JPH0613628B2 - Thermoplastic elastomer composition - Google Patents
Thermoplastic elastomer compositionInfo
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- JPH0613628B2 JPH0613628B2 JP60060154A JP6015485A JPH0613628B2 JP H0613628 B2 JPH0613628 B2 JP H0613628B2 JP 60060154 A JP60060154 A JP 60060154A JP 6015485 A JP6015485 A JP 6015485A JP H0613628 B2 JPH0613628 B2 JP H0613628B2
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はゴム弾性、柔軟性に優れ、かつ機械的強度に著
しく優れた熱可塑性エラストマー組成物に関するもので
ある。TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition having excellent rubber elasticity and flexibility and remarkably excellent mechanical strength.
（従来の技術） 近年、ゴム的な軟質材料であつて、加硫工程を要せず、
熱可塑性樹脂と同様な成形加工性を有する熱可塑性エラ
ストマー（以下ＴＰＥと略称する）が、自動車部品、家
電部品、医療，食品用機器部品、電線及び雑貨等の分野
で注目され使用されている。(Prior Art) In recent years, a rubber-like soft material that does not require a vulcanization step,
BACKGROUND ART A thermoplastic elastomer (hereinafter abbreviated as TPE) having a molding processability similar to that of a thermoplastic resin has been noticed and used in fields such as automobile parts, home electric appliance parts, medical and food equipment parts, electric wires and sundries.
このようなＴＰＥには現在、ポリオレフイン系、ポリウ
レタン系、ポリエステル系、ポリスチレン系等の種々の
系統のポリマーが開発され、市販されている。At present, various types of polymers such as polyolefin, polyurethane, polyester, polystyrene and the like have been developed and marketed for such TPE.
（発明が解決しようとする問題点） しかしながら、これ等ＴＰＥは、ゴムとしての広い用途
分野の１つである加硫ゴムの用途に於いて、品質面で加
硫ゴムの水準には達しておらず、従つて、加硫ゴム分野
での利用は極めて限定されている。(Problems to be solved by the invention) However, these TPEs have not reached the level of vulcanized rubber in terms of quality in the use of vulcanized rubber, which is one of the wide fields of application as rubber. Therefore, their use in the vulcanized rubber field is therefore very limited.
例えば、ポリオレフイン系ＴＰＥは、比較的安価で耐熱
性、耐候性にすぐれている反面、軟質のものが得られ
ず、最も柔軟なものでもＪＩＳ−Ａ硬度（ＪＩＳ Ｋ−
６３０１）で７０程度であり、一般の加硫ゴムのＪＩＳ
−Ａ硬度60に比べまだ硬すぎる。また、ＪＩＳ−Ａ硬度
70附近の低硬度領域における引張り強度は２５〜４５kg
／cm2で、加硫ゴムの約１００kg／cm2に比してかなり低
い。For example, while polyolefin olefin-based TPE is relatively inexpensive and has excellent heat resistance and weather resistance, it cannot be obtained as a soft one, and even the most flexible one has JIS-A hardness (JIS K-
6301) is about 70, and JIS of general vulcanized rubber
-It is still too hard compared to A hardness 60. Also, JIS-A hardness
Tensile strength in the low hardness region near 70 is 25 to 45 kg
/ Cm 2 , which is considerably lower than the vulcanized rubber of about 100 kg / cm 2 .
ポリエステル系ＴＰＥやポリウレタン系ＴＰＥもまた、
その市販品中最も柔軟なものでＪＩＳ−Ａ硬度が８０〜
９０で、加硫ゴムに比べて非常に硬く、加硫ゴムの用途
分野に適さない。Polyester TPE and polyurethane TPE are also available
The most flexible product on the market with JIS-A hardness of 80-
At 90, it is very hard as compared with vulcanized rubber and is not suitable for the application field of vulcanized rubber.
