continuous wire rod

Abstract

To provide a continuous wire made of polyester-based resin, wherein the wire has abrasion resistance and anti-fouling property both while having mechanical physical properties, durability, and heat resistance necessary for practical use.SOLUTION: Disclosed continuous wire is a polyester-based continuous wire having a wire diameter of 0.1 mm or over and with at least a surface layer of the wire being composed of a polyester resin composition, wherein the polyester resin composition has 0.5-10 pts.mass of a thermoplastic elastomer and 0.5-10 pts.mass of a hydrophilic component with respect to 100 pts.mass of the polyester.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a continuous wire made of a polyester resin, and particularly to a continuous wire used for various materials such as woven fabrics, knitted fabrics, nets, and ropes. [Background technology]

[0002] Polyester resins have traditionally been used in a wide range of applications, including molded products, films, fibers, and nonwoven fabrics, due to their excellent mechanical properties, heat resistance, chemical resistance, and dimensional stability, as well as their cost-effectiveness and recyclability. Continuous polyester resin wires are also used in a variety of applications, including papermaking, sewage filters, rubber reinforcement, fire hoses, hook-and-loop fasteners, fishing nets, ball-stop fences, industrial brushes, fishing line, and racket strings. Resin wires other than polyester include polyamide wires, which offer superior abrasion resistance and soil release properties compared to polyester wires and are therefore suitable for certain applications. However, polyamide wires have issues with dimensional stability and heat resistance, leading to a demand for replacement with polyester wires that offer improved abrasion resistance and soil resistance.

[0003] Techniques for improving the abrasion resistance of polyester wire include wire made from a polyester resin composition in which calcium carbonate having a specific particle distribution is added to polyester (Patent Document 1), and wire made from a polyester resin composition in which modified polyethylene is added to polyester (Patent Document 2). However, the technique disclosed in Patent Document 1 deteriorates the mechanical properties of the polyester wire due to the inclusion of inorganic particles such as calcium carbonate, and the technique disclosed in Patent Document 2 deteriorates the heat resistance due to the addition of modified polyethylene, making it difficult to apply to industrial material applications.

[0004] On the other hand, technologies for improving the antifouling properties of polyester wire include wire made from a polyester resin composition in which silicone oil is added to polyester (Patent Document 3) and wire made from a polyester resin composition in which fluororesin is added to polyester (Patent Document 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-107348 [Patent Document 2] Japanese Patent Application Publication No. 06-57528 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-242254 [Patent Document 4] Japanese Patent Application Publication No. 09-49121 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, although studies have been conducted to improve the abrasion resistance and stain resistance of polyester wires separately, no wires have been obtained that combine both abrasion resistance and stain resistance. An object of the present invention is to provide a continuous wire made of a polyester resin that combines the mechanical properties, durability, and heat resistance required for practical use, and also has both abrasion resistance and stain resistance. [Means for solving the problem]

[0007] The present invention solves the above-mentioned problems and provides a polyester-based continuous wire having a wire diameter of 0.1 mm or more, wherein at least a surface layer of the wire is made of a polyester resin composition, The polyester resin composition contains, relative to 100 parts by mass of polyester, Ester-based 0.5 to 10 parts by mass of thermoplastic elastomer, Polyetheramide polymer The gist is a continuous wire containing 0.5 to 10 parts by mass of a cellulose ester. [Effects of the Invention]

[0008] According to the present invention, at least the surface of the continuous wire is Ester-based Thermoplastic elastomer and Polyetheramide polymer Since the continuous wire is made of a polyester-based resin composition containing the above, it has practical mechanical properties, durability, and heat resistance, and also has both abrasion resistance and stain resistance, making it possible to provide a polyester-based continuous wire that is suitable for use in a variety of materials. DETAILED DESCRIPTION OF THE INVENTION

[0009] The polyester continuous wire of the present invention is a wire that is continuous in the longitudinal direction, i.e., the axial direction, and is made of a polyester resin. The external shape of the cross section of the continuous wire is not particularly limited, and may be circular, elliptical, polygonal, or the like, and may be appropriately selected depending on the application, but a circular cross section is preferred from the viewpoint of mechanical properties and versatility.

