JPH0331739B2 - - Google Patents
Info
- Publication number
- JPH0331739B2 JPH0331739B2 JP15612282A JP15612282A JPH0331739B2 JP H0331739 B2 JPH0331739 B2 JP H0331739B2 JP 15612282 A JP15612282 A JP 15612282A JP 15612282 A JP15612282 A JP 15612282A JP H0331739 B2 JPH0331739 B2 JP H0331739B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- rubber
- temperature
- acrylonitrile
- 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
- 229920001971 elastomer Polymers 0.000 claims description 93
- 239000005060 rubber Substances 0.000 claims description 93
- 239000000203 mixture Substances 0.000 claims description 67
- 229920005989 resin Polymers 0.000 claims description 61
- 239000011347 resin Substances 0.000 claims description 61
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 53
- 229920001577 copolymer Polymers 0.000 claims description 31
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 28
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 28
- 239000004800 polyvinyl chloride Substances 0.000 description 28
- 238000001879 gelation Methods 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 14
- 238000007796 conventional method Methods 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 229920006602 NBR/PVC Polymers 0.000 description 7
- 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 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 230000020169 heat generation Effects 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- -1 or after mixing both Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- RWNQRLATPAGHIM-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N.CC(=C)C=C RWNQRLATPAGHIM-UHFFFAOYSA-N 0.000 description 1
- URZCXTYHPLXUQK-UHFFFAOYSA-N buta-1,3-diene;butyl prop-2-enoate;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N.CCCCOC(=O)C=C URZCXTYHPLXUQK-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229960002447 thiram 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、アクリロニトリル−共役ジエン系共
重合ゴム、塩化ビニル系樹脂および加硫剤を含む
ゴム組成物からゴム加硫物を製造する方法に関
し、さらに詳しくは、加工性、作業性、発熱性等
が改良された耐油性、耐オゾン性を有するゴム加
硫物の製造方法に関する。
〔従来の技術〕
従来から、耐油性、耐オゾン性を有するゴム加
硫物を与えるゴム組成物として、アクリロニトリ
ル−ブタジエン共重合ゴム（NBR）と塩化ビニ
ル樹脂（PVC）とから成るゴム組成物が知られ
ている。
ところで、前記ゴム組成物を用いたゴム加硫物
が充分な耐オゾン性を発揮するためには、NBR
とPVCとが充分均一に混合され、かつ、PVCが
完全にNBRに溶解していることが必要である。
そのためには、従来、ゴム組成物を調製する際、
NBRとPVCを混合する段階で、あるいは両者を
混合した後、PVCが溶融する温度（ゲル化温度
という）より高い温度で剪断力により溶融PVC
をNBR中へ充分に溶解分散させ、PVCが粒子状
あるいは凝集塊としてNBR／PVC混合物中に残
存することがないようにしていた。
PVCのゲル化温度よりも低い温度でゴム組成
物を調製した場合、また、ゲル化温度よりも高い
温度であつても、混合が不充分である場合には、
充分な耐オゾン性は得られず、抗張力（引張強
さ）も充分な水準に達しない。したがつて、従
来、充分な水準の抗張力および耐オゾン性を有す
