JP2819186B2 - Aromatic polyamide short fiber for reinforcing thermoplastic resin, method for producing the same, and thermoplastic resin composition reinforced with the fiber - Google Patents
Aromatic polyamide short fiber for reinforcing thermoplastic resin, method for producing the same, and thermoplastic resin composition reinforced with the fiberInfo
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- JP2819186B2 JP2819186B2 JP2156496A JP15649690A JP2819186B2 JP 2819186 B2 JP2819186 B2 JP 2819186B2 JP 2156496 A JP2156496 A JP 2156496A JP 15649690 A JP15649690 A JP 15649690A JP 2819186 B2 JP2819186 B2 JP 2819186B2
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- Prior art keywords
- aromatic polyamide
- thermoplastic resin
- fiber
- reinforcing
- weight
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は熱可塑性樹脂補強用芳香族ポリアミド短繊
維、その製造方法、およびその繊維で補強された熱可塑
性樹脂組成物に関する。Description: TECHNICAL FIELD The present invention relates to an aromatic polyamide short fiber for reinforcing a thermoplastic resin, a method for producing the same, and a thermoplastic resin composition reinforced with the fiber.
［従来の技術］ 芳香族ポリアミド繊維は高強度、高モジュラス、耐熱
性大、寸法安定性大、錆ない等を優れた特性を有する。[Prior Art] Aromatic polyamide fibers have excellent properties such as high strength, high modulus, large heat resistance, large dimensional stability, and no rust.
芳香族ポリアミド繊維のかかる特長を利用し、これを
補強材として熱可塑性樹脂に配合し、熱可塑性樹脂の機
械的特性、耐摩耗性等の向上をはかることが行なわれて
いる。Utilizing such features of aromatic polyamide fibers, they are blended with a thermoplastic resin as a reinforcing material to improve the mechanical properties, abrasion resistance and the like of the thermoplastic resin.
例えば、特開昭60−255845号には芳香族ポリアミド繊
維のチョップ繊維を補強材として用いることが記載され
ており、また特開昭61−197654号ではフィブリル化アラ
ミド繊維を用いている。For example, JP-A-60-255845 describes that chopped fibers of aromatic polyamide fibers are used as a reinforcing material, and JP-A-61-197654 uses fibrillated aramid fibers.
しかし、熱可塑性樹脂の補強材として知られている従
来の芳香族ポリアミド短繊維には以下のような問題があ
る。すなわち、 （１）繊維長が短かく、軽いという短繊維の属性上飛散
しやすく、このためハンドリング時、例えば製造時にお
ける袋詰め等の出荷包装や熱可塑性樹脂への配合等に際
し飛散繊維が作業効率を低下させるなど、作業効率上お
よび衛生上の不都合がある。However, conventional aromatic polyamide short fibers known as reinforcing materials for thermoplastic resins have the following problems. That is, (1) the short fiber is short and the fiber is easily scattered due to the attribute of lightness. Therefore, the scattered fiber is difficult to handle during handling, for example, during shipping and packaging such as bagging at the time of manufacturing, or blending into a thermoplastic resin. There are inconveniences in working efficiency and hygiene such as lowering efficiency.
（２）ホッパー等に貯蔵している間に繊維同志が互着し
て綿状になるなど、互着によって塊状物を生じやすい。
その結果、熱可塑性樹脂に配合しても、樹脂中に繊維
が均一に分散せず、繊維濃度にかたよりが生じて配合樹
脂の強度を低下させたり、押出し成型時のカット性を悪
くする原因となる。また、熱可塑性樹脂との配合に際
し連続投入が容易なことからホッパーを使用することが
多いが、このホッパーを用いて樹脂に投入する際、互着
した短繊維がホッパーからスムーズに排出されず、作業
効率が低下するといった問題を生じる。(2) The fibers tend to adhere to each other during storage in a hopper or the like, forming a floc.
As a result, even when blended with a thermoplastic resin, the fibers are not evenly dispersed in the resin, and the concentration of the fibers is deflected, resulting in a decrease in the strength of the blended resin or a deterioration in cutability during extrusion molding. Becomes In addition, when compounding with a thermoplastic resin, a continuous hopper is easily used, so a hopper is often used.However, when the resin is charged into the resin using the hopper, the short fibers that have adhered to each other are not smoothly discharged from the hopper, There is a problem that the working efficiency is reduced.
（３）さらには繊維の分散性の良否は、これを配合した
熱可塑性樹脂の機械的強度に大きく影響するが、従来の
芳香族ポリアミド短繊維は上記の如く互着を生じるため
分散性の点で十分に満足できるものではなく、より一層
分散性をよくし、補強材として配合した時に熱可塑性樹
脂の物性をより向上させ得る芳香族ポリアミド短繊維が
望まれている。(3) Furthermore, the quality of the dispersibility of the fiber greatly affects the mechanical strength of the thermoplastic resin blended with the fiber. However, the conventional aromatic polyamide short fiber causes cohesion as described above, and thus the dispersibility is poor. However, there is a demand for an aromatic polyamide short fiber which can further improve dispersibility and further improve the physical properties of a thermoplastic resin when blended as a reinforcing material.
