TWI715733B - Colored polyethylene fibers, braided ropes, fishing lines, gloves, ropes, nets, knitted fabrics or braids, and methods for manufacturing colored polyethylene fibers - Google Patents

Abstract

The colored polyethylene fiber of the present invention is obtained by the CIE-L*a*b* color system. The L* value is 80 or less, and the color fastness to rubbing is 3 or more in the dry and wet state, or The solvent resistance obtained by the predetermined measurement method is 75% or more. Therefore, the colored polyethylene fiber of the present invention is colored into a dense color, and it is difficult to cause bleaching or color shift, and furthermore, it has both uniform dyeing with less unevenness and high strength.

Description

Colored polyethylene fiber, braided rope, fishing line, gloves, rope, net, knitted or braided fabric and manufacturing method of colored polyethylene fiber

The present invention relates to a colored polyethylene fiber.

Previously, various technologies have been disclosed as a method of manufacturing colored fibers. However, high-strength polyethylene has the following problems: due to its simple chemical structure or very high crystallinity, it is difficult to obtain polyethylene fibers with a hue or color fastness that meets market requirements. In order to solve this problem, for example, Patent Document 1 discloses a method of adding dyes from the raw material blending stage to obtain dyed yarns, and Patent Document 2 discloses a method of applying dyes to intermediate stretched yarns under heating. .

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent No. 3143886.

Patent Document 2: Japanese Patent Publication "Japanese Patent Laid-Open No. 4-289212".

However, in the case of dyeing raw yarns, there is a problem that it is difficult to color dense due to the limit of the concentration of dyes that can be added in the raw material blending stage. In addition, when dyes are applied to the intermediate stretched yarn under heating, there are the following problems: the thermal history of the intermediate stretched yarn affects the subsequent stretching, resulting in uneven fiber thickness, and it is difficult to achieve the strength in the longitudinal direction of the fiber. Uniform dyeing or less uneven dyeing.

Therefore, the object of the present invention is to solve the aforementioned problems. In other words, it provides a polyethylene fiber that is colored to a dense color and is difficult to decolor or color shift, and further provides a colored polyethylene fiber that has both uniform dyeing and high strength with less unevenness and a manufacturing method thereof.

The inventors of the present invention have made repeated efforts to solve the aforementioned problems and found that by applying a coloring material to the polyethylene fibrous substance under specific conditions and performing a heat treatment step, a colored polyethylene with deep color and excellent color fastness can be obtained. Fiber, thus completing the present invention.

That is, the colored polyethylene fiber of the present invention is characterized in that: the L ^* value obtained by the CIE (Commission Internationale de L'Eclairage; International Commission on Illumination)-L ^* a ^* b ^* color system is less than 80, and the friction The color fastness is above grade 3 in both dry and wet state.

In addition, the colored polyethylene fiber of the present invention is preferably in the longitudinal direction The coefficient of variation (CV) defined by the following formula 1 of the tensile strength measured at any 10 points is 10% or less.

Coefficient of variation of tensile strength (%)=(standard deviation of tensile strength/average value of tensile strength)×100 (Equation 1)

In addition, the colored polyethylene fiber of the present invention preferably has an acid value of 0.1 mgKOH/g or more and 50 mgKOH/g or less.

Alternatively, the colored polyethylene fiber of the present invention preferably contains a surfactant having an HLB value (Hydrophile-Lipophile Balance) of 7.0 or more and 14.0 or less of 0.4% or more and 5.0% or less.

The present invention also includes colored polyethylene fibers having a solvent resistance of 75% or more as determined by the following measurement method.

[Measurement method of solvent resistance]

The colored polyethylene fiber was immersed in acetone so that it might become 0.1g/mL, and it left still at room temperature for 24 hours. For acetone used to impregnate colored polyethylene fibers and acetone impregnated with colored polyethylene fibers and allowed to stand at 20°C±5°C for 24 hours, use an ultraviolet-visible spectrophotometer to measure the transmittance in the wavelength range from 350nm to 780nm, according to From the obtained transmittance curve, the integral value of the transmittance in the above-mentioned wavelength range is calculated, and the solvent resistance is calculated by the following formula 2.

Solvent resistance (%)=(T ₁ /T ₀ )×100 (Equation 2)

In Formula 2, T ₀ represents the integral value of the transmittance of acetone at a wavelength of 350 nm to 780 nm, and T ₁ represents the integral value of the transmittance of acetone after impregnating colored polyethylene fibers at a wavelength of 350 nm to 780 nm.

In addition, the colored polyethylene fiber of the present invention preferably has a fineness variation in the longitudinal direction of 10% or less. In addition, the tensile strength is preferably 18 cN/dtex or more. Furthermore, the colored polyethylene fiber of the present invention is preferably a colored material containing an oil-soluble dye. In addition, the monofilament fineness of the colored polyethylene fiber of the present invention is preferably 1 dtex or more and 80 dtex or less.

In addition, the present invention includes a braided rope containing at least one colored polyethylene fiber, a fishing line containing the colored polyethylene fiber, gloves, ropes, nets, knitted fabrics or knitted fabrics. The strength of the fiber obtained by untying the above braided rope is preferably 15 cN/dtex or more.

The method for producing colored polyethylene fiber of the present invention is characterized by comprising: spinning a polyethylene solution obtained by dissolving polyethylene in an organic solvent such that the concentration becomes 0.5% to 40% by mass to obtain polyethylene fiber In the step of forming a substance, the limiting viscosity [η] of the polyethylene is 5.0 dL/g or more and 25 dL/g or less, and the repeating unit of the polyethylene is composed of 90 mol% or more of ethylene; the content is less than 20% by mass The step of contacting the polyethylene fiber of the organic solvent with the coloring liquid, the coloring liquid contains the coloring material and the organic solvent, and the temperature is 0°C or more and less than 60°C; the content is less than 25% relative to the weight of the fiber provided with the coloring liquid The step of heating the polyethylene fiber material of organic solvent at 110°C for more than 10 seconds; And the step of extending the polyethylene fiber.

In addition, the method for producing colored polyethylene fibers of the present invention is characterized by comprising: spinning a polyethylene solution prepared by dissolving polyethylene in an organic solvent so that the concentration becomes 0.5% to 40% by mass to obtain poly In the step of ethylene fibrous material, the limit viscosity [η] of the polyethylene is 5.0 dL/g or more and 25 dL/g or less, and the repeating unit of the polyethylene is composed of 90 mol% or more of ethylene; The step of contacting the fibrous material with the coloring liquid. The coloring liquid contains a coloring material and a polyolefin with a hydrophilic group at one end, and the temperature is 0°C or more and less than 60°C; The step of heating for more than 10 seconds at a temperature above °C; and the step of stretching the aforementioned polyethylene fiber.

In addition, the method for producing colored polyethylene fibers of the present invention is characterized by comprising: spinning a polyethylene solution prepared by dissolving polyethylene in an organic solvent so that the concentration becomes 0.5% to 40% by mass to obtain poly In the case of ethylene fibrous material, the limit viscosity [η] of the polyethylene is 5.0 dL/g or more and 25 dL/g or less, and the repeating unit of the polyethylene is composed of 90 mol% or more of ethylene; The step of contacting the fibrous material with the coloring liquid, the coloring liquid contains a coloring material and a surfactant with an HLB value of 7.0 or more and 14.0 or less, and the temperature is 0°C or more and less than 60°C; the polyethylene fiber shape imparted with the coloring liquid The step of heating the material above 110°C for more than 10 seconds; and the step of extending the aforementioned polyethylene fiber.

In the method for producing the colored polyethylene fiber of the present invention, it is preferable that the temperature of the polyethylene fibrous material contacted with the coloring liquid is 50°C or less. In addition, it is preferable to perform the heating while applying a tension of 0.8 cN/dtex to 6.5 cN/dtex to the polyethylene fiber to which the coloring liquid is applied. In addition, it is preferable to include a step of stretching the polyethylene fiber to which the coloring liquid is applied at a stretching ratio of 2 times or more.

According to the present invention, it is possible to provide a colored polyethylene fiber that is colored to a deep color and has excellent color fastness to rubbing and/or solvent resistance. In addition, the polyethylene fiber has high strength and little unevenness in strength and fineness, so it can be suitably used as a material for braided ropes, fishing lines, gloves, ropes, nets, knitted fabrics, and woven fabrics. In addition, for this polyethylene fiber, if water is used as a solvent for the coloring material, it can be manufactured with reduced environmental load.

Hereinafter, the present invention will be described in detail.

[Embodiment 1]

The characteristics of the colored polyethylene fiber of this embodiment are: (I) The L ^* value obtained by the CIE-L ^* a ^* b ^* color system is less than 80, and the color fastness to rubbing is in the dry state and the wet state All are Grade 3 or higher; or (II) Solvent resistance determined by the following measurement method is 75% or higher.

[Measurement method of solvent resistance]

The colored polyethylene fiber was immersed in acetone so that it might become 0.1g/mL, and it left still at room temperature for 24 hours. For acetone used to impregnate colored polyethylene fibers and acetone impregnated with colored polyethylene fibers and allowed to stand at 20°C±5°C for 24 hours, use an ultraviolet-visible spectrophotometer to measure the transmittance in the wavelength range from 350nm to 780nm, according to From the obtained transmittance curve, the integral value of the transmittance in the above-mentioned wavelength range is calculated, and the solvent resistance is calculated by the following formula 2.

Solvent resistance (%)=(T ₁ /T ₀ )×100 (Equation 2)

In formula 2, T ₀ represents the integral value of the transmittance of acetone (reference, not impregnated with colored polyethylene fibers) in the above wavelength range, and T ₁ represents the transmittance of acetone after impregnating colored polyethylene fibers in the above wavelength range The integral value.

Based pigmented polyethylene fibers of the present embodiment aspect is colored a dark color, and the use of ^{L CIE-L * a * b} * color measurement method when the coloring or polyethylene fibers obtained by a measurement of the workpiece pigmented polyethylene fibers obtained ^* The value is 80 or less. The smaller the L ^* value, the denser the polyethylene fiber is colored. Therefore, the L ^* value is preferably 75 or less, more preferably 70 or less, and still more preferably 65 or less. Furthermore, the lower limit of the L ^* value is not particularly limited.

The colored polyethylene fiber of this embodiment has excellent color fastness to rubbing. More specifically, the color fastness to rubbing is 3 or higher both when dry and when wet. The higher the color fastness to rubbing, the higher the It shows that the more difficult the fiber is to produce discoloration and color shift. Therefore, the color fastness to rubbing is preferably 4 or higher, more preferably 5 grade. Regarding the color fastness to rubbing, use a Gakushin type rubbing tester to perform rubbing fastness in accordance with JIS L 0849 (2004) on samples prepared in accordance with JIS (Japanese Industrial Standards) L 0801 (2000) The test was evaluated using a gray scale for pollution (JIS L 0805 (2005)). The details of the test and evaluation method will be described in the examples.

In addition, the colored polyethylene fibers of this embodiment also include colored polyethylene fibers having a solvent resistance of 75% or more as determined by the measurement method described in (II) above. The solvent resistance is preferably 80% or more, more preferably 85% or more. Solvent resistance is an indicator of the amount of coloring material extracted from the colored polyethylene fiber. The larger the value of the solvent resistance, the less the amount of coloring material extracted from the colored polyethylene fiber. Therefore, the larger the value of the solvent resistance, the better, and the solvent resistance is more preferably 98% or more.

The colored polyethylene fiber preferably satisfies both (I) and (II) above. This polyethylene fiber is not only colored into a deep color, but also has excellent resistance to friction or organic solvents, and it can be said to be a fiber that is difficult to cause discoloration or color shift.

The tensile strength of the colored polyethylene fiber of this embodiment is preferably 18 cN/dtex or more. The tensile strength is more preferably 20 cN/dtex or more, and still more preferably 25 cN/dtex or more. The upper limit of the tensile strength is not particularly limited, but it is technically and technically to obtain a polyethylene fiber with a tensile strength exceeding 60 cN/dtex. It is difficult in terms of industrial production.

In addition, the colored polyethylene fiber is preferably the coefficient of variation (CV) (%) of the tensile strength calculated from the following formula 1 with respect to the tensile strength measured at any 10 locations in the longitudinal direction (length direction) of the fiber ) Is 10% or less.

Coefficient of variation of tensile strength (%)=(standard deviation of tensile strength/average value of tensile strength)×100 (Equation 1)

The coefficient of variation (%) of the tensile strength is more preferably 9% or less, still more preferably 8% or less, and still more preferably 5% or less. The coefficient of variation (%) of the tensile strength is that the deviation of the strength in the length direction of the polyethylene fiber within the above range is small, so it is preferable.

The elongation (elongation) at the maximum strength of the colored polyethylene fiber is preferably 3.0% or more. More preferably, it is 3.5% or more, and still more preferably 3.7% or more. The upper limit of the elongation is not particularly limited, but is preferably 6.0% or less.

The initial modulus of elasticity of the colored polyethylene fiber is preferably 500 cN/dtex or more and 2000 cN/dtex or less. The initial modulus of elasticity is more preferably 600 cN/dtex or more, further preferably 700 cN/dtex or more, more preferably 1600 cN/dtex or less, and still more preferably 1400 cN/dtex or less. If the initial modulus of elasticity is too high, it will become difficult to align the polyethylene fibers during the molding process into ropes or braided ropes, and it will also be prone to breakage of the monofilament. If the initial modulus of elasticity is within the above range, it will be difficult This problem occurs, so it is better.

The fineness of the monofilament constituting the colored polyethylene fiber is preferably 1 dtex or more and 80 dtex or less. If the monofilament fineness exceeds 80 dtex, it may become difficult to increase the strength while the polyethylene fiber becomes hard. It is preferably 70 dtex or less, more preferably 60 dtex or less. Fibers less than 1 dtex may be prone to fluffing during the stretching process of the fiber or the actual use of the polyethylene fiber. Preferably it is 2 dtex or more, More preferably, it is 5 dtex or more.

In addition, the unevenness of the fineness (coefficient of variation of the total fineness) of the colored polyethylene fiber is preferably 10% or less. If the unevenness of the fineness exceeds 10%, not only unevenness of the strength is likely to occur, but also unevenness of coloring due to the deviation of the fineness, and there is a risk of deviation of the visible hue. The unevenness of the fineness is less than 10%. Problem, so better. The unevenness of fineness is more preferably 6% or less, and still more preferably 5% or less.

The colored polyethylene fiber contains a colored material. As the coloring material, organic coloring materials are preferred, and dyes that are soluble in organic solvents can be preferably used. Examples of such coloring materials include oil-soluble dyes, disperse dyes, acid dyes, and cationic dyes. Among these dyes, oil-soluble dyes and disperse dyes have good compatibility with polyethylene, and it is easy to achieve coloring into dense polyethylene fibers, so they are preferred. As a preferable oil-soluble dye, for example, CI (Color Index; color index) Solvent Yellow 2 ("CI Solvent Yellow" is omitted below), 6, 14, 15, 16, 19, 21, 33, 56, 61, 80, CI Solvent Orange 1 ("CI Solvent Orange" is omitted below), 2, 5, 6, 14, 37, 40, 44, 45, CI Solvent Red 1 ("CI Solvent Red" is omitted below), 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, CI solvent Solvent Violet 8 ("CI Solvent Violet" is omitted below), 13, 14, 21, 27, CI Solvent Blue (Solvent Blue) 2 ("CI Solvent Blue" is omitted below) 11, 12, 25, 58, 36 , 55, 73, CI Solvent Green 3, etc. Examples of disperse dyes include: CI Disperse Red 4 ("CI Disperse Red" is omitted below), 5, 11, 17, 60, 74, 75, 86, 91, 92, 152, 153, 167, 179 , 200, 221, 302, are classified into disperse dyes such as CI Disperse Black, CI Disperse Orange 3 ("CI Disperse Orange" is omitted below), 13, 25, 31, 37, 45, 61 and 76 are classified as disperse dyes such as CI Disperse Grey, CI Disperse Yellow 3 ("CI Disperse Yellow" is omitted below), 5, 42, 49, 79, 82, 104, 134 , 149, 198, 211, 241 are classified into disperse dyes such as CI Disperse Green, CI Disperse Violet 1 ("CI Disperse Violet" is omitted below), 3, 28, 43, are classified Disperse dyes such as CI Disperse Brown, CI Disperse Blue 1 ("CI Disperse Blue" is omitted below), 3, 56, 60, 72, 77, 106, 148, 165, 183, 257 , 360, etc. These coloring materials can be used alone, or multiple coloring materials with different hues can be used in combination.

