JP2001089928A - Light emitting monofilament and fishing line comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a light emitting monofilament excellent in water resistance suppressing deterioration of light emissivity in using underwater and capable of sustaining afterglow characteristic for a long time and a fishing line comprising the light emitting monofilament suitable for night fishing. SOLUTION: The light emitting monofilament uses a resin composition comprising a thermoplastic synthetic resin having water absorption of <=0.5 wt.% measured in conformity to ASTM D570 after leaving at 23 deg.C in water for 24 hours, and a phosphor, as a constituent of at least a part. The fishing line comprising the light emitting monofilament exhibits an excellent visibility especially in used in night fishing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminous monofilament which emits light by an external stimulus by light and has a performance of maintaining self-emission in a dark place even after the external stimulus is removed. More specifically, the present invention relates to a luminescent monofilament which is excellent in water resistance, suppresses a decrease in luminescence when used in water, and has a long-lasting afterglow characteristic, and a fishing line composed of the luminescent monofilament and suitable for night fishing. is there.

[0002]

2. Description of the Related Art Luminescent synthetic fibers, which emit light when exposed to external stimuli and have the ability to maintain self-emission in the dark even after the external stimuli are removed, have been used mainly for carpets and night fishing. Widely used in applications such as fishing line.

Techniques for producing this type of luminescent fiber include (A) hollow luminescent fibers made of a thermoplastic resin mixed with a luminous pigment (Japanese Patent Application Laid-Open No. 2-53908).
(B) A fishing line containing a luminous paint on the surface of a fiber or containing a luminous paint in the fiber body (Japanese Patent Laid-Open No. 10-1)
No. 13107), (C) a fiber product having luminous fluorescent performance formed from a resin composition in which a specific luminous phosphor is blended with a thermoplastic resin such as polyamide or polyolefin (JP-A-8-127937); (D) Fishing line with phosphorescent paint applied to the surface (registered utility model 30249)
No. 04) has already been proposed.

However, the luminescent fiber of the above (A) is
Although there is an improvement in the luminance of emitted light, there is a problem that not only is the afterglow characteristic for maintaining light emission for a long time inferior, but also the strength is inferior because of the hollow fiber.

[0005] Further, the fishing line of the above (B) has a problem of environmental hygiene because the luminous paint contains radioactive substances such as radium and thorium.

Further, although the fiber product of the above (C) has a long-lasting afterglow characteristic, the luminescence is remarkably reduced when the fiber absorbs water, so that it was unsuitable as a fishing line for night fishing.

Further, the fishing line of (D) has a problem in light emission durability because the applied luminous paint is easily peeled off and dropped off.

[0008] Therefore, none of the conventional luminescent synthetic fibers has always been satisfactory in its improving effect.

[0009]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the above-mentioned problems in the prior art.

Accordingly, an object of the present invention is to provide a luminous monofilament which is excellent in water resistance, suppresses a decrease in luminescence during use in water, and has a long-lasting characteristic for a long time. It is an object of the present invention to provide a suitable fishing line.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a resin comprising a thermoplastic synthetic resin having a specific water absorption and a specific phosphorescent phosphor is used. Monofilament comprising the composition as a component,
The present inventors have found that the above objects are met, and have reached the present invention.

That is, the light-emitting monofilament of the present invention was measured according to ASTM D570.
A resin composition comprising a thermoplastic synthetic resin having a water absorption of 0.5% by weight or less after standing in water at 24 ° C. for 24 hours and a phosphorescent phosphor is at least a part of the constituent components.

In the luminescent monofilament of the present invention, the following conditions (1) to (6) are preferable conditions,
By satisfying these conditions, more excellent effects can be expected.

(1) The phosphorescent phosphor has the formula M _1-x Al
₂ O _4-X (where M represents at least one metal element selected from calcium, strontium and barium, and X represents a numerical value in the range of −0.33 to 0.60)
Crystals of the compound represented by are ground and classified.

(2) The phosphorescent phosphor further contains Eu (europium) and / or Dy (dystrosium) as an activator in a molar ratio of 0.001% to the metal element represented by M in the above formula. More than 10% or less should be added.

(3) The average particle size of the phosphorescent phosphor particles measured by the laser diffraction scattering method (cumulative particle size distribution ratio 50
% (D50)) is in the range of 1.0 to 3.5 μm.

