TWI695389B - Composite microparticles and dispersions, and their manufacturing methods and uses - Google Patents

Abstract

將金屬微粒之至少一部分的表面，以含有酸分解性聚合物之保護層被覆，調製成複合微粒。所得到之複合微粒可於低溫下燒結。前述複合微粒之平均粒徑可為3000nm以下。前述金屬微粒可為銅微粒。前述酸分解性聚合物可具有縮醛鍵。可藉由在該分散液中進一步添加酸性化合物及/或酸產生劑，調製成導電油墨或導電糊，並於200℃以下燒成，而製作配線基板。 At least a part of the surface of the metal fine particles is coated with a protective layer containing an acid-decomposable polymer to prepare composite fine particles. The resulting composite particles can be sintered at low temperature. The average particle diameter of the aforementioned composite fine particles may be 3000 nm or less. The aforementioned metal particles may be copper particles. The aforementioned acid-decomposable polymer may have an acetal bond. The wiring board can be produced by further adding an acidic compound and/or an acid generator to the dispersion liquid to prepare a conductive ink or a conductive paste, and firing at 200° C. or lower.

Description

複合微粒及分散液以及彼等之製造方法及用途 Composite microparticles and dispersions, and their manufacturing methods and uses

本發明係關於在微細配線(或配線圖案)等之形成上有用的複合微粒及含該複合微粒之分散液(或糊)以及彼等之製造方法及用途(油墨、塗膜、燒成膜、配線基板、電子裝置等)。 The present invention relates to composite particles useful in the formation of fine wiring (or wiring patterns), dispersion liquids (or pastes) containing the composite particles, and their manufacturing methods and uses (inks, coating films, fired films, etc.) Wiring boards, electronic devices, etc.).

先前以來，為了在電子基板等上得到微細之金屬配線圖案，研究使用含金屬微粒之分散液，並藉由印刷而形成配線圖案之方法。為了製造該金屬微粒，得到其分散液，必須防止金屬微粒之氧化及凝聚。因此，必須有將金屬微粒被覆之保護劑。在金屬微粒中，銅微粒由於導電性高，廉價，同時不易引起移行(migration)(金屬之滲出造成短路)，而在近年受到矚目，然而，其有「容易氧化，易高電阻化」的缺點。因此，為了防止銅微粒之氧化及凝聚，提出以各種保護劑被覆之銅微粒。 In the past, in order to obtain a fine metal wiring pattern on an electronic substrate or the like, a method of forming a wiring pattern by using a dispersion liquid containing metal fine particles and printing is studied. In order to produce the metal particles and obtain the dispersion liquid, it is necessary to prevent the oxidation and aggregation of the metal particles. Therefore, there must be a protective agent that coats the metal particles. Among metal particles, copper particles have high electrical conductivity, are inexpensive, and are not likely to cause migration (short circuit caused by metal leakage), and have attracted attention in recent years. However, they have the disadvantages of "easy oxidation and high resistance" . Therefore, in order to prevent the oxidation and aggregation of copper particles, copper particles coated with various protective agents have been proposed.

在日本專利第4978844號公報(專利文獻1)中，提出一種銅微粒分散液，其包含藉由水溶性高分子及羥基羧酸被覆之粒徑100nm以下之銅微粒，以及羥基羧酸、多元醇及/或極性溶劑。在此文獻中有記載：將前述分散液成膜後，於250~300℃下燒成。 Japanese Patent No. 4978844 (Patent Document 1) proposes a copper fine particle dispersion liquid comprising copper fine particles with a particle size of 100 nm or less coated with a water-soluble polymer and hydroxycarboxylic acid, and hydroxycarboxylic acid and polyol And/or polar solvents. It is described in this document that after forming the dispersion liquid into a film, it is fired at 250 to 300°C.

在日本專利第5063003號公報(專利文獻2)中，揭示一種銅奈米粒子之製造方法，其係在含有有機酸銅鹽及碳數8~16之單胺的溶液中添加還原劑，使銅金屬核形成並成長。在該文獻中，記載將所得到之含有銅奈米粒子的導電性組成物塗布於基板，並在50℃以上且小於500℃下進行熱處理，形成被覆層。 Japanese Patent No. 5063003 (Patent Document 2) discloses a method for producing copper nanoparticles, which comprises adding a reducing agent to a solution containing a copper salt of an organic acid and a monoamine having 8 to 16 carbon atoms to make copper The metal core forms and grows. In this document, it is described that the obtained conductive composition containing copper nanoparticles is applied to a substrate and heat-treated at a temperature of 50° C. or higher and less than 500° C. to form a coating layer.

在日本專利第5227828號公報(專利文獻3)中，揭示使銅源溶解於含有檸檬酸之溶劑中，生成銅離子後，添加還原劑，而製造銅奈米粒子之方法。在該文獻中，使用以前述方法所得到之耐氧化性銅奈米粒子，於400℃之加熱條件下將銅試驗片接合。 Japanese Patent No. 5227828 (Patent Document 3) discloses a method of producing copper nanoparticles by dissolving a copper source in a solvent containing citric acid, generating copper ions, and adding a reducing agent. In this document, the copper test pieces were joined under heating conditions of 400° C. using the oxidation-resistant copper nanoparticles obtained by the aforementioned method.

然而，此等文獻之銅微粒，為了使對銅之保護能力提高，使用高分子量化合物或極性高之化合物作為保護劑。因此，在以此等銅微粒形成配線圖案之情況，為將保護劑消除，必須於高溫下使其熱分解。若熱分解溫度為高溫，則其基材將被限定為玻璃或陶瓷等硬質無機材料，故而要在例如聚對苯二甲酸乙二酯(PET)等耐熱性低、柔軟之樹脂所形成的基材上形成配線圖案將變得困難。 However, the copper particles of these documents use high molecular weight compounds or highly polar compounds as protective agents in order to improve the copper's protective ability. Therefore, in the case of forming wiring patterns with such copper particles, in order to eliminate the protective agent, it is necessary to thermally decompose them at a high temperature. If the thermal decomposition temperature is high, the substrate will be limited to hard inorganic materials such as glass or ceramics. Therefore, bases formed from resins with low heat resistance and softness such as polyethylene terephthalate (PET) It becomes difficult to form wiring patterns on the material.

再者，在日本專利第5403740號公報(專利文獻4)中，揭示含有具有非環狀縮醛構造單元之樹脂、粉體及溶劑的燒成糊組成物。在此文獻中，就前述粉體而言，例示各種無機粒子及有機粒子，於實施例中，使用平均粒徑2μm之玻璃微粒、銀粉、粒徑40~70nm之碳奈米管、交聯有機粒子、平均粒徑1μm之礬土微粒、氧化 鎂。再者，實施例中，係將該糊組成物升溫至1500℃來進行燒結。 In addition, Japanese Patent No. 5403740 (Patent Document 4) discloses a fired paste composition containing a resin having a non-cyclic acetal structural unit, a powder, and a solvent. In this document, various inorganic particles and organic particles are exemplified for the aforementioned powder. In the examples, glass particles with an average particle diameter of 2 μm, silver powder, carbon nanotubes with a particle diameter of 40 to 70 nm, and crosslinked organic particles are used. Particles, alumina particles with an average particle size of 1 μm, oxidation magnesium. In the examples, the paste composition was heated to 1500°C and sintered.

然而，在此文獻中，具有縮醛構造之樹脂係作為黏合劑樹脂而摻合至組成物中，亦未記載金屬粉之粒徑。 However, in this document, a resin having an acetal structure is blended into the composition as a binder resin, and the particle size of the metal powder is not described.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第4978844號公報(請求項1、段落[0039]、實施例) [Patent Document 1] Japanese Patent No. 4978844 (Request 1, Paragraph [0039], Examples)

[專利文獻2]日本專利第5063003號公報(請求項1、段落[0023]) [Patent Document 2] Japanese Patent No. 5063003 (Request 1, Paragraph [0023])

[專利文獻3]日本專利第5227828號公報(請求項1、實施例) [Patent Document 3] Japanese Patent No. 5227828 (request item 1, example)

[專利文獻4]日本專利第5403740號公報(請求項1、段落[0002][0003][0044][0045]、實施例) [Patent Document 4] Japanese Patent No. 5403740 (Request Item 1, Paragraph [0002] [0003] [0044] [0045], Examples)

因此，本發明之目的係在於提供可於低溫下燒結之複合微粒及含該複合微粒之分散液(或糊)以及彼等之製造方法及用途(油墨、塗膜、燒成膜、配線基板、電子裝置等)。 Therefore, the object of the present invention is to provide composite particles that can be sintered at a low temperature and a dispersion liquid (or paste) containing the composite particles, as well as their manufacturing methods and uses (ink, coating film, fired film, wiring board, Electronic devices, etc.).

本發明之其他目的係在於提供不論是否含奈米大小之金屬，皆可抑制氧化或凝聚而安定性優良，同時能於200℃以下之低溫下燒結的複合微粒及含該複合 微粒之分散液以及彼等之製造方法及用途。 Another object of the present invention is to provide composite particles that can suppress oxidation or aggregation and have excellent stability regardless of whether they contain nano-sized metals or not, as well as composite particles that can be sintered at low temperatures below 200°C The dispersion of fine particles and their manufacturing methods and uses.

本發明之再一其他目的係在於提供可在可撓樹脂基板上，形成微細配線圖案等高密度導電體的複合微粒及含該複合微粒之分散液以及彼等之製造方法及用途。 Still another object of the present invention is to provide composite fine particles capable of forming high-density conductors such as fine wiring patterns on flexible resin substrates, dispersion liquids containing the composite fine particles, and their production methods and uses.

本發明之另外目的係在於提供對有機溶劑之溶解性優良的複合微粒及含該複合微粒之分散液以及彼等之製造方法及用途。 Another object of the present invention is to provide composite fine particles having excellent solubility in organic solvents, dispersion liquids containing the composite fine particles, and their production methods and uses.

本發明人等，為達成前述課題而專心檢討之結果，發現藉由將金屬微粒之表面以酸分解性聚合物被覆，則可於低溫下燒結，於是完成本發明。 The present inventors have intensively reviewed the results to achieve the above-mentioned problems, and found that by coating the surface of the metal fine particles with an acid-decomposable polymer, they can be sintered at a low temperature, and thus completed the present invention.

亦即，本發明之複合微粒係包含金屬微粒及保護層，該保護層將該金屬微粒之至少一部分表面被覆，且包含酸分解性聚合物。前述複合微粒之平均粒徑可為3000nm以下。前述金屬微粒可為銅微粒。前述酸分解性聚合物可具有縮醛鍵。前述酸分解性聚合物可為具有下述式(1)所表示之重複單元的聚合物、下述式(2)所表示之重複單元的聚合物、下述式(3)所表示之重複單元的聚合物、或下述式(4a)及(4b)所表示之二種重複單元的聚合物。 That is, the composite fine particles of the present invention include metal fine particles and a protective layer that covers at least a part of the surface of the metal fine particles and includes an acid-decomposable polymer. The average particle diameter of the aforementioned composite fine particles may be 3000 nm or less. The aforementioned metal particles may be copper particles. The aforementioned acid-decomposable polymer may have an acetal bond. The acid-decomposable polymer may be a polymer having a repeating unit represented by the following formula (1), a polymer having a repeating unit represented by the following formula (2), or a repeating unit represented by the following formula (3) Polymer or two types of repeating units represented by the following formulas (4a) and (4b).

(式中，R¹至R³，各個彼此相同或相異，表示氫原子、鹵素原子、羥基、氫過氧基、胺基、硫醇基、磺酸基或有機基，而且R¹至R³之2個以上可彼此鍵結而形成環；R⁴表示鹵素原子、羥基、氫過氧基、胺基、硫醇基、磺酸基或有機基)。 (In the formula, R ¹ to R ³ , each of which is the same as or different from each other, represents a hydrogen atom, a halogen atom, a hydroxyl group, a hydroperoxy group, an amine group, a thiol group, a sulfonic acid group, or an organic group, and R ¹ to R ^Three or more of ³ may be bonded to each other to form a ring; R ⁴ represents a halogen atom, a hydroxyl group, a hydroperoxy group, an amine group, a thiol group, a sulfonic acid group, or an organic group).

(式中，環Z表示可具有取代基，且包含作為雜原子之氧原子的飽和雜環，而且環Z可為相同之前述飽和雜環，也可為相異前述飽和雜環的組合)。 (In the formula, ring Z represents a saturated heterocyclic ring which may have a substituent and contains an oxygen atom as a hetero atom, and ring Z may be the same saturated heterocyclic ring or a combination of different saturated heterocyclic rings).

[式中，A¹表示可具有取代基之烴基、或-A²-(O-A³)_n-基(式中，A²及A³，各個彼此相同或相異，表示可具有取代基之烴基)，n為1以上之整數]。 [In the formula, A ¹ represents a hydrocarbon group which may have a substituent, or -A ² -(OA ³ ) _n -group (where A ² and A ³ are each the same or different from each other, and represent a hydrocarbon group which may have a substituent ), n is an integer of 1 or more].

[式中，A⁴表示可具有取代基之烴基、或-A⁶-(O-A⁷)_m-基(式中，A⁶及A⁷，各個彼此相同或相異，表示可具有取代基之烴基，m為1以上之整數)； A⁵表示可具有取代基之烴基、或-A⁸-(O-A⁹)_k-基(式中，A⁸及A⁹，各個彼此相同或相異，表示可具有取代基之烴基，k為1以上之整數)；A⁴及A⁵為相異的基]。 [In the formula, A ⁴ represents a hydrocarbon group which may have a substituent, or -A ⁶ -(OA ⁷ ) _m -group (where A ⁶ and A ⁷ , each of which is the same as or different from each other, represents a hydrocarbon group which may have a substituent , M is an integer of 1 or more); A ⁵ represents a hydrocarbon group which may have a substituent, or -A ⁸ -(OA ⁹ ) _k -group (where A ⁸ and A ⁹ , each of which is the same as or different from each other, means (A hydrocarbon group having a substituent, k is an integer of 1 or more); A ⁴ and A ⁵ are different groups].

在本發明中，亦包含前述複合微粒之製造方法，其包含以酸分解性聚合物將金屬微粒之至少一部分表面被覆的被覆步驟。在前述被覆步驟中，可於酸分解性聚合物存在下，將選自包含金屬氧化物、金屬鹽及金屬鹵化物之群組中的至少1種原料金屬化合物還原。前述原料金屬化合物可為選自包含氧化銅、硫酸銅、甲酸銅、乙酸銅及氯化銅之群組中的至少1種。在前述被覆步驟中，可使用肼作為還原劑。 The present invention also includes the method for producing the composite fine particles, which includes a coating step of covering at least a part of the surface of the metal fine particles with an acid-decomposable polymer. In the aforementioned coating step, at least one raw metal compound selected from the group consisting of metal oxides, metal salts, and metal halides can be reduced in the presence of an acid-decomposable polymer. The aforementioned raw metal compound may be at least one selected from the group consisting of copper oxide, copper sulfate, copper formate, copper acetate, and copper chloride. In the aforementioned coating step, hydrazine can be used as a reducing agent.

在本發明中，亦可包含分散液，其含有前述複合微粒及分散媒。前述分散媒可為有機溶劑。本發明之分散液可進一步含有酸性化合物及/或酸產生劑。本發明之分散液可進一步含有還原劑。本發明之分散液可為導電油墨或導電糊。 In the present invention, a dispersion liquid may also be included, which contains the aforementioned composite fine particles and a dispersion medium. The aforementioned dispersion medium may be an organic solvent. The dispersion liquid of the present invention may further contain an acidic compound and/or an acid generator. The dispersion of the present invention may further contain a reducing agent. The dispersion of the present invention may be conductive ink or conductive paste.

在本發明中，亦包含前述分散液之製造方法，其包含於加壓下進行分散處理之分散步驟。 The present invention also includes the aforementioned method for producing a dispersion liquid, which includes a dispersion step of performing a dispersion process under pressure.

在本發明中，亦包含塗膜之製造方法，其包含於基材上塗布前述分散液之塗布步驟。 In the present invention, a method for manufacturing a coating film is also included, which includes a coating step of coating the dispersion on the substrate.

在本發明中，亦包含燒成膜之製造方法，其包含將前述塗膜加熱，進行燒成之燒成步驟。在該方法中，燒成溫度可為200℃以下，可於惰性氣體環境下燒成。所得到之燒成膜之電阻率可為0.5Ω/□以下。在本發明 中，亦可包含使用該燒成膜作為配線基板之方法。 The present invention also includes a method for producing a fired film, which includes a firing step of heating the aforementioned coating film and firing. In this method, the firing temperature may be 200°C or lower, and firing may be performed in an inert gas environment. The resistivity of the obtained fired film may be 0.5 Ω/□ or less. In the present invention In addition, the method of using this fired film as a wiring board may also be included.

在本發明中，金屬微粒之表面係因為保護能力優良，且以可容易除去之酸分解性聚合物被覆，所以可於低溫下燒結。又，不論是否包含奈米大小之金屬，皆可抑制氧化或凝聚而安定性優良，同時能於200℃以下之低溫下燒結。又，由於金屬微粒為奈米大小，亦可調製高濃度之分散液(油墨或糊)，故能在可撓樹脂基板上，形成微細配線圖案等高密度導電體。再者，對有機溶劑之溶解性優良，尤其是包含具有前述式(3)所表示之重複單元、或前述式(4a)及(4b)所表示之二種重複單元之酸分解性聚合物的複合微粒可溶解於各種有機溶劑。 In the present invention, the surface of the metal fine particles is excellent in protection ability, and is coated with an acid-decomposable polymer that can be easily removed, so it can be sintered at a low temperature. In addition, whether it contains nano-sized metal or not, it can suppress oxidation or aggregation and has excellent stability, and at the same time, it can be sintered at a low temperature below 200°C. In addition, since the metal fine particles have a nanometer size, a high-concentration dispersion liquid (ink or paste) can also be prepared, so that a high-density conductor such as a fine wiring pattern can be formed on a flexible resin substrate. Furthermore, it is excellent in solubility in organic solvents, and particularly includes acid-decomposable polymers having a repeating unit represented by the aforementioned formula (3) or two repeating units represented by the aforementioned formulas (4a) and (4b) The composite particles can be dissolved in various organic solvents.

[第1圖]第1圖為實施例之聚合物合成例1所得到之聚合物的¹H-NMR光譜圖。 [Figure 1] Figure 1 is a ¹ H-NMR spectrum chart of the polymer obtained in Polymer Synthesis Example 1 of the examples.

[第2圖]第2圖為實施例之聚合物合成例2所得到之聚合物的¹H-NMR光譜圖。 [Figure 2] Figure 2 is a ¹ H-NMR spectrum chart of the polymer obtained in Polymer Synthesis Example 2 of the Examples.

[第3圖]第3圖為實施例之聚合物合成例3所得到之聚合物的¹H-NMR光譜圖。 [Figure 3] Figure 3 is a ¹ H-NMR spectrum chart of the polymer obtained in Polymer Synthesis Example 3 of the Examples.

[第4圖]第4圖為實施例之聚合物合成例3所得到之聚合物之TG-DTA的測定結果。 [Figure 4] Figure 4 is the measurement results of TG-DTA of the polymer obtained in Polymer Synthesis Example 3 of the Examples.

[第5圖]第5圖為實施例之複合微粒合成例1所得到之複合微粒的掃描型電子顯微鏡(SEM)照片(50000倍)。 [Figure 5] Figure 5 is a scanning electron microscope (SEM) photograph (50,000 times) of the composite particles obtained in the composite particle synthesis example 1 of the example.

[第6圖]第6圖為實施例之複合微粒合成例2所得到 之複合微粒的掃描型電子顯微鏡(SEM)照片(50000倍)。 [Fig. 6] Fig. 6 is obtained by the composite particle synthesis example 2 of the example Scanning electron microscope (SEM) photograph of the composite particles (50,000 times).

[第7圖]第7圖為實施例之複合微粒合成例3所得到之複合微粒的掃描型電子顯微鏡(SEM)照片(25000倍)。 [Fig. 7] Fig. 7 is a scanning electron microscope (SEM) photograph (25,000 times) of the composite particles obtained in the composite particle synthesis example 3 of the example.

[第8圖]第8圖為實施例之複合微粒合成例3所得到之複合微粒的X射線繞射圖。 [Figure 8] Figure 8 is an X-ray diffraction diagram of the composite particles obtained in the composite particle synthesis example 3 of the embodiment.

[第9圖]第9圖為實施例1所得到之塗膜及燒成膜的X射線繞射圖。 [Figure 9] Figure 9 is an X-ray diffraction diagram of the coating film and the fired film obtained in Example 1.

[第10圖]第10圖為實施例2所得到之塗膜及燒成膜的X射線繞射圖。 [Figure 10] Figure 10 is an X-ray diffraction diagram of the coating film and the fired film obtained in Example 2.

[第11圖]第11圖為實施例3所得到之塗膜及燒成膜的X射線繞射圖。 [Figure 11] Figure 11 is an X-ray diffraction diagram of the coating film and the fired film obtained in Example 3.

[實施發明之形態] [Forms for carrying out the invention]

本發明之複合微粒包含金屬微粒，及將該金屬微粒之至少一部分表面被覆的保護層。 The composite particles of the present invention include metal particles and a protective layer covering at least a part of the surface of the metal particles.

