JP4217802B2 - Colored high strength polyethylene fiber - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to colored high strength polyethylene fibers. More specifically, the present invention relates to a high-strength polyethylene fiber that is suitable as a material for ropes, nets, fishing lines, protective articles and clothing similar products that are required to have high strength and aesthetics.
[0002]
[Prior art]
Conventionally, high-strength polyethylene fibers have been widely used in the fields of ropes, fishing lines, cords, high-performance clothing such as uniforms, seat belts, safety belts, etc. by taking advantage of their excellent strength, elastic modulus and chemical resistance. I came. However, colored high-strength polyethylene fibers having excellent light fastness and sufficient fastness have not been obtained at present, and therefore the use of high-strength polyethylene fibers tends to be limited.
Coloring high-strength polyethylene fibers is generally performed after forming the fiber by forming a so-called “original method” in which raw materials are mixed with various dyes, pigments, or inorganic compounds such as carbon black and titanium oxide. There are methods for obtaining colored fibers by various dyeing techniques. In the original deposition method, an inorganic compound or the like is added in the manufacturing process, so that the additive acts as a defect in a crystal formation process for developing high strength, 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 crystallinity and simple structure is a dyed or colored product with sufficient fastness. It was difficult to get.
[0003]
[Problems to be solved by the invention]
The present invention relates to the particle size, aggregation state and content of pigments that do not act as defects in the crystal formation process for developing high strength, and the colored high strength polyethylene fibers are excellent in light resistance and sufficiently fastened. This is a result of intensive studies on a method for obtaining a high-strength polyethylene fiber having a high degree of strength.
[0004]
[Means for Solving the Problems]
That is, the present invention is 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.
As a specific embodiment, the particle aggregate is composed of 10 or less particles, and the content of the above-described strong polyethylene fiber and pigment is 0.01 to 2.50 wt%. The above-mentioned strong polyethylene fiber.
[0005]
For high-strength polyethylene fibers that are colored while maintaining sufficiently high strength, it is essential that the colorant contained in the fibers is composed of pigments such as organic, inorganic, and carbon black. This is because the pigment particles in the fiber are taken into the polyethylene crystal, and the migration to the outside of the fiber is suppressed, so that it is considered that the pigment particle is 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 does not act as a defect during orientation crystallization that occurs during the fiber formation process of polyethylene, and is taken into the crystal. That is, when the average particle diameter exceeds 100 nm, it acts as a defect during 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 is not preferable.
[0007]
The particle aggregate is preferably composed of 10 or less particles. If the number exceeds 10, the high-strength polyethylene fibers that have been colored are prevented from exhibiting high elongation, and as a result, the high-strength polyethylene fibers that have been colored have low strength. Preferably 1-8.
[0008]
In a high-strength polyethylene fiber colored while maintaining a sufficiently high strength, the content of the pigment as the colorant contained in the fiber is 0.01% to 2.50% by weight, preferably the pigment content If the amount is less than 0.01% by weight, which is 0.10% by weight to 2.00% by weight, the coloring effect cannot be exerted. If it exceeds 2.50% by weight, the weather resistance of the high strength polyethylene fiber is good. , Strength and initial elastic modulus are reduced.
[0009]
The high-strength polyethylene fiber colored here has at least a strength of 2.0 GPa or more, preferably 3.5 GPa or more, and an initial elastic modulus of 70 GPa or more, preferably 80 GPa or more.
[0010]
The strength elongation measurement was in accordance with JISL-1013 (1981). That is, an SS curve was measured under the conditions of a test length of 200 mm and a pulling speed of 100 mm / min using Tensilon manufactured by Orientec Co., Ltd., and an SS curve was measured under the conditions of a test length of 200 mm and a pulling speed of 100 mm / min. Were measured, and the tensile strength at break and initial tensile modulus were calculated. The initial tensile modulus was calculated from the maximum gradient near the origin of the curve.
[0011]
The weather resistance was evaluated by using machine stand sunshine super, long life, weather life, weather meter (WEL-SUN-HCH-B BR) with an irradiation temperature of 63 ± 3 ° C, an irradiation time of 150 hours, and a rain condition of 60 minutes with a period of 12 minutes. Evaluated by rainfall.