［発明が解決しようとする課題］ 本発明は芳香族ポリアミド短繊維が有する上述の如き
問題点に鑑みなされたもので、本発明の課題はこれら問
題点を解消し、 （１）ハンドリング時の飛散がなく、 （２）貯蔵中の互着がなく、 （３）配合樹脂との分散性がよく、また機械的強度等の
物性改善が可能で、さらには （４）樹脂成型時の押出カット性が良好な熱可塑性樹脂
補強用芳香族ポリアミド短繊維、その製造方法、および
その繊維で補強された熱可塑性樹脂組成物を提供するこ
とにある。[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems of the aromatic polyamide short fibers, and the object of the present invention is to solve these problems. (1) Scattering during handling (2) no cohesion during storage; (3) good dispersibility with the compounded resin; improved physical properties such as mechanical strength; and (4) extrusion cutability during resin molding Is to provide an aromatic polyamide short fiber for reinforcing a thermoplastic resin, a method for producing the same, and a thermoplastic resin composition reinforced with the fiber.
［課題を解決するための手段］ 本発明者等は鋭意検討の結果、特定のビカット軟化点
を有する炭素数２〜４のオレフィン系重合体で芳香族ポ
リアミド短繊維を被覆することが、上記課題解決のため
に有効であることを見出し、本発明に到達したものであ
る。[Means for Solving the Problems] As a result of intensive studies, the present inventors have found that coating an aromatic polyamide short fiber with an olefin polymer having 2 to 4 carbon atoms having a specific Vicat softening point is the above problem. The inventors have found that the present invention is effective for solving the problem, and have reached the present invention.
すなわち、本発明は、 １）ビカット軟化点が40℃以上の炭素数２〜４のオレフ
ィン系重合体で被覆された長さ0.1〜6mmの熱可塑性樹脂
補強用芳香族ポリアミドマルチフィラメント短繊維。That is, the present invention provides: 1) an aromatic polyamide multifilament staple fiber for reinforcing a thermoplastic resin having a Vicat softening point of at least 40 ° C. and having a length of 0.1 to 6 mm and coated with an olefin polymer having 2 to 4 carbon atoms.
２）オレフィン系重合体の被覆量が、芳香族ポリアミド
短繊維100重量部に対し１〜20重量部である前記１）の
熱可塑性樹脂補強用芳香族ポリアミドマルチフィラメン
ト短繊維。2) The aromatic polyamide multifilament short fiber for reinforcing a thermoplastic resin according to 1) above, wherein the coating amount of the olefin polymer is 1 to 20 parts by weight with respect to 100 parts by weight of the aromatic polyamide short fiber.
３）オレフィン系重合体がエチレン単独重合体またはエ
チレン共重合体である前記１）の熱可塑性樹脂補強用芳
香族ポリアミドマルチフィラメント短繊維。3) The aromatic polyamide multifilament staple fiber for reinforcing a thermoplastic resin according to 1) above, wherein the olefin polymer is an ethylene homopolymer or an ethylene copolymer.
４）ビカット軟化点が40℃以上の炭素数２〜４のオレフ
ィン系重合体を２〜50重量％含む水系分散液に芳香族ポ
リアミドマルチフィラメント長繊維を含浸し、含浸後の
芳香族ポリアミド長繊維を上記ビカット軟化点により20
℃以上高い温度で長乾燥し、次いで乾燥後の芳香族ポリ
アミド長繊維を長さ0.1〜6mmに切断することを特徴とす
る前記１）の熱可塑性樹脂補強用芳香族ポリアミドマル
チフィラメント短繊維。4) An aromatic polyamide multifilament filament is impregnated in an aqueous dispersion containing 2 to 50% by weight of an olefin polymer having 2 to 4 carbon atoms having a Vicat softening point of 40 ° C. or higher, and the aromatic polyamide filament is impregnated. The above Vicat softening point is 20
The aromatic polyamide multifilament short fiber for reinforcing a thermoplastic resin according to the above 1), wherein the aromatic polyamide long fiber is dried at a high temperature of not less than ℃ and then cut to a length of 0.1 to 6 mm.
５）前記１）の芳香族ポリアミドマルチフィラメント短
繊維を熱可塑性樹脂に配合、混練して得られる補強され
た熱可塑性樹脂組成物。5) A reinforced thermoplastic resin composition obtained by blending and kneading the aromatic polyamide multifilament staple fibers of 1) with a thermoplastic resin.
［作用］ 本発明の芳香族ポリアミドマルチフィラメント短繊維
はビカット軟化点が40℃以上の炭素数２〜４のオレフィ
ン系重合体で被覆してなるものであり、前述した繊維の
飛散や、貯蔵時における繊維の互着等の問題が解消さ
れ、熱可塑性樹脂に対する分散性に優れ、補強材として
配合することにより、熱可塑性樹脂の機械的特性や成型
性の改善に有効に寄与するものである。[Action] The aromatic polyamide multifilament staple fiber of the present invention is one coated with an olefin polymer having a Vicat softening point of 40 ° C. or higher and having 2 to 4 carbon atoms. In this case, the problem of mutual adhesion of fibers and the like is solved, the dispersibility in the thermoplastic resin is excellent, and the compounding as a reinforcing material effectively contributes to the improvement of the mechanical properties and moldability of the thermoplastic resin.
