TWI618574B - Metal nanoparticle protective polymer, metal colloidal solution and methods for producing the same - Google Patents

Metal nanoparticle protective polymer, metal colloidal solution and methods for producing the same Download PDF

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TWI618574B
TWI618574B TW103118712A TW103118712A TWI618574B TW I618574 B TWI618574 B TW I618574B TW 103118712 A TW103118712 A TW 103118712A TW 103118712 A TW103118712 A TW 103118712A TW I618574 B TWI618574 B TW I618574B
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metal
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metal nanoparticle
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TW201521863A (en
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李承澤
姚宗武
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Ｄｉｃ股份有限公司
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Abstract

本發明提供一種如下金屬奈米粒子保護聚合物、其製造方法、及將以金屬奈米粒子保護聚合物作為保護劑而成的含金屬奈米粒子的複合體分散於介質中而成的金屬膠體溶液、及其製造方法，該金屬奈米粒子保護聚合物的特徵在於：於1分子中具有將聚伸烷基亞胺中的一級胺的5mol%~95mol%、或一級胺的5mol%~95mol%及二級胺的5mol%~50mol%乙醯化，進而，將聚伸烷基亞胺中的全部氮原子數的0.5mol%~95mol%氧化而成的聚乙醯基伸烷基亞胺N-氧化物片段及親水性片段。 The present invention provides a metal nanoparticle-protecting polymer, a method for producing the same, and a metal colloid obtained by dispersing a metal nanoparticle-containing composite obtained by using a metal nanoparticle-protecting polymer as a protective agent in a medium. a solution and a method for producing the same, the metal nanoparticle-protecting polymer characterized by having 5 mol% to 95 mol% of a primary amine in a polyalkyleneimine or 5 mol% to 95 mol of a primary amine in one molecule 5% to 50 mol% of the secondary amine and acetonitrile, and further, the polyethyl fluorene alkylene imine N which is obtained by oxidizing 0.5 mol% to 95 mol% of the total number of nitrogen atoms in the polyalkyleneimine - an oxide fragment and a hydrophilic fragment.

Description

金屬奈米粒子保護聚合物、金屬膠體溶液及它們的 製造方法 Metal nanoparticle protective polymer, metal colloidal solution and their Production method

本發明是關於一種使用含有聚乙醯基伸烷基亞胺N-氧化物片段及親水性片段的聚合物、或其中進而含有疏水性片段的聚合物作為金屬奈米粒子的保護劑的金屬膠體溶液、其製造方法、以及該聚合物及其製造方法。 The present invention relates to a metal colloidal solution using a polymer containing a polyethyl fluorenylalkylenimine N-oxide fragment and a hydrophilic segment, or a polymer further containing a hydrophobic segment as a protective agent for metal nanoparticles. And a method for producing the same, and the polymer and a method for producing the same.

金屬奈米粒子是具有1奈米~數百奈米的粒徑的奈米粒子，其比表面積明顯大，因此著眼於多種領域而期待應用於電子材料、觸媒、磁性材料、光學材料、各種感測器(sensor)、有色材料、醫療檢查用途等中。 The metal nanoparticle is a nanoparticle having a particle diameter of from 1 nm to several hundreds of nanometers, and has a large specific surface area. Therefore, it is expected to be applied to electronic materials, catalysts, magnetic materials, optical materials, various kinds of various fields. In the sensor, colored materials, medical examination purposes, etc.

印刷配線板(printed wiring board)或半導體元件(semiconductor device)的製造是經由專門的光刻製程(photolithography process)而進行製造，但具有繁雜的多階段的製造步驟，因此注目於近年來逐步開發的如下塗佈型電子元件的製造技術：該塗佈型電子元件是將金屬奈米粒子分散於某些介質 中而製成油墨(ink)調配物，利用各種印刷方法將其圖案化，以元件的形式而組成。 The manufacture of a printed wiring board or a semiconductor device is performed through a dedicated photolithography process, but has a complicated multi-stage manufacturing process, and thus has been developed in recent years. Manufacturing techniques for coating-type electronic components in which metal nanoparticles are dispersed in certain media Ink is prepared as an ink, patterned by various printing methods, and composed in the form of components.

將此種技術稱為印刷電子技術(printed electronics)，該方法有能夠以卷對卷方式(roll-to-roll)大量生產電子電路圖案(pattern)或半導體元件的可能性，期待隨選性(on demand)及利用步驟的簡化與省資源化的經濟性，期待發展成顯示元件、發光元件、IC標籤(射頻識別(Radio Frequency Identification，RFID))等的廉價製造方法。該印刷電子技術所使用的導電材料油墨可使用以金、銀、鉑、銅等金屬奈米粒子為成分的導電性油墨，但就經濟性及操作容易度而言，先前開發出銀奈米粒子及其油墨。 This technology is called printed electronics, which has the possibility of mass-producing electronic circuit patterns or semiconductor components in a roll-to-roll fashion, and is expected to be selective ( On the basis of the simplification of the use of the steps and the economical efficiency of resource utilization, it is expected to develop into an inexpensive manufacturing method such as a display element, a light-emitting element, or an IC tag (Radio Frequency Identification (RFID)). The conductive material ink used in the printed electronic technology can use a conductive ink containing metal nanoparticles such as gold, silver, platinum, or copper as a component, but in terms of economy and ease of operation, silver nano particles have been previously developed. And its ink.

若將銀奈米粒子的金屬縮小至奈米尺寸(nanosize)，則與塊狀銀(bulk silver)相比，比表面積非常高，表面能量(energy)增大，因此相互熔合而降低表面能量的傾向強烈。其結果，以遠低於塊狀銀的熔點的溫度使粒子相互熔合。有時將其稱為量子尺寸效果(久保效果)，此時有以銀奈米粒子為導電材料的優點。然而，另一方面，其金屬奈米粒子彼此的熔合容易度會損及金屬奈米粒子的穩定化，使保存穩定性變差，因此為了將金屬奈米粒子穩定化，必須以用於防止該熔合的保護劑進行保護。 If the metal of the silver nanoparticle is reduced to a nanosize, the specific surface area is very high and the surface energy is increased as compared with the bulk silver, so that the surface energy is reduced by fusion with each other. Strong tendency. As a result, the particles are fused to each other at a temperature far lower than the melting point of the bulk silver. Sometimes it is called a quantum size effect (the long-term effect), and there is an advantage that silver nano particles are used as a conductive material. On the other hand, however, the ease of fusion of the metal nanoparticles may impair the stabilization of the metal nanoparticles and deteriorate the storage stability. Therefore, in order to stabilize the metal nanoparticles, it is necessary to prevent the metal nanoparticles from being stabilized. The fused protectant is protected.

通常，奈米材料(通常為具有奈米級(nanometer order)的大小的化合物)因其大小而經由特殊的製程(process)進行製造，因此容易變得昂貴，該情況成為阻礙普及的原因之一。金屬奈米粒子亦為了以低成本進行製造，有利的是無需如真空製程的特殊裝置的液相還原法。液相還原法是將金屬化合物於溶劑中與還原劑進行反應並進行還原而獲得金屬奈米粒子的方法，此時， 為了控制所產生的金屬奈米粒子的形狀及粒徑且形成穩定的分散狀態，而揭示有於分散穩定劑或亦稱為保護劑的化合物的存在下進行還原的技術。該保護劑多數情況下是以主要具有三級胺基、四級銨基、具有鹼性氮原子的雜環、羥基、羧基等可配位於金屬粒子上的官能基的方式進行設計的高分子化合物(例如參照專利文獻1)。 In general, a nanomaterial (usually a compound having a size of a nanometer order) is manufactured by a special process because of its size, and thus it is easy to become expensive, which is one of the reasons for hindering the spread. . Metal nanoparticle is also manufactured at a low cost, and it is advantageous to eliminate the liquid phase reduction method of a special device such as a vacuum process. The liquid phase reduction method is a method in which a metal compound is reacted with a reducing agent in a solvent and reduced to obtain metal nanoparticles. In order to control the shape and particle diameter of the produced metal nanoparticles and form a stable dispersion state, a technique of performing reduction in the presence of a dispersion stabilizer or a compound also called a protective agent is disclosed. In many cases, the protective agent is a polymer compound designed to have a functional group such as a tertiary amino group, a quaternary ammonium group, a heterocyclic ring having a basic nitrogen atom, a hydroxyl group or a carboxyl group which can be coordinated to a metal particle. (For example, refer to Patent Document 1).

如上所述，為了製造期待良好的低溫熔合現象的金屬奈米粒子，使用可控制適當的金屬奈米粒子的形狀及粒徑、獲得分散穩定性等的保護劑。然而，保護劑是對於經熔合的塊狀金屬以電阻成分的形式而降低導電性能，因此存在如下問題：隨著使用量的不同而變得不易表現出良好的低溫煅燒性(將塗佈有含金屬奈米粒子的導電油墨的薄膜於100℃~150℃下煅燒而獲得的比電阻顯示10-6Ωcm級的性能)。如此，就導電材料的設計觀點而言，保護劑必需將粒子縮小而製造的能力、進而使其穩定分散的能力、於燒結時迅速地自粒子表面脫離而不會阻礙金屬奈米粒子相互的熔合的能力，並且，就製造金屬奈米粒子的觀點而言，必須同時具備可容易地將所產生的金屬奈米粒子純化分離的能力的多種性質。作為此種保護劑的用途可提供如下技術：使用Solsperse(捷利康(Zeneca)公司商標)或Flowlen(共榮社化學公司商標)等市售的高分子顏料分散劑，主鏈/側鏈上具有顏料親和性基(胺)且具有多個溶劑合部分的高分子，或具有聚伸乙亞胺部分及聚環氧乙烷部分的共聚物的高分子的技術，但僅此而言，難以同時實現這些技術，必須進一步改良(例如參照專利文獻2~專利文獻4)。 As described above, in order to produce metal nanoparticles which are expected to have a good low-temperature fusion phenomenon, a protective agent which can control the shape and particle diameter of an appropriate metal nanoparticle, and obtain dispersion stability and the like is used. However, the protective agent lowers the electrical conductivity in the form of a resistive component for the fused bulk metal, and thus has a problem that it becomes difficult to exhibit good low-temperature calcinability depending on the amount of use (it will be coated) The specific resistance obtained by calcining a film of a conductive ink of metal nanoparticles at 100 ° C to 150 ° C shows a performance of 10 -6 Ωcm. Thus, in terms of the design of the conductive material, the protective agent must have the ability to shrink the particles to be manufactured, and thus the ability to stably disperse, and quickly detach from the particle surface during sintering without hindering the fusion of the metal nanoparticles with each other. In view of the ability to produce metal nanoparticles, it is necessary to have various properties capable of easily purifying and separating the produced metal nanoparticles. As a use of such a protective agent, the following techniques can be used: a commercially available polymer pigment dispersant such as Solsperse (trademark of Zeneca) or Flowlen (trade name of Kyoeisha Chemical Co., Ltd.), which has a main chain/side chain a polymer having a pigment affinity group (amine) and having a plurality of solvated portions, or a polymer having a copolymer of a polyethyleneimine moiety and a polyethylene oxide moiety, but it is difficult to simultaneously It is necessary to further improve these techniques (for example, refer to Patent Document 2 to Patent Document 4).

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2004-346429號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-346429

[專利文獻2]日本專利特開平11-080647號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 11-080647

[專利文獻3]日本專利特開2006-328472號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-328472

[專利文獻4]日本專利特開2008-037884號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-037884

本發明所欲解決的課題在於提供一種可意欲性地附加．調節良好的金屬奈米粒子控制能力、高分散穩定性、良好的低溫煅燒性、及金屬奈米粒子的容易的純化分離性的多種性質而表現出更實用的導電性的金屬奈米粒子保護聚合物、金屬膠體溶液及它們的製造方法。 The problem to be solved by the present invention is to provide an appreciative addition. Metal nanoparticle protective polymerization exhibiting more practical conductivity by adjusting the properties of metal nanoparticle control, high dispersion stability, good low temperature calcinability, and easy purification and separation of metal nanoparticles Materials, metal colloidal solutions and methods for their manufacture.

本發明者已揭示出對金屬奈米粒子的製造有效的是：鍵結有包含聚伸乙亞胺的聚伸烷基亞胺片段及包含聚氧伸烷基鏈的親水性片段的二元系高分子、或者於上述二元系高分子上進而鍵結環氧樹脂等疏水性片段而成的三元系高分子(上述專利文獻4等)。然而，該技術並非可以高度的等級兼備上述性能的技術，因此進一步進行了努力研究，結果發現有效的是：使用將聚伸烷基亞胺片段中的一級胺、或一級胺及二級胺部位乙醯化後，進而將三級胺部位氧化而轉化成N-氧化物的乙醯化N-氧化物系的新穎高分子，從而完成本發明。 The present inventors have revealed that it is effective for the production of metal nanoparticles by bonding a polyalkyleneimine fragment comprising a stretched imine and a binary system comprising a hydrophilic segment of a polyoxyalkylene chain. A ternary polymer in which a polymer or a hydrophobic component such as an epoxy resin is bonded to the above binary polymer (the above-mentioned Patent Document 4). However, this technique is not a technique that can attain a high level of the above-described performance, and further efforts have been made to find that it is effective to use a primary amine or a primary amine and a secondary amine moiety in a polyalkyleneimine fragment. After the acetylation, the tertiary amine moiety is further oxidized to be converted into an N-oxide acetylated N-oxide-based novel polymer, thereby completing the present invention.

即，本發明提供一種如下金屬奈米粒子保護聚合物、其 製造方法、及將以金屬奈米粒子保護聚合物作為保護劑而成的含金屬奈米粒子的複合體分散於介質中而成的金屬膠體溶液、及其製造方法，該金屬奈米粒子保護聚合物的特徵在於：於1分子中具有將聚伸烷基亞胺中的一級胺、或一級胺及二級胺部位乙醯化後，進而主要將三級胺部位氧化而成的聚乙醯基伸烷基亞胺N-氧化物片段(A)及親水性片段(B)。 That is, the present invention provides a metal nanoparticle-protecting polymer as follows a metal colloidal solution obtained by dispersing a metal nanoparticle-containing composite obtained by using a metal nanoparticle-protecting polymer as a protective agent in a medium, and a method for producing the same, the metal nanoparticle protective polymerization The product is characterized in that it has a polyamine group which is obtained by oxidizing a primary amine in a polyalkylenimine or a primary amine and a secondary amine in one molecule, and then mainly oxidizing a tertiary amine moiety. An alkylimine N-oxide fragment (A) and a hydrophilic fragment (B).

本發明中獲得的金屬膠體溶液顯示出良好的低溫煅燒性。此種低溫下的良好的導電性能得益於本發明中使用的保護聚合物於低溫下容易迅速地自金屬奈米粒子的表面脫離。另外，於該特定的保護聚合物的存在下獲得的金屬奈米粒子的粒徑充分小，為單分散粒徑且粒徑分佈亦狹窄，而顯示出良好的保存穩定性。其原因在於保護聚合物中的乙醯化結構部分、N-氧化物結構部分良好地保護金屬奈米粒子，並且藉由聚合物中的親水性片段或疏水性片段表現出對介質的分散性，且不損及作為分散體的分散穩定性而於溶劑中長期保持穩定的分散狀態。 The metal colloidal solution obtained in the present invention shows good low-temperature calcinability. The good electrical conductivity at such low temperatures is attributed to the fact that the protective polymer used in the present invention is easily and rapidly detached from the surface of the metal nanoparticles at a low temperature. Further, the metal nanoparticles obtained in the presence of the specific protective polymer have a sufficiently small particle diameter, a monodisperse particle diameter, and a narrow particle size distribution, and exhibit good storage stability. The reason for this is that the acetylated moiety and the N-oxide moiety in the protective polymer well protect the metal nanoparticles, and the dispersibility to the medium is exhibited by the hydrophilic segment or the hydrophobic segment in the polymer. Further, it does not impair the dispersion stability as a dispersion and maintains a stable dispersion state in a solvent for a long period of time.

於本發明中，在製造金屬膠體溶液的情況下，藉由還原獲得金屬奈米粒子後去除雜質的純化分離步驟中，僅利用向包含所產生的金屬奈米粒子及保護聚合物的複合體的分散液中添加不良溶劑的簡單的操作而將該複合體容易地沈澱分離，其得益於保護聚合物的強凝聚力，且幾乎無需複雜的步驟或緻密的條件設定等，因此作為工業製法的優勢大。 In the present invention, in the case of producing a metal colloidal solution, in the purification separation step of removing metal impurities by reduction to obtain impurities, only the composite containing the produced metal nanoparticles and the protective polymer is used. The simple operation of adding a poor solvent to the dispersion to easily precipitate and separate the composite, which benefits from the strong cohesive force of the protective polymer, and requires almost no complicated steps or dense condition setting, etc., and thus has an advantage as an industrial process. Big.

另外，本發明中獲得的金屬膠體溶液中的金屬奈米粒子具有比表面積大、表面能量高、具有電漿子(plasmon)吸收等作 為金屬奈米粒子的特徵，進而可效率良好地表現自組高分子分散體所具有的分散穩定性、保存穩定性等性質，可應用於對導電膏(conductive paste)等要求的兼備各種化學、電氣、磁性性能且涉及多方面的領域例如觸媒、電子材料、磁性材料、光學材料、各種感測器、有色材料、醫療檢查用途等中。 In addition, the metal nanoparticles in the metal colloid solution obtained in the present invention have a large specific surface area, a high surface energy, and have plasmon absorption. The characteristics of the metal nanoparticles, and the properties such as dispersion stability and storage stability of the self-assembled polymer dispersion can be efficiently expressed, and can be applied to various chemicals required for a conductive paste or the like. Electrical, magnetic properties and in many fields such as catalysts, electronic materials, magnetic materials, optical materials, various sensors, colored materials, medical inspection applications, and the like.

本發明的金屬奈米粒子保護聚合物是具有聚乙醯基伸烷基亞胺N-氧化物片段(A)及親水性片段(B)的高分子化合物、或具有上述聚乙醯基伸烷基亞胺N-氧化物片段(A)、親水性片段(B)、及疏水性片段(C)的高分子化合物。以具有此種結構的保護聚合物保護而成的金屬奈米粒子的分散體(金屬膠體溶液)的分散穩定性、導電特性優異，且具有金屬奈米粒子所具有的顯色、觸媒、電氣功能等作為各種含金屬的功能性分散體的能力。 The metal nanoparticle-protecting polymer of the present invention is a polymer compound having a poly(ethylene)alkyleneimine N-oxide fragment (A) and a hydrophilic segment (B), or having the above polyethylidene alkylene group A polymer compound of an amine N-oxide fragment (A), a hydrophilic fragment (B), and a hydrophobic fragment (C). The dispersion of the metal nanoparticles (metal colloidal solution) protected by the protective polymer having such a structure is excellent in dispersion stability and conductive properties, and has color development, catalyst, and electrical properties of the metal nanoparticles. Functionality, etc. as the ability of various metal-containing functional dispersions.