[0012]
The distribution of the pigment in the fiber cross section and the evaluation of the particle diameter were measured under the following conditions.
The sample was embedded in epoxy resin and allowed to cure overnight at 60 ° C. An ultra-thin slice having a thickness of about 70 mm was prepared from the cured embedded sample using an LKB ultramicrotome equipped with diamond. After the treatment for improving the section cutting property, the ultrathin section was placed on a carbon-deposited form bar support film to prepare a sample for TEM observation. JEM-2010 type TEM manufactured by JEOL Ltd. was used for TEM observation. The magnification is 50,000 times.
[0013]
As a method for producing a high-strength polyethylene fiber, a gel obtained by solution spinning a solution of ultrahigh molecular weight polyethylene as described in JP-A-55-107506 and JP-A-56-154508 A method of drawing a filament is used. Also in the present invention, it is performed according to the method described in the above publication.
[0014]
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not restrict | limited to each Example, unless the summary is exceeded.
[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 dissolved by a screw extruder set at a temperature of 180 ° C. to 220 ° C., and then from an orifice having a diameter of 0.5 mm. The material was taken out at a take-off speed of 75 m / min and then stretched 4 times in an oven under heated air (100 ° C.). At that time, a mixture of polyethylene and decahydronaphthalene was subjected to fine powdering treatment with carbon black REGAL 330R (aggregate average diameter: 1.41 mm, Max 9.29 mm, Min 0.22 mm) as a colorant. 0.05% by weight of carbon black was added to decahydronaphthalene.
The obtained intermediate stretched product was further stretched 4.3 times to obtain colored high-strength polyethylene fibers having a strength of 3.62 GPa and an initial elastic modulus of 129 GPa. The particle size of carbon black dispersed in the fiber cross section was in the range of 10 nm to 50 nm, and the number of aggregated particles was 1 to 6. Moreover, the evaluation result of the weather resistance of this fiber was as excellent as grade 4-5, and the strength retention was 90%.
[0016]
(Example 2)
A high-strength polyethylene fiber was produced in the same manner as in Example 1 except that 0.20% by weight of carbon black treated with fine powder was added to decahydronaphthalene.
The obtained colored high-strength polyethylene fiber had a strength of 2.5 GPa, an initial elastic modulus of 90 GPa, and the evaluation result of the weather resistance of the fiber was grade 4-5.
[0017]
(Example 3)
A high-strength polyethylene fiber was produced in the same manner as in Example 1 except that 0.25% by weight of carbon black treated with fine powder was added to decahydronaphthalene.
The obtained colored high strength polyethylene fiber had a strength of 1.9 GPa and an initial elastic modulus of 67 GPa. Moreover, the evaluation result of the weather resistance was 4-5 grade.
[0018]
(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 the 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 carbon black dispersed in the fiber cross-section had a particle diameter in the range of 50 nm to 100 nm, and the number of aggregated particles was about 15-30. Moreover, the weather resistance evaluation result of this fiber was not as good as the third grade. Since there was difficulty in spinnability, the evaluation of the above-mentioned fiber was carried out using an evaluable part.
[0019]
(Comparative Example 2)
Further, spinning was attempted by adding 0.10% by weight of carbon black not subjected to the above fine powder treatment, but spinning was impossible.
[0020]
【The invention's effect】
According to the present invention, it is possible to provide a colored high-strength polyethylene fiber having excellent weather resistance while maintaining high strength and high elastic modulus and sufficient fastness.

Claims (3)

A fiber produced after mixing ultra-high molecular weight polyethylene and a pigment, containing 0.01 to 2.50 wt % of a pigment composed of a particle aggregate having an average particle diameter of 10 to 100 nm, and a strength of 2.0 GPa or more, A high-strength polyethylene fiber having an initial elastic modulus of 70 GPa or more.  The high-strength polyethylene fiber according to claim 1, wherein the particle aggregate is composed of 10 or less particles. The high-strength polyethylene fiber according to claim 1 or 2 , wherein the pigment is carbon black.