JPH1112849A - Conjugated monofilament and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a conjugated monofilament having both physical characteristics suitable for uses of fisheries materials or various industrial materials and excellent flex recovery properties and perming properties and to provide a method for efficiently producing the conjugated monoifilament. SOLUTION: This conjugated monofilament is composed of a conjugated structure of an island-in-sea cross section and both the sea component A and the island component B are composed of a polyvinylidene fluoride-based resin having <=6.0 melt flow rate [(MFR) at 230 deg.C under 10 kg]. The melting point of polymer in the sea component A is >=150 deg.C and the melting point of the polymer in the island component B is 5-30 deg.C lower than that of the sea component A. The drawing in the final stage is carried out at a temperature Te satisfying the formula Ts-5 deg.C<Te<=Tu+20 deg.C [Te is the drawing temperature ( deg.C); Ts is the melting point ( deg.C) of the polymer in the island component B; Tu is the melting point ( deg.C) of the polymer in the sea component A], in a method for melt spinning at least the two kinds of the polyvinylidene fluoride- based resins different in melting point, cooling the spun filament and subsequently drawing the cooled filament so as to provide >=5.5 total draw ratio in one to many stages by using an apparatus for the conjugated spinning of the island-in-sea structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite monofilament having excellent physical properties and particularly suitable for use in marine materials and industrial materials, and a method for efficiently producing the composite monofilament.

[0002]

2. Description of the Related Art Synthetic resin monofilaments, especially polyvinylidene fluoride resin monofilaments, have useful properties such as toughness, high specific gravity, refractive index close to water, and low water absorption. Since it is provided, it is widely used for marine material applications such as fishing lines and fishing nets and various industrial material applications.

However, since the polyvinylidene fluoride resin monofilament has a large wire diameter, a difference in the fiber structure easily occurs in the cross-sectional direction of the monofilament in a normal manufacturing method, and the monofilament has a sufficient fiber diameter due to the structural difference. It is a bottleneck that it cannot express a great physical performance.

[0004] As a prior art in which the difference in structure of such a polyvinylidene fluoride resin monofilament is improved, (A)
A core-sheath type composite yarn (JP-A-59-144614) and (B) a monofilament having a concentric three-layer structure (JP-A-7-292519) have already been proposed.

Further, the present inventors (C) have a two-layer structure using a polyvinylidene fluoride resin for both the core and the sheath, the melting point of the core polymer is set to 150 ° C. or more, and the sheath is A composite monofilament (Japanese Patent Application No. 9-101581) in which the melting point of the polymer is 5 to 30 ° C. higher than the melting point of the core polymer has been found to have excellent properties, and has been proposed earlier.

[0006] However, the core-sheath type composite yarn (A) and the monofilament (B) having a concentric three-layer structure both have improved knot strength and the like, but the fiber structure in the cross-sectional direction has been improved. In terms of the uniformity, was not always satisfactory, and accordingly, physical performance such as impact strength could not be sufficiently exhibited.

The composite monofilament (C) is characterized in that the polyvinylidene fluoride resin forming the core component and the sheath component has an appropriate melting point difference so that the fluidity of the polymer in the inner and outer layers at the time of drawing the fiber is improved. It is possible to improve the uniformity of the fiber structure in the cross-sectional direction and sufficiently exert physical properties such as impact strength. It has much more useful properties than the composite yarn and the monofilament having the concentric three-layer structure of (B).

However, according to the results of further studies by the present inventors, the composite monofilament (C) described above has physical properties such as excellent impact strength, but is inferior in bending recovery, and has poor permeation due to abrasion. It has been found that the method has the disadvantage that the degree of occurrence is large.

[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 composite monofilament having both excellent physical properties suitable for use in marine materials and various industrial materials, excellent flexural recovery and perm properties, and this composite monofilament. An object of the present invention is to provide a method for efficiently manufacturing.

