JP2001148982A - Fishing line - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fishing line having a high strength and a high modulus of elasticity, further a low elongation and performances of high transparency and high water resistance and excellent in mechanical performances, strike and durability. SOLUTION: This fishing line is characterized in that the line is composed of a polyketone fiber comprising a polyketone polymer prepared by copolymerizing an olefin with carbon monoxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a high performance fishing line. More specifically, it is made of polyketone fiber with high strength, high elastic modulus, low elongation, high transparency, and high water resistance. The present invention relates to a fishing line having excellent characteristics such as being hardly perceived and having good durability and useful for fishing and leisure fishing.

[0002]

2. Description of the Related Art Conventionally, fishing line materials mainly include polyamide fibers such as nylon 6, nylon 6.6, polyester fibers such as polyethylene terephthalate, fibers made of general-purpose resins such as polyvinylidene fluoride fibers, and metal fibers such as tungsten. Has been used. However, polyamide fiber swells in water because it has a water absorption of 10% or more,
There has been a problem that the strength is reduced, and the durability to water is poor, so that repeated use is difficult. In addition, since the initial elastic modulus is low and the elongation is as high as 10 to several tens of percent, fishing signals are difficult to understand. In particular, in deep sea fishing and boat fishing where the line length is long, it is a problem that fishing signals are difficult to understand. . In addition, although polyester fiber has good water resistance,
The elongation was several tens of percent, and there was a problem that fish signals were difficult to understand and the strength was insufficient. Polyvinylidene fluoride fibers have a problem that the strength is low and the fineness must be increased in order to obtain sufficient strength. Also,
Tungsten fibers have a problem that since they are metal, they have a large specific gravity and are difficult to reduce in weight.

On the other hand, recently, fishing lines using polyvinyl alcohol fiber having high strength and high elastic modulus mechanical properties (Japanese Patent Application Laid-Open No. 2-160910) and fishing lines using ultra-high molecular weight polyethylene fiber (Japanese Patent Application Laid-Open No. 8-14053
No. 8) has been studied. However, polyvinyl alcohol fibers have high strength and high elastic modulus, but have extremely poor stability and durability against water, and have a problem that their performance is remarkably deteriorated by long-term use or continuous use. Ultra-high molecular weight polyethylene fiber has high strength, high elastic modulus, low elongation, and water resistance, but has a low melting point and easily breaks due to heat generated by friction. The problem is that the resin is easily peeled off during use due to poor adhesiveness to the fiber, the surface resin processing is required when coloring because it cannot be dyed, and the cost increases and the flexibility of the fishing line decreases. The specific gravity is less than 1. Therefore, there has been a problem that the fishing line floats on the water surface during fishing. As described above, a fishing line excellent in mechanical properties and also excellent in heat resistance, water resistance, and adhesion has not been known.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fishing line which is excellent in mechanical properties, water resistance and heat resistance and which is easy to understand. Specifically, the tensile strength is 10 cN / dtex or more, and the initial elastic modulus is 200 cN / dt.
ex, tensile elongation 6% or less, melting point 240
An object of the present invention is to provide a fishing line having a water resistance of not lower than ℃.

[0005]

SUMMARY OF THE INVENTION The present invention is a fishing line characterized by comprising a polyketone fiber comprising a polyketone polymer obtained by copolymerizing an olefin and carbon monoxide. The polymer constituting the polyketone fiber used in the fishing line of the present invention is a copolymer of olefin and carbon monoxide. From the viewpoints of mechanical properties such as strength and elastic modulus, heat resistance, water resistance, and adhesion to a resin, a polymer containing 1-oxotrimethylene as a main repeating unit in which ethylene and carbon monoxide are bonded is preferable. The proportion of 1-oxotrimethylene in the repeating unit is preferably at least 90% by weight, more preferably at least 97% by weight, particularly preferably at least 97% by weight, since a fiber having a high melting point and high mechanical properties can be obtained as much as possible. 100% by weight.

