TW201920306A - Method for producing metal fine particle composite - Google Patents

Method for producing metal fine particle composite Download PDF

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TW201920306A
TW201920306A TW107125712A TW107125712A TW201920306A TW 201920306 A TW201920306 A TW 201920306A TW 107125712 A TW107125712 A TW 107125712A TW 107125712 A TW107125712 A TW 107125712A TW 201920306 A TW201920306 A TW 201920306A
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metal
metal fine
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hyperbranched polymer
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TW107125712A
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小島圭介
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日商日產化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F112/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F112/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

To provide a more efficient production method for the mass production of a metal fine particle composite body. A method for producing a metal fine particle composite body, which is characterized by comprising: a step for preparing a hyperbranched polymer, which is represented by formula (4) and has an ammonium group at an end, in a reaction system; and a step for adding a metal salt into the reaction system in the presence of a reducing agent, or a step for directly adding metal fine particles into the reaction system after the preparation step. (In the formula, R1 represents a hydrogen atom or a methyl group; each one of R2 to R4 represents a hydrogen atom, an optionally substituted alkylene group, an aryl alkyl group or the like; or alternatively, two moieties among the R2 to R4 moieties may combine with each other to form an alkylene group, or the R2 to R4 moieties may combine with each other to form a ring together with nitrogen atoms to which the R2 to R4 moieties are bonded; X- represents a negative ion; n represents an integer of from 5 to 100,000; and A1 represents a structure represented by formula (2) (wherein A2 represents an alkylene group; and each one of Y1 to Y4 represents a hydrogen atom, an alkyl group, an alkoxy group or the like)).

Description

金屬微粒子複合物之製造方法Manufacturing method of metal microparticle composite

本發明係關於一種用來有效地製造超支化聚合物與金屬微粒子的複合物之製造方法。The present invention relates to a manufacturing method for effectively manufacturing a composite of a hyperbranched polymer and metal fine particles.

已知有一種在分子末端具有銨基的某種的超支化聚合物與金屬微粒子的複合物(以下稱為金屬微粒子複合物)，其係作為無電解鍍敷材料等為適合的。該在末端具有銨基的超支化聚合物，可例如藉由將胺化合物與在分子末端具有鹵素原子的超支化聚合物進行反應而得到(專利文獻1)。
[先前技術文獻]
[專利文獻]A complex of a certain hyperbranched polymer and metal fine particles (hereinafter referred to as a metal fine particle composite) having an ammonium group at a molecular terminal is known, and it is suitable as an electroless plating material or the like. The hyperbranched polymer having an ammonium group at the terminal can be obtained, for example, by reacting an amine compound with a hyperbranched polymer having a halogen atom at the molecular terminal (Patent Document 1).
[Prior technical literature]
[Patent Literature]

[專利文獻1]國際公開第2008/029688號說明書[Patent Document 1] International Publication No. 2008/029688

[發明所欲解決之課題][Problems to be Solved by the Invention]

以往，在金屬微粒子複合物的製造過程中包含著，一旦經確認銨鹽(在末端具有銨基的超支化聚合物)的生成後即將此者進行過濾・離析之步驟，但因此時的過濾性有不佳之情形，據此而存在金屬微粒子複合物本身的製造需要長時間之類的問題。因此，對於金屬微粒子複合物的大量生產係要求著更有效率的製造方法。

[解決課題之手段]In the past, the manufacturing process of metal microparticle composites included the steps of filtering and isolating the ammonium salt (hyperbranched polymer with an ammonium group at the end) once the formation of the ammonium salt was confirmed. In some cases, there is a problem that the production of the metal fine particle composite itself requires a long time. Therefore, there is a demand for a more efficient manufacturing method for mass production of metal fine particle composites.

[Means for solving problems]

本發明人為了達成上述目的經深入研究之結果發現，將在末端具有鹵素基的超支化聚合物與胺化合物進行反應來得到在分子末端具有銨基的超支化聚合物後，不用將反應液進行純化，而是直接添加金屬微粒子至反應液中從而得到金屬微粒子複合物，其結果，與將在分子末端具有銨基的超支化聚合物進行離析後再藉由將此者與金屬微粒子反應而得到複合物之情形相比時，例如，在作為金屬無電解鍍敷底塗劑來使用時的觸媒活性等之中，可得到同等品質的金屬微粒子複合物，因而完成本發明。As a result of intensive research in order to achieve the above-mentioned object, the present inventors have found that after reacting a hyperbranched polymer having a halogen group at an end with an amine compound to obtain a hyperbranched polymer having an ammonium group at a molecular end, the reaction solution is not required For purification, metal microparticles are directly added to the reaction solution to obtain a metal microparticle complex. As a result, a hyperbranched polymer having an ammonium group at the molecular end is isolated and then reacted with the metal microparticles. In comparison with the case of composites, for example, among the catalyst activities when used as a metal electroless plating primer, metal fine particle composites of the same quality can be obtained, and the present invention has been completed.

即，作為本發明之第1觀點係關於一種金屬微粒子複合物之製造方法，其特徵係包含下述步驟：
在反應系內將式[1]所表示的在末端具有鹵素基的超支化聚合物與式[3]所表示的胺化合物進行反應，來調製式[4]所表示的在末端具有銨基的超支化聚合物之步驟；
接續於前述調製步驟之後，以還原劑的存在下添加金屬鹽至該反應系內之步驟、或者直接添加金屬微粒子至該反應系內之步驟，

｛式[1]中，X表示鹵素原子，R1 分別獨立表示氫原子或甲基，A1 表示式[2]所表示的構造，

(式中，A2 表示可包含醚鍵或酯鍵的碳原子數1至30的直鏈狀、支鏈狀或環狀的伸烷基，Y1 至Y4 分別獨立表示氫原子、碳原子數1至20的烷基、碳原子數1至20的烷氧基、硝基、羥基、胺基、羧基或氰基)，n為重複單位構造的數量且表示2至100,000的整數｝；

｛R2 至R4 分別獨立表示氫原子、碳原子數1至20的直鏈狀、支鏈狀或環狀的烷基、碳原子數7至20的芳基烷基或-(CH2 CH2 O)m R5 (式中，R5 表示氫原子或甲基，m表示2～100的任意的整數)，上述烷基及芳基烷基可被烷氧基、羥基、銨基、羧基或氰基所取代，又，R2 至R4 中的2個基可在一起而表示直鏈狀、支鏈狀或環狀的伸烷基，或R2 至R4 與此等所鍵結的氮原子可在一起而形成環｝；

(R1 、R2 至R4 、A1 及n表示與前述相同的意義，X- 表示鹵素原子的陰離子)。
作為第2觀點係關於第1觀點所記載之金屬微粒子複合物之製造方法，其中，包含以還原劑的存在下添加金屬鹽至前述反應系內之步驟。
作為第3觀點係關於第1觀點或第2觀點所記載之金屬微粒子複合物之製造方法，其中，使用醇溶劑來作為前述還原劑。
作為第4觀點係關於一種金屬微粒子複合物，其係使用如第1觀點～第3觀點中任一觀點所記載之金屬微粒子複合物之製造方法而得到。

[發明的效果]That is, the first aspect of the present invention relates to a method for producing a metal fine particle composite, which is characterized by including the following steps:
In the reaction system, a hyperbranched polymer having a halogen group at the terminal represented by the formula [1] is reacted with an amine compound represented by the formula [3] to prepare a compound having an ammonium group at the terminal represented by the formula [4]. Step of hyperbranched polymer;
Following the aforementioned preparation step, a step of adding a metal salt to the reaction system in the presence of a reducing agent, or a step of directly adding metal fine particles to the reaction system,

In formula [1], X represents a halogen atom, R 1 independently represents a hydrogen atom or a methyl group, and A 1 represents a structure represented by formula [2].

(In the formula, A 2 represents a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, which may include an ether bond or an ester bond, and Y 1 to Y 4 each independently represent a hydrogen atom and a carbon atom. Alkyl groups of 1 to 20, alkoxy groups of 1 to 20 carbon atoms, nitro, hydroxyl, amino, carboxyl or cyano), n is the number of repeating unit structures and represents an integer of 2 to 100,000;

｛R 2 to R 4 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or-(CH 2 CH 2 O) m R 5 (wherein R 5 represents a hydrogen atom or a methyl group, and m represents an arbitrary integer from 2 to 100), and the alkyl and arylalkyl groups may be alkoxy, hydroxyl, ammonium, or carboxyl Or cyano substituted, and two of R 2 to R 4 may be taken together to represent a linear, branched, or cyclic alkylene, or R 2 to R 4 are bonded thereto Nitrogen atoms can form together to form a ring｝;

(R 1 , R 2 to R 4 , A 1 and n have the same meanings as described above, and X − represents an anion of a halogen atom).
As a second aspect, the method for producing a metal fine particle composite according to the first aspect includes a step of adding a metal salt to the reaction system in the presence of a reducing agent.
A third aspect is the method for producing a metal fine particle composite according to the first aspect or the second aspect, wherein an alcohol solvent is used as the reducing agent.
The fourth aspect relates to a metal fine particle composite, which is obtained by using the method for producing a metal fine particle composite according to any one of the first to third aspects.

[Effect of the invention]

依據本發明，可提供一種特定的超支化聚合物與金屬微粒子的金屬微粒子複合物之有效率的製造方法。According to the present invention, it is possible to provide an efficient method for producing a metal microparticle composite of a specific hyperbranched polymer and metal microparticles.

