TW201932980A - Photosensitive composition and use of same - Google Patents

Abstract

The present invention provides a photosensitive composition which contains a conductive powder and a photosensitive organic component. The conductive powder has a D50 particle diameter of 1-5 [mu]m on the volume basis as determined by a laser diffraction/scattering method; and the total of (1) a first conductive powder that has an organic component amount of 0.1% by mass or less as determined by thermogravimetric analysis and (2) a second conductive powder that has an organic component amount of at least 0.5% by mass as determined by thermogravimetric analysis, while having a surface to which a benzotriazole compound adheres, accounts for 90% by mass or more if the whole conductive powder is taken as 100% by mass.

Description

感光性組成物及其利用Photosensitive composition and use thereof

本發明是有關於一種感光性組成物及其利用。The present invention relates to a photosensitive composition and use thereof.

於電感器（inductor）等電子零件的製造中，已知有使用包含導電性粉末與感光性有機成分的感光性組成物並利用所謂的光微影法來形成導電層的方法（例如參照專利文獻1～專利文獻5）。於所述方法中，首先利用印刷法等將感光性組成物賦予至基材上並使其乾燥，從而將膜狀體成形。繼而，於所述成形的膜狀體上覆蓋具有規定的開口圖案的光罩，介隔光罩對膜狀體進行曝光。藉此，使經曝光的膜狀體部分光硬化。繼而，利用蝕刻液對由光罩遮光的未硬化的膜狀體部分進行腐蝕清洗並將其去除。然後，對其進行煅燒，藉此形成（燒附）經圖案化為所需形狀的導電層。根據此種方法，與使用現有的各種印刷法的情況相比，可形成微細圖案的導電層。
[現有技術文獻]
[專利文獻]In the manufacture of electronic parts such as inductors, a method of forming a conductive layer using a photosensitive composition containing a conductive powder and a photosensitive organic component and using a so-called photolithography method is known (for example, refer to Patent Literature) 1 to Patent Document 5). In the method, first, a photosensitive composition is applied to a substrate by a printing method or the like and dried to form a film-like body. Then, a mask having a predetermined opening pattern is covered on the formed film-shaped body, and the film-shaped body is exposed through the photomask. Thereby, the exposed film-like body part is light-hardened. Then, the non-hardened film-like body part which is shielded from light by the etching solution is subjected to corrosion cleaning with an etching solution and removed. Then, it is calcined, thereby forming (firing) a conductive layer that is patterned into a desired shape. According to this method, it is possible to form a fine-patterned conductive layer as compared with a case where various conventional printing methods are used.
[Prior Art Literature]
[Patent Literature]

[專利文獻1]日本專利第5163687號
[專利文獻2]國際公開2015/122345號手冊
[專利文獻3]日本專利申請公開2016-138310號公報
[專利文獻4]日本專利第5352768號
[專利文獻5]日本專利申請公開2006-193795號公報[Patent Document 1] Japanese Patent No. 5163687
[Patent Document 2] International Publication No. 2015/122345
[Patent Document 3] Japanese Patent Application Publication No. 2016-138310
[Patent Document 4] Japanese Patent No. 5352768
[Patent Document 5] Japanese Patent Application Publication No. 2006-193795

然而近年來，各種電子機器的小型化或高性能化快速發展，亦對安裝於電子機器中的電子零件要求進一步的小型化或高密度化。伴隨與此，當製造電子零件時，要求導電層的低電阻化與細線化（狹小化）。例如，要求形成構成導電層的配線的寬度（線寬）為30 μm以下、進而為20 μm以下的細實線（fine line）的導電層。However, in recent years, the miniaturization or high performance of various electronic devices has been rapidly developed, and further miniaturization or high density of electronic components mounted in electronic devices is required. Along with this, when manufacturing electronic parts, it is required to reduce the resistance of the conductive layer and reduce the thickness (narrowing) of the conductive layer. For example, it is required to form a conductive layer with a fine line having a width (line width) of 30 μm or less and further 20 μm or less.

但是，根據本發明者等人的研究，若使用如所述專利文獻中記載般的感光性組成物，則難以以高解析度形成導電層。作為一例，線寬發生擴展等，難以穩定地形成細線狀的配線。另外，作為另一例，當形成配線圖案時，如圖2的示意圖所示，有時於相鄰的配線彼此的間隙部分（空間）中星星點點地殘存利用蝕刻未完全去除的殘渣物（以下，稱作「線間殘渣」）。因此，有時因隧道效應（tunnel effect）而產生漏電流、或者配線間相連而發生短路不良。However, according to a study by the present inventors, it is difficult to form a conductive layer with high resolution by using a photosensitive composition as described in the aforementioned patent document. As an example, it is difficult to form a thin line-like wiring stably because the line width is expanded. In addition, as another example, when a wiring pattern is formed, as shown in the schematic diagram of FIG. 2, in some gaps (spaces) between adjacent wirings, residues that are not completely removed by etching (hereinafter, , Called "interline residue"). Therefore, a leakage current may occur due to a tunnel effect, or a short circuit may occur due to connection between wirings.

本發明是鑒於所述方面而成，其目的在於提供一種能夠以高解析度形成線間殘渣少的細實線的導電層的感光性組成物。另外，相關的另一目的是提供一種包括包含所述感光性組成物的乾燥體的導電膜的複合體。另外，相關的另一目的是提供一種包括包含所述感光性組成物的煅燒體的導電層的電子零件、及其製造方法。The present invention has been made in view of the above-mentioned aspects, and it is an object of the present invention to provide a photosensitive composition capable of forming a conductive layer with a fine solid line with little residue between lines at high resolution. In addition, another related object is to provide a composite including a conductive film including a dried body of the photosensitive composition. In addition, another related object is to provide an electronic component including a conductive layer including a fired body of the photosensitive composition, and a method for manufacturing the same.

根據本發明，提供一種包含導電性粉末與感光性有機成分的感光性組成物。所述導電性粉末的基於雷射繞射·散射法的體積基準的D₅₀ 粒徑為1 μm以上且5 μm以下，並且當將所述導電性粉末整體設為100質量%時，以下2種成分的合計佔90質量%以上：（1）基於熱重分析的有機成分量為0.1質量%以下的第1導電性粉末；（2）表面附著有苯并***系化合物，且基於熱重分析的有機成分量至少為0.5質量%的第2導電性粉末。According to the present invention, there is provided a photosensitive composition including a conductive powder and a photosensitive organic component. The D ₅₀ particle size of the conductive powder based on the volume basis of the laser diffraction and scattering method is 1 μm or more and 5 μm or less, and when the entire conductive powder is 100% by mass, the following two types are used. The total of the components accounts for more than 90% by mass: (1) the first conductive powder having an organic content of 0.1% by mass or less based on thermogravimetric analysis; (2) a benzotriazole-based compound adhered to the surface, and based on thermogravimetric analysis The second conductive powder having an organic content of at least 0.5% by mass.

於所述感光性組成物中，有機成分量不同的第1導電性粉末與第2導電性粉末混合存在於導電性粉末中，且第1導電性粉末與第2導電性粉末的合計佔導電性粉末整體的90質量%以上。藉由如此般併用第1導電性粉末與第2導電性粉末，例如與將該些導電性粉末分別單獨使用的情況相比，可穩定地形成細實線的導電層。另外，藉由第2導電性粉末包含苯并***系化合物，而線間殘渣不易殘存，從而可於配線間穩定地確保空間。因此，可減少漏電流並抑制短路不良的發生。以上效果相互結合，可形成解析度高的導電層。In the photosensitive composition, the first conductive powder and the second conductive powder having different amounts of organic components are mixed in the conductive powder, and the total of the first conductive powder and the second conductive powder accounts for conductivity. 90% by mass or more of the entire powder. By using the first conductive powder and the second conductive powder together in this way, for example, a thin solid line conductive layer can be formed more stably than when the conductive powders are used individually. In addition, since the second conductive powder contains a benzotriazole-based compound, residues between the wires are not easily left, and a space can be stably secured between the wiring rooms. Therefore, it is possible to reduce leakage current and suppress occurrence of short-circuit failure. The above effects are combined with each other to form a conductive layer with high resolution.

此處所揭示的較佳的一態樣中，所述導電性粉末包含銀系粒子。藉此，可實現成本與低電阻的平衡優異的導電層。In a preferred aspect disclosed herein, the conductive powder includes silver-based particles. Thereby, a conductive layer excellent in balance between cost and low resistance can be realized.

此處所揭示的較佳的一態樣中，所述第1導電性粉末與所述第2導電性粉末的質量比率為第1導電性粉末：第2導電性粉末=85：15～20：80。藉此，能夠以更高的水準發揮此處所揭示的技術的效果。例如，即便為進一步推進了細實線化的導電層，亦能夠精度良好地形成。In a preferred aspect disclosed herein, the mass ratio of the first conductive powder to the second conductive powder is the first conductive powder: the second conductive powder = 85: 15 to 20:80 . Thereby, the effect of the technology disclosed here can be exhibited at a higher level. For example, the conductive layer can be formed with high accuracy even if the conductive layer is further thinned.

此處所揭示的較佳的一態樣中，所述第1導電性粉末為包含成為核的金屬材料與將所述核的表面的至少一部分被覆的陶瓷材料的核殼粒子。藉此，可更良好地提升感光性組成物中的導電性粉末的穩定性，並且實現高耐久性的導電層。另外，例如於陶瓷製的基材上形成導電層來製造陶瓷電子零件的用途中，可提高與陶瓷基材的一體性。In a preferred aspect disclosed herein, the first conductive powder is a core-shell particle including a metal material serving as a core and a ceramic material covering at least a part of a surface of the core. Thereby, the stability of the conductive powder in the photosensitive composition can be improved, and a highly durable conductive layer can be realized. In addition, for example, in a use in which a conductive layer is formed on a ceramic substrate to manufacture a ceramic electronic component, the integration with the ceramic substrate can be improved.

此處所揭示的較佳的一態樣中，於基於日本工業標準（Japanese Industrial Standards，JIS）Z 8781：2013年的L*a*b*表色系統中，所述導電性粉末的明度L*為50以上。藉此，曝光時光穩定地到達未硬化的導電膜的深部為止，亦能夠穩定地實現厚膜狀的導電層。In a preferred aspect disclosed herein, in the L * a * b * color system based on Japanese Industrial Standards (JIS) Z 8781: 2013, the lightness L * of the conductive powder It is 50 or more. Thereby, the light can stably reach the deep part of the non-hardened conductive film at the time of exposure, and a thick film-like conductive layer can be stably realized.

此處所揭示的較佳的一態樣中，進而包含沸點為150℃以上且250℃以下的有機溶劑。藉此，可提升感光性組成物的保存穩定性或導電膜形成時的處理性，並且將印刷後的乾燥溫度抑制得低。In a preferred aspect disclosed herein, an organic solvent having a boiling point of 150 ° C. or higher and 250 ° C. or lower is further included. Thereby, the storage stability of the photosensitive composition and the handleability at the time of formation of a conductive film can be improved, and the drying temperature after printing can be suppressed low.

另外，根據本發明，提供一種複合體，其包括：生片（green sheet）；以及導電膜，配置於所述生片上，且包含所述感光性組成物的乾燥體。In addition, according to the present invention, there is provided a composite including a green sheet and a conductive film disposed on the green sheet and including a dried body of the photosensitive composition.