本発明で用いる炭素数２〜４のオレフィン系重合体と
は、これら炭素数範囲のオレフィンの単独重合体、およ
びこれら炭素数範囲のオレフィンと、これと共重合可能
な他の単量体との共重合体である。The olefin polymer having 2 to 4 carbon atoms used in the present invention includes homopolymers of olefins having these carbon ranges, and olefins having these carbon ranges and other monomers copolymerizable therewith. It is a copolymer.
本発明ではこれら単独重合体および共重合体はいずれ
も使用できるが、他のオレフィンに比べて比較的溶融温
度が低く、熱可塑性樹脂との混練が容易なエチレンの単
独重合体もしくは共重合体が特に好ましく用いられる。In the present invention, any of these homopolymers and copolymers can be used, but ethylene homopolymers or copolymers having a relatively low melting temperature compared to other olefins and easy to knead with a thermoplastic resin are used. Particularly preferably used.
本発明において炭素数２〜４のオレフィンの共重合体
成分として用いられる単量体としては、例えばアクリル
酸メチル、アクリル酸エチル、アクリル酸プロピル、ア
クリル酸ブチル、メタクリル酸メチル、メタクリル酸エ
チルなどのアクリル酸およびメタクリル酸のエステル
類；アクリル酸、メタクリル酸、フマール酸、マレイン
酸、イタコン酸、マレイン酸モノメチル、マレイン酸モ
ノエチル、フマール酸モノメチル、イタコン酸モノメチ
ルおよび無水マレイン酸などのカルボキシル基または酸
無水物を含有する単量体；および酢酸ビニルなどが挙げ
られる。これら共重合体成分は１種を単独で、または２
種以上を混合して用いることができる。Examples of the monomer used as a copolymer component of an olefin having 2 to 4 carbon atoms in the present invention include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate. Esters of acrylic acid and methacrylic acid; carboxyl groups such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, monomethyl fumarate, monomethyl itaconate and maleic anhydride, or acid anhydride And vinyl acetate. These copolymer components may be used alone or in combination.
A mixture of more than one species can be used.
さらには、例えばエチレンと、上記カルボキシル基ま
たは酸無水物を含有する単量体とを組合せ、これに亜
鉛、銅などのイオンを用いてイオン架橋したアイオノマ
ー樹脂の如く、これら共重合体成分に他の成分を加えて
なるものも本発明のオレフィン系重合体に含まれる。Further, for example, an ionomer resin obtained by combining ethylene with the above-mentioned monomer containing a carboxyl group or an acid anhydride, and ion-crosslinking with ions of zinc, copper, or the like, may be used in addition to these copolymer components. The addition of the above component is also included in the olefin polymer of the present invention.
本発明においてオレフィン系重合体として共重合体を
用いる場合には、芳香族ポリアミド短繊維で補強する熱
可塑性樹脂の特性を考慮し、上記広範な共重合体成分の
中から適当なものを適宜選択使用することができる。When a copolymer is used as the olefin polymer in the present invention, an appropriate one is selected from the above wide range of copolymer components in consideration of the properties of the thermoplastic resin reinforced with the short aromatic polyamide fibers. Can be used.
共重合体中のオレフィン含有量は特に限定されず、例
えばエチレン共重合体中におけるエチレン含有量は60重
量％以上が好ましく用いられる。The olefin content in the copolymer is not particularly limited. For example, the ethylene content in the ethylene copolymer is preferably 60% by weight or more.
本発明において芳香族ポリアミド短繊維の被覆に用い
るオレフィン系重合体はASTM D1525に準拠して測定さ
れたビカット軟化点が40℃以上のものである。In the present invention, the olefin polymer used for coating the aromatic polyamide short fiber has a Vicat softening point of 40 ° C. or higher as measured according to ASTM D1525.
ビカット軟化点が40℃未満であると、貯蔵中に繊維同
志が互着し、その結果、熱可塑性樹脂に対する分散性が
悪化し、配合樹脂の機械的特性の低下を招いたり、また
互着が著しい場合には、ホッパーを介しての熱可塑性樹
脂への混入操作が不能になる等の不都合を生じる。If the Vicat softening point is less than 40 ° C, the fibers mutually adhere to each other during storage, and as a result, the dispersibility in the thermoplastic resin is deteriorated, and the mechanical properties of the compounded resin are reduced, or the mutual adhesion is caused. In the case of a remarkable situation, there arises a problem that the mixing operation to the thermoplastic resin via the hopper becomes impossible.
本発明において芳香族ポリアミド短繊維に対するオレ
フィン系重合体の被覆量としては、被覆前の繊維100重
量部に対して、１〜20重量部が好ましく、より好ましく
は３〜15重量部である。In the present invention, the amount of the olefin polymer coated on the aromatic polyamide short fibers is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the fibers before coating.
被覆量が１重量部に満たない場合には、短繊維の飛散
防止効果が発揮できず、また20重量部を越えても、被覆
によって得られる飛散防止などの本発明の効果が飽和し
不経済である。If the coating amount is less than 1 part by weight, the effect of preventing short fibers from scattering cannot be exerted, and even if it exceeds 20 parts by weight, the effects of the present invention such as the scattering prevention obtained by coating are saturated and uneconomical. It is.
本発明の芳香族ポリアミド短繊維の長さは0.1〜6mmで
あり、好ましくは0.2〜4mm以下である。The length of the aromatic polyamide short fiber of the present invention is 0.1 to 6 mm, preferably 0.2 to 4 mm or less.
