JP2006009205A - Conjugate fiber made of polyoxymethylene resin - Google Patents
Conjugate fiber made of polyoxymethylene resin Download PDFInfo
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- JP2006009205A JP2006009205A JP2004189480A JP2004189480A JP2006009205A JP 2006009205 A JP2006009205 A JP 2006009205A JP 2004189480 A JP2004189480 A JP 2004189480A JP 2004189480 A JP2004189480 A JP 2004189480A JP 2006009205 A JP2006009205 A JP 2006009205A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/34—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated alcohols, acetals or ketals as the major constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/18—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by combining fibres, filaments, or yarns, having different shrinkage characteristics
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Abstract
Description
本発明は、特定の2種のポリオキシメチレン共重合体で芯と鞘が形成され、優れた結節強さ保持率を有する複合繊維に関する。 The present invention relates to a composite fiber having a core and a sheath formed of two specific polyoxymethylene copolymers and having excellent knot strength retention.
ポリオキシメチレン樹脂は、主としてオキシメチレン単位の繰り返しからなるポリマー骨格を有する重合体であり、結晶化度が高く、剛性、強度、耐薬品性、耐溶剤性等の点で優れていることが知られている。そして、結晶化速度が速く、成形サイクルが速いことから、主に射出成形材料として自動車、電気機器等の機構部品の分野で幅広く使われている。更に、ポリオキシメチレン樹脂は高結晶性であることから、延伸による配向結晶化により高強度、高弾性体となることが学術的に知られている(例えば、非特許文献1参照)。 The polyoxymethylene resin is a polymer having a polymer skeleton mainly composed of repeating oxymethylene units, and has a high degree of crystallinity and is excellent in terms of rigidity, strength, chemical resistance, solvent resistance, etc. It has been. Since the crystallization speed is high and the molding cycle is fast, it is widely used mainly in the field of mechanical parts such as automobiles and electrical equipment as injection molding materials. Furthermore, since polyoxymethylene resin is highly crystalline, it is known academically that it becomes a high-strength, high-elastic body by orientation crystallization by stretching (for example, see Non-Patent Document 1).
このようにポリオキシメチレン樹脂は優れた諸特性を有する樹脂材料であり、これを繊維用の素材として利用することに大きな期待が寄せられている。 As described above, the polyoxymethylene resin is a resin material having excellent properties, and there is a great expectation for using this as a raw material for fibers.
しかしながら、ポリオキシメチレン樹脂はその結晶化特性に起因してこれを繊維に加工することが難しく、また、ポリオキシメチレン樹脂からなる繊維は延伸による配向結晶化により優れた強度が発現するものの、結節強さがやや低く、実用化のためにはその改善が必要と考えられるものであった。
本発明の目的は上記のような課題を解決し、ポリオキシメチレン樹脂が有する優れた諸特性を有すると共に、高い結節強さ保持率を有する繊維を提供することにある。 An object of the present invention is to solve the above-mentioned problems and to provide a fiber having excellent properties of a polyoxymethylene resin and having a high knot strength retention.
本発明者らは、上記目的を達成するために鋭意研究した結果、溶融紡糸法でポリオキシメチレン樹脂からなる繊維を製造するにあたり、芯と鞘からなる複合繊維とし、芯と鞘をそれぞれ異なる特定のポリオキシメチレン共重合体で形成することにより、溶融紡糸における加工性に優れ、得られる複合繊維は高強度、高弾性率で且つ結節強さに優れることを見出し、本発明に到達した。 As a result of diligent research to achieve the above object, the inventors of the present invention have made a composite fiber composed of a core and a sheath in the production of a fiber composed of a polyoxymethylene resin by a melt spinning method. By forming the polyoxymethylene copolymer, the processability in melt spinning was excellent, and the resulting composite fiber was found to have high strength, high elastic modulus and excellent knot strength, and reached the present invention.
即ち本発明は、主としてオキシメチレン単位の繰り返しからなるポリマー鎖中にオキシメチレン単位100mol当たり0.1〜7.5molの下記一般式(1)で表されるオキシアルキレン単位を含み、かつメルトインデックス(190℃、荷重2160g)が1〜100g/10分であるポリオキシメチレン共重合体(a)からなる芯と、
主としてオキシメチレン単位の繰り返しからなるポリマー鎖中にオキシメチレン単位100mol当たり0.3〜8molの下記一般式(1)で表されるオキシアルキレン単位を含み、かつメルトインデックス(190℃、荷重2160g)が1〜100g/10分であるポリオキシメチレン共重合体(b)からなる鞘とで形成され、
且つポリオキシメチレン共重合体(a)とポリオキシメチレン共重合体(b)とが、それぞれの結晶融解温度をTma(℃)及びTmb(℃)とした時、下式(2)を満たすものであることを特徴とする複合繊維である。
That is, the present invention includes a polymer chain mainly composed of repeating oxymethylene units containing 0.1 to 7.5 mol of oxyalkylene units represented by the following general formula (1) per 100 mol of oxymethylene units, and a melt index (190 ° C., A core made of a polyoxymethylene copolymer (a) having a load of 2160 g) of 1 to 100 g / 10 min;
The polymer chain mainly composed of repeating oxymethylene units contains 0.3 to 8 mol of oxyalkylene units represented by the following general formula (1) per 100 mol of oxymethylene units, and has a melt index (190 ° C., load 2160 g) of 1 to 1. Formed with a sheath made of polyoxymethylene copolymer (b) that is 100 g / 10 min,
The polyoxymethylene copolymer (a) and the polyoxymethylene copolymer (b) satisfy the following formula (2) when their crystal melting temperatures are Tma (° C.) and Tmb (° C.), respectively. It is a composite fiber characterized by being.