另外，根據本發明，提供一種電子零件，其包括包含所述感光性組成物的煅燒體的導電層。根據所述感光性組成物，可穩定地實現線間殘渣少的細實線的導電層。因此，可較佳地實現包括小型及/或高密度的導電層的電子零件。In addition, according to the present invention, there is provided an electronic component including a conductive layer including a fired body of the photosensitive composition. According to the photosensitive composition, it is possible to stably realize a thin solid wire conductive layer with little residue between the wires. Therefore, an electronic part including a small-sized and / or high-density conductive layer can be preferably realized.

另外，根據本發明，提供一種電子零件的製造方法，其包括如下步驟：將所述感光性組成物賦予至基材上，進行光硬化及蝕刻處理後進行煅燒，形成包含所述感光性組成物的煅燒體的導電層。根據此種製造方法，可較佳地製造包括小型及/或高密度的導電層的電子零件。In addition, according to the present invention, there is provided a method for manufacturing an electronic component, which includes the steps of: applying the photosensitive composition to a substrate, performing photocuring and etching treatment, and then calcining to form the photosensitive composition. The conductive layer of the calcined body. According to such a manufacturing method, an electronic part including a small-sized and / or high-density conductive layer can be preferably manufactured.

以下，對本發明的較佳的實施形態進行說明。再者，於本說明書中特別提及的事項（例如，感光性組成物中所包含的導電性粉末）以外的事情且為本發明的實施中所需的事情（例如，感光性組成物的製備方法、導電膜或導電層的形成方法、電子零件的製造方法等）可基於由本說明書所指點的技術內容及該領域中的從業人員的一般的技術常識來理解。本發明可基於本說明書中所揭示的內容與該領域中的技術常識來實施。Hereinafter, preferred embodiments of the present invention will be described. Furthermore, matters other than those specifically mentioned in this specification (for example, conductive powder contained in a photosensitive composition) are matters required for the implementation of the present invention (for example, preparation of a photosensitive composition). Method, method of forming conductive film or conductive layer, method of manufacturing electronic parts, etc.) can be understood based on the technical content pointed out in this specification and the general technical common sense of practitioners in the field. The present invention can be implemented based on the contents disclosed in this specification and technical common sense in the field.

再者，以下說明中，將使導電性組成物於苯并***系化合物的沸點以下的溫度（大概200℃以下，例如100℃以下）下乾燥而成的膜狀體（乾燥物）稱作「導電膜」。導電膜包含未煅燒（煅燒前）的膜狀體全部。導電膜可為光硬化前的未硬化物，亦可為光硬化後的硬化物。另外，以下說明中，將使導電性組成物於導電性粉末的燒結溫度以上煅燒而成的燒結體（煅燒物）稱作「導電層」。導電層包含：配線（線狀體）；配線圖案；及整面圖案（filled pattern）。另外，本說明書中表示範圍的「A～B」的表述是指A以上且B以下。In the following description, a film-like body (dried product) obtained by drying a conductive composition at a temperature lower than the boiling point of a benzotriazole-based compound (approximately 200 ° C. or lower, for example, 100 ° C. or lower) is referred to as a dry body. "Conductive film". The conductive film includes all the film-like bodies that have not been calcined (before calcination). The conductive film may be an uncured material before light curing or a cured material after light curing. In the following description, a sintered body (fired product) obtained by firing a conductive composition at a temperature higher than the sintering temperature of the conductive powder is referred to as a "conductive layer". The conductive layer includes: a wiring (a linear body); a wiring pattern; and a filled pattern. In addition, the expression "A to B" which shows a range in this specification means A or more and B or less.

《感光性組成物》
此處所揭示的感光性組成物包含導電性粉末與感光性有機成分作為必需的成分。以下，對各構成成分依次進行說明。`` Photosensitive composition ''
The photosensitive composition disclosed here includes a conductive powder and a photosensitive organic component as essential components. Hereinafter, each component will be described in order.

＜導電性粉末＞
導電性粉末為對將感光性組成物煅燒所得的導電層賦予電傳導性的成分。於此處所揭示的技術中，導電性粉末為至少包含第1導電性粉末與第2導電性粉末的混合粉末。而且，當將導電性粉末整體設為100質量%時，第1導電性粉末與第2導電性粉末的合計佔90質量%以上。藉此，能夠以高解析度形成細實線的導電層。＜ Conductive powder ＞
The conductive powder is a component that imparts electrical conductivity to a conductive layer obtained by firing a photosensitive composition. In the technique disclosed herein, the conductive powder is a mixed powder including at least a first conductive powder and a second conductive powder. When the entire conductive powder is 100% by mass, the total of the first conductive powder and the second conductive powder accounts for 90% by mass or more. Thereby, a thin solid line conductive layer can be formed with a high resolution.

導電性粉末可由第1導電性粉末與第2導電性粉末構成，或者亦可包含該些以外的導電性粉末。就以更高的水準發揮此處所揭示的技術的效果的觀點而言，第1導電性粉末與第2導電性粉末的合計較佳為導電性粉末整體的95質量%以上，更佳為98質量%以上。The conductive powder may be composed of the first conductive powder and the second conductive powder, or may include other conductive powders. From the viewpoint of exerting the effects of the technology disclosed herein at a higher level, the total of the first conductive powder and the second conductive powder is preferably 95% by mass or more of the entire conductive powder, and more preferably 98% by mass. %the above.

第1導電性粉末為有機成分量抑制得低的導電性粉末。導電性粉末中所包含的有機成分主要源自附著於導電性粉末表面的有機表面被覆劑、或導電性粉末的製造中所使用的殘留有機成分例如有機溶劑。再者，關於有機表面被覆劑，於後述第2導電性粉末一欄中詳細說明。The first conductive powder is a conductive powder in which the amount of organic components is suppressed to be low. The organic component contained in the conductive powder is mainly derived from an organic surface coating agent adhered to the surface of the conductive powder or a residual organic component such as an organic solvent used in the production of the conductive powder. The organic surface coating agent will be described in detail in the second conductive powder column described later.

此處所揭示的技術中，第1導電性粉末的有機成分量為0.1質量%以下。第1導電性粉末除有機成分量為0.1質量%以下之外，並無特別限定。藉由在導電性粉末中包含如此般有機成分量得以抑制的第1導電性粉末，可提升導電膜的耐蝕刻性，即便於蝕刻處理後，亦能夠使已硬化的導電膜部分適當存留於基材上。因此，可抑制導電膜剝離、或者配線變得過細。就所述觀點而言，第1導電性粉末的有機成分量例如亦可為0.08質量%以下。In the technique disclosed here, the amount of the organic component of the first conductive powder is 0.1% by mass or less. The first conductive powder is not particularly limited except that the amount of the organic component is 0.1% by mass or less. By including the first conductive powder whose organic content is suppressed in the conductive powder, the etching resistance of the conductive film can be improved, and even after the etching treatment, the hardened conductive film portion can be appropriately retained on the substrate. Wood. Therefore, it is possible to suppress peeling of the conductive film or make the wiring excessively thin. From the viewpoint described above, the amount of the organic component of the first conductive powder may be, for example, 0.08% by mass or less.

第1導電性粉末可有意地或不可避免地包含有機成分，亦可不包含（為檢測下限值以下）。第1導電性粉末的有機成分量亦可為大概0.01質量%以上、例如0.03質量%以上。換言之，第1導電性粉末可於表面附著有有機表面被覆劑，或者亦可包含殘留溶劑。於第1導電性粉末包含有機表面被覆劑的情況下，較佳為包含與第2導電性粉末的有機表面被覆劑為相同種類者。例如，較佳為包含苯并***系化合物。The first conductive powder may include an organic component intentionally or inevitably, or may not be contained (below the detection lower limit value). The amount of the organic component of the first conductive powder may be approximately 0.01% by mass or more, for example, 0.03% by mass or more. In other words, the first conductive powder may have an organic surface coating agent adhered to the surface, or may include a residual solvent. When the first conductive powder contains an organic surface coating agent, it is preferred that the first conductive powder contains the same kind of organic surface coating agent as the second conductive powder. For example, it is preferable to include a benzotriazole-based compound.

再者，本說明書中所謂「有機成分量」，是指藉由下述測定方法測定的質量衰減率。即，首先，秤量規定量的導電性粉末作為測定用試樣，使用熱重測定裝置（thermogravimeter，TG）將該測定用試樣於大氣環境中以升溫速度10℃/分鐘自室溫（25℃）加熱至600℃。然後，利用下式：有機成分量（%）=[（加熱前的質量）-（加熱至600℃後的質量）]/（加熱前的質量）×100；算出加熱前後的質量變化（質量衰減率）。將以此種方式求出的質量衰減率稱作有機成分量。單位為質量%。In addition, the "amount of organic component" in this specification means the mass attenuation rate measured by the following measuring method. That is, first, a predetermined amount of conductive powder is weighed as a measurement sample, and the measurement sample is thermogravimeter (TG) in the atmospheric environment at a temperature increase rate of 10 ° C / min from room temperature (25 ° C). Heat to 600 ° C. Then, use the following formula: Organic content (%) = [(mass before heating)-(mass after heating to 600 ° C)] / (mass before heating) × 100; calculate the mass change (mass attenuation) before and after heating rate). The mass attenuation rate obtained in this manner is called an organic component amount. The unit is mass%.

第2導電性粉末為與第1導電性粉末相比有機成分量高的導電性粉末。此處所揭示的技術中，於第2導電性粉末的表面附著有苯并***系化合物。苯并***系化合物為有機表面被覆劑。第2導電性粉末的有機成分量至少為0.5質量%。第2導電性粉末除了表面附著有苯并***系化合物，且有機成分量至少為0.5質量%以外，並無特別限定。藉由在導電性粉末中包含此種第2導電性粉末，於蝕刻處理時可提升未硬化部分的剝離性，並抑制配線變得過寬。另外，於配線間的空間部分中不易殘存線間殘渣，可於配線間穩定地確保空間。因此，可減少漏電流並抑制短路不良的發生。The second conductive powder is a conductive powder having a higher amount of organic components than the first conductive powder. In the technique disclosed here, a benzotriazole-based compound is adhered to the surface of the second conductive powder. Benzotriazole-based compounds are organic surface coating agents. The amount of the organic component of the second conductive powder is at least 0.5% by mass. The second conductive powder is not particularly limited except that a benzotriazole-based compound is adhered to the surface and the amount of the organic component is at least 0.5% by mass. By including such a second conductive powder in the conductive powder, the peelability of the unhardened portion can be improved during the etching process, and the wiring can be prevented from becoming too wide. In addition, it is difficult for the inter-line residue to remain in the space portion of the wiring room, and the space can be stably secured in the wiring room. Therefore, it is possible to reduce leakage current and suppress occurrence of short-circuit failure.

就所述觀點而言，第2導電性粉末的有機成分量較佳為0.7質量%以上，較佳為0.75質量%以上，例如亦可為0.8質量%以上。另外，雖無特別限定，但若鑒於市售的導電性粉末的有機成分量的範圍，則第2導電性粉末的有機成分量的上限為大概2質量%以下。就導電層的緻密化或低電阻化的觀點而言，第2導電性粉末的有機成分量的上限較佳為1.5質量%以下，更佳為1質量%以下。From the viewpoint described above, the amount of the organic component of the second conductive powder is preferably 0.7% by mass or more, more preferably 0.75% by mass or more, and for example, it may be 0.8% by mass or more. Moreover, although it does not specifically limit, considering the range of the organic component amount of a commercially available conductive powder, the upper limit of the organic component amount of a 2nd conductive powder is about 2 mass% or less. From the viewpoint of densification of the conductive layer or reduction in resistance, the upper limit of the amount of the organic component of the second conductive powder is preferably 1.5% by mass or less, and more preferably 1% by mass or less.

