JP2006183201A - Polytrimethylene terephthalate polyester fiber having excellent water repellency and abrasion resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polytrimethylene terephthalate polyester fiber used for a fiber structure having excellent water repellency and abrasion resistance and good process passableness while having high stretchability and a soft touch feeling. <P>SOLUTION: The polytrimethylene terephthalate polyester fiber comprises a fatty acid bisamide and/or an alkyl group-substituted type fatty acid monoamide in an amount of 0.1-5 wt.% based on the whole fiber and has the excellent water repellency and abrasion resistance. The fiber is suitable for producing a false-twist textured yarn. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polytrimethylene terephthalate polyester fiber excellent in water repellency and abrasion resistance.

Conventionally, various treatment methods have been proposed for imparting water repellency to textile products. For example, a fiber structure such as a fabric is treated with a water repellent such as a fluorine water repellent (see Patent Document 1) or a silicone water repellent (see Patent Document 2) to form a water repellent on the fiber surface. There has been proposed a method of forming a film and imparting water repellency. However, in order to maintain sufficient water repellency by these methods, a large amount of water repellent must be adhered to the fiber structure, so that the texture of the fiber structure such as cloth becomes hard or clogged. For example, when polytrimethylene terephthalate polyester fiber is used as a fiber material, the soft texture and high stretch properties that are characteristic of polytrimethylene terephthalate polyester fiber are reduced. there were.
In addition, in these conventional methods, the water repellent film is cracked due to rubbing or itching during wearing or washing in clothes, or when treated with a fluorine-based water repellent, it is repelled by washing or dry cleaning. There was a problem that the water performance was greatly reduced.
Japanese Patent Laid-Open No. 7-166212 JP-A-5-106171

  Therefore, an object of the present invention is to provide a fiber structure having high stretchability and soft texture peculiar to polytrimethylene terephthalate-based polyester fibers, and further having water repellency, wear resistance, and good processability. It is an object of the present invention to provide a polytrimethylene terephthalate-based polyester fiber that can be used.

  The present invention solves the above-mentioned problems. The gist of the present invention is that a polyoxyethylene containing 0.1 to 5 wt% of a fatty acid bisamide and / or an alkyl group-substituted fatty acid monoamide with respect to the whole fiber. It is in trimethylene terephthalate polyester fiber.

  According to the present invention, a polytrimethylene terephthalate-based polyester fiber having a soft texture and high stretchability and excellent in water repellency and wear resistance can be obtained. Therefore, the application development range of the polytrimethylene terephthalate-based polyester fiber can be greatly expanded.

  Hereinafter, the polytrimethylene terephthalate polyester fiber of the present invention will be described in detail.

  In the present invention, the polytrimethylene terephthalate-based polyester fiber means a polyester fiber having a trimethylene terephthalate unit as a main repeating unit, and includes a trimethylene terephthalate unit in a range of about 50 mol% or more, preferably 90 mol% or more. Polyester fiber.

  The polytrimethylene terephthalate polyester used in the present invention can be polymerized using a known method. For example, terephthalic acid or a lower alcohol ester of terephthalic acid and excess 1,3-propanediol are subjected to a transesterification reaction in the presence of a catalyst such as tetrabutyl titanate, and then the resulting reaction product is converted to a catalyst such as tetrabutyl titanate. And a polycondensation reaction is performed to obtain a polytrimethylene terephthalate polymer.

  When copolymerization is performed, a comonomer can be added at any stage of the polymerization method. When copolymerizing a carboxylic acid typified by sulfoisophthalate and a derivative thereof, it is preferable to add a comonomer at the beginning of the polymerization. The polytrimethylene terephthalate-based polyester fiber used in the present invention can be obtained by extruding from a spinning nozzle, winding and then stretching.

