JP2002180331A - Thermal adhesive conjugate fiber, method for producing the same, and fiber molded body using the same - Google Patents
Thermal adhesive conjugate fiber, method for producing the same, and fiber molded body using the sameInfo
- Publication number
- JP2002180331A JP2002180331A JP2000380815A JP2000380815A JP2002180331A JP 2002180331 A JP2002180331 A JP 2002180331A JP 2000380815 A JP2000380815 A JP 2000380815A JP 2000380815 A JP2000380815 A JP 2000380815A JP 2002180331 A JP2002180331 A JP 2002180331A
- Authority
- JP
- Japan
- Prior art keywords
- component
- fiber
- propylene
- conjugate fiber
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 208
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 title claims description 51
- 230000001070 adhesive effect Effects 0.000 title claims 2
- -1 polypropylene Polymers 0.000 claims abstract description 62
- 239000004743 Polypropylene Substances 0.000 claims abstract description 61
- 229920001577 copolymer Polymers 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 58
- 229920001155 polypropylene Polymers 0.000 claims abstract description 58
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 238000009987 spinning Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000011144 upstream manufacturing Methods 0.000 claims description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims description 8
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 abstract description 68
- 239000000306 component Substances 0.000 description 92
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000012545 processing Methods 0.000 description 14
- 238000002788 crimping Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000000691 measurement method Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000008358 core component Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000877 morphologic effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 210000004177 elastic tissue Anatomy 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000001932 seasonal effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 206010016322 Feeling abnormal Diseases 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Multicomponent Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
(57)【要約】
【課題】 十分な嵩高性、高風合い、形態安定性、リサ
イクル性に優れた不織布等の繊維成形体が得られる熱接
着性複合繊維とその製造方法、およびそれを用いた不織
布に代表される繊維成形体を提供する。
【解決手段】 プロピレン系共重合体を第１成分、結晶
性ポリプロピレンを第２成分とし、その断面形状が第１
成分を鞘側、第２成分を芯側とする偏心鞘芯型もしくは
第１成分と第２成分との並列型の構造となるように両成
分を紡糸し、得られた複合未延伸糸を熱処理して第２成
分のみをハ−ドエラステイック結晶化させたのち、特定
の延伸条件で延伸することにより、立体捲縮のみを有
し、１２０℃で５分間加熱処理した際に捲縮数が実質的
に変化せず、かつ、強伸度曲線から求められる弾性領域
が４２％以上である複合繊維を製造し、該複合繊維を用
いて不織布等の繊維成形体とする。PROBLEM TO BE SOLVED: To provide a thermoadhesive conjugate fiber capable of obtaining a fiber molded article such as a non-woven fabric excellent in sufficient bulkiness, high texture, shape stability, and recyclability, a method for producing the same, and the use thereof. Provided is a fiber molded product represented by a nonwoven fabric. SOLUTION: A propylene-based copolymer is used as a first component, and a crystalline polypropylene is used as a second component.
The two components are spun so as to form an eccentric sheath-core type in which the component is the sheath side and the second component is the core side, or a parallel type structure of the first component and the second component, and the obtained composite undrawn yarn is heat-treated. Then, only the second component is hard-elastically crystallized and then stretched under specific stretching conditions to have only a three-dimensional crimp and substantially reduce the number of crimps when heated at 120 ° C. for 5 minutes. A conjugate fiber is produced that does not change substantially and has an elastic area of 42% or more as determined from a strength-elongation curve, and is used as a fiber molded article such as a nonwoven fabric.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、立体捲縮を有し、
かつ潜在捲縮性を実質的に持たない、衛生用品用途に好
適な嵩高性と柔軟性を保有し、リサイクル性にも優れた
熱接着性複合繊維、その製造方法および該熱接着性複合
繊維を用いた繊維成形体に関する。The present invention relates to a three-dimensional crimp,
A heat-adhesive conjugate fiber having substantially no potential crimping property, possessing bulkiness and flexibility suitable for sanitary goods use, excellent in recyclability, a method for producing the same, and a method for producing the same. The present invention relates to a fiber molded body used.
【０００２】[0002]
【従来の技術】使い捨て衛生用品において、嵩高性、柔
軟性といった基本的な機能は、衛生用品が人肌に触れる
ものであることから、その重要性は極めて高い。これま
でにも嵩高性、柔軟性を改良した不織布等を得る手法は
数多く提案されている。2. Description of the Related Art In disposable hygiene articles, basic functions such as bulkiness and flexibility are extremely important because the sanitary articles touch human skin. Many methods have been proposed for obtaining a nonwoven fabric or the like having improved bulkiness and flexibility.
【０００３】例えば、特開昭６３−１３５５４９号公報
には、高アイソタクティシティーのポリプロピレンを芯
成分とし、主としてポリエチレンよりなる樹脂を鞘成分
とした鞘芯型複合繊維を用いることで嵩高い不織布等を
得る方法が開示されている。この方法は複合繊維の芯側
に高剛性の樹脂を使用することで、得られる不織布等に
嵩高性、抗熱収縮性を保持させるものであるが、鞘側に
ポリエチレンを使用しているために特有のぬめり感があ
り、またペーパーライクな感触を持つため衛生材料用途
としては満足のできるものではなかった。For example, Japanese Unexamined Patent Publication (Kokai) No. 63-135549 discloses a bulky nonwoven fabric or the like by using a sheath-core type composite fiber having high isotacticity polypropylene as a core component and a sheath component mainly composed of polyethylene resin. Are disclosed. This method uses a high-rigidity resin on the core side of the composite fiber to maintain the bulkiness and heat shrinkage resistance of the obtained nonwoven fabric, but because polyethylene is used on the sheath side, It had a peculiar slimy feeling and a paper-like feel, and was not satisfactory as a sanitary material application.
【０００４】また、特開昭５８−１２６３５７号公報に
は、ポリエチレンと結晶性ポリプロピレンのように、伸
張時の弾性回復率（以下、伸張弾性率という）が大きく
異なる樹脂同士を組合わせて偏心鞘芯型もしくは並列型
の未延伸糸を得た後、延伸することにより、得られる複
合繊維にオーム状またはスパイラル状の立体捲縮を付与
する方法が開示されている。立体捲縮を有する複合繊維
からは、機械捲縮を施した複合繊維に比べて嵩高いウェ
ブを得ることができるため、その不織布等も嵩高くなる
という利点を有している。しかし、この方法では、例え
ばプロピレン共重合体／結晶性ポリプロピレンの組合せ
のように、伸張弾性率が近い同系統の樹脂同士の組合わ
せでは立体捲縮を発現させることができないため、伸張
弾性率に差のある樹脂同士を組み合わせなければなら
ず、その結果、得られる複合繊維はリサイクル性に欠け
るという問題がある。また、該発明ではポリエチレンを
使用しているため、不織布等は嵩高いものの触感はぬめ
り感のあるペーパーライクとなる欠点を有していた。Japanese Patent Application Laid-Open No. Sho 58-126357 discloses an eccentric sheath by combining resins such as polyethylene and crystalline polypropylene, which have significantly different elastic recovery ratios (hereinafter referred to as "extension elastic modulus") upon elongation. A method is disclosed in which a core-type or parallel-type undrawn yarn is obtained and then drawn to impart an ohmic or spiral three-dimensional crimp to the obtained conjugate fiber. Since a bulky web can be obtained from a conjugate fiber having a three-dimensional crimp as compared with a conjugate fiber subjected to mechanical crimping, the nonwoven fabric and the like have the advantage of being bulky. However, according to this method, a three-dimensional crimp cannot be developed with a combination of resins of the same type having similar elongation elastic moduli, such as a combination of propylene copolymer / crystalline polypropylene. It is necessary to combine resins having a difference, and as a result, there is a problem that the obtained composite fiber lacks recyclability. In addition, since polyethylene is used in the present invention, the nonwoven fabric and the like have a drawback that they are bulky but have a slimy paper-like feel.
【０００５】特願平１０−５２６４６８号公報には、リ
サイクル性に優れるプロピレン系共重合体／結晶性ポリ
プロピレンの組合せからなる複合繊維を用いて嵩高い不
織布等を得るための検討もなされている。しかし、ここ
に開示の複合繊維は機械捲縮のみを有する複合繊維であ
り、該複合繊維を用いて不織布等にしても、満足できる
嵩高性を有する不織布等は得られない。[0005] Japanese Patent Application No. 10-526468 also discusses a method of obtaining a bulky nonwoven fabric or the like using a composite fiber composed of a combination of a propylene-based copolymer and a crystalline polypropylene having excellent recyclability. However, the conjugate fiber disclosed herein is a conjugate fiber having only a mechanical crimp, and a nonwoven fabric or the like having a satisfactory bulkiness cannot be obtained by using the conjugate fiber as a nonwoven fabric.
【０００６】なお、前述した中で、伸張弾性率が近い同
系統の樹脂同士、例えばプロピレン系共重合体／結晶性
ポリプロピレンの組み合わせからなる複合繊維では立体
捲縮を発現させることができないと述べたが、プロピレ
ン系共重合体／結晶性ポリプロピレンの組合せからなる
複合繊維に立体捲縮を発現させる方法が過去に全く存在
しなかった訳ではない。例えば特開平１１−１５２６６
９号公報には、加熱すると捲縮が発現する、いわゆる潜
在捲縮性を有するプロピレン系共重合体／結晶性ポリプ
ロピレンの組合せからなる複合繊維を含むウェブを特定
条件下で立体捲縮を発現させることにより嵩高い不織布
を得ている。しかし、このような潜在捲縮性繊維は極め
て高い熱収縮性を有するため、該複合繊維のみを用いて
低目付けの不織布等を製造する場合、均一な地合いの不
織布等を得ることが難しく、また、充分な嵩高性を有す
る複合繊維を得ることが難しい、さらに、該複合繊維を
含むウェブを不織布等に加工する際に熱風循環型不織布
加工機の様な汎用機器が使用できないため、フローティ
ングドライヤ等の特殊な加工機を必要とし、工程が複雑
になる、余分な設備投資が必要になる、といった数多く
の問題を有している。[0006] In the above, it has been stated that three-dimensional crimping cannot be exhibited by resins of the same type having similar elongation elastic moduli, for example, a composite fiber comprising a combination of propylene-based copolymer / crystalline polypropylene. However, this does not mean that there has never been a method for expressing a three-dimensional crimp in a composite fiber composed of a combination of a propylene-based copolymer / crystalline polypropylene. For example, JP-A-11-15266
No. 9 discloses that a web containing composite fibers composed of a combination of a propylene copolymer / crystalline polypropylene having a so-called latent crimp, which develops a crimp when heated, develops a three-dimensional crimp under specific conditions. As a result, a bulky nonwoven fabric is obtained. However, since such latently crimpable fibers have extremely high heat shrinkability, it is difficult to obtain a nonwoven fabric having a uniform formation when producing a low-weight nonwoven fabric using only the conjugate fiber, and It is difficult to obtain a conjugate fiber having sufficient bulkiness. Further, when processing a web containing the conjugate fiber into a non-woven fabric or the like, a general-purpose device such as a hot-air circulating non-woven fabric processing machine cannot be used. There are many problems such as the need for special processing machines, complicated processes, and extra capital investment.
【０００７】[0007]
【発明が解決しようとする課題】以上のように、従来技
術では十分な嵩高性、高い風合い、リサイクル性を備え
た不織布等の繊維成形体の原料となる複合繊維を得るこ
とは非常に困難であった。本発明の目的は、これらの課
題を同時に解決できる熱接着性複合繊維とその製造方法
および該熱接着性複合繊維を用いた不織布等の繊維成形
体を提供することにある。As described above, it is very difficult with the prior art to obtain a conjugate fiber which is a raw material of a fiber molded article such as a nonwoven fabric having sufficient bulkiness, high texture and recyclability. there were. An object of the present invention is to provide a thermoadhesive conjugate fiber which can simultaneously solve these problems, a method for producing the same, and a fiber molded article such as a nonwoven fabric using the thermoadhesive conjugate fiber.
【０００８】[0008]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意検討した。その結果、特定樹脂の組合せ
からなる偏心鞘芯型もしくは並列型の構造を有し、か
つ、立体捲縮のみを有する複合繊維であって、加熱され
た際にも捲縮数が実質的に変化せず、強伸度曲線におい
て求められる弾性領域が４２％以上である熱接着性複合
繊維が、リサイクル性、形態安定性、嵩高性および柔軟
性に優れた不織布等の繊維成形体の原料として好適であ
り、特に使い捨て衛生用品として好適であることを見い
出し、この知見に基づいて本発明を完成した。Means for Solving the Problems The present inventors have intensively studied to solve the above problems. As a result, the composite fiber has an eccentric sheath-core or parallel-type structure made of a combination of specific resins, and has only a three-dimensional crimp, and the number of crimps substantially changes even when heated. A thermoadhesive conjugate fiber having an elasticity area of 42% or more as determined by a strength-elongation curve is suitable as a raw material for a fiber molded article such as a nonwoven fabric having excellent recyclability, form stability, bulkiness, and flexibility. And found that it was particularly suitable as a disposable sanitary article, and completed the present invention based on this finding.