Further, from the viewpoints of light resistance, heat resistance, and deterioration of physical properties at high temperatures, the content of the portion where olefins and carbon monoxide are alternately arranged is preferably as large as possible, and more preferably 97%.
% Or more, most preferably 100% by weight. In addition, if necessary, olefins other than ethylene such as propene, butene, hexene, cyclohexene, pentene, cyclopentene, octene, and nonene, methyl methacrylate, vinyl acetate, acrylamide, hydroxyethyl methacrylate, styrene, sodium styrene sulfonate, and allylsulfonic acid Sodium, vinylpyrrolidone,
A compound having an unsaturated hydrocarbon such as vinyl chloride may be copolymerized.

It is recommended that the polyketone fiber used in the fishing line of the present invention has a tensile strength of 5 cN / dtex or more and an initial elastic modulus of 100 cN / dtex or more.
As the tensile strength of the fiber is higher, the strength of the fishing line per the same weight becomes stronger, and fineness and weight reduction become possible,
It is preferably at least 5 cN / dtex, more preferably 1 cN / dtex.
0 cN / dtex or more, particularly preferably 15 cN / dt
ex or more is desirable. Also, the higher the initial elastic modulus of the fiber, the higher the rigidity of the fishing line and the higher the responsiveness of fishing signals. Therefore, it is preferably at least 100 cN / dtex, more preferably at least 200 cN / dtex, particularly preferably at least 300 cN / dtex. Desirably.
Furthermore, the lower the tensile elongation, the better the responsiveness of fishing signals, so it is preferably 8% or less, and more preferably 6% or less.
% Or less, particularly preferably 5% or less. However, if the tensile elongation is too low, the toughness of the fishing line decreases, so that the tensile elongation is desirably 3% or more.

[0008] It is also desired that not only mechanical properties but also heat resistance and water resistance be excellent. In the case of polyketone fiber, the higher the melting point of the fiber, the better the heat resistance.
It is desirable that the melting point is 40 ° C. or higher, more preferably 250 ° C. or higher, particularly preferably 260 ° C. or higher. The polyketone fiber constituting the fishing line of the present invention is required to have excellent water resistance and moisture and heat resistance. The polyketone fiber is a material having excellent water resistance, and has a strength retention of preferably 80% or more, more preferably 9%, after being immersed in room temperature water for one month.
Desirably, it is 0% or more. In addition, it is desirable to maintain sufficient strength even when a severe heat treatment at 120 ° C. and 100% humidity is performed for 30 minutes as a moisture and heat resistance.
It is desirable that the strength retention by wet heat treatment is preferably 80% or more, more preferably 90% or more. If it has the above-mentioned water resistance and moisture-heat resistance, it is expected that the fishing line will exhibit sufficient performance even when exposed to a harsh use environment such as seawater in summer.

Further, when the polyketone fiber is used without being colored by dyeing or resin processing, it is preferable that the transparency of the polyketone fiber is high in that the fishing line is hardly perceived by fish. In the polyketone fiber used in the fishing line of the present invention, since the higher the gloss, the higher the transparency, the gloss is preferably 30 or more, more preferably 40 or more. The number of filaments of the polyketone fiber having such properties may be monofilament or multifilament,
There is no particular limitation. In addition, the single-fiber fineness is not particularly limited, but is usually 10 to 100,000 for a monofilament.
dtex, 0.1 to 10 dte for multifilament
x.

