JPH0885761A - Composite reinforced resin composition - Google Patents
Composite reinforced resin compositionInfo
- Publication number
- JPH0885761A JPH0885761A JP7167272A JP16727295A JPH0885761A JP H0885761 A JPH0885761 A JP H0885761A JP 7167272 A JP7167272 A JP 7167272A JP 16727295 A JP16727295 A JP 16727295A JP H0885761 A JPH0885761 A JP H0885761A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- resin composition
- weight
- polyacrylonitrile
- molding
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリアクリロニトリル
系繊維及び無機充填剤補強樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a polyacrylonitrile fiber and an inorganic filler-reinforced resin composition.
【０００２】[0002]
【従来の技術】熱可塑性樹脂は、成形性、耐衝撃性に優
れるため自動車部品、家電製品部品、ＯＡ機器等様々な
分野に用いられる。しかし、他の材料と比較し（特に金
属材料）剛性が劣り、これを強化するため、通常、ガラ
ス繊維、炭素繊維、アラミド繊維等の繊維により補強し
た物が知られている。2. Description of the Related Art Thermoplastic resins are used in various fields such as automobile parts, home electric appliance parts and office automation equipment because of their excellent moldability and impact resistance. However, it is inferior in rigidity (in particular, a metal material) to other materials, and in order to reinforce it, a material reinforced with fibers such as glass fiber, carbon fiber and aramid fiber is generally known.
【０００３】特開昭６３−８１１６２号公報においてポ
リアクリロニトリル系繊維で熱可塑性樹脂を補強する発
明が、特開平５−７０６９８号公報にはポリアクリロニ
トリル系繊維と熱硬化性樹脂及び充填材からなる摩擦材
の発明が、特開平３−４５６３７号公報にはポリオレフ
ィン、無機系難燃剤、ポリアクリロニトリル系繊維から
なる難燃性電気絶縁組成物が記載されている。An invention of reinforcing a thermoplastic resin with a polyacrylonitrile fiber in JP-A-63-81162 is disclosed in JP-A-5-70698, and a friction composed of a polyacrylonitrile fiber, a thermosetting resin and a filler. The invention of the material is disclosed in JP-A-3-45637, which discloses a flame-retardant electrical insulating composition comprising a polyolefin, an inorganic flame retardant, and a polyacrylonitrile fiber.
【０００４】さらに、特公平５−１７２５０号公報には
特定形状のアクリル系繊維と充填剤とフェノール系樹
脂、エポキシ系樹脂、ポリイミド系樹脂、メラミン系樹
脂、天然あるいは合成ゴムなどの樹脂からなる摩擦材料
の発明が記載されている。また特開平３−４５６３７号
公報にはポリオレフィン、無機系難燃剤、ポリアクリロ
ニトリル系繊維からなる難燃性電気絶縁組成物の記載が
ある。ポリアクリロニトリル系繊維は軽く補強効果に優
れるが、熱可塑性樹脂をポリアクリロニトリル系繊維に
より補強するだけでは、剛性と衝撃強度の両方の物性に
優れた樹脂組成物を得るためには限界があった。Further, Japanese Patent Publication No. 5-17250 discloses a friction made of a resin such as an acrylic fiber having a specific shape, a filler, a phenol resin, an epoxy resin, a polyimide resin, a melamine resin, and a natural or synthetic rubber. Material inventions are described. Further, JP-A-3-45637 describes a flame-retardant electrical insulating composition comprising a polyolefin, an inorganic flame retardant and a polyacrylonitrile fiber. Polyacrylonitrile-based fibers are light and excellent in reinforcing effect, but there is a limit in obtaining a resin composition excellent in both physical properties of rigidity and impact strength only by reinforcing a thermoplastic resin with polyacrylonitrile-based fibers.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、剛性と衝撃
強度の両方の物性に優れた成形体を得ることにある。特
に熱可塑性樹脂において、剛性を上げるためにはガラス
繊維を用い、衝撃強度を上げるためにはエラストマー成
分を添加することが知られているが、例えばポリプロピ
レン樹脂を例にとれば曲げ弾性率１５０００ｋｇ／ｃｍ
2以上でかつＩｚｏｄ衝撃強度１０ｋｇ・ｃｍ／ｃｍ以
上の成形体は設計することが難しい。SUMMARY OF THE INVENTION It is an object of the present invention to obtain a molded product which is excellent in both physical properties such as rigidity and impact strength. Particularly in thermoplastic resins, it is known that glass fibers are used to increase the rigidity and an elastomer component is added to increase the impact strength. For example, in the case of polypropylene resin, the bending elastic modulus is 15000 kg / cm
It is difficult to design a molded product having an Izod impact strength of 10 kg · cm / cm or more and 2 or more.
