JP2602162B2 - Polyamide resin composition - Google Patents
Polyamide resin compositionInfo
- Publication number
- JP2602162B2 JP2602162B2 JP5060961A JP6096193A JP2602162B2 JP 2602162 B2 JP2602162 B2 JP 2602162B2 JP 5060961 A JP5060961 A JP 5060961A JP 6096193 A JP6096193 A JP 6096193A JP 2602162 B2 JP2602162 B2 JP 2602162B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- modified
- maleic anhydride
- weight
- resin
- 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 - Fee Related
Links
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- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明はポリアミド系樹脂組成物
に係り、詳しくは近年問題となっている樹脂廃材である
ポリアミド樹脂を熱可塑性樹脂とでアロイ化できる新た
な樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition, and more particularly to a new resin composition capable of alloying a polyamide resin, a resin waste material which has recently become a problem, with a thermoplastic resin. .
【0002】[0002]
【従来の技術】ポリアミド樹脂は最も代表的なエンジニ
ヤリングプラスチックであり、機械的強さ、耐衝撃性、
耐熱性、耐薬品性に優れ、しかも成形性も良いため、ギ
ヤ、ロール、摺動板などの多くの機械部品としても使用
されている。このポリアミド樹脂はε−カプロラクタム
を金型に注型してアニオン重合することによって得られ
る。この注型ポリアミド樹脂素材である板や丸棒を機械
加工する際に、多量の加工屑が発生している。しかし、
注型ポリアミド樹脂の加工屑は、高分子量、高結晶化、
高融点のため、再度これを押出機でペレット化して再利
用しようとしても、押出機に対する負荷が大きくて押出
量を小さくする必要があり、生産性が著しく劣ってい
る。このため、注型ポリアミド樹脂の加工屑の大部分は
産業廃棄物として破棄されていた。これを改善するた
め、注型ポリアミド樹脂の加工屑にステアリン酸カルシ
ウム、ステアリン酸亜鉛の様な滑剤や低粘度ポリアミド
樹脂を添加して粘度を低下させて押出成形する方法が提
案されている。2. Description of the Related Art Polyamide resin is the most representative engineering plastic, and has mechanical strength, impact resistance,
Because of its excellent heat resistance and chemical resistance and good moldability, it is also used as many mechanical parts such as gears, rolls, and sliding plates. This polyamide resin is obtained by casting ε-caprolactam into a mold and performing anionic polymerization. When a plate or a round bar made of the cast polyamide resin material is machined, a large amount of processing waste is generated. But,
Processing waste of cast polyamide resin is high molecular weight, high crystallization,
Because of its high melting point, even if it is pelletized again by the extruder and it is to be reused, the load on the extruder is large and the extruded amount needs to be reduced, and the productivity is extremely poor. For this reason, most of the processing waste of the cast polyamide resin has been discarded as industrial waste. In order to improve this, a method has been proposed in which a lubricant such as calcium stearate or zinc stearate or a low-viscosity polyamide resin is added to the processing waste of the cast polyamide resin to lower the viscosity and extrusion is performed.
【0003】[0003]
【発明が解決しようとする課題】しかし、注型ポリアミ
ド樹脂の加工屑にステアリン酸カルシウムの様な滑剤を
添加して粘度を低下させようとしても、多量に添加する
とスクリューへの食込性が悪くなるので、少量しか添加
できず、このため押出機に対する負荷が大きくて成形性
が大きく劣るものであった。また、低粘度ポリアミド樹
脂は注型ポリアミド樹脂に任意の割合で添加できるとい
う利点はあるが、少量では効果が小さく不満足なもので
あった。本発明はこのような問題点を改善するものであ
り、上記注型ポリアミド樹脂の加工屑を効率良く利用し
て、充分再利用できるポリアミド系樹脂組成物を提供す
ることを目的とする。However, even if a lubricant such as calcium stearate is added to the processing waste of the cast polyamide resin to lower the viscosity, the addition of a large amount deteriorates the biteability into the screw. Therefore, only a small amount could be added, and as a result, the load on the extruder was large and the moldability was significantly poor. Further, the low-viscosity polyamide resin has an advantage that it can be added to the cast polyamide resin at an arbitrary ratio, but the effect is small and unsatisfactory when the amount is small. An object of the present invention is to improve such a problem, and an object of the present invention is to provide a polyamide resin composition that can be sufficiently reused by efficiently using the processing waste of the cast polyamide resin.
