JPH0551685B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a method for producing polyester fibers having excellent color tone and sliminess, and having a soft texture. Specifically, the present invention relates to a method for producing polyester fibers containing a specific amount of a specific higher aliphatic monocarboxylic acid ester compound and having a good color tone, a durable slimy feel, and a soft texture. [Prior Art and its Problems] In recent years, various modification studies have been conducted on polyester fibers in order to obtain an appearance and feel similar to natural fibers. Among these, many studies have been made on polyester fibers that have an appearance and texture similar to high-quality animal hair. The texture of animal hair is expressed by its unique sliminess and soft texture.
Unless both of these functions are imparted, polyester fibers with an animal hair-like texture cannot be obtained. However, although various methods have been studied to provide either the slimy feel characteristic of animal hair or the soft texture characteristic of animal hair, no attempt has been made to create a polyester fiber that combines the characteristics of both. Furthermore, methods for giving polyester fibers the sliminess characteristic of animal hair include methods for incorporating easily slippery polymers such as polyorganosiloxane and polytetrafluoroethylene into polyester, and methods for adding wax or footwear after fiber formation. Although methods for attaching slippery organic compounds such as elementary compounds and silicone compounds to polyester fibers have been studied, sufficient results have not been obtained. In other words, it is true that adding slippery polymers such as polyorganosiloxane and polytetrafluoroethylene can give polyester fibers a slimy feel, but these slippery polymers are not compatible with polyester. Due to its poor solubility, it required a large amount to be added to give it a slimy feel, resulting in significant coloring, making it impossible to use it as animal hair-like polyester fiber. Specifically, an example in which polyethylene wax is included is proposed in JP-A-53-126316. Although the purpose of this proposal is to prevent yarn breakage and fuzz from occurring during the processing process,
The acid value and molecular weight of the polyethylene wax contained are large, and the effect of imparting sliminess is small. Also, JP-A-58-9844, JP-A-57-
143521 proposes an example of containing an organic compound or a fluorine compound, but this has not resulted in improvement of good color tone and durable sliminess. On the other hand, after fiber formation, wax, fluorine compounds,
When a slippery organic compound such as a silicone compound is attached to polyester fiber, it can give a slimy feel, but it comes off when washed, dry-cleaned, etc., resulting in poor durability. In addition, as a method of imparting the soft texture characteristic of animal hair to polyester fibers, a method of applying a softening agent such as a surfactant after fiber formation has been studied, but although it is possible to impart flexibility, washing
The fabric softener fell off the fibers during dry cleaning, resulting in poor durability. For this reason, it has been considered impossible in the art to obtain animal hair-like polyester fibers that have good color tone, durable sliminess, and soft texture. [Object of the Invention] An object of the present invention is to establish a method for producing polyester fibers having good color tone, durable slimy feel, and soft texture. [Structure of the Invention] The above object of the present invention is achieved by the following structure. That is, for 100 parts by weight of polyester whose main repeating unit is ethylene terephthalate, it contains 0.1 to 10.0 parts by weight of a compound whose main component is a higher aliphatic monocarboxylic acid ester having 34 to 64 carbon atoms and whose acid value is 5 or less. A method for producing modified polyester fibers, which is characterized in that after melt-spinning a polyester made of It's time. (However, Tm refers to the melting point of the polyester.) The polyester in the present invention may be a homopolyester or a copolyester as long as it is a polyester mainly composed of polyethylene terephthalate. Examples of copolymerizable components include diethylene glycol, propylene glycol, neopentyl glycol, polyalkylene glycol,
1,4-cyclohexanedimethanol, 1,4-
Diol components such as butanediol and tetraethylene glycol; dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid, dodecanedioic acid, and dimer acid; Examples include polyfunctional dicarboxylic acid components such as trimellitic acid and pyromellitic acid, and oxycarboxylic acid components such as p-oxyethoxybenzoic acid. The main component contained in the polyester of the present invention is a higher aliphatic monocarboxylic acid ester having 34 to 64 carbon atoms, and the compound has an acid value of 5 or less:
