WO2001071071A1

WO2001071071A1 - Colored poly(vinylidene fluoride)-based monofilament and method for producing the same

Info

Publication number: WO2001071071A1
Application number: PCT/JP2001/002178
Authority: WO
Inventors: Satoshi Hashimoto; Hiroshi Ochiai; Masaru Sato
Original assignee: Kureha Chemical Industry Co., Ltd.
Priority date: 2000-03-22
Filing date: 2001-03-19
Publication date: 2001-09-27
Also published as: JP4409036B2; JP2001271220A

Abstract

A monofilament comprising a poly(vinylidene fluoride) resin composition containing a perylene type fluorescent dye; a method for producing the monofilament, which comprises spinning the poly(vinylidene fluoride) resin composition at a set temperature for an extruder of 300°C or less and with a time of residence in the extruder of 60 minutes or less; and a fishing line comprising the monofilament. The monofilament has properties suitable for a fishing line, is free from the discoloration of a colorant due to hydrofluoric acid generated by the decomposition of a resin during spinning, is colored in a clear fluorescence color and can be used for producing a fishing line which is transparent and excellent in visibility.

Description

Technical Field Colored polyvinylidene fluoride monofilament and method for producing the same

The present invention relates to a colored monofilament composed of a polyvinylidene fluoride resin composition. More specifically, while maintaining the excellent characteristics of fishing line made of polyvinylidene fluoride monofilament, it is colored with a clear fluorescent color by a special fluorescent dye, and it is transparent and has excellent visibility. The present invention relates to a glittering transparent polyvinylidene fluoride-based monofilament containing a perylene-based higher dye and a method for producing the same. Background art

Polyvinylidene fluoride monofilaments are excellent in toughness, impact resistance, sensitivity (fish detection), light resistance, etc., and have a high specific gravity of 1.79 and easily sink in water. Since it has a refractive index (1.42) close to 3.33), it has little surface reflection in water and is transparent and difficult to see. Furthermore, since they have no water absorption, their properties can be maintained for a long time even in water, and they have been used particularly favorably for tex applications represented by Harris.

On the other hand, the polyvinylidene fluoride monofilaments have been used in lure lines and throw fishing lines, taking advantage of their impact resistance, high specific gravity and high sensitivity. For lure lines and road yarn applications, visibility from anglers is required, and coloring by dyeing has recently been attempted. However, since polyvinylidene fluoride monofilaments are inherently extremely difficult to dye, the dyed ones are pale in color and unclear. If the heat treatment temperature is raised to increase the color and the treatment time is increased, the initial physical properties such as tensile strength are reduced, so that satisfactory results in both visibility and strength have not been obtained. Furthermore, polyvinylidene fluoride resin is a color (The method of extruding and spinning the synthetic resin used to obtain monofilaments by extruding and spinning the synthetic resin itself with a colorant such as a dye, pigment, or pigment resin color before extrusion) Most of the colorants are discolored and decomposed due to the high temperature at the time and the hydrofluoric acid generated in trace amounts during melting. In addition, even a small portion of the pigments that can withstand the color tone is unclear, the transparency is low, and the dispersed particle size of the pigments is large. Satisfactory coloring was not achieved.

The present invention maintains the characteristics of a fishing line composed of a polyvinylidene fluoride monofilament, and does not recognize the discoloration of the coloring agent due to the generation of hydrofluoric acid due to the decomposition of the resin during spinning, so that it is colored in a clear fluorescent color. It is an object of the present invention to provide a monofilament that forms a transparent fishing line with excellent visibility and a method for producing the same. Disclosure of the invention

The present inventors have conducted intensive studies with the aim of solving the above problems, and as a result, have found that a monofilament made of a polyvinylidene fluoride resin composition containing a perylene-based fluorescent dye can solve such problems. The invention has been completed.

That is, the present invention provides a monofilament comprising a polyvinylidene fluoride resin composition containing a perylene fluorescent dye. In the above invention, there is provided a monofilament having a perylene fluorescent dye content of 0.01 to 0.5 parts by weight based on 100 parts by weight of a polyvinylidene fluoride resin. Further, the present invention provides the monofilament of the present invention having a knot strength represented by the following formula (1).

