JP2000192327A - Polyvinylidene fluoride-based resin yarn, its production and yarn for marine resources - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyvinylidene fluoride yarn having extremely excellent linearity in spite of high strength useful for a yarn for marine resources, especially for a fishing line. SOLUTION: This polyvinylidene fluoride yarn has >=0.04 mm diameter, satisfies conditions of >=5.0 orientation parameter Oa at each part from the surface of the yarn to <=10 μm toward the central point and >=6.0 orientation parameter Ob at each part from the surface of the yarn over 10 μm toward the central point in orientation parameters O by a laser Raman method shown by the formula O=Rh/Rv and has >=73% bending recovery ratio and >=5.5 g/d tensile strength. The yarn is drawn at a temperature Te satisfying the equation Tm-10 deg.C<=Te<Tm (Te is a drawing temperature ( deg.C) and Tm is the melting point ( deg.C) of the polymer) in 5.8-7.5 times draw ratio only by one stage.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinylidene fluoride fiber having excellent linearity and tensile strength, a method for producing the same, and a fiber for fishery materials suitably used as a fishing line.

[0002]

2. Description of the Related Art Polyvinylidene fluoride resin fibers have useful properties such as toughness, high specific gravity, refractive index close to water, and low water absorption. It is widely used for fishery materials such as fishing lines and fishing nets, and various industrial materials.

However, polyvinylidene fluoride resin fibers themselves have a relatively rigid fiber structure, and therefore have poor linearity as compared with other synthetic fibers such as polyamide resin fibers. In such a case, there is a problem that the fishing line is apt to stick and the fishing result is spoiled, which has been a big neck.

The prior art relating to such polyvinylidene fluoride resin fibers includes (A) a method for producing polyvinylidene fluoride fibers in which a first-stage drawing ratio is specified within a certain range by a two-stage drawing method (Japanese Patent Publication No. No. 53-22574), (B)
After the two-stage drawing, a tension heat treatment is performed at a temperature exceeding the melting point, and the surface is coated with a vinylidene fluoride-based resin monofilament whose surface layer is only low-oriented and a water-soluble resin (C).
Fishing line made of polyvinylidene fluoride-based resin monofilament with increased interline static friction coefficient (JP-A-8-214745)
Etc. have already been proposed.

[0005] That is, the production method (A) and the vinylidene fluoride resin monofilament (B) both have high knot strength or improved abrasion resistance. Fishing lines made of a polyvinylidene fluoride resin monofilament have been designed to improve the utilization rate of binding strength such as a needle knot, but none of them is necessarily satisfactory in terms of linearity.

[0006] Therefore, the conventional polyvinylidene fluoride resin fibers are all insufficient in linearity, and the improvement has been desired.

[0007]

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 polyvinylidene fluoride-based resin fiber having high strength and extremely excellent linearity, a method for producing the same, and a fiber for marine material which is suitably used particularly as a fishing line. It is in.

[0009]

A first gist of the present invention is as follows.
The diameter O is 0.04 mm or more, and the orientation parameter O by the laser Raman method represented by the formula O = Rh / Rv
(However, Rh: 1 in polarization measurement parallel to the fiber direction)
Rv: relative intensity of Raman band near 275 cm -1 and Raman band near 1430 cm -1, Rv: Raman band near 1275 cm -1 and 1 in polarization measurement perpendicular to fiber direction
Of the Raman band around 430 cm-1)
The orientation parameter Oa of each part from the fiber surface to the central point to 10 μm is 5.0 or more, and the orientation parameter Ob of each part from the fiber surface to the central point beyond 10 μm from the fiber surface to the central point is A polyvinylidene fluoride resin fiber characterized by satisfying each condition of 6.0 or more.