一方、スチレン−ブタジエン−スチレンブロツクポリマ
ー（ＳＢＳ）やスチレン−イソブレン−スチレン（ＳＩ
Ｓ）ブロツクポリマー等のポスチレン系ＴＰＥは、前記
のＴＰＥに比べて柔軟性に富み、良好なゴム弾性を有す
るが、ポリマー内にポリブタジエンブロツクあるいはポ
リイソプレンブロツクに二重結合を有しているため、耐
熱老化性（熱安定性）および耐候性に問題がある。On the other hand, styrene-butadiene-styrene block polymer (SBS) and styrene-isobrene-styrene (SI
S) Polystyrene type TPE such as block polymer is more flexible and has better rubber elasticity than the above TPE, but since it has a double bond in polybutadiene block or polyisoprene block in the polymer, There is a problem with heat aging resistance (heat stability) and weather resistance.
スチレンと共役ジエンのブロツク共重合体の分子内二重
結合を水素添加することによつて熱安定性の向上したエ
ラストマーを得ることができる。このエラストマーをゴ
ム成分とした熱可塑性エラストマーは、オレフイン系Ｔ
ＰＥに比べて柔軟性、ゴム弾性、強度ともに優れている
が、ＪＩＳ−Ａ硬度５０附近で７０〜９０kg／cm2であ
り、加硫ゴムに比べ劣つている。By hydrogenating the intramolecular double bond of the block copolymer of styrene and a conjugated diene, an elastomer having improved thermal stability can be obtained. A thermoplastic elastomer containing this elastomer as a rubber component is an olefin-based T
It is superior in flexibility, rubber elasticity, and strength to PE, but it is inferior to vulcanized rubber because the JIS-A hardness is around 70 to 90 kg / cm 2 around 50.
本発明者等は、柔軟かつ高強度のＴＰＥを開発すべく鋭
意検討した結果、ゴム成分としてスチレン−ブタジエン
ブロツクポリマーの水素添加誘導体を用いた熱可塑性エ
ラストマーにおいて、軟化剤として特定の合成軟化剤を
用いることにより、柔軟かつ加硫ゴムに匹適する高強度
を有することを見いだし本発明を完成した。The present inventors have conducted extensive studies to develop a flexible and high-strength TPE, and as a result, in a thermoplastic elastomer using a hydrogenated derivative of styrene-butadiene block polymer as a rubber component, a specific synthetic softening agent was used as a softening agent. The present invention was completed by finding out that it has flexibility and high strength comparable to vulcanized rubber.
（発明を解決するための手段） 即ち、本発明は、一般式 〔但し、式中のＡは、モノビニル置換芳香族炭化水素の
重合体ブロック、Ｂは共役ジエンのエラストマー性重合
体ブロックであり、ｎは１〜５の整数〕で表わされるブ
ロック共重合体の水素添加誘導体１００重量部、及び、
平均分子量が７００〜２５００のポリブテン７０〜３０
０重量部からなることを特徴とする熱可塑性エラストマ
ー組成物である。(Means for Solving the Invention) That is, the present invention is based on the general formula [Wherein A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5] hydrogen of a block copolymer 100 parts by weight of the added derivative, and
Polybutene 70 to 30 having an average molecular weight of 700 to 2500
It is a thermoplastic elastomer composition comprising 0 parts by weight.
（作用） 本発明に用いられるゴム成分の一般式 なるブロツク共重合体の水素添加誘導体における重合体
ブロツクＡを構成する単量体のモノビニル置換芳香族炭
化水素としては、種々のものが挙げられるが、特にスチ
レン、α−メチルスチレンが好適である。同一式中の重
合体ブロツクＢの共役ジエン単量体としては、ブタジエ
ンもしくはイソプレンが好適で、それら両者の混合物で
もよい。ブタジエンを単一の共役ジエン単量体として使
用して重合体ブロツクＢを形成する場合には、エラスト
マー性を保持する目的で、ポリブタジエンにおけるミク
ロ構造中の１，２−ミクロ構造が２０〜５０％となる重
合条件を採用することが好ましく、特に１，２−ミクロ
構造が３５〜４５％のものが適している。また、重合体
ブロツクＢの前記共重合体中に占める割合は、少なくと
も６５重量％にすることが好ましい。(Function) General formula of the rubber component used in the present invention As the monomeric monovinyl-substituted aromatic hydrocarbon constituting the polymer block A in the hydrogenated derivative of the block copolymer, various ones may be mentioned, and styrene and α-methylstyrene are particularly preferable. As the conjugated diene monomer of the polymer block B in the same formula, butadiene or isoprene is preferable, and a mixture of both may be used. When butadiene is used as the single conjugated diene monomer to form the polymer block B, the 1,2-microstructure in the microstructure of polybutadiene is 20 to 50% in order to maintain the elastomeric property. The following polymerization conditions are preferably adopted, and those having a 1,2-microstructure of 35 to 45% are particularly suitable. The proportion of the polymer block B in the copolymer is preferably at least 65% by weight.
