JP3442185B2 - Polyvinyl alcohol rope structure - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rope structure composed of polyvinyl alcohol (hereinafter referred to as PVA) -based multifilament yarns and having excellent utilization and weather resistance. It is about the body. 2. Description of the Related Art Rope structures such as cords, ropes and cables are used for mooring lines of large ships, large marine structures,
It is widely used in mooring lines for underwater structures, fishing gear used in the fishing industry, onshore, agricultural, etc. Generally, polyester, nylon, PVA (including vinylon) fibers and the like are used as raw material fibers for the rope structure, but aramid fibers and metal fibers are used particularly in fields where strength is required. . [0003] However, aramid fibers certainly have a high initial strength, but have the drawback that they have poor weather resistance and their strength is remarkably reduced with time, so that there is a problem as a fiber for rope structures used outdoors. There is also a disadvantage that the cost is high. In addition, metal fiber rope structures are heavy, have poor flexibility, are difficult to work with, are easily rusted, and are conductive, so if they are used as a suspension wire for hanging electric wires, insulators will be required. There is a problem. [0004] On the other hand, PVA-based fibers are superior in elastic modulus and weather resistance as compared with other general-purpose fibers, and are excellent as fibers for rope structures. However, conventional PV
Since the spun yarn having a strength of 10 g / d or less is used for the rope structure made of the A-based fiber, the strength of the rope structure is low even if the strength of the spun yarn is expressed as it is, and the fluff and twist spots are reduced. Therefore, the power utilization rate is reduced to 50% or less, and the elongation is also 10
% Or more, which is inferior in morphological stability and limited in use. In order to eliminate the drawbacks of the PVA-based fiber rope structure, Japanese Utility Model Laid-Open Publication No. 61-202496 discloses that
A rope structure obtained from a PVA-based multifilament yarn of 15 g / d or more and a rope structure coated with a resin such as polyethylene, polyvinyl chloride, and nylon have been proposed. This rope structure has high strength of the original yarn and is composed of multifilament yarns, so its strength is higher than that of the above spun yarn, but the multifilament yarn is twisted or braided. Fuzz is likely to occur when forming a rope structure, and the strong utilization rate is at most
It was only about 50%, and still had a problem peculiar to PVA-based fibers that water was bonded to hydroxyl groups and water resistance was reduced. [0006] The present invention solves the above-mentioned problems, and comprises a PVA-based multifilament yarn.
P with excellent strength, weather resistance, water resistance and shape stability
An object of the present invention is to provide a VA rope structure. The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have formed a rope structure with a PVA-based multifilament yarn treated with a special combination of resins. The present inventors have found that the strength utilization rate, the strength retention rate, the water resistance and the form stability can be remarkably improved by doing so. That is, according to the present invention, the strength is 12 g / d or more,
It is composed of PVA-based multifilament yarn that has an elongation of 7% or less and is treated with a treating agent containing urea formalin resin, silicone resin and fluorine resin as main components.
And a strong utilization rate of 80% or more, a strong retention rate of 80% or more,
A gist is a PVA-based rope structure having a water resistance of 70% or more. Hereinafter, the present invention will be described in detail. [0010] The rope structure of the present invention is composed of a PVA-based multifilament yarn having a strength of 12 g / d or more and an elongation of 7% or less. Multifilament yarn strength is 12g / d
Above, preferably at least 15 g / d.
At less than 12g / d, even if the rope structure has a
% Is not preferable because the absolute value of the strength becomes small. The elongation of the multifilament yarn is 7%.
The elongation should preferably be 5% or less, and if the elongation exceeds 7%, it is not preferable because a load is applied to the rope structure so that the rope structure easily elongates and the form stability decreases. [0012] The fineness of the single filament of the multifilament yarn is not particularly limited, and may be generally 1 to 10 denier. However, in order to improve the fatigue resistance of the rope structure, 5 to 10 denier is required.