るゴム加硫物を製造することは非常に困難であつ
た。
また、PVCのゲル化温度よりも高い温度で充
分に混合して調製されたゴム組成物は、それ自体
の粘度が高いため、充填剤、補強剤等を多量に添
加した場合には、ゴム組成物の粘度は著しく高く
なり、加工操作が困難になるとともに、ゴム焼け
を起こしたり、スコーチを起こす等の問題もあ
り、高硬度のゴム加硫物を製造することが難し
く、改善が求められていた。
〔発明が解決しようとする課題〕
本発明の目的は、前記従来技術の問題点を解決
し、加工性、作業性、発熱性等が改良された耐油
性、耐オゾン性を有するゴム加硫物の製造方法を
提供することにある。
本発明者は、鋭意研究した結果、アクリロニト
リル−共役ジエン系共重合ゴム、塩化ビニル系樹
脂および加硫剤を含むゴム組成物からゴム加硫物
を製造する場合、アクリロニトリル−共役ジエン
系共重合ゴムと平均粒子径が5μm以下の塩化ビニ
ル系樹脂とを、塩化ビニル系樹脂のゲル化温度よ
り低い温度条件下に、ラテツクス同士で混合、共
沈、乾燥して、塩化ビニル系樹脂が前記平均粒子
径を有する粒子形態を保持したままの状態でアク
リロニトリル−共役ジエン系共重合ゴム中に均一
に分散した混合物を得、次いで、加硫剤を含む配
合剤を塩化ビニル系樹脂のゲル化温度より低い温
度条件で混合し、得られたゴム組成物を用いて、
ゴム組成物中の塩化ビニル系樹脂がゲル化する温
度以上の温度条件で加硫することにより、高充填
であつても加工性が良好で、しかも耐油性、耐オ
ゾン性を有するゴム加硫物の得られることを見出
し、その知見に基づいて本発明を完成するに至つ
た。
〔課題を解決するための手段〕
かくして、本発明によれば、アクリロニトリル
−共役ジエン系共重合ゴム、塩化ビニル系樹脂お
よび加硫剤を含むゴム組成物からゴム加硫物を製
造する方法において、
(1) 塩化ビニル系樹脂として平均粒子径が5μm以
下の粒状樹脂を用い、
(2) アクリロニトリル−共役ジエン系共重合ゴム
と該塩化ビニル系樹脂とを、塩化ビニル系樹脂
のゲル化温度より低い温度条件下に、ラテツク
ス同士で混合、共沈、乾燥して、塩化ビニル系
樹脂が前記平均粒子径を有する粒子形態を保持
したままの状態でアクリロニトリル−共役ジエ
ン系共重合ゴム中に均一に分散した混合物を
得、次いで、
(3) 加硫剤を含む配合剤を塩化ビニル系樹脂のゲ
ル化温度より低い温度条件で混合し、
(4) 得られたゴム組成物を用いて、ゴム組成物中
の塩化ビニル系樹脂がゲル化する温度以上の温
度条件で加硫することを特徴とする耐油性、耐
オゾン性を有するゴム加硫物の製造方法が提供
される。
本発明の製造方法においては、加硫工程でゴム
組成物中の塩化ビニル系樹脂のゲル化温度以上の
高い温度で加硫する以外は、ゴム組成物を調製す
る工程、得られたゴム組成物を使用する加工工程
においても、塩化ビニル系樹脂を溶融（ゲル化）
させないことが必要である。その結果、アクリロ
ニトリル−共役ジエン系共重合ゴムと塩化ビニル
系樹脂との組成物の粘度は低くなり、配合剤を高
充填したときでもゴム組成物の粘度を低く抑える
ことができ、加工工程での電力消費、発熱による
焼け、スコーチが改善され、高硬度配合が容易と
なるなど、流動特性が改善される。
（塩化ビニル系樹脂）
本発明で使用する塩化ビニル系樹脂は、平均粒
子径が5μm以下、好ましくは1μm以下、さらに好
ましくは0.2μm以下の粒状樹脂である。このよう
な粒状塩化ビニル系樹脂を用いることにより、従
来法で製造されたものと同等の耐オゾン性を有す
るゴム加硫物を与え、しかもゴム組成物の加工工
程における流動性が改善される。平均粒子径が
5μmを越えると、加硫工程において、加硫時の熱
履歴だけでは塩化ビニル系樹脂をゲル化させてア
クリロニトリル−共役ジエン系共重合ゴム中へ溶
解させることが困難となり、耐オゾン性、強度特
性等が低下する。
塩化ビニル系樹脂の平均重合度は、通常、400
以上、好ましくは800〜2000の範囲のものが使用
される。後記の第１表に示すとおり、塩化ビニル
系樹脂の単味のゲル化温度は、主として平均重合
度によつて変化するが、後述するように、組成物
とした場合には、可塑剤の添加量や他の配合成分
の種類と量によつても変化し、例えば、可塑剤が
多量に配合されると、ゲル化温度は低下する。
塩化ビニル系樹脂としては、ポリ塩化ビニル樹
脂、塩化ビニル−酢酸ビニル共重合樹脂、塩化ビ
ニル−エチレン−酢酸ビニル共重合樹脂、変性ポ
リ塩化ビニル樹脂などが例示できる。
このような塩化ビニル系樹脂は、懸濁重合、乳
化重合、塊状重合などによつて製造することがで
きるが、アクリロニトリル−共役ジエン系共重合
ゴムとラテツクスブレンドするために、通常、乳
化重合により製造することが好ましい。
（アクリロニトリル−共役ジエン系共重合ゴム）
本発明で使用されるアクリロニトリル−共役ジ
エン系共重合ゴムは、アクリロニトリルと１，３
−ブタジエン、イソプレン、１，３−ペンタジエ
ンなどの共役ジエン系単量体の少なくとも一種と
の共重合体、さらにアクリル酸、メタクリル酸、
マレレン酸などのα，β−エチレン性不飽和化合
物、あるいはジカルボン酸およびそのエステル類
を共重合させた多元共重合体である。
具体的には、アクリロニトリル−ブタジエン共
重合ゴム、アクリロニトリル−イソプレン共重合
ゴム、アクリロニトリル−ブタジエン−イソプレ
ン三元共重合ゴム、アクリロニトリル−ブタジエ
ン−ブチルアクリレート三元共重合ゴムなどが例
示できる。
これらの共重合ゴムは、乳化重合、溶液重合な
どで製造することができるが、塩化ビニル樹脂と
ラテツクスブレンドするために、通常、乳化重合
により製造することが好ましい。
共重合ゴム中の結合アクリロニトリル量は、耐
油性ゴムの機能上および塩化ビニル系樹脂との相
溶性から、通常、10〜50重量％の範囲であり、ゴ
ム−樹脂組成物に要求される特性に応じて適した
