JPH0273845A - Crosslinked polyurethane vinyl chloride copolymer composition - Google Patents
Crosslinked polyurethane vinyl chloride copolymer compositionInfo
- Publication number
- JPH0273845A JPH0273845A JP22499688A JP22499688A JPH0273845A JP H0273845 A JPH0273845 A JP H0273845A JP 22499688 A JP22499688 A JP 22499688A JP 22499688 A JP22499688 A JP 22499688A JP H0273845 A JPH0273845 A JP H0273845A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- weight
- crosslinked
- polyurethane
- zeolite
- 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
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 16
- 239000004814 polyurethane Substances 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 229920001577 copolymer Polymers 0.000 title claims abstract description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 10
- 239000010457 zeolite Substances 0.000 claims abstract description 10
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 239000011342 resin composition Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 5
- 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 abstract description 2
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 238000003878 thermal aging Methods 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐熱老化性、耐水性が優れている架橋ポリウレ
タン塩化ビニル共重合体に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a crosslinked polyurethane vinyl chloride copolymer that has excellent heat aging resistance and water resistance.
（従来の技術）
ポリウレタンとポリ塩化ビニルのグラフト共重合体は、
両者の優れた特性をそれぞれ兼備するポリマーとして知
られ、各種のチューブ、電線被覆材、シート等の素材と
しで使用されている。(Prior art) A graft copolymer of polyurethane and polyvinyl chloride is
It is known as a polymer that has the excellent properties of both, and is used as a material for various tubes, wire coverings, sheets, etc.
（発明が解決しようとする課題）
ところで、各種の電線被覆材の場合、電線の使用環境が
変化して例えば周囲の温度が著しく上昇したりまたは電
線に過電流が流れて電線が高温になると、絶縁材として
使用していた上記被覆材が流動しはじめて、その原形を
保持し得なくなるという問題が生じている。(Problems to be Solved by the Invention) In the case of various wire coating materials, if the environment in which the wire is used changes and, for example, the surrounding temperature rises significantly, or if an overcurrent flows through the wire and the wire becomes hot, A problem arises in that the coating material used as an insulating material begins to flow and is no longer able to maintain its original shape.
このような高温下における変形を防止するためには、被
覆材を構成する樹脂組成物に更に架橋助剤を配合し、こ
れに例えば電子線を照射してリジットな架橋体にすると
いう方法が一般に採用されている。In order to prevent such deformation at high temperatures, a common method is to further add a crosslinking agent to the resin composition that makes up the coating material, and then irradiate this with, for example, an electron beam to create a rigid crosslinked product. It has been adopted.
しかしながら、前記したポリウレタンとポリ塩化ビニル
の共重合体の場合、これに架橋助剤を配合して電子線照
射により架橋せしめても、得られた架橋ポリウレタン塩
化ビニル共重合体は、その耐熱老化性と耐水性が著しく
劣化してしまい、例えば電線被覆剤としては到底使用に
耐え得ないのが現状である。However, in the case of the copolymer of polyurethane and polyvinyl chloride described above, even if a crosslinking aid is added to the copolymer and crosslinked by electron beam irradiation, the resulting crosslinked polyurethane vinyl chloride copolymer has poor heat aging resistance. As a result, the water resistance deteriorates significantly, and the current situation is that it cannot withstand use as a coating material for electric wires, for example.
本発明はポリウレタンとポリ塩化ビニル共重合体におけ
る上記した欠点をほぼ完全に解消し、耐熱老化性、耐水
性のいずれもが優れた架橋ポリウレタン塩化ビニル共重
合体組成物の提供を目的とする。The present invention aims to provide a crosslinked polyurethane vinyl chloride copolymer composition that almost completely eliminates the above-mentioned drawbacks of polyurethane and polyvinyl chloride copolymers and has excellent heat aging resistance and water resistance.
（課題を解決するための手段・作用）
本発明者らは上記目的を達成するために鋭意研究を重ね
たところ、前記グラフト共重合体に所定量のゼオライト
を配合すると有効であるとの事実を見出し、本発明の共
重合体組成物を開発するに到った。(Means and effects for solving the problem) In order to achieve the above object, the present inventors conducted extensive research and found that it is effective to blend a predetermined amount of zeolite into the graft copolymer. This led to the development of the copolymer composition of the present invention.
