WO2001071071A1 - Monofilament a base de poly(fluorure de vinylidene) colore et son procede de production - Google Patents

Monofilament a base de poly(fluorure de vinylidene) colore et son procede de production Download PDF

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Publication number
WO2001071071A1
WO2001071071A1 PCT/JP2001/002178 JP0102178W WO0171071A1 WO 2001071071 A1 WO2001071071 A1 WO 2001071071A1 JP 0102178 W JP0102178 W JP 0102178W WO 0171071 A1 WO0171071 A1 WO 0171071A1
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WO
WIPO (PCT)
Prior art keywords
monofilament
polyvinylidene fluoride
resin
perylene
producing
Prior art date
Application number
PCT/JP2001/002178
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English (en)
Japanese (ja)
Inventor
Satoshi Hashimoto
Hiroshi Ochiai
Masaru Sato
Original Assignee
Kureha Chemical Industry Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kureha Chemical Industry Co., Ltd. filed Critical Kureha Chemical Industry Co., Ltd.
Publication of WO2001071071A1 publication Critical patent/WO2001071071A1/fr

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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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • 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
    • D01F6/48—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 polymers of halogenated hydrocarbons

Definitions

  • the present invention relates to a colored monofilament composed of a polyvinylidene fluoride resin composition. More specifically, while maintaining the excellent characteristics of fishing line made of polyvinylidene fluoride monofilament, it is colored with a clear fluorescent color by a special fluorescent dye, and it is transparent and has excellent visibility.
  • the present invention relates to a glittering transparent polyvinylidene fluoride-based monofilament containing a perylene-based higher dye and a method for producing the same. Background art
  • Polyvinylidene fluoride monofilaments are excellent in toughness, impact resistance, sensitivity (fish detection), light resistance, etc., and have a high specific gravity of 1.79 and easily sink in water. Since it has a refractive index (1.42) close to 3.33), it has little surface reflection in water and is transparent and difficult to see. Furthermore, since they have no water absorption, their properties can be maintained for a long time even in water, and they have been used particularly favorably for tex applications represented by Harris.
  • the polyvinylidene fluoride monofilaments have been used in lure lines and throw fishing lines, taking advantage of their impact resistance, high specific gravity and high sensitivity.
  • visibility from anglers is required, and coloring by dyeing has recently been attempted.
  • polyvinylidene fluoride monofilaments are inherently extremely difficult to dye, the dyed ones are pale in color and unclear. If the heat treatment temperature is raised to increase the color and the treatment time is increased, the initial physical properties such as tensile strength are reduced, so that satisfactory results in both visibility and strength have not been obtained.
  • polyvinylidene fluoride resin is a color (The method of extruding and spinning the synthetic resin used to obtain monofilaments by extruding and spinning the synthetic resin itself with a colorant such as a dye, pigment, or pigment resin color before extrusion) Most of the colorants are discolored and decomposed due to the high temperature at the time and the hydrofluoric acid generated in trace amounts during melting. In addition, even a small portion of the pigments that can withstand the color tone is unclear, the transparency is low, and the dispersed particle size of the pigments is large. Satisfactory coloring was not achieved.
  • the present invention maintains the characteristics of a fishing line composed of a polyvinylidene fluoride monofilament, and does not recognize the discoloration of the coloring agent due to the generation of hydrofluoric acid due to the decomposition of the resin during spinning, so that it is colored in a clear fluorescent color. It is an object of the present invention to provide a monofilament that forms a transparent fishing line with excellent visibility and a method for producing the same. Disclosure of the invention
  • the present inventors have conducted intensive studies with the aim of solving the above problems, and as a result, have found that a monofilament made of a polyvinylidene fluoride resin composition containing a perylene-based fluorescent dye can solve such problems.
  • the invention has been completed.
  • the present invention provides a monofilament comprising a polyvinylidene fluoride resin composition containing a perylene fluorescent dye.
  • a monofilament having a perylene fluorescent dye content of 0.01 to 0.5 parts by weight based on 100 parts by weight of a polyvinylidene fluoride resin there is provided a monofilament having a knot strength represented by the following formula (1).
  • a method for producing the monofilament of the invention wherein the monofilament is spun at a temperature of 300 ° C. or less and an extruder residence time of 60 minutes or less.
  • a fishing line comprising the monofilament of the invention is provided. .
  • the polyvinylidene fluoride resin (PVDF) used in the present invention is preferably a vinylidene fluoride homopolymer, a copolymer containing 70% by mole or more of vinylidene fluoride as a constituent unit, A mixture of coalescence is mentioned.
  • Examples of the monomer copolymerized with vinylidene fluoride include ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride, ethylene trifluoride chloride, and vinyl fluoride. Also, at least one of these can be used.
  • i nh is preferably 0. 8 ⁇ 2.
