TW201241251A - Leather core type composite fiber having dyeing property, manufacturing method thereof and clothes utilizing the same - Google Patents

Abstract

An object of the invention is to provide a leather core type composite fiber capable of showing excellent dyeing property without damaging the light-weight feature of polyolefin such as polypropylene, polyethylene and the like. The leather core type composite fiber of the invention is produced from polypropylene, which is obtained by melting and blending polypropylene with nanometer fine spherical powder, and other polypropylenes by performing leather core composite spinning, hot drawing, shaping, rolling and processing based upon a specific weight percentage. The leather core composite fiber of the invention has good spinning property, excellent dyeing property and light weight properties.

Description

[Technical Field] The present invention relates to a skin type composite fiber, and more particularly to a skin type composite fiber which has both spinnability and excellent dye fastness. Further, the present invention also provides a method for producing the composite fiber and a garment made of the fiber. [Prior Art] Polyolefin fibers are widely used in ropes, bundled yarns, filter materials, wipers, diapers, and physiological products because of their excellent light weight, strength, and chemical resistance. However, the polyolefin-based fiber is lightweight, has excellent chemical properties, and does not have sufficient dyeability. In addition, when it is applied to non-clothing materials such as paper and non-woven fabrics, it is also insufficient in dyeability, and it cannot be applied in fields requiring subtle color matching. Among them, the polypropylene structure is difficult to color because it is highly regular and does not contain polar groups. A polyolefin fiber which is simply added by a color masterbatch for the purpose of coloring cannot be diversified in color. Although a raw material can be obtained by mixing a pigment, it is difficult to form a subtle color matching, and the color is dyed by a dye. Since the diversification is beneficial, there have been many research proposals for imparting dyeability to polyolefin fibers. For example, a conventional technique proposes a method of mixing or compounding a polyester or a polyamine having dyeability with a polyolefin polymer and then subjecting it to fiberization. In this case, the dyeability is improved, but since the polyolefin is incompatible with the polyester or the polyamine, peeling or staining at the interface occurs, and the difference in melting point is large, resulting in poor spinnability, so that it is not practical. 201241251 National Invention Patent Publication No. 561208 t refers to block copolymerization using a polymer block (B) composed of a polymer block (A) and a (meth)acrylic monomer unit of an olefin monomer unit. The material is used to improve the dyeability, but there is a problem that the manufacturing cost is too high and it is not practical. In addition, 曰本本表平1〇_5〇13〇9 bulletin proposes a method of mixing or grafting ethylene/acrylic acid alkaloids with polyacrylamide, but the dyeability is still not fully satisfied. To the point. The Journal of Textile Research (No. 2, Vol. 20, No. 2, pp. 2) mentions the dyeing of polypropylene and polyester, and the addition of the first-line to the wounded polypropylene-glycol maleic anhydride as a compatibilizer. In order to improve the compatibility of polypropylene and (4) blends, although the color of the dispersion is good for the dispersion, the specific gravity is 1.38, so it is still compared with the fiber material of the polypropylene-like weight ratio of 〇.9. The problem of overweight products and light weight of legal claims is to be solved ^ ^ m to solve the problem of polyacrylonitrile dyeing, the main method Γ Γ Γ = 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Considering the amount of environmental considerations, environmental protection, etc., there is currently no large-scale AS: method. Because the polypropylene is used as a catalyst for polymerization, the object of the present invention is to provide a method for producing a mixture of color and color. The fibrous core of the fiber caused by the thin fiber can eliminate the phase separation and have good spinnability, light weight and excellent dyeing fiber [invention] cattle. 201241251 The inventors of the present invention have actively researched and developed lightweight fibers having commercial value and good spinnability and superior dyeability in view of the lack of existing polyolefin fiber products. According to the present invention, there is provided a dyeable skin-like composite fiber having a specific gravity of less than 1. 〇g/cm3; wherein the fiber is composed of a skin layer and a layered layer, the skin layer being composed of It is composed of polypropylene, and the core layer is composed of polypropylene in which nano-microsphere powder is dispersed, and the average particle diameter of the nano-microsphere powder in the polypropylene is more than μ3 μmη and less than 50 μm. Further, according to the present invention, there is provided a method for producing a dyeable skin-type composite fiber; which is obtained by the following steps: (1) - 50 to 95 parts by weight of polypropylene and 5 to 5 After uniformly mixing the nano-microsphere powders of the bismuth parts, the blending temperature is 18 〇 25 25 (rc is subjected to screw blending, and then granulated to obtain a polypropylene having uniform dispersion of the nanosphere powder. And (2) such that the polypropylene (Β) and the above-mentioned polypropylene (Α) are melt-extruded at a spinning temperature of 180 to 260 C from an extruder having a Pipir-type cross-section spinning nozzle Polypropylene (Β) is used as the skin layer, polypropylene (Α) is used as the core layer and the compounding ratio is 80: 20~20: 8〇, and the spinning is performed at a spinning speed of 2000~4000m/min to obtain the skin-like composite. In addition, according to the present invention, there is provided a method for producing a skin-reducing composite fiber having dyeability; which is obtained by the following steps: (1). 50 to 95 parts by weight of polypropylene and 5 After mixing and mixing the nano-microsphere powder of ~5〇 parts by weight, the blending temperature is 18〇~25〇. (:The screw is extruded after the 201241251 blending, Saki Polypropylene (Α) having a Μ microsphere powder entangled dispersion; and (2) such that the propylene (Β) and the above poly propylene (Α) are melted and extruded at a spinning temperature of 180 to 26 GC Next, from the extruder with the Pirin-type cross-section spinning nozzle, the polypropylene layer is used as the cortex, the poly-(Α) is the core layer, and the complex s ratio is 8G · 2G~2G. 8Q is extruded, and then spun. The speed of 2_~35()()m/min is taken up to obtain the pebbled composite fiber as the undrawn yarn, and the temperature of the hot plate is, for example, 1 〇〇 to 2 〇〇. In addition, the manufacturing method of the above two kinds of skin-type composite fibers can also be used in step (1) to make polypropylene and nano-microsphere powders further added (for example, after adding The maleic anhydride grafted polypropylene compatibilizer is uniformly mixed in the total amount of 5% by weight or less of the mixture, and then subjected to subsequent processes such as blending, extrusion, pelletizing, etc. Further, according to the present invention, it is possible to provide a use of the above The skin-type composite fiber is used to produce a garment that is lightweight and has good dyeability. It is possible to provide a skin-type composite fiber having a skin layer and a core layer. When the skin-like composite section of the present invention is spun, since the skin layer is polypropylene, the phase separation of the polymer interface between the skins can be improved. The problem of poor spinnability and bundling property is obtained, and the dyeability of the present invention is excellent, and the problem that the conventional polyolefin-based fiber cannot be dyed can be solved. [Embodiment] The dyeable skin-type composite fiber of the present invention, fiber The specific gravity is small 201241251 at 1.0 g/cm 'characteristically, the fiber is composed of a skin layer and a core layer, and the skin layer is composed of polypropylene (B), which is composed of nanospheres dispersed therein. The powder is composed of poly (4), and the nano-microsphere powder has an average particle diameter of more than 0 3 μηι less than 5 〇. The "skin-type composite fiber" referred to in the present invention is obtained by extruding a core fiber as a coating layer and a skin fiber as a coating layer through an extruder having a specific section spinning nozzle; The term "skin type" as used herein, except that the core layer fiber is located in the center of the inner layer in a single beam, and the concentric structure of the outer layer of the cortical fiber (as shown in Fig. ,), the core layer is also included in the bundle. The method is dispersed in the cortical fiber (as shown in Fig. illusion. In addition, the cross-sectional shape of the composite fiber of the present invention may be selected from a triangular shape, a multi-leaf shape, a quadrangular shape, a cross shape, or the like. See the example of Figure 3. The composite fiber has a specific gravity of less than 丨〇g/cm3, preferably less than 〇99 g/cm, and more preferably less than 〇97. 