JP6996555B2 - Polyethylene fiber and products using it - Google Patents
Polyethylene fiber and products using it Download PDFInfo
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- JP6996555B2 JP6996555B2 JP2019509885A JP2019509885A JP6996555B2 JP 6996555 B2 JP6996555 B2 JP 6996555B2 JP 2019509885 A JP2019509885 A JP 2019509885A JP 2019509885 A JP2019509885 A JP 2019509885A JP 6996555 B2 JP6996555 B2 JP 6996555B2
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- 239000000835 fiber Substances 0.000 title claims description 108
- -1 Polyethylene Polymers 0.000 title claims description 76
- 239000004698 Polyethylene Substances 0.000 title claims description 76
- 229920000573 polyethylene Polymers 0.000 title claims description 76
- 239000002245 particle Substances 0.000 claims description 70
- 239000004744 fabric Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000011156 evaluation Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 2
- 238000000034 method Methods 0.000 description 21
- 238000009987 spinning Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000012779 reinforcing material Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000009940 knitting Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000002074 melt spinning Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000001891 gel spinning Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 210000003205 muscle Anatomy 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000002435 tendon Anatomy 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 201000004384 Alopecia Diseases 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 208000024963 hair loss Diseases 0.000 description 1
- 230000003676 hair loss Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
-
- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
- D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Knitting Of Fabric (AREA)
Description
本発明は、耐切創性に優れたポリエチレン繊維および該繊維を含む製品に関する。 The present invention relates to polyethylene fibers having excellent cut resistance and products containing the fibers.
従来、天然繊維の綿や一般的な有機繊維が耐切創性素材として用いられてきた。また、それらの繊維などを編みあげた手袋が耐切創性を必要とする分野で多く用いられてきた。そこで耐切創性機能の付与として、アラミド繊維などの高強度繊維の紡績糸からなる編物や織物などが考案されてきた。しかしながら、これらは、毛抜けや耐久性の観点で不満が見受けられた。一方、別の手段として、金属繊維を有機繊維や天然繊維と合わせて用いることにより耐切創性を向上させる試みが行われている。しかしながら、金属繊維を合わせることにより、風合いが堅くなり、柔軟性が損なわれるという問題がある。 Conventionally, natural fibers such as cotton and general organic fibers have been used as cut-resistant materials. In addition, gloves made by knitting these fibers have been widely used in fields where cut resistance is required. Therefore, knits and woven fabrics made of spun yarns of high-strength fibers such as aramid fibers have been devised to impart a cut resistance function. However, these were dissatisfied in terms of hair loss and durability. On the other hand, as another means, attempts have been made to improve cut resistance by using metal fibers in combination with organic fibers and natural fibers. However, there is a problem that the texture becomes hard and the flexibility is impaired by combining the metal fibers.
上記の問題を解決するため、重量平均分子量(Mw)、及び重量平均分子量と数平均分子量(Mn)の比(Mw/Mn)を規定した、耐切創性に優れるポリエチレン繊維の技術が知られている(例えば、特許文献1を参照)。 In order to solve the above problems, a technique of polyethylene fiber having excellent cut resistance, which defines a weight average molecular weight (Mw) and a ratio (Mw / Mn) of a weight average molecular weight to a number average molecular weight (Mn), is known. (See, for example, Patent Document 1).
また、硬質繊維を含む糸により耐切創性に優れる超高分子量ポリエチレン繊維の技術が知られている(例えば、特許文献2および3を参照)。 Further, a technique of ultra-high molecular weight polyethylene fiber having excellent cut resistance due to a thread containing a hard fiber is known (see, for example, Patent Documents 2 and 3).
しかし、近年安全意識の高まりから、従来よりも耐切創性の高い素材が求められている。また、特許文献2や3に開示の技術を溶融紡糸に利用すると、添加する硬質繊維が紡糸工程における濾過フィルターを目詰まりさせ、生産性を著しく低下させるという問題がある。 However, due to the growing awareness of safety in recent years, there is a demand for materials with higher cut resistance than before. Further, when the technique disclosed in Patent Documents 2 and 3 is used for melt spinning, there is a problem that the added hard fiber clogs the filtration filter in the spinning process and significantly reduces the productivity.
そこで、本発明は、かかる従来技術の課題を解決するためになされた。すなわち、本発明の目的は、優れた耐切創性を有し、生産性の高い新規なポリエチレン繊維、および該繊維を用いた製品を提供することにある。 Therefore, the present invention has been made to solve the problems of the prior art. That is, an object of the present invention is to provide a novel polyethylene fiber having excellent cut resistance and high productivity, and a product using the fiber.
本発明者らは鋭意検討した結果、以下に示す手段により、上記課題を解決できることを見出し、本発明を完成するに到った。すなわち、本発明は、以下の構成からなる。 As a result of diligent studies, the present inventors have found that the above problems can be solved by the means shown below, and have completed the present invention. That is, the present invention has the following configuration.
1.極限粘度[η]が0.8dL/g以上、4.9dL/g未満のポリエチレンからなる繊維であり、アスペクト比が3未満であり、平均粒子径が3.0μm以上15.0μm以下の硬質粒子を、ポリエチレン繊維中に5質量%以上含有することを特徴とするポリエチレン繊維。
2.上記硬質粒子は、シリカまたはアルミナである上記1に記載のポリエチレン繊維。
3.ヨーロッパ規格であるEN388による耐切創性評価において、350g/m2±35g/m2の布帛にした場合の耐切創性のレベルが4以上である上記1または2に記載のポリエチレン繊維。
4.上記1から3のいずれか1つに記載のポリエチレン繊維を含むことを特徴とする製品。1. 1. A fiber made of polyethylene having an ultimate viscosity [η] of 0.8 dL / g or more and less than 4.9 dL / g, a hard particle having an aspect ratio of less than 3, and an average particle diameter of 3.0 μm or more and 15.0 μm or less. , 5% by mass or more in the polyethylene fiber.
2. 2. The polyethylene fiber according to 1 above, wherein the hard particles are silica or alumina.
3. 3. The polyethylene fiber according to 1 or 2 above, wherein the level of cut resistance when a fabric of 350 g / m 2 ± 35 g / m 2 is used in the cut resistance evaluation according to the European standard EN388 is 4 or more.
4. A product comprising the polyethylene fiber according to any one of 1 to 3 above.
本発明により、優れた耐切創性を有し、生産性の高いポリエチレン繊維、および該繊維を用いた製品を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyethylene fiber having excellent cut resistance and high productivity, and a product using the fiber.
