TW201932551A - Metal ink, method for producing metal ink, and method for producing substrate with metal pattern - Google Patents

Abstract

A metal ink according to the present invention, which is applied to a substrate for the purpose of forming a metal pattern, contains a metal colloid and a dispersion medium. With respect to the substrate, at least a region where the metal pattern is to be formed contains a thermoplastic resin. The distance Dc between the Hansen solubility parameter of the dispersion medium and the Hansen solubility parameter of the metal colloid is 10 MPa0.5 or less; and the distance Ds between the Hansen solubility parameter of the dispersion medium and the Hansen solubility parameter of the thermoplastic resin is 10 MPa0.5 or more.

Description

金屬墨、金屬墨之製造方法及具金屬圖案之基材之製造方法Metal ink, method for producing metal ink, and method for manufacturing substrate with metal pattern

本發明係關於包含金屬膠體之金屬墨及其製造方法、以及具備使用金屬墨之金屬圖案之基材之製造方法。The present invention relates to a metal ink containing a metal colloid, a method for producing the same, and a method for producing a substrate having a metal pattern using a metal ink.

背景技術
於形成配線圖案或電極之導電層等金屬圖案時，使用包含金屬奈米粒子之金屬墨。金屬墨係於形成金屬圖案時塗佈於基材表面。於基材表面形成有樹脂膜等(例如專利文獻1)。BACKGROUND ART When forming a metal pattern such as a wiring pattern or a conductive layer of an electrode, a metal ink containing metal nanoparticles is used. The metallic ink is applied to the surface of the substrate when the metal pattern is formed. A resin film or the like is formed on the surface of the substrate (for example, Patent Document 1).

先行技術文獻
專利文獻
專利文獻1：日本特開2013-221058號公報Advance Technical Document Patent Document Patent Document 1: Japanese Patent Laid-Open Publication No. 2013-221058

發明概要
發明欲解決之課題
由於只要可以於由各種熱塑性樹脂形成之基材上直接形成金屬圖案，便可省略以樹脂膜被覆基材表面之步驟，故很簡便。然而，大多的熱塑性樹脂其耐溶劑性較低、容易被金屬墨所含之分散介質溶解。若基材因金屬墨而溶解，電阻會變大、金屬圖案之精度降低或發生製品不良。另一方面，若使用不會溶解熱塑性樹脂之分散介質，則金屬膠體於金屬墨中之穩定性會降低。SUMMARY OF THE INVENTION Problems to be Solved by the Invention As long as a metal pattern can be directly formed on a substrate formed of various thermoplastic resins, the step of coating the surface of the substrate with a resin film can be omitted, which is simple. However, most thermoplastic resins have low solvent resistance and are easily dissolved by a dispersion medium contained in the metallic ink. If the substrate is dissolved by the metallic ink, the electric resistance becomes large, the precision of the metal pattern is lowered, or the product is defective. On the other hand, if a dispersion medium which does not dissolve the thermoplastic resin is used, the stability of the metal colloid in the metallic ink is lowered.

用以解決課題之手段
本發明之一態樣係關於一種金屬墨，其係用以塗佈於基材上而形成金屬圖案者，
包含金屬膠體與分散介質，
前述基材中至少形成前述金屬圖案之區域包含熱塑性樹脂，
前述分散介質與前述金屬膠體之漢森溶解度參數之距離Dc為10MPa^0.5 以下，
前述分散介質與前述熱塑性樹脂之漢森溶解度參數之距離Ds為10MPa^0.5 以上。Means for Solving the Problem One aspect of the present invention relates to a metal ink for coating a substrate to form a metal pattern.
Contains metal colloids and dispersion media,
A region in which at least the aforementioned metal pattern is formed in the substrate includes a thermoplastic resin.
The distance Dc between the dispersion medium and the Hansen solubility parameter of the metal colloid is 10 MPa ^0.5 or less.
The distance Ds between the dispersion medium and the Hansen solubility parameter of the thermoplastic resin is 10 MPa ^0.5 or more.

本發明之另一態樣係關於一種金屬墨之製造方法，該金屬墨係包含金屬膠體與分散介質且用以塗佈於基材上而形成金屬圖案者，
前述基材中至少形成前述金屬圖案之區域包含熱塑性樹脂；
前述金屬墨之製造方法包含以下步驟：
準備前述分散介質之步驟，前述分散介質與前述金屬膠體之漢森溶解度參數之距離Dc為10MPa^0.5 以下，且前述分散介質與前述熱塑性樹脂之漢森溶解度參數之距離Ds為10MPa^0.5 以上；及
調製金屬墨之步驟，該金屬墨係使前述金屬膠體分散於前述分散介質中而成。Another aspect of the present invention relates to a method of manufacturing a metallic ink comprising a metal colloid and a dispersion medium and used for coating a substrate to form a metal pattern.
a region of the foregoing substrate in which at least the aforementioned metal pattern is formed comprises a thermoplastic resin;
The method for manufacturing the aforementioned metal ink comprises the following steps:
a step of preparing the dispersion medium, wherein the distance Dc between the dispersion medium and the Hansen solubility parameter of the metal colloid is 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the Hansen solubility parameter of the thermoplastic resin is 10 MPa ^0.5 or more; A step of a metallic ink obtained by dispersing the metal colloid in the dispersion medium.

本發明之另一態樣係關於一種具金屬圖案之基材之製造方法，其具備於基材上塗佈金屬墨而形成金屬圖案之步驟，
前述基材中至少形成前述金屬圖案之區域包含熱塑性樹脂，
前述金屬墨包含金屬膠體與分散介質，
前述分散介質與前述金屬膠體之漢森溶解度參數之距離Dc為10MPa^0.5 以下，
前述分散介質與前述熱塑性樹脂之漢森溶解度參數之距離Ds為10MPa^0.5 以上。Another aspect of the present invention relates to a method for producing a substrate having a metal pattern, comprising the steps of coating a metal ink on a substrate to form a metal pattern,
A region in which at least the aforementioned metal pattern is formed in the substrate includes a thermoplastic resin.
The foregoing metal ink comprises a metal colloid and a dispersion medium,
The distance Dc between the dispersion medium and the Hansen solubility parameter of the metal colloid is 10 MPa ^0.5 or less.
The distance Ds between the dispersion medium and the Hansen solubility parameter of the thermoplastic resin is 10 MPa ^0.5 or more.

發明效果
可確保金屬膠體於金屬墨中之高穩定性，且於基材之包含熱塑性樹脂之區域上使用金屬墨形成金屬圖案時，可抑制基材溶解。The effect of the invention can ensure high stability of the metal colloid in the metallic ink, and when the metal pattern is formed on the region containing the thermoplastic resin of the substrate, the dissolution of the substrate can be suppressed.

本發明之新穎特徵記載於所附申請專利範圍中，而關於本發明之構成及內容，可與本發明之其他目的及特徵一併由對照圖式之以下詳細說明來進一步清楚理解。The novel features of the invention are set forth in the appended claims.

用以實施發明之形態
對於利用來形成金屬圖案之金屬墨，有必要確保金屬膠體於金屬墨中之穩定性(具體而言為分散穩定性)。另一方面，於電子領域中，近年來一直在研究於由熱塑性樹脂形成之基板上使用金屬墨形成配線圖案之技術。然而，容易確保金屬膠體穩定性之分散介質容易溶解熱塑性樹脂。又，對於金屬墨，亦有必要均衡地調節基材與金屬墨之親和性、金屬墨所含分散介質之揮發性等。In order to carry out the invention, it is necessary to ensure the stability (specifically, dispersion stability) of the metal colloid in the metallic ink for the metallic ink used to form the metal pattern. On the other hand, in the field of electronics, in recent years, a technique of forming a wiring pattern using a metal ink on a substrate formed of a thermoplastic resin has been studied. However, a dispersion medium which easily ensures the stability of the metal colloid is easily dissolved in the thermoplastic resin. Further, in the case of the metallic ink, it is also necessary to adjust the affinity of the substrate to the metallic ink, the volatility of the dispersion medium contained in the metallic ink, and the like in a balanced manner.

本發明之一態樣之金屬墨，係包含金屬膠體與分散介質，且用以塗佈於基材上而形成金屬圖案的金屬墨。基材中至少形成金屬圖案之區域包含熱塑性樹脂。分散介質與金屬膠體之漢森溶解度參數(HSP)之距離Dc為10MPa^0.5 以下，且分散介質與熱塑性樹脂之HSP之距離Ds為10MPa^0.5 以上。再者，溶解度參數係表示物質之間的親和性的量度，HSP由分散項dD、極性項dP及氫鍵項dH之三維向量表示。又，本發明之另一態樣，亦包含用以塗佈於基材上而形成金屬圖案的上述金屬墨之用途。A metallic ink according to an aspect of the present invention is a metallic ink comprising a metal colloid and a dispersion medium and coated on a substrate to form a metal pattern. A region in which at least a metal pattern is formed in the substrate contains a thermoplastic resin. The distance Dc between the dispersion medium and the Hansen solubility parameter (HSP) of the metal colloid is 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the HSP of the thermoplastic resin is 10 MPa ^0.5 or more. Further, the solubility parameter is a measure of the affinity between the substances, and the HSP is represented by a three-dimensional vector of the dispersion term dD, the polar term dP, and the hydrogen bond term dH. Further, another aspect of the present invention also includes the use of the above-described metallic ink for forming a metal pattern on a substrate.

此種金屬墨可藉由包含以下步驟之製造方法而製造：準備分散介質之步驟，該分散介質與金屬膠體之HSP之距離Dc為10MPa^0.5 以下，且分散介質與熱塑性樹脂之HSP之距離Ds為10MPa^0.5 以上；及調製金屬墨之步驟，該金屬墨係使金屬膠體分散於分散介質中而成。本發明之進而其他態樣亦包含上述金屬墨之製造方法。Such a metallic ink can be produced by a manufacturing method comprising the steps of preparing a dispersion medium having a distance Dc of 10 MPa ^0.5 or less from the HSP of the metal colloid, and a distance Ds between the dispersion medium and the HSP of the thermoplastic resin. 10MPa ^0.5 or more; and a step of preparing a metal ink which is obtained by dispersing a metal colloid in a dispersion medium. Still other aspects of the invention also include a method of producing the above metal ink.