(4) The thermoplastic synthetic resin is a polyvinylidene fluoride resin, polypropylene terephthalate,
Polylactic acid, polybutylene (succinate / adipate)
At least one selected from a copolymer and a polyphenylene sulfide resin.

(5) The amount of the phosphorescent phosphor added is in the range of 2 to 20% by weight based on the thermoplastic synthetic resin.

(6) JIS L of the monofilament
Tensile strength measured according to 1013 is 50 kg /
mm ² or more.

The fishing line of the present invention is characterized by comprising the above-mentioned luminescent monofilament, and exhibits good visibility especially when used for night fishing.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The luminescent monofilament and fishing line of the present invention will be described below in detail.

The phosphorescent phosphor used in the present invention emits light by an external stimulus by light, and has such a performance that afterglow can be visually recognized in a dark place for a considerable time even after the external stimulus is removed. Which are known per se.

The phosphorescent phosphor is represented by the formula M _{1 -X} Al ₂ O
_4-X (where M represents at least one metal element selected from calcium, strontium and barium, and X represents a numerical value in the range of -0.33 to 0.60) Crystals obtained by grinding and classifying crystals are preferably used.

The phosphorescent phosphor represented by the above formula further contains Eu (europium) and / or
Alternatively, Dy (dystrosium) in which the molar ratio is 0.001% or more and 10% or less with respect to the metal element represented by M in the above formula is particularly preferably used because of its high emission luminance.

Further, the above-mentioned phosphorescent phosphor is dispersed in ethanol, and the average particle size is measured by a laser diffraction scattering method (cumulative particle size distribution ratio 50% (D50)).
Is more preferably in the range of 1.0 to 3.5 μm in terms of maintaining the strength required by the monofilament.

A specific example of such a phosphorescent phosphor is, for example, N-Night Luminova (registered trademark) G300FF manufactured by Nemoto Special Chemical Co., Ltd., but is not limited thereto.

Next, the thermoplastic synthetic resin constituting the luminescent monofilament of the present invention has a water absorption of 0.5% by weight or less after standing in water at 23 ° C. for 24 hours, which is measured in accordance with ASTM D570. In particular, it is an essential condition that the content is 0.23% by weight or less, and examples of the thermoplastic synthetic resin satisfying this condition include a fluorine-based resin, a polyester-based resin, a biodegradable polyester resin, and a polyphenylene sulfide-based resin. .

Here, specific examples of the fluororesin include:
Polyvinylidene fluoride resins, ethylene / tetrafluoroethylene copolymers and terpolymers of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride and the like can be mentioned, among which polyvinylidene fluoride resins are particularly preferably used. .

Specific examples of the polyester resin include aromatic polyesters such as polypropylene terephthalate, polybutylene terephthalate and polyethylene terephthalate. Among them, polypropylene terephthalate is particularly preferably used.

Specific examples of the biodegradable polyester resin include polylactic acid, polybutylene succinate, polyethylene succinate and polybutylene (succinate / adipate) copolymer. Among them, polylactic acid and polybutylene (succinate / Adipate)
Copolymers are particularly preferably used.

The above formula M _1-X Al ₂ O _4-X or M _1-X A
_{l 2 O 4-X · Eu} , phosphorescent phosphor comprising a compound represented by Dy are those having a very long excellent afterglow characteristics Among phosphorescent pigment, water by chemical reaction with water The weak point was that it became an oxide and light emission performance was lost.

The present inventors have assumed that the fishing line used in normal night fishing will be used almost overnight in one fishing line.
When the luminescence performance after immersion in water for 24 hours was evaluated, by using a resin composition in which the above-mentioned phosphorescent phosphor and the thermoplastic synthetic resin having the above specific water absorption were combined as a constituent material, It has been found that a luminescent monofilament having excellent properties such as excellent water resistance, suppression of a decrease in luminescent property when used in water, and persistence properties for a long time can be obtained.

It should be noted that, among the above-mentioned thermoplastic synthetic resins, when a polyvinylidene fluoride resin is used as a constituent material, more favorable effects can be expected.
Although the reason for this is not clear, it is assumed that the degree of electronegativity of the fluorine element in the polymer is due to the effective suppression of the chemical reaction between water and the phosphorescent phosphor.

The content of the phosphorescent phosphor contained in the luminescent monofilament of the present invention is in the range of 2 to 20% by weight, more preferably 5 to 15% by weight. By setting the content of the phosphorescent phosphor in the range of 2 to 20% by weight, it is possible to achieve both the strength of the monofilament and the light emission.