(式中、R1、R2は、水素、炭素数1〜8のアルキル基、炭素数1〜8のアルキル基を有する有機基、フェニル基、フェニル基を有する有機基から選ばれ、R1、R2は同一でも異なっていてもよい。mは2〜6の整数を示す。)
Tmb<Tma−3 (2)
(Tma(℃) ;ポリオキシメチレン共重合体(a)の結晶融解温度、Tmb(℃) ;ポリオキシメチレン共重合体(b)の結晶融解温度)
(Wherein, R 1, R 2 is hydrogen, an alkyl group having 1 to 8 carbon atoms, an organic group having an alkyl group of 1 to 8 carbon atoms, a phenyl group, selected from an organic group having a phenyl group, R 1 R 2 may be the same or different, and m represents an integer of 2 to 6.)
Tmb <Tma-3 (2)
(Tma (° C.); crystal melting temperature of polyoxymethylene copolymer (a), Tmb (° C.); crystal melting temperature of polyoxymethylene copolymer (b))
本発明によりポリオキシメチレン樹脂が有する優れた諸特性を有すると共に、高い結節強さ保持率を有する繊維を得ることができ、強度の高い、織布・不織布等の繊維集合体を得ることが可能となる。 According to the present invention, fibers having excellent properties possessed by polyoxymethylene resin and having high knot strength retention can be obtained, and fiber assemblies such as woven fabric and nonwoven fabric having high strength can be obtained. It becomes.
以下、本発明を詳細に説明する。本発明の複合繊維は、前述した如く、2種類のそれぞれ異なる特定のポリオキシメチレン共重合体で形成された芯と鞘からなることを特徴とする。尚、本発明における繊維の定義にはフィラメントと称されるものも包含する。 Hereinafter, the present invention will be described in detail. As described above, the conjugate fiber of the present invention is characterized by comprising a core and a sheath formed of two different specific polyoxymethylene copolymers. In addition, what is called a filament is included in the definition of the fiber in this invention.
本発明の複合繊維において、芯部に用いるポリオキシメチレン共重合体(a)は、主としてオキシメチレン単位の繰り返しからなるポリマー鎖中にオキシメチレン単位100mol当たり0.1〜7.5molの前記一般式(1)で表されるオキシアルキレン単位を含み、かつメルトインデックス(190℃、荷重2160g)が1〜100g/10分のものである。芯部に使用するかかるポリオキシメチレン共重合体(a)において、一般式(1)で表されるオキシアルキレン単位の割合は、好ましくはオキシメチレン単位100mol当たり0.5〜6mol、特に好ましくはオキシメチレン単位100mol当たり1.0〜5molである。 In the composite fiber of the present invention, the polyoxymethylene copolymer (a) used for the core is composed of 0.1 to 7.5 mol of the general formula (1) per 100 mol of oxymethylene units in the polymer chain mainly composed of repeating oxymethylene units. The melt index (190 ° C., load 2160 g) is 1 to 100 g / 10 min. In the polyoxymethylene copolymer (a) used for the core, the ratio of the oxyalkylene unit represented by the general formula (1) is preferably 0.5 to 6 mol, particularly preferably oxymethylene unit per 100 mol of oxymethylene unit. It is 1.0-5 mol per 100 mol.
本発明においては、芯部を形成するポリオキシメチレン共重合体(a)と鞘部を形成するポリオキシメチレン共重合体(b)の結晶融解温度に特定の温度差を持たせることが重要であり、このためにはポリオキシメチレン共重合体(a)及び(b)に導入するオキシアルキレン単位の量を相対的に調整する必要がある。ポリオキシメチレン共重合体(a)に導入するオキシアルキレン単位の割合が上記範囲を超えて多すぎる場合は結晶融解温度が低いものになり、鞘部を形成するポリオキシメチレン共重合体(b)との結晶融解温度差を生じさせることが困難になり、結節強度が低下してしまう問題がある。一方、鞘部を形成するポリオキシメチレン共重合体(b)に導入するオキシアルキレン単位の割合を後述する範囲を超えて過大量にすれば結晶融解温度は更に低いものになり、ポリオキシメチレン共重合体(a)との結晶融解温度差を生じさせることは可能であるが、この場合は、芯部、鞘部ともにオキシアルキレン単位の割合が過大なポリオキシメチレン共重合体で形成されることになり、最終的に得られる繊維の耐熱性や延伸後の強度が低くなるという問題がある。逆にポリオキシメチレン共重合体(a)に導入するオキシアルキレン単位の割合が上記範囲よりも少なすぎる場合は、熱安定性が劣るものとなり、繊維への加工性が低下する。 In the present invention, it is important to give a specific temperature difference between the crystal melting temperatures of the polyoxymethylene copolymer (a) forming the core and the polyoxymethylene copolymer (b) forming the sheath. For this purpose, it is necessary to relatively adjust the amount of oxyalkylene units introduced into the polyoxymethylene copolymers (a) and (b). When the proportion of the oxyalkylene unit introduced into the polyoxymethylene copolymer (a) exceeds the above range, the crystal melting temperature becomes low, and the polyoxymethylene copolymer (b) forming the sheath part There is a problem that it becomes difficult to cause a difference in the crystal melting temperature between the nodule and the knot strength. On the other hand, if the proportion of the oxyalkylene unit introduced into the polyoxymethylene copolymer (b) forming the sheath exceeds the range described later, the crystal melting temperature becomes even lower, and the polyoxymethylene copolymer becomes lower. Although it is possible to cause a crystal melting temperature difference with the polymer (a), in this case, the core and the sheath must be formed of a polyoxymethylene copolymer in which the ratio of oxyalkylene units is excessive. Thus, there is a problem that the heat resistance of the finally obtained fiber and the strength after stretching are lowered. On the contrary, when the ratio of the oxyalkylene unit introduced into the polyoxymethylene copolymer (a) is too smaller than the above range, the thermal stability is inferior and the processability to the fiber is lowered.