以下、本発明を詳述する。
本発明のポリエチレン繊維は、その極限粘度[η]が0.8dL/g以上、4.9dL/g未満であり、好ましくは1.0dL/g以上、4.0dL/g以下、更に好ましくは1.2dL/g以上、2.5dL/g以下である。Hereinafter, the present invention will be described in detail.
The polyethylene fiber of the present invention has an intrinsic viscosity [η] of 0.8 dL / g or more and less than 4.9 dL / g, preferably 1.0 dL / g or more and 4.0 dL / g or less, and more preferably 1. .2 dL / g or more and 2.5 dL / g or less.
極限粘度を4.9dL/g未満とすることにより、溶融紡糸法での製糸が容易になり、いわゆるゲル紡糸等で製糸する必要がない。そのため、製造コストの抑制、作業工程の簡略化の点で優位である。さらに、製造時に溶剤を用いないため、作業者や環境への影響も小さい。また製品となった繊維中の残留溶剤も存在しないため製品使用者に対する溶媒の悪影響がない。また、極限粘度を0.8dL/g以上とすることにより、ポリエチレンの分子末端基の減少により、繊維中の構造欠陥数を減少させることができる。そのため、強度や弾性率等の繊維の力学物性や耐切創性能を向上させることができる。 By setting the ultimate viscosity to less than 4.9 dL / g, spinning by the melt spinning method becomes easy, and it is not necessary to spin by so-called gel spinning or the like. Therefore, it is advantageous in terms of controlling manufacturing costs and simplifying work processes. Furthermore, since no solvent is used during manufacturing, the impact on workers and the environment is small. In addition, since there is no residual solvent in the fibers of the product, there is no adverse effect of the solvent on the product user. Further, by setting the ultimate viscosity to 0.8 dL / g or more, the number of structural defects in the fiber can be reduced by reducing the molecular terminal groups of polyethylene. Therefore, it is possible to improve the mechanical characteristics of the fiber such as strength and elastic modulus and the cut resistance performance.
また本発明に係るポリエチレン繊維の好ましい重量平均分子量(Mw)は50000~600000である。Mwを50000以上とすることにより、ポリエチレンの分子末端基の減少により、繊維中の構造欠陥数を減少させることができる。そのため、強度や弾性率等の繊維の力学物性や耐切創性能が向上する。一方、Mwを600000以下とすることにより、溶融紡糸法での製糸が容易になり、いわゆるゲル紡糸等で製糸する必要がない。そのため、製造コストの抑制、作業工程の簡略化の点で優位である。さらに、製造時に溶剤を用いないため、作業者や環境への影響も小さい。また製品となった繊維中の残留溶剤も存在しないため製品使用者に対する溶媒の悪影響がない。 The preferable weight average molecular weight (Mw) of the polyethylene fiber according to the present invention is 50,000 to 600,000. By setting Mw to 50,000 or more, the number of structural defects in the fiber can be reduced by reducing the molecular terminal groups of polyethylene. Therefore, the mechanical properties of the fiber such as strength and elastic modulus and the cut resistance are improved. On the other hand, when Mw is set to 600,000 or less, spinning by the melt spinning method becomes easy, and it is not necessary to spin by so-called gel spinning or the like. Therefore, it is advantageous in terms of controlling manufacturing costs and simplifying work processes. Furthermore, since no solvent is used during manufacturing, the impact on workers and the environment is small. In addition, since there is no residual solvent in the fibers of the product, there is no adverse effect of the solvent on the product user.
また本発明におけるポリエチレンは、その繰り返し単位が実質的にエチレンであればよく、当該エチレンと、少量の他のモノマー;例えばα-オレフィン、アクリル酸及びその誘導体、メタクリル酸及びその誘導体、ビニルシラン及びその誘導体等との共重合体であってもよい。或は、これら共重合体同士、またはエチレン単独ポリマーと上記共重合体との共重合体、更にはエチレン単独ポリマーと他のα-オレフィン等のホモポリマーとのブレンド体であってもよい。特にプロピレン、ブテン-1などのα-オレフィンとの共重合体を用いて短鎖または長鎖の分岐をある程度含有させることは、本発明のポリエチレン繊維を製造する上で、特に紡糸・延伸における製糸上の安定性が付与されるため、より好ましい。しかしながら、エチレン以外の含有量が増え過ぎると逆に延伸の阻害要因となるため、高強度・高弾性率のポリエチレン繊維を得るという観点からは、ポリエチレン繊維全体に占めるエチレン以外の成分の比率はモノマー単位で好ましくは0.2mol%以下、より好ましくは0.1mol%以下である。もちろん、本発明におけるポリエチレンはエチレン単独で構成されていてもよい。 Further, the polyethylene in the present invention may be used as long as the repeating unit thereof is substantially ethylene, and the ethylene and a small amount of other monomers; for example, α-olefin, acrylic acid and its derivative, methacrylic acid and its derivative, vinylsilane and its derivative. It may be a copolymer with a derivative or the like. Alternatively, these copolymers may be used together, a copolymer of an ethylene homopolymer and the above copolymer, or a blend of an ethylene homopolymer and another homopolymer such as α-olefin. In particular, the inclusion of short-chain or long-chain branches to some extent using a copolymer with an α-olefin such as propylene or butene-1 is used in producing the polyethylene fiber of the present invention, and in particular, in spinning and drawing. It is more preferable because it imparts the above stability. However, if the content other than ethylene increases too much, it will adversely affect stretching. Therefore, from the viewpoint of obtaining polyethylene fibers with high strength and high elastic modulus, the ratio of components other than ethylene to the total polyethylene fibers is monomer. The unit is preferably 0.2 mol% or less, more preferably 0.1 mol% or less. Of course, the polyethylene in the present invention may be composed of ethylene alone.
本発明のポリエチレン繊維は、アスペクト比が3未満である複数の硬質粒子を含有している。本発明のポリエチレン繊維が含有する硬質粒子のアスペクト比は、3未満であればよいが、好ましくは1以上2以下である。ここで、硬質粒子のアスペクト比とは、JIS8900-1に基づいて算出される値(すなわち、粒子の顕微鏡像において、(最大長径/最大長径に直交する幅)で定義される粒子の形状を表す指数)である。硬質粒子のアスペクト比の測定方法は、後記する実施例の欄で詳述する。硬質粒子のアスペクト比が3以上になると、紡糸時に濾過フィルターが目詰まりし、繊維の生産性を著しく低下させることが懸念される為、好ましくない。 The polyethylene fiber of the present invention contains a plurality of hard particles having an aspect ratio of less than 3. The aspect ratio of the hard particles contained in the polyethylene fiber of the present invention may be less than 3, but preferably 1 or more and 2 or less. Here, the aspect ratio of the hard particle represents the shape of the particle defined by a value calculated based on JIS89001 (that is, a width orthogonal to the maximum major axis / maximum major axis in the microscope image of the particle). Index). The method for measuring the aspect ratio of hard particles will be described in detail in the column of Examples described later. If the aspect ratio of the hard particles is 3 or more, the filtration filter may be clogged during spinning, which may significantly reduce the productivity of the fibers, which is not preferable.
