JP2798358B2 - Method for producing polymer composite in which fine particles are dispersed - Google Patents

Method for producing polymer composite in which fine particles are dispersed

Info

Publication number
JP2798358B2
JP2798358B2 JP25461794A JP25461794A JP2798358B2 JP 2798358 B2 JP2798358 B2 JP 2798358B2 JP 25461794 A JP25461794 A JP 25461794A JP 25461794 A JP25461794 A JP 25461794A JP 2798358 B2 JP2798358 B2 JP 2798358B2
Authority
JP
Japan
Prior art keywords
polymer
metal
layer
polymer layer
fine particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP25461794A
Other languages
Japanese (ja)
Other versions
JPH0892415A (en
Inventor
浩一 佐用
和生 後藤
良雄 山口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsuboshi Belting Ltd
Original Assignee
Mitsuboshi Belting Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsuboshi Belting Ltd filed Critical Mitsuboshi Belting Ltd
Priority to JP25461794A priority Critical patent/JP2798358B2/en
Publication of JPH0892415A publication Critical patent/JPH0892415A/en
Application granted granted Critical
Publication of JP2798358B2 publication Critical patent/JP2798358B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Landscapes

  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は微粒子を分散させた高分
子複合物の製造方法に係り、詳しくはナイロン１１から
なる高分子を熱分解した後に冷却して再生高分子を作製
し、この再生高分子から得られた高分子層の表面に金属
を密着した後に、この高分子層を加熱して金属あるいは
金属酸化物の微粒子を高分子層中に分散させる高分子複
合物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer composite in which fine particles are dispersed, and more particularly, to a method for producing a polymer composite from nylon 11.
The polymer is thermally decomposed and then cooled to produce a regenerated polymer. After a metal is adhered to the surface of the polymer layer obtained from the regenerated polymer, the polymer layer is heated to form a metal or metal oxide. The present invention relates to a method for producing a polymer composite in which fine particles of a substance are dispersed in a polymer layer.

【０００２】[0002]

【従来の技術】今日、金属あるいは金属酸化物の微粒子
−高分子複合物の製造方法として、高分子を真空蒸着し
て得られた熱力学的に準安定構造を有する高分子層に真
空蒸着して得られた金属層を積層した後、この高分子層
を熱力学的に安定させることによって金属層の金属を超
微粒子化させることが提案され、特開平３−２７３０６
０号公報に開示されている。2. Description of the Related Art Today, as a method for producing a metal-metal oxide fine particle-polymer composite, a polymer layer having a thermodynamically metastable structure obtained by vacuum-depositing a polymer is vacuum-deposited. It has been proposed that, after laminating the obtained metal layers, the polymer layer is thermodynamically stabilized to make the metal of the metal layer ultrafine.
No. 0 discloses this.

【０００３】あるいは、他の方法としては、特開平４−
３５６５２９号公報に記載されているように、高分子を
加熱して低粘度の液体とし、これを１００℃／秒以上の
冷却速度で超冷却して熱力学的に準安定構造を有する高
分子層を作製し、この高分子の表面に金属層を密着した
後、該融解温度以下で加熱して高分子層を安定化させる
ことで金属層の金属を微粒子化して高分子層内に分散さ
せる方法がある。このようにして得られた高分子複合物
は、例えば有機溶剤に溶解してペーストとし、これをセ
ラミックス基材上へ塗布することによって電極、配線、
回路等を作製していた。[0003] Alternatively, another method is disclosed in
As described in JP-A-356529, a polymer is heated to form a low-viscosity liquid, which is supercooled at a cooling rate of 100 ° C./sec or more, and a polymer layer having a thermodynamically metastable structure. A method in which a metal layer is adhered to the surface of the polymer, and then heated at a temperature equal to or lower than the melting temperature to stabilize the polymer layer so that the metal of the metal layer is finely divided and dispersed in the polymer layer. There is. The polymer composite obtained in this manner is, for example, dissolved in an organic solvent to form a paste, and the paste is applied to a ceramic substrate to form an electrode, wiring,
Circuits and the like were being manufactured.

