JPH06280108A - Highly strong polyethylene fiber excellent in adhesivity and its production - Google Patents

Abstract

PURPOSE:To produce a high strength polyethylene fiber having an adhesive strength sufficient for practical uses at a high production rate without damaging the surface of the fiber. CONSTITUTION:The characteristic of this highly strong polyethylene fiber is that the oxygen/carbon ratio of its surface is <5% and that the interlaminar shear strength of a product using the fiber is >=13MPa, and its production method is provided. The highly strong polyethylene fiber has a practically sufficient adhesive strength without applying any specific surface treatment and can be formed at a non-conventional level drawing rate.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、複合素材の補強素材な
どに広く用いることの可能な、接着強度を特別な表面処
理を施す事無く有し、かつ製造工程上での延伸速度が従
来に無く極めて高く、従って、強度等の力学特性と接着
特性と生産性という、いわゆるコストパフォーマンスに
非常に優れた新規な高強度ポリエチレン繊維並びにその
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an adhesive strength that can be widely used as a reinforcing material for composite materials, etc. without any special surface treatment, and has a conventional stretching speed in the manufacturing process. The present invention relates to a novel high-strength polyethylene fiber excellent in so-called cost performance such as mechanical properties such as strength, adhesive properties and productivity, and a method for producing the same.

【０００２】[0002]

【従来の技術】極限粘度〔η〕が１０を越えるようない
わゆる超高分子量ポリエチレンを原料にして高強度・高
弾性率繊維を得ようとする試みは、近年活発であり、非
常に高い強度・弾性率が報告されている。例えば、特開
昭５６−１５４０８号公報には、超高分子量ポリエチレ
ンを溶剤に溶解し得られたゲル状の繊維を高倍率に延伸
するという、いわゆるゲル紡糸法が開示されている。2. Description of the Related Art Attempts to obtain high-strength, high-modulus fibers using so-called ultra-high-molecular-weight polyethylene having an intrinsic viscosity [η] of more than 10 have been active in recent years, and have extremely high strength. Elastic moduli have been reported. For example, Japanese Patent Application Laid-Open No. 56-15408 discloses a so-called gel spinning method in which a gel fiber obtained by dissolving ultrahigh molecular weight polyethylene in a solvent is stretched at a high ratio.

【０００３】ゲル紡糸法により得られた高強度ポリエチ
レン繊維は有機繊維としては非常に高い強度・弾性率を
有するもののポリエチレンを主原料とする故に樹脂との
接着性に劣るという問題点があり、該繊維の例えば複合
素材の補強材などへの応用を困難にしていた。The high-strength polyethylene fiber obtained by the gel-spinning method has a very high strength and elastic modulus as an organic fiber, but since polyethylene is the main raw material, it has a problem that it has poor adhesiveness with a resin. It has been difficult to apply the fibers to, for example, a reinforcing material of a composite material.

【０００４】かかる問題点を克服するために、従来技術
として例えば特開昭６０−１４６０７８号公報や特開昭
６２−１８４１１０号公報あるいは特開昭６３−２１３
５０号公報に開示されているように糸表面にコロナ放電
やプラズマ放電を行い表面上に官能基を導入しようとい
う試みが広く行われてきた。しかし、これらの手法は高
強度ポリエチレンの製造工程に別の表面処理工程を必要
とするものであり、さらに処理スピードの制約から糸製
造工程そのものの速度も低く抑える必要があり、コスト
の著しい増加を避ける事はできなかった。また、これら
表面処理の手法は糸の表面でのダメージを避けることが
原理的に難しく、必然的に強度などが低下するという問
題点があった。In order to overcome such a problem, conventional techniques such as JP-A-60-146078, JP-A-62-184110 and JP-A-63-213 are known.
As disclosed in Japanese Patent Laid-Open No. 50, there have been widely made attempts to introduce a functional group onto the surface by performing corona discharge or plasma discharge on the yarn surface. However, these methods require a separate surface treatment step in the production process of high-strength polyethylene, and it is necessary to keep the speed of the yarn production process low due to the limitation of the processing speed, resulting in a significant increase in cost. I couldn't avoid it. Further, these surface treatment methods have a problem that it is difficult in principle to avoid damage on the surface of the yarn, and the strength and the like are inevitably lowered.

【０００５】[0005]

【発明が解決しようとする課題】以上の観点基づき、本
発明は、高強度ポリエチレン繊維の接着性を従来の煩雑
な処理を施す事無く改善し、同時に製糸工程での延伸速
度を落とす事無く、さらには従来よりも高速度の延伸速
度で製造可能な、接着性に優れる高強度ポリエチレン繊
維およびその製造方法に関する。Based on the above viewpoints, the present invention improves the adhesiveness of high-strength polyethylene fibers without performing conventional complicated processing, and at the same time, without lowering the drawing speed in the yarn making process, Furthermore, the present invention relates to a high-strength polyethylene fiber having excellent adhesiveness, which can be produced at a higher drawing speed than ever before, and a method for producing the same.