本發明中的保護聚合物中的聚乙醯基伸烷基亞胺N-氧化物片段(A)由於該片段中的乙醯基伸烷基亞胺單元及N-氧化物單元可與金屬或金屬離子配位鍵結，故而是能夠將金屬以奈米粒子的形式固定化的片段。於在親水性溶劑中製造或保存以該保護聚合物保護本發明中獲得的金屬奈米粒子而成的複合體的情況下，藉由在該溶劑中具有顯示親水性的聚乙醯基伸烷基亞胺N-氧化物片段(A)及親水性片段(B)，可表現出所獲得的金屬膠體溶 液尤其優異的分散穩定性及保存穩定性。 The polyethyl fluorenylalkylenimine N-oxide fragment (A) in the protective polymer of the present invention may be bonded to a metal or metal ion due to an acetamizylalkylene unit and an N-oxide unit in the fragment. Coordination bonding, so it is a fragment capable of immobilizing a metal in the form of nanoparticle. In the case of producing or preserving a composite obtained by protecting the metal nanoparticle obtained in the present invention with the protective polymer in a hydrophilic solvent, by having a polyethylhydrazine-based alkyl group exhibiting hydrophilicity in the solvent The imine N-oxide fragment (A) and the hydrophilic fragment (B) can exhibit the obtained metal colloidal dissolution The liquid is particularly excellent in dispersion stability and storage stability.

就工業製法的觀點而言，重要的是將使金屬化合物溶解或分散於介質中並將其還原所產生的金屬奈米粒子以上述保護聚合物保護而成的複合體的簡單的純化分離方法，較佳為採用於反應後的溶液中添加不良溶劑的丙酮等並進行沈澱分離的方法。本發明的保護聚合物的乙醯基伸烷基亞胺單元、N-氧化物單元由於極性高而具有於不良溶劑環境下迅速地進行含金屬奈米粒子的複合體彼此的凝聚的作用，一面形成大的凝聚群的塊體(block)一面容易地進行沈澱分離。 From the viewpoint of industrial process, it is important to carry out a simple purification separation method of a composite obtained by dissolving or dispersing a metal compound in a medium and reducing the metal nanoparticle produced by the above-mentioned protective polymer. Preferably, a method in which acetone or the like of a poor solvent is added to the solution after the reaction and precipitation is carried out is used. The ethyl fluorenylalkyleneimine unit and the N-oxide unit of the protective polymer of the present invention have a high polarity and have a function of rapidly agglomerating the metal nanoparticle-containing composites in a poor solvent environment. The block of the large agglomerated group is easily separated by precipitation.

另外，於將含金屬奈米粒子的複合體的分散液即金屬膠體溶液本身、或將該溶液製備為導電性油墨而成的導電材料印刷或塗佈於基材上後的燒結過程中，保護聚合物中的乙醯基伸烷基亞胺單元、N-氧化物單元與金屬的配位鍵結力弱，因此於低溫下亦容易自金屬奈米粒子表面除去覆蓋(decapping)，其結果顯示出良好的低溫煅燒性。 Further, in the sintering process after printing or coating a conductive material obtained by dispersing a metal nanoparticle-containing composite, that is, a metal colloidal solution itself, or a conductive material prepared by using the solution as a conductive ink, The ethylene-alkylene imide unit and the N-oxide unit in the polymer have weak coordination bonding force with the metal, so that it is easy to remove decapping from the surface of the metal nanoparticles at a low temperature, and the result shows that Good low temperature calcination.

本發明的金屬膠體溶液中的分散體(複合體)的粒徑不僅受所使用的保護聚合物的分子量或聚乙醯基伸烷基亞胺N-氧化物片段(A)的聚合度影響，而且受構成該保護聚合物的各成分即聚乙醯基伸烷基亞胺N-氧化物鏈(A)、下述親水性片段(B)、及下述疏水性片段(C)的結構或組成比影響。 The particle size of the dispersion (composite) in the metal colloidal solution of the present invention is affected not only by the molecular weight of the protective polymer used or the degree of polymerization of the polyethylenylene alkylene imine N-oxide fragment (A), but also The structure or composition ratio of the polyethylenylalkyleneimine N-oxide chain (A), the following hydrophilic segment (B), and the following hydrophobic segment (C) which are components constituting the protective polymer influences.

上述聚乙醯基伸烷基亞胺N-氧化物片段(A)的聚合度並無特別限定，若聚合度過低，則有作為保護聚合物的金屬奈米粒子的保護能力變得不充分的情況，若聚合度過高，則有包含金屬奈米粒子及保護聚合物的複合體粒子的粒徑變大的情況，而損 及保存穩定性。因此，為了使金屬奈米粒子的固定化能力或防止分散體粒子的巨大化的能力等更優異，上述聚乙醯基伸烷基亞胺N-氧化物片段(A)的伸烷基亞胺單元數(聚合度)通常為1~10,000的範圍，較佳為5~2,500的範圍，最佳為5~300的範圍。 The degree of polymerization of the above-mentioned polyethyl fluorenylalkylenimine N-oxide fragment (A) is not particularly limited, and if the degree of polymerization is too low, the protective ability of the metal nanoparticles as a protective polymer is insufficient. In the case where the degree of polymerization is too high, the particle size of the composite particles including the metal nanoparticles and the protective polymer is increased, and the particle diameter is increased. And preservation stability. Therefore, in order to further improve the immobilization ability of the metal nanoparticle or the ability to prevent the dispersion of the dispersion particles, the alkyleneimine unit of the above-mentioned polyethylene alkyleneamine N-oxide fragment (A) The number (degree of polymerization) is usually in the range of 1 to 10,000, preferably in the range of 5 to 2,500, and most preferably in the range of 5 to 300.

上述聚乙醯基伸烷基亞胺N-氧化物片段(A)可藉由如下方式簡單地獲得：於將作為其前驅物結構的聚伸烷基亞胺片段中的伸烷基亞胺部分以與乙醯化劑的反應進行乙醯化後，藉由與氧化劑的接觸而進行氧化。包含該聚伸烷基亞胺的片段只要為通常市售或可合成的片段，則可無特別限定地使用，但就工業獲取的容易度等而言，較佳為支鏈狀聚伸乙亞胺、支鏈狀聚伸丙亞胺，尤佳為包含支鏈狀聚伸乙亞胺的片段。 The above polyethyl fluorenylalkylenimine N-oxide fragment (A) can be obtained simply by: the alkylene imine moiety in the polyalkyleneimine fragment which will be its precursor structure After the reaction with the acetalizing agent is carried out, the oxidization is carried out by contact with an oxidizing agent. The fragment containing the polyalkyleneimine is not particularly limited as long as it is a commercially available or synthetic fragment, but in terms of ease of industrial acquisition, etc., it is preferably a branched polycondensation. Amine, a branched polycondensed propylene imine, and particularly preferably a fragment comprising a branched polyethylenimine.

構成本發明的保護聚合物的親水性片段(B)在使用水等親水性介質作為金屬膠體溶液的情況下，是具有與溶劑的高親和性且保持膠體溶液的保存穩定性的片段。另外，在使用疏水性溶劑的情況下，具有藉由該親水性片段(B)的分子內或分子間相互的強凝聚力而形成分散體粒子的核(core)的作用。親水性片段(B)的聚合度並無特別限定，在使用親水性溶劑的情況下，認為有如下可能性：若聚合度過低，則保存穩定性惡化，若聚合度過高，則會發生凝集，另外，在使用疏水性溶劑的情況下，若聚合度過低，則分散體粒子的凝聚力不足，若聚合度過高，則無法保持與溶劑的親和性。就這些觀點而言，親水性片段(B)的聚合度通常為1~10,000，較佳為3~3,000，就製造方法的容易度等方面而言，更佳為5~1,000。進而，在親水性片段為聚氧伸烷基鏈的情況下，聚合度尤佳為5~500。 The hydrophilic segment (B) constituting the protective polymer of the present invention is a fragment having a high affinity with a solvent and maintaining the storage stability of the colloidal solution when a hydrophilic medium such as water is used as the metal colloidal solution. Further, when a hydrophobic solvent is used, it has a function of forming a core of the dispersion particles by strong cohesive force in the molecule or the molecules of the hydrophilic segment (B). The degree of polymerization of the hydrophilic segment (B) is not particularly limited. When a hydrophilic solvent is used, it is considered that if the degree of polymerization is too low, the storage stability is deteriorated, and if the degree of polymerization is too high, it occurs. In the case of using a hydrophobic solvent, when the degree of polymerization is too low, the cohesive force of the dispersion particles is insufficient, and if the degree of polymerization is too high, the affinity with the solvent cannot be maintained. In view of the above, the degree of polymerization of the hydrophilic segment (B) is usually from 1 to 10,000, preferably from 3 to 3,000, and more preferably from 5 to 1,000 in terms of easiness of the production method. Further, in the case where the hydrophilic segment is a polyoxyalkylene chain, the degree of polymerization is particularly preferably from 5 to 500.

親水性片段(B)只要為通常市售或可合成的包含親水性聚合物鏈的親水性片段，則可無特別限定地使用。尤其在使用親水性溶劑的情況下，就可獲得穩定性優異的膠體溶液的方面而言，較佳為包含非離子性聚合物的親水性片段。 The hydrophilic segment (B) can be used without particular limitation as long as it is a commercially available or synthesizable hydrophilic segment containing a hydrophilic polymer chain. In particular, in the case of using a hydrophilic solvent, a hydrophilic segment containing a nonionic polymer is preferred in terms of obtaining a colloidal solution excellent in stability.

親水性片段(B)例如可列舉：聚氧伸乙基鏈、聚氧伸丙基鏈等聚氧伸烷基鏈，包含聚乙烯醇、部分皂化聚乙烯醇等聚乙烯醇類的聚合物鏈，包含聚丙烯酸羥基乙酯、聚甲基丙烯酸羥基乙酯、丙烯酸二甲基胺基乙酯、甲基丙烯酸二甲基胺基乙酯等水溶性聚(甲基)丙烯酸酯類的聚合物鏈，聚乙醯基伸乙亞胺、聚乙醯基伸丙亞胺、聚丙醯基伸乙亞胺、聚丙醯基伸丙亞胺等具有親水性取代基的聚醯基伸烷基亞胺鏈，包含聚丙烯醯胺、聚異丙基丙烯醯胺、聚乙烯吡咯啶酮等聚丙烯醯胺類的聚合物鏈等，於這些中，可獲得穩定性尤其優異的膠體溶液，另外，就容易工業獲取的方面而言，較佳為聚氧伸烷基鏈。 Examples of the hydrophilic segment (B) include a polyoxyalkylene chain such as a polyoxyethylene chain or a polyoxyalkylene chain, and a polymer chain of a polyvinyl alcohol such as polyvinyl alcohol or partially saponified polyvinyl alcohol. a polymer chain comprising a water-soluble poly(meth)acrylate such as polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate, dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate a polyfluorenylalkylene imine chain having a hydrophilic substituent, such as polyethyl fluorene acetimines, polyethyl fluorene propylene, polyacrylonitrile acetimines, polypropylene propylene propyl imino, etc., comprising polypropylene fluorene Among these, a polymer chain of a polyacrylamide such as an amine, polyisopropylacrylamide or polyvinylpyrrolidone can obtain a colloidal solution which is particularly excellent in stability, and is easy to be industrially obtained. In other words, a polyoxyalkylene chain is preferred.

於本發明中，亦可於保護聚合物中進而具有疏水性片段(C)。尤其在金屬膠體溶液將介質設為有機溶劑的情況下，較佳為使用具有疏水性片段(C)的聚合物作為保護劑。 In the present invention, it is also possible to further have a hydrophobic segment (C) in the protective polymer. Particularly in the case where the metal colloidal solution is a medium in which the medium is an organic solvent, it is preferred to use a polymer having a hydrophobic segment (C) as a protective agent.

疏水性片段(c)只要為通常市售或可合成的包含疏水性化合物的殘基的疏水性片段，則可無特別限定地使用。例如可列舉：聚苯乙烯、聚甲基苯乙烯、聚氯甲基苯乙烯、聚溴甲基苯乙烯等聚苯乙烯類，聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸2-乙基己酯、聚甲基丙烯酸2-乙基己酯等非水溶性聚(甲基)丙烯酸酯類，聚苯甲醯基伸乙亞胺、聚苯甲醯基伸丙亞胺、聚(甲基)丙烯醯基伸乙亞胺、聚(甲基)丙烯醯基伸丙亞胺、聚[N-{3-(全氟辛 基)丙醯基}伸乙亞胺]、聚[N-{3-(全氟辛基)丙醯基}伸丙亞胺]等具有疏水性取代基的聚醯基伸烷基亞胺類的聚合物的殘基或者環氧樹脂、聚胺基甲酸酯、聚碳酸酯等樹脂的殘基等，亦可為單獨的化合物的殘基或者預先使兩種以上不同的化合物反應而獲得的化合物的殘基。於這些中，就保護聚合物的合成於工業上容易的觀點、以及於印刷或塗佈所獲得的金屬膠體溶液時與基材的密接性優異的觀點而言，較佳為包含源自環氧樹脂的結構的疏水性片段，尤佳為包含源自雙酚A型環氧樹脂的結構的疏水性片段(C)。 The hydrophobic segment (c) can be used without particular limitation as long as it is a hydrophobic segment of a residue which is usually commercially available or can be synthesized and contains a hydrophobic compound. For example, polystyrene, polymethyl styrene, polychloromethyl styrene, polybromomethyl styrene, polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid 2-B Water-insoluble poly(meth)acrylates such as hexyl hexyl ester and polyethyl 2-ethylhexyl methacrylate, polybenzhydryl carbethylene imide, polybenzhydryl propylenimine, poly(methyl) Propylene fluorenyl eximide, poly(methyl) propylene decyl propylene, poly [N-{3-(perfluorooctyl) Poly(fluorenyl)alkylimine having a hydrophobic substituent such as poly(N-{3-(perfluorooctyl)propanyl}-propenimide] The residue of the polymer or the residue of a resin such as an epoxy resin, a polyurethane, or a polycarbonate may be a residue of a single compound or a compound obtained by reacting two or more different compounds in advance. Residues. Among these, from the viewpoint of industrially easy to synthesize the protective polymer and excellent adhesion to the substrate when printing or coating the obtained metal colloidal solution, it is preferred to include an epoxy-derived epoxy resin. A hydrophobic segment of the structure of the resin is particularly preferably a hydrophobic segment (C) comprising a structure derived from a bisphenol A type epoxy resin.

另外，疏水性片段(C)的聚合度並無特別限定，通常為1~10,000，在聚苯乙烯類、聚(甲基)丙烯酸酯類、具有疏水性取代基的聚醯基伸烷基亞胺類等情況下，較佳為3~3,000，更佳為10~1,000。另外，在包含環氧樹脂、聚胺基甲酸酯類、聚碳酸酯類等樹脂的殘基的情況下，其聚合度通常為1~50，較佳為1~30，尤佳為1~20。 Further, the degree of polymerization of the hydrophobic segment (C) is not particularly limited, but is usually from 1 to 10,000, and polyalkylene, poly(meth)acrylate, and polyalkylene alkyleneimine having a hydrophobic substituent. In the case of a class or the like, it is preferably from 3 to 3,000, more preferably from 10 to 1,000. Further, in the case of containing a residue of a resin such as an epoxy resin, a polyurethane, or a polycarbonate, the degree of polymerization is usually from 1 to 50, preferably from 1 to 30, particularly preferably from 1 to 20. .

本發明的金屬奈米粒子保護聚合物的製造方法例如可列舉如下方法：使用作為其前驅物化合物(I)的具有聚伸烷基亞胺片段及親水性片段(B)的化合物，或具有聚伸烷基亞胺片段、親水性片段(B)及疏水性片段(C)的化合物，使其與乙醯化劑進行反應後，繼而利用氧化劑進行處理。或者，可列舉如下方法：於使用聚伸烷基亞胺片段及親水性片段(B)的前驅物化合物(I)的製作反應時，併用乙醯化劑而進行乙醯化反應後，繼而以氧化劑進行處理。藉由使用此種方法，可容易地獲得如設計的保護聚合物。前驅物化合物(I)的製法可直接使用上述專利文獻4及日本專利特開2006-213887號公報中記載的方法。 The method for producing the metal nanoparticle-protecting polymer of the present invention may, for example, be a method of using a compound having a polyalkyleneimine fragment and a hydrophilic segment (B) as its precursor compound (I), or having a poly The compound of the alkylimine fragment, the hydrophilic fragment (B) and the hydrophobic fragment (C) is reacted with an acetylating agent and then treated with an oxidizing agent. Alternatively, a method in which a reaction of preparing a precursor compound (I) using a polyalkyleneimine fragment and a hydrophilic fragment (B) is carried out, and an acetonitrileization reaction is carried out with an acetalizing agent, followed by The oxidant is treated. By using such a method, a protective polymer as designed can be easily obtained. The method described in the above-mentioned Patent Document 4 and JP-A-2006-213887 can be used as the method for producing the precursor compound (I).

於獲得此種前驅物化合物(I)後，將其中所含的聚伸烷基亞胺片段中的一級胺、或一級胺及二級胺部位的氮原子乙醯化。或者，於使用聚伸烷基亞胺片段及親水性片段(B)的前驅物化合物(I)的製作反應時，將聚伸烷基亞胺片段中的一級胺、一級胺及二級胺部位的氮原子乙醯化。乙醯化反應是藉由添加具有乙醯基結構(CH3-CO-)的乙醯化劑而成。繼而，對上述經乙醯化的聚伸烷基亞胺片段中的氮原子進行氧化處理。氧化是藉由在上述經乙醯化的前驅物化合物(I)的水溶液中添加具有過氧化物結構(-O-O-、-N-O-)的化合物例如過氧化氫、金屬過氧化物、無機過酸及其鹽、有機過氧化合物、以及有機過酸及其鹽等過氧化物而成。 After obtaining such a precursor compound (I), the primary amine in the polyalkyleneimine fragment contained therein or the nitrogen atom of the primary amine and the secondary amine moiety is acetylated. Alternatively, in the preparation reaction using the precursor compound (I) of the polyalkyleneimine fragment and the hydrophilic fragment (B), the primary amine, the primary amine and the secondary amine moiety in the alkylimine fragment are polymerized. The nitrogen atom is acetylated. The acetamidine reaction is formed by adding an acetohydrating agent having an acetyl group structure (CH 3 -CO-). Then, the nitrogen atom in the above-mentioned acetylated polyalkyleneimine fragment is subjected to oxidation treatment. Oxidation is carried out by adding a compound having a peroxide structure (-OO-, -NO-) such as hydrogen peroxide, a metal peroxide, an inorganic peracid to an aqueous solution of the above-mentioned ethylated precursor compound (I). It is formed by peroxides such as salts, organic peroxy compounds, and organic peracids and salts thereof.

