JPH1121721A - Colored high-tenacity polyethylene yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject yarn having strength and initial modulus of elasticity of specific values or higher than them, respectively, suitable as materials such as rope, net, fishing line, protecting articles and articles close to clothing, by including a pigment comprising a particle aggregate having a specific particle diameter. SOLUTION: This yarn contains a pigment composed of a particle aggregate comprising <=10, preferably 1-8 particles having 10-100 nm average particle diameter and has >=2.0 GPa, preferably 3.5 GPa, >=70 GPa, preferably >=80 GPa initial modulus of elasticity. Preferably the content of the pigment is preferably 0.01-2.50 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored high-strength polyethylene fiber. More specifically, the present invention relates to ropes, nets, fishing lines,
The present invention relates to a high-strength polyethylene fiber suitable as a material for protective articles and clothing similar articles.

[0002]

2. Description of the Related Art Hitherto, high-strength polyethylene fibers have been used for ropes, fishing lines, cords, high-performance clothing such as uniforms, seat belts, safety belts, etc. by utilizing their excellent strength, elastic modulus and chemical resistance. It has been widely used in the field. However, a colored high-strength polyethylene fiber having excellent light fastness and sufficient fastness has not been obtained at present, and thus the use of the high-strength polyethylene fiber tends to be limited. Coloring of high-strength polyethylene fibers is generally performed by mixing the raw material polymer with various dyes, pigments, or inorganic compounds such as carbon black and titanium oxide. There is a method of obtaining colored fibers by various dyeing techniques. In the soaking method, an inorganic compound is added in the manufacturing process, so that the additive acts as a defect in a crystal forming process for expressing high strength, etc., which causes a decrease in strength, and therefore, at a high concentration. Is difficult to add. On the other hand, when applying the technique of dyeing after forming fibers to high-strength polyethylene fibers, polyethylene with a very high degree of crystallinity and a simple structure can be dyed or colored with sufficient fastness. Was difficult to obtain.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to the particle size, agglomeration state and content of a pigment which does not act as a defect in the process of forming crystals for expressing high strength, and also relates to colored high strength polyethylene fibers. Has been made as a result of intensive studies on a method for obtaining a high-strength polyethylene fiber having excellent light fastness and sufficient fastness.

[0004]

That is, the present invention provides a pigment containing a particle aggregate having an average particle diameter of 10 to 100 nm, a strength of 2.0 GPa or more, and an initial elastic modulus of 70 or more.
It is a high-strength polyethylene fiber characterized by GPa or more. As a specific embodiment thereof, the strong polyethylene fiber described above, wherein the particle aggregate is composed of 10 or less particles, and the content of the pigment is 0.0
The strong polyethylene fiber according to the above, wherein the content is 1 to 2.50 wt%.

[0005] For high-strength polyethylene fibers that are colored while maintaining a sufficiently high strength, it is essential that the coloring agent contained in the fibers be composed of pigments such as organic, inorganic and carbon black. This is because the pigment particles in the fiber are taken in the crystal of the polyethylene, so that migration outside the fiber is suppressed, so that the fiber is considered to be stably held.

[0006] In the colored high-strength polyethylene fiber, it is desirable that the average particle diameter of the pigment, which is a particle aggregate dispersed in the cross section of the fiber, is in the range of 10 nm to 100 nm. This is because the particle size of the pigment particles is such that the particles of the pigment do not act as defects at the time of orientational crystallization that occurs in the process of forming polyethylene fibers and are taken into the crystals. That is,
If the average particle size exceeds 100 nm, it acts as a defect at the time of crystallization, and the resulting colored high-strength polyethylene fiber has low strength. On the other hand, if the average particle size is less than 10 nm, migration occurs, which is not preferable.

It is preferable that the particle aggregate is composed of 10 or less particles. If the number exceeds 10, the high tensile strength of the colored high-strength polyethylene fiber is hindered, and as a result, the colored high-strength polyethylene fiber has a low tensile strength. Preferably, the number is 1 to 8.

[0008] In a high-strength polyethylene fiber colored while maintaining a sufficiently high strength, the content of a pigment as a colorant contained in the fiber is from 0.01% by weight to 2.%.
50% by weight, preferably 0.10% by weight pigment content
If it is less than 0.01% by weight which is less than 2.00% by weight, the coloring effect cannot be exhibited, and if it exceeds 2.50% by weight, the weather resistance of the high-strength polyethylene fiber is good, but the strength and the initial elastic modulus are low. descend.

The colored high-strength polyethylene fibers have a strength of at least 2.0 GPa, preferably 3.
5 GPa or more, the initial elastic modulus is 70 GPa or more, preferably 80 GPa or more.

The elongation is measured according to JISL-1013 (198).
According to 1). That is, the SS curve was measured using Orientec Tensilon at a test length of 200 mm and a tensile speed of 100 mm / min, and the S-S curve was measured with the tensile breaking strength at a test length of 200 mm and a tensile speed of 100 mm / min.
The S curve was measured, and the tensile strength at break and the initial tensile modulus were calculated. The initial tensile modulus was calculated from the maximum gradient near the origin of the curve.