附著於第2導電性粉末表面的苯并***系化合物為提升導電性粉末的穩定性或保存性的有機表面被覆劑。苯并***系化合物只要為具有苯并***骨架的化合物即可。作為一較佳例，可列舉具有一個或兩個以上的下述（1）所表示的1H-苯并***的結構部分、或者作為其互變異構物的2H-苯并***的結構部分的化合物。The benzotriazole-based compound adhered to the surface of the second conductive powder is an organic surface coating agent that improves the stability or storage stability of the conductive powder. The benzotriazole-based compound may be a compound having a benzotriazole skeleton. As a preferred example, there may be mentioned one or two or more structural parts of 1H-benzotriazole represented by the following (1), or structural parts of 2H-benzotriazole as tautomers thereof. compound of.

[化1]

[Chemical 1]

作為苯并***系化合物的具體例，可列舉：1H-苯并***、2H-苯并***、2-(2'-羥基-5'-甲基苯基)苯并***、2-(2'-羥基-3',5'-二-第三丁基苯基)苯并***、2-(2'-羥基-4'-正辛氧基苯基)苯并***、2-(2'-羥基-5'-第三辛基苯基)苯并***、2-(2'-羥基-3',5'-二-第三戊基苯基)苯并***、2-羥基-4-(2-羥基-3-甲基丙烯醯氧基)丙氧基二苯甲酮、2-(2'-羥基-3'-第三丁基-5'-甲基苯基)-5-氯苯并***、2-(2'-羥基-3'-第三丁基-5'-甲基苯基)-5-氯苯并***、2-(2'-羥基-3',5'-二-第三丁基苯基)-5-氯苯并***等。其中，較佳為不含鹵素元素（例如氟或氯）者。Specific examples of the benzotriazole-based compound include 1H-benzotriazole, 2H-benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-third-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-n-octyloxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-third octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-third-pentylphenyl) benzotriazole , 2-hydroxy-4- (2-hydroxy-3-methylpropenyloxy) propoxybenzophenone, 2- (2'-hydroxy-3'-third butyl-5'-methyl Phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-third butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and the like. Among them, those containing no halogen element (for example, fluorine or chlorine) are preferred.

典型而言，第2導電性粉末中所包含的有機成分將苯并***系化合物設為主體（以莫耳比計佔50莫耳%以上的成分）。關於第2導電性粉末的有機成分，苯并***系化合物可佔80莫耳%以上，進而可由苯并***系化合物構成。只要不明顯損害此處所揭示的技術的效果，則第2導電性粉末有意地或不可避免地除苯并***系化合物以外，亦可進而包含已知可作為有機表面被覆劑來使用的其他有機表面被覆劑。例如，當將第2導電性粉末的有機成分量整體設為100莫耳%時，除苯并***系化合物以外，亦可以大概未滿50莫耳%、較佳為10莫耳%以下、更佳為5莫耳%以下的比例包含其他有機表面被覆劑。第2導電性粉末更佳為不含羧酸等脂肪酸作為有機表面被覆劑。藉此，能夠以更高的水準發揮此處所揭示的技術的效果。再者，對於有機表面被覆劑包含苯并***系化合物，例如可藉由氣相層析-質量分析（gas chromatography-mass spectrometry，GC-MS）法來確認。Typically, the organic component contained in the second conductive powder is a benzotriazole-based compound (a component that accounts for 50 mol% or more in molar ratio). Regarding the organic component of the second conductive powder, the benzotriazole-based compound may account for 80 mol% or more, and may be composed of a benzotriazole-based compound. As long as the effects of the technology disclosed herein are not significantly impaired, the second conductive powder may intentionally or inevitably include other organic compounds known as organic surface coating agents in addition to benzotriazole-based compounds. Surface coating agent. For example, when the total amount of the organic component of the second conductive powder is 100 mol%, in addition to the benzotriazole-based compound, it may be less than 50 mol%, preferably 10 mol% or less, It is more preferable that the content is 5 mol% or less to include other organic surface coating agents. It is more preferable that the second conductive powder does not contain a fatty acid such as a carboxylic acid as an organic surface coating agent. Thereby, the effect of the technology disclosed here can be exhibited at a higher level. It is to be noted that the organic surface coating agent includes a benzotriazole-based compound by a gas chromatography-mass spectrometry (GC-MS) method.

雖無特別限定，但第1導電性粉末與第2導電性粉末的質量比率可為大概95：5～5：95、典型而言為90：10～10：90、較佳為85：15～20：80、更佳為60：40～20：80、其中為60：40～40：60。藉此，能夠以更高的水準發揮此處所揭示的技術的效果。例如，即便為進一步推進了細實線化的導電層，亦能夠以高解析度精度良好地形成。另外，藉由以規定值以上的比例包含第1導電性粉末，可減少煅燒時完全燃燒的成分的比例，並較佳地實現緻密性高、低電阻的導電層。Although not particularly limited, the mass ratio of the first conductive powder to the second conductive powder may be approximately 95: 5 to 5:95, typically 90:10 to 10:90, and preferably 85:15 to 20:80, more preferably 60:40 to 20:80, of which 60:40 to 40:60. Thereby, the effect of the technology disclosed here can be exhibited at a higher level. For example, even if the conductive layer is further thinned, it can be formed with high resolution and accuracy. In addition, by including the first conductive powder in a ratio of a predetermined value or more, it is possible to reduce the ratio of components that are completely burned at the time of firing, and to achieve a highly dense conductive layer with low resistance.

第1導電性粉末及第2導電性粉末的種類並無特別限定。作為第1導電性粉末及第2導電性粉末，可分別自現有公知者中根據用途等適當選擇1種或2種以上來使用。作為一較佳例，可列舉：金（Au）、銀（Ag）、銅（Cu）、鉑（Pt）、鈀（Pd）、鋁（Al）、鎳（Ni）、釕（Ru）、銠（Rh）、鎢（W）、銥（Ir）、鋨（Os）等金屬單體、及該些金屬單體的混合物或合金等。作為合金，例如可列舉：銀-鈀（Ag-Pd）、銀-鉑（Ag-Pt）、銀-銅（Ag-Cu）等銀合金。The types of the first conductive powder and the second conductive powder are not particularly limited. As the first conductive powder and the second conductive powder, one type or two or more types can be appropriately selected and used from conventionally known ones, depending on the application and the like. As a preferred example, gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), aluminum (Al), nickel (Ni), ruthenium (Ru), and rhodium can be listed. (Rh), tungsten (W), iridium (Ir), osmium (Os) and other metal monomers, and mixtures or alloys of these metal monomers. Examples of the alloy include silver alloys such as silver-palladium (Ag-Pd), silver-platinum (Ag-Pt), and silver-copper (Ag-Cu).

於較佳的一態樣中，第1導電性粉末及/或第2導電性粉末包含銀系粒子。銀的成本比較低廉，且電導度高。因此，藉由包含銀系粒子，可實現成本與低電阻的平衡優異的導電層。銀系粒子包含銀成分即可。作為一例，可列舉：將銀的單體、所述銀合金、銀系粒子作為核的核殼粒子等。In a preferred aspect, the first conductive powder and / or the second conductive powder include silver-based particles. Silver is relatively inexpensive and highly conductive. Therefore, by including silver-based particles, a conductive layer excellent in balance between cost and low resistance can be realized. The silver-based particles need only contain a silver component. As an example, a core-shell particle using a monomer of silver, the silver alloy, or silver-based particles as a core may be mentioned.

於另一較佳的態樣中，第1導電性粉末及/或第2導電性粉末包含金屬-陶瓷的核殼粒子。金屬-陶瓷的核殼粒子具有：包含金屬材料的核部；以及被覆部，被覆核部的表面的至少一部分且包含陶瓷材料。陶瓷材料的化學穩定性或耐熱性、耐久性優異。因此，藉由採用金屬-陶瓷的核殼粒子的形態，可更良好地提升感光性組成物中的導電性粉末的穩定性，並且實現高耐久性的導電層。另外，例如於陶瓷製的基材上形成導電層來製造陶瓷電子零件的用途中，藉由包含金屬-陶瓷的核殼粒子，可提高與陶瓷基材的一體性，從而可較佳地抑制煅燒後的導電層的剝離或斷線。In another preferred aspect, the first conductive powder and / or the second conductive powder include metal-ceramic core-shell particles. The metal-ceramic core-shell particle includes a core portion including a metal material, and a coating portion that covers at least a part of a surface of the core portion and includes a ceramic material. Ceramic materials are excellent in chemical stability, heat resistance, and durability. Therefore, by adopting the form of the metal-ceramic core-shell particles, the stability of the conductive powder in the photosensitive composition can be improved, and a highly durable conductive layer can be realized. In addition, for example, in the application where a conductive layer is formed on a ceramic substrate to manufacture ceramic electronic parts, the inclusion of metal-ceramic core-shell particles can improve the integration with the ceramic substrate, and can better suppress firing. After the peeling or disconnection of the conductive layer.

其中，較佳為有機成分量少的第1導電性粉末包含金屬-陶瓷的核殼粒子，更佳為第1導電性粉末由金屬-陶瓷的核殼粒子構成。有機成分量少的第1導電性粉末與有機成分量多的第2導電性粉末相比，於導電性組成物中的穩定性或保存性相對地容易變低。藉由第1導電性粉末包含金屬-陶瓷的核殼粒子，可彌補有機成分量之低，且更良好地提升導電性組成物整體的穩定性或保存性。Among them, it is preferred that the first conductive powder with a small amount of organic components includes metal-ceramic core-shell particles, and more preferably that the first conductive powder is composed of metal-ceramic core-shell particles. The first conductive powder having a small amount of organic components has relatively low stability and storage stability in the conductive composition compared with the second conductive powder having a large amount of organic components. The first conductive powder contains metal-ceramic core-shell particles, which can compensate for the low amount of organic components and further improve the overall stability or storage stability of the conductive composition.

於金屬-陶瓷的核殼粒子中，作為構成核部的金屬材料，例如可列舉所述金屬的單體、及該些金屬單體的混合物或合金。其中，就所述原因而言，較佳為銀系粒子。換言之，較佳為第1導電性粉末及/或第2導電性粉末包含銀-陶瓷的核殼粒子。Among the metal-ceramic core-shell particles, examples of the metal material constituting the core portion include a monomer of the metal and a mixture or alloy of the metal monomers. Among these, silver-based particles are preferred. In other words, it is preferable that the first conductive powder and / or the second conductive powder include silver-ceramic core-shell particles.