乙醯化劑可使用通常於工業上供給的乙醯化劑。例如可列舉：乙酸酐、乙酸、二甲基乙醯胺、乙酸乙酯、氯乙酸等。於這些乙醯化劑中，就獲取及操作容易的觀點而言，可尤佳地使用乙酸酐、乙酸、二甲基乙醯胺。 As the acetylating agent, an acetylating agent which is usually supplied industrially can be used. For example, acetic anhydride, acetic acid, dimethyl acetamide, ethyl acetate, chloroacetic acid, etc. are mentioned. Among these acetylating agents, acetic anhydride, acetic acid, and dimethyl acetamide are particularly preferably used from the viewpoint of easy availability and handling.

在聚伸烷基亞胺片段以支鏈狀聚伸烷基亞胺化合物為基礎的情況下，均等且無規地包含一級胺、二級胺及三級胺，在使這些胺與上述舉出的乙醯化劑反應的情況下，可對一級胺及/或二級胺的一個氮原子賦予一個氧乙醯基。並且，三級胺未進行乙醯化反應。即，乙醯化反應是使反應性更高的一級胺至二級胺與所使用的乙醯化劑定量地進行反應。以一級胺及/或二級胺的乙醯化率為目標，對乙醯化反應下的乙醯化率進行了研究，結果可知若於聚伸烷基亞胺片段中的一級胺的5mol%~95mol%、或一級胺的5mol%~95mol%及二級胺的5mol%~50mol%的範圍內進 行乙醯化，則可獲得顯示良好的導電性、分散穩定性及容易的純化分離性的保護聚合物。 In the case where the polyalkyleneimine fragment is based on a branched polyalkyleneimine compound, the primary amine, the secondary amine and the tertiary amine are uniformly and randomly included, and these amines are given above. In the case of the acetalization reaction, an oxetyl group may be imparted to one nitrogen atom of the primary amine and/or the secondary amine. Further, the tertiary amine was not subjected to the acetonitrile reaction. That is, the acetylation reaction is a quantitative reaction between the more reactive primary amine to the secondary amine and the acetamidine used. The acetamization rate of the acetamidine reaction was studied with the aim of the acetamidine rate of the primary amine and/or the secondary amine. As a result, it was found that 5 mol% of the primary amine in the polyalkyleneimine fragment was observed. ~95mol%, or 5mol%~95mol% of the primary amine and 5mol%~50mol% of the secondary amine By performing acetylation, a protective polymer which exhibits good conductivity, dispersion stability, and easy purification separation can be obtained.

繼而，對氮原子進行氧化處理，此時，在使用過氧化氫作為氧化劑的情況下，通常可使用以30%~50%的過氧化氫水的形式供給於工業上的氧化劑。作為金屬過氧化物的例，過氧化鈉、過氧化鉀、過氧化鋰、過氧化鎂、過氧化鋅等容易獲取，同樣可使用。無機過酸及其鹽可使用過硫酸、過碳酸、過磷酸、次過氯酸、Oxone(杜邦(Dupont)公司註冊商標，以過硫酸氫鉀為主體的氧化劑)、過硫酸銨、過硫酸鈉、過硫酸鉀、過碳酸鈉等。有機過氧化合物及有機過酸及其鹽可列舉：過乙酸、過苯甲酸、間氯苯甲酸、過氧化苯甲醯、過氧化第三丁基、1,2-二甲基二環氧乙烷、大衛試劑(Davis reagent)(2-(苯基磺醯基)-3-芳基氧氮環丙烷)等，這些亦可使用。於這些氧化劑中，可尤佳地使用獲取及操作容易且廉價的30%過氧化氫水、過硫酸銨、Oxone、過乙酸。 Then, the nitrogen atom is oxidized. In this case, when hydrogen peroxide is used as the oxidizing agent, an industrial oxidizing agent can be usually supplied in the form of 30% to 50% of hydrogen peroxide water. As an example of the metal peroxide, sodium peroxide, potassium peroxide, lithium peroxide, magnesium peroxide, zinc peroxide or the like can be easily obtained, and the same can be used. As the inorganic peracid and its salt, persulfuric acid, percarbonic acid, perphosphoric acid, hypoperchloric acid, Oxone (registered trademark of DuPont), oxidizing agent mainly based on potassium hydrogen persulfate, ammonium persulfate and sodium persulfate can be used. , potassium persulfate, sodium percarbonate, and the like. Examples of the organic peroxy compound and the organic peracid and the salt thereof include peracetic acid, perbenzoic acid, m-chlorobenzoic acid, benzammonium peroxide, tert-butyl peroxide, and 1,2-dimethylethylene oxide. Alkane, Davis reagent (2-(phenylsulfonyl)-3-aryloxazolidine), etc., can also be used. Among these oxidizing agents, 30% hydrogen peroxide water, ammonium persulfate, Oxone, and peracetic acid which are easily and inexpensively obtained and operated can be preferably used.

上述列舉的氧化劑可對一個氮原子賦予一個氧原子。所謂三級胺及二級胺，只要假定以1比1進行反應即可。假定與一級胺的反應的複雜度，不限於與氧化劑1分子的反應，可進而考慮與下一氧化劑的反應。以此種情況為目標，對氧化劑的量進行了研究，結果可知於添加與前驅物化合物(I)中的聚伸烷基亞胺片段中的全部氮原子數的0.5%~95%對應的氧化劑時，可獲得顯示出良好的導電性、分散穩定性及容易的純化分離性的保護聚合物。 The oxidizing agents listed above can impart an oxygen atom to a nitrogen atom. The tertiary amine and the secondary amine are assumed to be reacted in a ratio of 1 to 1. It is assumed that the complexity of the reaction with the primary amine is not limited to the reaction with one molecule of the oxidizing agent, and the reaction with the next oxidizing agent can be further considered. In view of such a situation, the amount of the oxidizing agent was investigated, and as a result, it was found that an oxidizing agent corresponding to 0.5% to 95% of the total number of nitrogen atoms in the polyalkyleneimine fragment in the precursor compound (I) was added. At the time, a protective polymer which exhibits good electrical conductivity, dispersion stability, and easy purification separation property can be obtained.

尤其在聚伸烷基亞胺片段以支鏈狀聚伸烷基亞胺化合物為基礎的情況下，均等且無規地包含一級胺、二級胺及三級胺， 在這些胺與氧化劑進行反應的情況下，就三級胺僅成為氧化胺(C-N+(O-)(-C)-C)，二級胺根據反應條件進一步與氧化胺(C-HN+(O-)-C)進行反應而成為羥胺(C-N(OH)-C)及其氧化物即硝酮(C=C-N+(O-)-C)，一級胺成為羥胺(C-NH(OH))、亞硝基(C-NO)、硝基(C-NO2)的可能性而言，推定出所獲得的保護聚合物為少量並且亦可包含以上結構。 Particularly in the case where the polyalkyleneimine fragment is based on a branched polyalkyleneimine compound, the primary amine, the secondary amine and the tertiary amine are homogeneously and randomly included, and the amine is reacted with the oxidizing agent. In the case where the tertiary amine is only an amine oxide (CN + (O - )(-C)-C), the secondary amine is further reacted with an amine oxide (C-HN + (O - )-C) depending on the reaction conditions. The reaction becomes hydroxylamine (CN(OH)-C) and its oxide, nitrone (C=CN + (O - )-C), and the primary amine becomes hydroxylamine (C-NH(OH)), nitroso (C In the possibility of -NO) and nitro (C-NO 2 ), it is presumed that the obtained protective polymer is a small amount and may also contain the above structure.

本發明的金屬奈米粒子保護聚合物與可使金屬奈米粒子穩定地存在的上述聚乙醯基伸烷基亞胺N-氧化物片段(A)不同，具有親水性片段(B)，或者進而具有疏水性片段(C)。如上所述，親水性片段(B)於疏水性溶劑中顯示出強凝聚力，於親水性溶劑中顯示出與溶劑的高親和性，另外，疏水性片段(C)於親水性溶劑中顯示出強凝聚力，於疏水性溶劑中顯示出與溶劑的高親和性。進而，在疏水性片段(C)中具有芳香環的情況下，亦可認為藉由該芳香環所具有的π電子與金屬進行相互作用，進而有助於將金屬奈米粒子穩定化。 The metal nanoparticle-protecting polymer of the present invention has a hydrophilic segment (B), or a hydrophilic segment (B), which is different from the above-mentioned polyethylidenealkyleneamine N-oxide segment (A) which can stably exist as a metal nanoparticle. Has a hydrophobic fragment (C). As described above, the hydrophilic segment (B) exhibits strong cohesive force in a hydrophobic solvent, exhibits high affinity with a solvent in a hydrophilic solvent, and the hydrophobic segment (C) shows strong in a hydrophilic solvent. Cohesive force exhibits high affinity with a solvent in a hydrophobic solvent. Further, when the hydrophobic segment (C) has an aromatic ring, it is considered that the π electrons possessed by the aromatic ring interact with the metal to contribute to stabilization of the metal nanoparticles.

本發明的金屬奈米粒子保護聚合物中，構成上述聚乙醯基伸烷基亞胺N-氧化物片段(A)及親水性片段(B)的各成分的鏈的聚合物的莫耳比(A)：(B)並無特別限定，就所獲得的膠體溶液的分散穩定性及保存穩定性優異的方面而言，通常為1：(1~100)的範圍，尤佳為1：(1~30)。另外，在亦具有疏水性片段(C)的聚合物的情況下，構成上述聚乙醯基伸烷基亞胺N-氧化物片段(A)、親水性片段(B)及疏水性片段(C)的各成分的鏈的聚合物的莫耳比(A)：(B)：(C)並無特別限定，就所獲得的膠體溶液的分散穩定性及保存穩定性優異的方面而言，通常為1：(1 ~100)：(1~100)的範圍，尤佳為1：(1~30)：(1~30)。由上可知，本發明的金屬奈米粒子保護聚合物的重量平均分子量較佳為1,000~500,000的範圍，尤佳為1,000~100,000的範圍。 In the metal nanoparticle-protecting polymer of the present invention, the molar ratio of the polymer constituting the chain of each component of the above-mentioned polyethylidene alkyleneamine N-oxide fragment (A) and the hydrophilic segment (B) A): (B) is not particularly limited, and is usually in the range of 1: (1 to 100), and particularly preferably 1: (1) in terms of excellent dispersion stability and storage stability of the obtained colloidal solution. ~30). Further, in the case of a polymer having a hydrophobic segment (C), the above-mentioned polyethylidenealkylene imine N-oxide segment (A), hydrophilic segment (B) and hydrophobic segment (C) are formed. The molar ratio (A) of the polymer of the chain of each component: (B): (C) is not particularly limited, and is generally excellent in terms of dispersion stability and storage stability of the obtained colloidal solution. 1: (1 ~100): Range of (1~100), especially 1: (1~30): (1~30). As apparent from the above, the weight average molecular weight of the metal nanoparticle-protecting polymer of the present invention is preferably in the range of 1,000 to 500,000, particularly preferably in the range of 1,000 to 100,000.

本發明的保護聚合物分散或溶解於各種介質中而用於製造金屬膠體溶液。可用作介質的物質並無限定，分散體可為O/W系或W/O系中的任一種。可依據金屬膠體溶液的製造方法或所獲得的金屬膠體溶液的使用目的等，選擇各種併用親水性溶劑、疏水性溶劑、或其混合溶劑、或如下述的其他溶劑的混合溶劑而使用。在使用混合溶劑的情況下，對於混合比而言，於O/W系時大量使用親水性溶劑，於W/O系時大量使用疏水性溶劑。混合比根據使用的種類而有所不同，因此無法一概而論，但若以通常的標準列舉例子，則於O/W系時較佳為使用疏水性溶劑的5倍體積以上的親水性溶劑，於W/O系時較佳為使用親水性溶劑的5倍體積以上的疏水性溶劑。 The protective polymer of the present invention is dispersed or dissolved in various media for use in the manufacture of metal colloidal solutions. The substance usable as the medium is not limited, and the dispersion may be any of an O/W system or a W/O system. Various types of a mixed solvent of a hydrophilic solvent, a hydrophobic solvent, a mixed solvent thereof, or another solvent as described below may be used depending on the method for producing the metal colloidal solution or the purpose of use of the obtained metal colloidal solution. In the case of using a mixed solvent, a hydrophilic solvent is used in a large amount in the O/W system and a hydrophobic solvent is used in a large amount in the W/O system. The mixing ratio differs depending on the type of use, and therefore cannot be generalized. However, when an example is given by a usual standard, it is preferable to use a hydrophilic solvent of 5 times or more by volume of a hydrophobic solvent in the case of O/W. In the case of /O, it is preferred to use 5 times or more of a hydrophobic solvent of a hydrophilic solvent.

親水性溶劑例如可列舉：甲醇、乙醇、異丙醇、四氫呋喃、丙酮、二甲基乙醯胺、二甲基甲醯胺、乙二醇、丙二醇、乙二醇單甲醚、丙二醇單甲醚、乙二醇二甲醚、丙二醇二甲醚、氧化二甲基碸、二環氧乙烷、N-甲基吡咯啶酮等，可單獨使用或混合兩種以上而使用。 Examples of the hydrophilic solvent include methanol, ethanol, isopropanol, tetrahydrofuran, acetone, dimethylacetamide, dimethylformamide, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether. Ethylene glycol dimethyl ether, propylene glycol dimethyl ether, dimethyl hydrazine oxide, diethylene oxide, N-methyl pyrrolidone or the like may be used alone or in combination of two or more.

疏水性溶劑例如可列舉：己烷、環己烷、乙酸乙酯、丁醇、二氯甲烷、氯仿、氯苯、硝基苯、甲氧基苯、甲苯、二甲苯等，可單獨使用或混合兩種以上而使用。 Examples of the hydrophobic solvent include hexane, cyclohexane, ethyl acetate, butanol, dichloromethane, chloroform, chlorobenzene, nitrobenzene, methoxybenzene, toluene, xylene, etc., which may be used alone or in combination. Use two or more.

可與親水性溶劑或疏水性溶劑混合使用的其他溶劑例如可列舉：乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙二 醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯等。 Other solvents which can be used in combination with a hydrophilic solvent or a hydrophobic solvent include, for example, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, and ethylene. Alcohol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.

使上述金屬奈米粒子保護聚合物分散於介質中的方法並無特別限定，通常可藉由在室溫下靜置或攪拌而容易地獲得，但亦可視需要進行超音波處理、過熱處理等。另外，在由於保護聚合物的結晶性等而使與介質的適應性低的情況下，例如亦可為以少量良溶劑使保護聚合物溶解或膨潤後，使其分散於目標介質中的方法。此時，若進行超音波處理或過熱處理，則更有效果。 The method of dispersing the metal nanoparticle-protecting polymer in the medium is not particularly limited, and it can be easily obtained by standing or stirring at room temperature. However, ultrasonic treatment, overheat treatment, or the like may be performed as needed. In addition, when the adaptability to the medium is low due to the crystallinity of the protective polymer or the like, for example, a method in which the protective polymer is dissolved or swollen with a small amount of a good solvent and then dispersed in the target medium may be employed. At this time, if ultrasonic treatment or overheat treatment is performed, it is more effective.

在混合親水性溶劑及疏水性溶劑而使用的情況下，無需對其混合方法、混合順序等施加特別限制，亦可利用各種方法進行。有時由於所使用的保護聚合物的種類或組成等而於與各種溶劑的親和性、分散性上產生差異，因此較佳為根據目的而適當選擇溶劑的混合比、混合順序、混合方法、混合條件等。 When it is used by mixing a hydrophilic solvent and a hydrophobic solvent, it is not necessary to impose a special limitation on the mixing method, the mixing order, etc., and it can carry out by various methods. In some cases, there is a difference in affinity and dispersibility with various solvents depending on the type or composition of the protective polymer to be used. Therefore, it is preferred to appropriately select the mixing ratio, mixing order, mixing method, and mixing of the solvent according to the purpose. Conditions, etc.

本發明的金屬膠體溶液的製造方法是於上述保護聚合物的溶液或分散液中將金屬離子還原而製成金屬奈米粒子，金屬離子的來源(source)可列舉：金屬的鹽或金屬的離子溶液。金屬離子的來源只要為水溶性金屬化合物即可，可使用金屬陽離子與酸基陰離子的鹽類的化合物，或者酸基的陰離子中含有金屬的化合物等，可較佳地使用具有過渡金屬等金屬種類的金屬離子。 The metal colloid solution of the present invention is produced by reducing metal ions in a solution or dispersion of the above protective polymer to form metal nanoparticles, and sources of metal ions include metal salts or metal ions. Solution. The source of the metal ion may be a water-soluble metal compound, and a compound of a salt of a metal cation and an acid anion or a compound containing a metal of an anion of an acid group may be used, and a metal having a transition metal or the like may preferably be used. Metal ions.

過渡金屬系離子可為過渡金屬陽離子(Mn+)或包含鹵素類鍵的陰離子(MLx n-)，可於錯合物狀態下較佳地配位。此外，於本說明書中，所謂過渡金屬，是指於週期表第4族~第12族中處於第4週期~第6週期的過渡金屬元素。 The transition metal-based ion may be a transition metal cation (M n+ ) or an anion (ML x n- ) containing a halogen-based bond, and may be preferably coordinated in a complex state. In addition, in the present specification, the term "transition metal" means a transition metal element in the fourth to sixth cycles of Groups 4 to 12 of the periodic table.

過渡金屬陽離子可列舉：下述過渡金屬的陽離子(Mn+)，例如：Cr、Co、Ni、Cu、Pd、Ag、Pt、Au等一價陽離子、 二價陽離子、三價陽離子或四價陽離子等。這些金屬陽離子的相對陰離子可為Cl、NO3、SO4、或羧酸類的有機陰離子中的任一種。 Examples of the transition metal cation include a cation (M n+ ) of a transition metal such as a monovalent cation such as Cr, Co, Ni, Cu, Pd, Ag, Pt or Au, a divalent cation, a trivalent cation or a tetravalent cation. Wait. The relative anion of these metal cations may be any of Cl, NO 3 , SO 4 , or an organic anion of a carboxylic acid.