また、ポリオキシメチレン共重合体(a)はメルトインデックス(MI)が1.2〜90g/10分のものが好ましく、特に好ましくは1.5〜80g/10分である。メルトインデックス(MI)が過小のポリオキシメチレン共重合体(a)では、溶融粘度が高くなり過ぎるために紡糸時の負荷が増大し押出しが困難となる。メルトインデックス(MI)が過大になると、樹脂のドローダウン等のため、フィラメント製造が不安定となり、また分子量低下に伴いフィラメントの強度も低いものとなる。なお、本発明において使用するポリオキシメチレン共重合体のメルトインデックス(MI)は、ASTM D-1238に従い、190℃、2160gの荷重下で測定されるものであり、以下、同様である。 The polyoxymethylene copolymer (a) preferably has a melt index (MI) of 1.2 to 90 g / 10 min, particularly preferably 1.5 to 80 g / 10 min. In the polyoxymethylene copolymer (a) having an excessively low melt index (MI), the melt viscosity becomes too high, so that the load at the time of spinning increases and extrusion becomes difficult. If the melt index (MI) is excessive, the filament production becomes unstable due to resin drawdown or the like, and the strength of the filament becomes low as the molecular weight decreases. The melt index (MI) of the polyoxymethylene copolymer used in the present invention is measured according to ASTM D-1238 under a load of 190 ° C. and 2160 g, and the same applies hereinafter.
次に、本発明の複合繊維において、鞘部に用いるポリオキシメチレン共重合体(b)は、主としてオキシメチレン単位の繰り返しからなるポリマー鎖中にオキシメチレン単位100mol当たり0.3〜8molの前記一般式(1)で表されるオキシアルキレン単位を含み、かつメルトインデックス(190℃、荷重2160g)が1〜100g/10分のものである。鞘部に使用するかかるポリオキシメチレン共重合体(b)において、一般式(1)で表されるオキシアルキレン単位の割合は、好ましくはオキシメチレン単位100mol当たり1.1〜7.1mol、特に好ましくはオキシメチレン単位100mol当たり1.6〜5.6molである。 Next, in the conjugate fiber of the present invention, the polyoxymethylene copolymer (b) used for the sheath is mainly 0.3 to 8 mol of the above general formula (100 mol per 100 mol of oxymethylene units in the polymer chain consisting of repeating oxymethylene units). The oxyalkylene unit represented by 1) is included, and the melt index (190 ° C., load 2160 g) is 1 to 100 g / 10 min. In such a polyoxymethylene copolymer (b) used for the sheath, the proportion of the oxyalkylene unit represented by the general formula (1) is preferably 1.1 to 7.1 mol, particularly preferably oxymethylene, per 100 mol of oxymethylene units. It is 1.6 to 5.6 mol per 100 mol unit.
鞘部を構成するポリオキシメチレン共重合体(b)のオキシアルキレン単位の割合が少なすぎる場合は結晶融解温度が高いものとなり、芯部を形成するポリオキシメチレン共重合体(a)のオキシアルキレン単位の割合を調整しても芯部と鞘部の結晶融解温度を所望の温度差の範囲に調整することが極めて困難となり、本発明の効果である優れた結節強度が得られなくなる問題がある。また、芯部を形成するポリオキシメチレン共重合体(a)のオキシアルキレン単位の割合を、前記範囲を超えて極小量に調整することにより結晶融解温度が一層高いものを調製し、鞘部を構成するポリオキシメチレン共重合体(b)との所望の結晶融解温度差が達成できたとしても、この場合は、芯部、鞘部ともにオキシアルキレン単位の割合が過小のポリオキシメチレン共重合体で形成されることになり、熱安定性、紡糸性、延伸性が低下して加工性を損なうばかりでなく、所望の物性が得られないという問題がある。逆にポリオキシメチレン共重合体(b)に導入するオキシアルキレン単位の割合が多すぎる場合は、最終的に得られる繊維の耐熱性や延伸後の強度が低くなるという問題がある。 When the proportion of the oxyalkylene unit of the polyoxymethylene copolymer (b) constituting the sheath is too small, the crystal melting temperature becomes high, and the oxyalkylene of the polyoxymethylene copolymer (a) forming the core portion Even if the ratio of the unit is adjusted, it becomes extremely difficult to adjust the crystal melting temperature of the core and the sheath within a desired temperature difference range, and there is a problem that the excellent knot strength that is the effect of the present invention cannot be obtained. . Further, by adjusting the ratio of the oxyalkylene unit of the polyoxymethylene copolymer (a) forming the core part to a minimum amount exceeding the above range, the one having a higher crystal melting temperature is prepared, and the sheath part is prepared. Even if the desired crystal melting temperature difference with the polyoxymethylene copolymer (b) can be achieved, in this case, the polyoxymethylene copolymer in which the ratio of oxyalkylene units is too small in both the core and the sheath As a result, the thermal stability, spinnability and stretchability are deteriorated, and not only the processability is impaired, but also the desired physical properties cannot be obtained. On the contrary, when the ratio of the oxyalkylene unit introduced into the polyoxymethylene copolymer (b) is too large, there is a problem that the heat resistance of the finally obtained fiber and the strength after stretching are lowered.
また、ポリオキシメチレン共重合体(b)のメルトインデックス(MI)は1.2〜90g/10分のものが好ましく、特に好ましくは1.5〜80g/10分である。ポリオキシメチレン共重合体(b)のメルトインデックス(MI)が過小の場合の挙動、過大の場合の挙動は、前記ポリオキシメチレン共重合体(a)の場合と同様である。 The melt index (MI) of the polyoxymethylene copolymer (b) is preferably from 1.2 to 90 g / 10 minutes, particularly preferably from 1.5 to 80 g / 10 minutes. The behavior of the polyoxymethylene copolymer (b) when the melt index (MI) is too small and the behavior when it is too large are the same as those of the polyoxymethylene copolymer (a).