Examples include hexyl montanate, ceryl montanate, octacosyl lignocerate, merisyl lignocerate, ceryl lignocerate, merisyl cerotate, seryl cerotate, and naturally occurring carnauba wax, prickly pear wax, and the like are also preferably used. The higher aliphatic monocarboxylic acid ester compound which is the main component must have 34 to 64 carbon atoms, preferably 40 to 62 carbon atoms. The number of carbon atoms is
If it is less than 34, the ester compound will have a low molecular weight, resulting in severe fouling of the die when the obtained polyester is made into fibers. Furthermore, those having more than 64 carbon atoms have poor compatibility with polyester, and therefore have a small sliminess imparting effect. There is no limit to the number of carbon atoms in the higher aliphatic monocarboxylic acid, but those having 20 to 35 are preferred because they have a large sliminess imparting effect. As the alcohol forming the higher aliphatic monocarboxylic acid ester, monohydric or dihydric aliphatic alcohols are preferred because of their great sliminess imparting effect. Furthermore, the main component used in the present invention has 34 carbon atoms.
The acid value of the compound consisting of a higher aliphatic monocarboxylic acid ester of ~64 must be 5 or less. If the acid value exceeds 5, the effect of imparting sliminess is small. The reason for this is that the acid present in the compound generates internal particles by reaction with the polyester polymerization catalyst, and these internal particles act as a crystal nucleating agent, increasing the crystallinity of the polyester fiber, eliminating threads, and creating a slimy feeling. This is thought to be due to a decrease in The main component of the present invention is a higher aliphatic monocarboxylic acid ester having 34 to 64 carbon atoms, and the compound having an acid value of 5 or less needs to be contained in the polyester in an amount of 0.1 to 10.0 parts by weight, preferably 0.5 ~
It is preferable to contain 8.0 parts by weight. The content is
If the amount is less than 0.1 part by weight, the effect of imparting sliminess and soft texture will be small. This is because by heat-treating the polyester fiber containing the higher aliphatic monocarboxylic acid ester compound used in the present invention, the compound oozes out onto the surface of the fiber, giving it a soft texture. less than
This effect cannot be achieved. Moreover, if the content exceeds 10.0 parts by weight, the resulting polyester fibers will be severely colored, making them unsuitable for practical use. In addition, the polyester of the present invention may contain stabilizers, heat resistant agents, weather resistant agents, antioxidants, antistatic agents,
Any additives such as a flame retardant and a matting agent such as TiO ₂ may be included. The method for producing the polyester of the present invention is not limited, and any known polymerization method may be used. There is no limit to the timing of adding the compound containing a higher aliphatic monocarboxylic acid ester as a main component to the polyester, and it may be added before the polycondensation reaction, during the polycondensation reaction, after the end of the polycondensation reaction, or when drying the chips. , after the completion of the polycondensation reaction is preferable in terms of the color tone of the polyester. Further, as a method for incorporating a certain amount of a compound containing this ester as a main component into the polyester, a method of diluting and mixing a polyester containing a large amount of a compound containing this ester as a main component with another polyester can also be adopted. There is no need to use any special method to melt-spun the polyester obtained in this way.
Conventional polyester fiber melt spinning methods are optionally employed. The fibers to be spun here may be solid fibers with no hollow portions or hollow fibers with hollow portions, and the outer shape and the shape of the hollow portions in the cross section of the spun fibers may be circular. It doesn't matter if it's a strange shape or not. The polyester fiber thus obtained may be heat-treated at the same time as or after the stretching, during false twisting, or after being made into a fabric, but preferably after being made into a fabric. Further, for the heat treatment, known means such as an oven or a hot roller can be used. The heat treatment temperature T°C in the present invention is 170≦T≦
It is necessary to satisfy Tm-5 (℃) and 200≦
It is preferable that T≦Tm−10 (° C.). (However, Tm refers to the melting point of polyester.) If the heat treatment temperature is less than 170°C, there will be little oozing of the higher aliphatic monocarboxylic acid ester compound onto the fiber surface, making it impossible to impart a soft texture. Also, the heat treatment temperature is Tm−