進而，下述金屬所含的陰離子(MLx n-)例如AgNO3、AuCl4、PtCl4、CuF6等將金屬配位於鹵素上而成的陰離子亦可較佳地於錯合物狀態下進行配位。 Further, an anion (ML x n- ) contained in the following metal, for example, an anion obtained by disposing a metal on a halogen such as AgNO 3 , AuCl 4 , PtCl 4 or CuF 6 may preferably be carried out in a complex state. Coordination.

於這些金屬離子中，尤其銀、金、鉑的金屬離子是於室溫或加熱狀態下自發性地進行還原，而轉化為非離子性金屬奈米粒子，故而較佳。另外，在使用所獲得的金屬膠體溶液作為導電材料的情況下，就導電性的表現能力或進行印刷．塗裝而獲得的覆膜的抗氧化性的觀點而言，較佳為使用銀的離子。 Among these metal ions, in particular, metal ions of silver, gold, and platinum are preferably spontaneously reduced at room temperature or in a heated state to be converted into nonionic metal nanoparticles. In addition, in the case of using the obtained metal colloidal solution as a conductive material, the ability to express electrical conductivity or printing. From the viewpoint of the oxidation resistance of the coating obtained by coating, it is preferred to use ions of silver.

另外，亦可將所含的金屬種類設為兩種以上。於此情況下，藉由同時或分別添加多種金屬的鹽或離子，而於介質中使多種金屬離子發生還原反應，產生多種金屬粒子，因此可獲得含有多種金屬的膠體溶液。 Further, the type of metal to be contained may be two or more. In this case, by simultaneously or separately adding a salt or an ion of a plurality of metals, a plurality of metal ions are reduced in the medium to produce a plurality of metal particles, and thus a colloidal solution containing a plurality of metals can be obtained.

於本發明中，亦可進而藉由還原劑將金屬離子還原。 In the present invention, the metal ions may be further reduced by a reducing agent.

上述還原劑可使用各種還原劑，並無特別限定，較佳為根據所獲得的金屬膠體溶液的使用用途或所含有的金屬種類等而選擇還原劑。可使用的還原劑例如可列舉：氫、硼氫化鈉、硼氫化銨等硼化合物，甲醇、乙醇、丙醇、異丙醇、乙二醇、丙二醇等醇類，甲醛、乙醛、丙醛等醛類，抗壞血酸、檸檬酸、檸檬酸鈉等酸類，丙基胺、丁基胺、二乙基胺、二丙基胺、二甲基乙基胺、三乙基胺、乙二胺、三伸乙基四胺、甲基胺基乙醇、二甲基胺基乙醇、三乙醇胺等胺類，肼、碳酸肼等肼類等。於這些中，就工業獲取的容易度、操作方面等而言，更佳為硼氫化鈉、抗壞 血酸、檸檬酸鈉、甲基胺基乙醇、二甲基胺基乙醇等。 The reducing agent can be used without any particular limitation, and it is preferred to select a reducing agent depending on the intended use of the obtained metal colloidal solution or the type of metal contained therein. Examples of the reducing agent which can be used include a boron compound such as hydrogen, sodium borohydride or ammonium borohydride, an alcohol such as methanol, ethanol, propanol, isopropanol, ethylene glycol or propylene glycol, formaldehyde, acetaldehyde or propionaldehyde. Aldehydes, acids such as ascorbic acid, citric acid, sodium citrate, propylamine, butylamine, diethylamine, dipropylamine, dimethylethylamine, triethylamine, ethylenediamine, triple extension An amine such as ethyltetramine, methylaminoethanol, dimethylaminoethanol or triethanolamine; an anthracene such as hydrazine or cesium carbonate. Among these, in terms of ease of industrial acquisition, handling, etc., it is more preferable to be sodium borohydride and to be resistant to deterioration. Blood acid, sodium citrate, methylaminoethanol, dimethylaminoethanol, and the like.

於本發明的金屬膠體溶液的製造方法中，保護聚合物與金屬離子的來源的使用比例並無特別限定，於將形成該保護聚合物中的聚乙醯基伸烷基亞胺N-氧化物片段的全部氮原子數設為100mol時，金屬通常為1mol~20,000mol的範圍，較佳為1mol~10,000mol的範圍，尤佳為50mol~7,000mol。 In the method for producing a metal colloidal solution of the present invention, the ratio of use of the source of the protective polymer to the metal ion is not particularly limited, and the polyethyl fluorene alkylene imine N-oxide fragment in the protective polymer will be formed. When the total number of nitrogen atoms is 100 mol, the metal is usually in the range of 1 mol to 20,000 mol, preferably in the range of 1 mol to 10,000 mol, particularly preferably 50 mol to 7,000 mol.

於本發明的金屬膠體溶液的製造方法中，將使保護聚合物分散或溶解的介質、與金屬的鹽或離子溶液混合的方法並無特別限定，可為於使該保護聚合物分散或溶解的介質中添加金屬的鹽或離子溶液的方法，其相反的方法，或者於另一容器中同時投入並進行混合的方法。攪拌等混合方法亦無特別限定。 In the method for producing a metal colloidal solution of the present invention, a method of mixing a medium for dispersing or dissolving a protective polymer with a metal salt or an ionic solution is not particularly limited, and the protective polymer may be dispersed or dissolved. A method of adding a metal salt or an ionic solution to a medium, the opposite method, or a method of simultaneously introducing and mixing in another container. The mixing method such as stirring is also not particularly limited.

另外，還原劑的添加方法並無限定，例如可直接添加還原劑，或者溶解、分散於水溶液或其他溶劑中並進行混合而添加。另外，添加還原劑的順序亦無限定，可為如下方法：預先於保護聚合物的溶液或分散液中添加還原劑，亦可於混合金屬的鹽或離子溶液時同時添加還原劑，進而，將保護聚合物的溶液或分散液與金屬的鹽或離子溶液加以混合後，經過數日或數週後混合還原劑。 Further, the method of adding the reducing agent is not limited, and for example, it may be directly added with a reducing agent, or dissolved, dispersed in an aqueous solution or another solvent, and mixed and added. Further, the order of adding the reducing agent is not limited, and may be a method in which a reducing agent is added to a solution or a dispersion of the protective polymer in advance, or a reducing agent may be simultaneously added to a salt or an ionic solution of the mixed metal, and further, After the solution or dispersion of the protective polymer is mixed with the metal salt or ionic solution, the reducing agent is mixed after several days or weeks.

於將本發明的製造方法中使用的金屬的鹽或其離子溶液添加至分散或溶解有保護聚合物的介質中時，無論O/W系或W/O系，均可直接或製備成水溶液而添加。銀、金、鈀、鉑等金屬離子是於配位於聚合物中的乙醯基伸烷基亞胺或N-氧化物單元上後，於室溫或加熱狀態下自發性地進行還原，因此藉由直接於室溫或加溫下靜置或攪拌而成為金屬奈米粒子，可獲得以保 護聚合物保護金屬奈米粒子而成的複合體的分散液，即金屬膠體溶液，但為了如上述般有效率地進行金屬離子的還原，較佳為使用還原劑，藉由在室溫或加溫下靜置或攪拌而獲得金屬膠體溶液。此時，還原劑較佳為直接使用或預先製備成水溶液而使用。於加溫的情況下的溫度由於保護聚合物的種類或所使用的金屬、介質、還原劑的種類等而有所不同，通常為100℃以下，較佳為80℃以下。 When a salt of a metal or an ionic solution thereof used in the production method of the present invention is added to a medium in which a protective polymer is dispersed or dissolved, an O/W system or a W/O system may be directly or prepared as an aqueous solution. Add to. Metal ions such as silver, gold, palladium, platinum, etc. are spontaneously reduced at room temperature or under heating after being placed on an ethyl sulfonylalkylene or an N-oxide unit in a polymer. It can be obtained by standing or stirring at room temperature or under heating to become metal nanoparticles. The polymer dispersion protects the dispersion of the composite of the metal nanoparticles, that is, the metal colloidal solution. However, in order to efficiently carry out the reduction of the metal ions as described above, it is preferred to use a reducing agent at room temperature or The metal colloidal solution is obtained by standing or stirring under temperature. At this time, the reducing agent is preferably used as it is or directly prepared as an aqueous solution. The temperature in the case of heating varies depending on the kind of the protective polymer, the type of the metal to be used, the medium, and the reducing agent, and is usually 100 ° C or lower, preferably 80 ° C or lower.

如上所述，藉由將金屬離子還原而析出金屬奈米粒子，並且以上述保護聚合物保護該粒子的表面而進行穩定化。於該還原反應後的溶液中含有與還原劑、金屬離子的相對離子、金屬奈米粒子的保護無關的保護聚合物等雜質，無法直接作為導電材料而表現出充分的性能。因此，必需要去除上述雜質等的純化步驟，但本案發明的保護聚合物藉由其保護能力高，可於反應液中添加不良溶劑而使以保護聚合物保護金屬奈米粒子而成的複合體效率良好地沈澱。經沈澱的複合體亦可利用離心分離等步驟進行濃縮或單離。於經濃縮後，依據金屬膠體溶液的用途等，以所需介質製備非揮發成分(濃度)而應用於各種用途。 As described above, the metal nanoparticles are precipitated by reducing the metal ions, and the surface of the particles is protected by the protective polymer to stabilize. The solution after the reduction reaction contains impurities such as a protective polymer irrespective of the reducing agent, the counter ion of the metal ion, and the protection of the metal nanoparticle, and cannot exhibit sufficient performance as a conductive material. Therefore, it is necessary to remove the above-mentioned impurities and the like, but the protective polymer of the present invention has a high protective ability, and a poor solvent can be added to the reaction liquid to protect the polymer from the metal nanoparticle. Precipitate efficiently. The precipitated complex may also be concentrated or isolated by means of centrifugation or the like. After concentration, a non-volatile component (concentration) is prepared in a desired medium depending on the use of the metal colloidal solution, etc., and is used for various purposes.

本發明中獲得的金屬膠體溶液中的金屬奈米粒子的含量並無特別限定，若含量過少，則不易表現作為膠體溶液的金屬奈米粒子的特性，另外，若含量過多，則膠體溶液中的金屬奈米粒子的相對重量增加，就預想到因兼顧其相對重量與保護聚合物的分散力而使膠體溶液的穩定性不足的觀點、以及利用保護聚合物中的乙醯基伸烷基亞胺N-氧化物單元的還原能力或配位能力等觀點而言，該金屬膠體溶液中的非揮發成分含有率較佳為10質量 %~80質量%的範圍，尤佳為20質量%~70質量%的範圍。就使用膠體溶液作為導電材料時的導電性的表現能力等觀點而言，其非揮發成分中的金屬奈米粒子的含有率較佳為93質量%以上，尤佳為95質量%以上。 The content of the metal nanoparticles in the metal colloidal solution obtained in the present invention is not particularly limited, and if the content is too small, the properties of the metal nanoparticles as a colloidal solution are not easily expressed, and if the content is too large, the colloidal solution is present. As the relative weight of the metal nanoparticles increases, it is expected that the stability of the colloidal solution is insufficient due to the balance between the relative weight and the protective polymer, and the use of the ethyl sulfonylalkylene amine N in the protective polymer. The content of the non-volatile component in the metal colloid solution is preferably 10 mass from the viewpoints of reducing ability or coordination ability of the oxide unit. The range of % to 80% by mass is particularly preferably in the range of 20% by mass to 70% by mass. The content of the metal nanoparticles in the nonvolatile component is preferably 93% by mass or more, and particularly preferably 95% by mass or more, from the viewpoint of the ability to express the conductivity when the colloidal solution is used as the conductive material.

本發明中獲得的金屬膠體溶液中的非揮發成分所含的金屬奈米粒子的粒徑並無特別限定，為了使金屬膠體溶液具有更高的分散穩定性，較佳為該金屬奈米粒子的粒徑為1nm~70nm的微粒子，更佳為粒徑為5nm~50nm的範圍的微粒子。 The particle diameter of the metal nanoparticles contained in the non-volatile component in the metal colloidal solution obtained in the present invention is not particularly limited, and in order to impart higher dispersion stability to the metal colloidal solution, the metal nanoparticle is preferably used. The fine particles having a particle diameter of 1 nm to 70 nm are more preferably fine particles having a particle diameter of 5 nm to 50 nm.

通常位於數十nm的尺寸區域的金屬奈米粒子依據其金屬種類而具有由表面電漿子激發引起的特徵的光學吸收。因此，藉由對本發明中獲得的金屬膠體溶液的電漿子吸收進行測定，可確認出於該溶液中金屬以奈米級的微粒子的形式存在，進而，亦可利用澆鑄該溶液所獲得的膜的穿透式電子顯微鏡(Transmission Electron Microscopy，TEM)照片等觀測其平均粒徑或分佈寬度等。 The metal nanoparticles generally located in the size region of several tens of nm have optical absorption of the characteristics caused by surface plasmon excitation depending on the metal species thereof. Therefore, by measuring the plasmonic absorption of the metal colloidal solution obtained in the present invention, it has been confirmed that the metal in the solution is in the form of nano-sized fine particles, and further, the film obtained by casting the solution can be used. The average particle diameter or distribution width of the transmission electron microscopy (TEM) photograph or the like is observed.

本發明中獲得的金屬膠體溶液長期穩定地分散於所有介質中，因此其用途並無限定，例如可用於觸媒、電子材料、磁性材料、光學材料、各種感測器、有色材料、醫療檢查用途等非常廣泛的領域中。就可容易地進行製備的方面而言，可含有的金屬種類或其比例亦可根據目的而有效率地表現效果。進而，就長期穩定地分散的觀點而言，能夠應對長期使用．長期保存且有用性高。另外，本發明的金屬膠體溶液的製造方法幾乎無需複雜的步驟或緻密的條件設定等，因此作為工業製法的優勢大。 The metal colloidal solution obtained in the present invention is stably dispersed in all the medium for a long period of time, and therefore its use is not limited, and can be used, for example, for a catalyst, an electronic material, a magnetic material, an optical material, various sensors, a colored material, and a medical examination. Waiting in a very wide range of fields. In terms of ease of preparation, the type of metal that can be contained or the ratio thereof can be effectively expressed according to the purpose. Furthermore, in terms of long-term stable dispersion, it can cope with long-term use. Long-term preservation and high usefulness. Further, since the method for producing a metal colloidal solution of the present invention requires almost no complicated steps or setting of dense conditions, etc., it is advantageous as an industrial process.

[實施例] [Examples]

以下，列舉實施例對本發明進一步進行詳細說明，但本 發明並不限定於這些實施例。此外，只要無特別說明，則「%」表示「質量%」。 Hereinafter, the present invention will be further described in detail by way of examples, but The invention is not limited to these embodiments. In addition, "%" means "% by mass" unless otherwise specified.

於以下的實施例中，所使用的機器種類及測定方法如下所述。 In the following examples, the types of machines and measurement methods used are as follows.

質子核磁共振(proton-Nuclear Magnetic Resonance，1H-NMR)：日本電子股份有限公司製造，AL300，300Hz Proton nuclear magnetic resonance (proton-Nuclear Magnetic Resonance, 1 H-NMR): Japan Electronics Manufacturing Co., AL300,300Hz

粒徑測定：大塚電子股份有限公司製造，FPAR-1000 Particle size measurement: manufactured by Otsuka Electronics Co., Ltd., FPAR-1000

電漿子吸收光譜(spectrum)：日立製作所股份有限公司製造，UV-3500 Plasma absorption spectrum (spectrum): manufactured by Hitachi, Ltd., UV-3500

利用1H-NMR的保護聚合物的結構確認 Structure confirmation of protective polymer by 1 H-NMR

將保護聚合物的溶液約3mL濃縮，充分進行減壓乾燥後，使殘渣溶解於例如含0.03%四甲基矽烷的氘氯仿等NMR測定用溶劑約0.8mL中，將其置於外直徑5mm的玻璃製NMR測定用樣品管中，藉由JEOL JNM-LA300型核磁共振吸收光譜測定裝置而取得1H-NMR光譜。化學位移值(chemical shift value)δ是以四甲基矽烷為基準物質而表示。 The solution of the protective polymer is concentrated in about 3 mL, and the mixture is sufficiently dried under reduced pressure, and then the residue is dissolved in, for example, about 0.8 mL of a solvent for NMR measurement such as ruthenium chloroform containing 0.03% tetramethylnonane, and placed in an outer diameter of 5 mm. In the sample tube for NMR measurement by glass, 1 H-NMR spectrum was obtained by a JEOL JNM-LA300 type nuclear magnetic resonance absorption spectrometer. The chemical shift value δ is represented by tetramethyl decane as a reference substance.

利用動態光散射法的粒徑測定 Particle size measurement by dynamic light scattering method

以純化水稀釋金屬膠體溶液的一部分，藉由FPAR-1000型濃厚系粒徑分析儀(analyzer)(大塚電子股份有限公司製造)測定粒徑分佈、平均粒徑。 A part of the metal colloidal solution was diluted with purified water, and the particle size distribution and the average particle diameter were measured by a FPAR-1000 type thick particle size analyzer (manufactured by Otsuka Electronics Co., Ltd.).

利用熱重量分析的非揮發物中的金屬含量測定 Determination of metal content in non-volatiles by thermogravimetric analysis

將金屬膠體溶液約1mL置於玻璃樣品瓶中，於沸騰水浴上、於氮氣氣流下進行加熱濃縮，進而將殘渣於50℃下真空乾燥8小時以上，而獲得非揮發物。以熱重量分析用鋁鍋(Aluminum Pan) 精密地測量該非揮發物2mg~10mg，並置於EXSTAR TG/DTA6300型示差熱重量分析裝置(精工電子(Seiko Instruments)股份有限公司製造)中，於空氣氣流下，以每分鐘10℃的比例自室溫升溫至500℃，對伴隨加熱的重量減少率進行測定。非揮發物中的銀含量是利用以下式計算。 Approximately 1 mL of the metal colloidal solution was placed in a glass sample vial, and concentrated by heating on a boiling water bath under a nitrogen gas stream, and the residue was vacuum dried at 50 ° C for more than 8 hours to obtain a nonvolatile matter. Aluminum Pan for Thermogravimetric Analysis (Aluminum Pan) The non-volatiles 2 mg to 10 mg were precisely measured and placed in an EXSTAR TG/DTA6300 differential thermal gravimetric analyzer (manufactured by Seiko Instruments Co., Ltd.) at room temperature of 10 ° C per minute from room temperature. The temperature was raised to 500 ° C, and the weight reduction rate accompanying heating was measured. The silver content in the non-volatile matter is calculated by the following formula.