本發明之另一態樣亦包含具金屬圖案之基材之製造方法，其具備於基材上塗佈金屬墨而形成金屬圖案之步驟。此處，基材中至少形成金屬圖案之區域包含熱塑性樹脂。金屬墨包含金屬膠體與分散介質。分散介質與金屬膠體之漢森溶解度參數之距離Dc為10MPa^0.5 以下，且分散介質與熱塑性樹脂之漢森溶解度參數之距離Ds為10MPa^0.5 以上。又，本發明之進而另一態樣，亦包含具金屬圖案之基材之製造方法中的上述金屬墨之用途。Another aspect of the present invention also includes a method of producing a substrate having a metal pattern, comprising the step of coating a metal ink on a substrate to form a metal pattern. Here, a region in which at least a metal pattern is formed in the substrate contains a thermoplastic resin. The metallic ink contains a metal colloid and a dispersion medium. The distance Dc between the dispersion medium and the Hansen solubility parameter of the metal colloid is 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the Hansen solubility parameter of the thermoplastic resin is 10 MPa ^0.5 or more. Furthermore, in still another aspect of the present invention, the use of the metal ink in the method for producing a substrate having a metal pattern is also included.

根據本發明之上述態樣，將分散介質與金屬膠體之HSP之距離Dc調節為10MPa^0.5 以下、將分散介質與基材(具體而言熱塑性樹脂)之HSP之距離Ds調節為10MPa^0.5 以上。藉此，可確保金屬膠體於金屬墨中之高穩定性，且可抑制於基材之包含熱塑性樹脂之區域上塗佈金屬墨時之基材溶解。藉由抑制基材(具體而言熱塑性樹脂) 因金屬墨而溶解，可抑制金屬圖案之電阻增加。又，藉由金屬膠體於金屬墨中之穩定性較高，可長期間穩定地保管金屬墨。再者，金屬膠體通常包含金屬粒子及與金屬粒子配位之分散劑。於本發明之上述態樣中，基於金屬膠體之HSP算出距離Dc。藉此，與利用分散劑或分散劑對金屬粒子之親和性較低的有機基(疏水性基等)之HSP與分散介質之HSP之距離之情形相比，由於可以高精度選擇適合金屬膠體之分散介質，故可確保金屬膠體於金屬墨中之高穩定性。According to the above aspect of the invention, the distance Dc between the dispersion medium and the HSP of the metal colloid is adjusted to 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the HSP of the substrate (specifically, the thermoplastic resin) is adjusted to 10 MPa ^0.5 or more. Thereby, high stability of the metal colloid in the metallic ink can be ensured, and dissolution of the substrate when the metallic ink is applied to the region containing the thermoplastic resin of the substrate can be suppressed. By suppressing the dissolution of the substrate (specifically, the thermoplastic resin) by the metallic ink, the increase in resistance of the metal pattern can be suppressed. Further, since the metal colloid has high stability in the metallic ink, the metallic ink can be stably stored for a long period of time. Further, the metal colloid usually contains metal particles and a dispersing agent coordinated to the metal particles. In the above aspect of the invention, the distance Dc is calculated based on the HSP of the metal colloid. Therefore, compared with the case where the HSP of the organic group (hydrophobic group or the like) having a low affinity for the metal particles by the dispersing agent or the dispersing agent is separated from the HSP of the dispersion medium, the metal colloid can be selected with high precision. Dispersing the medium ensures high stability of the metal colloid in the metallic ink.

又，距離Dc及Ds可如下求出。
首先，將金屬墨離心分離後沈降的沈降物與上清液分別回收。藉由進行氣相層析法分析而求出上清液所含分散介質的種類與組成(為混合物時為混合比)。然後，使用HSP計算軟體HSPiP(可從HSP及HSPiP之官方網站取得)從該種類與組成求出分散介質之HSP之分散項dD、極性項dP及氫鍵項dH。Further, the distances Dc and Ds can be obtained as follows.
First, the precipitate which settled after centrifuging the metallic ink and the supernatant were separately recovered. The type and composition of the dispersion medium contained in the supernatant were determined by gas chromatography analysis (mixing ratio in the case of a mixture). Then, using the HSP calculation software HSPiP (available from the official website of HSP and HSPiP), the dispersion term dD, the polar term dP, and the hydrogen bond term dH of the HSP of the dispersion medium are determined from the type and composition.

關於上述沈降物(金屬膠體)及基材(熱塑性樹脂)之HSP，可藉由試驗對表1所示23種介質各自的溶解性而求出。The HSP of the above-mentioned sediment (metal colloid) and the substrate (thermoplastic resin) can be determined by testing the solubility of each of the 23 kinds of media shown in Table 1.

[表1]
[Table 1]

金屬膠體之HSP具體而言如下求出。將上述沈降物以濃度成為0.1質量%之方式添加於表1之各介質中，藉由輥型振動器於室溫(25℃)下攪拌10分鐘。攪拌後，於室溫(25℃)下靜置1小時，若金屬膠體分散設為1，若金屬膠體沈澱設為0。將各介質之HSP(即dD、dP及dH)進行三維繪製，從金屬膠體分散之介質之HSP分布作成稱為漢森溶解球的球，將該球之中心座標設為金屬膠體的HSP。The HSP of the metal colloid is specifically determined as follows. The sediment was added to each medium of Table 1 at a concentration of 0.1% by mass, and stirred at room temperature (25 ° C) for 10 minutes by a roll type vibrator. After stirring, it was allowed to stand at room temperature (25 ° C) for 1 hour, and if the metal colloid dispersion was set to 1, the metal colloid precipitate was set to 0. The HSP (i.e., dD, dP, and dH) of each medium is three-dimensionally drawn, and a HSP distribution of a medium in which the metal colloid is dispersed is formed into a ball called Hansen's dissolution ball, and the center coordinates of the ball are set as HSP of the metal colloid.

基板(熱塑性樹脂)之HSP如下求出。將從基板(包含至少形成金屬圖案之區域(包含熱塑性樹脂之區域))切出的小片0.4g投入表1各介質2mL中，於室溫(25℃)放置24小時。然後，以目視觀察放置後之小片變化，若小片溶解或於小片產生裂紋設為1，若小片沒有變化則設為0。將各介質之HSP(即dD、dP及dH)進行三維繪製，從觀察到小片溶解或裂紋之介質之HSP分布作成稱為漢森溶解球的球，將該球之中心座標設為基板(熱塑性樹脂)的HSP。
從如此求得的分散介質及金屬膠體各自的HSP算出距離Dc(MPa^0.5 )。又，從分散介質及基板(熱塑性樹脂)各自的HSP算出距離Ds(MPa^0.5 )。The HSP of the substrate (thermoplastic resin) was determined as follows. 0.4 g of a small piece cut out from a substrate (including a region in which at least a metal pattern was formed (a region containing a thermoplastic resin)) was placed in 2 mL of each medium of Table 1, and left at room temperature (25 ° C) for 24 hours. Then, the change of the small piece after the placement was visually observed, and if the small piece was dissolved or the crack occurred in the small piece was set to 1, it was set to 0 if the small piece did not change. The HSP (ie dD, dP and dH) of each medium is three-dimensionally drawn, and the HSP distribution of the medium in which the small pieces are dissolved or cracked is formed into a ball called Hansen's dissolution ball, and the center coordinates of the ball are set as the substrate (thermoplastic). Resin) HSP.
The distance Dc (MPa ^0.5 ) was calculated from the HSP of each of the dispersion medium and the metal colloid thus obtained. Further, the distance Ds (MPa ^0.5 ) was calculated from the HSP of each of the dispersion medium and the substrate (thermoplastic resin).

熱塑性樹脂宜包含選自於由聚碳酸酯樹脂、苯乙烯樹脂及聚酯樹脂所構成群組中之至少一種。如此的熱塑性樹脂由於容易成形加工、強度亦高，故適合作為形成金屬圖案時的基材材料，但易溶解於例如利用於金屬墨的分散介質。根據本發明之上述態樣，即使於基材之上述包含熱塑性樹脂之區域塗佈金屬墨時，亦可抑制基材(具體而言熱塑性樹脂)溶解。The thermoplastic resin preferably contains at least one selected from the group consisting of polycarbonate resins, styrene resins, and polyester resins. Since such a thermoplastic resin is easy to be formed and has high strength, it is suitable as a base material for forming a metal pattern, but is easily dissolved in, for example, a dispersion medium used for a metallic ink. According to the above aspect of the invention, even when the metal ink is applied to the region of the base material containing the thermoplastic resin, the dissolution of the substrate (specifically, the thermoplastic resin) can be suppressed.

由進一步容易確保金屬膠體於金屬墨中之高穩定性之觀點，距離Dc宜為8.6MPa^0.5 以下。又，由可提高塗膜之燒結性、容易抑制金屬圖案之電阻值上升之觀點，距離Dc宜為3MPa^0.5 以上。From the viewpoint of further ensuring high stability of the metal colloid in the metallic ink, the distance Dc is preferably 8.6 MPa ^0.5 or less. Moreover, the distance Dc is preferably 3 MPa ^0.5 or more from the viewpoint of improving the sinterability of the coating film and suppressing an increase in the resistance value of the metal pattern.

距離Ds宜為15MPa^0.5 以下。此時，容易確保金屬墨對基板之高潤溼性，可抑制金屬墨於基板上被排斥。Distance Ds is suitably 15MPa ^0.5 or less. At this time, it is easy to ensure high wettability of the metal ink to the substrate, and it is possible to suppress the metallic ink from being repelled on the substrate.

金屬膠體所含金屬宜選自於由銀、銀合金、銅及銅合金所構成群組中之至少一種。此等金屬之導電性較高，適合形成配線圖案等金屬圖案。The metal contained in the metal colloid is preferably selected from at least one of the group consisting of silver, a silver alloy, copper, and a copper alloy. These metals have high conductivity and are suitable for forming metal patterns such as wiring patterns.

金屬膠體包含金屬奈米粒子及與金屬奈米粒子配位之分散劑，且金屬奈米粒子之平均粒徑宜為5nm以上且400nm以下。使用此種金屬膠體時，容易確保金屬奈米粒子於金屬墨中之高穩定性(具體而言分散穩定性)。又，由於藉由金屬奈米粒子之奈米尺寸效應，會於低於金屬熔點的溫度進行熔著，故可以較低溫燒成形成於基材上的金屬墨塗膜，容易減低所獲得的金屬圖案(金屬膜)的電阻。又，由於可以較低溫進行燒成，故亦可抑制包含熱塑性樹脂之基材因為熱所導致的劣化或變形。The metal colloid includes metal nanoparticles and a dispersant coordinated to the metal nanoparticles, and the average particle diameter of the metal nanoparticles is preferably 5 nm or more and 400 nm or less. When such a metal colloid is used, it is easy to ensure high stability (specifically, dispersion stability) of the metal nanoparticles in the metallic ink. Moreover, since the nano-size effect of the metal nano-particles is melted at a temperature lower than the melting point of the metal, the metal ink coating film formed on the substrate can be fired at a lower temperature, and the obtained metal is easily reduced. The resistance of the pattern (metal film). Further, since the firing can be performed at a relatively low temperature, deterioration or deformation due to heat due to heat of the substrate containing the thermoplastic resin can be suppressed.

