JP5441591B2 - Bending-resistant multifilament - Google Patents

Description

The present invention relates to a bending wear resistant multifilament .

  As fibers using a thermoplastic resin, polyamide fibers, polyester fibers, polylactic acid fibers, polyolefin fibers and the like are known.

<Polyamide fiber>
When working at high altitudes, in order to prevent a crash, it is mandatory under the Industrial Safety and Health Act to wear a safety belt in places where the height is 2 meters or more. As a rope-like fiber used for a safety belt, a nylon material is usually employed. This is determined in consideration of strength, shock absorption, weather resistance, wear resistance, mass, and the like.

  However, even if the same safety belt is used, the required performance varies greatly depending on the usage frequency, usage method, storage method, and the like. For example, in the case of safety belts that are used frequently on the construction site, etc., and are frequently used, in a usage environment where repeated bending loads in various forms are applied, in addition to aging due to natural deterioration, It may become dirty with soil, oil, etc. and wear resistance may be greatly reduced. Furthermore, when used over a long period of time with a lot of contact with the structure or the ground during walking, the rope-like fibers will become worn and become fuzzy, and the nylon fibers on the surface of the rope Many tend to be cut. Then, since it hardens and becomes a rod shape, it is severely deteriorated in strength and can hardly withstand the fall prevention. For this reason, in industrial material applications such as safety belts, there is always a demand for fibers with better bending wear resistance.

<Polyester fiber>
Polyester fibers have been developed for various uses such as general clothing use, interior use such as curtains and carpets, and vehicle interior use. Among these, polyethylene terephthalate fibers are expected to expand to various applications because of the good balance between the price and physical properties such as high elongation.

  However, polyester fibers have the drawback of poor wear resistance compared to polyamide fibers. For this reason, the development to the use in which abrasion resistance, bending abrasion resistance, etc. are requested | required among industrial material uses is not fully progressing. For example, taking high-strength polyethylene terephthalate fiber as an example, the higher the strength, the higher the molecular chain is oriented in the fiber axis direction. There is a disadvantage that the fibers easily fibrillate due to the above.

  Examples of fiber applications include safety nets used at construction sites and net-like bag materials such as bottom filters that are used by filling stones etc. in landfill revetments such as rivers and harbors. The use which performs net making processing can be mentioned. In such applications, since the knitting structure is complicated, the load and friction applied to the knitted fabric in the net making process are complicated not only in a straight line direction but also in multiple directions. Therefore, when polyester fiber is used for such applications, there is a drawback that fuzzing, yarn breakage, whitening, etc. occur in the processing step. In order to solve this problem, it is necessary to reduce the processing speed, which causes a problem that the operability is deteriorated.

  In addition, when using net-like bag materials, the product is subject to friction and impact caused by the flow of stones packed inside, while the product is subject to friction and impact caused by drift stones and driftwood outside the product. Become. There are problems in durability, such as fluffing and fiber fraying caused by loads from multiple directions repeatedly applied to the inside and outside of the product.

<Polylactic acid fiber>
Polylactic acid composed of aliphatic polyester is a biodegradable polymer made from lactic acid obtained by fermenting starch extracted from plants. Among biodegradable polymers using biomass, mechanical properties, heat resistance, It is an epoch-making polymer that has the best balance of cost and has the property of being completely decomposed and lost when left in an environment where many microorganisms exist or in an environment where seawater or fresh water is present after use. . Development of resin products, fibers, films, sheets, and the like using this has been performed at a rapid pitch.

  The development of applications for polylactic acid fibers is preceded by agricultural materials that make use of biodegradability. Subsequent large-scale applications include clothing, interiors such as curtains and carpets, automotive interiors, and industrial materials. Development to civil engineering materials is also expected.

  However, polylactic acid fibers have the disadvantage that they are inferior in bending wear resistance due to their high surface friction coefficient, and there is a problem that must be solved when entering the field where wear resistance and bending wear resistance are required. There are many. For this reason, conventionally, application development in fields such as industrial materials, civil engineering materials, clothing, interiors, and vehicle interior materials has not been sufficiently advanced.

<Conventional technology for improving fiber performance>
Several methods have been proposed to improve the performance of fibers composed of thermoplastic resins. For example, Patent Document 1 proposes a method of coating the surface of a monofilament made of synthetic fiber with a specific silane coating agent. However, the fiber obtained by this method has a problem that although the abrasion resistance is improved to some extent, it is still insufficient, and the manufacturing process becomes complicated and the cost is increased.

  Patent Document 2 includes an ethylene / 1-octene copolymer exhibiting flexibility and rubber elasticity, Patent Document 3 includes maleic anhydride-modified polyethylene / polypropylene rubber, and Patent Document 4 includes a specific polyolefin. Patent Document 5 describes that a polyamide fiber having abrasion resistance can be obtained by melt-kneading a fatty acid bisamide and / or an alkyl-substituted fatty acid monoamide in the production process of the polyamide fiber. Patent Document 6 proposes to add a fluororesin having a particle size of 50 μm or less in order to impart lubricity to the polyester.