'The nanosphere microsphere powder constituting the core layer may be selected from polystyrene or two kinds in addition to polymethyl methacrylate. The present invention is characterized in that phthalocyanine phthalate and the like are used. Rice microsphere powder is uniformly dispersed in a dispersed phase The polypropylene is formed into a spherical body in the continuous phase, and the average particle diameter thereof is preferably less than 50 μm. When the average particle diameter of the dispersed phase is more than 5 〇μπι, the spinning property is affected and the hairiness is easily formed in the latter stage, resulting in difficulty in production quality. Preferably, the average particle size is less than 20 μm. On the other hand, the average particle size is recommended to be greater than 0.3 μm. The reason is that if the average particle size is smaller than that of the 〇3 division, the 7 201241251 nanosphere powder is in the mixing process. It is prone to agglomeration and produces large-sized agglomerates, which may adversely affect the subsequent spinning properties. The particle size of the dispersed phase of the nanospheres can be measured by the melted polymer extruded from the extruder. The granules are cut and observed by an electron microscope to determine the particle size. The melt index (hereinafter referred to as MFR) of the polypropylene used in the skin layer and the core layer of the present invention is between 1 〇 6 6 g/l 〇 min. When the propylene melt index is less than 10g/10min, the nanosphere powder is easily dispersed unevenly. When the polypropylene smelting index is higher than 60g/l Omin, the fluidity is high, so that the viscoelasticity is insufficient and the yarn is easily broken. Lead to spinning Poor property. The polypropylene melt index is optimal between 20~40 g/l〇min. The MFR test method is tested by ASTM D-1238 test method with the measured temperature of 23 ° C and the load of 2.16 kg. The MF R value of the core layer can be arbitrarily adjusted as needed within the above range, and is not particularly limited. The nanofiber powder contained in the core layer of the composite fiber of the present invention, when the content thereof exceeds 50% by weight Then, the average particle diameter of the nanosphere powder which exists in the form of a dispersed phase in the polypropylene is increased and agglomerated, so that the dispersion effect is not satisfactory, thereby affecting the phase property of the whole polymer. On the other hand, when When the content of the nanosphere powder in the core layer is less than 5% by weight, and the content of the composite fiber as a whole is reduced to 3% by weight or less by the composite spinning, the dyeing property is lowered, and the man-made fiber cannot be obtained. The degree of dyeing required for commercialization. That is, the content of the nanosphere powder relative to the composite fiber as a whole has a direct influence on the dyeing property of the composite fiber. When the content of the nanosphere powder relative to the composite fiber is less than 3% by weight, the content of the composite fiber is less than 3% by weight. The dyeing performance of the composite fiber will be significantly reduced, resulting in the dyeing of the braid being too light. As the nano-microsphere powder content increases, its dyeing and coloring performance increases. However, when the content of the nanosphere powder relative to the entire composite fiber is more than 20% by weight, the composite fiber may have a tendency that the physical strength is lowered and the spinnability is deteriorated. The preferred nanosphere powder content is 5 to 17% by weight of the composite fiber as a whole, and the optimum nanosphere powder content is 5 to 15% by weight of the composite fiber. In the composite fiber of the present invention, the composite ratio of the skin layer to the core layer is between 80/20 and 20/80. If the proportion of cortex is less than 20%, the cortex cannot completely cover the core layer, which is easy to be damaged, which affects the spinning operation. On the other hand, if the ratio of the core layer is less than 20%, the content of the nanosphere powder is relatively increased. It is also not conducive to spinning workability. Further, the composite ratio is preferably 65/35 to 30/70, and most preferably 45/55 to 35/65. In the present invention, the polypropylene composite fiber as the skin layer may be a long fiber or a short fiber. In the present invention, a stabilizer, a UV absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, or the like may be added during the blending or in the subsequent steps, without affecting the purpose or effect thereof. Plasticizers, lubricants, heat stabilizers, etc., to increase their special functionality. The polypropylene of the skin layer and the polypropylene layer of the gel layer may also be added with at least one of the following particles: 0.5 to 3% by weight, such as inert particles such as cerium oxide, aluminum oxide, titanium oxide, calcium carbonate or barium sulfate. The composite fiber of the present invention is used for clothing, and its single root (*referred to as dpf 'danny divided by the number of 'such as 7〗 / 36 dpf = 2. 〇 8) fiber Dani number should be below 201241251 5d 'below 3d It is preferable to use 2 (1 or less. The polypropylene fiber as the base material of the present invention is inherently lightweight, and can additionally impart dye-dyeing effect to the polypropylene fiber. A method for producing a skin-type composite fiber according to the present invention. A method for producing a skin-reducing composite fiber having dyeability (hereinafter also referred to as a first production method of the present invention); which is obtained by the following steps: 1). 50 to 95 parts by weight of polypropylene and 5 to 5 parts by weight of the nanosphere powder are uniformly mixed, and then subjected to screw blending at a blending temperature of 18 〇 25 25 〇 1 for extrusion and pelletizing. Polypropylene (A) having a uniform dispersion of nanosphere powder; and (2) are obtained. The polypropylene (B) and the above polypropylene (A) are melt-extruded at 180 to 260. (: At the spinning temperature, the extruder with the Pipiral-type cross-section nozzle has polypropylene (B) as the skin layer and polypropylene as the core layer and the composite ratio. Extrusion at 80:20 to 20:80, and coiling at a spinning speed of 2000 to 400 〇m/min to obtain a skin-type conjugate fiber. The polypropylene used in the production of the above polypropylene (A) may be in the form of granules. It may be pulverized or pulverized, and these shapes may be used singly or in combination of two or more kinds, and a nano-microsphere powder such as polymethyl methacrylate or a suitable amount of a compatibilizing agent may be further added as appropriate (for example) The maleic anhydride grafted polypropylene compatibilizer is premixed, then blended and blended, and the blending temperature is carried out by a twin-screw kneading machine, a single-screw kneading machine, a twin-screw extruder or a single-screw extruder. Controlled between 18 〇 and 25 〇. 〇, preferably extruded between 201241251 and 200 to 240 ° C, and pelletized to obtain polypropylene (A) having nanosphere powder. According to the present invention The polypropylene (A) having a nanosphere powder as a core layer produced by the first manufacturing method can be produced by a known melt spinning device in the process of composite spinning with the polypropylene (B) as a skin layer. Specifically, it is a dyeing property of polypropylene (B) and nanosphere powder. Propylene (A), which is melt-extruded in an extruder with a Pirin-type composite spinning nozzle to form a Pipirite fiber. Spinning with a Pirin-type composite section improves the spinning of the polymer interface due to phase separation. The problem of poor property and clustering property. The yarn of the composite fiber sprayed from the spinning nozzle can be processed without being stretched and shaped, that is, after being wound up at a high speed, if necessary, it can be stretched, shaped, and wound at a south speed. , the processing or direct use, wherein the melt spinning method, according to different equipment, can produce polypropylene spun drawn yarn or polypropylene undrawn yarn and then false twisted to obtain polypropylene false twist processing silk, The polypropylene spun drawn yarn can also be subjected to air false twisting to obtain a polypropylene false twisted textured yarn. Specifically, the composite fiber production step of the first manufacturing method of the present invention is such that the polypropylene (B) and the polypropylene (A) having the nanosphere powder have a composite ratio of 80:20 to 20:80. The method is carried out by metering and polymer-conducting, and is respectively melted and extruded through an extruder having a skin-type cross-section spinning nozzle. At this time, the spinning temperature is controlled at 180 to 260 ° C, and then cooled and solidified by air cooling. The oil was then taken up at a spinning speed of 2000 to 4000 m/min to obtain a desired composite fiber. In addition, the composite fiber can be stretched at a stretching temperature of 50 to 1 HTC and a draw ratio of 4.5 to 1.5 times, and then set at a setting temperature of 80 to 150 ° C at 201241251, and then at a spinning speed of 2000 to 4000 m/ Min was taken up to obtain a polypropylene spun drawn yarn having a nanosphere microsphere powder content of 5 to 20% by weight based on the entire composite fiber. This spun drawn yarn can be further subjected to air false twisting to obtain a false twisted textured yarn. In the present invention, the blending temperature is controlled between 180 and 250 eC. The reason is that if the blending temperature is less than 180 ° C, the dispersibility of the microsphere powder in the polypropylene is poor, and aggregation tends to occur to form a large-sized dough to affect spinning. On the other hand, if the blending temperature is greater than 250 ° C, it is necessary to increase the energy cost, which is contrary to the current trend of energy saving. The blending temperature is also optimal at 200~240 °C. As described above, in the present invention, it is also possible to add an appropriate amount (for example, 5% by weight or less relative to the total amount of the mixture after the addition) of a compatibilizing agent (for example, maleic anhydride grafting) while mixing the polypropylene and the microsphere powder. Polypropylene compatibilizer) 'is more suitable for the compatibility of polypropylene and nano microsphere powder, which is more conducive to spinning workability and processing workability. Further, in the present invention, the spinning temperature is controlled at 180 to 260. (: The reason is that if the spinning temperature is lower than 18 〇ΐ, the fluidity of the polymer is insufficient, the spinning valley is easy to break; on the other hand, if the spinning temperature is higher, the viscoelasticity of the polymer is insufficient, and it is easy to break. The wire causes poor spinnability and increases energy cost. The spinning temperature is preferably from 2 to 25 Torr, and most preferably from 210 to 240 ton. In the present invention, the stretching temperature is controlled at 50 to 1 UTt. It is that when the temperature is lower than 5 〇, the monofilament is easily broken during the stretching process;

