7), p-xylene (8.8), toluene (8.9), methyl propyl ketone (8.9), ethyl acetate (8.9), tetrahydrofuran (9.2), methyl ethyl ketone (9.3), chloroform ( 9.4), acetone (9.8), dioxane (10.1), pyridine (10.8), isobutanol (11.0), n-butanol (11.1), nitroethane (11.1), isopropanol (11.2), meta Cresol (11.4), acetonitrile (11.9), n-propanol (12.1), furfuryl alcohol (12.5), nitromethane (12.7), ethanol (12.8), cresol (13.3), ethylene glycol (14.2), methanol ( 14.8), phenol, p-cresol, propyl acetate, isopropyl acetate, tert-butanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol, 3-methyl-1- Pentanol, 3-methyl-2-pentanol, 2-butanol, 1-hexanol, 2-hexanol, 2-pentanone, 2-heptanone, acetic acid 2-(2-ethoxyethoxy ) ethyl ester, 2-butoxyethyl acetate, 2-(2-butoxyethoxy)ethyl acetate, 2-methoxyethyl acetate, 2-hexoxyethanol and the like.

本實施形態的銀微粒子的粒徑較佳為如產生熔點下降的奈米尺寸，理想為1nm~200nm，視需要亦可包含微米尺寸的粒子。 The particle size of the silver microparticles in this embodiment is preferably a nanometer size that causes melting point depression, ideally 1 nm to 200 nm, and micron size particles may also be included if necessary.

再者，亦可直接使用所述銀微粒子分散體來形成導電性塗層6，但可藉由調整為適合於轉印印刷用的導電性油墨來使用，從而形成轉印印刷於樹脂層4上的導電性塗層6。以下，對該導電性油墨進行說明。 Furthermore, the silver microparticle dispersion can also be used directly to form the conductive coating 6, but it can be used by adjusting the conductive ink suitable for transfer printing to form transfer printing on the resin layer 4. conductive coating6. Hereinafter, this conductive ink will be described.

本實施形態的轉印印刷用導電性油墨的特徵在於包含：金屬粒子、包含乙醇的溶媒及0.1質量%~3.0質量%的具有羥基的高沸點溶劑。另外，包含以含有金屬粒子及有機成分的金屬粒子分散體(換言之，金屬膠體粒子)作為主成分的固體成分 及將該些固體成分分散的分散介質。其中，所述膠體液中，「分散介質」亦可溶解所述固體成分的一部分。 The conductive ink for transfer printing according to this embodiment is characterized by containing metal particles, a solvent containing ethanol, and 0.1% by mass to 3.0% by mass of a high-boiling-point solvent having a hydroxyl group. In addition, a solid component including a metal particle dispersion (in other words, metal colloid particles) containing metal particles and an organic component as a main component and a dispersion medium for dispersing these solid components. Wherein, in the colloidal liquid, the "dispersion medium" may also dissolve a part of the solid component.

依據此種金屬膠體液，由於包含有機成分，故而可提高金屬膠體液中的金屬膠體粒子的分散性，因此，即便增加金屬膠體液中的金屬成分的含量，金屬膠體粒子亦難以凝聚，可保持良好的分散穩定性。再者，此處所謂的「分散性」是表示剛製備金屬膠體液後，該金屬膠體液中的金屬粒子的分散狀態是否優異(是否均勻)，所謂「分散穩定性」是表示製備金屬膠體液且經過既定的時間後，該金屬膠體液中的金屬粒子的分散狀態是否得以維持，亦可稱為「低沈降凝聚性」。 According to this metal colloid liquid, since it contains an organic component, the dispersibility of the metal colloid particles in the metal colloid liquid can be improved. Therefore, even if the content of the metal component in the metal colloid liquid is increased, the metal colloid particles are also difficult to agglomerate and can maintain Good dispersion stability. Furthermore, the so-called "dispersibility" here refers to whether the dispersion state of the metal particles in the metal colloid liquid is excellent (whether uniform or not) immediately after the preparation of the metal colloid liquid, and the so-called "dispersion stability" refers to the preparation of the metal colloid liquid. And whether the dispersed state of the metal particles in the metal colloid liquid can be maintained after a predetermined period of time can also be referred to as "low sedimentation cohesion".

此處，所述金屬膠體液中，金屬膠體粒子中的「有機成分」是與所述金屬成分一併實質上構成金屬膠體粒子的有機物。該有機成分中，不包含如金屬中最初作為雜質而包含的微量有機物、於後述製造過程中混入的微量有機物附著於金屬成分上的有機物、於洗滌過程未徹底去除的殘留還原劑、殘留分散劑等般，微量附著於金屬成分上的有機物等。再者，所述所謂「微量」具體而言是指於金屬膠體粒子中小於1質量%。 Here, in the metal colloid liquid, the "organic component" in the metal colloid particles is an organic substance that substantially constitutes the metal colloid particles together with the metal component. This organic component does not contain traces of organic substances originally contained as impurities in metals, traces of organic substances mixed in the manufacturing process described later, organic substances attached to metal components, residual reducing agents that were not completely removed in the washing process, and residual dispersants. In general, trace amounts of organic substances attached to metal components, etc. Furthermore, the so-called "trace amount" specifically refers to less than 1% by mass in the metal colloid particles.

本實施形態中的金屬膠體粒子由於包含有機成分，故而於金屬膠體液中的分散穩定性高。因此，即便增大金屬膠體液中的金屬成分的含量，金屬膠體粒子亦難以凝聚，其結果為確保良好的分散性。 Since the metal colloid particles in this embodiment contain organic components, they have high dispersion stability in the metal colloid liquid. Therefore, even if the content of the metal component in the metal colloid liquid is increased, the metal colloid particles are difficult to aggregate, and as a result, good dispersibility is ensured.

另外，本實施形態中的金屬膠體液的所謂「固體成分」， 是指當使用二氧化矽凝膠等自金屬膠體液中去除分散介質後，例如於30℃以下的常溫(例如25℃)下乾燥24小時之時殘存的固體成分，通常包含金屬粒子、殘存有機成分以及殘留還原劑等。再者，作為使用二氧化矽凝膠自金屬膠體液中去除分散介質的方法，可採用多種方法，例如若藉由在玻璃基板上塗佈金屬膠體液，將帶有塗膜的玻璃基板於加入有二氧化矽凝膠的密閉容器中放置24小時以上而去除分散介質即可。 In addition, the so-called "solid content" of the metal colloid liquid in this embodiment, Refers to the solid content remaining when the dispersion medium is removed from the metal colloid liquid by using silica gel, etc., for example, at room temperature (for example, 25°C) below 30°C for 24 hours, and usually includes metal particles, residual organic matter, etc. Components and residual reducing agents, etc. Furthermore, as a method of using silica gel to remove the dispersion medium from the metal colloid liquid, various methods can be adopted, for example, if the metal colloid liquid is coated on the glass substrate, the glass substrate with the coating film is added Put the silica gel in a closed container for more than 24 hours and remove the dispersion medium.

本實施形態的金屬膠體液中，較佳的固體成分的濃度為1質量%~60質量%。若固體成分的濃度為1質量%以上，則可確保轉印印刷用導電性油墨中的金屬的含量，導電效率不會降低。另外，若固體成分的濃度為60質量%以下，則金屬膠體液的黏度不會增加，操作容易，於工業上有利，可形成平坦的薄膜。更佳的固體成分的濃度為5質量%~40質量%。 In the metal colloid liquid of the present embodiment, a preferable solid content concentration is 1% by mass to 60% by mass. When the solid content concentration is 1% by mass or more, the metal content in the conductive ink for transfer printing can be ensured, and the conductive efficiency will not be lowered. In addition, when the concentration of the solid content is 60% by mass or less, the viscosity of the metal colloid liquid does not increase, the handling is easy, it is advantageous industrially, and a flat thin film can be formed. A more preferable solid content concentration is 5% by mass to 40% by mass.

轉印印刷用導電性油墨的特徵在於包含0.1質量%~3.0質量%的具有羥基的高沸點溶劑。具有羥基的高沸點溶劑較佳為選自1,3-丁二醇(沸點：203℃)、2,4-二乙基-1,5-戊二醇(沸點：150℃/5mmHg，1氣壓下為200℃以上)或者辛二醇(沸點：243℃)中。 The conductive ink for transfer printing is characterized by containing 0.1% by mass to 3.0% by mass of a high boiling point solvent having a hydroxyl group. The high boiling point solvent with hydroxyl group is preferably selected from 1,3-butanediol (boiling point: 203°C), 2,4-diethyl-1,5-pentanediol (boiling point: 150°C/5mmHg, 1 atmosphere 200°C or higher) or octanediol (boiling point: 243°C).

所謂「高沸點溶劑」，是指具有200℃以上的沸點的溶劑。另外，藉由具有羥基而對水具有適度的親和性，存在將空氣中的水分吸收或吸附等而保濕的傾向，因此能夠以少的添加量來製成適合於轉印印刷法的油墨。進而，藉由將高沸點溶劑的添加 量設為必要最小限度，發揮可使塗佈於矽酮覆層上的油墨在短時間內半乾燥，可縮短印刷週期的效果。 The term "high boiling point solvent" refers to a solvent having a boiling point of 200°C or higher. In addition, since it has a moderate affinity for water due to having a hydroxyl group, it tends to absorb or absorb moisture in the air to keep it moisturized, so it can be prepared as an ink suitable for transfer printing with a small amount of addition. Furthermore, by adding a high boiling point solvent The amount is set to the necessary minimum, and the ink coated on the silicone coating can be semi-dried in a short time, and the printing cycle can be shortened.