  Polytrimethylene terephthalate-based polyester fibers can be suitably used as yarns such as false twisted yarns, drawn yarns, partially oriented undrawn yarns or undrawn yarns. The form of polytrimethylene terephthalate fiber is typically a continuous filament yarn composed of a plurality of single yarns, and the cross-section of the single yarn may be uniform or thick in the length direction, The cross-sectional shape may be a round cross-section, a triangular shape, a Y shape, an eight-leaf shape, or an irregular shape such as a flat shape. The polytrimethylene terephthalate fiber may be a short fiber as its form.

  In the present invention, a component comprising a polymer containing a fatty acid bisamide and / or an alkyl-substituted fatty acid monoamide and a homogenous or different polymer containing no such polymer, such as polyethylene terephthalate or polylactic acid, are separately produced and then blended. Alternatively, raw yarns obtained by composite spinning (core-sheath, side-by-side, etc.) may be used.

  Moreover, the polytrimethylene terephthalate-based polyester fiber of the present invention may be mixed with a substance made of a plant-derived raw material. Examples of the mixed use include those mixed with natural fibers such as silk and cotton, and regenerated fibers such as rayon and acetate, or woven or knitted.

  In the present invention, fatty acid bisamides and / or alkyl-substituted fatty acid monoamides are used because they have lower amide reactivity than ordinary fatty acid monoamides. This is because the reaction hardly occurs. Moreover, since these compounds have many high molecular weights, they generally have good heat resistance and are difficult to sublimate, and therefore can be used as more preferable lubricants.

  The fatty acid bisamide used in the present invention refers to a compound having two amide bonds in one molecule such as a saturated fatty acid bisamide, an unsaturated fatty acid bisamide, and an aromatic bisamide. Caprylic acid amide, methylene biscapric acid amide, methylene bislauric acid amide, methylene bismyristic acid amide, methylene bispalmitic acid amide, methylene bis stearic acid amide, methylene bisisostearic acid amide, methylene bisbehenic acid amide, methylene bis Oleic acid amide, methylene biserucic acid amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bismyristic acid amide, ethylene bispalmitic acid amide, ethyl Bisstearic acid amide, ethylene bis isostearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, butylene bis behenic acid amide, butylene bis behenic acid amide, butylene bis oleic acid amide , Butylene bis erucamide, hexamethylene bis stearamide, hexamethylene bis behenate amide, hexamethylene bis oleic acid amide, hexamethylene bis erucamide, m-xylylene bis stearamide, m-xylylene bis- 12-hydroxystearic acid amide, p-xylylene bis stearic acid amide, p-phenylene bis stearic acid amide, p-phenylene bis stearic acid amide, N, N′-distearyl adipic acid amide, N, '-Distearyl sebacic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide, N, N'-distearyl isophthalic acid amide, N, N'-distearyl terephthalic acid Examples include amide, methylene bishydroxystearic acid amide, ethylene bishydroxystearic acid amide, butylene bishydroxystearic acid amide, and hexamethylene bishydroxystearic acid amide. These fatty acid bisamides may be used alone or in combination.

  The alkyl-substituted fatty acid monoamide used in the present invention refers to a compound having a structure in which amide hydrogen such as saturated fatty acid monoamide or unsaturated fatty acid monoamide is replaced with an alkyl group. Such alkyl group-substituted fatty acid Examples of monoamides include N-lauryl lauric acid amide, N-palmityl palmitic acid amide, N-stearyl stearic acid amide, N-behenyl behenic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N- Examples include oleyl stearic acid amide, N-stearyl erucic acid amide, and N-oleyl palmitic acid amide. The alkyl group may have a substituent such as a hydroxyl group introduced into its structure, such as methylol stearamide, methylol behenic acid amide, N-stearyl-12-hydroxystearic acid amide, and N -Oleyl 12 hydroxystearic acid amide and the like are also included in the alkyl group-substituted fatty acid monoamide of the present invention. These alkyl group-substituted fatty acid monoamides may be used alone or in combination. In the present invention, the fatty acid bisamide and the alkyl group-substituted fatty acid monoamide may be used alone or in combination.

