JPS6353219B2 - - Google Patents
Info
- Publication number
- JPS6353219B2 JPS6353219B2 JP58123992A JP12399283A JPS6353219B2 JP S6353219 B2 JPS6353219 B2 JP S6353219B2 JP 58123992 A JP58123992 A JP 58123992A JP 12399283 A JP12399283 A JP 12399283A JP S6353219 B2 JPS6353219 B2 JP S6353219B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- vinyl chloride
- parts
- weight
- graft copolymer
- 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
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 229920000578 graft copolymer Polymers 0.000 claims description 18
- 230000005855 radiation Effects 0.000 claims description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 150000002611 lead compounds Chemical class 0.000 claims description 8
- -1 trimellitic acid ester Chemical class 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 3
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 claims description 2
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 claims 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- YPDXSCXISVYHOB-UHFFFAOYSA-N tris(7-methyloctyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC(C)C)C(C(=O)OCCCCCCC(C)C)=C1 YPDXSCXISVYHOB-UHFFFAOYSA-N 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
（産業上の利用分野）
本発明は耐放射線環境性塩化ビニルグラフト共
重合体組成物に関するものである。
（発明が解決しようとする問題点）
なお、本明細書において耐放射線環境性とは、
耐放射線性、耐熱性および耐高温水蒸気性の包括
概念である。
原子力発電所の１次格納容器内などでは、放射
線が常時存在し、かつ60〜70℃程度の熱雰囲気に
あり事故発生時にはさらに高温水蒸気が発生す
る。そのような場所に布設されるフレキシブル被
覆電線管やケーブル、電線など（以下、電線など
という）は、そうした特殊でかつ過酷な環境にも
耐えうるものでなければならない。しかしなが
ら、電線などの被覆材料として広く用いられてい
る塩化ビニル樹脂組成物には、前記の過酷な環境
に暴露されたとき、硬化したり脆くなつたりして
亀裂が生じてしまうという欠点があつた。
（問題点を解決するための手段）
本発明者らはかかる塩化ビニル樹脂組成物の欠
点を改善するべく鋭意研究を重ねた結果、塩化ビ
ニルグラフト共重合体100部（重量部、以下同様）
に鉛含有量が70重量％以上の鉛化合物が10〜100
部および芳香族カルボン酸エステルまたは脂肪酸
多価アルコールエステルが５〜50部配合されてな
る塩化ビニルグラフト共重合体組成物が、耐放射
線環境性にすぐれており、前記原子力発電所の１
次格納容器内に布設される電線などの被覆材料と
してきわめてすぐれていることを見出し、本発明
を完成した。
本発明における塩化ビニルグラフト共重合体に
はエチレン・酢酸ビニル・塩化ビニル三元共重合
体（Ｅ・VA・VC）が好適に使用されるが、そ
の中でもＥ・VA・VC中のエチレン・酢酸ビニ
ル（Ｅ・VA）含有量が35〜60重量％で、さらに
Ｅ・VA中の酢酸ビニル（VA）含有量が30〜45
重量％のものを使用することが好ましい。
本発明における鉛化合物は、鉛含有量が70重量
％以上のものであり、たとえば酸化鉛（PbO、
Pb2O3、Pb3O4など）、炭酸鉛（PbCO3）三塩基
性硫酸鉛（3PbO・PbSO4・H2O）、二塩基性亜
隣酸鉛（2PbO・PbHPO3・1/2H2O）、二塩基性
フタル酸鉛（C6H4（COOPbO）2Pb）、塩基性硅酸
鉛（PbO・2PbSiO3・H2O）またはそれらの混合
物があげらる。これらの鉛化合物は放射線遮蔽効
果を有し、耐水蒸気性を付与するものである。配
合量は前記のごとく、塩化ビニルグラフト共重合
体100部に対し10〜100部であり、好ましくは20〜
90部、とくに好まししくは30〜70部である、10部
より少ない時は耐放射線環境性の効果が充分でな
く、100部を超える時は成形時の加工性に劣ると
