WO1996006211A1 - Lignes de peche et produits associes - Google Patents

Lignes de peche et produits associes Download PDF

Info

Publication number
WO1996006211A1
WO1996006211A1 PCT/US1994/009144 US9409144W WO9606211A1 WO 1996006211 A1 WO1996006211 A1 WO 1996006211A1 US 9409144 W US9409144 W US 9409144W WO 9606211 A1 WO9606211 A1 WO 9606211A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
mole
fishing line
consists essentially
monofilament
Prior art date
Application number
PCT/US1994/009144
Other languages
English (en)
Inventor
Robert Benham Fish, Jr.
Francis Glenn Gallagher
James Michael Mckenna
Raymond Frank Tietz
Original Assignee
E.I. Du Pont De Nemours And Company
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
Priority claimed from US07/977,650 external-priority patent/US5354616A/en
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to PCT/US1994/009144 priority Critical patent/WO1996006211A1/fr
Priority to AU75637/94A priority patent/AU7563794A/en
Publication of WO1996006211A1 publication Critical patent/WO1996006211A1/fr

Links

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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K91/00—Lines
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent

Definitions

  • This invention relates to fishing lines, sometimes referred to as fishlines, including long line fishing lines and including related products, such as netting products for fishing, and is more particularly concerned with such lines as are novel and are degradable, advantageously, when immersed in water.
  • Nylon (i.e., polyamide) oriented monofilament has increasingly found acceptance as a preferred material for commercial fishlines, as discussed in U. S. Patents Nos 4,459,337 (Hansen) and 4,584,240 (Herbert and Rackley) and the art referred to therein.
  • This invention provides a fishline of a polymer that is preferentially degraded while immersed in fishable waters but that degrades much more slowly when not so immersed, i.e., during storage and when exposed to air, even under humid conditions. This combines an advantage in degradability when immersed, while better preserving useful properties when not immersed in water.
  • the invention is based on our concept of using the oxygen present in fishable waters (which are aerated, otherwise the fish could not survive) to oxidatively degrade the polymer of the fishline, especially those of segmented copolyetherester. We have been surprised to find that this occurs preferentially even when fishlines of selected compositions are immersed in aerated water vs. exposure to ambient air. We can increase this preferential degradation effect by adding to the fishline certain stabilizers, such as a water-extractable antioxidant, so the stabilizer can preserve the line during storage in air before use, but will allow the line to disintegrate faster after immersion. Clearly, it is not desirable, however, to include an antioxidant that prevents oxidative degradation of the polymer, and thus prevents disintegration of the fishline, when immersed.
  • our invention consists of a fishline made with a copolyester having copolymerized polyalkylene ether glycol units and, optionally, a suitable concentration of a stabilizer.
  • a stabilizer may be used to extend the useful lifetime of the line to a more desirable level, e.g., about a year in ambient air exposure, without excessively decreasing the disintegration time of line abandoned under water.
  • a selection of copolyetheresters which respond to a process of two stage drawing to yield tensile strengths over 50,000 psi is made.
  • a co-extruded sheath/core structure may be provided in which the core is a minor amount of the fiber cross section and has a higher modulus than the predominant sheath.
  • such a preferred aerated- water-degradable fishline comprises a copolyester monofilament consisting essentially of recurring structural units of the formula: - -C(O)-R-C(O)-OGO- wherein R is 75 to 100 mole T (para-phenylene), any remainder being another divalent hydrocarbylene radical, including aromatic radicals, aliphatic and cycloaliphatic radicals, such as are disclosed in copending U.S. Patents Nos. 5,097,004, 5,171,308, 5,171,309 and 5,295,985, and wherein G is
  • a polyethylene ether radical selected from the group consisting of -(CH2)2"O-(CH2)2- and -(CH2)2-O-(CH2)2-0-(CH2)2-, respectively, DEG and TEG,
  • C2-C4 lower alkylene groups such as 2G (ethylene) and 4G (tetramethylene).
  • the polyalkylene ether glycol is preferably polytetramethylene ether glycol or polyethylene ether glycol with molecular weight of 250 to 6000.