  In the present invention, it is important that the polytrimethylene terephthalate-based polyester fiber contains a fatty acid bisamide and / or an alkyl group-substituted fatty acid monoamide as a lubricant in an amount of 0.1 to 5 wt% based on the entire fiber. If the content of the fatty acid bisamide and / or the alkyl group-substituted fatty acid monoamide is less than 0.1 wt%, the desired water-repellent performance cannot be obtained. In addition, by making the content of fatty acid bisamide and / or alkyl group-substituted fatty acid monoamide 0.1 wt% or more, the surface friction coefficient of the fiber is reduced, and the abrasion resistance required for textiles and the like is required. And durability in repeated use, and at the same time, when made into a fabric, high water repellency can be added. Here, when the content of the fatty acid bisamide and / or the alkyl-substituted fatty acid monoamide exceeds 5 wt%, the fiber-forming property is deteriorated and a fiber having sufficient strength and elongation characteristics cannot be obtained. Therefore, the content of the fatty acid bisamide and / or the alkyl group-substituted fatty acid monoamide is preferably 0.1 to 5 wt%, more preferably 0.5 to 3 wt%.

  The reason why the polytrimethylene terephthalate polyester fiber having high water repellency can be obtained in the present invention is considered as follows. That is, fatty acid bisamide and / or alkyl group-substituted fatty acid monoamide is contained in polytrimethylene terephthalate-based polyester fiber and uniformly dispersed in the fiber to reduce the surface tension of the fiber. When this fiber structure is used, it exhibits good water repellency due to the effect of a lotus leaf.

  The method for incorporating the polytrimethylene terephthalate-based polyester fiber into the fatty acid bisamide and / or the alkyl group-substituted fatty acid monoamide is not particularly limited, and examples thereof include the following methods. First, in the kneading step, a kneaded chip containing a high proportion of polytrimethylene terephthalate polyester and fatty acid amide and / or alkyl group-substituted fatty acid monoamide is prepared, and when this is used in a spinning machine, fatty acid amide and An ordinary polytrimethylene terephthalate-based polyester chip is preferably blended and diluted so that the alkyl group-substituted fatty acid monoamide has a desired content.

  In the melt spinning process, a polytrimethylene terephthalate polyester and a fatty acid amide and / or an alkyl group-substituted fatty acid monoamide can be further finely kneaded by installing a static kneader in the spinning pack. . Aggregation of fatty acid amides and / or alkyl group-substituted fatty acid monoamides, and bleeding out to the fiber surface may cause deterioration of operability due to soiling of guides and rollers, and may cause physical properties and staining spots of textile products. In the kneading step and the melt spinning step, it is preferable to finely disperse the fatty acid amide and / or the alkyl group-substituted fatty acid monoamide in the polytrimethylene terephthalate polyester.

  Further, the kneading step and the melt spinning may be performed in the same step, and for example, the following method can be used.

  The first method is to dry a polytrimethylene terephthalate-based polyester chip and a chip containing a fatty acid amide and / or an alkyl group-substituted fatty acid monoamide, and then supply to a nitrogen-sealed extrusion kneader. A kneaded polymer melt of kneaded polytrimethylene terephthalate polyester and fatty acid amide and / or alkyl group-substituted fatty acid monoamide is guided to a spinning machine, and further finely kneaded by a stationary kneader installed in a spinning pack, It is a method of discharging from a die and performing melt spinning.

  In the second method, polytrimethylene terephthalate-based polyester and fatty acid bisamide and / or alkyl group-substituted fatty acid monoamide were separately melted, the melt was guided to a spinning machine, and installed in a spinning pack. This is a method of finely kneading with a static kneader and discharging from a die to perform melt spinning.