結合アクリロニトリル量を前記範囲内で適宜決定
することができる。
（ゴム組成物の製造）
アクリロニトリル−共役ジエン系共重合ゴムと
塩化ビニル系樹脂との混合割合は、使用目的に応
じて適宜決定すればよいが、通常は、アクリロニ
トリル−共役ジエン系共重合ゴム95〜45重量％に
対して、塩化ビニル系樹脂５〜55重量％である。
アクリロニトリル−共役ジエン系共重合ゴムと
塩化ビニル系樹脂との混合方法は、これらの重合
体のラテツクス同士を塩化ビニル系樹脂のゲル化
温度（平均重合度によつて異なるが、大体170℃
前後である）よりも低い温度で混合し、共沈さ
せ、乾燥させるラテツクスブレンド法を採用す
る。
本発明の方法においては、従来法のようにラテ
ツクスブレンドした場合でも、乾燥時に塩化ビニ
ル系樹脂のゲル化温度以上の高温で、剪断力下に
乾燥を行なう必要がなく、通常のアクリロニトリ
ル−共役ジエン系共重合ゴムを乾燥する場合と同
様の乾燥法を用いればよい（例えば、100℃以下
のハンドドライヤによる乾燥）。
本発明の前記アクリロニトリル−共役ジエン系
共重合ゴムと塩化ビニル系樹脂との混合物におい
ては、塩化ビニル系樹脂は全くゲル化せずに、塩
化ビニル系樹脂が前記平均粒子径を有する粒子形
態を保持したままの状態でアクリロニトリル−共
役ジエン系共重合ゴム中に均一に分散している。
アクリロニトリル−共役ジエン系共重合ゴムと
塩化ビニル系樹脂との混合物は、次いでカーボン
ブラツク、シリカ、炭酸カルシウム等の補強剤、
あるいは充填剤、加硫剤、加硫促進剤、可塑性、
加工助剤などの加硫剤を含む配合物と混合してゴ
ム組成物とする。これらの配合物を混合するに
は、ゴム組成物が加硫しない温度であつて、ゴム
組成物中の塩化ビニル系樹脂のゲル化温度より低
い温度で行なう。
（加硫工程）
前記ゴム組成物を用いて、ゴム加硫物を製造す
るには、ゴム組成物中の塩化ビニル系樹脂のゲル
化温度以上の温度で加硫する。それによつて、粒
状の塩化ビニル系樹脂が溶融し、従来法で製造さ
れたものと同等の耐オゾン性を示すゴム加硫物と
することができる。
塩化ビニル系樹脂のゲル化温度は、樹脂の平均
重合度にもよるが、ゴム組成物とした場合には、
可塑剤の配合量等に依存するから、予めゴム組成
物中における塩化ビニル系樹脂のゲル化温度を測
定しておき、好ましい加硫温度を設定することが
必要である。
ゴム組成物中における塩化ビニル系樹脂のゲル
化温度以上の温度で加硫を行なうと、塩化ビニル
系樹脂の粒子構造は完全に消失し、加硫後では本
発明の方法と従来法で製造された加硫物との見分
けはつかない。
〔実施例〕
以下、実施例により本発明を具体的に説明す
る。
実施例 １
アクリロニトリル−ブタジエン共重合ゴム（以
下、NBRと略記する、結合アクリロニトリル量
33重量％）と塩化ビニル樹脂（以下、PVCと略
記する）から成る組成物をラテツクス共沈法によ
り製造した。
通常の乳化重合法により製造した第１表記載の
８種のPVCラテツクスの夫々とNBRラテツクス
とを重合体の重量比３：７の割合で混合した。前
記混合物をその容積の10倍容の3.5重量％のCaCl2
の凝固剤水溶液中へ注ぎ、10分間撹拌を続け共沈
させた。共沈物を20メツシユの金網に移し十分に
水切をした後、減圧下、70℃で20時間乾燥した。
得られた共沈乾燥物を２分し、一方はそのままで
（本発明方法）、他方はPVCをゲル化するために
175℃に加熱した８インチロール上で５分間素練
した（従来法）。なお、この共沈乾燥物には、
NBRが含まれているために、PVCのゲル化温度
は単味の場合と比較して若干低下しており、175
℃で、剪断力下に、素練することにより、粒状
PVCは完全にゲル化した。
[Industrial Application Field] The present invention relates to a method for producing a rubber vulcanizate from a rubber composition containing an acrylonitrile-conjugated diene copolymer rubber, a vinyl chloride resin, and a vulcanizing agent. The present invention relates to a method for producing a rubber vulcanizate having improved workability, heat generation properties, etc., and has oil resistance and ozone resistance. [Prior Art] Conventionally, rubber compositions consisting of acrylonitrile-butadiene copolymer rubber (NBR) and vinyl chloride resin (PVC) have been used as rubber compositions that provide rubber vulcanizates with oil resistance and ozone resistance. Are known. By the way, in order for the rubber vulcanizate using the above rubber composition to exhibit sufficient ozone resistance, NBR
It is necessary that the NBR and PVC are sufficiently and uniformly mixed, and that the PVC is completely dissolved in the NBR.