【０００６】[0006]

【課題を解決するための手段】すなわち本発明は、実質
エチレン成分を主体とするポリエチレン繊維であり、そ
の強度が２８ｇ／ｄ以上、弾性率が７００ｇ／ｄ以上で
あり、かつ、その繊維の表面における酸素と炭素の比率
が５％未満であり、かつ、その層間せん断強度が１３Ｍ
Ｐａ以上、好ましくは１５ＭＰａ以上である高強度ポリ
エチレン繊維。さらには、その繊維の延伸速度指数（Ｅ
Ｆ）が次式を満足する事を特徴とする高強度ポリエチレ
ン繊維を提供するものである。 ＥＦ＞１０^A Ａ＝−２．７５−０．２５〔ηＢ〕 好ましくは Ａ＝−２．２５−０．２５〔ηＢ〕[Means for Solving the Problems] That is, the present invention is a polyethylene fiber mainly composed of an ethylene component, having a strength of 28 g / d or more and an elastic modulus of 700 g / d or more, and the surface of the fiber. The ratio of oxygen to carbon is less than 5%, and the interlaminar shear strength is 13M.
A high-strength polyethylene fiber having a Pa or higher, preferably 15 MPa or higher. Furthermore, the drawing speed index (E
F) provides a high strength polyethylene fiber characterized by satisfying the following formula. EF> 10 ^A A = −2.75−0.25 [ηB] Preferably A = −2.25−0.25 [ηB]

【０００７】さらに本特許は極限粘度〔ηＡ〕が１０以
上好ましくは１３以上さらに好ましくは１５以上の超高
分子量ポリエチレン５重量部乃至５０重量部と、溶剤９
５重量部乃至５０重量部の混合物を加熱溶解し押し出し
て得られた半完成糸を１０倍以上の延伸倍率にて延伸し
て得られた糸が、少なくとも２８ｇ／ｄ以上の強度と、
７００ｇ／ｄ以上の弾性率を有し、かつ、該繊維状態で
の極限粘度〔ηＢ〕が次式で定義される範囲にあり、か
つ、その繊維の層間せん断強度が１３ＭＰａ以上好まし
くは１５ＭＰａ以上であることを特徴とする高強度ポリ
エチレン繊維の製造方法を提供するものである。 ０．７×〔ηＡ〕≦〔ηＢ〕≦０．９×〔ηＡ〕 さらに、後述する本発明の効果のより好ましい範囲とし
ては次式が挙げられる ０．７×〔ηＡ〕≦〔ηＢ〕≦０．８×〔ηＡ〕Further, the present patent discloses that 5 to 50 parts by weight of ultrahigh molecular weight polyethylene having an intrinsic viscosity [ηA] of 10 or more, preferably 13 or more, more preferably 15 or more, and a solvent 9
A yarn obtained by drawing a semi-finished yarn obtained by heating and melting 5 parts by weight to 50 parts by weight of a mixture and extruding the mixture at a draw ratio of 10 times or more has a strength of at least 28 g / d or more,
It has an elastic modulus of 700 g / d or more, the intrinsic viscosity [ηB] in the fiber state is in the range defined by the following equation, and the interlaminar shear strength of the fiber is 13 MPa or more, preferably 15 MPa or more. The present invention provides a method for producing a high-strength polyethylene fiber, which is characterized in that 0.7 × [ηA] ≦ [ηB] ≦ 0.9 × [ηA] Further, as a more preferable range of the effect of the present invention described later, the following formula can be mentioned: 0.7 × [ηA] ≦ [ηB] ≦ 0.8 x [ηA]

【０００８】本発明における超高分子量ポリエチレンと
は、その繰り返し単位が実質的にエチレンであることを
特徴とし、少量の他のモノマー例えばα−オレフィン、
アクリル酸及びその誘導体、メタクリル酸及びその誘導
体、ビニルシラン及びその誘導体などとの共重合体であ
ってもよいし、これら共重合物同志あるいはエチレン単
独ポリマーと共重合体、さらには他のα−オレフィン等
のホモポリマーとのブレンド体であってもよい。エチレ
ン以外の含有量は本発明の原理 効果そのものには影響
しないが、高強度繊維を高い延伸速度で得ると言う観点
からはモノマー単位で５ｍｏｌ％以下であることが好ま
しい。The ultrahigh molecular weight polyethylene in the present invention is characterized in that its repeating unit is substantially ethylene, and a small amount of another monomer such as α-olefin,
It may be a copolymer with acrylic acid and its derivative, methacrylic acid and its derivative, vinyl silane and its derivative, etc., or these copolymers may be the same or copolymers with ethylene homopolymer, and other α-olefins. It may be a blend with a homopolymer such as. Although the content other than ethylene does not affect the principle effect of the present invention itself, it is preferably 5 mol% or less in monomer unit from the viewpoint of obtaining high-strength fiber at a high drawing speed.