Preferably, it is 10 denier. A PVA-based multifilament yarn having a strength of 12 g / d or more and an elongation of 7% or less as described above is, for example, a polymerization degree of 1500 as described in JP-A-3-806.
A spinning solution prepared by dissolving ~ 7000 PVA in an organic solvent such as dimethylsulfoxide (DMSO) is dry-wet-spun into a coagulation bath such as methanol through an air layer, and then the solvent is extracted with methanol or the like. After drying, it can be obtained by hot stretching to 15 times or more. In addition, PVA
Boric acid or a salt thereof in an aqueous solution is 0.5 to 5 with respect to PVA.
The spinning solution was added at 45-95 ° C.
After spinning in an alkaline coagulation bath, roller stretching, neutralization, wet heat stretching, washing with water, and drying, the total draw ratio is
It can be obtained by stretching so as to be 15 times or more. Next, the above-mentioned multifilament yarn needs to be treated with a treating agent containing urea formalin resin, silicone resin and fluorine resin as main components. By forming the rope structure with the multifilament yarn treated with silicone resin, the multifilament yarn is twisted or the frictional resistance when forming the rope structure as a braid is low, and the fluff is less likely to occur. For this reason, 80% or more of the strength of the multifilament yarn is expressed in the rope structure, and the strength utilization rate is 80% or more, preferably 90% or more.
%. As described above, the rope structure of the present invention expresses 80% or more of the strength of the multifilament yarn.
It becomes possible to make the diameter smaller than that of the low power utilization rate. Further, since the multifilament yarn is treated with a fluororesin, the good weather resistance characteristic of the PVA-based fiber is further improved by the fluororesin, so that the strength retention is preferably 80% or more. Is more than 90%
A rope structure having good durability with little decrease in strength over time. As described above, since the multifilament yarn is treated with the silicone resin and the fluorine resin, the rope structure is less likely to become soiled and the antifouling property is improved. Furthermore, since the multifilament yarn is treated with a urea formalin resin, the hydroxyl groups in the PVA-based fibers are hardly crosslinked with formalin and bonded to water, and thus the water resistance is remarkably improved. In the present invention, as a method of applying a treating agent to the multifilament yarn, a known method such as a spraying method, a coating method, a dipping method or the like can be employed, but urea formalin resin, silicon resin, fluorine resin and the like can be used. It is easiest to impregnate the multifilament yarn with a mixture of the aqueous dispersions of the resins and then dry it. In order to make the strength utilization rate of the rope structure 80% or more, at least the silicon resin must be provided at a stage before the multifilament yarn is twisted or braided. The formalin resin may be applied at the stage of the multifilament yarn or after the rope structure. The weight ratio of the urea formalin resin A, the silicone resin B and the fluorine resin C in the treating agent is determined by the following formulas in order to obtain the strong utilization factor, weather resistance and water resistance of the rope structure aimed at by the present invention. : B: C = 1-3: 1-3: 1
It is preferably from 3 to 3. The solid content of the treating agent is 1
-10%, particularly preferably 2-6%. The curing temperature is 130-170 ° C. and the curing time is 0.5
~ 4 minutes is preferred. If the curing temperature is lower than 130 ° C, the coating strength of the treating agent is hardly sufficient, and if the curing temperature is higher than 170 ° C, the coating tends to deteriorate. Further, the amount of the treatment agent deposited after the treatment is preferably 1 to 5% by weight in solid content. If the amount of adhesion is less than 1%, it is difficult to obtain a rope structure having a strong utilization rate, weather resistance and water resistance which are the objects of the present invention, and if it exceeds 5%, the rope structure becomes coarse and hard. Bending fatigue resistance tends to decrease. The urea-formalin resin used in the present invention is preferably a urone-based resin or a melamine-based resin which is an urea-melamine-formalin-based initial condensation resin.