金屬含量(%)=100-重量減少率(%) Metal content (%) = 100 - weight reduction rate (%)

由金屬膠體溶液獲得的金屬薄膜的電阻率測定 Determination of resistivity of metal film obtained from metal colloidal solution

將金屬膠體溶液約0.5mL滴加至2.5×5cm的潔淨玻璃板的上部，使用棒式塗佈機(bar coater)8號製成塗膜。於將所製成的塗膜風乾後，於125℃及180℃的熱風乾燥機中加熱30分鐘而製成煅燒塗膜。使用Optelics C130型實彩色共焦顯微鏡(Real Color Confocal Microscope)(Lasertec公司製造)測量所獲得的煅燒塗膜的厚度，繼而使用Loresta-EP MCP-T360型低電阻率計(三菱化學股份有限公司製造)，依據JIS K7194「導電性塑膠(plastic)的利用四探針法的電阻率試驗」測定表面電阻率(Ω/□)。塗膜厚度根據上述條件大致顯示出0.3μm的固定值，根據該厚度與表面電阻率(Ω/□)藉由下式算出體積電阻率(Ωcm)。 About 0.5 mL of the metal colloid solution was dropped onto the upper portion of a 2.5 × 5 cm clean glass plate, and a coating film was formed using a bar coater No. 8. After the prepared coating film was air-dried, it was heated in a hot air dryer at 125 ° C and 180 ° C for 30 minutes to prepare a calcined coating film. The thickness of the obtained calcined coating film was measured using an Optelics C130 Real Color Confocal Microscope (manufactured by Lasertec), and then a Loresta-EP MCP-T360 type low resistivity meter (manufactured by Mitsubishi Chemical Corporation) was used. The surface resistivity (Ω/□) was measured in accordance with JIS K7194 "Resistivity test of a conductive plastic using a four-probe method". The coating film thickness showed a fixed value of 0.3 μm in general according to the above conditions, and the volume resistivity (Ωcm) was calculated from the thickness and the surface resistivity (Ω/□) by the following formula.

體積電阻率(Ωcm)=表面電阻率(Ω/□)×厚度(cm) Volume resistivity (Ωcm) = surface resistivity (Ω / □) × thickness (cm)

合成例1 甲苯磺醯基化聚乙二醇單甲醚的合成 Synthesis Example 1 Synthesis of toluenesulfonylated polyethylene glycol monomethyl ether

於氮氣環境下，於甲氧基聚乙二醇[Mn=2,000]20.0g(10.0mmol)、吡啶8.0g(100.0mmol)、及氯仿20ml的混合溶液中，一面進行冰浴冷卻攪拌一面花30分鐘滴加含有對甲苯磺醯氯9.6g(50.0mmol)的氯仿(30ml)溶液。於滴加結束後，於浴槽溫度40℃下進而攪拌4小時。於反應結束後，添加氯仿50ml稀釋 反應液。繼而，依序利用5%鹽酸水溶液100ml、飽和碳酸氫鈉水溶液100ml、以及飽和鹽水溶液100ml洗淨後，以硫酸鎂進行乾燥、過濾、減壓濃縮。利用己烷將所獲得的固形物洗淨數次後，進行過濾，於80℃下進行減壓乾燥，獲得經甲苯磺醯基化的產物22.0g。 Under a nitrogen atmosphere, in a mixed solution of methoxypolyethylene glycol [Mn = 2,000] 20.0 g (10.0 mmol), pyridine 8.0 g (100.0 mmol), and chloroform (20 ml), the mixture was cooled in an ice bath while stirring 30 A solution of 9.6 g (50.0 mmol) of p-toluenesulfonyl chloride in chloroform (30 ml) was added dropwise thereto. After the completion of the dropwise addition, the mixture was further stirred at a bath temperature of 40 ° C for 4 hours. After the reaction was completed, add chloroform diluted to 50 ml. The reaction solution. Then, it was washed with 100 ml of a 5% hydrochloric acid aqueous solution, 100 ml of a saturated aqueous sodium hydrogencarbonate solution, and 100 ml of a saturated brine solution, and dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained solid matter was washed several times with hexane, filtered, and dried under reduced pressure at 80 ° C to obtain 22.0 g of toluenesulfonated product.

將所獲得的產物的1H-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=7.8(d,2H,J=7.8Hz，甲苯磺醯基)，7.3(d,2H,J=7.8，甲苯磺醯基)，4.2(t,2H,J=4.2Hz，磺酸酯鄰接位)，3.6-3.5(m，聚乙二醇甲醚(Poly(Ethylene Glycol Methyl Ether)，PEGM)亞甲基)，3.4(s,3H,PEGM鏈末端甲氧基)，2.4(s,3H，甲苯磺醯基甲基). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 7.8 (d, 2H, J = 7.8 Hz, toluenesulfonyl), 7.3 (d, 2H, J = 7.8, toluenesulfonyl), 4.2 (t, 2H, J = 4.2 Hz, sulfonate adjacent), 3.6-3.5 (m, Poly(Ethylene Glycol Methyl Ether), PEMM) methylene), 3.4 (s, 3H) , PEGM chain end methoxy), 2.4 (s, 3H, toluenesulfonylmethyl).

合成例2 聚伸乙亞胺-b-聚乙二醇共聚物的合成 Synthesis Example 2 Synthesis of Poly(ethyleneimine)-b-polyethylene glycol copolymer

將上述合成例1中獲得的甲苯磺醯基化聚乙二醇19.3g(9.0mmol)、及支鏈狀聚伸乙亞胺(日本觸媒股份有限公司製造，Epomin SP200)30.0g(3.0mmol)於氮氣環境下、於60℃下溶解，進行混合攪拌後，添加碳酸鉀0.18g，於反應溫度120℃下攪拌6小時。於反應結束後，於四氫呋喃(tetrahydrofuran，THF)溶劑中進行稀釋後，去除殘渣，其後於30℃下進行減壓濃縮。將所獲得的固形物再次溶解於THF溶劑後，添加庚烷進而使殘渣再沈澱，將其過濾分離，於減壓下濃縮，則可獲得淡黃色的固形物48.1g(產率99%)。 19.3 g (9.0 mmol) of toluenesulfonated polyethylene glycol obtained in the above Synthesis Example 1, and branched polyethylenimine (manufactured by Nippon Shokubai Co., Ltd., Epomin SP200) 30.0 g (3.0 mmol) After dissolving in a nitrogen atmosphere at 60 ° C and mixing and stirring, 0.18 g of potassium carbonate was added, and the mixture was stirred at a reaction temperature of 120 ° C for 6 hours. After completion of the reaction, the mixture was diluted with tetrahydrofuran (THF) solvent, and the residue was removed, followed by concentration under reduced pressure at 30 °C. After the obtained solid matter was redissolved in a THF solvent, heptane was added to further reprecipitate the residue, which was separated by filtration and concentrated under reduced pressure to obtain 48.1 g (yield: 99%) of pale yellow solid.

將所獲得的產物的1H-NMR、13C-NMR(日本電子股份 有限公司製造，AL300，300MHz)及元素分析的測定結果示於以下。 The measurement results of 1 H-NMR, 13 C-NMR (manufactured by JEOL Ltd., AL 300, 300 MHz) and elemental analysis of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=3.57(br s,PEGM亞甲基)，3.25(s,3H,PEGM鏈末端甲氧基)，2.65~2.40(m，支鏈聚伸乙亞胺(Polyethyleneimine，PEI)伸乙基). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 3.57 (br s, PEMM methylene), 3.25 (s, 3H, PEMM chain end methoxy), 2.65 ~ 2.40 (m, branched poly Polyethyleneimine (PEI) stretches ethyl).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=39.9(s),41.8(s),47.6(m),49.5(m),52.6(m),54.7(m),57.8(m)(以上為支鏈PEI伸乙基)，59.0(s),70.5(m),71.8(s)(以上為PEGM亞甲基及末端甲氧基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 39.9 (s), 41.8 (s), 47.6 (m), 49.5 (m), 52.6 (m), 54.7 (m), 57.8 ( m) (above is branched PEI extended ethyl), 59.0 (s), 70.5 (m), 71.8 (s) (above is PEMM methylene and terminal methoxy).

元素分析的測定結果：C(53.1%)、H(10.4%)、N(19.1%) Elemental analysis results: C (53.1%), H (10.4%), N (19.1%)

合成例3 聚伸乙亞胺-b-聚乙二醇-b-雙酚A型環氧樹脂的合成 Synthesis Example 3 Synthesis of Poly(ethyleneimine)-b-polyethylene glycol-b-bisphenol A type epoxy resin

將EPICLON AM-040-P(DIC股份有限公司製造，雙酚A型環氧樹脂，環氧當量933)37.4g(20mmol)、及4-苯基苯酚2.72g(16mmol)溶解於N,N-二甲基乙醯胺100mL後，添加65%乙酸乙基三苯基鏻的乙醇溶液0.52mL，於氮氣環境下，於120℃下使其反應6小時。放置冷卻後，滴加至大量水中，以大量水將所獲得的沈澱物洗淨。將殘渣減壓乾燥，獲得改質雙酚A型環氧樹脂。所獲得的產物的產率為98%。進行1H-NMR測定，研究環氧基的積分比，結果確認到於雙酚A型環氧樹脂1分子中殘留0.95個環氧環，產物為具有雙酚A骨架的單官能性的環氧樹脂。 EPICLON AM-040-P (manufactured by DIC Corporation, bisphenol A epoxy resin, epoxy equivalent 933) 37.4 g (20 mmol), and 4-phenylphenol 2.72 g (16 mmol) were dissolved in N,N- After 100 mL of dimethylacetamide, 0.52 mL of a 65% ethanolic solution of ethyltriphenylphosphonium chloride was added, and the mixture was reacted at 120 ° C for 6 hours under a nitrogen atmosphere. After standing to cool, it was added dropwise to a large amount of water, and the obtained precipitate was washed with a large amount of water. The residue was dried under reduced pressure to obtain a modified bisphenol A type epoxy resin. The yield of the obtained product was 98%. The 1 H-NMR measurement was carried out to study the integral ratio of the epoxy groups, and it was confirmed that 0.95 epoxy rings remained in the molecule of the bisphenol A type epoxy resin, and the product was a monofunctional epoxy having a bisphenol A skeleton. Resin.

將所獲得的單官能性的環氧樹脂的1H-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained monofunctional epoxy resin are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)：7.55~6.75(m),4.40~3.90(m),3.33(m),2.89(m),2.73(m),1.62(s) 1 H-NMR (CDCl 3 ) measurement results: δ (ppm): 7.55 to 6.75 (m), 4.40 to 3.90 (m), 3.33 (m), 2.89 (m), 2.73 (m), 1.62 (s)

於合成例2中獲得的聚伸乙亞胺-b-聚乙二醇共聚物20g(0.8mmol)的甲醇(150mL)溶液中，於氮氣環境下滴加上述改質環氧樹脂3.2g(1.6mmol)的丙酮(50mL)溶液後，於50℃下攪拌2小時。於反應結束後，於減壓下將溶劑蒸餾去除，進而進行減壓乾燥，藉此獲得聚伸乙亞胺-b-聚乙二醇-b-雙酚A型環氧樹脂。產率為100%。 In a solution of 20 g (0.8 mmol) of a polyethylenimine-b-polyethylene glycol copolymer obtained in Synthesis Example 2 in methanol (150 mL), the above modified epoxy resin 3.2 g (1.6) was added dropwise under a nitrogen atmosphere. After a solution of mmol (50 mL) was stirred at 50 ° C for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and further dried under reduced pressure to obtain a polyethylenimine-b-polyethylene glycol-b-bisphenol A type epoxy resin. The yield was 100%.

將所獲得的產物的1H-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=7.55~6.75(m),4.40~3.90(m),3.60(m),3.25(s),2.70~2.40(m),1.62(s). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 7.55 to 6.75 (m), 4.40 to 3.90 (m), 3.60 (m), 3.25 (s), 2.70 to 2.40 (m), 1.62 (s) ).

實施例1 保護聚合物(1-1)的合成 Example 1 Synthesis of Protective Polymer (1-1)

乙醯化反應：乙醯化物(1-1A)的合成 Acetyleneization reaction: synthesis of acetylated metal (1-1A)

將上述合成例1中獲得的甲苯磺醯基化聚乙二醇19.3g(9.0mmol)、及支鏈狀聚伸乙亞胺(日本觸媒股份有限公司製造，Epomin SP200)30.0g(3.0mmol)於氮氣環境下與N,N-二甲基乙醯胺270ml一併溶解後，添加碳酸鉀0.18g，於反應溫度120℃下攪拌6小時。於反應結束後，去除固形物，其後於70℃下進行減壓濃縮，於殘渣中添加乙酸乙酯200ml及己烷600ml的混合物而獲得沈澱物。將所獲得的沈澱物分離，於THF溶劑中進行稀釋後，去除殘渣，於30℃下進行減壓濃縮。將所獲得的固形物再次 溶解於THF溶劑中後，添加庚烷進而使殘渣再沈澱，將其過濾分離，於減壓下進行濃縮，則可獲得淡黃色的固形物47.8g(產率98%)。 19.3 g (9.0 mmol) of toluenesulfonated polyethylene glycol obtained in the above Synthesis Example 1, and branched polyethylenimine (manufactured by Nippon Shokubai Co., Ltd., Epomin SP200) 30.0 g (3.0 mmol) After dissolving in 270 ml of N,N-dimethylacetamide under a nitrogen atmosphere, 0.18 g of potassium carbonate was added, and the mixture was stirred at a reaction temperature of 120 ° C for 6 hours. After completion of the reaction, the solid matter was removed, and then concentrated under reduced pressure at 70 ° C, and a mixture of ethyl acetate (200 ml) and hexane (600 ml) was added to the residue to obtain a precipitate. The obtained precipitate was separated, diluted in a THF solvent, and the residue was removed, and concentrated under reduced pressure at 30 °C. Will get the solids again After dissolving in a THF solvent, heptane was added to further reprecipitate the residue, which was separated by filtration and concentrated under reduced pressure to obtain 47.8 g (yield: 98%) of pale yellow solid.

將所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=3.57(br s,PEGM亞甲基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.65~2.40(m，支鏈PEI伸乙基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 3.57 (br s, PEMM methylene), 3.25 (s, 3H, PEMM chain terminal methoxy), 3.16 (m, 2H, ethenyl) Adjacent methylene group of N, 2.65~2.40 (m, branched PEI extended ethyl), 1.90 (br s, 3H, primary N ethyl thiol).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=22.9(s)(一級N的乙醯基)，39.9(s),41.8(s),47.6(m),49.5(m),52.6(m),54.7(m),57.8(m)(以上為支鏈PEI伸乙基)，59.0(s),70.5(m),71.8(s)(以上為PEGM亞甲基及末端甲氧基)，173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 22.9 (s) (first-order N oxime), 39.9 (s), 41.8 (s), 47.6 (m), 49.5 (m) , 52.6 (m), 54.7 (m), 57.8 (m) (above is branched PEI ethyl), 59.0 (s), 70.5 (m), 71.8 (s) (above is PEMM methylene and terminal A Oxy), 173.4 (m) (ethinyl).

利用1H-NMR測定，根據將支鏈狀聚伸乙亞胺的一級胺乙醯化的1.90ppm波峰的積分比的計算，可認為支鏈狀聚伸乙亞胺中一級胺的11mol%被乙醯化。 According to the calculation of 1 H-NMR, according to the calculation of the integral ratio of the 1.90 ppm peak of the primary amine of the branched polyethylenimine, it is considered that 11 mol% of the primary amine in the branched polyethylenimine is Biehua.

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

將上述合成中獲得的乙醯化物(1-1A)的37.7g(N當量、531mmol)溶解於純水100mL後，一面進行攪拌一面於冰浴下緩慢地添加35%過氧化氫水5.16g(53.1mmol、10mol%相對N當量)，進行氧化反應5小時，定量地獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-1)。 37.7 g (N equivalent, 531 mmol) of the acetylated product (1-1A) obtained in the above-mentioned synthesis was dissolved in 100 mL of pure water, and then 5.16 g of 35% hydrogen peroxide water was slowly added to the ice bath while stirring. 53.1 mmol, 10 mol% relative to N equivalent), an oxidation reaction was carried out for 5 hours, and a protective polymer (1-1) having a polyethylamethylene acetamidide N-oxide chain and a hydrophilic segment as a product was quantitatively obtained.

將所獲得的產物的1H-NMR及13C-NMR(日本電子股份 有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(DMSO-d6)測定結果：δ(ppm)=3.6(br s,PEGM亞甲基)，3.3~3.2(m,N-氧化物伸乙基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.9(m,N-氧化物伸乙基)，2.7~2.4(m，支鏈PEI伸乙基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 3.6 (br s, PEMM methylene), 3.3 to 3.2 (m, N-oxide extended ethyl), 3.25 (s, 3H, PEGM chain end methoxy), 3.16 (m, 2H, acetonitrile N adjacent methylene), 2.9 (m, N-oxide extended ethyl), 2.7 ~ 2.4 (m, branched PEI extended ethyl ), 1.90 (br s, 3H, the first cytosolic N).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=36.0(m,N-氧化物伸乙基)，39.0(m),41.8(s),43.0(m,N-氧化物伸乙基)，46.0(m),48.0(m),51.0(m),53.0(m),56.0(m),59.0(s),63.0~68.0(m,N-氧化物伸乙基)，70.0(m),71.5(s),173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 36.0 (m, N-oxide extended ethyl), 39.0 (m), 41.8 (s), 43.0 (m, N-oxide extension Ethyl), 46.0 (m), 48.0 (m), 51.0 (m), 53.0 (m), 56.0 (m), 59.0 (s), 63.0 to 68.0 (m, N-oxide extended ethyl), 70.0 (m), 71.5(s), 173.4(m) (acetonitrile).

利用1H-NMR測定，於2.40ppm~2.70ppm的支鏈PEI伸乙基中，更高磁場的2.40ppm~2.55ppm的三級胺波峰下降，其積分比變小，但2.55ppm~2.60ppm的二級胺及2.60ppm~2.70ppm的一級胺的波峰幾乎無變化。13C-NMR測定結果亦同樣為51.0ppm~56.0ppm的三級胺波峰下降，但39.0ppm~51.0ppm的二級胺及一級胺的波峰幾乎無變化。另外，根據NMR測定的積分比，推定出將前驅物化合物的全部氮(N)的約10%的N氧化而形成N-氧化物。 According to the 1 H-NMR measurement, in the branched PEI extended ethyl group of 2.40 ppm to 2.70 ppm, the higher-field 2.40 ppm to 2.55 ppm tertiary amine peak decreased, and the integral ratio became smaller, but 2.55 ppm to 2.60 ppm. There are almost no changes in the peaks of the secondary amines and 2.65 ppm to 2.70 ppm of the primary amine. The 13 C-NMR measurement also showed a decrease in the peak of the tertiary amine of 51.0 ppm to 56.0 ppm, but the peak of the secondary amine and the primary amine of 39.0 ppm to 51.0 ppm hardly changed. Further, from the integral ratio measured by NMR, it is estimated that about 10% of all nitrogen (N) of the precursor compound is oxidized to form an N-oxide.