12 201241251 On the other hand, when the stretching temperature is higher than the litol:, it is easy to produce a silk shake, which affects the spinnability. In the present invention, the draw ratio is controlled to be 4.5 to 1.5 times, which is mainly adjusted in accordance with the elongation at break of the composite fiber. In the present invention, the 'setting temperature is controlled at 80 to 150 °C. The reason is that when the setting temperature is lower than 80 ° C, the monofilament is easily broken and the filament is many. On the other hand, when the setting temperature is higher than 150 ° C, the fiber is liable to cause glare on the heat. In general, too high or too low setting temperatures are detrimental to manufacturing management and affect spinning. In the present invention, the spinning speed is controlled at 2000 to 4 m/min. The reason for this is that if the spinning speed is less than 2 〇〇〇m/min, the production is still satisfactory. On the other hand, if the spinning speed is more than 4 〇〇〇m/min, the yarn breaking rate is improved and the spinning property is deteriorated. Further, the spinning speed is preferably controlled at 2500 to 3500 m/min', and the optimum control is 2600 to 3300 m/min. A method for producing a dyeable skin-type composite fiber of the present invention (hereinafter also referred to as a second production method of the present invention); which is obtained by the following steps: (1) . 50 to 95 The parts by weight of the polypropylene are uniformly mixed with 5 to 50 parts by weight of the nanosphere powder, and the blending temperature is 180 to 250. (: extrusion and granulation after screw blending to obtain polypropylene (A) having a uniform dispersion of nanosphere powder; and (2). The polypropylene (B) and the above polypropylene (A) are melted. The extrusion method is from the extruder with the skin type cross-section spinning nozzle at the spinning temperature of 180~260 °C, the polypropylene (B) is the skin layer, the polypropylene (A) is the core layer and the composite 13 201241251 ratio It is broadcasted at 80:20~20:80, and then taken up at a spinning speed of 2500 to 3300 m/min to obtain a skin-type composite fiber as an undrawn yarn, and then subjected to a hot plate temperature of 1 〇〇 to 230 Ϊ. The crucible-type composite fiber is obtained as a false twisted textured yarn. The process conditions related to the step (1) in the second manufacturing method of the present invention are the same as those described in the first manufacturing method of the present invention. The step (2) of the second manufacturing method of the present invention is such that polypropylene (β) and polypropylene having a nanosphere powder are obtained to achieve 80:20 to 20:80. The compounding method is used for metering and polymer guiding, and is respectively melted and extruded through an extruder having a skin-type cross-section spinning nozzle. The temperature of the wire is controlled at 180 to 260 ° C, and then cooled and solidified by air cooling, and oiled, and then taken up at a spinning speed of 2000 to 3500 m/min to obtain a skin-type composite fiber as an undrawn yarn. 100 to 200. The false twisting and false twisting processing results in a false twisted textured yarn. The spinning speed in the first manufacturing method of the present invention is controlled at 2000 to 3500 m/min, because the spinning speed is less than 2000 m/min. 'The manufacturing cost is high; on the other hand, if the spinning speed is more than 3500m/min', the appearance of the silk cake is not good, the processing process is prone to poor yarn output and affects the processability. The spinning speed is preferably controlled at 2500~3300m/min. 'The optimum control is 2600~3〇〇〇m/min. The invention can be stretched from the spinning nozzle regardless of whether the first manufacturing method or the second manufacturing method is used for stretching. Immediately stretching, or subsequently performing stretching, the present invention is applicable to any of the above methods. 201241251 The stretching can be carried out by usual hot stretching, hot plate drawing, hot stretching, etc. Hereinafter, specific examples are given. Illustrating the invention, but the invention is not In addition, in the present invention, the physical properties of the obtained product were measured and evaluated according to the following methods: 1. Spinning was continuously performed at 24 hours, and the number of broken wires during spinning was repeated. It is evaluated in the following three stages: 0 to 3 times △: 4 to 8 times X: 8 times or more 2. Dispersed phase particle size measurement The polypropylene particles containing the nanosphere powder as the core layer are sliced and used The microscope is magnified 1000 times, and the average particle diameter of the nano-microsphere powder is measured. 3. After the fiber specific gravity is sufficiently removed from the non-fibrous material and moisture, the fiber is left to stand in a suitable solution of known specific gravity for 24 hours. The specific gravity of the fiber was tested according to the proportion of its appearance. 4. Dyeability The obtained spun drawn yarn or false twisted yarn was dyed with a disperse dye at 130 ° C for 40 minutes, and then subjected to reduction washing, water washing, and drying to visually evaluate the dyeability. . The dyeing visual evaluation was carried out in the following four stages.