[0011]

In order to achieve the above-mentioned object, the composite monofilament of the present invention has a cross-sectional sea-island composite structure in which a plurality of island components are scattered in a sea component. Are MFR (230 ° C, 1
0Kg) composed of a polyvinylidene fluoride resin of 6.0 or less, wherein the melting point of the sea component polymer is 150 ° C. or more, and the melting point of the island component polymer is 5 to 5 points lower than the melting point of the sea component polymer.
It is characterized by being 30 ° C. lower.

[0012] The composite monofilament of the present invention comprises:
Having a cross-sectional sea-island composite structure in which a plurality of island components are rotationally symmetrically dotted in the sea component in the monofilament cross section,
MFR of polyvinylidene fluoride resin constituting sea component
(230 ° C., 10 Kg) is smaller than the MFR of the polyvinylidene fluoride resin constituting the island component, and the weight ratio of the sea component to the island component is in the range of 95/5 to 40/60. It is desirable to satisfy one of them, and in that case, it is possible to expect a more excellent effect.

[0013] In the method for producing a composite monofilament of the present invention having the above structure, at least two types of polyvinylidene fluoride resins having different melting points are melt-spun and cooled using a sea-island composite spinning apparatus. In a method of stretching in one stage or multiple stages so that the total stretching ratio is 5.5 times or more, the final stage of stretching is performed at a temperature Te that satisfies the following formula (1).
It is characterized by performing. Ts−5 ° C. <Te ≦ Tu + 20 ° C. (1) Where, Te = stretching temperature (° C.) Ts = melting point of island component polymer (° C.) Tu = melting point of sea component polymer (° C.)

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyvinylidene fluoride sea-island composite monofilament in which a low-melting polyvinylidene fluoride resin is used as an island component polymer and a high-melting polyvinylidene fluoride resin is used as a sea component polymer. It is characterized in that it is constructed and stretched at an appropriate temperature. Therefore, according to the present invention, it is possible to optimize the fluidity of the polymer in each sea-island layer at the time of stretching, the fiber structure such as the degree of orientation of the sea-island each layer polymer is made more uniform, and the impact strength is greatly improved. At the same time, by forming the sea-island composite structure, thermal distortion due to the difference in melting point of the polyvinylidene fluoride-based resin is reduced, and a composite monofilament having improved bending recovery and perm properties can be realized.

Hereinafter, the present invention will be described in detail.

The polyvinylidene fluoride resin constituting the sea component and the island component of the composite monofilament of the present invention has an MFR (230 ° C., 10 Kg) of 6.0 or less, and specific examples thereof are as follows. And vinylidene fluoride homopolymers and polyvinylidene fluoride copolymers comprising vinylidene fluoride as a main component and one or more comonomers copolymerizable therewith. Specific examples of the comonomer component here include, but are not limited to, tetrafluoroethylene, monochlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, and perfluoroisopropoxyethylene.

The above polymers 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 it is not inhibited.

With respect to the combination of the polyvinylidene fluoride resin constituting the sea component and the island component, the melting point of the polyvinylidene fluoride resin constituting the sea component is 150 ° C. or more, and the polyvinyl fluoride resin constituting the island component is used. There is no particular limitation as long as the melting point of the vinylidene resin is 5 to 30 ° C. lower than the melting point of the sea component polymer, but the MFR (230 ° C., 10 Kg) of the polyvinylidene fluoride resin constituting the sea component is not limited. It is preferably smaller than that of the island component.

Here, if the difference between the melting points of the polyvinylidene fluoride resin constituting the sea component and the island component is less than 5 ° C., the effect of improving the impact strength of the composite monofilament is not preferable.

The MFR of the polyvinylidene fluoride resin constituting the sea component and the island component (230 ° C., 10 kg)
Are respectively not more than 6.0, and when the melting point of the polyvinylidene fluoride-based resin constituting the sea component is lower than 150 ° C., the physical properties such as tensile strength are not sufficient, which is not preferable.

In the composite monofilament of the present invention,
The compounding ratio of the sea component and the island component is such that the weight ratio of the sea component and the island component is 95/5 to 40/60, particularly 90/10 to 50/50.
Is out of these ranges, it is not preferable because the effect of improving the impact strength is reduced.