實施例2 保護聚合物(1-2)的合成 Example 2 Synthesis of Protective Polymer (1-2)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

將上述實施例1中獲得的乙醯化物(1-1A)的37.7g(N當量、531mmol)溶解於純水100mL後，一面進行攪拌一面於冰浴下緩慢地添加35%過氧化氫水25.8g(265.5mmol、50mol%比N 當量)，進行氧化反應5小時，定量地獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-2)。 After dissolving 37.7 g (N equivalent, 531 mmol) of the acetylated product (1-1A) obtained in the above Example 1 in 100 mL of pure water, 35% hydrogen peroxide water was slowly added to the ice bath while stirring. g (265.5 mmol, 50 mol% ratio N Equivalent), an oxidation reaction was carried out for 5 hours, and a protective polymer (1-2) having a polyethylamethylene acetamidide N-oxide chain and a hydrophilic segment as a product was quantitatively obtained.

將所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(DMSO-d6)測定結果：δ(ppm)=3.6(br s,PEGM亞甲基)，3.3~3.2(m,N-氧化物伸乙基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.9(m,N-氧化物伸乙基)，2.7~2.5(m，支鏈PEI伸乙基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 3.6 (br s, PEMM methylene), 3.3 to 3.2 (m, N-oxide extended ethyl), 3.25 (s, 3H, PEGM chain end methoxy), 3.16 (m, 2H, acetonitrile N adjacent methylene), 2.9 (m, N-oxide extended ethyl), 2.7 ~ 2.5 (m, branched PEI extended ethyl ), 1.90 (br s, 3H, the first cytosolic N).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=36.0(m,N-氧化物伸乙基)，39.0(m),41.8(s),43.0(m,N-氧化物伸乙基)，46.0(m),48.0(m),51.0(m),53.0(m),59.0(s),63.0~68.0(m,N-氧化物伸乙基)，70.0(m),71.5(s),173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 36.0 (m, N-oxide extended ethyl), 39.0 (m), 41.8 (s), 43.0 (m, N-oxide extension Ethyl), 46.0 (m), 48.0 (m), 51.0 (m), 53.0 (m), 59.0 (s), 63.0-68.0 (m, N-oxide extended ethyl), 70.0 (m), 71.5 (s), 173.4 (m) (Ethyl).

利用1H-NMR測定，於2.40ppm~2.70ppm的支鏈PEI伸乙基中，更高磁場的2.40ppm~2.55ppm的三級胺波峰消失，2.55ppm~2.60ppm的二級胺及2.60ppm~2.70ppm的一級胺波峰下降，其積分比變小。13C-NMR測定結果亦同樣為51.0ppm~56.0ppm的三級胺波峰消失，39.0ppm~51.0ppm的二級胺及一級胺的波峰變小。另外，根據NMR測定的積分比，可認為將前驅物化合物的全部氮(N)的約50%的N氧化而形成N-氧化物。 Using a 1 H-NMR measurement, in the 2.40 ppm to 2.70 ppm branched PEI-extended ethyl group, the higher-field 2.40 ppm to 2.55 ppm tertiary amine peak disappeared, 2.55 ppm to 2.60 ppm of the secondary amine and 2.60 ppm. The peak of ~2.70 ppm of the primary amine decreases, and the integral ratio becomes smaller. The 13 C-NMR measurement results also showed that the tertiary amine peaks of 51.0 ppm to 56.0 ppm disappeared, and the peaks of the secondary amines and primary amines of 39.0 ppm to 51.0 ppm became small. Further, based on the integral ratio measured by NMR, it is considered that about 50% of all nitrogen (N) of the precursor compound is oxidized to form an N-oxide.

實施例3 保護聚合物(1-3)的合成 Example 3 Synthesis of Protective Polymer (1-3)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

將上述實施例1中獲得的乙醯化物(1-1A)的37.7g(N當 量、531mmol)溶解於純水100mL後，一面進行攪拌一面於冰浴下緩慢地添加35%過氧化氫水46.4g(477.9mmol、90mol%比N當量)，進行氧化反應5小時，定量地獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-3)。 37.7 g (N when the acetylated product (1-1A) obtained in the above Example 1 was After dissolving in 100 mL of pure water, 46.4 g (477.9 mmol, 90 mol% of N equivalent) of 35% hydrogen peroxide water was slowly added to the ice bath while stirring, and an oxidation reaction was carried out for 5 hours, and quantitatively obtained. As a product, a protective polymer (1-3) having a polyethyl fluorene ethyleneimine N-oxide chain and a hydrophilic segment.

將所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(DMSO-d6)測定結果：δ(ppm)=3.6(br s,PEGM亞甲基)，3.3~3.2(m,N-氧化物伸乙基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.9(m,N-氧化物伸乙基)，2.7~2.6(m，支鏈PEI伸乙基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 3.6 (br s, PEMM methylene), 3.3 to 3.2 (m, N-oxide extended ethyl), 3.25 (s, 3H, PEGM chain end methoxy), 3.16 (m, 2H, acetonitrile N adjacent methylene), 2.9 (m, N-oxide extended ethyl), 2.7 ~ 2.6 (m, branched PEI extended ethyl ), 1.90 (br s, 3H, the first cytosolic N).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=36.0(m,N-氧化物伸乙基)，39.0(m),43.0(m,N-氧化物伸乙基)，46.0(m),48.0(m),53.0(m),59.0(s),63.0~68.0(m,N-氧化物伸乙基)，70.0(m),71.5(s),173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 36.0 (m, N-oxide extended ethyl), 39.0 (m), 43.0 (m, N-oxide-extended ethyl), 46.0 (m), 48.0 (m), 53.0 (m), 59.0 (s), 63.0 to 68.0 (m, N-oxide extended ethyl), 70.0 (m), 71.5 (s), 173.4 (m) (B)醯基).

利用1H-NMR測定，於2.40ppm~2.70ppm的支鏈PEI伸乙基中，更高磁場的2.40ppm~2.55ppm的三級胺波峰消失，2.55ppm~2.60ppm的二級胺及2.60ppm~2.70ppm的一級胺波峰幾乎消失。13C-NMR測定結果亦同樣為51.0ppm~56.0ppm的三級胺波峰消失，39.0ppm~51.0ppm的二級胺及一級胺的波峰幾乎消失。另外，根據NMR測定的積分比，可認為將前驅物化合物的全部氮(N)的約90%的N氧化而形成N-氧化物。 Using a 1 H-NMR measurement, in the 2.40 ppm to 2.70 ppm branched PEI-extended ethyl group, the higher-field 2.40 ppm to 2.55 ppm tertiary amine peak disappeared, 2.55 ppm to 2.60 ppm of the secondary amine and 2.60 ppm. The ~2.70 ppm primary amine peak almost disappeared. The 13 C-NMR measurement results also showed that the tertiary amine peaks of 51.0 ppm to 56.0 ppm disappeared, and the peaks of the secondary amines and primary amines of 39.0 ppm to 51.0 ppm almost disappeared. Further, from the integral ratio measured by NMR, it is considered that about 90% of all nitrogen (N) of the precursor compound is oxidized to form an N-oxide.

實施例4 保護聚合物(1-4)的合成 Example 4 Synthesis of Protective Polymer (1-4)

乙醯化反應：乙醯化物(1-4A)的合成 Acetyleneization reaction: synthesis of acetylated metal (1-4A)

將上述合成例1中獲得的甲苯磺醯基化聚乙二醇19.3g(9.0mmol)、及支鏈狀聚伸乙亞胺(日本觸媒股份有限公司製造，Epomin SP200)30.0g(3.0mmol)於氮氣環境下與N,N-二甲基乙醯胺270ml一併溶解後，添加碳酸鉀0.18g，於反應溫度140℃下攪拌6小時。於反應結束後，去除固形物，其後於70℃下進行減壓濃縮，於殘渣中添加乙酸乙酯200ml及己烷600ml的混合物而獲得沈澱物。將所獲得的沈澱物分離，於THF溶劑中進行稀釋後，去除殘渣，於30℃下進行減壓濃縮。將所獲得的固形物再次溶解於THF溶劑後，添加庚烷進而使殘渣再沈澱，將其過濾分離，於減壓下進行濃縮，則可獲得淡黃色的固形物48.0g(產率98%)。 19.3 g (9.0 mmol) of toluenesulfonated polyethylene glycol obtained in the above Synthesis Example 1, and branched polyethylenimine (manufactured by Nippon Shokubai Co., Ltd., Epomin SP200) 30.0 g (3.0 mmol) After dissolving in 270 ml of N,N-dimethylacetamide under a nitrogen atmosphere, 0.18 g of potassium carbonate was added thereto, and the mixture was stirred at a reaction temperature of 140 ° C for 6 hours. After completion of the reaction, the solid matter was removed, and then concentrated under reduced pressure at 70 ° C, and a mixture of ethyl acetate (200 ml) and hexane (600 ml) was added to the residue to obtain a precipitate. The obtained precipitate was separated, diluted in a THF solvent, and the residue was removed, and concentrated under reduced pressure at 30 °C. After the obtained solid matter was dissolved again in a THF solvent, heptane was added to further reprecipitate the residue, which was separated by filtration and concentrated under reduced pressure to obtain a pale yellow solid (48.0 g, yield 98%). .

將所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=3.57(br s,PEGM亞甲基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.65~2.40(m，支鏈PEI伸乙基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 3.57 (br s, PEMM methylene), 3.25 (s, 3H, PEMM chain terminal methoxy), 3.16 (m, 2H, ethenyl) Adjacent methylene group of N, 2.65~2.40 (m, branched PEI extended ethyl), 1.90 (br s, 3H, primary N ethyl thiol).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=22.9(s)(一級N的乙醯基)，39.9(s),41.8(s),47.6(m),49.5(m),52.6(m),54.7(m),57.8(m)(以上為支鏈PEI伸乙基)，59.0(s),70.5(m),71.8(s)(以上為PEGM亞甲基及末端甲氧基)，173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 22.9 (s) (first-order N oxime), 39.9 (s), 41.8 (s), 47.6 (m), 49.5 (m) , 52.6 (m), 54.7 (m), 57.8 (m) (above is branched PEI ethyl), 59.0 (s), 70.5 (m), 71.8 (s) (above is PEMM methylene and terminal A Oxy), 173.4 (m) (ethinyl).

利用1H-NMR測定，根據將支鏈狀聚伸乙亞胺的一級胺乙醯化的1.90ppm波峰的積分比的計算，可認為支鏈PEI伸乙基一級胺的中的30mol%被乙醯化。 By the 1 H-NMR measurement, based on the calculation of the integral ratio of the 1.90 ppm peak of the primary amine acetylation of the branched polyethylenimine, it is considered that 30 mol% of the branched PEI extended ethyl primary amine is Degenerate.

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-4A)的39.6g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例1的氧化反應相同的方式進行乙醯化N-氧化物的合成，定量地獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-4)。 39.7 g (N equivalent, 531 mmol) of the acetylated product (1-4A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated compound (1-1A), and the oxidation reaction with the above Example 1 was carried out. The synthesis of the acetylated N-oxide was carried out in the same manner, and a protective polymer (1-4) having a polyethylene-ethyl carbamide N-oxide chain and a hydrophilic segment as a product was quantitatively obtained.

另外，利用所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例1相同的結果。 In addition, the same results as in the above Example 1 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例5 保護聚合物(1-5)的合成 Example 5 Synthesis of Protective Polymer (1-5)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-4A)的39.6g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例2的氧化反應相同的方式進行乙醯化N-氧化物的合成，定量地獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-5)。 39.7 g (N equivalent, 531 mmol) of the acetylide (1-4A) obtained in the above synthesis was used instead of 37.7 g of the above acetylate (1-1A), and the oxidation reaction with the above Example 2 was carried out. The synthesis of the acetylated N-oxide was carried out in the same manner, and a protective polymer (1-5) having a polyethylene-ethyl carbamide N-oxide chain and a hydrophilic segment as a product was quantitatively obtained.

另外，利用所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例2相同的結果。 In addition, the same results as in the above Example 2 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例6 保護聚合物(1-6)的合成 Example 6 Synthesis of Protective Polymer (1-6)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-4A)的39.6g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例3的氧化反應相同的方式進行乙醯化N-氧化物的合 成，定量地獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-6)。 39.7 g (N equivalent, 531 mmol) of the acetylated product (1-4A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated compound (1-1A), and the oxidation reaction with the above Example 3 was carried out. The same method is used to carry out the combination of acetylated N-oxides. As a product, a protective polymer (1-6) having a polyethylamethylene acetamidide N-oxide chain and a hydrophilic segment was quantitatively obtained.

另外，利用所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例3相同的結果。 In addition, the same results as in the above Example 3 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例7 保護聚合物(1-7)的合成 Example 7 Synthesis of Protective Polymer (1-7)

乙醯化反應：乙醯化物(1-7A)的合成 Acetyleneization: Synthesis of acetylated bismuth (1-7A)

將實施例4中獲得的乙醯化物(1-4A)(聚伸乙亞胺-b-聚乙二醇共聚物的一級胺的30mol%乙醯化物)9.98g(N當量、145mmol)溶解於氯仿45g後，一面進行攪拌一面於30℃下緩慢地添加1.48g的乙酸酐，進行乙醯化反應2小時。於反應後將進行強鹼處理所產生的殘渣過濾，其後於減壓下進行濃縮，則可獲得淡黃色的固形物10.5g(產率99%)。 9.94 g (N equivalent, 145 mmol) of the acetamide (1-4A) obtained in Example 4 (30 mol% acetamidine of the primary amine of the polyethylenimine-b-polyethylene glycol copolymer) was dissolved in After 45 g of chloroform, 1.48 g of acetic anhydride was slowly added thereto at 30 ° C while stirring, and an oximation reaction was carried out for 2 hours. After the reaction, the residue obtained by the strong alkali treatment was filtered, and then concentrated under reduced pressure to obtain 10.5 g (yield: 99%) of pale yellow solid.

將所獲得的產物的1H-NMR、13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=3.57(br s,PEGM亞甲基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.65~2.40(m，支鏈PEI伸乙基)，2.11(br s,3H，二級N的乙醯基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 3.57 (br s, PEMM methylene), 3.25 (s, 3H, PEMM chain terminal methoxy), 3.16 (m, 2H, ethenyl) Adjacent methylene group of N, 2.65~2.40 (m, branched PEI extended ethyl), 2.11 (br s, 3H, secondary N ethyl fluorenyl), 1.90 (br s, 3H, primary N oxime) base).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=21.4(s)(二級N的乙醯基)，22.9(s)(一級N的乙醯基)，39.9(s),41.8(s),47.6(m),49.5(m),52.6(m),54.7(m),57.8(m)(以上為支鏈PEI伸乙基)，59.0(s),70.5(m),71.8(s)(以 上為PEGM亞甲基及末端甲氧基)，173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 21.4 (s) (second-stage N ethyl fluorenyl), 22.9 (s) (first-order N ethyl fluorenyl), 39.9 (s), 41.8(s), 47.6(m), 49.5(m), 52.6(m), 54.7(m), 57.8(m) (above is branched PEI ethyl), 59.0(s), 70.5(m), 71.8(s) (above is PEMM methylene and terminal methoxy), 173.4 (m) (ethinyl).

利用1H-NMR測定，根據將支鏈狀聚伸乙亞胺的一級胺及二級胺乙醯化的1.90ppm及2.11ppm波峰的積分比的計算，可認為支鏈狀聚伸乙亞胺的一級胺中的58mol%及二級胺中的11mol%被乙醯化。 By the 1 H-NMR measurement, based on the calculation of the integral ratio of 1.90 ppm and 2.11 ppm peaks of the primary amine and the secondary amine of the branched polyethylenimine, the branched polyethylenimine can be considered. 58 mol% of the primary amine and 11 mol% of the secondary amine are acetylated.

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-7A)的43.4g(N當量、531mmol)代替的37.7g上述乙醯化物(1-1A)，除此以外，以與上述實施例1的氧化反應相同的方式進行乙醯化N-氧化物的合成。進行24小時反應，可獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-7)。 The oxidation reaction with the above Example 1 was carried out, except that 47.7 g (N equivalent, 531 mmol) of the acetylide (1-7A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated product (1-1A). The synthesis of acetylated N-oxides was carried out in the same manner. After 24 hours of reaction, a protective polymer (1-7) having a polyethylamethylene ethyleneimine N-oxide chain and a hydrophilic segment can be obtained as a product.

另外，藉由所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例1相同的結果。 In addition, the same results as in the above Example 1 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例8 保護聚合物(1-8)的合成 Example 8 Synthesis of Protective Polymer (1-8)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-7A)的43.4g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例2的氧化反應相同的方式進行乙醯化N-氧化物的合成。進行24小時反應，可獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-8)。 43.7 g (N equivalent, 531 mmol) of the acetylated product (1-7A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated compound (1-1A), and the oxidation reaction with the above Example 2 was carried out. The synthesis of acetylated N-oxides was carried out in the same manner. A protective polymer (1-8) having a polyethylamethylene acetamidide N-oxide chain and a hydrophilic segment as a product can be obtained by carrying out a reaction for 24 hours.

另外，藉由所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例2相同的結果。 In addition, the same results as in the above Example 2 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例9 保護聚合物(1-9)的合成 Example 9 Synthesis of Protective Polymer (1-9)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-7A)的43.4g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例3的氧化反應相同的方式進行乙醯化N-氧化物的合成。然而，氧化反應速度緩慢，進行24小時反應，獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-9)。 43.4 g (N equivalent, 531 mmol) of the acetylated product (1-7A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated compound (1-1A), and the oxidation reaction with the above Example 3 was carried out. The synthesis of acetylated N-oxides was carried out in the same manner. However, the oxidation reaction rate was slow, and the reaction was carried out for 24 hours to obtain a protective polymer (1-9) having a polyethylene-ethyl carbamide N-oxide chain and a hydrophilic segment as a product.