[金屬微粒] [Metal particles]

就構成金屬微粒之金屬而言，可列舉如：過渡金屬(例如，鈦、鋯等周期表第4A族金屬；釩、鈮等周期表第5A族金屬；鉬、鎢等周期表第6A族金屬；錳等周期表第7A族金屬；鐵、鎳、鈷、釕、銠、鈀、錸、銥、鉑等周期表第8族金屬；銅、銀、金等周期表第1B族金屬等)、周期表第2B族金屬(例如，鋅、鎘等)、周期表第3B族金屬(例如，鋁、鎵、銦等)、周期表第4B族金屬(例如，鍺、錫、鉛等)、周期表第5B族金屬(例如，銻、鉍等)等。金屬微粒可為以此等合金所形成之微粒，亦可為複數種 金屬微粒之組合。 Examples of metals constituting the metal particles include transition metals (eg, Group 4A metals of the periodic table such as titanium and zirconium; Group 5A metals of the periodic table such as vanadium and niobium; Group 6A metals of the periodic table such as molybdenum and tungsten ; Group 7A metals of the periodic table such as manganese; Group 8 metals of the periodic table such as iron, nickel, cobalt, ruthenium, rhodium, palladium, rhenium, iridium, platinum; Group 1B metals of the periodic table such as copper, silver, gold, etc.), Group 2B metals of the periodic table (eg, zinc, cadmium, etc.), Group 3B metals of the periodic table (eg, aluminum, gallium, indium, etc.), Group 4B metals of the periodic table (eg, germanium, tin, lead, etc.), periodic Table Group 5B metals (for example, antimony, bismuth, etc.), etc. The metal particles may be particles formed from these alloys, or a plurality of types Combination of metal particles.

在此等金屬微粒中，從導電性優良之觀點而言，以銅、銀、金等周期表第1B族金屬個體所形成的微粒為較佳，從不易引起移行(migration)，經濟性亦優良之觀點而言，以銅微粒為特佳。 Among these metal particles, from the viewpoint of excellent conductivity, particles formed of Group 1B metals of the periodic table, such as copper, silver, and gold, are preferred, since migration is unlikely to occur, and the economy is also excellent. From a viewpoint, copper particles are particularly preferred.

就金屬微粒之形狀而言，無特別限定，可列舉：球狀、橢圓體狀、多角體形(多角錘狀、正方體狀、直方體狀等)、板狀、棒狀、不定形狀等。其中，從分散性等優良之觀點而言，以略球狀等之等方形狀為較佳。 The shape of the metal fine particles is not particularly limited, and examples thereof include a spherical shape, an ellipsoid shape, a polygonal shape (polygonal hammer shape, cube shape, cuboid shape, etc.), a plate shape, a rod shape, and an indefinite shape. Among them, from the viewpoint of excellent dispersibility and the like, a substantially spherical shape or the like is preferred.

金屬微粒可為平均粒徑(數量平均一次粒徑)3000nm以下。尤其，金屬微粒之平均粒徑，以奈米大小為較佳，例如約1~1000nm，更佳為約10~500nm(例如20~400nm)，進一步更佳為約30~300nm(特佳為50~200nm)。若金屬微粒之粒徑過大，則用於使其燒結之燒成溫度變高，恐怕微細配線圖案之形成亦變得困難。另一方面，若過小，除調製變得困難之外，由於比表面積增大，恐怕變得容易氧化，同時再分散於糊或油墨等亦變得困難。再者，恐怕藉由彼等之複合因素而使導電性提高亦變得困難。 The metal fine particles may have an average particle diameter (number average primary particle diameter) of 3000 nm or less. In particular, the average particle size of the metal fine particles is preferably a nano size, for example, about 1 to 1000 nm, more preferably about 10 to 500 nm (for example, 20 to 400 nm), and even more preferably about 30 to 300 nm (particularly 50 ~200nm). If the particle diameter of the metal fine particles is too large, the firing temperature for sintering thereof becomes high, and it may become difficult to form fine wiring patterns. On the other hand, if it is too small, in addition to the difficulty in preparation, the increase in specific surface area may make it easy to oxidize, and it also becomes difficult to redisperse in paste or ink. Furthermore, it may become difficult to improve the conductivity by their combined factors.

在本發明中，金屬微粒之平均粒徑，可藉由使用掃描型電子顯微鏡(SEM)之圖像解析等的方法來測定。 In the present invention, the average particle diameter of the metal fine particles can be measured by a method such as image analysis using a scanning electron microscope (SEM).

[保護層] [The protective layer]

保護層包含酸分解性聚合物，該聚合物具有易被酸分解之特性。該酸分解性聚合物雖亦可在酸未存在下藉 由既定溫度之熱而分解，然而在酸存在下更能使分解性提高。具有此種特性之酸分解性聚合物，只要可使用於燒結金屬微粒之燒成溫度降低的聚合物即可，可列舉如：具有酯鍵、碳酸酯鍵、胺基甲酸酯鍵、縮醛鍵等之聚合物(polymer)等。在此等聚合物中，從酸分解性優良之觀點而言，以具有縮醛鍵之聚合物為較佳。尤其，就構成聚合物之主鏈的重複單元來說，若具有縮醛鍵(縮醛構造)，則可藉由與酸反應而容易分解。此種縮醛構造，由於對熱、光、還原劑等酸以外的通常刺激(粒子合成條件中之條件)而言為安定，所以形成保護層之聚合物，在酸不存在下具有高安定性。具有縮醛鍵之酸分解性聚合物可為具有前述式(1)所表示之重複單元的聚合物[聚合物(1)]、具有前述式(2)所表示之重複單元的聚合物[聚合物(2)]、具有前述式(3)所表示之重複單元的聚合物[聚合物(3)]、或具有前述式(4a)及(4b)所表示之二種重複單元的聚合物[聚合物(4)]。 The protective layer contains an acid-decomposable polymer, which has the property of being easily decomposed by acid. The acid-decomposable polymer can also be borrowed in the absence of acid Decomposition by heat at a predetermined temperature, but in the presence of acid can improve the decomposition. The acid-decomposable polymer having such characteristics may be any polymer that can reduce the firing temperature of the sintered metal fine particles, and examples thereof include ester bonds, carbonate bonds, urethane bonds, and acetals. Polymers such as bonds. Among these polymers, a polymer having an acetal bond is preferable from the viewpoint of excellent acid decomposability. In particular, if the repeating unit constituting the main chain of the polymer has an acetal bond (acetal structure), it can be easily decomposed by reacting with an acid. This acetal structure is stable to general stimuli other than acids such as heat, light, and reducing agents (conditions in particle synthesis conditions), so the polymer forming the protective layer has high stability in the absence of acid . The acid-decomposable polymer having an acetal bond may be a polymer having a repeating unit represented by the aforementioned formula (1) [Polymer (1)], or a polymer having a repeating unit represented by the aforementioned Formula (2) [polymerization (2)], a polymer having a repeating unit represented by the aforementioned formula (3) [Polymer (3)], or a polymer having two repeating units represented by the aforementioned formulas (4a) and (4b) [ Polymer (4)].

(聚合物(1)) (Polymer (1))

在前述式(1)之R¹~R⁴中，就鹵素原子而言，可列舉如氟原子、氯原子、溴原子、碘原子等。 In R ¹ to R ⁴ of the aforementioned formula (1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

就R¹~R⁴中之有機基而言，只要含有碳原子之基即可，無特別限定，可列舉如：可具有取代基之烴基、烷氧基、烯氧基、芳氧基、芳烷氧基、醯基、醯氧基、烷硫基、烯硫基、芳硫基、芳烷硫基、羧基、烷氧羰基、芳氧羰基、芳烷氧羰基、環氧基、含有環氧基之基、氧雜環丁基、含有氧雜環丁基之基、氰基、異氰酸 基、胺甲醯基、異硫氰酸基、取代胺基等。 The organic group in R ¹ to R ⁴ is not particularly limited as long as it contains a carbon atom, and examples include hydrocarbon groups, alkoxy groups, alkenyloxy groups, aryloxy groups, and aromatic groups that may have substituents. Alkoxy, acyl, acyloxy, alkylthio, alkenylthio, arylthio, aralkylthio, carboxyl, alkoxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, epoxy, epoxy-containing Group, oxetanyl group, oxetanyl group-containing group, cyano group, isocyanate group, amine group, isothiocyanate group, substituted amine group, etc.

就烴基而言，可列舉如：脂肪族烴基、脂環式烴基、芳香族烴基、彼等之2個以上鍵結而成的基等。 Examples of the hydrocarbon group include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, groups in which two or more of them are bonded, and the like.

就脂肪族烴基而言，可列舉如：烷基、烯基、炔基。就烷基而言，可列舉如：甲基、乙基、丙基、異丙基、丁基、己基、辛基、異辛基、癸基、十二烷基等C_1-20烷基(較佳為C_1-10烷基，更佳為C_1-4烷基)等。就烯基而言，可列舉如：乙烯基、烯丙基、甲基烯丙基、1-丙烯基、異丙烯基、丁烯基、戊烯基、己烯基等C_2-20烯基(較佳為C_2-10烯基，更佳為C_2-4烯基)等。就炔基而言，可列舉如：乙炔基、丙炔基等C_2-20炔基(較佳為C_2-10炔基，更佳為C_2-4炔基)等。 Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. Examples of alkyl groups include C _1-20 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, decyl, and dodecyl. It is preferably C _1-10 alkyl, more preferably C _1-4 alkyl) and the like. Examples of alkenyl groups include C _2-20 alkenyl groups such as vinyl, allyl, methallyl, 1-propenyl, isopropenyl, butenyl, pentenyl, and hexenyl. (Preferably C _2-10 alkenyl, more preferably C _2-4 alkenyl) and the like. Examples of the alkynyl group include C _2-20 alkynyl groups (preferably C _2-10 alkynyl groups, more preferably C _2-4 alkynyl groups) such as ethynyl groups and propynyl groups.

就脂環式烴基而言，可列舉如：環丙基、環丁基、環戊基、環己基、環十二烷基等C_3-12環烷基(尤其C_5-8環烷基)；環己烯基等C_3-12環烯基；雙環庚基、雙環庚烯基等C_4-15交聯環式烴基等。 Examples of the alicyclic hydrocarbon group include C _3-12 cycloalkyl groups (especially C _5-8 cycloalkyl groups) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclododecyl groups. ; C _3-12 cycloalkenyl such as cyclohexenyl; C _4-15 crosslinked cyclic hydrocarbon groups such as bicycloheptyl, bicycloheptenyl, etc.

就芳香族烴基而言，可列舉如：苯基、萘基等C_6-14芳基(尤其是C_6-10芳基)等。 Examples of the aromatic hydrocarbon group include C _6-14 aryl groups (especially C _6-10 aryl groups) such as phenyl and naphthyl.

再者，就烴基而言，可列舉如：環己基甲基、甲基環己基等脂肪族烴基與脂環式烴基鍵結而成之基；苄基、苯乙基等C_7-18芳烷基(尤其C_7-10芳烷基)；桂皮基等C_6-10芳基-C_2-6烯基；甲苯基等經C_1-4烷基取代之芳基、苯乙烯基等經C_2-4烯基取代之芳基等脂肪族烴基與芳香族烴基鍵結而成之基等。 In addition, the hydrocarbon group includes, for example, a group in which an aliphatic hydrocarbon group such as cyclohexylmethyl and methylcyclohexyl is bonded to an alicyclic hydrocarbon group; a C _{7-18 arane} such as benzyl and phenethyl Group (especially C _7-10 aralkyl group); C _6-10 aryl-C _2-6 alkenyl group such as cinnamyl group; aryl group substituted with C _1-4 alkyl group such as tolyl group, etc. _2-4 Alkenyl substituted aryl groups and other aliphatic hydrocarbon groups are bonded to aromatic hydrocarbon groups and the like.

就烷氧基而言，可列舉如：甲氧基、乙氧基 、丙氧基、異丙氧基、丁氧基、異丁氧基等C_1-10烷氧基(較佳為C_1-6烷氧基，更佳為C_1-4烷氧基)等。就烯氧基而言，可列舉如：烯丙氧基等C_2-10烯氧基(較佳為C_2-6烯氧基，更佳為C_2-4烯氧基)。就芳氧基而言，可列舉如：苯氧基、甲苯氧基、萘氧基等C_6-20芳氧基(尤其C_6-14芳氧基)等。再者，芳氧基在芳香環上可具有C_1-4烷基、C_2-4烯基、鹵素原子、C_1-4烷氧基等取代基。就芳烷氧基而言，可列舉如：苄氧基、苯乙氧基等C_6-20芳烷氧基(尤其是C_7-18芳烷氧基)等。 Examples of alkoxy groups include C _1-10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups (preferably C _{1 -6} alkoxy, more preferably C _1-4 alkoxy) and the like. Examples of alkenyloxy groups include C _2-10 alkenyloxy groups such as allyloxy groups (preferably C _2-6 alkenyloxy groups, and more preferably C _2-4 alkenyloxy groups). Examples of the aryloxy group include C _6-20 aryloxy groups (particularly C _6-14 aryloxy groups) such as phenoxy, tolyloxy, and naphthoxy. Furthermore, the aryloxy group may have a substituent such as C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, and C _1-4 alkoxy group on the aromatic ring. Examples of aralkoxy groups include C _6-20 aralkoxy groups (especially C _7-18 aralkoxy groups) such as benzyloxy and phenethoxy groups.

就醯基而言，可列舉如：乙醯基、丙醯基、(甲基)丙烯醯基、苄醯基等C_1-20醯基(尤其C_1-12醯基)等。就醯氧基而言，可列舉如：乙醯氧基、丙醯氧基、(甲基)丙烯醯氧基、苄醯氧基等C_1-20醯氧基(尤其C_1-12醯氧基)等。 Examples of the acyl group include C _1-20 acyl group (especially C _1-12 acyl group) such as ethyl acyl group, propionyl group, (meth)acryl acyl group, and benzyl acyl group. As for the acyloxy group, for example, C _1-20 acyloxy (especially C _1-12 acyloxy) such as acetoxy, propoxy, (meth)acryloyloxy, benzyloxy, etc. Base) etc.

就烷硫基而言，可列舉如：甲硫基、乙硫基等C_1-6烷硫基(尤其C_1-4烷硫基)等。就烯硫基而言，可列舉如：烯丙硫基等C_2-6烯硫基(尤其C_2-4烯硫基)等。就芳硫基而言，可列舉如：苯硫基、甲苯硫基、萘硫基等C_6-20芳硫基(尤其是C_6-14芳硫基)等。再者，芳硫基亦可在芳香環上具有C_1-4烷基、C_2-4烯基、鹵素原子、C_1-4烷氧基等取代基。就芳烷硫基而言，可列舉如：苄硫基、苯乙硫基等C_6-20芳烷硫基(尤其C_7-18芳烷硫基)等。 Examples of the alkylthio group include C _1-6 alkylthio groups (especially C _1-4 alkylthio groups) such as methylthio and ethylthio. Examples of the alkenylthio group include C _2-6 alkenylthio groups (especially C _2-4 alkenylthio groups) such as allylthio groups. Examples of the arylthio group include C _6-20 arylthio groups (especially C _6-14 arylthio groups) such as phenylthio, tolylthio, and naphthylthio. Furthermore, the arylthio group may have substituents such as C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, and C _1-4 alkoxy group on the aromatic ring. Examples of the aralkylthio group include C _6-20 aralkylthio groups (especially C _7-18 aralkylthio groups) such as benzylthio and phenethylthio.

就烷氧羰基而言，可列舉如：甲氧基羰基、乙氧基羰基、丙氧基羰基、丁氧基羰基等C_1-10烷氧羰基(尤其是C_1-6烷氧基-羰基)等。就芳氧羰基而言，可列舉如 苯氧基羰基、甲苯氧基羰基、萘氧基羰基等C_6-20芳氧基-羰基(尤其是C_6-14芳氧基-羰基)等。就芳烷氧羰基而言，可列舉如：苄氧基羰基等C_6-20芳烷氧基-羰基(尤其是C_7-18芳烷氧基-羰基)等。 Examples of alkoxycarbonyl groups include C _1-10 alkoxycarbonyl groups (especially C _1-6 alkoxy-carbonyl groups) such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and butoxycarbonyl. )Wait. Examples of the aryloxycarbonyl group include C _6-20 aryloxy-carbonyl groups (particularly C _6-14 aryloxy-carbonyl groups) such as phenoxycarbonyl group, tolyloxycarbonyl group, and naphthoxycarbonyl group. Examples of the aralkyloxycarbonyl group include C _6-20 aralkoxy-carbonyl groups (particularly C _7-18 aralkoxy-carbonyl groups) such as benzyloxycarbonyl.

就含有環氧基之基而言，可列舉如：縮水甘油基、縮水甘油基氧基等。就含有氧雜環丁基之基而言，可列舉如：乙基氧雜環丁氧基等C_1-10烷基-氧雜環丁氧基等。 Examples of the epoxy group-containing group include glycidyl group and glycidyloxy group. Examples of the oxetanyl group-containing group include C _1-10 alkyl-oxetanyloxy groups such as ethyl oxetanyloxy group.

就取代胺基而言，可列舉如：甲基胺基、乙基胺基、二甲基胺基、二乙基胺基等單或二烷基胺基(尤其是單或二-C_1-6烷基胺基)、乙醯基胺基、丙醯基胺基、苄醯基胺基等之醯基胺基(尤其C_1-11醯基胺基)等。 Examples of substituted amine groups include mono- or di-alkyl amine groups (especially mono- or di-C _1- groups such as methyl amine group, ethyl amine group, dimethyl amine group, and diethyl amine group). ₆ alkylamino groups), acetylamino groups, propylamino groups, benzylamino groups, etc. (especially C _1-11 acylamino groups) and the like.

有機基(尤其是烴基)亦可具有取代基，就取代基而言，可列舉前述之基，例如，鹵素原子(例如，氟等)、側氧基、羥基、氫過氧基、羰基、羧基、烷氧基、烯氧基、芳氧基、芳烷氧基、醯基、醯氧基、硫醇基、烷硫基、烯硫基、芳烷硫基、烷氧羰基、芳氧羰基、芳烷氧羰基、環氧基、含有環氧基之基、氧雜環丁基、含有氧雜環丁基之基、氰基、異氰酸基、胺甲醯基、異硫氰酸基等。取代基可為2個以上取代基經由C_1-6伸烷基鍵結而成之基。 The organic group (especially a hydrocarbon group) may have a substituent, and the substituent may include the aforementioned groups, for example, a halogen atom (for example, fluorine, etc.), a pendant oxygen group, a hydroxyl group, a hydroperoxy group, a carbonyl group, a carboxyl group , Alkoxy, alkenyloxy, aryloxy, aralkoxy, acetyl, acetyl, thiol, alkylthio, alkenylthio, aralkylthio, alkoxycarbonyl, aryloxycarbonyl, Aralkyloxycarbonyl group, epoxy group, epoxy group-containing group, oxetanyl group, oxetanyl group-containing group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, etc. . The substituent may be a group in which two or more substituents are bonded through C _1-6 alkylene.

在式(1)中，R¹~R³雖可2個以上互相鍵結而形成環，然而通常多為1價之基。就R¹及R²而言，以直鏈或分枝鏈狀之C_1-6烷基為較佳，以甲基等C_1-3烷基(尤其是甲基)為特佳。就R³而言，以氫原子、直鏈或分枝鏈狀 之C_1-6烷基為較佳，以氫原子為特佳。另一方面，R⁴為例示之1價基，以直鏈或分枝鏈狀之C_1-6烷基為較佳，以甲基等C_1-3烷基(尤其是甲基)為特佳。 In formula (1), although R ¹ to R ³ may be bonded to each other to form a ring, it is usually a monovalent group. R ¹ and R ² are preferably linear or branched C _1-6 alkyl groups, and particularly preferably C _1-3 alkyl groups (especially methyl groups) such as methyl groups. As for R ³ , a hydrogen atom, a linear or branched C _1-6 alkyl group is preferred, and a hydrogen atom is particularly preferred. On the other hand, R ^{4 is} an exemplified monovalent group, preferably a linear or branched C _1-6 alkyl group, and a C _1-3 alkyl group (especially a methyl group) such as a methyl group as a special group good.

聚合物(1)[具有式(1)所表示之重複單元的聚合物(1)]，可將用於形成式(1)所表示之重複單元之單體，即包含環氧乙烷化合物的單體予以陽離子聚合而得到。聚合物(1)之構造無特別限定，可為直鏈型、分枝鏈型、星型等任一種構造。 Polymer (1) [Polymer (1) having a repeating unit represented by formula (1)] can be used to form the monomer of the repeating unit represented by formula (1), that is, a compound containing an ethylene oxide compound The monomer is obtained by cationic polymerization. The structure of the polymer (1) is not particularly limited, and may be any structure such as a linear chain, a branched chain, or a star.

聚合物(1)可為均聚合物，亦可為共聚合物。共聚合物可為將式(1)所表示之重複單元以複數種(二種以上)組合而成的共聚合物，亦可為式(1)所表示之重複單元與其他共聚合性單體(具有其他陽離子聚合性之單體)所形成之重複單元的共聚合物。再者，共聚合物可為無規共聚合物，亦可為嵌段共聚合物。 The polymer (1) may be a homopolymer or a copolymer. The copolymer may be a copolymer obtained by combining the repeating units represented by formula (1) in plural (two or more), or may be a repeating unit represented by formula (1) and other copolymerizable monomers (Monomers with other cationic polymerizability) Copolymers of repeating units formed. Furthermore, the copolymer may be a random copolymer or a block copolymer.