【0004】[0004]
【課題を解決するための手段】即ち、本発明の特徴とす
るところは、240°Cで10分間あたりのメルトフロ
ーレートがゼロである注型ポリアミド樹脂の加工屑20
〜85重量%に、少なくとも該注型ポリアミド樹脂の融
点より低い融点もしくは軟化点を有する熱可塑性樹脂1
2〜77重量%と、相溶化剤3〜15重量%とを添加し
たポリアミド系樹脂組成物にある。尚、本発明で述べる
ポリアミド系樹脂組成物は、少なくとも注型ポリアミド
樹脂、該注型ポリアミド樹脂の融点より低い融点もしく
はこの融点より低い軟化点を有する熱可塑性樹脂そして
相溶化剤の3成分を単に混合したもの、あるいはこの混
合物を押出機を用いて溶融混練りしてポリマーアロイ化
してペレット状にしたもの、あるいはこのペレットを射
出成形によって成形体にしたものを含む。That is, the feature of the present invention is that the melt flow rate at 240 ° C. per 10 minutes is used.
Processing waste of cast polyamide resin with zero rate 20
Thermoplastic resin 1 having a melting point or softening point lower than the melting point of the cast polyamide resin at
The polyamide resin composition contains 2 to 77% by weight and 3 to 15% by weight of a compatibilizer. The polyamide resin composition described in the present invention comprises at least three components: a cast polyamide resin, a thermoplastic resin having a melting point lower than the melting point of the cast polyamide resin or a softening point lower than the melting point, and a compatibilizer. It includes those obtained by mixing, or the mixture is melt-kneaded using an extruder to form a polymer alloy into pellets, or the pellets are formed into a molded product by injection molding.
【0005】以下、本発明について更に詳しく説明す
る。上記注型ポリアミド樹脂は、5員環以上の実質的無
水のω−ラクタムであり、2−ピロリドン、ε−カプロ
ラクタム、ω−カプリロラクタム等を金型に注型してア
ニオン重合することによって得られたポリアミド樹脂で
ある。この製造方法については、例えば特公昭50−9
026号公報、特公昭51−1277号公報に開示され
ている。この方法によって得られた注型ポリアミド樹脂
は、金型内で充分に重合されるために他の重合方法によ
って得られたポリアミド樹脂に比べて分子量が高く、し
かも各分子も絡みあっているため、溶融粘度が高い。こ
のため、上記注型ポリアミド樹脂は240°Cで10分
間あたりのメルトフローレートはゼロである。この注型
ポリアミド樹脂の添加量は20〜85重量%であり、2
0重量%未満の場合には注型ポリアミド樹脂の本来有す
る耐熱性、高強度、高弾性率が有効に出現せず、また8
5重量%を越えると押出機への負荷が大きくなり、単位
時間当たりの押出量を小さくする必要がある。Hereinafter, the present invention will be described in more detail. The above cast polyamide resin is a substantially anhydrous ω-lactam having five or more ring members, and is obtained by casting 2-pyrrolidone, ε-caprolactam, ω-capryloractam, etc. into a mold and anion-polymerizing the same. It is the obtained polyamide resin. This production method is described in, for example, Japanese Examined Patent Publication No. 50-9.
No. 026 and Japanese Patent Publication No. 51-1277. The cast polyamide resin obtained by this method has a higher molecular weight than the polyamide resin obtained by another polymerization method because it is sufficiently polymerized in the mold, and since each molecule is also entangled, High melt viscosity. For this reason, the cast polyamide resin has a zero melt flow rate at 240 ° C. for 10 minutes. The added amount of the cast polyamide resin is 20 to 85% by weight.
If the amount is less than 0% by weight, the inherent heat resistance, high strength and high modulus of the cast polyamide resin do not appear effectively.