The amount of the coloring material contained in the colored polyethylene fiber is preferably from 0.2% by mass to 5% by mass. It is more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and still more preferably 2% by mass or more. As an upper limit, It is more preferably 4% by mass or less, and still more preferably 3% by mass or less. If the content of the coloring material is within the above-mentioned range, it is possible to achieve deep coloring, and there is less risk of affecting the mechanical properties of the fiber, so it is preferable. The amount of the coloring material contained in the colored polyethylene fiber can be obtained by the method described in the examples below.

Next, the manufacturing method of this embodiment is demonstrated.

In this embodiment, colored polyethylene fibers are produced by a solution forming method. The solution formation method is not particularly limited as long as it uses a previously known method. For example, it is preferable to use a solution spinning method, that is, dissolving polyethylene in a volatile organic solvent such as decalin or tetralin, or paraffin. In a non-volatile organic solvent, polyethylene is formed into fibers.

As the raw material polyethylene, a polyethylene having an ultimate viscosity [η] of 5.0 dL/g or more and 25 dL/g or less and a repeating unit composed of 90 mol% or more of ethylene is used. The ultimate viscosity is more preferably 7.0 dL/g to 22 dL/g, and still more preferably 8 dL/g to 20 dL/g. If the ultimate viscosity is too small, the dimensional stability will be poor, and there will be a tendency for changes in mechanical properties over time to increase, and it may be difficult to achieve a strength of 10 cN/dtex or more. On the other hand, when the ultimate viscosity is too large, although it is easy to achieve high strength and high modulus of elasticity, there is a risk of frequent breakage of single filaments in the step after processing polyethylene fibers into products such as braided ropes. By using polyethylene with an ultimate viscosity in the above range as a raw material, the molecular end group of the polyethylene becomes an appropriate range, which can reduce the number of structural defects in fibers or fiber products. The result can increase the strength of polyethylene fiber or Mechanical properties such as elastic modulus, dimensional stability and abrasion resistance, and in turn, can suppress changes in mechanical properties over time.

In the raw material polyethylene, more than 90 mol% of the repeating units are ethylene. The repeating unit of ethylene is preferably 92 mol% or more, more preferably 94 mol% or more, and most preferably a homopolymer of ethylene. Furthermore, the raw material polyethylene may contain components other than ethylene within a range that does not adversely affect the physical properties of the polyethylene fiber. For example, a copolymer of ethylene and a small amount of other monomers can be used as the raw material polyethylene. Specifically, α-olefin, acrylic acid and its derivatives, methacrylic acid and its derivatives, vinyl silane and its derivatives can be used Copolymers of other monomers and ethylene are used as raw material polyethylene.

In addition, as long as the ultimate viscosity is within the above range, the raw polyethylene can also be, for example, the weight of a blend of high-density polyethylene and ultra-high molecular weight polyethylene, and a blend of low-density polyethylene and ultra-high molecular weight polyethylene. A blend of polyethylenes with different average molecular weights. Furthermore, the raw material polyethylene may also be a blend of two or more ultra-high molecular weight polyethylenes with different weight average molecular weights, or a blend of two or more polyethylenes with different molecular weight distributions.

However, if the content of components other than ethylene is increased too much, it sometimes becomes a cause of hindering extension. Therefore, from the viewpoint of obtaining high-strength fibers, the number of branches present in polyethylene is preferably 3 or less with respect to 1000 carbon atoms in the main chain. More preferably 2 or less, further preferably 1.5 Below.

In order to suppress the deterioration of the physical properties of polyethylene fibers, additives such as antioxidants and light stabilizers can also be added to the raw polyethylene. When antioxidants are used as additives, in addition to suppressing changes in mechanical properties such as the strength of colored polyethylene fibers, it can also suppress changes in hue. The reason is that the degradation mechanism of coloring materials caused by ultraviolet rays is basically the same as that of polyethylene fibers. Therefore, it can be considered that when the polyethylene fiber contains an antioxidant, the strength reduction caused by the deterioration of the polyethylene fiber is suppressed. Similarly, the deterioration of the coloring material is also suppressed, resulting in a change in the hue of the colored polyethylene fiber Also suppressed. The amount of the additive used is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the raw material polyethylene.

The above-mentioned raw material polyethylene is dissolved in an organic solvent to prepare a polyethylene solution. The concentration of polyethylene is 0.5% by mass or more and 40% by mass or less, preferably 2.0% by mass or more and 30% by mass or less, and more preferably 4.0% by mass or more and 20% by mass or less. If the polyethylene concentration is too low, the production efficiency tends to decrease. On the other hand, if the concentration of polyethylene is too high, the molecular weight of the raw material polyethylene is very large, so it tends to be difficult to eject from the nozzle described later in the solution spinning method.

As an organic solvent for dissolving the raw material polyethylene, an organic solvent that can dissolve the raw material polyethylene and has a boiling point above the melting point of the raw material polyethylene is preferred. The solvent is more preferably an organic solvent with a boiling point 20°C or more higher than the melting point of the raw material polyethylene. Examples of the solvent include: n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-octadecane, liquid paraffin, kerosene and other aliphatic hydrocarbon solvents, xylene, naphthalene (naphthalene), tetralin (tetrahydronaphthalene), decalin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dodecylbenzene, dicyclohexyl, methyl Aromatic hydrocarbon solvents such as naphthalene and ethyl naphthalene or their hydrogenated derivatives, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,2,3-trichloropropane, Halogenated hydrocarbon solvents such as dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, and mineral oils such as paraffin-based processing oil, naphthenic-based processing oil, and aromatic-based processing oil. Among these organic solvents, volatile organic solvents can be used to remove the organic solvents from the polyethylene fiber during the stretching step described later, so it is preferred.

The polyethylene solution is preferably heated at a temperature higher than the melting point of the raw material polyethylene by more than 10°C (the melting point of the raw material polyethylene + 10°C or more), and then passed through a spinning nozzle (spinning nozzle) to form a polyethylene fiber (Unstretched filament) (spinning step). The heating temperature is more preferably the melting point of the raw material polyethylene + 20°C or more, and more preferably the melting point of the raw material polyethylene + 30°C or more. By heating in the above temperature range, the raw material polyethylene dispersed in the organic solvent can be dissolved to form a uniform solution.

The temperature of the spinning nozzle is preferably set to the melting point of the raw material polyethylene + 5° C. or more and the boiling point of the organic solvent used in the polyethylene solution. More preferably, the melting point of the raw material polyethylene is +10°C or higher. If the temperature of the spinning nozzle is too low, Sometimes the viscosity of the raw material polyethylene decreases, so it becomes difficult to extract the polyethylene fiber at the required speed. On the other hand, if the temperature of the spinning nozzle exceeds the boiling point of the organic solvent, the organic solvent will immediately boil after the polyethylene solution is sprayed from the spinning nozzle, which may cause frequent breakage directly under the spinning nozzle.

As the spinning nozzle, it is preferable to have an orifice (hole) with a diameter of 0.2 mm to 3.5 mm. The diameter of the orifice is more preferably 0.5 mm to 2.5 mm, and still more preferably 0.8 mm to 2.0 mm.

The molded product ejected from the spinning nozzle is cooled, solidified, and extracted to obtain a polyethylene fiber. The cooling method is not particularly limited, and the ejected molded product from the spinning nozzle can be naturally cooled by exposing it to the ambient temperature, or a cooling device can also be used. As a cooling method using a cooling device, it can be a dry quenching method using air or nitrogen gas, or a liquid that can be mixed with an organic solvent used in a polyethylene solution, or water, which is difficult to use in a polyethylene solution. The cooling method of liquid mixed with organic solvent.

The ejected molded product is preferably cooled and solidified, and deformed at a magnification of 1.1 times or more and 100 times or less until it becomes a polyethylene fibrous material. The deformation magnification is more preferably 2.0 times or more and 80 times or less, and more preferably 5.0 times or more and 50 times or less. The time required for deformation is preferably set to within 3 minutes. It is more preferably within 2 minutes, and still more preferably within 1 minute. If the time required for deformation exceeds 3 minutes, the polyethylene molecular chains that constitute the polyethylene fiber will relax, making it difficult to obtain high-strength, high-modulus polyethylene fibers. Yu. It is also possible to remove part of the solvent contained in the polyethylene fiber in the step of spinning the polyethylene solution to obtain the polyethylene fiber.

Then, the obtained polyethylene fiber (unstretched filament) is heated and stretched to several times (stretching step). The extension step can be a one-stage extension or a multi-stage extension with more than two stages. From the viewpoint of increasing the strength of the polyethylene fiber, it is preferable to perform multi-stage stretching in two or more stages. Furthermore, the "polyethylene fibrous material" in this specification refers to the polyethylene fibrous material after the spinning step and before being stretched to a preset stretching ratio.

The method of heating the polyethylene fibrous material in the stretching step is not particularly limited. Inert gases such as air and nitrogen, water vapor, liquid and other media can be used for heating, and heating rollers, contact heaters, etc. can also be used. The stretching temperature is preferably 110°C or higher, more preferably 120°C or higher, and still more preferably 130°C or higher. The upper limit of the stretching temperature should just be the range where the fiber does not melt.

Regarding the stretching ratio of the polyethylene fiber, based on the total stretching ratio of the roll, it is preferably 8 times or more, more preferably 10 times or more, and still more preferably 12 times or more. The upper limit of the stretching ratio is not particularly limited, as long as it can be determined in such a way that the required strength, elongation, and elastic modulus of polyethylene fibers can be obtained.

When the polyethylene solution contains a volatile organic solvent, the polyethylene fiber can also be extended while the fiber is contained Organic solvent removal (desolventization). On the other hand, when the organic solvent constituting the polyethylene solution is non-volatile, it is only necessary to remove the non-volatile organic solvent from the polyethylene fiber by extraction. For extraction, organic solvents such as chloroform, benzene, trichlorotrifluoroethane (TCTFE), hexane, heptane, nonane, decane, ethanol, and higher alcohols can be used.

The solvent removal step of removing the organic solvent from the polyethylene fiber may be implemented as a step different from the stretching step, or may be performed simultaneously with the stretching step.

The manufacturing method of the present embodiment includes, in addition to the above-mentioned spinning step and stretching step, a step of contacting the fibrous material of polyethylene with the coloring liquid (coloring liquid contact step). In the coloring liquid contacting step, the coloring liquid is brought into contact with a polyethylene fibrous material containing less than 20% by mass of an organic solvent. The coloring liquid contains a coloring material and an organic solvent, and the temperature is 0°C or more and less than 60°C. Thereby, a coloring material can be provided to the polyethylene fiber material.

As long as the coloring solution contacting step is performed on the polyethylene fibrous material with an organic solvent content of less than 20% by mass, the implementation period of the step is not limited. However, it is sometimes difficult to move the coloring material into the fibrous material after the crystallization of the polyethylene is completed, so it is preferable to extend the polyethylene fibrous material to the final stretching at a preset stretching ratio. Therefore, the coloring solution contacting step is preferably performed after the spinning step and before the stretching step. In the case of two-stage or more multi-stage stretching, it can also be performed between the stretching steps. For example, if it is a two-stage stretching, Can also be used in the first and second stages Between the extension steps of the segment.

The amount of organic solvent (residual solvent amount) contained in the polyethylene fibrous material is preferably 18% by mass or less, more preferably 15% by mass or less, and preferably 1% by mass or more, more preferably 2% by mass or more, and further Preferably, it is 3% by mass or more. It is considered that if it is before the solvent is completely removed, the coloring material can easily move into the polyethylene fibrous material, so the coloring material can be allowed to exist up to the core of each fibrous material. Therefore, from the viewpoint of achieving deep color and uniform coloring, it is preferable to perform the coloring liquid contact step in a state where the polyethylene fiber material contains a residual solvent to some extent. However, whether the amount of residual solvent is too much or too little, there is a tendency to hinder the movement of the coloring material into the fibrous material. Furthermore, when the amount of residual solvent is too much, it is recommended to perform the above-mentioned solvent removal before the coloring liquid contact step, and to adjust the amount of residual solvent to the above-mentioned range in advance.

As the organic solvent contained in the coloring liquid, the organic solvent exemplified in the preparation of the polyethylene solution or the organic solvent for extraction exemplified in the solvent removal step can be used. When the organic solvent used in the preparation of the polyethylene solution is used, there is no need to change the conditions of the solvent removal step according to the type of solvent, and there is no need to separate the recovered solvent into each solvent after the solvent removal step, so it is better .

As the coloring material, the above-mentioned coloring material can be preferably used. More preferably, they are oil-soluble dyes or disperse dyes. The concentration of the coloring material in the coloring solution is as long as It can be adjusted by containing 0.2% to 5% by mass of the coloring material in the colored polyethylene fiber. Generally, the concentration of the coloring material in the coloring liquid is preferably set to 1% to 28% by mass. It is more preferably 1.5% by mass or more and 25% by mass or less, and still more preferably 2% by mass or more and 23% by mass or less. If the concentration of the coloring material is too low, it may be difficult to achieve dense coloring. When the concentration of the coloring material is too high, sometimes excess coloring material remains on the surface of the fiber, which reduces the color fastness of the polyethylene fiber. Therefore it is not good.

The temperature of the coloring liquid should be above 0°C and less than 60°C. It is more preferably 5°C or higher, still more preferably 8°C or higher, still more preferably 10°C or higher, and preferably 50°C or lower, and still more preferably 40°C or lower. In addition, the temperature of the polyethylene fibrous material in contact with the coloring solution is preferably 50°C or lower, more preferably 45°C or lower, and still more preferably 40°C or lower. The lower limit of the temperature of the polyethylene fiber is not limited, and it is generally preferably above room temperature. The temperature of the polyethylene fiber material can be measured with a non-contact type thermometer such as an infrared thermometer, for example.

If the temperature of the coloring liquid is too high, the organic solvent evaporates quickly and only the coloring material remains on the surface of the polyethylene fibrous material, making it difficult to move the coloring material into the polyethylene fibrous material. In this case, the peripheral components may be contaminated in the subsequent steps, and the coloring material may fall off from the product using the polyethylene fiber obtained, which may cause contamination. Furthermore, in order to eliminate this problem, a step of washing the dye adhering to the surface is required, which may reduce the work efficiency. In addition, when the temperature of the coloring liquid is too high, The temperature of the polyethylene fiber in contact with the liquid increases, and the heat treatment step or the stretching step performed after the coloring liquid contact step has a greater effect on the tension loaded on the polyethylene fiber, resulting in uneven denier or strength. The fear of unevenness (unevenness of silk). Especially when the stretching step is performed after the coloring liquid contact step, if the temperature of the polyethylene fibrous material is too high, the stretching point may not be fixed and uneven stretching may occur.

Furthermore, even if the temperature of the polyethylene fiber is sufficiently low, when the temperature of the coloring liquid is high, the crystalline structure formed in the polyethylene fiber when it comes into contact with the coloring liquid is destroyed, resulting in discoloration. Both are concerned. If the temperature of the coloring liquid and the temperature of the polyethylene fibrous material are within the above-mentioned range, the above-mentioned problem is unlikely to occur, and therefore it is preferable.

The contact method of the polyethylene fibrous material and the coloring solution is not particularly limited as long as the polyethylene fibrous material can be given a coloring material, and various methods can be used. Specific contact methods include: a method of contacting the polyethylene fiber with the coloring liquid by guide oiling; a method of contacting the polyethylene fiber with the surface of the rotating roller to which the coloring liquid is attached Method; a method of spraying a coloring liquid on a moving polyethylene fiber; a method of contacting the polyethylene fiber through a bath of the coloring liquid, etc. In addition, when the polyethylene solution contains a non-volatile organic solvent (such as paraffin wax, etc.), the coloring solution obtained by dissolving the coloring material in the extraction solvent used in the solvent removal step can also be used as the extraction bath to make the polyethylene The fiber is passed through the extraction bath, and the polyethylene fiber is brought into contact with the coloring solution.