【０００４】また、一方、金属だけでなく有機色素も同
様に熱力学的に準安定構造を有する高分子層に色素蒸着
膜を作製した後、高分子層を熱処理することによって１
分子から数分子のクラスターとして高分子中に分散させ
ていた。この色素分子を分散させた高分子複合物は光学
フィルター、非線型光学素子等に応用されようとしてい
る。On the other hand, not only metals but also organic dyes are similarly thermodynamically prepared by forming a dye-deposited film on a polymer layer having a metastable structure and then subjecting the polymer layer to heat treatment.
It was dispersed in the polymer as a cluster of molecules to several molecules. The polymer composite in which the dye molecules are dispersed is going to be applied to optical filters, non-linear optical elements and the like.

【０００５】[0005]

【発明が解決しようとする課題】上記高分子複合物を作
製する過程で、熱力学的に準安定構造を有する高分子層
を作製する必要がある。真空蒸着や金型に流し込んで急
冷固化する方法が実験的にも容易でしかも確実に実施で
きるところから一般的であった。しかし、このような方
法では、熱力学的に準安定構造を有する高分子層や高分
子複合物を短時間に多量に生産することはできない大き
な問題があった。本発明は、このような問題点を改善す
るものであり、熱力学的に準安定構造を有するナイロン
１１の再生高分子を多量に回収し、この再生高分子を用
いて金属あるいは金属酸化物の微粒子を高分子層中に分
散させることができる高分子複合物の製造方法を提供す
ることを目的とする。In the process of preparing the above-mentioned polymer composite, it is necessary to prepare a polymer layer having a thermodynamically metastable structure. A method of vacuum solidification and rapid cooling and solidification by pouring into a mold has been generally used because it can be easily and experimentally performed. However, such a method has a serious problem in that a large amount of a polymer layer or a polymer composite having a thermodynamically metastable structure cannot be produced in a short time. The present invention has been made to solve such a problem, and a nylon having a thermodynamically metastable structure is provided.
A method for producing a polymer composite which can recover a large amount of the regenerated polymer of No. 11 and disperse metal or metal oxide fine particles in the polymer layer using the regenerated polymer. I do.

【０００６】[0006]

【課題を解決するための手段】即ち、本発明の微粒子を
分散させた高分子複合物の製造方法においては、減圧下
にある閉鎖した空間でナイロン１１からなる高分子材料
を熱分解して気化し、この気化物を該空間の非加熱領域
で冷却固化することで熱力学的に準安定構造を有するペ
ースト状のナイロン１１の再生高分子を回収し、この再
生高分子から得られた薄膜の高分子層の表面に真空蒸着
により得られた金属層を付着した後、高分子層を加熱し
て金属層から微粒子化した金属あるいは金属酸化物の微
粒子を高分子層内に分散させる方法にある。That is, in the method of the present invention for producing a polymer composite in which fine particles are dispersed, a polymer material made of nylon 11 is thermally decomposed in a closed space under reduced pressure. Paix However, having a thermodynamically metastable structure by cooling and solidifying the vapor product in a non-heated region of the space
The recycled polymer of nylon 11 in the form of a paste is recovered , and a metal layer obtained by vacuum evaporation is adhered to the surface of the polymer layer of the thin film obtained from the recycled polymer. There is a method of dispersing fine particles of metal or metal oxide from the layer into the polymer layer.

【０００７】[0007]

【０００８】本発明方法の第１の工程は、図１に示す装
置により再生高分子を作製する。この再生高分子の製造
装置１は高分子材料を熱分解した後に冷却固化するガラ
ス管２、高分子材料を加熱する加熱炉３、そしてガラス
管２内を減圧にする減圧装置４からなっている。In the first step of the method of the present invention, a regenerated polymer is produced using the apparatus shown in FIG. The apparatus 1 for producing a recycled polymer comprises a glass tube 2 for thermally decomposing and solidifying a polymer material, and a heating furnace 3 for heating the polymer material, and a pressure reducing device 4 for reducing the pressure inside the glass tube 2. .