[0010] The wire diameter of the continuous wire is 0.1 mm or more. If it is less than 0.1 mm, it will not be able to withstand the tension and abrasion that will be exerted during the process of producing materials such as woven or knitted fabrics, or during practical use after production. There is no particular upper limit to the wire diameter, but it should be around 3 mm.

[0011] At least the surface layer of the continuous wire of the present invention is composed of a specific polyester resin composition. By coating the surface of the continuous wire with this specific polyester resin composition, the continuous wire has both abrasion resistance and stain resistance. The continuous wire may be in a single-phase form composed solely of this specific polyester resin composition, or it may be a composite continuous wire in which the surface layer of the continuous wire is composed of the polyester resin composition and the remaining portion is composed of another polyester-based resin. A composite continuous wire preferably has a two-layer structure consisting of a core and a coating surrounding the core. In the case of a two-layer structure consisting of a core and a coating, the number of cores is preferably one, but may be multiple. When there are multiple cores, each of the multiple independent cores is present in the coating, forming a so-called sea-island structure in which the cores are islands and the coating is a sea. When there are multiple cores, the number of cores is preferably about 2 to 20. The composite ratio (area ratio) of the core to the coating is preferably core:coating = 100:5 to 200, and may be selected appropriately taking into consideration the mechanical properties required depending on the wire diameter and application, but in order to obtain both improved physical properties derived from the core and good abrasion resistance and stain resistance derived from the coating, it is more preferable that the core:coating = 100:10 to 100. In the case of a two-layer structure of a core and a coating, a combination in which the core is made of polyethylene terephthalate and the sheath is made of a specific polyester resin composition is preferred from the viewpoints of mechanical properties, durability, heat resistance, abrasion resistance, and stain resistance.

[0012] The polyester resin composition of the present invention contains, relative to 100 parts by mass of polyester, Ester-based 0.5 to 10 parts by mass of thermoplastic elastomer, Polyetheramide polymer The polyester resin composition contains 0.5 to 10 parts by mass, and constitutes at least the surface layer of the continuous wire, covering the surface of the continuous wire.

[0013] The polyester used in the present invention is not particularly limited as long as it has an ester bond in the molecule, and examples thereof include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate, and aliphatic polyesters such as polylactic acid, polybutylene succinate, and polycaprolactone. Of these, polyethylene terephthalate is preferred from the viewpoints of heat resistance, mechanical properties, and economy.

[0014] The polyester may be copolymerized with other dicarboxylic acid components, diol components, or oxycarboxylic acid components, or a blend of at least two of the polyesters described above, as long as the effects of the present invention are not impaired. Examples of other copolymerizable components include dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic anhydride, sebacic acid, adipic acid, azelaic acid, succinic acid, and ε-caprolactone, and examples of diol components include ethanediol, diethylene glycol, propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane glycol, and cyclohexanedimethanol.

[0015] The polyester used in the present invention may be virgin or recycled, or may be a combination of virgin polyester and recycled polyester in an appropriate ratio.

[0016] The relative viscosity of the polyester is preferably 1.4 or more, more preferably 1.5 or more, in order to improve the mechanical properties of the wire and obtain a wire with excellent dimensional stability. The relative viscosity of the polyester was measured at 20°C using an Ubbelohde viscometer and a 0.5% phenol / tetrachloroethane equal mass mixed solution as the solvent.