If the temperature is higher than 5°C, the single yarns will fuse together and the texture will harden. The heat treatment time in the present invention must be 0.1 seconds or more and 30 minutes or less, preferably 1 second or more and 20 minutes or less. If the heat treatment time is less than 0.1 seconds, the higher aliphatic monocarboxylic acid ester compound will not ooze out onto the fiber surface due to the heat treatment, and a soft texture cannot be imparted. If the heat treatment time is longer than 30 minutes, the higher aliphatic monocarboxylic acid ester compound will undergo thermal deterioration, resulting in poor color tone of the resulting polyester fiber. The denier of the fibers finally obtained by spinning and drawing heat treatment is not particularly limited, but the smaller the denier, the softer the texture, and the more animal hair-like texture is imparted, so it is preferably 3 denier or less. [Effects of the Invention] (1) Polyester fibers containing a specific amount of a specific higher aliphatic monocarboxylic acid ester compound are heat-treated at a specific temperature and time, so the polyester obtained by the method of the present invention The fiber has good color tone, slimy feel and soft texture. Therefore, it is a suitable fiber for use as an animal hair-like polyester fiber. (2) Since the polyester fiber containing a specific higher aliphatic monocarboxylic acid ester compound inside the polyester fiber is heat-treated at a specific temperature and time, the polyester fiber obtained by the method of the present invention cannot be washed or dry cleaned. Even if you do this, there will be no slimy feeling or loss of flexibility.
Excellent durability. The present invention will be explained in detail with reference to Examples below. In addition, each characteristic value of polyester and polyester fiber in Examples was measured by the following method. (Intrinsic viscosity) Determined from the value measured at 25°C in an orthochlorophenol solution. (Method for creating tubular knitting) The filament to be evaluated is used to knit tubular knitted fabric using a 27-gauge sock knitting machine (manufactured by Koike Kikai Seisakusho Co., Ltd.). (Scouring method) The tubular knitted fabric to be evaluated was treated with 0.2% nonionic activator (Sandet G-900 (manufactured by Sanyo Chemical Co., Ltd.) by a conventional method.
Scouring by boiling in boiling water containing 0.2% soda ash for 5 minutes, then washing and drying. (Color tone) It is expressed as a b value measured by stacking six or more pieces of tubular knitted fabric to be evaluated and using a digital measurement color difference calculator (manufactured by Suga Test Instruments Co., Ltd.) in a state where no irradiation light is transmitted. The larger the b value, the more yellowish the color tone becomes. (Sliminess) 110 panelists touched 1 g of the tubular knitted fabric with their hands and conducted a sensory test. 5 or more panelists rated it as ``slimy'', and 2 to 4 panelists rated it as ``slimy''. △ for things that are true, × for others
And so. (Flexibility) 1 g of the tubular knitted fabric to be evaluated was touched by 10 panelists with their hands and subjected to a sensory test. 5 or more panelists evaluated it as flexible, while 2 to 4 panelists evaluated it as flexible. Those that were marked were marked △, and the others were marked ×. (Spindle stain) We observed stains on the spindle when polyester was spun for 8 hours.
Slight staining was rated △, and severe staining was rated ×. (Melting point) Using Perkin-Elmer's DSC-1B, 10 mg of sample polymer was heated from room temperature at a rate of 16°C/min in a nitrogen gas atmosphere, the minimum point of the melting peak was measured, and the melting point was determined. And so. Example 1 100 parts by weight of dimethyl terephthalate, 62 parts by weight of ethylene glycol, 0.06 parts by weight of calcium acetate,
0.04 parts by weight of antimony trioxide was charged into a transesterification tank, transesterification was carried out in a conventional manner, and 0.05 parts by weight of trimethyl phosphate was added to the resulting product to carry out a polycondensation reaction. After the reaction was completed, the ester compounds shown in Table 1 were added and kneaded under reduced pressure for about 10 minutes. Table 1 shows the intrinsic viscosity and melting point of the obtained polyester. Diameter of these polyester
Melt spinning was performed using a spinneret with 24 spinning holes of 0.23 mm at a spinning temperature of 290°C and a discharge rate of 31 g/min,
The material was wound onto a bopin at a winding speed of 1200 m/min. The obtained undrawn yarn was drawn 3.7 times using a hot roller at 87℃ and a hot plate at 150℃, resulting in a strength of 4.9.
A 65 denier 24 filament polyester filament with ~5.0 g/d and an elongation of 33-37% was obtained. A cylindrical knitted fabric was prepared using this polyester filament, and after scouring, it was heat-treated in an oven at 230°C for 1 minute, and the color tone, sliminess, and nozzle stain were measured.
The results are shown in Table 1.