共に成形物の機械的特性（たとえば引張強度、引
張伸び）に問題が生ずる。
本発明に用いる特定のエステル化合物は、芳香
族カルボン酸エステルまたは脂肪酸多価アルコー
ルエステルで、耐熱性にすぐれており、かつ塩化
ビニルグラフト共重合体を可塑性する作用をも有
しているものである。しかし、かかるエステル化
合物に代えて他の塩化ビニルグラフト共重合体の
可塑剤、たとえばジオクチルフタレートやクレジ
ルジフエニルホスフエートなどを用いるときは、
本発明の目的である耐放射線環境性はえられな
い。
ここで芳香族カルボン酸エステルとしては、た
とえば一般式：
（式中、Ｒは炭素数８〜10個のアルキル基であ
る）で示されるトリメリツト酸エステルが好まし
く、具体例としてはトリオクチルトリメリテー
ト、トリイソノニルトリメリテート、トリイソデ
シルトリメリテートなどがあげられる。
また、脂肪酸多価アルコールエステルとして
は、たとえばジペンタエリスリトールヘキサカプ
ロエート、ジペンタエリスリトールヘキサブチレ
ート、ジペンタエリスリトールヘキサアジペート
などのジペンタエリスリトールと炭素数10個以下
の脂肪酸とのエステルが好ましい。炭素数10個以
下の脂肪酸の具体例としては、たとえばプロピオ
ン酸、酪酸、吉草酸、カプロン酸、エナント酸、
カプリル酸、ペラルゴン酸、カプリン酸などの飽
和モノカルボン酸、アクリル酸、クロトン酸など
の不飽和モノカルボン酸、蓚酸、マロン酸、コハ
ク酸、グルタール酸、アジピン酸などの飽和ジカ
ルボン酸、マレイン酸などの不飽和ジカルボン酸
などがあげられる。
これら特定のエステル化合物の配合量は、塩化
ビニルグラフト共重合体100部に対し５〜50部で
あり、好ましくは10〜40部、とくに好ましくは20
〜30部である。５部より少ないときは、組成物の
可塑性が不足し混練や押出時の成形加工性に劣る
と共に、耐放射線環境性の効果が充分でなく、50
部を超えるときは、組成物が可塑化し過ぎ混練や
押出時の成形加工性に劣ると共に、成形物の引張
強さおよび加熱変形性が著しく低下し、機械的強
度に劣る。
本発明の組成物のすぐれた耐放射線環境性は、
前記鉛化合物およびエステル化合物を特定量、塩
化ビニルグラフト共重合体に配合することにより
初めてえられるものであり、いずれか一方が欠け
ても所望の耐放射線環境性がえられない。
（本発明の効果）
本発明の塩化ビニルグラフト共重合体組成物
は、すぐれた耐放射線環境性、すなわち耐放射線
性、耐熱性および耐高温水蒸気性を有しているの
で、前記原子力発電所の１次格納容器内に限られ
ず、２次格納容器内、原子力船の格納容器内など
高温高湿で放射線が存在している原子力関連施設
のいずれにも用いることができる。
また本発明の塩化ビニルグラフト共重合体組成
物は、前記原子力関連施設用のケーブル、電線な
どの被覆物やフレキシブル被覆電線管の材料とし
て好適であるが、そのほかパツキング、シール
材、枠、ホース類などの材料としても有用であ
る。
（実施例）
つぎに本発明の塩化ビニルグラフト共重合体組
成物を実施例および比較例に基づいて説明する
が、本発明はかかる実施例のみに限定されるもの
ではない。
実施例１〜11および比較例１〜９
塩化ビニルグラフト共重合体（エチレン・酢酸
ビニル・塩化ビニル三元共重合体）100部に、第
１表、第２表に示す鉛化合物およびエステル化合
物を各表に示す量配合し、塩化ビニルグラフト共
重合体組成物をえた。
えられた組成物をロール練りにしたのち、加熱
プレスして１mm厚のシートに成形し、つぎの暴露
試験用の試料とした。
暴露試験は電気学会技術報告（部）第139号
における原子力発電所用電線・ケーブルの環境試
験方法ならびに耐延焼性試験方法に関する推奨案
に従つて、試料を121℃の温度に７日間維持（加
熱）したのち、γ線を1Mrad／hrで76Mrad照射
（放射線照射）し、ついで171℃の高温水蒸気雰囲
気中に９時間、さらに121℃の高温水蒸気雰囲気
中に312時間暴露（高温水蒸気暴露）することに
より行なつた。
加熱後、放射線照射後および高温水蒸気暴露後
にそれぞれ試料の柔軟性を調べた。結果を第１
表、第２表に示す。
第１表の各実施例の結果から、本発明の組成物
は、原子力発電所の万一の事故の発生時を想定し
た高温水蒸気暴露試験後も引張強度および引張伸
びの値が良好で、かつ成形加工性も良好なことが
わかる。このようなすぐれた耐放射線環境性と良
好な成形加工性を有する組成物は、前記した塩化
ビニルグラフト共重合体に、特定の鉛化合物およ
びエステル化合物を特定量配合することによつて
初めてえられるものであつて、第２表に示したよ
うな比較例の組成物ではえられるものではない。
(Industrial Application Field) The present invention relates to a radiation-resistant environment-resistant vinyl chloride graft copolymer composition. (Problems to be Solved by the Invention) In this specification, radiation resistance refers to