就其他共聚合性單體而言，可列舉如乙烯基醚化合物、環狀醚化合物、苄醛化合物、α-烯烴化合物、鏈狀共軛二烯化合物、具有五員環以上之環構造的烯烴系烴、環戊二烯化合物、環狀烯烴化合物、環狀共軛二烯化合物、含有雜環之乙烯基化合物、具有乙烯性不飽和鍵之矽烷化合物、內酯化合物等。此等單體可單獨或將二種以上組合而使用。具體而言，此等其他共聚合性單體，可為例如日本特開2013-237755號公報所記載之其他共聚合性單體。 Examples of other copolymerizable monomers include vinyl ether compounds, cyclic ether compounds, benzaldehyde compounds, α-olefin compounds, chain conjugated diene compounds, and olefins having a ring structure of five or more members. Hydrocarbons, cyclopentadiene compounds, cyclic olefin compounds, cyclic conjugated diene compounds, heterocyclic-containing vinyl compounds, silane compounds having ethylenic unsaturated bonds, lactone compounds, etc. These monomers can be used alone or in combination of two or more. Specifically, these other copolymerizable monomers may be, for example, other copolymerizable monomers described in Japanese Patent Laid-Open No. 2013-237755.

在聚合物(1)中，式(1)所表示之重複單元之比率可為50莫耳%以上(例如70~100莫耳%)，例如，80莫 耳%以上(例如80~100莫耳%)，較佳為90莫耳%以上(例如90~100莫耳%)，更佳為95莫耳%以上(尤其是99莫耳%以上)。若重複單元(1)之比率過少，恐怕藉由酸將聚合物分解後之殘餘物的處理將變得繁雜。 In the polymer (1), the ratio of the repeating unit represented by the formula (1) may be 50 mol% or more (eg, 70 to 100 mol%), for example, 80 mol Ear% or more (for example, 80-100 mole %), preferably 90 mole% or more (eg, 90-100 mole %), more preferably 95 mole% or more (especially 99 mole% or more). If the ratio of the repeating unit (1) is too small, it is feared that the treatment of the residue after decomposition of the polymer by acid will become complicated.

聚合物(1)之末端構造，無特別限定，可列舉如：由來自陽離子聚合反應之起始物(例如，乙烯基醚之鹵化氫化物等)之原子團所構成的末端構造、由來自聚合終止劑之原子團所構成的末端構造等。又，聚合物(1)之末端基，在聚合反應從質子開始之情況，可為藉由系統中之雜質、轉移反應等所形成的羥基等。 The terminal structure of the polymer (1) is not particularly limited, and examples include a terminal structure composed of atomic groups derived from a starting material of cationic polymerization reaction (for example, halogenated hydride of vinyl ether, etc.), and a termination structure derived from polymerization The terminal structure constituted by the atomic group of the agent. In addition, the terminal group of the polymer (1) may be a hydroxyl group formed by impurities in the system, a transfer reaction, or the like when the polymerization reaction starts from a proton.

聚合物(1)之數量平均分子量(Mn)，可為例如藉由GPC法(凝膠滲透層析法)測定時，以聚苯乙烯換算，為約2000以上，例如約2000~100000，較佳為約2500~50000，更佳為約3000~15000。若數量平均分子量過小，則恐怕對金屬微粒之保護能力降低，或分解前之聚合物的耐熱性或機械強度變得不足。另一方面，若過大，則恐怕聚合物之生產性降低，或溶解性不足，操作變得困難。 The number average molecular weight (Mn) of the polymer (1) can be, for example, measured by GPC (gel permeation chromatography), converted to polystyrene, and is about 2000 or more, for example, about 2000 to 100,000, preferably It is about 2,500 to 50,000, more preferably about 3,000 to 15,000. If the number-average molecular weight is too small, there is a fear that the protection capacity for metal fine particles is reduced, or the heat resistance or mechanical strength of the polymer before decomposition becomes insufficient. On the other hand, if it is too large, the productivity of the polymer may decrease, or the solubility may be insufficient, making handling difficult.

聚合物(1)之分子量分布[重量平均分子量(Mw)/數量平均分子量(Mn)]為例如約1.3以下(例如1.0~1.3)，較佳為約1.25以下(例如1.02~1.25)，更佳為約1.2以下(例如1.05~1.20)。若分子量分布過大，則恐怕複合微粒之粒徑之分布變大，或分解前之聚合物的耐熱性或機械強度變得不足。再者，聚合物之分子量分布亦可藉由例如GPC法，並以聚苯乙烯換算而計算出。 The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the polymer (1) is, for example, about 1.3 or less (for example, 1.0 to 1.3), preferably about 1.25 or less (for example, 1.02 to 1.25), more preferably It is about 1.2 or less (for example, 1.05 to 1.20). If the molecular weight distribution is too large, the particle size distribution of the composite fine particles may become large, or the heat resistance or mechanical strength of the polymer before decomposition may become insufficient. In addition, the molecular weight distribution of the polymer can also be calculated by polystyrene conversion by, for example, the GPC method.

聚合物(1)可依照慣用之陽離子聚合來製造，例如，可依照日本特開2013-237755號公報記載之製造方法進行製造。 The polymer (1) can be produced in accordance with conventional cationic polymerization, for example, it can be produced in accordance with the production method described in Japanese Patent Laid-Open No. 2013-237755.

(聚合物(2)) (Polymer (2))

在前述式(2)中，環Z只要為含有氧原子作為雜原子的飽和雜環即可。飽和雜環可為飽和單環式雜環(雜單環)，亦可為飽和縮合雜環。 In the aforementioned formula (2), the ring Z may be a saturated heterocyclic ring containing an oxygen atom as a hetero atom. The saturated heterocyclic ring may be a saturated monocyclic heterocyclic ring (heteromonocyclic ring) or a saturated condensed heterocyclic ring.

就飽和雜單環而言，可列舉如：氧雜環丁烷、四氫呋喃(氧雜環戊烷)、四氫哌喃(氧雜環己烷)、氧雜環庚烷、氧雜環辛烷等。其中，以四氫呋喃、四氫哌喃(尤其是四氫呋喃)為較佳。 Examples of saturated heteromonocycles include oxetane, tetrahydrofuran (oxetane), tetrahydropiperan (oxetane), oxepane, and oxetane Wait. Among them, tetrahydrofuran and tetrahydropiperan (especially tetrahydrofuran) are preferred.

飽和縮合雜環之縮合數(縮合之環之數)，可為2環式以上，亦可為3環式以上(例如3~4環式)，然而通常為2環式。飽和縮合雜環之員數(縮合環全體之員數)，為例如約6~20員環，較佳為約7~15員環，更佳為約8~12員環(尤其8~10員環)。飽和縮合雜環所含之氧原子之數目可為2個以上，例如約2~6個，較佳為約2~4個，更佳為約2~3個。2個以上之氧原子，可包含於相同之環，然而通常在各環中包含1個以上(例如1~2個，特佳為1個)。 The condensation number of the saturated condensed heterocyclic ring (the number of condensed rings) may be 2 or more ring types, or 3 or more ring types (for example, 3 to 4 ring types), but usually 2 ring types. The number of members of the saturated condensed heterocyclic ring (the total number of members of the condensed ring) is, for example, about 6 to 20 member rings, preferably about 7 to 15 member rings, and more preferably about 8 to 12 member rings (especially 8 to 10 member rings) ring). The number of oxygen atoms contained in the saturated condensed heterocyclic ring may be more than 2, for example, about 2 to 6, preferably about 2 to 4, more preferably about 2 to 3. Two or more oxygen atoms may be included in the same ring, but usually each ring contains more than one (for example, 1-2, particularly preferably one).

飽和縮合雜環之基本骨架(構成縮合環之各環之構造)，可列舉如前述飽和雜單環等。前述飽和雜單環中，以四氫呋喃、四氫哌喃(尤其是四氫呋喃)為較佳。縮合環係將此等環組合而成，可為相同環之組合，亦可為相異環之組合。 The basic skeleton of the saturated condensed heterocyclic ring (the structure of each ring constituting the condensed ring) includes the aforementioned saturated heteromonocyclic ring and the like. Among the aforementioned saturated heteromonocyclic rings, tetrahydrofuran and tetrahydropiperan (especially tetrahydrofuran) are preferred. The condensed ring is formed by combining these rings, which can be a combination of the same ring or a combination of different rings.

在此等飽和雜環中，從密著性等之觀點而言，以飽和縮合雜環作為環Z為較佳。 Among these saturated heterocycles, a saturated condensed heterocycle is preferred as ring Z from the viewpoint of adhesion.

就環Z所含之取代基而言，可列舉如：前述式(1)所例示之有機基、前述式(1)所示之有機基的取代基等。 Examples of the substituent contained in the ring Z include the organic group exemplified in the aforementioned formula (1), the substituent of the organic group represented in the aforementioned formula (1), and the like.

此種重複單元(2)可為下述式(2a)所表示之重複單元。 Such a repeating unit (2) may be a repeating unit represented by the following formula (2a).

(式中，R⁵~R¹²表示氫原子或取代基)。 (In the formula, R ⁵ to R ¹² represent a hydrogen atom or a substituent).

在前述式(2a)中，R⁵~R¹²可為選自此等取代基及氫原子的單種基，亦可為將二種以上組合而成之基。就R⁵~R¹²而言，從製造容易度及原料取得容易度等之觀點而言，以氫原子、甲基等C_1-4烷基為較佳，以氫原子為特佳。 In the aforementioned formula (2a), R ⁵ to R ¹² may be a single group selected from such substituents and hydrogen atoms, or a combination of two or more types. For R ⁵ to R ¹² , from the viewpoints of ease of production and ease of obtaining raw materials, C _1-4 alkyl groups such as a hydrogen atom and a methyl group are preferred, and a hydrogen atom is particularly preferred.

聚合物(2)[具有式(2)所表示之重複單元的聚合物(2)]，可藉由具有含氧飽和雜環骨架之二乙烯基醚與具有含氧飽和雜環骨架之二醇的反應，或具有含氧飽和雜環骨架之羥基乙烯基醚的聚合等而得到。聚合物(2)之構造，無特別限定，可為直鏈型、分枝鏈型、星型等之任一種構造。 The polymer (2) [the polymer (2) having a repeating unit represented by the formula (2)] can be obtained by a divinyl ether having an oxygen-containing saturated heterocyclic skeleton and a diol having an oxygen-containing saturated heterocyclic skeleton The reaction, or the polymerization of hydroxyvinyl ether having an oxygen-containing saturated heterocyclic skeleton is obtained. The structure of the polymer (2) is not particularly limited, and may be any structure such as a linear type, a branched type, or a star shape.

聚合物(2)可為均聚合物，亦可為共聚合物。共聚合物可為前述式(2)所表示之重複單元中，環Z係相 異飽和雜環之組合，例如，相異飽和雜單環彼此之組合、相異飽和縮合雜環彼此之組合、飽和雜單環與飽和縮合雜環之組合等的共聚合物。亦即，在前述式(2)中，環Z可為相同之前述飽和雜環，亦可為相異之前述飽和雜環之組合。再者，共聚合物可為前述式(2)所表示之重複單元與其他共聚合性單體(其他二乙烯基醚及/或其他二元醇)所形成之單元的共聚合物。再者，共聚合物可為無規共聚合物，亦可為嵌段共聚合物。 The polymer (2) may be a homopolymer or a copolymer. The copolymer may be a repeating unit represented by the aforementioned formula (2), and the ring Z system phase Copolymers of heterosaturated heterocyclic ring combinations, for example, heterosaturated heteromonocyclic rings, heterosaturated condensed heterocyclic rings, saturated heteromonocyclic rings and saturated condensed heterocyclic rings. That is, in the aforementioned formula (2), the ring Z may be the same saturated heterocyclic ring or a combination of different saturated heterocyclic rings. Furthermore, the copolymer may be a copolymer of a unit formed by the repeating unit represented by the aforementioned formula (2) and other copolymerizable monomers (other divinyl ether and/or other glycol). Furthermore, the copolymer may be a random copolymer or a block copolymer.

在聚合物(2)中，前述式(2)所表示之重複單元之比率可為50莫耳%以上(例如70~100莫耳%)，例如80莫耳%以上(例如80~100莫耳%)，較佳為90莫耳%以上(例如90~100莫耳%)，更佳為95莫耳%以上(尤其是99莫耳%以上)。若重複單元(2)之比率過少，則恐怕藉由酸將聚合物分解後之殘餘物的處理將變得繁雜。 In the polymer (2), the ratio of the repeating unit represented by the aforementioned formula (2) may be 50 mol% or more (eg, 70-100 mol%), such as 80 mol% or more (eg, 80-100 mol) %), preferably 90 mol% or more (for example, 90 to 100 mol%), more preferably 95 mol% or more (especially 99 mol% or more). If the ratio of the repeating unit (2) is too small, there is a fear that the treatment of the residue after the polymer is decomposed by acid will become complicated.

聚合物(2)之末端基為乙烯基醚基、羥基之任一種，可為單獨任一種，或為兩種基之組合。如此，本發明之聚合物由於在末端具有羥基及/或乙烯基，所以可藉由羥基賦予對於無機材料等所形成基材之密著性，或藉由乙烯基與其他聚合性基聚合，得到具有酸分解性之交聯構造的樹脂。 The terminal group of the polymer (2) is either a vinyl ether group or a hydroxyl group, and it may be either a single type or a combination of two types. In this way, since the polymer of the present invention has a hydroxyl group and/or vinyl group at the terminal, the adhesion to the base material formed of an inorganic material or the like can be imparted by the hydroxyl group, or can be obtained by polymerizing the vinyl group and other polymerizable groups Resin with acid-decomposable cross-linked structure.

聚合物(2)之重量平均分子量(Mw)，在藉由例如GPC法測定時，以聚苯乙烯換算，可為約1000以上，例如約1000~100000，較佳為約2000~50000，更佳為約3000~30000(尤其是4000~10000)。聚合物(2)儘管具有含氧飽和雜環，仍為高分子量。若重量平均分子量過小 ，則恐怕對金屬微粒之保護能力降低，或分解前之聚合物的耐熱性或機械強度變得不足。另一方面，若過大，則恐怕聚合物之生產性降低，或溶解性不足，操作將變得困難。 The weight average molecular weight (Mw) of the polymer (2), when measured by, for example, the GPC method, in polystyrene conversion, may be about 1,000 or more, such as about 1,000 to 100,000, preferably about 2,000 to 50,000, more preferably It is about 3000~30,000 (especially 4000~10000). The polymer (2) has a high molecular weight despite having an oxygen-containing saturated heterocycle. If the weight average molecular weight is too small , The protection ability of the metal particles may decrease, or the heat resistance or mechanical strength of the polymer before decomposition may become insufficient. On the other hand, if it is too large, the polymer productivity may be reduced, or the solubility may be insufficient, and the operation will become difficult.

聚合物(2)之分子量分布(Mw/Mn)可為例如約1~5，較佳為約1.1~3，更佳為約1.2~2.8(尤其是1.5~2.5)。若分子量分布過大，則恐怕複合微粒之粒徑分布大，或分解前之聚合物的耐熱性或機械強度變得不足。再者，聚合物之分子量分布，亦可藉由例如GPC法，以聚苯乙烯換算而計算出。 The molecular weight distribution (Mw/Mn) of the polymer (2) may be, for example, about 1 to 5, preferably about 1.1 to 3, and more preferably about 1.2 to 2.8 (especially 1.5 to 2.5). If the molecular weight distribution is too large, the particle size distribution of the composite fine particles may be large, or the heat resistance or mechanical strength of the polymer before decomposition may become insufficient. In addition, the molecular weight distribution of the polymer can also be calculated in terms of polystyrene by the GPC method, for example.

聚合物(2)係藉由包含使下述式(5)所表示之二乙烯基醚與下述式(6)所表示之二元醇進行反應之反應步驟的製造方法，或包含使下述式(7)所表示之羥基乙烯基醚聚合之反應步驟的製造方法等而得到的聚合物。 The polymer (2) is a production method including a reaction step of reacting a divinyl ether represented by the following formula (5) with a diol represented by the following formula (6), or includes the following A polymer obtained by a method for producing a reaction step of polymerizing a hydroxyvinyl ether represented by formula (7).

(式中，環Z表示可具有取代基，而且包含作為雜原子之氧原子的飽和雜環，並且環Z可為相同之前述飽和雜環，亦可為相異之前述飽和雜環之組合)。 (In the formula, ring Z represents a saturated heterocyclic ring which may have a substituent and contains an oxygen atom as a hetero atom, and ring Z may be the same saturated heterocyclic ring as described above, or may be a combination of different saturated heterocyclic rings) .

在反應步驟中，就二乙烯基醚(5)而言，可為以前述重複單元(2)所例示之環Z作為基本骨架的二乙烯基醚，其以下述式(5a)所表示之二乙烯基醚(尤其是具有前述重複單元(2a)所例示之取代基的二乙烯基醚)為較佳 。就二元醇(6)而言，可為以前述重複單元(2)所例示之環Z作為基本骨架的二元醇，其以下述式(6a)所表示之二元醇(尤其是具有前述重複單元(2a)所例示之取代基的二元醇)為較佳。就羥基乙烯基醚(7)而言，可為以前述重複單元(2)所例示之環Z作為基本骨架的羥基乙烯基醚，其以下述式(7a)所表示之羥基乙烯基醚(尤其是具有前述重複單元(2a)所例示之取代基的羥基乙烯基醚)為較佳。 In the reaction step, as for the divinyl ether (5), it may be a divinyl ether having the ring Z exemplified in the foregoing repeating unit (2) as a basic skeleton, which is represented by the following formula (5a). Vinyl ether (especially divinyl ether having a substituent exemplified in the aforementioned repeating unit (2a)) is preferred . As for the diol (6), it may be a diol having the ring Z exemplified in the aforementioned repeating unit (2) as a basic skeleton, and the diol represented by the following formula (6a) (especially having the aforementioned The diol of the substituent exemplified in the repeating unit (2a) is preferred. As for the hydroxyvinyl ether (7), it may be a hydroxyvinyl ether having the ring Z exemplified in the aforementioned repeating unit (2) as a basic skeleton, and the hydroxyvinyl ether represented by the following formula (7a) (especially It is preferably a hydroxyvinyl ether having a substituent exemplified in the aforementioned repeating unit (2a).

(式中，R⁵~R¹²表示氫原子或取代基)。 (In the formula, R ⁵ to R ¹² represent a hydrogen atom or a substituent).

在反應步驟中，除了二乙烯基醚(5)及二元醇(6)、或羥基乙烯基醚(7)之外，亦可添加共聚合性單體。就共聚合性單體而言，可列舉其他二乙烯基醚(例如，伸丁基二乙烯基醚、環己烷二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、2,2-降

烷二甲醇二乙烯基醚等)、其他二元醇(例如，乙二醇、丙二醇、四亞甲基二醇、二乙二醇、三乙二醇、環己烷二甲醇、雙酚A等)、其他羥基乙烯基醚(例如，羥基丁基乙烯基醚、羥基環己基乙烯基醚、二乙二醇單乙烯基醚、三乙二醇單乙烯基醚、2,2-降

烷二甲醇單乙烯基醚等)等。 In the reaction step, in addition to divinyl ether (5) and glycol (6), or hydroxyvinyl ether (7), a copolymerizable monomer may be added. Examples of the copolymerizable monomers include other divinyl ethers (for example, butyl divinyl ether, cyclohexane divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. Ether, 2,2-drop

Alkane dimethanol divinyl ether, etc.), other glycols (for example, ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, etc. ), other hydroxyvinyl ethers (for example, hydroxybutyl vinyl ether, hydroxycyclohexyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, 2,2-decane

Alkane dimethanol monovinyl ether, etc.).

其中，以二乙烯基醚(5)及二元醇(6)之交互聚合物為較佳。 Among them, the alternating polymer of divinyl ether (5) and glycol (6) is preferred.

二乙烯基醚(5)與二元醇(6)之比率(莫耳比)，可選自前者/後者=約10/1~1/10之範圍，然而從聚合性之觀點而言，可為例如約2/1~1/2，較佳為約1.5/1~1/1.5，更佳為約1.2/1~1/1.2(尤其是1.1/1~1/1.1)，通常約為等莫耳。 The ratio (mole ratio) of divinyl ether (5) to diol (6) can be selected from the former/the latter = about 10/1 to 1/10, but from the viewpoint of polymerizability, For example, about 2/1~1/2, preferably about 1.5/1~1/1.5, more preferably about 1.2/1~1/1.2 (especially 1.1/1~1/1.1), usually about Moore.

反應可在觸媒存在下進行。就觸媒而言，可利用慣用之觸媒，然而從反應促進性高之觀點而言，以酸觸媒為較佳。就酸觸媒而言，可為例如鹽酸、硫酸、對甲苯磺酸等強酸，然而從亦能保持生成之聚合物之安定性的觀點而言，以乙酸、磷酸、芳烴磺酸(例如，甲苯磺酸等)以及與鹼(例如，吡啶等弱鹼等)之鹽等弱酸為較佳，從聚合物之安定性及反應性的平衡優良之觀點而言，以對甲苯磺酸吡啶鎓等甲苯磺酸鹽為較佳。 The reaction can be carried out in the presence of a catalyst. As for the catalyst, a conventional catalyst can be used, but from the viewpoint of high reaction promotion, an acid catalyst is preferable. As for the acid catalyst, it may be strong acid such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc. However, from the viewpoint of keeping the stability of the polymer produced, acetic acid, phosphoric acid, aromatic sulfonic acid (e.g. toluene Sulfonic acids, etc.) and weak acids such as salts with bases (e.g., weak bases such as pyridine, etc.) are preferred, and from the viewpoint of excellent balance of stability and reactivity of the polymer, toluene such as pyridinium p-toluenesulfonate Sulfonates are preferred.

