JP2843420B2 - Method for producing stretch-oriented polyethylene molded article having excellent heat resistance - Google Patents
Method for producing stretch-oriented polyethylene molded article having excellent heat resistanceInfo
- Publication number
- JP2843420B2 JP2843420B2 JP15908690A JP15908690A JP2843420B2 JP 2843420 B2 JP2843420 B2 JP 2843420B2 JP 15908690 A JP15908690 A JP 15908690A JP 15908690 A JP15908690 A JP 15908690A JP 2843420 B2 JP2843420 B2 JP 2843420B2
- Authority
- JP
- Japan
- Prior art keywords
- molded article
- electron beam
- heat resistance
- strength
- polyethylene
- 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 - Lifetime
Links
- -1 polyethylene Polymers 0.000 title claims description 30
- 239000004698 Polyethylene Substances 0.000 title claims description 28
- 229920000573 polyethylene Polymers 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims description 64
- 238000010894 electron beam technology Methods 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 20
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 9
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 9
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000001891 gel spinning Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000886 hydrostatic extrusion Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、分子配向法により延伸して、引張強度を高
めたポリエチレン成形体の強度を損なうことなく耐熱性
を高めることができる延伸配向ポリエチレン成形体の製
造方法に関する。Description: TECHNICAL FIELD The present invention relates to a stretch-oriented polyethylene which can be stretched by a molecular orientation method to enhance heat resistance without impairing the strength of a polyethylene molded body having enhanced tensile strength. The present invention relates to a method for manufacturing a molded article.
（従来技術） ポリエチレンは、典型的な汎用樹脂で、従来より広範
囲の用途に使用されているが、他の材料に比較すると、
強度や耐熱性が劣るため、それらを必要とする過酷な用
途には従来あまり使用されていない。このため、従来よ
り強度や耐熱性を高めることが種々検討されている。(Prior art) Polyethylene is a typical general-purpose resin, which has been used for a wider range of applications than before.
Because of poor strength and heat resistance, they have not been used so far in severe applications requiring them. For this reason, conventionally, various studies have been made to increase strength and heat resistance.
強度を高める方法としては、ガラス繊維で補強する繊
維強化法や充填剤を用いる充填剤強化法などの方法があ
るが、これらの方法は、製造が繁雑であるため、近年は
補強剤を使用せずにポリエチレン自体の強度を高める分
子配向法が注目され、繊維、フィルムなどのような成形
体の製造に利用されている。例えば、引張強度30Kg/mm2
以上の高密度ポリエチレン成形体や引張強度70Kg/mm2以
上の超高分子量ポリエチレン成形体などの製造である。As a method for increasing the strength, there are methods such as a fiber reinforcement method of reinforcing with glass fiber and a filler reinforcement method using a filler, but since these methods are complicated to manufacture, in recent years, a reinforcing agent has been used. Attention has been paid to a molecular orientation method for increasing the strength of polyethylene itself without using it, and it has been used for producing molded articles such as fibers and films. For example, tensile strength 30Kg / mm 2
Production of the above high-density polyethylene molded article and ultra-high molecular weight polyethylene molded article having a tensile strength of 70 kg / mm 2 or more.
この分子配向法は、ポリエチレンに延伸加工を施し
て、分子配向を変えることにより強度を高くする方法
で、その原理は次のようになっている。すなわち、一般
に、ポリエチレンのような可撓性高分子に一軸延伸加工
を施すと、組織は分子鎖が延伸方向に高度に配向したフ
ィブリルの製造になるが、そのフィブリルは多数のミク
ロフィブリルから構成され、そのミクロフィブリルは、
さらに結晶境界に集中する数多くの折りたたみ分子鎖と
結晶間を結ぶタイ分子とから構成されるようになる。し
かして、このタイ分子がフィブリルに作用する張力を支
えて、可撓性高分子の強度を高めると推定されている。
そこで、折りたたみ分子を減少させ、タイ分子を増加さ
せるように延伸すれば、ポリエチレン強度を高くするこ
とができる。The molecular orientation method is a method of increasing the strength by subjecting polyethylene to stretching processing to change the molecular orientation, and its principle is as follows. That is, in general, when a uniaxial stretching process is performed on a flexible polymer such as polyethylene, the tissue becomes a fibril in which molecular chains are highly oriented in the stretching direction, and the fibril is composed of a large number of microfibrils. , The microfibrils
Further, it is composed of a large number of folded molecular chains concentrated on the crystal boundaries and tie molecules connecting the crystals. Thus, it is estimated that the tie molecules support the tension acting on the fibrils and increase the strength of the flexible polymer.
