JP2522947C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a fishing line. <Conventional technology and problems> Conventionally, a drawn line of an organic fiber such as polyamide or polyester has been used as a fishing line. However, fishing lines from these materials generally do not have sufficient strength, so they must be used with a large diameter, and are susceptible to the tide, and fish are not bite to feed because they are cautious. Because the elongation of the fishing line is large, the fish signal indicating that the fish has caught is attenuated easily and it is difficult to transmit to the hand and the pole tip, or because the elastic modulus is low, there is no waist and it is easy to get entangled and entangled, There are problems such as difficulty in handling and life due to high water absorption, and slow sinking speed of fishing line in throw fishing and deep sea fishing due to large thickness and low density. In order to improve these, various measures have been taken, such as applying a waterproofing treatment to the fishing line surface or using a multi-layer knitted structure, but this is not yet sufficient. High-strength polyethylene fibers are also being developed, but their density is lower than that of water, and aramid fibers are water-absorbing, and cannot solve the above-mentioned problems. Also, fibers such as metal fibers, glass fibers, and carbon fibers are difficult to handle. Therefore, there is a demand for a fishing line that is lightweight, has high strength and a high elastic modulus, and has high waist. An object of the present invention is to provide a fishing line in which such a problem is solved. <Means for Solving the Problems> The present invention relates to a method for producing a polyester obtained by melt spinning from an aromatic polyester exhibiting anisotropy upon melting (however, excluding those containing a residue of ethylene glycol as a constituent component). Breaking strength of 100 kg / mm ² or more, density of 1.38 g / cc or more,
The present invention relates to a fishing line made of an aromatic polyester fiber having an elastic modulus of 6 Ton / mm ² or more and an elongation of 10% or less. The aromatic polyester fiber in the present invention is, for example, Japanese Patent Publication No. 55-20008.
And JP-A-58-191219. Preferred aromatic polyester fibers are fibers obtained by melt spinning from an aromatic polyester that exhibits anisotropy when melted. Above all, those having an elastic modulus of 6 Ton / mm ² or more and an elongation of 10% or less are preferable in that they are stiff, have no entanglement or entanglement, and transmit fish signals sharply. The aromatic polyester exhibiting anisotropy when melted is formed from an aromatic dicarboxylic acid and an aromatic diol and / or an aromatic hydroxycarboxylic acid or a derivative thereof. Also included are diols (excluding ethylene glycol) and copolymers with these derivatives. Here, as the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, 4,4′-
Dicarboxydiphenyl, 2,6-dicarboxynaphthalene, 1,2-bis (4
-Carboxyphenoxy) ethane and the like, and their alkyl, aryl, alkoxy, and halogen-substituted halogen groups. Examples of the aromatic diol include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylethane, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl sulfide. , 2,6-dihydroxynaphthalene, 1,5-
Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,2′-bis (
4-hydroxyphenyl) propane and the like, and nucleus-substituted products of these alkyl, aryl, alkoxy and halogen groups. Examples of the aromatic hydroxycarboxylic acid include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid, 1-hydroxynaphthalene-5-carboxylic acid, p-4-hydroxyphenylbenzoic acid, and the like. Alkyl, aryl, alkoxy and halogen-substituted halogen groups. Examples of the alicyclic dicarboxylic acid include trans-1,4-dicarboxycyclohexane, cis-1,4-dicarboxycyclohexane, and the like, and nucleus-substituted alkyl, aryl, alkoxy, and halogen groups thereof. The alicyclic and aliphatic diols include xylylene diol, trans-1,4
-Dihydroxycyclohexane, cis-1,4-dihydroxycyclohexane and the like, and their alkyl, aryl, alkoxy and halogen-substituted products. The aromatic polyester used in the present invention can be obtained by subjecting a combination of the above-mentioned raw materials or their derivatives to polycondensation by esterification or transesterification. Examples of the aromatic polyester preferable as an object of the present invention include (1) A) a copolyester comprising 40 to 70 mol% of p-hydroxybenzoic acid residues, 15 to 30 mol% of the aromatic dicarboxylic acid residues and 15 to 30 mol% of aromatic diol residues, (2) terephthalic acid and / or A copolyester comprising isophthalic acid and chlorohydroquinone, phenylhydroquinone and / or hydroquinone, (3) from 20 to 80 mol% of p-hydroxybenzoic acid residues and 20 to 80 mol% of 2-hydroxynaphthalene-6-carboxylic acid residues And the like. As the polycondensation reaction, known bulk polymerization, solution polymerization, suspension polymerization, and the like can be adopted. Sb, Ti, and Ge compounds may be optionally added at 150 to 360 ° C. under normal pressure or 10 to 0.1 torr under reduced pressure. Polymerization catalysts, such as phosphorus-based compounds, TiO ₂ ,