雖無特別限定，但作為構成金屬-陶瓷的被覆部的陶瓷材料，例如可列舉：氧化鋯（zirconia）、氧化鎂（magnesia）、氧化鋁（alumina）、氧化矽（silica）、氧化鈦（titania）、氧化鈰（ceria）、氧化釔（yttria）、鈦酸鋇等氧化物系材料；堇青石（cordierite）、富鋁紅柱石（mullite）、鎂橄欖石（forsterite）、塊滑石（steatite）、矽鋁氮氧化物（Sialon）、鋯石（zircon）、肥粒鐵（ferrite）等複合氧化物系材料；氮化矽（silicon nitride）、氮化鋁（aluminum nitride）等氮化物系材料；碳化矽（silicon carbide）等碳化物系材料；羥磷灰石（hydroxyapatite）等氫氧化物系材料；等。例如於陶瓷製的基材上形成導電層來製造陶瓷電子零件的用途中，較佳為與陶瓷基材相同或者親和性優異的陶瓷材料。Although not particularly limited, examples of the ceramic material constituting the metal-ceramic coating include zirconia, magnesia, alumina, silica, and titanium oxide. ), Cerium oxide (ceria), yttria, barium titanate and other oxide-based materials; cordierite, mullite, forsterite, steatite, Silicon oxide aluminum nitride oxide (Sialon), zircon (zircon), ferrite (ferrite) and other composite oxide-based materials; silicon nitride (silicon nitride), aluminum nitride (aluminum nitride) and other nitride-based materials; carbonization Carbide-based materials such as silicon carbide; hydroxide-based materials such as hydroxyapatite; etc. For example, in the application for forming a ceramic electronic component by forming a conductive layer on a ceramic substrate, a ceramic material that is the same as or excellent in affinity with the ceramic substrate is preferred.

雖無特別限定，但陶瓷材料的含有比率例如相對於核部的金屬材料100質量份，例如亦可為0.01質量份～5.0質量份。再者，金屬-陶瓷的核殼粒子可藉由現有公知的方法來製作。例如，可藉由如本案申請人的在先申請案即日本專利第5075222號的段落0025～段落0028中所記載般，使金屬材料與具有目標金屬元素的有機系金屬化合物（例如金屬烷醇鹽或螯合化合物）或氧化物溶膠反應來製作。Although not particularly limited, the content ratio of the ceramic material may be, for example, 0.01 to 5.0 parts by mass relative to 100 parts by mass of the metal material of the core portion. The metal-ceramic core-shell particles can be produced by a conventionally known method. For example, as described in paragraphs 0025 to 0028 of Japanese Patent No. 5075222, which was the applicant's earlier application, the metallic material and the organic metal compound (for example, a metal alkoxide) having a target metal element can be used Or chelating compounds) or oxide sol.

就與曝光性能的平衡而言，導電性粉末的D₅₀ 粒徑為1 μm～5 μm。藉由將D₅₀ 粒徑設為所述範圍，可提升未硬化的導電膜的曝光性能，並穩定地形成細實線的導電層。第1導電性粉末及第2導電性粉末各自的D₅₀ 粒徑可處於所述範圍。就抑制導電性粉末的凝聚並提升導電性組成物的穩定性的觀點而言，導電性粉末的D₅₀ 粒徑例如亦可為1.5 μm以上、2.0 μm以上。就推進導電層的細實線化或緻密化、低電阻化的觀點而言，導電性粉末的D₅₀ 粒徑例如亦可為4.5 μm以下、4.0 μm以下。再者，本說明書中所謂「D₅₀ 粒徑」，是指於基於雷射繞射·散射法的體積基準的粒度分佈中，相當於自粒徑小的一側起累計值50%的粒徑。In terms of the balance with the exposure performance, the D ₅₀ particle diameter of the conductive powder is 1 μm to 5 μm. By setting the D ₅₀ particle diameter to the above range, it is possible to improve the exposure performance of the uncured conductive film and to form a thin solid conductive layer stably. The D ₅₀ particle size of each of the first conductive powder and the second conductive powder may be in the above range. From the viewpoint of suppressing the aggregation of the conductive powder and improving the stability of the conductive composition, the D ₅₀ particle diameter of the conductive powder may be, for example, 1.5 μm or more and 2.0 μm or more. The D ₅₀ particle diameter of the conductive powder may be, for example, 4.5 μm or less and 4.0 μm or less from the viewpoint of advancing thinning or densification of the conductive layer and reducing resistance. The “D ₅₀ particle size” in this specification refers to a particle size distribution corresponding to 50% of the cumulative value from the side with a smaller particle size in the particle size distribution based on the volume basis of the laser diffraction and scattering method. .

雖無特別限定，但第1導電性粉末與第2導電性粉末的D₅₀ 粒徑可相差至少0.5 μm、典型而言為0.5 μm～3.0 μm、例如1.0 μm～2.0 μm左右。換言之，導電性粉末整體的粒度分佈可具有多峰性。於一具體例中，有機成分量少的第1導電性粉末的D₅₀ 粒徑可處於大概3 μm～5 μm、例如3.5 μm～4.5 μm的範圍內，有機成分量多的第2導電性粉末的D₅₀ 粒徑可處於大概1 μm～3.5 μm、例如1.5 μm～3 μm的範圍。藉此，跟第1導電性粉末與第2導電性粉末的D₅₀ 粒徑的差小的情況相比，可提升導電層的緻密性或填充性。其結果，可較佳地提高導電層的低電阻化。Although not particularly limited, the D ₅₀ particle size of the first conductive powder and the second conductive powder may differ by at least 0.5 μm, typically 0.5 μm to 3.0 μm, for example, about 1.0 μm to 2.0 μm. In other words, the particle size distribution of the entire conductive powder may have multimodality. In a specific example, the D ₅₀ particle size of the first conductive powder having a small amount of organic components may be in a range of approximately 3 μm to 5 μm, for example, 3.5 μm to 4.5 μm, and the second conductive powder having a large amount of organic components The D ₅₀ particle size may be in the range of approximately 1 μm to 3.5 μm, such as 1.5 μm to 3 μm. Accordingly, as compared with the case where a small difference in particle diameter D ₅₀ of the first conductive powder and the second conductive powder, can improve the compactness or filling conductive layer. As a result, the resistance of the conductive layer can be improved.

雖無特別限定，但構成導電性粉末的導電性粒子的形狀典型而言為平均縱橫比（長徑/短徑比）為大概1～2的大致球狀，較佳為1～1.5、例如1～1.2的球狀。藉此，可更穩定地實現曝光性能。第1導電性粉末及第2導電性粉末各自的平均縱橫比可處於所述範圍。再者，本說明書中所謂「平均縱橫比」，是指利用電子顯微鏡觀察多個導電性粒子，並根據所獲得的觀察圖像而算出的縱橫比的算術平均值。另外，本說明書中所謂「球狀」，表示為整體上大概可看作球體（球）的形態，為可包含橢圓狀、多面體狀、圓盤球狀等的用語。Although not particularly limited, the shape of the conductive particles constituting the conductive powder is typically a substantially spherical shape having an average aspect ratio (longer diameter / shorter diameter ratio) of about 1 to 2, preferably 1 to 1.5, for example 1 Spherical to ~ 1.2. This makes it possible to achieve more stable exposure performance. The average aspect ratio of each of the first conductive powder and the second conductive powder may be in the above range. In addition, the "average aspect ratio" as used in this specification means the arithmetic average value of the aspect ratio calculated from the observation image obtained by observing a several electroconductive particle with an electron microscope. The term "spherical shape" as used in this specification refers to a form that can be roughly regarded as a sphere (ball) as a whole, and is a term that can include ellipses, polyhedrons, disks, and the like.

雖無特別限定，但導電性粉末整體於基於JIS Z 8781：2013年的L*a*b*表色系統中，明度L*可為50以上。藉此，曝光時照射光穩定地到達未硬化的導電膜的深部為止，例如亦能夠穩定地實現膜厚為5 μm以上、進而為10 μm以上般的較厚的導電層。就所述觀點而言，導電性粉末的明度L*亦可為大概55以上、例如60以上。明度L*例如可藉由所述導電性粉末的種類或D₅₀ 粒徑來調整。再者，明度L*的測定例如可利用依據JIS Z 8722：2009年的分光測色計來進行。Although not particularly limited, the conductive powder as a whole has an L * a * b * colorimetric system based on JIS Z 8781: 2013, and the brightness L * may be 50 or more. Thereby, it is possible to stably realize a thick conductive layer having a film thickness of 5 μm or more and further 10 μm or more until the irradiation light reaches the deep part of the uncured conductive film stably during exposure. From this viewpoint, the lightness L * of the conductive powder may be about 55 or more, for example, 60 or more. The lightness L * can be adjusted by, for example, the type of the conductive powder or the D ₅₀ particle size. The measurement of the lightness L * can be performed using, for example, a spectrophotometer based on JIS Z 8722: 2009.

雖無特別限定，但導電性粉末於感光性組成物整體中所佔的比例可為大概50質量%以上、典型而言為60質量%～95質量%、例如70質量%～90質量%。藉由滿足所述範圍，可形成緻密性或電傳導性高的導電層。另外，可提升感光性組成物的操作性或將導電膜成形時的作業性。Although not particularly limited, the proportion of the conductive powder in the entire photosensitive composition may be about 50% by mass or more, typically 60% to 95% by mass, for example, 70% to 90% by mass. By satisfying the above range, a conductive layer having high density or high electrical conductivity can be formed. Moreover, the handleability of a photosensitive composition or the workability | operativity at the time of shaping | molding a conductive film can be improved.

＜感光性有機成分＞
感光性有機成分為對導電膜賦予光硬化性的成分。感光性有機成分為具有藉由紫外線等的光能的照射而硬化的性質的成分。本說明書中所謂「感光性有機成分」，是指光聚合性或光改質的有機化合物全部。作為一較佳例，可列舉：包含具有不飽和鍵的感光性樹脂與產生活性種的光聚合起始劑的混合物；所謂的重氮樹脂（例如芳香族雙疊氮（bisazide）與甲醛的縮合體）；包含環氧化合物等加成聚合性化合物與二烯丙基碘鎓鹽等光酸產生劑的混合物；萘醌二疊氮系化合物；等。其中，就穩定性等觀點而言，較佳為包含感光性樹脂與光聚合起始劑的混合物。＜ Photosensitive organic component ＞
The photosensitive organic component is a component that imparts photocurability to a conductive film. A photosensitive organic component is a component which has the property which hardens | cures by irradiation of light energy, such as an ultraviolet-ray. The "photosensitive organic component" as used in this specification means all the photopolymerizable or photo-modified organic compounds. As a preferred example, a mixture including a photosensitive resin having an unsaturated bond and a photopolymerization initiator that generates an active species; a so-called diazo resin (such as condensation of aromatic bisazide and formaldehyde) Body); a mixture containing an addition polymerizable compound such as an epoxy compound and a photoacid generator such as diallyl iodonium salt; a naphthoquinonediazide compound; and the like. Among these, a mixture containing a photosensitive resin and a photopolymerization initiator is preferred from the viewpoint of stability and the like.