  The fatty acid bisamide and / or the alkyl group-substituted fatty acid monoamide is contained in an amount of 0.1 to 5 wt% with respect to the total amount of the polytrimethylene terephthalate polymer. By making the fatty acid amide contained 0.1% by weight or more, the surface friction coefficient of the fiber can be reduced and process passability can be improved. At the same time, when a fabric is used, high water repellency can be added. Further, by adjusting the fatty acid amide and / or alkyl group-substituted fatty acid monoamide to 5 wt% or less, excess fatty acid amide bleeds out from the molten polymer during kneading and spinning, and this sublimates or decomposes. Prevents deterioration of work environment such as smoke generation, and deterioration of operability such as contamination of extrusion kneaders and melt spinning machines due to excessive fatty acid amide and / or alkyl group-substituted fatty acid monoamide sublimates or decomposition products. be able to. Further, when the content of the fatty acid amide and / or the alkyl group-substituted fatty acid monoamide is 5 wt% or less, there is little aggregation of the fatty acid amide in the molten polymer during kneading and spinning, The reaction with the polytrimethylene terephthalate-based polyester is suppressed, and the bleed out from the molten polymer in the spinning process is suppressed, whereby the polymer discharge from the die is stabilized and the yarn unevenness is suppressed.

  In the present invention, a polytrimethylene terephthalate-based polyester fiber containing a fatty acid bisamide and / or an alkyl group-substituted fatty acid monoamide can be false twisted.

  In addition, when false twisting is performed in the present invention, in addition to so-called Woolley processing using only a single-stage heater, so-called bulerial processing using a single-stage heater and a two-stage heater is also included in the present invention and can be applied appropriately. It is also preferable to do.

  In false twisting, false twisting is preferably performed by setting the yarn temperature at the outlet of the twisted part heater and the secondary set heater to a temperature of 120 ° C. or higher and 210 ° C. or lower. In the false twisting method applied in the present invention, the yarn temperature at the outlet of the twisting heater of the polytrimethylene terephthalate-based polyester fiber is preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 140 ° C. or higher. False twisting is performed at a temperature of 180 ° C. or lower. When the twisted heater temperature is lower than 120 ° C, the crimp is not sufficiently imparted, and when it is higher than 200 ° C, the strength of the false twisted yarn is lowered and the productivity is lowered, which is not preferable. The yarn temperature at the heater outlet can be measured using a non-contact thermometer manufactured by Muratec Co., Ltd. immediately after the heater outlet.

  As the false twisting machine to be used, a friction disk or a belt nip type false twisting machine may be used in addition to the pin false twisting machine.

  In this false twisting process, a so-called Woolley process that does not perform a secondary set, a processed yarn having an expansion / contraction elongation ratio of about 50% to 300% can be obtained. A processed yarn having an elongation rate of about 1% to 200% can be obtained.

  The polytrimethylene terephthalate-based polyester fiber of the present invention can take a structure on various members such as woven fabrics, knitted fabrics, and non-woven fabrics, and may be used in combination with substances made of other raw materials. For example, it may be mixed with natural fibers such as silk and cotton, or regenerated fibers such as rayon and acetate, or woven or knitted. Moreover, it can be suitably used not only for clothing applications such as shirts, blousons and pants, but also for clothing material applications such as cups and pads, interior applications such as curtains and carpets, vehicle interior applications, industrial materials and nonwoven fabrics. .

  Hereinafter, embodiments of the polytrimethylene terephthalate-based polyester fiber of the present invention will be described, but the present invention is not limited to these examples. Moreover, evaluation was performed with the following measuring methods.

A. Water repellency;
The water repellency is measured by a waterproof test method described in JIS L 1092 (1992). 250 ml of water is sprayed on the test cloth in the shower state, and the water repellency is determined according to the following Table 1 in the state of water droplets adhering to the test cloth. The water repellency in the present invention is preferably 4th or higher. If it is 4th grade or higher, a dry and comfortable product can be obtained without moisture permeating inside when used as clothing.

