JP2007126758A - Polyamide filament yarn and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyamide having micropores for improving durability of functional chemical and to provide a method for producing the same. <P>SOLUTION: The polyamide filament yarn contains a specific amount of inorganic particles having specific micropores and satisfies all of the following conditions of (1) the maximum concentration D<SB>i</SB>of inorganic particles at five points in the fiber length direction of the yarn is 0.8D<SB>a</SB><D<SB>i</SB><1.2D<SB>a</SB>, (2) when the cross section of the yarn is divided into two parts of a segment close to the center of the fiber cross section and a segment close to the outer peripheral part of the yarn and the inorganic particle concentration of each segment is measured, the inorganic particle concentration of the high-concentration segment having micropores is D<SB>b</SB>and the inorganic particle concentration of the low-concentration segment having micropores is D<SB>c</SB>, D<SB>b</SB><1.2D<SB>c</SB>is exhibited, (3) coarse particles having ≥10 μm are ≤3 in 0.01 mm<SP>2</SP>and (4) when the weight cumulative values of weight distribution for particle diameters of the inorganic particles at 50% and 75% are U<SB>1</SB>and U<SB>2</SB>, respectively, U<SB>2</SB>-U<SB>1</SB><2μm is exhibited. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyamide filament yarn and a method for producing the same. More specifically, the present invention relates to a method for improving the washing durability and sustained release of the applied functional agent when various functional agents are applied to the polyamide filament yarn.

  Synthetic fibers such as polyester filament yarn and polyamide filament yarn are formed on a fabric and then impregnated and coated with various functional agents such as water repellents, water absorbents, antistatic agents, antifouling agents and antibacterial agents. In this way, various functions are given. However, functional drug application by these post-processing has the fault that a functional drug falls out by washing etc., and the effect decreases with progress of time. In addition, by impregnating fragrances, impregnating with scented clothes or vitamin derivatives, etc., drugs are taken into the human body from the skin during wearing, and there are also those aimed at health effects and whitening effects, The effect cannot be maintained for a long time just by attaching the chemical to the fiber surface. Patent Document 1 proposes a fiber that emits a scent by being impregnated with a medicine containing a microcapsule encapsulating a fragrance after forming a fabric and a binder. In the method of attaching the microcapsules after the formation of the fabric, the microcapsules attached to the fiber surface are poor in sustained release because the encapsulated drug is likely to diffuse. In the method of infiltrating the capsule, the liquid permeability and the particle size of the microcapsule are as large as a micrometer order, so that the microcapsule is difficult to penetrate into the hollow interior, and when processing such as twisting and false twisting is performed However, since the hollow portion is crushed, there is a problem that the microcapsules are more difficult to penetrate.

  Patent Document 2 proposes a method in which a polymer containing a microcapsule is joined to a sheath and a polymer not containing a microcapsule is arranged in a core in the spinneret, but the structure of the die is complicated. There is a problem that the cost becomes high. In addition, since the fiber produced by this method has microcapsules only on the surface, it cannot be said that the sustainability and sustained release of the functional drug are sufficient.

  Patent Document 3 proposes a polyester having excellent hygroscopicity, which contains silica-based inorganic particles having a defined pore volume and specific surface area, but small ones such as water molecules penetrate into the polyester. However, there is a problem that a functional drug having a large molecule is difficult to penetrate into the polyester. In addition, in the invention of Patent Document 3, the average pore radius is not mentioned in order to make the purpose different from the present invention of sustainability and sustained release of a functional drug.

Further, Patent Document 4 discloses a polyamide fiber containing a dye and a mesoporous material. A method of adding a mesoporous material at the time of polymerization of polyamide, a method of kneading in a process from polymerization to spinning (master pelletization). A method in which a polyamide chip is coated with a mesoporous material and then the polyamide chip is put into a spinning machine, and a method of kneading through a pipe in a spinning machine and a stationary kneader in a spinning pack is used. However, in the method of forming a master pellet, since particles such as mesoporous materials are likely to aggregate, coarse particles are likely to be generated. Therefore, it has been desired to further suppress the aggregation and further improve the spinning property. In addition, a method in which a polyamide chip is coated with a mesoporous material and then the polyamide chip is put into a spinning machine or a method of kneading through a stationary kneader in a spinning machine piping and a spinning pack is still applicable. The dispersibility of the substance is poor, the effect is insufficient, and depending on the type of pigment, problems such as uneven color due to insufficient dispersibility of the mesoporous substance may occur, and washing durability may be poor. Further improvement has been desired, such as being sufficient.
JP-A-6-228880 (paragraphs [0018] to [0024]) JP-A-11-350240 (paragraphs [009] to [0019]) JP 2001-329430 A (paragraphs [0013] to [0017]) JP 2003-27334 ([0007], [0021])

  In the present invention, a polyamide filament yarn added with the addition of inorganic particles having fine pores is stably manufactured at low cost, and the effect of the functional drug imparted by post-processing is improved and the sustained release is improved. The present invention relates to a polyamide filament yarn and a method for producing the same.

In order to solve the above-mentioned problems, the polyamide filament yarn of the present invention and the method for producing the same have the following requirements. That is,
(1) The specific surface area is 200 to 1000 m ² / g, the average pore diameter is 1 to 25 nm, the average particle diameter is 0.1 to 5 μm, and the content of the fine particles is 0.5 to 10 wt%. A polyamide filament yarn characterized by satisfying all of (A) to (D), blended as described above.

(A) Concentration _{D i} of the inorganic particles having fine pores at any five points of the fiber length direction of the polyamide filament yarn is _{0.8D a <D i <1.2D a} .
However, D _i is the concentration at any point, the D _a shows the mean concentration.

(B) In the cross section of the polyamide filament yarn, when divided into two segments, a segment near the center of the fiber cross section and a segment near the outer periphery, and measuring the concentration of inorganic particles having fine pores in each segment, When the concentration of inorganic particles having fine pores of high-concentration segments is D _b and the concentration of inorganic particles having fine pores of low-concentration segments is D _c , D _b <1.2D _c .

(C) The number of coarse particles of 10 μm or more is 3 or less in 0.01 mm ² .

(D) When the weight distribution when the weight distribution with respect to the particle diameter of the inorganic particles having fine pores is 50% and 75%, respectively, is U ₁ and U ₂ , U ₂ −U ₁ <2 μm.
(2) The polyamide filament yarn according to (1), wherein the inorganic particles having fine pores are silica.
(3) The polyamide filament yarn according to (1) or (2), which contains a functional drug.
(4) A method for producing a thermoplastic filament yarn, wherein inorganic particle powder having fine pores is continuously added to a thermoplastic resin pellet in front of a melting portion.
(5) An inorganic particle powder having fine pores having a specific surface area of 200 to 1000 m ² / g, an average pore diameter of 1 to 25 nm, and an average particle diameter of 0.1 to 5 μm is put on the thermoplastic pellets before the melting part. And continuously adding the thermoplastic filament yarn.
(6) The thermoplastic filament yarn according to (4) or (5), wherein the inorganic particle powder having fine pores is measured with a table feeder having the following configurations (A) to (C): Production method.

  (A) The table feeder is sealed so that the internal pressure of the table feeder is the same as the internal pressure of the spinning hopper.

  (B) It consists of two tanks with a powder storage tank at the top and a powder weighing tank at the bottom. Each tank has two kinds of stirring blades with the center of the tank as the rotation axis, and one of them is a stirring blade. Is a stirring blade that is attached perpendicularly to the rotating shaft and has a structure that decreases in thickness toward the rotating direction, and the other stirring blade has a stirring blade that extends vertically on the outer periphery of the tank.