To this end, conventionally, when preparing a rubber composition,
At the stage of mixing NBR and PVC, or after mixing both, PVC melts due to shearing force at a temperature higher than the temperature at which PVC melts (called gelation temperature).
was sufficiently dissolved and dispersed in NBR to prevent PVC from remaining in the NBR/PVC mixture in the form of particles or aggregates. If the rubber composition is prepared at a temperature lower than the gelling temperature of PVC, or if mixing is insufficient even at a temperature higher than the gelling temperature of PVC,
Sufficient ozone resistance cannot be obtained, and tensile strength (tensile strength) does not reach a sufficient level. Therefore, it has hitherto been very difficult to produce a rubber vulcanizate having a sufficient level of tensile strength and ozone resistance. In addition, rubber compositions prepared by thorough mixing at a temperature higher than the gelation temperature of PVC have a high viscosity, so if a large amount of fillers, reinforcing agents, etc. are added, the rubber composition may The viscosity of the product becomes extremely high, making processing operations difficult, and there are also problems such as rubber burning and scorch, making it difficult to produce rubber vulcanizates with high hardness, and improvements are needed. Ta. [Problems to be Solved by the Invention] An object of the present invention is to solve the problems of the prior art described above, and to provide a rubber vulcanizate having improved processability, workability, heat generation properties, etc., and having oil resistance and ozone resistance. The purpose of this invention is to provide a method for manufacturing the same. As a result of extensive research, the present inventor has found that when producing a rubber vulcanizate from a rubber composition containing an acrylonitrile-conjugated diene copolymer rubber, a vinyl chloride resin, and a vulcanizing agent, acrylonitrile-conjugated diene copolymer rubber and a vinyl chloride resin with an average particle diameter of 5 μm or less are mixed together, coprecipitated, and dried in the latex at a temperature lower than the gelation temperature of the vinyl chloride resin, so that the vinyl chloride resin forms the average particle size. A mixture is obtained which is uniformly dispersed in acrylonitrile-conjugated diene copolymer rubber while maintaining the particle morphology having a diameter, and then a compounding agent containing a vulcanizing agent is added at a temperature lower than the gelling temperature of the vinyl chloride resin. Using the rubber composition obtained by mixing under temperature conditions,
By vulcanizing at a temperature higher than the temperature at which the vinyl chloride resin in the rubber composition gels, the rubber vulcanizate has good processability even with high filling, and also has oil resistance and ozone resistance. The present invention was completed based on this finding. [Means for Solving the Problems] According to the present invention, in a method for producing a rubber vulcanizate from a rubber composition containing an acrylonitrile-conjugated diene copolymer rubber, a vinyl chloride resin, and a vulcanizing agent, (1) A granular resin with an average particle diameter of 5 μm or less is used as the vinyl chloride resin, and (2) the acrylonitrile-conjugated diene copolymer rubber and the vinyl chloride resin are heated at a temperature lower than the gelling temperature of the vinyl chloride resin. The latexes are mixed, co-precipitated, and dried under temperature conditions, and the vinyl chloride resin is uniformly dispersed in the acrylonitrile-conjugated diene copolymer rubber while maintaining the particle form having the above-mentioned average particle size. (3) Mix a compounding agent containing a vulcanizing agent at a temperature lower than the gelling temperature of the vinyl chloride resin; (4) Use the obtained rubber composition to form a rubber composition. Provided is a method for producing a rubber vulcanizate having oil resistance and ozone resistance, which is characterized in that vulcanization is carried out at a temperature equal to or higher than the temperature at which the vinyl chloride resin therein gels. In the manufacturing method of the present invention, except for vulcanizing at a high temperature higher than the gelation temperature of the vinyl chloride resin in the rubber composition in the vulcanization step, the steps of preparing the rubber composition, the obtained rubber composition Even in processing processes that use
It is necessary to prevent this from happening. As a result, the viscosity of the composition of acrylonitrile-conjugated diene copolymer rubber and vinyl chloride resin becomes low, and the viscosity of the rubber composition can be kept low even when highly loaded with compounding ingredients, making it possible to reduce the viscosity in the processing process. Power consumption, burning due to heat generation, and scorch are improved, and flow characteristics are improved, such as making it easier to formulate high-hardness formulations. (Vinyl Chloride Resin) The vinyl chloride resin used in the present invention is a granular resin with an average particle diameter of 5 μm or less, preferably 1 μm or less, and more preferably 0.2 μm or less. By using such a granular vinyl chloride resin, a rubber vulcanizate having ozone resistance equivalent to that produced by conventional methods can be obtained, and the fluidity of the rubber composition in the processing step can be improved. The average particle size is
If it exceeds 5 μm, it becomes difficult to gel the vinyl chloride resin and dissolve it into the acrylonitrile-conjugated diene copolymer rubber during the vulcanization process using only the heat history during vulcanization, resulting in poor ozone resistance and strength properties. etc. will decrease. The average degree of polymerization of vinyl chloride resin is usually 400.