本発明において「硬質粒子」とは、シリカ、アルミナ等のようにポリマー(ポリエチレン繊維)中で凝集し難いものを意味する。よって、本発明のポリエチレン繊維が含有する硬質粒子の主たる原料としては、例えばシリカ、アルミナが挙げられ、なかでも、シリカからなるものが好ましい。 In the present invention, the "hard particles" mean particles that are difficult to aggregate in a polymer (polyethylene fiber) such as silica and alumina. Therefore, examples of the main raw material of the hard particles contained in the polyethylene fiber of the present invention include silica and alumina, and among them, those made of silica are preferable.
本発明のポリエチレン繊維が含有する複数の硬質粒子の形状は、真球状、扁球状であることが好ましい。硬質粒子が繊維状の場合、紡糸時に濾過フィルターが目詰まりし、繊維の生産性を著しく低下させることが懸念されるため、好ましくない。 The shape of the plurality of hard particles contained in the polyethylene fiber of the present invention is preferably spherical or oblate. If the hard particles are fibrous, the filtration filter may be clogged during spinning, which may significantly reduce the productivity of the fibers, which is not preferable.
本発明のポリエチレン繊維が含有する複数の硬質粒子は、そのまま用いてもよいし、表面を修飾したものを用いてもよい。表面修飾としては、ジメチル基、エポキシ基、ヘキシル基、フェニル基、メタクリル基、ビニル基、イソシアネート基等が適用できる。 The plurality of hard particles contained in the polyethylene fiber of the present invention may be used as they are or may have a modified surface. As the surface modification, a dimethyl group, an epoxy group, a hexyl group, a phenyl group, a methacrylic group, a vinyl group, an isocyanate group and the like can be applied.
本発明のポリエチレン繊維が含有する複数の硬質粒子の平均粒子径は、3.0μm以上であり、好ましくは5.0μm以上である。硬質粒子の平均粒子径が15.0μmよりも大きくなると、紡糸時に濾過フィルターが目詰まりし、繊維の生産性を著しく低下させ、特に延伸性を大幅に低下させる。
なお上記硬質粒子の平均粒子径は、後記する硬質粒子のアスペクト比と同様の方法により硬質粒子10個のそれぞれについて長軸(最大長径)と短軸(最大短径)を測定し、最大長径と最大短径の合計(20個)の平均値を求めることで、平均粒子径を算出した。The average particle size of the plurality of hard particles contained in the polyethylene fiber of the present invention is 3.0 μm or more, preferably 5.0 μm or more. When the average particle size of the hard particles is larger than 15.0 μm, the filtration filter is clogged during spinning, and the productivity of the fiber is significantly reduced, and in particular, the stretchability is significantly reduced.
The average particle diameter of the hard particles is determined by measuring the major axis (maximum major axis) and minor axis (maximum minor axis) for each of the 10 hard particles by the same method as the aspect ratio of the hard particles described later. The average particle diameter was calculated by obtaining the average value of the total of the maximum minor diameters (20 particles).
本発明のポリエチレン繊維全体に含まれる上記複数の硬質粒子の含有量は、5質量%以上であり、好ましくは10質量%以上30質量%以下である。硬質粒子の含有量が5質量%未満であると、繊維中に存在する硬質粒子と刃の接触頻度が少なく、耐切創性を向上させる効果を得られ難い。 The content of the plurality of hard particles contained in the entire polyethylene fiber of the present invention is 5% by mass or more, preferably 10% by mass or more and 30% by mass or less. When the content of the hard particles is less than 5% by mass, the contact frequency between the hard particles existing in the fiber and the blade is low, and it is difficult to obtain the effect of improving the cut resistance.
本発明のポリエチレン繊維を紡糸する際、硬質粒子は、事前にポリエチレンと混練したマスターバッチとして用いてもよいし、単体で用いてもよい。 When spinning the polyethylene fiber of the present invention, the hard particles may be used as a masterbatch kneaded with polyethylene in advance, or may be used alone.
本発明のポリエチレン繊維は、単糸あたりの繊維径が45μm以下であるのが好ましく、37μm以下であるのがより好ましい。単糸あたりの繊維径が45μmよりも太くなると、織物または編物(織編物)に形成した際の風合いが堅くなり、柔軟性が損なわれる。なお、単糸あたりの繊維径は、例えば、dtexと繊維の比重より求める方法や、顕微鏡を用いて求める方法を用いることで求めることができる。その下限は、上記観点からは特に限定されないが、生産性などを考慮すると、おおむね10μm以上であることが好ましい。 The polyethylene fiber of the present invention preferably has a fiber diameter per single yarn of 45 μm or less, more preferably 37 μm or less. When the fiber diameter per single yarn is larger than 45 μm, the texture when formed into a woven fabric or a knitted fabric (woven or knitted fabric) becomes firm, and the flexibility is impaired. The fiber diameter per single yarn can be obtained, for example, by using a method of obtaining dtex and the specific gravity of the fiber, or a method of obtaining using a microscope. The lower limit is not particularly limited from the above viewpoint, but is preferably about 10 μm or more in consideration of productivity and the like.
本発明のポリエチレン繊維は、上記硬質粒子以外に、添加剤として、酸化防止剤、滑剤、帯電防止剤、過酸化物、顔料、染料、分散剤等を含んでもいても良い。 In addition to the above-mentioned hard particles, the polyethylene fiber of the present invention may contain an antioxidant, a lubricant, an antistatic agent, a peroxide, a pigment, a dye, a dispersant and the like as additives.
本発明のポリエチレン繊維の平均強度は、4cN/dtex以上であることが望ましく、好ましくは、6cN/dtex以上である。平均強度が4cN/dtex未満の場合、応用製品を作製したとき、強度が不足する可能性がある。その上限は、上記観点からは特に限定されないが、紡糸性などの生産性を考慮すると、おおむね50cN/dtex以下であることが好ましい。 The average strength of the polyethylene fiber of the present invention is preferably 4 cN / dtex or more, preferably 6 cN / dtex or more. If the average strength is less than 4 cN / dtex, the strength may be insufficient when the applied product is manufactured. The upper limit is not particularly limited from the above viewpoint, but is preferably about 50 cN / dtex or less in consideration of productivity such as spinnability.