本発明の複合繊維は、更に、芯部を構成するポリオキシメチレン共重合体(a)と鞘部を構成するポリオキシメチレン共重合体(b)とが、それぞれの結晶融解温度をTma(℃)、Tmb(℃)とした時、下式(2)を満たしていることが必要である。 In the conjugate fiber of the present invention, the polyoxymethylene copolymer (a) constituting the core part and the polyoxymethylene copolymer (b) constituting the sheath part each have a crystal melting temperature of Tma (° C. ), Tmb (° C.), it is necessary to satisfy the following formula (2).
Tmb<Tma−3 (2)
(Tma(℃) ;ポリオキシメチレン共重合体(a)の結晶融解温度、Tmb(℃) ;ポリオキシメチレン共重合体(b)の結晶融解温度)
ここで、結晶融解温度はDSCにより10℃/minで昇温させた時の結晶融解ピークのピーク温度として測定される温度である。
Tmb <Tma-3 (2)
(Tma (° C.); crystal melting temperature of polyoxymethylene copolymer (a), Tmb (° C.); crystal melting temperature of polyoxymethylene copolymer (b))
Here, the crystal melting temperature is a temperature measured as the peak temperature of the crystal melting peak when the temperature is raised by DSC at 10 ° C./min.
かかるポリオキシメチレン共重合体の結晶融解温度は、該共重合体を構成する前記一般式(1)で表されるオキシアルキレン単位の割合によって調整することができ、具体的にはオキシアルキレン単位の割合を増加させることにより、得られるポリオキシメチレン共重合体の結晶融解温度を低下させることができる。この挙動に基づき、芯部を形成するポリオキシメチレン共重合体(a)と鞘部を形成するポリオキシメチレン共重合体(b)のオキシアルキレン単位の割合を各々前述した範囲内で調整することにより、具体的にはポリオキシメチレン共重合体(b)のオキシアルキレン単位の割合をポリオキシメチレン共重合体(a)のオキシアルキレン単位の割合よりも適度に増加させたものにすることにより、上記(2)式で示される結晶融解温度の関係を満たすことができる。 The crystal melting temperature of such a polyoxymethylene copolymer can be adjusted by the ratio of the oxyalkylene unit represented by the general formula (1) constituting the copolymer. By increasing the ratio, the crystal melting temperature of the resulting polyoxymethylene copolymer can be lowered. Based on this behavior, the ratio of the oxyalkylene units of the polyoxymethylene copolymer (a) forming the core and the polyoxymethylene copolymer (b) forming the sheath should be adjusted within the above-mentioned ranges. Specifically, by making the ratio of the oxyalkylene unit of the polyoxymethylene copolymer (b) moderately increased from the ratio of the oxyalkylene unit of the polyoxymethylene copolymer (a), The relationship of the crystal melting temperature represented by the above formula (2) can be satisfied.
このようにオキシアルキレン単位の割合を変えて結晶融解温度を調整したポリオキシメチレン共重合体(a)とポリオキシメチレン共重合体(b)を使用することにより、芯部と鞘部の分子配向状態の高次構造に傾斜を持たせた複合繊維とすることができ、特に鞘部を形成するポリオキシメチレン共重合体(b)の特性が調整されることにより結節伸度が高められ、結果として、元の強度に対する結節強さの割合として算出される結節強さ保持率が高くなる。結晶融解温度の関係が(2)式を満たさないポリオキシメチレン共重合体(a)とポリオキシメチレン共重合体(b)とからなる複合繊維では、高い結節強さ保持率を得ることが困難である。この観点から、更に好ましい複合繊維は、結晶融解温度が下記(3)式を満たすポリオキシメチレン共重合体(a)とポリオキシメチレン共重合体(b)とからなるものである。 By using the polyoxymethylene copolymer (a) and the polyoxymethylene copolymer (b) in which the crystal melting temperature is adjusted by changing the ratio of the oxyalkylene units in this way, the molecular orientation of the core and the sheath is achieved. It is possible to obtain a composite fiber having an inclined state higher-order structure, and in particular, by adjusting the characteristics of the polyoxymethylene copolymer (b) forming the sheath, the nodular elongation is increased, and the result As a result, the nodule strength retention rate calculated as a ratio of the nodule strength to the original strength increases. It is difficult to obtain a high knot strength retention in the composite fiber composed of the polyoxymethylene copolymer (a) and the polyoxymethylene copolymer (b) whose crystal melting temperature does not satisfy the formula (2). It is. From this viewpoint, a more preferable composite fiber is composed of a polyoxymethylene copolymer (a) and a polyoxymethylene copolymer (b) whose crystal melting temperature satisfies the following formula (3).
Tmb<Tma−10 (3)
本発明で使用する上記の如きポリオキシメチレン共重合体(a)及び(b)の製造方法は特に限定されるものではなく、一般的にはトリオキサンとコモノマーである環状エーテル化合物或いは環状ホルマール化合物とを、主としてカチオン重合触媒を用いて塊状重合させる方法で得ることができる。重合装置としては、バッチ式、連続式等の公知の装置が何れも使用できる。ここで、前述した一般式(1)で表されるオキシアルキレン単位の導入割合は、共重合させるコモノマーの量により、また、メルトインデックス(MI)は、重合時に使用する連鎖移動剤、例えばメチラール等の添加量により調整することができる。
Tmb <Tma-10 (3)
The production method of the polyoxymethylene copolymers (a) and (b) as described above used in the present invention is not particularly limited, and in general, trioxane and a cyclic ether compound or cyclic formal compound which is a comonomer Can be obtained by a bulk polymerization method mainly using a cationic polymerization catalyst. As the polymerization apparatus, any known apparatus such as a batch system or a continuous system can be used. Here, the introduction ratio of the oxyalkylene unit represented by the general formula (1) described above depends on the amount of comonomer to be copolymerized, and the melt index (MI) is a chain transfer agent used at the time of polymerization, such as methylal. It can adjust with the addition amount of.