【０００９】上記ガラス管２は電気炉からなる加熱炉３
に挿入され、ナイロン１１のペレットからなる高分子材
料５を入れた容器６を加熱するようになっている。ガラ
ス管２の両端領域は加熱炉３から左右に突出して露出
し、一方の端部７は栓等の開閉器８により開閉可能にな
り、高分子材料５を容器６に入れる挿入口になってい
る。また他方の端部１０は、ガラス管２内を減圧にする
ために配管１１を連結している。この管１１は開閉弁１
２、トラップ１３、ロータリーポンプ１４からなる減圧
装置４に連結している。The glass tube 2 is a heating furnace 3 composed of an electric furnace.
To heat a container 6 containing a polymer material 5 composed of nylon 11 pellets. Both end regions of the glass tube 2 project right and left from the heating furnace 3 and are exposed, and one end 7 can be opened and closed by a switch 8 such as a stopper, and serves as an insertion port for putting the polymer material 5 into the container 6. I have. The other end 10 is connected to a pipe 11 to reduce the pressure inside the glass tube 2. This pipe 11 is an on-off valve 1
2, a trap 13 and a rotary pump 14 connected to a decompression device 4.

【００１０】まずガラス管２の開閉器８を開けた後、ガ
イド棒（図示せず）により容器６を入口まで移動させて
高分子材料５を容器６に入れ、そして容器６をガイド棒
により加熱領域まで押し込んで設置する。その後、開閉
器８を閉じ開閉弁１２を開放してロータリーポンプ１４
の作動により、ガラス管２内を１０-2〜１０-4ｔｏｒｒ
まで減圧し、これを維持する。そして、加熱炉３によっ
て高分子材料５を熱分解するまで加熱して気化させた
後、気化物を加熱炉３から突出したガラス管２の空冷領
域１７で付着させ、再生高分子１９を回収する。First, after the switch 8 of the glass tube 2 is opened, the container 6 is moved to the inlet by a guide rod (not shown), the polymer material 5 is put into the container 6, and the container 6 is heated by the guide rod. Push down to the area and install. Thereafter, the switch 8 is closed, the on-off valve 12 is opened, and the rotary pump 14 is opened.
, The inside of the glass tube 2 is 10 −2 to 10 −4 torr.
Reduce pressure and maintain. Then, the polymer material 5 is heated and vaporized by the heating furnace 3 until the polymer material 5 is thermally decomposed, and then the vaporized substance is adhered to the air-cooled region 17 of the glass tube 2 protruding from the heating furnace 3 to recover the regenerated polymer 19. .

【００１１】得られたナイロン１１の再生高分子１９
は、分子量１，０００〜５，０００の低粘度のペースト
状あるいは硬度の小さい柔軟な固形物状の高分子であ
り、熱力学的に準安定構造を有する材料になっている。
これは元の高分子材料の分子量に比べて１／１０〜１／
１００程度にかなり小さくなっている。また再生高分子
１９は、溶剤を含んでいないために室温雰囲気下に放置
しても粘度等に変化を起こさない。Regenerated polymer 19 of nylon 11 obtained
Is a low-viscosity paste-like polymer having a molecular weight of 1,000 to 5,000 or a soft solid material having a small hardness, and is a material having a thermodynamically metastable structure.
This is 1/10 to 1/1 / of the molecular weight of the original polymer material.
It is quite small, about 100. Further, since the regenerated polymer 19 does not contain a solvent, it does not change in viscosity or the like even when left in an atmosphere at room temperature.

【００１２】[0012]

【００１３】次いで、第２工程として図２に示すよう
に、再生高分子１９をガラス等に基材２０上に設置した
後に、ロールで押し付けて厚さ０．００５〜０．１ｍｍ
の薄膜の高分子層２１を作製する。このように高分子層
２１を薄膜にするのは、後述するように金属もしくは金
属酸化物の微粒子を全体にわたって均一に分散させるた
めである。Next, as shown in FIG. 2, as a second step, the recycled polymer 19 is placed on a substrate 20 on glass or the like, and then pressed with a roll to a thickness of 0.005 to 0.1 mm.
A thin polymer layer 21 is prepared. The reason why the polymer layer 21 is formed into a thin film is to uniformly disperse metal or metal oxide fine particles throughout as described later.