觸媒之比率，相對於100莫耳聚合成分之總莫耳數(例如，二乙烯基醚(5)及二元醇(6)之總莫耳數)，為例如約0.1~20莫耳，較佳為約0.3~15莫耳，更佳為約0.5~10莫耳(尤其是1~5莫耳)。若觸媒之比率過少，則反應性降低，若過多，則恐怕對聚合物之物性有不良影響。 The ratio of the catalyst is, for example, about 0.1 to 20 moles relative to the total moles of 100 moles of polymerized components (for example, the total moles of divinyl ether (5) and glycol (6)). It is preferably about 0.3 to 15 moles, and more preferably about 0.5 to 10 moles (especially 1 to 5 moles). If the ratio of the catalyst is too small, the reactivity will decrease, and if it is too large, the physical properties of the polymer may be adversely affected.

反應可在溶劑中進行，就溶劑而言，只要對前述二乙烯基醚及二元醇而言為無反應性之溶劑即可，無特別限定，可列舉如：烴類(甲苯、二甲苯等)、鹵素系溶劑(二氯甲烷、氯仿等)、醚類(二乙基醚等二烷基醚、四氫呋喃等環狀醚類等)、酮類(丙酮、甲基乙基酮等)、酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯等)、賽珞蘇乙酸酯類(乙基賽珞蘇乙酸酯等C_1-4烷基賽珞蘇乙酸酯、丙 二醇單甲醚乙酸酯等丙二醇單C_1-4烷基醚乙酸酯等)等。此等溶劑可單獨或將二種以上組合而使用。此等溶劑之中，賽珞蘇乙酸酯類(例如，丙二醇單甲基醚乙酸酯等丙二醇單C_1-4烷基醚乙酸酯等)被廣泛使用。 The reaction can be carried out in a solvent. The solvent is not particularly limited as long as it is a non-reactive solvent for the aforementioned divinyl ether and glycol, and examples include hydrocarbons (toluene, xylene, etc.) ), halogen solvents (dichloromethane, chloroform, etc.), ethers (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters (Methyl acetate, ethyl acetate, butyl acetate, etc.), Cylosulfoacetate (Ethyl cylosulfoacetate and other C _1-4 alkyl cylosulfoacetate, propylene glycol monomethyl ether ether Propylene glycol mono C _1-4 alkyl ether acetate, etc.) etc. These solvents can be used alone or in combination of two or more. Among these solvents, cellulose acetate (for example, propylene glycol mono C _1-4 alkyl ether acetate such as propylene glycol monomethyl ether acetate) is widely used.

溶劑之使用量，相對於100重量份聚合成分之總量(例如，二乙烯基醚(3)及二元醇(4)之總量)，為例如約10~1000重量份，較佳為約50~500重量份，更佳為約100~300重量份(尤其是150~200重量份)。 The amount of the solvent used is, for example, about 10 to 1000 parts by weight, preferably about 100 parts by weight of the total amount of the polymerization component (for example, the total amount of divinyl ether (3) and glycol (4)). 50 to 500 parts by weight, more preferably about 100 to 300 parts by weight (especially 150 to 200 parts by weight).

反應係可添加慣用之添加劑，例如，聚合促進劑、聚合抑制劑等而進行。再者，反應系統中可含有水分，亦可在含有來自原料等不可避免之水分存在下進行反應。 The reaction system can be carried out by adding conventional additives such as a polymerization accelerator and a polymerization inhibitor. Furthermore, the reaction system may contain moisture, or the reaction may be carried out in the presence of unavoidable moisture from raw materials.

在反應步驟中，可不要過度加熱或冷卻，使反應進行，反應溫度可為例如約0~60℃，較佳為約10~50℃，更佳為約20~45℃(尤其是30~40℃)。 In the reaction step, the reaction may proceed without excessive heating or cooling. The reaction temperature may be, for example, about 0 to 60°C, preferably about 10 to 50°C, and more preferably about 20 to 45°C (especially 30 to 40 ℃).

反應時間可為例如約30分~48小時，通常為約1~36小時，較佳為約2~24小時。再者，反應可在惰性環境(例如，氮、氦、氬等之環境)下進行。 The reaction time may be, for example, about 30 minutes to 48 hours, usually about 1 to 36 hours, preferably about 2 to 24 hours. Furthermore, the reaction can be carried out under an inert environment (eg, nitrogen, helium, argon, etc.).

經過反應步驟所得到之聚合物，可進一步提供於分離精製步驟。在分離精製步驟中，可藉由慣用之分離精製處理，例如，過濾、濃縮、再沉澱、萃取、晶析(再結晶等)等手段進行分離精製。再者，在使用酸觸媒之情況下，可依照慣用之方法用鹼中和。 The polymer obtained after the reaction step can be further provided in the separation and purification step. In the separation and purification step, separation and purification can be performed by conventional separation and purification treatments such as filtration, concentration, reprecipitation, extraction, crystallization (recrystallization, etc.). Furthermore, in the case where an acid catalyst is used, it can be neutralized with alkali in accordance with conventional methods.

(聚合物(3)及(4)) (Polymers (3) and (4))

在前述式(3)、(4a)及(4b)中，就A¹~A⁹(A¹~A⁹骨架 )之烴基而言，可列舉例如脂肪族烴基、脂環式烴基、芳香族烴基、此等2種以上鍵結而成之基。 In the aforementioned formulas (3), (4a) and (4b), examples of the hydrocarbon group of A ¹ to A ⁹ (A ¹ to A ⁹ skeleton) include, for example, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups , These two or more kinds of bonding base.

就脂肪族烴基而言，可列舉如：伸烷基、伸烯基、伸炔基。就伸烷基而言，可列舉如：亞甲基、伸乙基、伸丙基、三亞甲基、伸丁基、四亞甲基、六亞甲基、伸異己基、八亞甲基、伸異辛基、十亞甲基、十二亞甲基等之C_1-20伸烷基等。就伸烯基而言，可列舉如：伸乙烯基、伸烯丙基、伸甲基烯丙基、伸1-丙烯基、伸異丙烯基、伸丁烯基、伸戊烯基、伸己烯基等C_2-20伸烯基等。就伸炔基而言，可列舉如：伸乙炔基、伸丙炔基等C_2-20伸炔基等。 Examples of the aliphatic hydrocarbon group include alkylene groups, alkenyl groups, and alkynyl groups. Examples of alkylene groups include methylene, ethylidene, propylidene, trimethylene, butylidene, tetramethylene, hexamethylene, isohexylidene, octamethylene, C _1-20 alkylene such as iso-octyl, decamethylene, dodecamethylene, etc. Examples of the alkenyl group include vinylidene, vinylidene, methylallyl, 1-propenyl, isopropenyl, butenyl, pentenyl, and hexenyl. Alkenyl and other C _2-20 alkenyl and so on. Examples of the alkynyl group include C _2-20 alkynyl group such as ethynyl group and propynyl group.

就脂環式烴基而言，可列舉如：伸環丙基、伸環丁基、伸環戊基、伸環己基、環十二碳-二基等C_3-12環烷基(尤其是C_5-8環烷基)；伸環己烯基等C_3-12伸環烯基；伸雙環庚基、伸雙環庚烯基等C_4-15交聯環式烴基等。 Examples of the alicyclic hydrocarbon group include C _3-12 cycloalkyl groups (especially C), such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclododeca-diyl group. _5-8 cycloalkyl); C _3-12 cycloalkenyl such as cyclohexenyl; C _4-15 cross-linked cyclic hydrocarbon such as bicycloheptyl and bicycloheptenyl; etc.

就芳香族烴基而言，可列舉如：伸苯基、伸萘基等C_6-14伸芳基等。 Examples of the aromatic hydrocarbon group include C _6-14 arylidene groups such as phenylene and naphthyl.

再者，就烴基而言，亦可為例如選自脂肪族烴基、脂環式烴基及芳香族烴基之二種以上所鍵結而成的基。就脂肪族烴基與脂環式烴基所鍵結而成之基而言，可列舉如：伸環己基亞甲基、甲基伸環己基、二環己基甲烷-4,4’-二基、二環己基丙烷-4,4’-二基等。就脂肪族烴基與芳香族烴基所鍵結而成之基而言，可列舉如：伸甲苯基、伸二甲苯基、二苯基甲烷-4,4’-二基、二苯基丙烷-4,4’-二基等。 In addition, the hydrocarbon group may be, for example, a group obtained by bonding two or more kinds selected from an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the group formed by bonding an aliphatic hydrocarbon group and an alicyclic hydrocarbon group include: cyclohexyl methylene, methyl cyclohexyl, dicyclohexyl methane-4,4′-diyl, di Cyclohexylpropane-4,4'-diyl, etc. Examples of the group formed by bonding an aliphatic hydrocarbon group and an aromatic hydrocarbon group include: tolyl, xylyl, diphenylmethane-4,4'-diyl, and diphenylpropane-4, 4'-diyl and so on.

就此等烴基之取代基而言，可列舉如前述式(1)所例示之有機基的取代基等。 Examples of the substituents of these hydrocarbon groups include the substituents of the organic group exemplified in the aforementioned formula (1).

在式(3)、(4a)及(4b)中，n、m及k分別為1以上之整數，較佳為約1~10，更佳為約1~5(尤其是1~3)。 In formulas (3), (4a), and (4b), n, m, and k are integers of 1 or more, preferably about 1-10, more preferably about 1-5 (especially 1-3).

此等基之中，就A¹~A⁹而言，以碳數3以上之伸烷基(例如C_3-10伸烷基)為較佳，以三至八亞甲基(尤其是三至六亞甲基)為特佳。 Among these groups, as far as A ¹ to A ⁹ are concerned, an alkylene group having a carbon number of 3 or more (for example, C _3-10 alkylene group) is preferred, and a tri-octa methylene group (especially three to Hexamethylene) is particularly preferred.

再者，在本發明中，於式(3)、(4a)及(4b)中，A¹、A⁴及A⁵骨架不含包含氧原子作為雜原子之飽和雜環。 Furthermore, in the present invention, in the formulae (3), (4a) and (4b), the A ¹ , A ⁴ and A ⁵ skeletons do not contain saturated heterocycles containing oxygen atoms as heteroatoms.

聚合物(3)及(4)係可藉由具有A¹骨架之二乙烯基醚與具有A¹骨架之二元醇的反應、具有A⁴或A⁵骨架之二乙烯基醚與具有A⁵或A⁴骨架之二元醇的反應、或具有A¹骨架之羥基乙烯基醚的聚合等而得到。聚合物(3)及(4)之構造，無特別限定，可為直鏈型、分枝鏈型、星型等之任一種構造。 Polymers (3) and (4) can be reacted with divinyl ether having A ¹ skeleton and diol having A ¹ skeleton, divinyl ether having A ⁴ or A ⁵ skeleton and having A ⁵ It can be obtained by the reaction of the diol of the A ⁴ skeleton or the polymerization of the hydroxy vinyl ether having the A ¹ skeleton. The structure of the polymers (3) and (4) is not particularly limited, and may be any structure such as a linear chain, a branched chain, or a star.

聚合物(3)可為均聚合物，亦可為與其他共聚合性單體所形成之單元(可形成重複單元(3)之單體以外之單體所形成的單元)的共聚合物。共聚合物可為無規共聚合物，亦可為嵌段共聚合物。 The polymer (3) may be a homopolymer, or may be a copolymer of units formed with other copolymerizable monomers (units formed with monomers other than monomers that can form repeating units (3)). The copolymer may be a random copolymer or a block copolymer.

聚合物(4)為包含重複單元(4a)及(4b)之共聚合物，不過與聚合物(3)同樣地，可為進一步包含其他共聚合性單體所形成之單元(可形成重複單元(4a)及(4b)之單體以外之單體所形成的單元)的共聚合物。共聚合物可為無規共聚合物，亦可為嵌段共聚合物。 The polymer (4) is a copolymer containing repeating units (4a) and (4b), but like the polymer (3), it can be a unit formed by further containing other copolymerizable monomers (repeating units can be formed) (4a) and (4b) monomers other than monomers) copolymers. The copolymer may be a random copolymer or a block copolymer.

在本發明中，聚合物(3)及(4)中之其他共聚合性單體也不含包含氧原子作為雜原子的飽和雜環。 In the present invention, the other copolymerizable monomers in the polymers (3) and (4) also do not contain saturated heterocycles containing oxygen atoms as heteroatoms.

在聚合物(3)及(4)中，式(3)所表示之重複單元、或式(4a)及(4b)所表示之二種重複單元之比率，可分別為50莫耳%以上(例如70~100莫耳%)，例如80莫耳%以上(例如80~100莫耳%)，較佳為90莫耳%以上(例如90~100莫耳%)，更佳為95莫耳%以上(尤其是99莫耳%以上)。若前述重複單元之比率過少，則恐怕聚合物被酸分解後之殘餘物的處理將變得繁雜。 In the polymers (3) and (4), the ratio of the repeating units represented by formula (3) or the two types of repeating units represented by formulas (4a) and (4b) may be 50 mol% or more ( For example, 70 to 100 mol%), for example, 80 mol% or more (eg, 80 to 100 mol%), preferably 90 mol% or more (eg, 90 to 100 mol%), and more preferably 95 mol% Above (especially more than 99 mol%). If the ratio of the aforementioned repeating units is too small, there is a fear that the treatment of the residue after the acid decomposition of the polymer will become complicated.

在聚合物(3)及(4)中，從聚合物鏈具有均質分解性之觀點而言，以具有式(3)所表示之重複單元的聚合物(尤其是均聚合物)為較佳。在聚合物(3)中，A¹可為三至六亞甲基，較佳為四至五亞甲基，更佳為四亞甲基。 Among the polymers (3) and (4), a polymer having a repeating unit represented by the formula (3) (especially a homopolymer) is preferable from the viewpoint that the polymer chain has homogeneous decomposability. In the polymer (3), A ¹ may be three to six methylene, preferably four to pentamethylene, and more preferably tetramethylene.

聚合物(3)及(4)之末端基為乙烯基醚基、羥基之任一種，任一者可為單獨，或兩基之組合。依此，由於聚合物(3)及(4)在末端具有羥基及/或乙烯基，藉由羥基可賦予對於以無機材料等所形成之基材之密著性，或藉由乙烯基與其他聚合性基聚合，而得到具有酸分解性之交聯構造的樹脂。 The terminal groups of the polymers (3) and (4) are either vinyl ether groups or hydroxyl groups, either of which may be alone or a combination of two groups. Accordingly, since the polymers (3) and (4) have hydroxyl groups and/or vinyl groups at the ends, the hydroxyl groups can impart adhesion to substrates formed with inorganic materials, etc., or through vinyl groups and other The polymerizable group is polymerized to obtain a resin having an acid-decomposable cross-linked structure.

聚合物(3)及(4)之重量平均分子量(Mw)，在藉由GPC法測定時，以聚苯乙烯換算，分別可為1000以上，例如約1000~100000，較佳為約2000~50000，更佳為約3000~30000(尤其是4000~10000)。若重量平均分子量過小，則恐怕對金屬微粒之保護能力降低，或分解前之聚合物的耐熱性或機械強度變得不足。另一方面， 若過大，則恐怕聚合物之生產性降低，溶解性不足，操作變得困難。 The weight average molecular weights (Mw) of the polymers (3) and (4), when measured by the GPC method, in terms of polystyrene, can be more than 1,000, for example, about 1,000 to 100,000, preferably about 2,000 to 50,000 It is more preferably about 3000~30,000 (especially 4000~10000). If the weight-average molecular weight is too small, there is a fear that the protection ability to the metal fine particles is reduced, or the heat resistance or mechanical strength of the polymer before decomposition becomes insufficient. on the other hand, If it is too large, the productivity of the polymer may decrease, the solubility may be insufficient, and operation may become difficult.

聚合物(3)及(4)之分子量分布(Mw/Mn)，分別為例如約1~5，較佳為約1.1~3，更佳為約1.2~2.8(尤其是1.5~2.5)。若分子量分布過大，則恐怕分解前之聚合物之耐熱性或機械強度將變得不足。再者，聚合物之分子量分布亦可藉由例如GPC法，以聚苯乙烯換算而計算出。 The molecular weight distributions (Mw/Mn) of the polymers (3) and (4) are, for example, about 1 to 5, preferably about 1.1 to 3, and more preferably about 1.2 to 2.8 (especially 1.5 to 2.5). If the molecular weight distribution is too large, the heat resistance or mechanical strength of the polymer before decomposition may become insufficient. Furthermore, the molecular weight distribution of the polymer can also be calculated in terms of polystyrene by the GPC method, for example.

聚合物(3)及(4)係如前述，可藉由包含使對應之二乙烯基醚與對應之二元醇反應之反應步驟的製造方法，或包含使對應之羥基乙烯基醚聚合之反應步驟的製造方法等而得到。 The polymers (3) and (4) are as described above, and can be produced by a method including a reaction step of reacting the corresponding divinyl ether with the corresponding diol, or a reaction including polymerizing the corresponding hydroxyvinyl ether The manufacturing method of the steps is obtained.

在反應步驟中，就具有A¹、A⁴或A⁵骨架之二乙烯基醚而言，可列舉如：伸丁基二乙烯基醚、環己烷二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、2,2-降

烷二甲醇二乙烯基醚等。就具有A¹、A⁴或A⁵骨架之二元醇而言，可列舉如：四亞甲基二醇、二乙二醇、三乙二醇、環己烷二甲醇、雙酚A等。就具有A¹、A⁴或A⁵骨架之羥基乙烯基醚而言，可列舉如：羥基丁基乙烯基醚、羥基環己基乙烯基醚、二乙二醇單乙烯基醚、三乙二醇單乙烯基醚、2,2-降

烷二甲醇單乙烯基醚等。 In the reaction step, as for the divinyl ether having A ¹ , A ⁴ or A ⁵ skeleton, for example, it may include: butyl divinyl ether, cyclohexane divinyl ether, diethylene glycol diethylene Ether, triethylene glycol divinyl ether, 2,2-decyl

Alkane dimethanol divinyl ether, etc. Examples of the diol having an A ¹ , A ⁴ or A ⁵ skeleton include tetramethylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol, and bisphenol A. Examples of hydroxyvinyl ethers having an A ¹ , A ⁴ or A ⁵ skeleton include: hydroxybutyl vinyl ether, hydroxycyclohexyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol Monovinyl ether, 2,2-drop

Alkane dimethanol monovinyl ether, etc.

此等之中，以對應之二乙烯基醚與對應之二元醇的交替聚合物為較佳。前述二乙烯基醚與前述二元醇之比率(莫耳比)，可選自前者/後者=約10/1~1/10之 範圍，不過從聚合性之觀點而言，可為例如2/1~1/2，較佳為約1.5/1~1/1.5，更佳為約1.2/1~1/1.2(尤其是1.1/1~1/1.1)，通常約為等莫耳。 Among these, alternating polymers of the corresponding divinyl ether and the corresponding diol are preferred. The ratio (molar ratio) of the aforementioned divinyl ether to the aforementioned diol can be selected from the former/the latter=about 10/1 to 1/10 Range, but from the viewpoint of polymerizability, it may be, for example, 2/1 to 1/2, preferably about 1.5/1 to 1/1.5, more preferably about 1.2/1 to 1/1.2 (especially 1.1/ 1~1/1.1), usually about equal molar.

反應可於觸媒存在下進行。就觸媒而言，可利用慣用之觸媒，然而從反應促進性高之觀點而言，以酸觸媒為較佳。就酸觸媒而言，可利用在聚合物(2)之製造方法中所用的酸觸媒，並以與聚合物(2)之製造方法同樣之比率使用。 The reaction can be carried out in the presence of a catalyst. As for the catalyst, a conventional catalyst can be used, but from the viewpoint of high reaction promotion, an acid catalyst is preferable. As for the acid catalyst, the acid catalyst used in the manufacturing method of the polymer (2) can be used and used in the same ratio as the manufacturing method of the polymer (2).

反應可在溶劑中進行，就溶劑而言，可利用聚合物(2)之製造方法中所用的溶劑，能以與聚合物(2)之製造方法同樣之使用量使用。 The reaction can be carried out in a solvent. As for the solvent, the solvent used in the method for producing the polymer (2) can be used and can be used in the same amount as the method for producing the polymer (2).

再者，關於添加劑之添加、反應溫度及時間、所得到之聚合物之分離精製步驟，亦與聚合物(2)之製造方法相同。 Furthermore, the addition of additives, the reaction temperature and time, and the separation and purification steps of the obtained polymer are also the same as the production method of the polymer (2).

(保護層之特性) (Characteristics of protective layer)

保護層可包含酸分解性聚合物，亦可包含其他成分，例如，可包含在製造步驟中混入之觸媒或溶劑、還原劑之外的慣用添加劑。 The protective layer may contain an acid-decomposable polymer, and may also contain other components. For example, it may contain conventional additives other than the catalyst, solvent, and reducing agent mixed in the manufacturing step.