  However, although the fibers obtained by these methods also improve the abrasion resistance to some extent, there is a problem that the strength does not increase by mixing different polymers, or the balance between the abrasion resistance and the strength is bad, In addition, it does not have sufficient bending wear resistance.

  Further, Patent Document 6 proposes a method of adding metal particles as a method for improving bending wear resistance, and Patent Document 7 proposes a method of using a core-sheath composite fiber of polyester and nylon. However, the products using the fibers obtained by these methods have a problem that the bending wear resistance is improved to some extent, but the contact portion with the roller surface etc. is easily worn, and stable operation for a long time becomes difficult. There is a point.

JP 2005-273066 A Japanese Patent Laying-Open No. 2005-273025 JP 09-209212 A Japanese Patent Application Laid-Open No. 07-003526 Japanese Patent Laid-Open No. 2004-091968 Japanese Patent Laid-Open No. 03-076813 Japanese Patent Laid-Open No. 02-145894

The present invention provides a multifilament that solves the above-mentioned problems, is excellent in bending wear resistance, has a small decrease in strength, and has an excellent balance between bending wear resistance and strength. This is a major issue.

As a result of intensive studies to solve the above problems, the present inventors have found that a multifilament having excellent bending wear resistance can be obtained by containing a predetermined amount of molybdenum disulfide particles having a specific particle diameter. Reached. That is, the gist of the present invention is as follows.

(A) a bending wear resistant multifilament composed of a plurality of fibers containing a resin composition capable of exhibiting bending wear resistance;
The resin composition capable of expressing the bending wear resistance contains 0.3 to 15% by mass of molybdenum disulfide particles having a volume average particle diameter of 0.1 to 2.0 μm with respect to the amount of the resin composition substance,
The single filament fineness of the fibers constituting the multifilament is 1 to 200 dtex, the total fineness of the multifilament is 20 to 5000 dtex,
A string body made of the above-mentioned eight multifilaments is brought into contact with a round file at a 90 ° angle with a load of 0.018 g per decitex, a stroke width of 330 ± 30 mm, a stroke speed of 30 ±. The number of bending abrasion resistances of the reference string body is the same as that of the above string body except that it does not contain molybdenum disulfide particles when the string body breaks when reciprocating once per minute. der 1.3 times or more of is,
The bending-wear-resistant multifilament , wherein the fiber is a core-sheath composite fiber having a sheath part containing molybdenum disulfide particles and a core part not containing molybdenum disulfide particles .

(B) The resin constituting the resin composition is selected from a polyamide resin, a polyester resin, a polylactic acid resin, and a polyolefin resin. Flexible wear multifilament .

The bending-wear-resistant multifilament of the present invention includes a resin composition capable of exhibiting bending-wear resistance, and the resin composition capable of exhibiting bending-wear resistance has a volume average particle diameter of 0.1 to 2.0 μm. A predetermined amount of molybdenum disulfide particles. For this reason, the bending wear resistant multifilament of the present invention is excellent in wear resistance. Further, the molybdenum disulfide particles having such a volume average particle diameter are excellent in dispersibility in the thermoplastic resin constituting the resin composition, and even when added at a high concentration of 15% by mass, the multifilament strength Is very small, and the balance between the bending wear resistance and the strength is excellent. For this reason, it can be suitably used in various fields where repeated bending is imposed, such as apparel use, industrial material use, and civil engineering use.

Hereinafter, the present invention will be described in detail.
As the resin constituting the resin composition capable of exhibiting the bending abrasion resistance in the bending abrasion resistant multifilament of the present invention, any resin can be used as long as it is a thermoplastic resin capable of obtaining a synthetic fiber. . For example, polyamide, polyester, polyolefin and the like can be mentioned.

  Polyamides include polyimino-1-oxotetramethylene (nylon 4), polytetramethylene adipamide (nylon 46), polycoupleramide (nylon 6), polyhexamethylene adipamide (nylon 66), polyundecanamide (nylon) 11), polylaurolactamide (nylon 12), polymetaxylene adipamide, polyparaxylylene decanamide, polybiscyclohexylmethane decanamide and the like. These copolymers and blends may be used. Among these, nylon 6 is preferable because it is inexpensive and has excellent strength and durability.

  As polyester, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, or esters thereof are used as an acid component. , Homopolyesters or copolymers having diol components such as diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, and the like. Polylactic acid obtained by polymerizing lactic acid mainly composed of D-lactic acid and / or L-lactic acid may be used. To these polyesters, paraoxybenzoic acid, 5-sodium sulfoisophthalic acid, polyalkylene glycol, pentaerythritol, bisphenol A and the like may be added or copolymerized.