The weather resistance was evaluated using a machine sunshine super, long life, weather life, and weather meter (WEL-SUN-HCH-BBR) at an irradiation temperature of 63 ± 3 ° C., an irradiation time of 150 hours, and a rainfall condition of 60 minutes. Evaluation was performed with a 12-minute cycle rainfall.

The distribution and the particle size of the pigment on the fiber cross section were evaluated under the following conditions. Embed the sample in epoxy resin,
Allowed to cure overnight at 0 ° C. From the embedded sample after curing, an ultra-thin section having a thickness of about 70 mm was prepared using an ultramicrotome manufactured by LKB equipped with diamond. After processing for improving section cutability, the ultra-thin section was mounted on a carbon-deposited formvar supporting film to obtain a TEM observation sample. TEM observation was made by JEOL JEM-2
A 010 type TEM was used. The magnification is 50,000 times.

As a method for producing a high-strength polyethylene fiber, Japanese Patent Application Laid-Open No. 55-107506 and
A method of drawing a gel filament obtained by solution spinning a solution of ultra-high molecular weight polyethylene as described in JP-A-6-154508 is used. Also in the present invention, the method is performed according to the method described in the above-mentioned publication.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples.
It is not limited to each embodiment.

[0015]

【Example】

Example 1 A mixture of 10% by weight of ultrahigh molecular weight polyethylene having a viscosity average molecular weight of 3.2 million and 90% by weight of decahydronaphthalene was kneaded and melted by a screw extruder set at a temperature of 180 ° C. to 220 ° C. to obtain a diameter of 0. It was extruded through a 0.5 mm orifice, pulled at a pulling speed of 75 m / min, and then stretched 4 times in an oven under heated air (100 ° C.). At that time, a carbon black REGAL 330R (average diameter of agglomerates of 1.41) was used as a coloring agent in a mixture of polyethylene and decahydronaphthalene.
mm, Max 9.29 mm, Min 0.22 mm), and 0.05% by weight of decahydronaphthalene was added to the carbon black subjected to the fine powder treatment. The obtained intermediate stretched product was further stretched 4.3 times to obtain a colored high-strength polyethylene fiber having a strength of 3.62 GPa and an initial elastic modulus of 129 GPa. The particle size of the carbon black dispersed in the fiber cross section is from 10 nm to 50 nm.
In the range of nm, the number of aggregated particles was 1 to 6. In addition, the evaluation result of the weather resistance of the fiber was as excellent as 4-5 class, and the strength retention was 90%.

Example 2 A high-strength polyethylene fiber was produced in the same manner as in Example 1, except that 0.20% by weight of decahydronaphthalene was added to the carbon black subjected to the fine powder treatment. The strength of the obtained colored high-strength polyethylene fiber is 2.5 GPa, and the initial elastic modulus is 90 G
Pa, and the evaluation result of the weather resistance of the fiber was grade 4-5.

Example 3 A high-strength polyethylene fiber was produced in the same manner as in Example 1 except that 0.25% by weight of decahydronaphthalene was added to carbon black subjected to fine powder treatment. The strength of the obtained colored high-strength polyethylene fiber is 1.9 GPa and the initial elastic modulus is 67 G
Pa. Moreover, the evaluation result of the weather resistance was 4-5 grade.

Comparative Example 1 A high-strength polyethylene fiber was produced in the same manner as in Example 1 except that 0.05% by weight of carbon black not subjected to fine powder treatment of a colorant was added. The obtained fiber was a colored high-strength polyethylene fiber having a strength of 1.8 GPa and an initial elastic modulus of 60 GPa. The particle diameter of the carbon black dispersed in the fiber cross section was in the range of 50 nm to 100 nm, and the number of aggregated particles was about 15 to 30. The weather resistance evaluation result of this fiber was not good at class 3. There was a difficulty in spinnability, and the above fibers were evaluated using a portion that could be evaluated.

(Comparative Example 2) Spinning was attempted by adding 0.10% by weight of carbon black not subjected to the fine powder treatment, but spinning was impossible.

[0020]

According to the present invention, it has become possible to provide a colored high-strength polyethylene fiber having a high tenacity, a high modulus of elasticity, and excellent weather resistance and sufficient fastness.

Claims (3)

[Claims] 1. A high-strength polyethylene fiber containing a pigment composed of a particle aggregate having an average particle diameter of 10 to 100 nm, having a strength of 2.0 GPa or more and an initial elastic modulus of 70 GPa or more. 2. The high-strength polyethylene fiber according to claim 1, wherein the particle aggregate is composed of 10 or less particles. 3. A pigment content of 0.01 to 2.50 wt.
% Of the high-strength polyethylene fiber according to claim 1.