(C) It has a powder supply cylinder with an inner diameter of 10 to 200 mm.
(7) The method for producing a thermoplastic filament yarn according to any one of (4) to (6), wherein the thermoplastic resin is polyamide.
(8) The method for producing a thermoplastic filament yarn according to any one of (4) to (7), wherein the inorganic particles having fine pores are silica.

  By adding inorganic particles having fine pores to the polyamide filament yarn, the present invention can stably and inexpensively produce a polyamide filament yarn excellent in sustainability and sustained release of the effect of a functional drug applied by post-processing. It is possible to manufacture.

  The polyamide in the present invention is nylon 6 (polycaproamide), nylon 8 (polyoctaneamide), nylon 12 (polydodecanamide), nylon 66 (polyhexamethylene adipamide), nylon 610 (polyhexamethylene sebaca) As exemplified by (mid) and the like, it is a high molecular weight product in which hydrocarbon groups are linked through an amide bond, and the type thereof is not particularly limited. The polyamide in the present invention includes not only homopolymers but also copolymers of these polyamides. Moreover, various additives such as heat-resistant agents, light-proofing agents and anti-aging agents, and additives such as electrostatic agents and matting agents are usually used for polyamides used in fibers. As long as it does not inhibit, these additives may be included.

  The filament yarn of the present invention needs to be a polyamide. This is due to the following reason.

  In the present invention, the functional particles to be applied in a later step are incorporated into the inorganic particles having fine pores existing inside the filament yarn, and the functional agents are gradually released during use or function due to dropping or the like. The purpose is to prevent the effects of sex drugs from decreasing. From this point of view, polyester yarns such as polyethylene terephthalate and polybutylene terephthalate and polyolefin yarns such as polyethylene and polypropylene have a tightly packed fiber structure. The existing inorganic particles having fine pores are not effectively used. Therefore, the sustained release and sustainability of the functional drug are insufficient.

  Examples of the inorganic particles having fine pores in the present invention include silica, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, and the like. However, the inorganic particles are not particularly limited as long as they are inorganic particles having fine pores. Among these, silica is particularly preferable because it has poor reactivity with chemicals such as general acids and alkalis.

  Inorganic particles having fine pores can be produced by a generally known method, and an example of a method for producing silica having fine pores can be produced by the following method.

  Sodium silicate and water are mixed and stirred at a predetermined ratio, an aqueous acrylamide polymer solution is added and dispersed, and a 5% aqueous sulfuric acid solution is added with stirring and allowed to stand. The precipitate obtained by standing still is redispersed in water, 5% aqueous sulfuric acid solution is added with stirring, the precipitate is filtered, washed with water, dried and the resulting precipitate is dried, such as a Hensyl mixer or a ball mill. By pulverizing with a pulverizing mixer, silica having fine pores is obtained.

The inorganic particles having fine pores used in the present invention are required to have a specific surface area of 200 to 1000 m ² / g, an average pore diameter of 1 to 25 nm, and an average particle diameter of 0.1 to 5 μm. The preferred range is 300 to 700 m ² / g, the average pore radius is 1 to 10 nm, and the average particle size is 0.3 to 3 μm.

When the specific surface area is smaller than 200 m ² / g, since the volume of the micropores in the inorganic particles is small, the amount of the functional agent taken into the fiber is small, and the sustainability of the function becomes insufficient. From the standpoint of the function, the specific surface area is preferably 300 m ² / g or more. When the specific surface area is larger than 1000 m ² / g, agglomeration is likely to occur, so that it is difficult to obtain inorganic particles having a small particle size, and agglomeration also occurs during the spinning process, resulting in frequent yarn breakage. From the viewpoint of yarn breakage, the specific surface area is preferably 700 m ² / g or less. The specific surface area can be measured by the BET method.

  In addition, when the average pore diameter is smaller than 1 nm, the functional drug is not taken into the pores, so that the sustainability and sustained release of the function are insufficient. When the average pore diameter is larger than 25 nm, the functional drug is taken into the pores, but the pore diameter is too large compared to the molecular diameter of the functional drug. The outflow is large, the sustainability of the function and the sustained release are insufficient, and the average pore diameter is preferably 10 nm or less from the viewpoint of the sustainability of the function and the sustained release. The average pore diameter can be measured by the BET method.

  When the average particle size of the inorganic particles having fine pores is smaller than 0.1 μm, aggregation tends to occur, so that it is difficult to obtain inorganic particles having small variations in particle size at low cost. Even when inorganic particles having an average particle size of 0.1 μm or less are obtained, agglomeration occurs during melt spinning, resulting in frequent yarn breakage. From the viewpoint of preventing aggregation, the average particle size is preferably 0.3 μm or more. When the average particle size of the inorganic particles having fine pores is larger than 5 μm, the inorganic particles act as foreign matters in the fiber during spinning, so that yarn breakage occurs frequently. From the viewpoint of yarn breakage, the average particle size is 3 μm. The following is preferred. The average particle size is defined as a mode value of the weight distribution with respect to the particle size (particle size at which the weight value becomes the largest) obtained by measuring by a Coulter counter method using a dense particle size distribution measuring device.

  The polyamide filament yarn of the present invention needs to contain 0.5 to 10 wt% of inorganic particles having fine pores, and the content of the inorganic particles having fine pores is preferably in the range of 1 to 7 wt%. When the content of the inorganic particles having fine pores is less than 0.5 wt%, the amount of the functional agent taken into the polyamide filament yarn is reduced, so that the sustainability and sustained release of the function are insufficient. From the viewpoints of function sustainability and sustained release, the content of inorganic particles having fine pores is preferably 1 wt% or more. When the content of the inorganic particles having fine pores exceeds 10 wt%, the inorganic particles having fine pores act as foreign matters in the fiber formation, so that yarn breakage occurs frequently, and from the viewpoint of yarn breakage, It is preferable that the content of the inorganic particles having a content of 7 wt% or less.

Furthermore, the polyamide filament yarn of the present invention must satisfy the following requirements (1) to (4) from the viewpoint of sustained release and sustainability of the functional drug.
(1) Concentration _{D i} of the inorganic particles having fine pores at any five points of the fiber length direction of the polyamide filament yarn is _{0.8D a <D i <1.2D a} , preferably 0.9D _a <D _i <1.1D _a more preferably from _{0.95D a <D i <1.05D a} .
However, D _i is the concentration at any point, the D _a shows the mean concentration.
(2) In the cross section of the polyamide filament yarn, when divided into two segments, a segment near the center of the fiber cross section and a segment near the outer periphery, and measuring the concentration of inorganic particles having fine pores in each segment, When the concentration of inorganic particles having micropores in high-concentration segments is D _b and the concentration of inorganic particles having micropores in low-concentration segments is D _c , D _b <1.2D _c , preferably D _b <1.1D _c .
(3) The number of coarse particles of 10 μm or more is 3 or less in 0.01 mm ² , preferably 1 or less.
(4) When the weight distribution when the weight distribution with respect to the particle diameter of the inorganic particles having fine pores is 50% and 75%, respectively, is U ₁ and U ₂ , U ₂ -U ₁ <2 µm, preferably U ₂ -U ₁ <1.2 µm.

By setting it as the range of said (1) and (2), it means that there is no variation in the distribution state of the inorganic particle which has a micropore in the fiber length direction of a polyamide filament yarn, and the cross-sectional direction of a fiber.
If it deviates from the range of (1), it becomes a cause of quality defects such as vertical lines and horizontal stages when dyed by knitting, weaving or dyeing into yarn breaks or fabrics. When inorganic particles are present in the fiber, orientation and crystallization that occur before the fiber is taken up are suppressed. For this reason, when the dispersion state of the particles is uneven, the structure in the longitudinal direction of the fiber is varied, so that a quality defect such as a vertical line or a horizontal step is likely to occur.