A second gist of the present invention is to form a pair of loops having a diameter of 0.04 mm or more and intersecting from the fiber, fixing the upper loop to a stopper, and applying a load to the lower loop. (A weight [g] of 1/2 of the fiber fineness [denier]) is applied for 3 minutes to obtain a pair of pine needle-shaped samples formed at the intersections of the loops.
The sample was cut to a length of about 3 cm, collected, left for 60 minutes, and measured from the open angle (θ) to obtain the formula: θ / 180 × 100
The flex recovery rate calculated in (%) is 73% or more and JI
The tensile strength measured according to the provisions of SL1013 is 5.
It is a polyvinylidene fluoride resin fiber characterized by being at least 5 g / d.

A third gist of the present invention is a method of melt-spinning, cooling, and subsequently stretching a polyvinylidene fluoride resin at a temperature Te satisfying the following formula (I) and a stretching ratio of 5. The method for producing a polyvinylidene fluoride-based resin fiber as described above, wherein the stretching in the range of 8 to 7.5 times is performed in only one step.

Tm−10 ° C. ≦ Te <Tm (I) where Te = stretching temperature (° C.) Tm = melting point of polymer (° C.)

Further, a fourth aspect of the present invention resides in a fiber for marine material characterized by comprising the above-mentioned polyvinylidene fluoride resin fiber.

[0014]

DETAILED DESCRIPTION OF THE INVENTION First, a polyvinylidene fluoride resin fiber according to the first aspect of the present invention will be described. Hereinafter, the above fiber is abbreviated as fiber A. The polyvinylidene fluoride resin constituting the fiber A is a polyvinylidene fluoride homopolymer or copolymer containing at least 80% by weight of a vinylidene fluoride component. Here, when the amount of the copolymer is less than 20% by weight, examples of the copolymerization component include tetrafluoroethylene, trifluoromonochloroethylene, trifluoroethylene, monofluoroethylene, hexafluoropropylene, and a mixture thereof. Is preferred. It is also possible to blend another vinylidene fluoride homopolymer and / or copolymer with polyvinylidene fluoride having a vinylidene fluoride component content of 80% by weight or more. However, if the content of the vinylidene fluoride component in the polymer or the polymer mixture is less than 80% by weight, the crystallinity is lowered, and it is difficult to achieve the properties aimed at by the present invention.

The polyvinylidene fluoride resin used in the present invention preferably has an intrinsic viscosity index (ηinh) of 0.8 or more, particularly 1.0 or more, as measured with a 0.4 g / cc solution of dimethylformamide. , Ηinh is less than 0.8, sufficient physical properties may not be obtained.

Further, the polyvinylidene fluoride resin used in the present invention may contain various additives such as pigments, dyes, light stabilizers, ultraviolet absorbers, antioxidants, crystallization inhibitors, and plasticizers. Can be added in the polymerization step, after the polymerization, or immediately before the spinning, as long as the performance is not hindered.

The characteristic of the fiber A is that it has a fiber structure which is uniform and extremely highly oriented over the entire cross section of the fiber. That is, the fiber A is, for the reason described below,
The orientation degree parameter O by the laser Raman method represented by the formula O = Rh / Rv (where Rh is the relative intensity of the Raman band near 1275 cm @ -1 and the Raman band near 1430 cm @ -1 in polarization measurement parallel to the fiber direction, Rv :
Of the Raman band near 1275 cm -1 and the Raman band near 1430 cm -1 in the polarization measurement perpendicular to the fiber direction).
The orientation parameter Oa of each part up to 5.0 μm is 5.0 or more, and the orientation parameter Ob of each part from the fiber surface to the central point beyond 10 μm from the fiber surface to the central point is 6.0.
It is important to satisfy each condition of 0 or more.

As described above, conventional polyvinylidene fluoride fibers are mainly used for fishery materials such as fishing lines and fishing nets because of their toughness, high specific gravity, and refractive index close to water. Although widely used, polyvinylidene fluoride resin fibers themselves have a relatively rigid fiber structure, and therefore have poor linearity as compared with other synthetic fibers such as polyamide resin fibers. That is, for example, when used for fishing line, the bottleneck is that a curl is likely to be formed after winding on a reel, or a chip is likely to occur at the stage of making a device such as a knot. And
Poor linearity and poor knotting not only reduce handling, but also cause unnatural movement of fishing baits, resulting in impaired fishing results.