本発明のポリエチレン繊維は、芯鞘構造を適用してもよく、また星形、三角や、中空等の異形の形状を有していてもよい。 The polyethylene fiber of the present invention may have a core-sheath structure applied thereto, or may have an irregular shape such as a star shape, a triangle shape, or a hollow shape.
本発明のポリエチレン繊維を得る製造方法については、例えば、溶融紡糸法を用いることができる。ここで、例えば、溶剤を用いて行う超高分子量ポリエチレン繊維の製法の一つであるゲル紡糸法を用いると、高強度のポリエチレン繊維を得られるものの、生産性が低いばかりでなく、溶剤使用による製造作業者の健康や環境への影響、また繊維中に残留する溶剤が製品使用者の健康に与える影響が大きい。 As a production method for obtaining the polyethylene fiber of the present invention, for example, a melt spinning method can be used. Here, for example, when the gel spinning method, which is one of the methods for producing ultra-high molecular weight polyethylene fibers using a solvent, is used, high-strength polyethylene fibers can be obtained, but the productivity is not only low, but also due to the use of a solvent. It has a great impact on the health and environment of manufacturing workers, and the solvent remaining in the fiber has a great impact on the health of product users.
よって、本発明のポリエチレン繊維は溶融紡糸法を用いるのが好ましい。溶融紡糸法を用いて本発明のポリエチレン繊維を製造する方法について、具体的に以下に説明する。なお、本発明のポリエチレン繊維を製造する方法は、以下の工程や数値に限定されない。 Therefore, it is preferable to use the melt spinning method for the polyethylene fiber of the present invention. The method for producing the polyethylene fiber of the present invention by using the melt spinning method will be specifically described below. The method for producing the polyethylene fiber of the present invention is not limited to the following steps and numerical values.
上述したポリエチレン樹脂と粉末状態の硬質粒子とをブレンドし、押出機等を用いて、ポリエチレン樹脂の融点よりも例えば10℃以上、好ましくは50℃以上、更に好ましくは80℃以上高い温度で溶融押出しをして、定量供給装置を用いてポリエチレン樹脂の融点より例えば80℃、好ましくは100℃以上高い温度で紡糸ノズル(紡糸口金)に供給する。この時、押出機内に供給する不活性ガスの圧力は、0.001MPa以上、0.8MPa以下とするのが好ましく、より好ましくは0.05MPa以上、0.7MPa以下、更に好ましくは0.1MPa以上、0.5MPa以下とすることが推奨される。その後、例えば直径0.3mm以上、2.5mm以下、好ましくは直径0.5mm以上、1.5mm以下を有する紡糸ノズルより0.1g/min以上の吐出量で吐出する。紡糸ノズルから溶融樹脂を吐出する際の吐出線速度は、10cm/min以上、120cm/min以下とするのが好ましい。より好ましい吐出線速度は、20cm/min以上、110cm/min以下であり、更に好ましくは30cm/min以上、100cm/min以下である。 The above-mentioned polyethylene resin and hard particles in a powder state are blended and melt-extruded using an extruder or the like at a temperature higher than the melting point of the polyethylene resin, for example, 10 ° C. or higher, preferably 50 ° C. or higher, and more preferably 80 ° C. or higher. Then, using a fixed quantity supply device, the polyethylene resin is supplied to the spinning nozzle (spinning cap) at a temperature higher than the melting point of the polyethylene resin, for example, 80 ° C., preferably 100 ° C. or higher. At this time, the pressure of the inert gas supplied into the extruder is preferably 0.001 MPa or more and 0.8 MPa or less, more preferably 0.05 MPa or more, 0.7 MPa or less, still more preferably 0.1 MPa or more. , 0.5 MPa or less is recommended. Then, for example, a spinning nozzle having a diameter of 0.3 mm or more and 2.5 mm or less, preferably a diameter of 0.5 mm or more and 1.5 mm or less is discharged at a discharge amount of 0.1 g / min or more. The discharge line speed at the time of discharging the molten resin from the spinning nozzle is preferably 10 cm / min or more and 120 cm / min or less. More preferable discharge line velocities are 20 cm / min or more and 110 cm / min or less, and more preferably 30 cm / min or more and 100 cm / min or less.
次に、該吐出糸を5~40℃まで冷却した後に50m/min以上で巻き取り、更に得られた該未延伸糸を、少なくとも1回以上の回数で該未延伸糸の融点以下の温度で延伸する。具体的には、2段階以上に分けて延伸工程を行うことが好ましい。延伸の初期の温度は、上記未延伸糸の結晶分散温度未満が好ましく、より好ましくは80℃以下、更に好ましくは75℃以下である。次いで、上記未延伸糸の結晶分散温度以上、融点以下、好ましくは90℃以上、融点未満で延伸するのが好ましい。 Next, the discharged yarn is cooled to 5 to 40 ° C., then wound at 50 m / min or more, and the obtained undrawn yarn is further rolled at least once at a temperature equal to or lower than the melting point of the undrawn yarn. Stretch. Specifically, it is preferable to perform the stretching step in two or more steps. The initial temperature of drawing is preferably less than the crystal dispersion temperature of the undrawn yarn, more preferably 80 ° C. or lower, still more preferably 75 ° C. or lower. Next, it is preferable to draw the undrawn yarn at a crystal dispersion temperature or higher, a melting point or lower, preferably 90 ° C. or higher, and a melting point or lower.
ここで結晶分散温度とは、以下の方法によって測定される温度である。
まず固体粘弾性測定装置(T.A.インスツルメント社製、「DMA Q800」)を用いて固体粘弾性率を測定する。測定した固体粘弾性率の解析には、「T.A.Universal Analysis」(T.A.インスツルメント社製)を用いる。ここで測定開始温度を-140℃、測定終了温度を140℃、昇温速度を1.0℃/minとする。また、歪み量を0.04%とし、測定開始時の初荷重0.05cN/dtexとする。また、測定周波数を11Hzとする。次に、得られた固体粘弾性率に基づいて損失弾性率を計算し、温度分散を低温側より求め、損失弾性率の値を対数で縦軸に取り、横軸に温度を取ってプロットし、最も高温側に現れる損失弾性率のピーク値を結晶分散温度とする。Here, the crystal dispersion temperature is a temperature measured by the following method.