還原劑之比率，相對於保護層總量，為例如約10重量%以下(例如0.001~10重量%)，較佳為約5重量%以下，更佳為約1重量%以下。若還原劑之比率過多，則恐有燒成後導電性降低之虞。 The ratio of the reducing agent relative to the total amount of the protective layer is, for example, about 10% by weight or less (for example, 0.001 to 10% by weight), preferably about 5% by weight or less, and more preferably about 1% by weight or less. If the ratio of the reducing agent is too large, there is a fear that the conductivity after firing may decrease.

就慣用添加劑而言，可包含例如其他之聚合物(黏合劑)、安定劑(抗氧化劑、紫外線吸收劑等)、金屬腐蝕防止劑、界面活性劑或分散劑、水溶性高分子、蠟 、分散安定化劑、增黏劑或黏度調整劑、保濕劑、搖變性賦予劑、均塗劑、消泡劑、充填劑等。其他成分之比率，例如，可為相對於保護層總量之50重量%以下，例如約0.01~10重量%(尤其是0.1~5重量%)。 As for conventional additives, it may include, for example, other polymers (adhesives), stabilizers (antioxidants, ultraviolet absorbers, etc.), metal corrosion inhibitors, surfactants or dispersants, water-soluble polymers, waxes , Dispersing stabilizers, tackifiers or viscosity modifiers, moisturizing agents, shaking imparting agents, leveling agents, defoamers, fillers, etc. The ratio of other components may be, for example, 50% by weight or less relative to the total amount of the protective layer, for example, about 0.01 to 10% by weight (particularly 0.1 to 5% by weight).

保護層可將金屬微粒之至少一部分表面被覆，對金屬微粒之表面的被覆率可為10%以上，例如30%以上，較佳可為50%以上，更佳為80%以上(尤其是90%以上)，亦可將金屬微粒之全表面被覆。若保護層之被覆率過低，則恐怕金屬微粒變得容易氧化或凝聚，金屬微粒之安定性降低。 The protective layer can cover at least a part of the surface of the metal particles, and the coverage rate of the surface of the metal particles can be more than 10%, for example more than 30%, preferably more than 50%, more preferably more than 80% (especially 90% (Above), the entire surface of the metal particles can also be coated. If the coverage rate of the protective layer is too low, the metal particles may be easily oxidized or aggregated, and the stability of the metal particles may decrease.

[複合微粒之特性及製造方法] [Characteristics and manufacturing methods of composite particles]

本發明之複合微粒，平均粒徑(數量平均一次粒徑)可為3000nm以下。尤其，複合微粒之平均粒徑以奈米大小為較佳，例如約1~1000nm，更佳為約10~500nm(例如20~400nm)，進一步更佳為約30~300nm(尤其是50~200nm)。若複合微粒之粒徑過大，則恐怕用於燒結之燒結溫度將變高，微細配線圖案之形成亦將變得困難。另一方面，若過小，則除調製變得困難之外，由於比表面積增大，氧化變得容易，同時對糊或油墨等之再分散亦變得困難。再者，藉由此等複合性要因而要使導電性提高亦變得困難。 The composite fine particles of the present invention may have an average particle size (number average primary particle size) of 3000 nm or less. In particular, the average particle size of the composite particles is preferably a nanometer size, for example, about 1 to 1000 nm, more preferably about 10 to 500 nm (for example, 20 to 400 nm), and even more preferably about 30 to 300 nm (in particular, 50 to 200 nm ). If the particle size of the composite particles is too large, the sintering temperature for sintering will become higher, and the formation of fine wiring patterns will also become difficult. On the other hand, if it is too small, in addition to the difficulty in preparation, the increase in specific surface area makes it easy to oxidize, and it also becomes difficult to re-disperse the paste or ink. Furthermore, it is also difficult to improve the electrical conductivity due to these composite properties.

在本發明中，複合微粒之平均粒徑，可藉由以SEM照片為基準，測定任意100~300個粒徑，再算出平均值之方法而測定。 In the present invention, the average particle diameter of the composite fine particles can be measured by measuring arbitrary 100 to 300 particle diameters based on the SEM photograph and then calculating the average value.

本發明之複合微粒，可藉由包含以酸分解性 聚合物將金屬微粒之至少一部分表面被覆之被覆步驟的製造方法而得到。 The composite particles of the present invention can be acid decomposable by The polymer is obtained by a manufacturing method of a coating step in which at least a part of the surface of metal fine particles is coated.

在前述被覆步驟中，以酸分解性聚合物將金屬微粒被覆之方法，無特別限定，通常可利用於酸分解性聚合物存在下，將原料金屬化合物還原之方法。 In the aforementioned coating step, the method of coating the metal fine particles with an acid-decomposable polymer is not particularly limited, and it can generally be used to reduce the raw metal compound in the presence of an acid-decomposable polymer.

就原料金屬化合物而言，可列舉金屬氧化物、金屬鹽、金屬鹵化物等。此等原料金屬化合物，可單獨或將二種以上組合而使用。 Examples of raw metal compounds include metal oxides, metal salts, and metal halides. These raw metal compounds can be used alone or in combination of two or more.

原料金屬化合物可依照金屬微粒之種類而選擇。金屬鹵化物中，可包含金屬氯化物、金屬溴化物、金屬碘化物等。金屬鹽中，可包含金屬無機酸鹽(硫酸鹽、硝酸鹽、碳酸鹽、鹽酸鹽、磷酸鹽等)、金屬有機酸鹽(甲酸鹽、乙酸鹽、乳酸鹽等)等。金屬鹽可為水合物。 The raw metal compound can be selected according to the type of metal particles. The metal halide may include metal chloride, metal bromide, metal iodide and the like. The metal salt may include metal inorganic acid salts (sulfate, nitrate, carbonate, hydrochloride, phosphate, etc.), metal organic acid salts (formate, acetate, lactate, etc.), and the like. The metal salt may be a hydrate.

在金屬微粒係銅微粒之情況，氧化銅包含氧化銅(I)(氧化亞銅)、氧化銅(II)(氧化銅)。鹵化銅包含氯化銅(I)(氯化亞銅)、氯化銅(II)(氯化銅)、溴化銅(I)(溴化亞銅)、溴化銅(II)(溴化銅)等。金屬鹽包含硫酸銅、硝酸銅、甲酸銅、乙酸銅等。其中，以選自包含氧化銅、硫酸銅、甲酸銅、乙酸銅及氯化銅之群組中的至少1種為較佳。 In the case of metal particles of copper particles, copper oxide includes copper (I) oxide (cuprous oxide) and copper (II) oxide (copper oxide). Copper halides include copper (I) (cuprous chloride), copper (II) (copper chloride), copper (I) bromide (copper bromide), copper (II) bromide (bromide) Copper) etc. The metal salt includes copper sulfate, copper nitrate, copper formate, copper acetate, and the like. Among them, at least one selected from the group consisting of copper oxide, copper sulfate, copper formate, copper acetate, and copper chloride is preferred.

合成時之酸分解性聚合物的比率，相對於100重量份之原料金屬化合物，可選自約1~500重量份(尤其是3~400重量份)之範圍。尤其，在酸分解性聚合物為聚合物(1)或(2)之情況，酸分解性聚合物之比率，相對於100重量份之原料金屬化合物，為例如約5~400重量份， 較佳為約10~250重量份，更佳為約15~200重量份。在酸分解性聚合物為聚合物(3)或(4)之情況，酸分解性聚合物之比率，相對於100重量份之原料金屬化合物，為例如約3~30重量份，較佳為約5~20重量份，更佳為約6~10重量份。若酸分解性聚合物之比率過小，則恐怕金屬微粒之安定性降低，粗大粒子生成，若過大，則恐怕非常微細之粒子生成，得不到具有期望之粒徑的複合粒子，而於低溫下之燒結將變得困難。 The ratio of the acid-decomposable polymer during synthesis can be selected from the range of about 1 to 500 parts by weight (particularly 3 to 400 parts by weight) relative to 100 parts by weight of the raw metal compound. In particular, when the acid-decomposable polymer is the polymer (1) or (2), the ratio of the acid-decomposable polymer is, for example, about 5 to 400 parts by weight relative to 100 parts by weight of the raw metal compound. It is preferably about 10 to 250 parts by weight, and more preferably about 15 to 200 parts by weight. In the case where the acid-decomposable polymer is the polymer (3) or (4), the ratio of the acid-decomposable polymer is, for example, about 3 to 30 parts by weight with respect to 100 parts by weight of the raw metal compound, preferably about 5-20 parts by weight, more preferably about 6-10 parts by weight. If the ratio of the acid-decomposable polymer is too small, the stability of the metal fine particles may decrease and coarse particles may be generated. If the ratio is too large, very fine particles may be generated, and composite particles having a desired particle size may not be obtained. The sintering will become difficult.

就還原劑而言，可例示慣用之還原劑，例如，氫化硼鈉類、氫化鋁鋰、次磷酸或其鹽、硼烷類、福馬林、肼、胺類、醇類、具有酚性羥基之羧酸等。此等還原劑可單獨或將二種以上組合而使用。此等還原劑中，可泛用氫化硼鈉、肼、第3級胺、乙二醇、單寧酸等，以肼為較佳。肼可為水合物。 As for the reducing agent, conventional reducing agents can be exemplified, for example, sodium borohydride, lithium aluminum hydride, hypophosphorous acid or salts thereof, boranes, formalin, hydrazine, amines, alcohols, phenolic hydroxyl groups Carboxylic acid etc. These reducing agents can be used alone or in combination of two or more. Among these reducing agents, sodium boron hydride, hydrazine, tertiary amine, ethylene glycol, tannic acid, etc. can be widely used, with hydrazine being preferred. Hydrazine may be a hydrate.

還原劑之比率，相對於1莫耳之原料金屬化合物，可選自例如約0.1~50莫耳(尤其是0.2~40莫耳)之範圍。尤其，在酸分解性聚合物為聚合物(1)或(2)之情況，還原劑之比率為例如約0.5~30莫耳，較佳為約1~30莫耳，更佳為約3~10莫耳。在酸分解性聚合物為聚合物(3)或(4)之情況，還原劑之比率為例如約0.2~30莫耳，較佳為約0.3~10莫耳，更佳為約0.5~5莫耳。若還原劑之比率過少，則恐怕金屬離子之還原變得不足，若過多，則恐怕粒徑變小，得不到具有期望之粒徑的複合粒子，在反應後之精製上需要時間。 The ratio of the reducing agent can be selected from the range of about 0.1 to 50 mol (especially 0.2 to 40 mol) relative to 1 mol of the raw metal compound. In particular, when the acid-decomposable polymer is the polymer (1) or (2), the ratio of the reducing agent is, for example, about 0.5 to 30 mol, preferably about 1 to 30 mol, and more preferably about 3 to 10 moles. In the case where the acid-decomposable polymer is the polymer (3) or (4), the ratio of the reducing agent is, for example, about 0.2 to 30 moles, preferably about 0.3 to 10 moles, more preferably about 0.5 to 5 moles ear. If the ratio of the reducing agent is too small, the reduction of metal ions may become insufficient, and if it is too large, the particle size may become small, and composite particles having a desired particle size may not be obtained, which requires time for purification after the reaction.

使用還原劑之還原反應，雖可為常溫，然而 從能促進還原反應之觀點而言，亦可加熱。在加熱之情況，加熱溫度可為例如約40~80℃，較佳為約45~70℃，更佳為約50~60℃。反應時間可為例如約10分鐘~20小時，通常約30分鐘~10小時，較佳為約1~5小時。還原反應可於攪拌下進行。 The reduction reaction using a reducing agent can be normal temperature, but From the viewpoint of promoting the reduction reaction, it may be heated. In the case of heating, the heating temperature may be, for example, about 40 to 80°C, preferably about 45 to 70°C, and more preferably about 50 to 60°C. The reaction time may be, for example, about 10 minutes to 20 hours, usually about 30 minutes to 10 hours, preferably about 1 to 5 hours. The reduction reaction can be carried out with stirring.

還原反應可於溶劑存在下進行。溶劑可依照原料金屬化合物及還原劑之種類而選擇，例如，可列舉：水、乙醇或異丙醇等醇類；丙酮等酮類、二

烷或四氫呋喃等環狀醚類；二甲基乙醯胺等醯胺類等。此等溶劑可單獨或將二種以上組合而使用。此等溶劑之中，泛用水、四氫呋喃等環狀醚類。溶劑之比率，相對於100重量份之原料金屬化合物，為例如約10~5000重量份，較佳為約30~4000重量份，更佳為約50~3000重量份。 The reduction reaction can be carried out in the presence of a solvent. The solvent can be selected according to the type of the raw metal compound and the reducing agent, and examples include alcohols such as water, ethanol, and isopropanol; ketones such as acetone, and

Cyclic ethers such as alkane or tetrahydrofuran; amides such as dimethylacetamide. These solvents can be used alone or in combination of two or more. Among these solvents, cyclic ethers such as water and tetrahydrofuran are used. The ratio of the solvent is, for example, about 10 to 5000 parts by weight, preferably about 30 to 4000 parts by weight, and more preferably about 50 to 3000 parts by weight with respect to 100 parts by weight of the raw metal compound.

在還原反應中，可藉由慣用之方法，使用酸(鹽酸、硫酸、硝酸、磷酸等之無機酸、乙酸等有機酸)、鹼(氫氧化鈉、氨等無機鹼等)來調整pH。 In the reduction reaction, the pH can be adjusted by conventional methods using acids (inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and organic acids such as acetic acid) and alkalis (inorganic bases such as sodium hydroxide and ammonia).

被覆步驟中所得到之複合微粒，雖可將還原反應終了後之分散液就其原樣直接利用於油墨等，然而前述分散液通常係提供於分離精製步驟。在分離精製步驟中，可藉由將生成之複合微粒，以慣用之方法(例如，離心分離、膜過濾器、限外過濾等之過濾處理等)從溶劑分離後，將分離之複合微粒洗淨及乾燥而精製。 Although the composite particles obtained in the coating step can be used as they are in the ink as it is after the reduction reaction, the dispersion liquid is usually provided in the separation and purification step. In the separation and purification step, the resulting composite particles can be washed after separation from the solvent by conventional methods (for example, filtration treatment such as centrifugal separation, membrane filter, extra-limit filtration, etc.) And dry and refined.

[分散液] [Dispersions]

本發明之分散液可包含前述複合微粒及分散媒，雖可為如前述被覆步驟中所得到之分散液，然而通常依照 目的，藉由使經分離精製步驟所得到之複合微粒分散於分散媒中而得到。 The dispersion liquid of the present invention may include the aforementioned composite fine particles and a dispersion medium, and although it may be the dispersion liquid obtained in the aforementioned coating step, it is generally in accordance with The purpose is obtained by dispersing the composite fine particles obtained through the separation and purification step in a dispersion medium.

分散媒可依照複合微粒之種類而選擇，亦可為水，然而從可使高濃度之複合微粒分散之觀點而言，以有機溶劑為較佳。在本發明中，複合微粒(尤其以包含聚合物(3)或(4)之保護層被覆的複合微粒)，由於溶劑溶解性優良，而可分散於各種有機溶劑。若分散液能以高濃度含有複合微粒，由於容易形成緻密之燒成膜，分散液容易被利用作為導電糊或導電油墨。 The dispersion medium can be selected according to the type of the composite particles, or it can be water. However, from the viewpoint of dispersing the composite particles with a high concentration, an organic solvent is preferred. In the present invention, the composite fine particles (especially composite fine particles coated with a protective layer containing the polymer (3) or (4)) can be dispersed in various organic solvents due to their excellent solvent solubility. If the dispersion liquid can contain composite fine particles in a high concentration, the dispersion liquid can be easily used as a conductive paste or a conductive ink because a dense fired film is easily formed.

就有機溶劑而言，可列舉如：醇系溶劑(例如，甲醇、乙醇、異丙醇、丁醇等烷醇類；乙二醇、甘油等脂肪族多元醇類；環己醇、松油醇、二氫松油醇等脂環族醇類等)、酯系溶劑(例如，乙酸乙酯、乙酸丁酯、丙二醇單甲基醚單乙酸酯等乙酸酯類)、酮系溶劑(例如，丙酮等鏈狀酮類；環己酮等環狀酮類)、醚系溶劑(例如，丙二醇單甲基醚、二乙二醇二甲基醚等鏈狀醚類；二

烷、四氫呋喃等環狀醚類)、芳香族系溶劑(例如，甲苯、二甲苯等芳香族烴類)、鹵素系溶劑(例如，二氯甲烷、氯仿等鹵烷類)、腈系溶劑(例如，乙腈、苄腈等)、硝基系溶劑(例如，硝基苯等)等。此等分散媒可單獨或將二種以上組合而使用。 Examples of organic solvents include: alcohol-based solvents (for example, alkanols such as methanol, ethanol, isopropanol, and butanol; aliphatic polyhydric alcohols such as ethylene glycol and glycerin; cyclohexanol and terpineol , Alicyclic alcohols such as dihydroterpineol, etc.), ester solvents (for example, acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether monoacetate), ketone solvents (for example, Chain ketones such as acetone; cyclic ketones such as cyclohexanone), ether solvents (for example, chain ethers such as propylene glycol monomethyl ether and diethylene glycol dimethyl ether; two

Cyclic ethers such as alkane and tetrahydrofuran), aromatic solvents (for example, aromatic hydrocarbons such as toluene and xylene), halogen solvents (for example, haloalkanes such as methylene chloride and chloroform), and nitrile solvents (for example , Acetonitrile, benzonitrile, etc.), nitro-based solvents (for example, nitrobenzene, etc.), etc. These dispersion media can be used alone or in combination of two or more.

在此等分散媒中，泛用醇系溶劑、酯系溶劑、環狀醚系溶劑。可依照保護層之種類而選擇分散媒，在保護層含有聚合物(1)之情況，分散媒可為甲醇等C_1-4烷醇、四氫呋喃等環狀醚、乙酸乙酯等乙酸C_1-3烷酯等。 在保護層含有聚合物(2)之情況，分散媒可為松油醇等脂環族醇、四氫呋喃等環狀醚、乙酸乙酯等乙酸C_1-3烷酯等。在保護層含有聚合物(3)或(4)之情況，分散媒可為甲醇等C_1-4烷醇、松油醇等脂環族醇、四氫呋喃等環狀醚、乙酸乙酯等乙酸C_1-3烷酯。 Among these dispersion media, alcohol solvents, ester solvents, and cyclic ether solvents are commonly used. The dispersion medium can be selected according to the type of the protective layer. When the protective layer contains the polymer (1), the dispersion medium can be C _1-4 alkanol such as methanol, cyclic ether such as tetrahydrofuran, and acetic acid C _1- such as ethyl acetate ₃ alkyl esters, etc. When the protective layer contains the polymer (2), the dispersion medium may be an alicyclic alcohol such as terpineol, a cyclic ether such as tetrahydrofuran, a C _1-3 alkyl acetate such as ethyl acetate, or the like. When the protective layer contains the polymer (3) or (4), the dispersion medium may be C _1-4 alkanols such as methanol, alicyclic alcohols such as terpineol, cyclic ethers such as tetrahydrofuran, and acetic acid C such as ethyl acetate _1-3 alkyl esters.

分散媒之比率，相對於100重量份之複合微粒，為例如約10~1000重量份，較佳為約30~500重量份，更佳為約50~400重量份(尤其是80~300重量份)。若分散媒之比率過多，則恐怕於塗布後之乾燥過程中容易發生龜裂等，形成導電性高之燒結膜將變得困難；若過少，則恐有分散液之塗布性降低之虞。 The ratio of the dispersion medium is, for example, about 10 to 1000 parts by weight, preferably about 30 to 500 parts by weight, and more preferably about 50 to 400 parts by weight (especially 80 to 300 parts by weight) relative to 100 parts by weight of the composite particles. ). If the ratio of the dispersion medium is too large, cracks or the like may easily occur during the drying process after coating, and it becomes difficult to form a sintered film with high conductivity; if it is too small, there is a possibility that the coating properties of the dispersion liquid may be lowered.

本發明之分散液由於使低溫下之燒結提高，就酸分解性聚合物之分解助劑而言，可進一步包含酸性化合物及/或酸產生劑。 Since the dispersion liquid of the present invention improves sintering at a low temperature, the decomposition aid of the acid-decomposable polymer may further contain an acidic compound and/or an acid generator.

在酸性化合物中，包含無機酸、有機酸等。就無機酸而言，可列舉如：鹽酸、硫酸、硝酸、磷酸、硼酸等。就有機酸而言，可列舉如：甲酸、乙酸、丙酸、丁酸、辛酸、硬脂酸等脂肪族單羧酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、馬來酸等脂肪族二羧酸；環烷酸等脂環族羧酸；二醇酸、乳酸、酒石酸、蘋果酸、檸檬酸等羥基羧酸；甲苯磺酸等芳烴磺酸等。此等無機酸及有機酸可為金屬鹽(例如，鈉等鹼金屬鹽、鈣等鹼土金屬鹽、錫等周期表14族金屬鹽等)。此等酸性化合物可單獨或將二種以上組合而使用。在此等酸性化合物中，從抑制低溫下之燒結性、酸分解性聚合物之分解性亦 優良的觀點而言，以甲酸等C_1-4脂肪族單羧酸(尤其是甲酸)為較佳。 The acidic compound includes inorganic acids, organic acids, and the like. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid. Examples of organic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, and stearic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and horse Aliphatic dicarboxylic acids such as maleic acid; alicyclic carboxylic acids such as naphthenic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, tartaric acid, malic acid, citric acid; aromatic hydrocarbon sulfonic acids such as toluenesulfonic acid. These inorganic acids and organic acids may be metal salts (for example, alkali metal salts such as sodium, alkaline earth metal salts such as calcium, group 14 metal salts of the periodic table, etc.). These acidic compounds can be used alone or in combination of two or more. Among these acidic compounds, C _1-4 aliphatic monocarboxylic acids (especially formic acid) such as formic acid are preferred from the viewpoint of excellent sinterability at low temperatures and decomposability of acid-decomposable polymers. .