【０００６】本発明の課題は、剛性と衝撃強度の両方の
物性の優れた成形体を得ることを目的とするものであ
る。An object of the present invention is to obtain a molded product having excellent physical properties in both rigidity and impact strength.
【０００７】[0007]
【課題を解決するための手段】上記目的を本発明は無機
充填剤とポリアクリロニトリル系繊維を併用することに
より解決した。すなわち、本発明は、（ａ）熱可塑性樹
脂９８．９〜３０重量％、（ｂ）ポリアクリロニトリル
系繊維０．１〜５０重量％および（ｃ）無機充填剤１〜
６０重量％からなる樹脂組成物に関し、合わせてその成
形体にも関する。The present invention has solved the above object by using an inorganic filler in combination with a polyacrylonitrile fiber. That is, the present invention comprises (a) a thermoplastic resin of 98.9 to 30% by weight, (b) a polyacrylonitrile fiber of 0.1 to 50% by weight, and (c) an inorganic filler 1 to
It relates to a resin composition comprising 60% by weight, and also relates to a molded body thereof.
【０００８】本発明における熱可塑性樹脂とは、低、
中、高密度ポリエチレン、ポリプロピレン、ポリ塩化ビ
ニル、ポリスチレン、アクリロニトリル−スチレン共重
合体、アクリロニトリル−ブタジエン−スチレン共重合
体、ポリアミド、ポリアセタール、ポリカーボネート、
ポリエチレンテレフタレート、ポリブチレンテレフタレ
ート、ポリフェニレンエーテル、スチレン−ブタジエン
共重合体及びその水素添加組成物等を挙げることが出来
る。これらの熱可塑性樹脂は単独でまたは２種類以上併
用して用いることが出来る。The thermoplastic resin in the present invention is low,
Medium, high-density polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyacetal, polycarbonate,
Examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, styrene-butadiene copolymers and hydrogenated compositions thereof. These thermoplastic resins can be used alone or in combination of two or more kinds.
【０００９】本発明におけるポリアクリロニトリル系繊
維とはアクリロニトリル単独重合体あるいはアクリロニ
トリル９０重量％以上とアクリロニトリルと共重合可能
なビニル系モノマー１０重量％以下の共重合体から成る
ポリアクリロニトリル系重合体繊維であって、一般に知
られるポリアクリロニトリル系重合繊維の製造方法で作
られる繊維である。The polyacrylonitrile fiber in the present invention is a polyacrylonitrile polymer fiber composed of an acrylonitrile homopolymer or a copolymer of 90% by weight or more of acrylonitrile and 10% by weight or less of a vinyl monomer copolymerizable with acrylonitrile. A fiber produced by a generally known method for producing a polyacrylonitrile-based polymerized fiber.
【００１０】本発明におけるポリアクリロニトリル繊維
は、繊度０．５〜５０デニール、引張強度２．５ｇ／ｄ
以上、初期弾性率３０ｇ／ｄ以上あることが好ましい。
本発明におけるポリアクリロニトリル系繊維の繊維長は
０．５〜２０ｍｍが好ましく、さらに好ましくは１ｍｍ
〜１０ｍｍ、より好ましくは２ｍｍ〜６ｍｍである。
０．５ｍｍ未満では工業的に生産が困難である。また補
強効果を出すためには長い方が好ましいが、２０ｍｍを
越えると、ポリアクリロニトリル系繊維が熱可塑性樹脂
中で混練りされ、押し出される際に、ポリアクリロニト
リル系繊維同士での絡み合いが生じ分散性が悪くなり物
性低下を起こす。The polyacrylonitrile fiber in the present invention has a fineness of 0.5 to 50 denier and a tensile strength of 2.5 g / d.
As described above, it is preferable that the initial elastic modulus is 30 g / d or more.
The fiber length of the polyacrylonitrile fiber in the present invention is preferably 0.5 to 20 mm, more preferably 1 mm.
10 mm, more preferably 2 mm to 6 mm.