[實施發明之最佳形態][Best Mode for Implementing Invention]

本發明中所謂的「金屬微粒子複合物」，係指藉由式[4]所表示的在末端具有銨基的超支化聚合物的末端的銨基的作用，而以接觸或接近於金屬微粒子之狀態下兩者共存，並成為粒子狀的形態。換言之，「金屬微粒子複合物」係表現出具有前述超支化聚合物的銨基為附著或配位於金屬微粒子的構造的複合物。
因此，本發明中的「金屬微粒子複合物」，不僅是包含如上述般地金屬微粒子與在末端具有銨基的超支化聚合物鍵結而形成一個複合物之樣態，亦包含金屬微粒子與前述超支化聚合物不形成鍵結部分，而是各自獨立存在之樣態。
以下，對於本發明來進行詳細地說明。The "metal fine particle complex" in the present invention refers to the contact with or close to the metal fine particles by the action of the ammonium group at the terminal of the hyperbranched polymer having an ammonium group at the terminal represented by the formula [4]. In the state, the two coexist and form a granular form. In other words, the "metal fine particle composite" is a composite having a structure in which the ammonium group of the aforementioned hyperbranched polymer is adhered or coordinated to the metal fine particles.
Therefore, the "metal fine particle complex" in the present invention includes not only the state in which the metal fine particles are bonded to the hyperbranched polymer having an ammonium group at the end to form a composite, but also includes the metal fine particles and the foregoing Hyperbranched polymers do not form bonded portions, but rather exist independently of each other.
Hereinafter, the present invention will be described in detail.

本發明之製造方法包含下述步驟：在反應系內將式[1]所表示的在末端具有鹵素基的超支化聚合物與式[3]所表示的胺化合物進行反應，來調製式[4]所表示的在末端具有銨基的超支化聚合物之步驟；接續於前述調製步驟之後，以還原劑的存在下添加金屬鹽至該反應系內之步驟，或者，接續於前述調製步驟之後，直接添加金屬微粒子至該反應系內之步驟。The production method of the present invention includes the steps of reacting a hyperbranched polymer having a halogen group at the terminal represented by Formula [1] with an amine compound represented by Formula [3] in a reaction system to prepare Formula [4 A step of a hyperbranched polymer having an ammonium group at the end as indicated by []; followed by the step of adding the metal salt to the reaction system in the presence of a reducing agent after the aforementioned preparing step, or following the aforementioned preparing step, The step of directly adding metal fine particles to the reaction system.

[在反應系內調製式[4]所表示的在末端具有銨基的超支化聚合物之步驟]
藉由本步驟所使用的在末端具有鹵素基的超支化聚合物，係下述式[1]所表示的聚合物。

前述式[1]中，R1 分別獨立表示氫原子或甲基。
又，X表示鹵素原子，n為重複單位構造的數量且表示2至100,000的整數。
作為上述鹵素原子，可舉出氯原子、溴原子、碘原子等。[Step of preparing a hyperbranched polymer having an ammonium group at the terminal represented by the formula [4] in a reaction system]
The hyperbranched polymer having a halogen group at the terminal used in this step is a polymer represented by the following formula [1].

In the formula [1], R 1 each independently represents a hydrogen atom or a methyl group.
In addition, X represents a halogen atom, n is the number of repeating unit structures, and represents an integer of 2 to 100,000.
Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

上述式[1]中，A1 表示下述式[2]所表示的構造。

上述式[2]中，A2 表示可包含醚鍵或酯鍵的碳原子數1至30的直鏈狀、支鏈狀或環狀的伸烷基。
Y1 至Y4 分別獨立表示氫原子、碳原子數1至20的烷基、碳原子數1至20的烷氧基、硝基、羥基、胺基、羧基或氰基。In the above formula [1], A 1 represents a structure represented by the following formula [2].

In the above formula [2], A 2 represents a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms which may include an ether bond or an ester bond.
Y 1 to Y 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, an amine group, a carboxyl group, or a cyano group.

作為上述A2 的伸烷基的具體例，可舉出亞甲基、伸乙基、n-伸丙基、n-伸丁基、n-伸己基等的直鏈狀伸烷基、異伸丙基、異伸丁基、2-甲基伸丙基等的支鏈狀伸烷基。又，作為環狀伸烷基，可舉出碳原子數3～30的單環式、多環式及交聯環式的環狀構造的脂環式脂肪族基。具體而言，可舉出碳原子數4以上的具有單環、雙環、三環、四環、五環構造等的基。例如，於下述表示脂環式脂肪族基中的脂環式部分的構造例(a)～(s)。
Specific examples of the above-mentioned alkylene group of A 2 include linear alkylene groups and iso-alkylene groups such as methylene, ethylene, n-propylene, n-butylene, and n-hexyl. Branched alkylene groups such as propyl, isobutylene, and 2-methylalkylene. Examples of the cyclic alkylene group include alicyclic aliphatic groups having monocyclic, polycyclic, and crosslinked cyclic structures of 3 to 30 carbon atoms. Specifically, a group having a monocyclic, bicyclic, tricyclic, tetracyclic, pentacyclic structure, etc. having 4 or more carbon atoms can be mentioned. For example, structural examples (a) to (s) of the alicyclic portion in the alicyclic aliphatic group are shown below.

又，作為上述式[2]中的Y1 至Y4 的碳原子數1至20的烷基，可舉出甲基、乙基、異丙基、n-戊基、環己基等。作為碳原子數1至20的烷氧基，可舉出甲氧基、乙氧基、異丙氧基、n-戊氧基、環己氧基等。作為Y1 至Y4 係以氫原子或碳原子數1至20的烷基為較佳。Examples of the alkyl group having 1 to 20 carbon atoms for Y 1 to Y 4 in the formula [2] include a methyl group, an ethyl group, an isopropyl group, an n-pentyl group, and a cyclohexyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, an n-pentyloxy group, and a cyclohexyloxy group. Y 1 to Y 4 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

尚，前述A1 係以下述式[5]所表示的構造為較佳。
The above-mentioned A 1 is preferably a structure represented by the following formula [5].

本發明中使用的上述式[1]所表示的在分子末端具有鹵素原子的超支化聚合物，係根據國際公開第2008/029688號說明書之記載，可藉由在分子末端具有二硫代胺基甲酸酯基(dithiocarbamate group)的超支化聚合物從而來製造。該在分子末端具有二硫代胺基甲酸酯基的超支化聚合物可使用市售品，能夠適合使用日產化學工業(股)製的HYPERTECH (註冊商標)HPS-200等。The hyperbranched polymer having a halogen atom at the molecular terminal represented by the above formula [1] used in the present invention is described in the specification of International Publication No. 2008/029688, and can have a dithioamino group at the molecular terminal. Dithiocarbamate group hyperbranched polymers are thus manufactured. As the hyperbranched polymer having a dithiocarbamate group at the molecular terminal, a commercially available product can be used, and HYPERTECH (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd. can be suitably used.

又，藉由本步驟所使用的胺化合物為下述式[3]所表示的胺化合物。

前述式[3]中，R2 至R4 分別獨立表示氫原子、碳原子數1至20的直鏈狀、支鏈狀或環狀的烷基、碳原子數7至20的芳基烷基或-(CH2 CH2 O)m R5 (式中，R5 表示氫原子或甲基，m表示2～100的任意的整數)。
上述烷基及芳基烷基可被烷氧基、羥基、銨基、羧基或氰基所取代。又，R2 至R4 中的2個基可在一起而表示直鏈狀、支鏈狀或環狀的伸烷基，或R2 至R4 與此等所鍵結的氮原子可在一起而形成環。The amine compound used in this step is an amine compound represented by the following formula [3].

In the aforementioned formula [3], R 2 to R 4 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. Or-(CH 2 CH 2 O) m R 5 (wherein R 5 represents a hydrogen atom or a methyl group, and m represents an arbitrary integer from 2 to 100).
The above alkyl and arylalkyl groups may be substituted with an alkoxy group, a hydroxyl group, an ammonium group, a carboxyl group or a cyano group. In addition, two of R 2 to R 4 may be taken together to represent a linear, branched, or cyclic alkylene, or R 2 to R 4 may be taken together with the nitrogen atom to which they are bonded. And form a ring.

