JP2001148981A - Colored fishing gut - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored fishing gut which is a colored fishing gut composed of a polyvinylidene fluoride-based resin monofilament having far more improved slipperiness and feeling of a line than those of a conventional gut. SOLUTION: This colored fishing gut is characterized in that the gut is composed of a polyvinylidene fluoride-based resin monofilament dyed with a conjugated type cationic dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored tex made of polyvinylidene fluoride resin monofilament, which has much better thread slipperiness and feeling than conventional ones.

[0002]

2. Description of the Related Art Polyvinylidene fluoride resin monofilaments are excellent in toughness, impact resistance, transparency, light resistance, etc., are easily immersed in water at a high specific gravity (1.8), and have a refractive index of water (1). .33) (1.44)
And has extremely low surface reflection in water, so that it has been effectively used particularly for Tegus applications represented by Harris.

On the other hand, with the recent increase in the fishing boom and the fishing population, the use of specialty yarns in accordance with the use has been advanced, and the required performance thereof has been diversified.

[0004] In recent years, polyvinylidene fluoride resin monofilaments have been
It is further being used as a dedicated line such as a line for lure, a line for throw fishing, and a line with a fishing hook.

[0005] However, in the case of dedicated lines such as a lure line, a throw fishing line, and a fishing line with a fishing rod, it is required to color-code a single color or a plurality of colors according to the purpose of use. Polyvinylidene fluoride-based resin monofilaments were originally used in a colorless state reluctantly because they were originally extremely difficult to dye.

In view of such circumstances, the present inventors have studied a method for dyeing a polyvinylidene fluoride-based resin monofilament and a colored tex formed from the monofilament, and have already proposed it in Japanese Patent Application Laid-Open No. Hei 7-252722.

That is, the above proposal by the present inventors is as follows.
When dyeing a polyvinylidene fluoride resin monofilament, the surface tension of a dyeing solution using a disperse dye is adjusted to a specific range, and a dyeing method by specifying heat treatment conditions after dyeing, and the colored polyvinylidene fluoride resin monofilament The present invention relates to a colored tex comprising:

[0008] However, according to the above-mentioned proposals, although remarkable improvements in dyeing fastness, leveling property, tensile breaking strength and stiffness of the obtained colored tex are remarkable, the slipperiness and feeling of the yarn are improved. It was not always satisfactory in terms of the performance required as a tex, and the fact is that further improvements have been desired.

[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 colored tex comprising polyvinylidene fluoride-based resin monofilament, which has a far superior thread sliding property and feeling than conventional ones.

[0011]

Means for Solving the Problems In order to achieve the above object, the colored tex of the present invention is characterized by comprising a polyvinylidene fluoride resin monofilament dyed with a conjugated cationic dye.

In the colored tex of the present invention, the yarn of the polyvinylidene fluoride resin monofilament is used.
The coefficient of static friction between yarns (μs) is less than 0.2, the diameter of the polyvinylidene fluoride resin monofilament is in the range of 0.05 to 0.75 mm, and the conjugated cationic dye is a methine cation. Dye, at least one selected from azo-based cationic dyes and oxazine dyes are all preferable conditions,
By satisfying these conditions, more excellent effects can be expected.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the colored tex of the present invention will be described in detail.

The polyvinylidene fluoride resin monofilament used in the present invention means that the vinylidene fluoride component is 80%.
It is a monofilament composed of a polyvinylidene fluoride homopolymer or copolymer containing at least 10% by weight. Here, the other copolymer component occupying 20% by weight or less includes tetrafluoroethylene, hexafluoropropylene, trifluoromonochloroethylene, trifluoroethylene and the like. Further, a polyvinylidene fluoride copolymer of 20% by weight or less can be blended with a homopolymer of polyvinylidene fluoride of 80% by weight or more. In addition, a compatible polymer such as polymethyl methacrylate and a plasticizer component such as an aliphatic polyester can be further added to the polyvinylidene fluoride-based resin, if necessary.

As a method for producing a polyvinylidene fluoride resin monofilament, a known method described below can be applied.

That is, a polyvinylidene fluoride polymer chip is supplied to a melt spinning machine, melted at a temperature of about 260 to 280 ° C., and spun from a spinneret to obtain a spun monofilament.

Next, the spun monofilament is provided immediately below the spinneret, passes through a range of an atmosphere length of 150 mm heated to a temperature of about 300 ° C., and immediately in a low-temperature liquid having a temperature of 20 ° C. or less. And then rapidly solidified to form an undrawn monofilament.