另外，藉由所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例3相同的結果。 In addition, the same results as in the above Example 3 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例10 保護聚合物(1-10)的合成 Example 10 Synthesis of Protective Polymer (1-10)

乙醯化反應：乙醯化物(1-10A)的合成 Acetyleneization: Synthesis of acetylated hydrazine (1-10A)

將實施例4中獲得的乙醯化物(1-4A)(支鏈PEI伸乙基一級胺中的30mol%乙醯化物)9.98g(N當量、145mmol)溶解於氯仿45g後，一面進行攪拌一面於30℃下緩慢地添加2.96g的乙酸酐，進行乙醯化反應2小時。於反應後將進行強鹼處理所產生的殘渣過濾，其後於減壓下進行濃縮，則可獲得淡黃色的固形物11.0g(產率98%)。 9.88 g (N equivalent, 145 mmol) of the acetylated product (1-4A) (30 mol% acetamidine in the branched PEI-extended ethyl primary amine) obtained in Example 4 was dissolved in 45 g of chloroform, and stirred while stirring. 2.96 g of acetic anhydride was slowly added at 30 ° C to carry out an oximation reaction for 2 hours. After the reaction, the residue obtained by the strong alkali treatment was filtered, and then concentrated under reduced pressure to obtain a pale yellow solid (11.0 g, yield 98%).

將所獲得的產物的1H-NMR、13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=3.57(br s,PEGM亞甲基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.65~2.40(m， 支鏈PEI伸乙基)，2.11(br s,3H，二級N的乙醯基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 3.57 (br s, PEMM methylene), 3.25 (s, 3H, PEMM chain terminal methoxy), 3.16 (m, 2H, ethenyl) Adjacent methylene group of N, 2.65~2.40 (m, branched PEI extended ethyl), 2.11 (br s, 3H, secondary N ethyl fluorenyl), 1.90 (br s, 3H, primary N oxime) base).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=21.4(s)(二級N的乙醯基)，22.9(s)(一級N的乙醯基)，39.9(s),41.8(s),47.6(m),49.5(m),52.6(m),54.7(m),57.8(m)(以上為支鏈PEI伸乙基)，59.0(s),70.5(m),71.8(s)(以上為PEGM亞甲基及末端甲氧基)，173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 21.4 (s) (second-stage N ethyl fluorenyl), 22.9 (s) (first-order N ethyl fluorenyl), 39.9 (s), 41.8(s), 47.6(m), 49.5(m), 52.6(m), 54.7(m), 57.8(m) (above is branched PEI ethyl), 59.0(s), 70.5(m), 71.8(s) (above is PEMM methylene and terminal methoxy), 173.4 (m) (ethinyl).

利用1H-NMR測定，根據將支鏈狀聚伸乙亞胺的一級胺及二級胺乙醯化的1.90ppm及2.11ppm波峰的積分比的計算，可認為支鏈狀聚伸乙亞胺的一級胺中的88mol%及二級胺中的22mol%被乙醯化。 By the 1 H-NMR measurement, based on the calculation of the integral ratio of 1.90 ppm and 2.11 ppm peaks of the primary amine and the secondary amine of the branched polyethylenimine, the branched polyethylenimine can be considered. 88 mol% of the primary amine and 22 mol% of the secondary amine are acetylated.

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-10A)的47.4g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例1的氧化反應相同的方式進行乙醯化N-氧化物的合成。然而，氧化反應速度緩慢，進行72小時反應，獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-10)。 47.4 g (N equivalent, 531 mmol) of the acetylated product (1-10A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated compound (1-1A), and the oxidation reaction with the above Example 1 was carried out. The synthesis of acetylated N-oxides was carried out in the same manner. However, the oxidation reaction rate was slow, and the reaction was carried out for 72 hours to obtain a protective polymer (1-10) having a polyethylene-ethyl carbamide amine N-oxide chain and a hydrophilic segment as a product.

另外，藉由所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例1相同的結果。 In addition, the same results as in the above Example 1 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例11 保護聚合物(1-11)的合成 Example 11 Synthesis of Protective Polymer (1-11)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-10A)的47.4g(N當量、 531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例2的氧化反應相同的方式進行乙醯化N-氧化物的合成。進行72小時反應，獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-11)。 47.4 g (N equivalents, using acetamidine (1-10A) obtained in the above synthesis) The synthesis of the acetonitrile N-oxide was carried out in the same manner as in the oxidation reaction of the above Example 2, except that 37.7 g of the above acetylide (1-1A) was used instead. The reaction was carried out for 72 hours to obtain a protective polymer (1-11) having a polyethylamethylene acetamidide N-oxide chain and a hydrophilic segment as a product.

另外，藉由所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例2相同的結果。 In addition, the same results as in the above Example 2 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

實施例12 保護聚合物(1-12)的合成 Example 12 Synthesis of Protective Polymer (1-12)

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1-10A)的47.4g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例3的氧化反應相同的方式進行乙醯化N-氧化物的合成。然而，氧化反應速度緩慢，進行120小時反應，獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈及親水性片段的保護聚合物(1-12)。 47.4 g (N equivalent, 531 mmol) of the acetylated product (1-10A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated compound (1-1A), and the oxidation reaction with the above Example 3 was carried out. The synthesis of acetylated N-oxides was carried out in the same manner. However, the oxidation reaction rate was slow, and the reaction was carried out for 120 hours to obtain a protective polymer (1-12) having a polyethylene-ethyl carbamide amine N-oxide chain and a hydrophilic segment as a product.

另外，藉由所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定，獲得與上述實施例3相同的結果。 In addition, the same results as in the above Example 3 were obtained by measurement of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product.

比較例1 保護聚合物(1')的合成 Comparative Example 1 Synthesis of Protective Polymer (1')

乙醯化反應：乙醯化物(1'-A)的合成 Acetyleneization: Synthesis of acetylated bismuth (1'-A)

將實施例4中獲得的乙醯化物(1-4A)(聚伸乙亞胺-b-聚乙二醇共聚物的一級胺的30mol%乙醯化物)9.98g(N當量、145mmol)溶解於氯仿45g後，一面進行攪拌一面於30℃下緩慢地添加7.40g的乙酸酐，進行乙醯化反應2小時。於反應後將進行強 鹼處理所產生的殘渣過濾，其後於減壓下進行濃縮，則可獲得淡黃色的固形物12.0g(產率92%)。 9.94 g (N equivalent, 145 mmol) of the acetamide (1-4A) obtained in Example 4 (30 mol% acetamidine of the primary amine of the polyethylenimine-b-polyethylene glycol copolymer) was dissolved in After 45 g of chloroform, 7.40 g of acetic anhydride was slowly added thereto at 30 ° C while stirring, and the oximation reaction was carried out for 2 hours. Will be strong after the reaction The residue obtained by the alkali treatment was filtered, and then concentrated under reduced pressure to obtain 12.0 g (yield: 92%) of pale yellow solid.

將所獲得的產物的1H-NMR、13C-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=3.57(br s,PEGM亞甲基)，3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.65~2.40(m，支鏈PEI伸乙基)，2.11(br s,3H，二級N的乙醯基)，1.90(br s,3H，一級N的乙醯基). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 3.57 (br s, PEMM methylene), 3.25 (s, 3H, PEMM chain terminal methoxy), 3.16 (m, 2H, ethenyl) Adjacent methylene group of N, 2.65~2.40 (m, branched PEI extended ethyl), 2.11 (br s, 3H, secondary N ethyl fluorenyl), 1.90 (br s, 3H, primary N oxime) base).

13C-NMR(DMSO-d6)測定結果：δ(ppm)=21.4(s)(二級N的乙醯基)，22.9(s)(一級N的乙醯基)，39.9(s),41.8(s),47.6(m),49.5(m),52.6(m),54.7(m),57.8(m)(以上為支鏈PEI伸乙基)，59.0(s),70.5(m),71.8(s)(以上為PEGM亞甲基及末端甲氧基)，173.4(m)(乙醯基). 13 C-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 21.4 (s) (second-stage N ethyl fluorenyl), 22.9 (s) (first-order N ethyl fluorenyl), 39.9 (s), 41.8(s), 47.6(m), 49.5(m), 52.6(m), 54.7(m), 57.8(m) (above is branched PEI ethyl), 59.0(s), 70.5(m), 71.8(s) (above is PEMM methylene and terminal methoxy), 173.4 (m) (ethinyl).

藉由1H-NMR測定，根據將支鏈狀聚伸乙亞胺的一級胺及二級胺乙醯化的1.90ppm及2.11ppm波峰的積分比的計算，可認為支鏈狀聚伸乙亞胺的一級胺中的96mol%及二級胺中的98mol%被乙醯化。 By the 1 H-NMR measurement, according to the calculation of the integral ratio of 1.90 ppm and 2.11 ppm peaks of the primary amine and the secondary amine of the branched polyethylenimine, the branched polycondensation can be considered as a branch. 96 mol% of the primary amine of the amine and 98 mol% of the secondary amine are acetonitrile.

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(1'-A)的55.7g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例2的氧化反應相同的方式進行乙醯化N-氧化物的合成。氧化反應速度緩慢，進行120小時反應，進行所獲得的產物的1H-NMR及13C-NMR(日本電子股份有限公司製造，AL300， 300MHz)的測定，結果可獲得少量目標物的乙醯化N-氧化物。 55.7 g (N equivalent, 531 mmol) of the acetylide (1'-A) obtained in the above synthesis was used instead of 37.7 g of the above acetylate (1-1A), and the oxidation with the above Example 2 was carried out. The synthesis of the acetylated N-oxide is carried out in the same manner as the reaction. The oxidation reaction rate was slow, and the reaction was carried out for 120 hours, and 1 H-NMR and 13 C-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product were measured, and as a result, a small amount of the target was obtained. N-oxide.

實施例13 保護聚合物(2-1)的合成 Example 13 Synthesis of Protective Polymer (2-1)

乙醯化物(2-1A)的合成 Synthesis of acetylated metal (2-1A)

於實施例4中獲得的乙醯化物(1-4A)(支鏈PEI伸乙基一級胺中的30mol%乙醯化物)18.2g(1.25mmol)的甲醇(150mL)溶液中，於氮氣環境下滴加合成例3中合成的具有雙酚A骨架的單官能性的環氧樹脂，即改質環氧樹脂3.2g(1.6mmol)的丙酮(50mL)溶液後，於50℃下攪拌2小時。於反應結束後，於減壓下將溶劑蒸餾去除，進而進行減壓乾燥，藉此獲得聚乙醯基伸乙亞胺-b-聚乙二醇-b-雙酚A型環氧樹脂。產率為100%。 a solution of 18.5 g (1.25 mmol) in methanol (150 mL) of acetamidine (1-4A) (30% by weight of acetamidine in branched PEI-extended ethyl primary amine) obtained in Example 4 under a nitrogen atmosphere A monofunctional epoxy resin having a bisphenol A skeleton synthesized in Synthesis Example 3, that is, a solution of 3.2 g (1.6 mmol) of modified epoxy resin in acetone (50 mL) was added dropwise, followed by stirring at 50 ° C for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and further dried under reduced pressure to obtain a polyethylene-ethyl carbamide-b-polyethylene glycol-b-bisphenol A type epoxy resin. The yield was 100%.

將所獲得的產物的1H-NMR(日本電子股份有限公司製造，AL300，300MHz)的測定結果示於以下。 The measurement results of 1 H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.

1H-NMR(CDCl3)測定結果：δ(ppm)=7.55~6.75(m),4.40~3.90(m),3.57(br s,PEGM亞甲基)，3.33(m),3.25(s,3H,PEGM鏈末端甲氧基)，3.16(m,2H，乙醯基N的鄰接亞甲基)，2.89(m),2.73(m),2.65~2.40(m，支鏈PEI伸乙基)，1.90(br s,3H，一級N的乙醯基)，1.62(s). 1 H-NMR (CDCl 3 ) measurement results: δ (ppm) = 7.55 to 6.75 (m), 4.40 to 3.90 (m), 3.57 (br s, PEMM methylene), 3.33 (m), 3.25 (s, 3H, the end of the PEGM chain methoxy), 3.16 (m, 2H, the adjacent methylene group of the ethyl hydrazide N), 2.89 (m), 2.73 (m), 2.65 ~ 2.40 (m, branched PEI extended ethyl) , 1.90 (br s, 3H, the first-order N acetyl group), 1.62 (s).

藉由1H-NMR測定，根據將支鏈狀聚伸乙亞胺的一級胺乙醯化的1.90ppm波峰的積分比的計算，可認為支鏈狀聚伸乙亞胺的一級胺中的30mol%被乙醯化。 By the 1 H-NMR measurement, based on the calculation of the integral ratio of the 1.90 ppm peak of the primary amine oxime of the branched polyethylenimine, 30 mol of the primary amine of the branched polyethylenimine can be considered. % is converted to acetylation.

氧化反應：乙醯化N-氧化物的合成 Oxidation reaction: synthesis of acetylated N-oxide

使用上述合成中獲得的乙醯化物(2-1A)的43.9g(N當量、531mmol)代替37.7g的上述乙醯化物(1-1A)，除此以外，以與上述實施例2的氧化反應相同的方式進行乙醯化N-氧化物的合 成，定量地獲得作為產物的具有聚乙醯基伸乙亞胺N-氧化物鏈、親水性片段及疏水性片段的保護聚合物(2-1)。 43.7 g (N equivalent, 531 mmol) of the acetylated product (2-1A) obtained in the above synthesis was used instead of 37.7 g of the above acetylated compound (1-1A), and the oxidation reaction with the above Example 2 was carried out. The same method is used to carry out the combination of acetylated N-oxides. As a product, a protective polymer (2-1) having a polyethylidene-ethylenimine N-oxide chain, a hydrophilic segment, and a hydrophobic segment was quantitatively obtained.

將所獲得的產物的1H-NMR的測定結果示於以下。 The measurement results of 1 H-NMR of the obtained product are shown below.

1H-NMR(DMSO-d6)測定結果：δ(ppm)=7.55~6.75(m),4.40~3.90(m),3.6(m,PEGM亞甲基),3.30~3.20(m,N-氧化物伸乙基),3.25(s,PEGM鏈末端甲氧基),3.16(m,2H，乙醯基N的鄰接亞甲基),2.9(m,N-氧化物伸乙基),2.73(m),2.65~2.40(m，支鏈PEI伸乙基),1.90(br s,3H，一級N的乙醯基),1.62(s). 1 H-NMR (DMSO-d 6 ) measurement results: δ (ppm) = 7.55 to 6.75 (m), 4.40 to 3.90 (m), 3.6 (m, PEMM methylene), 3.30 to 3.20 (m, N- Oxide extended ethyl), 3.25 (s, PEGM chain end methoxy), 3.16 (m, 2H, acetonitrile N contiguous methylene), 2.9 (m, N-oxide extended ethyl), 2.73 (m), 2.65~2.40 (m, branched PEI extended ethyl), 1.90 (br s, 3H, first-order N-ethyl), 1.62 (s).

藉由1H-NMR測定，於2.40ppm~2.65ppm的支鏈PEI伸乙基中，更高磁場的2.40ppm~2.55ppm的三級胺波峰消失，2.55ppm~2.60ppm的二級胺及2.60ppm~2.70ppm的一級胺波峰下降，其積分比變小。根據NMR測定的積分比，可認為將前驅物化合物的全部氮(N)的約50%的N氧化而形成N-氧化物。 By the 1 H-NMR measurement, in the 2.40 ppm to 2.65 ppm branched PEI extending ethyl group, the higher magnetic field 2.40 ppm to 2.55 ppm tertiary amine peak disappeared, 2.55 ppm to 2.60 ppm of the secondary amine and 2.60. The primary amine peak of ppm~2.70ppm decreases, and the integral ratio becomes smaller. According to the integral ratio measured by NMR, it is considered that about 50% of all nitrogen (N) of the precursor compound is oxidized to form an N-oxide.

實施例14 利用實施例1的保護聚合物(1-1)的銀膠體溶液的合成 Example 14 Synthesis of Silver Colloid Solution Using Protective Polymer (1-1) of Example 1

於1L的反應釜中依序添加純水180g、上述實施例1中獲得的保護聚合物(1-1)的水溶液13.5g、N,N-二甲基胺基乙醇113g(1.27mol)並進行攪拌，而製備保護聚合物與還原劑的混合溶液。另外，將硝酸銀72.0g(0.424mol)溶解於純水120g中，於室溫下歷時約30分鐘滴加製備的硝酸銀水溶液，其後，於40℃下攪拌4小時。於結束反應並冷卻後，添加不良溶劑的丙酮1.4L(反應混合液的約3體積倍)，攪拌5分鐘。靜置約1小時而將銀奈米粒子與保護聚合物的複合體沈澱分離。去除上清液後，將所產生 的沈澱物離心分離。於經離心分離的糊狀沈澱物中添加純水80g，充分分散後，利用脫溶劑將殘留丙酮蒸餾去除並且進行減壓濃縮直至非揮發物成為約60%，而獲得銀膠體水溶液77.0g(非揮發物為46.2g、產率96%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.3%。 180 g of pure water, 13.5 g of an aqueous solution of the protective polymer (1-1) obtained in the above Example 1, and 113 g (1.27 mol) of N,N-dimethylaminoethanol were sequentially added to a 1 L reactor. The mixture of the protective polymer and the reducing agent was prepared by stirring. Separately, 72.0 g (0.424 mol) of silver nitrate was dissolved in 120 g of pure water, and the prepared silver nitrate aqueous solution was added dropwise at room temperature for about 30 minutes, and then stirred at 40 ° C for 4 hours. After the reaction was completed and cooled, 1.4 L of acetone (about 3 times by volume of the reaction mixture) of a poor solvent was added, and the mixture was stirred for 5 minutes. The composite of the silver nanoparticle and the protective polymer was precipitated by standing for about 1 hour. After removing the supernatant, it will be produced The precipitate was centrifuged. 80 g of pure water was added to the paste-like precipitate obtained by centrifugation, and after sufficiently dispersing, residual acetone was distilled off by desolvation and concentrated under reduced pressure until the nonvolatile matter became about 60%, and 77.0 g of a silver colloid aqueous solution was obtained. The volatiles were 46.2 g, yield 96%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.3%.

實施例15 利用實施例2的保護聚合物(1-2)的銀膠體溶液的合成 Example 15 Synthesis of Silver Colloid Solution Using Protective Polymer (1-2) of Example 2

使用上述實施例2中獲得的保護聚合物(1-2)的水溶液14.7g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.5g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.2%。 The same procedure as in Example 14 was carried out except that 14.7 g of the aqueous solution of the protective polymer (1-2) obtained in the above Example 2 was used instead of the aqueous solution of the protective polymer (1-1) obtained in Example 1 (13.5 g). In a manner of obtaining 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.5 g, yield 95%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.2%.