上記重合体ブロツクＡの平均分子量は5000から１２５０
００、ブロツクＢは１５０００から２５００００の範囲
にあることが好ましい。The average molecular weight of the polymer block A is 5000 to 1250.
00 and Block B are preferably in the range of 15,000 to 250,000.
本発明に用いられるブロツク共重合体は、水素添加処理
されたものである。The block copolymer used in the present invention is hydrogenated.
上述した一般式のブロツク共重合体の水素添加誘導体の
製造方法としては数多くの方法が提案されているが、代
表的な方法としては、例えば特公昭４２−８７０４号、
同４３−６６３６号等の公報に記載された方法がある。Although many methods have been proposed as a method for producing a hydrogenated derivative of a block copolymer of the above general formula, typical methods include, for example, Japanese Patent Publication No. 42-8704.
There is a method described in the gazettes of the same 43-6636.
その製造に際しての水素添加において、重合体ブロツク
Ｂ中のオレフイン型二重結合の少なくとも５０％、好ま
しくは８０％以上が水素添加され、重合体ブロツクＡ中
の芳香族性不飽和結合の２５％以下が水素添加されたも
のが好適である。このようなブロツクポイマーとして
は、市販のポリマーでありＫＲＡＴＯＮ−Ｇ（シエルケ
ミカル社製商品名）等を使用できる。In the hydrogenation during the production, at least 50%, preferably 80% or more of the olefin-type double bonds in the polymer block B are hydrogenated, and 25% or less of the aromatic unsaturated bonds in the polymer block A are hydrogenated. Is preferably hydrogenated. As such a block poimer, a commercially available polymer such as KRATON-G (trade name of Ciel Chemical Co.) can be used.
本発明に使用されるポリブテンとしては、イソブチレン
を主体とし、一部ｎ−ブテン共重合されたものであり、
平均分子量が７００から２５００、好ましくは８００か
ら２０００のものである。The polybutene used in the present invention is mainly isobutylene, and is partially copolymerized with n-butene,
It has an average molecular weight of 700 to 2500, preferably 800 to 2000.
平均分子量が７００未満の場合または2500を超える場合
は得られる熱可塑性エラストマーの強度物性が低くな
る。If the average molecular weight is less than 700 or more than 2500, the strength properties of the resulting thermoplastic elastomer will be poor.
また配合割合は、ゴム成分である先述のブロツクポリマ
ー１００重量部に対して70〜300重量部、好ましくは１
００〜２００重量部である。The compounding ratio is 70 to 300 parts by weight, preferably 1 to 100 parts by weight of the above-mentioned block polymer which is a rubber component.
It is from 00 to 200 parts by weight.
配合割合が７０未満の場合は成形加工性強度物性が低下
する。また、３００重量部を超える場合得られた熱可塑
性エラストマーの強度が低下するだけでなく成形品の外
観（ベタツキ）が悪化する。When the blending ratio is less than 70, the molding workability and the physical properties are deteriorated. Further, when it exceeds 300 parts by weight, not only the strength of the obtained thermoplastic elastomer is lowered but also the appearance (stickiness) of the molded product is deteriorated.