The amount of the coloring liquid applied to the polyethylene fibrous material is preferably in the range of 0.1% by mass to 15% by mass relative to the polyethylene fibrous material. It is more preferably 0.5% by mass or more, still more preferably 1% by mass or more, more preferably 12% by mass or less, and still more preferably 8% by mass or less. If the amount of the coloring liquid is too small, it may be difficult to color into a dense color. On the other hand, if the amount of the coloring liquid is too large, excess coloring materials may remain on the fiber surface and the color fastness may deteriorate. During the step, the coloring material may fall off from the fibrous material and contaminate peripheral components.

In the coloring liquid contact step, the amount of organic solvent contained in the polyethylene fibrous material may increase. However, if excess organic solvent is present in the polyethylene fiber, the crystal structure is likely to relax, or the fiber is likely to slide on the stretching roller, resulting in difficulty in uniform stretching, and unevenness in fineness and strength. The fear. Therefore, the amount of organic solvent contained in the polyethylene fiber after contact with the coloring solution (the amount of organic solvent contained in the polyethylene fiber used for the coloring solution contact step and the amount of organic solvent added in the coloring solution contact step The total of) is less than 25% by mass, preferably 20% by mass or less, and more preferably 18% by mass or less. The lower limit of the amount of organic solvent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more.

The coloring liquid contact step is preferably carried out while applying a tension of 0.05 cN/dtex or more and 3 cN/dtex or less to the polyethylene fibrous material. Better 0.1 cN/dtex or more and 1 cN/dtex or less, more preferably 0.2 cN/dtex or more and 0.8 cN/dtex or less. When the tension applied to the polyethylene fibrous material is too small, it may be difficult to move the polyethylene fibrous material stably, and vibration may occur, which may cause uneven application of the coloring material. On the other hand, if the tension is too high, the polyethylene fibrous materials may become bundled and the coloring liquid may not penetrate into the inside of the fibrous materials. In this case, not only the dyeing uniformity of the monofilament is impaired, but also a large amount of coloring material remains on the surface of the polyethylene fibrous material. As a result, the dye fastness may decrease.

In this embodiment, the heat treatment step (heat treatment step) of heating the polyethylene fiber to which the coloring liquid has been applied is heated at 110°C or higher for 10 seconds or longer. This promotes the penetration of the coloring liquid into the polyethylene fiber, and easily moves the coloring material to the core of the polyethylene fiber. As a result, colored polyethylene fibers with denser colors and improved fastness to dyeing can be obtained. It can be considered that the reason for the above results is that by performing the heat treatment step, the stretching step is performed in a state where the coloring material is present in the interior (core) of the polyethylene fiber, and the crystallization of the polyethylene caused by the stretching The coloring material is sealed inside the polyethylene fiber (core).

The heat treatment step can be performed at any timing as long as it is after the coloring liquid contact step. In addition, the heat treatment step may be performed separately or simultaneously with the stretching step. When the heat treatment step and the stretching step are performed at the same time, the movement of the coloring material into the polyethylene fiber caused by the penetration of the coloring liquid and the crystallization of the polyethylene caused by the stretching can be performed simultaneously. another In addition, when the heat treatment step and the elongation step are performed separately, the elongation step can be performed after the coloring material moves into the polyethylene fiber through the heat treatment step, so that the color fastness can be further improved. Preferably, the heat treatment step and the extension step are performed simultaneously.

The heating temperature is preferably 120°C or higher, more preferably 130°C or higher. Regarding the upper limit of the heating temperature, it is recommended to set it as a temperature that does not cause breakage due to fusing, that is, below the melting point of the polyethylene filament.

The heating method is not particularly limited. For example, well-known methods such as hot air, hot rollers, radiation panels, steam jets, and hot pins can be used. Furthermore, from the viewpoint of minimizing the contamination of the coloring material, it is preferable to adopt a non-contact heating method using hot air, a radiant panel, and steam injection.

The heating time is preferably 10 seconds or more, more preferably 12 seconds or more, and still more preferably 15 seconds or more. The upper limit of the heating time is not particularly limited. For example, it is preferably 150 seconds or less, more preferably 120 seconds or less, and still more preferably 100 seconds or less. When the heat treatment step is performed separately, it is preferable to perform the heat treatment step and the extension step within the above range.

The heat treatment step is preferably performed while applying tension to the polyethylene fiber. The tension applied to the polyethylene fiber is preferably set to 0.8 cN/dtex to 6.5 cN/dtex. More preferably, 1cN/dtex or more, and even more preferably It is 2 cN/dtex or more, more preferably 6 cN/dtex or less, and still more preferably 5 cN/dtex or less.

By loading the above-mentioned tension in the heat treatment step, the molecular chain of polyethylene is stretched, thereby generating capillary phenomenon, and further promoting the penetration of the coloring liquid into the fiber, which is preferable. When the tension in the heat treatment step is too small, it may be difficult to generate capillary phenomenon. On the other hand, if the tension is too high, fuzzing or the like will occur, and it may be difficult to obtain polyethylene fibers with less fineness and less uneven strength.

After the heat treatment step or in the stretching step performed simultaneously with the heat treatment step, it is preferable to stretch the polyethylene fibrous material at a magnification of at least 2 times. More preferably, it is 2.5 times or more. As the upper limit, in order to increase the strength, it is preferable to increase the stretching ratio as much as possible, but if it is too high, there is a possibility that hair breakage or fluff may be seen. Therefore, the stretching ratio is preferably 30 times or less.

Usually in the manufacture of high-strength polyethylene, in order to increase the strength of the fiber, it is stretched at a high stretching ratio. However, in the case of contact with a relatively high-temperature coloring solution before the stretching step, the polyethylene fiber material is softened during the stretching step. Therefore, if the high-magnification stretching is performed in this state, there is stretching If the dots are not fixed, there is a risk of uneven size or strength. Therefore, the stretching magnification in the stretching step performed after the heat treatment step or simultaneously with the heat treatment step is preferably set within the above-mentioned range.

[Embodiment 2]

The characteristic of the colored polyethylene fiber of this embodiment is that the L ^* value obtained by the CIE-L ^* a ^* b ^* coloring system is below 80, and the color fastness to rubbing is 3 in both dry and wet conditions Above, and the acid value is 0.1 mgKOH/g or more and 50 mgKOH/g or less.

Based pigmented polyethylene fibers of the present embodiment aspect is colored a dark color, and using the CIE-L ^* a ^* b ^* color difference obtained when L assay pigmented or polyethylene fibers obtained by a measurement of the workpiece pigmented polyethylene fibers ^* The value is 80 or less. The smaller the L ^* value, the denser the polyethylene fiber is colored. Therefore, the L ^* value must be 80 or less, preferably 75 or less, more preferably 70 or less, and still more preferably 65 or less. Furthermore, the lower limit of the L ^* value is not particularly limited.

The colored polyethylene fiber of this embodiment has excellent color fastness to rubbing. More specifically, the color fastness to rubbing is 3 or higher both when dry and when wet. The higher the grade of fastness to rubbing, the more difficult it is for the fiber to decolor and color shift. Therefore, the color fastness to rubbing is preferably 4 or higher, more preferably 5 grade. Regarding the color fastness to rubbing, the Gakushin type rubbing tester was used to conduct a rubbing fastness test in accordance with JIS L 0849 (2004) on the samples prepared in accordance with JIS L 0801 (2000), using the gray scale for pollution ( JIS L 0805 (2005)) for evaluation. The details of the test and evaluation method will be described in the examples.

The tensile strength of the colored polyethylene fiber of this embodiment is preferably Above 18cN/dtex. The tensile strength is more preferably 20 cN/dtex or more, and still more preferably 25 cN/dtex or more. The upper limit of the tensile strength is not particularly limited, but it is technically and industrially difficult to obtain polyethylene fibers with a tensile strength of more than 60 cN/dtex.

In addition, the colored polyethylene fiber is preferably the coefficient of variation (CV) (%) of the tensile strength obtained from the following formula 1 with respect to the tensile strength measured at any 10 locations in the longitudinal direction (length direction) of the fiber ) Is 10% or less.

Coefficient of variation of tensile strength (%) = standard deviation of tensile strength/average value of tensile strength×100 (Equation 1)

The coefficient of variation (%) of the tensile strength is more preferably 9% or less, still more preferably 8% or less, and still more preferably 5% or less. The coefficient of variation (%) of the tensile strength is that the deviation of the strength in the length direction of the polyethylene fiber within the above range is small, so it is preferable.

The elongation (elongation) at the maximum strength of the colored polyethylene fiber is preferably 3.0% or more. More preferably, it is 3.5% or more, and still more preferably 3.7% or more. The upper limit of the elongation is not particularly limited, but is preferably 6.0% or less.

The initial modulus of elasticity of the colored polyethylene fiber is preferably 500 cN/dtex or more and 2000 cN/dtex or less. The initial modulus of elasticity is more preferably 600 cN/dtex or more, and more preferably 700 cN/dtex or more. In addition, it is more preferably 1600 cN/dtex or less, and still more preferably 1400 cN/dtex or less. If the initial modulus of elasticity is too high, the polyethylene fiber may be used when forming a rope or braided rope. It is difficult to align the dimensions, and it is also easy to cause the single filament breakage. If the initial elastic modulus is within the above range, this problem is difficult to occur, so it is preferable.

The fineness of the monofilament constituting the colored polyethylene fiber is preferably 1 dtex or more and 80 dtex or less. If the monofilament fineness exceeds 80 dtex, it may become difficult to increase the strength while the polyethylene fiber becomes hard. It is preferably 70 dtex or less, more preferably 60 dtex or less. In addition, fibers less than 1 dtex may be prone to fluff during the stretching in the manufacturing process of the fiber or the actual use of the polyethylene fiber. Preferably it is 2 dtex or more, More preferably, it is 5 dtex or more.

In addition, the unevenness of the fineness (coefficient of variation of the total fineness) of the colored polyethylene fiber is preferably 10% or less. If the unevenness of fineness exceeds 10%, not only unevenness in strength is likely to occur, but also unevenness in coloration is likely to occur due to the unevenness in fineness, and there is a risk of deviation in the hue seen. When the fineness is not all 10% or less, it is difficult to cause such a problem, so it is preferable. The unevenness of fineness is more preferably 6% or less, and still more preferably 5% or less.

The colored polyethylene fiber contains a colored material. As the coloring material, an organic coloring material is preferable, and a coloring material having affinity with polyolefins having a hydrophilic group at one end can be preferably used. The reason is that by adding a polyolefin with a hydrophilic group at one end to the solvent of the organic coloring material to form an emulsion, water can be used as the solvent. This situation will be further explained below. By using water as a solvent, the environmental load during manufacturing and the environmental load of products can be suppressed.

Examples of such coloring materials include oil-soluble dyes, disperse dyes, acid dyes, and cationic dyes. Among these dyes, oil-soluble dyes and disperse dyes have good compatibility with polyolefins with a hydrophilic group at one end, and it is easy to realize densely colored polyethylene fibers, so they are preferred. As preferred oil-soluble dyes, for example, CI Solvent Yellow 2 ("CI Solvent Yellow" is omitted below), 6, 14, 15, 16, 19, 21, 33, 56, 61, 80, CI Solvent Orange 1 ( "CI Solvent Orange" is omitted below), 2, 5, 6, 14, 37, 40, 44, 45, CI Solvent Red 1 ("CI Solvent Red" is omitted below), 3, 8, 23, 24, 25, 27 , 30, 49, 81, 82, 83, 84, 100, 109, 121, CI Solvent Violet 8 ("CI Solvent Violet" is omitted below), 13, 14, 21, 27, CI Solvent Blue 2 ("CI Solvent Violet" is omitted below Solvent blue) 11, 12, 25, 58, 36, 55, 73, CI solvent green 3, etc. Examples of disperse dyes include: CI Disperse Red 4 (hereinafter "CI Disperse Red" is omitted), 5, 11, 17, 60, 74, 75, 86, 91, 92, 152, 153, 167, 179, 200, 221 , 302, are classified as CI Disperse Black, CI Disperse Orange 3 ("CI Disperse Orange" is omitted below), 13, 25, 31, 37, 45, 61, 76, are classified as CI Disperse Gray Disperse dyes, CI Disperse Yellow 3 (hereinafter "CI Disperse Yellow" is omitted), 5, 42, 49, 79, 82, 104, 134, 149, 198, 211, 241 are classified as CI Disperse Green and other disperse dyes, CI Disperse Violet 1 ("CI Disperse Violet" is omitted hereafter), 3, 28, 43, are classified as disperse dyes such as CI Disperse Brown, CI Disperse Blue 1 ("CI Disperse Blue" is omitted hereafter), 3, 56, 60 , 72, 77, 106, 148, 165, 183, 257, 360, etc. These coloring materials can be used alone or the color Combination of various coloring materials with different tunes.

The amount of the coloring material contained in the colored polyethylene fiber is preferably from 0.2% by mass to 5% by mass. It is more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and still more preferably 2% by mass or more. As the upper limit, it is more preferably 4% by mass or less, and still more preferably 3% by mass or less. If the content of the coloring material is within the above-mentioned range, it is possible to achieve deep coloring, and there is less risk of affecting the mechanical properties of the fiber, so it is preferable. The amount of the coloring material contained in the colored polyethylene fiber can be obtained by the method described in the examples below.

The acid value of the colored polyethylene fiber is preferably 0.1 mgKOH/g or more and 50 mgKOH/g or less, more preferably 0.5 mgKOH/g or more and 30 mgKOH/g or less, and further preferably 1.0 mgKOH/g or more and 10 mgKOH/g or less. In this embodiment, the acid value of the colored polyethylene fiber is affected by the polyolefin with a hydrophilic group at one end added to the solvent of the organic coloring material. The details will be described later. The acid value of the colored polyethylene fiber is less than 0.1 In the case of mgKOH/g, polyethylene fiber with high fastness cannot be obtained, so it is not good. On the other hand, even if the acid value exceeds 50 mgKOH/g, the fastness becomes poor and unsatisfactory.

Next, the manufacturing method of this embodiment is demonstrated. In this embodiment, the coloring liquid used for coloring is different from the coloring liquid of the first embodiment, but basically the same manufacturing method as that of the first embodiment is used to produce the colored polyethylene Olefin fiber. Therefore, the description of the same content in the steps described in Embodiment 1 is omitted.

The manufacturing method of the present embodiment includes, in addition to the above-mentioned spinning step and stretching step, a step of contacting the fibrous material of polyethylene with the coloring liquid (coloring liquid contact step). In the coloring liquid contact step, the coloring liquid is brought into contact with the polyethylene fibrous material. The coloring liquid contains a coloring material and a polyolefin having a hydrophilic group at one end, and the temperature is 0°C or more and less than 60°C. Thereby, a coloring material can be provided to the polyethylene fiber material. The coloring liquid contains a coloring material and a polyolefin having a hydrophilic group at one end, and is preferably in a state of being dispersed in water or emulsified.

As a polyolefin having a hydrophilic group at one end, it is preferable to add a low-weight polyethylene having an acid value of 1 mgKOH/g or more and 150 mgKOH/g or less to the coloring liquid.

The molecular weight of polyethylene added to the coloring liquid (hereinafter referred to as added polyethylene) is preferably 500 or more and 20,000 or less. When the molecular weight is less than 500, the melting point will decrease. When using colored polyethylene fiber products, polyethylene may be added to ooze out of the product, which is not good. On the other hand, if the molecular weight of the added polyethylene exceeds 20,000, the added polyethylene does not penetrate into the fiber, which is not preferable.

In addition, the acid value of added polyethylene is 1mgKOH/g or more and 150mgKOH/g or less, and the acid value is more preferably 3mgKOH/g or more 120 mgKOH/g or less, and the acid value is more preferably 5 mgKOH/g or more and 100 mgKOH/g or less. When the acid value is less than 1 mgKOH/g, the affinity with the above-mentioned coloring material is reduced, and polyethylene fiber with high fastness cannot be obtained, so it is not good. On the other hand, if the acid value exceeds 150 mgKOH/g, the affinity between polyethylene fiber and added polyethylene is reduced, so it adheres to the polyethylene fiber in the middle of the spinning step described below, and penetrates into the fiber when it penetrates into the fiber. Slow down. As a result, the coloring material remains on the surface of the fiber, so the fastness of the fiber becomes poor and poor.

