JPH0350001B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a monofilament of vinylidene fluoride resin (hereinafter typically referred to as "PVDE") that satisfies knot strength and tensile strength and has significantly superior abrasion resistance. . [Background technology] In addition to weather resistance, PVDF monofilament has
It has excellent knot strength and tensile strength, and is suitable for use as a material for fishing lines, fishing nets, ropes, etc. However, in the use of fishing lines and the like, since they are rubbed by rocks, sand, floating rubber, etc., abrasion resistance is also important in addition to the above-mentioned physical properties. Up until now, the manufacturing method for PVDF monofilament has been to carry out one drawing heat setting operation after melt spinning.
A method in which secondary stretching and secondary stretching are carried out at 80°C or higher (Japanese Patent Publication No. 43-13399), and the above primary stretching is carried out at a ratio between the primary inflection point and the secondary inflection point, and the stretching temperature is 150°C or higher. Method of heating to 170℃ (Tokukosho
53-22574), etc. have been reported. The monofilaments obtained by these methods are highly oriented (cross-sectional average birefringence ≧33×10 ^-3 ) by drawing and have excellent knot strength and tensile strength, but have poor abrasion resistance. The properties were not necessarily satisfactory (surface layer birefringence >30×10 ^-3 ). [Object of the Invention] An object of the present invention is to provide a PVDF monofilament that satisfies knot strength and tensile strength and has significantly improved abrasion resistance. [Summary of the Invention] According to the research conducted by the present invention, the drawing orientation adopted in the conventional method described above is effective in improving the knot strength and tensile strength of PVDF monofilament, but it is not effective in improving the abrasion resistance. This is not necessarily effective from the point of view, and when highly oriented, larger fibrils occur in the surface layer than in the surface layer due to the presence of relatively large spherulites in the inner layer, which is slowly cooled compared to the surface layer. This causes a significant decrease in wear resistance. Based on these findings, the present inventors further discovered that the desired PVDF monofilament can be obtained by creating a structure in which the surface layer of the monofilament, especially the surface orientation, is smaller than the orientation of the inner layer. did. Furthermore, when a monofilament having such a structure is used, for example, in a fluid at a temperature higher than the melting point of PVDF, which is the resin forming the surface layer, the composition of the resin forming the surface area of the surface layer of the monofilament is relaxed, but the inner layer is It was also discovered that this can be obtained by subjecting the composition of most of the constituent resins to a stress heat treatment for a short period of time to the extent that the composition is not relaxed. The vinylidene fluoride resin monofilament of the present invention is based on such knowledge. More specifically, in a thermoplastic resin monofilament in which at least the surface layer is made of a vinylidene fluoride resin, the monofilament of vinylidene fluoride resin can be made by relaxing the orientation of the surface layer. , the birefringence of the surface is 30×10 ^-3 or less, and the average birefringence of the cross section perpendicular to the fiber axis of the monofilament is 33×10 ^-3
It is characterized by the above. The present invention will be explained in detail below. [Detailed Description of the Invention] In the monofilament of the present invention, at least the surface layer is made of vinylidene fluoride resin. Therefore, the monofilament may be made entirely of PVDF, or the inner layer may be a single layer or multiple layers of a thermoplastic resin other than PVDF, such as polyamide or polyolefin. However, preference is given to using monofilaments consisting entirely of PVDF. Further, even if the entire monofilament is made of PVDF, the degree of polymerization of PVDF in the surface layer and the inner layer may be the same or different. however,
Preferably, the surface layer has a low degree of polymerization from the viewpoint of processability.
A material made of PVDF is used. With this invention
PVDF (vinylidene fluoride resin) is not limited to vinylidene fluoride homopolymers, but also includes vinylidene fluoride in a copolymer form containing 50 mol% or more of vinylidene fluoride as a constituent unit and copolymerizable with one or more monomers. A polymer or at least one of these polymers in an amount of 60% by weight or more, and other resins that can be mixed and molded with the polymer, such as poly(meth)acrylic ester, polycarbonate, polyester, etc., or various additives, such as a plasticizer. , crystal nucleating agent, dye,
This shall include resuscitation materials with pigments, etc. One of the characteristics of the monofilament of the present invention is that its surface has a birefringence index of 30×10 ⁻³ or less. The smaller the birefringence is, the more preferable it is from the viewpoint of abrasion resistance, and the birefringence is preferably 25×10 ⁻³ or less, more preferably 20×10 ⁻³ or less. Here, the birefringence of the surface is determined by the Betzke method.