First, the solid viscoelasticity is measured using a solid viscoelasticity measuring device (“DMA Q800” manufactured by TA Instruments). "TA Universal Analysis" (manufactured by TA Instruments) is used for the analysis of the measured solid viscoelasticity. Here, the measurement start temperature is −140 ° C., the measurement end temperature is 140 ° C., and the temperature rise rate is 1.0 ° C./min. Further, the strain amount is 0.04%, and the initial load at the start of measurement is 0.05 cN / dtex. The measurement frequency is 11 Hz. Next, the loss elastic modulus is calculated based on the obtained solid viscoelastic modulus, the temperature dispersion is obtained from the low temperature side, the value of the loss elastic modulus is plotted on the vertical axis and the temperature is plotted on the horizontal axis. The peak value of the loss elastic modulus that appears on the highest temperature side is defined as the crystal dispersion temperature.
延伸倍率は、合計で6倍以上とするのが好ましく、より好ましくは8倍以上であり、更に好ましくは10倍以上である。また、延伸倍率は、合計で30倍以下とするのが好ましく、より好ましくは25倍以下であり、更に好ましくは20倍以下である。なお、多段延伸を採用する場合、例えば、2段延伸を行う場合であれば、1段階目の延伸倍率は1.05倍以上、4.00倍以下とするのが好ましく、2段階目の延伸倍率は2.5倍以上、15倍以下とするのが好ましい。 The draw ratio is preferably 6 times or more in total, more preferably 8 times or more, and further preferably 10 times or more. The total draw ratio is preferably 30 times or less, more preferably 25 times or less, and further preferably 20 times or less. When multi-step stretching is adopted, for example, when two-step stretching is performed, the stretching ratio of the first step is preferably 1.05 times or more and 4.00 times or less, and the second step stretching is preferably performed. The magnification is preferably 2.5 times or more and 15 times or less.
本発明のポリエチレン繊維を使用した製品、例えば、織編物は、耐切創性織編物、手袋及びベスト等として好適に用いられる。例えば、手袋は、本発明のポリエチレン繊維を編み機に掛けることで得られる。もしくは、本発明のポリエチレン繊維を織り機に掛けて布帛を得、それを裁断、縫製して手袋とすることもできる。 Products using the polyethylene fibers of the present invention, for example, woven and knitted fabrics, are suitably used as cut resistant woven and knitted fabrics, gloves, vests and the like. For example, gloves can be obtained by hanging the polyethylene fibers of the present invention on a knitting machine. Alternatively, the polyethylene fiber of the present invention can be woven on a loom to obtain a cloth, which can be cut and sewn to make gloves.
このようにして得られた手袋は、例えば、そのまま手袋として使用することもできるが、必要であれば滑り止め性を付与するために、樹脂を塗布することもできる。ここで用いられる樹脂は、例えば、ウレタン系やエチレン系などが挙げられるが、特に限定されるものではない。 The gloves thus obtained can be used as, for example, gloves as they are, but if necessary, a resin can be applied to impart anti-slip properties. Examples of the resin used here include urethane-based and ethylene-based resins, but the resin is not particularly limited.
本発明のポリエチレン繊維は、後述の実施例からも分かるように、耐切創性能に優れている。具体的には、ヨーロッパ規格であるEN388による耐切創性評価において、350g/m2±35g/m2の布帛にした場合の耐切創性のレベルが4以上を満足する。
よって、本発明のポリエチレン繊維を使用した製品は、上記した手袋やベスト等の織編物以外にも、テープ、ロープ、ネット、釣糸、資材防護カバー、シート、カイト用糸、洋弓弦、セールクロス、幕材として好適に用いられる。もちろん、本発明のポリエチレン繊維を用いた製品はこれらに限定されない。As can be seen from the examples described later, the polyethylene fiber of the present invention has excellent cut resistance. Specifically, in the incision resistance evaluation according to the European standard EN388, the incision resistance level of a fabric of 350 g / m 2 ± 35 g / m 2 satisfies 4 or more.
Therefore, in addition to the above-mentioned woven and knitted fabrics such as gloves and vests, the products using the polyethylene fiber of the present invention include tapes, ropes, nets, fishing lines, material protective covers, sheets, kite threads, western bow strings, sail cloths, etc. It is suitably used as a curtain material. Of course, the products using the polyethylene fibers of the present invention are not limited to these.
また、本発明のポリエチレン繊維は、高い耐切創性を有するため、該耐切創性を活かした材料、例えば、繊維強化樹脂補強材、セメント補強材、繊維強化ゴム補強材、あるいは環境変化が想定される防護材、防弾材、医療用縫合糸、人工腱、人工筋肉、繊維強化樹脂補強材、セメント補強材、繊維強化ゴム補強材、工作機械部品、電池セパレーター、化学フィルターとして好適に用いられる。もちろん、本発明のポリエチレン繊維は、これらの材料に限定されず、様々な材料として用いることができる。 Further, since the polyethylene fiber of the present invention has high cut resistance, a material utilizing the cut resistance, for example, a fiber reinforced resin reinforcing material, a cement reinforcing material, a fiber reinforced rubber reinforcing material, or an environmental change is assumed. It is suitably used as a protective material, a bulletproof material, a medical suture, an artificial tendon, an artificial muscle, a fiber reinforced resin reinforcing material, a cement reinforcing material, a fiber reinforced rubber reinforcing material, a machine tool part, a battery separator, and a chemical filter. Of course, the polyethylene fiber of the present invention is not limited to these materials and can be used as various materials.
本願は、2017年3月29日に出願された日本国特許出願第2017-065331号に基づく優先権の利益を主張するものである。2017年3月29日に出願された日本国特許出願第2017-065331号の明細書の全内容が、本願に参考のため援用される。 This application claims the benefit of priority under Japanese Patent Application No. 2017-065331 filed on March 29, 2017. The entire contents of the specification of Japanese Patent Application No. 2017-065331 filed on March 29, 2017 are incorporated herein by reference.
以下に、実施例を例示し、本発明を具体的に説明する。しかし、本発明は下記実施例によって限定されるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and it is of course possible to carry out the present invention with appropriate modifications within a range that can meet the purposes of the preceding and the following, and both of them are the techniques of the present invention. It is included in the target range.
まず、後述の実施例および比較例で作製した繊維(繊維サンプル)およびそれを用いた筒編み物(編物サンプル)に対して行った特性値の測定及び評価について説明する。 First, the measurement and evaluation of the characteristic values performed on the fibers (fiber samples) produced in the examples and comparative examples described later and the tubular knitting (knitted sample) using the fibers will be described.