コモノマーとして用いられる環状エーテル化合物或いは環状ホルマール化合物としては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、オキセタン、テトラヒドロフラン、トリオキセパン、1,3−ジオキソラン、プロピレングリコールホルマール、ジエチレングリコールホルマール、トリエチレングリコールホルマール、1,4−ブタンジオールホルマール、1,5−ペンタンジオールホルマール、1,6−ヘキサンジオールホルマール等が挙げられ、その中でもエチレンオキシド、1,3−ジオキソラン、ジエチレングリコールホルマール、1,4−ブタンジオールホルマールが好ましい。また、コモノマーの重合によって形成される一般式(1)で表されるオキシアルキレン単位としては、オキシエチレン、オキシトリメチレン、オキシテトラメチレンが好ましい。また、本発明に使用するポリオキシメチレン共重合体は、分岐形成成分や多官能成分を共重合することにより分岐構造又は架橋構造を導入したものであってもよい。また、本発明で使用するポリオキシメチレン共重合体(a)と(b)とで、その製造に用いる上記コモノマーは同一でも異なっていてもよく、その重合の結果とし形成される前記一般式(1)で表されるオキシアルキレン単位も同一でも異なっていてもよい。 Examples of cyclic ether compounds or cyclic formal compounds used as comonomer include ethylene oxide, propylene oxide, butylene oxide, oxetane, tetrahydrofuran, trioxepane, 1,3-dioxolane, propylene glycol formal, diethylene glycol formal, triethylene glycol formal, 1,4- Examples include butanediol formal, 1,5-pentanediol formal, 1,6-hexanediol formal, and among these, ethylene oxide, 1,3-dioxolane, diethylene glycol formal, and 1,4-butanediol formal are preferable. The oxyalkylene unit represented by the general formula (1) formed by comonomer polymerization is preferably oxyethylene, oxytrimethylene, or oxytetramethylene. Further, the polyoxymethylene copolymer used in the present invention may be one in which a branched structure or a crosslinked structure is introduced by copolymerizing a branch forming component or a polyfunctional component. In the polyoxymethylene copolymers (a) and (b) used in the present invention, the comonomer used for the production thereof may be the same or different, and the general formula ( The oxyalkylene units represented by 1) may be the same or different.
本発明において使用するポリオキシメチレン共重合体(a)及び(b)において、かかるコモノマーによって形成される前記一般式(1)で表されるオキシアルキレン単位はポリオキシメチレン共重合体の分子鎖中に極力均一に分散していることが好ましく、前記一般式(1)で表されるオキシアルキレン単位が2個以上連鎖したものの割合は、オキシアルキレン単位全体の5mol%以下であるのが好ましい。 In the polyoxymethylene copolymers (a) and (b) used in the present invention, the oxyalkylene unit represented by the general formula (1) formed by such a comonomer is in the molecular chain of the polyoxymethylene copolymer. It is preferable that the oxyalkylene unit represented by the general formula (1) is preferably 5 mol% or less of the whole oxyalkylene unit.
重合によって得たポリオキシメチレン共重合体は、触媒の失活化処理、未反応モノマーの除去、重合体の洗浄、乾燥、不安定末端部の安定化処理等を行った後、更に各種安定剤の配合による安定化処理等を行って、実用に供される。代表的な安定剤としては、ヒンダードフェノール系化合物、窒素含有化合物、アルカリ或いはアルカリ土類金属の水酸化物、無機塩、カルボン酸塩等を挙げることができる。 The polyoxymethylene copolymer obtained by polymerization is subjected to catalyst deactivation treatment, removal of unreacted monomers, polymer washing, drying, stabilization of unstable terminal portions, etc., and various stabilizers. Stabilization treatment by blending is performed for practical use. Typical stabilizers include hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, carboxylates, and the like.
更に、本発明で使用するポリオキシメチレン共重合体には、必要に応じて、熱可塑性樹脂に対する一般的な添加剤、例えば染料、顔料等の着色剤、滑剤、核剤、離型剤、帯電防止剤、界面活性剤、或いは有機高分子材料、無機または有機のフィラメント状、板状、粉粒状の充填剤等の1種または2種以上を、本発明の目的を阻害しない範囲で添加することができる。 Furthermore, the polyoxymethylene copolymer used in the present invention may be added to general additives for thermoplastic resins, for example, coloring agents such as dyes and pigments, lubricants, nucleating agents, release agents, charging agents, if necessary. One or two or more of an inhibitor, a surfactant, an organic polymer material, an inorganic or organic filament, plate, or granular filler is added within a range that does not impair the object of the present invention. Can do.
次に、上記の如きポリオキシメチレン共重合体(a)及び(b)からなる本発明の複合繊維の製造方法について説明する。 Next, the manufacturing method of the composite fiber of this invention which consists of the above polyoxymethylene copolymers (a) and (b) is demonstrated.
本発明の複合繊維は、前述した2種類のポリオキシメチレン共重合体(a)及び(b)を用い、これを二台の押出機等で別々に可塑化し、複合紡糸ダイにてポリオキシメチレン共重合体(a)を芯部にポリオキシメチレン共重合体(b)を鞘部となるよう溶融紡糸することにより得ることができる。ここで用いる溶融紡糸装置の構成は特に限定されるものではなく、例えば、二台の一軸またはニ軸の押出機、ギヤポンプ、複合紡糸用吐出ノズルから構成される紡糸装置と、吐出ノズルから吐出された溶融ポリマーを繊維状に引き取り、これを巻き取るためのローラーとによって構成することができる。 The composite fiber of the present invention uses the above-mentioned two types of polyoxymethylene copolymers (a) and (b), which are separately plasticized by two extruders or the like, and are polyoxymethylene by a composite spinning die. The copolymer (a) can be obtained by melt-spinning the polyoxymethylene copolymer (b) as a core and a sheath as the sheath. The structure of the melt spinning apparatus used here is not particularly limited. For example, a spinning apparatus including two uniaxial or biaxial extruders, a gear pump, and a composite spinning discharge nozzle, and a discharge from the discharge nozzle. The melted polymer can be taken up into a fibrous form and constituted by a roller for winding it.