B. Abrasion resistance (fastness to dry friction);
In accordance with JIS L 0849 (1996), the dyed fabric sample was rubbed back and forth 100 times with a cotton cloth, and then the degree of color transfer to the cotton cloth was determined from 1 to 5 using a gray scale. In apparel applications, wear resistance of at least grade 3 is generally required.

C. Texture;
Ten persons were selected from a textile engineer, a knitting engineer, and a dyeing engineer, and the soft feeling of the fabric was judged by an eight-step evaluation by a sensory test method using a tactile sensation. Evaluation was performed with 8 being the softest case and 1 being the hardest case.

D. Strength and elongation;
The strength and elongation of the fiber were measured using “STATEMAT ME” manufactured by Texttechno at room temperature (25 ° C.), initial test length = 200 mm, pulling speed = 200 mm / min. Then, the strength and elongation were measured according to the tensile strength and elongation measurement method of JIS L 1013 (1992).

E. Expansion and contraction rate;
The stretch elongation rate was measured according to the stretch test method of JIS L 1013 (1992), and the average value was calculated 10 times. As a pretreatment of the sample, a dry heat treatment at 90 ° C. for 15 minutes was performed under a load of 0.3 mg / d, and the measurement was allowed to stand for 12 hours or more.

F. Hot water shrinkage;
The hot water shrinkage was measured according to the hot water shrinkage test method of JIS L 1013 (1992), and the average value was calculated 10 times. The temperature of hot water for treating the sample was 98 ° C.

[Production Example 1] (Production of polytrimethylene terephthalate: P1)
After adding 19.4 kg of dimethyl terephthalic acid, 15.2 kg of 1,3-propanediol and tetrabutyl titanate as a catalyst and titanium dioxide as a matting agent, and performing an esterification reaction at a temperature of 140 ° C. to 230 ° C., Further, a polycondensation reaction was performed for 3 hours under a constant temperature of 250 ° C. to obtain a polytrimethylene terephthalate prepolymer having an intrinsic viscosity [η] of 0.68. Next, the obtained polytrimethylene terephthalate prepolymer was pre-dried at a temperature of 120 ° C. for 1 hour, and then subjected to solid phase polymerization at a temperature of 200 ° C. for 4 hours under a reduced pressure of 1.2 to 0.7 hpa. A polytrimethylene terephthalate resin (hereinafter referred to as P1) having an intrinsic viscosity [η] of 0.98 was obtained. The obtained polytrimethylene terephthalate resin has a glass transition point of 48 ° C., a melting point of 227 ° C., a titanium dioxide content of 0.35% by weight, and an oligomer content soluble in chloroform of 0. 0.9% by weight.
[Production Example 2] (Production of polytrimethylene terephthalate containing 4% by weight of EBA added: P2)
P1 and ethylenebisstearic acid amide (EBA) [“Alfro H-50S” (registered trademark) manufactured by NOF Corporation] are dried and then melted by heating so that P1: EBA = 96: 4 (weight ratio). The polytrimethylene terephthalate resin (hereinafter referred to as P2) containing 4 wt% of EBA was measured by adding it to P1 while continuously weighing and adding it to P1 and using a biaxial kneading extruder with a cylinder temperature of 265 ° C. Obtained.

[Production Example 3] (Production of polytrimethylene terephthalate containing 7% by weight of EBA added; P3)
A polytrimethylene terephthalate resin (hereinafter referred to as P3) containing 7 wt% of EBA was obtained in the same manner as in Production Example 2 except that the ratio was changed to P1: EBA = 93: 7 (weight ratio). .

[Example 1]
Chip blend (EBA 1 wt%) was made so that P1: P2 = 3: 1 by weight ratio, charged into a hopper, melted at a temperature of 265 ° C. with an extruder to form a molten polymer, and then a temperature of 265 ° C. The molten polymer was introduced into a spinning pack installed in a spin block heated at a speed of 3500 m / min, and an undrawn yarn with a fineness of 100 dtex and 36 filaments was obtained. Spinnability was good.