具有羥基的高沸點溶劑的添加量為0.1質量%~3.0質量%。若小於0.1質量%，則量過少，難以成為適合於轉印印刷法的油墨狀，若超過3.0質量%，則達到適合於轉印印刷法的半乾燥狀態的時間延長，於印刷週期的方面變得不利。就更確實地容易成為適合於轉印印刷法的油墨狀，可縮短達到適合於轉印印刷法的半乾燥狀態的時間，於印刷週期的方面變得有利的觀點而言，具有羥基的高沸點溶劑的添加量特佳為0.3質量%~2.0質量%。 The addition amount of the high boiling point solvent which has a hydroxyl group is 0.1 mass % - 3.0 mass %. If it is less than 0.1% by mass, the amount is too small, and it is difficult to become an ink suitable for the transfer printing method. If it exceeds 3.0% by mass, the time to reach a semi-dry state suitable for the transfer printing method will be prolonged, and the printing cycle will change. Bad luck. It is easy to become an ink form suitable for the transfer printing method more reliably, the time to reach a semi-dry state suitable for the transfer printing method can be shortened, and it is advantageous in terms of the printing cycle. The addition amount of the solvent is particularly preferably 0.3% by mass to 2.0% by mass.

另外，轉印印刷用導電性油墨中，為了提高油墨的乾燥性而添加乙醇等高揮發性溶劑。藉由添加該溶劑，可將轉印印刷用導電性油墨快速地調整為適合於印刷的黏度。作為高揮發性溶劑，除了乙醇以外，還可使用選自甲醇、丙醇、異丙醇、丙酮、正丁醇、第二丁醇、第三丁醇等沸點小於100℃的溶劑的群組中的一種或兩種以上的低沸點溶劑。 In addition, in the conductive ink for transfer printing, a highly volatile solvent such as ethanol is added in order to improve the drying property of the ink. By adding this solvent, the conductive ink for transfer printing can be quickly adjusted to a viscosity suitable for printing. As a highly volatile solvent, in addition to ethanol, it is also possible to use among the group of solvents selected from methanol, propanol, isopropanol, acetone, n-butanol, second butanol, third butanol and the like with a boiling point of less than 100°C One or more low boiling point solvents.

進而，於轉印印刷用導電性油墨中，較佳為包含氫氟醚等氟溶劑。氟溶劑由於表面張力低而可對矽酮覆層發揮良好的潤濕性，且由於沸點相對較低而可賦予良好的乾燥性。其中，就臭氧破壞係數的觀點而言，較包含鹵素原子的氟溶劑而言，較佳為氫氟醚。 Furthermore, in the conductive ink for transfer printing, it is preferable to contain fluorine solvents, such as a hydrofluoroether. Fluorinated solvents can exhibit good wettability to the silicone coating due to low surface tension, and can impart good drying properties due to relatively low boiling point. Among these, hydrofluoroethers are more preferable than fluorinated solvents containing halogen atoms from the viewpoint of ozone destruction coefficient.

另外，較氫氟碳類而言，氫氟醚由於具有醚鍵而具有極性高、基本上不會使矽酮覆層膨潤的優點，發揮與乙醇等醇的相 容性良好、與分散於醇中的金屬粒子的相容性亦優異的效果，因此更佳。 In addition, compared with hydrofluorocarbons, hydrofluoroether has the advantages of high polarity due to its ether bond, and basically does not swell the silicone coating, and exerts its compatibility with alcohols such as ethanol. Since the compatibility is good and the compatibility with the metal particle dispersed in alcohol is also excellent, it is more preferable.

轉印印刷用導電性油墨中，出於提高對矽酮覆層的潤濕性的目的，亦可添加具有氟原子的氟系界面活性劑。但，於該情況下，若添加量過多，則使用轉印印刷用導電性油墨來製作的導電性塗層的導電性下降，若添加量過少，則潤濕性改善的效果不充分，因此較佳為0.01質量%~2質量%。 In the conductive ink for transfer printing, a fluorine-based surfactant having a fluorine atom may be added for the purpose of improving wettability to the silicone coating. However, in this case, if the amount added is too large, the conductivity of the conductive coating made using the conductive ink for transfer printing will decrease, and if the amount added is too small, the effect of improving wettability will not be sufficient. Preferably, it is 0.01% by mass to 2% by mass.

轉印印刷用導電性油墨中，表面張力為22mN/m以下。藉由將表面張力充分降低至22mN/m以下，可充分保證轉印印刷用導電性油墨對矽酮樹脂等覆層的潤濕性。將表面張力設為22mN/m以下，可藉由調整所述本發明的轉印印刷用導電性油墨的成分比來實現。表面張力的下限若為13mN/m左右即可。再者，本發明中所謂的表面張力是利用板法(plate method)(威廉(Wilhelmy)法)的原理進行測定而得者，例如可利用協和界面科學(股)製造的全自動表面張力計CBVP-Z等來測定。 In the conductive ink for transfer printing, the surface tension is 22 mN/m or less. By sufficiently reducing the surface tension to below 22mN/m, the wettability of the conductive ink for transfer printing to the coating such as silicone resin can be fully ensured. The surface tension can be adjusted to 22 mN/m or less by adjusting the component ratio of the conductive ink for transfer printing of the present invention. The lower limit of the surface tension may be about 13 mN/m. Furthermore, the so-called surface tension in the present invention is obtained by measuring the principle of the plate method (Wilhelmy method), for example, the fully automatic surface tension meter CBVP manufactured by Kyowa Interface Science Co., Ltd. can be used -Z etc. to determine.

(1-3-3)銀微粒子及銀微粒子分散體的製造方法 (1-3-3) Method for producing silver microparticles and silver microparticle dispersion

本實施形態的銀微粒子以及銀微粒子分散體的製造方法包括：生成銀微粒子的步驟；以及對所述銀微粒子添加、混合用以使所述銀微粒子分散的具有酸價的分散劑的步驟；進而包括：第一前步驟，製備可藉由還原而分解生成金屬銀的銀化合物、與分配係數logP為-1.0~1.4的短鏈胺的混合液；以及第二前步驟，藉由將該混合液中的所述銀化合物還原而生成於表面的至少一部分 上附著有碳數為5以下的短鏈胺的銀微粒子。 The manufacturing method of the silver microparticles and the silver microparticle dispersion of the present embodiment includes: a step of generating silver microparticles; and a step of adding and mixing a dispersant having an acid value for dispersing the silver microparticles to the silver microparticles; and then Including: the first pre-step, preparing a mixed solution of a silver compound that can be decomposed to generate metallic silver by reduction, and a short-chain amine with a distribution coefficient logP of -1.0 to 1.4; and a second pre-step, by making the mixed solution The reduction of the silver compound in at least a part of the surface Silver microparticles with short-chain amines with 5 or less carbon atoms attached to them.

於所述第一前步驟中，較佳為相對於1mol的金屬銀而添加2mol以上的短鏈胺。藉由將短鏈胺的添加量相對於1mol的金屬銀而設為2mol以上，可使藉由還原而生成的銀微粒子的表面附著適量的短鏈胺，可對該銀微粒子賦予對於多種溶媒(特別是高極性溶媒)而言的優異分散性及低溫燒結性。 In the first preceding step, it is preferable to add 2 mol or more of short-chain amine to 1 mol of metallic silver. By setting the addition amount of the short-chain amine to 2 mol or more relative to 1 mol of metallic silver, an appropriate amount of short-chain amine can be attached to the surface of the silver microparticles generated by reduction, and can be given to the silver microparticles for various solvents ( Excellent dispersibility and low-temperature sinterability especially for highly polar solvents.

再者，根據所述第一前步驟中的混合液的組成以及所述第二前步驟中的還原條件(例如加熱溫度以及加熱時間等)，較佳為將所獲得的銀微粒子的粒徑設為產生熔點下降的奈米尺寸，更佳為設為1nm~200nm。此處，視需要亦可包含微米尺寸的粒子。 Furthermore, according to the composition of the mixed solution in the first preceding step and the reducing conditions (such as heating temperature and heating time, etc.) in the second preceding step, it is preferable to set the particle diameter of the obtained silver particles to In order to produce a nanometer size with a reduced melting point, it is more preferably 1 nm to 200 nm. Here, micron-sized particles may also be included as needed.

自所述第二前步驟中獲得的銀微粒子分散體中取出銀微粒子的方法並無特別限定，例如可列舉對所述銀微粒子分散體進行洗滌的方法等。 The method of taking out the silver fine particles from the silver fine particle dispersion obtained in the second preceding step is not particularly limited, and examples thereof include a method of washing the silver fine particle dispersion and the like.

作為用以獲得由有機物(分配係數logP為-1.0~1.4的短鏈胺)被覆的銀微粒子的起始材料，可使用多種公知的銀化合物(金屬鹽或其水合物)，例如可列舉：硝酸銀、硫酸銀、氯化銀、氧化銀、乙酸銀、乙二酸銀、甲酸銀、亞硝酸銀、氯酸銀、硫化銀等銀鹽。該些銀鹽若為可還原者，則並無特別限定，可溶解於適當的溶媒中，亦可以分散於溶媒中的狀態來使用。另外，該些可單獨使用，亦可併用多種。 Various known silver compounds (metal salts or hydrates thereof) can be used as a starting material for obtaining silver microparticles coated with organic substances (short-chain amines with a partition coefficient logP of -1.0 to 1.4), for example: silver nitrate , silver sulfate, silver chloride, silver oxide, silver acetate, silver oxalate, silver formate, silver nitrite, silver chlorate, silver sulfide and other silver salts. These silver salts are not particularly limited as long as they are reducible, and may be used in a state of being dissolved in a suitable solvent or dispersed in a solvent. In addition, these may be used individually, and may use multiple types together.