作為上述R2 至R4 中的碳原子數1至20的直鏈狀的烷基，可舉出甲基、乙基、n-丙基、n-丁基、n-戊基、n-己基、n-庚基、n-辛基、n-壬基、n-癸基、n-十一烷基、n-十二烷基、n-十三烷基、n-十四烷基、n-十五烷基、n-十六烷基、n-十七烷基、n-十八烷基、n-十九烷基、n-二十烷基等。例如，若使用依據本發明之製造方法所得到的金屬微粒子複合物來作為無電解鍍敷的底塗劑之情形時，就該底塗劑難以溶出在無電解鍍敷液中的觀點而言，以碳原子數8以上的基為較佳，特別是以n-辛基為較佳。
作為支鏈狀的烷基，可舉出異丙基、異丁基、sec-丁基、tert-丁基等。
作為環狀的烷基，可舉出具有環戊基環、環己基環構造的基等。
又，作為R2 至R4 中的碳原子數7至20的芳基烷基，可舉出苄基、苯乙基等。
進而，作為R2 至R4 中的2個基在一起而成的直鏈狀的伸烷基，可舉出亞甲基、伸乙基、n-伸丙基、n-伸丁基、n-伸己基等。作為支鏈狀的伸烷基，可舉出甲基伸乙基(伸丙基)、丁烷-1,3-二基、2-甲基丙烷-1,3-二基等。
作為環狀的伸烷基，可舉出碳原子數3～30的單環式、多環式、交聯環式的環狀構造的脂環式脂肪族基。具體而言，可舉出碳原子數4以上的具有單環、雙環、三環、四環、五環構造等的基。該等伸烷基係在基中可包含氮原子、硫原子或氧原子。
又，式[3]所表示的構造中，R2 至R4 與此等所鍵結的氮原子在一起而形成的環，在環中也可包含氮原子、硫原子或氧原子，可舉出例如吡啶環、嘧啶環、吡嗪環、喹啉環、聯砒啶環等。Examples of the linear alkyl group having 1 to 20 carbon atoms in the above R 2 to R 4 include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl , N-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n -Pentadecyl, n-hexadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, n-icosyl and the like. For example, when the metal fine particle composite obtained by the manufacturing method of the present invention is used as a primer for electroless plating, from the viewpoint that the primer is difficult to dissolve in the electroless plating solution, A group having 8 or more carbon atoms is preferred, and an n-octyl group is particularly preferred.
Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, and tert-butyl.
Examples of the cyclic alkyl group include a group having a cyclopentyl ring and a cyclohexyl ring structure.
Examples of the arylalkyl group having 7 to 20 carbon atoms among R 2 to R 4 include a benzyl group and a phenethyl group.
Furthermore, examples of the linear alkylene group in which two groups of R 2 to R 4 are joined together include methylene, ethylene, n-propyl, n-butyl, and n -Nobuhiko and others. Examples of the branched alkylene group include methylethylene (propylene), butane-1,3-diyl, 2-methylpropane-1,3-diyl, and the like.
Examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic, or crosslinked cyclic structure having 3 to 30 carbon atoms. Specifically, a group having a monocyclic, bicyclic, tricyclic, tetracyclic, pentacyclic structure, etc. having 4 or more carbon atoms can be mentioned. The alkylene group may include a nitrogen atom, a sulfur atom, or an oxygen atom in the radical.
Further, in the structure represented by the formula [3], the ring formed by R 2 to R 4 together with the nitrogen atom bonded thereto may include a nitrogen atom, a sulfur atom, or an oxygen atom in the ring. For example, a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, a bipyridine ring, and the like are given.

作為該等R2 至R4 的組合，可舉出例如[甲基、甲基、甲基]、[甲基、甲基、乙基]、[甲基、甲基、n-丁基]、[甲基、甲基、n-己基]、[甲基、甲基、n-辛基]、[甲基、甲基、n-癸基]、[甲基、甲基、n-十二烷基]、[甲基、甲基、n-十四烷基]、[甲基、甲基、n-十六烷基]、[甲基、甲基、n-十八烷基]、[乙基、乙基、乙基]、[n-丁基、n-丁基、n-丁基]、[n-己基、n-己基、n-己基]、[n-辛基、n-辛基、n-辛基]等，其中，以[甲基、甲基、n-辛基]、[n-辛基、n-辛基、n-辛基]的組合為較佳。Examples of the combination of R 2 to R 4 include [methyl, methyl, methyl], [methyl, methyl, ethyl], [methyl, methyl, n-butyl], [Methyl, methyl, n-hexyl], [methyl, methyl, n-octyl], [methyl, methyl, n-decyl], [methyl, methyl, n-dodecane Group], [methyl, methyl, n-tetradecyl], [methyl, methyl, n-hexadecyl], [methyl, methyl, n-octadecyl], [ethyl Group, ethyl, ethyl], [n-butyl, n-butyl, n-butyl], [n-hexyl, n-hexyl, n-hexyl], [n-octyl, n-octyl , N-octyl], etc. Among them, a combination of [methyl, methyl, n-octyl], [n-octyl, n-octyl, n-octyl] is preferred.

本步驟中可使用的胺化合物，作為第一級胺，可舉出甲基胺、乙基胺、n-丙基胺、異丙基胺、n-丁基胺、異丁基胺、sec-丁基胺、tert-丁基胺、n-戊基胺、n-己基胺、n-庚基胺、n-辛基胺、n-壬基胺、n-癸基胺、n-十一烷基胺、n-十二烷基胺、n-十三烷基胺、n-十四烷基胺、n-十五烷基胺、n-十六烷基胺、n-十七烷基胺、n-十八烷基胺、n-十九烷基胺、n-二十烷基胺等的脂肪族胺；環戊基胺、環己基胺等的脂環式胺；苄基胺、苯乙基胺等的芳烷基胺；苯胺、p-n-丁基苯胺、p-tert-丁基苯胺、p-n-辛基苯胺、p-n-癸基苯胺、p-n-十二烷基苯胺、p-n-十四烷基苯胺等的苯胺類、1-萘基胺、2-萘基胺等的萘基胺類、1-胺基蒽、2-胺基蒽等的胺基蒽類、1-胺基蒽醌等的胺基蒽醌類、4-胺基聯苯、2-胺基聯苯等的胺基聯苯類、2-胺基茀、1-胺基-9-茀酮、4-胺基-9-茀酮等的胺基茀類、5-胺基茚烷等的胺基茚烷類、5-胺基異喹啉等的胺基異喹啉類、9-胺基菲等的胺基菲類等的芳香族胺。進而，可舉出N-(tert-丁氧基羰基)-1,2-伸乙二胺、N-(tert-丁氧基羰基)-1,3-伸丙二胺、N-(tert-丁氧基羰基)-1,4-伸丁二胺、N-(tert-丁氧基羰基)-1,5-五亞甲基二胺、N-(tert-丁氧基羰基)-1,6-六亞甲基二胺、N-(2-羥基乙基)胺、N-(3-羥基丙基)胺、N-(2-甲氧基乙基)胺、N-(2-乙氧基乙基)胺等的胺化合物。Examples of the amine compound usable in this step include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and sec- Butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecane Amine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine , N-octadecylamine, n-nonadecylamine, n-icosylamine, etc .; aliphatic amines such as cyclopentylamine, cyclohexylamine; benzylamine, benzene Aralkylamines such as ethylamine; aniline, pn-butylaniline, p-tert-butylaniline, pn-octylaniline, pn-decylaniline, pn-dodecylaniline, pn-tetradec Aniline such as alkylaniline, naphthylamine such as 1-naphthylamine, 2-naphthylamine, etc., aminoanthracene such as 1-aminoanthracene, 2-aminoanthracene, etc., 1-aminoanthraquinone And other amino anthraquinones, 4-amino biphenyls, 2-amino biphenyls, etc., 2-aminofluorene, 1-amino-9-fluorenone, 4-amino- Amine fluorenes such as 9-fluorenone, 5-aminoindene Aromatic amines such as aminoindenes such as alkane, aminoisoquinolines such as 5-aminoisoquinoline, and aminophenanthrenes such as 9-aminophenanthrene. Furthermore, N- (tert-butoxycarbonyl) -1,2-ethylenediamine, N- (tert-butoxycarbonyl) -1,3-propylenediamine, N- (tert- (Butoxycarbonyl) -1,4-butanediamine, N- (tert-butoxycarbonyl) -1,5-pentamethylenediamine, N- (tert-butoxycarbonyl) -1, 6-hexamethylene diamine, N- (2-hydroxyethyl) amine, N- (3-hydroxypropyl) amine, N- (2-methoxyethyl) amine, N- (2-ethyl Amine compounds such as oxyethyl) amine.

作為第二級胺，可舉出二甲基胺、二乙基胺、二-n-丙基胺、二異丙基胺、二-n-丁基胺、二異丁基胺、二-sec-丁基胺、二-n-戊基胺、乙基甲基胺、甲基-n-丙基胺、甲基-n-丁基胺、甲基-n-戊基胺、乙基異丙基胺、乙基-n-丁基胺、乙基-n-戊基胺、甲基-n-辛基胺、甲基-n-癸基胺、甲基-n-十二烷基胺、甲基-n-十四烷基胺、甲基-n-十六烷基胺、甲基-n-十八烷基胺、乙基異丙基胺、乙基-n-辛基胺、二-n-己基胺、二-n-辛基胺、二-n-十二烷基胺、二-n-十六烷基胺、二-n-十八烷基胺等的脂肪族胺；二環己基胺等的脂環式胺；二苄基胺等的芳烷基胺；二苯基胺等的芳香族胺；鄰苯二甲醯亞胺、吡咯、哌啶、哌嗪、咪唑等的含有氮的雜環式化合物。進而，可舉出雙(2-羥基乙基)胺、雙(3-羥基丙基)胺、雙(2-乙氧基乙基)胺、雙(2-丙氧基乙基)胺等。Examples of the secondary amine include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, and di-sec. -Butylamine, di-n-pentylamine, ethylmethylamine, methyl-n-propylamine, methyl-n-butylamine, methyl-n-pentylamine, ethyl isopropyl Methylamine, ethyl-n-butylamine, ethyl-n-pentylamine, methyl-n-octylamine, methyl-n-decylamine, methyl-n-dodecylamine, Methyl-n-tetradecylamine, methyl-n-hexadecylamine, methyl-n-octadecylamine, ethyl isopropylamine, ethyl-n-octylamine, di aliphatic amines such as -n-hexylamine, di-n-octylamine, di-n-dodecylamine, di-n-hexadecylamine, di-n-octadecylamine; two Aliphatic amines such as cyclohexylamine; aralkylamines such as dibenzylamine; aromatic amines such as diphenylamine; phthalimide, pyrrole, piperidine, piperazine, imidazole, etc. Heterocyclic compounds containing nitrogen. Furthermore, bis (2-hydroxyethyl) amine, bis (3-hydroxypropyl) amine, bis (2-ethoxyethyl) amine, bis (2-propoxyethyl) amine, etc. are mentioned.