[0017] The thermoplastic elastomer used in the present invention is ,mother From the viewpoint of compatibility with the polyester as the base material and heat resistance, ester-based thermoplastic elastomer Use Furthermore, for purposes such as improving compatibility with polyester, maleic anhydride groups, acrylic acid groups, acrylic acid esters, fumaric acid esters, epoxy groups, glycidyl groups, etc. may be copolymerized in the main chain or graft-polymerized in the side chain. In the present invention, the thermoplastic elastomer preferably has a durometer hardness measured according to JIS K 6253 of either a Type D durometer hardness of 50 or less or a Type A durometer hardness of 95 or less. A Type D durometer hardness exceeding 50 or a Type A durometer hardness exceeding 95 tends to make it difficult to improve the abrasion resistance of the resulting continuous wire. Furthermore, the melt index of the thermoplastic elastomer (JIS K 7210, measured at 230°C, load 2.16 kg) is preferably 15 g / 10 min or more, more preferably 20 g / 10 min or more. If the melt index of the thermoplastic elastomer is less than 15 g / 10 min, the resulting continuous wire will tend to be poorly dispersed in the polyester matrix, making it difficult to obtain an improved abrasion resistance. From the viewpoint of spinning stability when producing the continuous wire, the upper limit of the melt index is preferably 100 g / 10 min, and more preferably 60 g / 10 min or less.

[0018] In the polyester resin composition, Ester-based The thermoplastic elastomer is contained in an amount of 0.5 to 10 parts by mass, preferably 2 to 6 parts by mass, based on 100 parts by mass of polyester. Ester-based If the content of the thermoplastic elastomer is less than 0.5 parts by mass, the abrasion resistance of the continuous wire will not improve, and if it exceeds 10 parts by mass, the mechanical strength and dimensional stability of the continuous wire will tend to decrease, making it impossible to achieve the object of the present invention.

[0019] The resin composition of the present invention comprises:Polyetheramide polymers (polyetheresteramide, polyetheramide, polyetheramideimide, etc.) Includes From the viewpoint of heat resistance and ease of handling, polyetheramide polymers (polyetheresteramide, polyetheramide, polyetheramideimide, etc.) Let's say In the polyester resin composition, Polyetheramide polymer The content of the polyester resin is 0.5 to 10 parts by mass, preferably 2 to 5 parts by mass, based on 100 parts by mass of the polyester. Polyetheramide polymer If the content is less than 0.5 parts by mass, the stain resistance of the continuous wire cannot be improved, and if it exceeds 10 parts by mass, the continuous wire will not have sufficient strength for practical use, and the productivity and handling of the continuous wire will tend to be poor.

[0020] The polyester used in the present invention may contain a small amount of other thermoplastic resins, as long as the object of the present invention is achieved. Examples include polyamides, polyolefins, acrylic resins, vinyl acetate resins, vinyl chloride resins, vinylidene chloride resins, polytetrafluoroethylene, and silicone resins, and these may be added alone or in combination. The polyester used in the present invention may also contain various additives as desired. For example, dyes, pigments, dispersants, compatibilizers, spreaders, plasticizers, viscosity modifiers, flame retardants, lubricants, UV absorbers, infrared absorbing materials, microwave absorbing materials, light stabilizers, antioxidants, pH adjusters, antibacterial agents, preservatives, fillers, heat resistance agents, antistatic agents, conductive materials, thermally conductive materials, and crystal nucleating agents may be added. In particular, additives such as UV absorbers, light stabilizers, antioxidants, and heat resistance agents may be added to improve the performance of not only the polyester but also the thermoplastic elastomer and hydrophilic component. However, considering the maintenance of practical strength of the continuous wire, the total amount of additives (thermoplastic elastomer, hydrophilic component, and additives) in the polyester resin composition constituting the surface of the continuous wire is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, per 100 parts by mass of polyester.

[0021] In order for the continuous wire of the present invention to have heat resistance when applied to various material applications, it is desirable that the tensile strength after dry heat treatment at 180°C for 30 minutes be 4N or more. If it is less than 4N, it will not be able to withstand the loads during processing or practical use. A more preferable tensile strength is 30N or more, and even more preferably 60N or more. Note that the higher the tensile strength, the better, but an upper limit of approximately 1000N is considered sufficient. Note that if the wire diameter is large, the strength (N) of the wire as a whole will be high even if the strength per unit cross-sectional area (MPa) is low, but the strength per unit cross-sectional area (tensile strength after dry heat treatment at 180°C for 30 minutes) should be 300MPa or more, and preferably 400MPa or more. In the present invention, the tensile test after dry heat treatment at 180°C for 30 minutes is performed by placing a sample wound on a metal frame in a hot air dryer heated to 180°C, removing it after 30 minutes of constant-length heat treatment, storing it under standard conditions (temperature 20±2°C, relative humidity 65±4%) for 24 hours or more, and then applying a load to it until it broke using a tensile tester to measure it. The tensile test conditions were a grip distance of 250 mm, a pulling speed of 300 mm / min, and n=5. The maximum strength and elongation at break were averaged, and these average values ​​were used as the tensile strength and elongation at break.