  Examples of the polyolefin include aliphatic α-monoolefins having 2 to 18 carbon atoms, such as ethylene, propylene, butene-1, pentene-1,3-methylbutene-1, hexene-1, octene-1, dodecene-1, and octadecene. -1 is a homopolyolefin. Aliphatic α-monoolefins are polyolefins that are copolymerized with other ethylenically unsaturated monomers, such as similar ethylenically unsaturated monomers such as butadiene, isoprene, 1,3-pentadiene, styrene, α-methylstyrene. There may be. In the case of polyethylene, 10% by mass or less of propylene, butene-1, hexene-1, octene-1, or a similar higher α-olefin may be copolymerized with ethylene. In the case of polypropylene, 10% by mass or less of ethylene or a similar higher α-olefin may be copolymerized with propylene.

Flex grinding expressible resin composition耗性is as a main component a thermoplastic resin as mentioned above, so long as it does not impair the effects of the present invention, blending of other resin components or It may be copolymerized. When copolymerizing, it is preferable to contain 80 mol% or more of said thermoplastic resin components. If the content of the thermoplastic resin component is less than 80 mol%, the thermoplastic resin component will lose its inherent impact absorption, weather resistance, etc., and bend resistance, which is the target characteristic of the present invention. Abrasion and the like are impaired, which is not preferable.

Flex grinding expressible resin composition耗性are molybdenum disulfide particles, it is necessary to contain 0.3 to 15% by weight relative to the resin composition weight. Preferably it is 0.5-12 mass%, More preferably, it is 0.7-10.0 mass%. When the content of the molybdenum disulfide particles is less than 0.3% by mass, the effect of improving the bending wear resistance is insufficient in the obtained fiber. On the other hand, when the content exceeds 15% by mass, the frequency of occurrence of aggregates increases, and many microvoids are formed in the filament starting from the vicinity of the aggregates during the drawing process in the fiber manufacturing process. In addition to inferior characteristic values of fibers such as, yarn breakage frequently occurs during winding in the fiber manufacturing process, resulting in unstable operation.

  The volume average particle diameter (measured by the Fisher method described later) of molybdenum disulfide in the present invention needs to be 0.1 to 2.0 μm. It is preferable that it is 0.15-1.0 micrometer, and it is more preferable that it is 0.2-0.7 micrometer. When the volume average particle diameter is less than 0.1 μm, sufficient effects may not be exhibited with respect to bending wear resistance. On the other hand, when the volume average particle diameter exceeds 2.0 μm, the nozzle pressure is increased during fiber spinning. As a result, the yarn breakage or the like occurs.

  Molybdenum disulfide preferably has a maximum particle size of 10 μm or less, more preferably 6 μm or less, and even more preferably 2 μm or less. When the maximum particle size exceeds 10 μm, problems such as filter clogging and frequent yarn breakage occur during spinning, which is not preferable. The measurement of the maximum particle diameter can be performed by a normal method using, for example, a laser diffraction particle size distribution measuring apparatus.

  Molybdenum disulfide having a particle size as described above can be obtained by an ordinary method. For example, a natural bright molybdenum ore is physically finely pulverized by pulverization or the like, and is selected by a flotation method, thereby obtaining a particle having the above particle size.

Since such molybdenum disulfide particles are excellent in dispersibility in thermoplastic resin, the bending wear resistant multifilament of the present invention has improved bending abrasion resistance of the multifilament , and the molybdenum disulfide particles be a fiber that constitutes the multifilament have been added at high concentration stuff 15 mass%, the proportion of the strong decrease in the degree is small, an excellent multifilament balance between flex abrasion resistance and strength.

That is, bending abrasion multifilament of the present invention compared to those made of standard fiber without the molybdenum disulfide particles prepared under the same spinning and drawing conditions, capable of expressing a flex abrasion resistant resin Even if the composition contains molybdenum disulfide particles at a high concentration of 15% by mass, the decrease in strength is small. In detail, flex abrasion multifilament of the present invention preferably has its strength is obtained by holding the 60% intensity as compared with the intensity ratio of those made of fibers of the above criteria, retention of 70% or more More preferably, it is more preferably 80% or more. As the flex friction frequency ratio described later state, and are 1.30 times or more as compared with the fibers similarly criteria, good Mashiku be 1.40 times or more, is 1.50 times or more It is more preferable.

Note that in the possible resin composition expressing flex grinding耗性, the detailed mechanism of improving the flex abrasion resistance is not known by a specific amount containing molybdenum disulfide particles. However, since the molybdenum disulfide particles have a layered lattice structure, it is considered that the bending wear resistance is improved by cleaving molybdenum disulfide existing in the vicinity of the fiber surface due to the frictional stress applied to the fiber. In particular, by controlling the volume average particle diameter in a specific range as described above, the dispersion state of the molybdenum disulfide particles on the fiber surface becomes uniform, and the bending wear resistance is further improved. It is thought that there is.

Structure of the fibers constituting the flex abrasion multifilament of the present invention is not limited in particular. For example, single fibers and hollow fibers composed only of a resin composition that can express bending abrasion resistance by containing molybdenum disulfide particles, or composite fibers with other resins not containing molybdenum disulfide particles, etc. Any form can be selected. In the case of a composite fiber, for example, a core-sheath composite fiber, a side-by-side composite fiber, and a resin composition containing a molybdenum disulfide particle as a sheath component of a resin composition that can exhibit bending abrasion resistance. A sea-island type composite fiber used as a sea component or other deformed composite fiber can be selected as appropriate. In spinning the composite fiber, a normal method can be selected.