It is a comprehensive concept of radiation resistance, heat resistance, and high temperature steam resistance. In the primary containment vessel of a nuclear power plant, radiation is constantly present and the temperature is around 60 to 70 degrees Celsius, and even higher temperature steam is generated in the event of an accident. Flexible covered conduits, cables, electric wires, etc. (hereinafter referred to as electric wires, etc.) installed in such locations must be able to withstand such special and harsh environments. However, vinyl chloride resin compositions that are widely used as coating materials for electric wires, etc., have the disadvantage that they harden or become brittle, causing cracks when exposed to the above-mentioned harsh environments. . (Means for Solving the Problems) As a result of extensive research by the present inventors to improve the drawbacks of such vinyl chloride resin compositions, we found that 100 parts (parts by weight, the same shall apply hereinafter) of vinyl chloride graft copolymer
10 to 100 lead compounds with a lead content of 70% by weight or more
A vinyl chloride graft copolymer composition containing 5 to 50 parts of aromatic carboxylic acid ester or fatty acid polyhydric alcohol ester has excellent resistance to radiation environments and is suitable for use in nuclear power plants.
Next, they discovered that this material is extremely excellent as a coating material for electric wires and the like installed inside the containment vessel, and completed the present invention. Ethylene/vinyl acetate/vinyl chloride terpolymer (E/VA/VC) is preferably used as the vinyl chloride graft copolymer in the present invention, and among them, ethylene/acetic acid in E/VA/VC is preferably used. Vinyl (E/VA) content is 35 to 60% by weight, and vinyl acetate (VA) content in E/VA is 30 to 45% by weight.
It is preferable to use % by weight. The lead compound in the present invention has a lead content of 70% by weight or more, such as lead oxide (PbO,
Pb 2 O 3 , Pb 3 O 4 , etc.), lead carbonate (PbCO 3 ), tribasic lead sulfate (3PbO・PbSO 4・H 2 O), dibasic lead phosphite (2PbO・PbHPO 3・1/2H 2 O), dibasic lead phthalate (C 6 H 4 (COOPbO) 2 Pb), basic lead silicate (PbO・2PbSiO 3・H 2 O), or a mixture thereof. These lead compounds have a radiation shielding effect and provide water vapor resistance. As mentioned above, the blending amount is 10 to 100 parts, preferably 20 to 100 parts, per 100 parts of the vinyl chloride graft copolymer.