作為第三級胺，可舉出三甲基胺、三乙基胺、三-n-丙基胺、三-n-丁基胺、三-n-戊基胺、三-n-己基胺、三-n-辛基胺、三-n-十二烷基胺、二甲基乙基胺、二甲基-n-丁基胺、二甲基-n-己基胺、二甲基-n-辛基胺、二甲基-n-癸基胺、二乙基-n-癸基胺、二甲基-n-十二烷基胺、二甲基-n-十四烷基胺、二甲基-n-十六烷基胺、二甲基-n-十八烷基胺、二甲基-n-二十烷基胺等的脂肪族胺；吡啶、吡嗪、嘧啶、喹啉、1-甲基咪唑、4,4’-聯砒啶、4-甲基-4,4’-聯砒啶等的含有氮的雜環式化合物。Examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, Tri-n-octylamine, tri-n-dodecylamine, dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n- Octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecylamine, dimethyl Aliphatic amines such as n-hexadecylamine, dimethyl-n-octadecylamine, dimethyl-n- eicosylamine; pyridine, pyrazine, pyrimidine, quinoline, 1 -A nitrogen-containing heterocyclic compound such as methylimidazole, 4,4'-bipyridine, 4-methyl-4,4'-bipyridine, and the like.

相對於在分子末端具有鹵素原子的超支化聚合物的鹵素原子1莫耳，本步驟中所使用的胺化合物的使用量為0.1～20莫耳當量，較佳為0.5～10莫耳當量，又較佳可為1～5莫耳當量。The amount of the amine compound used in this step is 0.1 to 20 mole equivalents, preferably 0.5 to 10 mole equivalents, relative to 1 mole of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular terminal. It may preferably be 1 to 5 mole equivalents.

＜與胺化合物的反應＞
在分子末端具有鹵素原子的超支化聚合物與胺化合物的反應，係可以在水或有機溶劑中，以存在或不存在鹼的條件下來進行。所使用的溶劑係以能夠溶解於在分子末端具有鹵素原子的超支化聚合物與胺化合物者為較佳。
作為本反應中可使用的溶劑，只要不明顯阻礙本反應的進行者即可，可使用甲醇、乙醇、異丙醇等的醇類；N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAc)、N-甲基-2-吡咯啶酮(NMP)等的醯胺類、二甲基亞碸(DMSO)。該等的溶劑係可使用1種、或可混合2種以上來使用。又，相對於在分子末端具有鹵素原子的超支化聚合物的質量，使用量為0.2～1,000倍質量，較佳為1～500倍質量，又較佳為5～100倍質量，最佳為使用5～50倍質量的溶劑為較佳。＜ Reaction with amine compound ＞
The reaction between a hyperbranched polymer having a halogen atom at the molecular end and an amine compound can be carried out in water or an organic solvent in the presence or absence of a base. The solvent used is preferably one capable of dissolving in a hyperbranched polymer and an amine compound having a halogen atom at the molecular terminal.
As the solvent that can be used in this reaction, as long as it does not significantly hinder the progress of the reaction, alcohols such as methanol, ethanol, and isopropanol can be used; N, N-dimethylformamide (DMF), N , N-dimethylacetamidine (DMAc), N-methyl-2-pyrrolidone (NMP), and other amines, dimethylsulfinium (DMSO). These solvents may be used singly or in combination of two or more kinds. In addition, the amount used is 0.2 to 1,000 times the mass, preferably 1 to 500 times the mass, and still more preferably 5 to 100 times the mass with respect to the mass of the hyperbranched polymer having a halogen atom at the molecular terminal, and the most preferably used is 5 to 50 times the mass of the solvent is preferred.

在該反應中，以於反應開始前充分地去除反應系內的氧為較佳，可以利用氮、氬等的惰性氣體來取代系內。作為反應條件，可從反應時間為0.01～100小時、反應溫度為0～300℃來進行適當選擇。較佳以反應時間為0.1～72小時，反應溫度為20～150℃。In this reaction, it is preferable to sufficiently remove oxygen in the reaction system before the reaction starts, and an inert gas such as nitrogen or argon may be used in place of the system. The reaction conditions can be appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C. The reaction time is preferably from 0.1 to 72 hours and the reaction temperature is from 20 to 150 ° C.

作為胺化合物若使用第三級胺，並將此者與在分子末端具有鹵素原子的超支化聚合物進行反應之情形時，可得到式[4]所表示的超支化聚合物(前述的定義中，R2 至R4 皆為表示氫原子以外的基之情形時的聚合物)。
又，作為胺化合物若使用第一級胺或第二級胺化合物，並以不存在鹼的條件下，與在分子末端具有鹵素原子的超支化聚合物進行反應之情形時，可得到分別對應的超支化聚合物的末端第二級胺(第二級胺基：-NHR)及第三級胺(第三級胺基：-NRR’)被質子化的銨基末端(-N+ H2 R、 -N+ HRR’)的超支化聚合物。又，即使是使用鹼來進行反應之情形時，也可藉由在有機溶劑中與氯化氫、溴化氫、碘化氫等的酸的水溶液進行混合，而可得到對應的超支化聚合物的末端第二級胺及第三級胺被質子化的銨基末端的超支化聚合物。When a tertiary amine is used as the amine compound, and this is reacted with a hyperbranched polymer having a halogen atom at the molecular terminal, a hyperbranched polymer represented by the formula [4] (in the aforementioned definition) can be obtained R 2 to R 4 are polymers in the case where each represents a group other than a hydrogen atom).
If a primary amine or a secondary amine compound is used as the amine compound and reacted with a hyperbranched polymer having a halogen atom at the molecular end in the absence of a base, a corresponding one is obtained. The terminal secondary amine (secondary amine group: -NHR) and tertiary amine (tertiary amine group: -NRR ') of the hyperbranched polymer are protonated terminal ammonium groups (-N + H 2 R , -N + HRR '). In addition, even in the case of using a base to perform the reaction, the end of the corresponding hyperbranched polymer can be obtained by mixing with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an organic solvent. Protonated ammonium-terminated hyperbranched polymers of secondary and tertiary amines.

前述在末端具有銨基的超支化聚合物，藉由經凝膠滲透色譜法之聚苯乙烯換算所測得的重量平均分子量Mw為1,000～5,000,000，較佳為1,000～500,000，又較佳為2,000～200,000，最佳為3,000～100,000。又，作為分散度Mw(重量平均分子量)/Mn(數量平均分子量)為1.0～7.0，較佳為1.1～6.0，又較佳為1.2～5.0。The weight-average molecular weight Mw of the aforementioned hyperbranched polymer having an ammonium group at the terminal as measured by polystyrene conversion by gel permeation chromatography is 1,000 to 5,000,000, preferably 1,000 to 500,000, and more preferably 2,000 ~ 200,000, most preferably 3,000 ~ 100,000. The dispersion Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, and still more preferably 1.2 to 5.0.

如此般的在分子末端具有銨基的超支化聚合物，具體而言可舉出下述式[4]所表示的超支化聚合物。

前述式[4]中，R1 、R2 至R4 、A1 及n表示與上述為相同的意義，X- 表示鹵素原子的陰離子(鹵化物離子)。Specific examples of such a hyperbranched polymer having an ammonium group at the molecular terminal include a hyperbranched polymer represented by the following formula [4].

In the aforementioned formula [4], R 1 , R 2 to R 4 , A 1 and n have the same meanings as described above, and X − represents an anion (halide ion) of a halogen atom.

作為如此般的在分子末端具有銨基的超支化聚合物，較佳可舉出前述A1 為上述式[5]所表示的構造，X- 為氯化物離子的下述式[6]所表示的超支化聚合物。

前述式[6]中、R1 、R2 至R4 及n表示與上述為相同的意義。As such a hyperbranched polymer having an ammonium group at the molecular terminal, preferably, the structure in which A 1 is represented by the above formula [5], and X - is represented by the following formula [6] which is a chloride ion Hyperbranched polymer.

In the aforementioned formula [6], R 1 , R 2 to R 4, and n have the same meanings as described above.

[以還原劑的存在下添加金屬鹽至反應系內之步驟、或者直接添加金屬微粒子至該反應系內之步驟]
本步驟係可藉由如下述般來實施：接續於前述的在反應系內調製式[4]所表示的在末端具有銨基的超支化聚合物之步驟，實施以還原劑的存在下添加金屬鹽至反應系內、或者實施直接添加金屬微粒子至反應系內。
即，本發明之製造方法之特徵為：藉由上述在末端具有鹵素基的超支化聚合物與胺化合物的反應，從而得到上述式[4]所表示的在末端具有銨基的超支化聚合物(以下，也簡稱為超支化聚合物)後，不從反應系內離析該超支化聚合物，而是將構成金屬微粒子複合物的金屬微粒子源(金屬鹽或金屬微粒子)添加至包含該超支化聚合物的反應系(反應液)中。
尚，如後述般，若以還原劑的存在下添加金屬鹽至系內之情形時，由金屬鹽所產生的金屬離子在系內會因為還原劑的作用而被還原，而能以超支化聚合物與金屬微粒子的金屬微粒子複合物之形態來得到金屬微粒子。又，以照射紫外線等來替代添加還原劑，來進行金屬離子的還原，亦可得到金屬微粒子複合物。[Step of adding a metal salt into the reaction system in the presence of a reducing agent, or directly adding metal fine particles to the reaction system]
This step can be carried out as follows: Continuing the step of preparing the hyperbranched polymer having an ammonium group at the terminal represented by the formula [4] in the reaction system, and adding a metal in the presence of a reducing agent, as described below. Salt is added to the reaction system, or metal fine particles are directly added to the reaction system.
That is, the production method of the present invention is characterized in that by reacting the above-mentioned hyperbranched polymer having a halogen group at the terminal with an amine compound, a hyperbranched polymer having an ammonium group at the terminal represented by the formula [4] is obtained. (Hereinafter, also simply referred to as hyperbranched polymer), the hyperbranched polymer is not isolated from the reaction system, but a metal microparticle source (metal salt or metal microparticle) constituting the metal microparticle composite is added to the hyperbranched polymer. Polymer reaction system (reaction liquid).
However, as described later, if a metal salt is added to the system in the presence of a reducing agent, the metal ions generated by the metal salt are reduced in the system by the action of the reducing agent, and can be polymerized by hyperbranching. The form of the metal fine particle composite of the particles and the metal fine particles to obtain the metal fine particles. In addition, instead of adding a reducing agent by irradiating ultraviolet rays or the like to reduce metal ions, a metal fine particle composite can also be obtained.