繊維長が0.1mmに満たなくても効果上の問題は特にな
いが、短繊維は一般に高価であるので、経済上の観点か
ら工業的実施に際しこの程度が好ましい。また、長さが
6mmを越えると、これを配合した熱可塑性樹脂の成型加
工時の成型加工時における押出しカット性が悪化し、本
発明の目的を達成できない。Even if the fiber length is less than 0.1 mm, there is no particular problem in the effect, but since short fibers are generally expensive, this degree is preferable for industrial implementation from an economic viewpoint. Also, the length
If it exceeds 6 mm, the extrudability of the thermoplastic resin blended with the resin during the molding process will deteriorate, and the object of the present invention cannot be achieved.
本発明の短繊維を構成するポリアミドは、芳香族ポリ
アミドであれば特に限定はなく、例えばポリ−ｐ−フェ
ニレンテレフタルアミド、ポリ−ｐ−ベンズアミド、ポ
リ−ｍ−ベンズアミド、およびポリ−ｍ−フェニレイソ
フタルアミド等の芳香族ポリアミドを用いることができ
る。これら芳香族ポリアミドは１種を単独で、または２
種以上を混合して用いることができる。The polyamide constituting the short fiber of the present invention is not particularly limited as long as it is an aromatic polyamide. For example, poly-p-phenyleneterephthalamide, poly-p-benzamide, poly-m-benzamide, and poly-m-phenylene Aromatic polyamide such as isophthalamide can be used. These aromatic polyamides may be used alone or in combination of two or more.
A mixture of more than one species can be used.
本発明においては、芳香族ポリアミド短繊維は、上記
芳香族ポリアミドを単独で繊維化したもののほか、２種
以上の芳香族ポリアミドを併用して繊維化したものも用
いられている。また、一本の繊維中に上記芳香族ポリア
ミド構造が50重量％以上含まれるように芳香族ポリアミ
ド以外のポリマーを併用して繊維化したものも用いるこ
とができる。さらには、上記芳香族のポリアミド繊維50
重量％以上と他の繊維との混合物も使用することができ
る。In the present invention, as the aromatic polyamide short fiber, one obtained by fiberizing the aromatic polyamide alone or fiberized by using two or more aromatic polyamides in combination is used. Further, a fiber formed by using a polymer other than the aromatic polyamide in combination such that the aromatic polyamide structure is contained in one fiber in an amount of 50% by weight or more can also be used. Further, the aromatic polyamide fiber 50
Mixtures of weight percent or more with other fibers can also be used.
本発明における芳香族ポリアミド短繊維の太さは特に
限定されないが、被覆前の太さとして400〜10000デーニ
ル程度が好ましい。The thickness of the aromatic polyamide short fibers in the present invention is not particularly limited, but the thickness before coating is preferably about 400,000 to 10,000 denyl.
本発明の芳香族ポリアミド短繊維は種々の熱可塑性樹
脂の補強材として用いることができる。熱可塑性樹脂の
例としては、例えばポリエステル、ポリアミド、ポリエ
チレン、ポリプロピレン、アクリロニトリル−ブタジエ
ン−スチレン樹脂、アクリル樹脂、フェノール樹脂、ポ
リカーボネート樹脂、エチレン共重合体樹脂、ポリスチ
レン、ポリウレタン、スチレン−ブタジンエン樹脂、ポ
リエーテルエーテルケトン、ポリエーテルサルホンおよ
び塩化ビニル系樹脂等を挙げることができる。The aromatic polyamide short fiber of the present invention can be used as a reinforcing material for various thermoplastic resins. Examples of thermoplastic resins include, for example, polyester, polyamide, polyethylene, polypropylene, acrylonitrile-butadiene-styrene resin, acrylic resin, phenolic resin, polycarbonate resin, ethylene copolymer resin, polystyrene, polyurethane, styrene-butadiene resin, polyether Examples thereof include ether ketone, polyether sulfone, and vinyl chloride resin.
本発明の芳香族ポリアミドマルチフィラメント短繊維
は、前述したオレフィン系重合体を含む水系分散液に、
芳香族ポリアミドマルチフィラメントからなる長繊維を
含浸し、次いで含浸後の芳香族ポリアミド長繊維を前記
ビカット軟化点より20℃以上高い温度で乾燥し、次いで
乾燥後の芳香族ポリアミド長繊維を長さ0.1〜6mmに切断
することにより調製される。The aromatic polyamide multifilament staple fiber of the present invention is an aqueous dispersion containing the olefin polymer described above,
Impregnated with a long fiber consisting of an aromatic polyamide multifilament, then dried the impregnated aromatic polyamide long fiber at a temperature 20 ° C. or more higher than the Vicat softening point, and then dried the aromatic polyamide long fiber to a length of 0.1 Prepared by cutting to 66 mm.
ここで水系分散液は、前述したオレフィン系重合体を
有機溶媒（例えば、トルエン、キシレンなど）に溶解
し、この溶媒を乳化剤（アニオン系、カチオン系、非イ
オン系のいずれでもよい。）を含む水に置換することに
より得ることができる。Here, the aqueous dispersion dissolves the olefin polymer described above in an organic solvent (for example, toluene, xylene, etc.), and contains this solvent with an emulsifier (any of anionic, cationic, and nonionic). It can be obtained by substituting with water.