However, polyvinylidene fluoride resin fibers having a diameter of 0.04 mm or more generally have a non-uniform fiber orientation structure from the fiber surface of the fiber cross section toward the center point due to its thickness. The degree of orientation in the fiber axis direction is small near the surface, rises inward toward the center point, and the influence of the decrease in orientation extends to about 10 μm from the surface. The main reason for this is considered to be a difference in heat history between the inner and outer layers of the fiber in the spinning process, especially in the drawing process, and the orientation-reduced portion is at most about 10 μm from the surface of the fiber toward the center point, Surprisingly, it hardly changes with the thickness of the fiber. And the present inventors have found that the non-uniform structure of the degree of orientation of the fiber cross section affects the linearity,
Polyvinylidene fluoride based material having excellent linearity and toughness, with less decrease in the degree of orientation at each part from the fiber surface to the center to 10 μm, and having a highly oriented fiber structure throughout the fiber They have found that they are effective for obtaining fibers, and have reached the present invention.

That is, the parameters of the fiber A of the present invention are defined based on the above findings.
The fiber A has a uniform degree of orientation of the fiber cross section as compared with the conventional polyvinylidene fluoride resin fiber, that is, the degree of orientation parameter Oa of each portion from the fiber surface to the central point up to 10 μm. 5.0 or more, the orientation parameter Ob of each part from the fiber surface to the center point beyond 10 μm from the fiber surface to the center point satisfies each condition of 6.0 or more. The linearity is balanced and excellent.

Here, the orientation parameter in the fiber axis direction by the laser Raman method will be described in more detail.

The Raman band around 1430 cm -1 is C-
Raman band around 1275 cm -1 is C
-C skeleton stretching vibration and CF stretching vibration. 14
The transition moment of the Raman band near 30 cm -1 is almost perpendicular to the molecular chain, whereas the transition moment is 1275.
The transition moment of the Raman band near cm -1 is rather oriented in a direction parallel to the molecular chain. Therefore, the ratio R = I1275 / I1430 is a parameter expressing the molecular orientation. The larger the parameter, the more the molecular chain is oriented in the measured polarization direction. The characteristics of the orientation parameters are summarized as follows. Rh: band relative intensity in polarization measurement parallel to the fiber direction (I1275 / I1430) Rv: band relative intensity in polarization measurement perpendicular to the fiber direction (I1275 / I1430) Rh: The larger the degree, the greater the degree of orientation in the fiber axis direction. Show. Rv: The larger the Rv, the greater the degree of orientation in the direction perpendicular to the fiber.
In other words, the smaller the value, the higher the degree of orientation in the fiber axis direction. Rh / Rv: The larger the ratio, the higher the degree of orientation in the fiber axis direction. This parameter becomes 1 when the degree of fiber orientation is 0.

Next, a polyvinylidene fluoride resin fiber according to the second aspect of the present invention will be described. Hereinafter, the above fiber is abbreviated as fiber B. The polyvinylidene fluoride resin constituting the fiber B is the same as that of the fiber A.

The feature of the fiber B is that the fiber B has a diameter of 0.04 mm or more and has specific values for the flexural recovery rate and the tensile strength measured by the above-mentioned measuring method. That is, for the reason described below, it is important that the fiber B has a flexural recovery rate of 73% or more and a tensile strength of 5.5 g / d or more.

That is, the tensile strength is a physical property that affects the breaking of a thread, and a fiber having a high tensile strength makes it possible to catch a larger fish in fishing. On the other hand, as described above, the linearity is a necessary property that affects handling and fish eating, and the above-described bending recovery rate is defined.

Since the fiber B has a higher flexural recovery rate and a higher tensile strength than conventional polyvinylidene fluoride resin fibers, it has less thread breakage, has better operability to catch fish, and has improved fishing results. . In addition, the fiber B can also have the values of Oa and Ob defined above at the same time.