本発明は、熱可塑性エラストマーを得る際にこれら必須
成分を所定量含有させることを特徴としているが、熱可
塑性エラストマーは一般にゴム成分であるブロツクポリ
マー１００重量部に対し、パラフイン系オイル、ナフテ
ン系オイル等の炭化水素油を１００重量部以下；ポリエ
チレン、ポリプロピレン、エチレン−α−オレフイン共
重合体樹脂、プロピレン−α−オレフイン共重合体樹脂
等のポリオレフイン樹脂200重量部以下；炭酸カルシウ
ム、タルク、マイカ、カーボンブラツク等の無機フイラ
ー５００重量部以下を目標の品質に合わせて配合するも
のであり、本発明の熱可塑性エラストマーもこれに準じ
る。The present invention is characterized by containing a predetermined amount of these essential components when obtaining a thermoplastic elastomer. The thermoplastic elastomer is generally a paraffin-based oil or a naphthene-based oil based on 100 parts by weight of a block polymer which is a rubber component. 100 parts by weight or less of hydrocarbon oil such as polyethylene; polypropylene, ethylene-α-olefin copolymer resin, propylene-α-olefin copolymer resin or other polyolefin resin 200 parts by weight or less; calcium carbonate, talc, mica, An inorganic filler such as carbon black is blended in an amount of 500 parts by weight or less in accordance with the target quality, and the thermoplastic elastomer of the present invention is also in conformity therewith.
本発明の熱可塑性エラストマーを製造する方法は機械的
溶融混練によることができる。具体的にはバンバリーミ
キサー、各種ニーダー、押出機等の一般的溶融混練機を
用いることができる。The method for producing the thermoplastic elastomer of the present invention can be based on mechanical melt kneading. Specifically, a general melt kneader such as a Banbury mixer, various kneaders and an extruder can be used.
本発明の熱可塑性エラストマーは、必要に応じて顔料、
熱安定剤、抗酸化剤、紫外線吸収剤等の添加剤を加える
ことができる。The thermoplastic elastomer of the present invention, if necessary, a pigment,
Additives such as heat stabilizers, antioxidants and UV absorbers can be added.
また、射出成形、押出成形、ブロー成形等の熱可塑性樹
脂の成形法が適用可能である。Further, a molding method of a thermoplastic resin such as injection molding, extrusion molding or blow molding can be applied.
尚、本発明の熱可塑性エラストマーの使用分野として
は、家電、自動車部品等の工業用部品、食品、医療機器
部品、日用雑貨等に用いられる。The thermoplastic elastomer of the present invention may be used in industrial parts such as home electric appliances and automobile parts, foods, medical equipment parts, daily sundries and the like.
（実施例） 実施例において、各種の評価に用いた試験法は以下のと
おりである。但し、測定試料はすべて５オンスインライ
ンスクリユータイプ射出成形機にて射出圧力５００kg／
cm2、射出温度200℃、金型温度４０℃によつて成形した
２mm厚シートの横方向打抜きにより得た。(Example) In the examples, the test methods used for various evaluations are as follows. However, all measurement samples are injection pressure 500kg / in 5oz inline screw type injection molding machine.
It was obtained by lateral punching of a 2 mm thick sheet molded with cm 2 , injection temperature 200 ° C., mold temperature 40 ° C.
(1)ＪＩＳ−Ａ硬度〔−〕 ＪＩＳ−Ｋ−６３０１ (2)引張強度〔kg／cm2〕 ＪＩＳ−Ｋ−６３０１（試験片３号形） (3)引張伸度〔％〕 ＪＩＳ−Ｋ−６３０１（試験片３号形） (4)圧縮永久歪〔％〕 ＪＩＳ−Ｋ−６３０１（７０℃、２２時間） また、実施例に用いた各配合成分は次のとおりである。(1) JIS-A hardness [−] JIS-K-6301 (2) Tensile strength [kg / cm 2 ] JIS-K-6301 (Test piece No. 3 type) (3) Tensile elongation [%] JIS-K -6301 (Test piece No. 3 type) (4) Compression set [%] JIS-K-6301 (70 ° C, 22 hours) Further, each compounding component used in the examples is as follows.