感光性樹脂為藉由因光聚合起始劑的分解而產生的活性種進行聚合並硬化的成分。聚合反應可為加成聚合，亦可為開環聚合。感光性樹脂包含具有一個以上的不飽和鍵及/或環狀結構的單體、聚合物、寡聚物。作為感光性樹脂，可自現有公知者中根據用途或基材的種類等適當選擇1種或2種以上來使用。作為一較佳例，可列舉具有一個以上的(甲基)丙烯醯基或乙烯基之類的自由基聚合性反應基的自由基聚合性的單體。其中，較佳為具有(甲基)丙烯醯基的(甲基)丙烯酸酯單體。藉由包含(甲基)丙烯酸酯單體，可提升導電層的柔軟性或對基材的追隨性。其結果，能夠以更高的水準抑制剝離或斷線等不良情況的發生。再者，本說明書中，所謂「(甲基)丙烯醯基」，為包含「甲基丙烯醯基」及「丙烯醯基」的用語，所謂「(甲基)丙烯酸酯」，為包含「甲基丙烯酸酯」及「丙烯酸酯」的用語。The photosensitive resin is a component that is polymerized and hardened by an active species generated by the decomposition of a photopolymerization initiator. The polymerization reaction may be addition polymerization or ring-opening polymerization. The photosensitive resin includes a monomer, a polymer, and an oligomer having one or more unsaturated bonds and / or a cyclic structure. As the photosensitive resin, one or two or more kinds can be appropriately selected and used from conventionally known ones according to the use, the type of the substrate, and the like. As a preferable example, a radically polymerizable monomer having one or more radically polymerizable reactive groups such as a (meth) acrylfluorenyl group or a vinyl group may be mentioned. Among them, a (meth) acrylate monomer having a (meth) acrylfluorenyl group is preferred. By including a (meth) acrylic acid ester monomer, the flexibility of a conductive layer or the followability to a base material can be improved. As a result, it is possible to suppress the occurrence of defects such as peeling or disconnection at a higher level. In addition, in the present specification, the term "(meth) acrylfluorenyl" includes terms such as "methacrylfluorenyl" and "acrylfluorenyl", and the term "(meth) acrylic acid ester" includes "Acrylate" and "acrylate".

(甲基)丙烯酸酯單體包含：每一分子具有一個官能基的單官能(甲基)丙烯酸酯；每一分子具有兩個以上的官能基的多官能(甲基)丙烯酸酯；以及該些的改質物。作為(甲基)丙烯酸酯單體的具體例，可列舉：三乙二醇單丙烯酸酯、三乙二醇單甲基丙烯酸酯、四乙二醇單丙烯酸酯、四乙二醇單甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯等多官能(甲基)丙烯酸酯、或具有胺基甲酸酯鍵（-NH-C(=O)-O-）的胺基甲酸酯(甲基)丙烯酸酯等。其中較佳為(甲基)丙烯酸酯單體包含胺基甲酸酯(甲基)丙烯酸酯。藉此，可更良好地提升曝光部分的耐蝕刻性，並且進一步提升導電膜的伸縮性或柔軟性。因而，可提高與基材的一體性。另外，就提高光硬化性的觀點而言，較佳為(甲基)丙烯酸酯單體為每一分子具有五個以上的(甲基)丙烯醯基的單體。胺基甲酸酯(甲基)丙烯酸酯於感光性樹脂整體中所佔的比例以體積基準計可較佳為30體積%以上、例如50體積%以上。The (meth) acrylate monomer includes: a monofunctional (meth) acrylate having one functional group per molecule; a polyfunctional (meth) acrylate having two or more functional groups per molecule; and these The modifier. Specific examples of the (meth) acrylate monomer include triethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, and tetraethylene glycol monomethacrylic acid. Polyfunctional (meth) acrylates such as esters, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or have urethane bonds (-NH-C (= O) -urethane (meth) acrylate and the like. Among these, it is preferable that a (meth) acrylate monomer contains a urethane (meth) acrylate. Thereby, the etching resistance of the exposed portion can be improved better, and the stretchability or flexibility of the conductive film can be further improved. Therefore, it is possible to improve the integration with the substrate. Moreover, it is preferable that a (meth) acrylic acid ester monomer is a monomer which has five or more (meth) acryl fluorene groups per molecule from a viewpoint of improving photohardenability. The proportion of the urethane (meth) acrylate in the entire photosensitive resin may preferably be 30% by volume or more, for example, 50% by volume or more on a volume basis.

光聚合起始劑為因紫外線等的光照射而分解並產生自由基或陽離子等活性種，從而使感光性樹脂的聚合反應開始的成分。作為光聚合起始劑，可自現有公知者中根據感光性樹脂的種類等適當選擇1種或2種以上來使用。作為一較佳例，可列舉：2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、2,4-二乙基噻噸酮、二苯甲酮等。The photopolymerization initiator is a component that decomposes due to light irradiation such as ultraviolet rays and generates active species such as radicals and cations, thereby starting a polymerization reaction of the photosensitive resin. As the photopolymerization initiator, one or two or more kinds can be appropriately selected and used from conventionally known ones according to the type of the photosensitive resin and the like. As a preferred example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamine can be cited. 1- (4-morpholinophenyl) -butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzene Formamidinediphenylphosphine oxide, 2,4-diethylthioxanthone, benzophenone and the like.

雖無特別限定，但感光性有機化合物於感光性組成物整體中所佔的比例亦可為大概0.1質量%～25質量%、典型而言為0.5質量%～20質量%、例如1質量%～15質量%。另外，感光性樹脂的含有比率相對於導電性粉末100質量份，例如亦可為0.1質量份～30質量份。另外，光聚合起始劑的含有比率相對於感光性樹脂100質量份，亦可為大概0.001質量份～100質量份、例如0.01質量份～10質量份。Although not particularly limited, the proportion of the photosensitive organic compound in the entire photosensitive composition may be about 0.1% to 25% by mass, typically 0.5% to 20% by mass, for example, 1% by mass to 15% by mass. The content ratio of the photosensitive resin may be, for example, 0.1 to 30 parts by mass based on 100 parts by mass of the conductive powder. The content ratio of the photopolymerization initiator may be approximately 0.001 to 100 parts by mass, for example, 0.01 to 10 parts by mass, with respect to 100 parts by mass of the photosensitive resin.

＜有機系分散介質＞
感光性組成物除了所述必需的成分之外，亦可含有使該些分散的有機系分散介質。有機系分散介質為對感光性組成物賦予適度的黏性或流動性，並提升感光性組成物的操作性、或者提升將導電膜成形時的作業性的成分。作為有機系分散介質，可自現有公知者中根據感光性有機化合物的種類等適當選擇1種或2種以上來使用。作為一較佳例，可列舉：萜品醇（terpineol）、二氫萜品醇（薄荷腦（menthanol））、酯醇（texanol）、3-甲基-3-甲氧基丁醇、苄醇等醇系溶劑；乙二醇、丙二醇、二乙二醇等二醇系溶劑；二丙二醇甲醚、甲基溶纖劑（乙二醇單甲醚）、溶纖劑（乙二醇單***）、丁基卡必醇（二乙二醇單丁醚）等醚系溶劑；二乙二醇單丁醚乙酸酯、二丙二醇甲醚乙酸酯、丁基乙二醇乙酸酯（butyl glycol acetate）、丁基二甘醇乙酸酯（butyldiglycol acetate）、丁基溶纖劑乙酸酯、丁基卡必醇乙酸酯（二乙二醇單丁醚乙酸酯）、乙酸異冰片酯等酯系溶劑；甲苯、二甲苯、石油腦（naphtha）、石油系烴等烴系溶劑；礦油精（mineral spirit）；等有機溶劑。＜ Organic Dispersion Medium ＞
The photosensitive composition may contain an organic dispersion medium for dispersing these in addition to the above-mentioned essential components. An organic dispersion medium is a component which imparts moderate viscosity or fluidity to a photosensitive composition, improves the handleability of a photosensitive composition, or improves the workability at the time of shaping a conductive film. As an organic dispersion medium, 1 type, or 2 or more types can be selected suitably from the conventionally known ones according to the kind of photosensitive organic compound, etc., and can be used. As a preferred example, terpineol, dihydroterpineol (menthanol), texanol, 3-methyl-3-methoxybutanol, and benzyl alcohol can be listed. Other alcohol-based solvents; glycol-based solvents such as ethylene glycol, propylene glycol, and diethylene glycol; dipropylene glycol methyl ether, methyl cellosolve (ethylene glycol monomethyl ether), and cellosolve (ethylene glycol monoethyl ether) , Butyl carbitol (diethylene glycol monobutyl ether) and other ether solvents; diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, butyl glycol acetate acetate), butyldiglycol acetate, butyl cellosolve acetate, butylcarbitol acetate (diethylene glycol monobutyl ether acetate), isobornyl acetate and other esters Solvents; hydrocarbon solvents such as toluene, xylene, naphtha, petroleum hydrocarbons; mineral spirits; and other organic solvents.

其中，就提升感光性組成物的保存穩定性或導電膜形成時的操作性的觀點而言，較佳為沸點為150℃以上的有機溶劑、進而為170℃以上的有機溶劑。另外，作為另一較佳例，就將印刷導電膜後的乾燥溫度抑制得低的觀點而言，較佳為沸點為250℃以下的有機溶劑、進而為沸點為220℃以下的有機溶劑。藉此，可提升生產性，並且減少生產成本。Among them, an organic solvent having a boiling point of 150 ° C. or higher, and further an organic solvent of 170 ° C. or higher is preferred from the viewpoint of improving the storage stability of the photosensitive composition or the operability during formation of the conductive film. In addition, as another preferable example, an organic solvent having a boiling point of 250 ° C. or lower, and an organic solvent having a boiling point of 220 ° C. or lower are preferred from the viewpoint of suppressing the drying temperature after printing the conductive film to a low level. This can improve productivity and reduce production costs.

另外，例如於陶瓷製的基材上形成導電層來製造陶瓷電子零件的用途中，較佳為對陶瓷生片（ceramic green sheet）的滲透性低的有機溶劑。作為對陶瓷生片的滲透性低的有機溶劑，例如可列舉：如環己基或第三丁基等具有立體大體積結構的有機溶劑、或分子量比較大的有機溶劑。進而，例如亦較佳為將如上所述的對陶瓷生片的滲透性低的有機溶劑、與可較佳地溶解感光性組成物中所含有的成分（例如感光性有機成分）的有機溶劑以任意比例混合，並用作有機系分散介質。In addition, for example, in the application in which a conductive layer is formed on a ceramic substrate to manufacture ceramic electronic components, an organic solvent having low permeability to a ceramic green sheet is preferred. Examples of the organic solvent having low permeability to the ceramic green sheet include an organic solvent having a three-dimensional bulk structure such as a cyclohexyl group or a third butyl group, or an organic solvent having a relatively large molecular weight. Furthermore, for example, it is also preferable to use an organic solvent having low permeability to the ceramic green sheet as described above and an organic solvent that can better dissolve components (for example, photosensitive organic components) contained in the photosensitive composition. Mix in any ratio and use as an organic dispersion medium.

作為具有如上所述的性狀（沸點及對陶瓷生片的滲透性）的有機溶劑，例如可列舉：達瓦諾（Dowanol）DPM（商標）（沸點：190℃，陶氏化學公司（Dow Chemical Company）製造）、達瓦諾（Dowanol）DPMA（商標）（沸點：209℃，陶氏化學公司（Dow Chemical Company）製造）、薄荷腦（沸點：207℃）、薄荷腦P（沸點：216℃）、艾索帕（Isopar）H（沸點：176℃，關東燃料股份有限公司製造）、SW-1800（沸點：198℃，丸善石油股份有限公司製造）等。Examples of the organic solvent having the properties described above (boiling point and permeability to ceramic green sheets) include Dowanol DPM (trademark) (boiling point: 190 ° C, Dow Chemical Company )), Dowanol DPMA (trademark) (boiling point: 209 ° C, manufactured by Dow Chemical Company), menthol (boiling point: 207 ° C), menthol P (boiling point: 216 ° C) Isopar H (boiling point: 176 ° C, manufactured by Kanto Fuel Co., Ltd.), SW-1800 (boiling point: 198 ° C, manufactured by Maruzan Petroleum Co., Ltd.), etc.