  • the raw material polyvinylidene fluoride resin for the monofilament of the present invention may be a nucleating agent represented by a polyester plasticizer, a phthalate plasticizer, a flavantron, or a polymer as long as its properties are not impaired.
  • the composition includes a resin mixed with a resin having good compatibility with vinylidene fluoride resin such as methyl acrylate, polymethyl acrylate, and methyl acrylate / isobutylene copolymer.
  • the repeating unit composition is an ester of a dialcohol having 2 to 4 carbon atoms and a dicarboxylic acid having 4 to 6 carbon atoms, and the terminal group is a monovalent acid or monovalent acid having 1 to 3 carbon atoms.
  • the resins that can be added to the polyvinylidene fluoride resin methyl methacrylate is preferred, and may be contained in an amount of about 5% by weight based on 100% by weight of the polyvinylidene fluoride resin.
  • methyl polymethacrylate is an amorphous resin, so it has better compatibility with poly (vinylidene fluoride) resin than poly (vinylidene fluoride) resin, and the coloring property of dye. Can be expected to improve.
  • the mixing amount of the polymer methyl acrylate increases, the monofilament becomes flexible. Addition of 10% by weight or more is not preferable because there is a possibility that the strength and tensile strength may be reduced.
  • the perylene-based fluorescent dye used in the present invention has a perylene skeleton as disclosed in JP-A-57-125260, JP-A-58-40359 and JP-A-60-203650.
  • Lumogen TR F Yellow 083 manufactured by BASF Japan Co.
  • Lumogen TR F Orange 240 manufactured by BASF Japan Co.
  • Lumogen TR F Red 300 BASF Japan Co., Ltd.
  • perylene fluorescent dyes and the like for example, Lumogen TR F Yellow 083 (manufactured by BASF Japan Co.), Lumogen TR F Orange 240 (manufactured by BASF Japan Co.), Lumogen TR F Red 300 (BASF Japan Co., Ltd.) And perylene fluorescent dyes and the like.
  • the content of the perylene fluorescent dye is not particularly limited, but is usually 0.001 to 0.5 part by weight, and more preferably 0.005 to 0.1 part by weight based on 100 parts by weight of the polyvinylidene fluoride resin. It is particularly preferably 0.01 to 0.05 part by weight. When the content is in the range of 0.001 to 0.5 parts by weight, the luster can be exhibited and the visibility can be obtained. Furthermore, the characteristics of the polyvinylidene fluoride monofilament
  • calcium stearate improves the spinnability of the melt during melt spinning and has the effect of suppressing the occurrence of slabs on the yarn surface.
  • a perylene-based dye is added to polyvinylidene fluoride resin, slabs tend to be generated, probably because the fluidity of the resin with the metal inner wall such as a nozzle decreases and the adhesiveness increases.
  • the addition of metal stones is effective.
  • the amount of the metal stone added is preferably about 0.001 to 0.1 part by weight, more preferably about 0.05 to 0.5 part by weight, based on 100 parts by weight of the polyvinylidene fluoride resin.
  • additives such as an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antioxidant may be contained as long as the effects of the present invention are not impaired.
  • the perylene fluorescent dye, metal stones, and other additives may be added individually to each other, but it is so-called diluted with polyvinylidene fluoride resin or other resin used as a constituent material of the yarn.
  • a master batch is prepared and used in a predetermined amount.
  • the polyvinylidene fluoride resin composition is a resin composition comprising a polyvinylidene fluoride resin and at least a perylene fluorescent dye.
  • This resin composition may be a mixture of a polyvinylidene fluoride resin and a perylene fluorescent dye, a dry blend as described below, or a pellet.
  • the polyvinylidene fluoride resin composition can be prepared by a known method. For example, a perylene-based fluorescent dye previously prepared by diluting with polyvinylidene fluoride resin and optionally a batch of metal lithography can be added to polyvinylidene fluoride resin in a predetermined amount and dry blended to obtain a powdery material. Or a method of simply mixing the raw material polyvinylidene fluoride resin alone and the above-mentioned perylene-based fluorescent dye, or a method of keeping the resin composition in a pellet form.
  • the powder or pellet of the obtained resin composition is charged into an extruder, and extruded at an extrusion set temperature of 300 ° C. or lower, preferably 230 to 280 ° C., and 30 to 80 ° C. Quickly cool underwater. Then, it is stretched 4.5 to 6.5 times in a heat medium such as glycerin at 150 to 180 ° C. (in some cases, stretching may be performed in two or more stages). Perform a relaxation treatment of 2 to 12% in warm water of ⁇ 98 ° C. At this time, the molten resin composition stays in the extruder. The retention time is preferably within 60 minutes, more preferably 10 to 40 minutes.
  • the residence time in the extruder exceeds 60 minutes, decomposition of the resin composition, particularly a perylene dye, starts, and discoloration of the spun yarn and foaming on the surface of the yarn may occur, which is not preferable. Furthermore, when the polyvinylidene fluoride resin is combined with a perylene dye, and when the amount of the perylene dye added is increased to increase the color density, the dispersibility and compatibility of the dye in the resin are reduced. However, the residence time of the resin in the extruder is important because the perylene dye tends to be easily decomposed and discolored depending on the residence time in the extruder.
  • the yarn diameter of the monofilament is not particularly limited, but is usually 50 ⁇ 111 to 2.5 mm.
  • the obtained monofilament is used as a fishing line.
  • the knot strength of the monofilament satisfies the condition represented by the formula (1) from the viewpoint of toughness as a road yarn.