金屬膠體所含分散劑宜包含C_4-16 烷基胺。此時，由於在溫和條件下亦可形成金屬膜，故可抑制包含熱塑性樹脂之基材之劣化或變形。The dispersant contained in the metal colloid preferably contains a C _4-16 alkylamine. At this time, since the metal film can be formed under mild conditions, deterioration or deformation of the substrate containing the thermoplastic resin can be suppressed.

以下，就金屬墨及其製造方法、以及具金屬圖案之基板之製造方法進行更詳細說明。Hereinafter, the metal ink, the method for producing the same, and the method of manufacturing the substrate having the metal pattern will be described in more detail.

[金屬墨]
金屬墨包含分散介質、分散於分散介質中之金屬膠體。金屬膠體通常包含金屬粒子，大多包含金屬粒子及與金屬粒子配位之分散劑。金屬墨除此等成分以外，可包含聚合反應性化合物、聚合引發劑等。又，金屬墨宜為藉由對塗佈於基材表面而形成之塗膜進行燒成而形成金屬圖案之燒成型金屬墨。[metal ink]
The metal ink contains a dispersion medium and a metal colloid dispersed in the dispersion medium. Metal colloids usually contain metal particles, and most of them contain metal particles and a dispersant coordinated to the metal particles. The metal ink may contain a polymerization reactive compound, a polymerization initiator, or the like in addition to these components. Further, the metal ink is preferably a fired metal ink in which a metal pattern is formed by firing a coating film formed on the surface of the substrate.

(金屬粒子)
關於形成金屬粒子之金屬材料，係使用金屬單體或合金等。
關於金屬單體或合金所含之金屬元素，可列舉典型金屬元素、過渡金屬元素等。關於典型金屬元素，例如可列舉：Zn、Al、Ga、In、Ge、Sn、Pb、Sb、Bi等。關於過渡金屬元素，例如可列舉：Ti、Zr、V、Cr、Mn、Fe、Ru、Co、Ni、Pd、Pt、Cu、Ag、Au等。合金宜包含二種以上此等金屬元素。關於金屬元素，宜為Al、Sn、Ti、Ni、Pt、Cu、Ag、Au等。關於金屬材料(金屬膠體所含金屬)宜為Ag、Ag合金、Cu及Cu合金，其中較佳為Ag及Ag合金。此等金屬之導電性較高，適合形成配線圖案等金屬圖案。(metal particles)
As the metal material forming the metal particles, a metal monomer or an alloy or the like is used.
As the metal element contained in the metal monomer or alloy, a typical metal element, a transition metal element, or the like can be cited. Examples of typical metal elements include Zn, Al, Ga, In, Ge, Sn, Pb, Sb, and Bi. Examples of the transition metal element include Ti, Zr, V, Cr, Mn, Fe, Ru, Co, Ni, Pd, Pt, Cu, Ag, and Au. The alloy preferably contains two or more of these metal elements. As the metal element, it is preferably Al, Sn, Ti, Ni, Pt, Cu, Ag, Au or the like. The metal material (the metal contained in the metal colloid) is preferably Ag, an Ag alloy, Cu or a Cu alloy, of which Ag and Ag alloys are preferable. These metals have high conductivity and are suitable for forming metal patterns such as wiring patterns.

金屬墨亦可包含材料不同之複數種金屬粒子。例如金屬墨亦可組合由Ag、Ag合金、Cu或Cu合金形成之第1金屬粒子、與由前述例示金屬中Ag及Cu以外之金屬單體或Ag合金及Cu合金以外合金形成之第2金屬粒子而包含。此時，第1金屬粒子佔金屬粒子整體之比率宜為80質量%以上，亦可為80質量%以上且99質量%以下、或85質量%以上且99質量%以下。The metal ink may also comprise a plurality of metal particles of different materials. For example, the metal ink may be combined with a first metal particle formed of Ag, an Ag alloy, Cu, or a Cu alloy, and a second metal formed of an alloy other than Ag and Cu, or an alloy of Ag and Cu, and an alloy other than the Cu alloy. Contained by particles. In this case, the ratio of the first metal particles to the entire metal particles is preferably 80% by mass or more, and may be 80% by mass or more and 99% by mass or less, or 85% by mass or more and 99% by mass or less.

金屬粒子之平均粒徑例如為5nm以上且1500nm以下。
金屬墨宜包含金屬奈米粒子作為金屬粒子。此種金屬墨亦被稱為金屬奈米墨。若使用包含金屬奈米粒子之金屬膠體，由於藉由金屬奈米粒子之奈米尺寸效應，可以較低溫燒成形成於基材上的金屬墨塗膜，故容易減低所獲得的金屬圖案的電阻且亦可抑制包含熱塑性樹脂之基材因熱所致的劣化或變形。金屬奈米粒子之平均粒徑可從5nm以上且小於1000nm之範圍中選擇。金屬奈米粒子之平均粒徑宜為5nm以上且500nm以下(或5nm以上且400nm以下)、較佳為5nm以上且200nm以下、或5nm以上且100nm以下。藉由使用具有如此平均粒徑之金屬奈米粒子，可提高金屬奈米粒子間之接觸，且容易以較低溫度熔著金屬奈米粒子彼此，故使用金屬奈米墨形成之金屬圖案之導電性易於提高。The average particle diameter of the metal particles is, for example, 5 nm or more and 1500 nm or less.
The metal ink preferably contains metal nanoparticles as metal particles. Such metallic inks are also known as metallic nano inks. When a metal colloid containing metal nanoparticles is used, since the metal ink coating film formed on the substrate can be baked at a lower temperature by the nano-size effect of the metal nanoparticles, it is easy to reduce the resistance of the obtained metal pattern. Further, deterioration or deformation due to heat of the substrate containing the thermoplastic resin can also be suppressed. The average particle diameter of the metal nanoparticles can be selected from the range of 5 nm or more and less than 1000 nm. The average particle diameter of the metal nanoparticles is preferably 5 nm or more and 500 nm or less (or 5 nm or more and 400 nm or less), preferably 5 nm or more and 200 nm or less, or 5 nm or more and 100 nm or less. By using the metal nanoparticles having such an average particle diameter, the contact between the metal nanoparticles can be improved, and the metal nanoparticles can be easily fused at a lower temperature, so that the metal pattern formed by using the metal nano ink is electrically conductive. Sex is easy to improve.

再者，於本說明書中所謂平均粒徑係指體積基準之粒度分布之累積體積50%中之粒徑(D50)。平均粒徑(D50)係使用雷射繞射式粒度分布測定裝置，藉由雷射繞射散射法測定。又，金屬粒子之平均粒徑亦可於金屬墨塗膜之掃描式電子顯微鏡(SEM)照片中，藉由求出與由任意選擇之複數個(例如10個)金屬粒子之外緣所包圍的區域具有相同面積之圓(相當圓)之直徑，進行平均化而算出。Incidentally, the average particle diameter in the present specification means a particle diameter (D50) of 50% of the cumulative volume of the particle size distribution based on the volume. The average particle diameter (D50) was measured by a laser diffraction particle size distribution measuring apparatus by a laser diffraction scattering method. Further, the average particle diameter of the metal particles may be obtained by scanning electron microscopy (SEM) photographs of the metallic ink coating film by enclosing the outer edges of a plurality of (for example, ten) metal particles which are arbitrarily selected. The diameter of a circle (equivalent circle) having the same area is calculated and averaged.

金屬粒子之形狀並無特別限制，可為球狀、橢圓球狀、多角柱狀、多角錐狀、扁平形狀(薄片狀、鱗片狀、小片狀等)、或與此等類似的形狀等任何形狀。由容易提高金屬粒子間之接觸之觀點，較佳為球狀、橢圓球狀、扁平形狀、或與此等類似的形狀。The shape of the metal particles is not particularly limited, and may be any of a spherical shape, an elliptical shape, a polygonal column shape, a polygonal pyramid shape, a flat shape (flaky shape, a scale shape, a small piece shape, or the like), or the like. shape. From the viewpoint of easily increasing the contact between the metal particles, a spherical shape, an elliptical shape, a flat shape, or the like is preferable.

關於金屬粒子，可使用市售者，亦可使用藉由使金屬材料蒸發而形成者。又，亦可使用於液相或氣相中利用化學反應而製作的金屬粒子。As the metal particles, those commercially available can be used, and those formed by evaporating a metal material can also be used. Further, metal particles produced by a chemical reaction in a liquid phase or a gas phase may also be used.

(分散劑)
藉由使用分散劑，可抑制金屬粒子於金屬墨中凝集，可使金屬膠體於金屬墨中穩定化。分散劑可於調製金屬墨時添加而與金屬粒子配位，但亦可於調製金屬墨之前與金屬粒子配位。分散劑可與金屬粒子一同混合並視需要進行加熱，藉此而與金屬粒子配位，亦可藉由於金屬粒子之製作過程中使用分散劑而與金屬粒子配位。(Dispersant)
By using a dispersing agent, aggregation of metal particles in the metallic ink can be suppressed, and the metal colloid can be stabilized in the metallic ink. The dispersant may be added to coordinate with the metal particles when the metal ink is prepared, but may also be coordinated to the metal particles before the metal ink is prepared. The dispersing agent may be mixed with the metal particles and heated as needed, thereby coordinating with the metal particles, or by coordinating with the metal particles by using a dispersing agent in the production of the metal particles.

關於分散劑，例如使用有機化合物，該有機化合物具有與金屬粒子配位之極性之官能基與對金屬粒子之親和性較低之有機基(例如疏水性之有機基)。關於極性之官能基，例如可列舉含雜原子之基。關於雜原子，例如可列舉：氮原子、硫原子及/或氧原子。關於極性之官能基，例如可列舉：胺基、巰基、含氧基(例如羥基(包含酚性羥基)、羰基、酯基、羧基等)等。分散劑可包含一種極性之官能基、亦可包含二種以上。As the dispersant, for example, an organic compound having an organic group having a lower affinity for a metal particle and a lower affinity for a metal particle (for example, a hydrophobic organic group) is used. Examples of the functional group of the polar group include a group containing a hetero atom. Examples of the hetero atom include a nitrogen atom, a sulfur atom, and/or an oxygen atom. Examples of the functional group of the polar group include an amine group, a mercapto group, and an oxygen-containing group (for example, a hydroxyl group (including a phenolic hydroxyl group), a carbonyl group, an ester group, a carboxyl group, etc.). The dispersing agent may contain one functional group of one polarity, and may also contain two or more types.