就酸產生劑而言，可列舉慣用之酸產生劑，例如，鋶鹽(鋶離子與陰離子之鹽)、錪鹽(錪離子與陰離子之鹽)、硒鎓鹽(硒鎓離子與陰離子之鹽)、銨鹽(銨離子與陰離子之鹽)、鏻鹽(鏻離子與陰離子之鹽)、過渡金屬錯合物離子與陰離子之鹽、丙二烯-離子錯合物、鋁螯合物、三氟化硼胺錯合物等。此等酸產生劑可單獨或將二種以上組合而使用。在此等酸產生劑中，從酸性度高之觀點而言，以鋶鹽為較佳。 As for the acid generator, conventional acid generators can be cited, for example, osmium salts (salts of cations and anions), iodonium salts (salts of cations and anions), selenium salts (salts of selenium ions and anions) ), ammonium salt (ammonium ion and anion salt), phosphonium salt (phosphonium ion and anion salt), transition metal complex ion and anion salt, allene-ion complex, aluminum chelate, three Boron fluoride complex, etc. These acid generators can be used alone or in combination of two or more. Among these acid generators, from the viewpoint of high acidity, samium salts are preferred.

就鋶鹽而言，可列舉如：三苯基鋶鹽、三-對甲苯基鋶鹽、三-鄰甲苯基鋶鹽、參(4-甲氧基苯基)鋶鹽、1-萘基二苯基鋶鹽、2-萘基二苯基鋶鹽、參(4-氟苯基)鋶鹽、三-1-萘基鋶鹽、三-2-萘基鋶鹽、參(4-羥基苯基)鋶鹽、二苯基[4-(苯硫基)苯基]鋶鹽、4-(對甲苯硫基)苯基二-(對苯基)鋶鹽等三芳基鋶鹽；二苯基苄醯甲基鋶鹽、二苯基4-硝基苄醯甲基鋶鹽、二苯基苄基鋶鹽、二苯基甲基鋶鹽等二芳基鋶鹽；苯基甲基苄基鋶鹽、4-羥基苯基甲基苄基鋶鹽、4-甲氧基苯基甲基苄基鋶鹽等單芳基鋶鹽等。 Examples of samium salts include triphenylammonium salt, tri-p-tolylammonium salt, tri-o-tolylammonium salt, ginseng (4-methoxyphenyl)ammonium salt, and 1-naphthylbis Phenyl alkene salt, 2-naphthyl diphenyl alkoxide salt, ginseng (4-fluorophenyl) alkoxide salt, tri-1-naphthyl alkoxide salt, tri-2-naphthyl alkoxide salt, ginseng (4-hydroxybenzene) Group) sammonium salt, diphenyl[4-(phenylthio)phenyl]ammonium salt, 4-(p-tolylthio)phenyl bis-(p-phenyl)ammonium salt and other triarylammonium salt; diphenyl Diaryl benzyl salts such as benzyl methyl benzyl salts, diphenyl 4-nitrobenzyl methyl benzyl salts, diphenyl benzyl ammonium salts, diphenyl benzyl ammonium salts; phenyl methyl benzyl ammonium salts Salts, 4-hydroxyphenylmethylbenzyl alkoxide salts, 4-methoxyphenylmethylbenzyl alkoxide salts and other monoaryl alkoxide salts and the like.

就用於與鋶離子(陽離子)形成鹽之陰離子(對離子)而言，可列舉如：SbF^6-、PF^6-、BF^4-、氟化烷基氟磷酸離子[(CF₃CF₂)₃PF^3-、(CF₃CF₂CF₂)₃PF^3-等]、(C₆F₅)₄B^-、(C₆F₅)₄Ga^-、磺酸陰離子(三氟甲磺酸陰離子、五氟乙磺酸陰離子、九氟丁磺酸陰離子、甲磺酸陰離 子、苯磺酸陰離子、對甲苯磺酸陰離子等)、(CF₃SO₂)₃C^-、(CF₃SO₂)₂N^-、過鹵酸離子、鹵化磺酸離子、硫酸離子、碳酸離子、鋁酸離子、六氟鉍酸離子、羧酸離子、芳基硼酸離子、硫氰酸離子、硝酸離子等。此等陰離子之中，以PF^6-等磷之氟化物離子為較佳。 Examples of the anions (counter ions) used to form salts with cations (cations) include: SbF ^6- , PF ^6- , BF ^4- , and fluorinated alkyl fluorophosphate ions [(CF ₃ CF ₂ ) _{^{3 PF 3-, (CF 3 CF}} 2 CF 2) 3 PF 3- _{etc.], (C 6 F 5)} 4 B -, (C 6 F 5) 4 Ga -, sulfonic acid anion (trifluoromethanesulfonic acid anion , pentafluoroethane sulfonic acid anion, a nonafluorobutane sulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, toluenesulfonic acid anion, _{etc.), (CF 3 SO 2)} 3 C -, (CF 3 SO 2) 2 N ^-, perhalogen acid ion, a sulfonic acid halide ion, sulfate ion, carbonate ion, aluminate ion, a hexafluorophosphate ion bismuthate, a carboxylic acid ion, an aryl boronic acid ion, a thiocyanate ion, a nitrate ion. Among these anions, the fluoride ion such as PF ^6- is preferred.

酸產生劑可為熱酸產生劑，亦可為光酸產生劑。此等之中，就熱酸產生劑而言，可利用市售品，例如，可利用三新化學工業股份有限公司製「San-Aid SI-60L」、「San-Aid SI-60S」、「San-Aid SI-80L」、「San-Aid SI-100L」、「San-Aid SI-110L」，或ADEKA股份有限公司製「SP-66」、「SP-77」等。就光酸產生劑而言，可利用市售品，例如，可利用San-Apro股份有限公司製「HS-1」、「HS-1A」、「HS-1P」、「HS-1N」、「HS-1TF」、「HS-1NF」、「HS-1MS」、「HS-1CS」、「HS-1PC」、「LW-S1」、「LW-S1」、「LW-S1NF」、「K1-S」、「CPI-101A」、「CPI-100P」、「CPI300PG」等。 The acid generator may be a thermal acid generator or a photoacid generator. Among these, as the thermal acid generator, commercially available products can be used, for example, "San-Aid SI-60L", "San-Aid SI-60S", "San-Aid SI-60S" manufactured by Sanxin Chemical Industry Co., Ltd. San-Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-110L", or "SP-66" and "SP-77" manufactured by ADEKA Corporation. As for the photoacid generator, commercially available products can be used, for example, "HS-1", "HS-1A", "HS-1P", "HS-1N", "" manufactured by San-Apro Co., Ltd. "HS-1TF", "HS-1NF", "HS-1MS", "HS-1CS", "HS-1PC", "LW-S1", "LW-S1", "LW-S1NF", "K1- S", "CPI-101A", "CPI-100P", "CPI300PG", etc.

分解助劑可依照保護層所含之酸分解性聚合物之種類而選擇，在聚合物(1)、(3)及(4)可使用酸產生劑，在聚合物(2)可使用酸性化合物。此等之中，從簡便地使低溫燒結性提高之觀點而言，以酸產生劑為較佳，從可利用燒成步驟之熱的觀點而言，以熱酸產生劑為特佳。 The decomposition aid can be selected according to the type of acid-decomposable polymer contained in the protective layer, and acid generators can be used for the polymers (1), (3) and (4), and acidic compounds can be used for the polymer (2) . Among these, from the viewpoint of simply improving the low-temperature sinterability, an acid generator is preferable, and from the viewpoint of utilizing the heat of the firing step, a thermal acid generator is particularly preferable.

分解助劑(酸性化合物及/或酸產生劑)之比率，相對於100重量份之複合微粒，為例如約0.01~100重 量份，較佳為約0.03~80重量份，更佳為約0.05~50重量份。 The ratio of decomposition aids (acid compounds and/or acid generators) is, for example, about 0.01 to 100 parts by weight relative to 100 parts by weight of the composite fine particles The amount is preferably about 0.03 to 80 parts by weight, more preferably about 0.05 to 50 parts by weight.

尤其，在酸分解性聚合物為聚合物(1)、(3)或(4)之情況，分解助劑(尤其是酸產生劑)之比率，相對於100重量份之複合微粒，為例如約0.01~10重量份，較佳為約0.03~5重量份，更佳為約0.05~3重量份(尤其是0.08~2重量份)。 In particular, when the acid-decomposable polymer is the polymer (1), (3) or (4), the ratio of the decomposition aid (particularly the acid generator) is, for example, about 100 parts by weight of the composite fine particles. 0.01 to 10 parts by weight, preferably about 0.03 to 5 parts by weight, more preferably about 0.05 to 3 parts by weight (particularly 0.08 to 2 parts by weight).

另一方面，在酸分解性聚合物為聚合物(2)之情況，分解助劑(尤其是酸性化合物)之比率，相對於100重量份之複合微粒，為例如約1~100重量份，較佳為約5~80重量份，更佳為約10~50重量份(尤其是20~40重量份)。又，分解助劑(尤其是酸性化合物)之比率，相對於分散液(油墨)總量，為例如約1~30重量%，較佳為約3~20重量%，更佳為約5~15重量%。 On the other hand, when the acid-decomposable polymer is the polymer (2), the ratio of the decomposition aid (especially the acidic compound) is, for example, about 1 to 100 parts by weight relative to 100 parts by weight of the composite fine particles. It is preferably about 5 to 80 parts by weight, and more preferably about 10 to 50 parts by weight (especially 20 to 40 parts by weight). In addition, the ratio of decomposition aids (especially acidic compounds) relative to the total amount of the dispersion liquid (ink) is, for example, about 1 to 30% by weight, preferably about 3 to 20% by weight, and more preferably about 5 to 15 weight%.

若分解助劑之比率過多，則恐怕燒結後分解助劑殘存、導電性降低或分散液之安定性降低；若過少，則恐怕低溫燒結性降低，酸分解性聚合物之分解不足，造成導電性降低。 If the ratio of the decomposition aid is too large, the decomposition aid may remain after sintering, the conductivity may be reduced, or the stability of the dispersion may be reduced; if it is too small, the low temperature sinterability may be reduced, and the decomposition of the acid-decomposable polymer may be insufficient, resulting in conductivity reduce.

本發明之分散液，可依照用途，包含添加於導電糊或導電油墨中之慣用添加劑。就慣用添加劑而言，除保護層之項中所例示之慣用添加劑外，可列舉著色劑(染顏料等)、色相改良劑、染料固著劑、光澤賦予劑等。慣用之添加劑的比率，相對於分散液總量，可為約50重量%以下，例如為約0.01~10重量%(尤其是0.1~5重量%)。 The dispersion of the present invention may contain conventional additives added to conductive paste or conductive ink according to the application. The conventional additives include, in addition to the conventional additives exemplified in the section of the protective layer, colorants (dyeing pigments, etc.), hue modifiers, dye fixing agents, gloss-imparting agents, and the like. The ratio of conventional additives may be about 50% by weight or less relative to the total amount of the dispersion, for example, about 0.01 to 10% by weight (especially 0.1 to 5% by weight).

本發明之分散液，在將經由分離精製步驟所得到之複合微粒，經由於分散媒中分散處理之分散步驟而得到的情況，前述分散步驟可為加壓下分散處理之分散步驟。前述分散步驟之壓力，可為約10MPa以上，例如約30~500MPa，較佳為約50~300MPa，更佳為約80~200MPa(尤其是100~180MPa)。此種在加壓下之分散，可使用超高壓分散機進行分散處理。若壓力過低，則恐怕以高濃度調製均勻之分散液變得困難。加壓下之分散處理，在酸分解性聚合物為聚合物(1)或(2)之情況，特別有效。 In the case of the dispersion liquid of the present invention, when the composite fine particles obtained through the separation and purification step are obtained through a dispersion step of dispersion treatment in a dispersion medium, the aforementioned dispersion step may be a dispersion step of dispersion treatment under pressure. The pressure in the foregoing dispersion step may be about 10 MPa or more, such as about 30 to 500 MPa, preferably about 50 to 300 MPa, and more preferably about 80 to 200 MPa (especially 100 to 180 MPa). This type of dispersion under pressure can be dispersed using an ultra-high pressure disperser. If the pressure is too low, it may become difficult to prepare a uniform dispersion liquid at a high concentration. The dispersion treatment under pressure is particularly effective when the acid-decomposable polymer is the polymer (1) or (2).

再者，就加壓下之分散處理的前處理而言，可進行攪拌處理(使用自轉/公轉攪拌機之攪拌處理等)及/或超音波處理(例如約10~100kHz之超音波處理)。 In addition, as for the pretreatment of the dispersion treatment under pressure, stirring treatment (agitating treatment using a rotation/revolution mixer, etc.) and/or ultrasonic treatment (for example, ultrasonic treatment of about 10 to 100 kHz) may be performed.

[塗膜及燒成膜以及彼等之製造方法] [Coated film, fired film and their manufacturing method]

本發明之塗膜可經由在基材上將前述分散液塗布的塗布步驟而得到。基材可為無機材料，亦可為有機材料。就無機材料而言，可列舉如玻璃類(鈉玻璃、硼矽酸玻璃、冕牌玻璃(Crown glass)、含有鋇之玻璃、含有鍶之玻璃、含有硼之玻璃、低鹼玻璃、無鹼玻璃、結晶化透明玻璃、矽石玻璃、石英玻璃、耐熱玻璃等)、金屬氧化物(礬土、藍寶石、氧化鋯、氧化鈦、氧化釔、氧化銦-氧化錫系複合氧化物(ITO)、氟摻雜氧化錫(FTO)等)等。就有機材料而言，可列舉如聚甲基丙烯酸甲酯系樹脂、聚丙烯系樹脂、環狀聚烯烴系樹脂、苯乙烯系樹脂、氯乙烯系樹脂、聚酯系樹脂[包含聚伸烷基芳酯系樹脂(聚 對苯二甲酸乙二酯等)、聚芳酯系樹脂或液晶聚合物]、聚醯胺系樹脂、聚碳酸酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚醯亞胺系樹脂、纖維素衍生物、氟樹脂等。特別是因為可在低溫下燒結，故即便是聚對苯二甲酸乙二酯(PET)等耐熱性低之樹脂基材亦可燒結。基材之平均厚度，為例如約0.001~10mm，較佳為約0.01~5mm，更佳為約0.05~3mm。 The coating film of the present invention can be obtained through a coating step of coating the aforementioned dispersion on a substrate. The base material may be an inorganic material or an organic material. Examples of inorganic materials include glass (soda glass, borosilicate glass, crown glass), glass containing barium, glass containing strontium, glass containing boron, low-alkali glass, and alkali-free glass , Crystallized transparent glass, silica glass, quartz glass, heat-resistant glass, etc.), metal oxides (alumina, sapphire, zirconia, titanium oxide, yttrium oxide, indium oxide-tin oxide composite oxide (ITO), fluorine Doped tin oxide (FTO), etc.). Examples of organic materials include polymethyl methacrylate resins, polypropylene resins, cyclic polyolefin resins, styrene resins, vinyl chloride resins, and polyester resins [including polyalkylenes] Aryl ester resin (poly (Ethylene terephthalate, etc.), polyarylate resin or liquid crystal polymer], polyamide resin, polycarbonate resin, poly resin resin, polyether resin, polyimide resin , Cellulose derivatives, fluororesins, etc. In particular, because it can be sintered at a low temperature, even resin substrates with low heat resistance such as polyethylene terephthalate (PET) can be sintered. The average thickness of the substrate is, for example, about 0.001 to 10 mm, preferably about 0.01 to 5 mm, and more preferably about 0.05 to 3 mm.

就塗布方法而言，可利用慣用之方法，不過在以塗膜形成圖案(配線基板上之配線圖案等)之情況下，可利用例如網版印刷法、油墨噴射印刷法、凹版印刷法(例如，凹版印刷法(gravure printing)等)、平板印刷法、凹版平板印刷法(例如，凹版膠板印刷法(gravure offset printing)等)、凸版印刷法、柔性版印刷法、反轉印刷法等。 As for the coating method, a conventional method can be used, but in the case of forming a pattern with a coating film (wiring pattern on a wiring substrate, etc.), for example, a screen printing method, an ink jet printing method, or a gravure printing method (for example , Gravure printing (gravure printing, etc.), lithography, gravure lithography (eg, gravure offset printing, etc.), relief printing, flexographic printing, reverse printing, etc.

塗膜之平均厚度可為例如約0.5~100μm(例如1~20μm)，較佳為約1~80μm(例如3~10μm)，更佳為約5~50μm(尤其是10~40μm)。在塗膜為將微細配線圖案化之塗膜的情況，塗膜(配線圖案)之平均線寬，可為例如約0.5~30μm，較佳為約1~20μm，更佳為約2~10μm(尤其是3~8μm)。在本發明中，由於可調製以高濃度包含奈米大小之金屬微粒的分散液(糊或油墨)，亦可容易地形成微細之配線圖案。 The average thickness of the coating film may be, for example, about 0.5 to 100 μm (eg, 1 to 20 μm), preferably about 1 to 80 μm (eg, 3 to 10 μm), and more preferably about 5 to 50 μm (particularly, 10 to 40 μm). When the coating film is a coating film patterning fine wiring, the average line width of the coating film (wiring pattern) may be, for example, about 0.5 to 30 μm, preferably about 1 to 20 μm, and more preferably about 2 to 10 μm ( Especially 3~8μm). In the present invention, since a dispersion liquid (paste or ink) containing nano-sized metal fine particles at a high concentration can be prepared, a fine wiring pattern can also be easily formed.

本發明之燒成膜，係經由將所得到之塗膜加熱燒成之燒成步驟而得到。在燒成步驟中，加熱溫度可超過200℃，然而在分散液包含分解助劑之情況，可進行 低溫之燒結，可為約200℃以下，例如約60~200℃，較佳為約80~180℃(例如100~175℃)，更佳為約120~170℃(尤其是130~160℃)。再者，在酸分解性聚合物為聚合物(3)或(4)，且分散液包含分解助劑(尤其是酸產生劑)之情況，可進行更低溫之燒結，加熱溫度可為約120℃以下，例如約60~120℃，較佳為約80~110℃，更佳為約90~105℃。 The fired film of the present invention is obtained through a firing step of heating and firing the obtained coating film. In the firing step, the heating temperature can exceed 200°C, however, in the case where the dispersion contains a decomposition aid, it can be carried out Low temperature sintering may be about 200°C or lower, such as about 60-200°C, preferably about 80-180°C (eg 100-175°C), more preferably about 120-170°C (especially 130-160°C) . Furthermore, when the acid-decomposable polymer is the polymer (3) or (4), and the dispersion contains a decomposition aid (especially an acid generator), sintering at a lower temperature can be performed, and the heating temperature can be about 120 Below ℃, for example about 60-120 ℃, preferably about 80-110 ℃, more preferably about 90-105 ℃.

燒成時間(加熱時間)可依照燒成溫度等而調整，例如，為約10分鐘~10小時，較佳為約15分鐘~8小時，更佳為約20分鐘~6小時(尤其是30分鐘~5小時)。 The firing time (heating time) can be adjusted according to the firing temperature, etc. For example, it is about 10 minutes to 10 hours, preferably about 15 minutes to 8 hours, more preferably about 20 minutes to 6 hours (especially 30 minutes ~5 hours).

燒成步驟可於空氣等含氧之活性氣體環境下進行，然而從能抑制金屬微粒之氧化的觀點而言，以在氫、氮、氬等惰性氣體環境下燒成為較佳。惰性氣體可為含氫之二種以上之惰性氣體的組合，例如，可為將氫及氮以氫/氮=約0.1/99.9~20/80，較佳為約0.5/99.5~10/90，更佳為約1/99~5/95之體積比率混合的混合氣體。 The firing step can be carried out in an oxygen-containing active gas environment such as air. However, from the viewpoint of suppressing the oxidation of metal fine particles, firing in an inert gas environment such as hydrogen, nitrogen, or argon is preferred. The inert gas may be a combination of two or more inert gases containing hydrogen. For example, hydrogen and nitrogen may be hydrogen/nitrogen=about 0.1/99.9~20/80, preferably about 0.5/99.5~10/90. More preferably, it is a mixed gas mixed in a volume ratio of about 1/99 to 5/95.

本發明中，酸分解性聚合物可藉由分解而進行低溫燒結，例如，在分散液包含熱酸產生劑之情況，可藉由前述燒成步驟中之加熱使酸產生，將酸分解性聚合物分解。 In the present invention, the acid-decomposable polymer can be sintered at a low temperature by decomposition. For example, in the case where the dispersion liquid contains a thermal acid generator, the acid can be generated by heating in the aforementioned firing step to polymerize the acid decomposably Decomposition.