  • the polyvinylidene fluoride monofilament As the fishing line becomes thinner, the knot strength becomes more important as the fishing line becomes thinner. Conversely, as the thickness increases, the knot strength becomes more difficult to appear due to its nature.
  • the monofilament of the present invention is colored into a clear fluorescent color with a perylene fluorescent dye, and becomes a transparent and highly visible fishing line, particularly a transparent polyvinylidene fluoride monofilament suitable for road yarn.
  • Lumogen F Yellow 083 (a perylene fluorescent dye manufactured by Bas F Japan Co., Ltd.).
  • Lumogen F Orange 240 (a perylene-based fluorescent dye manufactured by BASF Japan Ltd.).
  • Lumogen F Red 300 (a perylene fluorescent dye manufactured by BAS F Japan Ltd.).
  • Epokara FP-1007 Yellow Green (Nippon Shokubai Co., Ltd., pigment resin color).
  • PVDF (Dallade KF # 1300) is used as the raw material resin for polyvinylidene fluoride monofilament, and the colorants and metal stones shown in Table 1 are added to this resin in predetermined amounts, and dry-blended to form each resin composition. Things. Next, this composition was extruded using a 35 mm ⁇ extruder and a 1.3 ⁇ 6-hole nozzle with an extruded resin temperature of 250 to 280 ° (: extruder gears and pump rotation speed of 6.1 rpm. And quenched in water at a cooling temperature of 50. Then, 5.5 times in a glycerin bath at 167 ° C. It was stretched and then subjected to 5% relaxation heat treatment in 85 hot water to obtain a monofilament having a diameter of 3 mm.
  • Example 2 The procedure was the same as in Example 1 except that a pigment resin color at a heat resistance temperature of 280, which was developed for use in nylon, was used as the fluorescent colorant.
  • the resulting monofilament had a dull yellow-green color, discolored, and had reduced strength.
  • Example 2 The procedure was performed in the same manner as in Example 1 except that an azine-based dye was used as a coloring agent.
  • the raw material formulation was the same as in Example 1 except that the rotation speed of the gear pump was reduced to 3.2 rpm to obtain a monofilament having a fine pattern, and a monofilament having a diameter of 0.22 mm was obtained.
  • the monofilament obtained had an orange color tone, degraded on the surface, swelled due to foaming, and had a reduced strength.
  • the measured residence time of the molten resin in the extruder was 98 minutes, which is considered to be the cause.
  • the nozzle was mm ⁇ X 24 holes, switch the extruding temperature from 255 to 290, set the gear pump rotation speed to 13 rpm, increase the discharge rate and spin.
  • a monofilament having a diameter of 0.22 mm was obtained under rapid cooling, stretching and relaxation conditions.
  • the monofilament thus obtained did not show any swelling due to decomposition or foaming on the surface, was colored in a clear fluorescent yellow, and had sufficient strength.
  • the residence time of the resin in the extruder was measured and was found to be as short as 25 minutes. This is considered to be able to suppress the decomposition of the dye.
  • Table 2 shows the evaluation results of the samples obtained in the examples and comparative examples.
  • Example 1 100 0.02 0 0 0 0.01 52
  • Example 2 100 0.005 0 0 0 0.01 52
  • Example 3 100 0. 01 0 0 0 0.01 52
  • Example 4 100 0.05 0 0 0 0.01 52
  • Example 5 100 0.02 0 0 0 0 0 52
  • Example 6 100 0 0.02 0 0 0 0. 01
  • Example 7 100 0 0 0.02 0 0 0.01
  • Example 8 100 0.02 0 0 0 0.01 25 Comparative example 1 100 0 0 0 0 0. 01 52
  • Comparative example 2 100 0 0 0 0.02 0 0.01 52
  • Comparative example 3 100 0 0 0 0 0.02 0.01 52
  • Comparative example 4 100 0.02 0 0 0 0 0.01 98
  • Example 4 0.30 0.50 520 21.6 Vivid Fluorescent Yellow Smooth Good
  • Example 5 0.30 0.52 52.2 Clear fluorescent yellow smooth (slightly with slabs)
  • Example 6 0.30 0.5 1 7 19.2 Clear fluorescent orange smooth good
  • Example 7 0.30 0.50 530 20.1 Clear fluorescent red Smooth Good
  • Example 8 0.22 0.597 20.1 Clear fluorescent yellow Smooth Good
  • Comparative Example 2 0.30 0.42 1 16.3 Degraded yellow-green Decomposition-There is swelling due to foaming Comparative Example 3 0.30. . 46 1 16.5 Orange-yellow yellow Decomposition / swelling due to foaming
  • the characteristics of the fishing line made of polyvinylidene fluoride monofilament are maintained by the monofilament made of the polyvinylidene fluoride resin composition containing the perylene fluorescent dye, and no discoloration of the colorant is observed. It is possible to provide a monofilament which forms a fishing line which is colored in a vivid fluorescent color and has excellent visibility, and a method for producing the same.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un monofilament constitué d'une composition de résine poly(fluorure de vinylidène) contenant un colorant fluorescent de type pérylène; un procédé de production du monofilament, lequel procédé comprend le filage de la composition de résine poly(fluorure de vinylidène) dans une machine d'extrusion à une température déterminée égale ou inférieure à 300 °C, avec une durée de séjour dans la machine d'extrusion égale ou inférieure à 60 minutes; et une ligne de pêche comprenant ledit monofilament. Ledit monofilament présente des propriétés appropriées pour une ligne de pêche, ne subit pas la décoloration d'un colorant due à la présence d'acide fluorhydrique généré par la décomposition de la résine pendant le filage, présente une couleur claire fluorescente et peut être utilisé pour produire une ligne de pêche transparente et extrêmement visible.
PCT/JP2001/002178 2000-03-22 2001-03-19 Monofilament a base de poly(fluorure de vinylidene) colore et son procede de production WO2001071071A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000080990A JP4409036B2 (ja) 2000-03-22 2000-03-22 着色ポリフッ化ビニリデン系モノフィラメント及びその製造方法
JP2000-80990 2000-03-22

