JPS58174433A - Melt molding of acrylic polymer composition - Google Patents
Melt molding of acrylic polymer compositionInfo
- Publication number
- JPS58174433A JPS58174433A JP5667882A JP5667882A JPS58174433A JP S58174433 A JPS58174433 A JP S58174433A JP 5667882 A JP5667882 A JP 5667882A JP 5667882 A JP5667882 A JP 5667882A JP S58174433 A JPS58174433 A JP S58174433A
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- Japan
- Prior art keywords
- acrylic polymer
- melt
- phosphoric acid
- polymer composition
- phosphite
- 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.)
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Abstract
Description
【発明の詳細な説明】
本発明はアクリル系重合体組成物の溶融成形法に関する
ものである。さらに詳しくはアクリル系重合体組成物に
、％定のリン成分含有化合物を配合することで、溶融成
形時に好適な熱安定性を有するアクリル系重合体組成物
の溶融成形法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for melt molding acrylic polymer compositions. More specifically, the present invention relates to a method of melt molding an acrylic polymer composition that has suitable thermal stability during melt molding by blending a certain percentage of a phosphorus component-containing compound into the acrylic polymer composition.
アクリロニトリルを主成分とするアクリル系重合体は、
加熱して溶融することが困難な重合体であり、その成形
法は溶媒に溶解して湿式又は乾式によるのが一般的であ
る。Acrylic polymers whose main component is acrylonitrile are
It is a polymer that is difficult to melt by heating, and its molding method is generally by dissolving it in a solvent and using a wet or dry method.
従来からアクリル系重合体を溶融成形しようとする試み
は数多くなされており、■アクリル系重合体の溶剤又は
高い誘電恒数を有する有機化合物をｂＪｗ剤として混合
する方法（特公昭３１−７０６５号公報、 ＵＪ、Ｐ、
２５８５４９９、Ｕ、Ｓ、Ｐ、３３８２０ ）、■水を
可履剤とする方法（Ｕ、Ｓ、Ｐ、２５８５４４４、特開
ＩＩ＠ ４８−４９８３９号公報、特開昭５４−９３１
２２号公報寿が提案されている。しかしながら上記の方
法は工業的に応用する上で次の橡な欠点を有している。Many attempts have been made to melt-mold acrylic polymers, including: (1) A method of mixing an acrylic polymer solvent or an organic compound with a high dielectric constant as a bJw agent (Japanese Patent Publication No. 31-7065); , U.J., P.
2585499, U, S, P, 33820), ■ Method using water as lubricant (U, S, P, 2585444, JP-A II@48-49839, JP-A-54-931)
Publication No. 22 Kotobuki has been proposed. However, the above method has the following disadvantages in industrial application.
即ち上記■の方法では、実質的に成形可能な状態にする
為には、多量の（例えば重合体と等量程度の）可塑剤を
用いなければならず、物性の優れた成形品を得る為には
、可塑剤の抽出回収工程が不可欠となる。又可塑剤量を
少なくして高温で成形することも可能ではあるが、アク
リル系重合体の分解着色が著しく実用的でない。■の方
法では可塑剤抽出工程は不要であるが５水の沸点以上の
温度で加熱溶融する必要がある為、常圧帯域忙開放した
り、押し出した場合発泡が起る。ス発泡を少なくする為
に水の量を少な（シ又高温で成形することも可能ではあ
るが、これもアクリル系重合体の分解着色が著しく実用
的でない。That is, in the method (2) above, a large amount of plasticizer (e.g., about the same amount as the polymer) must be used in order to make it substantially moldable, and in order to obtain a molded product with excellent physical properties. For this purpose, a plasticizer extraction and recovery process is essential. Although it is possible to reduce the amount of plasticizer and mold at high temperatures, the acrylic polymer decomposes and becomes discolored, making it extremely impractical. Method (2) does not require a plasticizer extraction step, but since it is necessary to heat and melt at a temperature above the boiling point of water, foaming occurs when the atmospheric pressure zone is opened or extruded. Although it is possible to use a small amount of water (or mold at a high temperature) to reduce foaming, this is also impractical as the acrylic polymer decomposes and becomes discolored.