As the low-temperature liquid in the cooling and solidification,
Water, polyvinylidene fluoride resin such as glycerin and polyethylene glycol and an inert liquid are used.

Subsequently, the undrawn monofilament cooled and solidified is continuously sent to a drawing zone such as dry heat, a steam atmosphere, or a liquid medium, and subjected to one-stage or two-stage or more multi-stage drawing. The stretching ratio in this stretching is 5.5-7.
A range of 5 times is preferable, and 0.85 to 1.
It is desirable to perform the heat treatment at 120 to 300 ° C. under 15 times tension or relaxation.

The average diameter of the stretched vinylidene polyfluoride-based resin monofilament thus obtained is desirably in the range of 0.05 to 0.75 mm in consideration of application to tex.

[0021] The colored tex of the present invention is obtained by spinning,
It is obtained by running the polyvinylidene fluoride resin monofilament obtained by stretching again, or by performing the following dyeing in the running process following the stretching step.

The dyeing solution used for dyeing is described in JP-A-7-25.
No. 2,722, the surface tension is 30 dyn.
The surface tension of water is reduced to 30 dyne / cm or less by adding an aqueous dispersion prepared so as to have a range of e / cm or less, for example, a fluorine-based surfactant, a fluororesin, or a silicon-based component to water. A mixture prepared by adding a conjugated cationic dye to the lowered aqueous dispersion so as to have a desired concentration is used.

Here, the type of dye used is limited to conjugated cationic dyes, and other dyes,
For example, when a disperse dye or the like is used, it is not possible to obtain a colored tex having excellent thread slipperiness and feeling, which is an object of the present invention.

The conjugated cationic dye used in the present invention means a methine cationic dye, an azo cationic dye, an oxazine dye and the like. Examples of the methine-based cationic dye include polymethine-based cationic dyes such as C.I. I. B
asicRed 14, 27, C.I. I. BasicOra
nge21, C.I. I. Basic Yellow 11, 2
2, 23, C.I. I. BasicViolet 16, 39
Azomethine-based cationic dyes such as C.I. I. Bas
ic Yellow 51, a diazatrimethine-based cationic dye C.I. I. Basic Yellow 24, 28, and the like, and the azo-based cationic dyes include triazole azo-based cationic dyes such as C.I. I. BasicRed2
2, C.I. I. Basic Yellow 25 and other thiazole azo-based cationic dyes such as C.I. I. BasicRe
d29 and other benzothiazole azo-based cationic dyes such as C.I. I. Basic Red 39, C.I. I. Basic
Blue 41, 66 and the like; I. BasicBlue3 is a specific example, but is not limited thereto.

The concentration of the dye in the dyeing solution can be arbitrarily selected according to the purpose, but is usually preferably about 0.1 to 10% by weight. If the concentration is too low, not only light dyeing and light resistance are deteriorated, but also the color fading tends to be severe, while if the concentration is too high, the washing workability of the dye attached to the surface of the polyvinylidene fluoride resin monofilament tends to deteriorate. Becomes

The contact of the polyvinylidene fluoride resin monofilament with the above-mentioned dyeing solution is carried out by passing the running monofilament through a dyeing solution at ordinary temperature. In this case, the contact time is as short as several seconds. I can't tell.

Next, the polyvinylidene fluoride resin monofilament contacted with the above-mentioned dyeing solution was immediately heated to 120 ° C.
Above, preferably in a dry heat bath heated to 130 ° C. or higher,
Processing magnification 0.85 to 1.15 times, preferably 0.90 to
Heat treated at 1.10 times.

Here, by setting the temperature of the dry heat bath to 120 ° C. or more, the dye can be sufficiently adsorbed in the polyvinylidene fluoride resin monofilament. The upper limit of the temperature of 120 ° C. or higher is not particularly limited, but it is preferable that the temperature is lower than the normal dye sublimation temperature (300 ° C.). However, the heat treatment time is usually several seconds to 60.
Since the heat treatment is performed in a short time of about seconds, for example, when the heat treatment is performed in a very short time of 10 seconds or less, a condition of 300 ° C. or more may be employed.

Further, by setting the processing magnification to 0.85 times to 1.15 times, it becomes possible to obtain high-quality colored tex without causing a decrease in strength or quality.