すなわち、本発明の架橋ポリウレタン塩化ビニル共重合
体組成物は、ポリウレタンと塩化ビニルのグラフト共重
合体１００重量部、ゼオライト０．２〜１５重量部、お
よび多官能性ポリマー１〜２０重量部から成る樹脂組成
物に、電離性放射線１〜３０ Ｍ ｒ ａ ｄを照射し
て架橋せめして成ることを特徴とする。That is, the crosslinked polyurethane vinyl chloride copolymer composition of the present invention comprises 100 parts by weight of a graft copolymer of polyurethane and vinyl chloride, 0.2 to 15 parts by weight of zeolite, and 1 to 20 parts by weight of a polyfunctional polymer. It is characterized in that it is crosslinked by irradiating a resin composition with ionizing radiation of 1 to 30 Mr.ad.
本発明の組成物は、上記組成を必須とする樹脂組成物の
架橋体である。The composition of the present invention is a crosslinked resin composition that essentially has the above composition.
この樹脂組成物において、母材であるグラフト共重合体
は、ポリウレタンを幹ポリマーとし、これに塩化ビニル
をグラフト重合せしめたものである。この場合、幹ポリ
マーは、その数平均分子量が１２００〜２５００である
ような重合度であることが好ましい。数平均分子量が１
２００未満の場合はその耐熱性が低下し、また２５００
より大きい場合は他の成分の配合が困難になるからであ
る。In this resin composition, the graft copolymer that is the base material has polyurethane as a backbone polymer, and vinyl chloride is graft-polymerized onto this. In this case, the degree of polymerization of the backbone polymer is preferably such that its number average molecular weight is 1200 to 2500. Number average molecular weight is 1
If it is less than 200, the heat resistance will decrease, and if it is less than 2500
This is because if the size is larger, it becomes difficult to mix other components.
また、このグラフト共重合体において、塩化ビニルのグ
ラフト化率は３０〜６５重量％であることが好ましい。Further, in this graft copolymer, the grafting rate of vinyl chloride is preferably 30 to 65% by weight.
この値が３０重量％未満の場合は成型体に腰がなくなり
、逆に６５重量％より大きい場合は柔軟性がなくなるか
らである。This is because if this value is less than 30% by weight, the molded product will lack stiffness, whereas if it is greater than 65% by weight, it will lack flexibility.
樹脂組成物における第２の必須成分はゼオライトである
。ゼオライトとしては、天然ゼオライト、合成ゼオライ
トのいずれをも使用することができる。The second essential component in the resin composition is zeolite. As the zeolite, both natural zeolite and synthetic zeolite can be used.
ゼオライトは、前記したポリウレタンと塩化ビニルのグ
ラフト共重合体１００重量部に対し０．２〜１５重量部
配合される。この配合量が０．２重量部未満の場合は、
得られた組成物の耐熱老化性、耐水性の向上が認められ
ず、一方、１５重量部を超えても、その配合の効果は飽
和に達してしまうからである。好ましい配合量はグラフ
ト共重合体１００重量部に対し１〜１０重量部である。Zeolite is blended in an amount of 0.2 to 15 parts by weight per 100 parts by weight of the above-mentioned graft copolymer of polyurethane and vinyl chloride. If this amount is less than 0.2 parts by weight,
This is because no improvement in heat aging resistance or water resistance of the obtained composition was observed, and on the other hand, even if the amount exceeded 15 parts by weight, the effect of the blend would reach saturation. The preferred amount is 1 to 10 parts by weight per 100 parts by weight of the graft copolymer.
多官能性モノマーは、後述の放射線照射時に樹脂組成物
を架橋せしめるために配合される架橋助剤で、例えば、
トリメチロールプロパンアクリレート、トリメチロール
プロパントリメタクリレート、トリアクリルホルマール
、トリアリルイソシアヌレートをあげることができる。The polyfunctional monomer is a crosslinking aid that is added to crosslink the resin composition during radiation irradiation, which will be described later.