另外，所述原料液中將該些銀化合物還原的方法並無特別限定，例如可列舉：使用還原劑的方法，照射紫外線等光、電 子束、超音波或熱能量的方法，進行加熱的方法等。其中，就容易操作的觀點而言，較佳為使用還原劑的方法。 In addition, the method for reducing these silver compounds in the raw material solution is not particularly limited, and examples thereof include: a method using a reducing agent, irradiating ultraviolet light or other light, electricity, etc. Methods of beamlet, ultrasonic or thermal energy, methods of heating, etc. Among these, the method using a reducing agent is preferable from the viewpoint of easy handling.

作為所述還原劑，可列舉：例如二甲基胺基乙醇、甲基二乙醇胺、三乙醇胺、菲尼酮(phenidone)、聯胺(hydrazine)等胺化合物；例如硼氫化鈉、碘化氫、氫氣等氫化合物；例如一氧化碳、亞硫酸等氧化物；例如硫酸亞鐵、氧化鐵、反丁烯二酸鐵、乳酸鐵、乙二酸鐵、硫化鐵、乙酸錫、氯化錫、二磷酸錫、乙二酸錫、氧化錫、硫酸錫等低原子價金屬鹽；例如乙二醇、甘油、甲醛、對苯二酚、鄰苯三酚、單寧、單寧酸、水楊酸、D-葡萄糖等糖等；若為可溶解於分散介質中而將所述金屬鹽還原者，則並無特別限定。於使用所述還原劑的情況下，亦可施加光及/或熱來促進還原反應。 Examples of the reducing agent include amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone, and hydrazine; examples include sodium borohydride, hydrogen iodide, Hydrogen compounds such as hydrogen; oxides such as carbon monoxide and sulfurous acid; such as ferrous sulfate, iron oxide, iron fumarate, iron lactate, iron oxalate, iron sulfide, tin acetate, tin chloride, tin diphosphate , tin oxalate, tin oxide, tin sulfate and other low atomic valence metal salts; such as ethylene glycol, glycerin, formaldehyde, hydroquinone, pyrogallol, tannin, tannic acid, salicylic acid, D- Sugars such as glucose and the like are not particularly limited as long as they can be dissolved in a dispersion medium to reduce the metal salt. In the case of using the reducing agent, light and/or heat may also be applied to promote the reduction reaction.

作為使用所述金屬鹽、有機成分、溶媒及還原劑來製備由有機物被覆的銀微粒子的具體方法，可列舉如下方法等：例如將所述金屬鹽溶解於有機溶媒(例如甲苯等)中來製備金屬鹽溶液，於該金屬鹽溶液中添加作為分散劑的短鏈胺或具有酸價的保護分散劑，繼而於其中緩緩滴加溶解有還原劑的溶液。 As a specific method for preparing silver microparticles coated with an organic substance using the metal salt, an organic component, a solvent, and a reducing agent, the following methods are mentioned: for example, the metal salt is dissolved in an organic solvent (such as toluene, etc.) to prepare A metal salt solution, adding a short-chain amine as a dispersant or a protective dispersant with an acid value to the metal salt solution, and then slowly adding a solution in which a reducing agent is dissolved.

於包含以所述方式獲得的由短鏈胺或具有酸價的保護分散劑所被覆的銀微粒子的分散液中，除了銀微粒子以外，還存在金屬鹽的相對離子、還原劑的殘留物或分散劑，存在溶液整體的電解質濃度或有機物濃度高的傾向。此種狀態的溶液由於導電度高等原因而產生銀微粒子的凝析，容易沈澱。或者，即便不沈 澱，若金屬鹽的相對離子、還原劑的殘留物、或者分散所必需的量以上的過剩的分散劑殘留，則存在使導電性惡化的顧慮。因此，藉由對包含所述銀微粒子的溶液進行洗滌而去除多餘的殘留物，可確實地獲得由有機物所被覆的銀微粒子。 In the dispersion liquid containing silver microparticles coated with short-chain amines or protective dispersants with acid values obtained in the above manner, in addition to the silver microparticles, there are also residues or dispersions of counter ions of metal salts and reducing agents. agent, there is a tendency for the electrolyte concentration or the organic substance concentration of the entire solution to be high. The solution in this state is easy to precipitate because of the high conductivity and other reasons for the coagulation of silver particles. Or, even if unsinkable For the precipitate, if the counter ion of the metal salt, the residue of the reducing agent, or the excess dispersant exceeding the amount required for dispersion remains, there is a possibility that the conductivity may be deteriorated. Therefore, by washing the solution containing the silver microparticles to remove excess residues, silver microparticles coated with organic matter can be reliably obtained.

作為所述洗滌方法，例如可列舉：將包含由有機成分所被覆的銀微粒子的分散液靜置一定時間，去除所產生的上清液後，添加使銀微粒子沈澱的溶媒(例如水、甲醇、甲醇/水混合溶媒等)而再次攪拌，進而靜置一定時間，去除所產生的上清液，將如上步驟反覆進行多次的方法；進行離心分離來代替所述靜置的方法；利用超濾裝置或離子交換裝置等來進行脫鹽的方法等。藉由如上所述的洗滌而去除多餘的殘留物，並且去除有機溶媒，藉此可獲得本實施形態的由「短鏈胺或具有酸價的分散劑」所被覆的銀微粒子。 As the washing method, for example, it is possible to enumerate: leaving a dispersion containing silver microparticles coated with an organic component for a certain period of time, removing the resulting supernatant, and then adding a solvent (such as water, methanol, Methanol/water mixed solvent, etc.) and stirred again, and then let stand for a certain period of time, remove the supernatant produced, the method that will repeat the above steps several times; carry out centrifugation to replace the method of standing still; Utilize ultrafiltration A method of desalting with a device or an ion exchange device, etc. The silver microparticles coated with "short-chain amine or dispersant having an acid value" of the present embodiment can be obtained by removing excess residues and removing the organic solvent by washing as described above.

本實施形態中，金屬膠體分散液是藉由將所述獲得的由短鏈胺或具有酸價的保護分散劑所被覆的銀微粒子、與所述本實施形態中所說明的分散介質進行混合而獲得。所述由「短鏈胺或具有酸價的保護分散劑」所被覆的銀微粒子與分散介質的混合方法並無特別限定，可使用攪拌機或攪拌器(stirrer)等，利用現有公知的方法來進行。可利用刮勺(spatula)之類者進行攪拌，或應用適當功率的超音波均質機。 In this embodiment, the metal colloid dispersion is prepared by mixing the obtained silver microparticles coated with a short-chain amine or a protective dispersant having an acid value, and the dispersion medium described in this embodiment. get. The method of mixing the silver microparticles coated with the "short-chain amine or protective dispersant with acid value" and the dispersion medium is not particularly limited, and can be performed using a conventionally known method using a stirrer or a stirrer. . A spatula or the like can be used for stirring, or an ultrasonic homogenizer of appropriate power can be used.

於獲得包含多種金屬的金屬膠體分散液的情況下，其製造方法並無特別限定，例如於製造包含銀與其他金屬的金屬膠體 分散液的情況下，於所述的由有機物所被覆的銀微粒子的製備中，可將包含銀微粒子的分散液、與包含其他金屬粒子的分散液分開製造，然後混合，亦可將銀離子溶液與其他的金屬離子溶液混合，然後還原。 In the case of obtaining a metal colloid dispersion containing multiple metals, the production method is not particularly limited, for example, in the production of metal colloids containing silver and other metals In the case of a dispersion liquid, in the preparation of the above-mentioned silver particles coated with organic matter, the dispersion liquid containing silver particles can be prepared separately from the dispersion liquid containing other metal particles, and then mixed, or the silver ion solution Mix with other metal ion solutions, then reduce.

亦可藉由以下步驟來製造銀微粒子：第一步驟，製備可藉由還原而分解生成金屬銀的銀化合物、與分配係數logP為-1.0~1.4的短鏈胺的混合液；以及第二步驟，藉由將該混合液中的所述銀化合物還原，而生成於表面的至少一部分上附著有碳數為5以下的短鏈胺的銀微粒子。 Silver microparticles can also be produced through the following steps: the first step is to prepare a mixed solution of a silver compound that can be decomposed to generate metallic silver by reduction, and a short-chain amine whose distribution coefficient logP is -1.0~1.4; and the second step , by reducing the silver compound in the mixed solution, silver microparticles having a short-chain amine having 5 or less carbon atoms adhered to at least a part of the surface are produced.

例如，可藉由對由包含銀的乙二酸銀等金屬化合物與短鏈胺所生成的錯合物進行加熱，使將該錯合物中所含的乙二酸根離子等金屬化合物分解而生成的原子狀的銀凝聚，來製造由短鏈胺的保護膜所保護的銀微粒子。 For example, it can be produced by heating a complex formed by metal compounds such as silver oxalate and short-chain amines to decompose metal compounds such as oxalate ions contained in the complex. Atomic silver condenses to produce silver particles protected by a protective film of short-chain amines.

如上所述，藉由將金屬化合物的錯合物於胺的存在下進行熱分解來製造由胺被覆的銀微粒子的金屬胺錯合物分解法中，藉由作為單一種類的分子的金屬胺錯合物的分解反應而生成原子狀金屬，因此可於反應體系內均勻地生成原子狀金屬，與藉由多種成分的反應來生成金屬原子的情況相比較，由構成反應的成分的組成不穩定所引起的反應不均勻得到抑制，特別是於以工業規模來製造大量銀微粒子時有利。 As described above, in the metalloamine complex decomposition method of producing amine-coated silver microparticles by thermally decomposing the complex of the metal compound in the presence of amine, the metalloamine complex, which is a single type of molecule, Atomic metals can be generated by the decomposition reaction of compounds, so atomic metals can be uniformly generated in the reaction system. Compared with the case where metal atoms are generated by the reaction of multiple components, the composition of the components constituting the reaction is unstable. The unevenness of the reaction caused is suppressed, which is particularly advantageous when producing a large amount of silver fine particles on an industrial scale.