【０００９】本発明は以下の構成からなる。 （１）．プロピレン系共重合体を第１成分、結晶性ポリ
プロピレンを第２成分として構成される複合繊維の断面
形状が、第１成分を鞘側、第２成分を芯側とする偏心鞘
芯型もしくは第１成分と第２成分との並列型の構造であ
り、立体捲縮のみを有するとともに、１２０℃で５分間
加熱した時に捲縮数が実質的に増加しない複合繊維であ
って、強伸度曲線において求められる弾性領域が４２％
以上であることを特徴とする熱接着性複合繊維。The present invention has the following constitution. (1). The composite fiber composed of a propylene-based copolymer as a first component and crystalline polypropylene as a second component has a cross-sectional shape of an eccentric sheath-core or first eccentric sheath having a first component as a sheath side and a second component as a core side. A composite fiber having only a three-dimensional crimp and having substantially no increase in the number of crimps when heated at 120 ° C. for 5 minutes. Required elastic area is 42%
A heat-adhesive conjugate fiber characterized by the above.
【００１０】（２）．１２０℃で５分間加熱した時の捲
縮数の増加が４個／２．５４ｃｍ以下または捲縮数が減
少することを特徴とする前記第１項記載の熱接着性複合
繊維。(2). 2. The heat-adhesive conjugate fiber according to claim 1, wherein the number of crimps when heated at 120 ° C. for 5 minutes is 4 pieces / 2.54 cm or less or the number of crimps decreases.
【００１１】（３）．熱接着性複合繊維が、該繊維を用
いてウェブとしたときに、熱収縮率が１４５℃で５分間
の加熱条件で１０％以下のウェブが得られる複合繊維で
ある前記第１項もしくは第２項のいずれか１項記載の熱
接着性複合繊維。(3). The above-mentioned item 1 or item 2, wherein the heat-adhesive conjugate fiber is a conjugate fiber which, when used as a web, has a heat shrinkage of 10% or less under a heating condition of 145 ° C for 5 minutes. Item 6. The heat-adhesive conjugate fiber according to any one of the above items.
【００１２】（４）． プロピレン系共重合体が、融点
Ｔｍ（℃）が１２０℃≦Ｔｍ≦１４７℃を有する共重合
体である前記第１項記載の熱接着性複合繊維。(4). 2. The heat-adhesive conjugate fiber according to claim 1, wherein the propylene-based copolymer is a copolymer having a melting point Tm (° C.) of 120 ° C. ≦ Tm ≦ 147 ° C.
【００１３】（５）．プロピレン系共重合体が、エチレ
ン４〜１０重量％、プロピレン９０〜９６重量％からな
るエチレン−プロピレン二元共重合体である前記第１項
もしくは前記第４項のいずれか１項記載の熱接着性複合
繊維。(5). The thermal adhesion according to any one of the above items 1 or 4, wherein the propylene-based copolymer is an ethylene-propylene binary copolymer composed of 4 to 10% by weight of ethylene and 90 to 96% by weight of propylene. Composite fiber.
【００１４】（６）．プロピレン系共重合体が、エチレ
ン１〜７重量％、プロピレン９０〜９８重量％、１−ブ
テン１〜５重量％からなるエチレン−プロピレン−ブテ
ン−１三元共重合体である前記第１項もしくは前記第４
項のいずれか１項記載の熱接着性複合繊維。(6). The above-mentioned item 1 or 1, wherein the propylene-based copolymer is an ethylene-propylene-butene-1 terpolymer comprising 1 to 7% by weight of ethylene, 90 to 98% by weight of propylene, and 1 to 5% by weight of 1-butene. The fourth
Item 6. The heat-adhesive conjugate fiber according to any one of the above items.
【００１５】（７）．プロピレン系共重合体を第１成
分、結晶性ポリプロピレンを第２成分として構成される
複合繊維の断面形状が、第１成分を鞘側、第２成分を芯
側とする偏心鞘芯型もしくは第１成分と第２成分との並
列型となるように、偏心鞘芯型紡糸口金または並列型紡
糸口金を備えた紡糸装置によって両成分を紡糸して得た
未延伸糸に熱処理を施した後、少なくとも１つの延伸セ
クションにおいて１．２倍〜１．７倍の延伸倍率で延伸
し、その延伸セクションにおける工程の上流側の延伸ロ
ールの温度を８０℃以下、下流側の延伸ロールの温度を
３０〜１１０℃とし、なおかつ該延伸装置における最上
流の延伸ロールと最下流の延伸ロールの速度比が１．２
〜２倍であることを特徴とする熱接着性複合繊維の製造
方法。(7). The composite fiber composed of a propylene-based copolymer as a first component and crystalline polypropylene as a second component has a cross-sectional shape of an eccentric sheath-core or first eccentric sheath having a first component as a sheath side and a second component as a core side. After a heat treatment is applied to an undrawn yarn obtained by spinning both components by a spinning device having an eccentric sheath-core spinneret or a parallel spinneret so as to be a parallel type of the component and the second component, at least In one stretching section, stretching is performed at a stretching ratio of 1.2 times to 1.7 times, and the temperature of the stretching roll on the upstream side of the process in the stretching section is 80 ° C. or less, and the temperature of the stretching roll on the downstream side is 30 to 110 °. ° C, and the speed ratio between the most upstream stretching roll and the most downstream stretching roll in the stretching apparatus is 1.2.
A method for producing a heat-adhesive conjugate fiber, which is twice as large.
【００１６】（８）．前記第１項〜第６項のいずれか１
項記載の熱接着性複合繊維を用いた繊維成形体。(8). Any one of the above items 1 to 6
A fiber molded article using the heat-adhesive conjugate fiber according to the above item.
【００１７】[0017]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明は、プロピレン系共重合体を第１成分、結晶性ポ
リプロピレンを第２成分として構成される複合繊維であ
り、その断面形状が、第１成分を鞘側、第２成分を芯側
とする偏心鞘芯型もしくは第１成分と第２成分との並列
型の構造を有し、立体捲縮のみを有するとともに、１２
０℃で５分間加熱した時に捲縮数が実質的に増加しない
複合繊維であって、強伸度曲線において求められる弾性
領域が４２％以上であることを特徴とする熱接着性複合
繊維とその製造方法および該熱接着性繊維を用いた不織
布等で代表される繊維成形体である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention is a composite fiber composed of a propylene-based copolymer as a first component and crystalline polypropylene as a second component, and the cross-sectional shape thereof is such that the first component is a sheath side and the second component is a core side. It has an eccentric sheath-core type or a parallel type structure of the first component and the second component, has only a three-dimensional crimp,
A heat-adhesive conjugate fiber, wherein the number of crimps does not substantially increase when heated at 0 ° C. for 5 minutes, wherein the elastic region determined by a strength-elongation curve is 42% or more, and It is a fiber molding represented by a manufacturing method and a nonwoven fabric using the heat-adhesive fiber.
【００１８】本発明の熱接着性複合繊維において、第１
成分として用いるプロピレン系共重合体は、プロピレン
を主成分（最も多い成分）とし、該プロピレンとエチレ
ンもしくは該プロピレンとエチレンおよび他のα−オレ
フィンとを共重合させることにより得ることができる。
該α−オレフィンとしては、例えば、ブテン−１、ペン
テン−１、ヘキセン−１、ヘプテン−１、オクテン−
１、４−メチル−ペンテン−１等を例示でき、またこれ
らのα−オレフィンのうち２種以上を併用することもで
きる。In the heat-adhesive conjugate fiber of the present invention, the first
The propylene-based copolymer used as a component can be obtained by using propylene as a main component (most component) and copolymerizing the propylene with ethylene or the propylene with ethylene and another α-olefin.
Examples of the α-olefin include butene-1, pentene-1, hexene-1, heptene-1, octene-
Examples thereof include 1,4-methyl-pentene-1, and two or more of these α-olefins can be used in combination.
【００１９】プロピレン系共重合体の具体例としてはエ
チレン−プロピレン二元共重合体、プロピレン−ブテン
−１二元共重合体、エチレン−プロピレン−ブテン−１
三元共重合体、プロピレン−ヘキセン−１二元共重合
体、プロピレン−オクテン−１二元共重合体等、および
これらの混合物等を例示することができる。これらの共
重合体は通常ランダム共重合体であるが、ブロック共重
合体であってもよい。Specific examples of the propylene-based copolymer include ethylene-propylene binary copolymer, propylene-butene-1 binary copolymer, and ethylene-propylene-butene-1.
Examples include a terpolymer, a propylene-hexene-1 binary copolymer, a propylene-octene-1 binary copolymer, and the like, and a mixture thereof. These copolymers are usually random copolymers, but may be block copolymers.
【００２０】中でも、不織布等の加工時における低温加
工性、カード加工性が良いことから、融点Ｔｍ（℃）が
１２０℃≦Ｔｍ≦１４７℃の範囲にあるプロピレン系共
重合体が好ましい。融点Ｔｍ（℃）が１２０℃未満であ
るプロピレン系共重合体はゴム弾性を示し、また高い表
面摩擦抵抗を持つため、得られる複合繊維のカード加工
性に悪影響を与えることがある。他方、融点Ｔｍ（℃）
が１４７℃を超えると、得られた複合繊維を不織布等の
繊維成形体に加工する際の低温加工性が悪化する。Above all, a propylene copolymer having a melting point Tm (° C.) in the range of 120 ° C. ≦ Tm ≦ 147 ° C. is preferred because of good low-temperature processability and card processability during processing of nonwoven fabric and the like. A propylene-based copolymer having a melting point Tm (° C.) of less than 120 ° C. exhibits rubber elasticity and high surface friction resistance, which may adversely affect the card processability of the obtained composite fiber. On the other hand, melting point Tm (° C)
If it exceeds 147 ° C., the low-temperature processability at the time of processing the obtained conjugate fiber into a fibrous formed body such as a nonwoven fabric deteriorates.
【００２１】また、該プロピレン系共重合体は、低温加
工性、コスト面から、エチレン４〜１０重量％、プロピ
レン９０〜９６重量％からなるエチレン−プロピレン二
元共重合体か、もしくはエチレン１〜７重量％、プロピ
レン９０〜９８重量％および１−ブテン１〜５重量％か
らなるエチレン−プロピレン−ブテン−１三元共重合体
が特に好ましい。The propylene-based copolymer is an ethylene-propylene binary copolymer composed of 4 to 10% by weight of ethylene and 90 to 96% by weight of propylene, An ethylene-propylene-butene-1 terpolymer comprising 7% by weight, 90-98% by weight of propylene and 1-5% by weight of 1-butene is particularly preferred.
【００２２】なお、本発明にあっては、必要に応じて２
種類以上のプロピレン系共重合体を混合したものを用い
てもよい。また、プロピレン系共重合体に対し他の熱可
塑性樹脂や、二酸化チタン，炭酸カルシウムおよび水酸
化マグネシウム等の無機物や、難燃剤、顔料等を添加し
ても差し支えない。In the present invention, if necessary,
A mixture of two or more propylene-based copolymers may be used. Further, other thermoplastic resins, inorganic substances such as titanium dioxide, calcium carbonate and magnesium hydroxide, flame retardants, pigments and the like may be added to the propylene-based copolymer.