Knot strength Numerical value of [GPa] ≥ {(25 / (numerical value of yarn diameter ^ m))) ^1/3 (1) Also, set the extrusion temperature of polyvinylidene fluoride resin composition containing perylene fluorescent dye. Provided is a method for producing the monofilament of the invention, wherein the monofilament is spun at a temperature of 300 ° C. or less and an extruder residence time of 60 minutes or less. A fishing line comprising the monofilament of the invention is provided. . BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The polyvinylidene fluoride resin (PVDF) used in the present invention is preferably a vinylidene fluoride homopolymer, a copolymer containing 70% by mole or more of vinylidene fluoride as a constituent unit, A mixture of coalescence is mentioned. Examples of the monomer copolymerized with vinylidene fluoride include ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride, ethylene trifluoride chloride, and vinyl fluoride. Also, at least one of these can be used. In Hirento viscosity of polyvinylidene fluoride (i _nh) is preferably 0. 8~2. 0 d 1 / g, more preferably 1.0 to 1.7 range dl / g. The raw material polyvinylidene fluoride resin for the monofilament of the present invention may be a nucleating agent represented by a polyester plasticizer, a phthalate plasticizer, a flavantron, or a polymer as long as its properties are not impaired. The composition includes a resin mixed with a resin having good compatibility with vinylidene fluoride resin such as methyl acrylate, polymethyl acrylate, and methyl acrylate / isobutylene copolymer. In particular, as a plasticizer, the repeating unit composition is an ester of a dialcohol having 2 to 4 carbon atoms and a dicarboxylic acid having 4 to 6 carbon atoms, and the terminal group is a monovalent acid or monovalent acid having 1 to 3 carbon atoms. Polyester having a molecular weight of 150 to 400, which is composed of the following alcohol residues, is preferably used. Among the resins that can be added to the polyvinylidene fluoride resin, methyl methacrylate is preferred, and may be contained in an amount of about 5% by weight based on 100% by weight of the polyvinylidene fluoride resin. Especially when polymethyl methacrylate is polymer blended, methyl polymethacrylate is an amorphous resin, so it has better compatibility with poly (vinylidene fluoride) resin than poly (vinylidene fluoride) resin, and the coloring property of dye. Can be expected to improve. However, when the mixing amount of the polymer methyl acrylate increases, the monofilament becomes flexible. Addition of 10% by weight or more is not preferable because there is a possibility that the strength and tensile strength may be reduced. The perylene-based fluorescent dye used in the present invention has a perylene skeleton as disclosed in JP-A-57-125260, JP-A-58-40359 and JP-A-60-203650. Compounds are collectively included. Among them, for example, Lumogen ^TR F Yellow 083 (manufactured by BASF Japan Co.), Lumogen ^TR F Orange 240 (manufactured by BASF Japan Co.), Lumogen ^TR F Red 300 (BASF Japan Co., Ltd.) And perylene fluorescent dyes and the like.

The content of the perylene fluorescent dye is not particularly limited, but is usually 0.001 to 0.5 part by weight, and more preferably 0.005 to 0.1 part by weight based on 100 parts by weight of the polyvinylidene fluoride resin. It is particularly preferably 0.01 to 0.05 part by weight. When the content is in the range of 0.001 to 0.5 parts by weight, the luster can be exhibited and the visibility can be obtained. Furthermore, the characteristics of the polyvinylidene fluoride monofilament

(Eg, high specific gravity, refractive index close to water, and lack of water absorption) can be maintained. When the content of the dye is less than 0.001 part by weight, the color tone is so thin that no glitter is exhibited and it is difficult to obtain sufficient visibility. On the other hand, if the content exceeds 0.5 parts by weight, the color becomes too dark, the light absorption increases, and conversely the glitter and the visibility may decrease, which is not preferable. In order to further exert the effect of the present invention, metal stones such as calcium stearate (Ca-St), zinc stearate, magnesium stearate, and lead stearate are preferably used. Of these, calcium stearate improves the spinnability of the melt during melt spinning and has the effect of suppressing the occurrence of slabs on the yarn surface. In particular, when a perylene-based dye is added to polyvinylidene fluoride resin, slabs tend to be generated, probably because the fluidity of the resin with the metal inner wall such as a nozzle decreases and the adhesiveness increases. Prevent this As a means for stopping the addition, the addition of metal stones is effective. The amount of the metal stone added is preferably about 0.001 to 0.1 part by weight, more preferably about 0.05 to 0.5 part by weight, based on 100 parts by weight of the polyvinylidene fluoride resin. In addition, additives such as an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antioxidant may be contained as long as the effects of the present invention are not impaired. The perylene fluorescent dye, metal stones, and other additives may be added individually to each other, but it is so-called diluted with polyvinylidene fluoride resin or other resin used as a constituent material of the yarn. Usually, a master batch is prepared and used in a predetermined amount. The polyvinylidene fluoride resin composition is a resin composition comprising a polyvinylidene fluoride resin and at least a perylene fluorescent dye. This resin composition may be a mixture of a polyvinylidene fluoride resin and a perylene fluorescent dye, a dry blend as described below, or a pellet. The polyvinylidene fluoride resin composition can be prepared by a known method. For example, a perylene-based fluorescent dye previously prepared by diluting with polyvinylidene fluoride resin and optionally a batch of metal lithography can be added to polyvinylidene fluoride resin in a predetermined amount and dry blended to obtain a powdery material. Or a method of simply mixing the raw material polyvinylidene fluoride resin alone and the above-mentioned perylene-based fluorescent dye, or a method of keeping the resin composition in a pellet form. The powder or pellet of the obtained resin composition is charged into an extruder, and extruded at an extrusion set temperature of 300 ° C. or lower, preferably 230 to 280 ° C., and 30 to 80 ° C. Quickly cool underwater. Then, it is stretched 4.5 to 6.5 times in a heat medium such as glycerin at 150 to 180 ° C. (in some cases, stretching may be performed in two or more stages). Perform a relaxation treatment of 2 to 12% in warm water of ~ 98 ° C. At this time, the molten resin composition stays in the extruder. The retention time is preferably within 60 minutes, more preferably 10 to 40 minutes. If the residence time in the extruder exceeds 60 minutes, decomposition of the resin composition, particularly a perylene dye, starts, and discoloration of the spun yarn and foaming on the surface of the yarn may occur, which is not preferable. Furthermore, when the polyvinylidene fluoride resin is combined with a perylene dye, and when the amount of the perylene dye added is increased to increase the color density, the dispersibility and compatibility of the dye in the resin are reduced. However, the residence time of the resin in the extruder is important because the perylene dye tends to be easily decomposed and discolored depending on the residence time in the extruder.

