JPS60262619A - Manufacture of cross linked formed product made of elastomer containing fluorine - Google Patents
Manufacture of cross linked formed product made of elastomer containing fluorineInfo
- Publication number
- JPS60262619A JPS60262619A JP59120342A JP12034284A JPS60262619A JP S60262619 A JPS60262619 A JP S60262619A JP 59120342 A JP59120342 A JP 59120342A JP 12034284 A JP12034284 A JP 12034284A JP S60262619 A JPS60262619 A JP S60262619A
- Authority
- JP
- Japan
- Prior art keywords
- tetrafluoroethylene
- copolymer
- fluororesin
- formed product
- cross linked
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/12—Articles with an irregular circumference when viewed in cross-section, e.g. window profiles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は含ふっ素エラストマ架橋成形体の製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a crosslinked fluorine-containing elastomer molded article.
Ｆ従来の技術］
四ノ５１つ化エチレンープロピレン系共重合体は、常温
から３００℃の広い温度範囲において押出成形加工およ
び架橋が可能なエラストマであり、その優れた電気絶縁
体、耐熱性、耐油性、耐薬品性を活かしてガスケット、
パツキン、ダイヤフラム、ホース等の用途に使用されて
きている。F. Prior Art] A 4-5 monoethylene-propylene copolymer is an elastomer that can be extruded and crosslinked in a wide temperature range from room temperature to 300°C, and has excellent electrical insulation, heat resistance, Gaskets that take advantage of their oil and chemical resistance,
It has been used for packings, diaphragms, hoses, etc.
しかしながら、従来の四ふつ化エチレン−プロピレン系
共重合体エラストマは、高温における機械的強度が十分
とはいえず、その結果高温で引張り、回転、捻れといっ
た機械的応力を受けた場合には破断するといった問題が
あり、実用に当っては種々の制限を受（プていた。However, conventional tetrafluorinated ethylene-propylene copolymer elastomers do not have sufficient mechanical strength at high temperatures, and as a result, break when subjected to mechanical stress such as tension, rotation, or twisting at high temperatures. Due to these problems, it has been subject to various limitations in practical use.
高温での機械的強度を上げるには、エチレン−四ふり化
エチレン共重合体やポリふっ化ビニリデンのようなふつ
そ樹脂をブレンドする方法が考えられるが、これらをブ
レンドした組成物は、ふっ素樹脂の結晶融点以上の温度
でないと押出成形ができないため、四ふっ化エチレン−
プロピレン系共重合体で通常行っているパーオキサイド
による架橋を行おうとすると、押出機内でパーオキサイ
ドが反応しヤケを生ずるため実施が困難な状況にある。In order to increase the mechanical strength at high temperatures, a method of blending ethylene-tetrafluoroethylene copolymer or a fluorine resin such as polyvinylidene fluoride may be considered; Tetrafluoroethylene cannot be extruded unless the temperature is higher than its crystal melting point.
When attempting to crosslink propylene-based copolymers with peroxide, which is commonly done, it is difficult to carry out because the peroxide reacts in the extruder and causes discoloration.
［発明が解決しようとする問題点］
本発明は、上記に基いてなされたものであって、四ふつ
化エチレンープロピレン共重合体の高温での機械的強度
の向上をパーオキサイド架橋により実現出来る架橋成形
体の製造方法の提供を目的とするものである。[Problems to be Solved by the Invention] The present invention has been made based on the above, and it is possible to improve the mechanical strength of a tetrafluorinated ethylene-propylene copolymer at high temperatures by peroxide crosslinking. The object of the present invention is to provide a method for producing a crosslinked molded body.
［問題点を解決するための手段１
本発明は、四ふつ化エチレン−プロピレン系共重合体１
００重量部に対し、粒径が１００μ以下のエチレンー四
ふっ化エチレン共重合体またはポリぶつ化ビニリチンか
ら選ばれたふっ素樹脂の少なくとも１種を１０〜１００
重量部含有し・、更に１００’Ｃにおける半減期が１０
時間以上である有機過酸化物を添加してなる樹脂組成物
を１５０′Ｃ以下の温度で押出成形し、しかる後上記ふ
っ素樹脂の融点以上の温度で加圧架橋せしめることを特
徴とするものである。[Means for solving the problems 1] The present invention provides a method for solving the problems by using a tetrafluoroethylene-propylene copolymer 1
00 parts by weight, 10 to 100 parts of at least one fluororesin selected from ethylene-tetrafluoroethylene copolymer or polyvinyritine fluoride having a particle size of 100 μ or less
Contains parts by weight, and has a half-life of 10 at 100'C.