一方アクリル系重合体に水を可塑剤及び発泡剤として兼
用し、発泡繊維を製造する方法が、近年盛んに提案され
又いる。（％開昭５４−９３１２埼公報）しかしこの方
法では、発泡させる為の水の量を多くすると、水蒸気の
吹出しＫよる切断等が多（なり、又水の量を少な（する
と溶融物の粘度が高く成形が困難になる。又溶融物を高
温にして、＾発泡度の繊維を得ることも可能ではあるが
、この方法でもアクリル系重合体の分解着色が著しく実
用的ではなかった。本発明者等は前述のアクリル系重合
体の分解着色に関する問題点を解決すべく、鋭意研究を
重ねた結果、特定のリン成分含有化合物を配合すること
によって溶融成形時に、優れた熱安定性を示すものであ
ることを見出し本発明に到達した。即ち、本発明は、ア
クリルニトリルを少なくとも４０重量％含むアクリルニ
） ＩＪル系重合体と可塑剤からなる組成物にアクリル
系１合体に対し１０．１〜５重量％のリン酸又はリン酸
エステルを含有せしめて溶融することを特徴とするアク
リル系重合体組成物の溶融成形法である。On the other hand, a method of producing foamed fibers using an acrylic polymer and water as both a plasticizer and a foaming agent has been proposed in recent years. (%Kaisei 54-9312 Saito Publication) However, in this method, if the amount of water for foaming is increased, there will be many cuts etc. due to the water vapor blowing out, and if the amount of water is decreased (if the viscosity of the melt is It is also possible to obtain fibers with a high degree of foaming by heating the melt to a high temperature, but even with this method, the decomposition and coloring of the acrylic polymer is extremely impractical.The present invention In order to solve the above-mentioned problems regarding decomposition and coloring of acrylic polymers, they have conducted intensive research and have developed a product that exhibits excellent thermal stability during melt molding by incorporating a specific phosphorus component-containing compound. Namely, the present invention provides a composition comprising an acrylonitrile polymer and a plasticizer containing at least 40% by weight of acrylonitrile. This is a method for melt-molding an acrylic polymer composition, which is characterized by containing 5% by weight of phosphoric acid or phosphoric acid ester and melting the composition.
以下本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明で（・うアクリル系重合体とは、アクリロミ
ニトリル単独又はアクリロニトリルを少なくとも４０重
量％以上、より好ましくは６０１Ｌ量％以上結合金有し
、残部が少なくとも１ｍのエチレン系不飽和化合物から
なるものである。ここでエチレン系不飽和化合物とは、
塩化ビニル、臭化ビニル。In the present invention, the acrylic polymer is composed of acrylonitrile alone or acrylonitrile containing at least 40% by weight, more preferably 601% or more by weight, and the remainder being an ethylenically unsaturated compound of at least 1 m. Here, ethylenically unsaturated compounds are
Vinyl chloride, vinyl bromide.
弗化ビニル、塩化ビニリデン等のハロゲン化ビニル及ヒ
ハロケン化ビニリデン類；アクリル酸、メタクリル酸、
マレイン酸、イタコン酸等の不飽和カルボン酸及びこれ
等の塩類；アクリル酸メチル。Vinyl halides such as vinyl fluoride and vinylidene chloride and vinylidene hyalogenides; acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as maleic acid and itaconic acid and their salts; methyl acrylate.
アクリル酸エチル、アクリル酸ブチル、アクリル酸オク
チル、アクリル酸メトキシエチル、アクリル酸フェニル
、アクリル酸シクロヘキシル等のアクリル酸エステル類
；メタクリル酸ブチル、メタクリル酸オクチル、メタク
リル酸メトキシエチル。Acrylic acid esters such as ethyl acrylate, butyl acrylate, octyl acrylate, methoxyethyl acrylate, phenyl acrylate, and cyclohexyl acrylate; butyl methacrylate, octyl methacrylate, and methoxyethyl methacrylate.