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WO2001071071A1 true WO2001071071A1 (fr) 2001-09-27

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ATE400826T1 (de) * 2004-03-26 2008-07-15 Deutsches Elektronen Synchr Wellenlängenwandler, verfahren zu ihrer herstellung und photovervielfacher enthaltend einen wellenlängenwandler
JP2006014679A (ja) * 2004-07-02 2006-01-19 Toray Monofilament Co Ltd ハリス
WO2016152440A1 (fr) * 2015-03-25 2016-09-29 株式会社クレハ Matériau favorisant la croissance pour un organisme réalisant la photosynthèse dans l'eau et son utilisation
US20190225725A1 (en) * 2016-09-27 2019-07-25 Daikin Industries, Ltd. Fluororubber molded article

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63165517A (ja) * 1986-12-26 1988-07-08 Nippon Ester Co Ltd 螢光性ポリエステル繊維
JPH0482917A (ja) * 1990-07-23 1992-03-16 Mitsubishi Rayon Co Ltd 光輝性複合繊維
EP0698649A1 (fr) * 1994-08-26 1996-02-28 Basf Aktiengesellschaft Utilisation de matériaux électroluminescents d'une stabilité de longue durée, façonnables à chaud
JPH10140421A (ja) * 1996-11-15 1998-05-26 Unitika Ltd 蓄光性複合繊維

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63165517A (ja) * 1986-12-26 1988-07-08 Nippon Ester Co Ltd 螢光性ポリエステル繊維
JPH0482917A (ja) * 1990-07-23 1992-03-16 Mitsubishi Rayon Co Ltd 光輝性複合繊維
EP0698649A1 (fr) * 1994-08-26 1996-02-28 Basf Aktiengesellschaft Utilisation de matériaux électroluminescents d'une stabilité de longue durée, façonnables à chaud
JPH10140421A (ja) * 1996-11-15 1998-05-26 Unitika Ltd 蓄光性複合繊維

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JP2001271220A (ja) 2001-10-02

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