As the silicone resin and the fluorine resin, nonionic resins are preferable. As a method of forming the rope structure from the multifilament yarns, a method of bundling the multifilament yarns, a method of forming a twine, a method of forming a braid, and a method in which the outer periphery of the bundled yarn bundled in a substantially non-twisted state is the same. There is a method of coating with a filament yarn. As a method for twisting, three hits, 4 hits,
There is a method such as twisting in hitting and eight hitting, etc. As the method of coating the outer periphery of the bundled yarn, knitting such as braiding in eight hitting, 16 hitting and 24 hitting, warp knitting, weft knitting and the like are available. is there. Furthermore, the flame retardancy can be improved by coating the surface of the rope structure with polyvinyl chloride or the like. The rope structure of the present invention has a strength of at least 12 g / d and an elongation of at most 7%, and is a PVA-based material treated with a treating agent containing urea formalin resin, silicone resin and fluorine resin as main components. Since it is composed of multifilament yarns, the strength utilization rate, strength retention rate, water resistance and form stability are remarkably improved compared to the rope structure obtained from conventional PVA-based fibers. For this reason, the rope structure of the present invention is suitable for mooring lines of large ships, mooring lines of large marine structures, undersea structures, etc., fishing gear materials used in the fishing industry, onshore, agricultural, etc. Yes, especially when used as a suspension wire for suspending electric wires, it is lightweight and highly flexible, so workability is good and it does not rust like metal fibers.
Furthermore, since it is insulating, an insulator is not required. The physical property values in the present invention are measured by the following methods. (1) Strength and elongation of multifilament yarn Measured according to JIS-L-1013. (2) Power utilization rate As described above, the power utilization rate is the percentage of the value obtained by dividing the strength of the rope structure by the strength of the multi-multifilament yarn constituting the rope structure x the number of components. . The strength of the rope structure is JIS-L-27.
03. (3) Strong retention rate According to JIS-A-1415, using a sunshine weather meter, irradiation for 110 minutes and spraying for 10 minutes were performed for 1000 times.
Repeated times, the rope structure was subjected to a weathering test, and the strength after the weathering test of the rope structure was divided by the strength before the weathering test, expressed as a percentage. (4) Water resistance After the rope structure is immersed in water at room temperature for 1 hour, it is taken out, the adhesion moisture percentage (%) is measured, and the value obtained by subtracting the adhesion moisture percentage (%) from 100 is defined as the water resistance percentage (%). indicate. (5) Morphological stability Evaluate the elongation of the rope structure. (6) Flame Retardancy Degree of Flame Retardation It is indicated by the limiting oxygen index measured in accordance with JIS-K-7201 (the greater the value, the more difficult it is to burn). Next, the present invention will be described specifically with reference to examples. Example 1, Comparative Examples 1-2 A spinning dope prepared by dissolving PVA having a polymerization degree of 3300 in DMSO was spin-dried and wet-spun into a methanol bath by a spinning draft 6.0 through a 50 mm air layer, and then methanol was spun. After extracting the solvent with and drying, it is hot-stretched by 17 times in two steps and the strength is 17g /
d, PVA-based multifilament yarn with elongation of 5% 1500d / 200f
I got The obtained PVA-based multifilament yarn
80 tubes are bundled, and urea formalin resin (Dec Nippon Ink Co., Ltd. Becamine N80) A, silicone resin (Dai Nippon Ink Co., Ltd. Dick Silicon SK-CONC) B and fluorine resin (Dai Nippon Ink Co., Ltd. Dic Guard F90N) Is A: B: C =
After impregnating the bundle yarn with an aqueous dispersion having a solid content of 5% and mixed so as to have a ratio of 1: 1: 1, the bundle is dried at a temperature of 100 to 105 ° C. for 1 minute, and then at a temperature of 150 to 170 ° C. Curing was performed for 1 minute to obtain a bunched yarn to which the treating agent was adhered at a solid content of 1.5% by weight. Next, twist the yarn into 8 hits using a bundled yarn.
A 960,000-denier rope structure with an outer diameter of 12 mm was obtained. On the other hand, for comparison, the weight ratio of the silicone resin B and the fluorine resin C used in Example 1 was B: C = 1: 1.