  In the case of a composite fiber, in order to effectively express the contribution of molybdenum disulfide particles to the bending wear resistance on the fiber surface, a resin that can exhibit bending wear resistance by containing molybdenum disulfide particles It is preferable that the composition is arranged so as to be exposed on at least a part of the fiber surface. Specifically, it is preferable that the resin composition containing molybdenum disulfide particles is arranged so as to be exposed at 25% or more of the fiber surface, more preferably 50% or more, and the entire surface of the fiber is made of the resin. Most preferably, the composition occupies. As a result, the bending wear resistant fiber of the present invention has a higher frequency that the surface in contact with the outside becomes a resin composition containing molybdenum disulfide particles, and therefore the overall bending wear resistance is effectively improved. .

  In the case of a composite fiber, the other resin component used together with the resin composition containing molybdenum disulfide particles is not particularly limited as long as it is a thermoplastic resin. Examples thereof include those similar to the thermoplastic resin used in the resin composition and not containing molybdenum disulfide particles, polyamides, polyesters based on polyethylene terephthalate, polylactic acid, polyolefin resins, and the like. Polyesters mainly composed of polyethylene terephthalate are copolymerized components such as dicarboxylic acid components such as isophthalic acid, 5-sodium sulfoisophthalic acid, phthalic anhydride, adipic acid and sebacic acid, 1,6-hexadiol and cyclohexane. A diol component such as dimethanol may be contained.

Flex abrasion multifilament of the present invention is a multi-filament composed of a single yarn of several double, single yarn fineness of the fibers constituting the multifilament Ru 1~200dtex der. Its total fineness, 20~5000dtex der is, it is good Masui is 40~3000dtex.

The cross-sectional shape of the single fiber may be a round cross section, an irregular cross section, or a hollow cross section. In addition, in the case of a composite fiber, the cross-sectional structure of the core-sheath type and the bonded type, as described above, parallel type (side-by-side), multiple parallel type (striped type), split type, multilayer type, radial type Type, sea island type, etc.

In the fiber constituting the bending-wear resistant multifilament of the present invention, as long as the effect is not impaired, for example, a heat stabilizer, a crystal nucleating agent, a matting agent, a pigment, a light-resistant agent, Various additives such as weathering agents, antioxidants, antibacterial agents, fragrances, plasticizers, dyes, surfactants, surface modifiers, various inorganic and organic electrolytes, fine powders, flame retardants and the like can be added. In order to increase the knot strength of the resulting fiber, fatty acid amides such as metaxylylene bisstearyl amide, metaxylylene bis oleyl amide, xylene bis stearamide, ethylene bis stearyl amide, ethylene bis stearamide, etc. Can be added.

Next, the manufacturing method of the fiber which comprises the bending abrasion-resistant multifilament of this invention is demonstrated using an example.
For example, in the case of a single fiber, a thermoplastic resin composition chip (master chip) containing molybdenum disulfide particles at a high concentration in advance is produced by a conventional method. In the spinning process, the master chip and the thermoplastic resin chip not containing molybdenum disulfide particles are appropriately melt-mixed and spun so that the concentration of the molybdenum disulfide particles falls within a predetermined range. To get the yarn. Alternatively, the target yarn can also be obtained by directly melt-mixing and spinning molybdenum disulfide particles and a thermoplastic resin chip not containing molybdenum disulfide particles so as to have a predetermined molybdenum disulfide particle content. be able to.

  In the case of a composite fiber, the target yarn can be obtained by melt spinning using an ordinary composite spinning apparatus using a resin composition containing molybdenum disulfide particles and other resin components. .

  Subsequently, the obtained yarn is cooled, applied with or without an oil agent, and once wound as an undrawn yarn or once without being wound up, stretched. At this time, the draw ratio is 2 to 8 times, and the target polyamide fiber is obtained by continuously performing the heat drawing and winding operation at 150 to 220 ° C. using a heating roller between the rollers. Can do.

  In order to uniformly disperse the molybdenum disulfide particles in the fiber, it is preferable to use a biaxial extruder as the melt extruder regardless of whether the fiber is a single fiber or a composite fiber.

In the present invention, since specific molybdenum disulfide particles are used as described above, the dispersibility in the thermoplastic resin is excellent, and even if this is added to the thermoplastic resin at a high concentration, the strength of the fiber is reduced. It is possible to obtain a multifilament with a small ratio and an excellent balance between bending wear resistance and strength.

Next, the present invention will be described specifically by way of examples. In addition, the measuring method of the characteristic value in a following example, a reference example, and a comparative example is as follows.

(1) Tensile strength [cN / dtex]
About the obtained multifilament , Shimadzu Corporation autograph AG-1 type | mold was used, the sample length was 25 cm, the tensile speed was 30 cm / min, and the initial load was measured as 0.05 g / dtex. If it was 60% or more in comparison with the tensile strength of the reference multifilament , it was considered acceptable.