對含有上述在分子末端具有銨基的超支化聚合物的反應系(反應液)中添加上述金屬鹽或上述金屬微粒子的添加量，相對於在分子末端具有上述銨基的超支化聚合物100質量份(換算成金屬量)，較佳為5～200質量份。金屬鹽(金屬量換算)及金屬微粒子的添加量若未滿5質量份時，金屬微粒子複合物中的有機物含有量會變多，故對於物性等將易於產生不良。若超過200質量份時，則上述金屬微粒子(金屬鹽之情形時為還原後的形態)的分散性為不足。又較佳為10～100質量份。尚，實際上係可將藉由作為原料的在末端具有鹵素基的超支化聚合物的使用量所換算的值，作為在分子末端具有銨基的超支化聚合物的使用量來操作。The amount of the metal salt or the metal fine particles added to the reaction system (reaction liquid) containing the above-mentioned hyperbranched polymer having an ammonium group at the molecular end is 100 masses relative to 100 masses of the above-branched hyperbranched polymer having the above-mentioned ammonium group at the molecular end. Parts (converted to the amount of metal), preferably 5 to 200 parts by mass. When the addition amount of the metal salt (conversion of the metal amount) and the metal fine particles is less than 5 parts by mass, the content of the organic matter in the metal fine particle composite will increase, so physical properties and the like are liable to cause defects. If it exceeds 200 parts by mass, the dispersibility of the metal fine particles (in the case of a metal salt, the form after reduction) is insufficient. It is more preferably 10 to 100 parts by mass. Actually, the value converted from the amount of the hyperbranched polymer having a halogen group at the terminal as a raw material can be used as the amount of the hyperbranched polymer having an ammonium group at the molecular terminal.

又，前述金屬微粒子的平均粒徑係以1～100nm為較佳。尚，所謂的上述的「金屬微粒子的平均粒徑」，係指在反應系內直接添加之情形時的金屬微粒子的平均粒徑、以及以超支化聚合物與金屬微粒子的金屬微粒子複合物之形態(藉由複合物而被穩定化的形態)下的金屬微粒子的平均粒徑之雙方。
上述之平均粒徑係以1～100nm為較佳，作為該理由是，該金屬微粒子的平均粒徑若超過100nm時，則表面積會減少而因此觸媒活性為降低。作為平均粒徑，係以75nm以下為更佳，以1～30nm為特佳。The average particle diameter of the metal fine particles is preferably from 1 to 100 nm. The above-mentioned "average particle diameter of the metal fine particles" refers to the average particle diameter of the metal fine particles when directly added in the reaction system, and the form of the metal fine particle composite of the hyperbranched polymer and the metal fine particles. Both the average particle diameter of the metal fine particles in the form stabilized by the composite.
The above-mentioned average particle diameter is preferably 1 to 100 nm. The reason is that if the average particle diameter of the metal fine particles exceeds 100 nm, the surface area is reduced and the catalyst activity is reduced. The average particle diameter is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.

作為本步驟中使用的金屬鹽及金屬微粒子，並無特別限定，作為該等的金屬種，可舉出鐵(Fe)、鈷(Co)、鎳(Ni)、銅(Cu)、鈀(Pd)、銀(Ag)、錫(Sn)、鉑(Pt)及金(Au)，可以是該等的金屬的1種類或2種以上的併用，又也可以是合金。其中，作為較佳的金屬種類可舉出鈀。The metal salt and metal fine particles used in this step are not particularly limited. Examples of the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and palladium (Pd). ), Silver (Ag), tin (Sn), platinum (Pt), and gold (Au) may be used in combination of one or two or more of these metals, or may be an alloy. Among these, palladium is mentioned as a preferable metal type.

作為前述金屬鹽(亦可使用於後述之金屬微粒子之製造)，可舉出氯化金酸、硝酸銀、硫酸銅、硝酸銅、乙酸銅、氯化錫、氯化第一鉑、氯化鉑酸、Pt(dba)2 [dba=二亞苄基丙酮]、Pt(cod)2 [cod=1,5-環辛二烯]、Pt(CH3 )2 (cod)、氯化鈀、乙酸鈀(Pd(OC(=O)CH3 )2 )、硝酸鈀、Pd2 (dba)3 ・CHCl3 、Pd(dba)2 、氯化銠、乙酸銠、氯化釕、乙酸釕、Ru(cod)(cot)[cot=環辛三烯]、氯化銥、乙酸銥、Ni(cod)2 等。Examples of the metal salt (which can also be used for the production of metal fine particles described later) include gold chloride, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, first platinum chloride, and platinum chloride. , Pt (dba) 2 [dba = dibenzylideneacetone], Pt (cod) 2 [cod = 1,5-cyclooctadiene], Pt (CH 3 ) 2 (cod), palladium chloride, palladium acetate (Pd (OC (= O) CH 3 ) 2 ), palladium nitrate, Pd 2 (dba) 3 · CHCl 3 , Pd (dba) 2 , rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru (cod ) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni (cod) 2 and the like.

前述金屬微粒子，例如通過藉由高壓水銀燈對前述所舉例的金屬鹽的水溶液進行光照射之方法、或在該水溶液中添加具有還原作用的化合物(所謂還原劑)之方法等，通過將金屬離子進行還原而可得到。
作為金屬微粒子的製造中所使用的還原劑，並無特別限定，可使用各種的還原劑，以依照所使用的金屬種類等來選擇還原劑為較佳。作為可使用的還原劑，可舉出例如氫化硼鈉、氫化硼鉀等的氫化硼金屬鹽；氫化鋁鋰、氫化鋁鉀、氫化鋁銫、氫化鋁鈹、氫化鋁鎂、氫化鋁鈣等的氫化鋁鹽；肼化合物；檸檬酸及其鹽；琥珀酸及其鹽；抗壞血酸及其鹽；甲醇、乙醇、異丙醇、多元醇等的一級醇類或二級醇類；三甲基胺、三乙基胺、二異丙基乙基胺、二乙基甲基胺、四甲基伸乙二胺[TMEDA]、伸乙二胺四乙酸[EDTA]等的第三級胺類；羥基胺；三-n-丙基膦、三-n-丁基膦、三環己基膦、三苄基膦、三苯基膦、三乙氧基膦、1,2-雙(二苯基膦)乙烷[DPPE]、1,3-雙(二苯基膦)丙烷[DPPP]、1,1’-雙(二苯基膦)二茂鐵[DPPF]、2,2’-雙(二苯基膦)-1,1’-聯萘[BINAP]等的膦類等。
又，作為金屬微粒子也可使用前述金屬種類中所舉出的金屬的氧化物。The metal fine particles are, for example, a method of light-irradiating an aqueous solution of the metal salt exemplified above with a high-pressure mercury lamp, or a method of adding a compound having a reducing action (so-called reducing agent) to the aqueous solution, and the like, Available by reduction.
The reducing agent used in the production of the metal fine particles is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the type of metal used and the like. Examples of usable reducing agents include boron hydride metal salts such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, aluminum cesium hydride, aluminum beryllium, magnesium aluminum hydride, calcium aluminum hydride, and the like. Aluminum hydride salts; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary alcohols such as methanol, ethanol, isopropanol, and polyols; trimethylamine, Tertiary amines such as triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine ; Tri-n-propylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphine) ethyl [DPPE], 1,3-bis (diphenylphosphine) propane [DPPP], 1,1'-bis (diphenylphosphine) ferrocene [DPPF], 2,2'-bis (diphenyl) Phosphine) Phosphines such as 1,1'-binaphtyl [BINAP] and the like.
In addition, as the metal fine particles, oxides of the metals listed in the aforementioned metal types can also be used.

＜藉由直接還原方法之金屬微粒子複合物之形成＞
本發明之製造方法中，在末端具有銨基的超支化聚合物(以下為超支化聚合物)與金屬微粒子的金屬微粒子複合物，如前述般，以還原劑的存在下添加金屬鹽至調製有超支化聚合物的反應系內之步驟，因此由金屬鹽所產生的金屬離子在系內會因為還原劑的作用而被還原，因而形成了該金屬微粒子複合物。本步驟係因為將金屬離子在反應系內直接還原，故也稱為「直接還原方法」。＜ Formation of metal microparticle composite by direct reduction method ＞
In the manufacturing method of the present invention, as described above, a metal fine particle composite of a hyperbranched polymer (hereinafter referred to as a hyperbranched polymer) having an ammonium group at the terminal and metal fine particles is added in the presence of a reducing agent to prepare a metal salt. The reaction of the hyperbranched polymer is a step in the reaction system. Therefore, metal ions generated by the metal salt are reduced in the system by the action of a reducing agent, thereby forming the metal microparticle composite. This step is also called a "direct reduction method" because the metal ions are directly reduced in the reaction system.