The shape of the luminescent monofilament of the present invention does not necessarily have to be a circular cross section, but may be any of a triangular cross section, a multi-leaf cross section, and the like. It is also possible to use a composite yarn such as a composite structure.

Further, luminescent monofilament of the present invention, in the case of using this as a particularly fishing line, the tensile strength of 50 Kg / mm ^2, more preferably 55 Kg / mm ²
It is necessary to have the above strength characteristics, and if the above-mentioned conditions are satisfied, it is possible to satisfy this tensile strength.

The luminescent monofilament of the present invention can be efficiently produced, for example, by the method described below.

First, when melt-spinning a monofilament, a usual extruder-type extruder can be employed. The polymer temperature is 200 to 350 ° C., the extrusion pressure is 10 to 500 kg / cm ² , and the die diameter is 0.1 to 5 mm. ,
Conditions such as a spinning speed of 0.3 to 100 m / min can be appropriately selected.

The monofilament spun from the extruder type extruder is cooled in a cooling bath after passing through a short gas zone, and the cooling medium here is a liquid inert to the polymer, usually a liquid. Water or polyethylene glycol is used.

The monofilament that has been cooled and solidified is then sent to the first stage of the drawing step. The drawing and heat setting atmosphere (bath) is a heated heat medium bath such as hot water, polyethylene glycol, glycerin and silicone oil. A dry hot gas bath and a steam bath are used.

Next, single-stage to multi-stage stretching is performed. The total stretching ratio varies depending on the thermoplastic resin constituting the monofilament, and is usually 4.0 times or more, preferably 5.0 times or more.

After the single-stage or multi-stage stretching, an appropriate constant-length or relaxation heat treatment can be performed for the purpose of removing the stretching strain, if necessary.

The luminescent monofilament of the present invention obtained as described above can maintain excellent luminescence even after being immersed in water for a long time, and has a property that the afterglow property is sustainable for a long time. Therefore, it is extremely useful for various marine and industrial materials, and particularly for fishing line use in night fishing.

The fishing line made of the luminescent monofilament of the present invention exhibits excellent luminescence when used for night fishing, has good visibility, and can greatly contribute to improvement of fishing results.

[0045]

EXAMPLES The present invention will be described below with reference to examples. The evaluation of a thermoplastic resin as a raw material and the monofilament in the examples was carried out according to the following method.

(1) Water absorption: The water absorption after standing in water at 23 ° C. for 24 hours was measured in accordance with the provisions of ASTM D570.

(2) Tensile strength: Measured in accordance with JIS L1013.

(3) Persistence of light emission: The monofilament was immersed in pure water at 23 ° C. for 24 hours and then air-dried at a temperature of 20 ° C. and a relative humidity of 65% RH for 24 hours. . However, the term "luminous property" as used herein means a property that afterglow by an external stimulus such as a fluorescent lamp or the like, even after the external stimulus is removed, afterglow can be visually recognized for a considerable time in a dark place.

(4) MFR: Nozzle 2.095φ × 8.
0 L, depending on the type of thermoplastic resin, temperature 2
The melt flow rate (g / 10 minutes) was measured by a melt indexer under appropriately selected conditions in the range of 00 to 350 ° C. and the load of 2.16 to 10.0 kg.

(5) Relative viscosity: Measured according to the method (sulfuric acid method) described in 4.4.1 of JIS-K6810.

(6) Intrinsic viscosity: A sample 0.10 was dissolved in 10 ml of orthochlorophenol, and measured at 25 ° C. using an Ostwald viscometer. [Example 1] MFR (230 ° C, 10 Kg) was 2.3.
In comparison with the polyvinylidene fluoride homopolymer having a water absorption of 0.04%, the N night light luminova G30 manufactured by Nemoto Special Chemical Co., Ltd.
OFF (SrAl ₂ O ₄ .Eu, Dy) containing 5% by weight of a resin composition was extruded by an extruder type extruder to 26%.
Melted at 0 ° C., spun through a die with a hole diameter of 2.5 mm,
It was further cooled in a polyethylene glycol bath at 20 ° C. to obtain an undrawn yarn.

Next, this unrolled yarn was drawn in the first stage at 4.5 times in a polyethylene glycol drawing bath at 165 ° C., and further drawn in the second stage at 1.42 times in a dry heat bath at 140 ° C. (total drawing). Magnification 6.4 times).