(2) Bending wear resistance (times)
About 8 of the obtained multifilaments, the string-making goods were created using the Kachibu Iron Works company make 8-striking string making machine. A round file (300 m / m, (12 ") Marunouchi manufactured by OCHI FILE WORK's was applied to the resulting 8-string product with a load of 0.018 g (1400 dtex x 8: 202 g) per decitex. use eye) to be contacted at an angle of 90 degrees, the stroke width 330 ± 30 mm, the stroke speed 30 ± 1 cycles / is double rubs min, braided products was measured times up to fracture. the reference multifilaments was as acceptable as long as 1.30 or more in comparison with the number of cases where the had.

(3) Volume average particle diameter of molybdenum disulfide The number and volume of particles were measured using a measurement device (Coulter Counter Multitizer III, manufactured by Beckman Coulter, Inc. (aperture tube 100 μm)) by an electric resistance method. Then, assuming a sphere of the same volume from the volume of each molybdenum disulfide particle, the diameter of this sphere was converted as the particle diameter, and the average value was defined as the volume average particle diameter (Fischer method).

(4) Fineness Measured according to JIS L-1013 “Positive Fineness”.

(5) Elongation It calculated | required from the elongation at the time of a fracture | rupture at the time of the measurement of the tensile strength of said (1).

(6) Relative viscosity of nylon 6 (polyamide) Measured at a concentration of 1 g / deciliter and a temperature of 25 ° C. using 96 mass% sulfuric acid as a solvent.

(7) Relative viscosity of polyethylene terephthalate (polyester) Using a mixed solution of phenol / tetrachloroethane = 1/1 (mass ratio), the viscosity was measured at a concentration of 0.5 g / deciliter and a temperature of 20 ° C.

(Preparation of multifilament made of reference polyamide fiber (Comparative Example 1))
Nylon 6 having a relative viscosity of 3.5 was supplied to a twin-screw extruder type melt spinning machine, and melt spinning was performed at a spinning temperature of 285 ° C. using a spinneret having a spinning hole diameter of 0.4 mm and a hole number of 210. The spin finish was applied to the spun the yarn, without once winding, subjected to a hot stretching to the stretching ratio is 4.8 times by the heat roller heated to 180 ° C., the total fineness 1400 dtex, nylon 6 fibers to obtain a multi-filler ment consisting.

The obtained multifilament made of nylon 6 fiber is used as a multifilament made of reference polyamide fiber, and the polyamide fiber containing molybdenum disulfide particles described in Reference Examples 1 to 7, Examples 8 to 9, and Comparative Examples 2 to 5 below. In comparison with the multifilament made of, their bending wear resistance and the like were evaluated.

(Production of multifilament made of reference polyester fiber (Comparative Example 6))
Polyethylene terephthalate having a relative viscosity of 1.72 was supplied to a biaxial extruder melt spinning machine, and melt spinning was performed at a spinning temperature of 305 ° C. using a spinneret having a spinning hole diameter of 0.5 mm and a hole number of 192. The spin finish was applied to the spun the yarn, once without winding, subjected to a hot stretching to the stretching ratio is 5.2 times by the heat roller heated to 220 ° C., the total fineness 1670 dtex, polyester fibers to obtain a multi-filler ment to be.

From the polyester fiber containing molybdenum disulfide particles described in the following Reference Examples 10 to 16, Examples 17 to 18, and Comparative Examples 7 to 10 as multifilaments consisting of the obtained polyester fibers as reference polyester fibers In comparison with the multifilaments, the bending wear resistance and the like were evaluated.

(Production of multifilament made of reference polylactic acid fiber (Comparative Example 11))
A polymerization temperature of 230 ° C., a number average molecular weight of 138200, and a polylactic acid resin mainly composed of L-lactic acid [L / D as a content ratio (molar ratio) of L-lactic acid to D-lactic acid is 98.5 / 1. .5] was obtained. This was dried by a conventional method. The dried polylactic acid was supplied to a twin-screw extruder melt spinning machine equipped with a spinneret having a spinning hole diameter of 0.5 mm and a hole number of 192, and melt spinning was performed at a spinning temperature of 220 ° C. The spin finish was applied to the spun the yarn, without once winding, draw ratio in the heat roller heated to 145 ° C. is subjected to a thermal drawing to be 6.7 times, the total fineness 1670 dtex, polylactic acid fiber to obtain a multi-filler ment consisting.

The polyfilaments containing molybdenum disulfide particles described in the following Reference Examples 19 to 25, Examples 26 to 27, and Comparative Examples 12 to 15 were obtained by using the obtained multifilaments made of polylactic acid fibers as multifilaments made of reference polylactic acid fibers. By comparing with multifilaments composed of lactic acid fibers, their bending wear resistance and the like were evaluated.