【０００９】本発明の骨子は、ポリマーを溶解する段階
でポリマーの劣化を促進し、ある適当な範囲に劣化させ
ると、得られた延伸糸も強度・弾性率が優れていること
に加え、驚くべき事に繊維の接着性に極めて優れ、しか
も延伸速度も極めて高くする事ができるという点にあ
る。特に、ポリマーの極限粘度を〔ηＡ〕、得られた延
伸糸の極限粘度を〔ηＢ〕とすると、〔ηＢ〕が下記の
式を満足する範囲にあるとき極めて優れた接着性および
延伸性が期待できる。 ０．７×〔ηＡ〕≦〔ηＢ〕≦０．９×〔ηＡ〕 さらに、次式の範囲はより好ましい。 ０．７×〔ηＡ〕≦〔ηＢ〕≦０．８×〔ηＡ〕The skeleton of the present invention accelerates the deterioration of the polymer in the step of dissolving the polymer, and when it is deteriorated to a certain suitable range, the drawn yarn obtained has excellent strength and elastic modulus, and is surprising. What is essential is that the adhesion of the fibers is extremely excellent, and the stretching speed can be made extremely high. In particular, assuming that the intrinsic viscosity of the polymer is [ηA] and the intrinsic viscosity of the obtained drawn yarn is [ηB], extremely excellent adhesiveness and stretchability are expected when [ηB] is in the range satisfying the following formula. it can. 0.7 × [ηA] ≦ [ηB] ≦ 0.9 × [ηA] Furthermore, the range of the following equation is more preferable. 0.7 × [ηA] ≦ [ηB] ≦ 0.8 × [ηA]

【００１０】従来技術として、得られた糸の劣化度につ
いてほとんど議論されてきておらず、かりに触れられて
も、いかに劣化度を押さえるかという目的が主眼であっ
た。これは、紡糸段階でポリマーの劣化がおこると強度
の低下がおこり、高物性の観点から好ましくないと信じ
られていた為であり、実際の紡糸では各種の酸化防止剤
が用いられるのが通常であった。従って、故意にある適
正度ポリマーを劣化させることを促進する事により、か
えって成形性・延伸性が向上し、高速延伸が可能であ
り、しかも得られた繊維の接着特性が特別な表面処理を
行わないのにも係わらず極めて優れたものが得られると
いう本発明は真に意外な事実である。As the prior art, there has been little discussion about the degree of deterioration of the obtained yarn, and the main purpose was to suppress the degree of deterioration of the yarn even if it was touched. This is because it was believed that deterioration of the polymer at the spinning stage causes a decrease in strength, which is not preferable from the viewpoint of high physical properties.In actual spinning, various antioxidants are usually used. there were. Therefore, by deliberately promoting deterioration of the polymer, the moldability / stretchability is improved, high-speed stretching is possible, and the adhesive properties of the resulting fiber undergo special surface treatment. The present invention is a truly surprising fact that an extremely excellent product can be obtained despite the absence.