Above, those in the range of 800 to 2000 are preferably used. As shown in Table 1 below, the simple gelation temperature of vinyl chloride resin varies mainly depending on the average degree of polymerization, but as described below, when it is made into a composition, the gelation temperature of vinyl chloride resin varies depending on the addition of a plasticizer. It also changes depending on the amount and the type and amount of other blended components. For example, if a large amount of plasticizer is blended, the gelling temperature will decrease. Examples of the vinyl chloride resin include polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-ethylene-vinyl acetate copolymer resin, and modified polyvinyl chloride resin. Such vinyl chloride resins can be produced by suspension polymerization, emulsion polymerization, bulk polymerization, etc., but in order to latex blend them with acrylonitrile-conjugated diene copolymer rubber, they are usually produced by emulsion polymerization. Preferably, it is manufactured. (Acrylonitrile-conjugated diene copolymer rubber) The acrylonitrile-conjugated diene copolymer rubber used in the present invention contains acrylonitrile and 1,3
- A copolymer with at least one conjugated diene monomer such as butadiene, isoprene, 1,3-pentadiene, and acrylic acid, methacrylic acid,
It is a multicomponent copolymer made by copolymerizing α,β-ethylenically unsaturated compounds such as malelenic acid, or dicarboxylic acids and their esters. Specific examples include acrylonitrile-butadiene copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylonitrile-butadiene-isoprene ternary copolymer rubber, and acrylonitrile-butadiene-butyl acrylate ternary copolymer rubber. These copolymer rubbers can be produced by emulsion polymerization, solution polymerization, etc., but it is usually preferable to produce them by emulsion polymerization in order to latex blend them with vinyl chloride resin. The amount of bound acrylonitrile in the copolymer rubber is usually in the range of 10 to 50% by weight, considering the functionality of the oil-resistant rubber and its compatibility with the vinyl chloride resin, and the amount of bound acrylonitrile is in the range of 10 to 50% by weight, depending on the properties required for the rubber-resin composition. A suitable amount of bound acrylonitrile can be appropriately determined within the above range. (Manufacture of rubber composition) The mixing ratio of acrylonitrile-conjugated diene copolymer rubber and vinyl chloride resin may be determined as appropriate depending on the purpose of use, but usually acrylonitrile-conjugated diene copolymer rubber 95 -45% by weight, and 5-55% by weight of vinyl chloride resin. The method of mixing acrylonitrile-conjugated diene copolymer rubber and vinyl chloride resin is to mix the latexes of these polymers together at the gelling temperature of the vinyl chloride resin (which varies depending on the average degree of polymerization, but is approximately 170°C).
A latex blending method is adopted in which the materials are mixed at a lower temperature than before and after the materials are mixed, co-precipitated, and dried. In the method of the present invention, even when latex blending is performed as in the conventional method, there is no need to dry under shearing force at a high temperature higher than the gelling temperature of vinyl chloride resin, and the conventional acrylonitrile-conjugated A drying method similar to that used for drying diene copolymer rubber may be used (for example, drying with a hand dryer at 100° C. or lower). In the mixture of the acrylonitrile-conjugated diene copolymer rubber and the vinyl chloride resin of the present invention, the vinyl chloride resin does not gel at all, and the vinyl chloride resin maintains a particle form having the above average particle diameter. As it is, it is uniformly dispersed in the acrylonitrile-conjugated diene copolymer rubber. The mixture of acrylonitrile-conjugated diene copolymer rubber and vinyl chloride resin is then treated with reinforcing agents such as carbon black, silica, and calcium carbonate.
Or fillers, vulcanizing agents, vulcanization accelerators, plasticity,
It is mixed with a compound containing a vulcanizing agent such as a processing aid to form a rubber composition. These compounds are mixed at a temperature at which the rubber composition is not vulcanized and which is lower than the gelling temperature of the vinyl chloride resin in the rubber composition. (Vulcanization Step) In order to produce a rubber vulcanizate using the rubber composition, vulcanization is performed at a temperature equal to or higher than the gelation temperature of the vinyl chloride resin in the rubber composition. As a result, the granular vinyl chloride resin is melted and a rubber vulcanizate exhibiting ozone resistance equivalent to that produced by conventional methods can be obtained. The gelation temperature of vinyl chloride resin depends on the average degree of polymerization of the resin, but when it is made into a rubber composition,
Since it depends on the amount of plasticizer blended, etc., it is necessary to measure the gelation temperature of the vinyl chloride resin in the rubber composition in advance and set a preferable vulcanization temperature. When vulcanization is carried out at a temperature higher than the gelation temperature of the vinyl chloride resin in the rubber composition, the particle structure of the vinyl chloride resin completely disappears, and after vulcanization, the difference between the inventive method and the conventional method. It is indistinguishable from other vulcanizates. [Example] Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 Acrylonitrile-butadiene copolymer rubber (hereinafter abbreviated as NBR, amount of bound acrylonitrile
33% by weight) and vinyl chloride resin (hereinafter abbreviated as PVC) was produced by a latex coprecipitation method. Each of the eight PVC latexes listed in Table 1 produced by a conventional emulsion polymerization method and NBR latex were mixed at a polymer weight ratio of 3:7. Add 10 times its volume to 3.5% CaCl2 by weight of the mixture.