【００１４】続いて、基材２０上に設置された再生高分
子からなる高分子層２１は、図３に示すようにその表面
に金属層２３を密着させる工程へ移される。この工程で
は真空蒸着装置によって金属を高分子層２１表面に蒸着
させるか、もしくは金属箔、金属板を直接高分子層２１
に密着させる等の方法で金属層２３を高分子層２１に積
層させる。その金属材料としては金、銀、白金、銅、
鉄、ニッケル、コバルト、スズ、亜鉛、セリウム、イッ
トリウム等であり、特に限定されない。Subsequently, the polymer layer 21 made of the regenerated polymer placed on the base material 20 is moved to a step of bringing the metal layer 23 into close contact with the surface as shown in FIG. In this step, a metal is vapor-deposited on the surface of the polymer layer 21 by a vacuum vapor deposition device, or a metal foil or a metal plate is directly
The metal layer 23 is laminated on the polymer layer 21 by, for example, bringing the polymer layer into close contact with the polymer layer 21. Gold, silver, platinum, copper,
Iron, nickel, cobalt, tin, zinc, cerium, yttrium and the like are not particularly limited.

【００１５】金属層２２と高分子層２１とを密着した積
層物２４を加熱し、高分子層２１を安定状態へ移行さ
せ、高分子複合物２６を得る。この工程では前記金属層
付の高分子層２１を恒温槽中で高分子材料の融解温度以
下において加熱する。その結果、図４に示されるように
金属層２２の金属は、粒径１，０００ｎｍ以下、好まし
くは３００ｎｍ以下、より好ましくは１００ｎｍ以下の
金属もしくは金属酸化物の微粒子２５となって高分子層
２１内へ拡散浸透し、この状態は高分子層２１が完全に
緩和するまで続く。高分子層２１に付着している金属層
２２はその厚さも減少して最終的に無くなる。The laminate 24 in which the metal layer 22 and the polymer layer 21 are in close contact with each other is heated to shift the polymer layer 21 to a stable state, thereby obtaining a polymer composite 26. In this step, the polymer layer 21 with the metal layer is heated in a thermostat at a temperature lower than the melting temperature of the polymer material. As a result, as shown in FIG. 4, the metal of the metal layer 22 becomes fine particles 25 of a metal or metal oxide having a particle size of 1,000 nm or less, preferably 300 nm or less, more preferably 100 nm or less. This state continues until the polymer layer 21 is completely relaxed. The thickness of the metal layer 22 adhering to the polymer layer 21 also decreases and eventually disappears.

【００１６】前記微粒子２５が金属酸化物の場合には、
それはＣｕ2 Ｏ、Ｆｅ3 Ｏ4 、ＺｎＯ、Ｙ2 Ｏ3 等であ
る。When the fine particles 25 are a metal oxide,
It is Cu 2 O, Fe 3 O 4 , ZnO, Y 2 O 3 or the like.

【００１７】尚、この工程で高分子層２１を加熱する
と、高分子層２１が金属もしくは金属酸化物の微粒子２
５との相互作用で固有の着色を示し、金属もしくは金属
酸化物の微粒子２５が高分子層２１内へ浸透しているこ
とがわかる。また、この色は金属もしくは金属酸化物の
種類、金属もしくは金属酸化物の微粒子径、高分子の種
類により変化しうる。このようにして得られた高分子複
合物２６は、図４に示すように微粒子２５が独立した状
態で分離分散している。When the polymer layer 21 is heated in this step, the polymer layer 21 is coated with fine particles 2 of metal or metal oxide.
5 shows an intrinsic coloring due to the interaction with 5, and it can be seen that the fine particles 25 of metal or metal oxide have penetrated into the polymer layer 21. Also, this color can vary depending on the type of metal or metal oxide, the particle size of the metal or metal oxide, and the type of polymer. In the polymer composite 26 thus obtained, the fine particles 25 are separated and dispersed independently as shown in FIG.