其中，由室溫穩定性之觀點，宜使用作為包含胺基之化合物之有機胺。有機胺可為一級胺、二級胺、三級胺中任一者。有機胺亦可為環狀胺及鏈狀胺中任一者。由容易與金屬粒子配位之觀點，宜為一級胺(尤其一級鏈狀胺)。關於有機胺，例如宜為烷基胺(正丁胺、戊胺、己胺、辛胺、癸胺、十二烷胺、十四烷胺等)。由金屬粒子之分散穩定性較高、於金屬圖案之製作過程中容易去除之觀點，較佳為C_4-16 烷基胺(例如C_4-15 烷基胺)、更佳為C_6-14 烷基胺或C_8-12 烷基胺。若使用此種胺，由於在溫和條件下亦可形成金屬膜，故可抑制包含熱塑性樹脂之基材之劣化或變形。其中，碳數較少之胺(例如C_4-10 烷基胺、較佳為C_6-10 烷基胺、更佳為C_8-10 烷基胺)由於反應性較高，故藉由低溫燒成等於溫和條件下形成金屬膜上更為有利。Among them, from the viewpoint of room temperature stability, an organic amine which is a compound containing an amine group is preferably used. The organic amine can be any of a primary amine, a secondary amine, and a tertiary amine. The organic amine may also be any of a cyclic amine and a chain amine. From the standpoint of easy coordination with metal particles, it is preferably a primary amine (especially a primary chain amine). As the organic amine, for example, an alkylamine (n-butylamine, pentylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, etc.) is preferable. From the viewpoint of high dispersion stability of the metal particles and easy removal during the production of the metal pattern, a C _4-16 alkylamine (for example, a C _4-15 alkylamine), more preferably a C _{6-14 is} preferable. Alkylamine or C _8-12 alkylamine. When such an amine is used, since a metal film can be formed under mild conditions, deterioration or deformation of the substrate containing the thermoplastic resin can be suppressed. Among them, an amine having a small carbon number (for example, a C _4-10 alkylamine, preferably a C _6-10 alkylamine, more preferably a C _8-10 alkylamine) is low in reactivity due to its high reactivity. It is more advantageous to form a metal film under firing conditions.

分散劑由於宜於金屬圖案形成過程之適當的階段去除，故宜為低分子化合物(例如分子量500以下之化合物)。The dispersant is preferably a low molecular compound (e.g., a compound having a molecular weight of 500 or less) because it is preferably removed at an appropriate stage of the metal pattern forming process.

相對於金屬粒子100質量份，金屬墨中所含分散劑(宜為與金屬粒子配位之分散劑)之量例如為0.1質量份以上且10質量份以下、較佳為0.3質量份以上且5質量份以下、更佳為0.5質量份以上且5質量份以下。分散劑量為上述範圍時，容易使金屬粒子於金屬墨中穩定化，亦容易去除分散劑。The amount of the dispersant (preferably a dispersant which is preferably coordinated to the metal particles) contained in the metallic ink is, for example, 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.3 parts by mass or more and 5 parts by mass based on 100 parts by mass of the metal particles. It is preferably 0.5 parts by mass or more and 5 parts by mass or less by mass or less. When the dispersing amount is in the above range, the metal particles are easily stabilized in the metallic ink, and the dispersing agent is easily removed.

(分散介質)
關於分散介質，係使用分散介質與金屬膠體之HSP之距離Dc為10MPa^0.5 以下、且分散介質與基材(熱塑性樹脂)之HSP之距離Ds為10MPa^0.5 以上的介質。關於上述介質，使用於室溫(25℃)下為液狀者。關於分散介質，可單獨使用一種介質，亦可組合二種以上介質而使用。於使用二種以上介質時，只要以二種以上介質之混合物之HSP之距離成為上述範圍之方式選擇介質、及/或調節各介質之比率即可。關於介質，宜為有機介質。(dispersion medium)
The dispersion medium is a medium in which the distance Dc between the dispersion medium and the HSP of the metal colloid is 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the HSP of the base material (thermoplastic resin) is 10 MPa ^0.5 or more. Regarding the above medium, it is used in a liquid state at room temperature (25 ° C). As the dispersion medium, one type of medium may be used alone or two or more types of medium may be used in combination. When two or more types of media are used, the medium may be selected and the ratio of each medium may be adjusted so that the distance between the HSPs of the mixture of two or more kinds of media is within the above range. Regarding the medium, it is preferably an organic medium.

距離Dc可為10MPa^0.5 以下(較佳為10.0MPa^0.5 以下)。若距離Dc超過10MPa^0.5 ，會大幅降低金屬膠體於金屬墨中的穩定性。距離Dc宜為9MPa^0.5 以下、較佳為8.6MPa^0.5 以下。距離Dc例如為1MPa^0.5 以上、較佳為3MPa^0.5 以上、更佳為4MPa^0.5 以上、再更佳為4.5MPa^0.5 以上或4.6MPa^0.5 以上。可將此等上限值與下限值任意地組合。若距離Dc為上述範圍時，可進而容易確保金屬膠體於金屬墨中的高穩定性。距離Dc例如亦可為1MPa^0.5 以上(或3MPa^0.5 以上)且10MPa^0.5 以下、1MPa^0.5 以上(或3MPa^0.5 以上)且10.0MPa^0.5 以下、1MPa^0.5 以上(或3MPa^0.5 以上)且9MPa^0.5 以下、1MPa^0.5 以上(或3MPa^0.5 以上)且8.6MPa^0.5 以下、4MPa^0.5 以上(或4.5MPa^0.5 以上)且10MPa^0.5 以下、4MPa^0.5 以上(或4.5MPa^0.5 以上)且10.0MPa^0.5 以下、4MPa^0.5 以上(或4.5MPa^0.5 以上)且9MPa^0.5 以下、4MPa^0.5 以上(或4.5MPa^0.5 以上)且8.6MPa^0.5 以下、4.6MPa^0.5 以上且10MPa^0.5 以下(或10.0MPa^0.5 以下)、或者4.6MPa^0.5 以上且9MPa^0.5 以下(或8.6MPa^0.5 以下)。Distance Dc can 10MPa ^0.5 or less (preferably 10.0MPa ^0.5 or less). If the distance Dc exceeds 10 MPa ^0.5 , the stability of the metal colloid in the metallic ink is greatly reduced. The distance Dc is preferably 9 MPa ^0.5 or less, preferably 8.6 MPa ^0.5 or less. For example, the above distance Dc 1MPa ^0.5, preferably 3MPa ^0.5 or more, more preferably 4MPa ^0.5 or more, and still more preferably 4.5MPa ^0.5 or more than 4.6MPa ^0.5. These upper limit values and lower limit values can be arbitrarily combined. When the distance Dc is in the above range, it is possible to further ensure high stability of the metal colloid in the metallic ink. Distance Dc or more, for example, may also be 1MPa ^0.5 (3MPa ^0.5 or more) and 10MPa ^0.5 or less, more 1MPa ^0.5 (3MPa ^0.5 or more) 10.0MPa ^0.5 and less than 1MPa ^0.5 (3MPa ^0.5 or more) and 9MPa ^0.5 or less, 1MPa ^0.5 or more ^(0.5 or more 3MPa) ^0.5 and 8.6 MPa or less, 4MPa ^0.5 or more ^(0.5 or more 4.5MPa) ^0.5 and 10 MPa or less, 4MPa ^0.5 or more ^(0.5 or more 4.5MPa) and 10.0MPa ^0.5 or less, 4MPa ^0.5 above (or 4.5MPa ^0.5 above) and 9MPa ^0.5 or less, 4MPa ^0.5 above (4.5MPa ^0.5 or more) and 8.6MPa ^0.5 or less, more 4.6MPa ^0.5 or less and 10MPa ^0.5 (10.0MPa ^0.5 or less), or more and 4.6MPa ^0.5 9MPa ^0.5 The following (or 8.6MPa ^0.5 or less).

距離Ds可為10MPa^0.5 以上(較佳為10.0MPa^0.5 以上)。距離Ds小於10MPa^0.5 時，會溶解基材之包含熱塑性樹脂之區域。距離Ds例如為20MPa^0.5 以下、較佳為15MPa^0.5 以下、更佳為13MPa^0.5 以下。距離Ds為上述範圍時，容易確保金屬墨對基板之高潤溼性，可抑制金屬墨於基板上被排斥。Distance Ds may be less than 10MPa ^0.5 (more preferably 10.0MPa ^0.5). When the distance Ds is less than 10 MPa ^0.5 , the region of the substrate containing the thermoplastic resin is dissolved. The distance Ds is, for example, 20 MPa ^0.5 or less, preferably 15 MPa ^0.5 or less, more preferably 13 MPa ^0.5 or less. When the distance Ds is in the above range, it is easy to ensure high wettability of the metal ink to the substrate, and it is possible to suppress the metallic ink from being repelled on the substrate.

關於分散介質(具體而言為上述介質)，例如只要距離Dc及Ds可滿足上述範圍即可，具體種類並無特別限定。若舉例分散介質(具體而言為上述介質)，可列舉：醇、醚、酯、酮、烴(脂環族烴、芳香族烴等)等。The dispersion medium (specifically, the above medium) may be, for example, the distances Dc and Ds may satisfy the above range, and the specific type is not particularly limited. Examples of the dispersion medium (specifically, the above medium) include alcohols, ethers, esters, ketones, hydrocarbons (alicyclic hydrocarbons, aromatic hydrocarbons, etc.).

分散介質之HSP之dD，例如為10以上且20以下、較佳為13以上且19以下、更佳為14以上且18以下。dP例如為10以下、較佳為1以上且9以下、更佳為2.5以上且8以下(例如為2.5以上且7.5以下)。dH例如為20以下、較佳為1以上且16以下、更佳為3以上且15以下。分散介質之HSP雖然不是限定於上述範圍，但各項於上述範圍時，容易取得距離Dc及Ds之平衡，容易獲得金屬粒子之高分散穩定性或基材之溶解抑制效果。The dD of the HSP of the dispersion medium is, for example, 10 or more and 20 or less, preferably 13 or more and 19 or less, and more preferably 14 or more and 18 or less. dP is, for example, 10 or less, preferably 1 or more and 9 or less, more preferably 2.5 or more and 8 or less (for example, 2.5 or more and 7.5 or less). dH is, for example, 20 or less, preferably 1 or more and 16 or less, more preferably 3 or more and 15 or less. The HSP of the dispersion medium is not limited to the above range, but when it is in the above range, the balance between the distances Dc and Ds is easily obtained, and the high dispersion stability of the metal particles or the dissolution suppressing effect of the substrate can be easily obtained.

