Preparation method of high-color-fastness strong horse fishing line

Abstract

The invention relates to a preparation method of a high-color-fastness vigorous horse fishing line, and belongs to the technical field of dyeing. According to the fishing line, ultra-high molecular weight polyethylene is used as a base material, and a two-step double coloring process is innovatively adopted: firstly, in a low-crystallinity primary filament stage before drafting, a low molecular weight dye is used for internal permeation dyeing; then, after the fibers are subjected to drafting orientation shaping, polar groups are grafted on the surfaces of the fibers through plasma treatment, and then the fibers are coated with a composite coloring coating for external bonding dyeing. The structural characteristics of the UHMWPE fiber in different processing stages are fully utilized, dual combination of dye molecules from the interior of the fiber to the surface of the fiber is achieved, and the prepared fishing line has high color fastness, color uniformity and weather resistance while maintaining the excellent mechanical properties such as ultrahigh strength and high modulus of the fishing line. The invention further provides a specific and industrialized preparation process of the fishing line.

Description

Technical Field

[0001] This invention relates to the field of dyeing technology, specifically to a method for preparing high color fastness Dyneema fishing line. Background Technology

[0002] Ultra-high molecular weight polyethylene (UHMWPE) fibers are classified as high-performance fibers due to their superior mechanical properties and chemical resistance. These fibers are derived from polyethylene, a polymer with a molecular weight typically exceeding 10. 6 UHMWPE filaments are linear thermoplastic polymers with a molecular weight of g / mol. This ultra-high molecular weight results in extremely long polymer chains, typically containing hundreds of thousands of monomer units, giving UHMWPE filaments exceptional strength and durability. These fibers have the highest impact resistance of all thermoplastic yarns and possess an excellent tensile strength-to-weight ratio, outperforming steel and other conventional materials at the same weight.

[0003] The main characteristics of UHMWPE fibers are their high crystallinity (up to 85%) and strong intermolecular van der Waals forces, which endow the fibers with excellent stiffness and tensile properties. These fibers are lightweight, with a density of less than 1 g / cm³. Furthermore, UHMWPE fibers exhibit excellent chemical resistance, UV radiation resistance, and moisture resistance. Due to their superior properties, UHMWPE fibers are widely used in ballistic protection (e.g., bulletproof vests), marine and industrial ropes, medical devices (e.g., orthopedic implants), defense and military industries, and sporting goods.

[0004] Despite these advantages, UHMWPE fibers exhibit weak interfacial adhesion to the polymer matrix due to their smooth surface, low surface energy, and chemical inertness. Furthermore, their high hydrophobicity and dense crystalline structure hinder dye penetration, making dyeing difficult and rendering traditional dyeing methods ineffective. Therefore, conventional dyeing processes yield poor results for UHMWPE fibers. Consequently, developing a method that maintains the mechanical properties of UHMWPE fibers while achieving high colorfastness is a pressing technical problem in this field. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies and provide a high-colorfastness Dyneema fishing line. This method, while maintaining the inherent high strength and high modulus of UHMWPE fibers, innovatively integrates the dyeing process with the UHMWPE fiber molding process through a synergistic "internal and external dual dyeing" strategy, achieving coloring in stages and through multiple mechanisms.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing high colorfastness Dyneema fishing line, characterized by comprising the following steps: Step 1: Gel spinning and preparation of nascent filaments UHMWPE powder is mixed with a solvent, dissolved, filtered, and degassed to form a gel spinning solution. The solution is then extruded through a spinneret and cooled to solidify, resulting in UHMWPE nascent gel fibers with low crystallinity and a high proportion of amorphous regions.

[0007] Step Two: First Staining – Internal Penetration Staining The nascent gel fibers obtained in step one are immersed in a first dyeing solution containing low molecular weight dyes to obtain dyed UHMWPE nascent gel fibers.

[0008] Step 3: Solvent extraction and multi-stage thermal stretching The gelatin fibers dyed in step two were immersed in an extractant to remove the solvent and then dried. The dried fibers were then subjected to multi-stage hot stretching to obtain high-strength UHMWPE fibers.

[0009] Step 4: Plasma surface grafting treatment The high-strength fibers obtained in step three are cleaned and dried, and then subjected to low-temperature plasma treatment. Oxygen- or nitrogen-containing active gases are introduced into the treatment atmosphere to graft polar groups -OH, -COOH, or -NH2 onto the fiber surface.