It can be carried out by adding a filler such as CaCO ₃ and talc. The obtained polymer may be used as it is, or in a powder form, and heat-treated in an inert gas or under reduced pressure to prepare a sample for spinning, or may be used after being granulated once by an extruder. As the melt spinning device, any device can be used as long as it has a plunger having a heating control mechanism, a melting portion such as a screw, a measuring portion such as a gear pump, and a spinning head including a spinneret. Suitable temperatures for spinning are 280-420C, preferably 300-400C. If the temperature is lower than 280 ° C., the load on the apparatus is increased, the uniformity of the melt of the sample is not sufficient, and if the temperature is high, decomposition occurs, so that stable spinning cannot be performed. As a spinneret used for spinning, a commonly used spinneret can be used as it is. However, a preferable spinneret has a hole diameter (d) of 0.15 mm or less and a ratio of the hole length (1) to the hole diameter (1). / D) is preferably 0.8 or more. Although the obtained fiber can be used as it is, it may be used after drawing, heat treatment or an operation combining these. The fiber thus obtained has high strength, high elastic modulus, low elongation, and low water absorption, but if the waist is too large, it is not a monofilament with a large diameter but a thin one to adjust the total repulsion force against bending. It can also be used by processing such as twisting, knitting and weaving with a plurality of filaments having a diameter. <Effect of the Invention> The fiber used in the present invention has a high strength, so that the diameter of the line can be reduced to obtain a necessary strong fishing line. It is easy to sink in water because it is less dense and has a higher density than water. Furthermore, since it has low elongation and high elasticity, a small amount of fish is transmitted to the tip of the rod sharply. It is also possible to use a transparent yarn. <Examples> Examples will be shown below to facilitate understanding of the present invention, but these are merely illustrative, and the gist of the present invention is not limited thereto. The specific values in the examples were measured and calculated as described below. (1) Optical Anisotropy at the Time of Melting The polymer powder was placed on a heating stage, heated at 25 ° C./min under polarized light, and visually observed. (2) Fiber Tensile Test Using a Tensilon II type tensile tester manufactured by Toyo Baldwin, the tensile distance was measured at a chuck distance of 20 mm and a tensile speed of 2 mm / min. The number of samples was 24, and the average value excluding the highest and lowest values was shown. Reference Example 7.2 kg (40 mol) of p-acetoxybenzoic acid, 2.49 kg of terephthalic acid
(15 mol), 0.83 kg (5 mol) of isophthalic acid, and 5.45 kg (20.2 mol) of 4,4′-diacetoxydiphenyl were charged into a polymerization tank having a comb-shaped stirring blade.
The temperature was raised while stirring in a nitrogen gas atmosphere, and polymerization was performed at 330 ° C. for 3 hours. The acetic acid generated during this time was removed, polymerization was carried out with vigorous stirring, and the polymer was taken out after cooling. The yield was 10.88 kg, which was 97.8% of the theoretical yield. This was pulverized with a hammer mill to obtain particles having a size of 2 mm or less, and the particles were embedded in a rotary kiln under a nitrogen atmosphere at 280 ° C. for 5 hours. As a result, optical anisotropy in a molten state at 350 ° C. or more was observed. Example 1 Using the polyester of the reference example, melt spinning was performed with a 30 mm diameter screw type extruder. The spinneret has a hole diameter of 0.07 mm, a hole length of 0.14 mm, and a number of 302 holes. A yarn having a single yarn denier of 2.87 (straight through about 17 μm) was obtained, which was treated in dehumidified air at 320 ° C. for 3 hours. The density of the obtained fiber is 1.40 g / cc, strength is 336 kg / mm ² , elongation at break is 2.7%, and elastic modulus is 12.6 Ton / mm ² . After applying a silicone oil, the fiber is twisted so as to be twisted once per cm, and an epoxy oil containing a red pigment (a color preferred by fish) is attached to the fiber to lightly harden the fishing line. And The handling was good, the sinking speed in water was fast, and the fish signal from a depth of about 5 m was clearly confirmed. Example 2 The polyester of the reference example was used as a spinneret with a hole diameter of 0.12 mm and a hole length of 0.3.
Melt spinning was carried out in the same manner as in Example 1 except that a material having 6 mm and 24 holes was used. A denier 29.8 (diameter of about 55 μm) yarn was obtained, which was treated in dehumidified air at 320 ° C. for 3 hours. The density of the obtained fiber is 1.38 g / cc, the strength is 205 kg / mm ² , the breaking elongation is 2.8%, and the elastic modulus is 7.6 Ton / mm ² . This fiber was treated and post-processed as in Example 1. Like the fishing line of Example 1, the handling is good, the sinking speed in water is fast, and the depth is about 5
The fish signal from m was also clearly confirmed.

Claims (1)

A tensile breaking strength of at least 100 kg / mm ² obtained by melt spinning from an aromatic polyester exhibiting anisotropy upon melting (however, excluding those containing a residue of ethylene glycol as a constituent component). , Density 1.38g / cc or more, elastic modulus 6T
A fishing line composed of an aromatic polyester fiber having an on / mm ² or more and an elongation of 10% or less.