メタクリル酸フェニル、メタクリル酸シクロヘキシル等
のメタクリル酸エステル類；メチルビニルケトン類；蟻
酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニ
ル、安息香酸ビニル等のビニルエステル類；メチルビニ
ルエーテル、エチルビニルエーテル等のビニルエーテル
類；アクリルアミド及びそのアルキル置換体；ビニルス
ルホン酸。Methacrylic acid esters such as phenyl methacrylate and cyclohexyl methacrylate; Methyl vinyl ketones; Vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether ; Acrylamide and its alkyl substituted products; Vinylsulfonic acid.
ｐ−スチレンスルホン酸等の不飽和スルボン酸及ヒソれ
等の塩類：スチレン α−メチルスチレ石りロロスチレ
７等のスチレン及びそのアルキル又はハロゲン置換体；
アリルアルコール及びそのエステル又はエーテル類；ビ
ニルピリジン、ビニルイミダゾール、ジメチルアミンエ
チルメタクリレート等の塩基性ビニル化合物類；アクロ
レイン。Unsaturated sulfonic acids such as p-styrene sulfonic acid and salts such as styrene: styrene and its alkyl or halogen substituted products such as styrene α-methylstyrene or lorostyrene 7;
Allyl alcohol and its esters or ethers; basic vinyl compounds such as vinylpyridine, vinylimidazole, dimethylamine ethyl methacrylate; acrolein.
メタクロレイン、シアン化ビニリデン、クリシジルメタ
クリレート、メタクリロニトリル等のビニル化合物等で
あり、これ等の混合物をも含む。These include vinyl compounds such as methacrolein, vinylidene cyanide, chrycidyl methacrylate, and methacrylonitrile, and also include mixtures thereof.
可塑剤の効果は、アクリル系重合体を可塑化溶融する為
のもので、本発明で〜・う可塑剤とは一般に知られて（
・るもので、水、ジメチルボルムアミド・ジメチルアセ
トアミド、ジメチルスルホオキシド、γ−ブチロラクト
ン、エチレンカーボネート、スルホラン等が用〜・もれ
るが、特に水、ジメチルホルムアミド、ジメチルスルホ
オキシド、エチレンカーボネートが、アクリル系重合体
の可塑性に優れており、その量は使用方法目的によって
任意に選ばれる。The effect of the plasticizer is to plasticize and melt the acrylic polymer, and in the present invention, the plasticizer is generally known as (
・Water, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, ethylene carbonate, sulfolane, etc. are used. The polymer has excellent plasticity, and its amount can be arbitrarily selected depending on the purpose of use.
本発明の目的を達成づ−る為には、このアクリル系重合
体と可塑剤にリン酸又はリン酸エステルを含有せしめる
ことで、溶融成形時に優れた熱安定性を有することがで
きることにある。In order to achieve the object of the present invention, by incorporating phosphoric acid or phosphoric acid ester into the acrylic polymer and plasticizer, it is possible to have excellent thermal stability during melt molding.
本発明で（・うリン酸とは、一般に知られているもので
、具体的には、メタリン酸、オルトリン酸。In the present invention, phosphoric acid is generally known, and specifically includes metaphosphoric acid and orthophosphoric acid.
三すン酸、四すン酸、ボ１３１Ｊン酸等である。又り７
［１ｘ ／ｌ、 ｆルとは、トリフェニルホスフェー
ト。These include trisonic acid, tetrasonic acid, boron 131J acid, and the like. Matari 7
[1x/l, fl means triphenyl phosphate.