At a measurement temperature of 20°C to 21°C, the refractive index n⊥ in the direction perpendicular to the fiber axis and the refractive index n in the direction parallel to the fiber are measured on the fiber surface, and the difference Δn = n - n Defined with ⊥. Another feature of the monofilament of the present invention is that the average birefringence perpendicular to the fiber axis is 33×10 ⁻³ or more. The larger this birefringence index is, the
It is preferable in terms of knot strength and tensile strength, and even more preferably 37×10 ⁻³ or more is used. Here, the average birefringence is a value measured by the retardation method at 23° C. and 65% humidity using a polarizing microscope equipped with a Berek convenser and using Na D line as a light source. Next, a method for manufacturing such a PVDF monofilament will be described. In this method, first, a monofilament in which at least the surface layer is made of PVDF oriented in the fiber axis direction is prepared. For such monofilaments oriented in the fiber axis direction, the more highly oriented they are in the fiber axis direction, the more remarkable the effect of this method is, and the average birefringence in the cross section perpendicular to the fiber axis is increased. is more preferably 25×10 ⁻³ or more, and even more preferably 35×10 ⁻³ or more. To obtain such an oriented monofilament, the stretching and orientation method described in the description of the prior art is typically used, but the method is not limited thereto. The method for producing the vinylidene fluoride resin of the present invention is simply a surface layer of such PVDF monofilaments blended in the fiber axis direction (the monofilaments are made of two or more material types or the same PVDF
However, regarding the case where a multilayer structure is obtained by using PVDF with a polymerization degree of 2 or more, if the entire cross section is made of a homogeneous material, it can be simply considered as a monofilament). The monofilament is subjected to a short stress heat treatment in a hot fluid to relax, but not to relax the composition of most of the constituent resins of the inner layer (which can simply be considered a monofilament if its entire cross section consists of a homogeneous material). do. If such heat treatment extends to most of the inner layer, the knot strength and tensile strength cannot be maintained. For this reason, it is necessary to limit the orientation relaxation to at most all of the surface layer and a portion of the inner layer. However, if there is a resin (for example, a polymer plasticizer) other than the main resin such as PVDF, polyamide, or polyolefin constituting the inner layer, it is possible that the orientation will be relaxed. Further, it is not necessary to relax the orientation of the entire surface layer, and it is sufficient to relax at least the surface layer portion of the surface layer. The thickness of the surface layer portion whose orientation is relaxed depends on the diameter of the monofilament, but is usually within the range of 1 to 10 μm. The orientation of the surface layer is relaxed to such an extent that the birefringence of the surface is 30×10 ⁻³ or less, preferably 25×10 ⁻³ or less, more preferably 20×10 ⁻³ or less. Specifically, a monofilament oriented in the fiber axis direction as described above may be treated for a short time in a fluid at a high temperature enough to relax the orientation of its surface layer. The temperature of the fluid at this time must be higher than the melting point of the resin constituting the surface layer. Vinylidene fluoride resin, which is the resin constituting the surface layer, may have a single melting point or multiple melting points, but in that case it is essential that it exceeds the melting point on the low temperature side; When the melting point is reached, it is further preferable to use a fluid whose temperature exceeds the main melting point. The melting point here refers to the melting endothermic peak when the temperature is raised in a nitrogen atmosphere using a differential scanning calorimeter.
The main melting point refers to the melting point at which the endothermic area based on the melting endothermic peak occupies a large proportion. When the fluid is a liquid, if the temperature is too high, the orientation relaxation of the entire monofilament will proceed too much even in a short period of time, making it inappropriate.The upper limit of the temperature is usually 30°C below the main melting point of the resin that makes up the surface layer. A temperature that cannot be exceeded is used. On the other hand, when the fluid is a gas, the thermal conductivity is low, so it is usually 200~
A temperature of around 500°C is used. The time for which the monofilament is brought into contact with the high-temperature fluid varies depending on the temperature and type of fluid, but is usually
It is about 0.1 to 8 seconds, preferably about 0.2 to 8 seconds. The monofilament must be kept under tension in such high temperature fluids. Otherwise, the composition will be relaxed over the entire cross section, making it impossible to satisfy the knot strength and tensile strength. In order to create a tensioned state, it is usually stretched 1.0 to 2.0 times. Naturally, the higher the temperature and the longer the time, the higher the stretching ratio becomes. Fluids used in the present invention for orientation relaxation include inert liquids such as glycerin and silicone oil, and inert gases such as heated air and steam, but are not limited to these examples. By the method described above, the monofilament of the present invention is generally formed to have a diameter in the range of 20 to 5000 μm. [Effects of the Invention] As described in detail above, according to the present invention, by making the orientation of the surface smaller than the orientation of the inner layer, it is possible to significantly improve the abrasion resistance while satisfying the knot strength and tensile strength. PVDF monofilament is provided. The PVDF monofilament thus obtained is
Taking advantage of its properties, it is typically used in the fields of line, filter, fishing net, etc., or as a rope material. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 Vinylidene fluoride homopolymer (melting point 177°C) with ηinh of 1.32 dl/g obtained by suspension polymerization was
Melt-spun at 285℃ using a mmφ extruder to adjust the diameter.