( Reference Example 1)
To nylon 6 having a relative viscosity of 3.5, molybdenum disulfide having a volume average particle size of 0.3 μm (“Superfine” manufactured by Daizo Co., Ltd.) was added so as to be 0.4 mass% with respect to the mass of the fiber. Were supplied to a twin-screw extruder type melt spinning machine. Other than that was carried out similarly to the manufacturing method of the said reference | standard polyamide fiber, and obtained the multifilament which consists of a polyamide fiber with the total fineness of 1400 dtex.

( Reference Examples 2-5, Comparative Examples 2-3)
The amount of molybdenum disulfide particles added was changed so that the content of molybdenum disulfide particles in the fibers would be the value shown in Table 1. Other than that was carried out similarly to the reference example 1, and obtained the multifilament which consists of polyamide fibers.

( Reference Examples 6-7)
In Reference Example 6, molybdenum disulfide having a volume average particle diameter of 0.45 μm (“M-5 powder” manufactured by Daizo) was used. In Reference Example 7, molybdenum disulfide having a volume average particle diameter of 1.2 μm (“C powder” manufactured by Daizo) was used. Other than that was carried out similarly to the reference example 3, and obtained the multifilament which consists of polyamide fibers.

(Example 8)
A resin composition obtained by adding molybdenum disulfide having a volume average particle size of 0.3 μm to nylon 6 having a relative viscosity of 3.5 so as to be 2% by mass (“Superfine” manufactured by Daizo). Nylon 6 to which these resin compositions and molybdenum disulfide particles are not added so that nylon 6 (relative viscosity of 3.5) to which the molybdenum disulfide particles are not added is arranged to the core while being arranged in the sheath. To a twin-screw extruder type melt spinning machine having a core-sheath nozzle, and a composite polyamide fiber (core-sheath ratio: 1/1 ( The mass ratio)) was discharged. Other than that was carried out similarly to the reference example 1, and obtained the multifilament which consists of a core sheath type composite polyamide fiber with the total fineness of 1400 dtex.

Example 9
The resin composition of the sheath was changed to nylon 6 in which molybdenum disulfide particles were blended so as to be 6% by mass. Thereby, the composite polyamide fiber was discharged so that the content of the molybdenum disulfide particles was 3% by mass with respect to the fiber mass. Otherwise in the same manner as in Example 8, the total fineness 1400 dtex, to give a multi-filler ment consisting of core-sheath type composite polyamide fibers.

(Comparative Example 4)
Compared to Reference Example 3, the volume average particle diameter of the molybdenum disulfide particles was changed to 3.5 μm (“T powder” manufactured by Daizo). Otherwise, in the same manner as in Reference Example 3, an attempt was made to produce a multifilament made of polyamide fiber.

(Comparative Example 5)
The amount of molybdenum disulfide added was changed so that the content of molybdenum disulfide particles in the fiber was 20% by mass as shown in Table 1. Otherwise, in the same manner as in Reference Example 1, an attempt was made to produce a multifilament made of polyamide fiber.

The results of measuring the tensile strength and bending wear resistance of the multifilaments made of the polyamide fibers obtained in Reference Examples 1 to 7, Examples 8 to 9, and Comparative Examples 1 to 3, and the results of Comparative Examples 4 to 5 are shown. It is shown in 1.

As is clear from Table 1, the multifilaments made of the polyamide fibers of Reference Examples 1 to 7 and Examples 8 to 9 contained a specific amount of molybdenum disulfide, and thus were excellent in both tensile strength and bending wear resistance. Met.

On the other hand, since the multifilament made of the polyamide fiber of Comparative Example 1 did not contain molybdenum disulfide, the multifilament made of the polyamide fiber of Reference Examples 1 to 7 and Examples 8 to 9 was more resistant to bending abrasion. It was inferior. Multifilament of polyamide fibers of Comparative Example 2, the double since the added amount of molybdenum disulfide was too low, likewise in Reference Examples 1-7, flex abrasion resistance as compared with a multifilament of polyamide fibers of Example 8-9 It was inferior to. Since the multifilament made of the polyamide fiber of Comparative Example 3 contained too much molybdenum disulfide, a large number of microvoids were generated inside the filament, so that the tensile strength was low and the bending wear resistance was poor. In Comparative Example 4, the volume average particle diameter of molybdenum disulfide was too large, and in Comparative Example 5, the content of molybdenum disulfide was too large. Many yarn breaks occurred at the time of taking, and fibers could not be obtained.

( Reference Example 10)
To a polyethylene terephthalate having a relative viscosity of 1.72, molybdenum disulfide having a volume average particle diameter of 0.3 μm (“Superfine” manufactured by Daizo Co., Ltd.) was added so as to be 0.4 mass% based on the fiber mass. Were supplied to a twin-screw extruder type melt spinning machine. Other than that was carried out similarly to the preparation method of the said reference | standard polyester fiber, and obtained the multifilament which consists of a polyester fiber of total fineness 1670dtex.

( Reference Examples 11-14, Comparative Examples 7-8)
The amount of molybdenum disulfide particles added was changed so that the content of molybdenum disulfide particles in the fibers would be the value shown in Table 2. Other than that was carried out similarly to Reference Example 10, and obtained the multifilament which consists of polyester fibers.

