JP6709554B2 - Polypropylene drawn fiber - Google Patents
Polypropylene drawn fiber Download PDFInfo
- Publication number
- JP6709554B2 JP6709554B2 JP2018521016A JP2018521016A JP6709554B2 JP 6709554 B2 JP6709554 B2 JP 6709554B2 JP 2018521016 A JP2018521016 A JP 2018521016A JP 2018521016 A JP2018521016 A JP 2018521016A JP 6709554 B2 JP6709554 B2 JP 6709554B2
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- Prior art keywords
- fiber
- stretching
- group
- polypropylene
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- Prior art date
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- -1 Polypropylene Polymers 0.000 title claims description 65
- 239000004743 Polypropylene Substances 0.000 title claims description 56
- 229920001155 polypropylene Polymers 0.000 title claims description 41
- 229920006240 drawn fiber Polymers 0.000 title claims description 35
- 239000000835 fiber Substances 0.000 claims description 136
- 239000013078 crystal Substances 0.000 claims description 37
- 238000009987 spinning Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 17
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 3
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- 238000005259 measurement Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 18
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- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 239000000523 sample Substances 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 239000004711 α-olefin Substances 0.000 description 15
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- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical group OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 230000003863 physical function Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Description
本発明は、ポリプロピレン製延伸繊維に関し、詳しくは耐熱クリープ性、破断強度、剛性に優れたポリプロピレン製延伸繊維に関する。 TECHNICAL FIELD The present invention relates to a polypropylene stretched fiber, and more particularly to a polypropylene stretched fiber having excellent heat creep resistance, breaking strength and rigidity.
ポリプロピレン繊維は、撥水性、非吸水性および耐摩擦性に優れ、低比重であるため軽く、また変色や退色がないことからロープやネットなどの産業資材、建造物や自動車などの内装材、医療・衛生材、衣料素材などに広く用いられている。
ポリプロピレンを延伸して作製する繊維は、不織布等に用いられる繊維とは異なり、高強度のファイバーとして電池のセパレータ用として高い評価を得ているほか、防水シート基布、産業用縫製糸、各種フィルター、ファブリックなどの用途への利用が期待されている。Polypropylene fiber is excellent in water repellency, non-water absorption and abrasion resistance, and has a low specific gravity, so it is light, and since it does not discolor or fade, it is an industrial material such as ropes and nets, interior materials such as buildings and automobiles, and medical equipment. -Widely used for sanitary and clothing materials.
The fibers produced by stretching polypropylene are highly evaluated as high-strength fibers for battery separators, unlike fibers used for nonwoven fabrics, as well as waterproof sheet base cloth, industrial sewing threads, and various filters. It is expected to be used for applications such as fabrics and fabrics.
ポリプロピレンとしては、チーグラー・ナッタ触媒などのマルチサイト触媒を使用したものと、メタロセン触媒を使用したものが知られている。メタロセン触媒を用いて得られたオレフィン系重合体は、従来のマルチサイト触媒を用いて得られたものに比べて、分子量分布および立体規則性分布が狭く、また共重合体にあっては、共重合組成分布が狭いという特徴を有しており、その結果様々な物性の向上や機能の向上がもたらされる。
メタロセン触媒を用いて得られたポリプロピレン系（共）重合体を延伸して作製した繊維として、特許文献１〜３が知られている。As polypropylene, those using a multi-site catalyst such as a Ziegler-Natta catalyst and those using a metallocene catalyst are known. The olefin polymer obtained by using the metallocene catalyst has a narrower molecular weight distribution and stereoregularity distribution than those obtained by using the conventional multi-site catalyst. It has a feature that the distribution of the polymerization composition is narrow, and as a result, various physical properties and functions are improved.
Patent Documents 1 to 3 are known as fibers produced by stretching a polypropylene-based (co)polymer obtained by using a metallocene catalyst.
特許文献１では、繊維基材として用いられるメタロセン触媒によるプロピレン系重合体は、アイソタクチックペンタッド分率（ＩＰＦ、ｍｍｍｍ分率ともいう）が比較的低いにもかかわらず、従来触媒を用いて得られた高ＩＰＦを有するプロピレン系重合体に匹敵する繊維強度をもつポリプロピレン系延伸繊維を得ることができるとされている。例えば、メタロセン触媒を用いて得られたＩＰＦ９３．０％のプロピレン系重合体を基材とする３３．３ｄＴｅｘの未延伸繊維を、水蒸気延伸処理法にて延伸倍率６．５で延伸処理した場合、延伸繊維の強度は１０．５ｃＮ／ｄＴｅｘであり、強度／延伸倍率比は１．６２である。これに対し、従来触媒を用いて得られたＩＰＦ９７．５％のプロピレン系重合体を基材とする３３．３ｄＴｅｘの未延伸繊維を、上記と同様に水蒸気延伸処理法にて延伸倍率１０．０で延伸処理した場合、延伸繊維の強度は９．５ｃＮ／ｄＴｅｘであり、強度／延伸倍率比は０．９５である。 In Patent Document 1, a propylene-based polymer with a metallocene catalyst used as a fiber base material uses a conventional catalyst, although the isotactic pentad fraction (IPF, mmmm fraction) is relatively low. It is said that it is possible to obtain a polypropylene-based drawn fiber having a fiber strength comparable to that of the obtained propylene-based polymer having a high IPF. For example, when a non-stretched fiber of 33.3 dTex based on a propylene-based polymer of 93.0% IPF obtained using a metallocene catalyst is stretched by a steam stretching method at a stretch ratio of 6.5, The strength of the drawn fiber is 10.5 cN/dTex, and the strength/draw ratio is 1.62. On the other hand, an unstretched fiber of 33.3 dTex based on a 97.5% IPF propylene-based polymer obtained by using a conventional catalyst was subjected to a steam stretching treatment method in the same manner as described above to obtain a stretching ratio of 10.0. In the case of being stretched by, the strength of the stretched fiber is 9.5 cN/dTex, and the strength/stretch ratio is 0.95.
特許文献２では、プロピレン重合体に少なくとも一軸方向の分子配向が有効に付与される程度に行なえばよく、延伸倍率は、通常５〜１０倍、好ましくは６〜８倍であることが望ましい、とされている。実施例では、ＩＰＦは不明であるが、４００デニール延伸倍率：８倍の例が示されている。 In Patent Document 2, it is sufficient that the propylene polymer is effectively imparted with at least uniaxial molecular orientation, and the draw ratio is usually 5 to 10 times, preferably 6 to 8 times. Has been done. In the examples, the IPF is unknown, but an example of 400 denier draw ratio: 8 times is shown.
特許文献３でも、ＩＰＦが８０％以上のポリプロピレンの延伸倍率は５〜１０倍であり、実施例は５〜７倍である。 In Patent Document 3 as well, the polypropylene having an IPF of 80% or more has a draw ratio of 5 to 10 times, and in Examples, 5 to 7 times.
ポリプロピレンを延伸して作製する繊維において、メタロセン系触媒で重合されるポリプロピレンにおいては、立体規則性がある程度以上高いと繊維の物性が低下する、高延伸できない、という問題があった。
特に、立体規則性としてＩＰＦ（ｍｍｍｍ分率）が９７％以上のメタロセン系ポリプロピレンにおいては、延伸倍率が１０倍以上の繊維の作製に成功した例は報告が無い。In the fiber produced by drawing polypropylene, polypropylene polymerized with a metallocene catalyst has problems that if the stereoregularity is higher than a certain level, the physical properties of the fiber are deteriorated and high drawing cannot be performed.
In particular, in the case of metallocene-based polypropylene having an IPF (mmmm fraction) of 97% or more as stereoregularity, there is no report of successful production of fibers having a draw ratio of 10 times or more.
また、ポリプロピレン繊維は、荷重をかけたときに生じた変形ひずみが荷重を除いた後も消失しにくい傾向があり、特に、長期間使用した際に問題となる。また、高温下で荷重をかけた場合にも、他の熱可塑性樹脂、特に極性を有するポリエステル等と比較して変形歪みが残りやすい、耐熱クリープ性が劣ることが知られている。さらに、ポリプロピレン繊維には、より高い破断強度及び剛性が求められている。 Further, polypropylene fibers tend to lose the deformation strain generated when a load is applied even after the load is removed, which is a problem particularly when used for a long period of time. Further, it is known that even when a load is applied at a high temperature, the deformation strain is more likely to remain and the heat creep resistance is inferior as compared with other thermoplastic resins, particularly polar polyesters. Further, polypropylene fibers are required to have higher breaking strength and rigidity.
そこで、本発明の目的は、耐熱クリープ性、破断強度、剛性に優れたポリプロピレン製延伸繊維を提供するものである。また、本発明ではこのようなポリプロピレン製延伸繊維を提供し得る延伸用繊維を提供することを目的とする。 Therefore, an object of the present invention is to provide a polypropylene-made stretched fiber having excellent heat creep resistance, breaking strength, and rigidity. Another object of the present invention is to provide a fiber for drawing which can provide such a polypropylene-made drawn fiber.
本発明者らが鋭意検討した結果、従来得られていなかった高立体規則性のメタロセン系ポリプロピレンを高延伸倍率で延伸して得られた繊維は、耐熱クリープ性、破断強度、剛性に優れるという知見を得て、本発明を完成するに至った。 As a result of diligent studies by the present inventors, a fiber obtained by stretching a metallocene-based polypropylene having a high stereoregularity which has not been conventionally obtained at a high draw ratio is found to have excellent heat creep resistance, breaking strength and rigidity. Thus, the present invention was completed.
すなわち、本発明の一形態によれば、下記要件（１）〜（３）を満たすホモポリプロピレンまたはα−オレフィン含量が５ｍｏｌ％以下のプロピレン・α−オレフィン共重合体を含む延伸用繊維を延伸時の応力が８０ＭＰａ以上、１００００ＭＰａ以下となる条件下、延伸倍率７倍以上で延伸することを特徴とする、ポリプロピレン延伸繊維の製造方法が提供される。
（１）ｍｍｍｍ分率が９７％以上。
（２）ＧＰＣによって求められる分子量分布（Ｍｗ／Ｍｎ）が３．０未満。
（３）メルトフローレート（２３０℃、２．１６ｋｇ）が１〜１００ｇ／１０分。That is, according to one aspect of the present invention, when a drawing fiber containing homopolypropylene satisfying the following requirements (1) to (3) or a propylene/α-olefin copolymer having an α-olefin content of 5 mol% or less is drawn: And a stress of 80 MPa or more and 10000 MPa or less are drawn at a draw ratio of 7 times or more.
(1) The mmmm fraction is 97% or more.
(2) The molecular weight distribution (Mw/Mn) determined by GPC is less than 3.0.
(3) Melt flow rate (230° C., 2.16 kg) is 1 to 100 g/10 minutes.
また、本発明の別の形態によれば、上記要件（１）〜（３）を満たすホモポリプロピレンまたはα−オレフィン含量が５ｍｏｌ％以下のプロピレン・α−オレフィン共重合体を７０質量％以上含み、
（Ａ）直径が７〜１５０μｍであり、
（Ｂ）（１１０）面の結晶配向度が０．９８４〜１．０である
ことを特徴とする、ポリプロピレン系延伸繊維、が提供される。
According to another aspect of the present invention, homopolypropylene satisfying the above requirements (1) to (3) or a propylene/α-olefin copolymer having an α-olefin content of 5 mol% or less is contained in an amount of 70% by mass or more,
(A) The diameter is 7 to 150 μm,
(B) (110) face crystal orientation degree is characterized by a 0.9 84 to 1.0, polypropylene drawn fiber, is provided.
本発明によれば、従来得られていなかった高立体規則性のメタロセン系ポリプロピレンを高延伸倍率で延伸した繊維が得られる。また、この延伸繊維は耐熱クリープ性に優れる。さらには、破断強度、剛性に優れる。 According to the present invention, a fiber obtained by drawing a metallocene-based polypropylene having high stereoregularity, which has not been obtained in the past, at a high draw ratio can be obtained. In addition, this drawn fiber has excellent heat resistance and creep resistance. Further, it has excellent breaking strength and rigidity.
以下、本発明の実施形態について説明するが、本発明はこれらの実施形態のみに限定されるものではない。 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
本発明では、ｍｍｍｍ分率が９７％以上であり、かつＧＰＣ（ゲル・パーミエーション・クロマトグラフィ）によって求められる分子量分布（Ｍｗ／Ｍｎ）が３．０未満のホモポリプロピレンまたはα−オレフィン含量が５ｍｏｌ％以下のプロピレン・α−オレフィン共重合体を溶融紡糸して得られたポリプロピレン系延伸用繊維を、延伸時の応力が８０ＭＰａ以上、１００００ＭＰａ以下となる条件で延伸する。 In the present invention, the mmmm fraction is 97% or more, and the homopolypropylene having a molecular weight distribution (Mw/Mn) determined by GPC (gel permeation chromatography) of less than 3.0 or an α-olefin content of 5 mol%. The polypropylene-based stretching fiber obtained by melt spinning the following propylene/α-olefin copolymer is stretched under the condition that the stress during stretching is 80 MPa or more and 10000 MPa or less.
ｍｍｍｍ分率は、１３Ｃ−ＮＭＲスペクトルにおけるＰｍｍｍｍ（プロピレン単位が５単位連続してアイソタクチック結合した部位における第３単位目のメチル基に由来する吸収強度）およびＰＷ（プロピレン単位の全メチル基に由来する吸収強度）の吸収強度から下記式により求められる。ＰｍｍｍｍおよびＰＷは１３Ｃ−ＮＭＲスペクトルにおけるピーク面積に相当する。
ｍｍｍｍ分率（％）＝（Ｐｍｍｍｍ／ＰＷ）×１００The mmmm fraction is P mmmm in 13 C-NMR spectrum (absorption intensity derived from the methyl group of the third unit in the site where 5 units of propylene units are continuously isotactically bonded) and P W (total of propylene units). It is calculated from the absorption intensity of (absorption intensity derived from methyl group) by the following formula. P mmmm and P W correspond to the peak areas in the 13 C-NMR spectrum.
mmmm fraction (%)=(P mmmm /P W )×100
上記の分子量分布の狭いホモポリプロピレンは、メタロセン触媒を用いて製造される。
メタロセン触媒としては、シクロペンタジエニル骨格を分子内に持つメタロセン化合物を含む重合触媒が好ましく用いられる。
シクロペンタジエニル骨格を有する配位子を分子内に含むメタロセン化合物としては、その化学構造から下記一般式［Ｉ］で表されるメタロセン化合物（Ｄ１）および下記一般式［ＩＩ］で表される架橋型メタロセン化合物（Ｄ２）の二種類を例示することができる。これらの中では、架橋型メタロセン化合物（Ｄ２）が好ましい。The above homopolypropylene having a narrow molecular weight distribution is produced using a metallocene catalyst.
As the metallocene catalyst, a polymerization catalyst containing a metallocene compound having a cyclopentadienyl skeleton in the molecule is preferably used.