本発明においては前記オレフィン系重合体を含有した
市販の水系分散液を用いることもできる。In the present invention, a commercially available aqueous dispersion containing the olefin polymer can also be used.
水系分散液中のオレフィン系重合体の濃度は２〜50重
量％であり、この濃度範囲とすることにより、前述の１
〜20重量％の所定の被覆量が得られるものである。The concentration of the olefin polymer in the aqueous dispersion is from 2 to 50% by weight.
A predetermined coating amount of 2020% by weight is obtained.
芳香族ポリアミド長繊維を水系分散液に含浸させるに
際し、含浸温度には特に制限はないが、室温程度で十分
である。In impregnating the aromatic polyamide filaments with the aqueous dispersion, the impregnation temperature is not particularly limited, but about room temperature is sufficient.
水系分散液を含浸させた芳香族ポリアミド長繊維は、
例えば温風乾燥等の任意の乾燥手段を用いて乾燥され
る。Aromatic polyamide filaments impregnated with an aqueous dispersion,
For example, drying is performed using any drying means such as hot air drying.
乾燥温度としては水分除去を十分に行なう観点から、
オレフィン系重合体のビカット軟化点より20℃以上高い
温度であることが必要であり、好ましくは軟化点より10
0℃以上高い温度である。軟化点よりも20℃未満高い温
度では十分な乾燥が行なえない。From the viewpoint of sufficiently removing moisture as the drying temperature,
It is necessary that the temperature is at least 20 ° C. higher than the Vicat softening point of the olefin polymer,
The temperature is higher than 0 ° C. If the temperature is lower than the softening point by less than 20 ° C., sufficient drying cannot be performed.
こうして乾燥した芳香族ポリアミド長繊維は周知の切
断方法を用いて所定の長さ、すなわち0.1〜6mmに切断さ
れ、前記オレフィン系重合体で被覆された本発明の芳香
族ポリアミド短繊維を得る。The aromatic polyamide filament thus dried is cut into a predetermined length, that is, 0.1 to 6 mm, using a known cutting method to obtain the aromatic polyamide short fiber of the present invention coated with the olefin polymer.
なお、芳香族ポリアミド短繊維の製造にあたっては、
本発明によらない方法として、オレフィン系重合体を熱
溶融、該熱溶融液に長繊維を含浸させるという別法も考
えられるが、オレフィン系重合体の熱溶融液は、一般
に、経時的に熱変質することが知られており、またこの
方法では被覆量をコントロールすることが難しく、工業
的利用価値が低い。一方、本発明の製造方法は、かかる
オレフィン系重合体の熱溶融液を用いることがないの
で、オレフィン系重合体の熱溶融時の熱変質を伴わず、
また被覆量を目的に応じてコントロールできる優れた方
法である。In producing aromatic polyamide short fibers,
As a method not according to the present invention, another method of hot-melting an olefin-based polymer and impregnating the hot-melt with a long fiber can be considered, but a hot-melt of an olefin-based polymer is generally heated over time. It is known to deteriorate, and it is difficult to control the coating amount by this method, and its industrial utility value is low. On the other hand, since the production method of the present invention does not use a hot melt of such an olefin polymer, it does not involve thermal deterioration during heat melting of the olefin polymer,
It is an excellent method that can control the amount of coating according to the purpose.
本発明の芳香族ポリアミド短繊維は補強材として前述
した各種の熱可塑性樹脂に配合され、機械的強度等にお
いて著しく改善された熱可塑性樹脂組成物を提供し得る
ものである。The aromatic polyamide staple fiber of the present invention is blended with the above-mentioned various thermoplastic resins as a reinforcing material, and can provide a thermoplastic resin composition having significantly improved mechanical strength and the like.
本発明の芳香族ポリアミド短繊維の熱可塑性樹脂への
配合量は、熱可塑性樹脂の最終用途によって求められる
補強強度等を考慮し、適宜最適配合量が決められる。一
般的には熱可塑性樹脂100重量部に対し、本発明の芳香
族ポリアミド短繊維１〜50重量部が適当である。The blending amount of the aromatic polyamide short fiber of the present invention with the thermoplastic resin is appropriately determined in consideration of the reinforcing strength and the like required for the final use of the thermoplastic resin. Generally, 1 to 50 parts by weight of the aromatic polyamide short fiber of the present invention is suitable for 100 parts by weight of the thermoplastic resin.
芳香族ポリアミド短繊維と熱可塑性樹脂との混練方法
は特に限定はなく、この技術分野で一般的に行なわれて
いる方法を特に限定することなく採用できる。The method of kneading the aromatic polyamide short fiber and the thermoplastic resin is not particularly limited, and a method generally used in this technical field can be employed without any particular limitation.
［実施例］ 以下、実施例および比較例により本発明をさらに詳細
に説明する。[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１ ビカット軟化点が60℃のエチレン−無水マレイン酸−
アクリル酸エチル共重合体の水系分散液（市販品，三菱
油化社製，商品名;MC−4400,カチオン系分散剤含有）を
水を希釈して、固形分濃度を21.5重量％に調整した。こ
の希釈液にポリ−ｐ−フェニレンテレフタルアミド（市
販品，アクゾー社（オランダ国）製,;商品名；トワロン
1000,太さ3000デニール）を含浸後、120℃で３分間乾燥
し、上記共重合体の被覆量が10.2重量％の芳香族ポリア
ミド長繊維を得た。次いで、この長繊維を2mmの長さに
切断し、本発明の芳香族ポリアミド短繊維を得た。Example 1 Ethylene-maleic anhydride having a Vicat softening point of 60 ° C.