If it is less than 0.5 mm, industrial production is difficult. In addition, it is preferable that the length is longer to obtain the reinforcing effect, but if it exceeds 20 mm, the polyacrylonitrile-based fibers are kneaded in the thermoplastic resin and are entangled with each other when extruded, resulting in dispersibility. Deteriorates and physical properties deteriorate.
【００１１】本発明の複合強化樹脂組成物は、ポリアク
リロニトリル系繊維が０．１〜５０重量％、好ましく
は、１〜４０重量％、さらに好ましくは１〜３０重量％
添加されているものである。本発明における無機充填剤
は、タルク、マイカ、合成マイカ、合成ハイドロタルサ
イト、炭酸カルシウム、クレー、カオリナイト、酸化チ
タン、酸化亜鉛、珪藻土、シリカ、ガラスビーズ、ガラ
ス中空球、ガラスフレーク、ガラスファイバー、炭化ケ
イ素ウイスカー、窒化ケイ素ウイスカー、酸化亜鉛ウイ
スカー、炭酸カルシウムウイスカー、硫酸バリウム、硫
酸カルシウム、ウォラストナイト、チタン酸カリウム、
セピオライト、ゾノトライト、ホウ酸アルミニウム、ス
メクタイト、カオリン、バーミキュライト、金属粉末、
金属繊維、金属箔、カーボンファイバー、カーボンブラ
ック等をあげることができる。これらの無機充填剤は、
そのままで又は表面処理等をして添加することが出来
る。In the composite reinforced resin composition of the present invention, the polyacrylonitrile fiber is 0.1 to 50% by weight, preferably 1 to 40% by weight, more preferably 1 to 30% by weight.
It has been added. The inorganic filler in the present invention is talc, mica, synthetic mica, synthetic hydrotalcite, calcium carbonate, clay, kaolinite, titanium oxide, zinc oxide, diatomaceous earth, silica, glass beads, glass hollow spheres, glass flakes, glass fiber. , Silicon carbide whiskers, silicon nitride whiskers, zinc oxide whiskers, calcium carbonate whiskers, barium sulfate, calcium sulfate, wollastonite, potassium titanate,
Sepiolite, xonotlite, aluminum borate, smectite, kaolin, vermiculite, metal powder,
Examples thereof include metal fiber, metal foil, carbon fiber, carbon black and the like. These inorganic fillers are
It can be added as it is or after surface treatment.
【００１２】本発明の樹脂組成物は、無機充填剤が１〜
６０重量％添加される。好ましくは５〜５０重量％、さ
らに好ましくは５〜４５重量％添加される。添加量が少
ないと効果が発現せず、添加量が多いと密度が増えるた
め好ましくない。本発明の樹脂組成物にはその特長を損
なわない範囲で、帯電防止剤、各種の安定剤、核剤、可
塑剤、難燃剤、顔料、着色剤等を公知の方法に従い適宜
添加して用いることができる。The resin composition of the present invention comprises 1 to 1 inorganic filler.
60% by weight is added. It is preferably added in an amount of 5 to 50% by weight, more preferably 5 to 45% by weight. If the added amount is small, the effect is not exhibited, and if the added amount is large, the density increases, which is not preferable. To the resin composition of the present invention, an antistatic agent, various stabilizers, nucleating agents, plasticizers, flame retardants, pigments, colorants, etc. may be appropriately added and used according to known methods within a range that does not impair the characteristics. You can
【００１３】[0013]
【実施例】以下実施例により本発明を具体的に説明する
が、本発明はこれらの実施例により限定される物ではな
い。尚、各測定は以下の条件で行う。 アイゾット衝撃強さ；ＡＳＴＭ Ｄ−２５６に準拠し
て測定する。 曲げ弾性率；ＡＳＴＭ Ｄ−７９０に準拠して測定す
る。The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. Each measurement is performed under the following conditions. Izod impact strength; measured according to ASTM D-256. Flexural modulus; measured according to ASTM D-790.