In this way, by adding polyethylene with a functional group terminal with a low molecular weight and an acid value of 1 mgKOH/g to 150 mgKOH/g to the coloring solution, a colored polymer with an acid value of 0.1 mgKOH/g to 50 mgKOH/g can be obtained. Vinyl fiber.

In addition, the melting point of the added polyethylene is preferably 80°C or higher. When the melting point is less than 80°C, the polyethylene will ooze out of the product when the product is used, so it is not good. There is a method of adding polyethylene added to the coloring liquid together with the coloring material in the coloring liquid into an emulsion shape and adding it. The solvent in this case is preferably water. By using water as a solvent as described above, the environmental load during manufacturing and the environmental load of products can be suppressed, and fibers that take care of the environment or the ecosystem can be manufactured.

As long as the coloring liquid contact step is performed on the polyethylene fibrous material, there is no limitation on the timing of the step. However, sometimes in the crystallization of polyethylene After completion, it is difficult to move the coloring material into the fibrous material, so it is preferable to implement it before the final stretching of the polyethylene fibrous material to a preset stretching ratio. Therefore, the coloring solution contacting step is preferably performed after the spinning step and before the stretching step. In the case of two-stage or more multi-stage stretching, it can also be performed between the stretching steps. For example, if it is a two-stage stretching, It can also be performed between the extension steps of the first stage and the second stage.

As the coloring material, the above-mentioned coloring material can be preferably used. More preferably, they are oil-soluble dyes or disperse dyes. The concentration of the coloring material in the coloring liquid only needs to be adjusted by containing 0.2% to 5% by mass of the coloring material in the colored polyethylene fiber. Generally, the concentration of the coloring material in the coloring liquid is preferably set to 1% by mass To 28% by mass. It is more preferably 1.5% by mass or more and 25% by mass or less, and still more preferably 2% by mass or more and 23% by mass or less. If the concentration of the coloring material is too low, it may be difficult to achieve dense coloring. When the concentration of the coloring material is too high, sometimes excess coloring material remains on the surface of the fiber, which reduces the color fastness of the polyethylene fiber. Therefore it is not good.

The temperature of the coloring liquid should be above 0°C and less than 60°C. It is more preferably 5°C or higher, still more preferably 8°C or higher, still more preferably 10°C or higher, and preferably 50°C or lower, and still more preferably 40°C or lower. In addition, the temperature of the polyethylene fibrous material in contact with the coloring solution is preferably 50°C or lower, more preferably 45°C or lower, and still more preferably 40°C or lower. The lower limit of the temperature of the polyethylene fiber is not limited, and it is generally preferably above room temperature. The temperature of the polyethylene fiber can be measured with a non-contact thermometer such as an infrared thermometer Determination.

If the temperature of the coloring liquid is too high, when the coloring material is dispersed in water, the water evaporates quickly and only the coloring material remains on the surface of the polyethylene fiber, making it difficult to move the coloring material into the polyethylene fiber. The tendency. In this case, the peripheral components may be contaminated in the subsequent steps, and the coloring material may fall off from the product using the polyethylene fiber obtained, which may cause contamination. Furthermore, in order to solve this problem, a step of washing the coloring material adhering to the surface is required, which may reduce the work efficiency. In addition, when the temperature of the coloring liquid is too high, the temperature of the polyethylene fibrous material in contact with the coloring liquid rises. In the heat treatment step or the stretching step performed after the coloring liquid contact step, the polyethylene fibrous material is loaded with The effect of tension becomes larger, and as a result, uneven size or uneven strength (uneven yarn) may occur. Especially when the stretching step is performed after the coloring liquid contact step, if the temperature of the polyethylene fibrous material is too high, the stretching point may not be fixed and uneven stretching may occur.

Furthermore, even if the temperature of the polyethylene fiber is sufficiently low, when the temperature of the coloring liquid is high, the crystalline structure formed in the polyethylene fiber when it comes into contact with the coloring liquid is destroyed, resulting in discoloration. Both are concerned. If the temperature of the coloring liquid and the temperature of the polyethylene fibrous material are within the above-mentioned range, the above-mentioned problem is unlikely to occur, and therefore it is preferable.

The contact method between the polyethylene fiber and the coloring solution is as long as it can be polymerized The coloring material provided by the vinyl fiber material is not particularly limited, and various methods can be used. Specific contact methods include: a method of contacting the polyethylene fiber with the coloring liquid by guiding and applying oil; a method of contacting the polyethylene fiber with the surface of the rotating roller to which the coloring liquid is attached; The method of spraying coloring liquid on polyethylene fiber; the method of contacting the polyethylene fiber by passing through the coloring liquid bath. In addition, when the polyethylene solution contains a non-volatile organic solvent (such as paraffin wax, etc.), the coloring solution obtained by dissolving the coloring material in the extraction solvent used in the solvent removal step can also be used as the extraction bath to make the polyethylene The fiber is passed through the extraction bath, and the polyethylene fiber is brought into contact with the coloring solution.

The amount of the coloring liquid applied to the polyethylene fibrous material is preferably in the range of 0.1% by mass to 15% by mass relative to the polyethylene fibrous material. It is more preferably 0.5% by mass or more, still more preferably 1% by mass or more, more preferably 12% by mass or less, and still more preferably 8% by mass or less. If the amount of the coloring liquid is too small, it may be difficult to color into a dense color. On the other hand, if the amount of the coloring liquid is too large, excess coloring materials may remain on the fiber surface and the color fastness may deteriorate. During the step, the coloring material may fall off from the fibrous material and contaminate peripheral components.

In this embodiment, the heat treatment step (heat treatment step) of heating the polyethylene fiber to which the coloring liquid has been applied is heated at 110°C or higher for 10 seconds or longer. This promotes the penetration of the coloring liquid into the polyethylene fiber, and easily moves the coloring material to the core of the polyethylene fiber. The results are available Colored polyethylene fiber with dense color and improved color fastness. It can be considered that the reason for the above results is that by performing the heat treatment step, the stretching step is performed in a state where the coloring material is present in the interior (core) of the polyethylene fiber, and the crystallization of the polyethylene caused by the stretching The coloring material is sealed inside the polyethylene fiber (core).

The heat treatment step can be performed at any timing as long as it is after the coloring liquid contact step. In addition, the heat treatment step may be performed separately or simultaneously with the stretching step. When the heat treatment step and the stretching step are performed at the same time, the movement of the coloring material into the polyethylene fiber caused by the penetration of the coloring liquid and the crystallization of the polyethylene caused by the stretching can be performed simultaneously. In addition, when the heat treatment step and the stretching step are performed separately, the stretching step can be performed after the coloring material moves into the polyethylene fiber through the heat treatment step, so that the color fastness can be further improved. Preferably, the heat treatment step and the extension step are performed simultaneously.

The heating temperature is preferably 120°C or higher, more preferably 130°C or higher. Regarding the upper limit of the heating temperature, it is recommended to set the temperature at which no end breakage occurs due to fusing, that is, below the melting point of the polyethylene filament.

The heating method is not particularly limited, and for example, known methods such as hot air, hot rollers, radiation panels, steam jets, and hot rods can be used. Furthermore, from the viewpoint of minimizing the contamination of the coloring material, it is preferable to adopt a non-contact heating method using hot air, a radiant panel, and steam injection.

The heating time is preferably 10 seconds or more, more preferably 12 seconds or more, and still more preferably 15 seconds or more. The upper limit of the heating time is not particularly limited. For example, it is preferably 150 seconds or less, more preferably 120 seconds or less, and still more preferably 100 seconds or less. When the heat treatment step is performed separately, it is preferable to perform the heat treatment step and the extension step within the above range.

If tension is applied to the polyethylene fiber in the heat treatment step, the molecular chain of the polyethylene is stretched, thereby generating capillary phenomenon, and further promoting the penetration of the coloring liquid into the fiber, which is preferable. When the tension in the heat treatment step is too small, it may be difficult to generate capillary phenomenon. On the other hand, if the tension is too high, fuzzing or the like will occur, and it may be difficult to obtain polyethylene fibers with less fineness and less uneven strength.

After the heat treatment step or in the stretching step performed simultaneously with the heat treatment step, it is preferable to stretch the polyethylene fibrous material at a magnification of at least 2 times. More preferably, it is 2.5 times or more. As the upper limit, in order to increase the strength, it is preferable to increase the stretching ratio as much as possible, but if it is too high, there is a possibility that hair breakage or fluff may be seen. Therefore, the stretching ratio is preferably 30 times or less.

Usually in the manufacture of high-strength polyethylene, in order to increase the strength of the fiber, it is stretched at a high stretching ratio. However, in the case of contact with a relatively high temperature coloring solution before the stretching step, the polyethylene fiber material is softened during the stretching step. Therefore, if the high-magnification For extension, the extension point may not be fixed and the size or strength may be uneven. Therefore, the stretching magnification in the stretching step performed after the heat treatment step or simultaneously with the heat treatment step is preferably set within the above-mentioned range.

The colored polyethylene fiber of this embodiment preferably has a residual solvent concentration of 1000 ppm or less after heat treatment and stretching. If the concentration of the residual solvent exceeds 1000 ppm, the impact on the environment and the ecosystem during manufacture and use of the product will increase, which is not good.

[Embodiment 3]

80以下，對摩擦之染色堅牢度於乾燥狀態及濕潤狀態下均為3級以上，且含有0.4%以上5.0%以下之HLB值為7.0以上14.0以下之界面活性劑。 The characteristic of the colored polyethylene fiber of this embodiment is: L ^* value obtained by CIE-L ^* a ^* b ^* color system

Below 80, the color fastness to rubbing is above grade 3 in both dry and wet state, and contains 0.4% to 5.0% of surfactants with HLB value of 7.0 to 14.0.

Based pigmented polyethylene fibers of the present embodiment aspect is colored a dark color, and the use of L CIE-L * a * b * color measurement method when the coloring or polyethylene fibers obtained by a measurement of the workpiece pigmented polyethylene fibers obtained ^* The value is 80 or less. The smaller the L ^* value, the denser the polyethylene fiber is colored. Therefore, the L* value must be 80 or less, preferably 75 or less, more preferably 70 or less, and still more preferably 65 or less. Furthermore, the lower limit of the L* value is not particularly limited.

The colored polyethylene fiber of this embodiment is strong against friction and dyeing Excellent performance. More specifically, the color fastness to rubbing is 3 or higher both when dry and when wet. The higher the grade of fastness to rubbing, the more difficult it is for the fiber to decolor and color shift. Therefore, the color fastness to rubbing is preferably 4 or higher, more preferably 5 grade. Regarding the color fastness to rubbing, the Gakushin type rubbing tester was used to conduct a rubbing fastness test in accordance with JIS L 0849 (2004) on the samples prepared in accordance with JIS L 0801 (2000), using the gray scale for pollution ( JIS L 0805 (2005)) for evaluation. The details of the test and evaluation method will be described in the examples.

The tensile strength of the colored polyethylene fiber of this embodiment is preferably 18 cN/dtex or more. The tensile strength is more preferably 20 cN/dtex or more, and still more preferably 25 cN/dtex or more. The upper limit of the tensile strength is not particularly limited, but it is technically and industrially difficult to obtain polyethylene fibers with a tensile strength of more than 60 cN/dtex.

In addition, the colored polyethylene fiber is preferably the coefficient of variation (CV) (%) of the tensile strength obtained from the following formula 1 with respect to the tensile strength measured at any 10 locations in the longitudinal direction (length direction) of the fiber ) Is 10% or less.

Coefficient of variation of tensile strength (%) = standard deviation of tensile strength/average value of tensile strength×100 (Equation 1)

The coefficient of variation (%) of the tensile strength is more preferably 9% or less, still more preferably 8% or less, and still more preferably 5% or less. The coefficient of variation (%) of the tensile strength is that the deviation of the strength in the length direction of the polyethylene fiber within the above range is small, so it is preferable.

The elongation (elongation) at the maximum strength of the colored polyethylene fiber is preferably 3.0% or more. More preferably, it is 3.5% or more, and still more preferably 3.7% or more. The upper limit of the elongation is not particularly limited, but is preferably 6.0% or less.

The initial modulus of elasticity of the colored polyethylene fiber is preferably 500 cN/dtex or more and 2000 cN/dtex or less. The initial modulus of elasticity is more preferably 600 cN/dtex or more, and more preferably 700 cN/dtex or more. In addition, it is more preferably 1600 cN/dtex or less, and still more preferably 1400 cN/dtex or less. If the initial modulus of elasticity is too high, it will become difficult to align the polyethylene fibers during the molding process into ropes or braided ropes, and it is also prone to breakage of the monofilament. This problem occurs, so it is better.

The fineness of the monofilament constituting the colored polyethylene fiber is preferably 1 dtex or more and 80 dtex or less. If the monofilament fineness exceeds 80 dtex, it may become difficult to increase the strength while the polyethylene fiber becomes hard. It is preferably 70 dtex or less, more preferably 60 dtex or less. In addition, fibers less than 1 dtex may be prone to fluff during the stretching in the manufacturing process of the fiber or the actual use of the polyethylene fiber. Preferably it is 2 dtex or more, More preferably, it is 5 dtex or more.

In addition, the unevenness of the fineness (coefficient of variation of the total fineness) of the colored polyethylene fiber is preferably 10% or less. If the unevenness of fineness exceeds 10%, not only unevenness in strength is likely to occur, but also unevenness in coloration is likely to occur due to the unevenness in fineness, and there is a risk of deviation in the hue seen. The size is not all under 10% The shape is difficult to cause such a problem, so it is better. The unevenness of fineness is more preferably 6% or less, and still more preferably 5% or less.

The colored polyethylene fiber contains a colored material. As the coloring material, organic coloring materials are preferred, and dyes having affinity with surfactants can be preferably used. The reason is that the surfactant and the coloring material form an emulsion by adding the surfactant to the solvent of the organic coloring material, so water can be used as the solvent. This situation will be further explained below. By using water as a solvent, the environmental load during manufacturing and the environmental load of products can be suppressed.

Examples of such coloring materials include oil-soluble dyes, disperse dyes, acid dyes, and cationic dyes. Among these dyes, oil-soluble dyes and disperse dyes have good compatibility with surfactants, and it is easy to achieve coloring into dense polyethylene fibers, so they are preferred. As preferred oil-soluble dyes, for example, CI Solvent Yellow 2 ("CI Solvent Yellow" is omitted below), 6, 14, 15, 16, 19, 21, 33, 56, 61, 80, CI Solvent Orange 1 ( "CI Solvent Orange" is omitted below), 2, 5, 6, 14, 37, 40, 44, 45, CI Solvent Red 1 ("CI Solvent Red" is omitted below), 3, 8, 23, 24, 25, 27 , 30, 49, 81, 82, 83, 84, 100, 109, 121, CI Solvent Violet 8 ("CI Solvent Violet" is omitted below), 13, 14, 21, 27, CI Solvent Blue 2 ("CI Solvent Violet" is omitted below Solvent blue) 11, 12, 25, 58, 36, 55, 73, CI solvent green 3, etc. Examples of disperse dyes include: C.I. Disperse Red 4 (hereinafter "C.I. Disperse Red" is omitted), 5, 11, 17, 60, 74, 75, 86, 91, 92, 152, 153, 167, 179, 200, 221, 302 are classified as disperse dyes such as CI Disperse Black, CI Disperse Orange 3 (hereinafter "CI Disperse Orange" is omitted), 13, 25, 31 , 37, 45, 61, 76, are classified into disperse dyes such as CI Disperse Gray, CI Disperse Yellow 3 (hereinafter "CI Disperse Yellow" is omitted), 5, 42, 49, 79, 82, 104, 134, 149, 198, 211, and 241 are classified as disperse dyes such as CI Disperse Green, CI Disperse Violet 1 ("CI Disperse Violet" is omitted below), 3, 28, and 43 are classified as disperse dyes such as CI Disperse Brown, CI Disperse Blue 1 ("CI Disperse Blue" is omitted below), 3, 56, 60, 72, 77, 106, 148, 165, 183, 257, 360, etc. These coloring materials can be used alone, or multiple coloring materials with different hues can be used in combination.