ブチルアシッドホスフェート、フトキシエチルアシンド
ホスフエート、２−エチルヘキシルアシッドホスフェー
ト、β−クロ四ニブルアシッドホスフェート、ジ（２−
エチルヘキシル）ホスフェート、エチレンクリコールア
シンドホスフエート。Butyl acid phosphate, phthoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, β-chloro4-nibyl acid phosphate, di(2-
ethylhexyl) phosphate, ethylene glycol acindophosphate.
（２〜ヒドロキシエチル）メタクリレートアシッドホス
フェート等の酸性リン酸エステル類；トリエチルホスフ
ァイト、トリｎ−ブチルホスファイト、トリフェニルホ
スファイト、トリステアリルホスファイト、トリデシル
ホスファイト、ジフェニルデシルホスファイト、ジステ
アリルペンタエリスリチルジホスファイト、テトラフェ
ニルジプロピレングリコールジホスファイト、ジラウリ
ルハイトロゲンホスファイト＋ ） ’）ス（２−エチ
ルヘキシル）ホスファイト、トリス（ノニルフエニ／Ｉ
／）ホスファイト、ジフェニルモノ（トリデシル）ホス
ファイト、ビスフェノールＡペンタエリスリトルホスフ
ァイト勢の亜リン酸エステル化合物等であり、これ等の
混合物をも含む。これ等の中でモ％に、トリデシルホス
ファイト、ジラウ’） ルハイドロゲンホスファイト、
ジフェニルデシルホスファイト、トリフェニルホスフェ
ートが、ｓａ成成形待時熱安定性に優れ″ＣＸ、・る。Acidic phosphate esters such as (2-hydroxyethyl) methacrylate acid phosphate; triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, tristearyl phosphite, tridecyl phosphite, diphenyldecyl phosphite, distearyl Pentaerythrityl diphosphite, tetraphenyl dipropylene glycol diphosphite, dilaurylhydrogen phosphite
/) Phosphite compounds such as phosphite, diphenylmono(tridecyl)phosphite, and bisphenol A pentaerythritorphosphite, and also include mixtures thereof. Among these, tridecyl phosphite, dihydrogen phosphite,
Diphenyldecyl phosphite and triphenyl phosphate have excellent thermal stability during SA forming.
次にこれらのリン酸又はリン酸エステルの配合比率につ
いて述べる。Next, the blending ratio of these phosphoric acids or phosphoric esters will be described.
リン酸又はリン酸エステルの量は、アクリル系重合体と
可塑剤からなる組成物にアクリル系重合体に対して０．
１〜５重量％好ましくは０．２〜２重量％である。リン
酸又はリン酸エステルが０．１１１量％に満たない場合
は熱安定性が不十分となるし、また５重量％を越える場
合は、経時的に最終製品の表面に吐出、漏出がおこるい
わゆるブルーミングが発生し、また加工中、金型などの
表面に固着して、はく離しなくなる〜・わゆるプレート
アウト等が発生するので好ましくない。The amount of phosphoric acid or phosphoric acid ester in the composition consisting of an acrylic polymer and a plasticizer is 0.0 to 1.
The amount is 1 to 5% by weight, preferably 0.2 to 2% by weight. If the amount of phosphoric acid or phosphoric acid ester is less than 0.111% by weight, thermal stability will be insufficient, and if it exceeds 5% by weight, so-called so-called Blooming occurs, and during processing, it adheres to the surface of the mold, etc., making it difficult to peel off, or so-called plate-out, which is undesirable.
本発明は、上記組成物を、アクリル系重合体の一般的な
溶融成形温度で溶融成形する際に非常に優れた熱安定性
を示すものである。The present invention exhibits extremely excellent thermal stability when the above composition is melt-molded at a general melt-molding temperature for acrylic polymers.
以上述べてきた様な組成物を加熱溶融して成形する方法
としては、程々の手段が用〜・られる。As a method of heat-melting and molding the composition as described above, a moderate number of methods can be used.