When used in a multifilament,
If necessary, it may be used as a processed yarn that has been subjected to processing such as false twisting, bulking, crimping, and winding. Further, between the single yarns or the surface of the filament may be processed with a resin or an adhesive. The type of the resin processing agent that can be used in the fishing line of the present invention is not particularly limited, and a conventionally known resin may be used as it is, or may be used after being improved, and may be used by mixing a plurality of types of resins as necessary. Good. Examples of usable resins include thermoplastic resins, such as polyamide resins, polyester resins, polyolefin resins, and polyether ketones.As thermosetting resins, unsaturated polyester resins,
Vinyl ester resin, epoxy resin, phenol resin,
Urethane resin, acrylic resin, and the like can be given. Among them, thermosetting resins such as epoxy resins, acrylic resins, urethane resins, and unsaturated polyester resins are preferably used. As the curing agent used for the thermosetting resin, a conventionally known curing agent can be used as it is or after modification. Examples of the curing agent include bisphenol S, bisphenol A, dicyandiamide, diaminodiphenylsulfone, diaminodiphenylmethane, tetramethylguanazine, phenol novolak resin, cresol novolak resin, aromatic (aliphatic) amine, imidazole derivatives and the like.

The fishing line of the present invention may be colored. There is no particular limitation on the coloring method, and a method using a pigment-containing polyketone fiber, a method for dyeing a polyketone fiber and / or a resin coated on the fiber surface, a method for coating a colored resin on the fiber surface, and the like are used. It can be arbitrarily selected according to the purpose. When dyeing a polyketone fiber, a dyeing method using a disperse dye is suitably used. In this case, it is preferable that the glossiness of the polyketone fiber is higher, since the fishing line can be dyed sharply.

Although the fishing line of the present invention is composed of polyketone fibers, a fiber material other than polyketone fibers can be used depending on the purpose if it is less than 50% by weight. There are no particular restrictions on the fibers that can be used, and polyamide fibers such as nylon 6, nylon 6.6, and nylon 4.6, polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate, liquid crystal polyester fibers, polyethylene, and polypropylene. Polyolefin fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyvinyl chloride fiber, polybenzazole fiber, aramid fiber,
Conventionally known fibers such as wool, polyacrylonitrile fiber, cellulose fiber such as cotton and viscose rayon, carbon fiber, ceramic fiber, and metal fiber can be used. If necessary, plural kinds of these fibers can be used. There is no problem if the fibers are used in combination. When a plurality of types of fibers are mixed, the method is not particularly limited, and may be subjected to processing such as false twisting or twisting to form a mixed fiber,
Fibers of the same kind may be used in combination with fibers having different thermal and mechanical properties, fibers having different fineness or filament number, or a combination of filaments of long fibers and spun yarns of short fibers.

[0013] The polyketone fiber used in the fishing line of the present invention and the mixed fiber may be a heat stabilizer, a leveling agent, a pigment,
Additives such as oils, concealing agents, matting agents, flame retardants, plasticizers, flameproofing agents, preservatives, antibacterial agents, antifouling agents, etc. may be contained on the fiber surface or in the fiber or between the filaments, but rather various Fibers coated with and containing drugs are desirable. There is no particular limitation on the use of the fishing line of the present invention. It may be used for any of fishing line for boat fishing and the like, and may be used for any of fishing and leisure fishing.

Hereinafter, a method for producing the polyketone fiber used in the fishing line of the present invention will be described. The method for producing the polyketone fiber is not particularly limited, and a conventionally known melt spinning method, dry spinning method, or wet spinning method can be used as it is or after modification (for example, JP-A-1-124617, JP-A-2-142). JP-A-112413, JP-A-4-228
No. 613, Japanese Patent Application Laid-Open No. 4-505344, Japanese Patent Application No. 7-508317, Japanese Patent Application No. 8-507328, WO9918143 published pamphlet, Japanese Patent Application No. 1
No. 0-236595, Japanese Patent Application No. 11-72091, Japanese Patent Application No. 11-77220, Japanese Patent Application No. 11-159258,
Japanese Patent Application No. 11-167370.