  In addition, when the concentration of inorganic particles having micropores is higher in the segment closer to the center of the fiber cross section than in the segment closer to the outer periphery, less functional drug is taken up in the segment closer to the outer periphery. For this reason, the effect of the initial functional drug is reduced, and in the case of a functional drug having a relatively large molecular weight, it is difficult to take in, so that the function is lowered and the time required for functional processing is increased.

  Conversely, when the concentration of inorganic particles having fine pores is lower in the segment closer to the center of the fiber cross section than in the segment closer to the outer periphery, more functional drugs are taken in the segment closer to the outer periphery. Therefore, since the functional drug is easily diffused out of the fiber, washing durability and sustainability of the functional drug are lowered.

The requirement (3) means that there are few coarse particles formed by aggregation of inorganic particles, that is, inorganic particles are dispersed without much aggregation. When the number of coarse particles of 10 μm or more exceeds 3 in 0.01 mm ² , the filter used in the spin pack is clogged, and the pressure in the spin pack rises, causing polymer leakage, Or get worse. Since the polymer leakage and the deterioration of the spinning property are more likely to occur as the number of coarse particles is larger, it is preferable that the number of coarse particles is smaller.
By setting it as the range of (4), it means that the dispersion | variation in the particle size of the inorganic particle which has a micropore contained in a polyamide filament yarn is small. When outside the range of (4), the variation in the particle size of the inorganic particles having fine pores is large, so that the functional drug is easily taken into the particles having a large particle size, and functions as particles having a small particle size. It becomes difficult to take in the sexing agent, the sustained release property is lowered, the fabric quality after dyeing is deteriorated, and the yarn-making property is deteriorated.

  Whether or not the above requirements (1) to (4) are satisfied can be confirmed by the method described in Examples described later.

  As a method of adding inorganic particles having fine pores to polyamide filament yarn to obtain the above-mentioned polyamide filament yarn, a method of producing a master pellet containing high concentration inorganic particles and blending the master pellet and the base pellet, polyamide polymerization Any method can be used as long as it satisfies the requirements of the present invention, such as a method of adding inorganic particles having fine pores therein, a method of adding inorganic particles having fine pores directly in front of the melting portion, or the like directly in the spinning process. Although a method may be used, a method of adding continuously in front of the melting part directly in the spinning step is preferable. In the method of manufacturing master pellets containing high concentration inorganic particles and blending the master pellets and the base pellets, the cost increases because the number of steps for manufacturing the master pellets increases. In the method of blending the master pellet and the base pellet, the master pellet and the base pellet are generally blended into the spinning hopper and manufactured. The separation between the master pellet and the base pellet occurs due to the difference in specific gravity or shape between the master pellet and the base pellet, and the concentration of inorganic particles having fine pores in the fiber longitudinal direction is likely to vary. For these reasons, a method of continuously adding inorganic particle powder having fine pores directly in front of the melted part in the spinning process is preferable. In addition, in order to minimize the variation in the concentration of inorganic particles with micropores in the longitudinal direction of the fiber, an extruder-type spinning machine is used in the melting part, or a static mixer is introduced into the pipe from the melting part to the spinning pack. It is preferable to do. Furthermore, as the screw of the extruder type spinning machine, it is more preferable to use a double flight type screw having a backflow function.

  Further, in the process of producing the master pellet, the polyamide polymer and the inorganic particles having fine pores are mixed. However, since the inorganic particles having high concentration of fine pores are added to the melted polyamide polymer, the fine pores are added. Agglomeration of inorganic particles having In order to avoid these disadvantages, a method in which inorganic particle powder having fine pores is continuously added before the melting portion is preferable.

  Further, in the method of adding inorganic particles having fine pores during polyamide polymerization, the inorganic particles tend to aggregate during the polymerization, the polymerization reaction inhibits the polymerization reaction, and the polymerization time becomes longer. When the thickness is small, thickening tends to occur. Therefore, it is preferable to use a method of adding continuously in front of the melting part directly in the spinning process.

  In addition, in the method in which the polyamide chip is put into the spinning machine after the polyamide chip is coated with the inorganic particle powder having the fine pores, the inorganic particle powder having the fine pores put into the hopper installed upstream of the spinning machine is used. While the coated polyamide chip is transported to the melting part, inorganic particle powder with fine pores adheres to the wall surface of the hopper or piping, causing a decrease in the concentration of addition, or cleaning is required every time the product is sold out. Deteriorating work efficiency. In addition, in the case of a process in which drying to spinning are performed as a whole, it is common to use air sending when sending chips from the drying process to the spinning process. In the air sending process, inorganic particle powder having fine pores is used. In order to separate the inorganic particle powder having micropores directly, it is necessary to add it to the polyamide chip immediately before the melting part of the spinning process. In this case, it is preferable that inorganic particle powder having a small amount of fine pores is continuously added to the polyamide chip immediately before the melting part in the spinning process.

  The cross-sectional shape of the polyamide filament yarn of the present invention is not particularly limited and can be produced by a melt spinning method used in a conventional method. That is, as shown in FIG. 1, polyamide pellets containing inorganic particles are melted, introduced into a spinning pack heated in a spin block 1, discharged from a base 2, cooled by a cooling air device 3, and refueled by an oil supply device 4. After that, it is manufactured by a process of entanglement with the entanglement device 5, drawing, drawing and winding. In the melting part, an extruder is preferable from the viewpoint of the kneadability of the polymer. In the take-up and drawing section, after winding the undrawn yarn, the UY / DT method in which drawing is performed in a later step, one step of winding the semi-drawn yarn (POY yarn) or drawn yarn (DSD yarn) in one step It can be produced by any method, and is preferably produced by a one-step method from the viewpoint of productivity.

  The polyamide filament yarn provided by the present invention can be knitted and woven by a commonly used method.

  As the knitting of the knitted fabric, the warp knitted tricot fabric, the raschel fabric, and the circular knitted fabric single circular knitted fabric, double circular knitted fabric, molded circular knitted fabric, or flat knitted fabric of flat knitted fabric Any of these may be used. In addition, the knitting organization includes warp knitted fabric half organization, back half organization, quinds cord organization, satin organization, satin net organization, power net organization, triconet organization, other change organization, etc. Tendon reversible tissue, milling tissue, interlock tissue, reversible tissue, and other changeable tissue can be used without particular limitation.

  As the weaving of the woven fabric, a general woven fabric structure such as a plain woven fabric, a twill woven fabric, a satin weaving fabric, a knotted woven fabric, a cocoon woven fabric, a dobby tissue, a jacquard tissue, or the like can be appropriately selected.

  The polyamide filament yarn provided by the present invention can be selected by appropriately selecting a fabric structure in accordance with its function, thereby allowing slipping, camisole, petticoat, shorts, tights, underpants, T-shirts, U-shirts for women. Neck shirt, round neck shirt, body suit, girdle etc. Men's underwear T-shirts, U-neck shirts, round neck shirts, running shirts, underpants, tights, briefs, etc. Running shirts / pants for sportswear, competition shirts / pants, golf shirts, tennis shirts, cycle shirts / pants, T-shirts, polo shirts, outdoor shirts, baseball undershirts, training wear, leotards, swimwear, athletic underpants , Ski inners, speed skate wear, etc. Sweaters and vests for general outerwear. Moreover, as materials, it can be used for gloves, supporters, sweat removing bands, hats, linings, shoe inner materials, interlinings, and the like.

  Further, the polyamide filament yarn provided by the present invention can be subjected to scouring / relaxation / dyeing / functional processing by a generally used method as appropriate, depending on the type of additive.・ Various chemicals such as metal sequestering chelating agents, fixing agents and leveling agents can be used. Also in functional processing, antifouling processing, antibacterial processing, antibacterial processing, deodorization processing, deodorization processing, sweat absorption processing, moisture absorption processing, anti-permeability processing, anti-friction processing, UV prevention processing, and embossing as post processing Depending on the required characteristics of the final target product such as processing, raising processing, opal processing, etc., it can be applied as appropriate.