In particular, in fishing line, when the pattern becomes fine, such as 0.1 line (diameter of 50 mm), the amount of extrusion decreases and the residence time in the extruder becomes extremely long. I need it.

The yarn diameter of the monofilament is not particularly limited, but is usually 50 ^ 111 to 2.5 mm. The obtained monofilament is used as a fishing line. Further, it is preferable that the knot strength of the monofilament satisfies the condition represented by the formula (1) from the viewpoint of toughness as a road yarn. As for the polyvinylidene fluoride monofilament, as the fishing line becomes thinner, the knot strength becomes more important as the fishing line becomes thinner. Conversely, as the thickness increases, the knot strength becomes more difficult to appear due to its nature. The monofilament of the present invention is colored into a clear fluorescent color with a perylene fluorescent dye, and becomes a transparent and highly visible fishing line, particularly a transparent polyvinylidene fluoride monofilament suitable for road yarn. Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In addition, the evaluation method was performed as follows.

Knot strength and elongation: Using a Strograph RII type tensile tester manufactured by Toyo Seiki Seisaku-sho, Ltd. in a room at 23 ° C and 65 RH%, a test length of 300 mm, a tensile speed of 300 mmZ, and measurement Number n = In step 5, a knot was provided at the center of the sample, and the knot strength was measured. Raw materials used

Polyvinylidene fluoride resin: KF # 1300 (manufactured by Kureha Chemical Co., Ltd., melting point 174 ° C, 77 inh = 1.3).

Color dyes and pigments:

Lumogen F Yellow 083 (a perylene fluorescent dye manufactured by Bas F Japan Co., Ltd.).

Lumogen F Orange 240 (a perylene-based fluorescent dye manufactured by BASF Japan Ltd.).

Lumogen F Red 300 (a perylene fluorescent dye manufactured by BAS F Japan Ltd.).

Epokara FP-1007 Yellow Green (Nippon Shokubai Co., Ltd., pigment resin color).

Nubian Black PC-0850 (Azine dye manufactured by Orient Chemical Co., Ltd.).

Metallic stone-based lubricant:

Calcium stearate (Ca-St) (manufactured by Kanto Chemical Co., Ltd.). (Examples 1 to 7)

PVDF (Dallade KF # 1300) is used as the raw material resin for polyvinylidene fluoride monofilament, and the colorants and metal stones shown in Table 1 are added to this resin in predetermined amounts, and dry-blended to form each resin composition. Things. Next, this composition was extruded using a 35 mm φ extruder and a 1.3 ηπηφΧ 6-hole nozzle with an extruded resin temperature of 250 to 280 ° (: extruder gears and pump rotation speed of 6.1 rpm. And quenched in water at a cooling temperature of 50. Then, 5.5 times in a glycerin bath at 167 ° C. It was stretched and then subjected to 5% relaxation heat treatment in 85 hot water to obtain a monofilament having a diameter of 3 mm.

(Comparative Example 1)

The procedure was carried out in the same manner as in Example 1 except that spinning was performed without adding a coloring agent. (Comparative Example 2)

The procedure was the same as in Example 1 except that a pigment resin color at a heat resistance temperature of 280, which was developed for use in nylon, was used as the fluorescent colorant. The resulting monofilament had a dull yellow-green color, discolored, and had reduced strength.

(Comparative Example 3)

The procedure was performed in the same manner as in Example 1 except that an azine-based dye was used as a coloring agent. A dye with a heat-resistant temperature of 300 ° C, which was developed for engineering plastic resins such as polycarbonate and polyethylene terephthalate, was used, but the resulting monofilament decomposed and swelled due to foaming on the surface. Also, the strength was reduced.