另外，金屬胺錯合物分解法中，推測為：於所生成的金屬原子上配位鍵結有短鏈胺分子，藉由配位於該金屬原子上的短 鏈胺分子的作用而產生凝聚時的金屬原子的運動得到控制。其結果為，依據金屬胺錯合物分解法，可製造非常微細且粒度分佈狹窄的銀微粒子。 In addition, in the metal amine complex decomposition method, it is speculated that a short-chain amine molecule is coordinate-bonded to the generated metal atom, and the short-chain amine molecule coordinated to the metal atom The movement of the metal atoms when the condensation occurs due to the action of chain amine molecules is controlled. As a result, very fine silver microparticles with a narrow particle size distribution can be produced by the metal amine complex decomposition method.

進而，於所製造的銀微粒子的表面，多數的短鏈胺分子亦產生相對較弱的力的配位鍵，該些於銀微粒子的表面形成緻密的保護塗層，因此可製造保存穩定性優異的表面清潔的被覆銀微粒子。另外，形成該塗層的短鏈胺分子可藉由加熱等而容易地脫離，因此可製造可於非常低的溫度下燒結的銀微粒子。 Furthermore, on the surface of the silver microparticles produced, many short-chain amine molecules also produce coordination bonds with relatively weak forces, and these form a dense protective coating on the surface of the silver microparticles, so it can be produced. Surface clean coated silver particles. In addition, the short-chain amine molecules forming the coating can be easily detached by heating or the like, so silver microparticles that can be sintered at a very low temperature can be produced.

另外，當將固體狀的金屬化合物與胺混合而生成錯合物等複合化合物時，藉由對構成被覆銀微粒子的塗層的具有酸價的分散劑，混合碳數為5以下的短鏈胺來使用，則錯合物等複合化合物的生成變得容易，可藉由短時間的混合來製造複合化合物。另外，藉由混合該短鏈胺來使用，可製造具有與各種用途對應的特性的被覆銀微粒子。 In addition, when a complex compound such as a complex is formed by mixing a solid metal compound and an amine, a short-chain amine having a carbon number of 5 or less is mixed with a dispersant having an acid value that constitutes a coating layer of silver particles. When used, the formation of complex compounds such as complexes becomes easy, and complex compounds can be produced by mixing for a short time. In addition, by mixing and using such short-chain amines, coated silver microparticles having characteristics corresponding to various uses can be produced.

以所述方式獲得的本實施形態的分散體可直接以所述狀態使用，可於不損及導電油墨、導電性漿的分散穩定性以及低溫燒結性的範圍內，添加多種無機成分或有機成分。 The dispersion of this embodiment obtained in the above manner can be used directly in the above state, and various inorganic components or organic components can be added within the range that does not impair the dispersion stability and low temperature sinterability of the conductive ink and conductive paste .

(2)導電性塗層複合體的製造方法 (2) Manufacturing method of conductive coating complex

圖2是本發明的導電性塗層複合體的製造方法的步驟圖。本發明的導電性塗層複合體的製造方法包括：第一步驟(S01)，將樹脂塗佈於基材2的至少一部分上而形成樹脂層4；第二步驟(S02)，將銀微粒子分散體塗佈於樹脂層4的至少一部分上；及 第三步驟(S03)，藉由外部加熱而使銀微粒子分散體中所含的銀微粒子燒結，從而形成導電性塗層6。以下，對形成聚胺基甲酸酯樹脂層作為樹脂層4的情況進行說明。 Fig. 2 is a step diagram of the method of manufacturing the conductive coating composite of the present invention. The manufacturing method of the conductive coating composite body of the present invention comprises: a first step (S01), resin is coated on at least a part of substrate 2 to form a resin layer 4; second step (S02), silver particles are dispersed body coating on at least a part of the resin layer 4; and In the third step ( S03 ), the silver particles contained in the silver particle dispersion are sintered by external heating, thereby forming the conductive coating layer 6 . Hereinafter, a case where a polyurethane resin layer is formed as the resin layer 4 will be described.

(2-1)樹脂層的形成(第一步驟(S01)) (2-1) Formation of resin layer (first step (S01))

是將溶解於溶劑中的水系聚胺基甲酸酯樹脂塗佈於基材2的至少一部分上而形成樹脂層4的步驟。樹脂層4的膜厚較佳為設為1μm以下。該膜厚可根據旋轉塗佈的轉速或稀釋液量等來適宜控制。再者，聚胺基甲酸酯樹脂較佳為溶解於溶劑中的水系。 This is a step of applying a water-based polyurethane resin dissolved in a solvent on at least a part of the substrate 2 to form the resin layer 4 . The film thickness of the resin layer 4 is preferably set to 1 μm or less. The film thickness can be appropriately controlled according to the rotational speed of spin coating, the amount of diluent, and the like. Furthermore, the polyurethane resin is preferably an aqueous solution dissolved in a solvent.

藉由使用斷裂伸長率為600%以上且具有-COO-H、-COOR、-COO^-NH⁺R₂及-COO^-NH₄ ⁺(其中，R、R₂分別獨立地表示直鏈或分支的可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的伸烷基、可具有取代基的氧伸烷基、可具有取代基的芳基、可具有取代基的芳烷基、可具有取代基的雜環基、可具有取代基的烷氧基、可具有取代基的烷氧基羰基、可具有取代基的醯基)中的任一種官能基的水系聚胺基甲酸酯樹脂，可有效地提高第二步驟(S02)及第三步驟(S03)中所形成的導電性塗層6與基材2的密接性，並且可形成具有優異的導電性的導電性塗層6。 By using the elongation at break of 600% or more and having -COO-H, -COOR, -COO ^- NH ⁺ R ₂ and -COO ^- NH ₄ ⁺ (wherein, R, R ₂ independently represent linear or branched An alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkylene group which may have a substituent, an oxyalkylene group which may have a substituent, an aryl group which may have a substituent, an aryl group which may have a substituent Alkyl, optionally substituted heterocyclic group, optionally substituted alkoxy group, optionally substituted alkoxycarbonyl group, optionally substituted acyl group) water-based polyamine group with any functional group The formate resin can effectively improve the adhesion between the conductive coating 6 formed in the second step (S02) and the third step (S03) and the substrate 2, and can form a conductive coating with excellent conductivity. Coating6.

例如，將水系聚胺基甲酸酯樹脂以溶解於溶劑中的狀態塗佈於基材2上，並形成樹脂層4。通常，水系聚胺基甲酸酯樹脂以分散於水中的狀態(乳膠)存在，並進行溶媒的揮發而成膜，但有根據成膜條件而受乳膠的粒子徑的影響地形成膜的情況，特 別是，於欲形成薄的樹脂層4的情況下，有表面粗糙度變大的問題。相對於此，藉由將水系聚胺基甲酸酯樹脂溶於溶媒(例如乙醇或丙酮等)中，乳膠破泡而成為均勻溶液，因此成膜形成性能(特別是薄膜中的膜質均勻性)提高，從而可形成良好的樹脂層4。 For example, a water-based polyurethane resin is applied on the substrate 2 in a state of being dissolved in a solvent to form the resin layer 4 . Usually, water-based polyurethane resin exists in a dispersed state (emulsion) in water, and volatilizes the solvent to form a film. However, depending on the film-forming conditions, a film may be formed under the influence of the particle size of the latex. special In particular, when the thin resin layer 4 is to be formed, there is a problem that the surface roughness becomes large. In contrast, by dissolving the water-based polyurethane resin in a solvent (such as ethanol or acetone, etc.), the latex foam is broken and becomes a uniform solution, so the film forming performance (especially the uniformity of film quality in the film) improve, so that a good resin layer 4 can be formed.

另外，藉由將斷裂伸長率600%以上的聚胺基甲酸酯樹脂用於密接層(樹脂層4)中，於使銀微粒子燒結的第三步驟(S03)中，可緩和基材2與導電性塗層6的熱膨脹係數差。其結果，銀微粒子的燒結順暢地進行，從而可獲得具有優異的導電性的導電性塗層6。 In addition, by using a polyurethane resin having an elongation at break of 600% or more for the adhesion layer (resin layer 4), in the third step (S03) of sintering the silver particles, the bond between the substrate 2 and the substrate 2 can be relaxed. The thermal expansion coefficient of the conductive coating layer 6 is poor. As a result, the sintering of the silver fine particles proceeds smoothly, and the conductive coating 6 having excellent conductivity can be obtained.

於將樹脂層4形成於基材2的表面上時，為了提高基材2與樹脂層4的密接性，亦可進行基材2的表面處理。作為該表面處理方法，例如可列舉進行電暈處理、電漿處理、紫外線(Ultraviolet，UV)處理、電子束處理等乾式處理的方法等。 When forming the resin layer 4 on the surface of the base material 2, in order to improve the adhesiveness of the base material 2 and the resin layer 4, you may perform the surface treatment of the base material 2. As this surface treatment method, the method of performing dry processing, such as a corona treatment, a plasma treatment, an ultraviolet (Ultraviolet, UV) treatment, an electron beam treatment, etc. are mentioned, for example.