【００１１】劣化度が増加すると接着性が向上する理由
は明確でないが、例えば分子鎖が切断される際に生じる
活性種が微量に存在する酸素などと反応を行い結果とし
て、接合性を向上させるに十分な官能基を生成せしめる
のではないかと推定している。しかしながら、本発明に
よる繊維は十分な接着性を有するにもかかわらず、後に
示す手法により測定した糸表面での酸素原子数と炭素原
子数との比率は予想に反して５％以下であり、例えばプ
ラズマ処理などにより得られた繊維が示す１０％などの
値より遥かに低い。このことから、本繊維の接着性は表
面における酸素に代表される官能基だけでなく、新規な
表面テキスチャーがその向上に関与しているものと推定
しているが定かではない。また、コロナ処理やプラズマ
処理などにより接着性を付与された従来技術の繊維と
は、前記の表面酸素量と表面炭素量の比率で区別される
ものであり、少なくとも本繊維は従来の接着の概念から
はずれた新規な物質であるということができる。従っ
て、本発明で得られる繊維の表面酸素量は５％未満、好
ましくは４％以下であり、その繊維を用いて得られる層
間せん断強度は１３ＭＰａ以上好ましくは１５ＭＰａ以
上である。表面酸素量が５％を越えると、表面が必要以
上の酸化処理を受けた事を示し、強度などの力学特性に
好ましくない影響を受ける。又層間せん断強度が１３Ｍ
Ｐａ未満の場合は得られた繊維と樹脂との接着性が良好
とは言えず、複合素材としての実用に適さない。Although the reason why the adhesiveness is improved as the degree of deterioration is increased is not clear, for example, active species generated when the molecular chain is cleaved reacts with a small amount of oxygen and the like to improve the bondability. It is presumed that sufficient functional groups can be generated in However, despite the fact that the fiber according to the present invention has sufficient adhesiveness, the ratio of the number of oxygen atoms to the number of carbon atoms on the yarn surface measured by the method described later is unexpectedly 5% or less, and for example, It is much lower than the value such as 10% shown by the fiber obtained by plasma treatment or the like. From this, it is presumed that not only the functional group represented by oxygen on the surface but also the novel surface texture is involved in the improvement of the adhesiveness of the present fiber, but it is not clear. Further, the fibers of the prior art to which the adhesiveness is imparted by the corona treatment or the plasma treatment are distinguished by the ratio of the surface oxygen amount and the surface carbon amount, and at least the present fiber is a conventional adhesion concept. It can be said that it is a new substance that is out of order. Therefore, the surface oxygen content of the fiber obtained in the present invention is less than 5%, preferably 4% or less, and the interlaminar shear strength obtained using the fiber is 13 MPa or more, preferably 15 MPa or more. If the surface oxygen content exceeds 5%, it means that the surface has been subjected to an excessive oxidation treatment, which adversely affects the mechanical properties such as strength. The interlaminar shear strength is 13M
When it is less than Pa, the adhesiveness between the obtained fiber and resin cannot be said to be good, and it is not suitable for practical use as a composite material.

【００１２】本発明において、劣化度に上限があるの
は、劣化度を上げすぎると平均的分子量自体の低下が著
しくなり、強度が低下するからであり、場合によって
は、分子切断で発生したラジカルによる架橋反応もおこ
り延伸性の著しい低下につながる。従って、得られる繊
維の極限粘度は重要であって、少なくも１０以上、好ま
しくは１３以上であることが必要である。また、原材料
の重合体の極限粘度も少なくとも１０以上、好ましくは
１３以上さらに好ましくは１５以上である必要がある。In the present invention, the upper limit of the degree of deterioration is that if the degree of deterioration is increased too much, the average molecular weight itself is remarkably reduced and the strength is lowered. In some cases, radicals generated by molecular cleavage are generated. The cross-linking reaction also occurs and leads to a marked decrease in stretchability. Therefore, the intrinsic viscosity of the obtained fiber is important and needs to be at least 10 or more, preferably 13 or more. Also, the intrinsic viscosity of the raw material polymer must be at least 10 or more, preferably 13 or more, and more preferably 15 or more.

【００１３】本発明において劣化度を促進する手段とし
て、熱・機械的剪断・酸化・紫外線等のエネルギーや過
酸化物等の劣化促進剤を添加する、等の種々の手法が挙
げられるが基本的には、劣化させる程度が重要であっ
て、その作用は手法の選択にはよらない。基本的に推奨
される手法としては、酸化防止剤類を用いない事であ
り、そのためには溶解工程での条件の設計が非常に重要
となる。In the present invention, various means such as adding energy such as heat / mechanical shearing / oxidation / ultraviolet rays or a deterioration accelerating agent such as peroxide may be used as means for promoting the degree of deterioration. For this reason, the degree of deterioration is important, and its effect does not depend on the method selected. Basically, the recommended method is to use no antioxidants, and for that purpose the design of conditions in the dissolution process is very important.

【００１４】また、本特許により提供される接着性に優
れた高強度ポリエチレン繊維の延伸速度は、延伸後の繊
維を用いて、後に示す方法による延伸速度指数として特
定する事ができる。Further, the stretching speed of the high-strength polyethylene fiber having excellent adhesiveness provided by the present patent can be specified by using the stretched fiber as a stretching speed index by a method described later.