於感光性組成物中包含有機系分散介質的情況下，雖無特別限定，但有機系分散介質於感光性組成物整體中所佔的比例亦可為大概1質量%～50質量%、典型而言為3質量%～30質量%、例如5質量%～20質量%。When an organic dispersion medium is included in the photosensitive composition, although it is not particularly limited, the proportion of the organic dispersion medium in the entire photosensitive composition may be approximately 1% to 50% by mass. It is 3 to 30% by mass, for example, 5 to 20% by mass.

＜有機黏合劑＞
感光性組成物除了所述必需的成分之外，亦可含有有機黏合劑。有機黏合劑為提高未硬化的導電膜與基材的接著性的成分。作為有機黏合劑，可自現有公知者中根據感光性有機化合物或基材的種類等適當選擇1種或2種以上來使用。作為一較佳例，可列舉：甲基纖維素、乙基纖維素、羧甲基纖維素、羥甲基纖維素等纖維素系高分子，丙烯酸樹脂，酚樹脂，醇酸樹脂，聚乙烯醇，聚乙烯丁醛（polyvinyl butyral）等。其中，於蝕刻中使用鹼性水溶液的情況下，較佳為具有羥基（-OH）、羧基（-C(=O)OH）、酯鍵（-C(=O)O-）、磺基（-SO₃ H）等顯示酸性的結構部分的化合物。另外，就利用蝕刻容易去除的觀點而言，較佳為纖維素系高分子或丙烯酸樹脂等親水性的有機黏合劑。＜ Organic Adhesives ＞
The photosensitive composition may contain an organic binder in addition to the essential components. An organic binder is a component which improves the adhesiveness of a non-hardened conductive film and a base material. As the organic binder, one or two or more kinds can be appropriately selected and used from conventionally known ones depending on the type of the photosensitive organic compound or the substrate. As a preferred example, cellulose polymers such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and hydroxymethyl cellulose, acrylic resin, phenol resin, alkyd resin, and polyvinyl alcohol can be cited. , Polyvinyl butyral and so on. Among them, when an alkaline aqueous solution is used for etching, it is preferable to have a hydroxyl group (-OH), a carboxyl group (-C (= O) OH), an ester bond (-C (= O) O-), and a sulfo group ( -SO ₃ H) and other compounds showing an acidic structural moiety. From the viewpoint of easy removal by etching, a hydrophilic organic binder such as a cellulose polymer or an acrylic resin is preferred.

＜其他成分＞
感光性組成物只要不明顯損害此處所揭示的技術的效果，則除了所述必需的成分以外，進而視需要可加入各種添加成分。作為添加成分，可自現有公知者中適當選擇1種或2種以上來使用。作為添加成分的一例，例如可列舉：無機填料、光增感劑、聚合抑制劑、自由基捕捉劑、抗氧化劑、光吸收劑、紫外線吸收劑、塑化劑、界面活性劑、調平劑、增稠劑、分散劑、消泡劑、防凝膠化劑、穩定劑、抗氧化劑、防腐劑、著色劑、顏料等。雖無特別限定，但添加成分於感光性組成物整體中所佔的比例可為大概5質量%以下、例如3質量%以下。＜ Other ingredients ＞
As long as the photosensitive composition does not significantly impair the effects of the technology disclosed herein, in addition to the necessary components, various additional components may be added as necessary. As an additive component, 1 type, or 2 or more types can be selected suitably from a conventionally known person, and can be used. Examples of the additive component include inorganic fillers, photosensitizers, polymerization inhibitors, radical scavengers, antioxidants, light absorbers, ultraviolet absorbers, plasticizers, surfactants, leveling agents, Thickener, dispersant, defoamer, anti-gelling agent, stabilizer, antioxidant, preservative, colorant, pigment, etc. Although not particularly limited, the proportion of the additive component in the entire photosensitive composition may be approximately 5% by mass or less, for example, 3% by mass or less.

＜感光性組成物的用途＞
根據此處所揭示的感光性組成物，能夠以高解析度穩定地形成線間殘渣少、且例如線寬較30 μm更微細的、進而線寬較20 μm更微細的細實線的導電層。另外，可減少導電層的剝離或斷線等。另外，可減少漏電流並抑制短路不良的發生。因此，此處所揭示的感光性組成物例如可較佳地用於電感（inductance）零件或電容器零件、多層電路基板等各種電子零件中的導電層的形成。＜ Application of photosensitive composition ＞
According to the photosensitive composition disclosed herein, it is possible to stably form a conductive layer having a fine solid line with less line-to-line residue and a finer line width of 30 μm and a finer line width of 20 μm. In addition, peeling or disconnection of the conductive layer can be reduced. In addition, it is possible to reduce leakage current and suppress occurrence of short-circuit failure. Therefore, the photosensitive composition disclosed herein can be preferably used, for example, to form conductive layers in various electronic components such as inductance components, capacitor components, and multilayer circuit boards.

電子零件可為表面安裝類型或通孔（through hole）安裝類型等各種安裝形態的電子零件。電子零件可為積層型，或者可為繞組型，亦可為薄膜型。作為電感零件的典型例，可列舉：高頻濾波器、共模濾波器（common mode filter）、高頻電路用電感器（線圈）、普通電路用電感器（線圈）、高頻濾波器、抗流線圈（choking coil）、變壓器（transformer）等。The electronic parts can be electronic parts of various mounting forms such as a surface mounting type or a through hole mounting type. The electronic component may be a laminated type, or may be a winding type, or may be a thin film type. Typical examples of inductive components include high-frequency filters, common mode filters, inductors (coils) for high-frequency circuits, inductors (coils) for general circuits, high-frequency filters, and Choking coil, transformer, etc.

另外，導電性粉末包含金屬-陶瓷的核殼粒子的感光性組成物可較佳地用於陶瓷電子零件的導電層的形成。再者，本說明書中，所謂「陶瓷電子零件」，包含具有非晶質的陶瓷基材（玻璃陶瓷基材）或結晶質（即，非玻璃）的陶瓷基材的電子零件全部。作為典型例，可列舉：具有陶瓷製的基材的高頻濾波器、陶瓷電感器（線圈）、陶瓷電容器、低溫煅燒積層陶瓷基材（低溫共燒陶瓷基材（Low Temperature Co-fired Ceramics Substrate：LTCC基材））、高溫煅燒積層陶瓷基材（高溫共燒陶瓷基材（High Temperature Co-fired Ceramics Substrate：HTCC基材））等。In addition, the photosensitive composition in which the conductive powder contains metal-ceramic core-shell particles can be preferably used for forming a conductive layer of a ceramic electronic component. In addition, in this specification, a "ceramic electronic component" includes all the electronic components which have an amorphous ceramic substrate (glass ceramic substrate) or a crystalline (that is, non-glass) ceramic substrate. Typical examples include high-frequency filters with ceramic substrates, ceramic inductors (coils), ceramic capacitors, low-temperature-fired laminated ceramic substrates (Low Temperature Co-fired Ceramics Substrate) : LTCC substrate)), high-temperature calcined laminated ceramic substrate (High Temperature Co-fired Ceramics Substrate: HTCC substrate), etc.

圖1是示意性地表示積層晶片電感器1的結構的剖面圖。再者，圖1中的尺寸關係（長度、寬度、厚度等）未必反映實際的尺寸關係。另外，圖式中的符號X、符號Y分別表示左右方向、上下方向。但是，其僅為說明上方便的方向。FIG. 1 is a cross-sectional view schematically showing the structure of a multilayer chip inductor 1. Moreover, the dimensional relationship (length, width, thickness, etc.) in FIG. 1 does not necessarily reflect the actual dimensional relationship. The symbols X and Y in the drawings indicate the left-right direction and the up-down direction, respectively. However, this is only a convenient direction for explanation.

積層晶片電感器1包括：本體部10；以及設置於本體部10的左右方向X的兩側面部分的外部電極20。積層晶片電感器1的形狀例如為1608形狀（1.6 mm×0.8 mm）、2520形狀（2.5 mm×2.0 mm）等尺寸。The multilayer chip inductor 1 includes a main body portion 10 and external electrodes 20 provided on both side portions of the main body portion 10 in the left-right direction X. The shape of the multilayer chip inductor 1 is, for example, a size of 1608 shape (1.6 mm × 0.8 mm), a shape of 2520 shape (2.5 mm × 2.0 mm), and the like.

本體部10具有將陶瓷層（介電質層）12與內部電極層14一體化而成的結構。陶瓷層12例如作為可構成導電性粉末的被覆部者而由如上所述的陶瓷材料構成。於上下方向Y上，於陶瓷層12之間配置有內部電極層14。內部電極層14是使用所述感光性組成物而形成。隔著陶瓷層12而於上下方向Y上相鄰的內部電極層14通過設置於陶瓷層12中的通路（via）16而被導通。藉此，內部電極層14構成為三維的旋渦形狀（螺旋狀）。內部電極層14的兩端分別與外部電極20連接。The main body portion 10 has a structure in which a ceramic layer (dielectric layer) 12 and an internal electrode layer 14 are integrated. The ceramic layer 12 is made of a ceramic material as described above, for example, as a coating part that can constitute a conductive powder. In the vertical direction Y, an internal electrode layer 14 is disposed between the ceramic layers 12. The internal electrode layer 14 is formed using the photosensitive composition. The internal electrode layers 14 adjacent to each other in the vertical direction Y with the ceramic layer 12 interposed therebetween are conducted through a via 16 provided in the ceramic layer 12. Thereby, the internal electrode layer 14 is formed into a three-dimensional spiral shape (spiral shape). Both ends of the internal electrode layer 14 are connected to the external electrode 20, respectively.

此種積層晶片電感器1例如可按照以下順序來製造。即，首先製備包含成為原料的陶瓷材料、黏合劑樹脂及有機溶劑的糊（paste），並將其供給至載片（carrier sheet）上，從而形成陶瓷生片。繼而，對該陶瓷生片進行軋製後，將其切割為所需尺寸，從而獲得多個陶瓷層形成用生片。繼而，使用穿孔機等在多個陶瓷層形成用生片的規定位置上適當形成通路孔（via hole）。Such a multilayer chip inductor 1 can be manufactured in the following procedure, for example. That is, first, a paste including a ceramic material, a binder resin, and an organic solvent as raw materials is prepared and supplied to a carrier sheet to form a ceramic green sheet. Next, after rolling the ceramic green sheet, the ceramic green sheet is cut into a desired size to obtain a plurality of green sheets for forming a ceramic layer. Then, a via hole is appropriately formed at a predetermined position of the plurality of green sheets for forming ceramic layers using a punch or the like.