Further, as for the sectional sea-island structure, it is more preferable that the island component has a sectional sea-island structure in which the island components are scattered rotationally symmetrically in the sea component in terms of the bending recovery property and the perm property.

The number of island components cannot be specified unconditionally depending on the filament diameter of the monofilament, the kind of the polyvinylidene fluoride-based resin to be constituted, the spinning conditions, etc., but may be two or more, particularly three or more. desirable. Although the upper limit of the number of island components is not particularly limited, islands in the composite monofilament having a wire diameter of 0.07 to 3.0 mm are naturally restricted due to the problem of the wire diameter of the composite monofilament and the accuracy in spinneret production. The number is usually 3 to 19, especially 3 to 1
A range of about 2 is preferred.

The dotted form of the island component in the composite monofilament of the present invention includes, for example, the embodiments shown in FIGS.

1 to 3 are enlarged sectional views showing an example of the composite monofilament of the present invention.
Indicates an aspect in which, for example, three island components B are concentrated in a position near the center of the monofilament cross section and scattered in the sea component A. FIG. 2 shows an aspect in which, for example, seven island components B having different sizes are scattered in a sea component A from the center to the outer periphery of the monofilament cross section. Further, FIG. 3 shows a mode in which thirteen island components B are scattered in a sea component A from the center to the outer periphery of the monofilament cross section.

In such an interspersed form of the island components, each of the island components is rotationally symmetric, that is, the angle is 2π / n (n
Is preferably scattered in such a manner as to be identical to the first figure for each integer of 2 or more, that is, the number of island components.

In the drawings, the cross-sectional shape of the island component is shown by a round shape. However, the cross-sectional shape of the island component may be changed to a Y-shaped, triangular or star-shaped cross-section to increase the contact area of the sea-island sea surface. It is possible.

The composite monofilament of the present invention can be produced efficiently by the method described below.

First, when melt-spinning a composite monofilament using the composite spinneret having the above-mentioned sea-island composite structure, ordinary conditions using a composite spinning machine can be adopted, and the polymer temperature is 200 to 300. ° C, extrusion pressure 10-500 Kg / cm ³ , die hole diameter 0.1-5
mm, a spinning speed of 0.3 to 100 m / min, and the like can be appropriately selected.

After the spun monofilament passes through a short gas zone, it is cooled in a cooling bath, wherein a liquid inert to the polymer, usually water or polyethylene glycol, is used as a cooling medium. . The cooling temperature is usually preferably about 20 ° C. to prevent devitrification.

The monofilament that has been cooled and solidified is then sent to the first stretching step. The stretching and heat setting atmosphere (bath) may be a heated heat medium bath such as polyethylene glycol, glycerin and silicone oil, or a dry medium. A hot gas bath, a pressurized steam bath, or the like is used.

Next, at the time of stretching, one-stage or multi-stage stretching is performed so that the total stretching ratio becomes 5.5 times or more. Here, the stretching at least in the final stage is as described in (1) below.
It is an essential condition to perform the process at a temperature Te that satisfies the equation. Ts−5 ° C. <Te ≦ Tu + 20 ° C. (1) Where, Te = stretching temperature (° C.) Ts = melting point of island component polymer (° C.) Tu = melting point of sea component polymer (° C.)

Here, the total stretching ratio is less than 5.5 times, or at least the stretching temperature in the final stretching step is (Ts-10).
C.), the physical properties such as tensile strength of the obtained composite monofilament cannot be sufficiently achieved, and if the stretching temperature in the final stretching step exceeds (Tu + 20 ° C.), the monofilament is not stretched at the time of stretching. It is not preferable because it causes melting.

After the single-stage or multi-stage stretching, an appropriate fixed length,
Alternatively, a relaxation heat treatment can be performed.

The composite monofilament of the present invention obtained in this way has excellent physical properties such as an impact strength of 0.9 GPa or more, and also has excellent bending recovery properties and perm properties. It is extremely useful for marine materials and various industrial materials.

[0036]

EXAMPLES The present invention will be further described below with reference to examples. The evaluation of monofilaments in the examples was performed according to the following method.