The metallocene compound containing a ligand having a cyclopentadienyl skeleton in the molecule is represented by the metallocene compound (D1) represented by the following general formula [I] and the following general formula [II] from its chemical structure. Two types of bridged metallocene compounds (D2) can be exemplified. Of these, the bridged metallocene compound (D2) is preferable.
〔上記一般式［Ｉ］および［ＩＩ］において、Ｍはチタン原子、ジルコニウム原子またはハフニウム原子を示し、Ｑはハロゲン原子、炭化水素基、アニオン配位子、または孤立電子対で配位可能な中性配位子であり、ｊは１〜４の整数であり、ｊが２以上の時は、Ｑは互いに同一でも異なっていてもよく、Ｃｐ１およびＣｐ２は、互いに同一か又は異なっていてもよく、Ｍと共にサンドイッチ構造を形成することができるシクロペンタジエニルまたは置換シクロペンタジエニル基である。ここで、置換シクロペンタジエニル基は、インデニル基、フルオレニル基、アズレニル基およびこれらが一つ以上のハイドロカルビル基で置換された基も包含し、インデニル基、フルオレニル基、アズレニル基の場合はシクペンタジエニル基に縮合する不飽和環の二重結合の一部は水添されていてもよい。一般式［ＩＩ］においてＹは、炭素原子数１〜２０の２価の炭化水素基、炭素原子数１〜２０の２価のハロゲン化炭化水素基、２価のケイ素含有基、２価のゲルマニウム含有基、２価のスズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ２−、−Ｇｅ−、−Ｓｎ−、−ＮＲａ−、−Ｐ（Ｒａ）−、−Ｐ（Ｏ）（Ｒａ）−、−ＢＲａ−または−ＡｌＲａ−を示す（但し、Ｒａは、互いに同一でも異なっていてもよく、炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のハロゲン化炭化水素基、水素原子、ハロゲン原子または窒素原子に炭素原子数１〜２０の炭化水素基が１個または２個結合した窒素化合物残基である。）。〕[In the above general formulas [I] and [II], M represents a titanium atom, a zirconium atom or a hafnium atom, and Q represents a halogen atom, a hydrocarbon group, an anion ligand, or a lone electron pair capable of being coordinated. Is a sex ligand, j is an integer of 1 to 4, when j is 2 or more, Q may be the same or different from each other, and Cp 1 and Cp 2 are the same or different from each other. It is also a cyclopentadienyl or substituted cyclopentadienyl group capable of forming a sandwich structure with M. Here, the substituted cyclopentadienyl group includes an indenyl group, a fluorenyl group, an azulenyl group and a group in which these are substituted with one or more hydrocarbyl groups, and in the case of an indenyl group, a fluorenyl group and an azulenyl group, A part of the double bond of the unsaturated ring condensed with the cyclopentadienyl group may be hydrogenated. In the general formula [II], Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, divalent germanium. containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - Ge -, - Sn -, - NR a -, - P (R a) -, - P (O) ( R a) -, - BR a - or -AlR a - are shown (however, R a may be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms , A halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen compound residue in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a nitrogen atom.). ]
本発明において好適に用いられる重合触媒は、本出願人によって既に国際公開（ＷＯ０１／２７１２４）されている下記一般式［ＩＩＩ］で表される架橋性メタロセン化合物、並びに、有機金属化合物、有機アルミニウムオキシ化合物およびメタロセン化合物と反応してイオン対を形成することのできる化合物から選ばれる少なくても１種以上の化合物、さらに必要に応じて粒子状担体とからなるメタロセン触媒であることが好ましい。 The polymerization catalyst preferably used in the present invention is a crosslinkable metallocene compound represented by the following general formula [III], which has already been published internationally (WO01/27124) by the present applicant, as well as an organometallic compound and an organoaluminumoxy compound. A metallocene catalyst comprising at least one compound selected from compounds capable of reacting with a compound and a metallocene compound to form an ion pair, and optionally a particulate carrier is preferred.
上記一般式［ＩＩＩ］において、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４は水素原子、炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよい。このような炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デカニル基などの飽和の、またはアリル基等の不飽和の、直鎖状脂肪族炭化水素基；イソプロピル基、ｔｅｒｔ−ブチル基、アミル基、３−メチルペンチル基、１，１−ジエチルプロピル基、１，１−ジメチルブチル基、１−メチル−１−プロピルブチル基、１，１−プロピルブチル基、１，１−ジメチル−２−メチルプロピル基、１−メチル−１−イソプロピル−２−メチルプロピル基などの分岐状脂肪族炭化水素基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、アダマンチル基などの脂環族炭化水素基；フェニル基、トリル基、ナフチル基、ビフェニル基、フェナントリル基、アントラセニル基などの芳香族炭化水素基；ベンジル基、クミル基、１，１−ジフェニルエチル基、トリフェニルメチル基などの芳香族炭化水素基で置換された脂肪族炭化水素基；メトキシ基、エトキシ基、フェノキシ基、フリル基、Ｎ−メチルアミノ基、Ｎ，Ｎ−ジメチルアミノ基、Ｎ−フェニルアミノ基、ピリル基、チエニル基などのヘテロ原子含有炭化水素基等を挙げることができる。ケイ素含有基としては、トリメチルシリル基、トリエチルシリル基、ジメチルフェニルシリル基、ジフェニルメチルシリル基、トリフェニルシリル基などを挙げることができる。また、Ｒ５からＲ１２の隣接した置換基は互いに結合して環を形成してもよい。このような置換フルオレニル基としては、ベンゾフルオレニル基、ジベンゾフルオレニル基、オクタヒドロジベンゾフルオレニル基、オクタメチルオクタヒドロジベンゾフルオレニル基、オクタメチルテトラヒドロジシクロペンタフルオレニル基などを挙げることができる。In the general formula [III], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are It is selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group and may be the same or different. As such a hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, Saturated linear aliphatic hydrocarbon group such as n-decanyl group or unsaturated group such as allyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group Group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2- Branched aliphatic hydrocarbon group such as methylpropyl group; alicyclic hydrocarbon group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, tolyl group, naphthyl group, Aromatic hydrocarbon group such as biphenyl group, phenanthryl group and anthracenyl group; Aliphatic hydrocarbon group substituted with aromatic hydrocarbon group such as benzyl group, cumyl group, 1,1-diphenylethyl group and triphenylmethyl group A hetero atom-containing hydrocarbon group such as methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N,N-dimethylamino group, N-phenylamino group, pyryl group, thienyl group, etc. You can Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group and a triphenylsilyl group. Further, the adjacent substituents R 5 to R 12 may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, an octamethyloctahydrodibenzofluorenyl group, and an octamethyltetrahydrodicyclopentafluorenyl group. Can be mentioned.
本発明に用いるメタロセン化合物としては、前記一般式［ＩＩＩ］において、シクロペンタジエニル環に置換するＲ１、Ｒ２、Ｒ３、Ｒ４は水素原子または炭素数１〜２０の炭化水素基であることが好ましく、Ｒ２およびＲ４が炭素数１〜２０の炭化水素基であることがより好ましく、Ｒ１およびＲ３が水素原子であり、Ｒ２およびＲ４が炭素数１〜５の直鎖状または分岐状アルキル基であることが特に好ましい。As the metallocene compound used in the present invention, in the general formula [III], R 1 , R 2 , R 3 and R 4 substituting the cyclopentadienyl ring are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms. It is preferable that R 2 and R 4 are hydrocarbon groups having 1 to 20 carbon atoms, R 1 and R 3 are hydrogen atoms, and R 2 and R 4 have 1 to 5 carbon atoms. A linear or branched alkyl group is particularly preferable.
また、前記一般式［ＩＩＩ］において、フルオレン環に置換する、Ｒ５からＲ１２は水素原子または炭素数１〜２０の炭化水素基であることが好ましい。炭素数１〜２０の炭化水素基としては、前述の炭化水素基を例示することができる。Ｒ５からＲ１２の隣接した置換基は互いに結合して環を形成してもよい。好ましい態様は、Ｒ７、Ｒ１１が同時に水素原子ではないフルオレン環であり、より好ましい態様はＲ６、Ｒ７、Ｒ１０及びＲ１１が同時に水素原子ではないフルオレン環である。
本発明に用いるメタロセン化合物としては、前記一般式［ＩＩＩ］において、シクロペンタジエニル環とフルオレニル環を架橋するＹが第１４族元素であることが好ましく、炭素、ケイ素、ゲルマニウムがより好ましく、炭素原子がより好ましい。
また、Ｙに置換するＲ１３、Ｒ１４は相互に同一でも異なっていてもよく、互いに結合して環を形成してもよい炭素数１〜２０の炭化水素基であり、好ましくは炭素数１〜３のアルキル基または炭素数６〜２０のアリール基から選ばれる。このような置換基としては、メチル基、エチル基、フェニル基、トリル基などが好ましい。なお、Ｒ１３、Ｒ１４は、Ｒ５からＲ１２の隣接した置換基またはＲ１からＲ４の隣接した置換基と互いに結合して環を形成してもよい。Further, in the general formula [III], R 5 to R 12 substituting the fluorene ring are preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned hydrocarbon groups. Adjacent substituents of R 5 to R 12 may combine with each other to form a ring. A preferred embodiment is a fluorene ring in which R 7 and R 11 are not simultaneously hydrogen atoms, and a more preferred embodiment is a fluorene ring in which R 6 , R 7 , R 10 and R 11 are not simultaneously hydrogen atoms.
As the metallocene compound used in the present invention, in the general formula [III], Y bridging the cyclopentadienyl ring and the fluorenyl ring is preferably a Group 14 element, more preferably carbon, silicon or germanium. Atoms are more preferred.
Further, R 13 and R 14 substituting for Y may be the same or different from each other and are a hydrocarbon group having 1 to 20 carbon atoms which may be bonded to each other to form a ring, preferably 1 carbon atom. Selected from an alkyl group having 3 to 3 or an aryl group having 6 to 20 carbon atoms. As such a substituent, a methyl group, an ethyl group, a phenyl group, a tolyl group and the like are preferable. In addition, R 13 and R 14 may combine with adjacent substituents of R 5 to R 12 or adjacent substituents of R 1 to R 4 to form a ring.
前記一般式［ＩＩＩ］において、Ｍは好ましくは第４族遷移金属であり、さらに好ましくはチタン原子、ジルコニウム原子またはハフニウム原子である。また、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれる。ｊは１〜４の整数であり、ｊが２以上の時は、Ｑは互いに同一でも異なっていてもよい。ハロゲンの具体例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、炭化水素基の具体例としては前述と同様のものなどが挙げられる。アニオン配位子の具体例としては、メトキシ、ｔｅｒｔ−ブトキシ、フェノキシなどのアルコキシ基、アセテート、ベンゾエートなどのカルボキシレート基、メシレート、トシレートなどのスルホネート基等が挙げられる。孤立電子対で配位可能な中性配位子の具体例としては、トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニルメチルホスフィンなどの有機リン化合物、テトラヒドロフラン、ジエチルエーテル、ジオキサン、１，２−ジメトキシエタンなどのエーテル類等が挙げられる。Ｑは少なくとも１つがハロゲンまたはアルキル基であることが好ましい。 In the general formula [III], M is preferably a Group 4 transition metal, more preferably a titanium atom, a zirconium atom or a hafnium atom. Further, Q is selected from the same or different combination from halogen, a hydrocarbon group, an anion ligand or a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Q may be the same or different. Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and specific examples of the hydrocarbon group include the same ones as described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. Examples thereof include ethers such as ethane. At least one Q is preferably a halogen or an alkyl group.
前記の好ましい架橋メタロセン化合物としては、ジメチルメチレン（３−ｔｅｒｔ−ブチル−５−メチルシクロペンタジエニル）（３，６−ジｔｅｒｔ−ブチルフルオレニル）ジルコニウムジクロリド、１−フェニルエチリデン（４−ｔｅｒｔ−ブチル−２−メチルシクロペンタジエニル）（オクタメチルオクタヒドロジベンゾフルオレニル）ジルコニウムジクロリド、［３−（１’，１’，４’，４’，７’，７’，１０’，１０’−オクタメチルオクタヒドロジベンゾ［ｂ，ｈ］フルオレニル）（１，１，３−トリメチル−５−ｔｅｒｔ−ブチル−１，２，３，３ａ−テトラヒドロペンタレン）］ジルコニウムジクロライド、ジメチルメチレン（３−ｔｅｒｔ−ブチル−５−メチルシクロペンタジエニル）（１，１，４，４，７，７，１０，１０−オクタメチルオクタヒドロジベンゾ［ｂ，ｈ］フルオレニル）ジルコニウムジクロリド等を例示することができる。
なお、本発明に用いるメタロセン触媒において、前記一般式［ＩＩＩ］で表わされるメタロセン化合物とともに用いられる、有機金属化合物、有機アルミニウムオキシ化合物、およびメタロセン化合物と反応してイオン対を形成する化合物から選ばれる少なくとも１種の化合物（共触媒）、さらには必要に応じて用いられる粒子状担体については、本出願人による前記公報（ＷＯ０１／２７１２４）や特開平１１−３１５１０９号公報中に開示された化合物を制限無く使用することができる。Examples of the preferable bridged metallocene compound include dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium dichloride and 1-phenylethylidene (4-tert). -Butyl-2-methylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [3-(1',1',4',4',7',7',10',10 '-Octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, dimethylmethylene(3- Examples include tert-butyl-5-methylcyclopentadienyl)(1,1,4,4,7,7,10,10-octamethyloctahydrodibenzo[b,h]fluorenyl)zirconium dichloride. ..
The metallocene catalyst used in the present invention is selected from the group consisting of an organometallic compound, an organoaluminumoxy compound, and a compound which forms an ion pair by reacting with the metallocene compound represented by the general formula [III]. Regarding the at least one compound (cocatalyst) and, if necessary, the particulate carrier, the compounds disclosed in the above-mentioned publication (WO01/27124) and JP-A No. 11-315109 by the present applicant are used. It can be used without limitation.
本発明におけるホモポリプロピレンとは、プロピレン単位の含有割合が、９５ｍｏｌ％以上、１００ｍｏｌ％以下の樹脂である。プロピレン単位以外の含有割合が５ｍｏｌ％を超えると、破断強度、初期弾性率が低いため実用性に貧しい。
好ましい組成は、プロピレン単位の含有割合が９７ｍｏｌ％以上、１００ｍｏｌ％以下、より好ましい組成は、９９ｍｏｌ％以上、１００ｍｏｌ％以下である。
プロピレン単位以外の構成成分は特に限定されないが、例えば、他のαオレフィン単位等を挙げることができる。
α−オレフィン単位としては、例えば、エチレン、炭素数４〜２０のα−オレフィン由来の単位が挙げられる。炭素数４〜２０のα−オレフィンとしては、具体的には１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン、４−メチル−１−ペンテン、２−メチル−１−ブテン、３−メチル−１−ブテン、３，３−ジメチル−１−ブテン、ジエチル−１−ブテン、トリメチル−１−ブテン、３−メチル−１−ペンテン、エチル−１−ペンテン、プロピル−１−ペンテン、ジメチル−１−ペンテン、メチルエチル−１−ペンテン、ジエチル−１−ヘキセン、トリメチル−１−ペンテン、３−メチル−１−ヘキセン、ジメチル−１−ヘキセン、３，５，５−トリメチル−１−ヘキセン、メチルエチル−１−ヘプテン、トリメチル−１−ヘプテン、エチル−１−オクテン、メチル−１−ノネンなどが挙げられる。これらの単位は一種でもよく、二種以上でもよい。これらの中でも、エチレン単位および炭素数４〜８のα−オレフィン由来の単位が好ましく、エチレン単位がより好ましい。
The homopolypropylene in the present invention is a resin having a propylene unit content of 95 mol% or more and 100 mol% or less. When the content of the components other than the propylene unit exceeds 5 mol %, the breaking strength and the initial elastic modulus are low, and the practicability is poor.