An undrawn yarn (monofilament) having a diameter of 380 μφ and a birefringence Δn of 3.2×10 ⁻³ was obtained. This is 165℃
1 float stretching to 5.4 times in heated glycerin at 165°C, and then second stretching to 1.18 times in heated glycerin at 165°C, resulting in a diameter of 152 μφ, an average birefringence of 36.5×10 ^-3 , and a surface birefringence of 31×. A drawn yarn of 10 ^-3 was obtained. This was further heat-treated in heated glycerin at 180° C. under tension such that 10% stretching occurred in 2 seconds to obtain a thread with a diameter of 146 μφ. This thread has an average birefringence of 38×10 ^-3 , a surface birefringence of 20×10 ^-3 , a tensile strength of 90 Kg/mm ² , a knot strength of 68 Kg/mm ² , and abrasion resistance (number of times of friction before breaking).
Showed the characteristics more than 1000 times. The tensile strength and knot strength are the breaking strengths at room temperature when a sample yarn with a sample length of 300 mm is pulled at a tensile speed of 300 mm using a Tensilon UTM model manufactured by Toyo Baldwin. Nodule strength is the breaking strength of a sample with a nodule point located at the center of the sample length. As shown in the attached drawing, the friction resistance was measured using a Gakushin type improved friction tester (manufactured by Tester Sangyo) 1 at 35 kg/
A monofilament 3 with a load 2 of mm ² applied is moved at a speed of 100 over a round rod 4 with an outer diameter of 100 mm covered with cotton fabric.
It was made to reciprocate at a rate of mm/sec and was defined as the number of reciprocations until cutting. Comparative Example 1 The average birefringence was 36.5×10 ^-3 and the surface birefringence was 31×.
10 ^-3 yarn has a tensile strength of 85Kg/ ^mm2 and a knot strength of 68Kg/mm2.
mm ² and abrasion resistance of 150 times. Example 2 A vinylidene fluoride homopolymer (melting point 177°C) with ηinh 1.32 dl/g obtained by suspension polymerization was used as the core, and a polyvinylidene fluoride homopolymer (melting point 177°C) with ηinh 1.10 dl/g was used as the sheath. 285℃
An undrawn yarn having an outer diameter of 380 μφ and an average birefringence Δn of 3.5×10 ⁻³ was obtained by melt spinning. this
Stretched 5.4 times in heated glycerin at 165°C, then stretched 1.18 times in heated glycerin at 167°C,
A drawn yarn with a diameter of 152 μφ and an average birefringence of 37×10 ⁻³ was obtained. This was further heated in glycerin at 180℃ for 2 hours.
A thread having a diameter of 146 μΦ was obtained by heat treatment under tension such that stretching occurred by 10% per second. This thread has an average birefringence of 39×10 ^-3 , a surface birefringence of 18×10 ^-3 , a tensile strength of 95 Kg/mm ² , and a knot strength of 72
Kg/mm ² and friction resistance (number of frictions until cutting) of over 1000 times. Comparative Example 2 After two-step stretching in the same manner as in Example 2, an average birefringence of 37×10 ^-3 obtained without the heat treatment of the present invention, and a birefringence of 33×10 ^-3 of the surface layer were obtained. The yarn exhibited properties of tensile strength of 90 Kg/mm ² , knot strength of 72 Kg/mm ² , and abrasion resistance of 140 cycles. Examples 3 to 6, Comparative Examples 3 to 8 According to Example 1 or Example 2, various sample yarns ( Monofilament) was obtained. The properties of these sample yarns measured according to Example 1 are summarized in Table 1 below, along with those of the above examples. More details of Comparative Example 8 are shown below. In addition, in the table below, regarding abrasion resistance, those that have been rubbed more than 300 times before cutting by the above method are *1 (good abrasion resistance), and those that are less than 300 times are *2
(poor wear resistance) is displayed. Especially comparative example 4,
The abrasion resistance of Nos. 5 and 6 was 200 times, 140 times and 170 times, respectively. Comparative Example 8 (Liquid phase excess heat treatment) After two-stage stretching in the same manner as in Example 2, the film was heat-treated in glycerin heated at 185°C under tension such that 20% stretching occurred in 8.5 seconds, resulting in a diameter of 141μφ.