較佳為於基材上塗佈金屬墨時可形成期望形狀之塗膜，且於塗佈後分散介質迅速揮發。由此觀點，分散介質之沸點例如為130℃以上且280℃以下、較佳為150℃以上且250℃以下。再者，於分散介質包含複數個介質時，宜至少一個介質之沸點落在上述範圍內，較佳為全部介質之沸點落在上述範圍內。It is preferred to form a coating film of a desired shape when the metal ink is coated on the substrate, and the dispersion medium is rapidly volatilized after coating. From this point of view, the boiling point of the dispersion medium is, for example, 130 ° C or more and 280 ° C or less, preferably 150 ° C or more and 250 ° C or less. Furthermore, when the dispersion medium comprises a plurality of media, it is preferred that the boiling point of at least one of the media falls within the above range, and preferably the boiling point of all the media falls within the above range.

分散介質之25℃下表面張力宜為20mN/m以上且40mN/m以下、較佳為25mN/m以上且40mN/m以下。此時，可提高金屬墨塗佈性。又，由於亦可抑制液滴過度擴展，故可形成微細的金屬圖案。
再者，於本說明書中，表面張力係使用接觸角計利用懸滴法而求出。The surface tension at 25 ° C of the dispersion medium is preferably 20 mN/m or more and 40 mN/m or less, preferably 25 mN/m or more and 40 mN/m or less. At this time, the metallic ink coating property can be improved. Further, since the droplets can be prevented from excessively expanding, a fine metal pattern can be formed.
Further, in the present specification, the surface tension is obtained by a hanging drop method using a contact angle meter.

分散介質於金屬墨中之比率宜為25質量%以上且95質量%以下，亦可為25質量%以上且90質量%以下。分散介質之比率於上述範圍時，容易使金屬墨所含金屬粒子等構成成分分散於分散介質中，容易確保良好的塗佈性。因此，金屬墨亦適合噴塗(噴墨方式等)。The ratio of the dispersion medium to the metallic ink is preferably 25% by mass or more and 95% by mass or less, and may be 25% by mass or more and 90% by mass or less. When the ratio of the dispersion medium is in the above range, constituent components such as metal particles contained in the metallic ink are easily dispersed in the dispersion medium, and it is easy to ensure good coatability. Therefore, the metallic ink is also suitable for spraying (inkjet method, etc.).

(聚合反應性化合物)
聚合反應性化合物可根據金屬墨期望的物性來選擇。只要可藉由經活化的聚合反應引發劑的作用進行聚合(亦包含交聯或硬化)而可形成高分子，可使用周知的聚合反應性化合物。關於聚合反應性化合物，可列舉高分子原料、例如單體或幾個單體連接而成之低聚物等前驅物，亦可使用硬化性樹脂(光硬化性樹脂、熱硬化性樹脂等)。(polymerizable reactive compound)
The polymerizable compound can be selected depending on the desired physical properties of the metal ink. As long as the polymer can be formed by polymerization (including crosslinking or hardening) by the action of the activated polymerization initiator, a known polymerizable compound can be used. Examples of the polymerization-reactive compound include a polymer raw material, for example, a precursor such as a monomer or an oligomer obtained by connecting a plurality of monomers, and a curable resin (photocurable resin, thermosetting resin, or the like) may be used.

關於硬化性樹脂，可列舉：環氧樹脂、丙烯酸樹脂、酚醛樹脂、矽樹脂、乙烯酯樹脂、乙烯醚樹脂、不飽和聚酯樹脂、鄰苯二甲酸二烯丙酯樹脂、聚胺酯樹脂等。
聚合性化合物可單獨使用一種，亦可組合二種以上使用。Examples of the curable resin include an epoxy resin, an acrylic resin, a phenol resin, an anthracene resin, a vinyl ester resin, a vinyl ether resin, an unsaturated polyester resin, a diallyl phthalate resin, and a polyurethane resin.
The polymerizable compounds may be used alone or in combination of two or more.

(聚合引發劑)
聚合引發劑可根據金屬墨期望的物性或聚合反應性化合物的種類等來選擇。聚合引發劑係使用藉由熱及/或光之作用而活化，進行聚合反應性化合物之聚合者，可使用周知聚合引發劑。關於聚合引發劑，例如使用自由基聚合引發劑或離子聚合引發劑等。又，關於聚合反應引發劑，亦可使用熱硬化性樹脂或光硬化性樹脂等的於硬化性樹脂使用的其他硬化劑。
聚合引起劑可單獨使用一種，亦可組合二種以上使用。(polymerization initiator)
The polymerization initiator can be selected depending on the desired physical properties of the metallic ink or the kind of the polymerization-reactive compound. The polymerization initiator is activated by the action of heat and/or light to carry out polymerization of the polymerization-reactive compound, and a known polymerization initiator can be used. As the polymerization initiator, for example, a radical polymerization initiator, an ionic polymerization initiator, or the like is used. Further, as the polymerization initiator, other curing agents used for the curable resin such as a thermosetting resin or a photocurable resin can be used.
The polymerization initiator may be used alone or in combination of two or more.

(其他)
金屬墨視需要亦可包含周知添加劑。例如金屬墨亦可包含黏結劑(樹脂黏結劑等)，金屬墨包含聚合反應性化合物及聚合引發劑時，亦可根據聚合反應性化合物的種類包含硬化促進劑、反應性稀釋劑、表面調整劑等。(other)
The metal ink may also contain well-known additives as needed. For example, the metal ink may contain a binder (resin binder, etc.), and when the metal ink contains a polymerization reactive compound and a polymerization initiator, it may contain a hardening accelerator, a reactive diluent, and a surface conditioner depending on the kind of the polymerization reactive compound. Wait.

金屬墨之25℃下黏度，例如宜為1mPa･s以上且10000mPa･s以下。由容易確保噴嘴噴出性之觀點，以噴墨方式將金屬墨塗佈於基材上時，宜將金屬墨於25℃下黏度設為3mPa･s以上且300mPa･s以下。
再者，本說明書中，黏度係使用E型黏度計以旋轉速度20rpm測定時的黏度。The viscosity at 25 ° C of the metallic ink is, for example, preferably 1 mPa·s or more and 10000 mPa·s or less. When the metallic ink is applied to the substrate by an inkjet method from the viewpoint of easily ensuring the discharge property of the nozzle, the viscosity of the metallic ink at 25 ° C is preferably 3 mPa·s or more and 300 mPa·s or less.
In the present specification, the viscosity is measured using an E-type viscometer at a rotational speed of 20 rpm.

金屬墨係塗佈於基材上於25℃經過1分鐘後、金屬墨相對於基材的接觸角宜為5°以上且30°以下、較佳為10°以上且25°以下。金屬墨由於對於基材之包含熱塑性樹脂之區域的親和性較高，故有金屬墨於基材上過度擴展之情形，但於接觸角為上述範圍時，可抑制金屬墨過度擴展。又，亦可抑制金屬墨於基材上被過度排斥。因此，容易形成精巧的金屬圖案。After the metal ink is applied to the substrate at 25 ° C for 1 minute, the contact angle of the metal ink with respect to the substrate is preferably 5° or more and 30° or less, preferably 10° or more and 25° or less. Since the metallic ink has a high affinity for the region containing the thermoplastic resin of the substrate, the metallic ink is excessively spread on the substrate. However, when the contact angle is in the above range, excessive expansion of the metallic ink can be suppressed. Further, it is also possible to suppress excessive repulsion of the metallic ink on the substrate. Therefore, it is easy to form a delicate metal pattern.

接觸角可使用接觸角計(例如共和界面科學(股)製、DM-501)從液滴的橫向測量。例如測定將金屬墨塗佈於基材上、於25℃經過1分鐘後的金屬墨相對於基材的接觸角。接觸角可使用接觸角計從橫向觀察來測量。The contact angle can be measured from the lateral direction of the droplet using a contact angle meter (e.g., Resin Interface Science, DM-501). For example, the contact angle of the metallic ink with respect to the substrate after applying the metallic ink to the substrate and passing at 25 ° C for 1 minute is measured. The contact angle can be measured from a lateral view using a contact angle meter.

金屬墨之表面張力宜為25mN/m以上且40mN/m以下、較佳為27mN/m以上且37mN/m以下。表面張力於上述範圍時，可抑制金屬墨過度擴展，且亦可抑制金屬墨被過度排斥，故有利於獲得精巧的金屬圖案。The surface tension of the metallic ink is preferably 25 mN/m or more and 40 mN/m or less, preferably 27 mN/m or more and 37 mN/m or less. When the surface tension is in the above range, excessive expansion of the metallic ink can be suppressed, and the metallic ink can be suppressed from being excessively repelled, so that it is advantageous to obtain a fine metal pattern.

如此的金屬墨，金屬膠體於金屬墨中之穩定性較高，可抑制塗佈於基材之包含熱塑性樹脂之區域上時之基材溶解。基材可於塗佈金屬墨之區域至少包含熱塑性樹脂，較佳為基材之塗佈金屬墨之區域由熱塑性樹脂形成。Such a metallic ink has high stability in the metallic ink, and can suppress dissolution of the substrate when it is applied to the region of the substrate containing the thermoplastic resin. The substrate may comprise at least a thermoplastic resin in the region where the metallic ink is applied, and preferably the region of the coated metal ink of the substrate is formed of a thermoplastic resin.

熱塑性樹脂(具體而言基材之包含熱塑性樹脂之區域部分)之HSP之dD，例如為15以上且25以下、較佳為16以上且22以下、更佳為17以上且19以下。dP例如為0以上且20以下、較佳為0以上且15以下、更佳為0以上且11以下。dH例如為1以上且23以下、較佳為1以上且15以下、更佳為1以上且7以下。此等dD、dP及dH之範圍可任意組合。熱塑性樹脂(具體而言基材之包含熱塑性樹脂之區域部分)之HSP並不限定於上述範圍，但各項於上述範圍時，容易調節距離Ds，容易獲得基材(熱塑性樹脂)之溶解抑制效果。The dD of the HSP of the thermoplastic resin (specifically, the portion of the substrate including the thermoplastic resin) is, for example, 15 or more and 25 or less, preferably 16 or more and 22 or less, more preferably 17 or more and 19 or less. dP is, for example, 0 or more and 20 or less, preferably 0 or more and 15 or less, more preferably 0 or more and 11 or less. dH is, for example, 1 or more and 23 or less, preferably 1 or more and 15 or less, more preferably 1 or more and 7 or less. The ranges of these dD, dP and dH can be arbitrarily combined. The HSP of the thermoplastic resin (specifically, the portion of the substrate containing the thermoplastic resin) is not limited to the above range, but when it is in the above range, the distance Ds is easily adjusted, and the dissolution inhibiting effect of the substrate (thermoplastic resin) is easily obtained. .