The amount is 90 parts, preferably 30 to 70 parts. If it is less than 10 parts, the effect of radiation resistance will not be sufficient, and if it exceeds 100 parts, the processability during molding will be poor and the molded product will not be easily processed by the machine. problems with physical properties (e.g. tensile strength, tensile elongation). The specific ester compound used in the present invention is an aromatic carboxylic acid ester or fatty acid polyhydric alcohol ester, which has excellent heat resistance and also has the effect of plasticizing the vinyl chloride graft copolymer. . However, when using other vinyl chloride graft copolymer plasticizers, such as dioctyl phthalate and cresyl diphenyl phosphate, in place of such ester compounds,
The radiation resistance, which is the objective of the present invention, cannot be achieved. Here, as the aromatic carboxylic acid ester, for example, the general formula: (In the formula, R is an alkyl group having 8 to 10 carbon atoms.) Preferred are trimellitic acid esters represented by the formula: trioctyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate. etc. Furthermore, as the fatty acid polyhydric alcohol ester, esters of dipentaerythritol and fatty acids having 10 or less carbon atoms are preferred, such as dipentaerythritol hexacaproate, dipentaerythritol hexasubtyrate, and dipentaerythritol hexaadipate. Specific examples of fatty acids having 10 or fewer carbon atoms include propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid,
Saturated monocarboxylic acids such as caprylic acid, pelargonic acid, and capric acid; unsaturated monocarboxylic acids such as acrylic acid and crotonic acid; saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; maleic acid, etc. Examples include unsaturated dicarboxylic acids. The blending amount of these specific ester compounds is 5 to 50 parts, preferably 10 to 40 parts, particularly preferably 20 parts to 100 parts of the vinyl chloride graft copolymer.
~30 copies. When the amount is less than 5 parts, the plasticity of the composition is insufficient, resulting in poor moldability during kneading and extrusion, and the effect of radiation resistance is insufficient.
When the amount exceeds 100%, the composition becomes too plasticized and has poor moldability during kneading and extrusion, and the tensile strength and heat deformability of the molded product are significantly reduced, resulting in poor mechanical strength. The excellent radiation resistance of the composition of the present invention is due to
It can only be obtained by blending specific amounts of the lead compound and ester compound into the vinyl chloride graft copolymer, and even if either one is lacking, the desired radiation resistance cannot be obtained. (Effects of the present invention) The vinyl chloride graft copolymer composition of the present invention has excellent resistance to radiation environments, that is, radiation resistance, heat resistance, and high temperature steam resistance. It can be used not only in the primary containment vessel, but also in any nuclear power-related facility where radiation is present at high temperature and humidity, such as in the secondary containment vessel and in the containment vessel of a nuclear ship. In addition, the vinyl chloride graft copolymer composition of the present invention is suitable as a material for coverings such as cables and electric wires for nuclear power-related facilities, and for flexible coated conduits, but also for packing, sealing materials, frames, hoses, etc. It is also useful as a material. (Examples) Next, the vinyl chloride graft copolymer composition of the present invention will be explained based on Examples and Comparative Examples, but the present invention is not limited only to these Examples. Examples 1 to 11 and Comparative Examples 1 to 9 The lead compounds and ester compounds shown in Tables 1 and 2 were added to 100 parts of vinyl chloride graft copolymer (ethylene/vinyl acetate/vinyl chloride terpolymer). The amounts shown in each table were blended to obtain a vinyl chloride graft copolymer composition. The resulting composition was kneaded with a roll, then heated and pressed to form a 1 mm thick sheet, which was used as a sample for the next exposure test. The exposure test was conducted by keeping the sample at a temperature of 121°C for 7 days (heating) in accordance with the recommendations for environmental test methods and fire spread resistance test methods for electric wires and cables for nuclear power plants in IEEJ Technical Report (Department) No. 139. After that, by irradiating with gamma rays at 1 Mrad/hr for 76 Mrad (radiation irradiation), then exposing to a high-temperature steam atmosphere at 171°C for 9 hours, and then exposing to a high-temperature steam atmosphere at 121°C for 312 hours (high-temperature steam exposure). I did it. The flexibility of the samples was examined after heating, irradiation, and high-temperature steam exposure. Results first
Table 2 shows the results. From the results of each example in Table 1, the composition of the present invention has good tensile strength and tensile elongation values even after a high-temperature steam exposure test assuming an accident at a nuclear power plant. It can be seen that the molding processability is also good. A composition with such excellent radiation resistance and good moldability can only be obtained by blending a specific amount of a specific lead compound and an ester compound with the above-mentioned vinyl chloride graft copolymer. This is not the case with the comparative compositions shown in Table 2.