  The method for producing the polyamide filament yarn provided by the present invention is not particularly limited as long as the requirements specified in the present invention are satisfied. However, the inorganic particle powder having fine pores is continuously formed in the polyamide pellet before the melted portion. It can manufacture by adding to. The manufacturing method in which the inorganic particle powder having fine pores is continuously added before the melting portion can be used as a method for adding the inorganic particles having fine pores with good dispersibility into thermoplastic resin pellets other than polyamide. . Examples of thermoplastic resins that can utilize a production method in which inorganic particle powder having fine pores is continuously added before the melting part include polyester resins such as polyester terephthalate and polytrimethylene terephthalate, and polyolefins such as polypropylene and polybutylene. Examples thereof include, but are not limited to, resins.

  That is, the method for producing a thermoplastic filament yarn of the present invention is characterized in that the inorganic particle powder having fine pores is continuously added to the thermoplastic resin pellets in front of the melting part.

  In the above, the inorganic particle powder having fine pores is a granular material having an average particle size of 20 μm or less and having fine pores, and the average particle size is also 0.1 to 5 μm. The effect is remarkable when used. When the particle diameter exceeds 20 μm, it is difficult to uniformly add powder to the thermoplastic resin pellets such as polyamide, and dispersion in the thermoplastic resin such as polyamide polymer in the melted portion becomes insufficient. In the case of adding such a large particle size, it is common to produce a master pellet and then mix the master pellet and the base polymer pellet, but the thermoplasticity provided by the present invention The merit of the method for producing the filament yarn is that the cost is lower than that for producing the master pellet, and the generation of coarse particles of inorganic particles that occur during the polymerization is avoided.

  Hereinafter, the method for producing a filament according to the present invention will be described in detail with a focus on a method for producing a polyamide filament yarn. This production method is particularly effective in polyamide, but can also be applied to other thermoplastic resins as described above. It is.

  As a continuous supply method, it is preferable to use a device that can stably supply at a constant speed and a constant amount. A supply method using a table feeder, a volumetric meter that adds powder by continuously rotating a measuring rod. Any method may be used as long as the polyamide filament yarn of the present invention can be obtained, such as a feeding method by a formula and a feeding method by a screw feeder. Although not particularly limited, a table feeder is used for suppressing aggregation and dispersing uniformly in a fiber. The supply method by is preferred. This is because the amount can be stably supplied at a constant speed with little fluctuation. Also, when powder with high adhesion is used, such as volumetric measurement using a measuring rod, it tends to remain on the measuring rod, and the concentration of inorganic particles having fine pores in the polyamide filament yarn tends to vary. Therefore, it is preferable to adopt a supply method using a table feeder that does not use a weighing rod or a supply method using a weight weighing type that controls the weight. When using a screw feeder, if powder with high adhesion is used, the powder tends to remain in the groove of the screw and the concentration of inorganic particles with fine pores in the polyamide filament yarn tends to vary. Become. In general, the smaller the particle size of the powder, the stronger the adhesion of the powder. Therefore, from the viewpoint of variation in the concentration of the inorganic particle powder having fine pores in the polyamide filament yarn, there is a supply method using a table feeder. preferable.

  The table feeder rotates at a constant speed determined by the amount to be added, introduces powder into a table with grooves, and discharges the powder introduced into the grooves with a cutting punch etc. A generally known form having a function of weighing the body can be used, but when adding inorganic powder having fine pores directly to polyamide, the amount added is very small. Therefore, in order to improve the meterability of the inorganic powder having fine pores, the groove width is preferably 1 to 10 mm. This is because, if the groove width is made too narrow, the inorganic powder having fine holes introduced into the groove easily adheres to the wall surface of the groove. If the groove width is too wide, if the amount of inorganic powder having fine pores is small, the number of rotations of the table must be reduced. Tend to decrease.

  In order to improve the stable discharge property of the powder, the following table feeder is preferable. This will be described below with reference to FIGS. FIG. 2 shows an example of a table feeder preferably used in the present invention. Fig.3 (a) is the schematic which looked at the example of the inside of the powder storage tank of a table feeder from upper direction, and FIG.3 (b) is the schematic which looked at it from the side. FIG. 4A is a schematic view of an example of the inside of the powder measuring tank of the table feeder as viewed from above, and FIG. 4B is a schematic view as viewed from the side thereof. FIG.4 (c) is explanatory drawing which showed the mode of the cutting hook.

  The table feeder is composed of two tanks having a powder storage tank 9 at the top and a powder measuring tank 10 at the bottom, and is rotated by a motor 16 and is installed in a horizontal direction with a rotating shaft 15 passing through the center of each tank. It is preferable to have two types of stirring blades 11 and 13 and stirring blades 12 and 14 installed in the vertical direction. The stirring blades do not have to be one set for each tank, and may be composed of a plurality of sets, or the stirring blades installed in the horizontal direction and the stirring blades installed in the vertical direction may be integrated. Is also possible. In this example, as shown in FIGS. 3A and 4A, the stirring blades 11 and 13 have a shape in which three stirring blades are integrated. This is because these rotor blades 11 to 14 have an effect of improving the stirring property of the powder and keeping the bulk specific gravity of the powder in the powder measuring tank 10 more constant.

  When the table feeder having the structure as shown in FIG. 2 is used, the inorganic powder having fine pores is charged into the powder storage tank 9 at the top of the table feeder (the inlet is not shown), and is horizontally oriented. While stirring with the installed stirring blade 11 and the stirring blade 12 installed in the vertical direction, through the opening 23 in the partition plate 18 installed between the powder storage tank 9 and the powder measurement tank 10, Move to the powder weighing tank 10. The inorganic powder having fine holes moved to the powder measuring tank 10 is stirred by the stirring blade 13 installed in the horizontal direction and the stirring blade 14 installed in the vertical direction, and enters the groove 24 installed in the table 19. The inorganic powder having the fine holes is discharged to the powder supply cylinder 17 by being slid by the measuring portion partition plate 25 and the cutting bar 26. The powder discharged to the powder supply cylinder 17 passes through the powder supply cylinder 17 and is added to the polyamide chip introduced into the spinning hopper 21. In order to prevent the inorganic powder having fine pores added to the polyamide chip from adhering to the wall surface of the spinning hopper 21 as much as possible, the distance between the lowermost part of the powder supply cylinder 17 and the molten part 22 of the polyamide chip (Refers to the distance from the lowermost part of the powder supply cylinder 17 to the part where the polyamide chip is in a molten state, and when the molten part is an extruder, it refers to the vertical distance to the center of the screw shaft) It is preferable to set it as follows, More preferably, it is 30 cm or less.

  Further, the inorganic particle powder having fine pores measured by the table feeder is added to the polyamide pellets in the spinning hopper 21, but the nitrogen brought in by the polyamide pellets supplied from the pipe 20 into the spinning hopper 21, There may be a difference between the spinning hopper internal pressure and the table feeder internal pressure. In this case, if the airtightness of the table feeder is low, nitrogen continues to flow into the table feeder from the spinning hopper 21 through the powder supply cylinder 17, and when the flow rate is high, inorganic particles having fine pores Affects the amount of powder added. From this point of view, it is preferable to have a sealed structure so that the internal pressure of the table feeder and the internal pressure of the spinning hopper are at the same pressure. Furthermore, it is more preferable to keep the pressure of the spinning hopper and the table feeder equal by a method such as providing a bypass separately from the powder flow path between the spinning hopper and the table feeder.