Examples include trimethylolpropane acrylate, trimethylolpropane trimethacrylate, triacryl formal, and triallyl isocyanurate.
多官能性モノマーの配合量は、前記グラフト共重合体１
００重量部に対し１〜２０重量部に設定される。配合量
が１重量部未満の場合は、架橋効果が発揮されず、また
２０重量部よりも多くても、その配合効果は飽和に達し
てしまうからである。The blending amount of the polyfunctional monomer is as follows:
It is set at 1 to 20 parts by weight per 00 parts by weight. If the amount is less than 1 part by weight, the crosslinking effect will not be exhibited, and if the amount is more than 20 parts by weight, the effect will reach saturation.
好ましくは、５〜１２重量部である。Preferably, it is 5 to 12 parts by weight.
本発明にかかる樹脂組成物は、上記３成分を必須とする
が、更に、Ｂａ−Ｚｎ系安定剤、ｐｂ系安定剤のような
安定剤を適量配合することもできス
本発明の組成物は、上記したような各成分の所定量を配
合し、これらを例えばロールを用いて混練したのち、シ
ート等の所定形状に形成し、この成形体に電離性放射線
を照射して製造される。The resin composition according to the present invention essentially contains the above three components, but may also contain an appropriate amount of a stabilizer such as a Ba-Zn stabilizer or a PB stabilizer. It is manufactured by blending predetermined amounts of each of the above-mentioned components, kneading them using, for example, a roll, forming them into a predetermined shape such as a sheet, and irradiating this molded body with ionizing radiation.
電離性の放射線としては、例えば電子線、Ｔ線をあげる
ことができる。また、このときの照射量は１〜３０Ｍｒ
ａ ｄに設定される。照射量が１Ｍｒａｄ未満の場合
は、前記した樹脂組成物の架橋が充分に進行せず、また
３０Ｍａｒｄより強い場合は得られた組成物の耐熱老化
性、耐水性が低下してしまうからである。好ましい照射
量は５〜２０Ｍｒａｄである。Examples of ionizing radiation include electron beams and T-rays. In addition, the irradiation amount at this time is 1 to 30 Mr
set to a d. If the irradiation dose is less than 1 Mrad, the crosslinking of the resin composition described above will not proceed sufficiently, and if it is stronger than 30 Mard, the heat aging resistance and water resistance of the resulting composition will decrease. The preferred dose is 5-20 Mrad.
（発明の実施例）
実施例１〜４、比較例１〜６
表示した各成分を表示の割合（重量部）で混合し、得ら
れた混合物をロールで混練したのち、厚み１＋ａｍのシ
ートをプレス成形した。このシートに５００ ＫＶの電
子線を１２Ｍｒ ａ ｄ照射して架橋せしめたのち、ダ
ンベル状に打抜いてサンプルとした。(Examples of the invention) Examples 1 to 4, Comparative Examples 1 to 6 The indicated components were mixed in the indicated proportions (parts by weight), and the resulting mixture was kneaded with a roll, and then a sheet with a thickness of 1+am was pressed. Molded. This sheet was cross-linked by irradiating 12 Mr ad of 500 KV electron beam, and then punched out into dumbbell shapes to prepare samples.
このサンプルを温度１３６°Ｃの恒温槽内に１６８時間
放置したのち、これを取り出してその引張り試験を行な
って伸びを測定し熱処理前の伸びに対する百分率（％）
を残率として算出し耐熱老化性を調べた。After leaving this sample in a constant temperature bath at a temperature of 136°C for 168 hours, it was taken out and subjected to a tensile test to measure the elongation, which was expressed as a percentage (%) of the elongation before heat treatment.
was calculated as the residual rate, and the heat aging resistance was investigated.
また、サンプルを９０°Ｃの温水中に１６８時間浸漬し
たのち、その伸びを測定し、浸漬前の伸びに対する残率
を算出して耐水性を調べた。In addition, after the sample was immersed in hot water at 90°C for 168 hours, its elongation was measured, and the residual ratio relative to the elongation before immersion was calculated to examine water resistance.