[0010] Step 5: Second staining – External bonding staining A surface-modifying solution and a second dyeing solution are prepared. The fibers treated in step four are then sequentially immersed in the surface-modifying solution and the second dyeing solution, and dried and cured to obtain a high-color-fastness Dyneema fishing line with an internal and external dual-coloring structure.

[0011] Preferably, the low molecular weight dye in step two has a molecular weight of less than 800 Da, and is preferably a disperse dye or an acid dye; the solvent of the first dyeing solution is an organic solvent or a water-organic solvent mixture capable of swelling UHMWPE fibers, the dyeing temperature is 40-80℃, and the immersion time is 5-30 min.

[0012] Preferably, the total draw ratio of the multi-stage hot drawing in step three is 30-80 times, wherein the first-stage drawing temperature is lower than the melting point of UHMWPE, which is 90-120℃.

[0013] Preferably, the working gas for plasma treatment in step four is a mixture of two or more of argon, nitrogen, oxygen, and ammonia, wherein the active gas accounts for 5%-30%; the treatment power is 30-100 W, and the treatment time is 2-10 min.

[0014] Preferably, the surface modification liquid in step five comprises, by weight: 1-3 parts of natural polysaccharides, 2-8 parts of organic acids, and 300-600 parts of water; the second dyeing liquid comprises, by weight: 400-700 parts of aprotic polar solvent, 3-10 parts of polymeric film-forming agent, 5-20 parts of nanoscale pigment, and 0.5-2 parts of dispersing agent.

[0015] Preferably, the natural polysaccharide is one or more of chitosan, sodium alginate, and carboxymethyl cellulose.

[0016] Preferably, the organic acid is one or a mixture of acetic acid, citric acid, and tartaric acid.

[0017] Preferably, the aprotic polar solvent is one or more of ethyl acetate, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0018] Preferably, the polymeric film-forming agent is one or more of polyurethane, acrylic resin, and epoxy resin.

[0019] Preferably, the nanoscale pigment is an organic or inorganic pigment with a particle size range of 20-100 nm.

[0020] Preferably, the dispersing agent is one or a mixture of sodium polyacrylate, polyvinylpyrrolidone, and sodium dodecyl sulfate.

[0021] Preferably, in step five, the temperature of the surface modification liquid for impregnation is 40-60℃, the impregnation time is 10-30 s, the drying temperature is 60-80℃, and the drying time is 5-10 min; the temperature of the second dyeing liquid for impregnation is 20-40℃, the impregnation time is 5-15 s, the curing temperature is 100-130℃, and the curing time is 15-30 min. Compared with the prior art, the beneficial effects of the present invention

[0022] Color fastness is effectively improved: the dual coloring mechanism of internal physical locking and surface chemical bonding solves the problem of weak adhesion of single dyeing methods.

[0023] Excellent mechanical properties are maintained: internal dyeing occurs during the loose fiber structure stage before drawing, which does not affect the subsequent super-heat drawing to establish a highly crystalline and highly oriented structure; the surface treatment is a mild plasma grafting and coating, which does not damage the fiber itself. The key indicators of the finished fishing line, such as strength, modulus, and knot strength, are at the same excellent level as the undyed raw yarn.

[0024] The colors are rich and uniform, and the selection is flexible: the internal dyes and external nano-pigments can be mixed to create rich and full color gradations. The nano-pigments produce vibrant colors, and the final color can be easily adjusted by changing the second dyeing solution, resulting in high production flexibility.

[0025] The process has industrialization potential: each step can be integrated with existing UHMWPE fiber production lines. For example, the first dyeing tank can be placed between the nascent fiber winding and the first drawing machine, and the plasma treatment and second dyeing line can be placed after the setting process, making it easy to achieve continuous and large-scale production. Detailed Implementation

[0026] To further understand the present invention, the following detailed description of a high color fastness Dyneema fishing line and its preparation method provided by the present invention is provided in conjunction with embodiments. The scope of protection of the present invention is not limited by the following embodiments.

[0027] Example 1: Preparation of red high colorfastness Dyneema fishing line Step 1: Gel spinning and preparation of nascent filaments UHMWPE powder and white oil were mixed at a mass ratio of 1:5, and 0.5 wt% antioxidant 1010 was added. The mixture was stirred and dissolved at 180°C for 3 h. After filtration through a 400-mesh screen and degassing, a gel spinning solution was obtained. The spinning solution was extruded through a spinneret (0.25 mm orifice) at 185°C. The nascent filaments were cooled in an air section and then solidified in an ice-water bath to obtain nascent gel fiber bundles.