【００２３】本発明の熱接着性複合繊維において、第２
成分として用いる結晶性ポリプロピレンとは、プロピレ
ン単独重合体もしくはプロピレンと少量の、通常は２重
量％以下のエチレンおよび／もしくはα−オレフィンと
の共重合体である。かかる結晶性ポリプロピレンとして
は、汎用のチーグラー・ナッタ触媒、メタロセン触媒か
ら得られる結晶性ポリプロピレンを例示でき、本発明に
おいては、これらの中でも結晶性が比較的高い、例え
ば、特開昭６３−１３５５４９号公報や特公平７−３５
６０７号公報において開示されているようなポリプロピ
レンを好適に用いることができる。また、本発明の効果
を著しく損なわなければ、前記結晶性ポリプロピレン同
士を混合したものや、異なる分子量分布、メルトフロー
レート等の物性が異なる結晶性ポリプロピレン同士を混
合したものを用いてもよい。また必要に応じて他の熱可
塑性樹脂や二酸化チタン、炭酸カルシウムおよび水酸化
マグネシウム等の無機物や、難燃剤、顔料及びその他の
ポリマーを添加してもよい。In the heat-adhesive conjugate fiber of the present invention, the second
The crystalline polypropylene used as a component is a propylene homopolymer or a copolymer of propylene with a small amount, usually 2% by weight or less, of ethylene and / or α-olefin. Examples of such crystalline polypropylene include crystalline polypropylene obtained from general-purpose Ziegler-Natta catalysts and metallocene catalysts. In the present invention, among these, the crystalline properties are relatively high, for example, JP-A-63-135549. Gazette and Tokuhei 7-35
For example, polypropylene as disclosed in JP-A-607 can be suitably used. If the effects of the present invention are not significantly impaired, a mixture of the crystalline polypropylenes or a mixture of the crystalline polypropylenes having different physical properties such as different molecular weight distributions and melt flow rates may be used. If necessary, other thermoplastic resins, inorganic substances such as titanium dioxide, calcium carbonate and magnesium hydroxide, flame retardants, pigments and other polymers may be added.
【００２４】本発明の熱接着性複合繊維は、前述したよ
うな、プロピレン系共重合体、結晶性ポリプロピレンを
それぞれ第１成分、第２成分として構成される複合繊維
であり、該複合繊維の断面形状は、第１成分を鞘側、第
２成分を芯側とする偏心鞘芯型構造であるか、第１成分
と第２成分との並列型構造のいずれかである（ここで、
偏心鞘芯型とは、該複合繊維の繊維軸方向と直交する方
向に切断した断面において、該複合繊維における鞘成分
の外周の中心と、芯成分の外周の中心が一致しないもの
をいう）。これ以外の断面形状であると、得られる熱接
着性複合繊維に充分な立体捲縮を付与することができな
いため、得られた不織布等の繊維成形体は嵩高性の乏し
いものになってしまう。The heat-adhesive conjugate fiber of the present invention is a conjugate fiber composed of a propylene copolymer and crystalline polypropylene as the first and second components, respectively, as described above. The shape is either an eccentric sheath-core structure in which the first component is the sheath side and the second component is the core side, or a side-by-side structure of the first component and the second component (here,
The term “eccentric sheath-core type” means that the center of the outer periphery of the sheath component does not coincide with the center of the outer periphery of the core component in a cross section of the conjugate fiber cut in a direction perpendicular to the fiber axis direction). If the cross-sectional shape is other than this, sufficient three-dimensional crimp cannot be imparted to the obtained heat-adhesive conjugate fiber, so that the resulting fibrous formed body such as a nonwoven fabric has poor bulkiness.
【００２５】また、本発明の熱接着性複合繊維に良好な
熱接着性と立体捲縮を付与するためには、該複合繊維の
第１成分と第２成分との体積比（該複合繊維を繊維軸方
向と直交する方向に切った切断面における両成分の面積
比）が、７０／３０〜３０／７０の範囲であることが好
ましく、本発明にあっては特に、鞘芯の体積比が５５／
４５〜４５／５５の範囲であることが好ましい。第１成
分と第２成分の体積比が５０／５０から大きく離れてい
ると、生産性の低下を招いたり、得られる複合繊維に十
分な立体捲縮や熱接着性を付与できなくなることがあ
る。In order to impart good thermal adhesiveness and three-dimensional crimp to the heat-adhesive conjugate fiber of the present invention, the volume ratio of the first component and the second component of the conjugate fiber (the conjugate fiber is The area ratio of the two components in a cut plane cut in a direction perpendicular to the fiber axis direction) is preferably in the range of 70/30 to 30/70. In the present invention, the volume ratio of the sheath core is particularly preferable. 55 /
It is preferably in the range of 45 to 45/55. If the volume ratio of the first component and the second component is far from 50/50, productivity may be reduced, or sufficient dimensional crimp or thermal adhesiveness may not be provided to the obtained conjugate fiber. .
【００２６】本発明の熱接着性複合繊維は、立体捲縮の
みを有し、実質的に潜在捲縮性を有しないため、１２０
℃で５分間加熱処理しても捲縮数が実質的に増加しない
か、減少するという特徴を有している。本発明でいう立
体捲縮とは、一般に自然捲縮、螺旋捲縮、３次元捲縮、
スパイラル捲縮などとも呼ばれ、クリンパーを用いて付
与するジグザグ状の機械捲縮ではなく、複合繊維を構成
する第１、第２成分間の伸張弾性率の差を利用して得ら
れるスパイラル状や丸みをおびたオーム状の捲縮をい
う。The heat-adhesive conjugate fiber of the present invention has only a three-dimensional crimp and substantially no latent crimp,
It is characterized in that the number of crimps does not substantially increase or decreases even after heat treatment at 5 ° C. for 5 minutes. The three-dimensional crimp in the present invention generally means natural crimp, spiral crimp, three-dimensional crimp,
It is also called spiral crimping or the like, and is not a zigzag mechanical crimp applied using a crimper, but a spiral shape obtained by using a difference in extension elastic modulus between the first and second components constituting the composite fiber. A rounded ohmic crimp.
【００２７】なお、冒頭で、従来技術においても、本発
明とほぼ同じ樹脂同士を用い、かつ、その断面形状も類
似した複合繊維に立体捲縮を付与する方法が存在する旨
記述したが、本発明の熱接着性複合繊維は、プロピレン
系共重合体の熱収縮性を利用して立体的な潜在捲縮を発
現させた該複合繊維とは根本的に異なるものである。例
えば特開平２−１９１７２０号公報に開示されている複
合繊維は、偏心鞘芯型または並列型の繊維断面を持つプ
ロピレン系共重合体／結晶性ポリプロピレンの組合せか
らなる潜在捲縮性複合繊維が有する高い潜在捲縮性を利
用した複合繊維であり、該複合繊維をパップ材、フロー
リングワイパーなどに好適な潜在捲縮性繊維として用い
ている。しかしながら、本発明の熱接着性複合繊維は、
上述したように、かかる通常のプロピレン系共重合体／
結晶性ポリプロピレン熱接着性複合繊維とは全く異な
り、潜在捲縮性を実質的に有しない特徴をもつものであ
るため、加熱処理後も捲縮数は実質的に増加せず、逆に
捲縮数が減少することもある。At the outset, the prior art also stated that there is a method of applying a three-dimensional crimp to a conjugate fiber using substantially the same resin as the present invention and having a similar cross-sectional shape. The heat-adhesive conjugate fiber of the present invention is fundamentally different from the conjugate fiber in which a three-dimensional latent crimp is developed by utilizing the heat shrinkage of the propylene-based copolymer. For example, the composite fiber disclosed in JP-A-2-191720 is a latently crimpable composite fiber composed of a combination of a propylene-based copolymer / crystalline polypropylene having an eccentric sheath-core or side-by-side fiber cross section. It is a conjugate fiber utilizing high latent crimpability, and the conjugate fiber is used as a latently crimpable fiber suitable for a pulp material, a flooring wiper and the like. However, the heat-adhesive conjugate fiber of the present invention,
As described above, such ordinary propylene-based copolymer /
Unlike crystalline polypropylene heat-bondable conjugate fiber, it has the characteristic of having substantially no latent crimping property, so the number of crimps does not substantially increase even after heat treatment, and conversely The number may decrease.
【００２８】従来技術により得られる偏心鞘芯型または
並列型の断面形状を有するプロピレン系共重合体／結晶
性ポリプロピレンの組合せからなる複合繊維では加熱し
た際、非常に高い潜在捲縮性を示す。このような繊維で
は通常１２０℃で１分程度加熱しただけでも３０個／
２．５４ｃｍ（１インチ）以上の潜在捲縮が発現する
が、本発明の繊維においては潜在捲縮が発現した場合に
おいても捲縮数の増加はせいぜい４個／２．５４ｃｍ以
下、ほとんどの場合２個／２．５４ｃｍ以下である。捲
縮数の増加が４個/２．５４ｃｍを大きく超える場合は
不織布等の加工時に地合が乱れる原因となる。なお、本
発明において捲縮数の増加とは、後述する方法により測
定した熱処理前後の捲縮数の差を指す。A composite fiber comprising a combination of a propylene-based copolymer / crystalline polypropylene having an eccentric sheath-core or side-by-side cross-sectional shape obtained by the prior art shows a very high potential crimp when heated. With such fibers, 30 fibers /
A latent crimp of 2.54 cm (1 inch) or more is developed, but in the fiber of the present invention, even when a latent crimp is developed, the number of crimps is at most 4 pieces / 2.54 cm or less, and in most cases, 2 pieces / 2.54 cm or less. If the increase in the number of crimps greatly exceeds 4 pieces / 2.54 cm, the formation will be disturbed during processing of a nonwoven fabric or the like. In the present invention, the increase in the number of crimps refers to the difference in the number of crimps before and after heat treatment measured by the method described below.
【００２９】本発明の熱接着性複合繊維は、上述のごと
く、実質的に潜在捲縮性を有していないため、該複合繊
維を用いてウェブにすると、得られるウェブの熱収縮率
は１４５℃で５分間の加熱条件で１０％以下であり、ほ
とんどの場合５％以下である。ウェブの状態で測定され
た熱収縮率は不織布加工時の加工性、形態安定性の目安
となり、熱収縮率が１０％以下であると、フローティン
グドライヤ等の特別な装置を使用しなくても良好な地合
の不織布等の繊維成形体が得られる。逆に、熱収縮率が
１０％を大きく超えると不織布等の加工時に不織布等の
地合いが乱れたり、また嵩が低下することがあり好まし
くない。As described above, since the heat-adhesive conjugate fiber of the present invention does not substantially have latent crimpability, when the conjugate fiber is used as a web, the resulting web has a heat shrinkage of 145. It is 10% or less under the heating condition at 5 ° C. for 5 minutes, and in most cases 5% or less. The heat shrinkage measured in the state of the web is a measure of workability and morphological stability when processing the nonwoven fabric. When the heat shrinkage is 10% or less, it is good without using a special device such as a floating dryer. Thus, a fibrous formed body such as a nonwoven fabric having a proper formation can be obtained. Conversely, if the heat shrinkage rate greatly exceeds 10%, the formation of the nonwoven fabric or the like may be disturbed during processing of the nonwoven fabric or the like, and the bulk may be reduced, which is not preferable.
【００３０】本発明の熱接着性複合繊維は、プロピレン
系共重合体、結晶性ポリプロピレンをそれぞれ第１成
分、第２成分とし、第１成分を鞘成分とする偏心鞘芯型
または第１成分と第２成分の並列型の繊維断面および立
体捲縮のみを有する熱接着性複合繊維であって、強伸度
曲線から求められる弾性領域が４２％以上であるため、
強い立体捲縮が発現しており、また、該複合繊維は従来
技術では抑制できなかった潜在捲縮性が実質的に無いた
め、該複合繊維を用いて得られる不織布等の繊維成形体
は柔軟性、風合い、嵩高性に極めて優れたものとなる。
なお、ここでいう弾性領域が４２％以上であるプロピレ
ン系共重合体／結晶性ポリプロピレンの組合せからなる
複合繊維を得る方法および弾性領域が４２％以上でなけ
ればならない理由を次に述べる。The heat-adhesive conjugate fiber of the present invention comprises an eccentric sheath-core type or a first component comprising a propylene copolymer and crystalline polypropylene as a first component and a second component, respectively, and the first component as a sheath component. A thermoadhesive conjugate fiber having only the parallel-type fiber cross-section and three-dimensional crimp of the second component, and the elastic region determined from the strength-elongation curve is 42% or more.
Since a strong three-dimensional crimp is developed and the conjugate fiber has substantially no latent crimp that could not be suppressed by the prior art, a fiber molded article such as a nonwoven fabric obtained using the conjugate fiber is flexible. It is extremely excellent in properties, texture and bulkiness.
The method for obtaining a conjugated fiber comprising a combination of a propylene-based copolymer / crystalline polypropylene having an elastic region of 42% or more and the reason why the elastic region must be 42% or more will be described below.
【００３１】結晶性ポリプロピレンを特定条件下で紡
糸、熱処理すると、長周期の増大、福屈折の増加ととも
に、結晶構造の変化により、１００％伸張時に１００％
近い伸長弾性率を示すようになることが報告されてい
る。つまり、繊維を２倍に伸ばしても、その張力を解放
すると、その繊維は元の状態に戻る程の形態安定性を有
することを意味する。このような特性を有する繊維は、
一般にハードエラスティック繊維と呼ばれている。When the crystalline polypropylene is spun and heat-treated under specific conditions, the crystal structure changes due to an increase in the long cycle and an increase in the refraction.