樹脂層4的成膜方法並無特別限定，例如可使用浸漬、噴霧式、棒塗佈式、旋轉塗佈、縫模塗佈式、氣刀式、逆輥塗佈式、凹版塗佈式、幕塗流動式等，另外，成膜溫度亦無特別限定，只要使用作為樹脂層4的原料而使用的組成物的最低成膜溫度以上的溫度即可。進而，視需要亦可於基材2的耐熱溫度以下的溫度下實施加熱處理。 The film-forming method of the resin layer 4 is not particularly limited, and for example, dipping, spraying, bar coating, spin coating, slot die coating, air knife, reverse roll coating, gravure coating, Curtain coating flow method and the like, and the film-forming temperature is not particularly limited, as long as it is at least the minimum film-forming temperature of the composition used as the raw material of the resin layer 4 . Furthermore, heat processing may be performed at the temperature below the heat-resistant temperature of the base material 2 as needed.

(2-2)銀微粒子分散體的塗佈(第二步驟(S02)) (2-2) Coating of silver microparticle dispersion (second step (S02))

是將銀微粒子分散體塗佈於基材2的表面上的步驟。銀微粒子分散體只要不損及本發明的效果，則並無特別限定，可使用現 有公知的多種銀微粒子分散體，較佳為使用如下銀微粒子分散體，其包含銀微粒子、碳數為5以下的短鏈胺、高極性溶媒及用以使銀微粒子分散的具有酸價的分散劑，且短鏈胺的分配係數logP為-1.0~1.4。 This is a step of coating the silver microparticle dispersion on the surface of the substrate 2 . The silver microparticle dispersion is not particularly limited as long as it does not impair the effect of the present invention, and existing There are many known silver particle dispersions, and it is preferable to use the following silver particle dispersion, which contains silver particles, a short-chain amine with a carbon number of 5 or less, a highly polar solvent, and a dispersion agent having an acid value for dispersing the silver particles. agent, and the distribution coefficient logP of short-chain amines is -1.0~1.4.

作為塗佈銀微粒子分散體的方法，可使用多種方法，例如可自浸漬、網版印刷、反轉印刷、微接觸印刷、噴霧式、棒塗佈式、旋轉塗佈式、噴墨式、分配器式、針轉移法、衝壓法、利用刷毛的塗佈方式、流延式、柔版式、凹版式、平版法、轉印法、親水疏水圖案法或注射器式等中適宜選擇而使用。 As a method of coating silver microparticle dispersion, various methods can be used, such as self-dipping, screen printing, reverse printing, microcontact printing, spraying, rod coating, spin coating, inkjet, dispensing, etc. Appropriately select and use from among device type, needle transfer method, stamping method, coating method using brush, casting method, flexographic method, gravure method, lithographic method, transfer printing method, hydrophilic and hydrophobic pattern method, or syringe method.

於將導電性塗層6形成於樹脂層4的表面上時，為了提高樹脂層4與導電性塗層6的密接性，亦可進行樹脂層4的表面處理。作為該表面處理方法，例如可列舉進行電暈處理、電漿處理、UV處理、電子束處理等乾式處理的方法等。 When forming the conductive coating layer 6 on the surface of the resin layer 4 , the surface treatment of the resin layer 4 may be performed in order to improve the adhesiveness of the resin layer 4 and the conductive coating layer 6 . As this surface treatment method, the method of performing dry processing, such as a corona treatment, a plasma treatment, a UV treatment, and an electron beam treatment, etc. are mentioned, for example.

(2-3)銀微粒子的煅燒(第三步驟(S03)) (2-3) Calcination of silver microparticles (third step (S03))

是藉由對在第二步驟(S02)中塗佈銀微粒子分散體的基材2進行加熱而燒結銀微粒子，從而形成導電性塗層6的步驟。 This is a step of forming the conductive coating layer 6 by heating the substrate 2 coated with the silver fine particle dispersion in the second step ( S02 ) to sinter the silver fine particles.

若使用本實施形態的銀微粒子分散體，則塗佈於基材2上後，可於相對較低的溫度(例如300℃以下，較佳為100℃~250℃)下進行加熱、煅燒而使銀微粒子燒結，從而獲得導電性塗層6。於進行煅燒時，亦可階段性地升高溫度或降低溫度。另外，亦可於塗佈銀微粒子分散體的面上預先塗佈界面活性劑或表面活化劑等。 If the silver microparticle dispersion of this embodiment is used, after being coated on the substrate 2, it can be heated and calcined at a relatively low temperature (for example, below 300°C, preferably 100°C to 250°C) to make Silver microparticles are sintered to obtain conductive coating 6 . During calcination, the temperature may also be raised or lowered step by step. In addition, a surface active agent, a surface active agent, or the like may be previously applied to the surface on which the silver fine particle dispersion is applied.

於本實施形態中，於銀微粒子分散體包含黏合劑成分的情況下，就塗膜的強度提高等的觀點而言，黏合劑成分亦進行燒結，但根據情況，可將為了適用於各種印刷法而調整銀微粒子分散體的黏度作為黏合劑成分的主要目的，控制煅燒條件而將黏合劑成分全部去除。 In this embodiment, when the silver fine particle dispersion contains a binder component, the binder component is also fired from the viewpoint of improving the strength of the coating film, etc. While adjusting the viscosity of the silver microparticle dispersion is the main purpose of the binder component, the calcination conditions are controlled to completely remove the binder component.

進行所述加熱、煅燒的方法並無特別限定，例如使用先前公知的烘箱等，以塗佈或描繪於基材2上的所述銀微粒子分散體的溫度例如成為300℃以下的方式進行加熱、煅燒，藉此可進行燒結。所述加熱、煅燒的溫度的下限未必限定，只要為不損及本發明的效果的範圍的溫度即可。此處，於所述燒結後的導電性塗層6中，就獲得儘可能高的強度及優異的導電性的方面而言，有機物的殘存量少為佳，但於不損及本發明的效果的範圍內亦可殘存有機物的一部分。 The method of performing the heating and firing is not particularly limited. For example, using a conventionally known oven or the like, heating is performed so that the temperature of the silver fine particle dispersion coated or drawn on the substrate 2 becomes, for example, 300° C. or lower. Calcination, whereby sintering can be performed. The lower limit of the heating and calcination temperature is not necessarily limited, as long as it is within the range that does not impair the effect of the present invention. Here, in the conductive coating layer 6 after sintering, it is better to have less residual organic matter in order to obtain as high strength as possible and excellent conductivity, but it does not impair the effect of the present invention. Part of the organic matter can also remain within the range.

以上，對本發明的具有代表性的實施形態進行了說明，但本發明並不僅限定於該些，可進行多種設計變更，且該些設計變更全部包含於本發明的技術範圍內。 The typical embodiments of the present invention have been described above, but the present invention is not limited thereto, and various design changes are possible, and all of these design changes are included in the technical scope of the present invention.

實施例 Example

以下，列舉實施例及比較例，對本發明的導電性塗層複合體及其製造方法進一步進行說明，但本發明不受該些實施例的任何限定。 Hereinafter, examples and comparative examples are given to further describe the conductive coating composite of the present invention and its manufacturing method, but the present invention is not limited by these examples.

《製備例1》 "Preparation Example 1"

將8.9g的3-甲氧基丙胺(和光純藥工業(股)製造的試劑 一級，碳數：4，logP：-0.5)、與0.3g的作為高分子分散劑的迪斯帕畢克(DISPERBYK)-111加以混合，利用磁力攪拌器進行充分攪拌而生成胺混合液(相對於銀，所添加的胺的莫耳比為10)。繼而，一邊進行攪拌，一邊添加3.0g的乙二酸銀。添加乙二酸銀後，於室溫下繼續攪拌，藉此使乙二酸銀變化為具有黏性的白色物質，於確認到該變化在外觀上結束的時刻終止攪拌。 8.9 g of 3-methoxypropylamine (a reagent manufactured by Wako Pure Chemical Industries, Ltd. First grade, carbon number: 4, logP: -0.5), mixed with 0.3g of DISPERBYK (DISPERBYK)-111 as a polymer dispersant, and fully stirred by a magnetic stirrer to generate an amine mixture (relatively For silver, the molar ratio of the added amine is 10). Then, while stirring, 3.0 g of silver oxalate was added. After adding the silver oxalate, stirring was continued at room temperature to change the silver oxalate into a viscous white substance, and the stirring was stopped when it was confirmed that the change had ended in appearance.

將所獲得的混合液轉移至油浴中，於120℃下進行加熱攪拌。於攪拌剛開始後，伴隨二氧化碳的產生的反應開始，然後，進行攪拌直至二氧化碳的產生完畢為止，藉此獲得銀微粒子懸浮於胺混合物中的懸浮液。 The obtained mixed solution was transferred to an oil bath, and heated and stirred at 120°C. Immediately after the stirring was started, the reaction accompanied by the generation of carbon dioxide started, and then the stirring was continued until the generation of carbon dioxide was completed, thereby obtaining a suspension in which silver particles were suspended in the amine mixture.

繼而，為了置換該懸浮液的分散介質，添加10mL的甲醇/水的混合溶媒進行攪拌，然後藉由離心分離，使銀微粒子沈澱而分離，對分離出的銀微粒子再次添加10mL的甲醇/水的混合溶媒，藉由進行攪拌、離心分離，使銀微粒子沈澱而分離，添加2.1g的乙醇/異丁醇/異丙醇(Isopropyl alcohol，IPA)(40/40/30v/v)混合溶媒作為分散溶媒，藉此獲得固體成分濃度48wt%的銀微粒子分散體A。 Then, in order to replace the dispersion medium of the suspension, 10 mL of methanol/water mixed solvent was added and stirred, then the silver fine particles were precipitated and separated by centrifugation, and 10 mL of methanol/water was added again to the separated silver fine particles. The mixed solvent is separated by stirring and centrifuging to precipitate silver particles, and 2.1 g of ethanol/isobutanol/isopropanol (Isopropyl alcohol, IPA) (40/40/30v/v) mixed solvent is added as a dispersion Solvent, thereby obtain the silver microparticle dispersion A of solid content concentration 48wt%.