15 S 201241251 χ :Stained light and stripy △: Stained light 〇: expected dyeing effect ◎: Deep dyeing effect 5. Color fastness Tested by ASTMATAC 61-2006 2A Method Reference Example 1 Take 50 parts by weight of polypropylene and 48 Parts by weight of polydecyl methacrylate micropowder particles and adding 2 parts by weight of polypropylene grafted maleic acid needle for premixing, blending in a extruder at a blending temperature of 21 (TC), then extruding and pelletizing To obtain a dye-containing polypropylene granule (A) containing a polymethyl acrylate methacrylate. Example 1 (I). Method for producing polypropylene granules (A) having dyeing properties. 81 parts by weight After propylene is premixed with 19 parts by weight of polymethyl group and fine powder spheres, it is blended in an extruder at 910 〇r, .y ^ at a blending temperature of 210 C, and then extruded and pelletized to obtain The average particle size of the dyed polyacrylic acid 3 2 micron powder spheres is 15 μηι. “No (2). Method for producing polypropylene composite fibers with dyeing properties. Polypropylene (Β) and Containing polymethyl methacrylate

St: granules (Α)' after being smelted separately by the extruder, the polymer ^ = silk head, with a composite ratio of 5 〇: 5 〇 i 皮蕊 c·' 敎 5 m / s cooling wind and cold phase formation 201241251 Acrylic yarn, and then stretched at a stretching temperature of 70 ° C and a draw ratio of 2.6 times, and then fixed at a temperature of 130 ° C and then coiled at 3500 m / min to obtain a polymethyl methacrylate containing The content of the ester nanosphere powder relative to the composite fiber as a whole was 9.5 wt/yf 75d/36f polypropylene spun drawn yarn (SDY). The obtained dyed polypropylene conjugate fiber was woven as a woven base material by a garter machine, and dyed using a disperse dye under the dyeing conditions of 130 ° C * 40 minutes. The dyed woven substrate is darkly colored and has a dye fastness of 4 to 5 or more (see Table 1). Example 2 (I) Method for producing dyeable polypropylene granules (A): 80 parts by weight of polypropylene and 19 parts by weight of polymethyl methacrylate micropowder spheres were added and 1 part by weight of polypropylene grafted Malay was added. The acid anhydride was pre-mixed and then blended in a extruder at a blending temperature of 2 μ〇〇c, and then extruded and pelletized to obtain a dye-containing polypropylene containing 19% by weight of polymethyl methacrylate. Granule (A), wherein the nanofine powder sphere has an average particle diameter of 13 μηι. (2) Method for producing dyed polypropylene composite fiber: Polypropylene (Β) and polypropylene pellet (Α) containing polymethyl methacrylate nanosphere powder are used as an extruder After melting separately, the polymer is diverted to the spinning powder, and the composite ratio of 50:50 is sprayed from the skin-type cross-section nozzle at 250 C to cool down and solidify the oil through a cooling air of 5 m/s to form a polypropylene. The thread is further stretched at a stretching temperature of 7 ° C and a draw ratio of 2,56 times. 'The sample is set at a temperature of l3 (rc is set, and then taken at 35 〇〇m/min) to obtain the contained poly Crepe acrylate nanosphere powder relative to