( Reference Examples 15 to 16)
In Reference Example 15, molybdenum disulfide having a volume average particle size of 0.45 μm (“M-5 powder” manufactured by Daizo) was used. In Reference Example 16, molybdenum disulfide having a volume average particle diameter of 1.2 μm (“C powder” manufactured by Daizo) was used. Other than that was carried out similarly to Reference Example 12, and obtained the multifilament which consists of polyester fibers.

(Example 17)
A resin composition obtained by adding molybdenum disulfide having a volume average particle diameter of 0.3 μm to polyethylene terephthalate having a relative viscosity of 1.72 (“Superfine” manufactured by Daizo Co., Ltd.) to 2% by mass. Polyethylene without addition of these resin compositions and molybdenum disulfide particles so that polyethylene terephthalate (relative viscosity: 1.72) without addition of molybdenum disulfide particles is arranged in the core while being arranged in the sheath. A terephthalate is supplied to a biaxial extruder type melt spinning machine having a core-sheath type nozzle, and a composite polyester fiber (core-sheath ratio: 1/1) in which the content of molybdenum disulfide particles is 1% by mass with respect to the fiber mass. (Mass ratio) was discharged. Other than that was carried out similarly to the reference example 10, and obtained the multifilament which consists of a core sheath type composite polyester fiber of total fineness 1671dtex.

(Example 18)
The resin composition of the sheath was changed to polyester in which molybdenum disulfide particles were blended so as to be 6% by mass. Thus, the composite polyester fiber was discharged so that the content of molybdenum disulfide particles was 3% by mass with respect to the mass of the fiber. Otherwise in the same manner as in Example 17, the total fineness 1671Dtex, to obtain a multi-filler ment consisting of core-sheath type composite polyester fiber.

(Comparative Example 9)
Compared to Reference Example 12, the volume average particle diameter of the molybdenum disulfide particles was changed to 3.5 μm (“T powder” manufactured by Daizo). Otherwise, in the same manner as in Reference Example 12, an attempt was made to produce a multifilament made of polyester fiber.

(Comparative Example 10)
The amount of molybdenum disulfide added was changed so that the content of molybdenum disulfide particles in the fiber was 20% by mass as shown in Table 2. Otherwise, in the same manner as in Reference Example 12, an attempt was made to produce a multifilament made of polyester fiber.

The results of measuring the tensile strength and bending wear resistance of the multifilaments made of the polyester fibers obtained in Reference Examples 10 to 16, Examples 17 to 18, and Comparative Examples 6 to 8, and the results of Comparative Examples 9 to 10 are shown. It is shown in 2.

As is clear from Table 2, the multifilament made of the polyester fibers of Reference Examples 10 to 16 and Examples 17 to 18 contained a specific amount of molybdenum disulfide, and thus was excellent in both tensile strength and bending wear resistance. Met.

On the other hand, since the multifilament made of the polyester fiber of Comparative Example 6 did not contain molybdenum disulfide, the multifilament made of the polyester fiber of Reference Examples 10 to 16 and Examples 17 to 18 was more resistant to bending abrasion. It was inferior. Since the multifilament made of the polyester fiber of Comparative Example 7 had too little added amount of molybdenum disulfide, it was similarly bent and abrasion resistant compared to the multifilament made of the polyester fiber of Reference Examples 10 to 16 and Examples 17 to 18. It was inferior to. Since the multifilament made of the polyester fiber of Comparative Example 8 contained too much molybdenum disulfide, many microvoids were generated inside the filament, the tensile strength was low, and the bending wear resistance was inferior. In Comparative Example 9, the volume average particle diameter of molybdenum disulfide was too large, and in Comparative Example 10, the content of molybdenum disulfide was too large. Frequently occurred and fibers could not be obtained.

( Reference Example 19)
A polymerization temperature of 230 ° C., a number average molecular weight of 138200, and a polylactic acid resin mainly composed of L-lactic acid [L / D as a content ratio (molar ratio) of L-lactic acid to D-lactic acid is 98.5 / 1. .5] was obtained. This was dried by a conventional method. To the polylactic acid after drying, molybdenum disulfide having a volume average particle size of 0.3 μm (“Superfine” manufactured by Daizo Co., Ltd.) was added so as to be 0.4% by mass with respect to the fiber mass, and biaxial It was supplied to an extruder type melt spinning machine. Other than that was carried out similarly to the production method of the said reference | standard polylactic acid fiber, and obtained the multifilament which consists of polylactic acid fiber of total fineness 1670dtex.

( Reference Examples 20-23, Comparative Examples 12-13)
The amount of molybdenum disulfide particles added was changed so that the content of molybdenum disulfide particles in the fibers would be the value shown in Table 3. Other than that was carried out similarly to the reference example 19, and obtained the multifilament which consists of a polylactic acid fiber.

( Reference Examples 24-25)
In Reference Example 24, molybdenum disulfide having a volume average particle diameter of 0.45 μm (“M-5 powder” manufactured by Daizo) was used. In Reference Example 25, molybdenum disulfide having a volume average particle diameter of 1.2 μm (“C powder” manufactured by Daizo) was used. Other than that was carried out similarly to the reference example 21, and obtained the multifilament which consists of a polylactic acid fiber.