即ち、アクリル系重合体と可塑剤にリン酸又はリン酸エ
ステルを特定比率で配合し、ボールミル等の適当な混合
機にて均一混合せしめて粉粒状、あるいは溶液状の組成
物を調整し、この組成物を、ビ）オートクレーブの如き
密閉可能な容器でｋ）って、弁を介して紡糸オリフィス
に接続する［１日を有する容器中で密閉下又は加圧雰囲
気下で加熱溶融し、溶融抜弁を開けてオリフィスより押
出す方法、（ロ）プランジャー型押出機のシリンダー中
で密閉下に加熱溶融し、しかる後、プランジャーを降１
させて押出す方法、Ｐ１成形用スクリュー押出機のホッ
パーに供給し加熱帯域中を移送しながら加熱溶融し、紡
糸オリフィスより押出す方法、に）前記ビ）（ロ）ｐ−
１のオリフィスの後に成形用金型を直結し金型に注入し
成形する方法等が採用できる。内紡糸メリフイスから押
出す際は必要に厄じ又ギヤーポンプ郷の計量器を用〜・
ることができる。また成形物は、延伸操作・熱処理を施
すことも必要に応じて行なうことができる。That is, acrylic polymer and plasticizer are blended with phosphoric acid or phosphoric acid ester in a specific ratio, and mixed uniformly in a suitable mixer such as a ball mill to prepare a powder or solution composition. b) k) in a sealable container such as an autoclave and connected to the spinning orifice via a valve; (b) Heat and melt in a closed cylinder of a plunger-type extruder, then lower the plunger.
A method of supplying it to the hopper of a screw extruder for P1 molding, heating and melting it while transferring it through a heating zone, and extruding it from a spinning orifice.
A method of directly connecting a mold for molding after the orifice 1 and injecting into the mold for molding can be adopted. When extruding from the internal spinning merifice, it is necessary to use a gear pump meter.
can be done. Further, the molded product may be subjected to stretching operation and heat treatment as necessary.
以上、詳しく述べた通り、本発明はアクリル系重合体と
可塑剤にリン酸又はリン酸エステルを配合し、溶融成形
することで、溶融成形時に優れた熱安定性を付与するこ
とができ、アクリル系重合体を溶融成形する方法として
注目に値いするものであり、今後アクリル系繊維、アク
リル系樹脂の溶融成形の方法として幅広（用（・られる
ものである。As described above in detail, the present invention is capable of imparting excellent thermal stability during melt molding by blending phosphoric acid or phosphate ester with an acrylic polymer and a plasticizer and melt molding the acrylic polymer and plasticizer. It is noteworthy as a method for melt molding acrylic polymers, and will be widely used in the future as a method for melt molding acrylic fibers and acrylic resins.
以下、実施例により本発明をさらに具体的に説明するが
、本発明はこれ等実施例の記載によって何等その範囲を
限定するものではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the scope of the present invention is not limited in any way by the description of these Examples.
向実施例に記載して〜・る着色度とは下記の方法にて測
定したものである。The degree of coloration described in the Examples below was measured by the following method.
本発明に於ける着色度とは、以下の方法で測定した可視
光線部の波長４０６ｎｍの吸光度（Ａｓ）と定―する。The degree of coloration in the present invention is defined as the absorbance (As) at a wavelength of 406 nm in the visible light region measured by the following method.
吸光度の測定法；
測定すべきサンプルをナイフで削り散り、０．１？を精
密天秤で計り、それを２５ｍ！三角フラスコに入れ、そ
れに濃硝酸を２０ｍｊ入れ、マグネットスターラーで攪
拌し、サンプルを溶解した。その溶液を１ｃｌＬ角形ガ
ラスセルに入れ分光光度針にて濃硝酸を対象標準液とし
て、波長４０６ ｎｍの吸光度を測定する。How to measure absorbance: Scrape the sample to be measured with a knife until it is 0.1? I measured it with a precision balance and measured it as 25m! The sample was placed in an Erlenmeyer flask, 20 mj of concentrated nitric acid was added thereto, and the sample was stirred with a magnetic stirrer to dissolve the sample. The solution is placed in a 1 clL rectangular glass cell, and the absorbance at a wavelength of 406 nm is measured using a spectrophotometric needle using concentrated nitric acid as a reference standard solution.