17 S 201241251 The overall content of the composite fiber is 9.5 wt/❶ 75d/36f polypropylene spun drawn yarn (SDY). The obtained dyed polypropylene conjugate fiber was woven as a woven base material by a garter machine, and dyed using a disperse dye under the dyeing conditions of 130 ° C * 40 minutes. The dyed woven substrate is darkly colored and has a dye fastness of 4 to 5 or more (see Table 1). Example 3 The method for producing polypropylene particles having dyeability according to Example 1 'Adjusting the ratio of polypropylene to polymethyl methacrylate fine powder spheres, adding polypropylene grafted maleic anhydride to obtain polyfluorene-containing groups Methyl acrylate 26% by weight of dyeable polypropylene granules, wherein the nanofine powder spheres have an average particle diameter of 15 μm. Polypropylene (Β) and dyed polypropylene granules (Α) were separately melted in an extruder, and then spouted at a mixing ratio of 50:50 from a skin type cross-section nozzle at 250 ° C, and passed through a 〇.5 m/ s cooling air, cooling and solidifying oil, forming a polypropylene thread, and then stretching at a stretching temperature of 70 ° C, a stretching ratio of 2. times, and then fixing at a setting temperature of 13 ° C, and then 3500 m / Min winding, the content of the polymethyl methacrylate nanosphere powder contained in the whole of the composite fiber was 13 weight. /. 75d/36/ polypropylene spun drawn yarn (SDY). The obtained dyed polypropylene composite fiber was woven with a garter machine as a woven base material, and dyed using a disperse dye at a dyeing condition of 130 ° C * 40 minutes. The dyed woven base material is darkly colored and has a dye fastness of 4 to 5 or more. Comparative Example 1 The method for producing polypropylene particles having dyeability according to Example 1 'The ratio of the polypropylene to the polymethyl methacrylate micropowder spheroids was added to the poly 2 201241251 olefin grafting horse to be used to obtain a polymethyl group. The base (iv) acid is from 5.6 wt% of the dyeable polypropylene particles (A), wherein the nanofine powder sphere has an average particle diameter of 13 μm. After the poly(4)(B) and the poly(tetra)granules (4)' are respectively smelted in an extruder, the composite ratio of 50:5G is sprayed by the Pirin-type cross-section nozzle at 25 (TC, and the cooling air is passed through 〇5 m/s. Cooling and solidifying oil to form a polypropylene filament yarn, and then stretching at a temperature of 7 G ° C and a draw ratio of 2.74 times, and then setting the temperature to 13 (TC is fixed to '35 μm/ Min coiling, obtaining a polypropylene spun drawn yarn containing a polyether methyl acrylate nanosphere powder having a content of 2.8% by weight relative to the entire composite fiber of 75 d/36 f. The resulting dyed poly The propylene composite fiber was woven with a garter machine as a woven substrate, and dyed with a disperse dye under dyeing conditions of l30 ° C * 4 〇 minutes. The dyed woven substrate was light in color and poor in coloring performance. Comparative Example 2 According to the method for producing dyeable polypropylene granules of Example 1, the ratio of polypropylene to polydecyl methacrylate micropowder spheres is adjusted by adding polypropylene grafted maleic anhydride to obtain polyether methyl acrylate 42 weight. % of the dyed polypropylene particles (A), wherein the nanofine powder sphere average particle # is 22 μιη. The propylene (b) and the dyeable polypropylene granule (A) are separately melted by an extruder, and then ejected at a C ratio of 50:50 from a skin-type cross-section nozzle at 250 C, and passed through a crucible of 5 m/s. Cooling the air, cooling and solidifying the oil to form a polypropylene filament strip, and then stretching at a stretching temperature of 7 〇ΐ and a draw ratio of 2.14 times, and then sizing at a setting temperature of 13 〇ΐ>, and then rolling at 3,500 m/min. Taking a 75d/36f polypropylene spun drawn yarn containing 21% by weight of polymethyl methacrylate nanospheres 201241251 powder relative to the composite fiber as a whole. The dyed polypropylene conjugate fiber was obtained. Then, it was woven with a garter machine as a woven base material, and dyed with a disperse dyeing dyeing at a dyeing condition of 130 ° C for 40 minutes. The dyed woven base material was darkly colored, but the spinning property was barely acceptable.

20 201241251 The target 铷 涨 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^