The mixture was poured into an aqueous coagulant solution, and stirring was continued for 10 minutes to cause coprecipitation. The coprecipitate was transferred to a 20-mesh wire mesh, thoroughly drained, and then dried under reduced pressure at 70°C for 20 hours.
The obtained co-precipitated dried product was divided into two parts, one part was left as is (method of the present invention) and the other part was used to gel the PVC.
It was masticated for 5 minutes on an 8-inch roll heated to 175°C (conventional method). In addition, this co-precipitated dried product includes
Due to the inclusion of NBR, the gelation temperature of PVC is slightly lower than that of the plain case, and 175
Granulated by masticating under shear at ℃
PVC completely gelled.
【表】
本発明法で調製した組成物と従来法の組成物
に、第２表の配合処方（標準配合）により、各配
合剤を冷却下の６インチロール（約50℃）上で添
加し配合ゴム組成物を得た。
次いで、150℃で20分、および180℃で５分の条
件で加圧、加熱して２mm厚の加硫シートを作り、
JIS Ｋ 6301に従つて常態物性、静的ならびに動
的オゾン試験を行なつた。なお、ゴム組成物に
は、第２表に示す可塑剤等が配合されているため
に、PVCのゲル化温度は、単味のものより低く
なつている。結果を第３表に示す。
第２表 配合処方（標準配合）
NBR／PVC混合物 100重量部
ステアリン酸 １ 〃
亜鉛華５ 〃
SRFカーボンブラツク 60 〃
可塑剤DOP(1) 20 〃
硫黄 0.5 〃
促進剤TT(2) 1.5 〃
促進剤CZ(3) 1.5 〃
(1) ジオクチルフタレート
(2) テトラメチルチウラムジスルフイド
(3) シクロヘキシルペンゾチアジルスルフエン
アミド[Table] Each compounding agent was added to the composition prepared by the method of the present invention and the composition prepared by the conventional method on a cooling 6-inch roll (approximately 50°C) according to the compounding recipe (standard compounding) in Table 2. A compounded rubber composition was obtained. Next, pressurize and heat at 150℃ for 20 minutes and 180℃ for 5 minutes to make a 2mm thick vulcanized sheet.
Normal physical properties, static and dynamic ozone tests were conducted in accordance with JIS K 6301. In addition, since the rubber composition contains the plasticizer shown in Table 2, the gelation temperature of PVC is lower than that of a plain rubber composition. The results are shown in Table 3. Table 2 Mixing prescription (standard formulation) NBR/PVC mixture 100 parts by weight Stearic acid 1 Zinc white 5 SRF carbon black 60 Plasticizer DOP (1) 20 Sulfur 0.5 Accelerator TT (2) 1.5 Accelerator CZ (3) 1.5 〃 (1) Dioctylphthalate (2) Tetramethylthiuram disulfide (3) Cyclohexylpenzothiazylsulfenamide
【表】
なお、第３表中、TBは引張強さ、EBは伸び、
HSは硬度を表わす。
また、オゾン劣化試験は、JIS Ｋ 6301−16に
規定されている試験方法と、評価基準を用いた。
すなわち、Ａ：亀裂少数、Ｂ：亀裂多数、Ｃ：亀
裂無数であり、NCは亀裂なしを、Cutは切断を
表わす。また、枝番１〜５は、１：肉眼では見え
ないが10倍の拡大鏡では確認できるもの、２：肉
眼で確認できるもの、３：亀裂が深くて比較的大
きなもの、４：亀裂が深くて大きいもの、５：３
mm以上の亀裂または切断を起こしそうなもの、を
示す。
第３表の結果から、本発明方法で調製したゴム
組成物は、150℃で20分の比較的低い加硫温度の
場合には、PVCのゲル化が不充分であり、従来
法のゴム組成物（既にゲル化したPVCを含む）
の加硫物に比較して耐オゾン性は極めて劣つてい
るが、180℃で５分間というゴム組成物中での
PVCのゲル化温度以上の温度で加硫した場合に
は、従来法のゴム組成物の加硫物とほぼ同等の耐
オゾン性が得られることが分る。したがつて、加
硫は、ゴム組成物中でのPVCのゲル化温度以上
の温度で、PVCの粒子構造が完全に消失するよ
うな温度条件で行なうことが好ましいことが分か
る。また、平均粒径の過大なPVCを用いた比較
例（実験番号８）の加硫物は、ゴム組成物中での
PVCのゲル化温度以上の温度で加硫しても、耐
オゾン性の劣悪なものであつた。
第１図〜第６図に本発明方法及び従来法で調製
したNBR／PVC混合物の分散状態を電子顕微鏡
で観察した結果を示す。
実験番号１および実験番号６のNBR／PVC混
合物（いずれも本発明方法で作成し、配合剤を全
く添加していないもの）と、これらの混合物を
PVCのゲル化温度より高い温度（180℃）で５分
間加圧したものをそれぞれ凍結させ、超ミクロト
ームを用いて超薄切片を作成し透過型電子顕微鏡
で観察し第１図〜第４図の結果を得た。
同様にして、実験番号８（比較例）の該混合物
に上記の熱履歴を与えた場合の結果を第６図に、
また実験番号11の混合物（従来法、上記の熱履歴
を与えていない）の結果を第５図に示す。これら
の結果を第４表にまてめて示す。[Table] In Table 3, TB is tensile strength, EB is elongation,
HS represents hardness. Further, the ozone deterioration test used the test method and evaluation criteria specified in JIS K 6301-16.