【００１８】[0018]

【実施例】次に、本発明を具体的な実施例により更に詳
細に説明する。 実施例１ ナイロン１１のポリマーペレット１０ｇをガラス管の入
口付近に移動させた容器に入れた後、この容器をガイド
棒で加熱領域まで移動させ、入口を栓で閉じた。そし
て、開閉弁を開いてロータリーポンプを作動させてガラ
ス管内を１０-3ｔｏｒｒまで減圧にし、これを維持し
た。加熱炉を４００°Ｃまで上昇させてナイロン１１を
熱分解して気化させ、気化物を加熱炉から突出したガラ
ス管の空冷領域に徐々に付着させて茶褐色のペースト状
の再生高分子７ｇを得た。収率は７０％であった。Next, the present invention will be described in more detail with reference to specific examples. Example 1 After 10 g of nylon 11 polymer pellets were placed in a container moved near the entrance of a glass tube, the container was moved to a heating area with a guide rod, and the entrance was closed with a stopper. Then, the on-off valve was opened and the rotary pump was operated to reduce the pressure inside the glass tube to 10 −3 torr, and this was maintained. The heating furnace is heated to 400 ° C. to pyrolyze and vaporize the nylon 11, and the vaporized substance is gradually attached to the air-cooled region of the glass tube protruding from the heating furnace to obtain 7 g of a brownish paste-like regenerated polymer. Was. The yield was 70%.

【００１９】次いで、この再生高分子をガラス基材上に
載せると、ロールで押し付けて厚さ約１００μｍの薄膜
の高分子層を作製した。Next, when this regenerated polymer was placed on a glass substrate, it was pressed with a roll to form a thin polymer layer having a thickness of about 100 μm.

【００２０】この高分子層を積層したガラス基材を真空
蒸着装置内に投入し、金を電子ビームにより加熱融解し
て１０-4〜１０-6ｔｏｒｒの真空下で蒸着を行い、高分
子層の上に金蒸着膜を付着した後に、ガラス基材を真空
蒸着装置から取り出した。そして、これを１２０℃に設
定した恒温槽中に３０分間放置して高分子複合物を得
た。The glass substrate on which the polymer layer is laminated is put into a vacuum deposition apparatus, and gold is heated and melted by an electron beam to perform deposition under a vacuum of 10 -4 to 10 -6 torr. After depositing a gold deposition film on the glass substrate, the glass substrate was taken out of the vacuum deposition apparatus. This was left in a thermostat set at 120 ° C. for 30 minutes to obtain a polymer composite.

【００２１】得られた高分子複合物の表面の色、及びこ
の複合物をＸ線回析法によって得られる回析ピークの半
値幅からシェラーの式より微粒子のサイズを求めた。こ
の結果、上記高分子複合物の表面の色は、赤色であり、
微粒子のサイズは１〜５ｎｍであった。From the color of the surface of the obtained polymer composite and the half width of the diffraction peak obtained by X-ray diffraction of this composite, the size of the fine particles was determined by Scherrer's formula. As a result, the color of the surface of the polymer composite is red,
The size of the fine particles was 1 to 5 nm.

【００２２】また、前記高分子層の上に金蒸着膜を付着
した試料と、これを加熱した後の試料を入射角１．０°
の薄膜Ｘ線回折装置（理学電機社製ＲＩＮＴ１２００）
を用いて、Ｘ線回折パターンを測定した。その結果を図
５に示す。Further, a sample having a gold vapor-deposited film adhered on the polymer layer and a sample after heating the sample were placed at an incident angle of 1.0 °.
Thin film X-ray diffractometer (RINT1200 manufactured by Rigaku Corporation)
Was used to measure the X-ray diffraction pattern. The result is shown in FIG.