Therefore, if the stretching is performed so as to reduce the number of folded molecules and increase the number of tie molecules, the strength of polyethylene can be increased.
分子配向法には、熱延伸法、ゾーン延伸法、固体押出
し法、ロール圧延法、マイクロ波選択加熱延伸法、Tip
Contact法、静水圧押出し法、ゲル紡糸法、溶融延伸配
向法などがあるが、高密度ポリエチレン成形体の場合、
熱延伸法、ゾーン延伸法、固体押出し法、ロール圧延
法、マイクロ波選択加熱延伸法、Tip Contact法、静水
圧押出し法などにより製造され、超高分子量ポリエチレ
ン成形体の場合は、先の延伸法のほかにゲル紡糸法、溶
融延伸配向法などにより製造されている。特にこれらの
配向法で製造した超高分子量ポリエチレンの繊維は、炭
素繊維やケブラー繊維のような高強度繊維より強度が大
きく、弾性率、比重なども優れている。The molecular orientation method includes hot stretching method, zone stretching method, solid extrusion method, roll rolling method, microwave selective heating stretching method, Tip
There are Contact method, hydrostatic extrusion method, gel spinning method, melt drawing orientation method, etc.
Manufactured by hot drawing, zone drawing, solid extrusion, roll rolling, microwave selective heating drawing, Tip Contact method, hydrostatic extrusion, etc. In addition, it is manufactured by a gel spinning method, a melt drawing orientation method, or the like. In particular, ultrahigh molecular weight polyethylene fibers produced by these orientation methods have higher strength than high-strength fibers such as carbon fibers and Kevlar fibers, and have excellent elastic modulus and specific gravity.
しかしながら、分子配向法で強度は改善されるもの
の、耐熱性が改善されず、耐熱性を必要とする用途には
使用できない。However, although the strength is improved by the molecular orientation method, the heat resistance is not improved and cannot be used for applications requiring heat resistance.
このポリエチレンの耐熱性を改善する方法としては橋
かけにより三次元網目構造にして、溶融による熱変形を
抑制する方法がある。この橋かけ法には、有機過酸化物
やシラン化合物で橋かけする化学的方法と紫外線や放射
線を照射して橋かけする物理的方法とがあるが、前者の
方法により橋かけする場合は、架橋剤の種類や添加量、
反応温度、時間を十分調整しなければならない。As a method of improving the heat resistance of polyethylene, there is a method of forming a three-dimensional network structure by crosslinking to suppress thermal deformation due to melting. In this crosslinking method, there are a chemical method of crosslinking with an organic peroxide or a silane compound and a physical method of crosslinking by irradiating ultraviolet rays or radiation, but in the case of crosslinking by the former method, The type and amount of crosslinking agent,
The reaction temperature and time must be sufficiently adjusted.
一方、後者の方法で橋かけする場合にはこのような問
題がないが、紫外線照射による場合は、毒性のある架橋
促進剤を添加するため、その残存が衛生上問題になる。
また、放射線照射による場合、線源コストが高価なた
め、製造コストが高くなるという問題がある。On the other hand, there is no such problem in the case of crosslinking by the latter method. However, in the case of ultraviolet irradiation, since a toxic crosslinking accelerator is added, the remaining residue becomes a hygienic problem.
Further, in the case of irradiation with radiation, there is a problem that the production cost is increased because the source cost is high.