另一方面，可依照酸分解性聚合物之有無或種類，另外設置用於分解酸分解性聚合物之聚合物分解步驟，作為前述燒成步驟之前步驟。例如，在分散液包含酸性化合物之情況，可設置例如於約35~100℃，較佳為約40~80℃，更佳為約45~60℃加熱的聚合物分解步 驟。 On the other hand, a polymer decomposition step for decomposing the acid-decomposable polymer may be additionally provided according to the presence or type of the acid-decomposable polymer as a step before the firing step. For example, in the case where the dispersion contains an acidic compound, it can be set at, for example, about 35 to 100°C, preferably about 40 to 80°C, and more preferably about 45 to 60°C. Step.

再者，在酸分解性聚合物為熱酸產生劑之情況，亦可另行設置用於將酸分解性聚合物分解之聚合物分解步驟，作為前述燒成步驟之前步驟。聚合物分解步驟中之加熱溫度，為例如約40~200℃，較佳為約50~180℃，更佳為約70~150℃。 In addition, when the acid-decomposable polymer is a thermal acid generator, a polymer decomposition step for decomposing the acid-decomposable polymer may be separately provided as a step before the firing step. The heating temperature in the polymer decomposition step is, for example, about 40 to 200°C, preferably about 50 to 180°C, and more preferably about 70 to 150°C.

在分散液包含光酸產生劑之情況，可設置照射可見光線或紫外線等，使酸產生之聚合物分解的步驟。該聚合物分解步驟，可對經前述塗布步驟之塗膜進行光照射後，供給燒成步驟。又，前述聚合物分解步驟，可為在燒成步驟中，與燒成同時進行光照射之步驟。再者，前述聚合物分解步驟，可於塗布步驟之前，在分散液之階段照射紫外線或可見光，使酸產生，然後，供給至塗布步驟及燒成步驟。就光照射之光源而言，可利用慣用之光源，在紫外線之情況，可列舉超高壓至低壓水銀燈或LED、氙燈等。 In the case where the dispersion contains a photoacid generator, a step of irradiating visible light or ultraviolet rays to decompose the acid-generated polymer may be provided. In this polymer decomposition step, the coating film subjected to the aforementioned coating step may be subjected to light irradiation and then supplied to the firing step. In addition, the aforementioned polymer decomposition step may be a step of irradiating light simultaneously with the firing step. In addition, the aforementioned polymer decomposition step may be performed by irradiating ultraviolet rays or visible light at the stage of the dispersion liquid before the coating step to generate an acid, and then supplying it to the coating step and the firing step. As a light source for light irradiation, a conventional light source can be used, and in the case of ultraviolet rays, ultra-high to low-pressure mercury lamps, LEDs, xenon lamps, etc. can be cited.

本發明之燒成膜，導電性優良，電阻率可為約0.5Ω/□以下，例如約0.01~0.5Ω/□，較佳為約0.02~0.3Ω/□，更佳為約0.03~0.1Ω/□。 The fired film of the present invention has excellent conductivity, and the resistivity can be about 0.5 Ω/□ or less, for example, about 0.01 to 0.5 Ω/□, preferably about 0.02 to 0.3 Ω/□, and more preferably about 0.03 to 0.1 Ω. /□.

又，本發明之燒結膜，比電阻率可為1×10^-5Ω‧cm以下，例如約1×10^-9~1×10^-6Ω‧cm，較佳為約1×10^-8~3×10^-6Ω‧cm，更佳為約5×10^-8~2×10^-6Ω‧cm。 In addition, the sintered film of the present invention may have a specific resistivity of 1×10 ^-5 Ω‧cm or less, for example, about 1×10 ^-9 ~1×10 ^-6 Ω‧cm, preferably about 1×10 ^-8 ~ 3×10 ^-6 Ω‧cm, more preferably about 5×10 ^-8 ~2×10 ^-6 Ω‧cm

[實施例] [Example]

以下，根據實施例，更詳細地說明本發明，不過本發明並不受此等實施例限定。茲將實施例及比較 例中所得到之聚合物、塗膜及燒成膜，藉由以下項目評價。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Examples and comparison The polymer, coating film, and fired film obtained in the examples were evaluated by the following items.

[聚合物之分子量] [Molecular weight of polymer]

在合成例1中所得到之聚合物之重量平均分子量(Mw)及數量平均分子量(Mn)，係使用連結3支管柱(TOSOH股份有限公司製「TSKgel MultiporeHXL-M」)，以氯仿作為移動相，並具備RI-8020檢測器之高速凝膠滲透管柱層析儀(TOSOH股份有限公司製「HLC-8220GPC」)，以於40℃、流速1.0mL/分鐘的條件進行，並以聚苯乙烯換算而求得。 The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer obtained in Synthesis Example 1 were connected with 3 columns ("TSKgel MultiporeHXL-M" manufactured by TOSOH Corporation) using chloroform as the mobile phase And a high-speed gel permeation column chromatograph ("HLC-8220GPC" manufactured by TOSOH Co., Ltd.) equipped with RI-8020 detector, under the conditions of 40 ℃, flow rate 1.0mL/min, and polystyrene It is calculated by conversion.

在合成例2及3中所得到之聚合物之重量平均分子量(Mw)及數量平均分子量(Mn)，係使用連結3支管柱(TOSOH股份有限公司製「TSKgel-superHZM-M」)，以四氫呋喃作為移動相，並具備RI-8020檢測器之高速凝膠滲透管柱層析儀(TOSOH股份有限公司製「HLC-8220GPC」)，以於40℃、流速0.6mL/分鐘的條件進行，並以聚苯乙烯換算而求得。 The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers obtained in Synthesis Examples 2 and 3 were connected with three columns (TOSOH Co., Ltd. "TSKgel-superHZM-M") using tetrahydrofuran As a mobile phase, a high-speed gel permeation column chromatograph ("HLC-8220GPC" manufactured by TOSOH Co., Ltd.) equipped with a RI-8020 detector was carried out at 40°C and a flow rate of 0.6 mL/min. It is obtained by converting polystyrene.

[聚合物之NMR] [NMR of polymer]

¹H-NMR係使用核磁共振裝置(日本電子股份有限公司製「JNM-ECA500」)，以測定溶劑：重氫化氯仿；頻率數：500MHz之條件測定。 ¹ H-NMR system uses a nuclear magnetic resonance apparatus ("JNM-ECA500" manufactured by JEOL Ltd.) to measure the solvent: heavy hydrogenated chloroform; frequency: 500 MHz.

[聚合物之溶解性] [Solubility of polymer]

在聚合物中以濃度成為20重量%之方式添加溶劑，於室溫下攪拌後，藉由目視觀察溶解狀態，並用以下之基準評價。 A solvent was added to the polymer so that the concentration became 20% by weight, and after stirring at room temperature, the dissolved state was visually observed and evaluated by the following criteria.

○：無混濁 ○: No turbidity

×：有混濁。 ×: There is turbidity.

[聚合物之TG-DTA] [TG-DTA of polymer]

TG-DTA係使用示差熱熱重量同時測定裝置(SII奈米技術股份有限公司製「TG-DTA6200」)，藉由以下之條件測定。 The TG-DTA system uses a differential thermo-thermogravimetric simultaneous measurement device ("TG-DTA6200" manufactured by SII Nano Technology Co., Ltd.), and is measured under the following conditions.

<測定條件> <Measurement conditions>

環境：N₂300mL/分鐘 Environment: N ₂ 300mL/min

溫度範圍：30~550℃ Temperature range: 30~550℃

升溫速度：5℃/分鐘 Heating rate: 5℃/min

樣本盤：Al。 Sample tray: Al.

[燒成膜之電阻率及比電阻率] [Resistivity and Specific Resistivity of Fired Film]

使用電阻率計(三菱化學分析技術股份有限公司製「Loresta GP MCP-T610」)，藉由4探針法，計測6點，算出平均值。 Using a resistivity meter ("Loresta GP MCP-T610" manufactured by Mitsubishi Chemical Analysis Technology Co., Ltd.), 6 points were measured by the 4-probe method, and the average value was calculated.

[複合微粒、塗膜及燒成膜之X射線繞射(XRD)] [X-ray diffraction (XRD) of composite particles, coating film and fired film]

使用桌上型X射線繞射裝置(理學股份有限公司製「MiniFlex II」)，以開始角度10°，終了角度110.005°，取樣寬0.015°，掃描速度每分鐘10.0°，電壓30kV，電流15mA來測定。 Use a desktop X-ray diffraction device ("MiniFlex II" manufactured by Rigaku Co., Ltd.) with a starting angle of 10° and a final angle of 110.005°, a sampling width of 0.015°, a scanning speed of 10.0° per minute, a voltage of 30 kV, and a current of 15 mA. Determination.

聚合物之合成例1 Polymer Synthesis Example 1

[保護層用聚合物(p-MOMPO)之合成] [Synthesis of polymer for protective layer (p-MOMPO)]

在乾燥氮氣環境下，將3.1mL之精製甲苯、0.25mL 之精製庚烷、0.4mL之四氫呋喃(THF)、及0.28mL之2-甲氧基-1-甲基環氧丙烷添加於容器1中，均勻地攪拌。 Under a dry nitrogen environment, 3.1mL of purified toluene, 0.25mL The purified heptane, 0.4 mL of tetrahydrofuran (THF), and 0.28 mL of 2-methoxy-1-methylpropylene oxide were added to the container 1 and stirred uniformly.

繼而，在其他容器2中，添加4.1mL之精製甲苯、及0.2mL之1.06M異丁氧基乙基氯化物(IBVE-HCl)之己烷溶液，攪拌至均勻。將0.5mL所得到之溶液添加於容器1中。 Then, in another container 2, 4.1 mL of purified toluene and 0.2 mL of a 1.06 M isobutoxyethyl chloride (IBVE-HCl) hexane solution were added and stirred until uniform. 0.5 mL of the resulting solution was added to container 1.

再者，在其他容器3中，添加3mL之精製甲苯、1mL之調製成200mM之氯化鎵(GaCl₃)的己烷溶液，攪拌至均勻，並冷卻至0℃。將0.5mL之所得到之溶液加入冷卻至0℃之容器1中的溶液，均勻地攪拌，開始聚合，並繼續攪拌4小時(聚合溫度保持於0℃)。 In addition, in another container 3, 3 mL of purified toluene and 1 mL of a hexane solution of 200 mM gallium chloride (GaCl ₃ ) were added, stirred until uniform, and cooled to 0°C. 0.5 mL of the resulting solution was added to the solution in container 1 cooled to 0°C, stirred uniformly, and polymerization was started, and stirring was continued for 4 hours (the polymerization temperature was maintained at 0°C).

再者，容器(容器1、容器2、容器3)全部使用安裝三方活栓之玻璃容器，係在乾燥氮氣環境下，使用輸出約400℃熱風之工業用噴氣機，加熱10分鐘，盡力除去吸附水者。 In addition, all the containers (container 1, container 2, and container 3) use glass containers with tripartite stoppers installed. In a dry nitrogen environment, an industrial jet with a hot air output of about 400°C is used for 10 minutes to remove the adsorbed water. By.

聚合開始時各成分之濃度如以下所示。 The concentration of each component at the start of polymerization is shown below.

[2-甲氧基-1-甲基環氧丙烷]=0.5M [2-methoxy-1-methylpropylene oxide]=0.5M

[IBVE-HCl]=5mM [IBVE-HCl]=5mM

[GaCl₃]=5mM [GaCl ₃ ]=5mM

[THF]=1M。 [THF]=1M.

然後(攪拌4小時後)，添加3mL之含約1%氨水的甲醇，使聚合停止。關於停止聚合之混合物(溶液)，以約20mL二氯甲烷稀釋後，用水洗淨，除去觸媒殘餘物，然後，藉由使溶劑等蒸發，回收生成物(聚合物)。 Then (after stirring for 4 hours), 3 mL of methanol containing about 1% ammonia water was added to stop the polymerization. The mixture (solution) for stopping the polymerization was diluted with about 20 mL of methylene chloride, washed with water to remove catalyst residues, and then the product (polymer) was recovered by evaporating the solvent or the like.

前述聚合之單體(2-甲氧基-1-甲基環氧丙烷) 的轉化率為89%(聚合時間：4小時)。又，所得到之聚合物的重量平均分子量(Mw)為5300，分子量分布(Mw/Mn)為1.30。 The aforementioned polymerized monomer (2-methoxy-1-methylpropylene oxide) The conversion rate was 89% (polymerization time: 4 hours). In addition, the weight average molecular weight (Mw) of the obtained polymer was 5,300, and the molecular weight distribution (Mw/Mn) was 1.30.

測定所得到之聚合物的¹H-NMR光譜時，確認在主鏈生成具有縮醛構造之聚合物(開環聚合物)。第1圖中，表示所得到之聚合物的¹H-NMR光譜圖。關於¹H-NMR光譜之峰歸屬於聚合物之何種質子，示於第1圖。在第1圖中，g質子之峰、b、c、h、及k質子之峰、a、f、及i質子之峰的積分比[g：(b、c、h、k)：(a、f、i)]為1：3：6。將所得到之聚合物的NMR數據示於以下。 When the ¹ H-NMR spectrum of the obtained polymer was measured, it was confirmed that a polymer having an acetal structure (ring-opening polymer) was formed in the main chain. Fig. 1 shows the ¹ H-NMR spectrum of the obtained polymer. The proton to which the peak of the ¹ H-NMR spectrum belongs is shown in Fig. 1. In the first graph, the integral ratio of peaks of g protons, b, c, h, and k protons, peaks of a, f, and i protons [g: (b, c, h, k): (a , F, i)] is 1:3:6. The NMR data of the obtained polymer are shown below.

(NMR數據) (NMR data)

¹H-NMR(CDCl₃)：δ(ppm)4.4-4.2(m)、4.1-3.9(m)、3.7-3.3(m)、1.9-1.7(m)、1.4-1.1(m)、1.0-0.8(m)。 ¹ H-NMR (CDCl ₃ ): δ (ppm) 4.4-4.2(m), 4.1-3.9(m), 3.7-3.3(m), 1.9-1.7(m), 1.4-1.1(m), 1.0- 0.8(m).

聚合物之合成例2 Polymer Synthesis Example 2

[保護層用聚合物(p-ISB)之合成] [Synthesis of protective layer polymer (p-ISB)]

將5g異山梨醇(isosorbide)(東京化成工業股份有限公司製)及0.43g吡啶鎓對甲苯磺酸鹽(東京化成工業股份有限公司製)添加於20g丙二醇單甲基醚乙酸酯(Daicel股份有限公司製)中，並於30℃以下滴入6.78g異山梨醇二乙烯基醚(Daicel股份有限公司製)。滴入後於40℃攪拌4小時。反應開始時有異山梨醇之未溶解部分存在，而於反應終了時，異山梨醇之未溶解部分消失。反應終了後，用5重量%碳酸氫鈉水溶液及水洗淨，並將有機層減壓濃縮，得到7g之聚合物。該聚合物之重量平均分子量Mw為5200，分子量分布(Mw/Mn)為2.2。將所得到之聚合物 的NMR數據示於以下，並將NMR圖示於第2圖中。 5g of isosorbide (made by Tokyo Chemical Industry Co., Ltd.) and 0.43g of pyridinium p-toluenesulfonate (made by Tokyo Chemical Industry Co., Ltd.) were added to 20g of propylene glycol monomethyl ether acetate (Daicel Corporation) Co., Ltd.), and 6.78 g of isosorbide divinyl ether (manufactured by Daicel Co., Ltd.) was added dropwise below 30°C. After dropping, the mixture was stirred at 40°C for 4 hours. The undissolved portion of isosorbide exists at the beginning of the reaction, and the undissolved portion of isosorbide disappears at the end of the reaction. After the reaction was completed, it was washed with a 5 wt% sodium bicarbonate aqueous solution and water, and the organic layer was concentrated under reduced pressure to obtain 7 g of a polymer. The weight-average molecular weight Mw of this polymer was 5200, and the molecular weight distribution (Mw/Mn) was 2.2. The resulting polymer The NMR data is shown below, and the NMR graph is shown in the second figure.

(NMR數據) (NMR data)

¹H-NMR(CDCl₃)：δ(ppm)1.334-1.344(d)、1.386-1.397(d)、3.858-4.006(m)4.029-4.063(m)、4.232-4.352(m)、4.410-4.419(m)、4.526-4.567(m)、5.045-5.091(m)、6.352-6.487(m)。 ¹ H-NMR (CDCl ₃ ): δ (ppm) 1.334-1.344(d), 1.386-1.397(d), 3.858-4.006(m) 4.029-4.063(m), 4.232-4.352(m), 4.410-4.419 (m), 4.526-4.567(m), 5.045-5.091(m), 6.352-6.487(m).

再者，將10mg所得到之聚合物溶解於4.5g四氫呋喃後，添加0.5g之1N鹽酸，並於50℃加溫30分鐘。測定鹽酸處理物之重量平均分子量Mw時，重量體之峰消失。另一方面，將10mg所得到之聚合物溶解於5g之四氫呋喃，並於50℃加溫30分鐘，測定重量平均分子量Mw時，確認重量體之峰無變化。 Furthermore, after dissolving 10 mg of the obtained polymer in 4.5 g of tetrahydrofuran, 0.5 g of 1N hydrochloric acid was added, and the mixture was heated at 50° C. for 30 minutes. When the weight average molecular weight Mw of the hydrochloric acid-treated product is measured, the peak of the weight body disappears. On the other hand, 10 mg of the obtained polymer was dissolved in 5 g of tetrahydrofuran and heated at 50° C. for 30 minutes. When the weight average molecular weight Mw was measured, it was confirmed that the peak of the weight body did not change.

聚合物之合成例3 Polymer Synthesis Example 3

[保護層用聚合物(p-BDO)之合成] [Synthesis of protective layer polymer (p-BDO)]

將57.2g之1,4-丁二醇(東京化成工業股份有限公司製)及1.59g之吡啶鎓對甲苯磺酸鹽(東京化成工業股份有限公司製)，添加於265g之用分子篩(和光純藥工業股份有限公司製「4A 1/16」)脫水過的丙二醇單甲基醚乙酸酯(Daicel股份有限公司製)並攪拌後，於40℃滴入100.2g之1,4-丁二醇二乙烯基醚(Sigma Aldrich公司製)。滴入後，於40℃攪拌2小時。反應終了後，添加5g丁基胺而急速停止反應。繼而，添加乙酸乙酯後，用水洗淨，並將有機層減壓濃縮，以72%之產率得到聚合物(polymer)。該聚合物之重量平均分子量Mw為9000，分子量分布(Mw/Mn)為2.1。將所得到之聚合物的NMR數據示於以下 ，並將NMR圖示於第3圖中。 57.2g of 1,4-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.59g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 265g of molecular sieve (Wako Pure Pharmaceutical Industry Co., Ltd. "4A 1/16") dehydrated propylene glycol monomethyl ether acetate (made by Daicel Co., Ltd.) and stirred, then 100.2g of 1,4-butanediol was added dropwise at 40°C Divinyl ether (manufactured by Sigma Aldrich). After dropping, it was stirred at 40°C for 2 hours. After the reaction was completed, 5 g of butylamine was added to quickly stop the reaction. Then, after ethyl acetate was added, it was washed with water, and the organic layer was concentrated under reduced pressure to obtain a polymer with a yield of 72%. The weight average molecular weight Mw of this polymer was 9000, and the molecular weight distribution (Mw/Mn) was 2.1. The NMR data of the obtained polymer are shown below , And the NMR chart is shown in Figure 3.

(NMR數據) (NMR data)

¹H-NMR(CDCl₃)：δ(ppm)1.285-1.295(d)、1.617-1.633(m)、3.387-3.457(m)、3.554-3.629(m)、4.651-4.683(q)、6.441-6.482(dd)。 ¹ H-NMR (CDCl ₃ ): δ (ppm) 1.285-1.295(d), 1.617-1.633(m), 3.387-3.457(m), 3.554-3.629(m), 4.651-4.683(q), 6.441- 6.482 (dd).

又，將0.4g之所得到之聚合物溶解於1.1g之四氫呋喃後，添加0.3g之5N鹽酸，並於室溫下攪拌30分鐘。測定鹽酸處理物之重量平均分子量Mw時，聚合物之峰消失。另一方面，將0.4g之所得到之聚合物溶解於1.1g之四氫呋喃，並於室溫下攪拌30分鐘，測定重量平均分子量時，確認無聚合物之峰的變化。 Furthermore, after dissolving 0.4 g of the obtained polymer in 1.1 g of tetrahydrofuran, 0.3 g of 5N hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. When the weight average molecular weight Mw of the hydrochloric acid-treated product was measured, the peak of the polymer disappeared. On the other hand, 0.4 g of the obtained polymer was dissolved in 1.1 g of tetrahydrofuran and stirred at room temperature for 30 minutes. When the weight average molecular weight was measured, it was confirmed that there was no change in the peak of the polymer.

再者，將所得到之聚合物之TG-DTA的測定結果示於第4圖中，並將評價溶解性之結果示於表1。 In addition, the measurement result of TG-DTA of the obtained polymer is shown in FIG. 4, and the result of evaluating solubility is shown in Table 1.