If it exceeds 5% by weight, the load on the extruder increases, and it is necessary to reduce the amount of extrusion per unit time.
【0006】上記熱可塑性樹脂は注型ポリアミド樹脂よ
り融点(220〜250°C)の低いポリプロピレン、
ポリエチレン、あるいは注型ポリアミド樹脂の融点より
低い軟化点を有するABS、ポリスチレン、ASであ
り、これらを2種以上併用することも可能である。ま
た、アロイ化されたもので注型ポリアミド樹脂より融点
の低いポリマーアロイあるいは注型ポリアミド樹脂の融
点より低い軟化点を有するポリマーアロイも使用可能で
あるが、この際注型ポリアミド樹脂とポリマーアロイは
相溶化剤によって相溶化され、ミクロ相分離構造を有す
ることが重要である。即ち、互いに分子レベルで均一に
混ざらず、相溶化したミクロ相分離構造中の熱可塑性樹
脂が著しく押出機への負荷(トルク)の低下に寄与して
いると思われる。The thermoplastic resin is a polypropylene having a lower melting point (220 to 250 ° C.) than the cast polyamide resin.
These are ABS, polystyrene, and AS having a softening point lower than the melting point of polyethylene or cast polyamide resin, and two or more of these can be used in combination. Further, it is also possible to use a polymer alloy having a softening point lower than the melting point of the cast polyamide resin or a polymer alloy having a melting point lower than that of the cast polyamide resin in which the cast polyamide resin and the polymer alloy are used. It is important that they are compatibilized by a compatibilizer and have a microphase-separated structure. That is, it is considered that the thermoplastic resins in the microphase-separated structure, which are not uniformly mixed with each other at the molecular level, significantly contribute to lowering the load (torque) on the extruder.
【0007】更に、上記熱可塑性樹脂の粘度は、240
°Cで10分間あたりのメルトフローレートが0.1g
以上/10分のものが流動性に富み押出機へ負荷が小さ
いため好ましい。尚、超高分子量ポリエチレンや超高分
子量ポリプロピレンは流動性が著しく乏しくて押出機へ
の負荷が逆に大きくなるので使用できない。上記熱可塑
性樹脂の添加量は12〜77重量%であり、12重量%
未満の場合には押出機への負荷を充分に小さくすること
ができず、また77重量%を越えると注型ポリアミド樹
脂の本来有する耐熱性、高強度、高弾性率が出現しなく
なる。Further, the viscosity of the thermoplastic resin is 240
0.1g melt flow rate per 10 minutes at ° C
A time of / 10 minutes or more is preferable because the fluidity is high and the load on the extruder is small. Ultrahigh molecular weight polyethylene and ultrahigh molecular weight polypropylene cannot be used because the flowability is extremely poor and the load on the extruder increases. The addition amount of the thermoplastic resin is 12 to 77% by weight, and 12% by weight.
If it is less than 70%, the load on the extruder cannot be sufficiently reduced, and if it exceeds 77% by weight, the inherent heat resistance, high strength and high elastic modulus of the cast polyamide resin will not be exhibited.