That is, A: few cracks, B: many cracks, C: countless cracks, NC means no cracks, and Cut means cutting. Branch numbers 1 to 5 are: 1: invisible to the naked eye but visible with a 10x magnifying glass, 2: visible to the naked eye, 3: cracks deep and relatively large, 4: cracks deep big one, 5:3
Indicates something that is likely to cause cracks or cuts larger than mm. From the results in Table 3, it can be seen that the rubber composition prepared by the method of the present invention has insufficient gelation of PVC at a relatively low vulcanization temperature of 150°C for 20 minutes, and the rubber composition prepared by the conventional method (including already gelled PVC)
The ozone resistance is extremely poor compared to the vulcanizate of
It can be seen that when vulcanized at a temperature equal to or higher than the gelation temperature of PVC, almost the same ozone resistance as the vulcanized product of the conventional rubber composition can be obtained. Therefore, it can be seen that vulcanization is preferably carried out at a temperature equal to or higher than the gelling temperature of PVC in the rubber composition, and at a temperature such that the particle structure of PVC completely disappears. In addition, the vulcanizate of the comparative example (experiment number 8) using PVC with an excessively large average particle size was
Even when vulcanized at a temperature higher than the gelling temperature of PVC, the ozone resistance was poor. Figures 1 to 6 show the results of observing the dispersion states of NBR/PVC mixtures prepared by the method of the present invention and the conventional method using an electron microscope. The NBR/PVC mixtures of Experiment No. 1 and Experiment No. 6 (both made by the method of the present invention and without any additives added) and these mixtures were
The samples were frozen by applying pressure for 5 minutes at a temperature higher than the gelling temperature of PVC (180℃), and ultrathin sections were prepared using an ultramicrotome and observed using a transmission electron microscope. Got the results. Similarly, the results when the above thermal history was given to the mixture of experiment number 8 (comparative example) are shown in Figure 6.
Further, the results of the mixture of Experiment No. 11 (conventional method, the above thermal history was not given) are shown in FIG. These results are summarized in Table 4.
【表】
実施例 ２
第６表記載の平均重合度及び平均粒径を有する
PVCラテツクスとNBRラテツクスとを用いて、
実施例１と同じ方法で本発明方法のゴム組成物及
び対照例としての従来法のゴム組成物を調製した
（NBR／PVC＝70／30重量比）。
第５表の配合処方（高硬度配合）により、実施
例１と同様にして配合ゴム組成物を作成し、JIS
Ｋ 6301に従つて配合物粘度、170℃×10分プレ
ス加硫物の常態物性、静的耐オゾン性ならびにオ
シレーテイング・デイスク・レオメーター（東洋
精機社製品）の最低トルクを求め第６表に結果を
示した。
第５表 配合処方（高硬度配合）
NBR／PVC混合物 100重量部
ステアリン酸 １ 〃
亜鉛華 ５ 〃
SRFカーボンブラツク 90 〃
可塑性DOP 20 〃
硫黄 0.5 〃
促進剤TT 1.5 〃
促進剤CZ 1.5 〃 [Table] Example 2 Having the average degree of polymerization and average particle size listed in Table 6
Using PVC latex and NBR latex,
A rubber composition of the present invention and a conventional rubber composition as a control example were prepared in the same manner as in Example 1 (NBR/PVC = 70/30 weight ratio). A compounded rubber composition was prepared in the same manner as in Example 1 using the compounding recipe (high hardness compounding) in Table 5, and JIS
According to K 6301, the compound viscosity, the normal physical properties of the 170°C x 10 minute press vulcanizate, the static ozone resistance, and the minimum torque of the oscillating disc rheometer (Toyo Seiki Co., Ltd. product) were determined in Table 6. The results were shown. Table 5 Mixing prescription (high hardness combination) NBR/PVC mixture 100 parts by weight Stearic acid 1 Zinc white 5 SRF carbon black 90 Plasticity DOP 20 Sulfur 0.5 Accelerator TT 1.5 Accelerator CZ 1.5
本発明によれば、アクリロニトリル−共役ジエ
ン系共重合ゴム、塩化ビニル系樹脂および加硫剤
を含むゴム組成物から耐油性、耐オゾン性を有す
るゴム加硫物を製造する場合に、加硫工程までは
PVCのゲル化が生じるような条件での加熱混練
処理を行なわないため、加工性、作業性、発熱
性、経済性等が改良された製造方法が提供され
る。また、ゴム組成物は、粘度（ムーニー粘度）
が低いため、混練作業性、発熱性、スコーチ性が
改良されるとともに、高温での配合物粘度（レオ
メーターの最低トルク）が高いため、加硫時の型
崩れ防止に有効である。
According to the present invention, when producing a rubber vulcanizate having oil resistance and ozone resistance from a rubber composition containing an acrylonitrile-conjugated diene copolymer rubber, a vinyl chloride resin, and a vulcanizing agent, the vulcanization step is performed. Until
Since heating and kneading treatment is not performed under conditions that would cause gelation of PVC, a manufacturing method with improved processability, workability, heat generation, economic efficiency, etc. is provided. In addition, the rubber composition has a viscosity (Mooney viscosity)
Since the compound is low, the kneading workability, heat generation property, and scorch property are improved, and the compound viscosity at high temperature (minimum rheometer torque) is high, so it is effective in preventing shape collapse during vulcanization.