(Comparative Example 4)

The raw material formulation was the same as in Example 1 except that the rotation speed of the gear pump was reduced to 3.2 rpm to obtain a monofilament having a fine pattern, and a monofilament having a diameter of 0.22 mm was obtained. The monofilament obtained had an orange color tone, degraded on the surface, swelled due to foaming, and had a reduced strength. The measured residence time of the molten resin in the extruder was 98 minutes, which is considered to be the cause.

(Example 8)

In order to obtain a monofilament having a fine pattern with the same raw material formulation as in Example 1, the nozzle was mm φ X 24 holes, switch the extruding temperature from 255 to 290, set the gear pump rotation speed to 13 rpm, increase the discharge rate and spin. A monofilament having a diameter of 0.22 mm was obtained under rapid cooling, stretching and relaxation conditions. The monofilament thus obtained did not show any swelling due to decomposition or foaming on the surface, was colored in a clear fluorescent yellow, and had sufficient strength. During the extrusion, the residence time of the resin in the extruder was measured and was found to be as short as 25 minutes. This is considered to be able to suppress the decomposition of the dye. Table 2 shows the evaluation results of the samples obtained in the examples and comparative examples.

P VDF resin Coloring agent Metal stone Extruder

(Parts by weight) (weight-parts) (parts by weight) Residence time

KF Lumogen F Lumogen F Lumogen F Eppocolor Nubian Black (min)

# 1300 Yellow Orange Red FP-1007 PC-0850 Ca-St Example 1 100 0.02 0 0 0 0 0.01 52 Example 2 100 0.005 0 0 0 0 0.01 52 Example 3 100 0. 01 0 0 0 0 0.01 52 Example 4 100 0.05 0 0 0 0 0.01 52 Example 5 100 0.02 0 0 0 0 0 52 Example 6 100 0 0.02 0 0 0 0. 01 52 Example 7 100 0 0 0.02 0 0 0.01 52 Example 8 100 0.02 0 0 0 0 0.01 25 Comparative example 1 100 0 0 0 0 0 0. 01 52 Comparative example 2 100 0 0 0 0.02 0 0.01 52 Comparative example 3 100 0 0 0 0 0.02 0.01 52 Comparative example 4 100 0.02 0 0 0 0 0.01 98

Table 2

Yarn diameter Knot strength Knot elongation Color tone Yarn appearance

, Mm) (GP a) (%)

Example 1 0.30-527 19.3 Vivid fluorescent yellow Smooth Good

Example 2 0.30 0.57 20.8 Vivid Fluorescent Yellow Green Smooth Good

Example 3 0.30 0.55 19.8 Clear fluorescent yellow Smooth Good

Example 4 0.30 0.50 520 21.6 Vivid Fluorescent Yellow Smooth Good

Example 5 0.30 0.52 52.2 Clear fluorescent yellow smooth (slightly with slabs) Example 6 0.30 0.5 1 7 19.2 Clear fluorescent orange smooth good

Example 7 0.30 0.50 530 20.1 Clear fluorescent red Smooth Good

Example 8 0.22 0.597 20.1 Clear fluorescent yellow Smooth Good

Comparative Example 1 0.30 0.53 533 20.1 Colorless Transparent Smooth Good

Comparative Example 2 0.30 0.42 1 16.3 Degraded yellow-green Decomposition-There is swelling due to foaming Comparative Example 3 0.30. . 46 1 16.5 Orange-yellow yellow Decomposition / swelling due to foaming

Industrial applicability

According to the present invention, the characteristics of the fishing line made of polyvinylidene fluoride monofilament are maintained by the monofilament made of the polyvinylidene fluoride resin composition containing the perylene fluorescent dye, and no discoloration of the colorant is observed. It is possible to provide a monofilament which forms a fishing line which is colored in a vivid fluorescent color and has excellent visibility, and a method for producing the same.

Claims

The scope of the claims

1. A monofilament made of a polyvinylidene fluoride resin composition containing a perylene fluorescent dye.

2. The monofilament according to claim 1, wherein the content of the perylene fluorescent dye is 0.001 to 0.5 part by weight based on 100 parts by weight of polyvinylidene fluoride.

3. The monofilament according to claim 1, wherein the knot strength is represented by the following formula (1).

Numerical value of knot strength [GPa] ≥ {(25 / (numerical value of thread diameter [m]))} ^1/3 (1)

4. The method for producing a monofilament according to any one of claims 1 to 3, wherein the polyvinylidene fluoride resin composition is spun within an extrusion set temperature of 300 or less and an extruder residence time of 60 minutes or less.

5. A fishing line comprising the monofilament according to any one of claims 1 to 3.