When spinning an ethylene / carbon monoxide alternating copolymer, a wet spinning method using a concentrated metal salt as a solvent is preferred. Examples of the concentrated metal salt include a zinc halide compound, and zinc chloride and zinc iodide are preferred in view of solubility, cost of a solvent, and stability of an aqueous solution. If necessary, the composition may contain 60% by weight or less of an alkali metal or alkaline earth metal halide such as sodium chloride, potassium chloride, and calcium chloride. In view of this, a dope containing 5 to 30% by weight of a metal salt such as sodium chloride or calcium chloride is preferable. The polyketone dope is discharged from a spinneret and, if necessary, is passed through an air gap to form a filament through a coagulation bath. The composition of the coagulation bath may be any one such as an organic solvent such as methanol and acetone, water, an aqueous solution of an organic substance, and an aqueous solution of an inorganic substance, but a solution containing water is preferred. The thus obtained filamentous material is washed with a metal salt as necessary, dried and stretched. Stretching is usually performed at a temperature equal to or lower than the melting point, and the stretching ratio is preferably 10 times or more in total, particularly preferably 15 times or more.
A multi-stage stretching method in which the stretching temperature is gradually increased is preferably used.

The polyketone fiber obtained by such a method has excellent mechanical properties as a fishing line having a high strength, a high elastic modulus and a low elongation and is stable against heat and wet heat. By applying to the fishing line, a fishing line that was not able to be obtained with conventional fiber materials, is lightweight, has excellent handleability, has low running water resistance, has excellent responsiveness to fishing signals, is hardly perceived by fish, and has excellent durability Can now be obtained.

[0017]

The present invention will be described in more detail with reference to the following examples, which do not limit the scope of the present invention. The measuring method of each measured value used in the description of the embodiment is as follows. (1) Intrinsic Viscosity Intrinsic viscosity [η] is a value obtained based on the following definition formula. [Η] = lim (T−t) / (t · C) [g / dl] C → 0 In the definition formula, t and T represent the viscosity of a dilute solution of polyketone dissolved in hexafluoroisopropanol at 25 ° C. Flow time. C is the solute weight value in grams in 100 ml of the solution. (2) Tensile strength / elongation of fiber and fishing line, initial elastic modulus Measured according to JIS-L-1013.

(3) Melting point A fiber cut into a length of 5 mm was used as a sample. The measurement was performed under the following conditions using a differential heat measurement device Pyris1 manufactured by Perkin Elmer. Sample weight: 1 mg Measurement temperature: 30 ° C. → 300 ° C. Heating rate: 20 ° C./min Atmosphere: Nitrogen, flow rate = 200 mL / min Maximum endothermic peak observed in the range of 200 ° C. to 300 ° C. in the obtained endothermic curve. Was determined as the melting point. (4) Water Resistance Strength Retention A fiber sample was put into pure water at 25 ° C. and allowed to stand for 30 days.
Measure the tensile strength after standing according to the method of (2),
Assuming that the fiber strength before the treatment was T and the fiber strength after the treatment was Tw, the water resistance strength retention Rw was determined by the following formula. Rw = Tw / T × 100 (%)

(5) Moisture and heat resistance retention rate Fiber or fishing line was put into an autoclave at a humidity of 100% and a temperature of 120 ° C., and was treated for 30 minutes. The tensile strength after the treatment was measured according to the method (2), and the fiber strength before the treatment was T and the fiber strength after the treatment was Ts, and the wet heat strength retention Rs was determined from the following equation. Rs = Ts / T × 100 (%) (6) Glossiness A piece of Western paper was attached to an aluminum plate having a length of 7 cm, a width of 5 cm, and a thickness of 1 mm, and a polyketone fiber was applied thereon by applying a load of 0.1 cN / dtex. Wound 6 times. The winding pitch was changed as follows according to the fineness so that there was no gap.

Winding pitch of sample plate for measuring glossiness Fineness: 30 to 60 (dtex); Pitch: 100 (books / cm) 60 to 90 (dtex); 70 (books / cm) 100 to 140 (dtex); 58 (Books / cm) 140 to 180 (dtex); 49 (books / cm) 180 to 230 (dtex); 44 (books / cm) 230 to 330 (dtex); 38 (books / cm) 330 to 400 (dtex) 35 (books / cm) 400 to 550 (dtex); 33 (books / cm) 550 to 700 (dtex); 30 (books / cm) The fiber sample plate was subjected to a digital bending gloss meter (manufactured by Suga Test Instruments Co., Ltd.). UGV-4D) and JIS-L-1013 (B
The glossiness at a measurement angle of 60 ° was measured according to the following method. In the test, measurements were made on the front and back of the sample plate, respectively, and the average value of the front and back was defined as the glossiness of the fiber.