（発明が解決しようとする問題点） しかし、近年、低エネルギー型の電子線加速器の開発
により放射線照射の線源コストの低減がはがられ、コス
ト的に工業上使用可能になってきている。しかしなが
ら、分子配向法により強度を高めた成形体に電子線を照
射して、橋かけにより耐熱性を向上させようとすると、
電子線照射前より強度が低下してしまうという問題があ
った。(Problems to be Solved by the Invention) However, in recent years, the development of low-energy electron beam accelerators has reduced the radiation source cost of radiation irradiation, and has become industrially usable in terms of cost. However, when irradiating an electron beam to a molded body having increased strength by a molecular orientation method and trying to improve heat resistance by crosslinking,
There is a problem that the strength is lower than before the electron beam irradiation.
そこで、本発明では、電子線照射で耐熱性を向上させ
ても、強度が低下しない延伸配向ポリエチレン成形体の
製造方法を提供するものである。Therefore, the present invention provides a method for producing a stretch-oriented polyethylene molded article whose strength does not decrease even when heat resistance is improved by electron beam irradiation.
（問題点を解決するための手段） 本発明は、分子配向法により延伸した延伸配向ポリエ
チレン成形体の表面をエチレン性二重結合を有するモノ
マーで被覆した後、電子線を５〜50Mrad照射することに
よりポリエチレン成形体を製造するようにした。(Means for Solving the Problems) In the present invention, the surface of a stretch-oriented polyethylene molded article stretched by a molecular orientation method is coated with a monomer having an ethylenic double bond, and then irradiated with 5 to 50 Mrad of an electron beam. To produce a polyethylene molded article.
以下本発明の製造法を説明する。 Hereinafter, the production method of the present invention will be described.
まず、本発明では、素材ポリエチレンとして、分子配
向法により延伸した延伸配向ポリエチレンの成形体を用
いる。このような成形体としては、高密度ポリエチレン
を分子配向法により延伸し、引張強度を30Kg/mm2以上に
高めた成形体や超高分子量ポリエチレンを同様に延伸
し、引張強度を70Kg/mm2以上に高めた成形体がある。こ
れらの成形体は、高配向可能な直鎖状ポリエチレンを前
記の従来の公知延伸法で延伸すれば得られる。しかし、
これらの成形体は、高密度ポリエチレンの場合、引張強
度が30Kg/mm2以上のものであることを必要とし、また、
超高分子量ポリエチレンの場合は、引張強度が70Kg/mm2
以上のものであることを必要とする。これは、引張強度
がこれらの強度未満であると、配向が不十分なため、電
子線照射により橋かけを行った場合、橋かけ点に応力が
集中し、強度が低下してしまうためである。なお、ここ
で言う高密度ポリエチレンとは、密度（g/cm3）が0.942
〜0.965で、平均分子量が２〜20万の直鎖状ポリエチレ
ンを意味し（JIS K6760、ポリエチレン試験方法）、ま
た、超高分子量ポリエチレンとは、密度（g/cm3）が0.9
40〜0.950で、平均分子量が100万以上の直鎖状ポリエチ
レンを意味する（高分子データハンドブック応用編、高
分子学会編、培風館発行）。First, in the present invention, a molded product of stretch-oriented polyethylene stretched by a molecular orientation method is used as the raw material polyethylene. As such a molded article, a high-density polyethylene is stretched by a molecular orientation method, and a molded article or an ultra-high molecular weight polyethylene having a tensile strength increased to 30 kg / mm 2 or more is similarly stretched to have a tensile strength of 70 kg / mm 2. There is a molded body that has been enhanced as described above. These molded products can be obtained by stretching a highly oriented linear polyethylene by the above-mentioned conventional known stretching method. But,
In the case of high-density polyethylene, these molded articles need to have a tensile strength of 30 kg / mm 2 or more, and
In the case of ultra high molecular weight polyethylene, the tensile strength is 70 kg / mm 2
You need to be more than that. This is because, if the tensile strength is less than these strengths, the orientation is insufficient, and when cross-linking is performed by electron beam irradiation, stress is concentrated at the cross-linking point, and the strength is reduced. . The high-density polyethylene referred to here has a density (g / cm 3 ) of 0.942.
0.965 means a linear polyethylene having an average molecular weight of 20,000 to 200,000 (JIS K6760, polyethylene test method), and ultra-high molecular weight polyethylene means that the density (g / cm 3 ) is 0.9.