A preferred composition has a propylene unit content of 97 mol% or more and 100 mol% or less, and a more preferred composition is 99 mol% or more and 100 mol% or less.
The constituent components other than the propylene unit are not particularly limited, but examples thereof include other α-olefin units and the like.
Examples of the α-olefin unit include a unit derived from ethylene and an α-olefin having 4 to 20 carbon atoms. As the α-olefin having 4 to 20 carbon atoms, specifically, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1- Tet La Defense Sen, 1-hexyl Sade Sen, 1-octene Polygonum Sen, 1-eicosene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl - 1-butene, diethyl-1-butene, trimethyl-1-butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl -1-hexene, trimethyl-1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, Examples include ethyl-1-octene and methyl-1-nonene. These units may be one kind or two or more kinds. Among these, an ethylene unit and a unit derived from an α-olefin having 4 to 8 carbon atoms are preferable, and an ethylene unit is more preferable.
また、本発明で使用する原料としては、上記要件を満たすホモポリプロピレンであり、本発明の効果を損なわない範囲であれば、上記の要件を満たさないメタロセン系のプロピレン系（共）重合体や、従来触媒を使用したプロピレン系（共）重合体、ポリエチレン、ポリブテンなどをブレンドして用いてもよい。上記要件を満たすホモポリプロピレンは原料組成物中に７０質量％以上含まれていることが好ましい。
プロピレン系共重合体としては、プロピレンとプロピレン以外のα−オレフィンとの共重合体であって、ランダム共重合体であっても、ブロック共重合体であってもよい。α−オレフィンとしては、上記のα−オレフィンが挙げられる。The raw material used in the present invention is homopolypropylene satisfying the above requirements, and a metallocene-based propylene-based (co)polymer which does not satisfy the above requirements, as long as the effects of the present invention are not impaired. A propylene-based (co)polymer using a conventional catalyst, polyethylene, polybutene, etc. may be blended and used. The homopolypropylene satisfying the above requirements is preferably contained in the raw material composition in an amount of 70% by mass or more.
The propylene-based copolymer is a copolymer of propylene and an α-olefin other than propylene, and may be a random copolymer or a block copolymer. Examples of the α-olefin include the above α-olefins.
本発明で使用するホモポリプロピレンは、以下の（１）〜（３）の要件を満たすものである。
（１）ｍｍｍｍ分率が９７％以上。
（２）ＧＰＣによって求められる分子量分布（Ｍｗ／Ｍｎ）が３．０未満。
（３）メルトフローレート（２３０℃、２．１６ｋｇ）が１〜１００ｇ／１０分。The homopolypropylene used in the present invention satisfies the following requirements (1) to (3).
(1) The mmmm fraction is 97% or more.
(2) The molecular weight distribution (Mw/Mn) determined by GPC is less than 3.0.
(3) Melt flow rate (230° C., 2.16 kg) is 1 to 100 g/10 minutes.
（１）の高立体規則性と（２）の分子量分布を同時に達成するには、上記の通りメタロセン系触媒を使用して原料ポリマーを製造する。 In order to achieve the high stereoregularity of (1) and the molecular weight distribution of (2) at the same time, the raw material polymer is produced using the metallocene catalyst as described above.
（３）のメルトフローレート（ＭＦＲ）は、得られる原料ポリマーの分子量を適宜調整することで達成できる。また、ホモポリプロピレンに前述したホモポリプロピレン以外の構成成分を適宜配合することでＭＦＲを調整することもできる。ＭＦＲが１ｇ／１０分未満では後述する紡糸工程での押し出しが困難となる。ＭＦＲが１００ｇ／１０分を超えると、紡糸繊維の強度が保てず破断し、巻き取りが困難となる。ＭＦＲは、５ｇ／１０分以上が好ましく、１０ｇ／１０分以上がより好ましい。また、ＭＦＲは、７０ｇ／１０分以下が好ましく、４０ｇ／１０分以下がより好ましい。 The melt flow rate (MFR) of (3) can be achieved by appropriately adjusting the molecular weight of the obtained raw material polymer. The MFR can also be adjusted by appropriately blending homopolypropylene with the above-mentioned constituent components other than homopolypropylene. If the MFR is less than 1 g/10 minutes, extrusion in the spinning step described later becomes difficult. If the MFR exceeds 100 g/10 minutes, the strength of the spun fiber cannot be maintained, and the spun fiber breaks, making winding difficult. The MFR is preferably 5 g/10 minutes or more, more preferably 10 g/10 minutes or more. The MFR is preferably 70 g/10 minutes or less, more preferably 40 g/10 minutes or less.
また、本発明で使用するホモポリプロピレンは、デカン可溶分が少ないことが好ましく、１質量％以下であることがより好ましい。
さらに、本発明で使用するホモポリプロピレンは、結晶化溶離分別（ＣＥＦ）の半値幅が、５℃以下であることが好ましい。
また、本発明で使用する原料組成物には、本発明の効果を損なわない範囲でこの分野で使用される各種添加剤を添加することができる。添加剤としては、適宜中和剤、酸化防止剤、熱安定剤、耐候剤、滑剤、紫外線吸収剤、帯電防止剤、アンチブロッキング剤、防曇剤、気泡防止剤、分散剤、難燃剤、抗菌剤、蛍光増白剤、架橋剤、架橋助剤等の添加剤、染料、顔料等の着色剤などが挙げられる。The homopolypropylene used in the present invention preferably has a small decane-soluble content, and more preferably 1% by mass or less.
Further, the homopolypropylene used in the present invention preferably has a half width of crystallization elution fractionation (CEF) of 5° C. or less.
Further, to the raw material composition used in the present invention, various additives used in this field can be added within a range not impairing the effects of the present invention. As the additive, as appropriate, a neutralizing agent, an antioxidant, a heat stabilizer, a weathering agent, a lubricant, an ultraviolet absorber, an antistatic agent, an antiblocking agent, an antifogging agent, an antifoaming agent, a dispersant, a flame retardant, an antibacterial agent. Agents, optical brighteners, crosslinking agents, additives such as crosslinking aids, and coloring agents such as dyes and pigments.
〔ポリプロピレン製延伸繊維の製造方法〕
本発明に係るポリプロピレン製延伸繊維の製造方法は、まず、上記のホモポリプロピレンを含む原料組成物を溶融紡糸して延伸用繊維を得る。[Method for producing polypropylene-made drawn fiber]
In the method for producing a stretched polypropylene fiber according to the present invention, first, the raw material composition containing the homopolypropylene is melt-spun to obtain a stretchable fiber.
（延伸用繊維の製造工程（紡糸工程））
上記の原料樹脂組成物を溶融し、溶融物を所定の孔径を有するノズルから押出して延伸用繊維（as spun繊維）を得る。
原料を溶融押出する手段としては、当該技術分野で通常使用されるプラスチック繊維の溶融押出技術を使用すればよい。溶融押出する手段としては、限定するものではないが、例えば、原料プラスチックを加熱、溶融した後、該溶融物を加圧押出する押出装置を挙げることができる。前記の押出装置を本工程に使用することにより、結果として得られる延伸繊維の繊維径を好適な範囲に調整することが可能となる。
特に、本発明では、以下の（Ａ−１）〜（Ａ−３）に記載の要件で溶融紡糸した繊維であることが好ましい。
（Ａ−１）メルトドローレシオ（Melt draw ratio：MDR）が８〜５００、
（Ａ−２）紡糸温度が２００〜２８０℃、
（Ａ−３）１ホール当りの吐出量が１〜１００ｇ／ｍｉｎ。(Manufacturing process of drawing fiber (spinning process))
The above raw material resin composition is melted and the melt is extruded from a nozzle having a predetermined pore size to obtain a fiber for stretching (as spun fiber).
As a means for melt-extruding the raw material, a melt-extrusion technique for plastic fibers, which is commonly used in the art, may be used. The means for melt-extruding is not limited, but for example, an extruder for heating and melting the raw material plastic and then extruding the melt under pressure can be mentioned. By using the above-mentioned extruder in this step, it becomes possible to adjust the fiber diameter of the resulting drawn fiber to a suitable range.
Particularly, in the present invention, it is preferable that the fiber is melt-spun under the conditions described in (A-1) to (A-3) below.
(A-1) Melt draw ratio (MDR) is 8 to 500,
(A-2) The spinning temperature is 200 to 280° C.,
(A-3) The discharge rate per hole is 1 to 100 g/min.
メルトドローレシオ（ＭＤＲ）とは、送り出し速度（m/min）に対する引（巻）き取り速度（紡糸速度）（m/min）の比であり、このＭＤＲを調整することにより、押出繊維中の晶質、非晶質等の配向状態をある程度制御することができる。本発明では高強度の繊維を得るために、比較的低いＭＤＲでas spun繊維を作製することが好ましい。また、紡糸速度は吐出量（g/min）と押出機のノズル孔径に依存していることから、吐出量を制御した上で巻き取り可能な最小ＭＤＲとなるように制御する。
ＭＤＲの下限は１０であることがより好ましく、上限は２００であることがより好ましい。１ホール当りの吐出量の下限は１．０ｇ／ｍｉｎであることがより好ましく、上限は５０ｇ／ｍｉｎであることがより好ましい。
紡糸速度は速くなるほど、生産性を高めることができる。紡糸速度は、通常は３０〜１００００ｍ／ｍｉｎである。本発明では、比較的高速の紡糸にも対応できる。The melt draw ratio (MDR) is the ratio of the drawing (winding) take-up speed (spinning speed) (m/min) to the delivery speed (m/min). By adjusting this MDR, It is possible to control the orientation state such as crystalline and amorphous to some extent. In the present invention, in order to obtain high strength fibers, it is preferable to produce as spun fibers with a relatively low MDR. Further, since the spinning speed depends on the discharge amount (g/min) and the nozzle hole diameter of the extruder, the discharge amount is controlled and then the minimum MDR that can be wound is controlled.
The lower limit of MDR is more preferably 10, and the upper limit is more preferably 200. The lower limit of the discharge rate per hole is more preferably 1.0 g/min, and the upper limit is more preferably 50 g/min.
The higher the spinning speed, the higher the productivity. The spinning speed is usually 30 to 10,000 m/min. The present invention can also support spinning at a relatively high speed.
as spun繊維は、溶融押出手段における加熱温度から所定の温度Ａに急冷され、該温度Ａにおいて、引取りながら紡糸されることが好ましい。ここで温度Ａは、原料樹脂のガラス転移温度（Ｔｇ）以上且つＴｇ＋２５℃以下の範囲の温度であることが好ましく、Ｔｇ以上且つＴｇ＋２０℃以下の範囲の温度であることがより好ましい、さらにＴｇ以上且つＴｇ＋１０℃以下の範囲の温度であることがより好ましい。なお、ポリプロピレンのＴｇは−２０〜５℃である。
冷却は、風冷あるいは冷媒、たとえば水、メタノール、エタノール、アセトンなどの強制冷却手段を用いて行うことが可能である。冷却することで結晶化速度を速めることができる。水などで強制的に冷却する場合（水冷）は、風冷の場合に比較して、冷却速度が速いため、as-spun繊維の結晶化度が低く、均一に延伸し易い。そのため、破断強度が高い延伸糸を得やすいので好適である。なお、水冷の場合は、ノズルと樹脂が固化する位置との間の距離が、風冷の場合に比較して短いため、溶融温度を高く設定し、樹脂の粘度を低くし、引き取りによる糸径の低下割合を大きくすることが好ましい。It is preferable that the as spun fiber is rapidly cooled to a predetermined temperature A from the heating temperature in the melt extrusion means, and at the temperature A, it is spun while being drawn. Here, the temperature A is preferably in the range of the glass transition temperature (Tg) of the raw material resin or higher and Tg+25° C. or lower, more preferably in the range of Tg or higher and Tg+20° C. or lower, and further Tg or higher. And it is more preferable that the temperature is within a range of Tg+10° C. or less. The Tg of polypropylene is -20 to 5°C.
Cooling can be carried out by air cooling or a forced cooling means such as water, methanol, ethanol or acetone. The crystallization speed can be increased by cooling. In the case of forced cooling with water (water cooling), the as-spun fiber has a low crystallinity and is easily stretched uniformly because the cooling rate is higher than in the case of air cooling. Therefore, a drawn yarn having a high breaking strength is easily obtained, which is preferable. In the case of water cooling, the distance between the nozzle and the position where the resin solidifies is shorter than in the case of air cooling, so the melting temperature is set high, the resin viscosity is low, and the yarn diameter It is preferable to increase the rate of decrease.
as spun繊維を温度Ａにおいて引取る手段は特に限定されない。例えば、前記冷媒に導入されたas spun繊維を、冷媒中、当該技術分野で慣用される通常の引取手段を用いて所定の引取速度で巻取軸に巻取り巻糸体を形成させるか、又は冷媒中を所定の引取速度で通過させた後、該冷媒の外で、通常の引取手段を用いて所定の引取速度で巻取軸に巻取り巻糸体を形成させることによって、as spun繊維を温度Ａにおいて引取ることができる。或いは、前記冷媒で温度Ａに急冷されたas spun繊維を、通常の引取手段を用いて所定の引取速度で引取りながら、予め温度Ａに冷却された容器に収容することによって、温度Ａにおいてas spun繊維を引取ることもできる。いずれの場合も本工程の実施形態に包含される。ここで、前記引取手段としては、限定するものではないが、例えば、ボビンのような巻取軸に繊維を巻取ることで巻糸体を形成させる巻取装置及びローラーを挙げることができる。また、as spun繊維は、引取によって付与された該繊維の緊張状態を維持したまま前記手段で回収され、次の延伸工程に供されるまでは所定の温度で維持されることが好ましい。
なお、紡糸速度を高めるほど、巻き取りが不安定になることが知られており、高速化の妨げとなる。本発明においては、従来得られていなかった高立体規則性のメタロセン系ポリプロピレンを適用することにより、例えば１０００ｍ／分以上の高速で紡糸することができる。The means for pulling the as spun fibers at the temperature A is not particularly limited. For example, as spun fibers introduced into the refrigerant, in the refrigerant, to form a take-up winding body on the take-up shaft at a predetermined take-up speed using a normal take-up means commonly used in the art, or After passing through the refrigerant at a predetermined take-up speed, outside the refrigerant, by forming a take-up wound body on the take-up shaft at a predetermined take-up speed using a normal take-up means, as spun fiber It can be collected at temperature A. Alternatively, the as spun fiber rapidly cooled to the temperature A by the refrigerant is accommodated in a container previously cooled to the temperature A while being collected at a predetermined take-up speed by using a normal take-up means, so You can also pick up spun fibers. Either case is included in the embodiment of this step. Here, the take-up means is not limited, but may be, for example, a take-up device or a roller that forms a wound body by winding a fiber around a take-up shaft such as a bobbin. Further, the as spun fiber is preferably recovered by the above-mentioned means while maintaining the tension state of the fiber applied by the drawing, and maintained at a predetermined temperature until it is subjected to the next drawing step.