Ml ^η 1 ιη 1 inch l inch inch inch inch ◎ ◎ ◎ <] ◎ 趄 趄 〇 〇 \ \ \ \ \ \ \ \ \ \ S S S S S S S S S S S S S S S S S S S S S S S S S 〇<] To stay 锬+奥丝你秦W顾$ W _颧踅3 l〇m UO m CN <Ν Take the reading W 轻 颧 颧 鲴鹎蜊 鲴鹎蜊 鲴鹎蜊 鲴鹎蜊 鲴鹎蜊 ♦ ♦ G ^ 〇 CO CO CO CO ;Ν ^ cn ^ Μ <N 201241251 Comparative Example 3 Preparation of dye-containing polyacrylic acid (Α) containing nanofine powder spheres (average particle size of about 22 μm). Polyacrylamide -) and the dyeing polyacryl (Α), after melting separately by the extruder, the composite ratio of 5〇: % is sprayed by the Pirin-type section nozzle at 25 (rc, cooled and solidified by G 5m/s cooling air to form polypropylene The thread is further stretched at a stretching temperature of 7 〇, 拉伸, and a draw ratio of 2.34 times, and then fixed at a setting temperature of 13 叱. Then, it was taken up at 350 () m/min, and the content of the polyacrylonitrile-containing acetaminophen microsphere powder was 95-denier relative to the composite fiber as a whole. The dyed heart propylene composite fiber is woven with (4) machine as the woven substrate, dyeing conditions are 13〇°C*4G minutes, and (4) disperse dyes are dyed. The dyed woven substrate is darkly colored, but the spinning property is not strong. Comparative Example 4 A dyed polypropylene (Α) containing Nai-_ (average particle size of about 65 μm) was prepared. The polypropylene (8) and the dyeable poly(嫌) were extruded. The machine is divided into _ after the 'combination ratio 5 〇: 5 〇 is sprayed from the Pi Pi segment nozzle in the C, to obtain the content of the polymethyl phthalate-containing nanosphere powder relative to the composite fiber It is 95% by weight of 75d/36f poly-spun fine silk. It is found to be very poor in the spinning process during the spinning process. 201241251 衂价e increase^f-Ιώ升,¥玉鸯W,?!, swirling ingot ^-教窭命罅寐 (日1)勃四霄午||资条^呆崦3< 许升UO 1 inch 1 inch 1 1 1 dyeability ◎ ◎ 1 1 1 fiber specific gravity 0.96 0.96 0.96 Silky 〇< X Disperse phase nano-fine powder sphere average particle size (μιη) m (N (N iT) to mine *4〇yn a\ liO σ^ 〇\ loading part Φ n^i , ^N love X ¢6 ο ο ο ο ο ο Example 1 Comparative Example 3 Comparative Example 4 £3 s 201241251 Examples 4 to 6 and Comparative Examples 5 to 6 were respectively obtained from polypropylene (B) (cortex) and polyacrylonitrile-containing acrylic acid. 19% by weight of the dyed polypropylene particles (A) (core layer), according to the different compounding ratios shown in Table 3, melted separately by an extruder, sprayed at 250 ° C by a Pi Pi type section nozzle After drying, the oil was cooled and solidified by a cooling air of 5 m/s to form a polypropylene filament, and then stretched at a stretching temperature of 7 ° C and a draw ratio of 2.34 times, and then set at a setting temperature of 130 ° C. It was then taken up at 3500 m/min to obtain a 75d/36f polypropylene spun drawn yarn (SDY). Further, a woven machine was used as a woven base material, and dyeing was carried out using a disperse dye under the dyeing conditions of 130 ° C * 40 minutes. Its fiber properties are shown in Table 3.

S 24 201241251 #磙客铡价^涨^趄^) up, face ^ music setting, seal, swirling tomb) 磐铁^^欺¥^^^配|<-£< color fastness 1 inch U^ Il inch l inch 1 inch III 1 1 1 dyeability ◎ ◎ ◎ 〇-Μ ^ -3⁄4} dish <] l X •9$^ 'tree λ3 Jcul 0.96 〇\ <d 0.98 in On Ο m Ο) ο 0.94 〇〇〇〇〇〇Disperse phase of nano-fine powder sphere average particle size (μιη) cn rH mmm cn Lingling 1 lack of platinum music - pounds _ 衾 衾 W Φ like ' On v〇 ^ c (N ι-Η Οο m ο 00 <N 〇|π 〇|π domain 刼苳 XX ^ < PQ ^0 铋 Ο Ο to U^) m Ο CN Ο οο ο οο ο CN ο ο 1—Η • · ο tn oo *zrr 军_iup (k (N ιη *%ζ ν〇aJ -u ja \〇201241251 Comparative Examples 7 to 9) After the polypropylene granules (B) and the polyester granules shown in Table 4 were separately melted in an extruder, The composite ratio of 50:50 was sprayed at 280 °C by a Pipiroid cross-section nozzle, cooled and solidified by a cooling air of 0.5 m/s to form a polypropylene filament, and then stretched at a temperature of 85 ° C and a draw ratio. Stretching at 2.0 times, setting at a setting temperature of 150 ° C, and then at 3500 m/min Take to obtain 75d/36f polypropylene spun drawn yarn (SDY), and then weave it as a woven substrate with a garter machine, dyeing with 130 ° C * 40 minutes, using disperse dyes. The fiber properties are shown in Table 4. .

26 201241251 #龄客^铷^涨^赵^升, Side ^ 资,? -1, 旋发"翁翁命的寂蓉命龄铋*配^唬_鸿寸< Color fastness 1______ 4~5 3~4 3~4 3~4 Dyeing J ◎ <<< Fiber specific gravity 0.96 1.12 1.15 1.03 Spinning ί_ 〇 <<<<>> Skin layer composition Polypropylene polypropylene polypropylene polypropylene layer composition i Take # JS PET PBT Nylon 6 Example 1 Comparative Example 7 Comparative Example 8 Comparative Example 9 201241251 Example 7 (I) Method for producing dyeable polypropylene granules (A): 61 parts by weight of polypropylene and 38 parts by weight of polymethyl methacrylate micropowder spheres and 1 part by weight of polypropylene grafted horse were taken. After the anhydride was mixed, it was blended in an extruder at a blending temperature of 220 ° C, and then extruded and pelletized to obtain a dye-containing polypropylene pellet containing 38% by weight of polymethyl methacrylate. (A), wherein the nanofine powder sphere has an average particle diameter of 13 μm. (2) The method for producing the dyed polypropylene composite fiber: firstly, the polypropylene (Β) and the polypropylene particles (Α) containing the polymethyl methacrylate nanosphere powder are in a weight ratio of 50:50. The dyed polypropylene particles (A-1) were metered and mixed into a 19% by weight of polydecyl methacrylate by a mixer. Then, the polypropylene (Β) and the polypropylene granules (Α-1) containing the polymethyl methacrylate nanosphere powder are melted separately in an extruder, and then the polymer is flowed to the spinning head to The compounding ratio of 50:50 is sprayed at 250 °C by the Pillar-type section nozzle, and the oil is cooled and solidified by 〇5m/s cooling air to form a polypropylene thread, and then stretched at a stretching temperature of 70 ° C. After stretching at a magnification of 2.56 times, the film was set at a molding temperature of 130 ° C, and then wound up at 3,500 m/min to obtain a content of 9.5 by weight of the polymethyl methacrylate nanosphere powder as a whole with respect to the composite fiber. % 75d/36f polypropylene spun drawn yarn (SDY). The obtained dyed polypropylene composite fiber was woven as a woven base material by a garter machine, and dyed using a disperse dye under the dyeing conditions of 130 ° C * 40 minutes. Dyed