FIG. 5 (a) is a schematic view of an example of a stirring blade installed in the horizontal direction of the table feeder as viewed from above, and FIG. 5 (b) is a diagram of the stirring blade 11 or 13 in FIG. 5 (a). Schematic showing an example of a stirring blade viewed from the direction of arrow (A), FIG. 5C is another example of the stirring blade viewed from the direction of arrow (A) of stirring blade 11 or 13 in FIG. FIG. Moreover, Fig.6 (a) is the schematic which looked at an example of the stirring blade installed in the perpendicular direction of the table feeder from upper direction, and FIG.6 (b) is the schematic which looked at it from the side. As shown in FIG. 5, it is preferable that the stirring blades 11 and 13 installed in the horizontal direction have a structure in which the thickness becomes thinner as the rotation direction proceeds, and the angle e is 10 to 45 °. More preferably. This is because, by adopting a structure in which the thickness is reduced toward the direction of rotation, the powder can be stirred so as to cut the powder, and the bulk specific gravity of the powder can be made more uniform.
As shown in FIG. 6, it is more preferable that the stirring blade 14 installed in the vertical direction has a structure that protrudes to the outer periphery as it goes in the direction of rotation. Further, the length of the vertical portion of the stirring blade 14 installed in the vertical direction is more preferably 0.3 to 0.9 times the height of the powder measuring tank 10, and the stirring blade 14 is installed in the vertical direction. The length of the vertical portion of the stirring blade 12 is more preferably 0.5 to 0.9 times the height of the powder measuring tank 9. This is from the viewpoint of stirring the powder and preventing the powder from forming a bridge. Further, the powder supply cylinder 17 from the table feeder to the spinning hopper preferably has an inner diameter of 10 to 200 mm, and more preferably has a mirror finish on the inner wall. If the inner diameter is less than 10 mm, the powder tends to clog the supply tube. If the inner diameter exceeds 200 mm, the table feeder itself becomes larger, and the spinning hopper also becomes larger. is there.

  The inorganic particles used in the method for producing a polyamide filament yarn provided by the present invention preferably have an angle of repose in the range of 30 to 50 °. In general, the smaller the particle size of the powder, the larger the angle of repose. Therefore, it is disadvantageous in terms of cost to produce a powder smaller than the angle of repose 30 °, and when the angle of repose exceeds 50 ° Since the fluidity of the powder is deteriorated, it is disadvantageous in terms of the uniformity of the powder.

  Hereinafter, the present invention will be described in more detail with reference to examples. The evaluation method is as follows.

(1) Specific surface area and average pore diameter Using a BET method, a specific surface area / pore distribution measuring device (Sorptomatic Series 1800 (manufactured by Carlo Elba Co., Ltd.)) was used.

(2) Average particle size Using a dense particle size distribution measuring device (“Multisizer3” manufactured by Beckman Coulter, Inc.), the particle size is measured by the Coulter counter method to obtain the weight distribution with respect to the particle size. The largest particle size).

(3) Content of inorganic particles in fiber After 5 g of a measured sample (filament yarn) is put in a magnetic crucible and completely ashed by heating and baking in an electric furnace at 800 ° C. for 3 hours, the inside of the desiccator And allowed to cool for 1 hour, the weight of the incinerated product was measured, and the content of inorganic particles in the fiber was determined. When there are a plurality of inorganic particles contained in the fiber, the collected ash is thermally decomposed with sulfuric acid and hydrofluoric acid, and dissolved with dilute nitric acid, subjected to atomic absorption analysis in the wavelength region of 300 to 600 nm, The ingredients were determined.

(4) Dispersion state of inorganic particles having fine pores (A) Concentration D _i and average concentration Da of inorganic particles having fine pores at arbitrary five points in the fiber length direction of the polyamide filament yarn
The polyamide filament yarn was cut out by 5 cm, melted, cast and formed into a film, and then analyzed with an X-ray microanalyzer. From the peak of the X-ray microanalyzer, the concentration (%) of inorganic particles having fine pores was determined. In a similar manner, for any part five places in the fiber length direction, performs a measurement of the concentration of the inorganic particles having fine pores, the average of the five locations was D _{a. Di} represents individual values (D ₁ , D ₂ , D ₃ , D ₄ , D ₅ ).
0.8D _a <requirements satisfying _D i <1.2D _a was _{that D} 1 to D ₅ satisfies all _{0.8D a <D i <1.2D a} .

(B) The particle size U ₁ when the weight cumulative value when the weight distribution with respect to the particle size of the inorganic particles having fine pores is 50% is obtained, and the particle size U ₂ when the weight cumulative value is 75%.
Using the film produced in (A) as a sample, the transmission particle (TEM) captures inorganic particles distributed in the polymer as an image (magnification 1000 times). From the captured image, the particle size and number distribution of the inorganic particles were measured. From the measured particle size and number distribution of the inorganic particles, in the weight distribution with respect to the particle size, the particle size at which the cumulative weight from the smaller one was 50% was defined as U ₁ and the particle size of 75 percent was defined as U ₂ . Incidentally, the particle diameter at a 50% U ₁ and 75% U ₂ the particle size of the different parts 5 points in the fiber length direction, respectively were measured and their average value. About the aggregated secondary particle, the particle size as a secondary particle was employ | adopted.

(C) Concentrations of inorganic particles D _b and D _c having fine pores in the fiber cross section near the center of the fiber cross section and the segment near the outer peripheral portion.
The cut surface of the polyamide filament yarn was cut out and subjected to quantitative elemental analysis with an electron beam microanalyzer to determine the concentration of inorganic particles having fine pores. The measurement was performed for each of the inner peripheral side region and the outer peripheral side region at the time of drawing a circumference having a radius of ½ from the center of the fiber cross section, and the average value of each was adopted. Of the concentration of the inorganic particles having the micropores in the segment near the center and the concentration of the inorganic particles having the micropores in the segment near the outer peripheral portion, the higher one is D _b and the lower one is D _c . .

(5) Washing durability test of ascorbyl tetrahexyldecanoate For the washing method of the fabric, the 103 method described in JIS L 0217 “Handling symbols and indication methods for textile products” was used. The tengu made in the example was used as the fabric. The number of washing was evaluated at 10 times and 20 times, and the blank was set as 0 times. It was measured how much the residual amount of ascorbyl tetrahexyldecanoate after each washing was compared to before washing. The residual amount was 60-100% before washing (0 washings), 40-59% Δ, 0-39% x. The case where it became x in either 10 times or 20 times was determined to be insufficient.

  Ascorbyl tetratetrahexyldecanoate was quantified by using 20 g of the cut out fabric as a sample, placing it in 300 ml of isopropanol solution, shaking at 37 ° C. for 2 hours to extract tetrahexyldecanoate ascorbyl, and then removing the supernatant by HPLC ( The peak area of the obtained ascorbyl tetrahexyl decanoate was determined by high performance liquid chromatography), and the peak area of the ascorbyl tetrahexyl decanoate obtained from 10 or 20 washes was obtained from the sample with 0 washes. It was determined by dividing by the peak area of the obtained ascorbyl tetrahexyldecanoate.

(6) Sustainability evaluation of ascorbyl tetrahexyldecanoate The residual amount of ascorbyl tetrahexyldecanoate after evaluation for 1 month (30 days) was compared with the residual amount of ascorbyl tetrahexyldecanoate before the evaluation.
Evaluation was carried out by preparing a tengu, cutting off the fabric after dipping ascorbyl tetrahexyldecanoate into the tengu, sewing both ends into a cylindrical shape, and wrapping the wrist around the skin for 5 hours per day . The case where the residual amount was 95 to 100% before evaluation was evaluated as x, 70 to 95% as O, 50 to 69% as Δ, and 0 to 49% as X. The case where it became x was determined to be insufficient.
The method for quantifying tetratetrahexyldecanoic acid was the same as in (5).