實施例16 利用實施例3的保護聚合物(1-3)的銀膠體溶液的合成 Example 16 Synthesis of Silver Colloid Solution Using Protective Polymer (1-3) of Example 3

使用上述實施例3中獲得的保護聚合物(1-3)的水溶液15.9g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.7g(非揮發物為46.0g、產率95.8%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為95.8%。 The same procedure as in Example 14 was carried out, except that 15.9 g of the aqueous solution of the protective polymer (1-3) obtained in the above Example 3 was used instead of the aqueous solution of the protective polymer (1-1) obtained in Example 1 (13.5 g). In a manner of obtaining 76.7 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter was 46.0 g, yield 95.8%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 95.8%.

實施例17 利用實施例4的保護聚合物(1-4)的銀膠體溶液的合成 Example 17 Synthesis of Silver Colloid Solution Using Protective Polymer (1-4) of Example 4

使用上述實施例4中獲得的保護聚合物(1-4)的水溶液14.2g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠 體水溶液76.8g(非揮發物為46.1g、產率96%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.2%。 The same procedure as in Example 14 was carried out, except that 14.2 g of the aqueous solution of the protective polymer (1-4) obtained in the above Example 4 was used in place of 13.5 g of the aqueous solution of the protective polymer (1-1) obtained in Example 1. Way to obtain a non-volatile matter of about 60% silver glue The aqueous solution of the solution was 76.8 g (nonvolatile matter was 46.1 g, yield 96%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.2%.

實施例18 利用實施例5的保護聚合物(1-5)的銀膠體溶液的合成 Example 18 Synthesis of Silver Colloid Solution Using Protective Polymer (1-5) of Example 5

使用上述實施例5中獲得的保護聚合物(1-5)的水溶液15.3g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.6g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.4%。 The same procedure as in Example 14 was carried out, except that 15.3 g of the aqueous solution of the protective polymer (1-5) obtained in the above Example 5 was used in place of 13.5 g of the aqueous solution of the protective polymer (1-1) obtained in Example 1. In a manner of obtaining 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.6 g, yield 95%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.4%.

實施例19 利用實施例6的保護聚合物(1-6)的銀膠體溶液的合成 Example 19 Synthesis of Silver Colloid Solution Using Protective Polymer (1-6) of Example 6

使用上述實施例6中獲得的保護聚合物(1-6)的水溶液16.5g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.6g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為95.9%。 The same procedure as in Example 14 was carried out except that 16.5 g of the aqueous solution of the protective polymer (1-6) obtained in the above Example 6 was used instead of the aqueous solution of the protective polymer (1-1) obtained in Example 1 (13.5 g). In a manner of obtaining 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.6 g, yield 95%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 95.9%.

實施例20 利用實施例7的保護聚合物(1-7)的銀膠體溶液的合成 Example 20 Synthesis of Silver Colloid Solution Using Protective Polymer (1-7) of Example 7

使用上述實施例6中獲得的保護聚合物(1-7)的水溶液15.5g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.6g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.1%。 The same procedure as in Example 14 was carried out, except that 15.5 g of the aqueous solution of the protective polymer (1-7) obtained in the above Example 6 was used instead of the aqueous solution of the protective polymer (1-1) obtained in Example 1 (13.5 g). In a manner of obtaining 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.6 g, yield 95%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.1%.

實施例21 利用實施例8的保護聚合物(1-8)的銀膠體 溶液的合成 Example 21 Silver colloid using the protective polymer (1-8) of Example 8 Solution synthesis

使用上述實施例6中獲得的保護聚合物(1-8)的水溶液16.7g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.6g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.4%。 The same procedure as in Example 14 was carried out, except that 16.7 g of the aqueous solution of the protective polymer (1-8) obtained in the above Example 6 was used instead of the aqueous solution of the protective polymer (1-1) obtained in Example 1 (13.5 g). In a manner of obtaining 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.6 g, yield 95%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.4%.

實施例22 利用實施例9的保護聚合物(1-9)的銀膠體溶液的合成 Example 22 Synthesis of Silver Colloid Solution Using Protective Polymer (1-9) of Example 9

使用上述實施例6中獲得的保護聚合物(1-9)的水溶液17.8g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.6g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為95.9%。 The same procedure as in Example 14 was carried out, except that 17.8 g of the aqueous solution of the protective polymer (1-9) obtained in the above Example 6 was used in place of 13.5 g of the aqueous solution of the protective polymer (1-1) obtained in Example 1. In a manner of obtaining 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.6 g, yield 95%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 95.9%.

實施例23 利用實施例10的保護聚合物(1-10)的銀膠體溶液的合成 Example 23 Synthesis of Silver Colloid Solution Using Protective Polymer (1-10) of Example 10

使用上述實施例6中獲得的保護聚合物(1-10)的水溶液16.9g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液75.1g(非揮發物為45.1g、產率94%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.1%。 The same procedure as in Example 14 was carried out, except that 16.9 g of the aqueous solution of the protective polymer (1-10) obtained in the above Example 6 was used instead of the aqueous solution of the protective polymer (1-1) obtained in Example 1 (13.5 g). In a manner of obtaining 75.1 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.1 g, yield 94%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.1%.

實施例24 利用實施例11的保護聚合物(1-11)的銀膠體溶液的合成 Example 24 Synthesis of Silver Colloid Solution Using Protective Polymer (1-11) of Example 11

使用上述實施例11中獲得的保護聚合物(1-11)的水溶液18.1g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除 此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液74.3g(非揮發物為44.6g、產率93%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為95.9%。 Using 18.1 g of an aqueous solution of the protective polymer (1-11) obtained in the above Example 11 in place of 13.5 g of an aqueous solution of the protective polymer (1-1) obtained in Example 1, except Further, 74.3 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (a nonvolatile matter of 44.6 g, a yield of 93%) was obtained in the same manner as in Example 14. Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 95.9%.

實施例25 利用實施例12的保護聚合物(1-12)的銀膠體溶液的合成 Example 25 Synthesis of Silver Colloid Solution Using Protective Polymer (1-12) of Example 12

使用上述實施例12中獲得的保護聚合物(1-12)的水溶液19.3g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.6g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.1%。 The same procedure as in Example 14 was carried out, except that 19.3 g of the aqueous solution of the protective polymer (1-12) obtained in the above Example 12 was used instead of the aqueous solution 13.5 g of the protective polymer (1-1) obtained in Example 1. In a manner of obtaining 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.6 g, yield 95%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.1%.

實施例26 利用實施例13的保護聚合物(2-1)的銀膠體溶液的合成 Example 26 Synthesis of Silver Colloid Solution Using Protective Polymer (2-1) of Example 13

使用上述實施例13中獲得的保護聚合物(2-1)的水溶液15.7g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液75.2g(非揮發物為45.1g、產率94%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為95.6%。 The same procedure as in Example 14 was carried out, except that 15.7 g of the aqueous solution of the protective polymer (2-1) obtained in the above Example 13 was used in place of 13.5 g of the aqueous solution of the protective polymer (1-1) obtained in Example 1. In a manner of obtaining 75.2 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (nonvolatile matter: 45.1 g, yield 94%). Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 95.6%.

比較例2 利用比較例1的保護聚合物(1')的銀膠體溶液的合成 Comparative Example 2 Synthesis of Silver Colloid Solution Using Protective Polymer (1') of Comparative Example 1

使用上述比較例1中獲得的保護聚合物(1')的水溶液21.0g代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液77.6g(非揮發物為46.6g、產率97%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為95.5%。 The same procedure as in Example 14 was carried out except that 21.0 g of the aqueous solution of the protective polymer (1') obtained in the above Comparative Example 1 was used instead of the aqueous solution of 13.5 g of the protective polymer (1-1) obtained in Example 1. In a manner, 77.6 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (a nonvolatile matter of 46.6 g, a yield of 97%) was obtained. Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 95.5%.

比較例3 利用合成例2的化合物的銀膠體溶液的合成 Comparative Example 3 Synthesis of Silver Colloid Solution Using Compound of Synthesis Example 2

使用將上述合成例2中獲得的化合物3.5g溶解於純水9.5g中而製備的水溶液代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.0g(非揮發物為45.6g、產率95%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為96.2%。 An aqueous solution prepared by dissolving 3.5 g of the compound obtained in the above Synthesis Example 2 in 9.5 g of pure water was used in place of 13.5 g of the aqueous solution of the protective polymer (1-1) obtained in Example 1, except that In the same manner as in Example 14, 76.0 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (a nonvolatile matter of 45.6 g, a yield of 95%) was obtained. Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 96.2%.

比較例4 利用合成例3的化合物的銀膠體溶液的合成 Comparative Example 4 Synthesis of Silver Colloid Solution Using Compound of Synthesis Example 3

使用將上述合成例3中獲得的前驅物化合物4.1g溶解於純水9.5g中而製備的水溶液代替實施例1中獲得的保護聚合物(1-1)的水溶液13.5g，除此以外，以與實施例14相同的方式獲得非揮發物為約60%的銀膠體水溶液76.8g(非揮發物為46.1g、產率96%)。進行熱分析(Tg/DTA)，結果非揮發物中的銀含量為95.8%。 An aqueous solution prepared by dissolving 4.1 g of the precursor compound obtained in the above Synthesis Example 3 in 9.5 g of pure water was used in place of 13.5 g of the aqueous solution of the protective polymer (1-1) obtained in Example 1, except that In the same manner as in Example 14, 76.8 g of a silver colloid aqueous solution having a nonvolatile content of about 60% (a nonvolatile matter of 46.1 g, a yield of 96%) was obtained. Thermal analysis (Tg/DTA) was carried out, and as a result, the silver content in the nonvolatile matter was 95.8%.

將實施例1~實施例13及比較例1中獲得的保護聚合物的NMR測定結果所得的一級胺及二級胺的乙醯化率、及利用氧化反應的N-氧化物化率示於表1。並且，使用實施例14~實施例26及比較例2~比較例4中獲得的銀膠體溶液，如上所述般對金屬薄膜的電阻值及平均粒徑進行測定。另外，將於合成時的利用丙酮的沈澱處理中處理所需的使用量與時間示於下述表中。進而，根據將所獲得的銀膠體溶液於室溫(25℃~35℃)下靜置保存1週時的外觀，對其穩定性進行評價。將結果示於表2~表3。此外，表2中的O.L.表示超刻度(Over Scale)。 The acetamylation ratio of the primary amine and the secondary amine obtained by the NMR measurement results of the protective polymers obtained in Examples 1 to 13 and Comparative Example 1 and the N-oxide conversion ratio by the oxidation reaction are shown in Table 1. . Further, the silver colloidal solutions obtained in Examples 14 to 26 and Comparative Examples 2 to 4 were used to measure the electric resistance value and the average particle diameter of the metal thin film as described above. In addition, the amount and time required for the treatment in the precipitation treatment using acetone at the time of synthesis are shown in the following table. Further, the stability of the obtained silver colloid solution was allowed to stand at room temperature (25 to 35 ° C) for one week, and the stability was evaluated. The results are shown in Tables 2 to 3. In addition, O.L. in Table 2 indicates an Over Scale.

結果可認為聚伸烷基亞胺片段中的一級胺的乙醯化率為5mol%~95mol%，及/或二級胺的乙醯化率為5mol%~50 mol%，並且，於使用N-氧化物化率為0.5%~95%的保護聚合物時，顯示出良好的導電性、分散穩定性及容易的純化分離性。 As a result, it is considered that the acetylation rate of the primary amine in the polyalkyleneimine fragment is 5 mol% to 95 mol%, and/or the acetylation ratio of the secondary amine is 5 mol% to 50. When the protective polymer having an N-oxide ratio of 0.5% to 95% is used, it exhibits good conductivity, dispersion stability, and easy purification separation.

可知比較例1的保護聚合物(一級胺的乙醯化率96%及二級胺的乙醯化率98%)即便於長達120小時的氧化反應下亦幾乎未進行氧化反應，NMR測定結果N-氧化物化率為5%以下，如比較例1的高乙醯化率的高分子未進行N-氧化物化。 It can be seen that the protective polymer of Comparative Example 1 (96% of the primary amine and 98% of the secondary amine) had almost no oxidation reaction even under the oxidation reaction for up to 120 hours. The N-oxide conversion rate was 5% or less, and the polymer having a high acetylation ratio of Comparative Example 1 was not N-oxided.

Claims (12)

一種金屬奈米粒子保護聚合物，其特徵在於：於1分子中具有如下聚乙醯基伸烷基亞胺N-氧化物片段(A)及包含聚氧伸烷基鏈的親水性片段(B)，該聚乙醯基伸烷基亞胺N-氧化物片段(A)是將聚伸烷基亞胺中的一級胺的5mol%~95mol%、或一級胺的5mol%~95mol%及二級胺的5mol%~50mol%乙醯化，進而，將聚伸烷基亞胺中的全部氮原子數的0.5mol%~95mol%氧化而成。A metal nanoparticle-protecting polymer characterized by having a poly(ethylene)alkyleneimine N-oxide segment (A) and a hydrophilic segment comprising a polyoxyalkylene chain in one molecule (B) The poly(ethylene)alkyleneimine N-oxide fragment (A) is 5 mol% to 95 mol% of the primary amine in the polyalkylenimine, or 5 mol% to 95 mol% of the primary amine and the secondary amine 5 mol% to 50 mol% of acetamidine, and further, 0.5 mol% to 95 mol% of all nitrogen atoms in the polyalkyleneimine are oxidized. 如申請專利範圍第1項所述之金屬奈米粒子保護聚合物，其進而於1分子中具有疏水性片段(C)。The metal nanoparticle-protecting polymer according to claim 1, which further has a hydrophobic segment (C) in one molecule. 如申請專利範圍第2項所述之金屬奈米粒子保護聚合物，其中上述疏水性片段(C)包含源自環氧樹脂的結構。The metal nanoparticle-protecting polymer according to claim 2, wherein the hydrophobic segment (C) comprises a structure derived from an epoxy resin. 如申請專利範圍第1項所述之金屬奈米粒子保護聚合物，其中上述聚乙醯基伸烷基亞胺N-氧化物片段(A)的伸烷基亞胺的單元數為5~2,500的範圍。The metal nanoparticle-protecting polymer according to claim 1, wherein the number of units of the alkylimine of the polyethyl fluorenylalkylenimine N-oxide fragment (A) is 5 to 2,500. range. 如申請專利範圍第1項至第4項中任一項所述之金屬奈米粒子保護聚合物，其重量平均分子量為1,000~100,000的範圍。The metal nanoparticle-protecting polymer according to any one of claims 1 to 4, wherein the weight average molecular weight is in the range of 1,000 to 100,000. 一種金屬奈米粒子保護聚合物的製造方法，其特徵在於：於使具有聚伸烷基亞胺片段的化合物與具有包含聚氧伸烷基鏈的親水性片段(B)的化合物聚合時，使用乙醯化劑將伸烷基亞胺單元乙醯化而獲得聚合物後，進而使用氧化劑進行氧化。A method for producing a metal nanoparticle-protecting polymer, characterized in that when a compound having a polyalkyleneimine fragment is polymerized with a compound having a hydrophilic segment (B) comprising a polyoxyalkylene chain, The acetamidine agent acetylates the alkylimine unit to obtain a polymer, and then oxidizes using an oxidizing agent. 一種金屬奈米粒子保護聚合物的製造方法，其特徵在於：使用1分子中具有聚伸烷基亞胺片段及包含聚氧伸烷基鏈的親水性片段(B)的化合物作為前驅物，對該化合物使用乙醯化劑將伸烷基亞胺單元乙醯化後，進而使用氧化劑進行氧化。A method for producing a metal nanoparticle-protecting polymer, characterized in that a compound having a polyalkyleneimine fragment and a hydrophilic segment (B) comprising a polyoxyalkylene chain in one molecule is used as a precursor, This compound is acetylated with an acetal iodide unit and then oxidized using an oxidizing agent. 一種金屬膠體溶液，其特徵在於：將以如下金屬奈米粒子保護聚合物保護金屬奈米粒子而成的複合體分散於介質中而成，該金屬奈米粒子保護聚合物具有將聚伸烷基亞胺中的一級胺的5mol%~95mol%、或一級胺的5mol%~95mol%及二級胺的5mol%~50mol%乙醯化，進而，將聚伸烷基亞胺中的全部氮原子數的0.5mol%~95mol%氧化而成的聚乙醯基伸烷基亞胺N-氧化物片段(A)及包含聚氧伸烷基鏈的親水性片段(B)。A metal colloid solution characterized in that a composite obtained by protecting a metal nanoparticle with a metal nanoparticle protective polymer dispersed in a medium having a polyalkylene group 5 mol% to 95 mol% of the primary amine in the imine, or 5 mol% to 95 mol% of the primary amine, and 5 mol% to 50 mol% of the secondary amine, and further, all the nitrogen atoms in the alkylimine will be polycondensed. The polyethylene alkyleneamine N-oxide fragment (A) oxidized from 0.5 mol% to 95 mol% and the hydrophilic segment (B) containing a polyoxyalkylene chain. 如申請專利範圍第8項所述之金屬膠體溶液，其中上述金屬奈米粒子為銀奈米粒子。The metal colloidal solution according to claim 8, wherein the metal nanoparticle is a silver nanoparticle. 如申請專利範圍第8項或第9項所述之金屬膠體溶液，其中上述金屬奈米粒子的粒徑為5nm~50nm的範圍。The metal colloidal solution according to claim 8 or 9, wherein the metal nanoparticles have a particle diameter of 5 nm to 50 nm. 一種金屬膠體溶液的製造方法，其特徵在於：於如下金屬奈米粒子保護聚合物的存在下，在介質中將金屬離子還原而製成金屬奈米粒子，該金屬奈米粒子保護聚合物是於1分子中具有將聚伸烷基亞胺中的一級胺的5mol%~95mol%、或一級胺的5mol%~95mol%及二級胺的5mol%~50mol%乙醯化，進而，將聚伸烷基亞胺中的全部氮原子數的0.5mol%~95mol%氧化而成的聚乙醯基伸烷基亞胺N-氧化物片段(A)及包含聚氧伸烷基鏈的親水性片段(B)。A method for producing a metal colloidal solution, characterized in that metal ions are reduced in a medium to form metal nanoparticles in the presence of a metal nanoparticle-protecting polymer, and the metal nanoparticle-protecting polymer is 1 molecule has 5 mol% to 95 mol% of the primary amine in the polyalkyleneimine, or 5 mol% to 95 mol% of the primary amine, and 5 mol% to 50 mol% of the secondary amine, and further, the polycondensation a poly(ethylene)alkyleneimine N-oxide fragment (A) obtained by oxidizing 0.5 mol% to 95 mol% of all nitrogen atoms in an alkylimine and a hydrophilic fragment comprising a polyoxyalkylene chain ( B). 如申請專利範圍第11項所述之金屬膠體溶液的製造方法，其中上述金屬奈米粒子為銀奈米粒子。The method for producing a metal colloidal solution according to claim 11, wherein the metal nanoparticle is a silver nanoparticle.
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