(Example 1) A polyketone polymer having an intrinsic viscosity of 5.9, in which ethylene and carbon monoxide were completely alternately copolymerized, prepared by a conventional method, was added to an aqueous solution containing 65% by weight of zinc chloride / 10% by weight of sodium chloride. The mixture was stirred and dissolved at 80 ° C. for 2 hours to obtain a dope having a polymer concentration of 8% by weight. The obtained dope was heated to 80 ° C. and filtered with a 20 μm filter, and then a spinning diameter of 0.10 mm and L / D = 1,2.
After passing through an air gap of 10 mm from a 50-hole spinneret, the mixture was extruded into water at 18 ° C. containing 5% by weight of zinc chloride at a discharge rate of 16 cc / min and solidified. The coagulated yarn is subsequently washed with an aqueous solution of sulfuric acid having a concentration of 2% by weight, further washed with water at 30 ° C., wound up at a winding speed of 2.5 m / min, and further dried at 220 ° C. Thus, an undrawn yarn was obtained.

After the undrawn yarn is drawn at 240 ° C. in the first stage, it is subsequently drawn at 260 ° C. in the second stage and at 270 ° C. in 3 stages.
A total of 15 times stretching is performed by stretching at the stage and 48 times.
A drawn yarn of 0 dtex / 250f was obtained. Fluff during stretching
No trouble such as thread breakage occurred. The obtained fiber had fiber properties, high melting point, and excellent performance in wet heat stability. The drawn yarn was ethylene glycol diglycidyl ether: 25.0% by weight, magnesium borofluoride catalyst: 1.0% by weight, magnesium acetate: 1.0% by weight,
Water: After passing through a 73.0% by weight liquid, it was preliminarily dried at 100 ° C. for 1 minute and heat-treated at 160 ° C. for 3 minutes. The adhesion between the fiber and the resin was good, and no peeled portion was observed even after repeated bending and rewinding.

Example 2 1-oxo-3- was prepared by a conventional method.
An ethylene / propene / carbon monoxide terpolymer having an intrinsic viscosity of 5.4 containing 3% by weight of methyltrimethylene unit was prepared. Example 1 except that the polymer was used, the dope concentration was 10% by weight, and the discharge rate was 14 cc / min.
Spinning and drying were performed in the same manner as described above to obtain an undrawn yarn. After passing the undrawn yarn through a roll heated to 180 ° C., the first stage drawing was performed at 220 ° C. on a hot plate having a length of 1 m around which heated air at 220 ° C. was flown. At the second stage, and at 245 ° C. at the third stage for a total stretching of 14.5 times and a fineness of 500 dt.
ex / 250f drawn yarn was obtained. The drawn yarn was processed with a resin in the same manner as in Example 1.

Example 3 1-oxo-3- was prepared by a conventional method.
An ethylene / propene / carbon monoxide terpolymer having an intrinsic viscosity of 1.6 containing 6% by weight of methyltrimethylene unit was prepared. Using this polymer, spinning and drying were performed in the same manner as in Example 1 except that the dope concentration was 22% by weight and the discharge rate was 6 cc / min to obtain an undrawn yarn. After passing this undrawn yarn through a roll heated to 180 ° C., the first stage drawing was performed at 200 ° C. on a hot plate having a length of 1 m around which heated air at 200 ° C. was flown. At the second stage and at 225 ° C. at the third stage for a total stretching of 12.5 times and a fineness of 480 dte.
x / 250f drawn yarn was obtained. Although the strength of this drawn yarn was almost equal to that of nylon 6.6, it was excellent in moisture and heat resistance. The drawn yarn was subjected to resin processing in the same manner as in Example 1.