40 to 0.950 means linear polyethylene having an average molecular weight of 1,000,000 or more (Applied Polymer Data Handbook, edited by The Society of Polymer Science, published by Baifukan).
次に、本発明では、このようなポリエチレン成形体表
面をエチレン性二重結合を有するモノマーで被覆して、
電子線を照射する。従来のように成形体表面をモノマー
で被覆せずに電子線照射により橋かけを行うと、強度が
低下するが、この強度低下の原因は、電子線照射により
ポリエチレン成形体表面に生成したラジカルが空気中の
酸素と反応して、パーオキサイドを生成し、それが分子
を酸化劣化させるためと考えられているが、成形体表面
を電子線反応型モノマーで被覆しておくと、モノマーが
成形体表面に生成したラジカルと反応して、グラフト重
合し、失活するため、分子を酸化劣化させることがな
い。Next, in the present invention, such a polyethylene molded body surface is coated with a monomer having an ethylenic double bond,
Irradiate electron beam. When crosslinking is performed by electron beam irradiation without coating the surface of the molded body with a monomer as in the past, the strength decreases.However, the cause of this strength decrease is that radicals generated on the polyethylene molded body surface by electron beam irradiation are reduced. It is thought that it reacts with oxygen in the air to generate peroxide, which oxidizes and degrades molecules.However, if the surface of the molded body is coated with an electron beam reactive monomer, It reacts with radicals generated on the surface to undergo graft polymerization and deactivate, so that molecules are not oxidized and degraded.
また、従来の方法で、成形体の強度が低下する他の原
因として、成形他内部に生成したラジカルが電子線照射
中に内部に拡散してきた酸素と反応して、内部にもパー
オキサイドを生成し、これがポリエチレン分子鎖を切断
することが考えられているが、成形体をモノマーで被覆
しておくと、電子線照射と同時に表面にグラフト層が形
成されるため、内部への酸素拡散は抑制され、パーオキ
サイドの生成とそのパーオキサイドによる分子鎖切断が
防止される。Another cause of the decrease in the strength of the molded body in the conventional method is that radicals generated inside the molded body react with oxygen that has diffused inside during electron beam irradiation to generate peroxide inside. This is thought to cut the polyethylene molecular chain.However, if the molded body is coated with a monomer, a graft layer is formed on the surface at the same time as electron beam irradiation, preventing oxygen diffusion into the interior. Thus, generation of peroxide and molecular chain breakage due to the peroxide are prevented.
成形体を被覆するモノマーは、エチレン性二重結合を
有するものであれば良く、例えば、アクリル酸、アクリ
ル酸メチル、アクリル酸エチル、アクリル酸ブチル、ア
クリル酸−２−エチルヘキシル、アクリル酸イソブチル
のようなアクリル酸誘導体、また、メタクリル酸、メタ
クリル酸メチル、メタクリル酸エチル、メタクリル酸プ
ロピル、メタクリル酸ブチル、メタクリル酸−２−ヒド
ロキシエチルなどのようなメタクリル酸誘導体、さらに
は、アクリロニトリルやスチレンなどのようにビニル基
を有するモノマー、アリルアルコールやアリルクロライ
ドなどのようなアリル基を有するモノマーなどを使用で
きる。The monomer for coating the molded article may be any one having an ethylenic double bond, and examples thereof include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and isobutyl acrylate. Acrylic acid derivatives, methacrylic acid derivatives such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, and further, such as acrylonitrile and styrene And a monomer having an allyl group such as allyl alcohol and allyl chloride.
電子線の照射は、線量が5Mrad未満であると、橋かけ
が不充分なため、充分なる耐熱性が得られず、50Mradを
越えると、強度が低下するので、５〜50Mradにする。If the dose of the electron beam is less than 5 Mrad, sufficient heat resistance cannot be obtained due to insufficient crosslinking, and if the dose exceeds 50 Mrad, the intensity is reduced.
電子線照射後成形体表面に未反応モノマーやホモポリ
マーが残存する場合もあるが、そのような場合には洗浄
すればよい。After the electron beam irradiation, unreacted monomers or homopolymers may remain on the surface of the molded body. In such a case, washing may be performed.