実施例１
アクリロニトリル９２重量％、アクリル酸メチル８重量
％よりなるアクリル系重合体を用（・て、第１表に示す
配合比率で、ボールミルを用（・て均一混合した粉粒状
組成物を作製し、それを内径１６■、長さ５０■のステ
ンレス製の容器に入れ、密栓した後２００℃に保ったウ
ッドメタル浴に入れ溶融した。Example 1 An acrylic polymer consisting of 92% by weight of acrylonitrile and 8% by weight of methyl acrylate was uniformly mixed using a ball mill at the blending ratio shown in Table 1 to produce a granular composition. Then, it was placed in a stainless steel container with an inner diameter of 16 cm and a length of 50 cm, and the container was sealed tightly and then placed in a wood metal bath kept at 200°C to melt it.
その後、１時間してから容器をウッドメタル浴より取り
出し、水に入れ冷却した後、容器の栓を開け、中の成形
物を取り出した。取り出した成形物の着色度と外観色を
第１表に示す。組成はすべてアクリル系重合体に対して
の重量％で示した。Thereafter, after one hour, the container was taken out of the wood metal bath, cooled in water, and then the stopper of the container was opened and the molded product inside was taken out. Table 1 shows the degree of coloring and appearance color of the molded product taken out. All compositions are expressed in weight percent relative to the acrylic polymer.
実施例２
実施例１と同じアクリル系重合体を用いて、実施例１と
同じ方法で、矛１表に示す配合比率で組成物を作製し、
高化式フローテスターで直径ｌ■、Ｌ／Ｄ ＝ １の細
孔を有するオリフィスを用い溶融押出しを行なった。尚
試料の溶融は試料を２４０℃のシリンダーに充填した後
、オリフィスに栓をして、６分間保持して行なった。そ
の後、手早くオリフィスの栓をはずして、押出荷重３０
ｋｌ／（ｇ”の条件下で押し出した。得られた押出物の
着色度と外観色を第１表に示す。組成はずべて、アクリ
ル系重合体に対しての重量％で示した。Example 2 Using the same acrylic polymer as in Example 1 and using the same method as in Example 1, a composition was prepared at the blending ratio shown in Table 1,
Melt extrusion was carried out using a Koka type flow tester using an orifice having a diameter of 1 and a pore of L/D = 1. The sample was melted by filling it into a cylinder at 240°C, plugging the orifice, and holding the cylinder for 6 minutes. After that, quickly remove the orifice stopper and apply an extrusion load of 30
It was extruded under the conditions of kl/(g"). The degree of coloration and appearance color of the extrudates obtained are shown in Table 1. All compositions are expressed in % by weight based on the acrylic polymer.