第１図〜第６図は実施例１のNBR／PVC混合
物の分散常態を示す電子顕微鏡写真である。スケ
ールは1μmである。
1 to 6 are electron micrographs showing the normal state of dispersion of the NBR/PVC mixture of Example 1. The scale is 1 μm.
Claims (1)
ム、塩化ビニル系樹脂および加硫剤を含むゴム組
成物からゴム加硫物を製造する方法において、 (1) 塩化ビニル系樹脂として平均粒子径が5μm以
下の粒状樹脂を用い、 (2) アクリロニトリル−共役ジエン系共重合ゴム
と該塩化ビニル系樹脂とを、塩化ビニル系樹脂
のゲル化温度より低い温度条件下に、ラテツク
ス同士で混合、共沈、乾燥して、塩化ビニル系
樹脂が前記平均粒子径を有する粒子形態を保持
したままの状態でアクリロニトリル−共役ジエ
ン系共重合ゴム中に均一に分散した混合物を
得、次いで、 (3) 加硫剤を含む配合剤を塩化ビニル系樹脂のゲ
ル化温度より低い温度条件で混合し、 (4) 得られたゴム組成物を用いて、ゴム組成物中
の塩化ビニル系樹脂がゲル化する温度以上の温
度条件で加硫することを特徴とする耐油性、耐
オゾン性を有するゴム加硫物の製造方法。[Scope of Claims] 1. A method for producing a rubber vulcanizate from a rubber composition containing an acrylonitrile-conjugated diene copolymer rubber, a vinyl chloride resin, and a vulcanizing agent, comprising: (1) average particles of the vinyl chloride resin; Using granular resin with a diameter of 5 μm or less, (2) mixing the acrylonitrile-conjugated diene copolymer rubber and the vinyl chloride resin with each other at a temperature lower than the gelling temperature of the vinyl chloride resin, Co-precipitate and dry to obtain a mixture in which the vinyl chloride resin is uniformly dispersed in the acrylonitrile-conjugated diene copolymer rubber while maintaining the particle form having the above-mentioned average particle diameter, and then (3) A compounding agent containing a vulcanizing agent is mixed at a temperature lower than the gelling temperature of the vinyl chloride resin, and (4) the vinyl chloride resin in the rubber composition is gelled using the obtained rubber composition. A method for producing a rubber vulcanizate having oil resistance and ozone resistance, the method comprising vulcanizing at a temperature higher than that temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15612282A JPS5945339A (en) | 1982-09-08 | 1982-09-08 | Preparation of rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15612282A JPS5945339A (en) | 1982-09-08 | 1982-09-08 | Preparation of rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5945339A JPS5945339A (en) | 1984-03-14 |
| JPH0331739B2 true JPH0331739B2 (en) | 1991-05-08 |
Family
ID=15620797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15612282A Granted JPS5945339A (en) | 1982-09-08 | 1982-09-08 | Preparation of rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5945339A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2515155B2 (en) * | 1988-07-15 | 1996-07-10 | 電気化学工業株式会社 | Thermoplastic elastomer composition |
| JP2805681B2 (en) * | 1988-07-15 | 1998-09-30 | 電気化学工業株式会社 | Thermoplastic elastomer composition |
| JP5942666B2 (en) * | 2012-07-24 | 2016-06-29 | 東ソー株式会社 | PVC latex for NBR and PVC compositions and NBR and PVC compositions |
-
1982
- 1982-09-08 JP JP15612282A patent/JPS5945339A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5945339A (en) | 1984-03-14 |
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