An aqueous dispersion of an ethyl acrylate copolymer (commercial product, manufactured by Mitsubishi Yuka Co., trade name; MC-4400, containing a cationic dispersant) was diluted with water to adjust the solid content concentration to 21.5% by weight. . This diluted solution was mixed with poly-p-phenylene terephthalamide (commercial product, manufactured by Akzo Co., The Netherlands); trade name: Twaron
(1000 denier, 3000 denier) and dried at 120 ° C. for 3 minutes to obtain an aromatic polyamide filament having a coating amount of the above copolymer of 10.2% by weight. Next, the long fiber was cut into a length of 2 mm to obtain an aromatic polyamide short fiber of the present invention.
こうして得た芳香族ポリアミド短繊維をホッパーに貯
蔵した後、ポリエチレン（市販品，住友化学社製，商品
名;G806）100重量部に対し上記短繊維が10重量部の配合
割合になるように、２軸の混練押出機にホッパーから投
入し190℃で混練した。After storing the aromatic polyamide staple fiber thus obtained in a hopper, the blending ratio of the staple fiber is 10 parts by weight with respect to 100 parts by weight of polyethylene (commercial product, manufactured by Sumitomo Chemical Co., Ltd .; G806). The mixture was charged from a hopper into a twin-screw kneading extruder and kneaded at 190 ° C.
次いで、得られた混練組成物を押出機から押出しカッ
トしてストランドペレットを得、さらにこのストランド
ペレットを150℃でプレス成型して2mm厚のプレスシート
を得た。Next, the obtained kneaded composition was extruded from an extruder and cut to obtain strand pellets, and the strand pellets were press-molded at 150 ° C. to obtain a 2 mm-thick press sheet.
得られたプレスシートを目視観察したところ、芳香族
ポリアミド短繊維がシート中に極めて均一に分散してい
ることが分った。Visual observation of the obtained press sheet showed that the aromatic polyamide short fibers were very uniformly dispersed in the sheet.
またシートの引張強度（JIS K7113による。以下、同
じ。）は4.3kg/mm2であり、本発明の芳香族ポリアミド
短繊維を含まない原料ポリエチレン（G806）の引張強度
（1.0kg/mm2）に比べ著しく改良されていることが分っ
た。Further, the tensile strength of the sheet (according to JIS K7113; the same applies hereinafter) is 4.3 kg / mm 2 , and the tensile strength (1.0 kg / mm 2 ) of the raw polyethylene (G806) containing no aromatic polyamide short fiber of the present invention. It has been found that it is remarkably improved as compared with.
また上記短繊維は貯蔵時においても、またホッパーか
らの投入操作の際にも全く互着が生じておらず、ハンド
リング中の飛散もなく、作業効率が極めて良好であっ
た。さらには、押出しカット時のカット性も良好であっ
た。In addition, the short fibers did not adhere to each other at all even during storage and during the charging operation from the hopper, did not scatter during handling, and had extremely good work efficiency. Furthermore, the cutability during extrusion cutting was also good.
実施例２ ビカット軟化点が65℃のエチレン−アクリル酸共重合
体の水系分散液（市販品，三菱油化社製，商品名;AC−2
010,カチオン系分散剤含有）を水で希釈して、固形分濃
度が15重量％となるように調整し、これに実施例１と同
じポリ−ｐ−フェニレンテレフタルアミドを含浸後、12
0℃で３分間乾燥し、上記共重合体の被覆量が6.3重量％
の芳香族ポリアミド長繊維を得た。次いで、この長繊維
を3mmの長さに切断し、本発明の芳香族ポリアミド短繊
維を得た。Example 2 An aqueous dispersion of an ethylene-acrylic acid copolymer having a Vicat softening point of 65 ° C (commercial product, manufactured by Mitsubishi Yuka Co., trade name; AC-2
010, containing a cationic dispersant), diluted with water to adjust the solid content to 15% by weight, and impregnated with the same poly-p-phenylene terephthalamide as in Example 1;
After drying at 0 ° C for 3 minutes, the coating amount of the above copolymer was 6.3% by weight.
Was obtained. Next, the long fiber was cut into a length of 3 mm to obtain an aromatic polyamide short fiber of the present invention.
こうして得た芳香族ポリアミド短繊維をホッパーに貯
蔵し、ポリプロピレン（市販品，住友化学社製，商品
名;AW564）100重量部に対し上記短繊維が10重量部の配
合になるように、２軸の混練押出機にホッパーから投入
し220℃で混練した。The aromatic polyamide staple fiber thus obtained was stored in a hopper, and the staple fiber was mixed with 100 parts by weight of polypropylene (commercial product, manufactured by Sumitomo Chemical Co., Ltd., AW564) so that the staple fiber was blended at 10 parts by weight. From a hopper and kneaded at 220 ° C.