【0008】更に、本発明で使用される相溶化剤として
は、ポリアミド末端のアミノ基と反応する官能基、例え
ばカルボン酸基や無水カルボン酸基、あるいはエポキシ
基を有し、そして添加する熱可塑性樹脂と相溶性の良好
なポリマーが化学結合しているものである。例えば、無
水マレイン酸変成ポリエチレン、無水マレイン酸変成ポ
リプロピレン、無水マレイン酸変成スチレン−エチレン
−ブチレン−スチレンブロック共重合体、無水マレイン
酸変成ABSから選ばれた無水マレイン酸変成樹脂、酸
変成アクリル−メチルメタクリレートグラフト共重合
体、酸変成アクリル−スチレングラフト共重合体、エポ
キシ変成ポリスチレン−メチルメタクリレートグラフト
共重合体等であり、使用する前記の熱可塑性樹脂に合わ
せて2種以上併用することも可能である。尚、無水マレ
イン酸変成ポリプロピレンは、注型ポリアミド樹脂とポ
リプロピレンの相溶化剤として使用されるが、熱可塑性
樹脂としてポリエチレン、ABS、ポリスチレン、AS
とともに使用するときは効果がない。一方、無水マレイ
ン酸変成スチレン−エチレン−ブチレン−スチレンブロ
ック共重合体は、注型ポリアミド樹脂と熱可塑性樹脂と
してポリプロピレン、ポリエチレン、ポリスチレンとの
相溶化剤として使用される。また、無水マレイン酸変成
ABSは、注型ポリアミド樹脂と熱可塑性樹脂としてA
BS、ASとの相溶化剤として使用される。Further, the compatibilizer used in the present invention has a functional group which reacts with the amino group at the terminal of the polyamide, for example, a carboxylic acid group, a carboxylic anhydride group, or an epoxy group. A polymer having good compatibility with the resin is chemically bonded. For example, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified styrene-ethylene-butylene-styrene block copolymer, maleic anhydride-modified ABS, maleic anhydride-modified resin, acid-modified acryl-methyl It is a methacrylate graft copolymer, an acid-modified acrylic-styrene graft copolymer, an epoxy-modified polystyrene-methyl methacrylate graft copolymer, or the like, and may be used in combination of two or more in accordance with the thermoplastic resin used. . The modified maleic anhydride polypropylene is used as a compatibilizer between the cast polyamide resin and the polypropylene. As the thermoplastic resin, polyethylene, ABS, polystyrene, and AS are used.
It has no effect when used with. On the other hand, the maleic anhydride-modified styrene-ethylene-butylene-styrene block copolymer is used as a compatibilizer between a cast polyamide resin and a thermoplastic resin such as polypropylene, polyethylene and polystyrene. The maleic anhydride-modified ABS is made of cast polyamide resin and thermoplastic resin.
Used as a compatibilizer with BS and AS.
【0009】上記相溶化剤の添加量は3〜15重量%、
好ましくは5〜10重量%である。3重量%未満の場合
には、酸の変成度合に関係なく充分な相溶化が行われ
ず、また15重量%を越えると、酸の変成度合が高い場
合、溶融混練り中にゲル化する場合があるばかりでな
く、相溶化剤の物性がポリマーアロイ全体の物性に影響
を与える。上記相溶化剤の粘度は、注型ポリアミド樹脂
の融点以下で溶融混練りできるならば特に限定されない
が、240°Cで10分間あたりのメルトフローレート
で0.1〜100g/10分が好ましい。尚、相溶化剤
中の無水マレイン酸の添加量は、0.1〜10重量%で
あり、0.1重量%未満であるとポリアミド樹脂との反
応点が少なすぎるため相溶化能力が劣り、一方10重量
%を越えるとポリアミド樹脂がゲル化して押出機への負
荷が大きくなったり、樹脂組成物の品質を損なう。The amount of the compatibilizer added is 3 to 15% by weight,
Preferably it is 5 to 10% by weight. If the amount is less than 3% by weight, sufficient compatibilization is not performed irrespective of the degree of conversion of the acid, and if it exceeds 15% by weight, the degree of conversion of the acid is high, and gelation may occur during melt-kneading. Not only that, the properties of the compatibilizer affect the properties of the entire polymer alloy. The viscosity of the compatibilizer is not particularly limited as long as it can be melt-kneaded below the melting point of the cast polyamide resin, but is preferably 0.1 to 100 g / 10 minutes at 240 ° C. at a melt flow rate per 10 minutes. The amount of maleic anhydride in the compatibilizer is 0.1 to 10% by weight. If the amount is less than 0.1% by weight, the number of reaction points with the polyamide resin is too small, so that the compatibilizing ability is poor. On the other hand, if it exceeds 10% by weight, the polyamide resin gels and the load on the extruder increases, or the quality of the resin composition is impaired.