The amount of the coloring material contained in the colored polyethylene fiber is preferably from 0.2% by mass to 5% by mass. It is more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and still more preferably 2% by mass or more. As the upper limit, it is more preferably 4% by mass or less, and still more preferably 3% by mass or less. If the content of the coloring material is within the above-mentioned range, it is possible to achieve deep coloring, and there is less risk of affecting the mechanical properties of the fiber, so it is preferable. The amount of the coloring material contained in the colored polyethylene fiber can be obtained by the method described in the examples below.

The amount of surfactant contained in the colored polyethylene fiber is preferably from 0.4% to 5.0%, more preferably from 0.4% to 3%, and still more preferably from 0.4% to 1%. The content of surfactant in colored polyethylene fiber is particularly It is affected by the surfactant added in the solvent of the coloring material used in the coloring in the manufacturing step. When the content of the surfactant in the colored polyethylene fiber is less than 0.4%, it is difficult to disperse the coloring material in the water solvent. Even if it is dispersible, the coloring liquid is attached to the polyethylene fiber in the middle of the spinning process described later. When it penetrates into the fiber, the penetration into the fiber becomes slow. As a result, the coloring material remained on the surface of the fiber, and therefore, the fastness became poor and was not good. On the other hand, if the content of the surfactant in the colored polyethylene fiber exceeds 5.0%, agglomeration of the coloring material contained in the coloring liquid will occur, or even if it can be colored, it will be affected by the excessively attached surfactant on the fiber surface. And produce stickiness. Therefore, the surface smoothness, fastness, and quality of the fiber surface or the processed product is impaired, and therefore it is not good.

In addition, the HLB value of the surfactant contained in the colored polyethylene fiber is preferably 7.0 or more and 14.0 or less. When the HLB value is less than 7, when the coloring liquid is applied to the polyethylene fiber, it is difficult for the surfactant to produce an aqueous dispersion, which is not preferable. In addition, if the HLB value exceeds 14, although the solubility of the surfactant in water is good, the solubility of the colorant becomes poor, which is not good.

The surfactant used in the colored polyethylene fiber of this embodiment is preferably a nonionic surfactant such as polyoxyalkylene alkyl ether, polyoxyethylene behenyl ether, polyoxyethylene stearyl ether, and other higher alcohol-based rings. Oxyethane adducts.

Next, the manufacturing method of this embodiment is demonstrated. In this embodiment, the coloring liquid used for coloring is different from the coloring liquid of the first embodiment, but the colored polyethylene fiber is basically produced by the same manufacturing method as that of the first embodiment. Therefore, the description of the same content in the steps described in Embodiment 1 is omitted.

The method for producing colored polyethylene fibers of this embodiment includes, in addition to the above-mentioned spinning step and stretching step, a step of contacting polyethylene fiber with a coloring liquid (coloring liquid contact step). In the coloring liquid contact step, the coloring liquid is brought into contact with polyethylene fibers containing less than 20% by mass of an organic solvent. The coloring liquid contains a coloring material, a surfactant within the range of the HLB value, and water, and the temperature is Above 0℃, less than 60℃. Thereby, a coloring material can be provided to the polyethylene fiber material. The coloring liquid contains a coloring material and a surfactant within the aforementioned HLB value range, and is preferably in a state of being dispersed in water or emulsified.

In the method for producing colored polyethylene fibers of this embodiment, the colored liquid used in the coloring liquid contact step preferably uses coloring materials, surfactants, and water to form a water dispersion or emulsion shape and add it to the polyethylene fiber. In the method. Regarding the emulsion method, as long as the state of the coloring liquid can be changed from the W/O (water in oil) phase to O/W (oil in water), a known method can be used. For example, the coloring material and the surfactant are mixed, and while stirring with a homogenizer or a high-speed mixer, a small amount of water is added dropwise. Therefore, the viscosity of the liquid slowly increases. The phase transition is reached at about the moment when it becomes pasty, and then water is added dropwise to obtain an emulsified coloring liquid. In order to promote the dissolution of the coloring material, an appropriate amount of solvent can also be added.

When making the emulsion, as long as it does not interfere with the spinning step and the coloring step, various functional doses can be added. For example, lightfast agents (ultraviolet absorbers, light stabilizers, etc.), antibacterial agents, smoothing agents, deodorants, etc. can be cited. The amount of the additive used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the coloring liquid.

Furthermore, the HLB value represents the balance of hydrophilicity and hydrophobicity, and can be obtained by various calculation methods such as Griffin method or Davis method. For example, the Griffin method is widely known: HLB value = 20×(hydrophilic group molecular weight)/(surfactant total molecular weight). If the HLB value is in the range of 8 to 18, it can be inferred that the surfactant Suitable for water dispersion or emulsion. For example, when the carbon number of polyoxyalkylene alkyl ether is 12 and the molar number of ethylene oxide is 10 (the atomic weight of hydrogen is set to 1, the atomic weight of carbon is set to 12, and the atomic weight of oxygen is set to 16. In case), the total molecular weight of the surfactant becomes 625, the molecular weight of the hydrophilic group becomes 396, and the HLB value=20×(440/625)=14.08.

The HLB value of the surfactant does not change in the fiber after the coloring solution containing the surfactant is applied.

In addition, the HLB of the surfactant can also be based on the acid absorption of cobalt tetrathiocyanate (II) Photometric method JIS1993, hydrogen bromide acid decomposition method, bismuth iodide method, liquid chromatography mass spectrometry or gas chromatography mass spectrometry, liquid paraffin O/W test, liquid paraffin W/O test (emulsion Information on known analysis methods such as the Foundation and Stability and Evaluation Technology Information Association) is obtained in the form of approximate values.

As a specific example of the surfactant of the higher alcohol-based ethylene oxide adduct used in the method of producing the colored polyethylene fiber of this embodiment, for example, the trade name "Nonion S-207" ( Manufactured by NOF Corporation, HLB value 10.7) or trade name "Naroacty CL-70" (manufactured by Sanyo Chemical Industry Co., Ltd., HLB value 11.5), etc.

As long as the coloring liquid contact step is performed on the polyethylene fibrous material, the execution time of this step is not limited. However, it is sometimes difficult to move the coloring material into the fibrous material after the crystallization of the polyethylene is completed, so it is preferable to extend the polyethylene fibrous material to the final stretching at a preset stretching ratio. Therefore, the coloring solution contacting step is preferably performed after the spinning step and before the stretching step. In the case of two-stage or more multi-stage stretching, it can also be performed between the stretching steps. For example, if it is a two-stage stretching, It can also be performed between the extension steps of the first stage and the second stage.

As the coloring material, the above-mentioned coloring material can be preferably used. More preferably, they are oil-soluble dyes or disperse dyes. The concentration of the coloring material in the coloring solution is as long as It can be adjusted by containing 0.2% to 5% by mass of the coloring material in the colored polyethylene fiber. Generally, the concentration of the coloring material in the coloring liquid is preferably set to 1% to 28% by mass. It is more preferably 1.5% by mass or more and 25% by mass or less, and still more preferably 2% by mass or more and 23% by mass or less. If the concentration of the coloring material is too low, it may be difficult to achieve dense coloring. When the concentration of the coloring material is too high, sometimes excess coloring material remains on the surface of the fiber, which reduces the color fastness of the polyethylene fiber. Therefore it is not good.

The temperature of the coloring liquid should be above 0°C and less than 60°C. It is more preferably 5°C or higher, still more preferably 8°C or higher, still more preferably 10°C or higher, and preferably 50°C or lower, and still more preferably 40°C or lower. In addition, the temperature of the polyethylene fibrous material in contact with the coloring solution is preferably 50°C or lower, more preferably 45°C or lower, and still more preferably 40°C or lower. The lower limit of the temperature of the polyethylene fiber is not limited, and it is generally preferably above room temperature. The temperature of the polyethylene fiber material can be measured with a non-contact type thermometer such as an infrared thermometer, for example.

If the temperature of the coloring liquid is too high, when the coloring material is dispersed in water, the water evaporates quickly and only the coloring material remains on the surface of the polyethylene fiber, making it difficult to move the coloring material into the polyethylene fiber. The tendency. In this case, the peripheral components may be contaminated in the subsequent steps, and the coloring material may fall off from the product using the polyethylene fiber obtained, which may cause contamination. Furthermore, in order to eliminate this problem, a step of washing the dye adhering to the surface is required, which may reduce the work efficiency. In addition, for coloring When the liquid temperature is too high, the temperature of the polyethylene fiber in contact with the coloring liquid rises, and the effect of the tension on the polyethylene fiber in the heat treatment step or the stretching step after the coloring liquid contact step changes As a result, uneven size or uneven strength (uneven yarn) may occur. Especially when the stretching step is performed after the coloring liquid contact step, if the temperature of the polyethylene fibrous material is too high, the stretching point may not be fixed and uneven stretching may occur.

Furthermore, even if the temperature of the polyethylene fiber is sufficiently low, when the temperature of the coloring liquid is high, the crystalline structure formed in the polyethylene fiber when it comes into contact with the coloring liquid is destroyed, resulting in discoloration. Both are concerned. If the temperature of the coloring liquid and the temperature of the polyethylene fibrous material are within the above-mentioned range, the above-mentioned problem is unlikely to occur, and therefore it is preferable.

The contact method of the polyethylene fibrous material and the coloring solution is not particularly limited as long as the polyethylene fibrous material can be given a coloring material, and various methods can be used. Specific contact methods include: a method of contacting the polyethylene fiber with the coloring liquid by guiding and applying oil; a method of contacting the polyethylene fiber with the surface of the rotating roller to which the coloring liquid is attached; The method of spraying coloring liquid on polyethylene fiber; the method of contacting the polyethylene fiber by passing through the coloring liquid bath. In addition, when the polyethylene solution contains a non-volatile organic solvent (such as paraffin wax, etc.), the coloring solution obtained by dissolving the coloring material in the extraction solvent used in the solvent removal step can also be used as the extraction bath to make the polyethylene The fiber is passed through the extraction bath Then, the polyethylene fiber is brought into contact with the coloring solution.

The amount of the coloring liquid applied to the polyethylene fibrous material is preferably in the range of 0.1% by mass to 15% by mass relative to the polyethylene fibrous material. It is more preferably 0.5% by mass or more, still more preferably 1% by mass or more, more preferably 12% by mass or less, and still more preferably 8% by mass or less. If the amount of the coloring liquid is too small, it may be difficult to color into a dense color. On the other hand, if the amount of the coloring liquid is too large, excess coloring materials may remain on the fiber surface and the color fastness may deteriorate. During the step, the coloring material may fall off from the fibrous material and contaminate peripheral components.

In this embodiment, the heat treatment step (heat treatment step) of heating the polyethylene fiber to which the coloring liquid has been applied is heated at 110°C or higher for 10 seconds or longer. This promotes the penetration of the coloring liquid into the polyethylene fiber, and easily moves the coloring material to the core of the polyethylene fiber. As a result, colored polyethylene fibers with denser colors and improved fastness to dyeing can be obtained. It can be considered that the reason for the above results is that by performing the heat treatment step, the stretching step is performed in a state where the coloring material is present in the interior (core) of the polyethylene fiber, and the crystallization of the polyethylene caused by the stretching The coloring material is sealed inside the polyethylene fiber (core).

The heat treatment step can be performed at any timing as long as it is after the coloring liquid contact step. In addition, the heat treatment step may be performed separately or simultaneously with the stretching step. In the case of simultaneous heat treatment step and extension step At the same time, the movement of the coloring material to the inside of the polyethylene fiber caused by the penetration of the coloring liquid and the crystallization of the polyethylene caused by the extension can be performed simultaneously. In addition, when the heat treatment step and the stretching step are performed separately, the stretching step can be performed after the coloring material moves into the polyethylene fiber through the heat treatment step, so that the color fastness can be further improved. Preferably, the heat treatment step and the extension step are performed simultaneously.

The heating temperature is preferably 120°C or higher, more preferably 130°C or higher. Regarding the upper limit of the heating temperature, it is recommended to set the temperature at which no end breakage occurs due to fusing, that is, below the melting point of the polyethylene filament.

The heating method is not particularly limited, and for example, known methods such as hot air, hot rollers, radiation panels, steam jets, and hot rods can be used. Furthermore, from the viewpoint of minimizing the contamination of the coloring material, it is preferable to adopt a non-contact heating method using hot air, a radiant panel, and steam injection.

The heating time is preferably 10 seconds or more, more preferably 12 seconds or more, and still more preferably 15 seconds or more. The upper limit of the heating time is not particularly limited. For example, it is preferably 150 seconds or less, more preferably 120 seconds or less, and still more preferably 100 seconds or less. When the heat treatment step is performed separately, it is preferable to perform the heat treatment step and the extension step within the above range.

If tension is applied to the polyethylene fiber in the heat treatment step, the molecular chain of the polyethylene is stretched, thereby generating capillary phenomenon and further promoting The coloring liquid penetrates into the inside of the fiber, so it is preferable. When the tension in the heat treatment step is too small, it may be difficult to generate capillary phenomenon. On the other hand, if the tension is too high, fuzzing or the like will occur, and it may be difficult to obtain polyethylene fibers with less fineness and less uneven strength.

After the heat treatment step or in the stretching step performed simultaneously with the heat treatment step, it is preferable to stretch the polyethylene fibrous material at a magnification of at least 2 times. More preferably, it is 2.5 times or more. As the upper limit, in order to increase the strength, it is preferable to increase the stretching ratio as much as possible, but if it is too high, there is a possibility that hair breakage or fluff may be seen. Therefore, the stretching ratio is preferably 30 times or less.

Usually in the manufacture of high-strength polyethylene, in order to increase the strength of the fiber, it is stretched at a high stretching ratio. However, in the case of contact with a relatively high-temperature coloring solution before the stretching step, the polyethylene fiber material is softened during the stretching step. Therefore, if the high-magnification stretching is performed in this state, there is stretching If the dots are not fixed, there is a risk of uneven size or strength. Therefore, the stretching magnification in the stretching step performed after the heat treatment step or simultaneously with the heat treatment step is preferably set within the above-mentioned range.

The colored polyethylene fiber of this embodiment preferably has a residual solvent concentration of 1000 ppm or less after heat treatment and stretching. If the concentration of the residual solvent exceeds 1000 ppm, the impact on the environment and people during manufacturing and product use will increase, which is not good.

The colored polyethylene fiber described in the above embodiment 1 to embodiment 3 is colored into a dense color, and has excellent dye fastness to rubbing and/or solvent resistance, so it can be suitably used as a braided rope, fishing line, and gloves , Ropes, nets, knitted fabrics and braids, etc. All the threads used in these applications may be the above-mentioned colored polyethylene fibers, and the above-mentioned colored polyethylene fibers may also be used for a part. For example, in the case of a braided rope, it is preferable to contain at least one colored polyethylene fiber.

The braided rope preferably has a strength of 15 cN/dtex or more of the fiber (multifilament) obtained by untying the braided rope. It is more preferably 18 cN/dtex or more, and still more preferably 20 cN/dtex or more. The upper limit of fineness is the same as the above-mentioned colored polyethylene fiber.

[Example]

The following examples are given to illustrate the present invention in more detail, but of course, the present invention is not limited by the following embodiments. Of course, it can also be implemented with appropriate changes within the scope that can conform to the foregoing and the following principles. These changes include Within the technical scope of the present invention. Furthermore, as long as there is no special description below, "parts" means "parts by mass" and "%" means "mass%".

First, the evaluation method of the colored polyethylene fiber (filament) obtained in the following examples and the like will be described.

(1) Determination of color (CIE-L*a*b* color system)

As the measurement conditions, the measurement was performed in accordance with JIS Z 8781-4 2013. Use Spectrophotometer (SPECTROPHOTOMETER) CM-3700d (manufactured by Konica Minola Co., Ltd.), use Datacolor Spectraflash model SF-300 colorimeter (Datacolor International, Lawrenceville, New Jersey) D65/10 degree light source for measurement.

The sample for measurement was produced by winding colored polyethylene fibers on a stainless steel (SUS304) plate so that no gaps were generated as much as possible.