關於塗佈金屬墨之基材所含熱塑性樹脂，例如可列舉：聚碳酸酯樹脂、苯乙烯樹脂(聚苯乙烯(PS)、丙烯腈苯乙烯共聚物(AS樹脂)、丙烯腈丁二烯苯乙烯共聚物(ABS樹脂)等)、烯烴樹脂、乙烯樹脂、丙烯酸樹脂、聚縮醛樹脂、聚醯胺樹脂、聚酯樹脂(即熱塑性聚酯樹脂)、含鹵素樹脂、聚苯醚樹脂、聚伸苯硫樹脂等。關於聚酯樹脂，例如可列舉：芳香族聚酯(聚伸烷芳酯(聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等)等)等。基材可包含一種此等熱塑性樹脂、亦可包含二種以上。其中，較佳為聚碳酸酯樹脂、苯乙烯樹脂及聚酯樹脂。此等熱塑性樹脂由於容易成形加工、強度亦高，故適合作為形成金屬圖案時的基材材料，但易溶解於例如利用於金屬墨的分散介質。於本發明中，即使於基材之包含上述熱塑性樹脂之區域塗佈金屬墨時，亦可抑制基材(熱塑性樹脂)溶解。Examples of the thermoplastic resin contained in the substrate coated with the metallic ink include polycarbonate resin, styrene resin (polystyrene (PS), acrylonitrile styrene copolymer (AS resin), acrylonitrile butadiene benzene. Ethylene copolymer (ABS resin), etc., olefin resin, vinyl resin, acrylic resin, polyacetal resin, polyamide resin, polyester resin (ie thermoplastic polyester resin), halogen-containing resin, polyphenylene ether resin, poly Stretching benzene sulfur resin, etc. Examples of the polyester resin include aromatic polyesters (polyalkylene aryl esters (polyethylene terephthalate, polybutylene terephthalate, etc.)) and the like. The base material may contain one type of these thermoplastic resins, or may contain two or more types. Among them, preferred are polycarbonate resins, styrene resins, and polyester resins. Since these thermoplastic resins are easy to be formed and have high strength, they are suitable as a base material for forming a metal pattern, but are easily dissolved in, for example, a dispersion medium used for a metallic ink. In the present invention, even when a metal ink is applied to a region of the substrate containing the thermoplastic resin, dissolution of the substrate (thermoplastic resin) can be suppressed.

[金屬墨之製造方法]
金屬墨可藉由包含如下步驟之製造方法而獲得：準備分散介質之步驟，該分散介質係HSP之距離Dc為10MPa^0.5 以下，且HSP之距離Ds為10MPa^0.5 以上；及調製金屬墨之步驟，該金屬墨係使金屬膠體分散於分散介質中而成。[Method of manufacturing metal ink]
The metal ink can be obtained by a manufacturing method comprising the steps of preparing a dispersion medium, the distance Dc of the dispersion medium HSP is 10 MPa ^0.5 or less, and the distance Ds of the HSP is 10 MPa ^0.5 or more; and the step of modulating the metallic ink, The metallic ink is obtained by dispersing a metal colloid in a dispersion medium.

(分散介質之準備步驟)
於本步驟中，準備用於調製金屬墨之分散介質。具體而言，根據金屬膠體及基材之形成金屬圖案之區域所含熱塑性樹脂各自的HSP，準備距離Dc及距離Ds成為上述範圍之分散介質。例如藉由選擇分散介質之種類、及/或調節複數個分散介質之混合比，而調節距離Dc及距離Ds。又，可以距離Dc及距離Ds成為上述範圍之方式準備已確定的分散介質，亦可根據已確定的分散介質混合比混合複數種分散介質，藉此準備分散介質。(Preparation step of dispersion medium)
In this step, a dispersion medium for modulating the metallic ink is prepared. Specifically, the dispersion medium having the distance Dc and the distance Ds in the above range is prepared based on the HSP of each of the thermoplastic resin contained in the metal colloid and the region where the metal pattern is formed. The distance Dc and the distance Ds are adjusted, for example, by selecting the type of dispersion medium and/or adjusting the mixing ratio of the plurality of dispersion media. Further, the predetermined dispersion medium may be prepared such that the distance Dc and the distance Ds are within the above range, and the plurality of dispersion mediums may be mixed according to the determined dispersion medium mixing ratio, thereby preparing the dispersion medium.

藉由製造方法包含分散介質之準備步驟，可確保金屬膠體於所得金屬墨中之高穩定性，且可抑制塗佈於基材之包含熱塑性樹脂之區域上時之基材(熱塑性樹脂)溶解。By the preparation step including the dispersion medium in the production method, high stability of the metal colloid in the obtained metal ink can be ensured, and dissolution of the substrate (thermoplastic resin) when applied to the region containing the thermoplastic resin of the substrate can be suppressed.

(金屬墨之調製步驟)
於本步驟中，只要可調製金屬膠體分散於分散介質中之狀態之金屬墨即可。例如可藉由將金屬墨之構成成分(例如金屬粒子與分散介質)混合來調製金屬墨。為了使構成成分更均勻地分散，可使用周知攪拌機、混合機等。(Metal ink modulation step)
In this step, as long as the metal ink in which the metal colloid is dispersed in the dispersion medium can be prepared. The metallic ink can be prepared, for example, by mixing constituent components of the metallic ink (for example, metal particles and a dispersion medium). In order to disperse the constituent components more uniformly, a well-known agitator, a mixer, or the like can be used.

構成成分之混合順序並無特別限制。例如可將一部分成分預先混合，添加剩餘成分後進一步進行混合。各成分可一次添加，亦可分複數次添加。分散劑可於混合金屬粒子與分散介質時添加，亦可於與金屬粒子配位後與分散介質混合。添加其他成分(聚合反應性化合物、聚合引發劑及/或添加劑等)之時機亦無特別限制。The order in which the constituents are mixed is not particularly limited. For example, a part of the components may be previously mixed, and the remaining components may be added and further mixed. Each component can be added at one time or added several times. The dispersing agent may be added when the metal particles are mixed with the dispersion medium, or may be mixed with the dispersion medium after being coordinated with the metal particles. The timing of adding other components (polymerization-reactive compound, polymerization initiator, and/or additives, etc.) is also not particularly limited.

於較佳實施形態中，金屬墨之調製步驟包含以下步驟：使分散劑與金屬粒子配位而製作金屬膠體之步驟；及使金屬膠體分散於分散介質中而獲得金屬墨之步驟。In a preferred embodiment, the step of preparing the metallic ink comprises the steps of: coordinating the dispersing agent with the metal particles to form a metal colloid; and dispersing the metal colloid in the dispersion medium to obtain a metallic ink.

於製作金屬膠體之步驟中，例如可藉由將金屬粒子、分散劑及液狀介質混合而使分散劑與金屬粒子配位。視需要於本步驟中，亦可添加其他成分(添加劑(黏結劑等)等)。In the step of producing the metal colloid, for example, the dispersing agent can be coordinated to the metal particles by mixing the metal particles, the dispersing agent, and the liquid medium. Other components (additives (adhesives, etc.), etc.) may also be added in this step as needed.

關於液狀介質，較佳為將分散劑溶解之室溫(25℃)下為液狀的介質(溶劑)。關於液狀介質，可根據分散劑種類來選擇。關於液狀介質，較佳為脂肪族醇、脂肪族酯等，但並不限定於此等。液狀介質可單獨使用一種，亦可組合二種以上使用。視必要，混合亦可於加熱下進行。製成之金屬膠體可利用離心分離等與液體介質分離而回收。The liquid medium is preferably a medium (solvent) which is liquid at room temperature (25 ° C) in which the dispersing agent is dissolved. The liquid medium can be selected depending on the type of the dispersant. The liquid medium is preferably an aliphatic alcohol or an aliphatic ester, but is not limited thereto. The liquid medium may be used singly or in combination of two or more. Mixing can also be carried out under heating, as necessary. The produced metal colloid can be recovered by separation from a liquid medium by centrifugal separation or the like.

於獲得金屬墨之步驟，將金屬膠體與分散介質混合。視需要於本步驟中，亦可添加其他成分(聚合反應性化合物、聚合引發劑及/或添加劑等)。為了使金屬膠體更均勻地分散於分散介質中，於本步驟中可使用周知攪拌機、混合機等。In the step of obtaining a metallic ink, the metal colloid is mixed with a dispersion medium. Other components (polymerizable reactive compound, polymerization initiator, and/or additive, etc.) may be added in this step as needed. In order to disperse the metal colloid more uniformly in the dispersion medium, a known mixer, a mixer or the like can be used in this step.

[具金屬圖案之基材之製造方法]
具金屬圖案之基材之製造方法係具備於基材上塗佈金屬墨而形成金屬圖案之步驟。金屬圖案形成步驟可包含如下步驟：將金屬墨塗佈於基材而形成塗膜之步驟；及對塗膜進行燒成而形成金屬圖案(金屬膜)之步驟。於本發明之一態樣中，亦包含本製造方法中上述金屬墨之用途及用以塗佈於基材上而形成金屬圖案的上述金屬墨之用途。[Method of Manufacturing Substrate with Metal Pattern]
A method for producing a substrate having a metal pattern includes a step of coating a metal ink on a substrate to form a metal pattern. The metal pattern forming step may include the steps of: applying a metal ink to the substrate to form a coating film; and baking the coating film to form a metal pattern (metal film). In one aspect of the invention, the use of the metal ink in the manufacturing method and the use of the metal ink for forming a metal pattern on a substrate are also included.

如上所述，基材係於塗佈金屬墨之區域至少包含熱塑性樹脂。較佳為基材之至少塗佈金屬墨之區域由熱塑性樹脂形成。例如，基材可於塗佈金屬墨之側之表面(或主面)及其附近具備包含熱塑性樹脂之層，亦可基材整體包含熱塑性樹脂。基材可於基材之塗佈金屬墨側之表面(或主面)整體具有包含熱塑性樹脂之層，亦可於基材之塗佈金屬墨側之表面(或主面)一部分具有包含熱塑性樹脂之層。As described above, the substrate contains at least a thermoplastic resin in the region where the metallic ink is applied. Preferably, at least the region of the substrate to which the metallic ink is applied is formed of a thermoplastic resin. For example, the substrate may have a layer containing a thermoplastic resin on the surface (or main surface) on the side where the metal ink is applied, and the base material may include a thermoplastic resin as a whole. The substrate may have a layer containing a thermoplastic resin as a whole on the surface (or main surface) of the coated metal ink side of the substrate, or may have a thermoplastic resin in a part of the surface (or main surface) of the coated metal ink side of the substrate. Layer.

關於基材之包含熱塑性樹脂之層之底層材質並無特別限制，例如可列舉玻璃、矽及/或硬化樹脂等。The material of the underlayer of the layer containing the thermoplastic resin of the substrate is not particularly limited, and examples thereof include glass, enamel, and/or a cured resin.