原料であるポリオキシメチレン共重合体(a)及び(b)は、このような溶融紡糸装置において溶融され、吐出ノズルから繊維状に吐出されて引き取られ、ローラーに巻き取られる。 The raw material polyoxymethylene copolymers (a) and (b) are melted in such a melt spinning apparatus, discharged from a discharge nozzle in a fiber shape, taken up, and wound around a roller.
この時、吐出ノズルから吐出される繊維状物を140〜250℃の雰囲気温度で加熱しながら引き取ることが望ましい。加熱する雰囲気温度が140℃未満では繊維の固化速度が速く、生産性が劣るものになると共に、高延伸倍率での延伸が可能な繊維を得るのが困難になり、高強度、高弾性率の繊維を得るのが難しくなる。一方、雰囲気温度が250℃以上では、繊維が十分に固化しないままローラーに巻き取られることになり、操作性が劣るものになる。吐出ノズルから吐出される繊維状物を加熱するための雰囲気温度として、好ましくは140〜220℃である。 At this time, it is desirable to take up the fibrous material discharged from the discharge nozzle while heating it at an atmospheric temperature of 140 to 250 ° C. If the atmospheric temperature to be heated is less than 140 ° C, the solidification rate of the fiber is high, the productivity is inferior, and it becomes difficult to obtain a fiber that can be drawn at a high draw ratio, and it has high strength and high elastic modulus. It becomes difficult to obtain fiber. On the other hand, when the atmospheric temperature is 250 ° C. or higher, the fiber is wound around the roller without being sufficiently solidified, and the operability is inferior. The atmospheric temperature for heating the fibrous material discharged from the discharge nozzle is preferably 140 to 220 ° C.
本発明の複合繊維において、芯部の断面形状としては円形が一般的であるが、その他に星型、多角形等、任意の形状を用いることが可能である。芯部と鞘部の断面積比も特に限定されるものではないが、複合繊維の強度は芯部の強度に大きく依存する傾向にあるため、繊維の全断面積に占める芯部の断面積比率は30%以上が好ましく、更に好ましくは70%以上である。 In the conjugate fiber of the present invention, the cross-sectional shape of the core is generally circular, but any other shape such as a star shape or a polygon can be used. The cross-sectional area ratio between the core part and the sheath part is not particularly limited, but the strength of the composite fiber tends to largely depend on the strength of the core part, so the cross-sectional area ratio of the core part in the total cross-sectional area of the fiber Is preferably 30% or more, more preferably 70% or more.
上記の紡糸工程で得られた繊維は更に延伸工程に付し、連続的或いは非連続的に延伸を行うことが出来る。延伸倍率は、巻出ロールと巻取ロールの速度比を適宜設定することによって調整することができ、所望の延伸倍率の繊維が得られる。この時の加熱方法は、加熱気体、加熱液体、熱板接触、遠赤外線加熱、レーザー光加熱、電磁誘導加熱等の方法を用いることが可能であり特に限定されるものではない。 The fiber obtained in the spinning process can be further subjected to a stretching process, and can be stretched continuously or discontinuously. The draw ratio can be adjusted by appropriately setting the speed ratio between the unwinding roll and the take-up roll, and a fiber having a desired draw ratio can be obtained. The heating method at this time can use methods such as heated gas, heated liquid, hot plate contact, far-infrared heating, laser beam heating, electromagnetic induction heating and the like, and is not particularly limited.
本発明においては、ポリオキシメチレン共重合体(a)のガラス転移点以上ポリオキシメチレン共重合体(b)の結晶融解温度以下の温度で延伸することが好ましい。延伸時の温度として特に好ましいのは、(ポリオキシメチレン共重合体(a)の結晶融解温度−50℃)〜(ポリオキシメチレン共重合体(b)の結晶融解温度−5℃)の範囲である。 In this invention, it is preferable to extend | stretch at the temperature below the crystal melting temperature of a polyoxymethylene copolymer (b) more than the glass transition point of a polyoxymethylene copolymer (a). Particularly preferred as the temperature during stretching is the range of (crystal melting temperature of polyoxymethylene copolymer (a) −50 ° C.) to (crystal melting temperature of polyoxymethylene copolymer (b) −5 ° C.). is there.
加熱不足状態で延伸を行なった場合は延伸応力が大きくなり、生産性が低下するばかりでなく断糸も発生しやすくなる。また、過加熱状態ではポリマーが溶融状態又はそれに近い状態となって溶融張力が低下し断糸するため好ましくない
また、延伸倍率は、前記範囲内で用途に応じて適宜設定するのが望ましい。延伸倍率の設定にあたっては、延伸倍率の上昇に伴い得られる延伸体の強度は向上し、逆に伸度が低くなり靭性や結節伸度等の実用特性の低下や繊維自体がフィブリル化し易くなる挙動を示すことを考慮し、汎用的な物性バランスを考慮した場合は例えば5倍から10倍程度の延伸倍率、織布の経糸に使用する等で高強度が必要である場合は8倍から20倍程度の高延伸倍率で延伸するのが好ましい。
When the drawing is performed in a state where the heating is insufficient, the drawing stress increases, and not only the productivity is lowered but also the yarn is easily broken. Further, in an overheated state, the polymer is in a molten state or a state close to it, which is not preferable because the melt tension is lowered and the yarn is broken. Further, the draw ratio is preferably set appropriately in accordance with the application within the above range. In setting the draw ratio, the strength of the stretched body obtained with an increase in the draw ratio is improved. On the contrary, the elongation is lowered, the practical properties such as toughness and knot elongation are lowered, and the fiber itself is easily fibrillated. For example, when considering a general balance of physical properties, for example, a draw ratio of about 5 to 10 times, or 8 to 20 times when high strength is required, such as when used for warp of woven fabric It is preferable to draw at a high draw ratio.