(7) Scent Washing Durability Test For the method for washing the fabric, the 103 method described in JIS L 0217 “Handling Symbols and Display Methods for Textile Products” was used. The number of washing was evaluated at 10 times and 20 times, and the blank was set as 0 times. About the difference in fragrance, sensory evaluation was performed on the following evaluation scales for 10 subjects, and the total score was used.
2 points: A fragrance equivalent to or better than that of 0 washings is felt.
1 point: Although it is inferior to one with 0 washings, a scent is felt.
0 point: No scent is felt.
Less than 10 points were considered insufficient.

(8) Sustainability evaluation of fragrance Compared to unused one when left at a temperature of 25 ° C and a humidity of 50% for one month (30 days) On the other hand, sensory evaluation was performed on the following evaluation scale, and the total score was used.
2 points: A fragrance equivalent to or higher than that of an unused one can be felt even if left untreated for one month.
1 point: The one left for 1 month is inferior to the unused one, but the scent is felt.
0 points: No fragrance is felt when left untreated for 1 month.
Less than 10 points were considered insufficient.

(9) Evaluation of yarn-forming property The number of yarn breaks when spinning for 1 t each was evaluated according to the following criteria.
○: 2 times / t or less Δ: 2 to 4 times / t
X: The case of x over 4 times / t was determined to be insufficient.

(10) Coarse particle number in yarn After 5 cm of polyamide filament yarn is cut, melted and formed into a film, inorganic particles distributed in the polymer are captured as an image (magnification 1000 times) with a transmission microscope (TEM). The number of particles of 10 μm or more was obtained from the captured image, and expressed as the number of particles in 0.01 mm ² . The measurement was performed 5 times and the average value was adopted.

(11) Dyeing evaluation Spinning was performed by the method shown in the following examples, and the paper tube was wound up at 6.0 kg. The drum was wound every 100 g, and 60 child yarns were collected. Using the outermost child yarn as a blank, the presence or absence of a dyeing difference with the remaining 59 child yarns was evaluated. Evaluation was made by creating a tube knitting so that the blank yarn and the remaining 59 yarns were alternated, dyed in a water bath adjusted to 80 ° C. and pH 5.0 for 40 minutes, and evaluated by 5 people. When the person made a visual judgment and there was even one dyeing difference, it was marked as x. When the evaluations of five people were divided, a number of evaluations were adopted.
As a dye, 1% owf of Nylon Milling Blue N-GFL 167% (manufactured by Clariant Japan Co., Ltd.) was used.

Example 1
Silica powder (SYLYSIA530 manufactured by Fuji Silysia Chemical Co., Ltd.) was supplied using a table feeder as shown in FIGS. FIG. 7 is a schematic view of the table feeder. FIG. 8A is a schematic view of the inside of the powder storage tank of the table feeder of FIG. 7 as viewed from above, and FIG. 8B is a schematic view of the same from the side. FIG. 9A is a schematic view of the inside of the powder measuring tank of the table feeder as viewed from above. FIG. 9B is a schematic view of the same as viewed from the side. FIG. 9 (c) is an explanatory view showing the state of the cutting shears.
FIG. 10 is a schematic view of the stirring blades 11 and 13 installed in the horizontal direction when viewed from the direction of the arrow (B) in FIGS. 8 (a) and 9 (a). FIG. 11 shows the powder of the table feeder. It is the schematic which looked at the vertical direction stirring blade installed in the body storage tank from upper direction. This table feeder is a sealed table feeder having a powder storage tank 9 having a height of 200 mm and a diameter of 200 mm, a powder measuring tank 10 having a height of 100 mm and a diameter of 200 mm, and a powder supply cylinder 17 having an inner diameter of 50 mm. . Using this table feeder, the silica powder is contained in nylon 6 pellets having a relative viscosity (sulfuric acid relative viscosity) of 2.6 measured in a 100% sulfuric acid solution at 25 ° C. and 98% concentration so that the content becomes 3 wt%. Added continuously. The average particle diameter, specific surface area, and average pore diameter of silica were as shown in Table 1. In the powder storage tank 9 of the table feeder, a stirring blade 11 installed in a horizontal direction having a height of 8 mm, an angle e of 39 °, and a length of 95 mm, and a vertically standing portion having a height of 150 mm extend from the rotating shaft. It consists of a stirring blade 12 installed in a vertical direction having an angle of 75 ° with respect to a horizontal portion having a length of 95 mm. The powder measuring tank 10 has a height of 8 mm, an angle e of 39 °, and a horizontal length of 95 mm. The stirring blade 13 installed in the direction and the vertically standing portion of 80 mm in height are composed of the stirring blade 14 installed in the vertical direction of 90 ° with respect to a horizontal portion of 95 mm in length extending from the rotating shaft, A partition plate 18 having four openings 23 having a diameter of 20 mm was installed between the powder storage tank 9 and the powder measurement tank 10. The groove width of the table was 5 mm and the depth was 5 mm. The distance between the lowermost part of the powder supply cylinder 17 and the melting part 22 of the polyamide chip was 170 mm. The cutting rod 26 was installed so as to scrape off all the powder between the groove 24 and the measuring portion partition plate 25.

  In such a table feeder, silica added to nylon 6 pellets is melted at 260 ° C. with an extruder having a 65 mm double flight screw, discharged from the spinneret of FIG. 1 connected to the extruder, and cooled. Thereafter, 1% by weight of a water-containing emulsion oil was supplied, and after entanglement, 10% by weight of a water-containing emulsion oil was supplied, and then taken up by a roller at 4000 m / min, and then with a heating roller heated to 150 ° C. The film was drawn at a draw ratio of 1.2 times and wound at 4600 m / min to obtain a nylon 6 yarn having a round cross section of 78 dtex 52 filaments. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 1 time / t.

  Using this nylon 6 yarn, a tengu of 18 / cm well and 27 / cm course was prepared using a 32 gauge single circular knitting machine. The prepared tengu was immersed in an aqueous solution containing 10 wt% ascorbyl tetrahexyldecanoate adjusted to 80 ° C. and 7 wt% lanillin alcohol for 1 hour. After drying this, a washing durability test and durability evaluation were performed. The results are shown in Table 3. The amount of ascorbyl tetrahexyldecanoate was determined by placing the sample in an isopropanol solution and shaking at 37 ° C. for 2 hours, then measuring the supernatant with HPLC (high performance liquid chromatography), and determining the peak area of the resulting ascorbyl tetrahexyldecanoate. It was determined by dividing the peak area of ascorbyl tetrahexyldecanoate obtained from 10 or 20 samples by the peak area of ascorbyl tetrahexyldecanoate obtained from a sample with 0 washes.

Example 2
Silica powder (SYLYSIA310 manufactured by Fuji Silysia Chemical Co., Ltd.) was added to nylon 66 pellets having a relative viscosity of sulfuric acid of 2.6 using a table feeder similar to Example 1 so that the content was 5 wt%. The average particle diameter, specific surface area, and average pore diameter of silica were as shown in Table 1. This is melted with an extruder having a double flight screw of 65φ at 295 ° C., discharged from the die, cooled, supplied with 1% by weight of a water-containing emulsion oil, and after entanglement, 10% by weight of a water-containing emulsion oil is added. After refueling, it was taken up by a roller at 4120 m / min, then drawn to a draw ratio of 1.15 times with a heated roller heated to 180 ° C., wound up at 4600 m / min, and a round cross section of 78 dtex 52 filaments Nylon 66 yarn was obtained. The obtained nylon 66 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 1 time / t.

  Using this nylon 66 yarn, using a 32-gauge single circular knitting machine, a tengu with 18 wells / cm and 27 courses / cm was prepared. The prepared tengu was immersed in cypress extracted essential oil. After drying this, a washing durability test and durability evaluation were performed. The results are shown in Table 3.