《製備例2》 "Preparation Example 2"

將8.9g的3-甲氧基丙胺(和光純藥工業(股)製造的試劑一級，碳數：4，logP：-0.5)、與0.3g的作為高分子分散劑的迪斯帕畢克(DISPERBYK)-102加以混合，利用磁力攪拌器進行充分攪拌而生成胺混合液(相對於銀，所添加的胺的莫耳比為5)。 繼而，一邊進行攪拌，一邊添加3.0g的乙二酸銀。添加乙二酸銀後，於室溫下繼續攪拌，藉此使乙二酸銀變化為具有黏性的白色物質，於確認到該變化在外觀上結束的時刻終止攪拌。 8.9 g of 3-methoxypropylamine (reagent grade 1 manufactured by Wako Pure Chemical Industries, Ltd., carbon number: 4, logP: -0.5), and 0.3 g of Dispapik ( DISPERBYK)-102 were mixed and fully stirred with a magnetic stirrer to generate an amine mixed solution (with respect to silver, the molar ratio of the added amine was 5). Then, while stirring, 3.0 g of silver oxalate was added. After adding the silver oxalate, stirring was continued at room temperature to change the silver oxalate into a viscous white substance, and the stirring was stopped when it was confirmed that the change had ended in appearance.

將所獲得的混合液轉移至油浴中，於120℃下進行加熱攪拌。於攪拌剛開始後，伴隨二氧化碳的產生的反應開始，然後，進行攪拌直至二氧化碳的產生完畢為止，藉此獲得銀微粒子懸浮於胺混合物中的懸浮液。 The obtained mixed solution was transferred to an oil bath, and heated and stirred at 120°C. Immediately after the stirring was started, the reaction accompanied by the generation of carbon dioxide started, and then the stirring was continued until the generation of carbon dioxide was completed, thereby obtaining a suspension in which silver particles were suspended in the amine mixture.

繼而，為了置換該懸浮液的分散介質，添加10mL的甲醇/水的混合溶媒進行攪拌，然後藉由離心分離，使銀微粒子沈澱而分離，對分離出的銀微粒子再次添加10mL的甲醇/水的混合溶媒，藉由進行攪拌、離心分離，使銀微粒子沈澱而分離，添加包含0.06g的索爾斯帕斯(SOLSPERSE)41000(日本路博潤(Lubrizol)(股)製造)的乙醇2.1g，藉此獲得固體成分濃度為48wt%的銀微粒子分散體B。 Then, in order to replace the dispersion medium of the suspension, 10 mL of methanol/water mixed solvent was added and stirred, then the silver fine particles were precipitated and separated by centrifugation, and 10 mL of methanol/water was added again to the separated silver fine particles. The mixed solvent was stirred and centrifuged to precipitate and separate the silver particles, and 2.1 g of ethanol containing 0.06 g of SOLSPERSE 41000 (manufactured by Lubrizol, Japan) was added, In this way, silver microparticle dispersion B having a solid content concentration of 48% by weight was obtained.

《製備例3》 "Preparation Example 3"

於添加3mL的10N-NaOH水溶液而成為鹼性的50mL水中，溶解17g的檸檬酸三鈉二水合物、0.36g的單寧酸。對所獲得的溶液添加3mL的3.87mol/L硝酸銀水溶液，進行2小時攪拌，獲得銀膠體水溶液。對所獲得的銀膠體水溶液進行透析直至導電率成為30μS/cm以下為止，藉此進行脫鹽。透析後，進行濃縮，以2100rpm(920 G)、10分鐘的條件進行離心分離，藉此去除粗大金屬膠體粒子，獲得固體成分濃度48wt%的銀微粒子分散體C。 17 g of trisodium citrate dihydrate and 0.36 g of tannic acid were dissolved in 50 mL of water made alkaline by adding 3 mL of a 10N-NaOH aqueous solution. 3 mL of a 3.87 mol/L silver nitrate aqueous solution was added to the obtained solution, followed by stirring for 2 hours to obtain an aqueous silver colloid solution. Desalination was performed by dialyzing the obtained silver colloid aqueous solution until the conductivity became 30 μS/cm or less. After dialysis, concentration was performed, and centrifugation was performed at 2100 rpm (920 G) for 10 minutes to remove coarse metal colloidal particles and obtain silver microparticle dispersion C with a solid content concentration of 48 wt%.

《製備例4》 "Preparation Example 4"

將200ml的甲苯(和光純藥工業(股)製造的試劑一級)與11g的丁胺(和光純藥工業(股)製造的試劑一級，碳數：4，logP：1.0)加以混合，利用磁力攪拌器進行充分攪拌(相對於銀，所添加的胺的莫耳比為2.5)。一邊進行攪拌，一邊於其中添加10g的硝酸銀(東洋化學工業(股)製造的試劑特級)，硝酸銀溶解後，添加10g的作為高分子分散劑的迪斯帕畢克(DISPERBYK)-2090與10g的己酸(和光純藥工業(股)製造的試劑特級)。於其中滴加在50ml的離子交換水中添加1g的硼氫化鈉(和光純藥工業(股)製造)而製備的0.02g/ml的硼氫化鈉水溶液，從而獲得包含銀微粒子的溶液。攪拌1小時後，添加200ml的甲醇(和光純藥工業(股)製造的試劑特級)而使銀微粒子凝聚、沈降。進而，藉由離心分離使銀微粒子完全沈降後，將作為上清液的甲苯及甲醇去除，並去除過剩的有機物，添加6g的2-戊醇，從而獲得固體成分濃度50wt%的銀微粒子分散體D。 Mix 200 ml of toluene (grade 1 reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 11 g of butylamine (grade 1 reagent, manufactured by Wako Pure Chemical Industries, Ltd., carbon number: 4, logP: 1.0), and stir with a magnetic force Agitator was used for thorough stirring (the molar ratio of amine added to silver was 2.5). While stirring, add 10g of silver nitrate (reagent special grade manufactured by Toyo Chemical Industry Co., Ltd.), and after the silver nitrate is dissolved, add 10g of DISPERBYK-2090 as a polymer dispersant and 10g of Hexanoic acid (a reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.). A 0.02 g/ml sodium borohydride aqueous solution prepared by adding 1 g of sodium borohydride (manufactured by Wako Pure Chemical Industries, Ltd.) to 50 ml of ion-exchanged water was added dropwise thereto to obtain a solution containing silver fine particles. After stirring for 1 hour, 200 ml of methanol (a reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) was added to aggregate and settle the silver fine particles. Furthermore, after the silver microparticles were completely settled by centrifugation, toluene and methanol as the supernatant were removed, and excess organic matter was removed, and 6 g of 2-pentanol was added to obtain a silver microparticle dispersion with a solid content concentration of 50 wt%. d.

將所述銀微粒子分散體A~銀微粒子分散體D與表1所示的其他成分添加、混合，從而獲得導電性油墨A~導電性油墨D。再者，表1所示的成分的量是由重量%表示。另外，將樹脂層形成油墨中所使用的樹脂示於表2中。 Conductive ink A to conductive ink D were obtained by adding and mixing the silver microparticle dispersion A to silver microparticle dispersion D and other components shown in Table 1. In addition, the quantity of the component shown in Table 1 is represented by weight%. In addition, the resins used in the resin layer forming ink are shown in Table 2.

[表1]

[Table 1]

《實施例1》 "Example 1"

藉由利用乙醇將迪愛生(DIC)公司製造的海德朗(Hydran)HW-312B稀釋3倍，從而形成樹脂層形成油墨。此時，HW-312B於目視下完全溶解。使用旋轉塗佈機，以2000rpm、30秒的條件將樹脂層形成油墨成膜於玻璃基板上，然後，於120℃下進行加熱30分鐘，藉此形成樹脂層。繼而，利用棒塗佈機(No.7)將導電性油墨B塗佈於矽酮製覆層上，並將帶樹脂層的基板按壓於覆層上，藉此將導電性塗層轉印於帶樹脂層的基板上。然後，藉由於120℃下實施30分鐘的煅燒，從而獲得實施導電性塗層複合體1。 A resin layer forming ink was formed by diluting Hydran HW-312B manufactured by DIC Corporation by 3 times with ethanol. At this time, HW-312B was completely dissolved under visual observation. Using a spin coater, the resin layer forming ink was formed into a film on a glass substrate at 2000 rpm for 30 seconds, and then heated at 120° C. for 30 minutes to form a resin layer. Next, the conductive ink B was coated on the silicone coating with a bar coater (No. 7), and the substrate with the resin layer was pressed against the coating to transfer the conductive coating to the on substrates with resin layers. Then, by performing calcination at 120° C. for 30 minutes, a conductive coating composite 1 was obtained.

《實施例2》 "Example 2"

藉由利用N-甲基-2-吡咯啶酮將迪愛生(DIC)公司製造的海德朗(Hydran)HW-311稀釋3倍，從而形成樹脂層形成油墨。此時，HW-311於目視下完全溶解。除此以外，與實施例1同樣地獲得實施導電性塗層複合體2。 A resin layer forming ink was formed by diluting Hydran HW-311 manufactured by DIC Corporation 3 times with N-methyl-2-pyrrolidone. At this time, HW-311 was completely dissolved under visual observation. Except for this, the implementation conductive coating composite body 2 was obtained similarly to Example 1.

《實施例3》 "Example 3"

除了使用導電性油墨C以外，與實施例1同樣地獲得實施導電性塗層複合體3。 Except having used the conductive ink C, it carried out similarly to Example 1, and obtained the implementation conductive coating complex 3.