【0010】 上記各成分を溶融混練りする温度は、通
常220〜300°Cである。温度が低くなると、押出
機への負荷が大きく、単位時間当たりの押出量を小さく
する必要がある。一方、温度が高くなると、得られた樹
脂組成物が着色する。溶融混練りは単軸、2軸押出機な
どの溶融混練機を使用して行う。本発明の樹脂組成物に
は、前記3成分以外に他の添加剤、例えば染顔料、核
剤、可塑剤、滑剤、酸化防止剤、紫外線吸収剤、難燃
剤、帯電防止剤、繊維補強材等を必要に応じて添加する
ことができる。The temperature at which the above components are melt-kneaded is usually from 220 to 300 ° C. When the temperature decreases, the load on the extruder increases, and it is necessary to reduce the amount of extrusion per unit time . On the other hand, when the temperature increases, the obtained resin composition is colored. Melt kneading is performed using a melt kneader such as a single screw or twin screw extruder. In the resin composition of the present invention, in addition to the above three components, other additives such as a dye / pigment, a nucleating agent, a plasticizer, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, an antistatic agent, and a fiber reinforcing material. Can be added as needed.
【0011】[0011]
【実施例】以下、実施例により本発明をより詳細に説明
する。 実施例1〜7、比較例1〜5 表1に示す配合を予め90°Cで5時間オーブン中で乾
燥した後、240°Cに設定した1軸押出機(商品名:
ラボプラストミルD20−20 東洋精機社製)を用い
て、シリンダー温度240°C、スクリュー回転数20
rpmの条件でトルクを測定した。その結果を表1に示
す。The present invention will be described in more detail with reference to the following examples. Examples 1 to 7 and Comparative Examples 1 to 5 After the compositions shown in Table 1 were previously dried in an oven at 90 ° C. for 5 hours, a single-screw extruder set at 240 ° C. (trade name:
Using a Labo Plast Mill D20-20 (manufactured by Toyo Seiki Co., Ltd.), the cylinder temperature was 240 ° C., and the screw rotation speed was 20.
The torque was measured under the condition of rpm. Table 1 shows the results.
【0012】また、上記と同様の配合物を240°Cに
設定した2軸押出機(商品名:PCM45 池貝鉄工社
製)により溶融混練りしてペレットを作製し、このペレ
ットをシリンダー温度240°Cの射出成形機(商品
名:SG25 住友重機械工業社製)を用いて金型温度
60°Cに設定した金型へ射出成形し、成形品(テスト
ピース)を作製した。得られた成形品の外観(表面状
態)と引張破断時の伸びをJIS K7113に準じて
測定した。その結果を表1に示す。Further, the same compound as described above is melt-kneaded with a twin screw extruder (trade name: PCM45 manufactured by Ikegai Iron Works Co., Ltd.) set at 240 ° C. to produce pellets, and the pellets are heated at a cylinder temperature of 240 ° C. Using a C injection molding machine (trade name: SG25, manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was performed on a mold set at a mold temperature of 60 ° C. to produce a molded product (test piece). The appearance (surface state) and elongation at break of tensile strength of the obtained molded article were measured in accordance with JIS K7113. Table 1 shows the results.
【0013】[0013]
【表1】 [Table 1]
【0014】この結果からも明らかなように、実施例の
樹脂組成物は外観、伸びにおいて良好な物性を保持して
おり、しかも小さなトルクで押出し、ペレットを成形で
きることが判る。As is clear from the results, the resin compositions of the examples have good physical properties in appearance and elongation, and can be extruded with a small torque to form pellets.
【0015】[0015]
【発明の効果】以上のように、本発明のポリアミド系樹
脂組成物では、240°Cで10分間あたりのメルトフ
ローレートがゼロであり、通常のポリアミド樹脂よりも
溶融粘度が高い注型ポリアミド樹脂の加工屑に、少なく
とも該注型ポリアミド樹脂の融点より低い融点もしくは
軟化点を有する熱可塑性樹脂と相溶化剤とを添加したも
ので、相溶化剤が注型ポリアミド樹脂と熱可塑性樹脂と
の間に存在し、これらを結合することでこの3成分を均
一に溶融混練りして押出性を大きく改善し、そして再ペ
レットの生産が実施可能となり、これによって注型ポリ
アミド樹脂の再利用に寄与し、しかもこのペレットから
得られた成形品も外観ばかりでなく、充分な物性を維持
できる効果も有している。As described above, in the polyamide resin composition of the present invention, the melt temperature per 240 minutes at 10 minutes is used.