更詳細而言，以前述所舉出的還原劑(以甲醇、乙醇、異丙醇、多元醇等的一級醇類或二級醇類(醇溶劑)為適合)的存在下，添加成為金屬離子源的上述金屬鹽、及後續所期望的溶劑至含有超支化聚合物的反應系內，利用前述還原劑(一級醇類或二級醇類)來還原金屬離子，藉此可得到作為目標的金屬微粒子複合物。
尚，前述之[在反應系內調製式[4]所表示的在末端具有銨基的超支化聚合物之步驟]中，作為溶劑若使用甲醇、乙醇、異丙醇等的一級醇或二級醇之情形時，可將該等直接視為本步驟中的還原劑，又，即便是此種之情形時，也可於本步驟中重新添加還原劑。
作為使用的溶劑，只要是能以所需濃度以上來溶解金屬離子(金屬離子源)與超支化聚合物的溶劑即可，並無特別限定，但具體而言可舉出甲醇、乙醇、丙醇、異丙醇等的醇類；二氯甲烷、氯仿等的鹵化烴類；四氫呋喃(THF)、2-甲基四氫呋喃、四氫吡喃等的環狀醚類；乙腈、丁腈等的腈類；N,N-二甲基甲醯胺(DMF)、N-甲基-2-吡咯啶酮(NMP)等的醯胺類；二甲基亞碸等的亞碸類等及該等的溶劑的混合液，較佳可舉出醇類、鹵化烴類、環狀醚類，又較佳可舉出乙醇、異丙醇、氯仿、四氫呋喃等。
還原反應的溫度，可使用通常為0℃～溶劑的沸點的範圍，較佳為室溫(大約25℃)～60℃的範圍。More specifically, in the presence of the aforementioned reducing agent (primary alcohols such as methanol, ethanol, isopropanol, and polyhydric alcohols or secondary alcohols (alcohol solvents) are suitable), they are added to form metal ions. The above-mentioned metal salt of the source and the subsequent desired solvent are used in the reaction system containing the hyperbranched polymer, and the aforementioned reducing agent (primary alcohol or secondary alcohol) is used to reduce metal ions, thereby obtaining the target metal. Microparticle complex.
In the aforementioned step of preparing a hyperbranched polymer having an ammonium group at the terminal represented by the formula [4] in the reaction system, if a primary alcohol or a secondary alcohol such as methanol, ethanol, and isopropanol is used as a solvent In the case of alcohol, these can be directly regarded as the reducing agent in this step, and even in this case, the reducing agent can be added again in this step.
The solvent to be used is not particularly limited as long as it can dissolve the metal ion (metal ion source) and the hyperbranched polymer at a desired concentration or more, but specific examples include methanol, ethanol, and propanol. , Alcohols such as isopropyl alcohol; halogenated hydrocarbons such as dichloromethane, chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile, butyronitrile ; N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and other amines; dimethyl fluorene and other fluorenes and the like Examples of the mixed liquid include alcohols, halogenated hydrocarbons, and cyclic ethers, and more preferably, ethanol, isopropanol, chloroform, and tetrahydrofuran.
The temperature of the reduction reaction may be generally in the range of 0 ° C to the boiling point of the solvent, and preferably in the range of room temperature (about 25 ° C) to 60 ° C.

作為上述以外之直接還原方法，即使是藉由添加金屬離子源、後續所期望的溶劑至含有超支化聚合物的反應系內，並以氫氣環境下來使其反應，亦可得到作為目標的金屬微粒子複合物。
作為於此所使用的金屬離子源，可使用上述之金屬鹽、或六羰基鉻[Cr(CO)6 ]、五羰基鐵[Fe(CO)5 ]、八羰基二鈷[Co2 (CO)8 ]、四羰基鎳[Ni(CO)4 ]等的金屬羰基錯合物。又，也可使用金屬烯烴錯合物或金屬膦錯合物、金屬氮錯合物等的0價的金屬錯合物。
作為使用的溶劑，只要是能以所需濃度以上來溶解金屬離子(金屬離子源)與超支化聚合物的溶劑即可，並無特別限定，但具體而言可舉出乙醇、丙醇等的醇類；二氯甲烷、氯仿等的鹵化烴類；四氫呋喃、2-甲基四氫呋喃、四氫吡喃等的環狀醚類；乙腈、丁腈等的腈類等及該等的溶劑的混合液，較佳可舉出四氫呋喃。
將金屬離子源與超支化聚合物進行混合的溫度係可使用通常為0℃～溶劑的沸點的範圍。As a direct reduction method other than the above, even by adding a metal ion source and a subsequent desired solvent to a reaction system containing a hyperbranched polymer and reacting it in a hydrogen atmosphere, the target metal fine particles can be obtained. Complex.
As the metal ion source used herein, the above-mentioned metal salt, or chromium hexacarbonyl [Cr (CO) 6 ], iron pentacarbonyl [Fe (CO) 5 ], and octacarbonyl dicobalt [Co 2 (CO) can be used. 8 ], metal tetracarbonyl nickel [Ni (CO) 4 ] and other metal carbonyl complexes. In addition, zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
The solvent used is not particularly limited as long as it can dissolve the metal ion (metal ion source) and the hyperbranched polymer at a desired concentration or more, but specific examples include ethanol, propanol, and the like. Alcohols; halogenated hydrocarbons such as dichloromethane and chloroform; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile, butyronitrile, and a mixture of these solvents Preferred examples include tetrahydrofuran.
The temperature at which the metal ion source is mixed with the hyperbranched polymer can be in the range of usually 0 ° C to the boiling point of the solvent.

又，進而作為另外的直接還原方法，藉由添加金屬離子源、及後續所期望的溶劑至在含有超支化聚合物的反應系內，並使其進行熱分解反應，而可得到作為目標的金屬微粒子複合物。
作為於此所使用的金屬離子源，可使用上述之金屬鹽或金屬羰基錯合物或其他的0價的金屬錯合物、氧化銀等的金屬氧化物。
作為使用的溶劑，只要是能以所需濃度以上來溶解金屬離子(金屬離子源)與超支化聚合物的溶劑即可，並無特別限定，但具體而言可舉出甲醇、乙醇、n-丙醇、異丙醇、乙二醇等的醇類；二氯甲烷、氯仿等的鹵化烴類；四氫呋喃(THF)、2-甲基四氫呋喃、四氫吡喃等的環狀醚類；乙腈、丁腈等的腈類；苯、甲苯等的芳香族烴類等及該等的溶劑的混合液，較佳可舉出甲苯。
將金屬離子源與超支化聚合物進行混合的溫度係可使用通常為0℃～溶劑的沸點的範圍，較佳為溶劑的沸點附近，例如，若為甲苯之情形時，則為110℃(加熱迴流)。Furthermore, as another direct reduction method, a target metal can be obtained by adding a metal ion source and a subsequent desired solvent to a reaction system containing a hyperbranched polymer and subjecting it to a thermal decomposition reaction. Microparticle complex.
As the metal ion source used herein, the aforementioned metal salts, metal carbonyl complexes, other zero-valent metal complexes, and metal oxides such as silver oxide can be used.
The solvent to be used is not particularly limited as long as it can dissolve the metal ion (metal ion source) and the hyperbranched polymer at a desired concentration or more, but specific examples include methanol, ethanol, and n- Alcohols such as propanol, isopropanol, ethylene glycol; halogenated hydrocarbons such as dichloromethane, chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran; acetonitrile, Nitriles such as butyronitrile; aromatic hydrocarbons such as benzene and toluene; and a mixed solution of these solvents, preferably, toluene is used.
The temperature at which the metal ion source is mixed with the hyperbranched polymer is generally in the range of 0 ° C to the boiling point of the solvent, preferably near the boiling point of the solvent. For example, in the case of toluene, it is 110 ° C (heating). Reflux).

＜藉由配位子交換法之金屬微粒子複合物之形成＞
藉由直接添加金屬微粒子至反應系內來取代上述之直接還原方法，亦可形成金屬微粒子複合物。
本方法，詳細而言係利用低階銨配位子來合成某一程度穩定化的金屬微粒子後，藉由以超支化聚合物來進行配位子交換，而形成複合物。
配位子交換法中，作為原料的利用低階銨配位子而成為某一程度穩定化的金屬微粒子，係可利用Jounal of Organometallic Chemistry 1996, 520, 143-162等所記載之方法來進行合成。藉由將所得到的金屬微粒子的反應混合溶液，與含有超支化聚合物的反應系進行混合，並以室溫(大約25℃)或進行加熱攪拌，而可得到作為目標的金屬微粒子複合物。
作為使用的溶劑，只要是能以所需濃度以上來溶解金屬微粒子與超支化聚合物的溶劑即可，並無特別限定，但具體而言可舉出乙醇、n-丙醇、異丙醇等的醇類；二氯甲烷、氯仿等的鹵化烴類；四氫呋喃(THF)、2-甲基四氫呋喃、四氫吡喃等的環狀醚類；乙腈、丁腈等的腈類等及該等的溶劑的混合液，較佳可舉出四氫呋喃。
將金屬微粒子的反應混合液與含有超支化聚合物的反應系進行混合的溫度，係可使用通常為0℃～溶劑的沸點的範圍，較佳為室溫(大約25℃)～60℃的範圍。
尚，配位子交換法中，除了胺系分散劑(低階銨配位子)以外，亦可使用膦系分散劑(膦配位子)來將金屬微粒子預先穩定化至某一程度。＜ Formation of metal microparticle complex by ligand exchange method ＞
Instead of the direct reduction method described above, metal fine particles can be directly added to the reaction system to form metal fine particle composites.
In this method, in detail, after a certain degree of stabilized metal fine particles are synthesized using a low-order ammonium ligand, a complex is formed by performing a ligand exchange with a hyperbranched polymer.
In the ligand exchange method, low-order ammonium ligands are used as raw materials to stabilize metal particles to a certain degree, and they can be synthesized by methods described in Jounal of Organometallic Chemistry 1996, 520, 143-162, etc. . The target metal fine particle composite can be obtained by mixing the reaction mixture solution of the obtained metal fine particles with a reaction system containing a hyperbranched polymer and heating and stirring at room temperature (about 25 ° C) or by heating.
The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the hyperbranched polymer at a desired concentration or more, but specific examples include ethanol, n-propanol, and isopropanol. Alcohols; halogenated hydrocarbons such as methylene chloride, chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile, butyronitrile, and the like Tetrahydrofuran is preferably used as the solvent mixture.
The temperature at which the reaction mixture of the metal fine particles and the reaction system containing the hyperbranched polymer is mixed can be in the range of usually 0 ° C to the boiling point of the solvent, preferably room temperature (about 25 ° C) to 60 ° C. .
In the ligand exchange method, in addition to an amine-based dispersant (low-order ammonium ligand), a phosphine-based dispersant (phosphine ligand) may be used to stabilize the metal fine particles in advance to a certain degree.