繼而，使用所述感光性組成物於多個陶瓷層形成用生片的規定位置上形成規定的線圈圖案的導電膜。作為一例，可藉由包含以下步驟的製造方法來形成未煅燒的狀態的導電膜：（步驟S1）將感光性組成物賦予至陶瓷層形成用生片上並加以乾燥，藉此將包含感光性組成物的乾燥體的膜狀體成形的步驟；（步驟S2）於膜狀體上覆蓋規定的開口圖案的光罩，並介隔光罩進行曝光，從而使膜狀體局部光硬化的步驟；（步驟S3）對光硬化後的膜狀體進行蝕刻並將未硬化的部分去除的步驟。Next, a conductive film having a predetermined coil pattern is formed at a predetermined position on a plurality of green sheets for forming a ceramic layer using the photosensitive composition. As an example, a non-calcinated conductive film can be formed by a manufacturing method including the following steps: (Step S1) A photosensitive composition is applied to a green sheet for forming a ceramic layer and dried to thereby contain the photosensitive composition. A step of forming a film-like body of the dried body of the object; (step S2) a step of covering the film-like body with a photomask having a predetermined opening pattern, and exposing through the photomask, thereby locally hardening the film-shaped body; Step S3) A step of etching the photo-cured film-like body and removing the non-hardened portion.

再者，當使用所述感光性組成物形成導電膜時，可適當使用現有公知的方法。例如，於（步驟S1）中，感光性組成物的賦予可使用網版印刷等各種印刷法、或棒塗機等來進行。感光性組成物的乾燥典型而言可於50℃～100℃下進行。於（步驟S2）中，曝光時可使用例如發出10 nm～400 nm的波長範圍的光線的曝光機，例如高壓水銀燈、金屬鹵化物燈、氙燈等紫外線照射燈。於（步驟S3）中，蝕刻時可使用例如包含氫氧化鈉或碳酸鈉等鹼成分的水溶液。When a conductive film is formed using the photosensitive composition, a conventionally known method can be appropriately used. For example, in (step S1), application of a photosensitive composition can be performed using various printing methods, such as screen printing, or a bar coater. Drying of the photosensitive composition is typically performed at 50 ° C to 100 ° C. In (Step S2), an exposure machine that emits light in a wavelength range of 10 nm to 400 nm, such as a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like, can be used for the exposure. In (Step S3), for example, an aqueous solution containing an alkali component such as sodium hydroxide or sodium carbonate can be used during etching.

繼而，將多片形成有未煅燒狀態的導電膜的陶瓷層形成用生片積層並進行壓接。藉此，製作未煅燒的陶瓷生片的積層體。繼而，例如於600℃～1000℃下對陶瓷生片的積層體進行煅燒。藉此，將陶瓷生片一體地燒結，從而形成包括陶瓷層12與包含感光性組成物的煅燒體的內部電極層14的本體部10。然後，對本體部10的兩端部賦予適當的外部電極形成用糊，並進行煅燒，藉此形成外部電極20。如以上般，可製造積層晶片電感器1。Next, a plurality of green sheets for forming a ceramic layer on which a conductive film in an unfired state is formed are laminated and pressure-bonded. Thereby, a laminated body of a ceramic green sheet which is not calcined is produced. Then, the laminated body of a ceramic green sheet is fired at 600 to 1000 ° C, for example. Thereby, the ceramic green sheet is sintered integrally, and the main body portion 10 including the ceramic layer 12 and the internal electrode layer 14 containing the fired body of the photosensitive composition is formed. Then, an appropriate external electrode forming paste is applied to both end portions of the main body portion 10 and then fired to form the external electrode 20. As described above, the multilayer chip inductor 1 can be manufactured.

以下，對與本發明有關的若干實施例進行說明，但並非意在將本發明限定於該實施例所示者。Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in the embodiments.

（銀粉末的準備）
首先，準備市售的7種銀粉末（銀粉末a～銀粉末g）。再者，該些銀粉末全部於基於JIS Z 8781：2013年的L*a*b*表色系統中，明度L*為50～80。
另外，使用銀粉末a來準備銀粉末h。具體而言，首先向甲醇中添加丁氧基鋯，從而製備塗佈液。繼而，向該塗佈液中添加銀粉末a並攪拌1小時。繼而，自塗佈液中回收固體成分，並於100℃下進行乾燥。藉此，獲得利用相對於銀粉末100質量份，以氧化鋯（ZrO₂ ）換算計成為0.5質量份的量的丁氧基鋯進行了表面塗佈的銀粉末（銀-氧化鋯的核殼粒子）。如此，準備了銀粉末h。(Preparation of silver powder)
First, seven kinds of commercially available silver powders (silver powder a to silver powder g) were prepared. In addition, all of these silver powders are in the L * a * b * color system based on JIS Z 8781: 2013, and the lightness L * is 50 to 80.
In addition, the silver powder h is prepared using the silver powder a. Specifically, zirconyl butoxyl was first added to methanol to prepare a coating liquid. Then, silver powder a was added to this coating liquid, and it stirred for 1 hour. Then, the solid content was recovered from the coating liquid and dried at 100 ° C. Thereby, a silver powder (silver-zirconia core-shell particles) was obtained by surface coating with zirconium oxide (ZrO ₂ ) conversion in an amount of 0.5 parts by mass based on 100 parts by mass of silver powder. ). In this way, silver powder h was prepared.

繼而，使用熱重測定裝置，於所述加熱條件下分別測定銀粉末a～銀粉末h的有機成分量。將結果示於表1、表2的「有機成分量」一欄。另外，表1、表2中一併示出藉由氣相層析-質量分析法（GC-MS）檢測的表面處理劑的種類、與基於雷射繞射·散射法的體積基準的D₅₀ 粒徑。再者，表面處理劑一欄的所謂「BTA系」，表示苯并***系化合物。Next, using a thermogravimetry device, the organic component amounts of the silver powder a to the silver powder h were measured under the heating conditions. The results are shown in the "organic component amount" column in Tables 1 and 2. In addition, Table 1 and Table 2 also show the types of surface treatment agents detected by gas chromatography-mass spectrometry (GC-MS) and D ₅₀ based on the volume basis of the laser diffraction and scattering method. Particle size. In addition, the so-called "BTA-based" in the column of surface treatment agent means a benzotriazole-based compound.

（感光性組成物的製備）
首先，準備表1、表2所示的銀粉末、與載色劑（vehicle）。載色劑是使作為感光性樹脂的胺基甲酸酯丙烯酸酯單體、作為光聚合起始劑的豔佳固（Irgacure）369（註冊商標）（汽巴精化（CIBA SPECIALTY CHEMICALS）股份有限公司製造）、有機黏合劑、聚合抑制劑、增感劑、防凝膠化劑、以及紫外線吸收劑溶解於作為有機溶媒的二丙二醇甲醚乙酸酯及二氫萜品醇中而製備。然後，將銀粉末與載色劑以77：23的質量比混合，藉此製備感光性組成物（例1～例8、比較例1～比較例7）。(Preparation of photosensitive composition)
First, the silver powders shown in Tables 1 and 2 and a vehicle are prepared. The vehicle is a urethane acrylate monomer as a photosensitive resin and Irgacure 369 (registered trademark) (CIBA SPECIALTY CHEMICALS) as a photopolymerization initiator. (Manufactured by the company), organic binders, polymerization inhibitors, sensitizers, anti-gelling agents, and ultraviolet absorbers are prepared by dissolving dipropylene glycol methyl ether acetate and dihydroterpineol as organic solvents. Then, the silver powder and the vehicle were mixed at a mass ratio of 77:23 to prepare a photosensitive composition (Examples 1 to 8 and Comparative Examples 1 to 7).

（配線圖案的製作）
首先，使用不鏽鋼製的網版，將所述製備的感光性組成物分別塗佈於市售的陶瓷生片上。繼而，使其於60℃下乾燥15分鐘，從而於生片上成形膜狀體。繼而，自膜狀體的上方覆蓋光罩。此時，作為光罩，使用配線圖案的線寬為20 μm、相鄰的線的間隔部分（空間）為20 μm的光罩（L/S=20 μm/20 μm的光罩）。於覆蓋有該光罩的狀態下，藉由曝光機以2500 mJ/cm² 的強度來照射光，從而使膜狀體局部硬化。曝光後，對陶瓷生生片噴附0.1質量%的Na₂ CO₃ 水溶液，將未硬化的膜狀體部分蝕刻去除後，利用純水進行清洗，並於室溫下使其乾燥。藉此，製作配線經配置為旋渦狀的配線圖案（螺旋圖案（spiral pattern））。(Production of wiring pattern)
First, using a stainless steel screen, the prepared photosensitive composition was coated on a commercially available ceramic green sheet, respectively. Then, it was made to dry at 60 degreeC for 15 minutes, and the film-like body was shape | molded on the green sheet. Then, a photomask is covered from above the film-shaped body. At this time, as the photomask, a photomask (L / S = 20 μm / 20 μm photomask) having a line pattern with a line width of 20 μm and an interval (space) between adjacent lines of 20 μm was used. In a state covered with the photomask, light was irradiated by an exposure machine at an intensity of 2500 mJ / cm ² to locally harden the film-like body. After the exposure, a 0.1% by mass Na ₂ CO ₃ aqueous solution was sprayed on the ceramic green sheet, and the unhardened film-like body was partially etched and removed, and then washed with pure water and dried at room temperature. Thereby, a wiring pattern (spiral pattern) in which the wiring is arranged in a spiral shape is produced.

（配線圖案的評價）
針對所述製作的配線圖案來評價殘渣、剝離、線寬，並基於該些評價來進行綜合評價。(Evaluation of wiring pattern)
The produced wiring pattern was evaluated for residue, peeling, and line width, and comprehensive evaluation was performed based on these evaluations.

·殘渣的評價：
利用電子顯微鏡來觀察配線圖案，根據所獲得的觀察圖像進行殘渣的評價。觀察圖像是以倍率200倍拍攝。然後，計數於觀察圖像中殘存於配線間的空間部分中的線間殘渣的數量。再者，線間殘渣的計數是針對多個視野來進行，將多個視野中的線間殘渣的算術平均值設為「線間殘渣的數量」。將結果示於表1、表2的「殘渣的評價」一欄中。該欄的表述如下所述。
「○」：線間殘渣的數量為0個/視野（未確認到線間殘渣）
「△」：線間殘渣的數量為1個/視野～3個/視野
「×」：線間殘渣的數量為4個以上/視野· Residue evaluation:
The wiring pattern was observed with an electron microscope, and the residue was evaluated based on the obtained observation image. The observation image was taken at a magnification of 200 times. Then, the number of residues between lines in the space portion remaining in the wiring room in the observation image was counted. The counting of the line-to-line residues is performed for a plurality of fields of view, and the arithmetic mean of the line-to-line residues in the plurality of fields of view is set to "the number of line-to-line residues". The results are shown in the "Evaluation of Residue" column in Tables 1 and 2. The expressions in this column are as follows.
"○": The number of residues between lines is 0 per field of vision (no residues between lines are confirmed)
"△": The number of residues between the lines is 1 per field of vision to 3 / field of vision. "×": The number of residues between the lines is 4 or more per field of vision.