Low rate is zero, which is lower than ordinary polyamide resin
Reduced processing waste of cast polyamide resin with high melt viscosity
Both a thermoplastic resin having a melting point or a softening point lower than the melting point of the cast polyamide resin and a compatibilizer are added, and the compatibilizer is present between the cast polyamide resin and the thermoplastic resin. By combining these three components, the three components are uniformly melt-kneaded to greatly improve the extrudability, and the production of re-pellets becomes feasible, thereby contributing to the reuse of the cast polyamide resin, and from the pellets. The obtained molded article not only has an appearance but also has an effect of maintaining sufficient physical properties.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C08L 23:26) (C08L 101/00 77:00 23:26) 審査官 阪野 誠司 (56)参考文献 特開 昭60−110740(JP,A) 特開 平1−294748(JP,A)──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical indication location C08L 23:26) (C08L 101/00 77:00 23:26) Examiner Seiji Sakano (56) References JP-A-60-110740 (JP, A) JP-A-1-294748 (JP, A)
Claims (3)
ローレートがゼロである注型ポリアミド樹脂の加工屑2
0〜85重量%に、少なくとも該注型ポリアミド樹脂の
融点より低い融点もしくは軟化点を有する熱可塑性樹脂
12〜77重量%と、相溶化剤3〜15重量%とを添加
したことを特徴とするポリアミド系樹脂組成物。1. Melt per 10 minutes at 240 ° C.
Processing waste of cast polyamide resin with zero low rate 2
0 to 85% by weight, at least 12 to 77% by weight of a thermoplastic resin having a melting point or softening point lower than the melting point of the cast polyamide resin, and 3 to 15% by weight of a compatibilizer. Polyamide resin composition.
載のポリアミド系樹脂組成物。2. The polyamide resin composition according to claim 1, wherein the compatibilizer is an acid-modified resin.
チレン、無水マレイン酸変成ポリプロピレン、無水マレ
イン酸変成スチレン.エチレン.ブチレン.スチレンブ
ロック共重合体、無水マレイン酸変成ABSから選ばれ
た無水マレイン酸変成樹脂である請求項2記載のポリア
ミド系樹脂組成物。3. An acid-modified resin comprising a maleic anhydride-modified polyethylene, a maleic anhydride-modified polypropylene, and a maleic anhydride-modified styrene. ethylene. Butylene. The polyamide resin composition according to claim 2, which is a modified maleic anhydride resin selected from a styrene block copolymer and a modified maleic anhydride ABS.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5060961A JP2602162B2 (en) | 1993-02-24 | 1993-02-24 | Polyamide resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5060961A JP2602162B2 (en) | 1993-02-24 | 1993-02-24 | Polyamide resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06248177A JPH06248177A (en) | 1994-09-06 |
JP2602162B2 true JP2602162B2 (en) | 1997-04-23 |
Family
ID=13157518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5060961A Expired - Fee Related JP2602162B2 (en) | 1993-02-24 | 1993-02-24 | Polyamide resin composition |
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JP (1) | JP2602162B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4886739B2 (en) * | 2008-06-27 | 2012-02-29 | インターテック株式会社 | Joining method of polyamide resin and olefin elastomer |
KR101287121B1 (en) * | 2013-05-31 | 2013-07-17 | (주)남일엔프라 | Processing method for cast nylon scrap |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60110740A (en) * | 1983-11-21 | 1985-06-17 | Mitsui Petrochem Ind Ltd | Propylene polymer composition |
JPH0725954B2 (en) * | 1987-11-12 | 1995-03-22 | 三井石油化学工業株式会社 | Method for producing resin composition |
-
1993
- 1993-02-24 JP JP5060961A patent/JP2602162B2/en not_active Expired - Fee Related
Also Published As
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JPH06248177A (en) | 1994-09-06 |
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