[0022] The tensile elongation of the continuous wire of the present invention is preferably 10 to 45%, and more preferably 12 to 40%. If it is less than 10%, the wire becomes more brittle and its durability against bending fatigue decreases. On the other hand, if it exceeds 45%, its rigidity as a material decreases, and when it is used for a filter, for example, the filtration accuracy may be insufficient.

[0023] An example of a method for producing a continuous wire of the present invention will be described below. A pre-dried polyester resin composition (basically in pellet form) is prepared, and melt-spun from a spinneret using an extruder-type spinning device at a spinning temperature of about 265 to 300°C. The spun material is cooled in a warm water bath of about 40 to 80°C to obtain an undrawn wire. This undrawn wire is subjected to a first-stage stretching (stretching ratio of about 2.5 to 4.5 times) in a water bath of about 70 to 95°C, and then to a second-stage stretching (stretching ratio of about 1.1 to 2.5 times) in a hot air atmosphere of about 100 to 300°C. This is followed by a relaxation heat treatment of about 0 to 20% in a hot air atmosphere of about 100 to 300°C to obtain the continuous wire of the present invention. In the case of a wire having a two-layer structure, the resin or resin composition (both basically in pellet form) to be placed in the core and the coating is prepared separately, and the wire is melt-spun from a core-sheath composite spinneret using an extruder-type spinning device at a spinning temperature of about 265 to 300°C, and then the wire can be produced in the same manner as above.

[0024] To prepare the polyester resin composition: Ester-based Thermoplastic elastomers and Polyetheramide polymer The other additives can be individually prepared and dry-blended with polyester pellets, which are then introduced into a melt spinning apparatus to produce wire. Alternatively, compound pellets or masterbatches, in which the raw materials are melt-kneaded in advance at a predetermined ratio, may be used. To adjust the handling properties and surface texture, a fiber oil or the like may be applied online before or after stretching, or a coating film may be applied by coating or dipping in a post-process. Furthermore, post-processing such as plasma treatment may be performed to adjust the affinity for water and processability. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 shows a schematic perspective view of a bending wear test for evaluating wear resistance. [Example]