  • an alkali metal or alkaline earth metal sulfonated comonomer may be present, with preferred amounts being 1 to 2.5 mole %.
  • a branching monomer may be present in amount less than 0.3 mole%.
  • the fishline is a copolyester from terephthalic acid and ethylene or tetramethylene glycol and 10 to 30 wt% polyalkylene ether radicals, and optionally 0.1 to 3 mole % sulfonated diacid, and 0 to 5 mole % diethylene glycol, and containing 2 to 2000 ppm of water-extractable stabilizers.
  • Suitable stabilizers may be present in amount up to 5 % by weight.
  • Suitable stabilizers may be mixtures of water-extractable antioxidants, such as hindered phenols, UV screeners such as substituted benzotriazole or benzophenones, and hindered amine light stabilizers.
  • the fishing line should completely disintegrate when left in water for a period of 1 year or less.
  • a suitably shortened test period for preferred fish lines may be 2 months, within which period the fishline should desirably lose at least about 15 % of its initial tensile strength when immersed in aerated water at 30 C, but should desirably retain at least about 95% (i.e., not lose more than about 5%) of its initial tensile strength when stored in ambient air in the dark, i.e., protected from light.
  • An antioxidant that we have used in Example 1 according to the invention is 1,6-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (Irganox 259 from Ciba Corporation).
  • antioxidants that prevent degradation more effectively in water, such as N.N'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) and N,N'-trimethylene bis-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), is reported at the end of Example 2.
  • Antioxidants that are readily extracted in water are expected to be useful in the practice of the invention.
  • light stabilizers are included, and are preferably less rapidly extracted than the antioxidants.
  • a route to provide a monofilament fishing line which has outstanding hook setting performance and feel as well as excellent castability is discussed in U. S. Patent No. 4,584,240, which is incorporated herein by reference, as is U. S. Patent No. 2,932,482.
  • the hook setting performance of the line may be improved by adding a core composed of a blend of, by weight, approximately 80% of a degradable copolyester and 20% of the polymer used in Example 2 A herein, where the core would comprise approximately 10% of the cross section.
  • This core copolyester may be, for example, one or more of the compositions covered in U. S. Patents Nos. 5,053,482, 5,097,004, 5,097,005 5,171,308 and 5, 171,309. Indeed, it may prove desirable to provide a small core of a less degradable polymer, if, for example, its small size (and low strength) will mean that the core will disintegrate sufficiently fast or will not pose a residual significant contaminant in the water for other reasons.
  • Such coextruded fishing lines desirably have a wet tensile strength of at least 50 Kpsi, and especially a tensile strength greater than 70 Kpsi and use a core polymer or polymer blend selected such that the wet initial tensile modulus of the core is significantly greater than the wet initial tensile modulus of the sheath.
  • the monofilaments should be (and were, when tested as herein described) allowed to equilibrate by storage in a conditioned environment (approximately 23 C and 50 or 65% relative humidity for at least 16 hours or by soaking in water maintained at approximately 23 C for at least 16 hours).
  • a recording stress-strain device is used wherein a straight 10 inch long section of monofilament is elongated at the rate of 10 inches per minute until it breaks. With samples which were not available in 10 inch lengths, a 1 inch length was used, and was elongated at a rate of 1 inch per minute. Tensile strength is calculated by dividing the breaking load in pounds by the cross- sectional area of the monofilament in square inches.
  • Storage in ambient air is considered herein to be storage under controlled laboratory conditions at 23 degrees C and 50% RH, and the materials should be stored in the dark, i.e., protected from light, unless otherwise indicated.
  • Aerated water exposure is considered herein to be exposure to aerated water (oxygen content 6-8 pp ) at 30 degrees C while in the dark, i.e., protected from light, with a water exchange rate at about 20 liters of water per gram of exposed material per day, unless otherwise indicated.