延伸工程で延伸処理されて得られた繊維は、加熱状態で分子状態を固定する熱固定処理を行うことが望ましく、これにより延伸体の寸法変化を低減させることができる。熱固定条件の一例としては、(ポリオキシメチレン共重合体(a)の結晶融解温度−30℃)以下の温度で熱固定することが挙げられる。 The fiber obtained by the drawing process in the drawing process is preferably subjected to a heat setting process in which the molecular state is fixed in a heated state, whereby the dimensional change of the drawn body can be reduced. An example of the heat setting condition is heat setting at a temperature equal to or lower than (the crystal melting temperature of the polyoxymethylene copolymer (a) —30 ° C.).
本発明の2種のポリオキシメチレン共重合体からなる複合繊維は、その結節強度保持率、高強度、高弾性率、耐溶剤性、耐熱性、耐屈曲疲労性等の優れた特性を活かし種々の用途がある。その長繊維を用いて撚糸、織布、編布 等の形態に加工することにより、土木、建築分野等各種産業用資材に利用可能である。 The composite fiber composed of the two types of polyoxymethylene copolymers of the present invention can be variously utilized taking advantage of its excellent properties such as knot strength retention, high strength, high elastic modulus, solvent resistance, heat resistance, and bending fatigue resistance. There are uses. The long fibers can be used for various industrial materials such as civil engineering and construction by processing into twisted yarn, woven fabric, knitted fabric, etc.
また、繊維を目的に応じて適宜切断して短繊維として使用することも可能であり、その高強度、高弾性率、耐溶剤性、耐熱性、耐疲労性、耐アルカリ性、高温剛性 等の優れた特性を活かし、例えば各種造形素材(コンクリート、モルタル、合成樹脂、石膏)の補強材や不織布への加工、その他種々の用途への使用が可能である。 It is also possible to cut the fiber appropriately according to the purpose and use it as a short fiber, and it is excellent in its high strength, high elastic modulus, solvent resistance, heat resistance, fatigue resistance, alkali resistance, high temperature rigidity, etc. Taking advantage of these characteristics, it is possible to process various molding materials (concrete, mortar, synthetic resin, gypsum) into reinforcing materials and nonwoven fabrics, and other various uses.
以下、実施例により本発明を更に具体的に説明するが、本発明はこれに限定されるものではない。
実施例1〜8
ポリオキシメチレン共重合体(a)、ポリオキシメチレン共重合体(b)は次に記す方法にて作製した。外側に熱(冷)媒を通すジャケットが付き、断面が2つの円が一部重なる形状を有するバレルと、パドル付き回転軸で構成される連続式混合反応機を用い、パドルを付した2本の回転軸をそれぞれ150rpmで回転させながら、液状のトリオキサン、コモノマーとして環状エーテル又は環状ホルマール(1,3−ジオキソラン、1,4−ブタンジオールホルマール、ジエチレングリコールホルマール)を加え、更に分子量調節剤としてメチラール、同時に触媒の三フッ化ホウ素50ppm(全モノマーに対し)を重合機に連続的に供給しながら塊状重合を行い、それぞれ表1に示すコモノマー単位の量(オキシアルキレン単位の割合)の重合体を調製した。重合機から排出された反応生成物は速やかに破砕機に通しながら、トリエチルアミンを0.05重量%含有する60℃の水溶液に加え触媒を失活した。さらに、分離、洗浄、乾燥後、粗ポリオキシメチレン共重合体を得た。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
Examples 1-8
The polyoxymethylene copolymer (a) and the polyoxymethylene copolymer (b) were produced by the following method. Two with paddles using a continuous mixing reactor composed of a barrel that has a shape with two circular cross-sections and a rotating shaft with paddles. While rotating the rotating shaft of each at 150 rpm, liquid trioxane, cyclic ether or cyclic formal (1,3-dioxolane, 1,4-butanediol formal, diethylene glycol formal) as a comonomer, and methylal as a molecular weight regulator, At the same time, bulk polymerization is carried out while continuously supplying 50 ppm of boron trifluoride (based on the total monomers) to the polymerization machine, and polymers of the amount of comonomer units (oxyalkylene unit ratio) shown in Table 1 are prepared. did. While rapidly passing the reaction product discharged from the polymerization machine through a crusher, it was added to a 60 ° C. aqueous solution containing 0.05% by weight of triethylamine to deactivate the catalyst. Further, after separation, washing and drying, a crude polyoxymethylene copolymer was obtained.
次いで、この粗ポリオキシメチレン共重合体100重量部に対して、トリエチルアミン5重量%水溶液を4重量部、ペンタエリスリチル−テトラキス〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート〕を0.3重量部添加し、2軸押出機にて210℃で溶融混練し不安定部分を除去した。 Next, 4 parts by weight of a 5% by weight aqueous solution of triethylamine and pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) are added to 100 parts by weight of the crude polyoxymethylene copolymer. ) Propionate] was added, and melt-kneaded at 210 ° C. with a twin-screw extruder to remove unstable parts.
上記の方法で得たポリオキシメチレン共重合体100重量部に、安定剤としてペンタエリスリチル−テトラキス〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート〕を0.03重量部およびメラミン0.15重量部を添加し、2軸押出機にて210℃で溶融混練し、ポリオキシメチレン共重合体を基体樹脂とするペレット状の樹脂組成物を得た。 0.03 parts by weight of pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as a stabilizer is added to 100 parts by weight of the polyoxymethylene copolymer obtained by the above method. Then, 0.15 part by weight of melamine was added and melt-kneaded at 210 ° C. with a twin-screw extruder to obtain a pellet-shaped resin composition having a polyoxymethylene copolymer as a base resin.
