JPS6230131A - Foamed fluorohydrocarbon resin - Google Patents
Foamed fluorohydrocarbon resinInfo
- Publication number
- JPS6230131A JPS6230131A JP11097286A JP11097286A JPS6230131A JP S6230131 A JPS6230131 A JP S6230131A JP 11097286 A JP11097286 A JP 11097286A JP 11097286 A JP11097286 A JP 11097286A JP S6230131 A JPS6230131 A JP S6230131A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- resin foam
- titanate
- foamed
- pore
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
-
- 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
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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 a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、特に気孔（セル）の分布性および均一性に優
れた新規発泡フルオロ炭化水素樹脂に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel foamed fluorohydrocarbon resin particularly excellent in pore (cell) distribution and uniformity.
（従来の技術および
発明が解決しようとする問題点）
発泡フルオロカーボンプラスチック類の製造方法に関し
て、従来製造中に注入するシステムによりガスをポリフ
ルオロ炭化水素中に注入する方法が使用されていた。こ
の方法は、そのシステムに多額の開発費を要し、生産コ
ストが高くかつその複雑のゆえに問題が発生しやすい複
雑な方法である。PRIOR ART AND PROBLEMS SOLVED BY THE INVENTION Regarding methods of manufacturing expanded fluorocarbon plastics, conventional methods have been used in which gas is injected into the polyfluorohydrocarbon by an injection system during manufacturing. This method is a complex method that requires a large amount of development cost for the system, has high production costs, and is prone to problems due to its complexity.
ドイツ連邦共和国特許出願筒３０２７１４９号には、無
機または有機性のフィラーをも含有する熱可塑性樹脂お
よび繊維形成性ポリテトラフルオロエチレン樹脂混合物
をアゾジカルボンアミドまたはｐ−トルエンスルホニル
セミカルバジドからなる発泡剤によって発泡させる手段
が記載されている。German Patent Application No. 3027149 discloses that a mixture of thermoplastic resin and fiber-forming polytetrafluoroethylene resin, which also contains inorganic or organic fillers, is foamed with a blowing agent consisting of azodicarbonamide or p-toluenesulfonyl semicarbazide. The means to do so are described.
アメリカ合衆国特許第４，３９４，４６０号は、・例え
ばヒドラゾジカルボキシレートまたはｐ−トルエンスル
ホニルセミカルバジドである発泡剤またはブローイング
剤（ｂｌｏｗｉｎｇ ａｇｅｎｔ ） 、および核剤と
して作用する二価金屑酸化物または炭ｍｕを使用して調
製されるエチレン／クロロトリフルオロエチレンコポリ
マーから成る発泡体を開示する。U.S. Pat. No. 4,394,460 discloses: - a blowing agent, such as a hydrazodicarboxylate or p-toluenesulfonyl semicarbazide; and a divalent gold scrap oxide or charcoal to act as a nucleating agent. A foam comprising an ethylene/chlorotrifluoroethylene copolymer prepared using mu is disclosed.
従って、本発明の目的は、特に微細気孔、特に均一な気
孔径分布および特に大きな全気孔容積を特徴とする発泡
フルオロカーボンプラスチック類を提供することである
。It is therefore an object of the present invention to provide expanded fluorocarbon plastics which are characterized by particularly fine pores, a particularly uniform pore size distribution and a particularly large total pore volume.
（問題点を解決するための手段）
本発明は、ポリフルオロ炭化水素樹脂、化学発泡剤およ
び多くの均一な気孔形成促進剤を混合することにより得
られてなる合成樹脂発泡体に関する。本発明は、添加配
合剤として核剤を含むことを特徴とする上記合成樹脂発
泡体に関する。本発明は、該セル形成促進剤が有機チタ
ネートであることを特徴とする上記合成−樹脂発泡体に
関する。(Means for Solving the Problems) The present invention relates to a synthetic resin foam obtained by mixing a polyfluorohydrocarbon resin, a chemical blowing agent, and a number of uniform pore formation promoters. The present invention relates to the above synthetic resin foam characterized in that it contains a nucleating agent as an additive. The present invention relates to the above synthetic resin foam, characterized in that the cell formation promoter is an organic titanate.