【００１５】以下に本明細書記載の特性値に関する測定
法および測定条件を説明する。 （延伸速度指数）本発明でいう延伸速度指数（ＥＦ）と
は、５０℃の温度に調節した無荷重時の長さ５０Ｃｃｍ
の糸サンプルに９ｇ／ｄの荷重を加える。２時間後およ
び２２時間後の試料の長さをそれぞれＬ１．Ｌ２（ｃ
ｍ）とし、ＥＦ（ｓｅｃ^-1）は次式で求めた。 ＥＦ′（ｓｅｃ^-1）＝（Ｌ２−Ｌ１）／（２０×３６０
０×５０） さらに次式に従いその測定に使用したサンプルのヤーン
デニール（Ｄ）及びその引っ張り弾性率（Ｅ）（その単
位はｇ／ｄである）により換算が必要で真の延伸速度指
数（ＤＩ）は次式で与えられる。単位は秒^-1で表す。 ＥＦ＝１０^B ×ＥＦ′ Ｂ＝（−６．５×１０^-4×Ｅ）−（１×１０^-5×Ｄ）＋
０．８３The measuring method and measuring conditions for the characteristic values described in this specification will be described below. (Stretching speed index) The stretching speed index (EF) referred to in the present invention means a length of 50 Ccm when no load is applied and adjusted to a temperature of 50 ° C.
A load of 9 g / d is applied to the yarn sample. The lengths of the samples after 2 hours and after 22 hours were respectively set to L1. L2 (c
m) and EF (sec ⁻¹ ) was calculated by the following equation. EF '(sec ^-1 ) = (L2-L1) / (20 × 360
0 × 50) Furthermore, conversion based on the yarn denier (D) of the sample used for the measurement and its tensile elastic modulus (E) (its unit is g / d) according to the following equation is necessary, and the true stretching speed index (DI ) Is given by the following equation. The unit is seconds- ¹ . EF = 10 ^B × EF ′ B = (− 6.5 × 10 ⁻⁴ × E) − (1 × 10 ⁻⁵ × D) +
0.83

【００１６】（強度・弾性率）本明細書での強度、弾性
率は、オリエンティック社製「テンシロン」を用い、試
料長２００ｍｍ、伸長速度１００％／分の条件で歪一応
力曲線を雰囲気温度２０℃、相対湿度６５％条件下で測
定し、曲線の破断点での応力を強度（ｇ／ｄ）、曲線の
原点付近の最大勾配を与える接線より弾性率（ｇ／ｄ）
を計算して求めた。なお、各値は１０回の測定値の平均
値を使用した。(Strength / Elastic Modulus) The strength and elastic modulus in the present specification are "tensilon" manufactured by Orientic Co., Ltd., and the strain-stress curve is measured under the conditions of a sample length of 200 mm and an elongation rate of 100% / min. Measured at 20 ° C and 65% relative humidity, the stress at the break point of the curve is strength (g / d), and the elastic modulus (g / d) is obtained from the tangent line that gives the maximum gradient near the origin of the curve
Was calculated and calculated. In addition, each value used the average value of the measured value of 10 times.

【００１７】（極限粘度）１３５℃のデカリンにてウベ
ローデ型毛細粘度管により、種々の希薄溶液の比粘度を
測定し、その粘度の濃度にたいするプロットの最小２乗
近似で得られる直線の原点への外挿点より極限粘度を測
定した。測定に際し、原料ポリマーのがパウダー状場合
はその形状のまま、パウダーが塊状であったり糸状サン
プルの場合は約５ｍｍ長にサンプルを分割または切断
し、ポリマーに対して１ｗｔ％の酸化防止剤（商品名
「ヨシノックスＢＨＴ」吉富製薬製）を添加し、１３５
℃で４時間撹拌溶解して測定溶液を調整した。(Intrinsic Viscosity) The specific viscosities of various dilute solutions were measured with decalin at 135 ° C. using an Ubbelohde-type capillary viscous tube, and the straight line to the origin of the straight line obtained by the least square approximation of the plot of the concentration of the viscosity was measured. The intrinsic viscosity was measured from the extrapolated points. In the measurement, if the raw material polymer is in the form of powder, the shape is kept as it is, and if the powder is a lump or a filamentous sample, the sample is divided or cut into about 5 mm length, and 1 wt% of the antioxidant (commercial Name "Yoshinox BHT" made by Yoshitomi Pharmaceutical Co., Ltd., and added 135
A measurement solution was prepared by stirring and dissolving at 4 ° C. for 4 hours.

【００１８】（層間せん断強度）繊維体積分率５０％に
処方した、試料繊維とエポキシ樹脂（商標名「エポン９
１０２Ａ」油化シェル社製）に対して、７６ｐｈｒの硬
化剤（商標名「エポン９１０２Ｂ」）及び１Ｐｈｒの促
進剤（商標名「エポン９１０２Ｃ」）を添加し、加熱・
加圧成形により、厚さ３ｍｍ、幅６ｍｍ、長さ１８ｍｍ
の直方体状の試料体を成形した。この成形体を、支点間
隔１２ｍｍ（１／ｈ＝４）、クロスヘッド速度１ｍｍ／
分の速度で曲げ応力を測定し、その最大応力値Ｐ（Ｋ
ｇ）と成形体の平均断面積Ａ（ｍｍ² ）から層間せん断
強度（ＩＬＳＳ）を求めた。 ＩＬＳＳ（ＭＰａ）＝９．８×３×Ｐ／４／Ａ(Interlaminar Shear Strength) A sample fiber and an epoxy resin (trade name "Epon 9") formulated to have a fiber volume fraction of 50%.
102A "manufactured by Yuka Shell Co., Ltd.), 76 phr of a curing agent (trade name" Epon 9102B ") and 1 Phr accelerator (trade name" Epon 9102C ") were added and heated.
By pressure molding, thickness 3mm, width 6mm, length 18mm
A rectangular parallelepiped sample body was molded. This molded product was subjected to a fulcrum interval of 12 mm (1 / h = 4) and a crosshead speed of 1 mm /
The bending stress is measured at the speed of minute, and the maximum stress value P (K
The interlaminar shear strength (ILSS) was determined from g) and the average cross-sectional area A (mm ² ) of the molded body. ILSS (MPa) = 9.8 × 3 × P / 4 / A