Example 3
The addition concentration of silica powder (SYLYSIA530 manufactured by Fuji Silysia Chemical Co., Ltd.) to nylon 6 was 10 wt%, and other conditions were the same as in Example 1. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 3 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3.

Example 4
The addition concentration of silica powder (SYLYSIA740 manufactured by Fuji Silysia Chemical Co., Ltd.) to nylon 6 was 0.7 wt%, and other conditions were the same as in Example 1. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 2 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3.

Example 5
A 40% NaOH aqueous solution and aluminum hydroxide were mixed at a weight ratio of 3: 2 while being stirred, heated at 110 ° C. for 1 hour and then cooled to a composition of Na ₂ O: 21%, Al ₂ O ₃ : 28%. No. 3 water glass comprising Na ₂ O: 9.7% and SiO ₂ : 29.8% in a solution obtained by mixing sodium aluminate and 40% NaOH aqueous solution 1: 1. And an aqueous solution prepared by mixing a calcium chloride aqueous solution adjusted to 0.2% at a weight ratio of 2: 5, and the mixture was added dropwise and held at 80 ° C. for 2 hours. This was filtered, washed with water, and dried to obtain zeolite powder as shown in Table 1. This zeolite powder was added to nylon 6 pellets so that the content would be 3 wt% using a screw feeder as shown in FIGS. FIG. 14 is a schematic view of the screw feeder, FIG. 15 is a schematic view of the screw portion inside the screw feeder as seen from above, and FIG. 16 is an enlarged schematic view of the screw portion. As the screw feeder, a screw feeder comprising a powder storage layer 27 having a height of 300 mm and a diameter of 200 mm and a biaxial screw 28 operated by a motor 29 was used. The screw 28 consisted of two screws having a length of 300 mm and a diameter of 40 mm. Each screw had a groove with a groove width of 7 mm, and the pitch between the grooves was 1.5 mm. The distance between the screws was 2 mm. The zeolite powder charged into the powder reservoir 27 moves to the end of the screw from the 30 mm square opening 30 formed in the lower portion of the powder reservoir 27 and is transported to the screw tip by the screw. . The zeolite powder conveyed to the tip is discharged from a powder discharge port 31 that is 15 mm in the direction parallel to the screw and 40 mm in the direction perpendicular to the screw, and is added to the polyamide pellets. Other conditions were the same as in Example 1. The obtained polyamide yarn was measured for the dispersion state of zeolite and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 1 time / t. Tendon was prepared in the same manner as in Example 1, and washing durability and durability evaluation were performed. The results are shown in Table 3.

Example 6
Silica powder (SYLYSIA530 manufactured by Fuji Silysia Chemical Co., Ltd.) was added to nylon 66 pellets having a relative viscosity of sulfuric acid of 2.6 using a table feeder similar to Example 1 so that the content would be 1 wt%. The average particle diameter, specific surface area, and average pore diameter of silica were as shown in Table 1. This is melted with an extruder having a double flight screw of 65φ at 290 ° C, discharged from the die, cooled, supplied with 1 wt% water-containing emulsion oil, and after entanglement, 10 wt% water-containing emulsion oil is added. After refueling, it was taken up by a roller at 4120 m / min, then drawn to a draw ratio of 1.15 times with a heated roller heated to 180 ° C., wound up at 4600 m / min, and a round cross section of 78 dtex 52 filaments Nylon 66 yarn was obtained. The obtained nylon 66 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 1 time / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3.

Example 7
Instead of the table feeder used in Example 1, the stirring blades 11 and 13 installed in the horizontal direction are 8 mm high, 10 mm wide, and 95 mm long as shown in FIG. As shown in FIG. 13, the vertical agitating blade 14 installed in the measuring tank is 90 ° with respect to a horizontal portion of 95 mm in length extending from the rotating shaft, except that it has a powder supply cylinder with an inner diameter of 50 mm. Using the same table feeder as in Example 1, nylon 6 yarn was obtained in the same manner as in Example 1 under other conditions. FIG. 12 is a schematic view of the stirring blades installed in the horizontal direction installed in the powder storage tank and powder measuring tank of the table feeder as seen from the direction of the arrow (B) in FIGS. 8 (a) and 9 (B). FIG. 13 is a schematic view seen from above the vertical stirring blade installed in the powder storage tank of the table feeder.

  The obtained nylon 6 yarn was dispersed in silica and the number of coarse particles was measured, and dyeing evaluation was performed. The results are shown in Tables 1 to 3. The spinning performance was 2 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3.

Comparative Example 1
The addition concentration of silica powder (SYLYSIA530 manufactured by Fuji Silysia Chemical Co., Ltd.) to nylon 6 was 15 wt%, and other conditions were the same as in Example 1. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 6 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3. The spinning performance in melt spinning was poor, resulting in insufficient results.

Comparative Example 2
The addition concentration of silica powder (SYLYSIA530 manufactured by Fuji Silysia Chemical Co., Ltd.) to nylon 6 was 0.3 wt%, and other conditions were the same as in Example 1. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 0 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3. The result was insufficient washing durability.

Comparative Example 3
Example 1 was performed except that nylon 6 of silica powder (SYLYSIA770 manufactured by Fuji Silysia Chemical Co., Ltd.) was added. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 8 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3. The spinning performance in melt spinning was poor, resulting in insufficient results.

Comparative Example 4
Example 1 was performed except that nylon 6 of silica powder (SUNSPHERE H-53 manufactured by Asahi Glass Co., Ltd.) was added. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was insufficient at 6 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3. The result was insufficient washing durability.

Comparative Example 5
The same procedure as in Example 1 was performed except that nylon 6 of silica powder (SUNSPHERE NP-30 manufactured by Asahi Glass Co., Ltd.) was added. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 4 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3. Washing durability and durability evaluation were insufficient.

Comparative Example 6
Using the table feeder used in Example 1, the powder used in Example 1 was added to polyethylene terephthalate pellets having a relative viscosity of 1.3 so that the content was 3 wt%, and this was 65 φ at 290 ° C. Melted with an extruder with a double flight screw, discharged from the die, cooled, lubricated, entangled, taken up by a roller at 4050 m / min, and drawn with a heated roller heated to 180 ° C. with a draw ratio of 1.2 The film was stretched by a factor of 2, and wound at 4500 m / min.

  A polyethylene terephthalate yarn having a round cross section of 78 dtex 52 filaments was obtained. In the obtained polyethylene terephthalate yarn, the dispersion state of silica and the number of coarse particles were measured, and dyeing evaluation was performed. The results are shown in Tables 1-3. The spinning property was 2 times / t.

  Using this polyethylene terephthalate yarn, using a 32 gauge single circular knitting machine, a well with 20 wells / cm and a course with 29 strands / cm was prepared, and the washing durability test and sustainability were performed in the same manner as in Example 1. Sex assessment was performed. The results are shown in Table 3. Washing durability and durability evaluation were insufficient.

Comparative Example 7
A slurry in which silica powder (SYLYSIA 530 manufactured by Fuji Silysia Chemical Co., Ltd.) was dispersed was melt-mixed with nylon 66 pellets to obtain a 10% by weight silica-containing master chip. This silica-containing master chip and nylon 6 pellets are mixed at a weight ratio of 1: 9, melted at 290 ° C. in a pressure melter type melt spinning machine, discharged from the die, cooled, and then cooled to 1% by weight. Emulsion oil is supplied, entangled, 10% by weight of water-containing emulsion oil is supplied, then taken up by a roller at 4120 m / min, and then drawn to 1.15 times with a heated roller heated to 180 ° C. And was wound at 4600 m / min to obtain a nylon 66 yarn having a round cross section of 78 dtex 52 filaments. The obtained nylon 66 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning performance was insufficient at 5 times / t. A tengu was prepared in the same manner as in Example 1, and a washing durability test and durability evaluation were performed. The results are shown in Table 3. As a result, the spinning performance, dyeing evaluation, and washing durability were insufficient.