如此般所得到的超支化聚合物與金屬微粒子的複合物，經過再沉澱等的純化處理，可使成為粉末等的固形物的形態。

[實施例]The complex of the hyperbranched polymer and metal fine particles obtained in this manner can be converted into a solid form such as a powder through a purification process such as reprecipitation.

[Example]

以下，舉出實施例來更具體地說明本發明，但本發明並不被限定於下述之實施例中。
尚，於實施例中，樣品的調製及物性的分析中使用的裝置及條件係如以下般。
(1)GPC(凝膠滲透色譜法)
裝置：Tosoh(股)製HLC-8220GPC
管柱：昭和電工(股)製Shodex(註冊商標)KF-804L+ KF-803L
管柱溫度：40℃
溶劑：四氫呋喃
檢測器：UV(254nm)、RI
(2)1 H NMR頻譜
裝置：日本電子(股)製JNM-L400
溶劑：CDCl3
內部標準：四甲基矽烷(0.00ppm)
(3)ICP發光分析(感應耦合等離子發光分析)
裝置：島津製作所(股)製ICPM-8500
(4)TEM(穿透式電子顯微鏡)影像
裝置：Hitachi High-Technologies(股)製H-8000Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
In the examples, the devices and conditions used for the preparation of samples and analysis of physical properties are as follows.
(1) GPC (gel permeation chromatography)
Device: HLC-8220GPC made by Tosoh
Column: Showa Denko Shodex (registered trademark) KF-804L + KF-803L
Column temperature: 40 ℃
Solvent: Tetrahydrofuran Detector: UV (254nm), RI
(2) 1 H NMR spectrum device: JNM-L400 manufactured by Japan Electronics Co., Ltd.
Solvent: CDCl 3
Internal standard: tetramethylsilane (0.00ppm)
(3) ICP luminescence analysis (inductively coupled plasma luminescence analysis)
Installation: ICPM-8500, manufactured by Shimadzu Corporation
(4) TEM (transmission electron microscope) imaging device: H-8000, manufactured by Hitachi High-Technologies

又，所使用的簡稱代號係如以下般。
HPS：超支化聚苯乙烯[日產化學工業(股)製
HYPERTECH (註冊商標)HPS-200]
IPA：2-丙醇
IPE：二異丙基醚The abbreviations used are as follows.
HPS: Hyperbranched Polystyrene [Made by Nissan Chemical Industries, Ltd.]
HYPERTECH (registered trademark) HPS-200]
IPA: 2-propanol
IPE: Diisopropyl ether

[製造例1]HPS-Cl的製造



在500mL的反應燒瓶中裝入硫醯氯(sulfuryl chloride) [Kishida Chemical(股)製]27g及氯仿50g，進行攪拌使其均勻地溶解。在氮氣流下將該溶液冷卻至0℃為止。
在另一個300mL的反應燒瓶中裝入在分子末端具有二硫代胺基甲酸酯基的超支化聚合物HPS15g及氯仿150g，在氮氣流下進行攪拌直到呈均勻為止。
在氮氣流下，使用送液泵，從裝有HPS/氯仿溶液的前述300mL的反應燒瓶，以反應液的溫度成為-5～5℃之方式並以60分鐘來添加該溶液至前述之冷卻至0℃的硫醯氯/氯仿溶液中。添加結束後，一邊將反應液的溫度維持在-5～5℃一邊攪拌6小時。
進而，對於該反應液，以反應液的溫度成為-5～5℃之方式，添加氯仿50g中為溶解有環己烯[東京化成工業(股)製]16g的溶液。添加結束後，將該反應液添加至IPA1,200g中，並使聚合物沉澱。將該沉澱予以過濾取出而得到白色粉末，將該白色粉末溶解至氯仿100g中，將此者添加至IPA500g中並使聚合物再沉澱。將該沉澱物進行減壓過濾，並進行真空乾燥，從而得到作為白色粉末的在分子末端具有氯原子的超支化聚合物(HPS-Cl)8.5g (收率99%)。
將所得到的HPS-Cl的1 H NMR頻譜表示於圖1。因源自於二硫代胺基甲酸酯基的波峰(4.0ppm、3.7ppm)為消失，故可明確得知所得到的HPS-Cl係HPS分子末端的二硫代胺基甲酸酯基幾乎全部被取代成氯原子。又，所得到的HPS-Cl的藉由以GPC之聚苯乙烯換算所測得的重量平均分子量Mw為14,000、分散度Mw/Mn為2.9。[Production Example 1] Production of HPS-Cl



A 500 mL reaction flask was charged with 27 g of sulfuryl chloride [manufactured by Kishida Chemical Co., Ltd.] and 50 g of chloroform, and stirred to dissolve them uniformly. The solution was cooled to 0 ° C under a stream of nitrogen.
A 300 mL reaction flask was charged with 15 g of a hyperbranched polymer HPS having a dithiocarbamate group at the molecular end and 150 g of chloroform, and the mixture was stirred under a nitrogen flow until uniform.
Under a nitrogen flow, using a liquid feed pump, from a 300 mL reaction flask containing an HPS / chloroform solution, the solution was added so that the temperature of the reaction solution became -5 to 5 ° C and the solution was cooled to 0 to 60 minutes before Thiochlorine / chloroform solution at ℃. After the addition was completed, the reaction solution was stirred for 6 hours while maintaining the temperature of the reaction solution at -5 to 5 ° C.
Further, to this reaction solution, a solution in which 16 g of cyclohexene [manufactured by Tokyo Chemical Industry Co., Ltd.] was dissolved in 50 g of chloroform was added so that the temperature of the reaction liquid became -5 to 5 ° C. After the addition was completed, the reaction solution was added to 1,200 g of IPA, and a polymer was precipitated. This precipitate was filtered and taken out to obtain a white powder. This white powder was dissolved in 100 g of chloroform, and this was added to 500 g of IPA to reprecipitate the polymer. This precipitate was filtered under reduced pressure and vacuum-dried to obtain 8.5 g of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular terminal as a white powder (yield: 99%).
The 1 H NMR spectrum of the obtained HPS-Cl is shown in FIG. 1. Since the peak (4.0 ppm, 3.7 ppm) derived from the dithiocarbamate group disappears, the dithiocarbamate group at the end of the obtained HPS-Cl-based HPS molecule is clearly known Almost all are replaced with chlorine atoms. The weight average molecular weight Mw of the obtained HPS-Cl measured in terms of GPC polystyrene was 14,000, and the degree of dispersion Mw / Mn was 2.9.

[實施例1]
在反應燒瓶中裝入製造例1所製造的HPS-Cl(763mg)及氯仿(2.5g)，並進行攪拌直到呈均勻為止。對於該溶液，添加在另外容器中所調製的N,N-二甲基辛基胺(825mg)的氯仿(1.25g)溶液後，在前述容器內使用氯仿(1.25g)來洗滌前述含HPS-Cl之溶液。進而，加入乙醇(1.25g)，以氮環境下60℃來加熱攪拌該混合物8小時。將所得到的溶液冷卻至室溫為止(溶液A)。[Example 1]
The reaction flask was charged with HPS-Cl (763 mg) and chloroform (2.5 g) produced in Production Example 1, and stirred until homogeneous. To this solution, a chloroform (1.25 g) solution of N, N-dimethyloctylamine (825 mg) prepared in a separate container was added, and the aforementioned HPS-containing solution was washed with chloroform (1.25 g) in the container. Cl solution. Further, ethanol (1.25 g) was added, and the mixture was heated and stirred at 60 ° C. under a nitrogen atmosphere for 8 hours. The obtained solution was cooled to room temperature (solution A).

預先在另外容器中調製氯仿(8.45g)中為溶解有乙酸鈀(1.43g)的溶液，並將此者加入至先前所調製的溶液A中，在前述容器內使用氯仿(800mg)來洗滌前述溶液A。以氮環境下、50℃來加熱攪拌該溶液6小時後，冷卻至室溫為止(溶液B)。A solution in which palladium acetate (1.43 g) was dissolved in another container was prepared in advance in a separate container, and this was added to the previously prepared solution A. The foregoing container was washed with chloroform (800 mg). Solution A. The solution was heated and stirred under a nitrogen atmosphere at 50 ° C. for 6 hours, and then cooled to room temperature (solution B).