A rope structure was obtained in the same manner as in Example 1 except that the treating agent blended to be No. 1 was used (Comparative Example 1). Also, a rope structure was obtained in the same manner as in Example 1 except that no treatment agent was applied (Comparative Example 2). Table 1 shows the evaluation results of the strength utilization rate, strength retention rate, water resistance and form stability of the obtained rope structure. Example 2, Comparative Examples 3-4 Boric acid was added to an aqueous solution of PVA having a degree of polymerization of 1700 to the PVA in an amount of 1.
5% by weight was added to the spinning stock solution, which was spun into an alkaline coagulation bath at 45 ° C and spin-drawn, neutralized, wet-heat drawn, washed with water and dried according to the conventional method, and the total draw ratio was increased to 15 times. Then, it was subjected to a heat-shrinking treatment of 2% to obtain a PVA-based multifilament yarn 2250d / 375f having a strength of 16 g / d and an elongation of 7%. The obtained PVA-based multifilament yarn was converted to a urea formalin resin (Sumitex UL manufactured by Sumitomo Chemical Co., Ltd.).
W) The weight ratio of A, silicone resin (Sumitomo Chemical Co., Ltd. Sumitex Silicon Softer-10) B and fluorine resin (Sumitomo Chemical Co., Ltd. Sumifuru Oil EM3) C is A: B: C = 1: 1: 1. After impregnating the yarn with an aqueous dispersion having a solid content of 6%, the mixture is dried at a temperature of 100 to 105 ° C for 1 minute, and then cured at a temperature of 140 to 160 ° C for 2 minutes. A yarn to which the treating agent adhered at a solid content of 2% by weight was obtained. Next, 55 yarns after the treatment were twisted at 10 T / M, and then tied into eight strikes using the twisted yarn to obtain a rope structure having an outer diameter of 14 mm and a denier of 990,000. On the other hand, for comparison, the weight ratio of the silicone resin B and the fluorine resin C used in Example 2 was B: C = 1:
A rope structure was obtained in the same manner as in Example 2 except that the treating agent blended to give No. 1 was used (Comparative Example 3). Also, a rope structure was obtained in the same manner as in Example 2 except that no treatment agent was applied (Comparative Example 4). Table 2 shows the evaluation results of the strength utilization rate, strength retention rate, water resistance and form stability of the obtained rope structure. [Table 1] [Table 2] As is clear from Tables 1 and 2, Examples 1 to
The rope structure obtained in 2 had extremely high strength utilization and strength retention of about 90%, a water resistance of at least 80%, and also had good shape stability. On the other hand, in Comparative Examples 1 and 3 each composed of a multifilament yarn treated with a treating agent containing no urea formalin resin, and in Comparative Examples 2 and 4 each composed of a multifilament yarn not treated with a treating agent. All of the obtained rope structures were inferior in water resistance, and none of the strength utilization and the strength retention satisfied the present invention. Furthermore, when the surface of the rope structure obtained in Examples 1 and 2 was coated with polyvinyl chloride using the extrusion molding method, the limiting oxygen index was 30 to 45 and the flame retardancy was excellent. A rope structure was obtained. The rope structure according to the present invention is a conventional PVA.
It has significantly improved strength utilization, strength retention, water resistance and morphological stability compared to rope structures obtained from staple fibers, and as a result, mooring lines for large vessels, large offshore structures,
It is suitable for fields such as mooring lines for underwater structures, fishing gear materials used in the marine industry, suspension lines for railways, cable-stayed wires, etc., for land use, agricultural use, and the like.

Claims (1)

(57) [Claims] [Claim 1] It has a strength of 12 g / d or more and an elongation of 7% or less, and is treated with a treating agent containing urea formalin resin, silicone resin and fluorine resin as main components. Polyvinyl alcohol-based rope structure, which is composed of a polyvinyl alcohol-based multifilament yarn, and has a strength utilization rate of 80% or more, a strength retention rate of 80% or more, and a water resistance rate of 70% or more. .