(1) Impact strength: Tensile impact strength (Kg) was measured with a pendulum type impact tester manufactured by Shimadzu, and tensile impact strength (GPa) was determined as the tensile impact strength per unit weight. The tensile impact strength (Kg) was measured using a pendulum hammer for 50 kg · cm and a load cell of 10 kg, and the test length was 300 m.
m, and the measured value was determined by reading the height of the peak that appeared on the chart of the visit graph. (The number of measurements was 5 and the average was shown.) (2) Bending recovery: A pair of crossed loops was made, the upper loop was fixed to a clasp, and the load ( A 1/2 denier weight of monofilament is applied 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.

(3) Permanence: A rectangular metal holder (dimensions 100 L × 45 H × 60 W) set on the crosshead of a tensile tester “Tensilon” manufactured by Orientec Co., Ltd.
Hang the yarn at a right angle and apply a constant load (monofilament 1).
/ 2 denier weight), the metal holder was moved up and down under the following measurement conditions, and the degree of the monofilament generated by repeatedly rubbing the monofilament against the edge of the metal holder was evaluated. (1) Elevating speed of the crosshead (metal holder) of the tensile tester; 300 mm / min. (2) Repeated stroke; 10 cm (3) Number of reciprocations; 10 times For the permanent property, the scraped portion was stretched to 6 cm. The relative evaluation was made based on the number of loops observed in the state. The smaller the number of loops, the better the perm property.

The evaluations (1) to (3) were made after conditioning the sample under the conditions of 20 ° C. and 65% RH.

(4) Melting point: D described in JIS-K7121
It was measured according to the SC method.

(5) MFR (230 ° C., 10 kg): Using a 2.095 φ × 8.0 L nozzle, the temperature was 230
The melt flow rate (g / 10 minutes) was measured with a melt indexer under the conditions of ° C and a load of 10.0 kg.

[Example 1] Polyvinylidene fluoride homopolymer (melting point: 176 ° C, MFR (230 ° C, 10K
g): 2.3... Polymer A1) as a sea component (60 parts by weight)
And a copolymer of vinylidene fluoride and hexafluoropropylene (melting point: 165 ° C, MFR (230 ° C, 10K
g) 2.8 Using the polymer B1) as an island component (40 parts by weight), the composite spinneret is melted at 270 ° C. by an extruder-type composite spinning machine to form a sea-island structure composite monofilament having a cross-sectional shape shown in FIG. (Pore diameter 1.5 mm), and further cooled in a polyethylene glycol bath at 20 ° C.

Next, this undrawn yarn is drawn 4.5 times (E1) in a 160 ° C. polyethylene glycol one-stage drawing bath, and subsequently drawn in a 165 ° C. second stage polyethylene glycol bath. .6 times (E2) and the total stretching ratio (E1
× E2) was obtained 7.2 times as a composite monofilament.

Subsequently, by passing through a dry heat bath at 155 ° C. at a treatment magnification of 0.92 times and performing heat treatment, a composite monofilament having a sea-island composite ratio shown in Table 1 and a diameter of 0.20 mm was obtained. .

Example 2 Polyvinylidene fluoride homopolymer (melting point: 174 ° C., MFR (230 ° C., 10K
g): 2.5 A2) as a sea component (50 parts by weight), a copolymer of vinylidene fluoride and hexafluoropropylene (melting point: 158 ° C, MFR (230 ° C, 10 Kg):
3.2 Using the polymer B2) as an island component (50 parts by weight), a composite spinneret (hole diameter) melted at 265 ° C. with an extruder-type composite spinning machine to form a sea-island structure composite monofilament having a cross-sectional shape shown in FIG. (1.5 mm) and further cooled in a polyethylene glycol bath at 20 ° C.

Next, this undrawn yarn is drawn 4.5 times (E1) in a first stage polyethylene glycol drawing bath at 160 ° C., and subsequently in a second stage polyethylene glycol bath at 165 ° C. for 1.times. The film is stretched 67 times (E2), and the total stretch ratio (E
A composite monofilament having 1 × E2) of 7.5 times was obtained.