【００１４】[0014]
【実施例１】３０００デニール／１０００フィラメント
で強度１３ｇ／ｄ、初期弾性率６０ｇ／ｄの性能を有す
るポリアクリロニトリル系繊維（アクリロニトリル単独
重合体繊維）を、ビスフェノールＡ型エポキシ樹脂（旭
化成工業株式会社製ＡＥＲ６６１）の濃度８重量％のエ
マルジョン液中を浸漬通過させ、乾燥後、３ｍｍの長さ
に切断したポリアクリロニトリル系繊維チョップドスト
ランドを作製する。Example 1 A polyacrylonitrile fiber (acrylonitrile homopolymer fiber) having a performance of 3000 denier / 1000 filaments, a strength of 13 g / d and an initial elastic modulus of 60 g / d was mixed with a bisphenol A type epoxy resin (made by Asahi Kasei Kogyo Co., Ltd.). A poly (acrylonitrile-based fiber chopped strand) cut into a length of 3 mm is prepared by dipping and passing in an emulsion liquid having a concentration of AER661) of 8% by weight.
【００１５】このポリアクリロニトリル系繊維チョップ
ドストランド２０重量％、ポリプロピレン（旭化成工業
株式会社製Ｍ８６００）６９．５重量％、タルク（日本
タルク株式会社製ミクロエースＰ−３）１０．５重量
％、核剤（旭電化株式会社製アデカスタブＮＡ−１１）
０．０１重量％を混合し、押出機（池貝鉄工株式会社製
ＰＣＭ４５ｍｍ二軸押出機）を用い２３０℃で溶融混練
りしペレット化する。このペレットを射出成形機（ＦＵ
ＮＡＣ ＡＵＴＯＳＨＯＴ Ｔｓｅｒｉｅｓ ＭＯＤＥ
Ｌ ５０Ｄ）で２３０℃、金型温度５０℃の条件で試験
片を作成し、評価を行う。20% by weight of this polyacrylonitrile fiber chopped strand, 69.5% by weight of polypropylene (M8600 manufactured by Asahi Kasei Kogyo Co., Ltd.), 10.5% by weight of talc (Microace P-3 manufactured by Nippon Talc Co., Ltd.), a nucleating agent. (Adeka Stab NA-11 manufactured by Asahi Denka Co., Ltd.)
0.01 wt% is mixed and melt-kneaded at 230 ° C. into pellets by using an extruder (PCM45 mm twin-screw extruder manufactured by Ikegai Tekko KK). Injection molding machine (FU
NAC AUTOSHOT Tseries MODE
L 50D), a test piece is prepared under the conditions of 230 ° C. and a mold temperature of 50 ° C., and evaluation is performed.
【００１６】[0016]
【比較例１】実施例１で作製したポリアクリロニトリル
系繊維チョップドストランド２０重量％、ポリプロピレ
ン（旭化成工業株式会社製Ｍ８６００）８０重量％、核
剤（旭電化株式会社製アデカスタブＮＡ−１１）０．０
１重量部を混合した以外は実施例１と同様な方法で試験
片を作成し評価する。Comparative Example 1 20% by weight of polyacrylonitrile fiber chopped strand produced in Example 1, 80% by weight of polypropylene (M8600 manufactured by Asahi Kasei Corporation), nucleating agent (ADEKA STAB NA-11 manufactured by Asahi Denka Co., Ltd.) 0.0
A test piece is prepared and evaluated in the same manner as in Example 1 except that 1 part by weight is mixed.
【００１７】[0017]
【比較例２】ポリプロピレン（旭化成工業株式会社製Ｍ
８６００）８５重量％、タルク（日本タルク株式会社製
ミクロエースＰ−３）１５重量％、核剤（旭電化株式会
社製アデカスタブＮＡ−１１）０．０１重量部を混合し
た以外は実施例１と同様な方法で試験片を作成し評価す
る。Comparative Example 2 Polypropylene (M manufactured by Asahi Kasei Corporation
8600) 85% by weight, talc (Nippon Talc Co., Ltd. Microace P-3) 15% by weight, and nucleating agent (Asahi Denka Co., Ltd. ADEKA STAB NA-11) 0.01 parts by weight, and Example 1 Test pieces are prepared and evaluated in the same manner.
【００１８】実施例、比較例の評価結果を表１に示す。
この表で判るようにポリアクリロニトリル系繊維、無機
充填剤各々個別に添加した場合（比較例１、２）では達
成できなかった剛性（曲げ強度）とアイゾット衝撃強度
の両物性に優れた組成物が得られた。Table 1 shows the evaluation results of Examples and Comparative Examples.
As can be seen from this table, a composition excellent in both physical properties of rigidity (flexural strength) and Izod impact strength, which could not be achieved when the polyacrylonitrile fiber and the inorganic filler were individually added (Comparative Examples 1 and 2), was obtained. Was obtained.