  • This Example describes the preparation of a polymer, and its spinning and drawing to a monofilament, i.e., a fish line, and properties thereof, of composition 2G/DEG/PEG(600)(89/5/6)-T/5SI (98/2) with about 0.2 wt% trimethyl trimellitate (TMTM) branching agent.
  • This polymer contained 15 wt% polyethylene ether(600) radicals (PEG) with 0.15% Irganox 259 added with the PEG, so present during polymerization.
  • Irganox 259 is a stabilizer (anti-oxidant) whose presence did not prevent more degradation occurring during immersion in water than during storage in air, as will be related.
  • the polymer was prepared in a 35 gallon reactor containing a stirrer, a nitrogen inlet and a distillation column. In the reactor were placed: 37920 grams dimethyl terephthalate (DMT) 23133 grams ethylene glycol (2G) 1092 grams diethylene glycol (DEG) 6771 grams PEG (MW 600) containing 1 % Irganox 259 1182 grams dimethyl Na 5-sulfoisophthalate (5SI) 90 grams trimethyl trimellitate (TMTM) 8.75 grams Na(OAc).3H2 ⁇ 39.3 grams Sb2 ⁇ 3 27.8 grams Mn(OAc)2-4H2O
  • the temperature of the reactor was slowly increased and 12000 ml distillate collected between 155 and 213 C. A second distillate (5400 ml) was collected between 224-240 C. The resultant oligomer was transferred to a second vessel containing an agitator and vacuum capabilities. Then 19.3 g of 85% phosphoric acid was added to the material and the temperature raised to 276 C and the maximum vacuum (0.6 mm Hg) was established over 90 minutes. After 2.5 hours at these conditions, the contents of the reactor were discharged through a ribbon die into a water quench. The ribbon was cut to flake and dried at 60 C overnight in a vacuum tray dryer with a vacuum between 1 and 2 mm Hg and a nitrogen purge.
  • Dried flake of this polymer was extruded at a rate of about 2.5 cu in./min. at a melt temperature of 260 C through a round spinnerette orifice having a diameter of 0.041 inches.
  • the filament so formed was passed vertically downward through an air gap for 1 inch, quenched in a 12 C water bath for a distance of 5.5 feet and passed to a feed roll having a surface speed of 75 feet per minute.
  • the filament was then passed through a 19 in. long radiant heater which exposes the filament to a temperature of 300 C.
  • the filament was passed to unheated first stage draw rolls having a surface speed of 475 feet per minute to stretch the filament 6.33X.
  • the filament was passed through radiant heaters, having a combined length of 110 inches, and exposing the filament to a temperature of 450 C, on to second set of unheated draw rolls running at a speed of 1150 feet per minute which stretched the filament an additional 2.42X.
  • the filament was collected on a spool.
  • the filament was light brown with a substantially round, 15.1 mil diameter cross-section. It had a tensile strength of 65,100 psi and an elongation to break of 19.7% (50% RH).
  • the filament After being soaked in 23 C water overnight, the filament had a lower tensile strength of 54,800 psi and an elongation to break of 24.7%. After the filament was immersed in an 80 C water bath for 53 days, it was brittle and it disintegrated into powder on handling. The Mn of the residual powder was 4750.
  • the T/E/M were 68.6 Kpsi/40 %/ 511 Kpsi (1 inch gage length, 65% RH). There was little change from its initial strength.
  • This Example shows the preparation of fishlines (without stabilizer) from two segmented copolyether ester compositions (4G/PTMEG(1000)-T) and degradation of their strength in water, in contrast to their stability in air.
  • the molar proportions of the glycols were 96/4 and 92/8, respectively, 4G/PTMEG(1000) for 2A and 2B, corresponding to 16% and 26% by weight, respectively, of the high molecular weight polyalkylene radicals.
  • the 2A polymer was prepared in a 35 gallon reactor containing a stirrer, a nitrogen inlet and a distillation column. In the reactor were placed:
  • the temperature of the reactor was slowly increased. Distillate (10800 ml methanol) was collected between 136 and 194 C. The resultant oligomer was transferred to a second vessel containing an agitator and vacuum capabilities. The temperature was raised to 252 C and the maximum vacuum (2.2 mm Hg) was established over 45 minutes. After 4.5 hours at these conditions, the contents of the reactor were discharged through a ribbon die into a water quench. The ribbon was cut to flake and dried at 100 C for at least 8 hours in a Patterson Kelly double cone vacuum dryer with a vacuum less than 5 mm Hg and a nitrogen purge.
  • the 2B polymer was prepared similarly. In a 35 gallon reactor containing a stirrer, a nitrogen inlet and a distillation column were placed: 30209 grams dimethyl terephthalate (DMT) 20411 grams 1,4 butane diol (4G)