Subsequently, by passing through a dry heat bath at 155 ° C. at a treatment magnification of 0.90 times and performing heat treatment, a composite monofilament having a sea-island composite ratio shown in Table 1 and a diameter of 0.20 mm was obtained. .

Example 3 An extruder-type composite spinning machine using the polymer B1 used in Example 1 as a sea component (60 parts by weight) and the polymer B2 used in Example 2 as an island component (40 parts by weight). Melted at 260 ° C. and spun through a composite spinneret (2.0 mm hole diameter) to form a sea-island structure composite monofilament having the cross-sectional shape shown in FIG.
It was further cooled in a polyethylene glycol bath at 20 ° C.

Next, this undrawn yarn was drawn 4.5 times (E1) in a first stage drawing bath of polyethylene glycol at 150 ° C., and subsequently in a second stage polyethylene glycol bath at 160 ° C. for 1.times. The film is stretched 69 times (E2), and the total stretching ratio (E
1 × E2) obtained a 7.6 times composite monofilament.

Subsequently, a monofilament having a sea-island composite ratio shown in Table 1 and a diameter of 0.20 mm was obtained by passing through a dry heat bath at 150 ° C. at a treatment magnification of 0.92 and performing heat treatment.

Comparative Example 1 Polymer A used in Example 1
1 was used alone, and a monofilament having a diameter of 0.20 mm was obtained under the yarn-making conditions described in Table 1.

Comparative Example 2 Polymer A used in Example 2
The monofilaments having a diameter of 0.20 mm were obtained by using 2 alone and employing the spinning conditions described in Table 1.

Comparative Example 3 Polymer B used in Example 1
1 was used alone, and a monofilament having a diameter of 0.20 mm was obtained under the yarn-making conditions described in Table 1.

Comparative Example 4 Polymer B used in Example 2
The monofilaments having a diameter of 0.20 mm were obtained by using 2 alone and employing the spinning conditions described in Table 1.

Comparative Example 5 A copolymer of vinylidene fluoride and hexafluoropropylene (melting point: 160 ° C., MFR
(230 ° C., 10 Kg): 2.3 Polymer A3) was used as a sea component (60 parts by weight), and polymer B used in Example 2 was used.
Using 2 as an island component (40 parts by weight) and employing the yarn-making conditions shown in Table 1, a composite monofilament having a diameter of 0.20 mm and a composite ratio shown in Table 1 was obtained.

Comparative Example 6 A composite monofilament having a diameter of 0.20 mm was obtained in the same manner as in Example 1 except that the final stretching temperature (second stage stretching temperature) was 155 ° C. I got

Comparative Example 7 A composite monofilament having a diameter of 0.20 mm was obtained in the same manner as in Example 1 except that the final stretching temperature (second stage stretching temperature) was changed to 200 ° C. I got

Comparative Example 8 The same manufacturing method as in Example 1 was adopted except that the ratio of the sea component polymer A1 was 97 parts by weight and the ratio of the island component polymer B1 was 3 parts by weight. A composite monofilament having a diameter of 0.20 mm and a composite ratio shown in Table 1 was obtained.

Comparative Example 9 The same manufacturing method as in Example 1 was used except that the ratio of the polymer A1 of the sea component was changed to 30 parts by weight and the ratio of the polymer B1 of the island component was changed to 70 parts by weight. A composite monofilament having a diameter of 0.20 mm and a composite ratio shown in Table 1 was obtained.

Comparative Example 10 Example 1 was repeated except that the polymer B1 used in Example 1 had a core component (40 parts by weight) and the polymer A1 had a sheath component (60 parts by weight). 0.20mm
Thus, a composite monofilament having a composite ratio shown in Table 2 was obtained.

[Comparative Example 11] A core-shell type cross-sectional structure was used in which the polymer B2 used in Example 2 was a core component (50 parts by weight) and the polymer A2 was a sheath component (50 parts by weight). 0.20mm
Thus, a composite monofilament having a composite ratio shown in Table 2 was obtained.