【表】【table】
Claims (1)
含有量が70重量％以上の鉛化合物が10〜100重量
部および芳香族カルボン酸エステルまたは脂肪酸
多価アルコールエステルが５〜50重量部配合され
てなる耐放射線環境性塩化ビニルグラフト共重合
体組成物。 ２ 前記塩化ビニルグラフト共重合体が、エチレ
ン・酢酸ビニル・塩化ビニル三元共重合体である
特許請求の範囲第１項記載の組成物。 ３ 前記鉛化合物が酸化鉛、炭酸鉛、三塩基性硫
酸鉛、二塩基性亜隣酸鉛、二塩基性フタル酸鉛、
塩基性硅酸鉛またはそれらの混合物である特許請
求の範囲第１項記載の組成物。 ４ 前記芳香族カルボン酸エステルが一般式： （式中、Ｒは炭素数８〜10のアルキル基である）
で示されるトリメリツト酸エステルである特許請
求の範囲第１項記載の組成物。 ５ 前記脂肪酸多価アルコールエステルがジペン
タエリスリトールの脂肪酸エステルである特許請
求の範囲第１項記載の組成物。[Scope of Claims] 1. 10 to 100 parts by weight of a lead compound having a lead content of 70% by weight or more and 5 to 50 parts by weight of an aromatic carboxylic acid ester or a fatty acid polyhydric alcohol ester in 100 parts by weight of a vinyl chloride graft copolymer. A radiation-resistant environmentally resistant vinyl chloride graft copolymer composition containing parts by weight. 2. The composition according to claim 1, wherein the vinyl chloride graft copolymer is an ethylene/vinyl acetate/vinyl chloride terpolymer. 3. The lead compound is lead oxide, lead carbonate, tribasic lead sulfate, dibasic leadite, dibasic lead phthalate,
A composition according to claim 1, which is a basic lead silicate or a mixture thereof. 4 The aromatic carboxylic acid ester has the general formula: (In the formula, R is an alkyl group having 8 to 10 carbon atoms)
The composition according to claim 1, which is a trimellitic acid ester represented by: 5. The composition according to claim 1, wherein the fatty acid polyhydric alcohol ester is a fatty acid ester of dipentaerythritol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12399283A JPS6015449A (en) | 1983-07-06 | 1983-07-06 | Radioactive environment-resistant vinyl chloride graft copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12399283A JPS6015449A (en) | 1983-07-06 | 1983-07-06 | Radioactive environment-resistant vinyl chloride graft copolymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6015449A JPS6015449A (en) | 1985-01-26 |
| JPS6353219B2 true JPS6353219B2 (en) | 1988-10-21 |
Family
ID=14874355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12399283A Granted JPS6015449A (en) | 1983-07-06 | 1983-07-06 | Radioactive environment-resistant vinyl chloride graft copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6015449A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4825739A (en) * | 1971-08-09 | 1973-04-04 | ||
| JPS4925035A (en) * | 1972-06-30 | 1974-03-06 |
-
1983
- 1983-07-06 JP JP12399283A patent/JPS6015449A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4825739A (en) * | 1971-08-09 | 1973-04-04 | ||
| JPS4925035A (en) * | 1972-06-30 | 1974-03-06 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6015449A (en) | 1985-01-26 |
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