S 28 201241251 The woven substrate is darkly colored and has a dye fastness of 4 to 5 or more. Example 8 The polypropylene (B) and the dyeable polypropylene granules (A) of Example 1 were respectively melted by an extruder, and the composite ratio was 5 〇: 5 〇 by the gu-shaped section nozzle at 250 Ϊ Ejected, cooled and solidified by 0.5m/s cooling air: oil 'formed polypropylene filaments' and then shaped at a stretching temperature of 7 (rc, stretching ratio 2.15 times), and then shaped at a setting temperature of i3〇°c. 3500 m/min was taken up to obtain a 78 d/36f polypropylene spun drawn yarn containing a polymethyl methacrylate nanosphere powder having a content of 9.5% by weight relative to the entire composite fiber. The product was shaped by a temperature of 15 (TC, a draw ratio of 1.35 times, and a set temperature of 150 ° C to obtain a polypropylene false twisted silk (DTY) of 50 d / 36 f. The obtained dyed polypropylene composite fiber was further The machined fabric was woven as a woven substrate, and dyed with a disperse dye under dyeing conditions of 130 ° C * 40 minutes. The dyed woven substrate was darkly colored, and the dyeing fastness was 4 to 5 or more. The polypropylene (B) and the dyed polypropylene pellet (A) obtained by the production method of Example 1 were divided into extruders. After melting, the composite oil is sprayed at 250 ° C in a composite ratio of 50:50. The cooling oil is cooled and solidified by a cooling air of 5 m/s to form a polypropylene filament, and then a tensile temperature of 70 is obtained. After stretching at a stretching ratio of 2.56 times at °C, the film was deformed at a setting temperature of 13 CTC and then taken up at 35 〇〇m/min to obtain a yttrium-containing microsphere powder containing polyfluorenyl acrylate S. The 78d/36f polypropylene spun drawn yarn is 9.5% by weight relative to the whole of the composite fiber. The spun 29 201241251 drawn yarn is then subjected to an air false twisting process to obtain a polypropylene air false twist of 78d/36f. Silk (ATY). The obtained dyed polypropylene composite fiber is woven with a garter machine as a woven substrate, and dyed with a disperse dye in minutes. The dyed woven substrate is darkly colored and dyed. The fastness is up to 4 to 5. Example 10 Polypropylene (Β) and the dyed polypropylene granules obtained by the production method of Example 1 are separately melted in an extruder to have a compounding ratio of 50. : 50 is sprayed by a Pirin-type section nozzle at 25 (TC, cooled and solidified by a cooling air of 0.5 m/s, A polypropylene fiber strand was formed and directly drawn at a spinning speed of 2800 m/min without stretching by heating to obtain a polydexton methyl acrylate nanosphere powder having a content of 9.5% by weight relative to the entire composite fiber of 120%. /36f polypropylene undrawn yarn. The undrawn yarn was stretched at a temperature of 150 ° C and a draw ratio of 1.7 times, and set at a set temperature of 150 ° C to obtain a 75d/36f polypropylene false twisted yarn. (DTY) The obtained dyed polypropylene composite fiber was woven with a garter machine as a woven base material, and dyed under a dyeing condition of 13 (TC*40 minutes using a disperse dye). The dyed woven substrate has a deep dark color and a dyeing fastness of 4 to 5 or more. It can be seen from the above Table 1 that the 'composite fibers of Examples 1 to 3' have an average particle diameter of about 13//111 to about 0.1% by weight of the polymethyl methacrylate nanosphere powder dispersed in the polypropylene (A). Between 15/zm' and its content relative to the entire composite fiber is between 9.5 and 13% by weight, so it is excellent in terms of spinnability, dyeability and color fastness. In contrast, in the composite fiber of Comparative Example 1, the average particle diameter of the polymethyl methacrylate nanosphere powder dispersed in the polypropylene (A) was 13/zm as in the case of Example 2, but The content of the composite fiber alone was only 2.8% by weight, and as a result, although good results were obtained in terms of spinnability and fiber specific gravity, it was not sufficient in dyeability; and the composite fiber of Comparative Example 2 was dispersed. The poly(methyl methacrylate) nanosphere powder in the polypropylene (A) has an average particle diameter of 22# m and is as high as 21% by weight based on the total amount of the composite fiber, and as a result, the dyeability is good. However, the spinning is barely acceptable. As is clear from Table 2, the composite fiber of Example 2 was excellent in spinnability, dyeability, and color fastness, and the polymethyl methacrylate nanosphere powder in the composite fiber of Comparative Example 3 was obtained. The average particle size is about 22/zm (greater than 20/zm), so although the dyeing property and the color fastness are good, the effect on spinning is not good; and the polyfluorene in the composite fiber of Comparative Example 4 The average particle diameter of the methyl acrylate nanosphere powder is about 65/zm (greater than 50# m), so the spinnability is very poor. It can be seen from Table 3 that the composite fibers of Examples 2 and 4 to 6 have a spinning ratio, dyeability and color fastness, since the compounding ratio selected in the manufacturing process is between 20:80 and 80:20. Both are good. In contrast, 'Comparative Example 5 is that a single fiber made of only a single layer of polypropylene' has good spinnability but cannot be dyed; and the composite fiber of Comparative Example 6 has a compounding ratio of 15:85, so The spinnability and fiber specific gravity are good, but the content of the polymethyl methacrylate nanosphere powder is only 2.8% by weight relative to the composite fiber as a whole, and the dyeability is poor and the skin layer is provided.