[0026] The present invention will be specifically described below using examples, in which various values ​​were measured as follows. (1) Wire diameter The continuous wire was measured at 20 points at 50 cm intervals, and the average value was taken as the wire diameter (mm). (2) Tensile test Since continuous wire rods are usually wound up, the required amount was unwound and left at room temperature for at least 24 hours, after which a load was applied until the wire broke using a tensile tester, and the maximum strength and breaking elongation were measured. The tensile test conditions were a grip distance of 250 mm, a pulling speed of 300 mm / min, and the average values ​​measured with n=5 were used as the maximum strength (N) and breaking elongation (%). (3) Tensile test (after heat treatment) The required amount of continuous wire was unwound and tightly wound around a metal frame. The wire was then placed in a hot air dryer heated to 180°C, removed after 30 minutes, and left for at least 24 hours under standard conditions (temperature 20±2°C, relative humidity 65±4%) before being measured in a tensile tester. A load was applied until the wire broke, and the maximum strength and breaking elongation were measured. The tensile test conditions were a grip distance of 250 mm, a pulling speed of 300 mm / min, and n=5. The average values ​​measured were used as the maximum strength (N) and breaking elongation (%). (4) Abrasion resistance (flexural abrasion test) A stainless steel hexagonal rod with opposite sides of 12 mm was used as the abrasion body, and as shown in Figure 1, the sample (wire rod) was brought into contact with this abrasion body at an angle of approximately 90 degrees, and a predetermined load was applied to one end of the sample, causing it to rub back and forth at a stroke width of 300 mm and a stroke speed of 30 times / min, and the number of reciprocations until the sample broke was measured. Measurements were made for n=5 for each sample, and the average of the obtained numbers was taken as the number of abrasion times for abrasion resistance. The predetermined load was determined based on the cross-sectional area (mm 2 For example, if the wire diameter is 0.4 mm, a load of 400 g is used. (5) Pull-out test (stain resistance) A 4 mm diameter circular hole was drilled in a resin board (5 mm thick), and a continuous wire rod of sufficient length (approximately 20 cm) was passed through the center of the hole so that at least 15 cm of the continuous wire rod protruded from the top surface of the resin board. Wood putty (manufactured by Cemedine Co., Ltd., product name "Wood Putty A Ash White") was filled in, and the board was left to dry at room temperature. If the volume of the wood putty decreased due to drying while it was left standing, additional wood putty was filled in so that the top and bottom surfaces of the filled wood putty and the top and bottom surfaces of the resin board were approximately the same. After the final filling, the resin board was left for at least two days to allow the wood putty to dry thoroughly. The wire protruding from the bottom of the resin board and excess wood putty were then cut off along the bottom surface of the board with a cutter. The resin board with the wire secured by the wood putty was then horizontally fixed to the bottom of a tensile tester. Meanwhile, the wire protruding at least 15 cm from the top surface of the resin board was vertically lifted and secured in a capstan chuck. The wire (sample) was secured in the capstan chuck with a 100 mm chuck distance (the distance from the top surface of the resin board to the capstan chuck), a tensile speed of 100 mm / min, and n = 5. The maximum strength of the tensile test was measured, and the average value was taken as the pull-out strength (N). The smaller the pull-out strength, the easier it was to remove firmly adhered dirt (wood putty), and this was used to evaluate soil release properties. (6) Melt index The melt index of the thermoplastic elastomer was determined in accordance with JIS K7210 using a melt indexer at a measurement temperature of 230°C and a load of 2.16 kg, with n=5, and the average value was calculated. (7) Durometer hardness The durometer hardness of the thermoplastic elastomer was measured at a temperature of 20°C using a durometer on a plate-shaped test piece having a thickness of 6 mm prepared by hot press molding in accordance with JIS K6253. (8) Relative viscosity The relative viscosity of the polyester chips was measured at a temperature of 20°C using an Ubbelohde viscometer with a 0.5% concentration phenol / tetrachloroethane mixed solution in equal mass as a solvent.

[0027] Example 1 A chip blend of 100 parts by weight of polyethylene terephthalate chips (relative viscosity 1.5), 4 parts by weight of a thermoplastic elastomer (ester-based, melt index 30 g / 10 min, durometer hardness D30), and 2 parts by weight of a polyether ester amide block copolymer was melt-spun at 280°C using a conventional extruder-type melt spinning apparatus. The spun continuous wire was cooled in a hot water bath at 50°C to obtain an unstretched wire. Without winding, this unstretched wire was subjected to a first-stage stretching at a draw ratio of 3.8x in a 90°C hot water bath. It was then passed through a heating zone at 200°C for a second-stage stretching (draw ratio of 1.4x) to a total draw ratio of 5.4x. It was then passed through a heating zone at 200°C for a 4% relaxation heat treatment to obtain a continuous wire. The resulting continuous wire had a diameter of 0.4 mm.

[0028] Example 2 A continuous wire was obtained in the same manner as in Example 1, except that the blending amount of the thermoplastic elastomer was 8 parts by mass and the blending amount of the hydrophilic component was 5 parts by mass. The wire diameter of the obtained continuous wire was 0.4 mm.