The measurement system uses the international reference color measurement method. The international reference color measurement method uses the reference color coordinates of mCIELAB's L ^* a ^* b ^* color space, and is determined by "Commission Internationale de L'Eclairage" (Paris, France) (with lighting The relevant international society (International Society for Illumination/Lighting) ("CIE") public table. 『L ^* 』represents brightness coordinates, 『a ^* 』represents red/green coordinates (+a ^* represents red, -a ^* represents green), 『b ^* 』represents yellow/blue coordinates (+b ^* represents yellow, -b ^* Indicates blue).

(2) Dyeing fastness to rubbing

Prepare samples according to JIS L 0801 (2000). For dry and wet samples, a friction tester II (Gakushin type) was used to test the color fastness to friction in accordance with JIS L 0849 (2013). The staining gray scale (JIS L 0805 (2005)) was used for the result to judge the color fastness by visual method.

Furthermore, fix at least one colored polyethylene fiber as a sample The sample table of the vibration type friction tester is measured. When the length of the fiber is sufficient, arrange a plurality of fibers and fix them on the sample table for measurement. Or, for a rectangular cardboard of the same size as the sample table, the fibers are densely and firmly wound parallel to the longitudinal direction of the cardboard to make a sample and measure the sample, or by circular knitting Wait for the state of fabric to be measured. It can also be used directly when the sample is fabric.

(3) Solvent resistance (measured only in Example 1-1 to Example 1-5, Comparative Example 1-1 to Comparative Example 1-5, Reference Example 1-1, Reference Example 1-2)

In a transparent glass container, the colored polyethylene fiber was immersed in acetone so as to be 0.1 g/mL, and it was allowed to stand at room temperature (20°C) for 24 hours. The acetone used to impregnate colored polyethylene fibers (acetone as a reference) and the acetone impregnated with colored polyethylene fibers and allowed to stand for 24 hours are measured with an ultraviolet-visible spectrophotometer (manufactured by Hitachi, Ltd., U-3210 type) For the transmittance in the wavelength range of 350nm to 780nm, calculate the integral value T ₀ of the transmittance in the above wavelength range from the obtained transmittance curve (reference substance, acetone used for impregnating colored polyethylene fibers), T ₁ (impregnating coloring) Acetone after polyethylene fiber), and the solvent resistance is calculated from the following formula 2.

Solvent resistance (%)=(T ₁ /T ₀ )×100 (Equation 2)

(4) The size of silk and the size of silk are uneven

The polyethylene fiber was cut into 50 cm at three different positions in the longitudinal direction, the weight of the three places was measured, and the average value of the weight was used to obtain the fineness of the thread. The monofilament fineness can be calculated based on the silk fineness.

The unevenness of fineness in the longitudinal direction was measured by the following method. The colored polyethylene fiber was continuously cut 10 pieces per 10 cm, and the weight of the 10 fibers was measured respectively, and the fineness unevenness (variation coefficient of the total fineness) was obtained using the following formula 3.

Uneven size (%)=(standard deviation of size/average value of size)×100 (Equation 3)

(5) Tensile strength, elongation, elastic modulus

Measured in accordance with JIS L1013 8.5.1. Regarding the tensile strength and elastic modulus, use the "Tensilon Universal Material Testing Machine" manufactured by Orientec Co., Ltd. The sample length is 200mm (length between clamps) and the elongation speed is 100%/ Measure the strain-stress curve under the conditions of 20°C ambient temperature and 65% relative humidity, calculate the strength (cN/dtex) and elongation (%) according to the stress and elongation at the breaking point, according to the origin of the curve The tangent to obtain the maximum gradient is calculated to obtain the elastic modulus (cN/dtex). The initial load applied to the polyethylene fiber during the measurement was set to 1/10 of the fineness (cN/dtex). In addition, each value is the average of 10 measurements.

(6) Uneven tensile strength in the longitudinal direction of the fiber (coefficient of variation)

With regard to the longitudinal direction of the colored polyethylene fiber, the above-mentioned strength test is carried out at 10 arbitrary locations, and the coefficient of variation (CV) (%) of the tensile strength is obtained by the following (Equation 1). Furthermore, as long as the sample is taken from the same fiber (filament), it is not particularly limited. It can be taken continuously in the direction of the fiber length, or taken After taking one sample, take the next sample with an interval.

Coefficient of variation of tensile strength (%)=(standard deviation of tensile strength/average value of tensile strength)×100 (Equation 1)

(7) Ultimate viscosity

The specific viscosity of various dilute solutions is measured by Ubbelohde’s capillary viscosity tube with decalin at 135℃, and the limit viscosity is determined based on the point of extension of the straight line obtained by the least square approximation of the viscosity versus concentration graph. . Furthermore, the ultimate viscosity is not only measured on the raw material polyethylene, but also on the manufactured polyethylene fiber.

(8) Amount of organic solvent (only measured in Example 1-1 to Example 1-5, Comparative Example 1-1 to Comparative Example 1-5, Reference Example 1-1, Reference Example 1-2)

After the polyethylene fiber (multifilament) is extracted from the spinning step and the coloring solution contact step and the weight is measured (the weight before drying), the extracted polyethylene fiber is vacuumed at the temperature at which the organic solvent volatilizes After drying for 24 hours, the weight (weight after drying) is measured again. The amount of organic solvent (residual solvent amount) contained in the polyethylene fibrous material was calculated from the obtained weight and the following formula.

Residual solvent amount (%) = (weight before drying-weight after drying) / weight before drying × 100

(9) Residual volatile solvent concentration (only measured in Example 2-1 to Example 2-4, Comparative Example 2-1 to Comparative Example 2-6, Reference Example 2-1)

The residual solvent concentration was measured using a "gas chromatograph" manufactured by Shimadzu Corporation. First, set 10 mg of polyethylene fiber as a sample in the glass block of the injection port of the gas chromatograph, and then heat the injection port above the boiling point of the solvent, and use nitrogen to flush the solvent generated by heating into the tube In the column. Then, the column temperature was set to 40°C, and the solvent was captured for 5 minutes. Then, the column temperature was raised to 80°C and the measurement was started. Determine the residual solvent concentration from the peak value obtained.

(10) Acid value of fiber (only measured in Example 2-1 to Example 2-4, Comparative Example 2-1 to Comparative Example 2-6, Reference Example 2-1)

After dissolving 1g to 2g of a sample of polyethylene fiber in 20ml of hot xylene heated to 130°C, adding phenolphthalein, titrating with a 0.1mol/L potassium/methyl alcohol titration solution to obtain the acid value.

(11) Surfactant dosage in fiber (only measured in Example 3-1 to Example 3-7, Comparative Example 3-1 to Comparative Example 3-4)

The colored polyethylene fiber is extracted, separated and purified, and the remaining in the fiber is determined by structural analysis such as NMR (Nuclear Magnetic Resonance), LC/MS (Liquid Chromatography-Mass Spectrometry; Liquid Chromatography-Mass Spectrometry) and other known methods. Interface active dose.

(Example 1-1)

Use ultra-high molecular weight polyethylene with an ultimate viscosity of 18.5dL/g and 98% of the repeating units as ethylene as the raw material polyethylene to disperse the raw material polyethylene A dispersion liquid with a polyethylene concentration of 8% by mass was prepared in decalin. After the dispersion was heated at 190°C by an extruder to make a solution, it was ejected from a spinning nozzle with a hole diameter of φ 1.0mm and composed of 30H at a nozzle surface temperature of 180°C and a single-hole ejection volume of 2.0 g/min. . The ejected thread was deformed by 8 times until it was solidified, and was cooled in a water cooling bath at 30°C to obtain a polyethylene fiber (unstretched thread). The residual solvent amount in the undrawn yarn was 12% by mass.

Then, by the guide oiling method, the coloring solution (30°C) with 20% by mass of CI Solvent Blue 58 dissolved in decalin was 6% by mass relative to the mass of the polyethylene fiber Attachment by the amount of attachment. The temperature of the polyethylene fiber when the coloring liquid is in contact is 30°C, the tension is 1.2 cN/dtex, and the amount of organic solvent in the polyethylene fiber after the coloring liquid is in contact is 16.8% by mass.

Then, while applying a tension of 3.7 cN/dtex to the polyethylene fibrous material, heat treatment was performed with hot air of nitrogen at 120°C for 11 seconds, and then stretched 3 times at the same temperature (first stage). Then, the polyethylene fiber after one stage of stretching was stretched 5 times (second stage) in an oven at 150° C. and then taken up. The ultimate viscosity of the colored polyethylene fiber obtained at this time is 16dL/g. The manufacturing conditions used in Example 1-1 are shown in Table 1, and the physical properties of the resulting colored polyethylene fiber are shown in Table 2.

The color measurement of the obtained colored polyethylene fiber showed that the L ^* value was 41.25, the a ^* value was 1.62, and the b ^* value was -42.05. Then, it was left standing at room temperature (20°C) for 24 hours at a bath ratio of 1:20 (polyethylene fiber:acetone, mass ratio) in acetone, and then taken out, and color measurement was performed in the same manner. The hue L ^* value of the polyethylene fiber after acetone treatment is 42.10, a ^* value is 1.73, and b ^* value is -41.06. Even with visual comparison with polyethylene fiber before acetone treatment, no change in hue was seen.

Taking Example 1-1 as an example, the method of studying the structure and content of the coloring material contained in the fiber is described. Furthermore, when different coloring materials are used, as long as an appropriate solvent or device corresponding to the coloring material is used, the structure of the coloring material contained in the fiber can be similarly identified and the content of the coloring material can be calculated.

Using 120 mL of acetone as a solvent, 3 g of the colored polyethylene fiber obtained in Example 1-1 was subjected to Soxhlet extraction for 4 hours. 15 mg of the residue obtained by drying the extract was dissolved in 0.6 mL of deuterated chloroform, and the ¹ H-NMR spectrum was measured using AVANCE500 manufactured by BRUKER BIOSPIN.

In addition, 1 mg of the above-mentioned residue was dissolved in 20 mL of a methanol/chloroform mixed solvent (2/1 volume ratio), and precise mass measurement was performed by electrospray ionization using micrOTOF manufactured by BRUKER DALTONICS.

According to the obtained ¹ H-NMR spectrum and the results of precise mass measurement, it was confirmed that the CI solvent blue 58 in the polyethylene fiber of Example 1-1 was not decomposed, but contained the CI solvent blue 58.

In addition, the content of the coloring material in the coloring polyethylene fiber of Example 1-1 can be determined as follows. The residue obtained by the above-mentioned Soxhlet extraction was dissolved in acetone to prepare a sample solution with a concentration of 10 mg/L, and the UV-visible absorption spectrum was measured using an ultraviolet-visible spectrophotometer (for example, SolidSpec-3700 manufactured by Shimadzu Corporation, etc.). In contrast, prepare at least 3 different concentrations of CI Solvent Blue 58 in acetone, measure the UV-Vis absorption spectrum in the same way, and make the maximum absorption wavelength between 350nm and 700nm (in the case of CI Solvent Blue 58, 440nm) The calibration curve of the relationship between absorbance and solution concentration below. Then, the amount of coloring material contained in the polyethylene fiber can be calculated based on the calibration curve and the measurement result of the sample (10 mg/L acetone solution of the residue). Furthermore, when using coloring materials other than C.I. Solvent Blue 58, it is sufficient to use an appropriate solvent or device corresponding to the coloring material.

(Example 1-2)

Except that 1.7% by mass of antioxidant was added to the raw material polyethylene used in Example 1-1, spinning and stretching were performed under the same conditions as in Example 1-1 to produce polyethylene fibers. The ultimate viscosity of the colored polyethylene fiber obtained in Example 1-2 is 16 dL/g. The manufacturing conditions are shown in Table 1, and the physical properties of the resulting colored polyethylene fiber are shown in Table 2.

(Example 1-3)

Change the temperature of the coloring liquid to 45°C, and change the extension step of the second stage The stretching temperature in the step was changed to 148°C, and the conditions shown in Table 1 were further adopted, except that spinning and stretching were performed under the same conditions as in Example 1-1 to produce polyethylene fibers. The ultimate viscosity of the colored polyethylene fiber obtained in Examples 1-3 is 16 dL/g. The manufacturing conditions are shown in Table 1, and the physical properties of the resulting colored polyethylene fiber are shown in Table 2.

Compared with Example 1-1, the temperature of the coloring liquid was higher, so tension relaxation occurred in the heat treatment step and the first-stage stretching step, but the physical properties were not greatly reduced.

(Example 1-4)

In the stretching step of the first stage after contact with the coloring solution, the stretching speed is kept constant to extend the furnace length of the stretching furnace, and the heat treatment and stretching temperature (first stage) is set to 130°C, and then the temperature shown in Table 1 Except for the conditions, spinning and stretching were performed under the same conditions as in Example 1-1 to produce polyethylene fibers. The ultimate viscosity of the colored polyethylene fiber obtained in Examples 1-4 is 16 dL/g. The manufacturing conditions are shown in Table 1, and the physical properties of the obtained polyethylene fiber are shown in Table 2.

Compared with other examples, the furnace length of the stretching furnace is longer, so the heat treatment time and deformation time are longer, and tension relaxation occurs during the heat treatment and the first stage of stretching, but the physical properties of the polyethylene fiber are the same as those in Example 1-1 There is no big difference in comparison. Furthermore, compared with the polyethylene fibers of other examples, the polyethylene fibers of Examples 1-4 have a denser color (L ^* value 39.32), but the extraction amount of the coloring material in acetone is less, and it is resistant to solvents. Excellent performance (95%). It is presumed that the reason for this situation is that compared with other examples, the heat treatment temperature after the contact of the coloring liquid is higher, and the heat treatment time is also longer, thus promoting the movement of the coloring material into the polyethylene fiber.

(Example 1-5)

In Example 1-1, the polyethylene fibrous material (undrawn yarn) obtained in the spinning step was not brought into contact with the coloring solution, and heat treatment was carried out at the same temperature with hot air of nitrogen at 120°C for 11 seconds. Extension of 3 times the extension ratio (first stage). By the guide oiling method, the coloring liquid (20% by mass CI solvent blue 58 decalin solution, 30°C) is made to have an adhesion amount of 6% by mass relative to the mass of the polyethylene fiber Attached to the polyethylene fibrous material after one-stage stretching (9% by mass of residual solvent). The temperature of the polyethylene fiber in contact with the coloring solution is 30°C, and the tension is 0.5cN/dtex.

Then, the polyethylene fiber material contacted with the coloring liquid was heat-treated at 150°C for 18 seconds (tension 4.5 cN/dtex), and then stretched 5 times at the same temperature and wound up. The ultimate viscosity of the colored polyethylene fiber obtained in Examples 1-5 is 16 dL/g. The manufacturing conditions are shown in Table 1, and the physical properties of the obtained polyethylene fiber are shown in Table 2.

Even if the coloring solution contacting step is performed after the extension step of the first stage, the physical properties of the colored polyethylene fiber are not much different from those of Example 1-1, and the colored polyethylene fiber can be colored into a dense color and has excellent color fastness. And solvent-resistant colored polyethylene fiber.

(Comparative Example 1-1)

Except changing the temperature of the coloring solution in contact with the polyethylene fibrous material (undrawn yarn) obtained in the spinning step to 140°C, it is desired to perform spinning and drawing under the same conditions as in Example 1-1, However, because the temperature of the coloring liquid is too high, it softens when the undrawn yarn comes into contact with the coloring liquid, resulting in breakage during the stretching step, and polyethylene fibers cannot be obtained.

(Comparative example 1-2)

The temperature of the coloring solution in contact with the polyethylene fiber (undrawn yarn) obtained in the spinning step was changed to 110°C, the tension was changed to 0.02 cN/dtex, and the temperature of the heat treatment step and the first step of the elongation step It was changed to 110°C, the stretching ratio was changed to 5 times, the stretching temperature in the stretching step of the second stage was changed to 145°C, and the stretching ratio was changed to 4 times, except that the same as in Example 1-1 Under the conditions of spinning and stretching to obtain polyethylene fiber. The ultimate viscosity of the colored polyethylene fiber obtained in Comparative Example 1-2 is 16 dL/g. The manufacturing conditions are shown in Table 1, and the physical properties of the resulting colored polyethylene fiber are shown in Table 2.