It is known that the higher the spinning speed is, the more unstable the winding is, which hinders the speeding up. In the present invention, by applying a metallocene-based polypropylene having a high stereoregularity which has not been obtained in the past, it is possible to perform spinning at a high speed of, for example, 1000 m/min or more.
本発明では、このように紡糸した延伸用繊維を用いることで、従来得られていなかった高立体規則性のメタロセン系ポリプロピレンを、例えば１０倍以上の高延伸倍率で延伸した繊維が得られる。したがって、このような延伸用繊維も本発明の対象である。なお、高速紡糸を行った場合、紡糸段階である程度延伸もされて配向性が高まるため、延伸用繊維からさらに１０倍以上の延伸が適当でない場合もある。したがって、後述するように延伸繊維を得る場合は延伸応力で制御することが肝要となる。
なお、延伸前の繊維の配向度が低いほど、延伸糸の最高到達強度は高くなるため、好適である。配向度が低い繊維を得るためには低速で紡糸することが必要であるが、産業上の利用の観点からは好ましくない場合があり、適宜適正な条件を選択すればよい。
延伸倍率と結晶配向度の間には良好な相関関係がある。本発明において、高倍率で延伸された繊維とは、結局のところ、延伸後の結晶配向度が高いものである。
延伸前の配向度が高いと、延伸倍率は低くなるが、延伸後の結晶配向度が所望のレベルに達していれば良い。In the present invention, by using the thus drawn fiber for drawing, a fiber obtained by drawing a metallocene-based polypropylene having a high stereoregularity, which has not been obtained conventionally, at a high draw ratio of 10 times or more can be obtained. Therefore, such drawing fibers are also the subject of the present invention. When high-speed spinning is performed, the fiber is also stretched to some extent at the spinning stage to enhance the orientation, and therefore it may not be appropriate to stretch the fiber for stretching 10 times or more. Therefore, it is important to control the stretching stress when obtaining the stretched fiber as described later.
The lower the degree of orientation of the fiber before drawing, the higher the ultimate strength of the drawn yarn, which is preferable. Spinning at a low speed is necessary to obtain a fiber having a low degree of orientation, but this may not be preferable from the viewpoint of industrial use, and appropriate conditions may be appropriately selected.
There is a good correlation between the draw ratio and the degree of crystal orientation. In the present invention, a fiber stretched at a high ratio is, after all, a fiber having a high degree of crystal orientation after stretching.
When the degree of orientation before stretching is high, the stretching ratio is low, but it is sufficient if the degree of crystal orientation after stretching reaches a desired level.
本発明に係る延伸用繊維の特徴としては、
（Ａ）直径が３０〜３００μｍであり、
（Ｂ）糸径のばらつきＣＶが２％以下である。
直径がこの範囲より大きいと加熱延伸の際に繊維を均一に加熱することが難しく、延伸の際に破断しやすい。また、直径がこの範囲より小さいと延伸により細くなりすぎ、破断しやすい。糸径のばらつきがこの範囲より大きいと加熱延伸の際に破断しやすくなる。
Ｍｗ／Ｍｎ＜３でないとＣＶ≦２％が達成できないことから、従来の高立体規則性のチーグラー・ナッタ系ポリプロピレンではこのようなＣＶ値は達成できなかった。The characteristics of the drawing fiber according to the present invention include:
(A) has a diameter of 30 to 300 μm,
(B) The variation CV of the yarn diameter is 2% or less.
When the diameter is larger than this range, it is difficult to uniformly heat the fibers during the heat drawing, and the fibers are easily broken during the drawing. Further, if the diameter is smaller than this range, it becomes too thin due to stretching and is easily broken. If the variation in the yarn diameter is larger than this range, the yarn tends to break during the hot drawing.
Since CV≦2% cannot be achieved unless Mw/Mn<3, such a CV value could not be achieved by the conventional high stereoregular Ziegler-Natta polypropylene.
（延伸工程）
以上のように得られたas spun繊維は、延伸工程によって延伸されて目的の延伸繊維とする。
本発明において、as spun繊維の延伸は、当該技術分野で通常に使用される延伸手段を用いて行うことができる。例えば、図１に示すように、送出ローラー１と巻取ローラー５との速度差によって繊維を連続的に延伸している。送出ローラー１と巻取ローラー５との速度差によって延伸倍率が規定される。送出ローラー１から引き出されたas spun繊維６は、ヒーター２で所定の温度に加熱されて延伸される。ヒーター２での加熱温度はas spun繊維６がヒーター２表面に融着せずに安定して延伸できる範囲であれば良い。一方、加熱温度に依存して延伸倍率の違いにより延伸繊維７が白化する現象が見られる。つまり、加熱温度により延伸後の繊維が白化しない倍率（以降、白化限界倍率）が異なることとなる。
延伸時のヒーター温度はas spun繊維の融点（Ｔｍ）未満であり、Ｔｍ−２２±１０℃の範囲であることが好ましい。
加熱に適用するヒーターの形状、仕組みに特に制限はなく、繊維を所望の温度にすることができればよく、プレートヒーター、ロールヒーター、熱風炉、温水浴、飽和水蒸気炉などを適用することができる。(Stretching process)
The as spun fiber obtained as described above is drawn in the drawing step to obtain the target drawn fiber.
In the present invention, the as spun fiber can be drawn by using a drawing means that is commonly used in this technical field. For example, as shown in FIG. 1, the fibers are continuously drawn by the difference in speed between the feeding roller 1 and the winding roller 5. The draw ratio is defined by the speed difference between the delivery roller 1 and the winding roller 5. The as spun fiber 6 drawn out from the delivery roller 1 is heated to a predetermined temperature by the heater 2 and drawn. The heating temperature in the heater 2 may be in the range where the as spun fiber 6 can be stably stretched without being fused to the surface of the heater 2. On the other hand, there is a phenomenon that the stretched fiber 7 is whitened due to the difference in the draw ratio depending on the heating temperature. That is, the magnification at which the fiber after stretching does not whiten (hereinafter, the whitening limit magnification) varies depending on the heating temperature.
The heater temperature at the time of stretching is lower than the melting point (Tm) of the as spun fiber, and is preferably in the range of Tm-22±10°C.
The shape and mechanism of the heater used for heating are not particularly limited as long as the fiber can be heated to a desired temperature, and a plate heater, a roll heater, a hot air oven, a hot water bath, a saturated steam oven, etc. can be applied.
延伸工程では、延伸繊維７の張力を張力計３で測定し、さらに延伸繊維７の糸径を寸法測定器４で測定し、得られた延伸張力をその場測定で得られた延伸後の糸径（直径）で割ることで延伸応力を算出することができる。
本発明では、この延伸応力が８０ＭＰａ以上、１００００ＭＰａ以下となる条件下、延伸倍率７倍以上で延伸する。延伸応力が８０ＭＰａ未満では、所望の延伸倍率まで延伸することができない場合がある。延伸応力が１００００ＭＰａを超えると破断し延伸することができない。
実際は、高い延伸倍率で延伸することで、高い配向状態にし、高い強度、初期弾性率を発現させる。延伸倍率は、送出ローラー１から引き出されるas spun繊維６の送り出し速度（ｍ／ｍｉｎ）と巻取ローラー５での延伸繊維の巻き取り速度（ｍ／ｍｉｎ）の比（ドローレシオ、ＤＲ）を意味する。
延伸時の加熱温度が一定の条件では、延伸倍率が高くなるほど延伸応力が大きくなる傾向にある。このましい延伸倍率は、延伸前の糸の配向状態によって異なる。延伸前の糸の配向性が低いほど、延伸により高倍率で延伸することができる。その結果、高結晶配向度の延伸糸を形成することができる。
延伸倍率の上限は特に限定されるものではないが、好ましくは４０倍である。延伸倍率が４０倍以下であれば、上記延伸応力の範囲内で破断なく延伸することができる。In the drawing step, the tension of the drawn fiber 7 is measured by the tensiometer 3, the yarn diameter of the drawn fiber 7 is further measured by the dimension measuring device 4, and the obtained drawing tension is obtained by the in-situ measurement. The stretching stress can be calculated by dividing by the diameter (diameter).
In the present invention, stretching is performed at a stretching ratio of 7 times or more under the condition that the stretching stress is 80 MPa or more and 10000 MPa or less. If the stretching stress is less than 80 MPa, it may not be possible to stretch to a desired stretching ratio. If the stretching stress exceeds 10,000 MPa, the sheet breaks and cannot be stretched.
Actually, by stretching at a high stretch ratio, a high orientation state is obtained, and high strength and initial elastic modulus are exhibited. The draw ratio means the ratio (draw ratio, DR) of the delivery speed (m/min) of the as spun fiber 6 drawn from the delivery roller 1 and the winding speed (m/min) of the drawn fiber on the winding roller 5. ..
When the heating temperature during stretching is constant, the stretching stress tends to increase as the stretching ratio increases. The preferable draw ratio depends on the orientation state of the yarn before drawing. The lower the orientation of the yarn before drawing, the higher the draw ratio that can be achieved by drawing. As a result, a drawn yarn having a high degree of crystal orientation can be formed.
The upper limit of the draw ratio is not particularly limited, but is preferably 40 times. If the draw ratio is 40 times or less, the film can be drawn without breaking within the range of the drawing stress.
また、延伸は、図示するような１段階で延伸でもよいが、２段階以上に延伸してもよい。
２段延伸では、１回目の延伸において、結晶分散温度付近の温度で比較的低倍率で延伸し、２回目の延伸において、延伸前の融点を超える温度で延伸をする。１段延伸に比較して、総延伸倍率が大きくすることできる。そのため強度をさらに高めることができる。PP繊維の場合は、延伸過程において、内部にボイドが発生することがあるが、２段延伸により抑制することができる。この場合も２回の延伸で得られる延伸糸の結晶配向度が所望の範囲になるように延伸すればよく、１段延伸の場合に比較して、結晶配向度が高い延伸糸を形成することができる。
本発明における好ましい延伸倍率は、紡糸工程におけるMDRとのバランスで設定する。該MDRが小さい場合は、as-spun繊維の配向が小さいため、高い倍率で延伸する。逆に大きい場合は、as-spun繊維の配向が大きいため、MDRが小さい場合に比較して、低い倍率で延伸する。紡糸工程におけるMDRは通常８〜３００である。
本発明における延伸倍率は、延伸を１段階で完了する場合は、好ましくは７倍以上、２０倍以下、より好ましくは７倍以上、１６倍以下である。
２段階で延伸する場合は、延伸倍率（１段目）は、３倍以上、１５倍以下である。好ましくは、５倍以上、１２倍以下、より好ましくは７倍以上、１１倍以下である。
２段階で延伸する場合総延伸倍率（１段目と２段目の積）は、７倍以上、４０倍以下であり、７倍以上、３６倍以下であることが好ましく、１０倍以上、３０倍以下がより好ましく、１２倍以上、２２倍以下であることが最も好ましい。Further, the stretching may be performed in one step as shown in the drawing, but may be performed in two or more steps.
In the two-stage stretching, in the first stretching, the stretching is performed at a relatively low ratio at a temperature near the crystal dispersion temperature, and in the second stretching, the stretching temperature is higher than the melting point before stretching. The total stretching ratio can be increased as compared with the one-stage stretching. Therefore, the strength can be further increased. In the case of PP fibers, voids may be generated inside during the drawing process, but this can be suppressed by the two-stage drawing. Also in this case, the drawn yarn obtained by drawing twice may be drawn so that the degree of crystal orientation of the drawn yarn is within a desired range, and a drawn yarn having a higher degree of crystal orientation than in the case of single-stage drawing is formed. You can
The preferred draw ratio in the present invention is set in balance with the MDR in the spinning process. When the MDR is small, the orientation of the as-spun fiber is small, so that the fiber is drawn at a high ratio. On the contrary, when the MDR is large, the orientation of the as-spun fibers is large, so that the fiber is stretched at a lower ratio than when the MDR is small. The MDR in the spinning process is usually 8 to 300.
The stretching ratio in the present invention is preferably 7 times or more and 20 times or less, more preferably 7 times or more and 16 times or less when the stretching is completed in one step.
In the case of stretching in two stages, the stretching ratio (first stage) is 3 times or more and 15 times or less. It is preferably 5 times or more and 12 times or less, more preferably 7 times or more and 11 times or less.
In the case of stretching in two stages, the total stretching ratio (the product of the first stage and the second stage) is 7 times or more and 40 times or less, preferably 7 times or more and 36 times or less, and 10 times or more, 30 times or more. It is more preferably not more than twice, and most preferably not less than 12 times and not more than 22 times.
本発明における延伸後の繊維の直径は７〜１５０μｍである。この範囲より直径が小さい繊維は、元となるas-spun繊維が細いため、延伸工程で破断しやすく作製が困難である。直径が大きい繊維は、元となるas-spun繊維の直径が大きいため、延伸工程において均一に加熱することが困難なため破断しやすく、作製が困難である。 The diameter of the fiber after drawing in the present invention is 7 to 150 μm. Fibers having a diameter smaller than this range are difficult to produce because the original as-spun fibers are thin and are easily broken during the drawing process. A fiber having a large diameter has a large diameter of the original as-spun fiber, and thus it is difficult to uniformly heat the fiber in the drawing process, and thus the fiber easily breaks and is difficult to manufacture.
ここで、本発明における結晶配向度はポリプロピレンの（１１０）面に対する強度プロフィールを使って求めた値である。延伸繊維の好適な結晶配向度は、０．９６０以上、１．０以下であり、より好ましくは０．９７０以上、１．０以下、さらに好ましくは、０．９８０以上、１．０以下であり、特に好ましくは０．９８２以上、１．０以下である。なお、ポリプロピレンの（０４０）、（１３０）面から求めた結晶配向度に関しても、（１１０）面から求めたものと同様に延伸倍率と良好な相関を示すので、適用することができる。
また、延伸糸を構成するフィブリルが太いほど高い耐熱クリープ特性が発現することが期待される。フィブリルの太さはＳＡＸＳ測定により得られる相関長により推測することができる。本発明における相関長は、３ｎｍ以上、１００ｎｍ以下、好ましくは５ｎｍ以上、１００ｎｍ以下、より好ましくは７ｎｍ以上、１００ｎｍ以下である。Here, the degree of crystal orientation in the present invention is a value obtained by using the strength profile for the (110) plane of polypropylene. The preferred crystal orientation degree of the drawn fiber is 0.960 or more and 1.0 or less, more preferably 0.970 or more and 1.0 or less, and further preferably 0.980 or more and 1.0 or less. It is particularly preferably 0.982 or more and 1.0 or less. It should be noted that the crystal orientation degree obtained from the (040) and (130) planes of polypropylene also has a good correlation with the draw ratio similarly to that obtained from the (110) plane, and thus can be applied.