S 31 201241251 The problem is not well covered. As is apparent from Table 4, in Example 1, since both the core layer and the skin layer were polypropylene conjugate fibers, they were excellent in spinnability, dyeability, and color fastness. On the other hand, in Comparative Examples 7 to 9, the core layer and the skin layer were made of different materials, and as a result, the spinnability, the fiber specific gravity, the dyeability, and the color fastness were poor, and the polymer interface between the skin layers was Serious phase separation. According to the skin-type conjugate fiber produced by the above-described production method of the present invention, it is possible to obtain a garment which is light in weight and excellent in dyeability, and can solve the problem that although the polyolefin fiber-made garment can retain the lightweight property, it cannot be excellent. Dyeing problem. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a skin-type composite fiber of the present invention. Fig. 2 is a schematic cross-sectional view showing another embodiment of the skin-type composite fiber of the present invention. 3A to 3C are schematic cross-sectional views showing other embodiments of the skin-type composite fiber of the present invention. [Explanation of main component symbols] A Polypropylene (rock layer) B Polypropylene (cortex) 32

Claims (1)

201241251 VII. Patent application scope: 1. A skin-type composite fiber with dyeability, the specific gravity of the fiber is less than 1.0g/cm3; characterized in that the fiber is composed of a skin layer and a core layer, and the skin layer is composed of The polypropylene layer is composed of polypropylene in which the nanosphere powder is dispersed, and the average particle diameter of the nanosphere powder in the polypropylene is greater than 〇.3μιη less than 50μιη ° 2. The skin-type composite fiber having dyeability according to the first aspect of the patent application, wherein the nano-microsphere powder has an average particle diameter of less than 20 μm in the polyolefin. 3. The skin-type conjugate fiber having dyeability according to claim 1 or 2, wherein the material of the nanosphere powder is one selected from the group consisting of decyl acrylate and polystyrene. the above. 4. The skin-type composite fiber having dyeability according to claim 1 or 2, wherein the nanosphere powder accounts for 3 to 20% by weight based on the total amount of the composite fiber. 5. The skin-type composite fiber having dyeability according to claim 1 or 2, wherein the nanosphere powder accounts for 5 to 15% by weight based on the total amount of the composite fiber. 6. The skin-like composite fiber having the dyeability of claim 1 or 2, wherein the fiber specific gravity is less than 〇.99 g/cm3. 7. The skin-like composite fiber with dyeability as claimed in item 6 of the patent application, wherein the fiber specific gravity is less than 0.97 g/cm3. 33 S 8. 9. 10. 11. 12. 13. 14. 15. If the scope of application for the patent is combined with fiber, the single-stranded skin type in * is equivalent to 5d or less in the 8lg range of the patent application. Dimensional, in which the single (four) & item has the skin type composite fiber ^, the range of item 9 has the pico, the single fiber of f has a Danny number of 2 (1 below the fiber such as the application of the patent scope i < Combining fibers, wherein the complex 4:2 dyeable skin type is made up of W °° fiber as a spinning drawn yarn. qi i is the first or second item of dyeable skin type Complex: = true = the composite fiber is a fake twisted processed wire. Synthetic fiber II it cofferdam 1 or 2 of the dyeable skin-like type of retort 〃 layer with step-by-step containing maleic anhydride grafted polypropylene phase A kind of clothing-using a skin-type composite fiber having dyeability as in any one of the items 1 to 13 of the patent application. A method for producing a dyeable skin-like composite fiber, The invention relates to a spirulina type composite fiber which can be directly dyeable according to any one of the items (4) of the patent application scope; the method includes the following steps: (1)· 50 to 95 parts by weight of polyene and 5 to 5 After uniformly mixing the nano-microsphere powder of the weight fraction, the blending temperature is 180 to 250 ° C, and the mixture is extruded and pelletized to obtain a uniform dispersion of the nano microsphere powder. Alkene (8); and S 34 201241251 (2). The polypropylene (B) and the above polypropylene (A) are melt-extruded at a spinning temperature of 180 to 26 (the spinning temperature of the TC has a shape of the pistil The extruder of the surface spinning nozzle adopts polypropylene (B) as the skin layer and polypropylene (A) as the core layer and the compounding ratio is 80: 20~20: 80 for extrusion 'spinning speed 2000~4000m/min. And obtaining a skin-type composite fiber. 16. A method for producing a dyeable skin-type composite fiber according to claim 15 wherein step (1) is to make polypropylene, nano-microsphere powder and further The added maleic anhydride grafted polypropylene compatibilizer is uniformly mixed and then blended at a temperature of 180 to 250. (: After being subjected to screw blending, extrusion and pelletizing are carried out to obtain a polypropylene having uniform dispersion of nanosphere powder. (A) 17. The method for producing a smectite composite fiber having dyeability as set forth in claim 15 or 16 is further stretched for the spirulina conjugate fiber obtained in the step (2) The temperature is 50~11〇°C, the stretching ratio is 4·5~1.5 times, and the drawing is performed at a setting temperature of 80~150°C. The film is obtained by winding at a spinning speed of 2000 to 4000 m/min to obtain a skin-retic type composite fiber as a spun drawn yarn. 18. A method for producing a skin-reducing composite fiber having dyeability as claimed in claim 17 The false-twisting process of the skin-type composite fiber as a spinning-stretched yarn is obtained as a skin-plastic composite fiber which is a false-twisted silk. 35 201241251 19. The skin of the dyeable body according to claim 15 or 16 A method for producing a core type composite fiber, wherein the material of the nanosphere powder is one selected from the group consisting of polymethyl methacrylate and polystyrene. A method for producing a dyeable skin-type composite fiber, which is used for producing a dyeable skin-type composite fiber according to claim 12; and comprising the following steps: (1) . 50 to 95 parts by weight of polypropylene and 5 to 50 parts by weight of the nanosphere powder are uniformly mixed, and then blended at a temperature of 18 Torr to 25 Torr. 〇Extrusion and granulation after screw blending to obtain polypropylene (A) having uniform dispersion of nanosphere powder; and (2), so that polypropylene (B) and polypropylene (A) are melt extruded The method is as follows: at a spinning temperature of 180 to 260 ° C, an extruder having a skin type cross-section spinning nozzle has a polypropylene (B) as a skin layer and a polypropylene (A) as a core layer and a compound ratio of 80: 20~2〇: 80 is extruded> and then coiled at a spinning speed of 2〇〇〇~3500m/min to obtain a skin-type composite fiber as an undrawn yarn, which is then subjected to false twisting processing.皮 捻 捻 之 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Step-added Malay riding grafted polypropylene phase S 36 201241251 After the mixture is uniformly mixed, the mixture is extruded at a blending temperature of 180~250 °C, and then granulated to obtain a uniform dispersion of the nanosphere powder. Polypropylene (A). 22. The method for producing a dyeable skin-type composite fiber according to claim 20 or 21, wherein the material of the nanosphere powder is selected from the group consisting of polymethyl methacrylate and polystyrene. More than one. 37 S