次いで、得られた混練組成物を押出機から押出しカッ
トしてストランドペレットを得、さらにこのストランド
ペットを230℃でプレス成型して2mm厚のプレスシートを
得た。Next, the obtained kneaded composition was extruded from an extruder and cut to obtain strand pellets, and the strand pet was press-molded at 230 ° C. to obtain a press sheet having a thickness of 2 mm.
得られたプレスシートを目視観察したところ、芳香族
ポリアミド短繊維がシート中に極めて均一に分散してい
ることがわかった。Visual observation of the obtained press sheet revealed that the aromatic polyamide short fibers were very uniformly dispersed in the sheet.
またシートの引張強度は5.6kg/mm2であり、本発明の
芳香族ポリアミド短繊維を含まない原料ポリプロピレン
（AW564）の引張強度（2.2kg/mm2）に比べ十分に改良さ
れていることが分った。The tensile strength of the sheet is 5.6 kg / mm 2, which is sufficiently improved compared to the tensile strength (2.2 kg / mm 2 ) of the raw polypropylene (AW564) containing no aromatic polyamide short fiber of the present invention. I understand.
また上記短繊維は貯蔵時においても、またホッパーか
らの投入操作に際しても全く互着が生じておらず、ハン
ドリング中の飛散もなく、作業効率が極めて良好であっ
た。さらには、押出しカット時のカット性も良好であっ
た。In addition, the short fibers did not adhere to each other at all during storage and also during the charging operation from the hopper, were not scattered during handling, and had extremely good work efficiency. Furthermore, the cutability during extrusion cutting was also good.
比較例１ 実施例１においてエチレン−無水マレイン酸−アクリ
ル酸エチル共重合体による被覆処理を行なわなかったこ
と以外は実施例１と同様に行なった。Comparative Example 1 The procedure of Example 1 was repeated, except that the coating treatment with the ethylene-maleic anhydride-ethyl acrylate copolymer was not performed.
その結果、この短繊維を配合して得られたプレスシー
トは引張強度については4.0kg/mm2と実施例１に比して
劣るものであった。As a result, the press sheet obtained by blending the short fibers had a tensile strength of 4.0 kg / mm 2 , which was inferior to Example 1.
さらに、被覆処理を施さなかった本例の芳香族ポリア
ミド短繊維は、貯蔵時およびホッパーからの投入操作に
際し互着が生じており、一部が綿状となって投入操作ス
ムースに行なわれなかった。Furthermore, the aromatic polyamide short fibers of this example which were not subjected to the coating treatment had mutual adhesion at the time of storage and at the time of the charging operation from the hopper, and a part thereof became cotton-like and was not smoothly performed. .
またこの短繊維はハンドリング時の飛散が著しく、作
業効率上および衛生上問題があった。In addition, the staple fibers are remarkably scattered during handling, and have problems in working efficiency and hygiene.
比較例２ 実施例１において繊維長を10mmとしたこと以外は実施
例１と同様に行なった。Comparative Example 2 The procedure of Example 1 was repeated, except that the fiber length was changed to 10 mm.
その結果、この繊維を配合して得られた混練組成物は
押出しカット時のカット性が悪く、このため作業効率が
低下し、またカットして得られるストランドペレットの
長さも不揃いになるという問題があった。As a result, the kneading composition obtained by blending this fiber has a problem that the cutability at the time of extrusion cutting is poor, so that the working efficiency is reduced, and the length of the strand pellet obtained by cutting is also irregular. there were.
比較例３ 実施例１においてビカット軟化点が60℃のエチレン−
無水マレイン酸−アクリル酸エチル共重合体の水系分散
液にかえて、ビカット軟化点が40℃未満のエチレン−酢
酸ビニル共重合体の水系分散液（市販品，三井石油化学
社製，商品名;V−100）を用いたこと以外は実施例１と
同様の方法により、2mmの長さの芳香族ポリアミド短繊
維を得た。Comparative Example 3 Ethylene having a Vicat softening point of 60 ° C. in Example 1.
Instead of an aqueous dispersion of a maleic anhydride-ethyl acrylate copolymer, an aqueous dispersion of an ethylene-vinyl acetate copolymer having a Vicat softening point of less than 40 ° C (commercial product, manufactured by Mitsui Petrochemical Co., trade name; By the same method as in Example 1 except that V-100) was used, 2 mm long aromatic polyamide short fibers were obtained.
しかしながら、この短繊維は貯蔵中の互着が著しく、
以後の操作に使用することができなかった。However, this short fiber has a remarkable mutual adhesion during storage,
It could not be used for subsequent operations.
［発明の効果］ 以上説明したように、本発明によって、ハンドリング
時における繊維の飛散や貯蔵時の互着の問題が解消され
た芳香族ポリアミド短繊維およびその製造方法が提供さ
れた。また、カット性および引張強度に優れた補強され
た熱可塑性樹脂組成物が提供された。[Effects of the Invention] As described above, the present invention has provided an aromatic polyamide short fiber which has solved the problem of scattering of fibers during handling and mutual adhesion during storage, and a method for producing the same. Further, a reinforced thermoplastic resin composition having excellent cut properties and tensile strength has been provided.
Claims (5)
のオレフィン系重合体で被覆された長さ0.1〜6mmの熱可
塑性樹脂補強用芳香族ポリアミドマルチフィラメント短
繊維。1. A carbon number of 2 to 4 having a Vicat softening point of 40 ° C. or higher.