Example 4 The dope prepared in Example 1 was passed through an air gap of 10 mm from a monohole spinneret having a spinning diameter of 1 mmφ and L / D = 1, and then 5 wt% of zinc chloride and 0 wt. Extruded into 32 ° C. water containing 1% by weight hydrochloric acid at a discharge rate of 2.5 cc / min.
To obtain a coagulated polyketone yarn. Subsequently, the coagulated yarn is washed at a concentration of 2% by weight on two sets of rolls having a diameter of 300 mm through which a sulfuric acid aqueous solution having a temperature of 40 ° C. flows through 30 laps, and further, the two sets of rolls having a diameter of 300 mm through which water at 60 ° C. flows are washed with 30 laps. After finishing washing through the wrap, the film was wound at a winding speed of 3.2 m / min.

After simple dehydration of the obtained filamentous material, 12
0 ° C. for 1 minute, followed by 180 ° C. for 1 minute, then 24 hours
It was dried at 0 ° C. for 1 minute to obtain an undrawn yarn having a fineness of 1132.1 dtex. After passing this undrawn yarn through a roll heated to 220 ° C., the first stage drawing was performed at 240 ° C. on a hot plate having a length of 1 m around which heated air at 240 ° C. was flown, and then 255 ° C. 2nd stage, 27 more
The third stage of drawing was performed at 0 ° C., and a total of 15 times drawing was performed to obtain a monofilament having a fineness of 78.2 dtex.
The polyketone monofilament had practically sufficient characteristics as a fishing line.

Comparative Example 1 An epoxy resin was processed in the same manner as in Example 1 using nylon 6.6 fiber (480 dtex / 80f) produced by a known melt spinning method. Tensile strength is significantly inferior to polyketone fiber,
In particular, it was significantly reduced by wet heat treatment. The fiber was resin-processed in the same manner as in Example 1. (Comparative Example 2) Nylon 6.6 monofilament (fineness = 100 dtex) produced by a known melt spinning method was significantly inferior to polyketone monofilament in strength, modulus of elasticity, and wet heat resistance.

(Comparative Example 3) Polyvinyl alcohol having a degree of polymerization of 7000 was dissolved in DMSO to a concentration of 7% by weight, and spinning, drying and stretching were performed according to a conventional method using cold methanol as a coagulation bath, and stretched to a fineness of 355 dtex / 250f. Yarn was obtained. The mechanical properties of the fibers were equivalent to those using polyketone fibers, but the strength was greatly reduced by wet heat treatment. The fiber was resin-processed in the same manner as in Example 1.
Table 1 summarizes the properties of the fibers used in Examples 1 to 4 and Comparative Examples 1 to 3 of the present invention. Example 1 of the present invention
Table 2 summarizes the characteristics of the fishing lines (resin processed products) of Comparative Examples 1 to 4 and Comparative Examples 1 to 3.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

The fishing line of the present invention has a high strength and a high elastic modulus,
It is made of polyketone fiber which has excellent mechanical properties as a low elongation fishing line and is stable against heat and wet heat.It is hard to cut, light weight, low running water resistance, excellent handling and durability, and Has made it possible to provide a fishing line that has excellent responsiveness to fishing signals and is excellent in fishing performance that is hardly perceived by fish.

Claims (5)

[Claims] 1. A fishing line comprising a polyketone fiber made of a polyketone polymer obtained by copolymerizing an olefin and carbon monoxide. 2. The polyketone fiber has a tensile strength of 10c.
N / dtex or more, initial elastic modulus is 200 cN / dtex
The fishing line according to claim 1, wherein the tensile elongation is 6% or less. 3. The fishing line according to claim 1, wherein the glossiness of the polyketone fiber is 30 or more. . 4. The fishing line according to claim 1, wherein 97% by weight or more of the repeating unit constituting the polyketone polymer is 1-oxotrimethylene. 5. The fishing line according to claim 1, wherein the repeating unit constituting the polyketone polymer comprises only 1-oxotrimethylene.