[0029] Example 3 To obtain a continuous wire with a composite cross section consisting of a core surrounded by a coating, polyethylene terephthalate chips (relative viscosity 1.5) were used as the resin for the core, and a chip blend of 100 parts by mass of polyethylene terephthalate chips (relative viscosity 1.5) with 4 parts by mass of a thermoplastic elastomer (ester-based, melt index 30 g / 10 min, durometer hardness D30) and 2 parts by mass of a polyether ester amide block copolymer was prepared as the resin composition for the coating. The mixture was then melt-spun at 280°C using a conventional extruder-type melt conjugate spinning device. The core and coating were weighed so that the volume ratio of the core to the coating was 7 / 3. The spun continuous wire was cooled in a 50°C warm water bath to obtain an undrawn wire. Without being wound up, this undrawn wire was subjected to a first-stage drawing at a draw ratio of 3.8 in a 90°C hot water bath, then to a second-stage drawing (draw ratio of 1.4) while passing through a heating zone at 200°C so that the total draw ratio was 5.4, and then to a 4% relaxation heat treatment by passing through a heating zone at 200°C, yielding a continuous wire with a two-layer structure. The resulting continuous wire had a wire diameter of 0.4 mm and a core / coat area ratio of 7 / 3 in its cross section.

[0030] Comparative Example 1 A single-layer continuous wire made of only polyethylene terephthalate was obtained in the same manner as in Example 1, except that only polyethylene terephthalate chips were used in Example 1. The wire diameter of the obtained continuous wire was 0.4 mm.

[0031] Comparative Example 2 A single-layer continuous wire was obtained in the same manner as in Example 1, except that a polyester resin composition prepared by chip-blending 100 parts by mass of polyethylene terephthalate chips with 4 parts by mass of thermoplastic elastomer was used. The diameter of the obtained continuous wire was 0.4 mm.

[0032] Comparative Example 3 A single-layer continuous wire was obtained in the same manner as in Example 1, except that a chip blend of 2 parts by mass of a hydrophilic component was used with 100 parts by mass of polyethylene terephthalate chips. The diameter of the obtained continuous wire was 0.4 mm.

[0033] The physical properties of the obtained continuous wires of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.

[0034] [Table 1]

[0035] The continuous wires of Examples 1 to 3 had practically sufficient tensile strength and tensile strength comparable to those of Comparative Example 1, which was made only of polyester, and also had better abrasion resistance than Comparative Example 1. Furthermore, the pull-out strength of Examples 1 to 3 was significantly smaller than that of Comparative Example 1, and they had excellent soil release properties. This is thought to be because the hydrophilicity of the wire surface of the continuous wires of the Examples was improved, allowing wood putty that had been attached as dirt to be easily removed.

[0036] In Comparative Example 2, improved abrasion resistance was observed, but the pull-out strength was about the same as in Comparative Example 1, and the soil release properties were insufficient. In Comparative Example 3, improved soil release properties were observed, but the abrasion resistance was poor.

[0037] As is clear from Table 1, the continuous wires of Examples 1 to 3 of the present invention have the mechanical properties and heat resistance required for practical use, and because the wire surface has been modified, they also have excellent wear resistance and soil release properties.

Claims

1. A polyester continuous wire having a wire diameter of 0.1 mm or more, at least a surface layer of the wire being made of a polyester resin composition, A continuous wire material characterized in that the polyester resin composition contains 0.5 to 10 parts by mass of an ester-based thermoplastic elastomer and 0.5 to 10 parts by mass of a polyetheramide-based polymer relative to 100 parts by mass of polyester.

2. The cross section of the continuous wire has a two-layer structure consisting of a core and a coating surrounding the core, The core is made of polyethylene terephthalate, 2. The continuous wire according to claim 1, wherein the coating portion is composed of a polyester resin composition containing 0.5 to 10 parts by mass of an ester-based thermoplastic elastomer and 0.5 to 10 parts by mass of a polyetheramide-based polymer, relative to 100 parts by mass of polyester.

3. The relative viscosity of the polyester constituting the continuous wire is 1.4 or more, the melt index (temperature 230°C, load 2.16 kg) of the ester-based thermoplastic elastomer contained in the polyester resin composition is 15 g / 10 min or more; 3. The continuous wire according to claim 1, wherein the continuous wire is an ester-based thermoplastic elastomer having a durometer hardness measured in accordance with JIS K 6253 of either a Type D durometer hardness of 50 or less or a Type A durometer hardness of 95 or less.

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