[0028] Step 2: First staining Disperse red dye (CI Disperse Red 60) with a molecular weight of approximately 600 was dissolved at a concentration of 3% owf (relative to fiber mass) in a mixed solvent of cyclohexanone and water (volume ratio 7:3), heated to 70°C, and stirred until homogeneous. Narrative gel fiber bundles were passed through an impregnation tank containing the dye solution at a speed of 5 m / min for approximately 5 min. The impregnated fibers were then placed in a first-stage washing tank to remove surface dye.

[0029] Step 3: Solvent extraction and multi-stage thermal stretching The dyed gel fibers were immersed in hexane (liquid ratio 1:100) and ultrasonically extracted at 40℃ for 90 min, with the extraction solvent replaced twice. Then, the fibers were vacuum dried at 50℃ for 1.5 h. The dried fibers were then subjected to four stages of hot stretching at 100℃, 120℃, 130℃, and 145℃, with a total stretching ratio of 50 times, to obtain high-strength fibers.

[0030] Step 4: Plasma Surface Pretreatment The drawn fibers were ultrasonically cleaned with anhydrous ethanol for 12 min and vacuum dried at 70℃ for 2.5 h. They were then placed in a low-temperature plasma device, and a mixed gas (90% argon, 10% oxygen, total flow rate 30 sccm) was introduced. The chamber pressure was 30 Pa, the discharge power was 50 W, and the gases passed through the treatment zone at a linear velocity of 1.5 m / min for 3 min, thereby grafting oxygen-containing polar groups onto the fiber surface.

[0031] Step 5: Second staining Preparation of the surface modification solution: Weigh 2 parts of chitosan and add it to 500 parts of deionized water, stirring until evenly dispersed. Then add 4 parts of acetic acid and continue stirring until the chitosan is completely dissolved, obtaining a clear surface modification solution. Preparation of the second dyeing solution: Measure 550 parts of dimethylformamide and add 6 parts of polyurethane resin, stirring until completely dissolved. Then add 12 parts of red nano-sized organic pigment and 1 part of sodium polyacrylate, stirring at high speed for 60 min to obtain a uniformly dispersed red dyeing solution. Immerse the plasma-treated Dyneema fishing line in the surface modification solution at a speed of 2 m / min for approximately 10 s. After removal, dry in an 80℃ hot air oven for 5 min. Subsequently, immerse the line in the second dyeing solution at a speed of 2 m / min for approximately 10 s. After removal, cure and dry in a 100℃ hot air oven for 15 min to obtain the finished red Dyneema fishing line.

[0032] Example 2: Preparation of blue high color fastness Dyneema fishing line The steps are basically the same as in Example 1, except that: First dyeing solution: Use disperse blue dye (CI Disperse Blue 56) with a molecular weight of approximately 450, dimethylformamide as the solvent, and dyeing temperature of 60℃. Second dyeing solution: Measure 500 parts of dimethylacetamide, add 5 parts of epoxy resin, and stir until completely dissolved. Then add 8 parts of blue nano-sized organic pigment and 0.8 parts of sodium dodecyl sulfate, and stir at high speed for 60 min to obtain a uniformly dispersed blue dye solution.

[0033] Comparative Example 1: Surface staining only The first dyeing and plasma pretreatment are omitted. Instead, the fibers that have been drawn are directly surface-cleaned, then coated with a surface-modifying solution and a second dye solution. Other steps are the same as in Example 1.

[0034] Comparative Example 2: Internal staining only Only the first staining and stretching fixation were performed, omitting plasma pretreatment and the second staining. The other steps were the same as in Example 1.

[0035] Comparative Example 3: Traditional Dyeing Process The high-temperature and high-pressure dyeing method was adopted: the untreated UHMWPE raw yarn was placed in a high-temperature and high-pressure dyeing machine containing disperse dye and dyed at 130℃ and 0.3 MPa for 60 min, followed by washing with water, soaping, and drying.

[0036]

[0037] Conclusion: 1. Examples 1 and 2: Double coloring inside and outside was successfully achieved, and the mechanical properties were almost the same as those of the undyed raw yarn.

[0038] 2. Comparative Example 1: Due to the lack of internal dyeing and effective surface grafting, the adhesion of the physical coating is extremely weak, the color fastness is poor, and the color will fade with slight rubbing.

[0039] 3. Comparative Example 2: Although internal dyeing has no effect on mechanical properties, the color is lighter due to the lack of surface coloring and protective layers, and the internal dye still migrates to a certain extent during friction and washing, resulting in unsatisfactory color fastness.

[0040] 4. Comparative Example 3: The traditional high-temperature method severely damages the highly oriented structure of UHMWPE fibers, resulting in a decrease in mechanical properties and the presence of an uneven dyeing "white core" phenomenon, with generally poor color fastness.