Subsequently, the resultant was passed through a dry heat bath at 155 ° C. at a processing magnification of 0.9 and subjected to a heat treatment to obtain a luminescent monofiment having a diameter of 0.285 mm.

The monofilament has a tensile strength of 65K.
g / mm ² , and as a result of evaluation of light emission persistence,
Light emission was performed in the same manner as before the immersion in pure water, and no decrease in light emission was observed.

Further, when the luminescent monofilament was actually wound on a reel for night fishing as a fishing line, and illuminated with a mercury lamp for 10 minutes every two hours, and the filaments caused by light emission when the light was long-cast at night were investigated, The filaments could be clearly recognized throughout the night. [Example 2] MFR (316 ° C, 5Kg) was 100,
Polyphenylene sulfide homopolymer having a water absorption of 0.2% is compared with N Luminova G30 manufactured by Nemoto Special Chemical Co., Ltd.
The resin composition containing 5% by weight of 0FF was melted at 330 ° C. by an extruder extruder, spun through a die having a hole diameter of 1.2 mm, and further cooled in a hot water bath at 85 ° C. to obtain an undrawn yarn. Was.

Next, the unstretched yarn was first stretched 3.8 times in a steam stretching bath at 100 ° C., and further stretched 1.13 times in a 150 ° C. dry heat bath (total stretching ratio). 4.3 times)
did.

Subsequently, the resultant was passed through a dry heat bath at 170 ° C. at a treatment magnification of 0.97 to perform a heat treatment to obtain a luminescent monofilament having a diameter of 0.285 mm.

The luminescent monofilament had a tensile strength of 52 Kg / mm ² , and was evaluated for sustained luminescence. As a result, the luminescent monofilament emitted light in the same manner as before pure water immersion, and no decrease in luminescence was observed.

Further, when this luminescent monofilament was actually wound on a reel for night fishing as a fishing line, and illuminated with a mercury lamp for 10 minutes every two hours, a line streak caused by light emission when the light was cast long distance at night was investigated. The filaments could be clearly recognized continuously throughout the night. Example 3 MFR (200 ° C., 2.16 Kg) was 1.
5, with a polylactic acid homopolymer having a water absorption of 0.2%, Nemoto Special Chemical N Luminescent G300FF
The resin composition containing wt% was melted at 230 ° C. by an extruder type extruder, spun through a die having a hole diameter of 1.5 mm, and further cooled in a hot water bath at 40 ° C. to obtain an undrawn yarn.

Next, the unstretched yarn was first stretched 8.0 times in a steam stretching bath at 100 ° C., and further stretched 1.25 times in a 150 ° C. dry heat bath (total stretching ratio). 10.0
Times).

Subsequently, the substrate was passed through a dry heat bath at 150 ° C. at a processing magnification of 1.0 and subjected to a heat treatment to obtain a luminescent monofilament having a diameter of 0.285 mm.

The tensile strength of this monofilament is 57K
g / mm ² , and as a result of evaluation of light emission persistence,
Light emission was performed in the same manner as before the immersion in pure water, and no decrease in light emission was observed.

Further, when this luminescent monofilament was actually wound on a reel for night fishing as a fishing line, and irradiated with a mercury lamp for 10 minutes every two hours, a line streak caused by light emission when the light was cast far away at night was investigated. The filaments could be clearly recognized throughout the night. [Example 4] In contrast to polypropylene terephthalate having an intrinsic viscosity of 1.0 and a water absorption of 0.2% (water absorption of 0.2%),
A resin composition containing 5% by weight of N Luminescent Luminova G300FF manufactured by Nemoto Special Chemical Co., Ltd. was melted at 280 ° C. by an extruder type extruder, spun through a die having a hole diameter of 0.8 mm, and further cooled in a hot water bath at 50 ° C. By doing so, an undrawn yarn was obtained.

Next, this undrawn yarn was drawn in the first stage at a draw ratio of 5.0 in a hot water drawing bath at 60 ° C., and further drawn in the second stage at a draw ratio of 1.1 in a dry heat bath at 130 ° C. (total drawing). Magnification 5.5 times).

Subsequently, the resultant was passed through a dry heat bath at 180 ° C. at a processing magnification of 1.0 and subjected to a heat treatment to obtain a luminescent monofilament having a diameter of 0.285 mm.

The tensile strength of this monofilament is 50K
g / mm ² , and as a result of evaluation of light emission persistence,
Light emission was performed in the same manner as before the immersion in pure water, and no decrease in light emission was observed.