本発明は、該セル形成促進剤が窒化ボロンであることを
特徴とする上記合成樹脂発泡体に関する。The present invention relates to the above synthetic resin foam, wherein the cell formation promoter is boron nitride.
本発明は、該発泡剤がアゾジカルボンアミドであること
を特徴とする上記合成樹脂発泡体に関する。The present invention relates to the above synthetic resin foam, characterized in that the blowing agent is azodicarbonamide.
本発明により始めて下記諸特性が最適値である発泡フル
オロ炭化水素樹脂が明らかとなった：１、発泡安定性
２、流れ特性
３、に−ファクター
４、密度分布
５、セルの細かさ
６、寸法安定性
７、圧縮強度
は、必要により発泡剤を混入して本発明によって得られ
る：
化学発泡（またはブローイング）剤、適切な場合には、
核剤、および、特に均一気孔形成を促進する他の添加剤
。The present invention has revealed, for the first time, a foamed fluorohydrocarbon resin with optimal values for the following properties: 1. Foaming stability 2. Flow properties 3. Factor 4. Density distribution 5. Cell fineness 6. Dimensions. Stability 7, compressive strength is obtained according to the invention with optional blowing agents: chemical blowing (or blowing) agents, if appropriate;
Nucleating agents and other additives that particularly promote uniform pore formation.
フルオロ イ水素樹脂
全ての現在の一般的なフルオロ炭化水素プラスチック類
は、出発物質として使用し得る。その例としてポリテト
ラフルオロエチレン（ＰＴＦＥ）、ポリ（フルオロエチ
レン プロピレン＞（ＦＥＰ）、ポリフルオロアルコキ
シ（ＰＦＡ）、ポリ（エチレンテトラフルオロエチレン
＞（ＥＴＦＥ）、ポリ（エチレンクロロトリフルオロエ
チレン）（ＥＣＴＦＥ）、ポリビニリデンフルオライド
（ＰＶＦ２ ）およびポリビニル フルオライド（ＰＶ
Ｆ）等が挙げられる。Fluorohydrogen resins All current common fluorohydrocarbon plastics can be used as starting materials. Examples include polytetrafluoroethylene (PTFE), poly(fluoroethylene propylene (FEP)), polyfluoroalkoxy (PFA), poly(ethylenetetrafluoroethylene (ETFE)), poly(ethylene chlorotrifluoroethylene) (ECTFE). , polyvinylidene fluoride (PVF2) and polyvinyl fluoride (PV
F) etc.
化ｊノＬ致濃−
もし発泡材料特性に負効果を及ぼさなければ、すなわち
不活性であれば全ての主要で一般的な化学発泡剤または
ブローイング剤が適する。これらの好適な発泡剤として
、炭酸マグネシウムのような無機発泡剤またはアゾジカ
ルボンアミド、変性アゾジカルボンアミドまたはｐ−ト
ルエンスルホニルセミカルバジドのような有機発泡剤を
挙げることができる。化学発泡剤は、全混合物に対して
０．５〜３０重量％加えられる。All major common chemical blowing or blowing agents are suitable if they do not have a negative effect on the foam material properties, ie are inert. These suitable blowing agents may include inorganic blowing agents such as magnesium carbonate or organic blowing agents such as azodicarbonamide, modified azodicarbonamide or p-toluenesulfonyl semicarbazide. Chemical blowing agents are added in an amount of 0.5 to 30% by weight based on the total mixture.
■
添加可能な核剤は、発泡剤による均一なガス発生を促進
しようとする。好適な核剤は、窒化ホウ素（ＢＮ）のよ
うな無機化合物を細かく分配させたものである。■ Nucleating agents that can be added attempt to promote uniform gas generation by the blowing agent. A suitable nucleating agent is a finely divided inorganic compound such as boron nitride (BN).
気孔形成剤は、本発明に使用される最も基本的な添加物
である。この気孔形成剤は、全混合物に対して０．１〜
４重層％加えられる有機チタネートである。多くの有機
チタネート類が好ましい。Pore formers are the most basic additives used in the present invention. This pore-forming agent is added to the total mixture from 0.1 to
4% organic titanate added. Many organic titanates are preferred.