《實施例4》 "Example 4"

相對於樹脂層形成油墨，以5重量%的比例將日本觸媒製造的艾坡酷勞斯(Epocros)WS-700添加於實施例2的樹脂層形成油墨中，除此以外，與實施例2同樣地獲得實施導電性塗層複合體4。 With respect to the resin layer forming ink, the Epocros (Epocros) WS-700 manufactured by Nippon Shokubai was added to the resin layer forming ink of Example 2 in a ratio of 5% by weight. A conductive coating composite 4 was similarly obtained.

《實施例5》 "Example 5"

除了使用導電性油墨D以外，與實施例1同樣地獲得實施導電性塗層複合體5。 Except having used the conductive ink D, it carried out similarly to Example 1, and obtained the implementation conductive coating composite body 5.

《實施例6》 "Example 6"

藉由利用水將第一工業製藥公司製造的超級弗萊克斯(Superflex)420稀釋3倍，從而形成樹脂層形成油墨。使用旋轉塗佈機，以2000rpm、30秒的條件將樹脂層形成油墨成膜於玻璃基板上，然後，於120℃下進行加熱30分鐘，藉此形成樹脂層。繼而，使用導電性油墨A，利用與實施例1相同的方法而獲得實施導電性塗層複合體6。 The ink was formed by diluting Superflex 420 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. three times with water to form a resin layer. Using a spin coater, the resin layer forming ink was formed into a film on a glass substrate at 2000 rpm for 30 seconds, and then heated at 120° C. for 30 minutes to form a resin layer. Next, using the conductive ink A, an implemented conductive coating composite 6 was obtained by the same method as in Example 1.

《實施例7》 "Embodiment 7"

使積水化學公司製造的艾斯萊克(S-REC)BL-S溶解於乙醇/甲苯(=1/1W/W)溶液中，以使固體成分濃度成為10wt%，從而形成樹脂層形成油墨。除此以外，與實施例1同樣地獲得實施導電性塗層複合體7。 Sekisui Chemical Co., Ltd. made S-REC BL-S dissolved in an ethanol/toluene (=1/1W/W) solution so that the solid content concentration became 10 wt%, to form a resin layer forming ink. Except for this, the implementation conductive coating composite body 7 was obtained similarly to Example 1.

《實施例8》 "Embodiment 8"

藉由利用水將第一工業製藥公司製造的超級弗萊克斯(Superflex)150HS稀釋3倍，從而形成樹脂層形成油墨，除此以外，與實施例1同樣地獲得實施導電性塗層複合體8。 By diluting Superflex (Superflex) 150HS manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. by 3 times with water to form a resin layer forming ink, the conductive coating composite 8 was obtained in the same manner as in Example 1. .

《實施例9》 "Example 9"

藉由利用水將第一工業製藥公司製造的超級弗萊克斯(Superflex)650稀釋2倍，從而形成樹脂層形成油墨，除此以外， 與實施例1同樣地獲得實施導電性塗層複合體9。 In addition to diluting Superflex 650 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. twice with water to form a resin layer to form an ink, In the same manner as in Example 1, a conductive coating composite 9 was obtained.

《實施例10》 "Example 10"

藉由利用水將迪愛生(DIC)公司製造的海德朗(Hydran)ADS-120稀釋3倍，從而形成樹脂層形成油墨，除此以外，與實施例1同樣地獲得實施導電性塗層複合體10。 By diluting Hydran (Hydran) ADS-120 manufactured by Di Aisheng (DIC) Co., Ltd. by 3 times with water to form a resin layer to form an ink, a conductive coating composite was obtained in the same manner as in Example 1 10.

《實施例11》 "Example 11"

利用乙醇將迪愛生(DIC)公司製造的海德朗(Hydran)HW-312B稀釋1.5倍，並將旋轉塗佈機的成膜條件設為1000rpm、30sec，除此以外，與實施例1同樣地獲得實施導電性塗層複合體11。 Using ethanol to dilute Hydran (Hydran) HW-312B manufactured by Di Aisheng (DIC) Company 1.5 times, and set the film forming conditions of the spin coater to 1000rpm, 30sec, except that, obtain in the same manner as in Example 1 Conductive coating composite 11 is implemented.

《比較例1》 "Comparative Example 1"

藉由利用水將迪愛生(DIC)公司製造的海德朗(Hydran)HW-312B稀釋3倍，從而形成樹脂層形成油墨。使用棒塗佈機No.10，將樹脂層形成油墨塗佈於玻璃基板上，並成膜樹脂層，然後，於120℃下進行加熱30分鐘，藉此形成樹脂層。繼而，利用棒塗佈機(No.7)將導電性油墨A塗佈於矽酮製覆層上，並將帶樹脂層的基板按壓於覆層上，藉此將導電性塗層轉印於帶樹脂層的基板上。然後，藉由於120℃下實施30分鐘的煅燒，從而獲得比較導電性塗層複合體1。 The resin layer forming ink was formed by diluting Hydran HW-312B manufactured by DIC Corporation 3 times with water. Using bar coater No. 10, the ink for forming a resin layer was applied on a glass substrate to form a resin layer, and then heated at 120° C. for 30 minutes to form a resin layer. Next, the conductive ink A was coated on the silicone coating with a bar coater (No. 7), and the substrate with the resin layer was pressed against the coating to transfer the conductive coating to the on substrates with resin layers. Then, by performing calcination at 120° C. for 30 minutes, a comparative conductive coating composite 1 was obtained.

《比較例2》 "Comparative Example 2"

針對第一工業製藥公司製造的超級弗萊克斯(Superflex)470，使用棒塗佈機No.10而成膜樹脂層後，於120℃下進行加熱 30分鐘，藉此形成樹脂層。除此以外，與實施例1同樣地獲得比較導電性塗層複合體2。 For Superflex 470 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., a resin layer is formed using a bar coater No. 10, and then heated at 120°C 30 minutes, whereby a resin layer was formed. Except for this, it carried out similarly to Example 1, and obtained the comparative electroconductive coating composite body 2.

《比較例3》 "Comparative Example 3"

除了不使用樹脂層形成油墨以外，與比較例1同樣地獲得比較導電性塗層複合體3。 A comparative conductive coating composite 3 was obtained in the same manner as in Comparative Example 1 except that no resin layer forming ink was used.

《比較例4》 "Comparative Example 4"

除了使用第一工業製藥公司製造的超級弗萊克斯(Superflex)210以外，與比較例2同樣地獲得比較導電性塗層複合體4。 A comparative conductive coating composite 4 was obtained in the same manner as in Comparative Example 2 except that Superflex 210 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. was used.

《比較例5》 "Comparative Example 5"

除了使用導電性油墨C以外，與比較例4同樣地獲得比較導電性塗層複合體5。 Except having used the conductive ink C, it carried out similarly to the comparative example 4, and obtained the comparative conductive coating complex 5.

《比較例6》 "Comparative Example 6"

除了使用東亞合成公司製造的阿隆瑪伊體(Aronmighty)AS-60作為樹脂層形成油墨以外，與比較例1同樣地獲得比較導電性塗層複合體6。 A comparative conductive coating composite 6 was obtained in the same manner as in Comparative Example 1 except that Aronmighty AS-60 manufactured by Toagosei Co., Ltd. was used as the resin layer forming ink.

《比較例7》 "Comparative Example 7"

除了使用棒塗佈機No.6以外，與比較例1同樣地獲得比較導電性塗層複合體7。 Except having used the bar coater No. 6, it carried out similarly to the comparative example 1, and obtained the comparative electroconductive coating composite body 7.

[評價試驗] [Evaluation test]

(1)樹脂層的膜厚測定 (1) Film thickness measurement of the resin layer

利用剃刀等銳利的刀具削取樹脂層，利用共焦點顯微鏡(基恩斯(Keyence)VK-X150)對玻璃基板與樹脂層的厚度差進行 計測，藉此對樹脂層的膜厚進行計測。將所獲得的值示於表3中。 Use a sharp tool such as a razor to cut off the resin layer, and use a confocal microscope (Keyence (Keyence) VK-X150) to measure the thickness difference between the glass substrate and the resin layer. By measuring, the film thickness of the resin layer is measured. The obtained values are shown in Table 3.

(2)密接性評價 (2) Adhesion evaluation

將膠帶(米其邦(Nichiban)18mm)貼附於實施例及比較例中所獲得的導電性塗層複合體，一下子撕下而進行試驗。將於目視時觀察不到剝離的情況設為◎，將觀察到僅極少一部分(2%以下)剝離的部位的情況設為○，將觀察到僅剝離10%以下的面積的情況設為△，將觀察到剝離20%以上的情況設為×，並將結果示於表3中。 An adhesive tape (Nichiban 18 mm) was attached to the conductive coating composites obtained in Examples and Comparative Examples, and the test was performed by tearing it off at once. The case where no peeling was observed visually was designated as ◎, the case where only a very small part (2% or less) of peeling was observed was designated as ○, and the case where only 10% or less of the peeled area was observed was designated as △, The case where 20% or more peeling was observed was marked as ×, and the results are shown in Table 3.

(3)導電性評價 (3) Conductivity evaluation

針對導電性塗層複合體的導電性，使用三菱化學分析技術(Mitsubishi Chemical Analytech)公司製造的勞萊斯特(Loresta)GP MCP-T610來測定表面電阻，並乘以膜厚，藉此算出體積電阻值。將體積電阻值為20μΩ．cm以下設為◎，將50μΩ．cm以下設為○，將超過50μΩ．cm設為×，並將結果示於表3中。再者，關於密接性評價中為○以上且導電性評價中為○的樣品，將綜合判定設為○，並將結果示於表3中。 Regarding the conductivity of the conductive coating composite, the surface resistance was measured using Loresta GP MCP-T610 manufactured by Mitsubishi Chemical Analytech, and the volume was calculated by multiplying the film thickness resistance. The volume resistance value is 20μΩ. Below cm is set as ◎, and 50μΩ. Below cm is set as ○, and it will exceed 50μΩ. cm was set to ×, and the results are shown in Table 3. In addition, about the sample which was ◯ or more in the adhesive evaluation and ◯ in the electrical conductivity evaluation, the overall judgment was made into ◯, and the results are shown in Table 3.