It has been reported that they exhibit close elongation modulus. That is, even if the fiber is stretched twice, when the tension is released, the fiber has morphological stability enough to return to the original state. Fibers with such properties are
It is generally called hard elastic fiber.
【００３２】本発明者らは、このハードエラスティック
繊維について検討を続けた結果、ポリプロピレン系樹脂
の中でも結晶性が高いものほど伸長弾性率が向上しやす
く、結晶性が低いものほど伸張弾性率が向上しにくいと
の知見を得た。この知見をもとに、従来技術において
は、伸張弾性率が非常に近いプロピレン共重合体と結晶
性ポリプロピレンを複合紡糸しているため立体捲縮を付
与できないばかりか、高い潜在捲縮性を抑制することが
できなかった偏心鞘芯型もしくは並列型の複合形態を有
するプロピレン共重合体／結晶性ポリプロピレンの組合
せからなる複合繊維であっても、その特定の製造条件下
で、結晶性ポリプロピレンのハードエラスティック結晶
化を選択的に促進させ、鞘芯間の伸張弾性率差を大きく
することで、広い温度範囲で立体捲縮を発現させること
ができることを見出したものである。The present inventors have continued to study this hard elastic fiber. As a result, the higher the crystallinity among the polypropylene resins, the easier the elongation modulus is improved, and the lower the crystallinity, the more the elongation modulus. It was found that it was difficult to improve. Based on this knowledge, in the prior art, the propylene copolymer and the crystalline polypropylene, which have very close elongational elastic moduli, are combined and spun, so that not only three-dimensional crimping cannot be imparted, but also high latent crimpability is suppressed. Under the specific manufacturing conditions, even a composite fiber comprising a combination of a propylene copolymer / crystalline polypropylene having an eccentric sheath-core type or a parallel type composite form, It has been found that three-dimensional crimping can be developed in a wide temperature range by selectively promoting elastic crystallization and increasing the difference in extension modulus between the sheath and the core.
【００３３】結晶性ポリプロピレン単独からなるハード
エラスティック繊維は、強伸度曲線において、後述する
図１に示すような明瞭な一次降伏点と二次降伏点が観察
されることが知られており、これはハードエラスティッ
ク結晶が生成しているかどうかを示す有効な指標とな
る。ただし、本発明の熱接着性複合繊維では、ハードエ
ラスティック結晶化しやすい高結晶性のポリプロピレン
とハードエラスティック結晶化しにくい比較的結晶性の
低いプロピレン系共重合体を複合紡糸しており、強伸度
曲線において、ハードエラスティック結晶化した結晶性
ポリプロピレンとハードエラスティック結晶化していな
いプロピレン系共重合体の応力、伸びの挙動が合成され
て出現するため、後述する図２のように、ハードエラス
ティック結晶化した結晶性ポリプロピレン繊維で観察さ
れる一次降伏点は観察されず、前記二次降伏点に相当す
る通常の降伏点のみが観察される。It is known that a hard elastic fiber consisting of crystalline polypropylene alone has a clear primary yield point and a secondary yield point as shown in FIG. This is an effective index indicating whether a hard elastic crystal is formed. However, the heat-bonding conjugate fibers of the present invention, a composite spinning hard elastic crystals turned into easy high crystalline polypropylene and hard elastic crystals turned into hard relatively low crystallinity propylene copolymer, TsuyoShin in time curve, since the hard elastic crystals phased crystalline polypropylene and hard elastic crystals turned into non propylene based copolymer stress, the behavior of the elongation appearing been synthesized, as shown in FIG. 2 to be described later, Hadoera the primary yield point observed in crystalline polypropylene fibers has been turned into the stick crystal is not observed, only ordinary yield point corresponding to the secondary yield point is observed.
【００３４】本発明では、清水らによって提案されてい
る方法（繊維学会誌 Vol.36, No.4, T-169, (1980)）
を用いて、ハードエラスティック結晶が生成しているか
どうかを、強伸度曲線から求める弾性領域の大きさによ
り評価した。弾性領域は紡糸速度に依存して大きく変化
することが知られているが、本発明者らの検討では、熱
処理工程、延伸工程を調節することにより、最終的に得
られる複合繊維の弾性領域を４２％以上にすると、鞘芯
両成分間に十分な伸張弾性率の差が生じるため、強い立
体捲縮を付与することができ、不織布等の加工時に第１
成分の融点以上の温度で加熱処理を施しても、ウェブの
嵩が低下しにくくなり、不織布等の嵩高性が向上すると
ともに柔軟性も大きく向上する。この弾性領域が４２％
を下回ると、不織布等の嵩が低下し、また感触も硬くな
ってしまう。In the present invention, a method proposed by Shimizu et al. (Journal of the Textile Society of Japan, Vol. 36, No. 4, T-169, (1980))
Was used to evaluate whether or not a hard elastic crystal was formed, based on the size of the elastic region determined from the strength-elongation curve. It is known that the elastic region greatly changes depending on the spinning speed.However, in the study of the present inventors, by adjusting the heat treatment step and the drawing step, the elastic region of the composite fiber finally obtained is adjusted. When the content is 42% or more, a sufficient difference in elongation modulus between the sheath and the core occurs, so that a strong three-dimensional crimp can be provided, and the first non-woven fabric is processed at the time of processing a nonwoven fabric or the like.
Even if a heat treatment is performed at a temperature equal to or higher than the melting point of the components, the bulk of the web is hardly reduced, and the bulkiness of a nonwoven fabric or the like is improved, and the flexibility is greatly improved. This elastic area is 42%
If the ratio is less than 0.1, the bulk of the nonwoven fabric or the like is reduced, and the feel becomes hard.
【００３５】なお、本発明における弾性領域とは、後述
する図２に示した、強伸度曲線上における原点から降伏
点に達するまでの伸びから、次式を用いて決定する値で
ある。 弾性領域（％）＝降伏点までの伸び（ｍｍ）／試料長
（ｍｍ）×１００ なお、本発明でいう降伏点とは、ひずみ＝−１に相当す
る点、すなわち伸度−１００％の点から強伸度曲線へ引
いた接線が強伸度曲線と接する点と定義する。Note that the elastic region in the present invention is a value determined from the elongation from the origin on the strength-elongation curve to the yield point shown in FIG. Elastic region (%) = elongation to yield point (mm) / sample length (mm) × 100 The yield point referred to in the present invention is a point corresponding to strain = −1, that is, a point of elongation−100%. Is defined as the point where the tangent drawn from to the strong elongation curve is in contact with the strong elongation curve.
【００３６】以上のような特徴を本発明の熱接着性繊維
が有していることは、本発明の熱接着性複合繊維が従来
技術により製造される複合繊維と比べて、優れた不織布
加工性、形態安定性を保有していると同時に、本発明の
熱接着性複合繊維からは立体捲縮により得られる嵩高い
ウェブが持つ特性をそのまま生かした不織布、繊維成形
体が得られることを意味している。The fact that the heat-adhesive fiber of the present invention has the above-mentioned characteristics means that the heat-adhesive conjugate fiber of the present invention has an excellent nonwoven fabric processability as compared with the conjugate fiber manufactured by the prior art. Meaning that, while retaining the morphological stability, the heat-adhesive conjugate fiber of the present invention can provide a nonwoven fabric and a fiber molded product that directly utilize the properties of a bulky web obtained by three-dimensional crimping. ing.
【００３７】かかる本発明の熱接着性複合繊維の製造方
法および製造条件に限定はないが、公知の方法では得る
ことはできない。公知の立体捲縮繊維製造方法の一例と
して、特開昭５８−１２６３５７号公報で開示されてい
る内容を挙げることができる。該公報には、偏心鞘芯型
または並列型の複合形態を有するポリエチレン／結晶性
ポリプロピレンの組合せからなる熱接着性複合繊維の未
延伸糸を、２組の延伸ロールからなる延伸装置によって
延伸する際、生産ラインの流れにおける最初の延伸ロー
ル（以下、Ｎｏ．１延伸ロールという）を８０℃以上、
その次の延伸ロール（以下、Ｎｏ．２延伸ロールとい
う）を５０℃以下に温度設定した上で、Ｎｏ．１延伸ロ
ールとＮｏ．２延伸ロールの速度比を、該未延伸糸の延
伸倍率が３倍以上となるように調節し、該複合繊維に立
体捲縮を与える方法が開示されている。しかし、ポリエ
チレン／結晶性ポリプロピレンの組合せからなる複合繊
維に立体捲縮を与えるための一般的な条件を、近似した
伸張弾性率を有する樹脂を組合わせているプロピレン系
共重合体／結晶性ポリプロピレンの組合せからなる複合
繊維に応用しても、全く立体捲縮が発現しないばかり
か、１２０℃程度で１分程度加熱しただけでも３０個／
２．５４ｃｍ以上の捲縮が発現するような高潜在捲縮性
繊維となってしまう。仮にこの方法で立体捲縮が得られ
たとしても、高倍率で延伸することによりプロピレン系
共重合体の分子配向が進み、融点が上昇してしまうた
め、熱接着性に劣る複合繊維しか得られない。このた
め、従来の方法では、プロピレン系共重合体／結晶性ポ
リプロピレンの組合せからなる複合繊維においては低温
加工性に優れ、なおかつ熱に対して安定な立体捲縮を得
ることは極めて困難であった。The method and conditions for producing the heat-adhesive conjugate fiber of the present invention are not limited, but cannot be obtained by a known method. As an example of a known method for producing a three-dimensional crimped fiber, the content disclosed in JP-A-58-126357 can be mentioned. This publication discloses that an undrawn yarn of a heat-adhesive conjugate fiber composed of a combination of polyethylene / crystalline polypropylene having a composite form of an eccentric sheath-core type or a parallel type is drawn by a drawing device including two sets of drawing rolls. The first stretching roll in the flow of the production line (hereinafter referred to as No. 1 stretching roll)
After setting the temperature of the next stretching roll (hereinafter, referred to as No. 2 stretching roll) to 50 ° C. or lower, the No. 2 No. 1 stretching roll and No. 1 A method is disclosed in which the speed ratio of the two stretch rolls is adjusted so that the stretch ratio of the undrawn yarn is 3 times or more, and the composite fiber is given a three-dimensional crimp. However, the general conditions for imparting three-dimensional crimp to a composite fiber composed of a combination of polyethylene / crystalline polypropylene are set to the values of propylene-based copolymer / crystalline polypropylene combining resins having similar elongation moduli. Even when applied to a composite fiber composed of a combination, not only three-dimensional crimps are not expressed at all but also 30 fibers /
A high latent crimping fiber that develops a crimp of 2.54 cm or more is obtained. Even if a three-dimensional crimp is obtained by this method, since the molecular orientation of the propylene-based copolymer advances by stretching at a high magnification and the melting point rises, only a composite fiber having poor thermal adhesiveness is obtained. Absent. For this reason, in the conventional method, it is extremely difficult to obtain a three-dimensional crimp excellent in low-temperature processability and stable against heat in a composite fiber composed of a combination of a propylene-based copolymer / crystalline polypropylene. .
【００３８】しかし、本発明の製造方法によれば、かか
る熱接着性複合繊維を実用的に効率よく生産できる。す
なわち、プロピレン系共重合体を第１成分、結晶性ポリ
プロピレンを第２成分として構成される複合繊維であっ
て、その断面形状が、第１成分を鞘側、第２成分を芯側
とする偏心鞘芯型もしくは第１成分と第２成分との並列
型となるように、偏心鞘芯型紡糸口金または並列型紡糸
口金を備えた紡糸装置によって両成分を紡糸して得た複
合未延伸糸に熱処理を施して第２成分のみを選択的にハ
−ドエラステイック結晶化したのち、少なくとも１つの
延伸セクションにおいて１．２倍〜１．７倍の延伸倍率
で延伸し、その延伸セクションにおける工程の上流側の
延伸ロールの温度を８０℃以下、下流側の延伸ロールの
温度を３０〜１１０℃とし、かつ、該延伸装置における
最上流の延伸ロールと最下流の延伸ロールの速度比が
１．２〜２倍にすることを特徴とする熱接着性複合繊維
の製造方法により、製造することができる。However, according to the production method of the present invention, such a heat-adhesive conjugate fiber can be produced practically and efficiently. That is, the composite fiber is composed of a propylene-based copolymer as a first component and a crystalline polypropylene as a second component, and has a cross section having an eccentricity in which the first component is a sheath side and the second component is a core side. A composite undrawn yarn obtained by spinning both components by a spinning device equipped with an eccentric sheath-core spinneret or a parallel spinneret so as to be a sheath-core type or a parallel type of the first component and the second component. After heat treatment to selectively hard-elastically crystallize only the second component, it is stretched in at least one stretching section at a stretching ratio of 1.2 to 1.7 times, and upstream of the process in the stretching section. The temperature of the downstream stretching roll is 80 ° C. or less, the temperature of the downstream stretching roll is 30 ° C. to 110 ° C., and the speed ratio of the most upstream stretching roll and the most downstream stretching roll in the stretching apparatus is 1.2 to Double The method for producing a heat-adhesive composite fiber characterized by, can be produced.
【００３９】本発明では、公知の溶融複合紡糸装置を用
いることができるが、本発明の製造方法では、得られた
複合繊維の第２成分を選択的にハードエラスティック結
晶化させることが重要であり、このためには第２成分と
して用いる原料樹脂の結晶性に加え、紡糸条件も大きな
要因となる。In the present invention, a known melt composite spinning apparatus can be used. However, in the production method of the present invention, it is important to selectively crystallize the second component of the obtained composite fiber into a hard elastic crystal. For this purpose, spinning conditions are a major factor in addition to the crystallinity of the raw material resin used as the second component.
【００４０】本発明においては、プロピレン系共重合体
を第１成分、結晶性ポリプロピレンを第２成分として用
いるが、第１成分として用いるプロピレン系共重合体の
メルトフローレートは特に制限はなく、一般的に溶融紡
糸法において使用できる範囲、例えば０．１〜８０ｇ／
１０ｍｉｎのものを用いることができるが、可紡性、工
程安定性等の点から３〜４０ｇ／１０ｍｉｎのものがよ
り好ましい。In the present invention, the propylene copolymer is used as the first component and the crystalline polypropylene is used as the second component. The melt flow rate of the propylene copolymer used as the first component is not particularly limited. Range that can be used in the melt spinning method, for example, 0.1 to 80 g /
Although 10 min can be used, 3 to 40 g / 10 min is more preferable in view of spinnability, process stability and the like.
【００４１】また、第２成分として用いる結晶性ポリプ
ロピレンはメルトフローレートが０．１〜４０ｇ／１０
ｍｉｎのものを用いることができ、３〜２０ｇ／１０ｍ
ｉｎのものがより好ましい。該結晶性ポリプロピレンの
メルトフローレートが低すぎると可紡性、加工性に影響
を及ぼすことがあり、逆にメルトフローレートが高すぎ
ると、該結晶性ポリプロピレンの結晶性が低下するため
熱処理によるハードエラスティック結晶化が進みにくく
なり、鞘芯両成分間に立体捲縮を発現させるために必要
な伸長弾性率差を付与できなくなる。The crystalline polypropylene used as the second component has a melt flow rate of 0.1 to 40 g / 10
min to 3 g to 20 g / 10 m
In is more preferred. If the melt flow rate of the crystalline polypropylene is too low, spinnability and processability may be affected, and if the melt flow rate is too high, the crystallinity of the crystalline polypropylene is reduced, so that hardening by heat treatment is performed. Elastic crystallization does not easily proceed, and a difference in elongation modulus required for developing three-dimensional crimp between the sheath and core components cannot be provided.
【００４２】本発明の熱接着性複合繊維製造のために
は、まず第１成分を鞘側、第２成分を芯側とする偏心鞘
芯型もしくは第１成分と第２成分との並列型となるよう
に、偏心鞘芯型紡糸口金または並列型紡糸口金を備えた
押出機によって両成分を紡糸して複合繊維の未延伸糸を
得るが、この際、第２成分がハードエラスティック結晶
化しやすくするために第２成分の分子配向を抑制してお
く必要があり、このため紡糸速度をできる限り低くする
ことが好ましい。また、立体捲縮の発現性は繊度の影響
を受けるので、細繊化のためには第１成分、第２成分の
押出前後のメルトフローレートをそれぞれできるだけ低
くし、かつ、第１成分の押出後のメルトフローレートと
第２成分の押出後のメルトフローレートの差を小さくす
ることが好ましい。In order to produce the heat-adhesive conjugate fiber of the present invention, first, an eccentric sheath-core type in which the first component is the sheath side and the second component is the core side, or a parallel type of the first component and the second component is used. Thus, both components are spun by an extruder equipped with an eccentric sheath-core type spinneret or a parallel type spinneret to obtain an undrawn yarn of a conjugate fiber. At this time, the second component is easily crystallized by hard elastic crystallization. Therefore, it is necessary to suppress the molecular orientation of the second component, and it is therefore preferable to reduce the spinning speed as much as possible. In addition, since the expression of the three-dimensional crimp is affected by the fineness, the melt flow rates before and after the extrusion of the first component and the second component are reduced as much as possible for fineness, and the extrusion of the first component is reduced. It is preferable to reduce the difference between the subsequent melt flow rate and the melt flow rate after extrusion of the second component.
【００４３】本発明においては、得られた未延伸糸に用
いられている第２成分である結晶性ポリプロピレンをハ
ードエラスティック結晶化させるために、延伸前に熱処
理を施す必要がある。熱処理には、トウを乾燥するため
の汎用型のサクションドライヤなどの公知の熱処理装
置、乾燥装置などを用いることができる。熱処理の温度
と時間は未延伸糸の繊度に依存し、繊度が大きいほどハ
ードエラスティック結晶化が進みやすい。熱処理時間、
熱処理温度の目安として、特公平７−３５６０７号公報
に記載されているような熱処理条件（例えば、１１０℃
で熱処理した場合には４分程度、１００℃で１０分程
度）を採用できる。この熱処理により、第１成分と第２
成分との間に、立体捲縮を発現させるだけの十分な伸張
弾性率差を生じさせることができる。In the present invention, it is necessary to perform a heat treatment before drawing in order to crystallize the crystalline polypropylene as the second component used in the obtained undrawn yarn into a hard elastic crystal. For the heat treatment, a known heat treatment device such as a general-purpose suction dryer for drying the tow, a drying device, or the like can be used. The temperature and time of the heat treatment depend on the fineness of the undrawn yarn, and the higher the fineness, the easier the hard elastic crystallization proceeds. Heat treatment time,
As a standard of the heat treatment temperature, heat treatment conditions (for example, 110 ° C.) described in JP-B-7-35607.
For about 4 minutes, and about 100 minutes at 100 ° C.). By this heat treatment, the first component and the second component
A sufficient difference in elongation modulus between the components can be generated so as to develop a three-dimensional crimp.
【００４４】本発明の製造方法では、熱処理された未延
伸糸は、公知の延伸装置を用いて延伸することができ
る。公知の延伸装置とは、複数の加熱ロールを有する通
常２〜３組程度の延伸ロールからなる延伸装置を指す。
また、延伸装置には延伸ロール間にスチーム、電気など
による予熱装置や、延伸後のトウを引き取るためのロー
ル、圧縮空気による開繊機などが設置されているものも
あるが、これらは必要に応じて使用することができる。In the production method of the present invention, the undrawn yarn that has been heat-treated can be drawn using a known drawing device. The known stretching apparatus refers to a stretching apparatus that generally includes about two to three sets of stretching rolls having a plurality of heating rolls.
Some stretching devices are equipped with a preheating device such as steam or electricity between the stretching rolls, a roll for taking out the tow after stretching, and an opener using compressed air. Can be used.
【００４５】本発明の熱接着性複合繊維の製造方法で
は、２組以上の延伸ロールを有する延伸装置を用いて延
伸する際に、少なくとも１つの延伸セクションにおいて
１．２〜１．７倍の延伸倍率で延伸し、該延伸セクショ
ンにおける工程の上流側の延伸ロールの温度を８０℃以
下、下流側の延伸ロールの温度を３０〜１１０℃とし、
なおかつ該延伸装置における最上流の延伸ロールと最下
流の延伸ロールの速度比が１．２〜２倍である必要があ
る。ここでいう延伸セクションとは、例えば３組の延伸
ロールを有する延伸装置であれば、Ｎｏ．１延伸ロール
とＮｏ．２延伸ロール、Ｎｏ．２延伸ロールとＮｏ．３
延伸ロールのように、隣接する延伸ロールの対を指す。In the method for producing a heat-adhesive conjugate fiber according to the present invention, when drawing is performed using a drawing apparatus having two or more sets of drawing rolls, at least one drawing section has a draw ratio of 1.2 to 1.7 times. Stretching at a draw ratio, the temperature of the stretching roll on the upstream side of the process in the stretching section is 80 ° C. or less, the temperature of the stretching roll on the downstream side is 30 to 110 ° C.,
In addition, the speed ratio between the most upstream stretching roll and the most downstream stretching roll in the stretching apparatus needs to be 1.2 to 2 times. The stretching section referred to here is, for example, a stretching apparatus having three sets of stretching rolls. No. 1 stretching roll and No. 1 No. 2 stretching roll, No. No. 2 stretching roll and No. 2 3
Like a draw roll, refers to a pair of adjacent draw rolls.
【００４６】なお、Ｎｏ．１延伸ロールの設定温度を８
０℃を超える温度にまで上げると、弾性領域の減少が認
められるとともに、捲縮発現性が低下する。捲縮発現性
の低下を延伸倍率を上げることによって補おうとする
と、得られる複合繊維の潜在捲縮性が高くなり、不織布
加工時における形態安定性が低下してしまう。また、Ｎ
ｏ．２延伸ロールの設定温度は３０〜１１０℃の範囲で
あれば安定して捲縮を発現させることができるが、６５
〜９５℃の範囲であることが好ましい。なお、該延伸セ
クションの上流側延伸ロールの設定温度の下限値につい
ては特に制限はなく、延伸ロールの温度制御装置を切っ
た状態で本発明の熱接着性複合繊維を製造しても一向に
問題がなく、また該延伸ロールを冷却してもよい。しか
し、延伸ロールの冷却はコストが嵩むため現実的ではな
く、また、延伸ロールの温度制御装置を切った状態では
季節間の温度差により、品質に季節間変動が見られるこ
ともあるので、品質管理の点から４０℃程度を下限とす
ることが好ましく、より好ましくは４０〜８０℃、さら
に好ましくは４０〜６０℃である。No. Set temperature of 1 stretch roll to 8
When the temperature is raised to a temperature exceeding 0 ° C., a decrease in the elastic region is recognized, and the crimping property decreases. If an attempt is made to compensate for the decrease in crimp development by increasing the draw ratio, the latent crimpability of the resulting composite fiber will increase, and the morphological stability during nonwoven fabric processing will decrease. Also, N
o. 2 If the set temperature of the stretching roll is in the range of 30 to 110 ° C., the crimp can be stably developed.
It is preferably in the range of ９５95 ° C. The lower limit of the set temperature of the upstream stretching roll of the stretching section is not particularly limited, and even if the thermoadhesive conjugate fiber of the present invention is manufactured in a state where the temperature control device of the stretching roll is turned off, there is no problem. Alternatively, the stretching roll may be cooled. However, the cooling of the stretching rolls is not realistic because of the high cost.In addition, when the temperature control device for the stretching rolls is turned off, the seasonal temperature difference may cause a seasonal variation in the quality. From the viewpoint of management, the lower limit is preferably about 40 ° C, more preferably 40 to 80 ° C, and still more preferably 40 to 60 ° C.
【００４７】また、延伸倍率を低く設定することによ
り、熱処理によって生成した結晶性ポリプロピレン内部
の積層ラメラ構造を、延伸によって破壊せずに済み、芯
成分に高い弾性を持たせたまま、強い立体捲縮を得るこ
とができるので、１つの延伸セクションにおける延伸倍
率は１．２〜１．７倍とし、延伸工程全体としての延伸
倍率は１．２〜２倍の範囲とする必要がある。１．２倍
未満の延伸倍率では、該未延伸糸は実質的にほとんど延
伸されない状態であるため捲縮が発現し難く、逆に、１
つの延伸セクションにおいて１．７倍を大きく上回るよ
うな倍率で、または全体として２倍を超える延伸倍率で
延伸してしまうと第１成分の分子配向が進むとともに、
第１成分の融点が上昇し、両成分間の融点差が小さくな
るため、得られる複合繊維の低温加工性が悪化する、不
織布加工時に潜在捲縮が発現し形態安定性が悪化する、
クリンプが細かくなりすぎてしまいカード性に悪影響を
与えるなどの問題が発生する。By setting the stretching ratio to a low value, the laminated lamella structure inside the crystalline polypropylene formed by the heat treatment can be prevented from being broken by stretching, and a strong three-dimensional winding can be performed while the core component has high elasticity. Since shrinkage can be obtained, the stretching ratio in one stretching section needs to be 1.2 to 1.7 times, and the stretching ratio in the entire stretching process needs to be in the range of 1.2 to 2 times. At a draw ratio of less than 1.2 times, the undrawn yarn is in a state where it is substantially not drawn, so that it is difficult to develop crimp.
If the stretching is performed at a stretching ratio that greatly exceeds 1.7 times in one stretching section, or at a stretching ratio that exceeds 2 times as a whole, the molecular orientation of the first component proceeds, and
Since the melting point of the first component is increased and the difference in melting point between the two components is reduced, the low-temperature processability of the obtained conjugate fiber is deteriorated.
Problems such as the crimp becoming too fine and adversely affecting the card properties occur.
【００４８】以上のような製造方法で得られた熱接着性
複合繊維は、強伸度曲線から求められる弾性領域が４２
％以上となり、かかる複合繊維を用いると得られる不織
布等は柔軟性、風合い、嵩高性に極めて優れたものとな
る。The heat-adhesive conjugate fiber obtained by the above-mentioned production method has an elastic region of 42 determined from the strength-elongation curve.
% Or more, and the nonwoven fabric and the like obtained by using such a conjugate fiber are extremely excellent in flexibility, texture and bulkiness.
【００４９】本発明の熱接着性複合繊維は、公知の溶融
紡糸法等を用い、マルチフィラメント、モノフィラメン
ト、ステープルファイバー、チョップ、トウとして適宜
得ることができる。本発明の熱接着性複合繊維をカード
工程を必要とするステープルファイバーとして使用する
場合には、該複合繊維に良好なカード通過性を付与する
ために、捲縮数を適切な範囲とすることが望ましい。最
適捲縮数は該複合繊維の繊度によって変わってくるが、
通常は、４〜１２山／２．５４ｃｍであることが好まし
い。捲縮数は延伸倍率を変えることで調整できる。捲縮
数が４山／２．５４ｃｍを大きく下回る場合には、カー
ド加工時に該複合繊維がシリンダーやドッファに巻き付
いたり、ウェブが切れてしまったりといった問題が生じ
やすくなり、逆に１２山／２．５４ｃｍを大きく超える
場合には、カード加工時にネップが発生したり、均一な
ウェブを得ることが難しくなるといった問題が生じる。The heat-adhesive conjugate fiber of the present invention can be appropriately obtained as a multifilament, a monofilament, a staple fiber, a chop, and a tow using a known melt spinning method or the like. When the heat-adhesive conjugate fiber of the present invention is used as a staple fiber requiring a card step, in order to impart good card permeability to the conjugate fiber, the number of crimps may be set to an appropriate range. desirable. The optimal number of crimps varies depending on the fineness of the composite fiber,
Usually, it is preferable to be 4 to 12 peaks / 2.54 cm. The number of crimps can be adjusted by changing the stretching ratio. If the number of crimps is significantly less than 4 crests / 2.54 cm, problems such as the wrapping of the composite fiber around a cylinder or a doffer or breakage of the web during card processing are likely to occur. If it exceeds 0.54 cm, problems occur such as nep generation during card processing and difficulty in obtaining a uniform web.
【００５０】本発明の熱接着性複合繊維の繊度は特に限
定されるものではない。第１成分として使用するプロピ
レン系共重合体の物性や、該複合繊維の用途に応じて適
宜選択すればよい。例えば、使い捨てオムツ、生理用ナ
プキンの表面材等の吸収性物品等に代表される衛生材料
に用いる場合には１〜１０ｄｔｅｘの範囲、ニードルパ
ンチカーペットやタフテッドカーペット等に用いる場合
には、８〜８０ｄｔｅｘの範囲、モノフィラメント等の
土木材料に用いる場合には、５０〜７０００ｄｔｅｘの
範囲がそれぞれ好ましい。The fineness of the heat-adhesive conjugate fiber of the present invention is not particularly limited. What is necessary is just to select suitably according to the physical property of the propylene-type copolymer used as a 1st component, and the use of this composite fiber. For example, when used for sanitary materials such as absorbent articles such as disposable diapers and sanitary napkin surface materials, the range is 1 to 10 dtex, and when used for needle punch carpets and tufted carpets, 8 to 10 dtex. When used for civil engineering materials such as monofilaments in the range of 80 dtex, the range of 50 to 7000 dtex is preferable.
【００５１】本発明の熱接着性複合繊維の繊度は特に限
定されるものではない。該複合繊維の加工法、用途に応
じて適宜選択すればよい。ローラーカード機またはラン
ダムウエバー等により、ランダムウェブ、パラレルウェ
ブやクロスラップウェブ等の繊維ウェブを作製する場合
にはカット長は２０〜１２５ｍｍとすることが好まし
く、またカード通過性、地合いの良い不織布等を得るた
めには、２５〜７５ｍｍのカット長がより好ましい。ま
た、エアーレイド法、抄紙法により繊維ウェブを作製す
る場合には、カット長は２０ｍｍ未満とすることが好ま
しい。The fineness of the heat-adhesive conjugate fiber of the present invention is not particularly limited. What is necessary is just to select suitably according to the processing method and use of this composite fiber. When fabricating a fibrous web such as a random web, a parallel web or a cross-wrap web with a roller card machine or a random weber, the cut length is preferably 20 to 125 mm, and a nonwoven fabric with good card passing properties and good formation In order to obtain, a cut length of 25 to 75 mm is more preferable. When a fiber web is produced by an air laid method or a papermaking method, the cut length is preferably less than 20 mm.
【００５２】本発明の熱接着性複合繊維を用いて不織布
等に代表される繊維成形体を得るためには、主として該
複合繊維からなるウェブに熱処理を施こす必要がある。
不織布等の加工には、汎用の熱風循環型不織布加工機が
使用できる。In order to obtain a fibrous molded article typified by a nonwoven fabric or the like using the heat-adhesive conjugate fiber of the present invention, it is necessary to heat-treat a web mainly composed of the conjugate fiber.
A general-purpose hot air circulation type nonwoven fabric processing machine can be used for processing the nonwoven fabric and the like.
【００５３】また、本発明の熱接着性複合繊維で不織布
等の繊維成形体を得る場合には、該不織布等の繊維成形
体の目付は、使用目的によって適宜選ぶことができる。
例えば、吸収性物品の表面材等に使用する場合には、５
〜１００ｇ／ｍ2の範囲、ドレーン材等の土木資材に用
いる場合には、５０〜２０００ｇ／ｍ2の範囲がそれぞ
れ好ましい。When a fiber molded article such as a nonwoven fabric is obtained from the heat-adhesive conjugate fiber of the present invention, the basis weight of the fiber molded article such as the nonwoven fabric can be appropriately selected depending on the purpose of use.
For example, when used as a surface material of an absorbent article, 5
To 100 g / m 2 range, when used in construction materials of the drain member and the like, a preferred range of 50 to 2000 g / m 2, respectively.
【００５４】また、不織布等の繊維成形体は目的に応じ
て積層することができ、スパンボンド不織布／ポリプロ
ピレン系熱接着性複合繊維からなる不織布等の組み合わ
せ、スパンボンド不織布／メルトブロー不織布／潜在捲
縮性複合繊維からなる不織布等の組み合わせ等を例示で
きる。A fiber molded article such as a nonwoven fabric can be laminated according to the purpose, and a combination of a spunbonded nonwoven fabric / a nonwoven fabric made of a polypropylene-based heat-adhesive conjugate fiber, a spunbonded nonwoven fabric / a melt-blown nonwoven fabric / a latent crimp. And combinations of nonwoven fabrics and the like made of conductive composite fibers.
【００５５】[0055]
【実施例】次に、本発明を実施例によって具体的に説明
するが、本発明は以下の実施例に限定されるものではな
い。なお、明細書、実施例、比較例において用いられて
いる用語の定義及び測定方法は以下の通りである。Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to the following examples. The definitions of terms used in the description, examples, and comparative examples and measurement methods are as follows.
【００５６】（１）ＭＦＲ：（単位 ｇ／１０分） 樹脂のメルトフローレートはＪＩＳ Ｋ ７２１０ 条
件１４（２３０℃、２１．１８Ｎ）に準じて測定した。
なお、表中に示したメルトフローレートは紡糸前のプロ
ピレン系重合体を試料とし測定した値である。(1) MFR: (unit: g / 10 minutes) The melt flow rate of the resin was measured according to JIS K 7210 condition 14 (230 ° C., 21.18 N).
The melt flow rate shown in the table is a value measured using a propylene polymer before spinning as a sample.
【００５７】（２）融点：（単位 ℃） ＤｕＰｏｎｔ社製示差走査熱量計ＤＳＣ−１０により、
原料樹脂または繊維を１０℃／ｍｉｎで昇温した時に得
られた融解吸収曲線上のピークに対応する温度をその樹
脂または繊維の融点とした。(2) Melting point: (unit: ° C.) According to a differential scanning calorimeter DSC-10 manufactured by DuPont,
The temperature corresponding to the peak on the melting absorption curve obtained when the temperature of the raw resin or fiber was raised at 10 ° C./min was defined as the melting point of the resin or fiber.
【００５８】（３）Ｑ値：（重量平均分子量／数平均分
子量） Ｑ値は、ゲルパーミエイションクロマトグラフ法により
求めた樹脂の重量平均分子量（Ｍｗ）と数平均分子量
（Ｍｎ）の比（Ｍｗ／Ｍｎ）である。なお、ここでは紡
糸前の樹脂の値を示した。(3) Q value: (weight average molecular weight / number average molecular weight) The Q value is determined by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the resin obtained by gel permeation chromatography. Mw / Mn). Here, the values of the resin before spinning are shown.
【００５９】（４）強度（単位ｃＮ／ｄｔｅｘ）および
伸度（単位 ％） 繊度が８８０〜１３２０ｄｔｅｘとなるように繊維束を
採取し、これを試料として島津製作所製ＡＧ−５００Ｄ
を用いて、試料長５０ｍｍ、引っ張り速度５０ｍｍ／ｍ
ｉｎ（１００％／ｍｉｎ）の条件で試料の強度、伸度を
測定した。なお、ここでいう強度とは試料が示した最大
の強度を試料の繊度で除したものであり、伸度は試料の
破断伸度を指す。(4) Strength (unit: cN / dtex) and elongation (unit:%) A fiber bundle was collected so that the fineness became 880 to 1320 dtex, and this was used as a sample to make AG-500D manufactured by Shimadzu Corporation.
Using a sample length of 50 mm and a pulling speed of 50 mm / m
The strength and elongation of the sample were measured under the conditions of in (100% / min). The strength referred to herein is a value obtained by dividing the maximum strength of the sample by the fineness of the sample, and the elongation indicates the elongation at break of the sample.
【００６０】（５）繊度：（単位 ｄｔｅｘ） 繊維を走査型電子顕微鏡によって観察し、得られた画像
から１００本の繊維の直径を測定し、その平均値から繊
度を算出した。(5) Fineness: (unit: dtex) The fibers were observed with a scanning electron microscope, the diameter of 100 fibers was measured from the obtained image, and the fineness was calculated from the average value.
【００６１】（６）熱処理前後の捲縮数：（単位 山／
２．５４ｃｍ） まず、試料原綿についてＪＩＳ Ｌ１０１５ ７．１
２．１の条件に準じ、２０本の繊維についてデニール当
たり２ｍｇの荷重をかけたときの２．５４ｃｍ（１イン
チ）当たりの捲縮数を数え、平均した値を捲縮数（熱処
理前）とした。さらに、この試料原綿をクラフト紙上に
拡げ、１２０℃に維持した熱風循環型乾燥機内で直接熱
風が当たらないようにして状態で５分間加熱処理した。
この熱処理を施した原綿について、同様にして捲縮数を
数え、熱処理後の捲縮数から熱処理前の捲縮数を差し引
いたものを捲縮の増加分とした。(6) Number of crimps before and after heat treatment: (unit mountain /
2.54 cm) First, JIS L1015 7.1 for the sample raw cotton
According to the conditions in 2.1, the number of crimps per 2.54 cm (1 inch) when a load of 2 mg per denier was applied to 20 fibers was counted, and the average value was defined as the number of crimps (before heat treatment). did. Further, the sample raw cotton was spread on kraft paper, and was heated for 5 minutes in a hot air circulation type drier maintained at 120 ° C. so as not to be directly exposed to hot air.
The number of crimps of the raw cotton subjected to the heat treatment was similarly counted, and the value obtained by subtracting the number of crimps before the heat treatment from the number of crimps after the heat treatment was defined as an increase in crimp.