(1)極限粘度[η]
極限粘度は、溶媒として135℃に加熱したデカリンを用い、ウベローデ型毛細粘度管を用いて測定した。具体的には、種々の希薄溶液の比粘度を測定し、その粘度の濃度に対するプロットの最小2乗近似で得られる直線の原点への外挿点より極限粘度を決定した。比粘度の測定に際し、繊維サンプルを約5mm長に分割または切断し、ポリマーに対して1質量%の酸化防止剤(ヨシノックスBHT(登録商標)、吉富製薬製)を添加し、135℃で4時間攪拌溶解して測定溶液を調整した。(1) Extreme viscosity [η]
The ultimate viscosity was measured using a Ubbelohde-type capillary viscosity tube using decalin heated to 135 ° C. as a solvent. Specifically, the specific viscosities of various dilute solutions were measured, and the ultimate viscosity was determined from the extrapolation point to the origin of the straight line obtained by the minimum square approximation of the plot with respect to the concentration of the viscosity. When measuring the specific viscosity, the fiber sample was divided or cut into pieces of about 5 mm length, 1% by mass of an antioxidant (Yoshinox BHT®, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the polymer, and the temperature was 135 ° C. for 4 hours. The measurement solution was prepared by stirring and dissolving.
(2)硬質粒子のアスペクト比
硬質粒子のアスペクト比は、SEM写真を用いることによって求めた。繊維サンプルをるつぼの中に入れ、灰と炭素質物質になるまで燃焼をさせた後、電気炉に入れ、ポリエチレンの分解温度以上で加熱した。炭素質物質が完全に灰になったら、デシケータ中で放冷して灰分を得た。灰分のSEM写真を撮影し、無作為に選択した硬質粒子10個のそれぞれについて、長軸(最大長径)および最大長径に直交する幅を測定し、最大長径を、最大長径に直交する幅で除して、その平均値を求めることで、アスペクト比を算出した。なお、硬質粒子は硬度が高い為、加熱しても形状が変化しないと考えられる。(2) Aspect ratio of hard particles The aspect ratio of hard particles was determined by using an SEM photograph. The fiber sample was placed in a crucible, burned until it became ash and a carbonaceous substance, then placed in an electric furnace and heated above the decomposition temperature of polyethylene. When the carbonaceous material was completely ash, it was allowed to cool in a desiccator to obtain ash. SEM photographs of the ash are taken, and for each of the 10 randomly selected hard particles, the major axis (maximum major axis) and the width orthogonal to the maximum major axis are measured, and the maximum major axis is divided by the width orthogonal to the maximum major axis. Then, the aspect ratio was calculated by obtaining the average value. Since the hard particles have high hardness, it is considered that the shape does not change even when heated.
(3)硬質粒子の含有量
硬質粒子の含有量は、JIS-2272に基づき、灰分測定を用いることによって求めた。繊維サンプル1.0gをるつぼの中に入れ、灰と炭素質物質になるまで燃焼をさせた後、電気炉に入れ、ポリエチレンの分解温度以上で加熱した。炭素質物質が完全に灰になった後、デシケータ中で放冷して質量を測定し、灰分を求めた。得られた灰分量と上記繊維量の合計に対する灰分量の質量比率に基づき、硬質粒子の含有量を求めた。(3) Content of hard particles The content of hard particles was determined by using ash content measurement based on JIS-2272. 1.0 g of the fiber sample was placed in a crucible and burned until it became ash and a carbonaceous substance, then placed in an electric furnace and heated at a temperature higher than the decomposition temperature of polyethylene. After the carbonaceous substance was completely turned into ash, it was allowed to cool in a desiccator and the mass was measured to determine the ash content. The content of hard particles was determined based on the mass ratio of the ash content to the total of the obtained ash content and the fiber content.
(4)耐切創性
耐切創性は、クープテスター(ソドマット(SODMAT)社製)の装置を用い、ヨーロッパ規格であるEN388法に基づいて測定を行った。具体的には、後記する方法で作製した各ポリエチレン繊維を用い、島精機製作所社製の丸編み機を用いて、目付が350g/m2±35g/m2の筒編み物を作製した。得られた筒編み物のクープテスターのインデックス値を以下のようにして算出して、耐切創性を評価した。(4) Cut resistance The cut resistance was measured based on the EN388 method, which is a European standard, using a device of a coup tester (manufactured by SODMAT). Specifically, using each polyethylene fiber produced by the method described later, a tubular knitting machine having a basis weight of 350 g / m 2 ± 35 g / m 2 was produced using a circular knitting machine manufactured by Shima Seiki Seisakusho Co., Ltd. The index value of the obtained tube knitting coup tester was calculated as follows to evaluate the cut resistance.
ここで、上記装置の試料台にはアルミ箔が設けられており、この上に編物サンプルを載置した。次いで、装置に備えられた円形の刃を、走行方向とは逆方向に回転させながら試料の上を走らせた。なお、編物サンプルが切断されると、円形刃とアルミ箔とが接触して通電することで、耐切創性試験が終了したことが検知された。円形刃が作動している間中、装置に取り付けられているカウンターがカウントを行うので、その数値を記録した。 Here, an aluminum foil is provided on the sample table of the above device, and the knitted sample is placed on the aluminum foil. Then, the circular blade provided in the device was run on the sample while rotating in the direction opposite to the running direction. When the knitted sample was cut, it was detected that the cut resistance test was completed by the contact between the circular blade and the aluminum foil and energization. While the circular blade was operating, the counter attached to the device counted and recorded the value.
この試験では、目付け約200g/m2の平織りの綿布をブランクとし、編物サンプルの切創レベルを評価した。ブランクからテストを開始し、ブランクのテストと編物サンプルのテストとを交互に行い、編物サンプルを5回テストし、最後に6回目のブランクをテストして、1セットの試験を終了した。以上の試験を5セット行い、5セットの平均のIndex値(インデックス値)を耐切創性の代用評価とした。インデックス値が高いほど、耐切創性に優れることを意味する。本実施例では、上記インデックス値のレベルが4以上を合格とした。In this test, a plain weave cotton cloth with a basis weight of about 200 g / m 2 was used as a blank, and the cut level of the knitted sample was evaluated. The test was started from the blank, the blank test and the knitted sample test were alternated, the knitted sample was tested 5 times, and finally the 6th blank was tested to complete one set of tests. Five sets of the above tests were performed, and the average Index value (index value) of the five sets was used as a substitute evaluation for cut resistance. The higher the index value, the better the cut resistance. In this embodiment, the index value level of 4 or higher is regarded as acceptable.
インデックス値は、次式により算出される。
A=(サンプルテスト前の綿布のカウント値+サンプルテスト後の綿布のカウント値)/2
インデックス値=(サンプルのカウント値+A)/AThe index value is calculated by the following formula.