(4)耐熱性評價 (4) Evaluation of heat resistance

對導電性塗層複合體的耐熱性進行評價。將玻璃凸版按壓於塗佈有各種導電性油墨的覆層上，並轉印非圖像部(不需要部分)而去除。進而，藉由將帶樹脂層的基材按壓於覆層材上而將圖案轉印於基材。圖案設為細線，線寬度設為10μm、20μm、30μm、50μm、100μm，長度設為10mm。進而，藉由以120℃、30分鐘 的條件進行煅燒，從而獲得導電性塗層複合體。所獲得的導電性塗層的厚度為約0.3μm。繼而，針對所獲得的導電性塗層複合體，反覆進行180℃×1分鐘的高溫短時間曝露5次後，顯微鏡觀察圖案形狀。將確認到圖案彎曲或斷線等變形的情況設為×，將幾乎未確認到的情況設為○，將完全未確認到的情況設為◎，並將結果示於表3中。 The heat resistance of the conductive coating composite was evaluated. A glass relief plate is pressed onto the coating coated with various conductive inks, and the non-image portion (unnecessary portion) is transferred and removed. Furthermore, the pattern is transferred to the base material by pressing the base material with the resin layer on the cladding material. The pattern was made into a thin line, the line width was set to 10 μm, 20 μm, 30 μm, 50 μm, and 100 μm, and the length was set to 10 mm. Furthermore, by heating at 120°C for 30 minutes Calcined under certain conditions to obtain a conductive coating composite. The thickness of the obtained conductive coating was about 0.3 μm. Next, after short-time high-temperature exposure of 180° C.×1 minute was repeated five times for the obtained conductive coating composite, the pattern shape was observed with a microscope. Table 3 shows the results when a deformation such as pattern bending or disconnection was confirmed as ×, when almost no deformation was observed as ◯, and when no deformation was observed at all.

關於所有的實施導電性塗層複合體，可確認到兼具密接性與良好導電性。相對於此，根據比較導電性塗層複合體3與實施導電性塗層複合體的比較，於不形成樹脂層的情況下，無法獲得良好的密接性。 It was confirmed that both adhesion and good conductivity were achieved in all the conductive coating composites. On the other hand, according to the comparison of the comparative electroconductive coating composite 3 and the actual electroconductive coating composite, when not forming a resin layer, favorable adhesiveness cannot be acquired.

另外，關於實施導電性塗層複合體的耐熱性評價的結 果，得知：藉由將樹脂層的膜厚設為1μm以下，可對導電性塗層複合體賦予良好的耐熱性。 In addition, the results of the heat resistance evaluation of the conductive coating composite As a result, it was found that good heat resistance can be imparted to the conductive coating composite by setting the film thickness of the resin layer to 1 μm or less.

1:導電性塗層複合體 1: Conductive coating complex

2:基材 2: Substrate

4:樹脂層 4: resin layer

6:導電性塗層 6: Conductive coating

Claims (11)

一種導電性塗層複合體，其特徵在於包括：基材；樹脂層，形成於所述基材的至少一部分上；及導電性塗層，形成於所述樹脂層的至少一部分上，所述導電性塗層是由銀微粒子形成，所述樹脂層的膜厚為1μm以下，所述樹脂層的主成分為斷裂伸長率為600%以上的聚胺基甲酸酯樹脂，所述聚氨基甲酸酯樹脂具有-COO-H、-COOR、-COO^-NH⁺R₂及-COO^-NH₄ ⁺中的任一種官能基，其中，R、R₂分別獨立地表示直鏈或分支的可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的伸烷基、可具有取代基的氧伸烷基、可具有取代基的芳基、可具有取代基的芳烷基、可具有取代基的雜環基、可具有取代基的烷氧基、可具有取代基的烷氧基羰基、可具有取代基的醯基。 A conductive coating composite, characterized by comprising: a substrate; a resin layer formed on at least a part of the substrate; and a conductive coating formed on at least a part of the resin layer, the conductive The protective coating is formed of silver particles, the film thickness of the resin layer is 1 μm or less, the main component of the resin layer is polyurethane resin with an elongation at break of 600% or more, and the polyurethane The ester resin has any functional group in -COO-H, -COOR, -COO ^- NH ⁺ R ₂ and -COO ^- NH ₄ ⁺ , wherein, R, R ₂ independently represent linear or branched and may have substitution An alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkylene group that may have a substituent, an oxyalkylene group that may have a substituent, an aryl group that may have a substituent, an aralkyl group that may have a substituent, An optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, and an optionally substituted acyl group. 如申請專利範圍第1項所述的導電性塗層複合體，其中於所述聚胺基甲酸酯樹脂中添加選自異氰酸酯基由封端劑保護的聚合物及包含噁唑啉基的聚合物中的一種以上作為交聯劑。 The conductive coating composite as described in item 1 of the scope of the patent application, wherein the polyurethane resin is added with polymers selected from polymers whose isocyanate groups are protected by blocking agents and polymers containing oxazoline groups. One or more of the compounds are used as cross-linking agents. 如申請專利範圍第2項所述的導電性塗層複合體，其中所述交聯劑相對於所述聚胺基甲酸酯樹脂的固體成分的固體成分量為10重量%以內。 The conductive coating composite according to claim 2, wherein the solid content of the crosslinking agent relative to the solid content of the polyurethane resin is within 10% by weight. 如申請專利範圍第1項至第3項中任一項所述的導電性塗層複合體，其中所述導電性塗層是由銀微粒子分散體形成，所述銀微粒子分散體包含：所述銀微粒子；短鏈胺；溶媒；及用以使所述銀微粒子分散的分散劑。 The conductive coating composite as described in any one of the first item to the third item in the patent scope of the application, wherein the conductive coating is formed by a dispersion of silver particles, and the dispersion of silver particles comprises: the silver microparticles; short-chain amine; solvent; and a dispersant for dispersing the silver microparticles. 如申請專利範圍第4項所述的導電性塗層複合體，其中所述短鏈胺的碳數為5以下。 The conductive coating composite as described in claim 4 of the patent application, wherein the carbon number of the short-chain amine is 5 or less. 如申請專利範圍第4項所述的導電性塗層複合體，其中所述溶媒為高極性溶媒。 The conductive coating complex as described in claim 4 of the patent application, wherein the solvent is a highly polar solvent. 如申請專利範圍第4項所述的導電性塗層複合體，其中所述分散劑具有酸價。 The conductive coating composite as described in claim 4, wherein the dispersant has an acid value. 如申請專利範圍第4項所述的導電性塗層複合體，其中所述短鏈胺的分配係數logP為-1.0~1.4。 The conductive coating complex as described in item 4 of the scope of the patent application, wherein the distribution coefficient logP of the short-chain amine is -1.0~1.4. 如申請專利範圍第4項所述的導電性塗層複合體，其中所述短鏈胺為烷氧基胺。 The conductive coating composite as described in claim 4 of the patent application, wherein the short-chain amine is an alkoxylamine. 一種導電性塗層複合體的製造方法，其特徵在於包括：第一步驟，將樹脂塗佈於基材的至少一部分上而形成樹脂層，所述樹脂層的主成分為斷裂伸長率為600%以上的聚胺基甲酸酯樹脂，所述聚氨基甲酸酯樹脂具有-COO-H、-COOR、-COO^-NH⁺R₂及-COO^-NH₄ ⁺中的任一種官能基，其中，R、R₂分別 獨立地表示直鏈或分支的可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的伸烷基、可具有取代基的氧伸烷基、可具有取代基的芳基、可具有取代基的芳烷基、可具有取代基的雜環基、可具有取代基的烷氧基、可具有取代基的烷氧基羰基、可具有取代基的醯基；第二步驟，將銀微粒子分散體塗佈於所述樹脂層的至少一部分上；及第三步驟，藉由外部加熱而使所述銀微粒子分散體中所含的銀微粒子燒結，從而形成導電性塗層。 A method for manufacturing a conductive coating composite, characterized in that it includes: a first step, coating a resin on at least a part of a substrate to form a resin layer, the main component of the resin layer being 600% elongation at break The above polyurethane resin, the polyurethane resin has any functional group in -COO-H, -COOR, -COO ^- NH ⁺ R ₂ and -COO ^- NH ₄ ⁺ , wherein, R and _R independently represent linear or branched alkyl groups that may have substituents, cycloalkyl groups that may have substituents, alkylene groups that may have substituents, oxyalkylene groups that may have substituents, or alkylene groups that may have substituents. Aryl group which may have a substituent, aralkyl group which may have a substituent, heterocyclic group which may have a substituent, alkoxy group which may have a substituent, alkoxycarbonyl group which may have a substituent, acyl group which may have a substituent base; the second step, coating the silver microparticle dispersion on at least a part of the resin layer; and the third step, sintering the silver microparticles contained in the silver microparticle dispersion by external heating, thereby forming Conductive coating. 如申請專利範圍第10項所述的導電性塗層複合體的製造方法，其中將所述樹脂層的膜厚設為1μm以下。 The method for producing a conductive coating composite according to claim 10, wherein the film thickness of the resin layer is set to be 1 μm or less.

Images