JPS62259815A - Method for crosslinking thermoplastic high polymeric organic substance - Google Patents
Method for crosslinking thermoplastic high polymeric organic substanceInfo
- Publication number
- JPS62259815A JPS62259815A JP10442186A JP10442186A JPS62259815A JP S62259815 A JPS62259815 A JP S62259815A JP 10442186 A JP10442186 A JP 10442186A JP 10442186 A JP10442186 A JP 10442186A JP S62259815 A JPS62259815 A JP S62259815A
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking
- organic substance
- polymeric organic
- high polymeric
- thermoplastic high
- 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
- 238000004132 cross linking Methods 0.000 title claims abstract description 21
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 18
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000126 substance Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000620 organic polymer Polymers 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920009638 Tetrafluoroethylene-Hexafluoropropylene-Vinylidenefluoride Copolymer Polymers 0.000 claims 1
- 239000003566 sealing material Substances 0.000 abstract description 7
- 238000007789 sealing Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 description 7
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- UJXFNIQSAHCTTA-UHFFFAOYSA-N 1-butylperoxyhexane Chemical compound CCCCCCOOCCCC UJXFNIQSAHCTTA-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
Abstract
Description
【発明の詳細な説明】
崖！上皇肌里公団
本発明は、熱可塑性有機高分子の電子線照射による新規
な架橋方法に関する。[Detailed description of the invention] Cliff! The present invention relates to a novel method for crosslinking thermoplastic organic polymers by electron beam irradiation.
従来の技′荷並びに” を すべき口 白熱可塑性有機
高分子を酸素の存在下で電子線照射により架橋したので
は架橋と酸化劣化とが同時に進行することから、通常は
照射室を窒素ガスで置換し窒素ガス雰囲気中で照射架橋
が行われている。ところで、照射室を完全に窒素ガスで
置換することは実際上困難であり、このため照射架橋さ
れた物品は照射室に僅かに残存する酸素により架橋が妨
害され（表面の分解が優先する）、表面に未架橋層が生
じる。この表面の未架橋層は、常温においては勿論、特
に７０°Ｃ以上の高温度において粘着性を示す。照射架
橋により生産される物品が、たとえば０リングなどのソ
ール材である場合には、この表面の粘着性のためにシー
ル面（金属表面）に粘着してシール材の表面がシール面
にとられる問題がある。When crosslinking incandescent plastic organic polymers by electron beam irradiation in the presence of oxygen, crosslinking and oxidative deterioration occur simultaneously, so the irradiation chamber is usually filled with nitrogen gas. Irradiation cross-linking is carried out in a nitrogen gas atmosphere.By the way, it is practically difficult to completely replace the irradiation chamber with nitrogen gas, so a small amount of the irradiation-crosslinked article remains in the irradiation chamber. Crosslinking is hindered by oxygen (surface decomposition takes precedence), and an uncrosslinked layer is formed on the surface.This uncrosslinked layer on the surface exhibits tackiness not only at room temperature but especially at high temperatures of 70°C or higher. When the article produced by irradiation crosslinking is a sole material such as an O-ring, the adhesiveness of this surface causes it to stick to the sealing surface (metal surface) and the surface of the sealing material is stuck to the sealing surface. There's a problem.
問題仁を解 するための手
本発明は、０リングなどのシール材の製造にも適用可能
な照射架橋方法を提供しようとするものである。すなわ
ち本発明においては、前記した通り、架橋すべき熱可塑
性有機高分子またはその成形品、たとえばＯリングを水
中に設置して電子腺を照射することを特徴とする。SUMMARY OF THE INVENTION The present invention aims to provide an irradiation crosslinking method that can also be applied to the production of sealing materials such as O-rings. That is, as described above, the present invention is characterized in that the thermoplastic organic polymer to be crosslinked or its molded product, such as an O-ring, is placed in water and the electron gland is irradiated.
立ユ蓋乏堡皿果
架橋すべき熱可塑性有機高分子またはその成形品を水中
に設置することにより、極めて簡単に酸素フリーの状態
とすることが可能である。そしてこの状態で電子線照射
することにより、窒素ガス置換の照射室内で照射架橋さ
れた場合と比較して表面が充分に架橋した架橋物品を得
ることができる。従って本発明の架橋方法を適用して０
リングなどのシール材を製造したとき、得られたシール
材は、粘着性が少なくてシール面（金属表面）に粘着す
る問題がない。By placing the thermoplastic organic polymer to be cross-linked or its molded product in water, it is possible to create an oxygen-free state very easily. By irradiating the product with an electron beam in this state, it is possible to obtain a crosslinked article whose surface is sufficiently crosslinked, compared to the case where crosslinking is performed by irradiation in an irradiation chamber substituted with nitrogen gas. Therefore, by applying the crosslinking method of the present invention,
When manufacturing a sealing material such as a ring, the obtained sealing material has low adhesiveness and does not have the problem of sticking to the sealing surface (metal surface).