A = (count value of cotton cloth before sample test + count value of cotton cloth after sample test) / 2
Index value = (sample count value + A) / A
耐切創性の評価に使用したカッターは、OLFA株式会社製のロータリーカッターL型用φ45mmである。材質はSKS-7タングステン鋼であり、刃厚0.3ミリ厚であった。また、テスト時にかかる荷重は3.14N(320gf)にして評価を行った。 The cutter used for the evaluation of cut resistance is a rotary cutter L-shaped φ45 mm manufactured by OLFA Co., Ltd. The material was SKS-7 tungsten steel, and the blade thickness was 0.3 mm. Moreover, the load applied at the time of the test was set to 3.14N (320gf) and the evaluation was performed.
(実施例1)
極限粘度が1.9dL/gであるポリエチレンペレット88質量%と、アスペクト比が1.4、平均粒子径が3μmであるシリカ粒子(硬質粒子)12質量%とを混ぜてブレンドポリマーを作製した。なお、硬質粒子のアスペクト比は、上記したように10個の平均であり、その範囲は1.1から2.3であった。このブレンドポリマーを押出機に供給して280℃で溶融し、オリフィス径φ0.8mm、30Hからなる紡糸口金からノズル面温度288℃にて単孔吐出量0.32g/minで吐出させた。(Example 1)
A blend polymer was prepared by mixing 88% by mass of polyethylene pellets having an ultimate viscosity of 1.9 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.4 and an average particle size of 3 μm. The aspect ratio of the hard particles was an average of 10 particles as described above, and the range was 1.1 to 2.3. This blended polymer was supplied to an extruder, melted at 280 ° C., and discharged from a spun mouthpiece having an orifice diameter of φ0.8 mm and 30 H at a nozzle surface temperature of 288 ° C. and a single hole discharge rate of 0.32 g / min.
吐出された糸条を10cmの保温区間通過させ、その後18℃、0.5m/secのクエンチで冷却後、紡糸速度200m/minでチーズ形状に捲き取り、未延伸糸を得た。次いで、上記の未延伸糸を2個の駆動ロール間で3倍、次いで100℃の熱風で加熱して安定に延伸できる最大の延伸倍率にて巻き取って延伸糸を得た。延伸糸を全体として880dtex±88dtexとなるように合糸し、実施例1のポリエチレン繊維を得た。得られたポリエチレン繊維を用いて、上記方法により筒編み物を作製して耐切創性を評価した。これらの結果を表1に示す。なお、本実施例を含め以下の実施例及び比較例では、延伸糸を所望のdtexとなるように合糸を行ったが、分繊を行う場合もある。 The discharged yarn was passed through a heat insulating section of 10 cm, cooled at 18 ° C. at 0.5 m / sec, and then wound into a cheese shape at a spinning speed of 200 m / min to obtain an undrawn yarn. Next, the undrawn yarn was wound three times between the two drive rolls and then heated with hot air at 100 ° C. at the maximum draw ratio capable of stable drawing to obtain a drawn yarn. The drawn yarns were combined so as to have a total of 880 dtex ± 88 dtex to obtain the polyethylene fiber of Example 1. Using the obtained polyethylene fiber, a tubular knitted fabric was produced by the above method and the cut resistance was evaluated. These results are shown in Table 1. In the following examples and comparative examples including this example, the drawn yarns are combined so as to have a desired dtex, but fiber splitting may be performed.
(実施例2)
実施例1の条件において、アスペクト比が1.5、平均粒子径が7μmであるシリカ粒子(硬質粒子)12質量%を用いた以外は、実施例1と同様にして未延伸糸を得た。得られた未延伸糸から実施例1と同様にして延伸糸を得た。得られた延伸糸から、実施例1と同様に、実施例2のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表1に示す。(Example 2)
Undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 μm were used under the conditions of Example 1. A drawn yarn was obtained from the obtained undrawn yarn in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 2 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
(実施例3)
実施例1の条件において、極限粘度が1.9dL/gであるポリエチレンペレット95質量%と、アスペクト比が1.5、平均粒子径が7μmであるシリカ粒子(硬質粒子)5質量%とを用いた以外は、実施例1と同様にして未延伸糸を得た。得られた未延伸糸から実施例1と同様にして延伸糸を得た。得られた延伸糸から、実施例1と同様に、実施例3のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表1に示す。(Example 3)
Under the conditions of Example 1, 95% by mass of polyethylene pellets having an ultimate viscosity of 1.9 dL / g and 5% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle size of 7 μm were used. An undrawn yarn was obtained in the same manner as in Example 1 except that the undrawn yarn was obtained. A drawn yarn was obtained from the obtained undrawn yarn in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 3 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
(実施例4)
実施例1の条件において、アスペクト比が1.5、平均粒子径が15μmであるシリカ粒子(硬質粒子)12質量%を用いた以外は、実施例1と同様にして未延伸糸を得た。得られた未延伸糸から実施例1と同様にして延伸糸を得た。得られた延伸糸から、実施例1と同様に、実施例4のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表1に示す。(Example 4)
Undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 15 μm were used under the conditions of Example 1. A drawn yarn was obtained from the obtained undrawn yarn in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 4 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
(実施例5)
実施例1の条件において、アスペクト比が1.6、平均粒子径が7μmであるアルミナ粒子(硬質粒子)12質量%を用いた以外は、実施例1と同様にして未延伸糸を得た。得られた未延伸糸から実施例1と同様にして延伸糸を得た。得られた延伸糸から、実施例1と同様に、実施例5のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表1に示す。(Example 5)
Undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of alumina particles (hard particles) having an aspect ratio of 1.6 and an average particle diameter of 7 μm were used under the conditions of Example 1. A drawn yarn was obtained from the obtained undrawn yarn in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 5 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
(比較例1)
実施例1の条件において、極限粘度が1.9dL/gであるポリエチレンペレット80質量%と、アスペクト比が1.5、平均粒子径が2μmであるシリカ粒子(硬質粒子)20質量%とを用いた以外は、実施例1と同様にして未延伸糸を得た。得られた未延伸糸から実施例1と同様にして延伸糸を得た。得られた延伸糸から、実施例1と同様に、比較例1のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表1に示す。(Comparative Example 1)
Under the conditions of Example 1, 80% by mass of polyethylene pellets having an ultimate viscosity of 1.9 dL / g and 20% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle size of 2 μm were used. An undrawn yarn was obtained in the same manner as in Example 1 except that the undrawn yarn was obtained. A drawn yarn was obtained from the obtained undrawn yarn in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Comparative Example 1 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
(比較例2)
実施例1の条件において、アスペクト比が1.5、平均粒子径が17μmであるシリカ粒子(硬質粒子)12質量%を用いてブレンドポリマーを作製したが、紡糸時、詰まりが発生し、未延伸糸を得ることができなかった。(Comparative Example 2)
Under the conditions of Example 1, a blend polymer was prepared using 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 17 μm, but clogging occurred during spinning and unstretched. I couldn't get the thread.