The fibers A and B have a diameter of 0.1 mm.
Although it is not less than 04 mm, its use is mainly in the range of 0.04 to 0.45 mm in diameter for applications such as fishing line, and it is particularly useful in that category.

Next, a manufacturing method according to the third aspect of the present invention will be described. Both the fibers A and B of the present invention have a draw ratio of 5.8 to 7.0 at a temperature Te that satisfies the above-mentioned formula (I) in a method in which a polyvinylidene fluoride resin is melt-spun, cooled, and subsequently drawn. It can be manufactured according to a manufacturing method in which stretching in a range of 5 times is performed in only one step.

In the present invention, when melt-spinning polyvinylidene fluoride resin fibers, ordinary conditions using an extrusion spinning machine can be adopted.
30-320 ° C., extrusion pressure 10-500 Kg / cm 2,
Cap diameter 0.1-5mm, spinning speed 0.3-100m /
A range such as minutes can be appropriately selected.

After the spun monofilament passes through a short gas zone, it is cooled in a cooling bath usually at a temperature of about 20 ° C. The cooling medium used here is water, glycerin and polyfluorinated compounds such as polyethylene glycol. A liquid compound that is inert to the vinylidene-based resin may be used.

The cooled fiber is sent to the first-stage drawing zone after the cooling medium is removed by an ordinary method. The atmosphere (bath) at the time of drawing and heat-setting in the present invention is, for example, polyethylene glycol. , Glycerin and silicone
A heat medium bath in which a liquid such as oil is heated, a dry hot gas bath, and a heated or pressurized steam bath are used.

Here, it is important that stretching is performed in only one step, and the stretching ratio is 5.8 to 7.5 times, preferably 5.
The stretching temperature is 9 to 6.5 times, and the stretching temperature is selected from the range of the formula (I). In addition, the passing time of the stretching bath is usually several seconds at most, and no particular preheating is required.

That is, the feature of this production method is that a high draw ratio is performed at a stretch at a high temperature close to the melting point of the polymer, thereby achieving a uniform and highly oriented fiber structure from the fiber surface to the center point. it can. Further, in the present invention, it is more preferable to perform relaxation heat fixing after stretching.

The polyvinylidene fluoride resin fiber of the present invention thus obtained has excellent linearity and tensile strength, and thus is extremely useful for use as a fiber for fishery materials such as fishing line.

[0035]

EXAMPLES Next, the present invention will be described based on examples, but the present invention is not limited to the following examples unless it departs from the gist. In addition, evaluation of the fiber obtained in the following examples was performed according to the following method.

(1) Tensile strength: measured in accordance with JIS L1013.

(2) Orientation degree parameter by laser Raman method Apparatus: Ramanor T-64000 (Jobin Yvon /
Atago Bussan) Measurement method: The fiber was embedded in an epoxy resin, a longitudinal section was created by a microtome, and the Raman spectrum of each section was measured for the section by the microprobe method (Spot diameter: 1). Measurement points are 1 μm, 2 μm, 3 μm, 4 μm, 6 μm, and 8 μm from the fiber surface toward the center point.
m, 10 μm according to each part of 10 μm and the thickness of the fiber
Several points from the point m to the center point were appropriately selected. The orientation parameter O of each part of the fiber cross section is calculated from the Raman spectrum by the method described in the text, where Oa is the lowest value of O of each part from 1 to 10 μm from the fiber surface, and Ob is 10 μm from the fiber surface. And the lowest value of O at each site up to the center point.

(3) Bending recovery rate: A set of two crossed loops is formed, the upper loop is fixed to a clasp, and the lower loop is loaded with a load (g [1/2] of the fiber fineness [denier]). ] For 3 minutes. Next, a pair of pine needle-shaped samples formed at the intersections of the loops were cut to a length of about 3 cm, collected, left for 60 minutes, and then measured for the opening angle (θ). The recovery rate was calculated. Flex recovery rate (%) = θ / 180 × 100 The number of measurements was four, and the average value was shown. The larger the value, the better the bending recovery.