Further, it is expected that the thicker the fibrils constituting the drawn yarn, the higher the heat-resistant creep property will be developed. The thickness of fibrils can be estimated from the correlation length obtained by SAXS measurement. The correlation length in the present invention is 3 nm or more and 100 nm or less, preferably 5 nm or more and 100 nm or less, more preferably 7 nm or more and 100 nm or less.
このように延伸した本発明に係るポリプロピレン製延伸繊維は、高い強度、剛性、耐熱性を有する。その結果、従来の高立体規則性のチーグラー・ナッタ系ポリプロピレン、あるいは低立体規則性のメタロセン系ポリプロピレンの高延伸繊維に比較して、強度、剛性（初期弾性率）、耐熱性（クリープ特性）が優れている。これは、次のように推察される。 The polypropylene stretched fiber according to the present invention thus stretched has high strength, rigidity and heat resistance. As a result, the strength, rigidity (initial elastic modulus), and heat resistance (creep property) are higher than those of conventional high stereoregular Ziegler-Natta polypropylene or low stereoregular metallocene polypropylene highly stretched fiber. Are better. This is guessed as follows.
＜延伸繊維に引張応力がかかった際の挙動＞
延伸繊維は、配向した結晶部とそれをつなぐ（緊張）タイ分子鎖からなるフィブリルの束で構成される。引張応力を加えることによる応力とひずみの関係は、初期の段階では主に結晶と結晶間に束縛されている非晶部の配向で決定される。フィブリル間で滑りが生じ始める点が降伏点と呼ばれ、該降伏点において一部の結晶が破壊され、外力が緊張タイ分子鎖に集中する。この際、引張応力がいったん急激に低下することもある。
さらに引張応力を加えるとタイ分子鎖の破断もしくはタイ分子鎖間の滑りを伴う結晶の破壊をきっかけに繊維全体の破断に至る。その点が、破断強度を示す点となる。
例えば、タイ分子の密度が高い場合は、耐応力が高く、破断強度が高いと考えられる。<Behavior when tensile stress is applied to the drawn fiber>
Stretched fibers are composed of a bundle of fibrils composed of oriented crystal parts and tie molecular chains that connect them (tension). The stress-strain relationship due to the application of tensile stress is determined mainly by the orientation of the amorphous part, which is bound between the crystals in the initial stage. The point at which slippage begins to occur between fibrils is called the yield point, at which point some crystals are broken and the external force concentrates on the tension tie molecular chains. At this time, the tensile stress may drop suddenly once.
When tensile stress is further applied, breakage of the tie molecular chains or breakage of crystals accompanied by slippage between tie molecular chains leads to breakage of the entire fiber. That point becomes the point indicating the breaking strength.
For example, when the density of tie molecules is high, it is considered that the stress resistance is high and the breaking strength is high.
剛性（初期弾性率）は、降伏点の前の応力とひずみの直線関係の係数であり、主にフィブリルをまたいだ結晶の硬さと非晶部の配向に由来する。例えば、結晶部が均一で破壊しにくく、タイ分子鎖密度も高いと剛性は高くなると考えらえる。また、分子量分布が狭いと、より均一に配向したタイ分子鎖ができ易く、結果として個々のフィブリルに印加される応力も均一になり易いため、より大きな繊維強度を発現することができる。
熱クリープは、熱エネルギーにより分子の運動性が高まった状態において、弱い引張応力がかかった際の変形挙動を示す。
分子鎖間の相互作用が弱いので、一部の結晶の破壊に伴うフィブリル間でのずれが生じ、繊維が伸びる。
特に後述する実施例で測定している温度は結晶分散温度以上なので、結晶自体は融解しないものの、分子鎖軸方向に沿った結晶内での分子鎖運動が可能であり、結晶の変形や破壊が起こりやすい。変形は微結晶の完全性に依存する。分子量分布が広いと（低分子量成分からなる）完全性の低い微結晶が形成されやすく、結果としてクリープが大きくなり易いと考えられる。Rigidity (initial elastic modulus) is a coefficient of the linear relationship between stress and strain before the yield point, and is mainly derived from the hardness of crystals across fibrils and the orientation of amorphous parts. For example, it can be considered that the rigidity increases when the crystal part is uniform and is not easily broken and the tie molecular chain density is high. Further, when the molecular weight distribution is narrow, more uniformly oriented tie molecular chains are likely to be formed, and as a result, the stress applied to each fibril is also likely to be uniform, so that greater fiber strength can be expressed.
Thermal creep shows a deformation behavior when a weak tensile stress is applied in a state where the mobility of molecules is increased by thermal energy.
Since the interaction between the molecular chains is weak, the fibrils are displaced due to the breakage of some crystals, and the fibers are elongated.
In particular, the temperature measured in the examples described below is higher than the crystal dispersion temperature, so the crystal itself does not melt, but the molecular chain movement in the crystal along the molecular chain axis direction is possible, and the deformation or destruction of the crystal occurs. It is easy to happen. Deformation depends on the perfection of the crystallites. When the molecular weight distribution is wide, it is considered that fine crystals with low integrity (comprising low molecular weight components) are likely to be formed, resulting in large creep.
（マルチフィラメント）
また、本発明におけるポリプロピレン製延伸繊維は、複数のホールを有する紡糸ノズルを適用して形成することにより、複数の糸が束になった状態に形成してもよい。(Multifilament)
In addition, the polypropylene drawn fiber in the present invention may be formed into a bundle of a plurality of yarns by applying a spinning nozzle having a plurality of holes.
（複合繊維）
また、本発明で得られたポリプロピレン製延伸繊維は、各種複合繊維の一部材として、例えば、代表的には芯鞘延伸複合繊維の芯材として好適に使用できる。
そのような繊維としては、例えば、以下のような構成のものを挙げることができる。
芯材の直径が０．５〜７０μｍ、芯材と鞘材を合わせた繊維の直径が１〜１００μｍであり、繊維の断面における鞘材と芯材の比率が、断面積比において７０：３０〜４０：６０である。
なお、鞘材と芯材との断面における位置関係は同心であっても、偏心であってもよい。
また、鞘材を構成する重合体としては、例えば高密度、中密度、低密度ポリエチレンや直鎖状低密度ポリエチレンなどのエチレン系重合体、プロピレン単独重合体、プロピレンと他のα−オレフィンとの共重合体、具体的にはプロピレン−ブテン−１ランダム共重合体、プロピレン−エチレン−ブテン−１ランダム共重合体、あるいは軟質ポリプロピレンなどの非結晶性プロピレン系重合体、ポリ４−メチルペンテン−１などを挙げることができる。これらのオレフィン系重合体は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
上記のような、芯材として本発明に係る延伸繊維を用いた延伸複合繊維においては、剛性と破断強度のバランスに優れ、さらに良好な耐熱クリープ性を有する複合繊維を得ることができる。(Composite fiber)
Further, the polypropylene drawn fiber obtained in the present invention can be suitably used as a member of various composite fibers, for example, typically as a core material of core-sheath drawn composite fiber.
Examples of such fibers include those having the following configurations.
The diameter of the core material is 0.5 to 70 μm, the diameter of the combined fiber of the core material and the sheath material is 1 to 100 μm, and the ratio of the sheath material to the core material in the cross section of the fiber is 70:30 to 70 in cross sectional area ratio. It is 40:60.
The positional relationship between the sheath material and the core material in the cross section may be concentric or eccentric.
Examples of the polymer constituting the sheath material include ethylene-based polymers such as high-density, medium-density, low-density polyethylene and linear low-density polyethylene, propylene homopolymers, and propylene and other α-olefins. Copolymer, specifically propylene-butene-1 random copolymer, propylene-ethylene-butene-1 random copolymer, or non-crystalline propylene-based polymer such as soft polypropylene, poly-4-methylpentene-1 And so on. These olefin-based polymers may be used alone or in combination of two or more.
In the stretched conjugate fiber using the stretched fiber according to the present invention as the core material as described above, it is possible to obtain a conjugate fiber having an excellent balance of rigidity and breaking strength and further having good heat creep resistance.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
プライムポリマー株式会社製の以下の３種類のポリプロピレン樹脂を用いて紡糸を行った。 Spinning was performed using the following three types of polypropylene resins manufactured by Prime Polymer Co., Ltd.
（１）分子量分布（Ｍｗ／Ｍｎ、Ｍｚ／Ｍｗ）
分子量分布（Ｍｗ／Ｍｎ）は、Ｗａｔｅｒｓ社製ゲル浸透クロマトグラフＡｌｌｉａｎｃｅ ＧＰＣ−２０００型を用い、以下のようにして測定した。
分離カラムは、ＴＳＫｇｅｌ ＧＮＨ６−ＨＴを２本およびＴＳＫｇｅｌ ＧＮＨ６−ＨＴＬを２本であり、カラムサイズはいずれも直径７．５ｍｍ、長さ３００ｍｍであり、カラム温度は１４０℃とした。移動相にはｏ−ジクロロベンゼンおよび酸化防止剤としてＢＨＴ０．０２５質量％を用い、１．０ｍｌ／分で移動させた。試料（プロピレン単独重合体）濃度は１５ｍｇ／１０ｍＬとし、試料注入量は４００μＬとし、検出器として示差屈折計を用いた。標準ポリスチレンは、東ソー社製を用いた。(1) Molecular weight distribution (Mw/Mn, Mz/Mw)
The molecular weight distribution (Mw/Mn) was measured as follows using a Gel Permeation Chromatograph Alliance GPC-2000 type manufactured by Waters.
The separation columns were two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column sizes were all 7.5 mm in diameter and 300 mm in length, and the column temperature was 140°C. O-dichlorobenzene and 0.025% by mass of BHT as an antioxidant were used as the mobile phase, and the mobile phase was moved at 1.0 ml/min. The sample (propylene homopolymer) concentration was 15 mg/10 mL, the sample injection amount was 400 μL, and a differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation.
（２）ＩＰＦ（ｍｍｍｍ分率）
プロピレン単独重合体のＩＰＦ（ｍｍｍｍ分率）は、Ａ．ｚａｍｂｅｌｌｉらのＭａｃｒｏｍｏｌｅｃｕｌｅｓ，８，６８７（１９７５）に示された帰属により定められた値であり、１３Ｃ−ＮＭＲにより、下記条件で測定し、ＩＰＦ＝（２１．７ｐｐｍでのピーク面積）／（１９〜２３ｐｐｍでのピーク面積）とした。
〈測定条件〉
種類 ＪＮＭ−Ｌａｍｂａｄａ４００（日本電子（株）社製）
分解能 ４００ＭＨｚ
測定温度 １２５℃
溶媒 １，２，４−トリクロロベンゼン／重水素化ベンゼン＝７／４
パルス幅 ７．８μｓｅｃ
パルス間隔 ５ｓｅｃ
積算回数 ２０００回
シフト基準 ＴＭＳ＝０ｐｐｍ
モード シングルパルスブロードバンドデカップリング(2) IPF (mmmm fraction)
The IPF (mmmm fraction) of the propylene homopolymer was measured by A. zambelli et al Macromolecules, a value determined by the assignment shown in 8,687 (1975), by 13 C-NMR, was measured under the following conditions, IPF = (peak area at 21.7ppm) / (19 The peak area at 23 ppm).
<Measurement condition>
Type JNM-Lambada400 (manufactured by JEOL Ltd.)
Resolution 400 MHz
Measurement temperature 125℃
Solvent 1,2,4-trichlorobenzene/deuterated benzene=7/4
Pulse width 7.8μsec
Pulse interval 5sec
Accumulation count 2000 times Shift standard TMS=0ppm
Mode Single pulse Broadband decoupling
（３）メルトフローレート（ＭＦＲ）
プロピレン単独重合体のメルトフローレート（ＭＦＲ）を、ＡＳＴＭ Ｄ１２３８に準拠し、２３０℃、２．１６ｋｇ荷重で測定した。(3) Melt flow rate (MFR)
The melt flow rate (MFR) of the propylene homopolymer was measured according to ASTM D1238 at 230° C. under a load of 2.16 kg.
（４）融点（Ｔｍ）
ＤＳＣ測定により求めた。ＤＳＣ測定の詳細については下記に示す。
装置名：パーキンエルマー社製 Diamond DSC(3)
測定条件：30℃〜230℃
１st昇温温度： 500℃/min
保持温度：230℃
保持時間：5min
降温速度：10℃/min
保持温度50℃
保持時間：1min
2nd昇温速度： 10℃/min
サンプル容器：通常パン
測定雰囲気：チッソ
サンプル重量：約5mg(4) Melting point (Tm)
It was determined by DSC measurement. Details of the DSC measurement are shown below.
Device name: Perkin Elmer Diamond DSC(3)
Measurement conditions: 30℃-230℃
1st temperature rising temperature: 500℃/min
Holding temperature: 230℃
Hold time: 5min
Cooling rate: 10℃/min
Holding temperature 50℃
Hold time: 1min
2nd heating rate: 10℃/min
Sample container: Normal pan Measurement atmosphere: Chisso Sample weight: About 5 mg
（５）ガラス転移温度（Ｔｇ）
ＤＳＣ測定により求めた。ＤＳＣ測定の詳細については下記に示す。
装置名：パーキンエルマー社製 Diamond DSC(3)
測定条件：30℃〜230℃
１st昇温温度： 500℃/min
保持温度：230℃
保持時間：5min
降温速度：500℃/min
保持温度：-70℃
保持時間：5min
2nd昇温速度： 20℃/min
サンプル容器：通常パン
測定雰囲気：ヘリウム
サンプル重量：約5mg(5) Glass transition temperature (Tg)
It was determined by DSC measurement. Details of the DSC measurement are shown below.
Device name: Perkin Elmer Diamond DSC(3)
Measurement conditions: 30℃-230℃
1st temperature rising temperature: 500℃/min
Holding temperature: 230℃
Hold time: 5min
Cooling rate: 500℃/min
Holding temperature: -70℃
Hold time: 5min
2nd heating rate: 20℃/min
Sample container: Normal pan Measurement atmosphere: Helium Sample weight: Approximately 5 mg
（６）ｎ−デカン可溶分
１ｇ程度のポリマー試料（このときの正確な質量をａとする）を、ｎ−デカン２００ｍｌと、試料量に対し約１％のＢＨＴ（３，５−ジ−ｔ−ブチル−４−ヒドロキシトルエン）とともに、三角フラスコに入れる。１８０℃に加熱し、２時間以上撹拌溶解する。試料が完全に溶解したことを確認し、１昼夜放冷する。その後、マグネチックスターラーで１時間撹拌しながらポリマーを析出させる。吸引瓶とロート（３２５メッシュスクリーン）にて、析出したポリマーを吸引ろ過する。ろ液を蒸発乾固させてｎ−デカン可溶部を回収した。ｎ−デカン可溶分の回収量をｂとする。
ｎ−デカン可溶分は次式によって算出する。
ｎ−デカン可溶分（％）＝（ｂ／ａ）×１００
ａ：ポリマー試料の質量（ｇ）、ｂ：ｎ−デカン可溶分の回収量（ｇ）(6) n-decane-soluble component A polymer sample of about 1 g (the exact mass at this time is defined as a) was added with 200 ml of n-decane and about 1% of BHT (3,5-di-) based on the sample amount. Erlenmeyer flask with t-butyl-4-hydroxytoluene). Heat to 180°C and stir to dissolve for 2 hours or more. After confirming that the sample is completely dissolved, allow it to cool overnight. Then, the polymer is precipitated while stirring with a magnetic stirrer for 1 hour. The precipitated polymer is suction filtered with a suction bottle and a funnel (325 mesh screen). The filtrate was evaporated to dryness and the n-decane-soluble portion was recovered. Let b be the amount of n-decane-soluble matter recovered.