I got the thread. This thread has an average birefringence of 20×10 ^-3 ,
The birefringence of the surface is 8.3×10 ^-3 and the overall orientation is excessively relaxed, and the tensile strength is 35 Kg/mm ² and the nodule strength is 26 Kg/mm 2 .
The characteristics of mm were shown. The friction resistance could not be measured because the threads were cut due to the load (35 kg/mm ² ).

[Table] Examples and comparative examples in which heat treatment after stretching was performed in a gas phase are shown below. Example 7 Two-step stretching was carried out in the same manner as in Example 1 using the usual method, and then 10
Heat treated under tension such that % elongation occurs.
A thread of 152 μφ was obtained. This thread has an average birefringence of 37.5×
10 ^-3 , surface birefringence 26.5×10 ^-3 , tensile strength 90
Kg/mm ² , knot strength 65 Kg/mm ² , and friction resistance (number of frictions until cutting) of over 700 times. Comparative Example 9 Two-stage stretching was carried out in the same manner as in Example 1, followed by stretching at 5 times for 2 seconds in dry heat (air) at 180°C.
A thread with a diameter of 154 μΦ was obtained by heat treatment to cause % relaxation. This thread has an average birefringence of 36×10 ^-3 , a surface birefringence of 31×10 ^-3 , a tensile strength of 85 Kg/mm ² , and a knot strength.
62Kg/ ^mm2 , friction resistance (number of frictions until cutting) 110
The characteristics of the times were shown. In other words, the surface orientation relaxation effect is mostly recognized, and the overall strength is only slightly reduced.
The abrasion resistance is also rather reduced. Comparative Example 10 Two-stage stretching and dry heat at 190°C (air) as in Example 1
The yarn was heat-treated under tension in a vacuum chamber under tension so that 10% elongation occurred for 2 seconds to obtain a yarn with a diameter of 152 μΦ. This thread has an average birefringence of 37.5×10 ^-3 and a surface birefringence of 30.8×
10 ^-3 , tensile strength of 90 Kg/mm ² , knot strength of 62 Kg/mm ² , and friction resistance (number of frictions until cutting) of 120 times. Comparative Example 11 After two-stage stretching in the same manner as in Example 1, heat treatment was performed in dry heat (air) at 210°C under tension such that 10% stretching occurred in 8 seconds, resulting in a diameter of 150μφ.
I got the thread. This thread has an average birefringence of 18.5×
10 ^-3 , surface birefringence 12.5×10 ^-3 , tensile strength 31
Kg/mm ² and nodule strength of 25 Kg/mm ² . The friction resistance could not be measured because the threads were cut due to the load (35 kg/mm ² ). Summarizing the above examples and comparative examples of gas phase treatment,
It is shown in Table 2 below. In addition, *1 to *4 in the evaluation column are as follows:
It has the same meaning as in the previous table.

[Table] Comparative Example 12 ηinh obtained by suspension polymerization was 0.85 dl/g.
The PVDF homopolymer was stretched in two stages in the same manner as in Example 1, and then heat-treated in heated glycerin at 180°C under tension such that 10% stretching occurred in 2 seconds, resulting in a diameter of 143μφ. I got the thread. This thread has an average birefringence of 20×10 ^-3 and a surface birefringence of
At 7.5×10 ⁻³ , the orientation was excessively relaxed throughout, and exhibited properties of a tensile strength of 30 Kg/mm ² and a knot strength of 25 Kg/mm ² . The friction resistance could not be measured because the threads were cut due to the load (35 kg/mm ² ).

[Brief explanation of drawings]

The drawing is an explanatory diagram of a friction resistance test of monofilaments obtained in Examples or Comparative Examples. 1... Gakushin type friction tester, 2... Load, 3...
Monofilament, 4... Round rod covered with cotton fabric.

Claims (1)

[Claims] 1. A thermoplastic resin monofilament in which at least the surface layer is made of vinylidene fluoride resin,
Due to the orientation relaxation of the surface layer, the birefringence of the surface increases.
A vinylidene fluoride resin monofilament characterized by having an average birefringence of 30×10 ^-3 or less and an average birefringence perpendicular to the fiber axis of the monofilament of 33×10 ^-3 or more. 2. The monofilament according to claim 1, wherein the monofilament is entirely made of vinylidene fluoride resin throughout the cross section perpendicular to the fiber axis. 3. The monofilament according to claim 1 or 2, wherein the vinylidene fluoride resin constituting at least the surface layer has an ηinh of about 1.1 dl/g or more.