【００２３】このＸ線回折パターンにおいて、熱処理前
は高分子層と金蒸着膜との積層物であり、熱処理後はこ
の積層物を１２０℃で３０分恒温槽に放置して熱処理し
た後の複合物を示す。これによると熱処理前のパターン
では、金及びナイロン１１の回折ピークが出現してお
り、ナイロン１１の高分子層に金属の蒸着膜を積層した
構成であることを示している。また、熱処理後のパター
ンはナイロン１１の構造が変化し、熱処理によって緩和
していることがわかる。そして、金の回折ピーク幅（半
価幅）が大きくなっているところから、金が微粒子化し
てナイロン１１中に分散していることを示している。In this X-ray diffraction pattern, the composite before heat treatment was a laminate of a polymer layer and a gold vapor-deposited film, and after the heat treatment, the laminate was left in a thermostat at 120 ° C. for 30 minutes and heat-treated. Indicates an object. According to this, in the pattern before the heat treatment, diffraction peaks of gold and nylon 11 appeared, indicating that the structure was such that a metal vapor deposition film was laminated on the polymer layer of nylon 11. Further, it can be seen that the pattern after the heat treatment changed the structure of the nylon 11 and was relaxed by the heat treatment. And, from where the diffraction peak width (half-value width) of gold is large, it indicates that gold is finely divided and dispersed in nylon 11.

【００２４】また、図６は熱処理した後の複合物の光吸
収スペクトルを示すものであり、金微粒子のコロイド吸
収が見られ、金が微粒子化していることが判る。FIG. 6 shows the light absorption spectrum of the composite after the heat treatment. The colloidal absorption of the fine gold particles can be seen, and it can be seen that gold is finely divided.

【００２５】実施例２ 実施例１で得られた高分子層を積層したガラス基材を真
空蒸着装置内に投入し、銅を電子ビームにより加熱融解
して１０-4〜１０-6ｔｏｒｒの真空下で蒸着を行い、高
分子層の上に銅蒸着膜を付着した後に、ガラス基材を真
空蒸着装置から取り出した。そして、これを１２０℃に
設定した恒温槽中に３０分間放置して高分子複合物を得
た。Example 2 A glass substrate on which a polymer layer obtained in Example 1 was laminated was put into a vacuum evaporation apparatus, and copper was heated and melted by an electron beam to obtain a vacuum of 10 -4 to 10 -6 torr. The glass substrate was taken out from the vacuum deposition apparatus after performing vapor deposition underneath and attaching a copper vapor deposition film on the polymer layer. This was left in a thermostat set at 120 ° C. for 30 minutes to obtain a polymer composite.

【００２６】得られた高分子複合物の表面の色は、青緑
色であり、微粒子はＣｕ2 Ｏで、そのサイズは１〜１０
ｎｍであった。The color of the surface of the obtained polymer composite is blue-green, the fine particles are Cu 2 O, and the size thereof is 1 to 10
nm.

【００２７】実施例３ 実施例１で得られた高分子層を積層したガラス基材を真
空蒸着装置内に投入し、銀を電子ビームにより加熱融解
して１０-4〜１０-6ｔｏｒｒの真空下で蒸着を行い、高
分子層の上に銀蒸着膜を付着した後に、ガラス基材を真
空蒸着装置から取り出した。そして、これを１２０℃に
設定した恒温槽中に３０分間放置して高分子複合物を得
た。Example 3 The glass substrate on which the polymer layer obtained in Example 1 was laminated was put into a vacuum evaporation apparatus, and silver was heated and melted by an electron beam to obtain a vacuum of 10 -4 to 10 -6 torr. The glass substrate was taken out of the vacuum evaporation apparatus after vapor deposition was performed below and a silver evaporation film was attached on the polymer layer. This was left in a thermostat set at 120 ° C. for 30 minutes to obtain a polymer composite.

【００２８】得られた高分子複合物の表面の色は、黄色
であり、微粒子のサイズは１〜５ｎｍであった。The color of the surface of the obtained polymer composite was yellow, and the size of the fine particles was 1 to 5 nm.