本発明においては、従来より照射架橋の対象とされてい
た多くの熱可塑性有機高分子を照射架橋の対象とするこ
とができる。たとえば、ポリエチレン、ポリスチロール
、ナイロン、ポリビニールアルコール、４フッ化エチレ
ン−６フン化プロピレン一フフ化ビニリデン共重合エラ
ストマーなどである。特にＯリングなどのシール材を製
造する上で好ましものは、ポリエチレン、４フッ化エチ
レン−６フン化プロピレン−フッ化ヒニリデン共重合エ
ラストマーなどである。In the present invention, many thermoplastic organic polymers that have conventionally been subjected to radiation crosslinking can be subjected to radiation crosslinking. Examples include polyethylene, polystyrene, nylon, polyvinyl alcohol, tetrafluoroethylene-hexafluoropropylene monovinylidene fluoride copolymer elastomer, and the like. Particularly preferred for manufacturing sealing materials such as O-rings are polyethylene, tetrafluoroethylene-hexafluoropropylene-hynylidene fluoride copolymer elastomer, and the like.
これらの熱可塑性有機高分子は、単独で、あるいは、２
種以上の混合物で用いて良い、また必要に応じて、熱可
塑性有機高分子に通常配合される薬剤、たとえば酸化防
止剤、可塑剤、充填剤、加工助剤、安定剤、難燃剤など
を配合しても良い。These thermoplastic organic polymers may be used alone or in combination with two
It can be used in a mixture of more than one species, and if necessary, it can also contain chemicals that are usually added to thermoplastic organic polymers, such as antioxidants, plasticizers, fillers, processing aids, stabilizers, flame retardants, etc. You may do so.
さらに照射架橋の架橋助剤として用いる多官能性化合物
、たとえばトリアリルイソシアヌレート、トリアリルシ
アヌレート、あるいは、有機パーオキサイド、たとえば
ジキュミルパーオキサイド、２．５ジメチル−２，５ジ
（ｔ−ブチル・パーオキシ）ヘキサンなどを熱可塑性有
機高分子１００重量部あたり０．１〜１０重量部重量部
台して架橋効率を向上させることも好ましい。Furthermore, polyfunctional compounds used as crosslinking aids in radiation crosslinking, such as triallyl isocyanurate, triallyl cyanurate, or organic peroxides, such as dicumyl peroxide, 2.5 dimethyl-2,5 di(t- It is also preferable to add 0.1 to 10 parts by weight of butyl (peroxy)hexane or the like per 100 parts by weight of the thermoplastic organic polymer to improve the crosslinking efficiency.
照射架橋の対象とする熱可塑性有機高分子またはその成
形品は、水中において照射架橋される。The thermoplastic organic polymer to be crosslinked by radiation or a molded article thereof is crosslinked by radiation in water.
通常の水は、１０容量％程度の空気を溶解しているが、
溶存空気による架橋の妨害作用は実質上無く、従ってそ
の存在は問題とならない、しかしながら特に精密な用途
に用いられる０リングの製造の場合には、真空処理によ
り充分に脱気した清浄水、たとえば脱気イオン交換水中
で照射することが好ましい。Ordinary water has about 10% air dissolved in it by volume.
Dissolved air has virtually no interfering effect on crosslinking, so its presence is not a problem. However, in the production of O-rings used in particularly precise applications, clean water that has been thoroughly degassed by vacuum treatment, e.g. Preferably, the irradiation is carried out in ion-exchanged water.
照射方法に関しては、大気中に設置した照射源から大気
中を通過して水中に照射しても良く、また水中に設置し
た照射源から直接水中の被照射物に照射しても良い。Regarding the irradiation method, the radiation may be passed through the atmosphere from an irradiation source installed in the atmosphere and irradiated into the water, or the irradiation object in the water may be directly irradiated from the irradiation source installed in the water.