それらの化学構造によってこれらの化合物を次のように
分類し得る：
１、アルコキシ化合物、ネオアルコキシトリイソステア
ロイルチタネート、イソプロピルトリイソステアロイル
チタネート、メタクリルジイソステアロイルチタネート
およびジ（クミルファニル）オキシアセテートチタネー
トのような長鎖エーテルアルカノイル誘導体のチタネー
ト、
２、スルホニル化合物、例えばドデシルベンゼンスルホ
ニルチタネートおよびトリドデシルベンゼンスルホニル
チタネートのような長鎖アルキルベンゼンスルホニルチ
タネート、
３、トリ（ジオクチルホスファト）チタネート、トリ（
ジオクチルピロホスファト）ヂタネー１〜、テトライソ
ブロビルージ（ジオクチルホスフィト）チタネート、テ
トラオクチルオキシチタニウムジ（ジトリデシルホスフ
ィツト）、テトラ−〈２，２−ジアリロキシメチル−１
，１−ブトキシチタニウムージ（ジトリデシルホスフィ
ツト）、チタニウムジー（ジオクチルホスファト）オキ
シアセテート、ジ（ジオクチルピロホスファト）オキシ
アセテートおよびジ（ジオクチルピロホスファト）エチ
レンヂタネート、ジ（ブチルメチルホスファト）エチレ
ンチタネートジ（ジオクチルハイドロジエンホスフィツ
ト）のようなホスホラス化合物、４、トリ＜Ｎ−エチル
アミノ−エチルアミノ）チタネートのようなキレート化
合物（すでに上でｊ！べた以外のもの）、
５、アクリル基を′＠するアミン類のような第四チタネ
ート類。According to their chemical structure, these compounds can be classified as follows: 1. Alkoxy compounds, such as neoalkoxytriisostearoyl titanate, isopropyltriisostearoyl titanate, methacryl diisostearoyl titanate and di(cumylphanyl)oxyacetate titanate. titanates of long-chain ether alkanoyl derivatives, 2. sulfonyl compounds, such as long-chain alkylbenzenesulfonyl titanates, such as dodecylbenzenesulfonyl titanate and tridodecylbenzenesulfonyl titanate; 3. tri(dioctylphosphato) titanate, tri(
Dioctylpyrophosphato) nitane 1~, Tetraisobrovir di(dioctylphosphite) titanate, Tetraoctyloxytitanium di(ditridecylphosphite), Tetra-<2,2-diallyloxymethyl-1
, 1-butoxytitanium di(ditridecyl phosphite), titanium di(dioctyl phosphato) oxyacetate, di(dioctyl pyrophosphato) oxyacetate and di(dioctyl pyrophosphato) ethylene ditanate, di(butyl methyl Phosphorous compounds such as (dioctylhydrogen phosphite) ethylene titanate, 4, chelate compounds (other than those already mentioned above), such as tri<N-ethylamino-ethylamino) titanate, 5 , quaternary titanates such as amines containing acrylic groups.
気孔形成剤は、さらに他の確かな副作用がある二発泡材
料の膨張を増大することである。最高４５容醋％の空気
割合が気孔形成剤の不存在下で得られるのに対して、気
孔形成剤を使用すると６０容醋％およびそれ以上の空気
割合が得られる。Pore formers increase the expansion of bifoamed materials, which has yet another definite side effect. Air contents of up to 45% by volume are obtained in the absence of pore-forming agents, whereas air contents of 60% by volume and more are obtained with pore-forming agents.
本発明により調製されたポリフルオロ炭化水素発泡体は
、さらに押し出し、射出成形または他のプラスチックス
製造方法で製造される。本発明による新ＭＡ発泡材料の
最も好適な使用は、空気割合が高いためにその材料の誘
導率が小さく、同軸ケーブル外装として、さらに本発明
による改良された柔軟性がさらに柔軟なケーブルを誘導
する多導体ケーブル外装としてである。The polyfluorohydrocarbon foams prepared according to the present invention can be further manufactured by extrusion, injection molding or other plastics manufacturing methods. The most preferred use of the new MA foam material according to the present invention is as a coaxial cable sheath, due to the high air content and the low conductivity of the material, and the improved flexibility according to the present invention leads to even more flexible cables. As a multi-conductor cable sheath.
本発明は、典型的な実施態様によりさらに詳細に説明さ
れる。The invention will be explained in more detail by means of exemplary embodiments.