It is characterized by extrusion molding a resin composition to which an organic peroxide is added for more than an hour at a temperature of 150'C or less, and then crosslinking it under pressure at a temperature of at least the melting point of the fluororesin. be.
［作用］
本発明に４３いて、四ふつ化エチレン−プロピレン系共
重合体としては、主成分の四ふつ化エチレンとプロピレ
ンに加えて、これらと共重合可能な成分、例えばエチレ
ン、ブデンー１、イソブチン、アクリル酸およびそのア
ルキルエステル、メタクリル酸およびそのアルキルエス
テル、ふつ化ビニル、ぶつ化ビニリテ゛ン、ヘキサフル
オロプロペン、クロロエチルビニルエーテル、グリシジ
ルビニルエーテル、クロロトリフルオロエチレン、パー
フルオロアルキルビニルエーテル等を適当に含有せしめ
たものであってもよい。[Function] In the present invention, the tetrafluoroethylene-propylene copolymer includes, in addition to the main components tetrafluoroethylene and propylene, components copolymerizable with these, such as ethylene, budene-1, and isobutyne. , acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, vinyl fluoride, vinyl fluoride, hexafluoropropene, chloroethyl vinyl ether, glycidyl vinyl ether, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, etc. It may be something.
かかる共重合体において、四ふつ化エチレン／プロピレ
ンの含有モル比としては９５１５〜３０／７０、特に９
０／１０〜４５１５５の範囲から選定することが耐熱性
、成形性等の面から好ましく、また、適宜加えられる主
成分以外の成分の含有量としては通常５０モル％以下、
特に３０モル％以下の範囲から選定することが好ましい
。In such a copolymer, the molar ratio of tetrafluoroethylene/propylene is 9515 to 30/70, particularly 9
It is preferable to select from the range of 0/10 to 45155 from the viewpoint of heat resistance, moldability, etc., and the content of components other than the main component, which may be added as appropriate, is usually 50 mol% or less,
In particular, it is preferable to select from a range of 30 mol% or less.
上記四ふつ化エチレン−プロピレン系共重合体にブレン
ドするふっ素樹脂としてはエチレン−四ぶつ化エチレン
共重合体あるいはポリぶつ化ビニリデンの少なくとも１
種である。The fluororesin to be blended with the above-mentioned tetrafluoroethylene-propylene copolymer is at least one of ethylene-tetrafluoroethylene copolymer or polyvinylidene tetrafluoride copolymer.
It is a seed.
かかるふっ素樹脂は、粒径が１００μ以下のものを選ぶ
必要があり、これ以上のものを使用すると、成形品の表
面荒れが激しくなると〜ともに十分な架橋物性を得られ
ない。It is necessary to select such a fluororesin having a particle size of 100 μm or less; if a particle size larger than this is used, the surface of the molded product becomes severely rough and sufficient crosslinking properties cannot be obtained.
また、ふっ素樹脂の混和量は、四ふつ化エゲレンープロ
ピレン共重合体１００重量部に対して１０〜１００重量
部の範囲どする必要があり、１０手ｍ部未満では高温で
の機械強度の改善効果が殆んどなく、１００重量部を越
えると押出成形が不可能となる。In addition, the amount of fluororesin mixed must be in the range of 10 to 100 parts by weight per 100 parts by weight of the tetrafluoroegelene-propylene copolymer, and if it is less than 10 parts by weight, the mechanical strength at high temperatures will deteriorate. There is almost no improvement effect, and if it exceeds 100 parts by weight, extrusion molding becomes impossible.
本発明において使用される架橋剤としては、１００℃に
おける半減期が１０時間以上を右するパーオキサイドで
ある。半減期が１０時間未満のもので゛は押出成形時に
早期架橋を生じるためである。The crosslinking agent used in the present invention is a peroxide having a half-life of 10 hours or more at 100°C. The reason for the half-life of less than 10 hours is that premature crosslinking occurs during extrusion molding.