  The unstretched yarn of polytrimethylene terephthalate obtained by the above method is made by Murata Machine's MACH33H false twisting machine (twisting part heater is contact type, secondary set heater is non-contact type, processing mechanism is belt nip type) Twist part heater temperature 160 ° C, secondary set heater temperature 160 ° C, feed rate 12% in secondary set heater, processing rate 300m / min, draw ratio 1.35, false twist number 2300T / m A two-stage heater false twisting was performed to obtain a false twisted yarn of 84 dtex and 36 filaments. The yarn temperature at the twisted portion heater outlet was 158 to 160 ° C, and the yarn temperature at the secondary set heater outlet was 158 to 160 ° C. The false twist processability was also good.

  The obtained false twisted yarn showed good yarn properties such as a strength of 3.0 cN / dtex, an elongation of 40%, a stretch elongation of 9.5%, and a hot water shrinkage of 2.8%.

  A plain woven fabric (weaving density: warp 95 / inch, weft 80 / inch) was prepared using this false twisted yarn for warp and weft. Furthermore, relax scouring (98 ° C., 20 minutes), intermediate set (180 ° C., 30 seconds), and immersion in 3% caustic soda aqueous solution in this plain woven fabric, and 20% alkali weight reduction processing, Dianix After dyeing with Navy Blue ERFS200 dye [manufactured by Dystar Japan], reduction washing (80 ° C., 20 minutes) was performed according to a conventional method, followed by washing with water and drying. Next, heat treatment was performed at a temperature of 160 ° C. for 30 seconds. There was almost no yarn breakage or fluffing in the weaving process at this time, and excellent processability was exhibited. Further, the obtained fabric had a high stretch characteristic peculiar to polytrimethylene terephthalate and exhibited an excellent texture that was supple and soft. As shown in Table 2, the wear resistance and water repellency were also good.

[Example 2]
Using only P2 (EVA content of 4 wt%), melt spinning, false twisting, weaving and dyeing were carried out in the same manner as in Example 1 to obtain a plain fabric. There was almost no yarn breakage or fluffing in the false twisting process and weaving process at this time, and excellent processability was exhibited. In addition, as in Example 1, it exhibited an excellent texture that was highly stretchable and flexible. As shown in Table 2, the wear resistance and water repellency were also good.

[Comparative Example 1]
Using only P1 (only polytrimethylene terephthalate), spinning, false twisting, weaving and dyeing were carried out in the same manner as in Example 1 to obtain a plain fabric. Compared with Example 1, the passability in the false twisting process and weaving process at this time tended to deteriorate. Moreover, in the texture, the same excellent stretchability and softness as in Example 1 were obtained. However, as shown in Table 2, the abrasion resistance and water repellency were inferior to those of Examples 1 and 2.

[Comparative Example 2]
Using only P3 (EVA content of 7 wt%), in the same manner as in Example 1, melt spinning, false twisting, weaving and dyeing were performed to obtain a plain fabric. At this time, yarn breakage frequently occurred in the spinning process, and the passability in the false twisting process and the weaving process tended to deteriorate. Further, as shown in Table 2, the processed yarn strength was low, and the texture, abrasion resistance, and water repellency of the fabric were inferior to those of Examples 1 and 2.

  The polytrimethylene terephthalate-based polyester fiber of the present invention has a soft texture and high stretchability, and is excellent in water repellency and abrasion resistance. be able to.

Claims (2)

  A polytrimethylene terephthalate-based polyester fiber excellent in water repellency and abrasion resistance, comprising 0.1 to 5 wt% of a fatty acid bisamide and / or an alkyl group-substituted fatty acid monoamide based on the whole fiber.   2. The polytrimethylene terephthalate-based polyester fiber excellent in water repellency and abrasion resistance according to claim 1, wherein the polytrimethylene terephthalate polyester fiber is used as a false twisted yarn having an expansion / contraction elongation rate of 1 to 300%.