【００１９】（表面酸素および炭素の比率）島津製作所
製の装置「ＥＳＣＡ−８５０」を用い室温、約５×１０
^-6Ｐａの真空度条件および８ＫＶ３０ｍＡのフィラメン
ト加電圧条件で発生する励起Ｘ線のＭｇ−Ｋα線を使用
し得られるＥＳＣＡスペクトルの２８５ｅＶに補正され
た探索原子スペクトルＣ18の面積（Ｈ0 ）、および５３
２ｅＶ付近で得られる酸素原子スペクトルＯ18ピークの
面積（Ｈ0 ）を２．８５の感度係数で除した値の比より
算出した。具体的には次式で計算した。 表面酸素原子数／炭素原子数比（Ｏ／Ｃ）（％）＝１０
０×（Ｈ0 ／Ｈ0 ）／２．８５ なお、測定に先だって試料に付着の油剤類は十分に脱離
させた。(Ratio of Surface Oxygen and Carbon) Room temperature, about 5 × 10, using an apparatus “ESCA-850” manufactured by Shimadzu Corporation.
Area (H0) of the search atomic spectrum C18 corrected to 285 eV of the ESCA spectrum obtained by using Mg-Kα line of excited X-ray generated under the vacuum degree condition of ⁻⁶ Pa and the filament applied voltage condition of 8 KV30 mA, and 53
It was calculated from the ratio of the values obtained by dividing the area (H0) of the oxygen atom spectrum O18 peak obtained at around 2 eV by the sensitivity coefficient of 2.85. Specifically, it was calculated by the following formula. Surface oxygen atom number / carbon atom number ratio (O / C) (%) = 10
0 × (H0 /H0)/2.85 The oils adhering to the sample were sufficiently desorbed before the measurement.

【００２０】[0020]

【実施例】以下、実施例をもって本特許を説明する。 （実施例１〜３）極限粘度〔ηＡ〕が１８．５、主鎖炭
素１０００個あたり０．８個のメチル分岐を有する超高
分子量ポリエチレンを１０重量部とデカヒドロナフタレ
ン９０重量部を混合したスラリー状液体をスクリュー型
押し出し機（３０ｍｍφ）に供給した。この際、酸化防
止剤は用いなかった。EXAMPLES The present invention will be described below with reference to examples. (Examples 1 to 3) 10 parts by weight of an ultrahigh molecular weight polyethylene having an intrinsic viscosity [ηA] of 18.5 and 0.8 methyl branch per 1000 main chain carbons and 90 parts by weight of decahydronaphthalene were mixed. The slurry liquid was supplied to a screw type extruder (30 mmφ). At this time, no antioxidant was used.

【００２１】スクリュー内の押し出し条件をコントロー
ルする事により表１に示すように種々の極限粘度を有す
る高強度ポリエチレン繊維を作成した。各種条件で押し
出された溶解物は引き続いて１８０℃に調整した０．８
φの穴を３０個有する紡糸口金から押し出されゲル状フ
ィラメントは空気流で冷却され６０ｍ／分の速度で引き
取りローラーを通過し、引き続いて１２０℃に温度調節
された空気加熱オーブン中で３倍に延伸、巻取られた。
従って、巻取り速度は１８０ｍ／分であった。High-strength polyethylene fibers having various intrinsic viscosities as shown in Table 1 were prepared by controlling the extrusion conditions in the screw. The melt extruded under various conditions was subsequently adjusted to 180 ° C.
The gel-like filament extruded from the spinneret having 30 holes of φ was cooled by an air stream, passed through a take-off roller at a speed of 60 m / min, and then tripled in an air-heated oven temperature-controlled at 120 ° C. It was stretched and wound.
Therefore, the winding speed was 180 m / min.