The n-decane soluble component is calculated by the following formula.
n-decane soluble content (%)=(b/a)×100
a: Mass of polymer sample (g), b: Recovery amount of n-decane-soluble component (g)
なお、通常はデカン不溶部とろ別したろ液に多少のアセトンを加えてデカン可溶部を析出させるが、今回の使用ではデカン可溶部を目視で確認することができなかった。そのため、上記の方法によりデカン可溶部を得た。 Note that normally, some acetone is added to the filtrate separated from the decane-insoluble portion to precipitate the decane-soluble portion, but the decane-soluble portion could not be visually confirmed in this use. Therefore, a decane-soluble portion was obtained by the above method.
（７）ＣＥＦ（Crystallization Elution Fractionation）半値幅
下記条件で降温後、昇温時に観測されるピークの半値幅を求めた。
装 置： ハイスループット組成分布分析装置、ＣＥＦ（Polymer Char社製）
検出器（内蔵）： ＩＲ５型赤外分光光度計（Polymer Char社製）
検出波長： 濃度センサー:ＣＨ２ νａ ３．４２μｍ（２，９２０ｃｍ−１）
メチルセンサー：ＣＨ３ νａ ３．３８μｍ（２，９６０ｃｍ−１）；
メーカー非公表
カラム：ＣＥＦカラム（Polymer Char社製）、長さ１５０ｍｍ、容量２．２ｍＬ
移動相：ｏ−ジクロロベンゼン（ＯＤＣＢ）、ＢＨＴ添加
試料濃度：１６ｍｇ／８ｍＬ
溶解条件：１５０℃，６０ｍｉｎ（Ｎ２雰囲気下）
注入量：０．２ｍＬ
降温条件：９５℃→−２０℃，１．０℃／ｍｉｎ，流量：０．０１２ｍＬ／ｍｉｎ
昇温条件：−２０℃→１４０℃，４．０℃／ｍｉｎ，流量：１．０ｍＬ／ｍｉｎ(7) Full width at half maximum of CEF (Crystallization Elution Fractionation) The full width at half maximum of the peak observed when the temperature was raised after the temperature was lowered under the following conditions was determined.
Equipment: High throughput composition distribution analyzer, CEF (made by Polymer Char)
Detector (built-in): IR5 infrared spectrophotometer (made by Polymer Char)
Detection wavelength: Concentration sensor: CH 2 νa 3.42 μm (2,920 cm −1 ).
Methyl sensor: CH 3 νa 3.38 μm (2,960 cm −1 );
Manufacturer's undisclosed column: CEF column (manufactured by Polymer Char), length 150 mm, capacity 2.2 mL
Mobile phase: o-dichlorobenzene (ODCB), BHT addition Sample concentration: 16 mg/8 mL
Melting conditions: 150° C., 60 min (under N 2 atmosphere)
Injection volume: 0.2 mL
Cooling condition: 95°C → -20°C, 1.0°C/min, flow rate: 0.012 mL/min
Temperature rising condition: -20°C → 140°C, 4.0°C/min, flow rate: 1.0 mL/min
＜紡糸手法＞
（実施例Ａ１、Ａ２、比較例Ａ１〜Ａ４）
溶融紡糸は、プラスチック工学研究所社製の二軸押出機ＢＴ−３０−Ｓ２−４２−Ｌを用いた。ノズルは直径０．７ｍｍ、Ｌ／Ｄ＝３の１ｈｏｌｅを使用した。紡糸温度２２０℃、吐出量１．５ｇ／ｍｉｎと３．０ｇ／ｍｉｎで押し出しを行い、紡糸ノズルから４．３ｍの位置において、空冷後の巻取が可能な最小ＭＤＲの条件をサンプリングした。空冷のための空気温度は２０℃であり、溶融紡糸された樹脂が該温度相当まで冷却される。該温度は、ＴｇからＴｇ＋２０℃の温度範囲に該当する。詳細を表２に記載する。<Spinning method>
(Examples A1, A2, Comparative Examples A1 to A4)
For the melt spinning, a twin-screw extruder BT-30-S2-42-L manufactured by Plastic Engineering Laboratory Co., Ltd. was used. As the nozzle, 1 hole having a diameter of 0.7 mm and L/D=3 was used. Extrusion was carried out at a spinning temperature of 220° C. and a discharge rate of 1.5 g/min and 3.0 g/min, and at a position 4.3 m from the spinning nozzle, the minimum MDR condition that allows winding after air cooling was sampled. The air temperature for air cooling is 20° C., and the melt-spun resin is cooled to the temperature. The temperature corresponds to a temperature range of Tg to Tg+20°C. Details are shown in Table 2.
平均直径及びその変動係数（Ｃ．Ｖ）は、下記の測定及び算出法によって求めた。
紡糸後の繊維直径を測定器（（株）ＫＥＹＥＮＣＥ製高速・高精度ディジタル寸法測定器ＬＳ−７０１０（商品名））を用いて測定した。平均直径はサンプリング周期１００ｍｓで測定した５分間のデータ（３０００データ）を平均した値であり、変動係数は５分間のデータから得られた標準偏差を平均値で除すことで得られた値である。The average diameter and its coefficient of variation (CV) were determined by the following measurement and calculation methods.
The fiber diameter after spinning was measured using a measuring device (high-speed and high-precision digital dimension measuring device LS-7010 (trade name) manufactured by KEYENCE Co., Ltd.). The average diameter is a value obtained by averaging data (3000 data) for 5 minutes measured at a sampling cycle of 100 ms, and the coefficient of variation is a value obtained by dividing the standard deviation obtained from the data for 5 minutes by the average value. is there.
（実施例Ｂ１、Ｂ２、比較例Ｂ１）
溶融紡糸において、水冷後に巻き取りを行った。実施例１の場合と同じ押し出し機を用いた。ノズル下７８ｃｍの位置に水槽の水面が来るように水浴槽（水温２０℃）を設置して繊維を冷却・固化させた後、繊維を巻き取った。詳細を表２に示した。
なお、以下の実施例、比較例において、空冷紡糸した延伸用繊維を使用した例をＡ群、水冷紡糸した延伸用繊維を使用した例をＢ群として、各番号前に表示した。(Examples B1 and B2, Comparative example B1)
In melt spinning, winding was performed after cooling with water. The same extruder as in Example 1 was used. A water bath (water temperature: 20° C.) was installed so that the water surface of the water tank was 78 cm below the nozzle to cool and solidify the fiber, and then the fiber was wound. Details are shown in Table 2.
In the following Examples and Comparative Examples, examples using the air-cooled spun fiber for stretching are shown as Group A, and examples using water-cooled spun fiber for stretching are shown as Group B, which are shown before each number.
（実施例Ａ３〜Ａ７、比較例Ａ５〜Ａ１５）
次に、得られた延伸用繊維（実施例Ａ１、比較例Ａ１、Ａ２）を表３−１に示す各種条件で延伸して、延伸繊維を得た。延伸手法、延伸繊維の各種物性評価方法については以下の通りである。結果を表３−１に併せて示す。(Examples A3 to A7, Comparative Examples A5 to A15)
Next, the obtained drawing fibers (Example A1, Comparative Examples A1 and A2) were drawn under various conditions shown in Table 3-1 to obtain drawn fibers. The stretching method and the evaluation method for various physical properties of the stretched fiber are as follows. The results are also shown in Table 3-1.
＜延伸手法＞
実施例で用いたヒーター延伸装置の概要図を図１に示す。送出ローラー１（送出速度１ｍ／ｍｉｎ）と巻取ローラー５との速度差によって繊維を連続的に延伸している。繊維とヒーター２の接触長は２２５ｍｍ、加熱温度は、延伸時にヒーター表面に繊維が融着しない最大温度としてＴｍ−２２℃（１２５℃および１４０℃）に設定した。サンプリングは、１０分間安定して延伸が可能な最大倍率までの範囲で行った。
延伸中の張力を、定格１００ｇｆのテンションピックアップセンサー３を装備したエイコー測器（株）製のテンションメータＨＳ−１５００Ｓ型（商品名）により測定した。また、延伸後の繊維直径を測定器４（（株）ＫＥＹＥＮＣＥ製高速・高精度ディジタル寸法測定器ＬＳ−７０１０（商品名））を用いてその場測定した。測定された張力と直径のデータは、（株）ＫＥＹＥＮＣＥ製ＮＲ−２０００（商品名）を介して平均回数１２８回、サンプリング周期１００ｍｓでコンピュータに取り込んだ。得られた延伸張力をその場測定で得られた延伸後の直径で割ることで延伸応力を算出した。<Stretching method>
A schematic diagram of the heater stretching device used in the examples is shown in FIG. The fibers are continuously drawn by the speed difference between the delivery roller 1 (delivery speed 1 m/min) and the winding roller 5. The contact length between the fiber and the heater 2 was 225 mm, and the heating temperature was set to Tm-22° C. (125° C. and 140° C.) as the maximum temperature at which the fiber did not fuse to the heater surface during stretching. Sampling was performed within a range up to the maximum magnification that enables stable stretching for 10 minutes.
The tension during stretching was measured by a tension meter HS-1500S type (trade name) manufactured by Eiko Sokki Co., Ltd. equipped with a tension pickup sensor 3 having a rating of 100 gf. In addition, the fiber diameter after drawing was measured in-situ using a measuring device 4 (a high-speed and high-precision digital dimension measuring device LS-7010 (trade name) manufactured by KEYENCE Co., Ltd.). The measured tension and diameter data were loaded into a computer at an average number of 128 times and a sampling cycle of 100 ms via NR-2000 (trade name) manufactured by KEYENCE CORPORATION. The stretching stress was calculated by dividing the obtained stretching tension by the diameter after stretching obtained by in-situ measurement.
＜引張試験＞
得られた延伸繊維について、（株）島津製作所製のオートグラフＡＧＳ−Ｘ（商品名）引張試験機で引張特性を調べた。測定には５０Ｎのロードセルと５０Ｎ用のエアーチャックを用いた。測定は室温で行い、初期試料長は４０ｍｍ、引張速度は４０ｍｍ／ｍｉｎである。測定本数は１２本とし、サーチ株式会社製オートバイブ口式繊度測定器ＤＥＮＩＣＯＮ ＤＣ−２１（商品名）を用いて測定した繊度の値を使用した。得られた公称応力−歪曲線から破断強度、破断伸び、初期弾性率を算出した。それぞれの平均値を求めた。<Tensile test>
The tensile properties of the obtained stretched fiber were examined with an Autograph AGS-X (trade name) tensile tester manufactured by Shimadzu Corporation. For the measurement, a load cell of 50N and an air chuck for 50N were used. The measurement is performed at room temperature, the initial sample length is 40 mm, and the pulling speed is 40 mm/min. The number of measurements was 12, and the value of the fineness measured using a motorcycle mouth type fineness measuring instrument DENICON DC-21 (trade name) manufactured by Search Co., Ltd. was used. The breaking strength, breaking elongation, and initial elastic modulus were calculated from the obtained nominal stress-strain curve. The average value of each was calculated.
（実施例Ｂ３〜Ｂ１０、比較例Ｂ２〜Ｂ５）
実施例Ｂ１，Ｂ２，比較例Ｂ１で得られた延伸用繊維を表３−２に示す各種条件で、上記延伸手法で延伸して、延伸繊維を得た。延伸繊維の各種物性評価結果を表３−２に併せて示す。(Examples B3 to B10, Comparative Examples B2 to B5)
The drawn fibers obtained in Examples B1, B2 and Comparative Example B1 were drawn by the above-mentioned drawing method under various conditions shown in Table 3-2 to obtain drawn fibers. The results of evaluation of various physical properties of the drawn fiber are also shown in Table 3-2.
強度は、延伸倍率１０倍以上の場合に、ｍ−ｉＰＰ（Ｈ）＞ＺＮ−ＰＰである。
破断強度は、タイ分子部分の耐応力が律速となっていると考えられる。
結晶分散温度以上（１２０〜１４０℃）において、熱収縮応力（表４参照）はｍ−ｉＰＰ（Ｈ）＞ＺＮ−ＰＰであるため、ｍ−ｉＰＰ（Ｈ）は、タイ分子から結晶部に大きな力を加えることができている。このことからタイ分子の密度が高いことが推定される。タイ分子の密度が高いため、耐応力が高く、破断強度が高いと考えることができる。The strength is m-iPP(H)>ZN-PP when the draw ratio is 10 times or more.
Regarding the breaking strength, it is considered that the stress resistance of the tie molecule part is rate-determining.
At the crystal dispersion temperature or higher (120 to 140° C.), the heat shrinkage stress (see Table 4) is m-iPP(H)>ZN-PP, so that m-iPP(H) is large from the tie molecule to the crystal part. I can apply force. This suggests that the density of Thai molecules is high. Since the density of tie molecules is high, it can be considered that the stress resistance is high and the breaking strength is high.
剛性も、延伸倍率１０倍以上の場合）に、ｍ−ｉＰＰ（Ｈ）＞ＺＮ−ＰＰである。剛性は、主に結晶部の硬さと非晶配向に由来する。
ｍ−ｉＰＰ（Ｈ）の方が結晶部が均一で破壊しにくい上、とタイ分子鎖密度も高い考えらえる。水冷紡糸の場合は、空冷紡糸の場合に比較して低いMDRで紡糸することができるため、同一条件で延伸した場合の破断強度が高い。
例えば、同じ延伸倍率１４倍では、実施例Ｂ５の強度は、実施例Ａ５に比較して高い。The rigidity is also m-iPP(H)>ZN-PP when the draw ratio is 10 times or more). Rigidity is mainly derived from the hardness of the crystal part and the amorphous orientation.
It can be considered that m-iPP(H) has a more uniform crystal part and is less likely to be broken, and that the tie molecular chain density is higher. In the case of water-cooled spinning, since the MDR can be spun at a lower MDR than in the case of air-cooled spinning, the breaking strength is high when stretched under the same conditions.
For example, at the same draw ratio of 14 times, the strength of Example B5 is higher than that of Example A5.