(Example 26)
The number average molecular weight is 138200, and the polylactic acid resin mainly composed of L-lactic acid [L / D, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid is 98.5 / 1.5], is volume average. The resin composition obtained by adding molybdenum disulfide particles having a particle diameter of 0.3 μm (“Superfine” manufactured by Daizo Co., Ltd.) so as to be 2% by mass is disposed on the sheath, and the molybdenum disulfide particles are Polylactic acid not added (number average molecular weight is 138200, L / D which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid is 98.5 / 1.5) is arranged in the core, These resin compositions and polylactic acid to which no molybdenum disulfide particles are added are supplied to a twin-screw extruder type melt spinning machine having a core-sheath nozzle, and the content of molybdenum disulfide particles is 1 with respect to the fiber mass. Composite polylactic acid fiber (core-sheath) of mass% Rate: jetted 1/1 (mass ratio)). Otherwise in the same manner as in Reference Example 21, a multifilament made of core-sheath type composite polylactic acid fiber having a total fineness of 1670 dtex was obtained.

(Example 27)
The resin composition of the sheath was changed to polylactic acid in which molybdenum disulfide particles were blended so as to be 6% by mass. Thereby, the composite polylactic acid fiber was discharged so that the content of the molybdenum disulfide particles was 3% by mass with respect to the mass of the fiber. Otherwise in the same manner as in Example 26, the total fineness 1671Dtex, to obtain a multi-filler ment consisting of core-sheath type composite polylactic acid fibers.

(Comparative Example 14)
Compared to Reference Example 21, the volume average particle diameter of molybdenum disulfide particles was changed to 3.5 μm (“T powder” manufactured by Daizo). Otherwise, in the same manner as in Reference Example 21, an attempt was made to produce a multifilament made of polylactic acid fiber.

(Comparative Example 15)
The amount of molybdenum disulfide added was changed so that the content of molybdenum disulfide particles in the fiber was 20% by mass as shown in Table 3. Otherwise in the same manner as in Reference Example 21, an attempt was made to produce a multifilament made of polyester fiber.

The results of measuring the tensile strength and bending wear resistance of the multifilaments made of the polylactic acid fibers obtained in Reference Examples 19 to 25, Examples 26 to 27 and Comparative Examples 11 to 13, and the results of Comparative Examples 14 to 15 are shown. Table 3 shows.

As is clear from Table 3, the multifilaments composed of the polylactic acid fibers of Reference Examples 19 to 25 and Examples 26 to 27 contained a specific amount of molybdenum disulfide particles, and thus were excellent in both tensile strength and bending wear resistance. It was.

On the other hand, since the multifilament made of the polylactic acid fiber of Comparative Example 11 did not contain molybdenum disulfide particles, it was more resistant to bending than the multifilament made of the polylactic acid fiber of Reference Examples 19 to 25 and Examples 26 to 27. It was inferior to wear. Since the multifilament made of the polylactic acid fiber of Comparative Example 12 contained too little molybdenum disulfide particles, the multifilament was similarly resistant to the multifilament made of the polylactic acid fiber of Reference Examples 19 to 25 and Examples 26 to 27. The bending abrasion was inferior. The multifilament made of the polylactic acid fiber of Comparative Example 13 contained too much molybdenum disulfide particles, so that many microvoids were generated inside the filament, the tensile strength was low, and the bending wear resistance was poor. In Comparative Example 14, the volume average particle diameter of the molybdenum disulfide particles was too large. In Comparative Example 15, the content of the molybdenum disulfide particles was too large. Many yarn breaks occurred and fibers could not be obtained.

Claims (2)

Bending and abrasion-resistant multifilament composed of a plurality of fibers containing a resin composition capable of expressing bending and abrasion resistance.
The resin composition capable of expressing the bending wear resistance contains 0.3 to 15% by mass of molybdenum disulfide particles having a volume average particle diameter of 0.1 to 2.0 μm with respect to the amount of the resin composition substance,
The single filament fineness of the fibers constituting the multifilament is 1 to 200 dtex, the total fineness of the multifilament is 20 to 5000 dtex,
A string body made of the above-mentioned eight multifilaments is brought into contact with a round file at a 90 ° angle with a load of 0.018 g per decitex, a stroke width of 330 ± 30 mm, a stroke speed of 30 ±. The number of bending abrasion resistances of the reference string body is the same as that of the above string body except that it does not contain molybdenum disulfide particles when the string body breaks when reciprocating once per minute. der 1.3 times or more of is,
The bending-wear-resistant multifilament , wherein the fiber is a core-sheath composite fiber having a sheath part containing molybdenum disulfide particles and a core part not containing molybdenum disulfide particles . 2. The bending-wear resistance according to claim 1, wherein the resin constituting the resin composition is selected from a polyamide-based resin, a polyester-based resin, a polylactic acid-based resin, and a polyolefin-based resin. Multifilament .