【００１９】[0019]
【実施例２〜１２、比較例３〜１２】表２、表３中に示
す樹脂、無機充填剤、アクリル繊維を各々表中に示す量
比で押出、射出成形した。尚、表中ＡＳとはアクリロニ
トリル−スチレン強重合体（旭化成工業株式会社製 ７
８９Ｈ）を示し、ｂ−ＰＰとはブロックポリプロピレン
でＭＩ＝６５の物を示し、ＨＤＰＥとは高密度ポリエチ
レン（旭化成工業株式会社製 Ｊ３１１）を示し、ＧＰ
ＰＳ１はポリスチレン（旭化成工業株式会社製Ｇ９３０
３）、ＧＰＰＳ２はポリスチレン（旭化成工業株式会社
製 ６８０）を示す。Examples 2 to 12 and Comparative Examples 3 to 12 Resins, inorganic fillers, and acrylic fibers shown in Tables 2 and 3 were extruded and injection-molded at the ratios shown in the tables. In the table, AS means acrylonitrile-styrene strong polymer (7 manufactured by Asahi Kasei Kogyo Co., Ltd.
89H), b-PP is a block polypropylene having MI = 65, HDPE is high density polyethylene (J311 manufactured by Asahi Kasei Corporation), GP
PS1 is polystyrene (G930 manufactured by Asahi Kasei Corporation)
3) and GPPS2 are polystyrene (680 made by Asahi Kasei Corporation).
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【表３】 [Table 3]
【００２３】[0023]
【発明の効果】本発明の樹脂組成物は、従来のものに比
べて、剛性、衝撃強度両方の物性に優れる。本発明の樹
脂組成物を用いた成形体は、曲げ弾性率、アイゾット衝
撃強度が従来のものに比べて高い物である。The resin composition of the present invention is superior in physical properties such as rigidity and impact strength as compared with the conventional ones. The molded product using the resin composition of the present invention has higher flexural modulus and Izod impact strength than conventional products.
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Claims (2)
（ｂ）ポリアクリロニトリル系繊維０．１〜５０重量％
および（ｃ）無機充填剤１〜６０重量％からなる樹脂組
成物。1. A thermoplastic resin of 98 to 30% by weight,
(B) Polyacrylonitrile fiber 0.1 to 50% by weight
And (c) a resin composition comprising 1 to 60% by weight of an inorganic filler.
形、圧縮成形、ブロー成形、および真空成形してなる成
形体。2. A molded product obtained by subjecting a resin composition to injection molding, extrusion molding, compression molding, blow molding, and vacuum molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7167272A JPH0885761A (en) | 1994-07-20 | 1995-07-03 | Composite reinforced resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-167916 | 1994-07-20 | ||
| JP16791694 | 1994-07-20 | ||
| JP7167272A JPH0885761A (en) | 1994-07-20 | 1995-07-03 | Composite reinforced resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0885761A true JPH0885761A (en) | 1996-04-02 |
Family
ID=26491362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7167272A Withdrawn JPH0885761A (en) | 1994-07-20 | 1995-07-03 | Composite reinforced resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0885761A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014519546A (en) * | 2011-04-13 | 2014-08-14 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Method for producing a component using powder injection molding, preferably based on the use of organic yarns or fibers together with the use of supercritical CO 2 |
| CN104194123A (en) * | 2014-09-10 | 2014-12-10 | 黑龙江大学 | Polyacrylonitrile fiber/high-density polyethylene composite material and preparation method thereof |
| CN104974399A (en) * | 2015-07-13 | 2015-10-14 | 苏州科茂电子材料科技有限公司 | Electric cable polyethylene material and preparation method thereof |
-
1995
- 1995-07-03 JP JP7167272A patent/JPH0885761A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014519546A (en) * | 2011-04-13 | 2014-08-14 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Method for producing a component using powder injection molding, preferably based on the use of organic yarns or fibers together with the use of supercritical CO 2 |
| CN104194123A (en) * | 2014-09-10 | 2014-12-10 | 黑龙江大学 | Polyacrylonitrile fiber/high-density polyethylene composite material and preparation method thereof |
| CN104974399A (en) * | 2015-07-13 | 2015-10-14 | 苏州科茂电子材料科技有限公司 | Electric cable polyethylene material and preparation method thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20020903 |