·剝離的評價：
根據所述觀察圖像來確認剝離與斷線的有無。將結果示於表1、表2的「剝離的評價」一欄中。該欄的表述如下所述。
「○」：無剝離
「×」：有剝離Evaluation of peeling:
The presence or absence of peeling and disconnection was confirmed from the observation image. The results are shown in the "Evaluation of peeling" column in Tables 1 and 2. The expressions in this column are as follows.
"○": No peeling "×": Peeling

·線寬的評價：
根據所述觀察圖像來測量配線圖案的線寬。再者，線寬的測量是針對多個視野來進行，將其算術平均值設為線寬。將結果示於表1、表2的「線寬」一欄中。另外，評價一欄的表述如下所述。
「○」：20 μm～25 μm（目標值）
「△」：25 μm～28 μm
「×」：28 μm以上· Evaluation of line width:
The line width of the wiring pattern is measured based on the observation image. In addition, the measurement of the line width is performed for a plurality of fields of view, and the arithmetic average is set to the line width. The results are shown in the "line width" column of Tables 1 and 2. The expression in the evaluation column is as follows.
"○": 20 μm to 25 μm (target value)
"△": 25 μm ～ 28 μm
"×": 28 μm or more

·綜合評價：
「○」：於所述殘渣、剝離、線寬的各評價中，一個×亦不存在
「×」：於所述殘渣、剝離、線寬的各評價中，存在一個以上的×·Overview:
"○": One x does not exist in each evaluation of the residue, peeling, and line width. "×": One or more x exists in each evaluation of the residue, peeling, and line width.

[表1]
[Table 1]

[表2]
[Table 2]

如表1所示，比較例1為僅使用有機成分量少的銀粉末a的試驗例。比較例1中，配線圖案中線寬的偏差大，於各處確認到線寬的擴展。其結果，平均線寬較目標值而變得過大，難以穩定地形成細實線。作為其原因，認為：由於導電膜的光硬化性過高，因此由自光罩的開口部分散射的光將遮光部分的導電膜的一部分硬化，或者由於導電膜的耐蝕刻性過高，因此，蝕刻時未硬化部分的去除不完全。另外，比較例2為僅使用有機成分量相對較多的銀粉末b的試驗例。比較例2中，於配線圖案中確認到許多剝離或斷線，難以形成配線圖案。作為其原因，認為蝕刻時硬化部與未硬化部分一起流動。另外，比較例3為僅使用表面附著有脂肪酸與苯并***系化合物的銀粉末e的試驗例。比較例3中，於配線圖案中確認到許多剝離或斷線，難以形成細實線。進而，於配線間的空間部分殘存有許多線間殘渣。As shown in Table 1, Comparative Example 1 is a test example using only silver powder a having a small amount of organic components. In Comparative Example 1, the variation of the line width in the wiring pattern was large, and the expansion of the line width was confirmed everywhere. As a result, the average line width becomes too large compared with the target value, and it is difficult to form a thin solid line stably. It is considered that the light-curing property of the conductive film is too high, so that a part of the light-shielding conductive film is hardened by light scattered from the opening of the photomask, or the conductive film has too high etching resistance. The removal of the unhardened portion during etching is incomplete. In addition, Comparative Example 2 is a test example using only silver powder b having a relatively large amount of organic components. In Comparative Example 2, a lot of peeling or disconnection was confirmed in the wiring pattern, and it was difficult to form the wiring pattern. For this reason, it is considered that the hardened portion flows together with the unhardened portion during the etching. In addition, Comparative Example 3 is a test example using only silver powder e having fatty acids and benzotriazole-based compounds adhered to the surface. In Comparative Example 3, many peeling or disconnection was confirmed in the wiring pattern, and it was difficult to form a thin solid line. Furthermore, a lot of inter-line residue remained in the space portion of the wiring room.

例1～例4為併用銀粉末a與銀粉末b的試驗例。例1～例4中，與所述比較例1～比較例3相比，能夠以高解析度形成無線間殘渣、且線寬被抑制為28 μm以下、進而為25 μm以下的細實線的配線圖案。即，可形成不存在配線的剝離或斷線、不存在短路不良、且於配線間穩定地確保了空間的細實線的配線圖案。Examples 1 to 4 are test examples in which silver powder a and silver powder b are used in combination. In Examples 1 to 4, compared with the above Comparative Examples 1 to 3, it is possible to form a wireless line residue with a high resolution, and the line width is suppressed to a thin solid line of 28 μm or less and further 25 μm or less. Wiring pattern. That is, it is possible to form a thin solid line wiring pattern in which there is no peeling or disconnection of the wiring, no short-circuit failure, and a space is stably secured between the wirings.

表2中對2種以上的銀粉末的混合體系進一步進行了研究。例5、例6為代替銀粉末b而使用銀粉末c或銀粉末d的試驗例。例7為除銀粉末a與銀粉末b以外亦使用銀粉末g的試驗例。例8為代替銀粉末a而使用銀粉末h的試驗例。如表2所示，例5、例6或例7、例8中，與例1～例4同樣地，亦能夠以高解析度形成細實線的配線圖案。In Table 2, the mixed system of two or more silver powders was further studied. Examples 5 and 6 are test examples using silver powder c or silver powder d instead of silver powder b. Example 7 is a test example using silver powder g in addition to silver powder a and silver powder b. Example 8 is a test example using silver powder h instead of silver powder a. As shown in Table 2, in Example 5, Example 6, or Example 7, and Example 8, as in Examples 1 to 4, a thin solid line wiring pattern can be formed at a high resolution.

另一方面，比較例4～比較例6為代替銀粉末b而分別使用銀粉末e～銀粉末g的試驗例。比較例7為使銀粉末a與銀粉末b的合計減少為銀粉末整體的80%的試驗例。比較例4～比較例6及比較例7中，於配線間的空間部分殘存有許多線間殘渣。另外，比較例5、比較例6中，配線圖案中線寬的偏差大，線寬較目標值稍大。On the other hand, Comparative Examples 4 to 6 are test examples in which silver powder e to silver powder g were used instead of silver powder b, respectively. Comparative Example 7 is a test example in which the total of the silver powder a and the silver powder b was reduced to 80% of the entire silver powder. In Comparative Examples 4 to 6 and Comparative Example 7, many inter-line residues remained in the space portion between the wirings. In Comparative Examples 5 and 6, the variation in the line width in the wiring pattern was large, and the line width was slightly larger than the target value.

根據以上結果可知，併用基於熱重分析的有機成分量為0.1質量%以下的第1導電性粉末、與表面附著有苯并***系化合物且基於熱重分析的有機成分量至少為0.5%的第2導電性粉末，並且將該些導電性粉末的合計設為導電性粉末整體的90質量%以上的比例，藉此能夠以高解析度形成線間殘渣少的細實線的配線圖案。該些結果表示此處所揭示的技術的意義。Based on the above results, it can be seen that the first conductive powder having an organic component content of 0.1% by mass or less based on thermogravimetric analysis and a benzotriazole-based compound adhered to the surface and having an organic component content of at least 0.5% by thermogravimetric analysis are used in combination. As the second conductive powder, a total solid conductive powder having a ratio of 90% by mass or more of the entire conductive powder can form a fine solid line wiring pattern with low residue between lines at a high resolution. These results indicate the significance of the techniques disclosed herein.

以上對本發明進行了詳細說明，但該些僅為例示，本發明可於不偏離其主旨的範圍內加以各種變更。The present invention has been described in detail above, but these are merely examples, and the present invention can be modified in various ways without departing from the spirit thereof.

1‧‧‧積層晶片電感器1‧‧‧Multilayer Chip Inductor

10‧‧‧本體部 10‧‧‧Body

12‧‧‧陶瓷層 12‧‧‧ceramic layer

14‧‧‧內部電極層 14‧‧‧Internal electrode layer

16‧‧‧通路 16‧‧‧ access

20‧‧‧外部電極 20‧‧‧External electrode

X‧‧‧左右方向 X‧‧‧ Left and right direction

Y‧‧‧上下方向 Y‧‧‧ Up and down direction

圖1是示意性地表示一實施形態的積層晶片電感器的結構的剖面圖。FIG. 1 is a cross-sectional view schematically showing the structure of a multilayer chip inductor according to an embodiment.

圖2是用以說明線間殘渣的示意圖。 FIG. 2 is a schematic diagram for explaining residues between lines.

Claims (9)

一種感光性組成物，包含導電性粉末與感光性有機成分， 所述導電性粉末的基於雷射繞射·散射法的體積基準的D₅₀ 粒徑為1 μm以上且5 μm以下，並且當將所述導電性粉末整體設為100質量%時，以下2種成分的合計佔90質量%以上： （1）基於熱重測定的有機成分量為0.1質量%以下的第1導電性粉末； （2）表面附著有苯并***系化合物，且基於熱重測定的有機成分量至少為0.5質量%的第2導電性粉末。A photosensitive composition comprising a conductive powder and a photosensitive organic component. The D ₅₀ particle diameter of the conductive powder based on the volume basis of the laser diffraction and scattering method is 1 μm or more and 5 μm or less. When the entire conductive powder is 100% by mass, the total of the following two components accounts for more than 90% by mass: (1) the first conductive powder having an organic content of 0.1% by mass or less based on thermogravimetric measurement; (2) ) A second conductive powder having a benzotriazole-based compound adhered to its surface and having an organic component content of at least 0.5% by mass measured by thermogravimetry. 如申請專利範圍第1項所述的感光性組成物，其中 所述導電性粉末包含銀系粒子。The photosensitive composition according to item 1 of the scope of patent application, wherein The conductive powder includes silver-based particles. 如申請專利範圍第1項或第2項所述的感光性組成物，其中 所述第1導電性粉末與所述第2導電性粉末的質量比率為第1導電性粉末：第2導電性粉末=85：15～20：80。The photosensitive composition according to claim 1 or claim 2, wherein The mass ratio of the first conductive powder to the second conductive powder is the first conductive powder: the second conductive powder = 85: 15 to 20:80. 如申請專利範圍第1項或第2項所述的感光性組成物，其中 所述第1導電性粉末為包含成為核的金屬材料與將所述核的表面的至少一部分被覆的陶瓷材料的核殼粒子。The photosensitive composition according to claim 1 or claim 2, wherein The first conductive powder is a core-shell particle including a metal material serving as a core and a ceramic material covering at least a part of a surface of the core. 如申請專利範圍第1項或第2項所述的感光性組成物，其中 於基於日本工業標準Z 8781：2013年的L*a*b*表色系統中，所述導電性粉末的明度L*為50以上。The photosensitive composition according to claim 1 or claim 2, wherein In the L * a * b * color system based on Japanese Industrial Standard Z 8781: 2013, the brightness L * of the conductive powder is 50 or more. 如申請專利範圍第1項或第2項所述的感光性組成物，其 進而包含沸點為150℃以上且250℃以下的有機溶劑。The photosensitive composition as described in claim 1 or 2, Furthermore, organic solvents having a boiling point of 150 ° C or higher and 250 ° C or lower are included. 一種複合體，包括：生片；以及導電膜，配置於所述生片上，且包含如申請專利範圍第1項至第6項中任一項所述的感光性組成物的乾燥體。A composite body includes: a green sheet; and a conductive film disposed on the green sheet and including a dried body of the photosensitive composition according to any one of claims 1 to 6 of a patent application scope. 一種電子零件，包括：導電層，包含如申請專利範圍第1項至第6項中任一項所述的感光性組成物的煅燒體。An electronic part includes a conductive layer including a calcined body of the photosensitive composition according to any one of claims 1 to 6 of the scope of patent application. 一種電子零件的製造方法，包括如下步驟：將如申請專利範圍第1項至第6項中任一項所述的感光性組成物賦予至基材上，進行光硬化及蝕刻處理後進行煅燒，形成包含所述感光性組成物的煅燒體的導電層。A method for manufacturing an electronic part includes the steps of: applying the photosensitive composition according to any one of claims 1 to 6 on a base material, performing photo-hardening and etching treatment, and then firing, A conductive layer containing the fired body of the photosensitive composition is formed.