Comparative Example 8
30 kg of silica powder (SYLYSIA530 manufactured by Fuji Silysia Chemical Co., Ltd.) and 970 kg of nylon 6 pellets having a relative viscosity (sulfuric acid relative viscosity) of 2.6 measured in a 100% sulfuric acid solution at 25 ° C. and 98% concentration. Is melted with an extruder having a double flight screw of 65φ at 260 ° C, discharged from the mouthpiece, cooled, supplied with 1 wt% aqueous emulsion oil, and after entanglement, 10 wt% aqueous emulsion oil was added. After refueling, it was taken up by a roller at 4000 m / min, stretched at a draw ratio of 1.2 with a heated roller heated to 150 ° C., wound up at 4600 m / min, and a round cross section of 78 dtex 52 filament Nylon 6 yarn was obtained. The obtained nylon 6 yarn was measured for the dispersion state of silica and the number of coarse particles, and was evaluated for dyeing. The results are shown in Tables 1-3. The spinning property was 4 times / t. The silica concentration in the polyamide filament yarn was as low as 2.7 wt%, the variation in the silica concentration in the fiber length direction was large, and the dyeing evaluation was insufficient.

  As can be seen from the results shown in Tables 1 to 3, the method of the present invention makes it possible to produce a polyamide yarn having fine pores that improve the durability of the functional drug with good spinning properties.

It is an example of the process figure used for manufacturing the polyamide filament yarn which this invention provides. It is an example of the table feeder preferably used by this invention. Fig.3 (a) is the schematic which looked at the example of the inside of the powder storage tank of a table feeder from upper direction, and FIG.3 (b) is the schematic which looked at it from the side. FIG. 4A is a schematic view of an example of the inside of the powder measuring tank of the table feeder as viewed from above, and FIG. 4B is a schematic view as viewed from the side thereof. FIG.4 (c) is explanatory drawing which showed the mode of the cutting hook. FIG. 5A is a schematic view of an example of a stirring blade installed in the horizontal direction of the table feeder as viewed from above, and FIG. 5B is a view of the arrows (11) of the stirring blade 11 or 13 in FIG. FIG. 5C is a schematic diagram showing another example of the stirring blade viewed from the direction of arrow A of the stirring blade 11 or 13 in FIG. 5A. is there. Fig.6 (a) is the schematic which looked at an example of the stirring blade installed in the perpendicular direction of the table feeder from upper direction, and FIG.6 (b) is the schematic which looked at it from the side. It is the schematic of the table feeder used in Examples 1-4, Examples 6-7, and Comparative Examples 1-6. FIG. 8A is a schematic view of the inside of the powder storage tank of the table feeder of FIG. 7 as viewed from above, and FIG. 8B is a schematic view of the same from the side. FIG. 9A is a schematic view of the inside of the powder measuring tank of the table feeder as viewed from above. FIG. 9B is a schematic view of the same as viewed from the side. FIG. 9 (c) is an explanatory view showing the state of the cutting shears. It is the schematic of the stirring blades 11 and 13 installed in the horizontal direction when it sees from the arrow (B) direction of Fig.8 (a) and Fig.9 (a). It is the schematic which looked at the vertical direction stirring blade installed in the powder storage tank of the table feeder used in Examples 1-4, Example 6, and Comparative Examples 1-6 from the upper direction. It is the schematic of the stirring blade installed in the horizontal direction installed in the powder storage tank and powder measuring tank of the table feeder seen from the arrow (B) direction in FIG. 8 (a) and FIG. 9 (B). It is the schematic seen from the upper direction of the vertical direction stirring blade installed in the powder storage tank of the table feeder used in Example 7. FIG. 6 is a schematic view of a screw feeder used in Example 5. FIG. It is the schematic which looked at the screw part inside the screw feeder of FIG. 14 from the top. FIG. 16 is an enlarged schematic view of the screw portion of FIG.

Explanation of symbols

1: Melting zone (spin block)
2: Cap 3: Cooling air device 4: Oil supply device 5: Entangling device 6: Cold roller 7: Hot roller 8: Winder 9: Powder storage tank 10: Powder metering tank 11: Stirring installed in the horizontal direction Blade 12: Stirring blade installed in the vertical direction 13: Stirring blade installed in the horizontal direction 14: Stirring blade installed in the vertical direction 15: Rotating shaft 16: Motor 17: Powder supply cylinder 18: Partition plate 19: Table 20: Piping of polyamide chip 21: Spinning hopper 22: Melting part 23: Opening (powder passage)
24: Groove 25: Metering part partition plate 26: Cutting rod 27: Powder feeder powder storage tank 28: Screw 29: Motor 30: Opening 31: Powder discharge port

Claims (8)

The specific surface area is 200 to 1000 m ² / g, the average pore diameter is 1 to 25 nm, the average particle diameter is 0.1 to 5 μm, and the content of the inorganic particles having micropores is 0.5 to 10 wt%. A blended polyamide filament yarn characterized by satisfying all of (1) to (4).
(1) Concentration _{D i} of the inorganic particles having fine pores at any five points of the fiber length direction of the polyamide filament yarn is _{0.8D a <D i <1.2D a} .
However, D _i is the concentration at any point, the D _a shows the mean concentration.
(2) In the cross section of the polyamide filament yarn, when divided into two segments, a segment near the center of the fiber cross section and a segment near the outer periphery, and measuring the concentration of inorganic particles having fine pores in each segment, When the concentration of inorganic particles having fine pores of high-concentration segments is D _b and the concentration of inorganic particles having fine pores of low-concentration segments is D _c , D _b <1.2D _c .
(3) The number of coarse particles of 10 μm or more is 3 or less in 0.01 mm ² .
(4) When the weight distribution when the weight distribution with respect to the particle diameter of the inorganic particles having fine pores is 50% and 75%, respectively, is U ₁ and U ₂ , U ₂ −U ₁ <2 μm. The polyamide filament yarn according to claim 1, wherein the inorganic particles having fine pores are silica. The polyamide filament yarn according to claim 1 or 2, which contains a functional drug. A method for producing a thermoplastic filament yarn, wherein inorganic particle powder having fine pores is continuously added to a thermoplastic resin pellet in front of a melting part. Into the thermoplastic resin pellet, an inorganic particle powder having fine pores having a specific surface area of 200 to 1000 m ² / g, an average pore size of 1 to 25 nm, and an average particle size of 0.1 to 5 μm is provided in front of the melting part. A method for producing a thermoplastic filament yarn, characterized by being continuously added. The method for producing a thermoplastic filament yarn according to claim 4 or 5, wherein the inorganic particle powder having fine pores is measured by a table feeder having the following configuration.
(1) The table feeder is sealed so that the internal pressure of the table feeder is the same as the internal pressure of the spinning hopper.
(2) It consists of two tanks with the powder storage tank at the top and the powder weighing tank at the bottom, and each tank has two types of stirring blades with the center of the tank as the rotation axis. Is a stirring blade that is attached perpendicularly to the rotating shaft and has a structure that decreases in thickness toward the rotating direction, and the other stirring blade has a stirring blade that extends vertically on the outer periphery of the tank.
(3) It has a powder supply cylinder having an inner diameter of 10 to 200 mm. The method for producing a thermoplastic filament yarn according to any one of claims 4 to 6, wherein the thermoplastic resin is polyamide. The method for producing a thermoplastic filament yarn according to any one of claims 4 to 7, wherein the inorganic particles having fine pores are silica.

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