【００２９】[0029]

【発明の効果】以上のように本発明の微粒子を分散させ
た高分子複合物の製造方法では、減圧下にある閉鎖した
空間でナイロン１１からなる高分子を加熱により熱分解
して気体にし、この気体を該空間の非加熱領域で固化す
ることで再生高分子を回収し、この再生高分子から得ら
れた高分子層の表面に金属層を密着した後、高分子層を
加熱して金属層から微粒子化した金属あるいは金属酸化
物の微粒子を高分子層内に均一に分散させることができ
ることはむろん、上記製造方法では多くの熱力学的に準
安定な構造を有する再生高分子を多量に生産することが
できる。特に、再生高分子がペースト状であると、所定
の厚みを有する高分子層の作製が容易になる。As described above, in the method for producing a polymer composite in which fine particles are dispersed according to the present invention, a polymer made of nylon 11 is thermally decomposed into gas by heating in a closed space under reduced pressure. The regenerated polymer is recovered by solidifying this gas in the non-heating area of the space, and a metal layer is adhered to the surface of the polymer layer obtained from the regenerated polymer, and then the polymer layer is heated to form a metal. Of course, fine particles of metal or metal oxide from the layer can be uniformly dispersed in the polymer layer, but in the above-mentioned production method, a large amount of regenerated polymer having a thermodynamically metastable structure can be produced in a large amount. Can be produced. In particular, when the regenerated polymer is in a paste form, it becomes easy to produce a polymer layer having a predetermined thickness.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明に係る製造方法に使用する再生高分子を
作製する装置の概略図を示す。FIG. 1 shows a schematic view of an apparatus for producing a regenerated polymer used in the production method according to the present invention.

【図２】本発明に係る製造方法の工程であり、再生高分
子からなる薄膜の高分子層を基材上に作製した状態を示
す断面図である。FIG. 2 is a cross-sectional view showing a step of a manufacturing method according to the present invention, in which a polymer layer of a thin film made of a regenerated polymer is formed on a base material.

【図３】本発明に係る製造方法の工程であり、高分子層
の表面に金属層を密着した状態を示す断面図である。FIG. 3 is a cross-sectional view showing a step of the manufacturing method according to the present invention and showing a state in which a metal layer is adhered to the surface of the polymer layer.

【図４】本発明に係る製造方法によって得られた高分子
複合物を断面図である。FIG. 4 is a cross-sectional view of a polymer composite obtained by the production method according to the present invention.

【図５】熱処理前の高分子層と金蒸着膜との積層物と高
分子層とこの積層物を熱処理した後の高分子複合物のＸ
線回折パターンを示す。FIG. 5 shows a laminate of a polymer layer and a gold vapor-deposited film before heat treatment, a polymer layer, and X of a polymer composite after heat treatment of the laminate.
3 shows a line diffraction pattern.

【図６】高分子層と金蒸着膜との積層物を熱処理した後
の高分子複合物の光吸収スペクトルを示す。FIG. 6 shows a light absorption spectrum of a polymer composite after heat treatment of a laminate of a polymer layer and a gold vapor-deposited film.

【符号の説明】[Explanation of symbols]

１ 再生高分子の製造装置 ２ ガラス管 ３ 加熱炉 ４ 減圧装置 ５ 高分子材料 ６ 容器 １７ 空冷領域 １９ 再生高分子 ２１ 高分子層 ２３ 金属層 ２５ 微粒子 ２６ 高分子複合物 DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus of regenerated polymer 2 Glass tube 3 Heating furnace 4 Decompression device 5 Polymer material 6 Container 17 Air-cooled area 19 Regenerated polymer 21 Polymer layer 23 Metal layer 25 Fine particles 26 Polymer composite

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C08K 3/00 - 3/40 C08F 2/00 C08J 3/00,5/18────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C08K 3/00-3/40 C08F 2/00 C08J 3/00, 5/18