(1)ゴム成分（ブロツクポリマー） 前記の一般式におけるＡブロックが平均分子量30,000の
スチレンブロック、Ｂブロックが同120,000のブタジエ
ンブロック、ｎが１であり、両末端のＡ部が全体の約33
重量％である共重合体の水素添加物のシェルケミカル社
製ＫＲＡＴＯＮ−Ｇ1651（Brookfield粘度；２０重量％
トルエン溶液で２０００cps、７７゜Ｆ） (2)ポリブテン成分 日本石油化学製ポリブテン ＨＶ１５ （平均分子量５４０） 同 上 ＨＶ１００ （平均分子量９７０） 同 上 ＨＶ３００ （平均分子量１３５０） 同 上 ＨＶ１９００ （平均分子量２７００） 三井石油化学工業製ポリブテン樹脂 Ｍ０２００ （ＭＦＲ1.8g/10分、引張り弾性率2700kg/cm2） (3)その他 ポリオレフイン系樹脂 三菱油化社製ＳＰＸ９８００（プロピレン−αオレフイ
ン共重合体ポリマー；２３０℃、２．１６kg荷重のＭＦ
Ｒ１．０ｇ／１０分） パラフイン系オイル 出光興産社製ＰＷ９０（４０℃動粘度９５．５４cst） 無機フイラー 炭酸カルシウム（平均粒径２．５ミクロン、高級脂肪酸
エステル表面処理） 実施例１ 第１表に示した配合にて、バンバリーミキサーを用いて
１７０℃、８０rpmで１０分間混練し、シートカツトし
て熱可塑性エラストマーペレツトを得た。このペレツト
を用いて射出成形により厚さ２mmのシートを成形した。
成形性は良好であり、成形品外観も良好であつた。(1) Rubber component (block polymer) In the above general formula, the A block is a styrene block having an average molecular weight of 30,000, the B block is a butadiene block having the same molecular weight of 120,000, n is 1, and the A parts at both ends are about 33% of the total.
KRATON-G1651 (Brookfield viscosity; 20% by weight, manufactured by Shell Chemical Co., Ltd.), which is a hydrogenated product of a copolymer which is by weight
2000 cps in toluene solution, 77 ° F) (2) Polybutene component Polybutene manufactured by Nippon Petrochemicals HV15 (Average molecular weight 540) Same as above HV100 (Average molecular weight 970) Same as above HV300 (Average molecular weight 1350) Same as above HV1900 (Average molecular weight 2700) Mitsui Petrochemical Industrial Polybutene Resin M0200 (MFR 1.8g / 10min, Tensile Elastic Modulus 2700kg / cm 2 ) (3) Other Polyolefin Resins Mitsubishi Yuka SPX9800 (Propylene-α olefin copolymer polymer; 230 ° C, 2 MF with a load of 16 kg
R1.0g / 10 minutes) Parafuin system oil PW90 (40 ° C kinematic viscosity 95.54cst) manufactured by Idemitsu Kosan Co., Ltd. Inorganic filler Calcium carbonate (average particle size 2.5 microns, higher fatty acid ester surface treatment) Example 1 Table 1 Using the Banbury mixer, the composition shown was kneaded at 170 ° C. and 80 rpm for 10 minutes and cut into sheets to obtain thermoplastic elastomer pellets. Using this pellet, a sheet having a thickness of 2 mm was formed by injection molding.
The moldability was good, and the appearance of the molded product was also good.
得られた射出成形シートを用いて硬度、引張強度、伸度
および圧縮永久歪を評価したところ第１表に示すとおり
ＪＩＳ−Ａ硬度で53〜55、引張強度１１０〜１２０kg／
cm2、伸度７３０〜７９０％、圧縮永久歪３５〜４０％
と良好なものであつた。When the hardness, tensile strength, elongation and compression set were evaluated using the obtained injection-molded sheet, as shown in Table 1, JIS-A hardness was 53 to 55 and tensile strength was 110 to 120 kg /
cm 2 , elongation 730 to 790%, compression set 35 to 40%
And it was a good one.
また、比較例についても第１表の通り検討した。Further, comparative examples were also examined as shown in Table 1.
以上の実施例、比較例から判る通り、本発明の熱可塑性
エラストマーは柔軟性にすぐれ、かつ加硫ゴム並の強度
を有するものであることが理解される。As can be seen from the above Examples and Comparative Examples, it is understood that the thermoplastic elastomer of the present invention has excellent flexibility and strength equivalent to that of vulcanized rubber.