Further, when this luminescent monofilament was actually wound on a reel for night fishing as a fishing line, and irradiated with a mercury lamp for 10 minutes every two hours, a line streak caused by light emission when the light was cast far away at night was investigated. The filaments could be clearly recognized continuously throughout the night. [Comparative Example 1] An extruder-type extruder comprising a resin composition containing 5% by weight of N night light luminova G300FF manufactured by Nemoto Special Chemical Co., Ltd. with respect to polycaproamide having a relative viscosity of 4.2 and a water absorption of 1.6%. At 280 ° C with a pore size of 0.8
The fiber was spun through a base having a diameter of 10 mm and further cooled in a water bath at 10 ° C. to obtain an undrawn yarn. .

Next, the unstretched yarn was first stretched 3.5 times in a steam stretching bath at 100 ° C. and further stretched 1.77 times in a dry heat bath at 200 ° C. (total stretching). Magnification 6.2
Times).

Subsequently, a monofilament having a diameter of 0.285 mm was obtained by passing through a dry heat bath at 180 ° C. at a treatment magnification of 0.9 and performing a heat treatment.

The tensile strength of this monofilament is 60K
g / mm ² , and as a result of evaluation of light emission persistence,
After immersion in pure water, no luminescence could be observed.

Further, when this monofilament was actually wound on a reel for night fishing as a fishing line, and illuminated with a mercury lamp for 10 minutes every two hours, a line of light emitted by long-distance casting at night was investigated. Although the streak was clearly recognized, the light emission gradually stopped during use, and the streak could not be recognized.

[0072]

As described above, the luminescent monofilament of the present invention can maintain excellent luminescence even after being immersed in water for a long period of time, and has a property that the afterglow characteristics can be maintained for a long time. Because it has, it is very useful for various marine and industrial materials applications, especially for fishing line applications in night fishing.

The fishing line composed of the luminescent monofilament of the present invention exhibits excellent luminescence when used for night fishing, has good visibility, and greatly contributes to improvement of fishing results.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masashi Abe 1 Kawara, Showa-cho, Okazaki City, Aichi Prefecture 1 Toray Monofilament Co., Ltd. 72) Inventor Yuhei Maeda 4845 Mishima-shi, Shizuoka Toray Industries, Inc. Mishima Plant (72) Inventor Minoru Tagaya 4845 Mishima-shi, Shizuoka Toray Industries, Inc. Mishima Factory F-term (reference) BB85 BB89 BB91 CC02 CC07 DD14 EE07 EE08 FF02 JJ02 JJ05 KK01 KK05 MF02

Claims (8)

[Claims] 1. A resin composition comprising a thermoplastic synthetic resin having a water absorption of 0.5% by weight or less after standing in water at 23 ° C. for 24 hours, measured according to ASTM D570, and a phosphorescent phosphor. A luminescent monofilament comprising at least a part of the components. 2. The phosphorescent phosphor of the formula M _1-x Al ₂ O
_4-X (where M represents at least one metal element selected from calcium, strontium and barium, and X represents a numerical value in the range of -0.33 to 0.60) The luminescent monofilament according to claim 1, wherein the crystal is crushed and classified. 3. The phosphorescent phosphor further comprises Eu (europium) and / or Dy (dystrosium) as an activator in a molar ratio of at least 0.001% to the metal element represented by M in the above formula. The luminescent monofilament according to claim 1, wherein the luminescent monofilament is added in an amount of 10% or less. 4. An average particle size (cumulative particle size distribution ratio of 50%) of the phosphorescent phosphor particles measured by a laser diffraction scattering method.
The luminescent monofilament according to any one of claims 1 to 3, wherein (D50)) is in a range of 1.0 to 3.5 µm. 5. The thermoplastic synthetic resin is at least one selected from the group consisting of polyvinylidene fluoride resin, polypropylene terephthalate, polylactic acid, polybutylene (succinate / adipate) copolymer, and polyphenylene sulfide resin. Claim 1
5. The luminescent monofilament according to any one of 4. 6. The light emission according to claim 1, wherein the amount of the phosphorescent phosphor added is in the range of 2 to 20% by weight based on the thermoplastic synthetic resin. Monofilament. 7. The monofilament according to JIS L10.
Tensile strength measured according to the provisions of 13 is 50Kg / mm
The luminescent monofilament according to any one of claims 1 to 6, wherein the number is ² or more. 8. A fishing line comprising the luminescent monofilament according to any one of claims 1 to 7.