上記で得られた二種のポリオキシメチレン共重合体(a)及び(b)を用い、その各々を別個の25mm一軸押出機に供給してシリンダー設定温度200℃で可塑化・溶融し、口径0.5mm、24hole、円穴の同心円型芯鞘複合ダイにポリオキシメチレン共重合体(a)が芯、ポリオキシメチレン共重合体(b)が鞘となるように供給して該複合ダイより連続的に押出し、これを引取ロール速度300m/minで巻き取った。フィラメント断面積に対する芯部の断面積割合は72%とした。次に(ポリオキシメチレン共重合体(b)の結晶融解温度−10℃)にて加熱した延伸板に連続的に接触させ、これを長さ方向に延伸した。延伸倍率は、ロール捲取速度比を調整することにより行ない、具体的には巻出しローラー速度を46m/min、巻取ローラー速度を285m/minに制御することにより6.2倍延伸を行なった。
比較例1〜9
本発明の規定外の複合紡糸を作製し、実施例と同様の条件で未延伸体を調製しさらに延伸糸を調製した。実施例と同様に評価した結果を表1に示す。
Using the two types of polyoxymethylene copolymers (a) and (b) obtained above, each was supplied to a separate 25 mm single screw extruder and plasticized and melted at a cylinder set temperature of 200 ° C. A 0.5mm, 24hole, circular hole concentric core-sheath composite die is continuously supplied from the composite die by supplying the polyoxymethylene copolymer (a) as a core and the polyoxymethylene copolymer (b) as a sheath. This was extruded and wound at a take-up roll speed of 300 m / min. The cross-sectional area ratio of the core with respect to the cross-sectional area of the filament was 72%. Next, it was made to contact continuously with the extending | stretching board heated with (the crystal melting temperature of polyoxymethylene copolymer (b) -10 degreeC), and this was extended | stretched in the length direction. The draw ratio was adjusted by adjusting the roll take-up speed ratio. Specifically, the take-up roller speed was controlled to 46 m / min and the take-up roller speed was controlled to 285 m / min to perform 6.2-fold drawing.
Comparative Examples 1-9
A composite spun outside the scope of the present invention was prepared, an undrawn body was prepared under the same conditions as in the Examples, and a drawn yarn was further prepared. The results evaluated in the same manner as in Examples are shown in Table 1.
尚、実施例・比較例における評価項目、その測定方法・評価基準等は以下の通りである。
[メルトインデックス(MI)測定]
ASTMD-1238に従い、190℃、2160gの荷重下で測定した。
[ポリマー組成分析]
物性評価に用いたポリマーを、ヘキサフルオロイソプロパノールd2に溶解し、1H−NMR測定を行った。各ユニットに対応するピーク面積より定量した。
[結晶融解温度]
DSCにより10℃/minで昇温させた時の結晶融解ピークのピーク温度として測定した。
[結節強さ]
JIS L1013に準じてフィラメント単糸での結節強さ評価を行い、フィラメント強度に対する結節強度の割合である結節強度保持率を算出した。
In addition, the evaluation items in the examples and comparative examples, the measurement methods, the evaluation criteria, and the like are as follows.
[Melt index (MI) measurement]
According to ASTMD-1238, measurement was performed at 190 ° C. under a load of 2160 g.
[Polymer composition analysis]
The polymer used for the physical property evaluation was dissolved in hexafluoroisopropanol d2, and 1 H-NMR measurement was performed. It quantified from the peak area corresponding to each unit.
[Crystal melting temperature]
It was measured as the peak temperature of the crystal melting peak when the temperature was raised by DSC at 10 ° C./min.
[Nodule strength]
The knot strength of the filament single yarn was evaluated according to JIS L1013, and the knot strength retention ratio, which is the ratio of the knot strength to the filament strength, was calculated.
Claims (2)
主としてオキシメチレン単位の繰り返しからなるポリマー鎖中にオキシメチレン単位100mol当たり0.3〜8molの下記一般式(1)で表されるオキシアルキレン単位を含み、かつメルトインデックス(190℃、荷重2160g)が1〜100g/10分であるポリオキシメチレン共重合体(b)からなる鞘とで形成され、
且つポリオキシメチレン共重合体(a)とポリオキシメチレン共重合体(b)とが、それぞれの結晶融解温度をTma(℃)及びTmb(℃)とした時、下式(2)を満たすものであることを特徴とする複合繊維。
Tmb<Tma−3 (2)
(Tma(℃) ;ポリオキシメチレン共重合体(a)の結晶融解温度、Tmb(℃) ;ポリオキシメチレン共重合体(b)の結晶融解温度) The polymer chain mainly composed of repeating oxymethylene units contains 0.1 to 7.5 mol of oxyalkylene units represented by the following general formula (1) per 100 mol of oxymethylene units, and the melt index (190 ° C., load 2160 g) is 1. A core composed of a polyoxymethylene copolymer (a) that is ˜100 g / 10 min;
The polymer chain mainly composed of repeating oxymethylene units contains 0.3 to 8 mol of oxyalkylene units represented by the following general formula (1) per 100 mol of oxymethylene units, and has a melt index (190 ° C., load 2160 g) of 1 to 1. Formed with a sheath made of polyoxymethylene copolymer (b) that is 100 g / 10 min,
The polyoxymethylene copolymer (a) and the polyoxymethylene copolymer (b) satisfy the following formula (2) when their crystal melting temperatures are Tma (° C.) and Tmb (° C.), respectively. The composite fiber characterized by being.
Tmb <Tma-3 (2)
(Tma (° C.); crystal melting temperature of polyoxymethylene copolymer (a), Tmb (° C.); crystal melting temperature of polyoxymethylene copolymer (b))
The composite fiber according to claim 1, wherein the oxyalkylene unit represented by the general formula (1) is selected from oxyethylene, oxytrimethylene, and oxytetramethylene.
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KR1020050054501A KR101184857B1 (en) | 2004-06-28 | 2005-06-23 | A composite fiber made of polyoxy methylene resins |
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CN100529206C (en) | 2009-08-19 |
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