Example 1 Dimethylformamide 0.1
Intrinsic viscosity index (ηin at 30 ° C. of 4 g / cc solution)
h) A polyvinylidene fluoride polymer chip having a melting point of 1.2 (melting point: 176 ° C.) is melted at 260 ° C. by an extruder type spinning machine, spun through a die having a hole diameter of 1.5 mm, and further subjected to a polyethylene glycol bath at 20 ° C. Cooled in.

Next, this undrawn yarn was drawn in a first stage drawing bath of polyethylene glycol at 168 ° C. by 6.0 times only in one step to obtain a polyvinylidene fluoride resin fiber having a diameter of 0.22 mm. .

Example 2 After stretching in one step in the same manner as in Example 1, the fiber was further passed through a dry heat bath at 155 ° C. at a ratio of 0.98 times to remove a polyvinylidene fluoride resin fiber having a diameter of 0.22 mm. Obtained.

Example 3 The same polyvinylidene fluoride polymer chip as in Example 1 was extruded using an extruder type spinning machine.
It was melted at 60 ° C., spun through a die having a pore size of 0.4 mm, and further cooled in a polyethylene glycol bath at 20 ° C.

Next, this unstretched yarn is stretched in the first stage drawing bath of polyethylene glycol at 167 ° C. by 6.0 times only in one stage, and then passed through a dry heat bath at 155 ° C. by 0.98 times. As a result, a polyvinylidene fluoride resin fiber having a diameter of 0.07 mm was obtained.

Example 4 The same polyvinylidene fluoride polymer chips as in Example 1 were extruded using an extruder type spinning machine.
It was melted at 60 ° C., spun through a die having a pore size of 2.0 mm, and further cooled in a polyethylene glycol bath at 20 ° C.

Next, this unstretched yarn is stretched in a first stage drawing bath of polyethylene glycol at 169 ° C. by 6.0 times only in one stage, and subsequently passed through a dry heat bath at 155 ° C. by 0.98 times. As a result, a polyvinylidene fluoride resin fiber having a diameter of 0.40 mm was obtained.

Comparative Example 1 The stretching ratio of only one stage was 5.6.
Except for doubling, a polyvinylidene fluoride resin fiber having a diameter of 0.22 mm was obtained by the same manufacturing method as in Example 2.

[Comparative Example 2] The stretching ratio of only one stage was 7.7.
Except for doubling, a polyvinylidene fluoride resin fiber having a diameter of 0.22 mm was obtained by the same manufacturing method as in Example 2.

[Comparative Example 3] The stretching temperature of only one stage was 165
A polyvinylidene fluoride resin fiber having a diameter of 0.22 mm was obtained in the same manner as in Example 2 except that the temperature was changed to ° C.

[Comparative Example 4] The stretching temperature of only one stage was set to 180.
A polyvinylidene fluoride resin fiber having a diameter of 0.22 mm was obtained in the same manner as in Example 2 except that the temperature was changed to ° C.

[Comparative Example 5] The first stage of stretching was carried out at 160 ° C.
The same process as in Example 2 was repeated except that the film was stretched at 4.5 times and then stretched in two steps at 165 ° C. and 1.45 times (total stretching ratio of 6.5 times). A vinylidene fluoride resin fiber was obtained.

[Comparative Example 6] After the spun yarn was cooled in a water bath at 40 ° C, the first stage drawing was carried out at 165 ° C and 5.2 times, and subsequently at 170 ° C and 1.10 times (total drawing ratio). 6.2 times)
, And a polyvinylidene fluoride resin fiber having a diameter of 0.22 mm was obtained in the same manner as in Example 2 except that the fiber was passed through a dry heat bath at 85 ° C. at a ratio of 0.95. Was.