Aromatic polyamide multifilament staple fibers 0.1 to 6 mm in length coated with an olefin polymer for reinforcing thermoplastic resin.
リアミド短繊維100重量部に対し１〜20重量部である請
求項１記載の熱可塑性樹脂補強用芳香族ポリアミドマル
チフィラメント短繊維。2. The aromatic polyamide multifilament short fiber for reinforcing a thermoplastic resin according to claim 1, wherein the coating amount of the olefin polymer is 1 to 20 parts by weight based on 100 parts by weight of the aromatic polyamide short fiber.
またはエチレン共重合体である請求項１記載の熱可塑性
樹脂補強用芳香族ポリアミドマルチフィラメント短繊
維。3. The staple aromatic polyamide multifilament for reinforcing a thermoplastic resin according to claim 1, wherein the olefin polymer is an ethylene homopolymer or an ethylene copolymer.
のオレフィン系重合体を２〜50重量％含む水系分散液に
芳香族ポリアミドマルチフィラメント長繊維を含浸し、
含浸後の芳香族ポリアミド長繊維を上記ビカット軟化点
より20℃以上高い温度で長乾燥し、次いで乾燥後の芳香
族ポリアミド長繊維を長さ0.1〜6mmに切断することを特
徴とする請求項１記載の熱可塑性樹脂補強用芳香族ポリ
アミドマルチフィラメント短繊維。4. A carbon number of 2 to 4 having a Vicat softening point of 40 ° C. or higher.
Aqueous dispersion containing 2 to 50% by weight of an olefin-based polymer is impregnated with an aromatic polyamide multifilament filament,
2. The method according to claim 1, wherein the impregnated aromatic polyamide filaments are long-dried at a temperature higher than the Vicat softening point by at least 20 DEG C., and the dried aromatic polyamide filaments are cut to a length of 0.1 to 6 mm. The aromatic polyamide multifilament staple fiber for reinforcing a thermoplastic resin according to the above.
ィラメント短繊維を熱可塑性樹脂に配合、混練して得ら
れる補強された熱可塑性樹脂組成物。5. A reinforced thermoplastic resin composition obtained by blending and kneading the aromatic polyamide multifilament short fibers according to claim 1 with a thermoplastic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2156496A JP2819186B2 (en) | 1990-06-14 | 1990-06-14 | Aromatic polyamide short fiber for reinforcing thermoplastic resin, method for producing the same, and thermoplastic resin composition reinforced with the fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2156496A JP2819186B2 (en) | 1990-06-14 | 1990-06-14 | Aromatic polyamide short fiber for reinforcing thermoplastic resin, method for producing the same, and thermoplastic resin composition reinforced with the fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0450377A JPH0450377A (en) | 1992-02-19 |
| JP2819186B2 true JP2819186B2 (en) | 1998-10-30 |
Family
ID=15629027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2156496A Expired - Lifetime JP2819186B2 (en) | 1990-06-14 | 1990-06-14 | Aromatic polyamide short fiber for reinforcing thermoplastic resin, method for producing the same, and thermoplastic resin composition reinforced with the fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2819186B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08151483A (en) * | 1994-11-30 | 1996-06-11 | Idemitsu Petrochem Co Ltd | Fiber reinforced polyolefin resin molding material, molding method, and molded article |
| JP2004115958A (en) * | 2002-09-26 | 2004-04-15 | Du Pont Toray Co Ltd | High-strength fiber provided with chemical resistance and composite thereof |
| TWI352146B (en) * | 2005-07-08 | 2011-11-11 | Teijin Aramid Bv | Method for improving filament cohesiveness of chop |
| JP4956974B2 (en) * | 2005-12-02 | 2012-06-20 | 三菱化学株式会社 | Conductive thermoplastic resin composition and molded article |
| JP2007224209A (en) * | 2006-02-24 | 2007-09-06 | Mitsubishi Chemicals Corp | Conductive thermoplastic resin molded article |
| JP2010065347A (en) * | 2008-09-11 | 2010-03-25 | Unitika Ltd | Functional fiber |
| JP2016160536A (en) * | 2015-02-26 | 2016-09-05 | 東レ・デュポン株式会社 | Short fiber for polyamide composite and polyamide composite |
| JP2016160535A (en) * | 2015-02-26 | 2016-09-05 | 東レ・デュポン株式会社 | Polyparaphenylene terephthalamide fiber composite and manufacturing method therefor |
| JP6917143B2 (en) * | 2016-12-27 | 2021-08-11 | 東レ・デュポン株式会社 | Polyparaphenylene terephthalamide fiber composite, polycarbonate resin composite containing it |
| JP6941940B2 (en) * | 2016-12-27 | 2021-09-29 | 東レ・デュポン株式会社 | Polyparaphenylene terephthalamide fiber composite, polycarbonate resin composite containing it |
| JP6890370B2 (en) * | 2017-01-13 | 2021-06-18 | 東レ・デュポン株式会社 | Aramid short fiber bundle for rubber reinforcement |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58214582A (en) * | 1982-06-01 | 1983-12-13 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Coated polyamide monofilament |
| JPS61197654A (en) * | 1985-02-28 | 1986-09-01 | Nippon Mektron Ltd | Thermoplastic elastomer composition |
-
1990
- 1990-06-14 JP JP2156496A patent/JP2819186B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0450377A (en) | 1992-02-19 |
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