似ト仝偽） ′ｊＩＰ１表(similar to false) 'jIP1 table
Claims (2)
むアクリル系重合体と可履剤からなる組成物に、アクリ
ル系重合体に対して０．１〜５重量％のリン酸又はリン
酸エステルを含有せしめて溶融することを善黴とするア
クリル系重合体組成物の溶融成形法(1) A composition consisting of an acrylic polymer containing at least 40% by weight of acrylonitrile and a lubricant is melted by adding 0.1 to 5% by weight of phosphoric acid or phosphoric acid ester to the acrylic polymer. Melt-molding method for acrylic polymer compositions that are moldable
ルスルホキシド、エチレンカーボネート、及びこれ等の
混合物である特許請求の範囲第１項記載のアクリル系重
合体組成物の溶融成形法（３） りン酸エステルがト
リデシルホスファイト。 ジラウリルハイドロゲンホスファイト、ジフェニルデシ
ルホスファイト、トリフェニルホスフェート及びこれ等
の混合物である特許諸本の範［１ｊ１１１項記載のアク
リル系重合体組成−の溶融成形法(2) Melt molding method for an acrylic polymer composition according to claim 1, wherein the lubricant is water, dimethylformamide, dimethyl sulfoxide, ethylene carbonate, or a mixture thereof (3) Phosphoric acid The ester is tridecyl phosphite. Melt molding method of acrylic polymer composition described in Section 1j111 of patents which are dilauryl hydrogen phosphite, diphenyldecyl phosphite, triphenyl phosphate, and mixtures thereof
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5667882A JPS58174433A (en) | 1982-04-07 | 1982-04-07 | Melt molding of acrylic polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5667882A JPS58174433A (en) | 1982-04-07 | 1982-04-07 | Melt molding of acrylic polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58174433A true JPS58174433A (en) | 1983-10-13 |
| JPH0149183B2 JPH0149183B2 (en) | 1989-10-23 |
Family
ID=13034078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5667882A Granted JPS58174433A (en) | 1982-04-07 | 1982-04-07 | Melt molding of acrylic polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58174433A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304590A (en) * | 1992-01-21 | 1994-04-19 | Solcas Polymer, Inc. | Acrylonitrile polymer compositions and articles and methods for their preparation |
| US5434205A (en) * | 1992-01-21 | 1995-07-18 | Solcas Polymer Limited Partnership | Acrylonitrile polymer compositions and articles and methods for their preparation |
| WO2007147224A3 (en) * | 2006-06-19 | 2008-03-20 | Nilton Pereira Alves | Acrylic and modacrylic polymer fusion process derivated from acrylonitrile and molded articles made from the same |
| JP2014012917A (en) * | 2009-03-31 | 2014-01-23 | Donghua Univ | Carbon fiber and raw yarn thereof, and method for producing pre-oxidized fiber |
| CN103556282A (en) * | 2013-10-24 | 2014-02-05 | 东华大学 | Preparation method for novel warm-keeping type polyacrylonitrile hollow fiber |
| WO2016132877A1 (en) * | 2015-02-16 | 2016-08-25 | 株式会社カネカ | Method for producing acrylic fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53127583A (en) * | 1977-04-12 | 1978-11-07 | Mitsubishi Electric Corp | Production of light-resistant plastics |
-
1982
- 1982-04-07 JP JP5667882A patent/JPS58174433A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53127583A (en) * | 1977-04-12 | 1978-11-07 | Mitsubishi Electric Corp | Production of light-resistant plastics |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304590A (en) * | 1992-01-21 | 1994-04-19 | Solcas Polymer, Inc. | Acrylonitrile polymer compositions and articles and methods for their preparation |
| US5434205A (en) * | 1992-01-21 | 1995-07-18 | Solcas Polymer Limited Partnership | Acrylonitrile polymer compositions and articles and methods for their preparation |
| US5589520A (en) * | 1992-01-21 | 1996-12-31 | Solcas Polymer, Limited Partnership | Acrylonitrile polymer composition and articles and methods for their preparation |
| WO2007147224A3 (en) * | 2006-06-19 | 2008-03-20 | Nilton Pereira Alves | Acrylic and modacrylic polymer fusion process derivated from acrylonitrile and molded articles made from the same |
| JP2014012917A (en) * | 2009-03-31 | 2014-01-23 | Donghua Univ | Carbon fiber and raw yarn thereof, and method for producing pre-oxidized fiber |
| CN103556282A (en) * | 2013-10-24 | 2014-02-05 | 东华大学 | Preparation method for novel warm-keeping type polyacrylonitrile hollow fiber |
| WO2016132877A1 (en) * | 2015-02-16 | 2016-08-25 | 株式会社カネカ | Method for producing acrylic fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0149183B2 (en) | 1989-10-23 |
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