Claims (1)
重合体ブロック、Ｂは共役ジエンのエラストマー性重合
体ブロックであり、ｎは１〜５の整数〕で表わされるブ
ロック共重合体の水素添加誘導体１００重量部、及び、
平均分子量が７００〜２５００のポリブテン７０〜３０
０重量部からなることを特徴とする熱可塑性エラストマ
ー組成物。1. A general formula [Wherein A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5] hydrogen of a block copolymer 100 parts by weight of the added derivative, and
Polybutene 70 to 30 having an average molecular weight of 700 to 2500
A thermoplastic elastomer composition comprising 0 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60060154A JPH0613628B2 (en) | 1985-03-25 | 1985-03-25 | Thermoplastic elastomer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60060154A JPH0613628B2 (en) | 1985-03-25 | 1985-03-25 | Thermoplastic elastomer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61218650A JPS61218650A (en) | 1986-09-29 |
| JPH0613628B2 true JPH0613628B2 (en) | 1994-02-23 |
Family
ID=13133948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60060154A Expired - Lifetime JPH0613628B2 (en) | 1985-03-25 | 1985-03-25 | Thermoplastic elastomer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613628B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9365706B2 (en) | 2011-09-15 | 2016-06-14 | Asahi Kasei Chemicals Corporation | Crosslinked composition, method for producing crosslinked composition, and molded product |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61247460A (en) * | 1985-04-26 | 1986-11-04 | 塩谷エムエス株式会社 | Stop plug for injection drug |
| JPS6422519A (en) * | 1987-07-18 | 1989-01-25 | Toyoda Gosei Kk | Injection molded form of coating soft resin |
| JPS6422516A (en) * | 1987-07-18 | 1989-01-25 | Toyoda Gosei Kk | Soft resin insert molded form |
| US5929165A (en) * | 1995-10-27 | 1999-07-27 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
| US5936037A (en) | 1996-05-28 | 1999-08-10 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
| US7425591B2 (en) | 2001-10-16 | 2008-09-16 | Exxonmobil Chemical Patents Inc | Elastomeric composition |
| US6939921B2 (en) * | 2001-10-16 | 2005-09-06 | Exxonmobil Chemical Patents Inc. | Colorable elastomeric composition |
| JP6425477B2 (en) * | 2014-09-15 | 2018-11-21 | リケンテクノス株式会社 | Thermoplastic elastomer composition |
| JP6440444B2 (en) * | 2014-10-09 | 2018-12-19 | リケンテクノス株式会社 | Thermoplastic elastomer composition |
| JP6440445B2 (en) * | 2014-10-09 | 2018-12-19 | リケンテクノス株式会社 | Thermoplastic elastomer composition |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138378A (en) * | 1977-12-23 | 1979-02-06 | Phillips Petroleum Company | Liquid polyalkene in thermoplastic elastomer sealant formulation |
| JPS5638338A (en) * | 1979-09-06 | 1981-04-13 | Asahi Chem Ind Co Ltd | Thermoplastic resin composition |
| JPS5650943A (en) * | 1979-10-04 | 1981-05-08 | Asahi Chem Ind Co Ltd | Thermoplastic adhesive resin composition |
| JPS58196244A (en) * | 1982-05-12 | 1983-11-15 | Mitsubishi Petrochem Co Ltd | How to add softener to elastomer |
| JPS58206644A (en) * | 1982-05-27 | 1983-12-01 | Mitsubishi Petrochem Co Ltd | Elastomer composition |
| JPS596236A (en) * | 1982-07-05 | 1984-01-13 | Mitsubishi Petrochem Co Ltd | Production of elastomeric composition |
| JPS59131613A (en) * | 1983-01-18 | 1984-07-28 | Mitsubishi Petrochem Co Ltd | Preparation of elastomer ic composition |
| JPH0465880A (en) * | 1990-07-06 | 1992-03-02 | Matsushita Electric Ind Co Ltd | Manufacture of photovoltaic element |
-
1985
- 1985-03-25 JP JP60060154A patent/JPH0613628B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9365706B2 (en) | 2011-09-15 | 2016-06-14 | Asahi Kasei Chemicals Corporation | Crosslinked composition, method for producing crosslinked composition, and molded product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61218650A (en) | 1986-09-29 |
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