（実施例） 実施例１ 高密度ポリエチレン（密度0.950以上）を熱延伸法ま
たはロール圧延法で延伸して成形体を製造した。熱延伸
法は温度125℃、延伸速度1.5cm/minで延伸し、ロール圧
延法はロール温度120℃延伸した。(Example) Example 1 A high-density polyethylene (density of 0.950 or more) was stretched by a hot stretching method or a roll rolling method to produce a molded body. In the hot stretching method, stretching was performed at a temperature of 125 ° C. and a stretching speed of 1.5 cm / min. In the roll rolling method, stretching was performed at a roll temperature of 120 ° C.
次に、この成形体の表面にエチレン性二重結合を有す
るモノマーを塗布して、被覆した後、または被覆後二軸
延伸したポリエチレンテレフタレートフィルム（厚さ25
μｍ）を積層して電子線を照射した。Next, a monomer having an ethylenic double bond is applied to the surface of the molded product and coated, or after coating, biaxially stretched polyethylene terephthalate film (thickness 25)
μm) and irradiated with an electron beam.
その後、このようにして製造した成形体の耐熱性と強
度保持率を次の方法で評価した。Thereafter, the heat resistance and the strength retention of the molded article thus manufactured were evaluated by the following methods.
（１）耐熱性 成形体に2.5kg/cm2の荷重をかけた状態で毎分５℃の
割合で加温し、溶融破断する温度を測定した。(1) Heat resistance The molded body was heated at a rate of 5 ° C./min under a load of 2.5 kg / cm 2 , and the temperature at which the melt fractured was measured.
（２）強度保持率 電子線照射前と後の成形体の引張破断強度を測定し
て、照射後／照射前の百分率を算出した。(2) Strength retention The tensile breaking strength of the molded body before and after electron beam irradiation was measured, and the percentage after irradiation / before irradiation was calculated.
第１表、第２表に熱延伸法による成形体の耐熱性と強
度保持率を、また、第３表、第４表にロール圧延法によ
る成形体の耐熱性と強度保持率を示す。Tables 1 and 2 show the heat resistance and strength retention of the molded article by the hot stretching method, and Tables 3 and 4 show the heat resistance and strength retention of the molded article by the roll rolling method.
また、第１図に熱延伸法により６倍に延伸した成形体
をメタクリル酸で被覆して電子線を照射した場合と、被
覆せずに電子線を照射した場合の溶融破断温度と線量の
関係を、第２図にロール圧延法により11倍に延伸した成
形体を同様にメタクリル酸で被覆して電子線を照射した
場合と、被覆せずに電子線を照射した場合の溶融破断温
度と線量の関係を示す。FIG. 1 shows the relationship between the melting rupture temperature and the dose when a molded article stretched 6 times by the hot stretching method was coated with methacrylic acid and irradiated with an electron beam, and when the molded article was irradiated with an electron beam without coating. In FIG. 2, the melt rupture temperature and the dose in the case where the molded body stretched 11 times by the roll rolling method was similarly coated with methacrylic acid and irradiated with an electron beam, and in the case where the coated body was irradiated with an electron beam without coating. Shows the relationship.
成形体を熱延伸法で延伸し、引張強度を30Kg/mm2以上
にしたものの場合、耐熱性の溶融破断温度は、第１表、
第２表に示すように、電子線照射前83〜86℃（No.7、1
5、17）であったが、電子線を照射すると、156〜165℃
と高くなる。この溶融破断温度の上昇は、第１図に示す
ように、モノマーで被覆して製造したものも、被覆しな
いで製造したものもあまり差がないので、モノマーの被
覆によるものでないことが明らかである。 In the case where the molded body is stretched by the hot stretching method and the tensile strength is set to 30 kg / mm 2 or more, the heat-resistant melting rupture temperature is as shown in Table 1.
As shown in Table 2, 83-86 ° C. before electron beam irradiation (No. 7, 1
5, 17), but when irradiated with an electron beam, 156-165 ° C
And higher. As shown in FIG. 1, the rise in the melting rupture temperature is not caused by the monomer coating because there is not much difference between those manufactured by coating with the monomer and those manufactured without the coating. .