Comparative Example 12 Example 3 was the same as Example 3 except that the polymer B2 used in Example 3 had a core component (40 parts by weight) and the polymer B1 had a sheath component (60 parts by weight). 0.20mm
Thus, a composite monofilament having a composite ratio shown in Table 2 was obtained.

With respect to the monofilaments obtained in Examples 1 to 3 and Comparative Examples 1 to 12, the results of evaluating the characteristics as monofilaments are shown in Tables 1 and 2.

[0064]

[Table 1]

[Table 2] As is clear from the results of Tables 1 and 2, each of the sea component and the island component is composed of a polyvinylidene fluoride resin having an MFR (230 ° C., 10 Kg) of 6.0 or less,
A cross-section sea-island in which a plurality of island components having a melting point of 5 to 30 ° C. lower than the sea component and a plurality of island components are scattered in a sea component made of a polyvinylidene fluoride resin having a melting point of 150 ° C. or more. The composite monofilament according to the present invention, which has a structure (Examples 1 to 3), has excellent physical properties such as an impact strength of 0.9 GPa or more, as well as an excellent bending recovery rate and permanent It has both sexes.

On the other hand, the monofilaments of various polyvinylidene fluoride resins alone (Comparative Examples 1 to 4) and the composite monofilament having a small difference in melting point between the sea component and the island component (Comparative Example 5) were compared with the composite monofilament of the present invention. And the impact strength was inferior.

The weight ratio of the sea component / island component is 95/5.
４０40/60 out of the range (Comparative Examples 8 and 9), and the composite monofilament in which the drawing temperature in the final stage drawing step was out of the range of the above formula (1) (Comparative Example 6). , 7) did not melt during stretching or did not sufficiently satisfy the effects aimed at by the present invention.

Further, although having a composite structure, a composite monofilament composed of a cross-section core-sheath structure (Comparative Example 1)
Nos. 0 to 12) had excellent physical properties such as an impact strength of 0.9 GPa or more, but had insufficient flexural recovery properties and permanent properties.

[0068]

As described above, the composite monofilament of the present invention has an unprecedentedly high impact strength, and also has excellent flex recovery and perm properties. Very useful for industrial material applications.

Further, according to the method for producing a composite monofilament of the present invention, a composite monofilament having the above characteristics can be produced efficiently.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view showing an example of a composite monofilament of the present invention.

FIG. 2 is an enlarged sectional view showing another example of the composite monofilament of the present invention.

FIG. 3 is an enlarged sectional view showing another example of the composite monofilament of the present invention.

[Explanation of symbols]

 A Sea component B Island component

Claims (5)

[Claims] 1. A polyvinylidene fluoride having a cross-sectional sea-island composite structure in which a plurality of island components are scattered in a sea component, wherein each of the sea component and the island component has an MFR (230 ° C., 10 kg) of 6.0 or less. A composite monofilament comprising a base resin, wherein the melting point of the sea component polymer is 150 ° C or higher, and the melting point of the island component polymer is 5 to 30 ° C lower than the melting point of the sea component polymer. 2. The composite monofilament according to claim 1, wherein the monofilament has a cross-section sea-island composite structure in which a plurality of island components are scattered rotationally symmetrically in the sea component. 3. The polyvinylidene fluoride resin constituting the sea component has a lower MFR (230 ° C., 10 kg) than the polyvinylidene fluoride resin constituting the island component. Or the composite monofilament according to 2. 4. The weight ratio of the sea component to the island component is 95/5 to 5.
4. The method according to claim 1, wherein the ratio is in the range of 40/60.
The composite monofilament according to any one of the above. 5. A sea-island composite spinning apparatus, wherein at least two kinds of polyvinylidene fluoride resins having different melting points are melt-spun and cooled, followed by one or more stages and a total draw ratio of 5.5 or more. The method for producing a composite monofilament according to any one of claims 1 to 4, wherein the stretching in the final step is performed at a temperature Te that satisfies the following formula (1). Ts−5 ° C. <Te ≦ Tu + 20 ° C. (1) where Te = stretching temperature (° C.) Ts = melting point of island component polymer (° C.) Tu = melting point of sea component polymer (° C.)