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 減圧下にある閉鎖した空間でナイロン１
１からなる高分子材料を熱分解して気化し、この気化物
を該空間の非加熱領域で冷却固化することで熱力学的に
準安定構造を有するペースト状の再生高分子を回収し、
この再生高分子から得られた薄膜の高分子層の表面に真
空蒸着により得られた金属層を付着した後、高分子層を
加熱して金属層から微粒子化した金属あるいは金属酸化
物の微粒子を高分子層内に分散させることを特徴とする
微粒子を分散させた高分子複合物の製造方法。1. Nylon 1 in a closed space under reduced pressure
The polymer material consisting of 1 is thermally decomposed and vaporized, and the vaporized product is cooled and solidified in a non-heating region of the space to recover a thermodynamically metastable paste-like regenerated polymer,
After attaching a metal layer obtained by vacuum evaporation to the surface of the polymer layer of the thin film obtained from the regenerated polymer, the polymer layer is heated to remove fine particles of metal or metal oxide from the metal layer. A method for producing a polymer composite in which fine particles are dispersed, wherein the polymer composite is dispersed in a polymer layer.
JP25461794A 1994-09-21 1994-09-21 Method for producing polymer composite in which fine particles are dispersed Expired - Fee Related JP2798358B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP25461794A JP2798358B2 (en) 1994-09-21 1994-09-21 Method for producing polymer composite in which fine particles are dispersed

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP25461794A JP2798358B2 (en) 1994-09-21 1994-09-21 Method for producing polymer composite in which fine particles are dispersed

Publications (2)

Publication Number Publication Date
JPH0892415A JPH0892415A (en) 1996-04-09
JP2798358B2 true JP2798358B2 (en) 1998-09-17

Family

ID=17267529

Family Applications (1)

Application Number Title Priority Date Filing Date
JP25461794A Expired - Fee Related JP2798358B2 (en) 1994-09-21 1994-09-21 Method for producing polymer composite in which fine particles are dispersed

Country Status (1)

Country Link
JP (1) JP2798358B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4576947B2 (en) * 2004-09-21 2010-11-10 株式会社デンソー Manufacturing method of composite material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0699585B2 (en) * 1989-11-24 1994-12-07 三ツ星ベルト株式会社 Polymer composite having fine particles dispersed therein and method for producing the same

Also Published As

Publication number Publication date
JPH0892415A (en) 1996-04-09

Similar Documents

Publication Publication Date Title
US5966580A (en) Process for making a thin film using a metal paste
JP2561537B2 (en) Metal paste and manufacturing method thereof
EP0449309B9 (en) Method of making metalic thin film
US6911385B1 (en) Interface layer for the fabrication of electronic devices
DE112008001037T5 (en) Film forming process, heat conducting element, power module, vehicle inverter and vehicle
EP3347303A1 (en) Method for producing structured surfaces
JP3030309B2 (en) Thin film manufacturing equipment
DE1950126A1 (en) Process for applying insulating films and electronic components
JP2798358B2 (en) Method for producing polymer composite in which fine particles are dispersed
DE2457888A1 (en) COMPOSITE FILMS MADE OF METALS AND POLYMERS
AT10749U1 (en) PROCESS FOR PREPARING CLATHRATE COMPOUNDS
WO2015022143A1 (en) Method for deposition of thermoelectric material
JP2848521B2 (en) Production equipment for regenerated polymer with thermodynamically metastable structure
EP3658698B1 (en) Method of manufacturing a single phase intermetallic compound film
JP2004190089A (en) Method for manufacturing inorganic-nanoparticle fusion or accretion structure, and fusion or accretion structure
WO2012095311A1 (en) Method for producing a silicon layer
DE3228584C2 (en)
JP2982055B2 (en) Method for producing fine metal particles of gold, silver or copper
JP2535303B2 (en) Ultra fine particle dispersed glass and its manufacturing method
DE69706290T2 (en) POLARIZING GLASSES WITH INTEGRATED NON-POLARIZING ZONES
JP2678336B2 (en) Method for producing ultrafine particle-dispersed glassy material
JP2623421B2 (en) Method for producing polymer composite in which fine particles of metal sulfide are dispersed
Veith Precursorchemistry with metalalkoxides and their use for nano-scaled materials
JP2611888B2 (en) Method for producing polymer composite in which fine particles are dispersed
JP2691215B2 (en) Ceramic composite film and manufacturing method thereof

Legal Events

Date Code Title Description
LAPS Cancellation because of no payment of annual fees