強度保持率は、第１表のNo.1〜８と第２表のNo.8〜10
を比較してみれば明らかなように、モノマー未被覆で製
造したものが69〜79％であるのに対して、モノマーで被
覆して製造したものは97〜99％と良好である。また、第
２表のNo.12〜14にみられるごとく、モノマーで被覆し
ても電子線照射線量が50Mradを越えると、強度保持率は
74〜76％と低い。さらに、成形体の引張強度が30Kg/mm2
未満である（第２表のNo.3、６）と、強度保持率が引張
強度30Kg/mm2以上のものより低くなる。The strength retention was measured in Nos. 1 to 8 in Table 1 and Nos. 8 to 10 in Table 2.
As is clear from the comparison of the above, 69-79% was produced without monomer coating, whereas 97-99% was produced with monomer coating. Also, as can be seen from Nos. 12 to 14 in Table 2, when the electron beam irradiation dose exceeds 50 Mrad even when coated with a monomer, the intensity retention rate becomes higher.
It is as low as 74-76%. Furthermore, the molded product has a tensile strength of 30 kg / mm 2
If it is less than (Nos. 3 and 6 in Table 2), the strength retention is lower than that of a tensile strength of 30 kg / mm 2 or more.
第３表、第４表および第２図に示す成形体をロール延
伸法で製造したものの場合も熱延伸法で製造したものの
場合と同様の傾向である。The molded articles shown in Tables 3, 4 and 2 produced by the roll stretching method have the same tendency as those produced by the hot stretching method.
実施例２ 超高分子量ポリエチレン（分子量250万）を熱延伸法
またはゲル紡糸法で延伸して成形体を製造した。両延伸
法での延伸は、延伸温度125℃で行った。Example 2 Ultra-high molecular weight polyethylene (molecular weight 2.5 million) was drawn by a hot drawing method or a gel spinning method to produce a molded article. The stretching in both stretching methods was performed at a stretching temperature of 125 ° C.
次に、この成形体の表面にエチレン性二重結合を有す
るモノマーを実施例１と同要領で塗布して、電子線を照
射し、成形体の耐熱性と強度保持率を評価した。Next, a monomer having an ethylenic double bond was applied to the surface of the molded article in the same manner as in Example 1, and irradiated with an electron beam to evaluate the heat resistance and the strength retention of the molded article.
第５表、第６表に熱延伸法による成形体の耐熱性と強
度保持率を、また、第７表、第８表にゲル紡糸法による
成形体の耐熱性と強度保持率を示す。Tables 5 and 6 show the heat resistance and strength retention of the molded article by the hot drawing method, and Tables 7 and 8 show the heat resistance and strength retention of the molded article by the gel spinning method.
また、第３図に熱延伸法により14倍に延伸した成形体
をメタクリル酸で被覆して電子線を照射した場合と、被
覆せずに電子線を照射した場合の溶融破断温度と線量の
関係を、第４図にゲル紡糸法により14倍に延伸した成形
体を同様にメタクリル酸で被覆して電子線を照射した場
合と、被覆せずに電子線を照射した場合の溶融破断温度
と線量の関係を示す。Fig. 3 shows the relationship between the melting rupture temperature and the dose when the molded article stretched 14 times by the hot stretching method was coated with methacrylic acid and irradiated with an electron beam, and when the electron beam was irradiated without coating. Fig. 4 shows the melting rupture temperature and the dose when the molded product stretched 14 times by the gel spinning method was similarly coated with methacrylic acid and irradiated with an electron beam, and when the molded product was irradiated with an electron beam without coating. Shows the relationship.
成形体を熱延伸法で延伸し、引張強度を70Kg/mm2以上
にしたものの場合も、耐熱性の溶融破断温度は、第５
表、第６表に示すように、電子線照射前96〜102℃（第
６表No.47、55、57）であったが、電子線を照射する
と、167〜171℃と高くなる。この溶融破断温度の上昇
は、第３図に示すように、モノマーで被覆して製造した
ものも、被覆しないで製造したものもあまり差がないの
で、高密度ポリエチレン成形体の場合と同様にモノマー
の被覆によるものでないことが明らかである。 In the case where the molded body is stretched by the hot stretching method and the tensile strength is set to 70 kg / mm 2 or more, the heat-resistant melting rupture temperature is 5th.