Compared with the examples, the obtained colored polyethylene fiber has larger unevenness in fineness and uneven strength. In Comparative Example 1-2, it can be considered that the reason for this situation is: because the temperature of the coloring liquid is too high, the undrawn yarn softens at the moment when the undrawn yarn comes into contact with the coloring liquid, and high tension cannot be maintained during the coloring liquid contact step. In this state, the first-stage extension step is performed, so the extension point is not fixed, and it is difficult to achieve uniform extension.

In addition, although the polyethylene fiber is colored into a deep color, its color fastness to rubbing and solvent resistance are both inferior to the examples. It is presumed that the reason for this situation is that because the temperature of the coloring liquid is high, the decalin as a solvent quickly volatilizes from the coloring liquid attached to the unstretched silk, and the concentration of the dye on the fiber surface becomes too high, and the coloring material is difficult to transfer The unstretched wire moves inside.

(Comparative Example 1-3)

Set the tension applied to the polyethylene fibrous material when it comes into contact with the coloring solution to 0.9cN/dtex, then heat treatment at 90°C for 5 seconds with a tension of 4.2cN/dtex, and set the stretching ratio in the first stage to 2 times Except that the stretching temperature of the stretching step of the second stage was set to 141°C and the stretching ratio was set to 2.5 times, the spinning and stretching were performed under the same conditions as in Example 1-1 to obtain colored polyethylene fibers. The limiting viscosity of the colored polyethylene fiber obtained in Comparative Examples 1-3 was 16 dL/g. The manufacturing conditions are shown in Table 1, and the physical properties of the resulting colored polyethylene fiber are shown in Table 2.

Compared with the colored polyethylene fibers of the examples, the resulting colored polyethylene fiber has poorer color fastness to rubbing. It is believed that the reason for this situation is that the temperature of the heat treatment after the coloring liquid contact step is low and the time is short, so it is difficult to promote the penetration of the coloring material into the fibrous material. This situation is also indicated by the solvent resistance of 64%.

In addition, compared with the examples, the colored polyethylene fibers of Comparative Examples 1-3 have lower strength and elastic modulus, and uneven strength and fineness. It can be considered that the reason for this situation is: the extension temperature of the first stage is low, so it is In both the first stage and the second stage, the stretching ratio cannot be increased. In addition, the stretching point is not fixed due to the influence of the coloring material and the solvent remaining on the surface of the fibrous material, and the stretching cannot be performed uniformly.

(Comparative Example 1-4)

Use the coloring solution (solvent: decalin) with the concentration of the coloring material (CI Solvent Blue 58) of 30% by mass, and set the amount of the coloring solution to the polyethylene fiber material to 20% by mass. Spinning and stretching were performed under the same conditions as in Example 1-1 to obtain polyethylene fibers. Furthermore, the organic solvent (the total amount of the organic solvent after the spinning step and the organic solvent derived from the coloring liquid) contained in the polyethylene fiber after the coloring liquid contact step is 26% by mass. The ultimate viscosity of the colored polyethylene fiber obtained in Comparative Examples 1-4 is 16 dL/g. The manufacturing conditions are shown in Table 1, and the physical properties of the obtained polyethylene fiber are shown in Table 2.

Although the obtained polyethylene fiber has a dense color, it is inferior in dye fastness and solvent resistance compared with the examples, and uneven strength and fineness are also large. It is believed that the reason for this situation is that the excess coloring material is maintained on the fiber surface and passed through the stretching step. In addition, it is considered that the cause of this situation is that the polyethylene fibrous material after the coloring liquid contact step contains a large amount of residual solvent, so that the elongation becomes uneven.

(Reference Example 1-1, Comparative Example 1-5)

In the raw material polyethylene dispersion (polyethylene concentration 8% by mass), the concentration is 0.1% by mass relative to the solvent (Reference Example 1-1), 0.01% by mass Except that C.I. Solvent Blue 58 was added as% (Comparative Example 1-5) and the coloring liquid contact step was not performed, spinning and drawing were performed in the same manner as in Example 1-1 to obtain a colored polyethylene fiber. Among them, in the stretching step of the second stage of Reference Example 1-1, if the stretching magnification is set to 5 times, a large number of broken ends will be generated, so the stretching magnification is set to 4 times. The limiting viscosity of the colored polyethylene fiber of Reference Example 1-1 is 16 dL/g, and the limiting viscosity of the colored polyethylene fiber of Comparative Example 1-5 is 16 dL/g. Furthermore, the colored material contained in the colored polyethylene fiber of Reference Example 1-1 was 1.2% by mass, and the colored material contained in the colored polyethylene fiber of Comparative Example 5 was 0.12% by mass. The manufacturing conditions and physical properties are shown in Table 1 and Table 2, respectively.

The polyethylene fiber obtained in Reference Example 1-1 has low strength, elongation, and elastic modulus, and the deviation of the strength and fineness in the fiber (filament) is also greater than that of the polyethylene fiber of the embodiment. It can be considered that in Reference Example 1-1, a coloring material is added to the raw polyethylene dispersion in the spinning stage. Therefore, although the coloring material may exist in the deep part of the crystal structure of polyethylene, the coloring material functions as a foreign substance , It is difficult to increase the stretching ratio. On the other hand, in Comparative Examples 1-5, since the content ratio of the coloring material was reduced, the effect of foreign matter was reduced, and polyethylene fibers with the same strength, elongation and elastic modulus as the examples were obtained, but Since the added amount of coloring materials is small, the L ^* value is higher than 80 and it is light color.

(Reference example 1-2)

Except for the contact between the unstretched silk and the coloring solution, the same as the embodiment 1-1 Polyethylene fiber is produced in the same manner. The limiting viscosity of the colored polyethylene fiber of Reference Example 1-2 is 16dL/g. The manufacturing conditions and physical properties are shown in Table 1 and Table 2, respectively.

In Table 1, the amount of organic solvent 1 indicates the amount of organic solvent contained in the polyethylene fibrous material used in the coloring liquid contact step, and the amount of organic solvent 2 indicates the organic solvent contained in the polyethylene fibrous material after the coloring liquid contact step The amount (the total of organic solvent 1 and the organic solvent derived from the coloring liquid), the silk temperature represents the temperature of the silk supplied to the coloring liquid contact step.

(Example 2-1)

An ultra-high molecular weight polyethylene with an ultimate viscosity of 17.0 dL/g and 98% of the repeating units being ethylene was used as the raw material polyethylene, and the raw material polyethylene was dispersed in decalin to prepare a dispersion with a polyethylene concentration of 9% by mass. After the dispersion was heated to 200°C with an extruder to form a solution, it was ejected from a spinning nozzle with an orifice diameter of φ1.0 mm and composed of 30H at a nozzle surface temperature of 180°C and a single-hole ejection rate of 2.0 g/min. The ejected thread was deformed by 8 times until it was solidified, and was cooled in a water cooling bath at 30°C to obtain a polyethylene fiber (unstretched thread).

Then, the coloring liquid (30°C) was brought into contact with the polyethylene fibrous material by the guide oiling method, and the coloring liquid system used purified water as a solvent, and CI solvent blue 35 (10% by mass) and acid value 20mgKOH , Modified polyethylene with a molecular weight of 3000 (addition of polyethylene) (10% by mass) is made into an emulsion shape in water, so that the coloring liquid is 1% by mass relative to the mass of the polyethylene fiber The way to attach. The temperature of the polyethylene fiber (the temperature of the silk) when the coloring liquid is in contact is 30°C.

Then, the polyethylene fiber with the coloring liquid attached was heat-treated with hot air of 100°C nitrogen for 15 seconds, and then stretched 4 times at the same temperature (first stage). Then, the polyethylene fibrous material after one stage of stretching was stretched 4 times (second stage) in an oven at 150°C and taken up. The manufacturing conditions used in Example 2-1 and the resulting colored polyethylene fiber The physical properties are shown in Table 3.

(Example 2-2)

For the added polyethylene added to the coloring liquid, the added polyethylene with a molecular weight of 4000 and an acid value of 30 mgKOH was used, and the extension time of the first stage was set to 25 seconds, except that it was the same as in Example 2-1 Manufacture of colored polyethylene fibers. Table 3 shows the manufacturing conditions used in Example 2-2 and the physical properties of the resulting colored polyethylene fiber.

(Example 2-3)

For the added polyethylene added to the coloring solution, use added polyethylene with a molecular weight of 3000 and an acid value of 60mgKOH, and set the extension time of the first stage to 25 seconds and the extension ratio of the first stage to 3.5 times. Except for this, a colored polyethylene fiber was produced in the same manner as in Example 2-1. Table 3 shows the manufacturing conditions used in Example 2-3 and the physical properties of the resulting colored polyethylene fiber.

(Example 2-4)

For the added polyethylene added to the coloring solution, the added amount is set to 20% by mass, the added polyethylene with a molecular weight of 5000 and an acid value of 40mgKOH is used, and the extension time of the first stage is set to 25 seconds, and the first Except that the draw ratio of the stage was set to 3.5 times, a colored polyethylene fiber was produced in the same manner as in Example 2-1. Table 3 shows the production conditions used in Examples 2-4 and the physical properties of the resulting colored polyethylene fiber.

(Comparative Example 2-1)

An ultra-high molecular weight polyethylene with an ultimate viscosity of 18.5 dL/g and 96% of the repeating units being ethylene was used as the raw material polyethylene, and the raw material polyethylene was dispersed in decalin to prepare a dispersion with a polyethylene concentration of 8% by mass. After the dispersion was heated at 190°C by an extruder to form a solution, it was ejected from a spinning nozzle with a hole diameter of 0.8 mm and composed of 30H at a nozzle surface temperature of 180°C and a single-hole ejection rate of 2 g/min. The ejected thread was deformed by 16 times until it was solidified, and was cooled in a water cooling bath at 30°C to obtain a polyethylene fiber (undrawn thread).

Then, the coloring solution (30°C) with 10% by mass of CI Solvent Blue 58 dissolved in decalin was brought into contact with the polyethylene fibrous material by the guide oiling method, so as to be opposed to the polyethylene fibrous material. The mass is 1% by mass. The temperature of the polyethylene fiber (the temperature of the silk) when the coloring liquid is in contact is 30°C.

Then, the polyethylene fibrous material was heat-treated for 11 seconds with hot air of nitrogen at 120°C, and then stretched 3 times at the same temperature (the first stage). Then, the polyethylene fiber after one stage of stretching was stretched 5 times (second stage) in an oven at 150° C. and then taken up. Table 2 shows the production conditions used in Comparative Example 2-1 and the physical properties of the resulting colored polyethylene fiber.

(Comparative Example 2-2)

The coloring solution (110°C) with 15% by mass of CI solvent blue 35 dissolved in decalin was brought into contact with the above-mentioned polyethylene fiber by the guided oiling method, and the second stage was implemented in an oven at 135°C Except for the stretching, a colored polyethylene fiber was produced in the same manner as in Comparative Example 2-1. Table 4 shows the production conditions used in Comparative Example 2-2 and the physical properties of the resulting colored polyethylene fiber.

(Comparative example 2-3)

In the same raw material polyethylene dispersion as in Comparative Example 2-1, CI Solvent Blue 35 was added so that the concentration became 0.05% by mass, and the unstretched yarn and the coloring solution were not contacted (not dyed), except that In the same manner as in Comparative Example 2-1, colored polyethylene fibers were produced. Table 4 shows the manufacturing conditions used in Comparative Example 2-3 and the physical properties of the resulting colored polyethylene fiber.

(Comparative Example 2-4)

Use a coloring solution in which 20% by mass of CI Solvent Blue 58 is dissolved in decalin, and after heat treatment with 90°C nitrogen hot air for 5 seconds, it is extended twice at the same temperature (first stage) After that, the polyethylene fibrous material after the one-stage stretch was stretched 4 times in an oven at 90° C. (the second stage), and except for that, a colored polyethylene fiber was produced in the same manner as in Comparative Example 2-1. Table 4 shows the manufacturing conditions used in Comparative Examples 2-4 and the physical properties of the resulting colored polyethylene fiber.

(Comparative example 2-5)

Use a coloring solution in which 20% by mass of CI Solvent Blue 58 is dissolved in decalin, and adhere to the amount of 12% by mass relative to the mass of the polyethylene fibrous material, and implement it in an oven at 135°C Except for the stretching in the second stage, colored polyethylene fibers were produced in the same manner as in Comparative Example 2-1. Table 4 shows the manufacturing conditions used in Comparative Examples 2-5 and the physical properties of the resulting colored polyethylene fiber.

(Comparative example 2-6)

C.I. Solvent Blue 35 (10% by mass) was used as a coloring material, purified water was used as a solvent, and no added polyethylene was used to prepare a coloring liquid. The coloring liquid does not become a uniform solution, but a state where the coloring material is dispersed in water. Except for using this coloring liquid, polyethylene fiber was produced in the same manner as in Example 2-4. However, the coloring material only adheres to the fiber surface and cannot color the polyethylene fiber. Table 4 shows the production conditions used in Comparative Examples 2-6 and the physical properties of the obtained polyethylene fiber.

(Reference example 2-1)

A polyethylene fiber was produced in the same manner as in Comparative Example 2-1, except that the contact between the undrawn yarn and the coloring solution was not performed (dyeing was not performed), and the stretching was performed 3.5 times in the first stage of stretching. Table 4 shows the production conditions used in Reference Example 2-1 and the physical properties of the obtained polyethylene fiber.

According to Table 3 and Table 4, it is clear that water is used as the solvent of the coloring liquid and the acid value of the fiber is within the range of 0.1 mgKOH/g or more and 50 mgKOH/g or less in Examples 2-1 to 2-4 and coloring materials The solvent uses an organic solvent (decahydronaphthalene in the comparative example) and the acid value of the fiber is 0. Compared with Comparative Example 2-1 to Comparative Example 2-5, the residual volatile solvent concentration is relatively low, and it is difficult to cause environmental load. . In addition, it is known that the fibers of Examples 2-1 to 2-4 are obtained by the CIE-L ^* a ^* b ^* color system. The L ^* value is less than 80, and the color fastness to rubbing is in a dry state and a wet state. In the state, they are all grade 3 or higher, and the acid value is 0.1 mgKOH/g or more and 50 mgKOH/g or less, so it is a fiber that is colored into a deep color and has excellent dye fastness and/or solvent resistance.

(Example 3-1)

First, in Example 3-1, a coloring liquid was produced as follows. While stirring CI Solvent Blue 58 as a coloring material and a commercially available surfactant with an HLB value of 11.7 composed of polyoxyalkylene alkyl ether as the main component, the purified water was slowly added dropwise to obtain an emulsified coloration liquid. Furthermore, the prepared emulsified coloring liquid is adjusted so that it becomes 3% by mass of coloring material, 1.2% by mass of surfactant, and 95.8% by mass of purified water.

The state of the coloring liquid prepared as described above was observed and the result was good. Here, the observation of the coloring liquid is performed as follows. Add a small amount of emulsified coloring liquid or water-dispersed coloring liquid to commercially available rough straw paper, etc., and observe the bleeding of the dyeing liquid. If the coloring liquid spreads equally to the rough paper, it is judged It is good. When the coloring material agglomerates on rough straw paper, etc., and the bleeding occurs separated from water, it cannot be sufficiently emulsified, and it is an unstable coloring liquid. Even if it is colored, the color is lightened, so it is not suitable for use.

Next, the spinning in Example 3-1 will be described.

An ultra-high molecular weight polyethylene with an ultimate viscosity of 17.0 dL/g and 98% of the repeating units being ethylene was used as the raw material polyethylene, and the raw material polyethylene was dispersed in decalin to prepare a dispersion with a polyethylene concentration of 9% by mass. After the dispersion was heated at 200°C with an extruder to form a solution, it was ejected from a spinning nozzle with an orifice diameter of φ1.0 mm and composed of 30H at a nozzle surface temperature of 180°C and a single-hole ejection rate of 2.0 g/min. The ejected thread was deformed by 8 times until it was solidified, and was cooled in a water cooling bath at 30°C to obtain a polyethylene fiber (unstretched thread).