After contacting with the dyeing solution as described above, a dry heat treatment is performed, and the polyvinylidene fluoride resin monofilament adsorbed with the dye is then subjected to reduction washing or the like in order to remove excess dye attached to the surface. While scouring is performed, an oil agent is applied as needed.

The colored tex comprising the polyvinylidene fluoride resin monofilament of the present invention thus obtained is
In addition to excellent dyeing fastness, level dyeing, tensile breaking strength, and stiffness, the yarn has excellent yarn slipperiness and feeling that could not be obtained by the prior art.

Although the reason for the effect of the present invention is not necessarily clear, it is presumed as follows.

That is, the colored tex made of the polyvinylidene fluoride resin monofilament dyed with the conjugated cationic dye of the present invention adheres to the surface of the tex and remains because the specific water-soluble dye is used. It is considered that the slip property is remarkably improved by almost eliminating the dye component.

On the other hand, in a colored tex made of a conventional polyvinylidene fluoride resin monofilament dyed with a conventional disperse dye, the disperse dye itself is insoluble in water, so that the dye remains on the surface of the tex and the slip property of the yarn is reduced. Is considered to be impaired.

The slip property of the yarn of the colored tex of the present invention can be measured by the coefficient of friction between the yarn (μ) measured by the method described below.
s).

That is, the yarn-to-yarn static friction coefficient (μs) in the present invention refers to the MA shown in FIG. 1 and FIG.
EDA MFG. CO. It is a value measured by the following method using a static friction tester.

First, a pair of circular mounting frames 2 having 32 grooves 2a at regular intervals on a circumference of 32.5 mm in diameter are arranged in parallel with a length of 24 mm. The test monofilaments 1 are tensioned horizontally at a tension of 1 g / d one by one at intervals of a total of 32 between the grooves 2a to form a cylindrical thread having a diameter of 32.5 mm. I do.

A similar test monofilament 1 'is suspended at a right angle substantially at the center of the cylindrical monofilament 1 having a width of 8 mm due to the interposition of the intermediate frame 3.

Next, a load 4 is hung on one end of the monofilament 1 'to make its initial tension (T ₀ ) 1 g / d, the other end is connected to a tension detector 5, and a pair of circular attachments is mounted. Frame 2 is rotated in the direction of the arrow (load side) at a rotational speed of 0.02 m.
By rotating at / min, the tension (T ₁ ) generated at the other end is measured by the tension detector 5, and the static friction coefficient (μs) between the yarns in this case is calculated by the following equation.

Μs = (T ₁ −T ₀ ) / (T ₁ + T ₀ ) The smaller the coefficient of static friction between the yarns (μs), the better the slipperiness of the yarns. Yarn-to-yarn static friction coefficient (μs) of colored tex made of polyvinylidene fluoride-based resin monofilament dyed by
On the other hand, since the coefficient of friction (μs) between the yarn and the yarn of the colored tex of the present invention is very small, less than 0.2, the slipperiness of the yarn is far improved compared with the conventional art. Therefore, the colored grease of the present invention in which the yarn has improved slipperiness has improved the flexibility required for the performance of the glove, and not only reduces the parquet from the reel when wound on the reel, but also reduces the grease. The smoothness of the surface eliminates the feeling of roughness and greatly improves the texture of the tex, so it is used as colored tex, especially for harris, lure lines, throwing fishing line, and fishing line with a fishing boat. Very useful for

[0041]

EXAMPLES The present invention will be described below with reference to examples. The method for evaluating colored tex according to the present invention was carried out according to the following method. (A) Color fastness: Sunshine Long Life Weather Meter (WEL-SUN-HC) manufactured by Suga Test Instruments Co., Ltd.
The color fastness was evaluated by the degree of discoloration after irradiation for 50 hours using H). The evaluation method used a gray scale for discoloration and fading according to JIS L0804 to determine what number of the color chart the degree of discoloration before and after the process was, and evaluated the degree.
(For example, if it corresponds to the color difference of No. 4, it is displayed as 4th grade). In other words, the degree of discoloration and discoloration increases from the fifth grade to the first grade. (B) Leveling: Judgment with the naked eye (…: good, x: poor stained state). (C) Yarn-yarn static friction coefficient: Measured by the method described above. (D) Hand: rough feeling when the yarn is traced with a finger in the length direction (○: no rough feeling;
... with a feeling of roughness). (E) Tensile breaking Measured according to the method of JIS L1013. Example 1 A 0.4 g / cc dimethylformamide solution had an intrinsic viscosity index (ηinh) of 1.2 at 30 ° C.
Polyvinylidene fluoride polymer chip (melting point Tm = 17)
6 ° C.) at an extruder type spinning machine of 260 ° C.,
The fiber was spun through a die having a pore size of 1.3 mm and further cooled in a polyethylene glycol bath at 20 ° C.