(金屬圖案形成步驟)
(塗膜形成步驟)
於塗膜形成步驟中，於基材表面塗佈金屬墨。金屬墨之塗佈並無特別限制，可藉由周知塗佈方法(旋轉塗佈、噴塗、刮刀塗佈、網版印刷、噴墨等)進行。又，塗膜可為如配線或填充之圖案膜、亦可為平坦膜。(metal pattern forming step)
(coating film forming step)
In the coating film forming step, a metal ink is applied to the surface of the substrate. The application of the metallic ink is not particularly limited, and it can be carried out by a known coating method (spin coating, spray coating, knife coating, screen printing, inkjet, or the like). Further, the coating film may be a pattern film such as a wiring or a filling, or may be a flat film.

上述金屬墨由於金屬膠體於金屬墨中之穩定性較高，故適用於非接觸之噴塗(噴墨方式等)。再者，所謂藉由噴墨之塗佈係指非接觸之噴塗。所謂非接觸之噴塗係利用空氣壓力、彈簧彈性、壓電元件(壓電元件)之振動等將金屬墨噴至墨之被著體之塗佈方法，例如使用機械式或壓電式之非接觸噴射分配機進行塗佈。非接觸之噴塗亦適用於朝三維造型物表面形成配線圖案、或製作多層基板等。於此，所謂三維造型物指具有三維構造之電路構件之成為基材的材料。The above metal ink is suitable for non-contact spraying (inkjet method, etc.) because of the high stability of the metal colloid in the metallic ink. Further, the coating by inkjet refers to non-contact spraying. The non-contact spraying is a coating method in which a metal ink is sprayed onto an ink body by using air pressure, spring elasticity, vibration of a piezoelectric element (piezoelectric element), or the like, for example, using mechanical or piezoelectric non-contact. The spray dispenser is used for coating. Non-contact spraying is also suitable for forming a wiring pattern on a surface of a three-dimensional shaped object, or making a multilayer substrate or the like. Here, the three-dimensional shaped object refers to a material that becomes a substrate of a circuit member having a three-dimensional structure.

(乾燥步驟)
具有於塗膜形成步驟獲得之塗膜之基材，可於燒成步驟之前視需要進行乾燥。乾燥條件可視金屬墨之構成成分等而適當決定。於乾燥步驟中，宜去除揮發性成分(分散介質等)。
乾燥溫度並無特別限制，可於可去除揮發性成分之溫度下進行。乾燥溫度宜比後述燒成溫度低。(drying step)
The substrate having the coating film obtained in the coating film forming step can be dried as needed before the firing step. The drying conditions can be appropriately determined depending on the constituent components of the metallic ink and the like. In the drying step, it is preferred to remove volatile components (dispersion medium, etc.).
The drying temperature is not particularly limited and can be carried out at a temperature at which volatile components can be removed. The drying temperature is preferably lower than the firing temperature described later.

(燒成步驟)
於燒成步驟中，對具有於塗膜形成步驟獲得之塗膜之基材進行燒成。塗膜內所含金屬粒子彼此因燒成而熔著，可大幅減低所獲得金屬膜之電阻。於為金屬奈米粒子時，因為粒子之奈米尺寸效應，會於低於金屬熔點的溫度進行熔著，故即使較低溫燒成亦可獲得充分地減低金屬膜電阻之效果。(burning step)
In the baking step, the substrate having the coating film obtained in the coating film forming step is fired. The metal particles contained in the coating film are fused by firing, and the electrical resistance of the obtained metal film can be greatly reduced. When it is a metal nanoparticle, since the nanometer size effect of the particle is melted at a temperature lower than the melting point of the metal, the effect of sufficiently reducing the electrical resistance of the metal film can be obtained even at a lower temperature.

燒成可根據金屬粒子之金屬種類適當選擇，例如可於50℃以上且250℃以下進行、亦可於100℃以上且250℃以下、或150℃以上且250℃以下進行。若使用碳數較少的胺作為分散劑，即使於溫和條件下亦可形成金屬膜。此時，燒成溫度宜為150℃以下(例如50℃以上且150℃以下)、亦可為100℃以上且150℃以下。The baking can be appropriately selected depending on the kind of the metal particles, and can be carried out, for example, at 50 ° C or higher and 250 ° C or lower, or at 100 ° C or higher and 250 ° C or lower, or 150 ° C or higher and 250 ° C or lower. When an amine having a small carbon number is used as a dispersing agent, a metal film can be formed even under mild conditions. In this case, the baking temperature is preferably 150° C. or lower (for example, 50° C. or higher and 150° C. or lower), and may be 100° C. or higher and 150° C. or lower.

燒成亦可視需要於還原劑存在下進行。
燒成可於惰性氣體氛圍下進行、亦可於大氣中進行。
燒成時間並無特別限制，例如可為5分鐘以上且120分鐘以下。The firing may also be carried out in the presence of a reducing agent.
The firing can be carried out in an inert gas atmosphere or in the atmosphere.
The firing time is not particularly limited and may be, for example, 5 minutes or longer and 120 minutes or shorter.

於使用藉由熱作用而活化者作為聚合反應引發劑時，亦可藉由於乾燥步驟及/或燒成步驟給予之熱而活化、使聚合反應性化合物進行聚合。於使用藉由光作用而活化者作為聚合反應引發劑時，宜於從塗膜形成到燒成步驟之適當階段對塗膜照射光。亦可於光照射下進行乾燥步驟及/或燒成步驟。When a person activated by thermal action is used as a polymerization initiator, the polymerization-reactive compound may be polymerized by activation by heat applied in a drying step and/or a calcination step. When a person activated by light action is used as a polymerization initiator, it is preferred to irradiate the coating film with light at an appropriate stage from the formation of the coating film to the firing step. The drying step and/or the firing step can also be carried out under light irradiation.

[實施例]
以下，基於實施例及比較例具體地說明本發明，但本發明並不限定於以下實施例。[Examples]
Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

《實施例1~10及比較例1~5》
(1)製作金屬膠體
將硝酸銀20g、異丁醇100g、十二烷胺(分散劑)100g加以混合。將獲得之混合物加熱至溫度100℃為止，進行5小時回流。使用離心分離將獲得混合物中之固體成分沈降後回收。將回收的固體成分以甲醇洗淨三回後，進行離心分離，藉此回收配位有十二烷胺之銀奈米粒子。銀奈米粒子及與銀奈米粒子配位之十二烷胺之質量比為100：0.5。"Examples 1 to 10 and Comparative Examples 1 to 5"
(1) Preparation of Metal Colloid 20 g of silver nitrate, 100 g of isobutyl alcohol, and 100 g of dodecylamine (dispersant) were mixed. The obtained mixture was heated to a temperature of 100 ° C and refluxed for 5 hours. The solid components in the obtained mixture were collected by centrifugation and recovered. The recovered solid component was washed three times with methanol, and then centrifuged to recover silver nanoparticles having dodecylamine coordinated thereto. The mass ratio of the silver nanoparticles and the dodecylamine coordinated to the silver nanoparticles is 100:0.5.

使用三個輥將回收的銀奈米粒子分散於二乙二醇單丁醚中，藉此調製分散糊料。將獲得之分散糊料利用旋轉塗佈塗佈於基材，拍攝銀奈米粒子之SEM照片。利用上述方法從該拍攝圖像中算出銀奈米粒子之平均粒徑，結果為約40nm。The recovered silver nanoparticles were dispersed in diethylene glycol monobutyl ether using three rolls, thereby dispersing the dispersion paste. The obtained dispersion paste was applied to a substrate by spin coating, and an SEM photograph of silver nanoparticles was taken. The average particle diameter of the silver nanoparticles was calculated from the captured image by the above method and found to be about 40 nm.

(2)調製金屬墨
使用均質機使上述(1)回收之包含銀奈米粒子之金屬膠體分散於表2所示之分散介質後，使用網目1μm之圓盤過濾機進行過濾，調製金屬墨。金屬墨中之金屬膠體之濃度為40質量%。(2) Preparation of Metal Ink Using the homogenizer, the metal colloid containing the silver nanoparticles collected in the above (1) was dispersed in the dispersion medium shown in Table 2, and then filtered using a 1 μm mesh disk filter to prepare a metallic ink. The concentration of the metal colloid in the metal ink was 40% by mass.

(3)評價
進行以下評價。
(a)測定HSP、以及算出距離Dc及Ds
使用金屬墨按上述程序求出分散介質及金屬膠體各自的HSP。將分散介質之HSP顯示於表2。金屬膠體之HSP，dD為19.5、dP為4.1、dH為8.8。
又，對於由聚碳酸酯樹脂(帝人(股)製、Panlite L-1225Y)形成之板狀基板(基板A)及由丙烯腈苯乙烯丁二烯樹脂(UMG ABS(股)製、UMG ABS EX18A 11001)形成之板狀基板(基板B)，分別按上述程序求出各自的HSP。兩種基板均dD為18.4、dP為10.1、dH為2.4。再者，HSP計算軟體使用HSPiP 4th Edition 4.1.07。
由此等HSP算出距離Dc及Ds。(3) Evaluation The following evaluations were performed.
(a) Determination of HSP, and calculation of distances Dc and Ds
The HSP of each of the dispersion medium and the metal colloid was determined by the above procedure using a metallic ink. The HSP of the dispersion medium is shown in Table 2. The HSP of the metal colloid had a dD of 19.5, a dP of 4.1, and a dH of 8.8.
Further, a plate-like substrate (substrate A) formed of a polycarbonate resin (manufactured by Teijin Co., Ltd., Panlite L-1225Y) and an acrylonitrile styrene butadiene resin (UMG ABS (manufactured by U.S.), UMG ABS EX18A) 11001) The formed plate-shaped substrate (substrate B) was obtained for each HSP according to the above procedure. Both substrates had dD of 18.4, dP of 10.1, and dH of 2.4. Furthermore, the HSP computing software uses HSPiP 4th Edition 4.1.07.
Thus, the distances Dc and Ds are calculated by the HSP.

(b)分散穩定性
將金屬墨於25℃下保管1個月後，以目視觀察有無沈澱，以下述基準進行評價。
A：確認沒有沈澱。
B：確認有沈澱。(b) Dispersion stability After the metal ink was stored at 25 ° C for one month, the presence or absence of precipitation was visually observed, and the evaluation was carried out based on the following criteria.
A: Confirm that there is no precipitation.
B: Confirmation of precipitation.

(c)體積電阻率
使用棒塗機將金屬墨分別塗佈於基板A及基板B，藉由送風乾燥機於120℃進行30分鐘加熱燒成，藉此形成金屬圖案。對於形成的金屬圖案，使用電阻率計((股)三菱Chemical Analytech製、Loresta)利用四端子法測定體積電阻率(μΩ･cm)。
將(a)~(c)評價結果顯示於表2。(c) Volume resistivity Metal ink was applied to the substrate A and the substrate B by a bar coater, and heated and baked at 120 ° C for 30 minutes in a blow dryer to form a metal pattern. The volume resistivity (μΩ·cm) of the formed metal pattern was measured by a four-terminal method using a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Loresta).
The evaluation results of (a) to (c) are shown in Table 2.