叉立勇
以下、実施例および比較例により本発明を一層詳細に説
明する。Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１
４フッ化エチレン−６フン化プロビレン一フフ化ビニリ
デン共重合エラストマー（ダイキン工業社製の商品名ダ
イエルサーモプラスチック Ｔ−５３０を使用）につき
、０リング成形用金型を用いて２３０℃、１分間のプレ
ス成形にて断面直径３．５３龍、リング内径２５．００
鶴の未架橋０リングを得た。Example 1 A polyethylene tetrafluoride-propylene hexafluoride-vinylidene fluoride copolymer elastomer (trade name Daiel Thermoplastic T-530 manufactured by Daikin Industries, Ltd. was used) was heated at 230°C using an O-ring mold. , cross-sectional diameter 3.53mm, ring inner diameter 25.00mm after 1 minute press forming
An uncrosslinked 0-ring of Tsuru was obtained.
この未架橋０リングをＩｏｔａの深さにイオン交換水を
張ったシャーレの該水中に入れ、ついでコバルト６０を
線源としてＯリングを均一にγ線照射し、架橋０リング
を得た。This uncrosslinked O-ring was placed in a petri dish filled with ion-exchanged water to a depth of Iota, and then the O-ring was uniformly irradiated with gamma rays using cobalt 60 as a radiation source to obtain a crosslinked O-ring.
比較例１
未架！１１０リングを窒素置換室中で照射架橋した点に
おいてのみ実施例１とことなる方法にて架橋し、架橋０
リングを得た。Comparative example 1 Unshelf! 110 ring was crosslinked by irradiation in a nitrogen-substituted chamber using a method different from Example 1, resulting in 0 crosslinking.
Got the ring.
下表に実施例１、比較例１で照射された各Ｏリングの照
射量、表面粘着性、および圧縮歪をそれぞれ示す。なお
、表面粘着性および圧縮歪は、それぞれ次の方法により
評価した。The table below shows the irradiation amount, surface tackiness, and compressive strain of each O-ring irradiated in Example 1 and Comparative Example 1. Note that the surface tackiness and compressive strain were each evaluated by the following methods.
１里艮ｌ箪：
下記の圧縮歪試験後の圧縮Ｖｉ、（クロムメッキ鉄板）
の表面を目視で観察し、０リングの跡のないものを優、
跡が残っているものを可、Ｏリングの一部が金属面に残
っているものを不可とした。1. Compression Vi after the following compressive strain test (chrome-plated iron plate)
Visually observe the surface of the
Items with traces remaining were accepted, and items with part of the O-ring remaining on the metal surface were accepted.
圧箪歪：
２枚の圧縮板（クロムメッキ鉄板）間に０リングを挟み
、７０℃ｘ７０時間、および１００℃Ｘ７０時間、該０
リングを２５％圧縮し、この圧縮後における圧縮歪（％
）を求めた。Compression strain: An O ring was placed between two compression plates (chrome-plated iron plates), and the 0 ring was placed at 70°C for 70 hours and at 100°C for 70 hours
The ring was compressed by 25%, and the compression strain after this compression (%
) was sought.
実施例１の結果 比較例１の結果Results of Example 1 Results of comparative example 1
Claims (1)
することを特徴とする熱可塑性有機高分子の架橋方法。 ２、熱可塑性有機高分子が、ポリエチレン、ポリスチロ
ール、ナイロン、ポリビニールアルコール、４フッ化エ
チレン−６フッ化プロピレン−フッ化ビニリデン共重合
エラストマーからなる群から選ばれた少なくとも１種で
ある特許請求の範囲第１項に記載の熱可塑性有機高分子
の架橋方法。[Scope of Claims] 1. A method for crosslinking thermoplastic organic polymers, which comprises irradiating electron beams to thermoplastic organic polymers placed in water. 2. A patent claim in which the thermoplastic organic polymer is at least one selected from the group consisting of polyethylene, polystyrene, nylon, polyvinyl alcohol, and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer elastomer A method for crosslinking a thermoplastic organic polymer according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10442186A JPS62259815A (en) | 1986-05-06 | 1986-05-06 | Method for crosslinking thermoplastic high polymeric organic substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10442186A JPS62259815A (en) | 1986-05-06 | 1986-05-06 | Method for crosslinking thermoplastic high polymeric organic substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62259815A true JPS62259815A (en) | 1987-11-12 |
Family
ID=14380228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10442186A Pending JPS62259815A (en) | 1986-05-06 | 1986-05-06 | Method for crosslinking thermoplastic high polymeric organic substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62259815A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173637A (en) * | 1990-09-18 | 1995-07-11 | Internatl Business Mach Corp <Ibm> | Crosslinking and reduction of halide |
-
1986
- 1986-05-06 JP JP10442186A patent/JPS62259815A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173637A (en) * | 1990-09-18 | 1995-07-11 | Internatl Business Mach Corp <Ibm> | Crosslinking and reduction of halide |
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