對於IPE(185.7g)/己烷(18.6g)混合溶液倒入溶液B，並進行再沉澱純化。過濾分離已析出的黑色粉末，並以50℃下將該粉末進行真空乾燥，從而得到作為黑色粉末的在分子末端具有銨基的超支化聚合物與Pd粒子的複合物(Pd[HPS-N(Me)2 OctCl])1.27g。
從ICP發光分析的結果可得知，所得到的Pd[HPS-N(Me)2 OctCl]的Pd含有量為42.6質量%。
又，將所得到的複合物的TEM影像表示於圖2、以及圖3(圖2的放大圖)。經TEM觀察，藉由所得到的複合物而被穩定化的金屬微粒子的粒徑為2～5nm，此者和藉由將銨鹽(在末端具有銨基的超支化聚合物)進行離析後再與金屬微粒子反應而得到的以往製法的複合物相比時，係具有相同程度的大小。For IPE (185.7 g) / hexane (18.6 g) mixed solution was poured into solution B, and reprecipitation purification was performed. The precipitated black powder was separated by filtration, and the powder was vacuum-dried at 50 ° C. to obtain a composite of a hyperbranched polymer having an ammonium group at the molecular terminal and Pd particles (Pd [HPS-N ( Me) 2 OctCl]) 1.27 g.
From the results of ICP emission analysis, it was found that the Pd content of the obtained Pd [HPS-N (Me) 2 OctCl] was 42.6% by mass.
The TEM images of the obtained composite are shown in FIG. 2 and FIG. 3 (enlarged view of FIG. 2). The TEM observation showed that the particle size of the metal fine particles stabilized by the obtained composite was 2 to 5 nm, and this was after the ammonium salt (a hyperbranched polymer having an ammonium group at the end) was isolated. Compared with the composite produced by the conventional manufacturing method obtained by the reaction of metal fine particles, it has the same size.

[參考例1]無電解鎳鍍敷液之調製
在2L的燒杯中裝入Kanigen(註冊商標)BLUE SUMER [日本Kanigen(股)製]40mL，進而加入純水將溶液的總量設為200mL。將該溶液進行攪拌並作為無電解鎳鍍敷液。[Reference Example 1] Preparation of Electroless Nickel Plating Solution A 2L beaker was charged with 40 mL of Kanigen (registered trademark) BLUE SUMER [manufactured by Kanigen (Japan)], and pure water was added to set the total solution to 200 mL. This solution was stirred and used as an electroless nickel plating solution.

[參考例2：作為無電解鍍敷底塗劑之使用]
將實施例1所得到的在分子末端具有銨基的超支化聚合物與Pd粒子的複合物(Pd[HPS-N(Me)2 OctCl])(100mg)溶解至1-丙基醇(10g)中，從而得到無電解鍍敷底塗劑。利用桿塗，將所得到的無電解鍍敷底塗劑塗佈至PET薄膜(東洋紡Cosmoshine A-400)上。以80℃將此者進行乾燥，從而得到在PET薄膜的單面上具備有基底層的PET薄膜。
將該PET薄膜浸漬在已加熱至90℃的參考例1所調製的無電解鎳鍍敷液中2分鐘。取出PET薄膜並以目視來觀察時，確認在底塗劑(觸媒)塗佈面上可得到鎳鍍敷層。[Reference Example 2: Use as an electroless plating primer]
The complex (Pd [HPS-N (Me) 2 OctCl]) (100 mg) of the hyperbranched polymer having an ammonium group at the molecular terminal and Pd particles obtained in Example 1 was dissolved in 1-propyl alcohol (10 g) Medium, thereby obtaining an electroless plating primer. The obtained electroless plating primer was applied to a PET film (Toyobo Cosmoshine A-400) by rod coating. This was dried at 80 ° C to obtain a PET film having a base layer on one side of the PET film.
This PET film was immersed in an electroless nickel plating solution prepared in Reference Example 1 heated to 90 ° C for 2 minutes. When the PET film was taken out and visually observed, it was confirmed that a nickel plating layer was obtained on the primer (catalyst) coating surface.

如上述般，經TEM觀察，藉由本發明之製造方法所得到的金屬微粒子複合物係具有大約2～5nm左右的粒徑。又，和使用以往製法的複合物(其係藉由離析銨鹽後再與金屬微粒子反應而得到者)之情形為相同地，藉由本發明之製造方法所得到的金屬微粒子複合物在作為無電解鍍敷底塗劑的材料使用時，可得到鍍敷層，並經確認和藉由以往製法的複合物為具有同等的觸媒活性。As described above, when observed by TEM, the metal fine particle composite system obtained by the production method of the present invention has a particle diameter of about 2 to 5 nm. In the same manner as in the case of using a composite produced by a conventional method (which is obtained by isolating an ammonium salt and reacting with metal fine particles), the metal fine particle composite obtained by the production method of the present invention is electroless When the material of the plating primer is used, a plating layer can be obtained, and it has been confirmed that the composite produced by the conventional method has the same catalytic activity.

[圖1]圖1表示製造例1所製造的在分子末端具有氯原子的超支化聚合物(HPS-Cl)的1 H NMR頻譜之圖。[Fig. 1] Fig. 1 shows a 1 H NMR spectrum of a hyperbranched polymer (HPS-Cl) having a chlorine atom at a molecular terminal produced in Production Example 1. [Fig.

[圖2]圖2表示實施例1所製造的在分子末端具有銨基的超支化聚合物與Pd粒子的複合物(Pd[HPS-N(Me)2 OctCl])的TEM影像之圖(標尺杆：20nm)。[Fig. 2] Fig. 2 shows a TEM image of a complex (Pd [HPS-N (Me) 2 OctCl]) of a hyperbranched polymer having an ammonium group at the molecular end and Pd particles produced in Example 1 (scale bar) Rod: 20nm).

[圖3]圖3表示實施例1所製造的在分子末端具有銨基的超支化聚合物與Pd粒子的複合物(Pd[HPS-N(Me)2 OctCl])的TEM影像之圖(標尺杆：5nm)。[Fig. 3] Fig. 3 shows a TEM image of a complex (Pd [HPS-N (Me) 2 OctCl]) of a hyperbranched polymer having an ammonium group at the molecular end and Pd particles produced in Example 1 (scale bar) Rod: 5nm).

Claims (4)

一種金屬微粒子複合物之製造方法，其特徵係包含下述步驟： 在反應系內將式[1]所表示的在末端具有鹵素基的超支化聚合物與式[3]所表示的胺化合物進行反應，來調製式[4]所表示的在末端具有銨基的超支化聚合物之步驟； 接續於前述調製步驟之後，以還原劑的存在下添加金屬鹽至該反應系內之步驟、或者直接添加金屬微粒子至該反應系內之步驟， ｛式[1]中，X表示鹵素原子，R1 分別獨立表示氫原子或甲基，A1 表示式[2]所表示的構造， (式中，A2 表示可包含醚鍵或酯鍵的碳原子數1至30的直鏈狀、支鏈狀或環狀的伸烷基，Y1 至Y4 分別獨立表示氫原子、碳原子數1至20的烷基、碳原子數1至20的烷氧基、硝基、羥基、胺基、羧基或氰基)，n為重複單位構造的數量且表示2至100,000的整數｝； ｛R2 至R4 分別獨立表示氫原子、碳原子數1至20的直鏈狀、支鏈狀或環狀的烷基、碳原子數7至20的芳基烷基或-(CH2 CH2 O)m R5 (式中，R5 表示氫原子或甲基，m表示2～100的任意的整數)，上述烷基及芳基烷基可被烷氧基、羥基、銨基、羧基或氰基所取代，又，R2 至R4 中的2個基可在一起而表示直鏈狀、支鏈狀或環狀的伸烷基，或R2 至R4 與此等所鍵結的氮原子可在一起而形成環｝； (R1 、R2 至R4 、A1 及n表示與前述相同的意義，X- 表示鹵素原子的陰離子)。A method for producing a metal microparticle composite, which comprises the following steps: a reaction system comprising a hyperbranched polymer having a halogen group at a terminal represented by formula [1] and an amine compound represented by formula [3]; Reaction to prepare a step of a hyperbranched polymer having an ammonium group at the terminal represented by formula [4]; following the above-mentioned preparation step, a step of adding a metal salt to the reaction system in the presence of a reducing agent, or directly The step of adding metal particles to the reaction system, In formula [1], X represents a halogen atom, R 1 independently represents a hydrogen atom or a methyl group, and A 1 represents a structure represented by formula [2]. (In the formula, A 2 represents a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, which may include an ether bond or an ester bond, and Y 1 to Y 4 each independently represent a hydrogen atom and a carbon atom. Alkyl groups of 1 to 20, alkoxy groups of 1 to 20 carbon atoms, nitro, hydroxyl, amino, carboxyl or cyano), n is the number of repeating unit structures and represents an integer of 2 to 100,000; ｛R 2 to R 4 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or-(CH 2 CH 2 O) m R 5 (wherein R 5 represents a hydrogen atom or a methyl group, and m represents an arbitrary integer from 2 to 100), and the alkyl and arylalkyl groups may be alkoxy, hydroxyl, ammonium, or carboxyl Or cyano substituted, and two of R 2 to R 4 may be taken together to represent a linear, branched, or cyclic alkylene, or R 2 to R 4 are bonded thereto Nitrogen atoms can form together to form a ring｝; (R 1 , R 2 to R 4 , A 1 and n have the same meanings as described above, and X − represents an anion of a halogen atom). 如請求項1之金屬微粒子複合物之製造方法，其中，包含以還原劑的存在下添加金屬鹽至前述反應系內之步驟。The method for producing a metal fine particle composite according to claim 1, further comprising the step of adding a metal salt to the aforementioned reaction system in the presence of a reducing agent. 如請求項1或2之金屬微粒子複合物之製造方法，其中，使用醇溶劑來作為前述還原劑。The method for producing a metal fine particle composite according to claim 1 or 2, wherein an alcohol solvent is used as the reducing agent. 一種金屬微粒子複合物，其係使用如請求項1～3中任一項之金屬微粒子複合物之製造方法而得到。A metal fine particle composite obtained by using the method for producing a metal fine particle composite according to any one of claims 1 to 3.
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