[表2]
[Table 2]

如表2所示，HSP之距離Dc為10MPa^0.5 以下且距離Ds為10MPa^0.5 以上的實施例，可確保金屬膠體之高分散穩定性。又，體積電阻率亦降低。其原因認為是抑制了基板因金屬墨而溶解之故。As shown in Table 2, in the examples in which the distance Dc of the HSP was 10 MPa ^0.5 or less and the distance Ds was 10 MPa ^0.5 or more, the high dispersion stability of the metal colloid was ensured. Also, the volume resistivity is also lowered. The reason for this is considered to be that the substrate is inhibited from being dissolved by the metallic ink.

另一方面，HSP之距離Dc超過10MPa^0.5 之比較例1及2，於保管後之金屬墨確認到沈澱，金屬膠體之分散穩定性降低。又，距離Ds未達10MPa^0.5 之比較例3~5，體積電阻率變非常大。其原因認為係基板溶解變得顯著之故。On the other hand, in Comparative Examples 1 and 2 in which the distance Dc of the HSP exceeded 10 MPa ^0.5 , precipitation was confirmed in the metallic ink after storage, and the dispersion stability of the metal colloid was lowered. Further, in Comparative Examples 3 to 5 in which the distance Ds was less than 10 MPa ^0.5 , the volume resistivity became extremely large. The reason for this is considered to be that the dissolution of the substrate becomes remarkable.

再者，於上述實施例中雖然顯示使用包含聚碳酸酯樹脂及苯乙烯樹脂之基材之例，但若HSP之Dc及Ds為10MPa^0.5 以下，即使使用包含聚酯樹脂(例如聚對苯二甲酸丁二酯樹脂(例如Wintech Polymer公司製之Duranex2002))等其他熱塑性樹脂之基材時，確認亦可獲得與上述實施例相同或類似的效果。Further, although the above embodiments show cases of using a substrate comprising a polycarbonate resin and the styrene resin, but if the HSP and Dc Ds is 10MPa ^0.5 or less, even if containing a polyester resin (e.g. polyethylene terephthalate When a substrate of another thermoplastic resin such as a butylene formate resin (for example, Duranex 2002 manufactured by Wintech Polymer Co., Ltd.) is used, it is confirmed that the same or similar effects as those of the above examples can be obtained.

雖然對本發明當前較佳實施態樣進行了說明，但不應該對本發明揭示進行限定解釋。通過閱讀上述發明揭示，屬於本發明之技術領域中的該業者可清楚地明白各種變化及改變。因此，於不脫離本發明真實精神之範圍內，當將所附申請專利範圍解釋為包含所有變化及改變。While the presently preferred embodiments of the invention have been described, the invention Various changes and modifications will become apparent to those skilled in the <RTIgt; Therefore, the scope of the appended claims is intended to cover all modifications and alternatives

產業上之可利用性
根據本發明實施形態之金屬墨，金屬膠體之分散穩定性較高，可抑制熱塑性樹脂溶解。因此，適合於具有包含熱塑性樹脂之區域之基材上形成配線圖案等金屬圖案。又，亦可利用在對三維造型物表面形成配線圖案、或製作多層基板等。INDUSTRIAL APPLICABILITY According to the metal ink of the embodiment of the present invention, the dispersion stability of the metal colloid is high, and the dissolution of the thermoplastic resin can be suppressed. Therefore, it is suitable for forming a metal pattern such as a wiring pattern on a substrate having a region containing a thermoplastic resin. Further, a wiring pattern may be formed on the surface of the three-dimensional shaped object, or a multilayer substrate or the like may be produced.

Claims (15)

一種金屬墨，其係用以塗佈於基材上而形成金屬圖案者， 包含金屬膠體與分散介質， 前述基材中至少形成前述金屬圖案之區域包含熱塑性樹脂， 前述分散介質與前述金屬膠體之漢森溶解度參數之距離Dc為10MPa^0.5 以下， 前述分散介質與前述熱塑性樹脂之漢森溶解度參數之距離Ds為10MPa^0.5 以上。A metal ink for coating a substrate to form a metal pattern, comprising a metal colloid and a dispersion medium, wherein at least a region in which the metal pattern is formed in the substrate comprises a thermoplastic resin, the dispersion medium and the metal colloid The distance Dc of the Hansen solubility parameter is 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the Hansen solubility parameter of the thermoplastic resin is 10 MPa ^0.5 or more. 如請求項1之金屬墨，其中前述熱塑性樹脂包含選自於由聚碳酸酯樹脂、苯乙烯樹脂及聚酯樹脂所構成群組中之至少一種。The metal ink according to claim 1, wherein the thermoplastic resin comprises at least one selected from the group consisting of polycarbonate resins, styrene resins, and polyester resins. 如請求項1或2之金屬墨，其中前述距離Dc為8.6MPa^0.5 以下。The metal ink of claim 1 or 2, wherein the aforementioned distance Dc is 8.6 MPa ^0.5 or less. 如請求項1至3中任一項之金屬墨，其中前述距離Dc為3MPa^0.5 以上。The metallic ink according to any one of claims 1 to 3, wherein the aforementioned distance Dc is 3 MPa ^0.5 or more. 如請求項1至4中任一項之金屬墨，其中前述距離Ds為15MPa^0.5 以下。The metallic ink according to any one of claims 1 to 4, wherein the aforementioned distance Ds is 15 MPa ^0.5 or less. 如請求項1至5中任一項之金屬墨，其中前述分散介質之漢森溶解度參數之分散項dD為10以上且20以下，極性項dP為10以下，氫鍵項dH為20以下。The metallic ink according to any one of claims 1 to 5, wherein the dispersion term dD of the Hansen solubility parameter of the dispersion medium is 10 or more and 20 or less, the polar term dP is 10 or less, and the hydrogen bond term dH is 20 or less. 如請求項1至6中任一項之金屬墨，其中前述熱塑性樹脂之漢森溶解度參數之分散項dD為15以上且25以下，極性項dP為0以上且20以下，氫鍵項dH為1以上且23以下。The metallic ink according to any one of claims 1 to 6, wherein the dispersion term dD of the Hansen solubility parameter of the thermoplastic resin is 15 or more and 25 or less, the polar term dP is 0 or more and 20 or less, and the hydrogen bond term dH is 1. Above and below 23. 如請求項1至7中任一項之金屬墨，其中前述金屬膠體所含金屬係選自於由銀、銀合金、銅及銅合金所構成群組中之至少一種。The metal ink according to any one of claims 1 to 7, wherein the metal contained in the metal colloid is selected from at least one selected from the group consisting of silver, a silver alloy, copper, and a copper alloy. 如請求項1至8中任一項之金屬墨，其中前述金屬膠體包含金屬奈米粒子及與前述金屬奈米粒子配位之分散劑， 前述金屬奈米粒子之平均粒徑為5nm以上且400nm以下。The metal ink according to any one of claims 1 to 8, wherein the metal colloid comprises metal nanoparticles and a dispersing agent coordinated to the metal nanoparticles. The metal nanoparticles have an average particle diameter of 5 nm or more and 400 nm or less. 如請求項9之金屬墨，其中前述分散劑包含C_4-16 烷基胺。The metallic ink of claim 9, wherein the aforementioned dispersing agent comprises a C _4-16 alkylamine. 如請求項1至10中任一項之金屬墨，其中前述金屬墨中前述分散介質之比率為25質量%以上且95質量%以下。The metal ink according to any one of claims 1 to 10, wherein a ratio of the dispersion medium in the metal ink is 25% by mass or more and 95% by mass or less. 一種金屬墨之製造方法，該金屬墨係包含金屬膠體與分散介質且用以塗佈於基材上而形成金屬圖案者， 前述基材中至少形成前述金屬圖案之區域包含熱塑性樹脂； 前述金屬墨之製造方法包含以下步驟： 準備前述分散介質之步驟，前述分散介質與前述金屬膠體之漢森溶解度參數之距離Dc為10MPa^0.5 以下，且前述分散介質與前述熱塑性樹脂之漢森溶解度參數之距離Ds為10MPa^0.5 以上；及 調製金屬墨之步驟，該金屬墨係使前述金屬膠體分散於前述分散介質中而成。A metal ink system comprising a metal colloid and a dispersion medium and applied to a substrate to form a metal pattern, wherein at least a region in which the metal pattern is formed in the substrate comprises a thermoplastic resin; The manufacturing method comprises the steps of: preparing the dispersion medium, the distance Dc between the dispersion medium and the Hansen solubility parameter of the metal colloid is 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the Hansen solubility parameter of the thermoplastic resin It is 10 MPa ^0.5 or more; and the step of preparing a metallic ink in which the metal colloid is dispersed in the dispersion medium. 如請求項12之金屬墨之製造方法，其中前述熱塑性樹脂包含選自於由聚碳酸酯樹脂、苯乙烯樹脂及聚酯樹脂所構成群組中之至少一種。The method of producing a metallic ink according to claim 12, wherein the thermoplastic resin comprises at least one selected from the group consisting of a polycarbonate resin, a styrene resin, and a polyester resin. 一種具金屬圖案之基材之製造方法，其具備於基材上塗佈金屬墨而形成金屬圖案之步驟， 前述基材中至少形成前述金屬圖案之區域包含熱塑性樹脂， 前述金屬墨包含金屬膠體與分散介質， 前述分散介質與前述金屬膠體之漢森溶解度參數之距離Dc為10MPa^0.5 以下， 前述分散介質與前述熱塑性樹脂之漢森溶解度參數之距離Ds為10MPa^0.5 以上。A method for producing a substrate having a metal pattern, comprising the steps of applying a metal ink to a substrate to form a metal pattern, wherein at least a region in which the metal pattern is formed in the substrate comprises a thermoplastic resin, and the metal ink comprises a metal colloid and In the dispersion medium, the distance Dc between the dispersion medium and the Hansen solubility parameter of the metal colloid is 10 MPa ^0.5 or less, and the distance Ds between the dispersion medium and the Hansen solubility parameter of the thermoplastic resin is 10 MPa ^0.5 or more. 如請求項14之具金屬圖案之基材之製造方法，其中前述熱塑性樹脂包含選自於由聚碳酸酯樹脂、苯乙烯樹脂及聚酯樹脂所構成群組中之至少一種。A method of producing a substrate having a metal pattern according to claim 14, wherein the thermoplastic resin comprises at least one selected from the group consisting of polycarbonate resins, styrene resins, and polyester resins.