かかるパーオキサイドとしては、ジクミルパーオキサイ
ド、２．５−ジメチル−２，５−ジ（［−ブチルパーオ
キシ）ベンゼン、１，３−ビス（を−ブチルパーオキシ
イソプロビル）ベンゼン、ｔ−ブチルクミルパーオキサ
イド、ジーｔ−プチルパーオキザイド、２，５−ジメチ
ル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３
，２，２−ジ（ｔ−ブチルパーオキシ）ブタン等があげ
られる。これらは単独あるいは２種以上併用して使用可
能であり、添加量は通常樹脂成分１００重量部に対して
０．１〜１０重量部、好ましくは０．５〜５重量部であ
る。Such peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di([-butylperoxy)benzene, 1,3-bis(butylperoxyisopropyl)benzene, t-butyl Cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3
, 2,2-di(t-butylperoxy)butane, and the like. These can be used alone or in combination of two or more, and the amount added is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the resin component.
本発明においては、架橋剤に加えて架橋助剤の使用か可
能であり、かかる架橋助剤としてはフタル酸シアリル、
リン酸トリアリル、シアヌル酸１−シアリル、イソシア
ヌルＭ ｌ−シアリル等があげられる。架橋助剤の添加
量−は、樹脂成分１００重量部に対して０．１〜２０重
量部、好ましくは０． ２〜１０重量部である。In the present invention, it is possible to use a crosslinking aid in addition to the crosslinking agent, and such crosslinking aids include sialyl phthalate,
Examples include triallyl phosphate, 1-sialyl cyanurate, M 1-sialyl isocyanurate, and the like. The amount of the crosslinking aid added is 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the resin component. It is 2 to 10 parts by weight.
本発明において使用可能な組成物は、上記成分以外に充
填剤、補強剤、顔料、滑剤、押出助剤、酸化防止剤、安
定剤等を含有することができる。The composition usable in the present invention may contain fillers, reinforcing agents, pigments, lubricants, extrusion aids, antioxidants, stabilizers, etc. in addition to the above-mentioned components.
かかる組成物は、そのムー二粘度ＭＬ１＋４（１００℃
）が２０〜１５０１特に３０〜９０であることが成形性
、成形品の表面状態等の面から好ましい。Such a composition has a Mouni viscosity ML1+4 (100°C
) is preferably from 20 to 1501, particularly from 30 to 90, from the viewpoint of moldability, surface condition of the molded product, etc.
また、組成物中に各配合成分が均一に分散せしめられて
いることが望ましく、例界ば従来から使用されてきてい
るゴム混線用ロールまたはバリバリーミキサー等を使用
し、３０〜８０℃の温度範囲で１０〜３０分程度混練す
ることによって均一分散が達成可能である。In addition, it is desirable that each compounded component is uniformly dispersed in the composition. For example, a conventionally used rubber mixing roll or a burr ball mixer is used, and the temperature is 30 to 80°C. Uniform dispersion can be achieved by kneading within a range of about 10 to 30 minutes.
かくして得られた組成物は、１５０℃以下の温度で押出
成形する必要があり、これ以上の温度では押出機内で早
期架橋を発生することになる。The composition thus obtained must be extruded at a temperature below 150° C.; temperatures higher than this will cause premature crosslinking in the extruder.
また、押出成形後の架橋は、ふっ素樹脂の融点以上の温
度で行う必要があり、これ以下の温度では高温での機械
的強度を十分に改善できない。Further, crosslinking after extrusion molding must be performed at a temperature equal to or higher than the melting point of the fluororesin, and if the temperature is lower than this, the mechanical strength at high temperatures cannot be sufficiently improved.
「実施例」
各種成分を第１表の各側に示すような配合割合でもって
、５０〜６０℃に保持した８インチロールでもって１５
分間混練した。"Example" Various ingredients were mixed in the proportions shown on each side of Table 1, and 15 cm
Kneaded for a minute.
続いて、ヘッド：１００°Ｃ１シリンダー１：１００℃
、シリンダー２：８０℃に設定した押出１１（Ｌ／Ｄ＝
２２）に導入し、外径１．６ｍのスズメッキ銅撚線外周
に厚さ１ｍｍに被覆し、第１表の各側に示す条件でもっ
て加熱架橋した。Next, head: 100°C 1 cylinder 1: 100°C
, Cylinder 2: Extrusion 11 set at 80°C (L/D=
22), the outer periphery of a tin-plated copper stranded wire having an outer diameter of 1.6 m was coated to a thickness of 1 mm, and heat crosslinked under the conditions shown on each side of Table 1.
得られた被覆電線の表面平滑性および引張強さについて
の評価結果を第１表の下欄に示す。The evaluation results regarding the surface smoothness and tensile strength of the obtained covered wire are shown in the lower column of Table 1.