以上の結果を一括して第１表に示した。The above results are collectively shown in Table 1.
（以下余白）
（発明の効果）
以上の説明で明らかなように、本発明の架橋ポリウレタ
ン塩化ビニル共重合体組成物は、従来のものに比べ耐熱
老化性、耐水性のいずれもが優れておりその工業的価値
は極めて大である。(The following is a blank space) (Effects of the invention) As is clear from the above explanation, the crosslinked polyurethane vinyl chloride copolymer composition of the present invention has superior heat aging resistance and water resistance compared to conventional compositions. Its industrial value is extremely large.
Claims (1)
量部、ゼオライト０．２〜１５重量部、および多官能性
ポリマー１〜２０重量部から成る樹脂組成物に、電離性
放射線１〜３０Ｍｒａｄを照射して架橋せめして成るこ
とを特徴とする架橋ポリウレタン塩化ビニル共重合体組
成物。A resin composition consisting of 100 parts by weight of a graft copolymer of polyurethane and vinyl chloride, 0.2 to 15 parts by weight of zeolite, and 1 to 20 parts by weight of a polyfunctional polymer was crosslinked by irradiating ionizing radiation of 1 to 30 Mrad. A crosslinked polyurethane vinyl chloride copolymer composition comprising at least the following:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22499688A JPH0273845A (en) | 1988-09-08 | 1988-09-08 | Crosslinked polyurethane vinyl chloride copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22499688A JPH0273845A (en) | 1988-09-08 | 1988-09-08 | Crosslinked polyurethane vinyl chloride copolymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0273845A true JPH0273845A (en) | 1990-03-13 |
Family
ID=16822453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22499688A Pending JPH0273845A (en) | 1988-09-08 | 1988-09-08 | Crosslinked polyurethane vinyl chloride copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0273845A (en) |
-
1988
- 1988-09-08 JP JP22499688A patent/JPH0273845A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Stelescu et al. | Vulcanization of ethylene‐propylene–terpolymer‐based rubber mixtures by radiation processing | |
| DE69934556T2 (en) | Thermoplastic polyester resin and insulated wire made therefrom, electrically insulated cable and heat shrinkable tube | |
| JPH01502676A (en) | polymer composition | |
| US3580829A (en) | Process for irradiating polyvinylidene fluoride and a compatible polyfunctional monomer and product thereof | |
| EP0807128A1 (en) | Crosslinked thermoplastic elastomers | |
| JPH0273845A (en) | Crosslinked polyurethane vinyl chloride copolymer composition | |
| JPH07238220A (en) | Polyurethane resin composition and electric wire | |
| JP3435467B2 (en) | Heat-resistant flame-retardant polyurethane elastomer composition and electric wire therefrom | |
| JPS6023703B2 (en) | Method for producing heat-resistant ethylene/tetrafluoroethylene copolymer composition molded products | |
| JP2517876B2 (en) | Non-halogen flame-retardant resin molding for radiation exposure environment | |
| JP2002332384A (en) | Heat-resistant flame-retardant resin composition | |
| JP2636948B2 (en) | Manufacturing method of high hardness silicone rubber | |
| JP3178265B2 (en) | Radiation-resistant insulation composition for electric wires and cables | |
| JPS631683B2 (en) | ||
| JPH0573135B2 (en) | ||
| JPH037755A (en) | Phenylene oxide polymer composition | |
| JPH04149238A (en) | Flame retardant silane-crosslinked polyolefin composition | |
| JPS6116940A (en) | Heat-resistant and transparent polyolefin resin compostion | |
| JP2644340B2 (en) | Heat resistant wire | |
| JPS59131643A (en) | Vinyl chloride resin composition | |
| JPS60168745A (en) | Vinyl composition | |
| JPH06271630A (en) | Heat resistant polyolefin resin composition | |
| JP2863865B2 (en) | Heat resistant elastomer composition | |
| JPH039912A (en) | Crosslinked polyurethane-vinyl chloride copolymer composition | |
| JPS6116941A (en) | Heat-resistant and transparent polyolefin resin composition |