As shown in Tables and Table 6, the temperature was 96 to 102 ° C before electron beam irradiation (Table 6, Nos. 47, 55 and 57). As shown in FIG. 3, the rise in the melt rupture temperature is not significantly different between those manufactured by coating with the monomer and those manufactured without the coating. It is clear that this is not due to the coating.
強度保持率は、第５表のNo.41〜48と第６表のNo.48〜
50を比較してみれば明らかなように、モノマー未被覆で
製造したものが64〜77％であるのに対して、モノマーで
被覆して製造したものは97〜99％と良好である。また、
第６表のNo.52〜54にみられるごとく、モノマーで被覆
しても電子線照射線量が50Mradを越えると、強度保持率
は70〜72％と低い。さらに、成形体の引張強度が70Kg/m
m2未満である（第６表のNo.43、46）と、強度保持率が
引張強度70Kg/mm2以上のものより低くなる。The strength retention rates are as shown in Table 5 No. 41-48 and Table 6 No. 48-
As is clear from a comparison of 50, those manufactured without the monomer coating are 64 to 77%, whereas those manufactured by coating with the monomer are 97 to 99%, which is good. Also,
As can be seen from Tables Nos. 52 to 54 in Table 6, when the electron beam irradiation dose exceeds 50 Mrad even when coated with a monomer, the strength retention is as low as 70 to 72%. Furthermore, the tensile strength of the molded body is 70 kg / m
If it is less than m 2 (Nos. 43 and 46 in Table 6), the strength retention is lower than that of a tensile strength of 70 kg / mm 2 or more.
第７表、第８表および第４図に示す成形体をゲル紡糸
法で製造したものの場合も熱延伸法で製造したものの場
合と同様の傾向である。In the case where the molded articles shown in Tables 7, 8 and 4 were produced by the gel spinning method, the same tendency as in the case of those produced by the hot drawing method was observed.
（発明の効果） 以上のように、分子配向法により延伸して、ポリエチ
レン成形体の耐熱性を高める場合、本発明によれば、強
度を低下させることなく耐熱性を高めることができる。(Effect of the Invention) As described above, when the polyethylene molded body is stretched by the molecular orientation method to increase the heat resistance, according to the present invention, the heat resistance can be increased without lowering the strength.
【図面の簡単な説明】 第１図は、熱延伸法により６倍に延伸した高密度ポリエ
チレン成形体をメタクリル酸で被覆して電子線を照射し
た場合と、被覆せずに電子線を照射した場合の溶融破断
温度と線量の関係を示すグラフである。 第２図は、ロール圧延法により11倍に延伸した高密度ポ
リエチレン成形体を同様にメタクリル酸で被覆して電子
線を照射した場合と、被覆せずに電子線を照射した場合
の溶融破断温度と線量の関係を示すグラフである。 第３図は、熱延伸法により14倍に延伸した超高分子量ポ
リエチレン成形体をメタクリル酸で被覆して電子線を照
射した場合と、被覆せずに電子線を照射した場合の溶融
破断温度と線量の関係を示すグラフである。 第４図は、ゲル紡糸法により14倍に延伸した超高分子量
ポリエチレン成形体を同様にメタクリル酸で被覆して電
子線を照射した場合と、被覆せずに電子線を照射した場
合の溶融破断温度と線量の関係を示すグラフである。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a case where a high-density polyethylene molded article stretched 6 times by a hot drawing method is coated with methacrylic acid and irradiated with an electron beam, and a case where the electron beam is irradiated without coating. 6 is a graph showing the relationship between the melting rupture temperature and the dose in the case. FIG. 2 shows the melting rupture temperature of the case where a high-density polyethylene molded article stretched 11 times by the roll rolling method was similarly covered with methacrylic acid and irradiated with an electron beam, and the case where the uncoated body was irradiated with an electron beam. 6 is a graph showing the relationship between and dose. FIG. 3 shows the melting rupture temperature when the ultra-high molecular weight polyethylene molded article stretched 14 times by the hot stretching method was coated with methacrylic acid and irradiated with an electron beam, and when the electron beam was irradiated without coating. It is a graph which shows the relationship of a dose. Fig. 4 shows the melt fracture when the ultra-high molecular weight polyethylene molded article stretched 14 times by the gel spinning method was similarly coated with methacrylic acid and irradiated with an electron beam, and when the electron beam was irradiated without coating. 4 is a graph showing the relationship between temperature and dose.