第１表
第１表から明らかな通り、本発明の範囲にある実施例１
〜４ではいずれも良好が押出外観であり、また１００℃
の引張強さも優れている。Table 1 As is clear from Table 1, Example 1 within the scope of the present invention
- 4, the extrusion appearance is good in all cases, and 100°C
It also has excellent tensile strength.
比較例１はふっ素樹脂を混和しないものであり、押出外
観は優れているが、引張強さが劣る。比較例２は粒径が
本発明で規定するよりも大きい５００μのふっ素樹脂を
使用したものであり、押出外観が劣り、また分散が悪く
十分な引張強さを得られない。比較例３は架橋をエチレ
ンー四ぶつ化エチレン共重合体の融点以下の温度で行っ
たものであり、引張強ざが十分でない。Comparative Example 1 does not contain a fluororesin, and has an excellent extruded appearance but poor tensile strength. In Comparative Example 2, a fluororesin having a particle size of 500 μm larger than that specified in the present invention was used, and the extrusion appearance was poor, and dispersion was poor, making it impossible to obtain sufficient tensile strength. In Comparative Example 3, crosslinking was carried out at a temperature below the melting point of the ethylene-tetrabutylene copolymer, and the tensile strength was insufficient.
［発明の効果コ
以上説明してぎた通り、本発明によればパーオキザイド
架橋によって高温での機械強度に優れ、しかも良好な押
出外観を有する含ふっ素エラストマ架橋成形体を得るこ
とが可能となる。[Effects of the Invention] As explained above, according to the present invention, peroxide crosslinking makes it possible to obtain a crosslinked fluorine-containing elastomer molded product that has excellent mechanical strength at high temperatures and has a good extrusion appearance.
Claims (1)
０重量部に対し、粒径が１００μ以下のエチレンー四ふ
つ化エチレン共重合体またはポリぶつ化ビニリデンから
選ばれたふっ素樹脂の少なくとも１種を１０〜１００重
量部含有し、更に１００℃にお【プる半減期が１０時間
以上である有機過酸化物を添加してなる樹脂組成物を１
５０℃以下の温度で押出成形し、しかる後上記ふっ素樹
脂の融点以上の湿度で加圧架橋せしめることを特徴と１
−る含ふっ素エラストマ架橋成形体の製造方法。(1) Tetrafluoroethylene-propylene copolymer 10
0 parts by weight, contains 10 to 100 parts by weight of at least one fluororesin selected from ethylene-tetrafluoroethylene copolymer or polyvinylidene butyrate with a particle size of 100 μ or less, and further heated to 100 ° C. 1. A resin composition containing an organic peroxide having a half-life of 10 hours or more.
It is characterized by extrusion molding at a temperature of 50° C. or lower, and then crosslinking under pressure at a humidity higher than the melting point of the fluororesin.
- A method for producing a crosslinked fluorine-containing elastomer molded article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59120342A JPS60262619A (en) | 1984-06-11 | 1984-06-11 | Manufacture of cross linked formed product made of elastomer containing fluorine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59120342A JPS60262619A (en) | 1984-06-11 | 1984-06-11 | Manufacture of cross linked formed product made of elastomer containing fluorine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60262619A true JPS60262619A (en) | 1985-12-26 |
| JPH0116651B2 JPH0116651B2 (en) | 1989-03-27 |
Family
ID=14783870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59120342A Granted JPS60262619A (en) | 1984-06-11 | 1984-06-11 | Manufacture of cross linked formed product made of elastomer containing fluorine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60262619A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624708A (en) * | 1985-07-01 | 1987-01-10 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Gelled fluoroelastomer |
| JP2008001875A (en) * | 2006-05-26 | 2008-01-10 | Asahi Glass Co Ltd | Cross-linkable fluoroelastomer, its composition and cross-linked rubber molded product |
-
1984
- 1984-06-11 JP JP59120342A patent/JPS60262619A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624708A (en) * | 1985-07-01 | 1987-01-10 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Gelled fluoroelastomer |
| JPH0144243B2 (en) * | 1985-07-01 | 1989-09-26 | Ii Ai Deyuhon De Nimoasu Ando Co | |
| JP2008001875A (en) * | 2006-05-26 | 2008-01-10 | Asahi Glass Co Ltd | Cross-linkable fluoroelastomer, its composition and cross-linked rubber molded product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0116651B2 (en) | 1989-03-27 |
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