(比較例3)
実施例1の条件において、極限粘度が1.9dL/gであるポリエチレンペレット97質量%と、アスペクト比が1.5、平均粒子径が7μmであるシリカ粒子(硬質粒子)3質量%とを用いた以外は、実施例1と同様にして未延伸糸を得た。得られた未延伸糸から実施例1と同様にして延伸糸を得た。得られた延伸糸から、実施例1と同様に、比較例3のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表1に示す。(Comparative Example 3)
Under the conditions of Example 1, 97% by mass of polyethylene pellets having an ultimate viscosity of 1.9 dL / g and 3% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle size of 7 μm were used. An undrawn yarn was obtained in the same manner as in Example 1 except that the undrawn yarn was obtained. A drawn yarn was obtained from the obtained undrawn yarn in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Comparative Example 3 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
(比較例4)
実施例1の条件において、極限粘度が5.5dL/gであるポリエチレンペレット88質量%と、アスペクト比が1.5、平均粒子径が7μmであるシリカ粒子(硬質粒子)12質量%とを混ぜてブレンドポリマーを作製したが、ポリマーと硬質粒子とが混ざり合わず未延伸糸が得られなかった。(Comparative Example 4)
Under the conditions of Example 1, 88% by mass of polyethylene pellets having an ultimate viscosity of 5.5 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle size of 7 μm are mixed. However, the polymer and the hard particles did not mix with each other, and an undrawn yarn could not be obtained.
(比較例5)
実施例1の条件において、極限粘度が0.5dL/gであるポリエチレンペレット88質量%と、アスペクト比が1.5、平均粒子径が7μmであるシリカ粒子(硬質粒子)12質量%とを用いた以外は、実施例1と同様にして未延伸糸を得た。得られた未延伸糸から実施例1と同様にして延伸糸を得た。得られた延伸糸から、実施例1と同様に、比較例5のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表1に示す。(Comparative Example 5)
Under the conditions of Example 1, 88% by mass of polyethylene pellets having an ultimate viscosity of 0.5 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle size of 7 μm were used. An undrawn yarn was obtained in the same manner as in Example 1 except that the undrawn yarn was obtained. A drawn yarn was obtained from the obtained undrawn yarn in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Comparative Example 5 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
(比較例6)
実施例1の条件において、アスペクト比が18、平均粒子径が7μmであるシリカ粒子(硬質粒子)12質量%を用いてブレンドポリマーを作製したが、紡糸時、詰まりが発生し、未延伸糸を得ることができなかった。(Comparative Example 6)
Under the conditions of Example 1, a blend polymer was prepared using 12% by mass of silica particles (hard particles) having an aspect ratio of 18 and an average particle diameter of 7 μm, but clogging occurred during spinning, and undrawn yarn was produced. I couldn't get it.
表1から分かるように、実施例1~5のポリエチレン繊維;詳細には極限粘度が0.8dL/g以上4.9dL/g未満であり、アスペクト比が3未満であり、平均粒子径が3.0μm以上15.0μm以下の複数の硬質粒子を含有するポリエチレン繊維を用いた筒編み物では、インデックス値が高く、つまり、耐切創性レベルが高い。このように、上記実施例1~5および比較例1~6の対比から、本発明の要件を満足するポリエチレン繊維は、耐切創性に優れた繊維であることがわかる。 As can be seen from Table 1, the polyethylene fibers of Examples 1 to 5; in detail, the ultimate viscosity is 0.8 dL / g or more and less than 4.9 dL / g, the aspect ratio is less than 3, and the average particle size is 3. In a tubular knitting using polyethylene fibers containing a plurality of hard particles of 0.0 μm or more and 15.0 μm or less, the index value is high, that is, the cut resistance level is high. As described above, from the comparison between Examples 1 to 5 and Comparative Examples 1 to 6, it can be seen that the polyethylene fiber satisfying the requirements of the present invention is a fiber having excellent cut resistance.
以上、本発明の実施の形態および各実施例について説明したが、今回開示された実施の形態および各実施例はすべての点で例示であって制限的なものではない。本発明の範囲は特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内での全ての変更が含まれる。 Although the embodiments and the embodiments of the present invention have been described above, the embodiments and the embodiments disclosed this time are exemplary in all respects and are not limiting. The scope of the present invention is indicated by the scope of claims and includes all modifications within the meaning and scope equivalent to the scope of claims.
本発明のポリエチレン繊維は、高い耐切創性を有するため、該耐切創性を活かした耐切創性織編物、例えば手袋及びベスト等に利用可能である。また、該ポリエチレン繊維単独としてテープ、ロープ、ネット、釣糸、資材防護カバー、シート、カイト用糸、洋弓弦、セールクロス、幕材、防護材、防弾材、医療用縫合糸、人工腱、人工筋肉、繊維強化樹脂補強材、セメント補強材、繊維強化ゴム補強材、工作機械部品、電池セパレーター、化学フィルター等の産業用資材に利用可能である。このように、本発明のポリエチレン繊維は、優れた性能を発揮でき、幅広く応用できるため、産業界へ大きく寄与できる。 Since the polyethylene fiber of the present invention has high cut resistance, it can be used for cut resistant woven and knitted fabrics utilizing the cut resistance, such as gloves and vests. In addition, as the polyethylene fiber alone, tape, rope, net, fishing thread, material protective cover, sheet, kite thread, western bow string, sail cloth, curtain material, protective material, bulletproof material, medical suture thread, artificial tendon, artificial muscle , Fiber reinforced resin reinforcing material, cement reinforcing material, fiber reinforced rubber reinforcing material, machine tool parts, battery separators, chemical filters and other industrial materials. As described above, the polyethylene fiber of the present invention can exhibit excellent performance and can be widely applied, so that it can greatly contribute to the industrial world.
Claims (4)
アスペクト比が1以上2以下であり、平均粒子径が5.0μm以上15.0μm以下の無機酸化物粒子を、ポリエチレン繊維中に10質量%以上30質量%以下含有することを特徴とするポリエチレン繊維。 A fiber made of polyethylene having an ultimate viscosity [η] of 0.8 dL / g or more and less than 4.9 dL / g.
Polyethylene characterized by containing 10% by mass or more and 30% by mass or less of inorganic oxide particles having an aspect ratio of 1 or more and 2 or less and an average particle size of 5.0 μm or more and 15.0 μm or less in the polyethylene fiber. fiber.
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