フロントページの続き (72)発明者 増原 憲一 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社新材料研究所内 (56)参考文献 特開 昭62−277441（ＪＰ，Ａ) 特開 昭62−34928（ＪＰ，Ａ) 特公 昭41−8957（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C08J 7/00 - 7/18Continuing from the front page (72) Inventor Kenichi Masuhara 7th, Takatani Shinmachi, Ichikawa City, Chiba Prefecture Nisshin Steel Co., Ltd. New Materials Research Laboratory (56) References JP-A-62-277441 (JP, A) JP-A-62 −34928 (JP, A) JP 41-8957 (JP, B1) (58) Fields investigated (Int. Cl. 6 , DB name) C08J 7/00-7/18
Claims (3)
チレン成形体の表面をエチレン性二重結合を有するモノ
マーで被覆した後、電子線を５〜50Mrad照射することを
特徴とする耐熱性に優れた延伸配向ポリエチレン成形体
の製造方法。An excellent heat resistance characterized in that the surface of a stretch-oriented polyethylene molded article stretched by a molecular orientation method is coated with a monomer having an ethylenic double bond and then irradiated with an electron beam at 5 to 50 Mrad. A method for producing a stretch-oriented polyethylene molded article.
Kg/mm2以上の高密度ポリエチレンの成形体であることを
特徴とする耐熱性に優れた延伸配向ポリエチレン成形体
の製造方法。2. The stretch-oriented polyethylene molded product has a tensile strength of 30.
A method for producing a stretch-oriented polyethylene molded article having excellent heat resistance, which is a molded article of high-density polyethylene of Kg / mm 2 or more.
Kg/mm2以上の超高分子量ポリエチレンの成形体であるこ
とを特徴とする耐熱性に優れた延伸配向ポリエチレン成
形体の製造方法。3. The stretch-oriented polyethylene molded product has a tensile strength of 70.
A method for producing a stretch-oriented polyethylene molded article having excellent heat resistance, characterized in that the molded article is an ultra-high molecular weight polyethylene molded article of Kg / mm 2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15908690A JP2843420B2 (en) | 1990-06-18 | 1990-06-18 | Method for producing stretch-oriented polyethylene molded article having excellent heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15908690A JP2843420B2 (en) | 1990-06-18 | 1990-06-18 | Method for producing stretch-oriented polyethylene molded article having excellent heat resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0450245A JPH0450245A (en) | 1992-02-19 |
| JP2843420B2 true JP2843420B2 (en) | 1999-01-06 |
Family
ID=15685929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15908690A Expired - Lifetime JP2843420B2 (en) | 1990-06-18 | 1990-06-18 | Method for producing stretch-oriented polyethylene molded article having excellent heat resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2843420B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014103172A (en) | 2012-11-16 | 2014-06-05 | Toshiba Corp | Magnetic thin film, manufacturing method therefor, high frequency oscillation device using magnetic thin film, magnetic head, magnetic recording medium, and magnetic recorder/reproducer |
| JP2020158191A (en) * | 2019-03-28 | 2020-10-01 | 大日本印刷株式会社 | Base materials, laminates, packaging materials, packaging bags and stand pouches |
| JP7576232B2 (en) * | 2019-03-28 | 2024-10-31 | 大日本印刷株式会社 | Laminate, packaging material, packaging bag and stand-up pouch |
| JP2020157723A (en) * | 2019-03-28 | 2020-10-01 | 大日本印刷株式会社 | Laminates, packaging materials, packaging bags and stand pouches |
-
1990
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0450245A (en) | 1992-02-19 |
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