複合微粒之合成例1 Synthetic example of composite particles 1

[經p-MOMPO被覆之銅粒子的合成] [Synthesis of copper particles coated with p-MOMPO]

將1.2802g之在聚合物之合成例1中所得到的 p-MOMPO於室溫下溶解於含有0.4M之氨的20mL四氫呋喃溶液中之後，添加0.8094g之氧化銅(II)(日進Chemco股份有限公司製「N-130」)，攪拌同時加熱至60℃，並於攪拌狀態下添加24mL之含有1M肼的四氫呋喃溶液。添加12分鐘後，確認來自反應液之發泡。發泡終了後，繼續於60℃下反應2小時。反應終了後，將生成之粒子以口徑0.2μm之過濾器進行過濾，並將過濾之粒子用四氫呋喃、水洗淨，及於室溫下真空乾燥，得到0.5g之經p-MOMPO被覆的銅微粒(複合微粒)。將該複合微粒用SEM(50000倍)觀察，測定粒徑時，中位數徑為123.8nm。將SEM之測定結果示於第5圖中。 1.2802g of the polymer obtained in Synthesis Example 1 After p-MOMPO was dissolved in 20 mL of tetrahydrofuran solution containing 0.4 M of ammonia at room temperature, 0.8094 g of copper (II) oxide ("N-130" manufactured by Nissin Chemco Co., Ltd.) was added and heated to 60°C while stirring , And add 24mL of a tetrahydrofuran solution containing 1M hydrazine under stirring. After 12 minutes of addition, foaming from the reaction liquid was confirmed. After the foaming was completed, the reaction was continued at 60°C for 2 hours. After the reaction was completed, the generated particles were filtered with a filter with a diameter of 0.2 μm, and the filtered particles were washed with tetrahydrofuran and water, and vacuum-dried at room temperature to obtain 0.5 g of p-MOMPO-coated copper particles (Composite particles). The composite fine particles were observed with SEM (50,000 times), and when the particle diameter was measured, the median diameter was 123.8 nm. The measurement results of SEM are shown in Fig. 5.

複合微粒之合成例2 Synthetic example of composite particles 2

[經p-ISB被覆之銅粒子的合成] [Synthesis of copper particles coated with p-ISB]

將3.3g之在聚合物之合成例2中所得到的p-ISB及12.5g之硫酸銅(II)5水合物添加於10mL之蒸餾水中，並於50℃下攪拌1小時，使其溶解。在該混合液中添加12.5mL之肼1水合物，並於50℃下攪拌3小時，使其反應。在反應液中添加蒸餾水，以5000rpm離心沉降5分鐘，以緩傾方式洗淨2次後，進一步添加乙醇，並以5000rpm離心沉降5分鐘，再以緩傾方式洗淨2次。將所得到之粒子於氮氣環境在室溫下乾燥，得到3.2g之經p-ISB被覆的銅微粒(複合微粒)。將該複合微粒用SEM(50000倍)觀察，測定粒徑時，中位數徑為90nm。將SEM之測定結果示於第6圖。 3.3 g of p-ISB obtained in Polymer Synthesis Example 2 and 12.5 g of copper (II) sulfate 5 hydrate were added to 10 mL of distilled water, and stirred at 50° C. for 1 hour to dissolve. 12.5 mL of hydrazine monohydrate was added to this mixed liquid, and it stirred at 50 degreeC for 3 hours, and was made to react. Distilled water was added to the reaction solution, and it was centrifugally settled at 5000 rpm for 5 minutes. After washing twice by gentle tilting, ethanol was further added, and it was centrifugally settled at 5000 rpm for 5 minutes, and then washed twice by gentle tilting. The obtained particles were dried at room temperature in a nitrogen atmosphere to obtain 3.2 g of p-ISB-coated copper fine particles (composite fine particles). The composite fine particles were observed by SEM (50,000 times), and the median diameter was 90 nm when the particle size was measured. The measurement result of SEM is shown in FIG. 6.

複合微粒之合成例3 Synthesis Example 3 of Composite Particles

[經p-BDO被覆之銅粒子的合成] [Synthesis of copper particles coated with p-BDO]

在500mL四氫呋喃中，將1.67g之在聚合物之合成例3中所得到之p-BDO於室溫下溶解後，添加20g氧化銅(II)(日進Chemco股份有限公司製「N-130」)並攪拌，同時加熱至50℃，在此混合液中添加12.5mL之肼1水合物，並於50℃下攪拌3小時，使其反應。在反應液中添加蒸餾水，以5000rpm進行5分鐘離心沉降，以緩傾方式進行2次洗淨後，進一步添加乙醇，並以5000rpm離心沉降5分鐘，再以緩傾方式洗淨2次。將所得到之銅粒子於氮氣環境下室溫中乾燥，得到16.02g之經p-BDO被覆的銅微粒(複合微粒)。將該複合微粒以SEM(25000倍)觀察，測定粒徑時，中位數徑為150.9nm。將SEM之測定結果示於第7圖。又，測定複合微粒之X射線繞射(XRD)。將XRD之測定結果示於第8圖。 In 500 mL of tetrahydrofuran, after dissolving 1.67 g of p-BDO obtained in Polymer Synthesis Example 3 at room temperature, 20 g of copper (II) oxide ("N-130" manufactured by Nissin Chemco Co., Ltd.) was added While stirring and heating to 50°C, 12.5 mL of hydrazine monohydrate was added to the mixture, and the mixture was stirred at 50°C for 3 hours to react. Distilled water was added to the reaction solution, centrifugal sedimentation was performed at 5000 rpm for 5 minutes, and washing was performed twice in a gentle tilting manner, ethanol was further added, and centrifugal sedimentation was performed at 5000 rpm for 5 minutes, and then washed twice in a gentle tilting manner. The obtained copper particles were dried at room temperature under a nitrogen atmosphere to obtain 16.02 g of p-BDO-coated copper fine particles (composite fine particles). The composite fine particles were observed by SEM (25,000 times), and when the particle diameter was measured, the median diameter was 150.9 nm. The measurement result of SEM is shown in FIG. 7. In addition, the X-ray diffraction (XRD) of the composite particles was measured. The measurement results of XRD are shown in Fig. 8.

實施例1 Example 1

(銅油墨之製造及燒成評價) (Manufacturing and firing evaluation of copper ink)

將經p-MOMPO被覆之銅微粒(複合微粒)以60網孔之篩進行篩分，關於通過篩之複合微粒，用乳鉢粉碎。在0.1260g之複合微粒中添加50mL甲醇，並以混合機(THINKY股份有限公司製「自轉/公轉Hybrid-Mixer」)攪拌8分鐘後，照射40kHz之超音波10分鐘，並用400網孔之過濾器過濾。使用超高壓分散機(Sugino Machine股份有限公司製「Star Burst」)，將濾液以噴射壓150MPa進行分散處理5次，以100MPa進行分散處理1次，得到複合微粒之分散液。將該分散液於減壓下除去甲醇，使甲醇 含量成為50重量%後，相對於複合微粒，添加0.1重量%之酸產生劑(三新化學工業股份有限公司製「SI-110L」)，得到銅油墨。使用刮刀(doctor blade)，將該銅油墨以20μm之膜厚塗布於礬土板上，並於150℃、混合有3%氫之氮氣下進行燒成4小時。燒成後之塗膜的表面電阻為0.232Ω/□。測定複合微粒、塗布後之塗膜及燒成膜之X射線繞射(XRD)。將XRD之測定結果示於第9圖中。 The copper fine particles (composite fine particles) coated with p-MOMPO were sieved with a 60-mesh sieve, and the composite fine particles passing through the sieve were crushed with a mortar. Add 50mL of methanol to 0.1260g of composite particles and stir for 8 minutes with a mixer ("Hybrid/Revolution Hybrid-Mixer" manufactured by THINKY Co., Ltd.), irradiate 40kHz ultrasonic wave for 10 minutes, and use a 400 mesh filter filter. Using an ultra-high pressure dispersing machine ("Star Burst" manufactured by Sugino Machine Co., Ltd.), the filtrate was subjected to dispersion treatment 5 times at a spray pressure of 150 MPa and once at 100 MPa to obtain a dispersion liquid of composite fine particles. Remove methanol from this dispersion under reduced pressure to make methanol After the content became 50% by weight, an acid generator ("SI-110L" manufactured by Sanshin Chemical Industry Co., Ltd.) was added to the composite fine particles by 0.1% by weight to obtain a copper ink. Using a doctor blade, the copper ink was coated on an alumina plate with a film thickness of 20 μm, and fired at 150° C. under nitrogen mixed with 3% hydrogen for 4 hours. The surface resistance of the coating film after firing was 0.232Ω/□. X-ray diffraction (XRD) of composite particles, coated film and fired film was measured. The measurement results of XRD are shown in Fig. 9.

實施例2 Example 2

將3.0g之經p-ISB被覆的銅微粒(複合微粒)及7.0g之α-松油醇添加於30mL甲醇後，使用混合機(THINKY股份有限公司製「自轉/公轉Hybrid-Mixer」)攪拌32分鐘。攪拌後，使用超高壓分散機(Sugino Machine股份有限公司製「Star Burst」)，以噴射壓150MPa進行分散處理5次，得到複合微粒之分散液。將該分散液於減壓下濃縮，除去甲醇後，在1.4mL之濃縮液中添加0.13mL之甲酸，得到銅油墨。使用刮刀，將該銅油墨以40μm之膜厚塗布於礬土板上，並於60℃、氮氣下，進行脫溶媒2小時後，在150℃、混合有3%氫之氮下進行燒成2小時。燒成後之塗膜之電阻率，為0.3036Ω/□。測定複合微粒、塗布後之塗膜及燒成膜之X射線繞射(XRD)。將XRD之測定結果示於第10圖。 After adding 3.0 g of p-ISB-coated copper fine particles (composite fine particles) and 7.0 g of α-terpineol to 30 mL of methanol, it was stirred using a mixer (“rotation/revolution Hybrid-Mixer” manufactured by THINKY Co., Ltd.) 32 minutes. After stirring, an ultra-high pressure dispersing machine ("Star Burst" manufactured by Sugino Machine Co., Ltd.) was used to perform a dispersion treatment 5 times at a spray pressure of 150 MPa to obtain a dispersion liquid of composite fine particles. This dispersion liquid was concentrated under reduced pressure, and after removing methanol, 0.13 mL of formic acid was added to 1.4 mL of the concentrated liquid to obtain a copper ink. Using a doctor blade, apply the copper ink to a bauxite plate with a film thickness of 40 μm, perform desolvation at 60°C under nitrogen for 2 hours, and fire at 150°C under nitrogen mixed with 3% hydrogen 2 hour. The resistivity of the coating film after firing was 0.3036Ω/□. X-ray diffraction (XRD) of composite particles, coated film and fired film was measured. The XRD measurement result is shown in Fig. 10.

實施例3 Example 3

除了在實施例1中不添加酸產生劑以外，以與實施例1同樣之方式得到銅油墨。使用刮刀，將該銅油墨以20μm之膜厚塗布於礬土板上，並於200℃、空氣下進行脫溶媒 4小時後，於200℃、混合有3%氫之氮氣下進行燒成2小時。燒成後之塗膜之電阻率為0.071Ω/□。測定複合微粒、塗布後之塗膜、脫溶媒後之塗膜及燒成膜的X射線繞射(XRD)。將XRD之測定結果示於第11圖。 A copper ink was obtained in the same manner as in Example 1, except that no acid generator was added in Example 1. Using a doctor blade, apply the copper ink to the alumina plate with a film thickness of 20 μm, and remove the solvent at 200° C. in air After 4 hours, firing was carried out at 200°C under nitrogen mixed with 3% hydrogen for 2 hours. The resistivity of the coating film after firing is 0.071Ω/□. The X-ray diffraction (XRD) of the composite particles, the coating film after coating, the coating film after solvent removal, and the fired film was measured. The XRD measurement results are shown in Fig. 11.

實施例4 Example 4

(銅粒子之藉由熱壓的導電性評價) (Evaluation of conductivity of copper particles by hot pressing)

將1g之在複合微粒之合成例3中所得到之複合微粒與10mg之酸產生劑(三新化學工業股份有限公司製「SI-100」)混合，以表2之各個溫度，於空氣下，以100MPa實施30分鐘熱壓(Φ13mm)。另一方面，將1g之在複合微粒之合成例3中所得到的複合微粒，以表2之各個溫度，於空氣下，以100MPa實施30分鐘熱壓(Φ13mm)。將所得到之銅膜的膜厚及比電阻率示於表2。 Mix 1 g of the composite particles obtained in Synthesis Example 3 of the composite particles with 10 mg of an acid generator ("SI-100" manufactured by Sanshin Chemical Industry Co., Ltd.) at various temperatures in Table 2 under air. Hot pressing (Φ13 mm) was performed at 100 MPa for 30 minutes. On the other hand, 1 g of the composite fine particles obtained in Synthesis Example 3 of composite fine particles was subjected to hot pressing (Φ13 mm) at 100 MPa for 30 minutes at 100 MPa at various temperatures in Table 2. Table 2 shows the film thickness and specific resistivity of the obtained copper film.

如表2之結果所明示，藉由於室溫(25℃)之加壓(100MPa)，顯示約10^-6Ω‧cm。無論酸產生劑存在或不存在，於80℃、100MPa，比電阻率分別減少至1.5×10^-6及1.4×10^-6Ω‧cm；再者，在酸產生劑A存在下，藉由於 100℃、100MPa之加熱/加壓，比電阻率減少至2.9×10^-7Ω‧cm。此現象可推測係由於100℃時從酸產生劑產生酸，聚合物分解之故。 As the results in Table 2 clearly show, the pressure (100 MPa) at room temperature (25°C) shows about 10 ^-6 Ω‧cm. Regardless of the presence or absence of the acid generator, at 80 ℃, 100 MPa, the specific resistivity is reduced to 1.5×10 ^-6 and 1.4×10 ^-6 Ω‧cm; in addition, in the presence of the acid generator A, due to 100 Heating/pressurization at ℃ and 100MPa reduces the specific resistance to 2.9×10 ^-7 Ω‧cm. This phenomenon can be presumed because the acid is generated from the acid generator at 100°C, and the polymer is decomposed.

[產業上之可利用性] [Industry availability]

本發明之複合微粒係可依導電油墨或導電糊形態，而利用於各種導電體之形成，不過由於金屬微粒為奈米大小，所以可調製成高濃度之油墨或糊，而可有效地利用於高密度化之微細配線圖案的形成。因此，本發明之複合微粒，以利用於形成有微細配線圖案之透明配線基板、及具備該配線基板之電子裝置為較佳。 The composite particles of the present invention can be used in the formation of various conductors according to the form of conductive ink or conductive paste. However, because the metal particles are nano-sized, they can be adjusted to high-concentration inks or pastes, which can be effectively used The formation of high-density fine wiring patterns. Therefore, the composite fine particles of the present invention are preferably used for a transparent wiring board on which a fine wiring pattern is formed, and an electronic device provided with the wiring board.

Claims (14)

一種複合微粒，其包含銅微粒及保護層，該保護層係將該銅微粒之至少一部分之表面被覆，而且包含酸分解性聚合物，其平均粒徑為10~500nm，該酸分解性聚合物具有下述式(1)所表示之重複單元、下述式(2)所表示之重複單元、下述式(3)所表示之重複單元、或下述式(4a)及(4b)所表示之二種重複單元；

式中，R¹至R³，各個彼此相同或相異，表示氫原子、鹵素原子、羥基、氫過氧基、胺基、硫醇基、磺酸基或有機基，而且R¹至R³之2個以上可彼此鍵結而形成環；R⁴表示鹵素原子、羥基、氫過氧基、胺基、硫醇基、磺酸基或有機基；

式中，環Z表示可具有取代基，且包含作為雜原子之氧原子的飽和雜環，而且環Z可為相同之前述飽和雜環的組合，也可為相異前述飽和雜環的組合；

式中，A¹表示可具有取代基之烴基、-A²-(O-A³)_n-基；式中，A²及A³，各個彼此相同或相異、表示可具 有取代基之烴基，n為1以上之整數；

式中，A⁴表示可具有取代基之烴基、-A⁶-(O-A⁷)_m-基；式中，A⁶及A⁷，各個彼此相同或相異，表示可具有取代基之烴基，m為1以上之整數；A⁵表示可具有取代基之烴基、-A⁸-(O-A⁹)_k-基；式中，A⁸及A⁹，各個彼此相同或相異，表示可具有取代基之烴基，k為1以上之整數；A⁴及A⁵為相異之基。 A composite particle comprising copper particles and a protective layer covering at least a part of the surface of the copper particles and containing an acid-decomposable polymer with an average particle size of 10 to 500 nm. The acid-decomposable polymer It has a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), or represented by the following formulas (4a) and (4b) Two kinds of repeating units;

In the formula, R ¹ to R ³ , each of which is the same as or different from each other, represents a hydrogen atom, a halogen atom, a hydroxyl group, a hydroperoxy group, an amine group, a thiol group, a sulfonic acid group, or an organic group, and R ¹ to R ³ Two or more of them can be bonded to each other to form a ring; R ⁴ represents a halogen atom, a hydroxyl group, a hydroperoxy group, an amine group, a thiol group, a sulfonic acid group or an organic group;

In the formula, ring Z represents a saturated heterocyclic ring which may have a substituent and contains an oxygen atom as a hetero atom, and ring Z may be the same combination of the aforementioned saturated heterocyclic rings or a combination of different saturated heterocyclic rings;

In the formula, A ¹ represents a hydrocarbon group which may have a substituent, -A ² -(OA ³ ) _n -group; in the formula, A ² and A ³ , each of which is the same or different from each other, represent a hydrocarbon group which may have a substituent, n It is an integer above 1;

In the formula, A ⁴ represents a hydrocarbon group which may have a substituent, -A ⁶ -(OA ⁷ ) _m -group; in the formula, A ⁶ and A ⁷ , each of which is the same as or different from each other, represents a hydrocarbon group which may have a substituent, m Is an integer of 1 or more; A ⁵ represents a hydrocarbon group which may have a substituent, -A ⁸ -(OA ⁹ ) _k -group; in the formula, A ⁸ and A ⁹ , each of which is the same as or different from each other, means that it may have a substituent Hydrocarbon group, k is an integer of 1 or more; A ⁴ and A ⁵ are different groups. 一種如請求項1之複合微粒之製造方法，其包含以酸分解性聚合物被覆銅微粒之至少一部分之表面的被覆步驟。 A method for manufacturing composite particles as claimed in claim 1, comprising a coating step of coating at least a part of the surface of the copper particles with an acid-decomposable polymer. 如請求項2之製造方法，其中在被覆步驟中，於酸分解性聚合物之存在下，將選自包含銅氧化物、銅鹽及銅鹵化物之群組中之至少1種原料銅化合物還原。 The manufacturing method according to claim 2, wherein in the coating step, at least one raw material copper compound selected from the group consisting of copper oxide, copper salt and copper halide is reduced in the presence of an acid-decomposable polymer . 如請求項3之製造方法，其中原料銅化合物係選自包含氧化銅、硫酸銅、甲酸銅、乙酸銅及氯化銅之群組中之至少1種，以及使用肼作為還原劑。 The manufacturing method according to claim 3, wherein the raw material copper compound is at least one selected from the group consisting of copper oxide, copper sulfate, copper formate, copper acetate, and copper chloride, and hydrazine is used as a reducing agent. 一種分散液，其包含如請求項1之複合微粒及分散媒，該分散媒為選自包含醇系溶劑、酯系溶劑、酮系溶劑、醚系溶劑、芳香族系溶劑、鹵素系溶劑、腈系溶劑及硝基系溶劑之群組中之至少1種，且該分散媒之比率，相對於100重量份之複合微粒， 為10~1000重量份。 A dispersion liquid comprising the composite fine particles according to claim 1 and a dispersion medium selected from the group consisting of alcohol-based solvents, ester-based solvents, ketone-based solvents, ether-based solvents, aromatic-based solvents, halogen-based solvents, and nitriles At least one of the group of solvents and nitro solvents, and the ratio of the dispersion medium to 100 parts by weight of the composite particles, It is 10~1000 parts by weight. 如請求項5之分散液，其進一步包含酸性化合物及/或酸產生劑。 The dispersion liquid according to claim 5, which further contains an acidic compound and/or an acid generator. 如請求項5或6之分散液，其進一步包含還原劑。 The dispersion liquid according to claim 5 or 6, further contains a reducing agent. 如請求項5或6之分散液，其係導電油墨或導電糊。 If the dispersion liquid of claim 5 or 6, it is conductive ink or conductive paste. 一種如請求項5至8中任一項之分散液之製造方法，其包含於加壓下進行分散處理的分散步驟。 A method for manufacturing a dispersion liquid according to any one of claims 5 to 8, which includes a dispersion step of performing a dispersion process under pressure. 一種塗膜之製造方法，其包含於基材之上塗布如請求項5至8中任一項之分散液。 A method for manufacturing a coating film, which comprises applying a dispersion liquid according to any one of claims 5 to 8 on a substrate. 一種燒成膜之製造方法，其包含將以如請求項10之方法所得到之塗膜加熱及燒成的燒成步驟。 A method for manufacturing a fired film, which includes a firing step of heating and firing the coating film obtained by the method of claim 10. 如請求項11之製造方法，其中燒成溫度係於200℃以下，且於惰性氣體環境下燒成。 The manufacturing method according to claim 11, wherein the firing temperature is below 200°C, and firing is performed in an inert gas environment. 如請求項11或12之製造方法，其中所得到之燒成膜之電阻率係0.5Ω/□以下。 The manufacturing method according to claim 11 or 12, wherein the resistivity of the obtained fired film is 0.5 Ω/□ or less. 一種使用以如請求項11至13中任一項之製造方法所得到之燒成膜作為配線基板之方法。 A method of using a fired film obtained by the manufacturing method according to any one of claims 11 to 13 as a wiring substrate.

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