  • DMT dimethyl terephthalate
  • 4G 1,4 butane diol
  • the temperature of the reactor was slowly increased. Distillate (10000 ml methanol) was collected between 139 and 196 C. The temperature was raised to 252 C and the maximum vacuum (1.4 mm Hg) was established over 45 minutes. After 3.25 hours, the contents of the reactor were discharged through a ribbon die, quenched , flaked and dried as in 2A.
  • Dried flake of each polymer was extruded at a melt temperature of 215 degrees Celsius through a round spinnerette orifice having a diameter of 0.045 inches.
  • the filament so formed was passed vertically downward through an air gap for 5 inches, quenched in a water bath at 30 degrees Celsius for a distance of 5.5 feet and passed to a feed roll having a surface speed of 90 feet per minute.
  • the filament was then passed through a first stage radiant heater having a length of 4 inches and a temperature of 1000 deg C. After passing through the radiant heater, the filament was passed to unheated first stage draw rolls having a surface speed of 405 feet per minute (referred to in the Table below as 2nd rolls).
  • the filament was stretched 4.5X. From the first stage rolls the filament was passed through a second stage radiant heater (having a combined length of 110 inches and a temperature of 250 degrees Celsius) to second stage draw rolls running at a speed of 639 feet per minute which stretched the filament an additional 1.58X (and are referred to as 3rd rolls in the Table below).
  • a second stage radiant heater having a combined length of 110 inches and a temperature of 250 degrees Celsius
  • second stage draw rolls running at a speed of 639 feet per minute which stretched the filament an additional 1.58X (and are referred to as 3rd rolls in the Table below).
  • the filament was passed through radiant heaters having a total length of 84 inches and a temperature of 200 degrees Celsius and then to third stage rolls running at a speed of 607 feet per minute, which allowed the filament to shrink 5% (and are referred to as 4th rolls in the Table below). The filament was then wound onto a package.
  • First roll (fpm) 90 90 1st stage heater temperature (deg C) 1000 1000 2nd rolls (fpm) 405 405 2nd stage heater temperature (deg C) 250 210 3rd rolls (fpm) 639 639 3rd stage heater temperature (deg C) 200 200 4th rolls (fpm) 607 607
  • the polymers used for "A" and “B H in this test were chemically similar to those for the 2A and 2B polymers, respectively, except that about 0.1 % by weight of TMTM branching agent was used (see Example 1) and about 0.15% by weight each of N,N'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), and N,N'-trimethylene bis-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide).
  • This Example describes the preparation of unstabilised fishline from compositions like those in Example 2 except that 2 mole % Na 5-sulfoisophthalate (5SI) radicals were present in the copolyetheresters (98/2-T/5SI, instead of all T).
  • 5SI 5-sulfoisophthalate
  • Polymer 3A was prepared similarly to 2A from: 34064 grams dimethyl terephthalate (DMT) 23587 grams 1,4 butane diol (4G)
  • Polymer 3B was prepared from:
  • First roll (fpm) 90 90 1st stage heater temperature (deg C) 1000 1000 2nd rolls (fpm) 405 405 2nd stage heater temperature (deg C) 210 210 3rd rolls (fpm) 649 639 3rd stage heater temperature (deg C 200 200 4th rolls (fpm) 615 607
  • the T/E M/diameter of the 3A line was 84.5 Kpsi/22.2%/313 Kpsi/10.4 mils and that of the 3B line was 63.2 Kpsi/27.5%/175 Kpsi/10.4 mils
  • T/E/M 83.2 Kpsi/50%/234 Kpsi and 65.3 Kpsi/61%/91 Kpsi.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Animal Husbandry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne de nouvelles lignes de pêche, ainsi que les produits associés, en particulier des produits monofilamentaires, de polyesters qui sont biodégradables et qui se désintègrent lorsqu'ils sont immergés dans l'eau sur une période de quelques semaines ou mois, afin d'éviter de polluer les environnements aqueux, mais sont stables au stockage, c'est-à-dire qu'ils ne se désintègrent pas au contact de l'air, avant une longue immersion dans l'eau.
PCT/US1994/009144 1992-11-16 1994-08-24 Lignes de peche et produits associes WO1996006211A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1994/009144 WO1996006211A1 (fr) 1992-11-16 1994-08-24 Lignes de peche et produits associes
AU75637/94A AU7563794A (en) 1992-11-16 1994-08-24 Fishing lines and related products