【００６２】（７）熱収縮率：（単位 ％） ２５×２５ｃｍ、目付約２００ｇ／ｍ2のウェブを、ク
ラフト紙にのせて１４５℃に維持した対流型熱風乾燥機
に入れ、５分間加熱処理した。熱処理前後のウェブのＭ
Ｄ、ＣＤのそれぞれの長さから、熱収縮率を次式により
算出した。 熱収縮率（％）＝（１−ａ／２５）×１００ なお、式中のａは熱処理後のウェブの機械方向の長さで
ある。(7) Heat shrinkage ratio: (unit%) A web having a size of 25 × 25 cm and a basis weight of about 200 g / m 2 was put on a kraft paper, placed in a convection hot air dryer maintained at 145 ° C., and heated for 5 minutes. did. M of web before and after heat treatment
From the respective lengths of D and CD, the heat shrinkage was calculated by the following equation. Heat shrinkage (%) = (1−a / 25) × 100 where a is the length of the web after heat treatment in the machine direction.
【００６３】（８）弾性領域：（単位 ％） （４）で得られた強伸度曲線から降伏点を求め、原点か
ら降伏点に達するまでの伸びから、次式を用いて算出し
た。 弾性領域（％）＝降伏点までの伸び（ｍｍ）／試料長
（ｍｍ）×１００ なお、本発明でいう降伏点とは、ひずみ＝−１に相当す
る点、すなわち伸度−１００％の点から強伸度曲線へ引
いた接線が強伸度曲線と接する点を指す。(8) Elastic region: (unit%) The yield point was determined from the strength-elongation curve obtained in (4), and was calculated from the elongation from the origin to the yield point using the following equation. Elastic region (%) = elongation to yield point (mm) / sample length (mm) × 100 The yield point referred to in the present invention is a point corresponding to strain = −1, that is, a point of elongation−100%. Refers to the point where the tangent drawn from to the strength-elongation curve touches the strength-elongation curve.
【００６４】（９）比容積：（単位 ｃｍ3／ｇ） それぞれの試料を不織布化し、東洋精機製デジシックネ
ステスタを用い、２ｇ／ｃｍ2の荷重が不織布に加えら
れた時の厚みを測定し、比容積を算出した。(9) Specific volume: (unit: cm 3 / g) Each sample was made into a non-woven fabric, and the thickness of the non-woven fabric when a load of 2 g / cm 2 was applied to the non-woven fabric was measured using a Toyo Seiki Digisic nest tester. The specific volume was calculated.
【００６５】（１０）ウェブの地合い 試料原綿約５０ｇをミニチュアカード機に投入し、約２
５ｇ／ｍ2のウェブを得た。このウェブの地合いを以下
の基準で目視判定した。 ○：均一に開繊され全く乱れがないもの ×：未開繊の繊維が若干混じっているかまたはネップが
発生しているもの(10) Web formation About 50 g of raw cotton wool was put into a miniature card machine, and
A web of 5 g / m 2 was obtained. The formation of the web was visually determined according to the following criteria. ：: Uniformly opened and completely undisturbed ×: Unopened fibers are slightly mixed or neps are generated
【００６６】（１1）不織布の風合い 目付２５ｇ／ｍ2のスルーエア不織布を作製し、その不
織布の触感を１０人のパネラーによる官能試験によっ
て、以下の基準で風合いを４段階で採点した。 ◎：柔軟な感触を有し、嵩高いもの ○：嵩高性または柔軟性のいずれかが若干欠けるが、実
用上全く問題ないもの △：若干収縮が認められ、嵩が減少しているか、または
嵩が低いもの ×：収縮により地合いが乱れ、実用上使用できないと考
えられるもの(11) Texture of Nonwoven Fabric A through-air nonwoven fabric having a basis weight of 25 g / m 2 was prepared, and the feel of the nonwoven fabric was scored on a 4-point scale based on the following criteria by a sensory test conducted by 10 panelists. ◎: Soft feeling and bulky ○: Either bulkiness or flexibility is slightly lacking, but there is no practical problem at all △: Slight shrinkage is observed and bulk is reduced or bulk Low: ×: The texture is disturbed by shrinkage, and it is considered that it cannot be used practically.
【００６７】実施例１〜６ 後述の表１に示される第１成分（Co.-PPはプロピレン系
共重合体を意味する）と第２成分（結晶性ポリプロピレ
ン）とを、押出機、孔径０．８ｍｍの偏心鞘芯型紡糸口
金または並列型紡糸口金、巻取り装置等を備えた紡糸装
置ならびに２組の延伸ロールと引き取りロールを備えた
延伸装置から構成される紡糸装置において、表１に示さ
れる条件で紡糸し、実施例１〜６の各々の複合繊維を得
た。得られた各複合繊維の繊維物性を（４）〜（７）の
測定方法に準拠して測定した。得られた結果は表１の糸
質の項目に示した。また、各複合繊維のカード性、不織
布物性を（８）〜（１１）の測定方法に準拠して測定し
た。得られた結果は表１の不織布物性の項目に示した。
これらの結果より、いずれの実施例においても、従来、
偏心鞘芯型または並列型のプロピレン系共重合体／結晶
性ポリプロピレンの組合せからなる複合繊維において最
大の問題であった熱収縮率は極めて低く抑制されてお
り、またこれらの複合繊維からは嵩高性、風合いに優れ
た不織布が得られた。Examples 1 to 6 A first component (Co.-PP means a propylene-based copolymer) and a second component (crystalline polypropylene) shown in Table 1 below were mixed with an extruder and a pore size of 0. Table 1 shows a spinning apparatus including an eccentric sheath-core spinneret or a parallel-type spinneret of 0.8 mm, a spinning apparatus having a winding device, and a drawing device having two sets of drawing rolls and a take-up roll. The composite fiber of each of Examples 1 to 6 was obtained. The fiber properties of each of the obtained composite fibers were measured according to the measurement methods (4) to (7). The obtained results are shown in the item of yarn quality in Table 1. The card properties and nonwoven fabric properties of each composite fiber were measured according to the measurement methods (8) to (11). The obtained results are shown in Table 1 in the item of physical properties of the nonwoven fabric.
From these results, in any of the examples,
The most problematic thermal shrinkage of composite fibers composed of eccentric sheath-core or side-by-side propylene-based copolymer / crystalline polypropylene combinations is extremely low, and these composite fibers are bulky. Thus, a nonwoven fabric having an excellent texture was obtained.
【００６８】実施例７〜１２ 後述の表２に示される第１成分（Co.-PPはプロピレン系
共重合体を意味する）と第２成分（結晶性ポリプロピレ
ン）とを、押出機、孔径０．８ｍｍの偏心鞘芯型紡糸口
金または並列型紡糸口金、巻取り装置等を備えた紡糸装
置ならびに２組の延伸ロールと引き取りロールを備えた
延伸装置から構成される紡糸装置において、表２に示さ
れる条件で紡糸し、実施例７〜１２の各々の複合繊維を
得た。得られた各複合繊維の繊維物性を（４）〜（７）
の測定方法に準拠して測定した。得られた結果は表１の
糸質の項目に示した。また、各複合繊維のカード性、不
織布物性を（８）〜（１１）の測定方法に準拠して測定
した。得られた結果は表２の不織布物性の項目に示し
た。これらの結果より、いずれの実施例においても、従
来、偏心鞘芯型または並列型のプロピレン系共重合体／
結晶性ポリプロピレンの組合せからなる複合繊維におい
て最大の問題であった熱収縮率は極めて低く抑制されて
おり、またこれらの複合繊維からは嵩高性、風合いに優
れた不織布が得られた。Examples 7 to 12 A first component (Co.-PP means a propylene-based copolymer) and a second component (crystalline polypropylene) shown in Table 2 below were mixed with an extruder and a pore size of 0. Table 2 shows a spinning apparatus including a 0.8 mm eccentric sheath-core type spinneret or a parallel type spinneret, a spinning apparatus having a winding device, and a drawing device having two sets of drawing rolls and a take-up roll. The conjugate fiber of each of Examples 7 to 12 was obtained. The fiber properties of each of the obtained composite fibers were determined in (4) to (7).
The measurement was performed according to the measurement method described above. The obtained results are shown in the item of yarn quality in Table 1. The card properties and nonwoven fabric properties of each composite fiber were measured according to the measurement methods (8) to (11). The obtained results are shown in Table 2 in the item of physical properties of the nonwoven fabric. From these results, in any of the examples, the eccentric sheath-core type or the parallel type propylene-based copolymer /
The heat shrinkage, which was the biggest problem in the composite fiber composed of a combination of crystalline polypropylene, was suppressed to an extremely low level, and a nonwoven fabric excellent in bulkiness and texture was obtained from these composite fibers.
【００６９】比較例1〜6 後述の表３に示される第１成分（Co.-PPはプロピレン系
共重合体を意味する）と第２成分（結晶性ポリプロピレ
ン）とを、押出機、孔径０．８ｍｍの偏心鞘芯型紡糸口
金または並列型紡糸口金、巻取り装置等を備えた紡糸装
置ならびに２組の延伸ロールと引き取りロールを備えた
延伸装置から構成される紡糸装置において、表３に示さ
れる条件で紡糸し、比較例１〜６の各々の複合繊維を得
た。得られた各複合繊維の繊維物性を（４）〜（７）の
測定方法に準拠して測定した。得られた結果は表３の糸
質の項目に示した。また、各複合繊維のカード性、不織
布物性を（８）〜（１１）の測定方法に準拠して測定し
た。得られた結果は表３の不織布物性の項目に示した。
比較例１〜６は延伸前に熱処理をせずに立体捲縮を発現
させた繊維である。これらの繊維はカード性、不織布物
性は問題なかったものの、嵩高性が若干不十分であっ
た。Comparative Examples 1 to 6 A first component (Co.-PP means a propylene-based copolymer) and a second component (crystalline polypropylene) shown in Table 3 below were mixed with an extruder and a pore size of 0. Table 3 shows a spinning apparatus including a 0.8 mm eccentric sheath-core spinneret or a parallel spinneret, a spinning apparatus having a winding device, and a drawing device having two sets of drawing rolls and a take-up roll. The composite fiber of each of Comparative Examples 1 to 6 was obtained. The fiber properties of each of the obtained composite fibers were measured according to the measurement methods (4) to (7). The obtained results are shown in the item of yarn quality in Table 3. The card properties and nonwoven fabric properties of each composite fiber were measured according to the measurement methods (8) to (11). The obtained results are shown in Table 3 in the item of physical properties of the nonwoven fabric.
Comparative Examples 1 to 6 are fibers in which a three-dimensional crimp is developed without heat treatment before stretching. These fibers had no problem in cardability and physical properties of non-woven fabric, but had slightly insufficient bulkiness.
【００７０】比較例7〜1０ 後述の表４に示される第１成分（Co.-PPはプロピレン系
共重合体を意味する）と第２成分（結晶性ポリプロピレ
ン）とを、押出機、孔径０．８ｍｍの偏心鞘芯型紡糸口
金または並列型紡糸口金、巻取り装置等を備えた紡糸装
置において、２組の延伸ロールとクリンパーを備えた延
伸装置を用いて比較例７、８の複合繊維を、２組の延伸
ロールと引き取りロールを備えた延伸装置を用いて比較
例９、１０の複合繊維をそれぞれ製造した。得られた各
複合繊維の繊維物性を（４）〜（７）の測定方法に準拠
して測定した。得られた結果は表４の糸質の項目に示し
た。また、各複合繊維のカード性、不織布物性を（８）
〜（１１）の測定方法に準拠して測定した。得られた結
果は表４の不織布物性の項目に示した。比較例７、８
は、実施例１、２、３、４、６等と同じ原料樹脂を用
い、常法により製造した複合繊維であるが、表から明ら
かなように、高潜在捲縮性の繊維となり、得られた不織
布は収縮による引きつりが見られ劣悪であった。また比
較例９ではNo.1延伸ロールの温度を９０℃としたが、立
体捲縮を発現させるためには延伸倍率を１．８倍まで上
げなければならなかったため、比較例７、８と同様な高
潜在捲縮性繊維となり、高い収縮を示した。このため、
この繊維から得られた不織布は引きつりがみられ形態安
定性、嵩高性にかけるものであった。比較例１０は延伸
倍率が本発明の製造方法と異なるものであるが、捲縮が
細かくなりすぎてしまったため、ウェブの地合いは悪
く、また高い潜在捲縮性を示すようになった。Comparative Examples 7 to 10 A first component (Co.-PP means a propylene-based copolymer) and a second component (crystalline polypropylene) shown in Table 4 below were mixed with an extruder and a pore size of 0. In a spinning apparatus equipped with a 0.8 mm eccentric sheath-core spinneret or a parallel spinneret, a winding device, and the like, the conjugate fibers of Comparative Examples 7 and 8 were drawn using a drawing apparatus having two sets of drawing rolls and a crimper. The conjugate fibers of Comparative Examples 9 and 10 were produced using a drawing apparatus provided with two sets of drawing rolls and take-up rolls. The fiber properties of each of the obtained composite fibers were measured according to the measurement methods (4) to (7). The obtained results are shown in the item of yarn quality in Table 4. In addition, the card properties and non-woven fabric properties of each conjugate fiber were determined by (8)
It measured based on the measuring method of-(11). The obtained results are shown in Table 4 in the item of physical properties of the nonwoven fabric. Comparative Examples 7 and 8
Is a conjugate fiber produced by a conventional method using the same raw material resin as in Examples 1, 2, 3, 4, 6 and the like. The non-woven fabric was poor due to pulling due to shrinkage. In Comparative Example 9, the temperature of the No. 1 stretching roll was 90 ° C., but in order to develop three-dimensional crimping, the stretching ratio had to be increased to 1.8 times. High crimped fiber with high shrinkage. For this reason,
The non-woven fabric obtained from the fibers was found to be stiff and had a dimensional stability and bulkiness. In Comparative Example 10, although the stretching ratio was different from that of the production method of the present invention, the crimp was too fine, so that the web had poor texture and high potential crimpability.