【００２２】巻取られた部分延伸糸は、同じく１４５℃
に温度調節された空気加熱オーブンにて最終の延伸速度
３００ｍ／分の高速度で延伸され、破断が起こらない倍
率までの糸を試作した。表１に各実験での安定延伸可能
な到達延伸倍率（１段延伸倍率×２段延伸倍率）、及び
その倍率での諸物性（極限粘度・強度・弾性率・層間せ
ん断強度・延伸速度指数・Ｏ／Ｃ）をまとめる。The partially drawn yarn wound is the same at 145 ° C.
A yarn was drawn in a temperature-controlled air heating oven at a final drawing speed of 300 m / min at a high speed, and a yarn up to a ratio at which breakage did not occur was made as a trial. Table 1 shows the ultimate stretch ratio (1 stage stretch ratio x 2 stage stretch ratio) that allows stable stretching in each experiment, and the various physical properties at that ratio (intrinsic viscosity, strength, elastic modulus, interlayer shear strength, stretching speed index, etc.). O / C) are summarized.

【００２３】（実施例５〜９）極限粘度〔ηＡ〕が１
５．２であり、メチル分岐が主鎖１０００炭素あたり、
１．０個を有する超高分子量ポリエチレンを用いた他
は、実施例１−４と同一の条件で紡糸を行った。表１に
その結果をまとめる。実施例１−４に比較すると相対的
に強度は低下するものの、同様の傾向と好ましい結果が
得られた。(Examples 5 to 9) The intrinsic viscosity [ηA] was 1
5.2, the methyl branch is per 1000 carbons of the main chain,
Spinning was performed under the same conditions as in Examples 1-4, except that ultra high molecular weight polyethylene having 1.0 was used. The results are summarized in Table 1. Although the strength was relatively reduced as compared with Examples 1-4, a similar tendency and favorable results were obtained.

【００２４】（実施例９）極限粘度〔ηＡ〕が２０．０
であり、エチル分岐が主鎖１０００炭素あたり、０．３
個を有する超高分子量ポリエチレンを用いた他は、実施
例４と同一の条件で紡糸を行った。到達延伸倍率および
諸物性は、表１に示すように極めて優れた物であった。Example 9 Intrinsic viscosity [ηA] is 20.0
And the ethyl branch is 0.3 per 1000 carbons in the main chain.
Spinning was carried out under the same conditions as in Example 4, except that ultra high molecular weight polyethylene having a number of pieces was used. The ultimate draw ratio and various physical properties were extremely excellent as shown in Table 1.

【００２５】[0025]

【表１】 [Table 1]

【００２６】（比較例１〜３）実施例１、５、９とまっ
たく同一ポリマーおよび同一紡糸条件で紡糸を行った。
ただしポリマーと溶剤の混合物、ポリマーに対して１重
量％の酸化防止剤（商標名「ヨシノックスＢＨＴ」吉富
製薬（株）製）を添加した。得られた糸の延伸性および
到達可能物性を表２に示す。表のごとく、酸化防止剤に
より劣化が抑制された本実験例では、接着性の指標とな
る層間せん断強度も低くまた延伸性も悪く、かつ、強
度、弾性率も満足にいく値とはならない。この結果の悪
さは、押し出し後の極限粘度だけでは説明できないの
は、例えば、実施例２−４と比較例２−４の比較におい
て明らかであり、分子量の適度の劣化が繊維の接着性と
延伸性を極めて改良することを示すものである。(Comparative Examples 1 to 3) Spinning was performed under the same polymer and spinning conditions as in Examples 1, 5, and 9.
However, a 1% by weight antioxidant (trade name "Yoshinox BHT" manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the mixture of the polymer and the solvent. Table 2 shows the drawability and reachable physical properties of the obtained yarn. As shown in the table, in the present experimental example in which the deterioration was suppressed by the antioxidant, the interlaminar shear strength, which is an index of adhesiveness, was low, the stretchability was poor, and the strength and elastic modulus were not satisfactory values. The reason why this poor result cannot be explained only by the intrinsic viscosity after extrusion is clear in, for example, a comparison between Example 2-4 and Comparative Example 2-4. It shows that the property is extremely improved.

【００２７】（比較例４〜５）実施例４および、８とま
ったく同一の製糸条件で糸を作成した。ただしポリマー
と溶剤の混合物をスクリューに供給するとき、常圧の酸
素存在下にする点のみ変更した。酸化防止剤は用いなか
った。表２に示すように、そこそこの接着性は得られた
ものの、強度、弾性率が低かった。劣化の度合が高すぎ
たと考えられる。(Comparative Examples 4 to 5) Threads were prepared under the same spinning conditions as in Examples 4 and 8. However, when supplying the mixture of the polymer and the solvent to the screw, the only difference was that the presence of oxygen under normal pressure was changed. No antioxidant was used. As shown in Table 2, although moderate adhesiveness was obtained, the strength and elastic modulus were low. It is considered that the degree of deterioration was too high.