Then, by the guide oiling method, the coloring liquid (30°C) produced above is made 1% by mass relative to the mass of the polyethylene fiber material, and the main component contained in the coloring liquid is poly The total surface active amount of the surfactant of the oxyalkylene alkyl ether (the total of the surface active agent contained in the coloring liquid and the surface active agent contained in the oil dressing agent) is attached so that it becomes 0.93% by mass. The temperature of the polyethylene fiber when the coloring liquid is in contact is 30°C, and the tension is 1.2cN.

Then, while applying a tension of 3.7 cN/dtex to the polyethylene fiber with the coloring liquid attached, the hot air at 110°C was used for 25 After the second heat treatment, the extension is 4 times at the same temperature (the first stage). Then, the polyethylene fibrous material after one stage of stretching was stretched 4 times (second stage) in an oven at 150°C and taken up.

The colored polyethylene fiber after the adhesion of the coloring solution (after coloring) has good color development, dry rubbing fastness is 4, wet rubbing fastness is 4, and the amount of surfactant remaining in the fiber is 0.89% by mass. The manufacturing conditions used in Example 3-1 and the physical properties of the resulting colored polyethylene fiber are shown in Table 5.

(Example 3-2)

As for the main component of the surfactant contained in the coloring liquid, a commercially available surfactant composed of polyoxyethylene behenyl ether with an HLB value of 7.0 was used, except that it was produced in the same manner as in Example 3-1. Colored polyethylene fiber.

If a small amount of the coloring solution of Example 3-2 is added to the rough straw paper, there is no aggregate of the coloring material, the dyeing solution is evenly bleed, and the state of the coloring solution is good. The colored polyethylene fiber of Example 3-2 has good color development, dry rubbing fastness is grade 4, wet rubbing fastness is grade 4, and the surfactant dose remaining in the fiber is 0.91% by mass. The manufacturing conditions used in Example 3-2 and the physical properties of the resulting colored polyethylene fiber are shown in Table 5.

(Example 3-3)

For the main component of the surfactant contained in the coloring liquid, use a commercially available product made of polyoxyethylene behenyl ether with an HLB value of 14.0. Except for these agents, colored polyethylene fibers were produced in the same manner as in Example 3-1.

If a small amount of the coloring solution of Example 3-3 is added to the rough straw paper, there is no aggregation of the coloring material, the dyeing solution is evenly bleed, and the state of the coloring solution is good. The colored polyethylene fiber of Example 3-3 has good color development, dry rubbing fastness is 4, wet rubbing fastness is 4, and the amount of surfactant remaining in the fiber is 0.79% by mass. The production conditions used in Example 3-3 and the physical properties of the resulting colored polyethylene fiber are shown in Table 5.

(Example 3-4)

For the main component of the surfactant contained in the coloring liquid, a commercially available surfactant composed of polyoxyethylene stearyl ether with an HLB value of 10.7 was used, except that it was produced in the same manner as in Example 3-1. Colored polyethylene fiber.

If a small amount of the coloring solution of Example 3-4 is added to the rough straw paper, there is no aggregate of the coloring material, the dyeing solution is evenly bleed, and the state of the coloring solution is good. The colored polyethylene fiber of Example 3-4 has good color development, dry rubbing fastness is grade 4, wet rubbing fastness is grade 4, and the amount of surfactant remaining in the fiber is 0.87 mass%. Table 5 shows the production conditions used in Example 3-4 and the physical properties of the resulting colored polyethylene fiber.

(Example 3-5)

A coloring liquid was produced in the same manner as in Example 3-1 except that the prepared emulsified coloring liquid was adjusted so that the coloring material was 3% by mass, the surfactant was 0.6% by mass, and the purified water was 96.4% by mass. Using this coloring liquid, the total surface active dose is relative to the mass of the polyethylene fiber The colored polyethylene fiber was produced in the same manner as in Example 3-1 except that it adhered so as to have an adhesion amount of 0.67% by mass.

If a small amount of the coloring solution of Example 3-5 is added to the rough straw paper, there is no aggregation of the coloring material, and the dyeing solution is evenly bleed, and the state of the coloring solution is good. The colored polyethylene fiber of Example 3-5 has good color development, dry rubbing fastness is grade 4, wet rubbing fastness is grade 3-4, and the surfactant dose remaining in the fiber is 0.58% by mass. The manufacturing conditions used in Examples 3-5 and the physical properties of the resulting colored polyethylene fiber are shown in Table 5.

(Example 3-6)

A coloring liquid was produced in the same manner as in Example 3-1 except that the prepared emulsified coloring liquid was adjusted so that the coloring material was 3% by mass, the surfactant 0.24% by mass, and the purified water was 96.76% by mass. Using this coloring liquid, it adhered so that the total surface active amount might become 0.51 mass% of adhesion amount with respect to the mass of the polyethylene fiber material, and except that it carried out similarly to Example 3-1, the colored polyethylene fiber was produced.

The colored polyethylene fibers of Examples 3-6 have good color development, dry rubbing fastness is grade 4, wet rubbing fastness is grade 3-4, and the amount of surfactant remaining in the fiber is 0.49% by mass. Table 5 shows the production conditions used in Examples 3-6 and the physical properties of the resulting colored polyethylene fiber.

(Example 3-7)

It is adjusted in such a way that the emulsified coloring solution becomes 3% by mass of coloring material, 10% by mass of surfactant, and 87% by mass of purified water. Except for this, a coloring liquid was produced in the same manner as in Example 3-1. Using this coloring liquid, it was adhered so that the total amount of interfacial active agent became an adhesion amount of 4.6% by mass relative to the mass of the polyethylene fibrous material. Except for this, a colored polyethylene was produced in the same manner as the spinning of Example 3-1 fiber.

The colored polyethylene fibers of Examples 3-7 have good color development and a slight sticky feeling when touched by hand, but the dry rubbing fastness is grade 3, the wet rubbing fastness is grade 3, and the amount of interfacial active remaining in the fiber is 4.1% by mass. Table 5 shows the production conditions used in Examples 3-7 and the physical properties of the resulting colored polyethylene fiber.

(Comparative Example 3-1)

As for the main component of the surfactant contained in the coloring liquid, a commercially available surfactant composed of polyoxyethylene stearyl ether with an HLB value of 6.0 was used, and it was produced in the same manner as in Example 3-1, except that Colored polyethylene fiber.

For the coloring solution of Comparative Example 3-1, when the dyeing solution was dropped onto the rough straw paper, the coloring material aggregated and separated from water. The coloring was studied while stirring the coloring solution, but the colored polyethylene fiber obtained in Comparative Example 3-1 was light-colored, with dry rubbing fastness of grade 3, wet rubbing fastness of grade 2, and the amount of surfactant remaining in the fiber was 0.46 quality%. Regarding the occurrence of agglomeration in the coloring liquid, it can be considered that the HLB value of the surfactant is low and cannot be sufficiently emulsified, and the coloring is not performed and the fastness is also poor. Table 6 shows the production conditions used in Comparative Example 3-1 and the physical properties of the resulting colored polyethylene fiber.

(Comparative Example 3-2)

As for the main component of the surfactant contained in the coloring liquid, a commercially available surfactant composed of polyoxyethylene alkyl ether with an HLB value of 14.7 was used, except that it was produced in the same manner as in Example 3-1. Colored polyethylene fiber.

The coloring liquid system of Comparative Example 3-2 is apparently stable, but when a small amount is dropped onto rough straw paper, the coloring material aggregates and separates from water. The coloring was studied while stirring the coloring solution, but the colored polyethylene fiber obtained in Comparative Example 3-2 was light-colored, with a dry rubbing fastness of grade 2 and a wet rubbing fastness of grade 1-2, and the amount of surfactant remaining in the fiber It was 0.93% by mass. It is believed that if the surfactant has high hydrophilicity, it is difficult to be compatible with hydrophobic coloring materials, and the emulsification is insufficient, which affects the coloring. Table 6 shows the production conditions used in Comparative Example 3-2 and the physical properties of the resulting colored polyethylene fiber.

(Comparative Example 3-3)

The emulsification was investigated using a surfactant with a HLB value of 11.7 as a commercially available product consisting of a main component of 0.05% by mass of polyoxyethylene alkyl ether, and other than that according to Example 3-1. However, for the coloring liquid produced, the coloring material cannot be mixed with water and cannot be emulsified, so coloring is abandoned. Table 6 shows the production conditions used in Comparative Example 3-3 and the physical properties of the resulting colored polyethylene fiber.

(Comparative Example 3-4)

For the main component of the surfactant contained in the coloring liquid, use 12.5% by mass of a commercially available surfactant composed of polyoxyethylene alkyl ether with an HLB value of 11.7, and the total amount of surfactant is 5.7% by mass. Except that the coloring liquid was adhered in a quantitative manner, colored polyethylene fibers were produced in the same manner as in Example 3-1.

If a small amount of the coloring solution of Comparative Example 3-4 is added to the rough straw paper, there is no aggregate of the coloring material, and the state of the coloring solution obtained in Comparative Example 3-4 is good. The colored polyethylene fiber of Comparative Example 3-4 has a dry rubbing fastness of 2-3 and a wet rubbing fastness of 2, and the amount of surfactant remaining in the fiber is 5.2% by mass. However, the fiber has a slightly sticky feel, and the wet rubbing fastness is poor. Table 6 shows the manufacturing conditions used in Comparative Example 3-4 and the physical properties of the resulting colored polyethylene fiber.

As is clear from Table 5 and Table 6, the fibers of Example 3-1 to Example 3-7 are compared with the fibers of Comparative Example 3-1 to Comparative Example 3-4 by CIE-L ^* a ^* b ^* The L ^* value obtained by the color system is below 80, and the color fastness to rubbing is above grade 3 in dry and wet conditions, and contains 0.4% above 5.0% with HLB value above 7.0 and below 14.0 interface activity It is a fiber that has been colored to a deep color and has excellent color fastness and/or solvent resistance.

Each embodiment and each example described above are examples in all respects and are not restrictive. The technical scope of the present invention is defined by the scope of the patent application, and additionally includes the meaning equivalent to the description of the patent scope and all changes within the scope.

(Industrial availability)

According to the present invention, it is possible to provide a colored polyethylene fiber that is colored into a deep color and has excellent dye fastness and/or solvent resistance. The colored polyethylene fiber has little unevenness in strength and fineness. Therefore, it can be suitably used for braiding and fishing Materials such as fishing line, gloves, ropes, nets, knitted fabrics and woven fabrics.

Claims (21)

A colored polyethylene fiber, L ^* value obtained by CIE-L ^* a ^* b ^* color system is below 80, and the color fastness to rubbing is above grade 3 in both dry and wet conditions; The tensile strength measured at any 10 locations in the longitudinal direction, the coefficient of variation defined by the following formula 1 is less than 10%; the coefficient of variation of tensile strength (%) = (standard deviation of tensile strength / tensile strength Average)×100 (Equation 1). The colored polyethylene fiber described in claim 1 has an acid value of 0.1 mgKOH/g or more and 50 mgKOH/g or less. The colored polyethylene fiber described in claim 1, which contains a surfactant with a hydrophilic-lipophilic balance value of 7.0 or more and 14.0 or less of 0.4% or more and 5.0% or less. For the colored polyethylene fiber described in claim 1, the solvent resistance obtained by the following measurement method is 75% or more; the solvent resistance measurement method is: the colored polyethylene fiber is 0.1g/mL The method is immersed in acetone and allowed to stand at room temperature for 24 hours; for acetone used for impregnating colored polyethylene fibers and acetone after impregnating colored polyethylene fibers and standing at 20°C±5°C for 24 hours, use The UV-visible spectrophotometer measures the transmittance in the wavelength range from 350nm to 780nm, and calculates the integral value of the transmittance in the aforementioned wavelength range based on the obtained transmittance curve, and calculates the solvent resistance by the following formula 2; solvent resistance (% )=(T ₁ /T ₀ )×100 (Formula 2); In formula 2, T ₀ represents the integral value of the transmittance of acetone at a wavelength of 350 nm to 780 nm, and T ₁ represents the impregnated colored polyethylene at a wavelength of 350 nm to 780 nm The integral value of the transmittance of acetone after fiber. For the colored polyethylene fibers described in claim 1 or 4, the fineness in the longitudinal direction is not all 10% or less. The colored polyethylene fiber described in claim 1 or 4 has a tensile strength of 18 cN/dtex or more. The colored polyethylene fiber described in claim 1 or 4, which contains oil-soluble dye-colored materials. The colored polyethylene fiber described in claim 1 or 4, wherein the monofilament contained therein has a fineness of 1 dtex or more and 80 dtex or less. A braided rope containing at least one colored polyethylene fiber as described in any one of claims 1 to 8. The braided rope described in claim 9, wherein the strength of the fiber obtained by untying the braided rope is 15 cN/dtex or more. A fishing line containing the colored polyethylene fiber described in any one of claims 1 to 8. A glove containing the colored polyethylene fiber described in any one of claims 1 to 8. A rope containing the colored polyethylene fiber described in any one of claims 1 to 8. A net containing colored polyethylene fibers as described in any one of claims 1 to 8. A knitted fabric or woven fabric containing any of claims 1 to 8 A recorded colored polyethylene fiber. A method for producing colored polyethylene fiber, which is used to produce the colored polyethylene fiber described in any one of claims 1 to 8, including: dissolving polyethylene in a concentration of 0.5% to 40% by mass The step of spinning a polyethylene solution in an organic solvent to obtain a polyethylene fibrous material. The limiting viscosity [η] of the polyethylene is 5.0 dL/g or more and 25 dL/g or less, and the repeating unit of the polyethylene It is composed of 90 mol% or more of ethylene; the step of contacting a polyethylene fiber containing less than 20% by mass of an organic solvent with a coloring liquid, the coloring liquid contains a coloring material and an organic solvent, and the temperature is above 0°C Less than 60°C; the step of heating the polyethylene fibrous material containing less than 25% of the organic solvent with respect to the weight of the fiber provided with the coloring liquid at 110°C for more than 10 seconds; and the step of extending the polyethylene fibrous material. A method for producing colored polyethylene fiber, which is used to produce the colored polyethylene fiber described in any one of claims 1 to 8, including: dissolving polyethylene in a concentration of 0.5% to 40% by mass The step of spinning a polyethylene solution in an organic solvent to obtain a polyethylene fibrous material. The limiting viscosity [η] of the polyethylene is 5.0 dL/g or more and 25 dL/g or less, and the repeating unit of the polyethylene It is composed of 90 mol% or more of ethylene; the step of bringing the aforementioned polyethylene fibrous material into contact with the coloring liquid, the coloring liquid contains a coloring material and a polyolefin with a hydrophilic group at one end Hydrocarbon, and the temperature is 0°C or higher and less than 60°C; the step of heating the polyethylene fiber with the coloring liquid to 110°C or higher for 10 seconds or more; and the step of extending the polyethylene fiber. A method for producing colored polyethylene fiber, which is used to produce the colored polyethylene fiber described in any one of claims 1 to 8, including: dissolving polyethylene in a concentration of 0.5% to 40% by mass The step of spinning a polyethylene solution in an organic solvent to obtain a polyethylene fibrous material. The limiting viscosity [η] of the polyethylene is 5.0 dL/g or more and 25 dL/g or less, and the repeating unit of the polyethylene It is composed of 90 mol% or more of ethylene; the step of contacting the polyethylene fibrous material with the coloring liquid, the coloring liquid contains the coloring material and a surfactant with a hydrophilic-lipophilic balance value of 7.0 or more and 14.0 or less, and the temperature It is a step of heating the polyethylene fibrous material to which the coloring liquid is imparted at 110°C or higher for 10 seconds or more; and the step of extending the polyethylene fibrous material. The method for producing a colored polyethylene fiber according to any one of claims 16 to 18, wherein the temperature of the polyethylene fibrous material in contact with the coloring liquid is 50°C or less. The method for producing a colored polyethylene fiber as described in any one of claims 16 to 18, wherein a tension of 0.8 cN/dtex to 6.5 cN/dtex is applied to the polyethylene fiber to which the coloring liquid is applied Perform the aforementioned heating. The method for producing a colored polyethylene fiber described in any one of claims 16 to 18, which includes the step of stretching the polyethylene fiber to which the coloring liquid has been applied at a stretching ratio of 2 times or more.