【００７１】[0071]
【表１】 [Table 1]
【００７２】[0072]
【表２】 [Table 2]
【００７３】[0073]
【表３】 [Table 3]
【００７４】[0074]
【表４】 [Table 4]
【００７５】[0075]
【発明の効果】プロピレン系共重合体を第１成分とし、
結晶性ポリプロピレンを第２成分として構成され、偏心
鞘芯型または並列型の繊維断面および４２％以上の弾性
領域を有する本発明の熱接着性複合繊維は、従来のかか
る樹脂の組み合わせからなる複合繊維にはなかった、熱
に対して安定な立体捲縮のみを有し、潜在捲縮性を有さ
ず、かつ、高い立体捲縮発現性を有しているために、１
２０℃で５分間加熱処理しても捲縮数が実質的に増加し
ない。このため、本発明の複合繊維からは、プロピレン
系共重合体／結晶性ポリプロピレンの組合せからなる複
合繊維では従来得られなかった嵩高性、柔軟性を有する
不織布等の繊維成形体を得ることが可能となった。さら
に本発明の繊維は第１成分、第２成分に同種系統の樹脂
を使用しているため、リサイクル性にも優れている。さ
らに、本発明の複合繊維の製造方法によれば、第１成分
を鞘成分、第２成分を芯成分とした偏芯鞘芯型または第
１成分と第２成分が並列型になるように紡糸された未延
伸糸を熱処理し、第２成分のみを選択的にハードエラス
ティック結晶化させた後、２組以上の延伸ロールを有す
る延伸装置を用いて延伸する際に、少なくとも一つの延
伸セクションにおいて１．２〜１．７倍で延伸し、該延
伸セクションにおける上流側延伸ロールを８０℃以下、
下流側延伸ロールを６０〜１１０℃とし、さらに該延伸
装置における最上流延伸ロールと最下流の延伸ロールと
の速度比を１．２〜２倍に設定することにより、良好な
立体捲縮が発現するとともに、実質的に潜在捲縮性を有
しない複合繊維を容易に製造することができる。According to the present invention, a propylene copolymer is used as a first component,
The heat-adhesive conjugate fiber of the present invention, which is composed of crystalline polypropylene as the second component and has an eccentric sheath-core or side-by-side fiber cross section and an elastic area of 42% or more, is a conjugate fiber composed of a conventional combination of such resins. It has only a three-dimensional crimp that is stable to heat, has no latent crimpability, and has a high three-dimensional crimp development property.
The number of crimps does not substantially increase even after heat treatment at 20 ° C. for 5 minutes. For this reason, from the composite fiber of the present invention, it is possible to obtain a fibrous molded article such as a nonwoven fabric having bulkiness and flexibility, which has not been conventionally obtained with a composite fiber composed of a combination of a propylene-based copolymer / crystalline polypropylene. It became. Further, the fibers of the present invention are excellent in recyclability since the same type of resin is used for the first component and the second component. Furthermore, according to the method for producing a conjugate fiber of the present invention, spinning is performed such that an eccentric sheath-core type in which the first component is a sheath component and a second component is a core component, or the first component and the second component are in a parallel type. After the heat treatment of the drawn undrawn yarn and selective hard elastic crystallization of only the second component, when drawing using a drawing device having two or more sets of drawing rolls, at least one drawing section Stretching at 1.2 to 1.7 times, the upstream stretching roll in the stretching section is 80 ° C. or less,
By setting the downstream stretching roll to 60 to 110 ° C. and setting the speed ratio between the most upstream stretching roll and the most downstream stretching roll in the stretching apparatus to 1.2 to 2 times, a good three-dimensional crimp is developed. In addition, a composite fiber having substantially no latent crimpability can be easily produced.
【図１】ハードエラスティック結晶化したポリプロピレ
ン単繊維の強伸度曲線の模式図FIG. 1 is a schematic diagram of a strength and elongation curve of a hard elastic crystallized polypropylene single fiber.
【図２】本発明により得られる熱接着性複合繊維の強伸
度曲線の模式図FIG. 2 is a schematic diagram of a strength-elongation curve of a heat-adhesive conjugate fiber obtained according to the present invention.
A:ハードエラスティック結晶化したポリプロピレン単繊
維の強伸度曲線において観察される一次降伏点を示す。 B: ハードエラスティック結晶化したポリプロピレン単
繊維の強伸度曲線において観察される二次降伏点を示
す。 C:ハードエラスティック結晶化したポリプロピレン単繊
維の弾性領域を示す。 D:本発明により得られる熱接着性複合繊維の降伏点（ひ
ずみ＝−１に相当する点、すなわち伸度−１００％の点
から強伸度曲線へ引いた接線が強伸度曲線と接する点）
を示す。 E:本発明の熱接着性複合繊維における弾性領域（伸度０
％の点から降伏点までの伸度）を示す。A: shows the primary yield point observed in the strength-elongation curve of the hard elastic crystallized polypropylene single fiber. B: shows the secondary yield point observed in the strength-elongation curve of the hard elastic crystallized polypropylene single fiber. C: Elastic region of hard elastic crystallized polypropylene single fiber. D: Yield point of heat-adhesive conjugate fiber obtained according to the present invention (point corresponding to strain = -1, ie, point where a tangent drawn from a point of elongation -100% to a strong elongation curve is in contact with the strong elongation curve) )
Is shown. E: Elastic region (elongation 0) in the heat-adhesive conjugate fiber of the present invention
% To the yield point).
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4L041 AA07 AA14 AA20 BA02 BA05 BA09 BA22 BC04 BD03 BD11 CA38 CA42 DD01 DD05 4L047 AA14 AA27 BA09 BB02 BB09 CB10 EA02 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4L041 AA07 AA14 AA20 BA02 BA05 BA09 BA22 BC04 BD03 BD11 CA38 CA42 DD01 DD05 4L047 AA14 AA27 BA09 BB02 BB09 CB10 EA02
Claims (8)
ポリプロピレンを第２成分として構成される複合繊維の
断面形状が、第１成分を鞘側、第２成分を芯側とする偏
心鞘芯型もしくは第１成分と第２成分との並列型の構造
を有し、立体捲縮のみを有するとともに、１２０℃で５
分間加熱した時に捲縮数が実質的に増加しない複合繊維
であって、強伸度曲線において求められる弾性領域が４
２％以上であることを特徴とする熱接着性複合繊維。1. An eccentric sheath having a propylene copolymer as a first component and a cross-sectional shape of a composite fiber comprising crystalline polypropylene as a second component, wherein the first component is a sheath side and the second component is a core side. It has a core type or a parallel type structure of the first component and the second component, has only a three-dimensional crimp, and has a 5
A composite fiber in which the number of crimps does not substantially increase when heated for 4 minutes, and the elastic region determined in the strength-elongation curve is 4
A heat-adhesive conjugate fiber having a content of 2% or more.
加が４個／２．５４ｃｍ以下もしくは捲縮数が減少する
ことを特徴とする請求項１記載の熱接着性複合繊維。2. The heat-adhesive conjugate fiber according to claim 1, wherein an increase in the number of crimps when heated at 120 ° C. for 5 minutes is 4 pieces / 2.54 cm or less, or a decrease in the number of crimps.
ブとしたときに、熱収縮率が１４５℃で５分間の加熱条
件で１０％以下のウェブが得られる複合繊維である請求
項１もしくは請求項２のいずれか１項記載の熱接着性複
合繊維。3. The heat-adhesive conjugate fiber is a conjugate fiber having a heat shrinkage of 10% or less when heated to 145 ° C. for 5 minutes when the fiber is used as a web. The heat-adhesive conjugate fiber according to claim 1 or claim 2.
が１２０℃≦Ｔｍ≦１４７℃を有する共重合体である請
求項１記載の熱接着性複合繊維。4. The propylene-based copolymer has a melting point Tm (° C.)
Is a copolymer having 120 ° C ≦ Tm ≦ 147 ° C.
０重量％、プロピレン９０〜９６重量％からなるエチレ
ン−プロピレン二元共重合体である請求項１もしくは請
求項４のいずれか１項記載の熱接着性複合繊維。5. A propylene-based copolymer comprising ethylene 4-1
The heat-adhesive conjugate fiber according to claim 1, which is an ethylene-propylene binary copolymer comprising 0% by weight and 90 to 96% by weight of propylene.
重量％、プロピレン９０〜９８重量％、１−ブテン１〜
５重量％からなるエチレン−プロピレン−ブテン−１三
元共重合体である請求項１もしくは請求項４のいずれか
１項記載の熱接着性複合繊維。6. A propylene-based copolymer comprising ethylene 1 to 7
Wt%, propylene 90-98 wt%, 1-butene 1
5. The heat-adhesive conjugate fiber according to claim 1, which is an ethylene-propylene-butene-1 terpolymer composed of 5% by weight.
ポリプロピレンを第２成分として構成される複合繊維の
断面形状が、第１成分を鞘側、第２成分を芯側とする偏
心鞘芯型もしくは第１成分と第２成分との並列型となる
ように、偏心鞘芯型紡糸口金もしくは並列型紡糸口金を
備えた紡糸装置によって両成分を紡糸して得た未延伸糸
に熱処理を施した後、少なくとも１つの延伸セクション
において１．２倍〜１．７倍で延伸し、その延伸セクシ
ョンにおける工程の上流側の延伸ロールの温度を８０℃
以下、下流側の延伸ロールの温度を３０〜１１０℃と
し、なおかつ該延伸装置における最上流の延伸ロールと
最下流の延伸ロールの速度比が１．２〜２倍であること
を特徴とする熱接着性複合繊維の製造方法。7. An eccentric sheath having a propylene-based copolymer as a first component and a cross-sectional shape of a conjugate fiber composed of crystalline polypropylene as a second component, wherein the first component is a sheath side and the second component is a core side. The undrawn yarn obtained by spinning both components by a spinning device equipped with an eccentric sheath core spinneret or a parallel spinneret so as to be a core type or a parallel type of the first component and the second component is subjected to heat treatment. After the application, the film is stretched at a ratio of 1.2 to 1.7 in at least one stretching section, and the temperature of the stretching roll on the upstream side of the process in the stretching section is set to 80 ° C.
In the following, the temperature of the downstream stretching roll is 30 to 110 ° C., and the speed ratio of the most upstream stretching roll to the most downstream stretching roll in the stretching apparatus is 1.2 to 2 times. A method for producing an adhesive conjugate fiber.
性複合繊維を用いた繊維成形体。8. A fiber molded article using the heat-adhesive conjugate fiber according to any one of claims 1 to 6.
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| JP2000380815A JP4505987B2 (en) | 2000-12-14 | 2000-12-14 | Thermal adhesive composite fiber, method for producing the same, and fiber molded body using the same |
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| JP4505987B2 JP4505987B2 (en) | 2010-07-21 |
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| WO2008016788A1 (en) | 2006-07-31 | 2008-02-07 | 3M Innovative Properties Company | Pleated filter with monolayer monocomponent meltspun media |
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| WO2010050407A1 (en) * | 2008-10-29 | 2010-05-06 | 三井化学株式会社 | Crimped composite fiber, and non-woven fabric comprising the fiber |
| US7754041B2 (en) | 2006-07-31 | 2010-07-13 | 3M Innovative Properties Company | Pleated filter with bimodal monolayer monocomponent media |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62184173A (en) * | 1986-02-03 | 1987-08-12 | チッソ株式会社 | Elastic nonwoven fabric and its production |
-
2000
- 2000-12-14 JP JP2000380815A patent/JP4505987B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62184173A (en) * | 1986-02-03 | 1987-08-12 | チッソ株式会社 | Elastic nonwoven fabric and its production |
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