次に、得られた延伸繊維について、以下の評価を行った。
＜ＤＳＣ測定＞
Ｒｉｇａｋｕ（株）製ＴｈｅｒｍｏｐｌｕｓＤＳＣ８２３０（商品名）を用いてＤＳＣ測定を行った。昇温は１０Ｋ／ｍｉｎで室温から２００℃の範囲で測定した。また測定中はＮ２を流し続けた。なお、基準試料にはＡｌを用い、各繊維を長さ１ｍｍ以下に切り刻み、粉末上にした後、アルミパンに封入したものを用いた。得られたＤＳＣ曲線から融解熱（ΔＨｍ）を読み取り、ＰＰの完全結晶融解熱（ΔＨ０ ｍ）＝２０７ｋＪ／ｋｇから、式（１−１）によって結晶化度Ｘｃ（％）を算出した。Next, the following evaluation was performed on the obtained drawn fiber.
<DSC measurement>
DSC measurement was performed using ThermoplusDSC8230 (trade name) manufactured by Rigaku Corporation. The temperature rise was measured at 10 K/min from room temperature to 200°C. Further, N 2 was kept flowing during the measurement. Al was used as a reference sample, and each fiber was cut into pieces with a length of 1 mm or less, powdered, and then enclosed in an aluminum pan. The heat of fusion (ΔH m ) was read from the obtained DSC curve, and the crystallinity Xc (%) was calculated from the complete crystal fusion heat of PP (ΔH 0 m )=207 kJ/kg by the formula (1-1).
＜広角Ｘ線回折測定＞
Ｒｉｇａｋｕ社製ＲＡ−Ｍｉｃｒｏ７型高輝度Ｘ線回折装置を用いて、広角Ｘ線回折像を撮像した。光源には管電圧４０ｋＶ、管電流２０ｍＡで発生させた波長０．１５４ｎｍのＣｕ−Ｋα線を用いた。撮像には縦横３０ｃｍ，３０００×３０００ｐｉｘｅｌのイメージングプレート（ＩＰ）を用い、カメラ長２５０ｍｍで各１０分間撮像した。撮影後、Ｒｉｇａｋｕ社製Ｒ−ＡＸＩＳ−ＩＶ＋＋によってＩＰをスキャンし、ディジタル情報としてコンピュータに取り込んだ。その後、フリーソフトＦＩＴ２Ｄを用いて、広角Ｘ線回折像から赤道・方位角方向に対する強度プロフィールを求めた。赤道方向の強度プロフィールを、回折角が低角度のピークから（１１０）面回折、（０４０）面回折、（１３０）面回折とし、メゾ相（２θ＝１５．４°）および非晶ハローのピーク（２θ＝１７．６°）［西田幸次、小西隆士、金谷利治、繊維学会誌、６３（１２）、４１２−４１６（２００７）参照］も加えた総和と考え、各ピークに式（２−１）のＧａｕｓｓ型曲線を仮定して分離した。なお、Ｉ０はピーク強度、２θ０はピーク位置、βは半価幅である。得られたピーク強度と幅より各ピークの総積分強度を求め、全てのピークの総積分強度に対する、非晶ハローの割合、メゾ相の割合、結晶回折ピークの割合を求めた。また、フィッティングにより得られた回折角θ０からＢｒａｇｇの式（２−２）により各面の面間隔ｄｈｋｌを、半価幅βからＳｃｈｅｒｒｅｒの式（２−３）を用いて微結晶サイズＬｈｋｌを求めた．ここでλはＸ線の波長であり、また強度プロフィールの分離にＧａｕｓｓ型曲線を用いたので、Ｋ＝０．９１８とした。<Wide-angle X-ray diffraction measurement>
A wide-angle X-ray diffraction image was taken using a RA-Micro7 type high brightness X-ray diffractometer manufactured by Rigaku. A Cu-Kα ray having a wavelength of 0.154 nm generated at a tube voltage of 40 kV and a tube current of 20 mA was used as a light source. An imaging plate (IP) having a size of 30 cm in length and width of 3000×3000 pixels was used for imaging, and each image was captured for 10 minutes with a camera length of 250 mm. After photographing, the IP was scanned by R-AXIS-IV++ manufactured by Rigaku Co., and captured in a computer as digital information. After that, the intensity profile in the equator/azimuth direction was determined from the wide-angle X-ray diffraction image using free software FIT2D. The intensity profile in the equatorial direction was changed from a peak with a low diffraction angle to (110) plane diffraction, (040) plane diffraction, and (130) plane diffraction, and the peaks of the mesophase (2θ=15.4°) and the amorphous halo were obtained. (2θ=17.6°) [See Koji Nishida, Takashi Konishi, Toshiharu Kanaya, Journal of the Textile Society, 63(12), 412-416 (2007)], and the formula (2-1) is applied to each peak. ). Note that I 0 is the peak intensity, 2θ 0 is the peak position, and β is the half width. The total integrated intensity of each peak was determined from the obtained peak intensities and widths, and the ratio of the amorphous halo, the ratio of the mesophase, and the ratio of the crystal diffraction peak to the total integrated intensity of all the peaks were calculated. Further, from the diffraction angle θ 0 obtained by the fitting, the interplanar spacing d hkl is calculated from the Bragg equation (2-2), and the half-width β is calculated from the half-width β to the Scherrer equation (2-3). I calculated hkl . Here, λ is the wavelength of the X-ray, and K=0.918 because the Gauss type curve was used for separating the intensity profile.
なお、ピーク幅βは実測した強度プロフィールからピークフィッティングによって半価幅βｅを求め、測定装置に由来するピークの広がりβＩを使って式β２＝βｅ ２−βＩ ２で補正した。βＩには粉末状Ａｌ２Ｏ３の（０１２）面回折強度プロフィールから求めた半価幅０．１°を用いた。
上記解析に加えて、延伸繊維については方位角方向に対する強度プロフィールについて式（３−１）のＰｅａｒｓｏｎ ＶＩＩ型でピークフィッティングを行った。ここで、φｐはピーク位置、τは半価幅、ｍは曲線の形状を反映する係数であり２．５とした。各回折面の方位角方向に対する強度プロフィールから、式（３−２）および式（３−３）によって繊維軸に対する各面法線の配向度ｆを求め、これらから式（３−４）によって配向軸（繊維軸）に対するｃ軸の配向度ｆｃを推定した。The peak width β was corrected by the equation β 2 =β e 2 −β I 2 using the half width β e obtained by peak fitting from the actually measured intensity profile and using the peak spread β I derived from the measuring device. The half-value width of 0.1° obtained from the (012) plane diffraction intensity profile of powdered Al 2 O 3 was used for β I.
In addition to the above analysis, the drawn fiber was subjected to peak fitting with the Pearson VII type of the formula (3-1) for the strength profile in the azimuth direction. Here, φ p is a peak position, τ is a half-value width, and m is a coefficient reflecting the shape of the curve and is set to 2.5. From the intensity profile of each diffractive surface in the azimuth direction, the orientation degree f of each surface normal to the fiber axis is obtained by the formula (3-2) and the formula (3-3), and the orientation is calculated by the formula (3-4). The degree of orientation f c of the c-axis with respect to the axis (fiber axis) was estimated.
＜小角Ｘ線散乱測定（ＳＡＸＳ）＞
延伸倍率１５倍の実施例Ａ６と比較例Ａ１４について小角Ｘ線散乱測定を行った。測定装置には、リガク製ＮａｎｏＶｉｅｗｅｒを用いて撮像した。光源には管電圧４０ｋＶ、管電流３０ｍＡで発生させた波長０．１５４ｎｍのＣｕ−Ｋα線を用いた。撮像には縦横３０ｃｍ，３０００×３０００ｐｉｘｅｌのイメージングプレート（ＩＰ）を用い、カメラ長１３５０．３８ｍｍで各１時間撮像した。撮影後、Ｒｉｇａｋｕ社製Ｒ−ＡＸＩＳ−ＩＶ＋＋によってＩＰをスキャンし、ディジタル情報としてコンピュータに取り込んだ。得られたＸ線散乱像から空気散乱を差し引いた後、赤道・子午線、両方向に対する強度プロフィールを求めた。測定に適用した試料の厚みは約１５０μｍである。
この結果、いずれの散乱像についても、子午線方向に長周期ピークは観察されなかった。このことは、いずれの試料でも、明瞭な長周期構造は形成されていないことを意味する。すなわち、形成されているラメラ結晶の量はいずれも少なく、ほぼフィブリル状の構造からなって居ることを想定することができる。また、赤道方向の強度プロフィールＩ（ｑ）について、式（３−５）で示されるＤｅｂｙｅ Ｐｌｏｔによって繊維軸と垂直方向に対する相関長ａを見積もった。ここで、ｑ＝４πｓｉｎθ／λは散乱ベクトル（λ：Ｘ線の波長、θ：散乱角）の大きさである。<Small-angle X-ray scattering measurement (SAXS)>
Small-angle X-ray scattering measurement was performed on Example A6 and Comparative Example A14 with a draw ratio of 15 times. An image was taken using a NanoViewer manufactured by Rigaku as a measuring device. A Cu-Kα ray having a wavelength of 0.154 nm generated at a tube voltage of 40 kV and a tube current of 30 mA was used as a light source. An imaging plate (IP) having a size of 30 cm in length and width of 3000×3000 pixels was used for imaging, and each camera was imaged for 1 hour with a length of 1350.38 mm. After photographing, the IP was scanned by R-AXIS-IV++ manufactured by Rigaku Co., and captured in a computer as digital information. After subtracting air scattering from the obtained X-ray scattering image, intensity profiles for the equator/meridian and both directions were obtained. The thickness of the sample applied for measurement is about 150 μm.
As a result, no long period peak was observed in the meridian direction in any of the scattered images. This means that no clear long-period structure was formed in any of the samples. In other words, it can be assumed that the amount of lamella crystals formed is small and that the lamella crystals have an almost fibrillar structure. Further, with respect to the intensity profile I(q) in the equatorial direction, the correlation length a with respect to the fiber axis and the direction perpendicular to the fiber axis was estimated by the Debye Plot represented by the formula (3-5). Here, q=4πsin θ/λ is the magnitude of the scattering vector (λ: wavelength of X-ray, θ: scattering angle).
得られた相関長は、実施例Ａ６が９．７ｎｍ、比較例Ａ１４が７．７ｎｍであり、実施例Ａ６の方が優位に大きい。得られた相関長が長いことは、フィブリルのサイズが太いこと、言い替えればフィブリル間を結んだ微結晶のサイズや完全性が高いことを意味している。このことは、特に結晶分散温度以上でのフィブリル間滑りを阻害することから、当該条件でのクリープに関して、比較例Ａ１４と比べて実施例Ａ６の方が明瞭に抑制される事実を裏付けている。
さらにナノサイズボイド割合として、インバリアント／総ボイド量を見積もった。
インバリアントＱは、赤道方向の強度プロフィールＩ（ｑ）について、式（３−５−２）に従ってその積分値として得た。The obtained correlation length is 9.7 nm in Example A6 and 7.7 nm in Comparative Example A14, and Example A6 is significantly larger. The obtained long correlation length means that the size of the fibrils is large, in other words, the size and perfection of the microcrystals connecting the fibrils are high. This supports the fact that in Example A6, the creep under the above conditions is clearly suppressed as compared with Comparative Example A14, because slippage between fibrils particularly at the crystal dispersion temperature or higher is inhibited.
Further, the invariant/total void amount was estimated as the ratio of nano-sized voids.
The invariant Q was obtained as the integral value of the intensity profile I(q) in the equatorial direction according to the equation (3-5-2).
該インバリアントＱは、ナノサイズのボイドの量を示す。また、総ボイド量を繊維の測定外径と理論外径から求めた。ここで理論外径とは、as-spun繊維の直径（測定値）を基準とし、延伸による密度変化がないと仮定して、延伸倍率に応じた外径を算出したものである。すなわち、インバリアント／総ボイド量は、総ボイド量に占めるナノサイズのボイド量の割合を示す。
同一の延伸倍率におけるｍ−ｉＰＰとＺＮ−ＰＰとの比較を行う。例えば、１５倍延伸の場合に、実施例Ａ６はナノサイズボイド割合が、比較例Ａ１４に比較して明確に大きい。その他の延伸倍率の場合も同様の傾向である。さらに後述の２段延伸の場合も同様の傾向である。
小角Ｘ線に対して赤道散乱が生じる主な原因は、主にフィブリル間に形成されるナノサイズのボイドと考えられる。ｍ−ｉＰＰの方がナノサイズボイド割合が大きくなったことは、延伸応力が大きいことと良く対応しており、延伸応力がより多くのフィブリルに作用したため、フィブリル間に形成されるナノサイズボイドの量も増えたとして説明できる。
しかるに、繊維直径から推定される総ボイド量は、逆にＺＮ−ＰＰの方が大きい。ＺＮ−ＰＰの方がナノサイズボイド量が少ないにも関わらず、総ボイド量が多いことは、小角散乱では観察されない様な大きなボイドが、より多く形成されることを意味する。この現象は、ＺＮ−ＰＰの場合、フィブリルに印加される延伸応力が不均一なため、一部のフィブリルに過大な応力が集中すると考えれば説明できる。すなわち、一部のフィブリルに応力が集中するため、フィブリル間に大きな滑りが生じ易く、大きな裂け目が形成され易い一方、滑りによって応力が解放されるために延伸応力は小さい値に留まる。応力が一部のフィブリルに集中するために個々のフィブリルが破断し易く、さらにフィブリル間に大きな裂け目が生じることから、得られる繊維の強度も小さくなると考えられる。一方のｍ−ｉＰＰでは、ＺＮ−ＰＰと比較してより多くのフィブリルに延伸応力が作用するため、フィブリル間には多くのナノボイドが形成されるものの、フィブリル間の滑りは起こり難く、結果として大きなボイドはでき難い。フィブリル内のタイ分子鎖により均等に応力が印加され、フィブリル間の裂け目もでき難いため、より大きな繊維強度が得られたと推測される。The invariant Q indicates the amount of nano-sized voids. Further, the total void amount was obtained from the measured outer diameter of the fiber and the theoretical outer diameter. Here, the theoretical outer diameter refers to the diameter (measured value) of the as-spun fiber as a reference, and the outer diameter according to the draw ratio is calculated assuming that there is no density change due to drawing. That is, the invariant/total void amount indicates the ratio of the nano-sized void amount to the total void amount.
A comparison is made between m-iPP and ZN-PP at the same draw ratio. For example, in the case of 15-fold stretching, the nano-sized void ratio of Example A6 is clearly larger than that of Comparative Example A14. The same tendency is obtained for other stretching ratios. Furthermore, the same tendency is obtained in the case of the two-stage stretching described later.
The main cause of equatorial scattering for small-angle X-rays is considered to be nano-sized voids mainly formed between fibrils. The larger proportion of nano-sized voids in m-iPP corresponds well to the larger stretching stress, and the stretching stress acted on more fibrils, so that the nano-sized voids formed between the fibrils were larger. It can be explained as the amount increased.