【table】

[Table] As is clear from Table 1, Experimental Examples No. 2, No. 3, No. 8, No. 9, and No. 10, which are within the scope of the present invention, had good color tone, sliminess, and nozzle stain. It was hot. It also had excellent flexibility. Experimental example with a small amount added
Experiment No. 1 has poor sliminess and flexibility, and Experimental Example No. 5 and No. 7 have a high acid value, and Experimental Example No. 4 has poor sliminess, and Experimental Example No. 4, which has a large amount added, has inferior color tone, and the main component is ester. Experimental example No. 6, which had a small number of carbon atoms, had severe fouling of the cap. Further, Experimental Examples No. 11 and No. 12, which contained a compound having a structure different from that of the present invention, had no sliminess at all. Example 2 A tubular knitted fabric was created using the polyester filament of Experimental Example No. 3 of Example 1, and after scouring, heat treatment was performed in an oven for 1 minute with the heat treatment temperature changed as shown in Table 2 to remove sliminess. The properties and flexibility were measured. The results are shown in Table 2.

[Table] As is clear from Table 2, the flexibility changes depending on the heat treatment temperature, and experimental examples No. 8 and 9
Since the heat treatment temperature was within the range of the present invention, the flexibility was good, but Experimental Examples No. 7 and No. 10, in which the heat treatment temperature was outside the range of the present invention, had poor flexibility. Example 3 100 parts by weight of terephthalic acid and ethylene glycol
A slurry was prepared by kneading 43 parts by weight. into the reactor
The slurry was continuously added at a constant rate to a reactant of 50 parts by weight of terephthalic acid and 21.5 parts by weight of ethylene glycol stored at 245°C, and the esterification reaction was carried out at 245°C under normal pressure, and the resulting water was rectified. It was continuously distilled out of the system from the tower. The supply time of the slurry was completed in 3 hours and 30 minutes, and the esterification reaction was completed in 4 hours. From the obtained reaction products, an esterification reaction product equivalent to 100 parts by weight of terephthalic acid was transferred to a polymerization apparatus, and after adding 0.045 parts by weight of phosphoric acid and 0.023 parts by weight of antimony trioxide, a polycondensation reaction was performed. After the reaction was completed, 4.5 parts by weight of carnauba wax was added under normal pressure, followed by kneading under reduced pressure for 15 minutes. The obtained polyester had an intrinsic viscosity of 0.62 and a melting point of 260°C.
This polyester was spun using a spinneret with 24 spinning holes with a diameter of 0.23 mm at a spinning temperature of 290°C and a discharge rate of 31 mm.
It was melt spun at a speed of g/min and wound onto a bobbin at a winding speed of 1200 m/min. The obtained undrawn yarn was heated using a hot roller at 87°C and a hot roller at 150°C.
After sharp stretching, heat treatment was carried out using a hot roller at 230° C. while changing the heat treatment time as shown in Table 3. A tubular knitted fabric was created using these polyester filaments, and after scouring, the sliminess and flexibility were measured. The results are shown in Table 3.

[Table] As is clear from Table 3, the flexibility changes depending on the heat treatment time, and Experimental Examples No. 12 and 13
Since the heat treatment time was within the range of the present invention, the flexibility was good, but Experimental Example No. 11, in which the heat treatment time was outside the range of the present invention, had poor flexibility. Example 4 A tubular knitted fabric was created using the polyester filament of Experimental Example No. 3 of Example 1, and after scouring, heat treatment was performed in an oven at 230°C with varying heat treatment times as shown in Table 4. Sliminess, flexibility, and color tone were measured. The results are shown in Table 4.

[Table] As is clear from Table 4, Examples No. 14 and No. 15, which are within the scope of the present invention, were excellent in sliminess, flexibility, and color tone, but Experimental Example No. 16, which took a long heat treatment time, The color tone was poor.

Claims (1)

[Claims] 1 For 100 parts by weight of polyester whose main repeating unit is ethylene terephthalate, add a compound whose main component is a higher aliphatic monocarboxylic acid ester having 34 to 64 carbon atoms and whose acid value is 5 or less.
Modification characterized by melt-spinning a polyester containing 0.1 to 10.0 parts by weight and then heat-treating it at a temperature T°C satisfying 170≦T≦Tm−5 (°C) for a period of 0.1 seconds or more and 30 minutes or less Method of manufacturing polyester fiber. (However, Tm refers to the melting point of polyester.)