【００２８】（比較例６）比較例５により得られた繊維
をコロナ処理することにより接着性を付与する事を試み
た、処理速度は２０ｍ／分と低速度であり、使用電極の
電極密度は２０ＫＷ／ｃｍ² で常圧大気中で処理を行っ
た。得られた糸の強度・弾性率はそれぞれ２８ｇ／ｄ、
１００２ｇ／ｄであり、若干の低下が見られた。層間せ
ん断強度は１９ＭＰａと良好であったり、Ｏ／Ｃは６％
であった。また、糸の延伸速度指数は２．６×１０^-6と
処理糸前と変化しなかった。(Comparative Example 6) An attempt was made to impart adhesiveness by subjecting the fiber obtained in Comparative Example 5 to corona treatment. The treatment speed was as low as 20 m / min, and the electrode density of the electrode used was The treatment was carried out in the atmospheric pressure at 20 kW / cm ² . The obtained yarn has a strength and elastic modulus of 28 g / d, respectively.
It was 1002 g / d, and a slight decrease was observed. Interlaminar shear strength is as good as 19 MPa, and O / C is 6%
Met. The drawing speed index of the yarn was 2.6 × 10 ⁻⁶ , which was unchanged from that before the treated yarn.

【００２９】[0029]

【表２】 [Table 2]

【００３０】[0030]

【発明の効果】本発明は、コロナ処理などの特別な表面
処理を行うことなく実用レベルに十分の接着性を有する
高強度ポリエチレン繊維を、極めて高い延伸速度で得る
事が可能であり、コストパフォーマンスに優れた本繊維
の活用範囲をさらに広げるものである。INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a high-strength polyethylene fiber having a sufficient adhesiveness to a practical level at an extremely high drawing speed without performing a special surface treatment such as corona treatment, and the cost performance is improved. This will further expand the range of utilization of this excellent fiber.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 コース メンケ オランダ国 6229 イー・エー マースト リヒト、ヤクエス シーゼダマイン 13 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor's course Menke Netherlands 6229 EA Maastricht, Yakussiezedamine 13

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 エチレン成分を主体とするポリエチレン
繊維であり、その強度が２８ｇ／ｄ以上、弾性率が７０
０ｇ／ｄ以上であり、かつ、その繊維の表面における酸
素原子数と炭素原子数の比率が５％未満であり、かつ、
その繊維を用いて得られる層間せん断強度が１３ＭＰａ
以上であることを特徴とする接着性に優れた高強度ポリ
エチレン繊維。1. A polyethylene fiber mainly comprising an ethylene component, having a strength of 28 g / d or more and an elastic modulus of 70.
0 g / d or more, and the ratio of the number of oxygen atoms and the number of carbon atoms on the surface of the fiber is less than 5%, and
Interlaminar shear strength obtained using the fiber is 13 MPa
The high-strength polyethylene fiber excellent in adhesiveness characterized by the above. 【請求項２】 特許請求の範囲の請求項１項の繊維であ
り、なおかつ、その繊維の延伸速度指数（ＥＦ）が次式
を満足する事を特徴とする高強度ポリエチレン繊維。 ＥＦ≧１０^A Ａ＝−２．７５−０．２５〔ηＢ〕2. A high-strength polyethylene fiber, which is the fiber according to claim 1 and has a drawing speed index (EF) satisfying the following equation. EF ≧ 10 ^A A = −2.75−0.25 [ηB] 【請求項３】 極限粘度〔ηＡ〕が１０以上の超高分子
量ポリエチレン５重量部乃至５０重量部と、溶剤９５重
量部乃至５０重量部の混合物を加熱溶解し、押し出して
得られた半完成糸を１０倍以上の延伸倍率にて延伸して
得られた糸が、少なくとも２８ｇ／ｄ以上の強度と、７
００ｇ／ｄ以上の弾性率を有し、かつ、該繊維状態での
極限粘度〔ηＢ〕が次式で定義される範囲にあり、層間
せん断強度が１３ＭＰａ以上であることを特徴とする高
強度ポリエチレン繊維の製造方法。 ０．７×〔ηＡ〕≦〔ηＢ〕≦０．９×〔ηＡ〕3. A semi-finished yarn obtained by heat-melting and extruding a mixture of 5 to 50 parts by weight of ultrahigh molecular weight polyethylene having an intrinsic viscosity [ηA] of 10 or more and 95 to 50 parts by weight of a solvent. The yarn obtained by drawing at a draw ratio of 10 times or more has a strength of at least 28 g / d,
A high-strength polyethylene having an elastic modulus of 00 g / d or more, an intrinsic viscosity [ηB] in the fiber state within a range defined by the following equation, and an interlaminar shear strength of 13 MPa or more. Fiber manufacturing method. 0.7 × [ηA] ≦ [ηB] ≦ 0.9 × [ηA]