On the contrary, the total void amount estimated from the fiber diameter is larger in ZN-PP. Although ZN-PP has a smaller amount of nano-sized voids, the fact that the total amount of voids is larger means that more large voids, which are not observed by small-angle scattering, are formed. This phenomenon can be explained by considering that in the case of ZN-PP, the stretching stress applied to the fibrils is non-uniform, so that excessive stress concentrates on some fibrils. That is, since stress concentrates on a part of the fibrils, a large slip is likely to occur between the fibrils and a large crack is likely to be formed, while the stress is released by the slip, so that the stretching stress stays at a small value. Since the stress concentrates on a part of the fibrils, the individual fibrils are easily broken, and a large tear is generated between the fibrils, so that the strength of the obtained fiber is considered to be low. On the other hand, in m-iPP, stretching stress acts on more fibrils as compared with ZN-PP, so many nanovoids are formed between the fibrils, but slippage between fibrils is unlikely to occur, resulting in a large amount. Voids are hard to make. It is speculated that greater fiber strength was obtained because stress was evenly applied by the tie molecular chains within the fibrils and it was difficult for crevices to form between the fibrils.
＜ＴＭＡ測定＞
熱収縮応力、クリープひずみ測定を行った。測定装置には、ＳＩＩナノテクノロジー（株）社製ＴＭＡ／ＳＳ６１００熱分析レオロジーシステムＴＭＡ（Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ）を用いた。熱収縮応力の測定は、試料長１０ｍｍ、初期荷重１０ｍＮ、室温から２５０℃まで５Ｋ／ｍｉｎで昇温した。熱収縮率の測定は、初期試料長１０ｍｍ、一定荷重１０ｍＮ、室温から２３０℃まで５Ｋ／ｍｉｎで昇温した。クリープ歪の測定は、初期試料長１０ｍｍ、一定応力５０ＭＰａ、室温から２５−３０分で１２５℃まで昇温し、その後約５０分間温度を保持して測定した。
以上の結果をまとめて、表４に示す。<TMA measurement>
Thermal shrinkage stress and creep strain were measured. A TMA/SS6100 thermal analysis rheology system TMA (Thermo Mechanical Analyzer) manufactured by SII Nano Technology Co., Ltd. was used as a measuring device. The heat shrinkage stress was measured by increasing the sample length 10 mm, the initial load 10 mN, and the temperature from room temperature to 250° C. at 5 K/min. The heat shrinkage was measured by increasing the initial sample length 10 mm, a constant load 10 mN, and the temperature from room temperature to 230° C. at 5 K/min. The creep strain was measured by measuring the initial sample length of 10 mm, a constant stress of 50 MPa, heating from room temperature to 125° C. in 25 to 30 minutes, and then maintaining the temperature for about 50 minutes.
The above results are summarized in Table 4.
クリープひずみは、最大破断強度を発現する延伸倍率１５倍で比較した場合、ＺＮ−ＰＰ＞ｍ−ｉＰＰ（Ｈ）である。ＺＮ−ＰＰは、フィブリル間においてすべり易いためと考えられる。おそらく、完全性の低い微結晶ができ易いことと対応する。分子量分布の広さに由来して、不均一な状態でフィブリルが形成されるためと考えらえる。 The creep strain is ZN-PP>m-iPP(H) when compared at a draw ratio of 15 times that produces the maximum breaking strength. It is considered that ZN-PP easily slips between fibrils. Perhaps this corresponds to the tendency to form crystallites with low perfection. It is considered that fibrils are formed in a non-uniform state due to the wide molecular weight distribution.
(実施例Ａ８〜Ａ１０、比較例Ａ１６〜Ａ１８)
実施例Ａ１と同様に空冷紡糸において、紡糸速度を変更して延伸用繊維を得た後、延伸を行った。各条件及び延伸繊維物性を表５に示す。(Examples A8 to A10, Comparative Examples A16 to A18)
In the air-cooled spinning as in Example A1, the spinning speed was changed to obtain the fibers for drawing, and then the drawing was performed. Table 5 shows each condition and the physical properties of the drawn fiber.
表５において、ｍ−ｉＰＰ（Ｈ）では実施例Ａ１０の延伸倍率が約８倍の場合に最大強度、初期弾性率を示した。紡糸速度１０００ｍ／ｍｉｎの場合もｍ−ｉＰＰ（Ｈ）は高い強度、初期弾性率を有する。ｍ−ｉＰＰ（Ｌ）では比較例Ａ１７の延伸倍率が約６．５倍の時最大強度を示した。それぞれの最大強度を示す延伸繊維を比較した場合、ｍ−ｉＰＰ（Ｈ）は、ｍ−ｉＰＰ（Ｌ）に対して、強度、剛性共に格段に優れることがわかった。ＺＮ−ＰＰでは、ＣＶが２％以下の延伸用繊維が得られず、延伸繊維も破断伸びが低下した。
実施例Ａ１０及び比較例Ａ１７について、得られた延伸繊維の結晶化度、結晶配向度、クリープひずみを上記と同様に測定した。結果を表６に示す。In Table 5, for m-iPP(H), the maximum strength and the initial elastic modulus were shown when the stretching ratio of Example A10 was about 8 times. Even at a spinning speed of 1000 m/min, m-iPP(H) has high strength and initial elastic modulus. In m-iPP(L), the maximum strength was exhibited when the stretching ratio of Comparative Example A17 was about 6.5 times. When the stretched fibers showing the respective maximum strengths were compared, it was found that m-iPP(H) was remarkably superior in strength and rigidity to m-iPP(L). With ZN-PP, a stretching fiber having a CV of 2% or less was not obtained, and the stretched fiber also had a reduced elongation at break.
Regarding Example A10 and Comparative Example A17, the crystallinity, crystal orientation, and creep strain of the obtained drawn fiber were measured in the same manner as above. The results are shown in Table 6.
（実施例Ａ１１−Ａ１７，Ｂ１１−Ｂ１４、比較例Ａ１９−Ａ２８、Ｂ６−Ｂ７）
次に、各延伸繊維を２段延伸した例について説明する。まず、一段目延伸として延伸倍率１０倍で延伸し、続いて、２段目の延伸を行って、それぞれ、最終的に総延伸倍率が１４倍、１６倍、１８倍、２０倍、２２倍、３０倍、３６倍となるように延伸した。各条件及び延伸繊維物性を表７に示す。(Examples A11-A17, B11-B14, Comparative Examples A19-A28, B6-B7)
Next, an example in which each drawn fiber is drawn in two stages will be described. First, as the first stage stretching, stretching is performed at a draw ratio of 10 times, and then, the second stage stretching is performed, and finally the total draw ratio is 14 times, 16 times, 18 times, 20 times, 22 times, respectively. It was stretched so as to be 30 times and 36 times. Table 7 shows each condition and the physical properties of the drawn fiber.
表７における実施例Ａ１１の１８倍延伸においてｍ−ｉＰＰ（Ｈ）が最大強度を発現し、表３に示す１段延伸の場合に比較して、強度、初期弾性率が高い。
ｍ−ｉＰＰ（Ｌ）では１６倍延伸（比較例Ａ２０）において、ＺＮ−ＰＰでは１８倍延伸（比較例Ａ２２）において、最大強度を達成している。
以上から、ｍ−ｉＰＰ（Ｈ）は、ｍ−ｉＰＰ（Ｌ）及びＺＮ−ＰＰに対して強度、剛性共に格段に優れることがわかった。
水冷紡糸の場合は空冷紡糸の場合に比較して強度が高いことが分かった。例えば実施例Ｂ１３は、実施例Ａ１４に比較して強度が高い。
二段延伸については、測定器（（株）ＫＥＹＥＮＣＥ製高速・高精度ディジタル寸法測定器ＬＳ−９００６（商品名））を用いて繊維直径を測定した。
さらに、実施例Ａ１１，Ａ１２，Ａ１５，Ａ１６，Ａ１７，Ｂ１２，Ｂ１４，比較例Ａ１９、Ａ２１、Ａ２２，Ａ２５，Ａ２７，Ａ２８，Ｂ６，Ｂ７について、得られた延伸繊維の結晶化度、結晶配向度を上記と同様に測定した。また、一部ナノサイズボイド割合を算出した。結果を表８に示す。
最大破断強度を発現する延伸倍率１８倍で実施例Ａ１１と比較例Ａ２２において、クリープひずみを上記と同様に測定した。両者を比較した場合、クリープひずみは、ＺＮ−ＰＰ＞ｍ−ｉＰＰ（Ｈ）である。M-iPP(H) expresses the maximum strength in the 18-fold stretching of Example A11 in Table 7, and the strength and the initial elastic modulus are higher than in the case of the single-stage stretching shown in Table 3.
The maximum strength was achieved in the 16 times stretched m-iPP (L) (Comparative Example A20) and in the 18 times stretched ZN-PP (Comparative Example A22).
From the above, it was found that m-iPP(H) is remarkably superior in strength and rigidity to m-iPP(L) and ZN-PP.
It was found that the strength of the water-cooled spinning was higher than that of the air-cooled spinning. For example, Example B13 has higher strength than Example A14.
Regarding the two-stage drawing, the fiber diameter was measured using a measuring device (high speed/high precision digital size measuring device LS-9006 (trade name) manufactured by KEYENCE Co., Ltd.).
Further, for Examples A11, A12, A15, A16, A17, B12, B14 and Comparative Examples A19, A21, A22, A25, A27, A28, B6, B7, the crystallinity and the crystal orientation of the obtained drawn fiber were obtained. Was measured in the same manner as above. Further, the proportion of some nano-sized voids was calculated. The results are shown in Table 8.
The creep strain was measured in the same manner as described above in Example A11 and Comparative Example A22 at a draw ratio of 18 times to develop the maximum breaking strength. When the two are compared, the creep strain is ZN-PP>m-iPP(H).
本発明で得られたポリプロピレン製延伸繊維は、ロープ、ネット、ケーブルなどの産業資材、建造物や自動車などの内装材、医療・衛生材、衣料素材などに使用でき、特に耐熱クリープ性に優れることから、電池のセパレータ用として高い評価を得ているほか、防水シート基布、産業用縫製糸、各種フィルター、ファブリック等に好適に使用できる。
また、本発明で得られたポリプロピレン製延伸繊維は、各種複合繊維の一部材として、例えば、代表的には芯鞘複合繊維の芯材として好適に使用できる。芯材として本発明に係る延伸繊維を使用すると、複合強度が高まり、従来にない高い強度を有する複合繊維を得ることができる。The polypropylene stretched fiber obtained in the present invention can be used for industrial materials such as ropes, nets and cables, interior materials such as buildings and automobiles, medical/sanitary materials, clothing materials, etc., and particularly excellent in heat creep resistance. Therefore, in addition to being highly evaluated as a battery separator, it can be suitably used as a waterproof sheet base cloth, industrial sewing thread, various filters, fabrics and the like.
Further, the polypropylene drawn fiber obtained in the present invention can be suitably used as a member of various composite fibers, for example, typically as a core material of core-sheath composite fiber. When the stretched fiber according to the present invention is used as the core material, the composite strength is increased, and a composite fiber having a high strength which has never been obtained can be obtained.
１ 送出ローラー
２ ヒーター
３ 張力計（テンションピックアップセンサー）
４ 寸法測定器
５ 巻取ローラー
６ 延伸用繊維（as spun繊維）
７ 延伸繊維1 Sending roller 2 Heater 3 Tension meter (tension pickup sensor)
4 Dimension measuring device 5 Winding roller 6 Stretching fiber (as spun fiber)
7 Stretched fiber
Claims (7)
（１）ｍｍｍｍ値が９７％以上である；
（２）ＧＰＣによって求められる分子量分布（Ｍｗ／Ｍｎ）が３．０未満である；
（３）メルトフローレート（２３０℃、２．１６ｋｇ）が１〜１００ｇ／１０分である。 It is characterized by including a step of drawing a drawing fiber containing homopolypropylene that satisfies the following requirements (1) to (3) at a draw ratio of 7 times or more under the condition that the stress during drawing is 80 MPa or more and 10000 MPa or less. And a method for producing a polypropylene drawn fiber:
(1) mmmm value is 97% or more;
(2) The molecular weight distribution (Mw/Mn) determined by GPC is less than 3.0;
(3) Melt flow rate (230° C., 2.16 kg) is 1 to 100 g/10 minutes.
（Ａ−１）メルトドローレシオ（Melt draw ratio：MDR）が８〜５００、
（Ａ−２）紡糸温度が１８０〜３００℃、
（Ａ−３）１ホール当りの吐出量が１〜１００ｇ／ｍｉｎ。 The method for producing a stretched polypropylene fiber according to claim 1, wherein the stretching fiber is a fiber melt-spun according to the requirements described in (A-1) to (A-3) below:
(A-1) Melt draw ratio (MDR) is 8 to 500,
(A-2) The spinning temperature is 180 to 300° C.,
(A-3) The discharge rate per hole is 1 to 100 g/min.
（Ａ）結晶分散温度で、延伸倍率３倍以上、１５倍以下で延伸、
（Ｂ）延伸前の融点を超える温度で、総延伸倍率７倍以上４０倍以下となるように延伸。 The method for producing a polypropylene drawn fiber according to claim 1 or 2, wherein the drawing fiber is drawn in at least two stages of (A) and (B) below:
(A) Stretching at a crystal dispersion temperature at a stretching ratio of 3 times or more and 15 times or less,
(B) Stretching is performed at a temperature exceeding the melting point before stretching so that the total stretching ratio is 7 times or more and 40 times or less.
（Ａ）直径が７〜１５０μｍであり、
（Ｂ）（１１０）面の結晶配向度が０．９８４〜１．０である、
ことを特徴とする、ポリプロピレン系延伸繊維：
（１）ｍｍｍｍ値が９７％以上である；
（２）ＧＰＣによって求められる分子量分布（Ｍｗ／Ｍｎ）が３．０未満である;
（３）メルトフローレート（２３０℃、２．１６ｋｇ）が１〜１００ｇ／１０分である。 Including homopolypropylene that satisfies the following requirements (1) to (3),
(A) The diameter is 7 to 150 μm,
(B) (110) face crystal orientation degree of 0.9 84 to 1.0,
Polypropylene-based drawn fiber characterized by:
(1) mmmm value is 97% or more;
(2) The molecular weight distribution (Mw/Mn) determined by GPC is less than 3.0;
(3) Melt flow rate (230° C., 2.16 kg) is 1 to 100 g/10 minutes.
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| JP2016111025 | 2016-06-02 | ||
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| PCT/JP2017/020628 WO2017209283A1 (en) | 2016-06-02 | 2017-06-02 | Stretched fibers formed from polypropylene |
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| JPH07258911A (en) * | 1994-03-16 | 1995-10-09 | Tonen Chem Corp | Polypropylene resin composition for fiber and production of fiber using the same |
| JPH10195714A (en) * | 1996-12-27 | 1998-07-28 | Mitsui Chem Inc | Fiber made of polypropylene |
| JP3130288B2 (en) * | 1997-10-24 | 2001-01-31 | 宇部日東化成株式会社 | Stretching method and stretched product |
| EP0987356B1 (en) * | 1998-03-31 | 2009-09-16 | Ube Nitto Kasei Co., Ltd. | Drawing method |
| JP2001123322A (en) * | 1999-10-15 | 2001-05-08 | Ube Nitto Kasei Co Ltd | Polypropylene-based drawn fiber, nonwoven fabric and method for producing the drawn fiber |
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