（実施例）
９５．７ｆｆｉ１１％（７）ＥＴＦＥ、２． Ｌｆｆｉ
ｆｆｉ％ノアゾジカルボンアミド、０．５重量％のイソ
プロピルトリ（ジオクチルピロホスファト）チタネート
および１．０重量％の窒化ホウ素をドラムミキサー中で
充分に混合した。その後、その混合物を２９０℃の温度
で操作される押し出し機に移した。(Example) 95.7ffi11% (7) ETFE, 2. Lffi
ffi% noazodicarbonamide, 0.5% by weight isopropyl tri(dioctylpyrophosphato) titanate and 1.0% by weight boron nitride were thoroughly mixed in a drum mixer. The mixture was then transferred to an extruder operated at a temperature of 290°C.
その混合物と接触する押し出し機の全ての部分は化学的
に作用しない材料製であることが重要である。このため
ステンレススチールは好ましくない。It is important that all parts of the extruder that come into contact with the mixture are made of chemically non-active materials. For this reason, stainless steel is not preferred.
好適な材料は、ホストアロイ（Ｈｏ５ｔａｌ １ｏｙ）
である。結局、空気充填セルの６０容醋％からなる発泡
状構造が得られた。A preferred material is host alloy (Ho5tal 1oy)
It is. In the end, a foam-like structure consisting of 60% by volume of air-filled cells was obtained.
特許出願人 オビ、ヤコブソンホルスト、シュ
ルツPatent Applicant Obi, Jacobson Horst, Schulz
Claims (1)
な気孔形成促進剤を混合することにより得られてなる合
成樹脂発泡体 ２）添加配合剤として核剤を含むことを特徴とする特許
請求の範囲第１項に記載の合成樹脂発泡体。 ３）該気孔形成促進剤が有機チタネートであることを特
徴とする特許請求の範囲第１項または第２項に記載の合
成樹脂発泡体。 ４）該気孔形成剤が窒化ボロンであることを特徴とする
特許請求の範囲第２項または第３項に記載の合成樹脂発
泡体。 ５）該発泡剤がアゾジカルボンアミドであることを特徴
とする特許請求の範囲第１項から第４項までのいずれか
１項に記載の合成樹脂発泡体。[Claims] 1) A synthetic resin foam obtained by mixing a polyfluorohydrocarbon resin, a chemical blowing agent, and a uniform pore formation promoter. 2) A nucleating agent is included as an additive. A synthetic resin foam according to claim 1. 3) The synthetic resin foam according to claim 1 or 2, wherein the pore formation promoter is an organic titanate. 4) The synthetic resin foam according to claim 2 or 3, wherein the pore forming agent is boron nitride. 5) The synthetic resin foam according to any one of claims 1 to 4, wherein the blowing agent is azodicarbonamide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3517731.4 | 1985-05-17 | ||
| DE19853517731 DE3517731A1 (en) | 1985-05-17 | 1985-05-17 | Foamed fluorohydrocarbon resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6230131A true JPS6230131A (en) | 1987-02-09 |
Family
ID=6270935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11097286A Pending JPS6230131A (en) | 1985-05-17 | 1986-05-16 | Foamed fluorohydrocarbon resin |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS6230131A (en) |
| DE (1) | DE3517731A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4764538A (en) * | 1987-12-16 | 1988-08-16 | E. I. Du Pont De Nemours And Company | Foam nucleation system for fluoropolymers |
| EP1935931A1 (en) * | 2006-12-20 | 2008-06-25 | Nexans | High processing temperature foaming polymer composition |
| EP1942134A1 (en) * | 2006-12-20 | 2008-07-09 | Nexans | High processing temperature foaming polymer composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5821431A (en) * | 1981-07-29 | 1983-02-08 | Hitachi Cable Ltd | Foamed material composition prepared with fluorine- containing copolymer |
-
1985
- 1985-05-17 DE DE19853517731 patent/DE3517731A1/en not_active Withdrawn
-
1986
- 1986-05-16 JP JP11097286A patent/JPS6230131A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5821431A (en) * | 1981-07-29 | 1983-02-08 | Hitachi Cable Ltd | Foamed material composition prepared with fluorine- containing copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3517731A1 (en) | 1986-11-20 |
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