Claims

1. A process for the preparation of high color fastness Dai-Ma fishing line, characterized by, Comprising the following steps: Step one: gel spinning and nascent fiber preparation UHMWPE powder is mixed with solvent, dissolved, filtered, and degassed to form a gel spinning solution. The solution is extruded through a spinneret and cooled to solidify, resulting in a UHMWPE nascent gel fiber with low crystallinity and a high proportion of amorphous regions. Step two: first dyeing - internal penetration dyeing The nascent gel fiber obtained in step one is immersed in a first dyeing solution containing low molecular weight dyes to obtain dyed UHMWPE nascent gel fiber. Step three: solvent extraction and multi-stage heat drawing The dyed gel fiber from step two is immersed in an extractant to remove the solvent, dried, and then subjected to multi-stage heat drawing to obtain high-strength UHMWPE fiber. Step four: plasma surface grafting treatment The high-strength fiber from step three is washed and dried, then subjected to low-temperature plasma treatment in an atmosphere containing oxygen or nitrogen-containing active gas to graft -OH, -COOH, or -NH2 polar groups onto the fiber surface. Step five: second dyeing - external bonding dyeing A surface modification solution and a second dyeing solution are prepared, and the treated fiber from step four is immersed in the surface modification solution and then the second dyeing solution, dried and solidified to obtain high-color-fastness Dyneema fishing line with internal and external double coloring structures.

2. The method of claim 1, wherein the high color fastness Dai-Ma fishing line is prepared by the steps of: In step two, the low molecular weight dye has a molecular weight less than 800 Da, preferably a disperse dye or an acid dye; the solvent of the first dyeing solution is an organic solvent or a water-organic solvent mixture that can swell the UHMWPE fiber, the dyeing temperature is 40-80℃, and the immersion time is 5-30 min.

3. The method of claim 1, wherein the high color fastness Dai-Ma fishing line is prepared by the steps of: In step three, the total draw ratio of multi-stage heat drawing is 30-80 times, and the first stage draw temperature is lower than the melting point of UHMWPE, which is 90-120℃. ​ 4. The method of claim 1, wherein the high color fastness Dai-Ma fishing line is prepared by the steps of: In step four, the working gas for plasma treatment is a mixture of two or more of argon, nitrogen, oxygen, and ammonia, with an active gas proportion of 5%-30%; the treatment power is 30-100 W, and the treatment time is 2-10 min. ​ 5. The method for preparing a high color fastness Dyneema fishing line according to claim 1, characterized in that, In step five, the surface modification solution includes, by weight: 1-3 parts of natural polysaccharide, 2-8 parts of organic acid, and 300-600 parts of water; the second dyeing solution includes, by weight: 400-700 parts of aprotic polar solvent, 3-10 parts of high molecular film forming agent, 5-20 parts of nano-sized pigment, and 0.5-2 parts of dispersion aid.

6. The method for preparing a high colorfastness Dyneema fishing line according to claim 1, characterized in that, In step five, the temperature for immersing the surface modification solution is 40-60℃, the immersion time is 10-30 s, the drying temperature is 60-80℃, and the drying time is 5-10 min; the temperature for immersing the second dyeing solution is 20-40℃, the immersion time is 5-15 s, the solidification temperature is 100-130℃, and the solidification time is 15-30 min.

7. The method for preparing a high color fastness Dyneema fishing line according to claim 5, characterized in that, The natural polysaccharide is a mixture of one or more of chitosan, sodium alginate, and carboxymethyl cellulose.

8. The method of claim 5, wherein the high color fastness Dai-Ma fishing line is prepared by the steps of: The organic acid is a mixture of one or more of acetic acid, citric acid, and tartaric acid. ​ 9. The method of claim 5, wherein the high color fastness Dai-Ma fishing line is prepared by the steps of: The non-protic polar solvent is a mixture of one or more of ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone; the high molecular film forming agent is a mixture of one or more of polyurethane, acrylic resin, epoxy resin; the nano-scale pigment is an organic pigment or an inorganic pigment, and the particle size range is 20-100 nm; the dispersing aid is a mixture of one or more of sodium polyacrylate, polyvinylpyrrolidone, sodium dodecyl sulfate. ​ 10. The method of claim 1-9, wherein the high color fastness Dai-Ma fishing line is prepared by the steps of: The fishing line has a straight line strength of greater than or equal to 120 N, an elongation at break of 10-15%, and a knot strength of greater than or equal to 40 N.

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