Next, the undrawn yarn is drawn 4.5 times in a first stage drawing bath of polyethylene glycol at 160 ° C., and subsequently drawn in a bath of polyethylene glycol at 165 ° C.
After a 98-fold relaxation heat treatment, the film was stretched again 1.5-fold in a second stage polyethylene glycol stretching bath at 165 ° C.

Subsequently, a dry heat treatment is further performed to remove the stretching strain of the drawn monofilament.
After the monofilament is brought into contact with a predetermined dyeing solution in this step, a dry heat treatment is performed at 150 ° C. and 0.90 times, and the dyeing is performed to form a colored tex made of a polyvinylidene fluoride resin monofilament having a diameter of 0.22 mm. Obtained.

The dyeing solution used here was a fluorosurfactant "Unidyne DS-202" manufactured by Daikin Industries, Ltd.
The surface tension is reduced to 14 dyne by adding 1% by weight.
To 97.5% by weight of the aqueous dispersion prepared to
Company A's BasacrylBrilliantRedBG
It contains 2.5% by weight of (CI Basic Violet 16). [Examples 2 to 7] The dyes in Example 1 were changed to the respective dyes shown in Table 1. Comparative Example 1 The dye used in Example 1 was changed to a red disperse dye (Dyanix ACE Red: Disperse Dye A, manufactured by Mitsubishi Kasei Hoechst). Comparative Example 2 The dye used in Example 1 was changed to a yellow disperse dye (Dyanix ACE Yellow: Disperse Dye B, manufactured by Mitsubishi Kasei Hoechst Co.). Comparative Example 3 The dye in Example 1 was changed to a blue disperse dye (Dyanix ACE Blue: Disperse Dye C, manufactured by Mitsubishi Kasei Hoechst).

Table 1 shows the evaluation results of the colored tex made of each polyvinylidene fluoride resin monofilament thus obtained.

[0046]

[Table 1] As is evident from the results in Table 1, the colored tex (Examples 1 to 7) comprising the polyvinylidene fluoride resin monofilament of the present invention satisfies the dyeing fastness, leveling property, and tensile breaking strength, as well as the conventional technology. It has the slipperiness and feeling of the yarn that could not be obtained.

On the other hand, the colored tex formed of a conventional polyvinylidene fluoride resin monofilament using a disperse dye (Comparative Examples 1 to 3) is excellent in dyeing fastness, leveling property, tensile breaking strength, and the like. Cannot satisfy the slipperiness and feeling of the leather.

When the colored tex made of the polyvinylidene fluoride resin monofilament of the present invention was wound around a reel as a lure fishing line, the variation from the reel was significantly reduced as compared with the conventional colored tex.

[0049]

As described above, the colored tex of the present invention makes use of the excellent properties of polyvinylidene fluoride-based resin monofilaments and has excellent color fastness.
It satisfies the smoothness and feel of the yarn in addition to the leveling properties, tensile breaking strength, and crispness.Taking advantage of the characteristics, it is particularly useful for harris, lure lines, throwing fishing line, and fishing boat hangers. It is extremely useful for applications such as attached yarn.

[Brief description of the drawings]

FIG. 1 is a front view showing a main part of an apparatus used for measuring a static friction coefficient (μs) between yarns.

FIG. 2 is a side view of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Test monofilament 2 Mounting frame 3 Intermediate frame 4 Load 5 Tension detector

Claims (4)

[Claims] 1. A colored tex comprising a polyvinylidene fluoride resin monofilament dyed with a conjugated cationic dye. 2. The colored tex according to claim 1, wherein the polyvinylidene fluoride resin monofilament has a yarn-to-yarn static friction coefficient (μs) of less than 0.2. 3. The colored tex according to claim 1, wherein a diameter of the polyvinylidene fluoride resin monofilament is in a range of 0.05 to 0.75 mm. 4. The method according to claim 1, wherein the conjugated cationic dye is at least one selected from a methine cationic dye, an azo cationic dye, and an oxazine dye. Colored tex.