[Comparative Example 7] The first stretching was carried out at 165 ° C.
5.4 times, followed by two-stage stretching at 165 ° C. at 1.18 times (total stretching ratio of 6.4 times), and further passing through a dry heat bath at 180 ° C. at 1.10 times. By the same method as in Example 2, a polyvinylidene fluoride resin fiber having a diameter of 0.22 mm was obtained.

[Comparative Example 8] The first-stage stretching was performed at 167 ° C and 5.
Except that the film was stretched at 7 times, stretched at 167 ° C. to 1.10 times (total stretch ratio of 6.3 times) and stretched in two steps, and further passed through a dry heat bath at 155 ° C. at 0.90 times. By the same method as in Example 2, a polyvinylidene fluoride resin fiber having a diameter of 0.22 mm was obtained.

Table 1 also shows the results of evaluating the above-mentioned properties of each of the polyvinylidene fluoride-based resin fibers thus obtained.

[0055]

[Table 1]

[0056]

As described above, according to the present invention,
It is possible to efficiently produce polyvinylidene fluoride-based resin fibers with high strength and extremely excellent linearity, and this polyvinylidene fluoride-based resin fiber is suitable for use as a fiber for fishery materials such as fishing lines. Can be used for

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shin Okano No. 1 Kawahara, Showa-cho, Okazaki-shi, Aichi Prefecture Toray Monofilament Co., Ltd. (72) Inventor Yuhei Maeda 1- Exit of Yahagi-cho, Okazaki-shi, Aichi Toray Co., Ltd. (72) Inventor Hideo Nakata 1st exit of Yahagi-cho, Okazaki City, Aichi Prefecture Toray Co., Ltd. Okazaki Plant F-term (reference) 2B107 CA04 4L035 BB31 BB57 BB74 BB85 BB89 BB91 DD14 EE07 EE08 EE20 FF02 MB15

Claims (6)

[Claims] 1. The method according to claim 1, wherein the diameter is at least 0.04 mm and the formula O =
Orientation degree parameter O by the laser Raman method represented by Rh / Rv (where Rh: Raman band near 1275 cm @ -1 and 143 in polarization measurement parallel to the fiber direction)
Relative intensity of the Raman band near 0 cm -1, Rv (the relative intensity of the Raman band near 1275 cm -1 and the Raman band near 1430 cm -1 in polarization measurement perpendicular to the fiber direction) from the fiber surface toward the center point. And the orientation parameter Oa of each part from the fiber surface to the center point and beyond 10 μm to the center point is 6.0 or more. A polyvinylidene fluoride resin fiber characterized by satisfying the following. 2. A pair of two loops each having a diameter of 0.04 mm or more and intersecting from the fiber are formed, an upper loop is fixed to a clasp, and a load (a fiber fineness [denier] of 1%) is applied to a lower loop. / 2 load (g) for 3 minutes, a pair of pine needle-shaped bent samples formed at the intersections of the loops were cut to a length of about 3 cm and collected.
From the open angle (θ) measured after standing for 60 minutes, the formula: θ
/ Bending recovery rate calculated by 180 × 100 (%) is 73%
A polyvinylidene fluoride resin fiber having a tensile strength of 5.5 g / d or more as measured according to JIS L1013. 3. The polyvinylidene fluoride resin fiber according to claim 2, wherein said flexural recovery ratio is 73 to 85%, and said tensile strength is 5.5 to 7.0 g / d. 4. The polyvinylidene fluoride resin fiber according to claim 1, having a diameter of 0.04 to 0.45 mm. 5. A polyvinylidene fluoride resin is melt-spun.
In the method of cooling and subsequently stretching, at a temperature Te satisfying the following formula (I), the stretching ratio is 5.8 to 7.5.
The method for producing a polyvinylidene fluoride-based resin fiber according to any one of claims 1 to 4, wherein the stretching in the double magnification is performed in only one step. ◎ Tm−10 ° C. ≦ Te <Tm (I) where Te = stretching temperature (° C.) Tm = melting point of polymer (° C.) 6. A fiber for a marine material, comprising the polyvinylidene fluoride resin fiber according to any one of claims 1 to 4.