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/977,650 US5354616A (en) 1990-05-11 1992-11-16 Fishing lines and related products
PCT/US1994/009144 WO1996006211A1 (fr) 1992-11-16 1994-08-24 Lignes de peche et produits associes

Publications (1)

Publication Number Publication Date
WO1996006211A1 true WO1996006211A1 (fr) 1996-02-29

Family

ID=26788362

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/009144 WO1996006211A1 (fr) 1992-11-16 1994-08-24 Lignes de peche et produits associes

Country Status (1)

Country Link
WO (1) WO1996006211A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6630493B1 (en) 1998-04-20 2003-10-07 Basf Aktiengesellschaft Heterocyclically substituted amides, their preparation and use
EP1520918A1 (fr) * 1996-05-14 2005-04-06 Kanebo, Ltd. Fibres dégradables spontanement et articles constitués de celles-ci

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01260017A (ja) * 1988-04-01 1989-10-17 Toray Ind Inc 高強度水崩壊型ポリビニルアルコール系複合繊維
US5053482A (en) * 1990-05-11 1991-10-01 E. I. Du Pont De Nemours And Company Novel polyesters and their use in compostable products such as disposable diapers
JPH03259029A (ja) * 1990-03-06 1991-11-19 Gunze Ltd 分解性釣糸及びその製造法
US5244731A (en) * 1990-06-15 1993-09-14 Gunze Limited Marine fishery thread articles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01260017A (ja) * 1988-04-01 1989-10-17 Toray Ind Inc 高強度水崩壊型ポリビニルアルコール系複合繊維
JPH03259029A (ja) * 1990-03-06 1991-11-19 Gunze Ltd 分解性釣糸及びその製造法
US5053482A (en) * 1990-05-11 1991-10-01 E. I. Du Pont De Nemours And Company Novel polyesters and their use in compostable products such as disposable diapers
WO1991018036A1 (fr) * 1990-05-11 1991-11-28 E.I. Du Pont De Nemours And Company Polyesters et leur emploi dans des produits transformables en compost tels que des couches jetables
US5244731A (en) * 1990-06-15 1993-09-14 Gunze Limited Marine fishery thread articles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 4789, Derwent World Patents Index; Class A14, AN 89-345913 *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 063 (C - 0911) 18 February 1992 (1992-02-18) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1520918A1 (fr) * 1996-05-14 2005-04-06 Kanebo, Ltd. Fibres dégradables spontanement et articles constitués de celles-ci
US6630493B1 (en) 1998-04-20 2003-10-07 Basf Aktiengesellschaft Heterocyclically substituted amides, their preparation and use

Similar Documents

Publication Publication Date Title
US5354616A (en) Fishing lines and related products
JP3188687B2 (ja) 平滑なポリエステル繊維
EP0724030B1 (fr) Fibre hygroscopique contenant un copolyester hygroscopique
EP0427496A2 (fr) Ustensile de pêche
KR20030072548A (ko) 수지 조성물, 모노필라멘트, 그 제조방법,및 낚시줄
WO1996006211A1 (fr) Lignes de peche et produits associes
EP0985751B1 (fr) Fibre de polyethylene naphtalate
JP4256243B2 (ja) ポリ乳酸系親水性繊維
JP2009185397A (ja) ポリ乳酸繊維、その製造方法および繊維製品
US5853878A (en) Elastic fiber, process for the same and polyester elastomer used thereof
JP4664167B2 (ja) 生分解性の制御された生分解性樹脂フィラメント及びその製造方法
JP4952287B2 (ja) 板ベルト状ロープ及び樹木の支持具
JP3156811B2 (ja) 生分解性漁業用繊維集合体
JP4637538B2 (ja) 人工藻場
JP7452424B2 (ja) ポリエステル組成物
JP2002173827A (ja) モノフィラメント、モノフィラメントの製造方法、及び、釣り糸
JPH10110332A (ja) 生分解性モノフィラメントおよびその用途
JP2010043373A (ja) 耐湿熱性に優れたポリエステル繊維
EP4364560A1 (fr) Matériau marin et son procédé de production
JPS602710A (ja) 高結節強度ポリエステルモノフイラメント
JP4742993B2 (ja) ポリ乳酸モノフィラメントの製造方法およびポリ乳酸モノフィラメント糸条パッケージ
JP2007321320A (ja) 仮撚加工用生分解性ポリエステル繊維
EA001161B1 (ru) Рыболовные снасти
JP2021050454A (ja) 芯鞘型複合繊維
JP3720987B2 (ja) 水産資材

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AM AU BB BG BR BY CA CN CZ EE FI GE HU JP KG KP KR KZ LK LT LV MD MG MN NO NZ PL RO RU SI SK TJ TT UA UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA