JP2012207318A - Artificial hair polyester fiber, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an artificial hair polyester fiber having flame retardancy, excellent in heat resistant characteristics, giving surface luster and texture close to those of human hair by applying post-processing, such as alkali volume reduction treatment, through state modification of a fiber surface, low-cost without the need of special equipment/facilities, and allowing quantitative production while retaining a state with less fluff in long term production, and to provide a method for producing the fiber.SOLUTION: This artificial hair polyester fiber includes 0.4-5 wt.% of colloidal silica particulates having a 0.02-0.1 μm average primary particle diameter, based on 100 wt.% of the fiber whole weight, and polyester made by copolymerizing bifunctional phosphorus compounds. The artificial hair polyester fiber is such that the total size, single fiber size, shrinkage stress [F] at 100°C dry heat, shrinkage stress [F] at 180°C dry heat, temperature [T] giving a maximum shrinkage stress, degree of intermingle (l), and tear value (l) each satisfy specific values.

Description

  The present invention relates to a polyester fiber for artificial hair and a production method. In detail, it has flame retardancy, excellent heat resistance, and by surface modification of the fiber surface, it can give surface gloss and texture close to human hair by post-processing such as alkali weight loss treatment, The present invention relates to a polyester fiber for artificial hair that can be quantitatively produced while maintaining a state of low fuzz in a low cost and long-term production without requiring a specific device / equipment, and a method for producing the same.

  Fibers made of polyethylene terephthalate or polyester mainly composed of polyethylene terephthalate have high melting point, high elastic modulus and excellent heat resistance and chemical resistance, so curtains, rugs, clothing, blankets, sheets, and tables Widely used in cloth, upholstery, wall coverings, automotive interior materials, outdoor reinforcements, safety nets, etc.

On the other hand, in hair products such as wigs, hair wigs, extensions, hair bands, doll hairs, conventionally, human hair or artificial hair (modacrylic fibers, polyvinyl chloride fibers) and the like are used. However, in recent years, it has become difficult to provide human hair, and the demand for artificial hair has increased. As the artificial hair material, modacrylic that makes use of the flame-retardant characteristics has been used, but there is a problem that the heat-resistant temperature is insufficient, so polyester represented by polyethylene terephthalate with excellent heat resistance is used. Artificial hair fibers using fibers as the main component have been proposed. However, when polyethylene terephthalate is used as an artificial hair material, flame retardancy is required from the viewpoint of safety. In addition, with the increase in demand for artificial hair, additional properties such as tensile strength, easy setting properties, set retention properties, combing properties, and light discoloration are also required. Furthermore, in the case of fibers mainly composed of polyester typified by polyethylene terephthalate, which is produced by ordinary methods, the surface of the yarn is flat and the refractive index of the polyester itself is high, so the surface gloss is strong and human hair required for artificial hair. There is a problem that moderate matte properties and colors close to those cannot be obtained. In order to satisfy such performance, several proposals regarding artificial hair fibers have been made so far.
For example, the cross-section of polyester fiber is glasses-type, the degree of necking is 2.5-8, and the surface of the fiber is very similar to human hair, and has excellent combability and gloss. However, since the heat treatment temperature at the time of production is as low as about 150 ° C., the fiber obtained by this method has poor heat resistance, and 200 ° C. When a hair iron having a high temperature exceeding 1 is used, it has a problem that it easily exhibits shrinkage behavior and is inferior in durability and shape stability.

  In addition, the polyalkylene terephthalate fiber has a dumbbell-shaped (glasses-type) cross section, and is a man-made material with excellent heat resistance, setability, tactile sensation, combability, and weather resistance, including a bromine-containing flame retardant, antimony compound and light stabilizer A method for obtaining hair (for example, see Patent Document 2) has been proposed. The fiber obtained by this method uses a bromine-containing flame retardant in the production process, but in recent years, non-halogenation is required.

  Furthermore, it is a polyester containing 0.4 to 5% by weight of colloidal silica fine particles having an average primary particle size of 0.02 to 0.1 μm, and has a boiling water shrinkage of 4 to 25%. There has been proposed a method for obtaining a polyester thick yarn having a thick and thin direction, which can be used for raw yarns and is suitable for use in a thin fabric knitting and excellent in black color development (see, for example, Patent Document 3). The resulting yarn has a small amount of surface reflection and good color development, so the texture is very similar to human hair, but the boiling water shrinkage is as high as 4-25%, so when using a hair iron with a high temperature exceeding 200 ° C, etc. Has a problem that it easily exhibits shrinkage behavior and is inferior in durability and shape stability.

  Furthermore, it has gloss and texture suitable for human hair similar to human hair to which 0.01 to 1.0% by weight of colloidal silica having an average primary particle size of 150 to 500 nm is applied, and its characteristics are sustained. A method for obtaining a polyester fiber for artificial hair that can be produced (see, for example, Patent Document 4) has been proposed, but the fiber obtained by this method has a small amount of surface reflection and good color developability, but has an average primary particle size. Is as large as 150 to 500 nm, yarn breakage frequently occurs during yarn production, and yarn breakage and fluffing occur during high-order processing, resulting in a problem that the quality of the product is lowered.

  As described above, the conventional technology has flame retardancy, excellent heat resistance, and has a surface gloss and texture close to human hair, while maintaining low cost and low fluff in long-term production. However, a fiber that satisfies all the requirements for quantitative production at the same time and a method for producing the same have not been obtained.

JP2007-146306 JP 2006-316395 JP 2003-105628 A JP2008-274453

  The present invention is suitable for polyester fibers for artificial hair and a method for producing the same, solves the problems of the prior art, has flame retardancy, excellent heat resistance, and further reduces alkali weight by modifying the condition of the fiber surface. By applying post-processing such as treatment, surface gloss and texture similar to human hair can be imparted, and there is no need for special equipment / equipment. It is an object of the present invention to provide a polyester fiber for artificial hair that can be quantitatively produced while maintaining it and a method for producing the same.

In order to achieve the above object, according to the present invention, the colloidal silica fine particles having an average primary particle diameter of 0.02 to 0.1 μm are 0.4 to 5 wt% when the total weight of the fibers is 100 wt%. %, And a polyester fiber containing a polyester obtained by copolymerization of a bifunctional phosphorus compound, which satisfies the following characteristics (1) to (5): The
(1) Total fineness: 560-3300 dtex
(2) Single fiber fineness: 15 to 85 dtex
(3) Shrinkage stress at dry heat of 100 ° C. (F ₍₁₀₀₎ ): 0.01 to 0.06 cN / dtex
Shrinkage stress at 180 ° C. dry heat (F ₍₁₈₀₎ ): 0.03 to 0.1 cN / dtex
Temperature giving maximum shrinkage stress (T _(max) ): 200-240 ° C
(4) Entanglement (l ₁ ): 1 ≦ l ₁ ≦ 5
(5) Tear value (l ₂ ): 0 <l ₂ ≦ 1.

In the polyester fiber for artificial hair of the present invention,
The shape of the cross section of the single fiber is glasses, and the degree of necking (b / c) is 1.1 to 2.3,
It is preferable that the amount of phosphorus atoms is 0.3 to 1.0% by weight when the weight of the entire polyester fiber containing polyester obtained by copolymerization of a bifunctional phosphorus compound is 100% by weight. As a condition.

  Moreover, the method for producing polyester fiber for artificial hair according to the present invention is a direct spinning drawing method in which a fiber extruded from a spinneret is subjected to a cooling treatment using a cooling device and then subjected to a drawing heat treatment. It is characterized by being 250 ° C.

  The polyester fiber for artificial hair of the present invention has flame retardancy, excellent heat resistance, and surface gloss and texture close to human hair by performing post-processing such as alkali weight loss treatment by modifying the condition of the fiber surface. Can be granted. Since the production method of the present invention can be quantitatively produced while maintaining a state where there is little fluff in long-term production without requiring special equipment and facilities, it can be obtained by the production method of the present invention. The polyester fiber can be suitably used as artificial hair.

FIG. 1 is a fiber cross-sectional view showing an example of a polyester fiber for artificial hair according to the present invention. FIG. 2 shows an example of the entanglement imparting device and is a cross-sectional view when cut along a plane parallel to the running direction of the yarn. FIG. 3 is a cross-sectional view taken along a plane perpendicular to the running direction of the yarn, showing details of the entanglement processing portion in FIG.

  The polyester in the present invention is preferably one in which the main acid component is terephthalic acid or an ester-forming derivative thereof, and the main glycol component is ethylene glycol. The polyester fiber for artificial hair of the present invention contains colloidal silica fine particles and is bifunctional. It consists of a polyester fiber containing polyester obtained by copolymerizing a functional phosphorus compound.

  In addition, the polyester fiber used in the present invention includes matting agents such as titanium oxide, calcium carbonate, kaolin, and clay, pigments, dyes, lubricants, antioxidants, heat-resistant agents, heat-resistant agents, and light-resistant agents as necessary. , UV absorbers, antistatic agents, fluorescent agents, plasticizers, and the like.

  In the present invention, the colloidal silica fine particles added to the polyester have an average primary particle size of 0.02 to 0.1 μm, more preferably 0.03 to 0.09 μm, and still more preferably 0.04 to 0.08 μm. is there. When the average primary particle diameter is larger than 0.1 μm, the void diameter on the surface of the polyester fiber formed after the alkali weight loss treatment becomes too large, and the reflected light on the fiber surface cannot be sufficiently suppressed. In addition to not being able to obtain satisfactory matteness and sufficient black color development property, the breaking strength of the fiber after alkali treatment is also significantly reduced.

  Further, the colloidal silica fine particles cause wear of the guides, which causes a problem in industrial production by inducing deterioration of the yarn-making property such as generation of fluff. On the other hand, when the average primary particle size is less than 0.02 μm, the colloidal silica fine particles are aggregated, so that yarn breakage at the time of spinning is induced and stable spinning becomes difficult.

  The average primary particle size of the colloidal silica fine particles is 20% by weight when the colloidal silica (manufactured by Nissan Chemical Industries, Ltd.) is 100% by weight of ethylene glycol slurry using a HORIBA particle size analyzer (LA-700). Scattered light (light is scattered either forward, sideward, or backward depending on the particle diameter) generated by irradiating particles contained in a well-stirred ethylene glycol slurry dispersion with Mie scattering theory It is the value obtained by analysis.

  In order to sufficiently express the appropriate matteness and color close to human hair, which is the object of the present invention, the amount of colloidal silica fine particles added is 0.4 to 5% by weight when the total fiber is 100% by weight. %, More preferably 0.7 to 4.5% by weight, still more preferably 1 to 4% by weight. If the amount of colloidal silica fine particles added exceeds 5% by weight, moderate matteness and color similar to human hair can be obtained, but wear of the guides is caused, and the yarn-making property and the ability to pass through higher-order processes are reduced. A problem occurs. On the other hand, when the added amount is less than 0.4% by weight, the wear of the guides is improved, but there is a problem that an appropriate matte property and color close to human hair cannot be obtained.

  The colloidal silica in the present invention refers to those in which fine particles present mainly as a silicon oxide and present in a single particle form are present as a colloid using water or a monovalent alcohol or diol or a mixture thereof as a dispersion medium.

  As a method for adding the colloidal silica to the polymer, a method of adding the colloidal silica in a slurry in which the colloidal silica is well dispersed in ethylene glycol is preferable. The addition timing of the slurry may be any timing of esterification of the polyester, transesterification reaction or polycondensation reaction, and can be appropriately selected.

  The polyester fiber of the present invention contains polyester in which a bifunctional phosphorus compound is copolymerized in a polymer molecule for the purpose of imparting flame retardancy. As the bifunctional phosphorus compound, phosphonate, phosphinate and phosphine oxide are preferably used, but not limited thereto.

  As phosphonates, dimethyl phenylphosphonate, diphenyl phenylphosphonate and the like are preferably used. Phosphinates include (2-carboxylethyl) methylphosphinic acid, (2-methoxycarbonylethyl) methylphosphinic acid methyl, (2-carboxylethyl) phenylphosphinic acid, (2-methoxycarbonylethyl) methylphosphinic acid methyl, Methyl 4-methoxycarbonylphenyl) phenylphosphinate, ethylene glycol ester of [2- (β-hydroxyethoxycarbonyl) ethyl] methylphosphinic acid and the like are preferably used. Examples of phosphine oxides include (1,2-dicarboxyethyl) dimethylphosphine oxide, (2,3-dicarboxypropyl) dimethylphosphine oxide, (1,2-dimethoxycarbonylethyl) dimethylphosphine oxide, (2,3- Dimethoxycarbonylethyl) dimethylphosphine oxide, [1,2 di (β-hydroxyethoxycarbonyl) ethyl] dimethylphosphine oxide, [2,3 di (β-hydroxyethoxycarbonyl) ethyl] dimethylphosphine oxide and the like are preferably used. .

  Among these compounds, phosphine oxides are preferably used because of their good copolymerization reactivity with polyester and low scattering during the polymerization reaction.

  The polyester fiber used in the present invention is a polyester fiber containing a polyester (copolymerized polyester) obtained by copolymerizing the above bifunctional phosphorus compound, and the entire amount may be a copolymerized polyester or a mixture of the copolymerized polyester and the polyester. May be.

  Further, in this polyester fiber, the amount of phosphorus atoms is 0.3 to 1.0% by weight when the weight of the whole polyester fiber containing polyester obtained by copolymerization of a bifunctional phosphorus compound is 100% by weight. Preferably, it is 0.35 to 0.95% by weight, more preferably 0.4 to 0.9%. If the amount of phosphorus atoms exceeds 1.0% by weight, the mechanical properties and heat resistance of the resulting fiber tend to be impaired. Conversely, if the amount is less than 0.3% by weight, the flame-retardant effect tends to be difficult to obtain. is there.

  About the method of adding the phosphorus compound in the process for producing the copolyester, it can be added at any stage of the polyester production process, and it may be any of the esterification or transesterification reaction and the polycondensation reaction. From the viewpoint of contamination of the esterification reaction can and the late addition of the polycondensation reaction, the polycondensation time is extended, and therefore, the addition is preferably performed after the completion of the esterification reaction and early in the polycondensation. Also preferred is a method in which the phosphorus compound is added in advance after being mixed, dissolved or heat-condensed with a diol component such as ethylene glycol or other solvent.

  In addition, colloidal silica can be added before or during the polymerization of the copolyester or polyester, or it may be added after the polymerization, but the content of colloidal silica relative to the fiber weight or bifunctionality may be added. It adjusts suitably so that the copolymerization amount of a phosphorus compound may become a desired range.

  The polyester fiber of the present invention has a total fineness of 560 to 3300 dtex, preferably 700 to 2500 dtex, more preferably 830 to 1840 dtex, while maintaining a low cost and a small amount of fluff in long-term production. Enables production. When the total fineness is less than 560 dtex, not only the productivity per unit time is deteriorated and the quantitative productivity is impaired, but also the work efficiency is deteriorated because the number of polyester fibers necessary for producing a wig is increased. Conversely, when it exceeds 3300 dtex, it becomes difficult to obtain uniform cooling properties in the cooling step after spinning, and there is a concern about deterioration in quality.

  The polyester fiber of the present invention needs to have a single fiber fineness of 15 to 85 dtex, and preferably 30 to 70 dtex for artificial hair. When the single fiber fineness is less than 15 dtex, the wear resistance is deteriorated and there is a problem in the combing property. On the other hand, when the single fiber fineness exceeds 85 dtex, there is a problem that the texture and texture close to those of human hair cannot be obtained due to the strong stiffness of the yarn.

Heat shrinkage stress of the polyester fiber of the present invention, shrinkage stress at dry heat ₁₀₀ ℃ _{F (100),} contraction stress _{F (180)} in dry heat 180 ° C., respectively 0.01~0.06cN / dtex, 0.03~ It is essential that the temperature T _(max) when applying the maximum shrinkage stress is 200 to 240 ° C. is 0.1 cN / dtex. Dry heat shrinkage stress _{F (100)} at 100 ° C., shrinkage stress _{F (180)} in dry heat 180 ° C., respectively 0.01cN / dtex, if it is less than 0.03cN / dtex thermal dimensional stability is excellent in heat resistance Although it is high, it is difficult to obtain curl setting with a cosmetic heat appliance (such as a high-temperature hair iron) required for artificial hair. Conversely, contraction stress _{F (100)} in dry heat 100 ° C., shrinkage stress _{F (180)} in dry heat 180 ° C., if more each 0.06cN / dtex, a 0.1 cN / dtex, have poor heat resistance However, there is a problem that the dimensions change with a cosmetic heat appliance (such as a dryer). Further, when the temperature T _(max) when applying the maximum shrinkage stress is less than 200 ° C., the heat resistance is inferior as described above, and there is a problem in handling the artificial hair because it causes a dimensional change due to heat. Conversely, when the temperature T _(max) when applying the maximum shrinkage stress exceeds 240 ° C., it is not only technically difficult due to the thermal characteristics (melting point) of the polyester component, but also a cosmetic heat appliance required for artificial hair. It is difficult to obtain curl setting properties (such as high-temperature hair iron).

The polyester fiber of the present invention must have an entanglement degree (l ₁ ) of 1 ≦ l ₁ ≦ 5 and a tear value (l ₂ ) of 0 <l ₂ ≦ 1. According to the method of JIS L1013, the degree of entanglement (l ₁ ) referred to in the present invention is a so-called method of obtaining the number of entanglements from the distance moved by hooking a hook with a load on a vertically stretched raw yarn. The value obtained by the hook drop method is indicated, and the tear value (l ₂ ) indicates a value obtained by a relational expression of l ₂ = 1000 / L ₂ . L ₂ here refers to when the original yarn is divided in the longitudinal direction so that the filaments are halved at any point in the yarn, and the filaments divided in half are split apart by the left and right fingers. The average value (mm, measured 50 times) of the tear length (equal to the distance between the entangled entanglement points) when no further tearing is possible with a certain force. Note that the entanglement degree (l ₁ ) and tear value (l ₂ ) in the present invention are not similar, and the clear difference is that the measurement of the entanglement degree (l ₁ ) is 0 for the yarn fineness (tex). This is an advantageous method for measuring the number of confounding because it uses a very light load (mN) multiplied by .22. On the other hand, since the tear value (l ₂ ) is evaluated while breaking the slight confounding that gives light convergence to the yarn, the number of confounding points per 1 m of the raw yarn evaluated by the tear length is the general confounding Even if the given polyester fiber is taken as an example, it is considerably small as 1/2 to 1/20 of the number of entanglement points determined by the degree of entanglement (l ₁ ), so that it is advantageous for measuring the strength of entanglement. You can say that. In addition, since the measurement of tear length is often performed by human hands, there is a concern that the measured value varies depending on the measurer, but when the fiber cannot be torn due to entanglement, the resistance to the tearing force suddenly increases, so measurement There will be no significant difference in the results of each person. When the degree of entanglement (l ₁ ) 1 ≦ l ₁ ≦ 5 and tear value (l ₂ ) 0 <l ₂ ≦ 1 of the present invention is satisfied, the convergence is maintained when passing the process (suppression of yarn traversing, It is possible to produce in a quantitative manner while suppressing the yarn parakeet, and unraveling without problems when passing through a high load like a human hand. It was found that is possible. Furthermore, it has also been found that such fiber characteristics can be satisfied by appropriately controlling the entanglement processing apparatus in the manufacturing process. Confounding degree (l ₁₎ is step spinnability convergence can not be obtained at the time of passage in the case of less than 1, there is a problem that higher order pass is lowered, while the confounding degree (l ₁₎ is more than 5 In this case, the convergence at the time of passing through the process can be obtained sufficiently, but the number of confounding is excessive, and it is difficult to obtain the tear value (l ₂ ) as in the present invention with the current technology. If the tear value (l ₂ ) is 0, it is impossible to satisfy the theory. On the other hand, if the tear value (l ₂ ) exceeds 1, it has a high entanglement strength, and thus artificial hair. However, there is a problem that the combing ability required for the above becomes extremely worse.

  The shape of the cross section of the single fiber is not particularly limited as long as the effect of the polyester fiber of the present invention is not impaired. For example, a circle, an ellipse, a glasses type, a triangle, T, Y, H, +, −5 leaves, 6 leaves , 7 leaves, 8 leaves and other multi-leaf shapes, squares, rectangles, rhombuses, horseshoe shapes, etc., and some of these shapes may be modified, but gloss similar to human hair From the point of erasability, it is preferable to use a glasses type as shown in FIG. Moreover, 1.1-2.3 can be illustrated as an example of the degree of necking degree (b / c) of the glasses-type cross section. When the degree of necking of the glasses-type cross section satisfies the above range, it is preferable because combing properties are good, moderate matteness and color close to human hair are obtained, and there are no practical problems such as breaking of the glasses part. . In use, filaments having various cross-sectional shapes can be appropriately combined and used as long as the effects of the polyester fiber of the present invention are not impaired. Here, the degree of necking is a value expressed by the length of the short diameter part (b) / the length of the narrowest part (c) in the cross-sectional shape of the glasses as shown in FIG.

  Next, the method for producing the polyester fiber of the present invention will be described. The production method is not particularly limited, and a known spinning method can be adopted, but in a low-cost and long-term production, there is little fuzz. Since it is preferable to employ polyethylene terephthalate melt spinning capable of quantitative production while maintaining, an example will be described below.

  First, a base polyester chip containing colloidal silica particles stored in a spinning hopper and a master polyester chip copolymerized with a bifunctional phosphorus compound are mixed and supplied to a uniaxial extruder melt spinning apparatus. And melt spun. The molten polymer is weighed with a gear pump in accordance with the final fineness of the multifilament, filtered through a metal nonwoven fabric filter in a spinning pack, and spun from the die. The spun fiber was cooled and solidified with a cooling device, and then manufactured by a direct spinning drawing method in which it was hot drawn. Details of each step will be described below.

  The intrinsic viscosity (IV) of the polyester used in the present invention is preferably in a specific range from the viewpoint of controlling the breaking strength and elongation. In the case of the above-described base polyester chip and master polyester chip, the intrinsic viscosity is 0.5. The range of -1.3 is preferable, More preferably, it is 0.6-1.0.

  A base polyester chip containing colloidal silica fine particles filled in a hopper in a nitrogen atmosphere and a master polyester chip obtained by copolymerizing a bifunctional phosphorus compound are colloidal having an average primary particle size of 0.02 to 0.1 μm. Silica fine particles are melt kneaded with a single screw extruder at a ratio of 0.4 to 5% by weight when the total weight of the fiber is 100% by weight, and this molten polymer is mixed with a multifilament by a metering pump. After weighing according to the final fineness, it can be obtained by introducing into a spinning pack, filtering with a metal nonwoven fabric filter in the spinning pack, and discharging from the die. In addition to the uniaxial extruder, melt kneading may be performed with a biaxial extruder, roll, Banbury mixer, kneader, or the like as long as the polyester fiber of the present invention is obtained. The polyester chip used may be a bifunctional phosphorus compound copolymerized polyester chip containing colloidal silica fine particles, or a bifunctional phosphorus compound copolymerized master polyester chip containing colloidal silica fine particles. A combination of polyester chips may also be used. Furthermore, when adding the above-mentioned additives, a method of directly mixing with an extruder or a method of creating a polyester chip containing a high concentration of additives in advance and blending the chips before melting is adopted. it can.

  The melt spinning temperature can be appropriately changed depending on the intrinsic viscosity, polymer type, and the like, but is preferably 270 to 330 ° C. When spinning at less than 270 ° C, sufficient fluidity may not be obtained when the polymer is melted, resulting in quality variations. On the other hand, at temperatures exceeding 330 ° C, the polymer is decomposed and There is a possibility that the polyester fiber of the invention cannot be obtained. Immediately below the spinneret is an atmosphere in which the upper end is 0 to 15 cm from the spinneret surface, the range of 5 to 60 cm from the upper end is surrounded by a heating tube and / or a heat insulating tube, and the spinning yarn is heated to 250 to 350 ° C. It is preferable to cool and solidify with cooling air of 10 to 80 ° C, preferably 15 to 50 ° C. When the cooling air is less than 10 ° C., a large cooling device is required separately from the normal device, which is not preferable. On the other hand, when the cooling air exceeds 80 ° C., the single fiber at the time of spinning is not sufficiently cooled, and the Worcester yarn unevenness of the yarn becomes large, which leads to deterioration in quality and quality. Such an air cooling device may be a horizontal blowing type (uniflow type) or an annular blowing type. Moreover, when a high cooling effect is required like a monofilament, a cooling method such as water cooling can be adopted. By passing through such a temperature history, fibers having mechanical properties such as linear strength and elongation suitable for artificial hair can be produced with high quality.

  The unstretched yarn that has been cooled and solidified is then applied with an oil agent by an oil supply device. The oil agent may be aqueous or non-aqueous. It is preferable to have an oil composition containing a smoothing agent as a main component, including a surfactant, an antistatic agent, an extreme pressure agent component, and the like, and excluding components active in a polyester resin. For example, an alkyl ether ester as a smoothing agent component, an alkylene oxide adduct of a higher alcohol as a surfactant component, and a non-aqueous oil agent in which an organic phosphate salt or the like is diluted with mineral oil as an extreme pressure agent component is more preferable.

  The unstretched yarn provided with the oil agent is wound around a take-up roll and taken up. The surface speed of the take-up roll, that is, the take-up speed is preferably 300 m / min or more, more preferably 500 m / min or more. Polyester fibers can be obtained even at a take-up speed of less than 300 m / min, but are difficult to employ because of low production efficiency. Although there is no particular upper limit to the take-up speed, the take-up speed is preferably 4000 m / min or less, more preferably 3000 m / min or less when producing polyester fibers as in the present invention stably industrially. In the case of a take-up speed exceeding 4000 m / min, the single fiber is not sufficiently cooled, and the Worcester yarn unevenness of the yarn is increased, leading to deterioration in quality and quality, and a large cooling device is required to avoid the problem. Absent.

  The undrawn yarn taken up at the take-up speed may be subjected to normal heat drawing, and the draw ratio is changed by the birefringence of the undrawn yarn, the drawing temperature, and the drawing ratio distribution during multi-stage drawing. However, it is preferable that the film is heat-stretched at a draw ratio of 1 to 5 times, once wound or continuously without being wound, more preferably 1.5 to 4.5 times, and still more preferably 2 to 2 times. 4 times. If the draw ratio is less than 1 time, it is difficult to produce with the current technology. Conversely, if the draw ratio exceeds 5 times, the strength and elastic modulus of the yarn becomes too high, and the stiffness of the yarn is strong and the human hair is strong. There is a problem that it is difficult to obtain a touch and texture close to.

  For example, as a drawing method, similarly to the take-up roll (1FR), a Nelson type roll having two rolls as one unit is a yarn feeding roll (2FR), a first drawing roll (1DR), and a heat set roll (2DR). The yarns are arranged side by side with the relaxation rolls (RR), and the yarns are sequentially wound and subjected to the drawing heat treatment under the above-mentioned conditions. At this time, the number of drawing stages, the number of rolls, and the drawing ratio between the rolls are not particularly limited.

  Usually, stretching is performed between 1FR and 2FR to focus the yarn. The stretch ratio is preferably in the range of 1 to 8% when the overall stretch ratio is 100%. 1FR is heated to 50 to 90 ° C., and the take-up yarn is preheated and sent to the next drawing step.

  Stretching is performed between 2FR and 2DR, and the temperature of 2FR is set to 70 to 120 ° C, and then the range of 60 to 80% when the entire stretching ratio is set to 100% at 1DR (100 to 140 ° C). It is preferable to perform heat stretching, and it is preferable to perform heat treatment while stretching the yarn in a range of 12 to 39% when the total stretching ratio is 2% in 2DR. In the case of the polyester fiber of the present invention, the stretched yarn has a surface temperature of 2DR (heat treatment temperature) of 200 in order to impart thermal dimensional stability when using a hair iron having a high temperature exceeding 200 ° C. It is effective to set it to -250 degreeC, especially 230-250 degreeC. After stretching, a relaxation heat treatment is performed between 2DR and RR. In the case of the polyester fiber of the present invention, the relaxation rate is relatively high, and specifically, it may be set to about 0.5 to 5%. In the relaxation treatment, not only the strain caused by thermal stretching can be removed, but also the orientation of the amorphous region can be relaxed, the thermal shrinkage rate can be lowered, and the thermal dimensional stability can be increased. RR is preferably a non-heated roll or a roll heated to 150 ° C. or lower. By performing the relaxation heat treatment under these conditions, it becomes easy to obtain a fiber that satisfies the heat shrinkage stress as in the present invention and has excellent heat resistance and thermal dimensional stability.

Further, in order to obtain a high-quality polyester fiber by converging the yarn and reducing the occurrence of fluff, a high-pressure fluid is blown onto the fiber yarn between 2FR and 1DR, and the fiber is configured. It is preferable to draw the yarn to be entangled and stretch the yarn while converging it, and the fluid pressure can be changed by the total fineness of the yarn, the single fiber fineness, the drawing speed, etc. It is preferable to set in the range of 0.8 MPa. As described above, the entanglement imparting device for entanglement and focusing of yarns for satisfying the degree of entanglement (l ₁ ) 1 ≦ l ₁ ≦ 5 and tear value (l ₂ ) 0 <l ₂ ≦ 1 The thread is caused to travel to an entanglement processing part that is surrounded by a wall surface and is open at both ends, and a fluid is ejected from the wall surface of the entanglement processing part via three injection nozzles to cause the traveling yarn to run. In the yarn entanglement processing apparatus adapted to process the shape, the shape from the yarn introduction part to the entanglement processing end is a truncated cone shape such that the introduction part is wide and the entanglement treatment end is narrow, and It is preferable that the portion after the entanglement processing end to the exit of the yarn has a cylindrical shape. For example, it preferably has the shape and function shown in FIGS. That is, the yarn Y is caused to travel to the entanglement processing unit 2 including a cavity surrounded by the wall surface 1 and open at both ends, and a plurality of injection nozzles 4 are provided from the wall surface of the entanglement processing unit 2 to the entanglement processing unit 2. In the yarn entanglement processing apparatus in which the compressed yarn 3 is ejected through the yarn to process the traveling yarn Y, the shape from the yarn introduction part 5 to the entanglement processing part 2 is widely entangled. This is an entanglement imparting device that has a conical shape such that the processing unit 2 becomes narrow and has a cylindrical shape from the entanglement processing unit 2 to the yarn outlet 6. With such a shape, when the yarn passes through the turbulent gas flow, the yarn tension can be locally reduced by the backflow action, and the compressed air after confounding is efficiently discharged to the outside. Can be made. By using the entanglement imparting device, the degree of entanglement (l ₁ ) 1 ≦ l ₁ ≦ 5 and the tear value (l ₂ ) 0 <l ₂ ≦ 1 as in the present invention can be satisfied. The entanglement imparting device is effective when used in the first stage of stretching, but may be used during the second and third stages of stretching in addition to the first stage. Furthermore, it is preferable that the yarn subjected to the relaxation heat treatment is passed through the entanglement processing apparatus set in a fluid pressure range of 0.6 to 0.9 MPa immediately before winding. By applying the entanglement with the fluid pressure in such a range, the unwinding property of the yarn from the wound product and the processability of the yarn can be improved, and troubles in the high-order processing step can be avoided. Thus, the polyester fiber of the present invention is obtained.

  Hereinafter, the present invention will be described specifically by way of examples. In addition, the definition of the characteristic used for the specification text and the examples, and the measurement and calculation methods of each physical property are as follows.

[Total fineness]:
Based on JIS L1013 (1999) 8.3.1a) Method A, using a measuring machine manufactured by Nakayama Electric Industry Co., Ltd., an initial load of display fineness x 0.45 mN / dtex was applied, and the total fineness and did.

[Single fiber fineness]:
The total fineness was calculated by dividing by the number of single fibers. Here, the number of single fibers was calculated according to JIS L1013 (1999) 8.4.

[Intrinsic viscosity]:
The relative viscosity ηr of a solution obtained by adding 8.0 g of sample to 100 mL of orthochlorophenol and dissolving by heating at 160 ° C. for 10 minutes was measured at 25 ° C. using an Ostwald viscometer, and calculated according to the following approximate expression.
Intrinsic viscosity = 0.0242 ηr + 0.2634

[Average primary particle diameter of colloidal silica]:
Using a HORIBA particle size analyzer (LA-700), the colloidal silica (manufactured by Nissan Chemical Industries, Ltd.) is contained in an ethylene glycol slurry dispersion containing 20% by weight and sufficiently stirred when the ethylene glycol slurry is 100% by weight. Scattered light generated when light is irradiated onto particles existing in (the light is scattered forward, sideward, or backward depending on the particle diameter) was analyzed and calculated by Mie scattering theory.

[Temperature T (max) when applying shrinkage stress and maximum shrinkage stress]:
The sample was attached to a Toyo Baldwin SS-207D-UE strain measuring machine, and a temperature-heat shrinkage stress curve was drawn while raising the temperature using a Toyo Baldwin TKC-IIIS heating furnace. The temperature at which stress was applied was read. The sample length at this time was 250 mm, and an initial load of 0.045 cN / dtex was applied. The measurement temperature range was 25 ° C. to 260 ° C., and the temperature increase rate was set to 5 ° C./min. Each sample was measured twice to obtain an average value.

[Degree of confounding]:
According to JIS L1013 (1999) 8.15, the weight of the weight is 0.22 mN / tex × display tex number, the predetermined load display tex number / filament number × 1.09 mN at the other end of the hook, and the descending speed is 10-20 mm / sec. It was lowered and calculated by the following formula.
Degree of confounding (l ₁ ) = 1000 (mm) / Descent distance (mm)

[Tear value]:
Divide the original yarn in the longitudinal direction so that the filaments are roughly halved at any point on the yarn, and tear apart the filaments that were split in half with the left and right fingers. The tear length (mm) at the time of disappearance was used to calculate by the following formula. In addition, the average value obtained by measuring 50 times is used.
Tear value (l ₂ ) = 1000 (mm) / Tear length (mm)

[Process passability]:
After the start of production, the guide and rolls are not exchanged, and the polyester fibers obtained 24 hours and 240 hours after continuous spinning are unwound at a speed of 500 m / min, and light sensing type manufactured by Ohiro Co., Ltd. Fluff contained in the yarn (single yarn breakage) was detected by the fluff detection device, and the number of fluff per 100,000 m of yarn length was evaluated according to the following criteria.
Number of fluff (pieces / 100,000m)
◎: 0 to 1
○: 1 to 5
Δ: 5-50
×: 50 or more

[Flame retardance]:
In accordance with JIS L1091 (2002) textile product flammability test method D (flame contact test), the number of times of flame contact of a sample produced with a cylindrical knitting machine was measured. The flame retardance required was evaluated by setting the number of times of flame contact to 2 or less and x to 3 times or more.

[Heat-resistant]:
After heat treatment for 5 minutes in Testrite Patent Thermal Shrinkage Oven Mk 3 (TS10 AB3) manufactured by Testrite Ltd. set at 150 ° C and 190 ° C, with the indicated number of texes / number of filaments x 1.09 mN applied as the specified load The numerical value (dry heat shrinkage rate) indicated by the test light needle was confirmed and calculated according to the following formula. In addition, the average value obtained by measuring three times for each temperature is used.
Dimensional change (%) = Dry heat shrinkage at 190 ° C (%)-Dry heat shrinkage at 150 ° C (%)
Each evaluation standard is as follows.
: Excellent heat resistance (Dimensional change (%) <2)
○: Slightly superior in heat resistance (2 ≦ dimensional change (%) <4)
Δ: Slightly inferior in heat resistance (4 ≦ dimensional change (%) <6)
×: Inferior in heat resistance (6 ≦ Dimensional change (%))

[Matte and color tone]:
The polyester fiber obtained by the spinning method described in Examples and Comparative Examples was 80 ° C. in an aqueous solution (15% owf) containing 1.5 g / L of hydrosulfite, 1 g / L of caustic soda, and 1 g / L of amylazine. , After 20 minutes alkali weight loss treatment, Diaix Black BG-FS (manufactured by Mitsubishi Chemical Corporation, disperse dye) 15% o.d. w. What was dyed in the dye bath prepared in f at 130 ° C. for 60 minutes was visually judged at an incident angle of sunlight of 10 to 55 ° at a window in a room exposed to direct sunlight. The color tone was evaluated. Each evaluation standard is as follows.
◎: Gloss and color tone very similar to human hair ○: Dull gloss and color tone similar to human hair △: Slightly strong gloss and color tone ×: Strong gloss and color tone

[Combination]:
The uppermost part of the multifilament having a length of 250 mm and a total fineness of 10,000 dtex was held with one hand, and combing was performed 100 times in a state of hanging vertically, and combing property evaluation was performed. Each evaluation standard is as follows.
◎: No resistance at all ○: Almost no resistance △: Some resistance ×: Very resistance or comb-through

[Curl setting]:
A filament with an initial yarn length of 400 mm left in a temperature-controlled room set at a temperature of 20 ° C and a humidity of 65% for one day is wound around a fixed length section of a hair iron set at 200 ° C and held for 10 seconds. Was removed, and one end of the curled filament was fixed, and the state of curling was visually evaluated by hanging down vertically. Each evaluation standard is as follows.
○: The shape of the curl is good. △: The curl is slightly stretched. ×: The shape of the curl is broken and collapsed, or the size is changed by shrinking.

[Example 1]
Highly pure terephthalic acid (manufactured by Mitsui Chemicals) and colloidal silica having an average primary particle size of 0.06 μm (manufactured by Nissan Chemical Industries, Ltd.) contained 20% by weight and sufficiently stirred when the ethylene glycol slurry was 100% by weight. The ethylene glycol slurry and further magnesium acetate and antimony oxide as reaction catalysts were all charged in a transesterification can and gradually heated from 150 ° C. to 250 ° C. in a nitrogen atmosphere to conduct a transesterification reaction. The transesterification reaction was controlled so that the colloidal silica content was 6% by weight when the obtained colloidal silica-containing low polymer was 100% by weight.

  Further, the polymerization reaction system was gradually depressurized to 13.3 Pa over 1 hour and 30 minutes, and the temperature was raised to 280 ° C., and this degree of decompression and temperature were maintained until the target intrinsic viscosity was reached. The base polyester chip | tip was obtained by drying the chip | tip of intrinsic viscosity 0.7 so that the moisture content might be 200 ppm or less under vacuum.

  Next, when the bis-β-humanoxy terephthalate obtained by direct esterification of high-purity terephthalic acid (Mitsui Chemicals) and ethylene glycol (Nippon Shokubai Co., Ltd.) and its low polymer were 100% by weight, 2 2-methyl-2,5-dioxo-1,2-oxaphospholane, which is a functional phosphorus compound, was added while adjusting the phosphorus atom to 1.6% by weight, and 285 from 250 ° C. in 30 minutes. The temperature was raised to 0 ° C., and the reaction system was reduced from normal pressure to 66.7 Pa in 30 minutes. This temperature and degree of pressure reduction were maintained until the target intrinsic viscosity was reached. The master polyester chip was obtained by drying the chip No. 7 to a moisture content of 200 ppm or less under vacuum.

  The weight ratio of the base polyester chip and the master polyester chip obtained by the above method was mixed at a ratio of 50:50, and continuously fed to a single screw extruder type extruder at 295 ° C. and melted. The molten polymer was kneaded with an eight-stage static mixer through a pipe at 295 ° C., adjusted to a discharge rate of 375 g / min with a metering pump, and then led to a spin pack at 295 ° C. After passing through the filter, spinning was performed from a die having 30 round single holes having a hole diameter of 0.6 mmφ and a hole length of 0.78 mm.

  The spun yarn is passed through a heating tube having a length of 300 mm and an atmospheric temperature of 285 ° C. provided under the base, and then solidified by blowing cold air of 40 ° C. at a speed of 30 m / min using an annular chimney. It was. Next, an oil agent (manufactured by Sanyo Kasei Co., Ltd .: Sun Oil F) is applied to the cooling yarn with an oil agent roll, and the obtained yarn is wound at 1 FR (70 ° C.) having a surface speed of 625 m / min. And subjected to a stretching process.

  2FR (100 ° C.) at a speed of 675 m / min, 1DR at a speed of 2000 m / min (110 ° C.), 2DR at a speed of 2500 m / min (230 ° C.), a speed of 2450 m / min without winding the yarn that has passed 1 FR Stretching was performed by continuously subjecting to RR (non-heated) for minutes. The entanglement processing device (described in FIGS. 2 and 3) is installed between 2FR-1DR, between 2DR-RR, and between RR and winder, and injects high-pressure fluid at settings of 0.4, 0.5, and 0.7 MPa, respectively. As a result, it was entangled and wound up by a winder to obtain 1500 dtex-30 filament polyester fiber for artificial hair.

[Example 2]
The base polyester chip and the master polyester chip were prepared by the method described in Example 1 so that the blending ratio shown in Example 2 of Table 1 was obtained, and the discharge rate was adjusted to 250 g / min with a metering pump. Example 1 except that a base having 25 round single holes with a hole diameter of 0.6 mmφ and a hole length of 0.78 mm was used, and the speed was changed to 2DR (200 ° C.) of 2500 m / min. According to the method, 1000 dtex-25 filament polyester fiber for artificial hair was obtained.

[Example 3]
Except that the base polyester chip and the master polyester chip were prepared by the method described in Example 1 so that the blending ratio shown in Example 3 of Table 1 was obtained, and the speed was changed to 2DR (250 ° C.) of 2500 m / min. The same operation as in Example 2 was performed.

[Example 4]
The base polyester chip and the master polyester chip were prepared by the method described in Example 1 so that the blending ratio shown in Example 4 in Table 1 was obtained, and the entanglement processing device (described in FIGS. 2 and 3) was connected between 2FR-1DR and 1DR. -2DR, 2DR-RR, and RR-winder, and entangled by applying high-pressure fluid at settings of 0.4, 0.5, 0.6, and 0.7 MPa, respectively. Except that, the same procedure as in Example 1 was performed.

[Example 5]
The base polyester chip and the master polyester chip were prepared by the method described in Example 1 so that the blending ratio shown in Example 5 of Table 1 was obtained, and there were 25 glasses-type single holes having a hole diameter of 0.6 mmφ and a hole length of 0.78 mm. A polyester fiber for artificial hair with 1500 dtex-25 filament (ring degree of 1.7) was obtained in the same manner as in Example 1 except that the cap was opened.

[Example 6]
The base polyester chip and the master polyester chip were prepared by the method described in Example 1 so that the blending ratio shown in Example 6 of Table 1 was obtained, and the discharge rate was adjusted to 750 g / min with a metering pump. A polyester fiber for artificial hair of 3000 dtex-40 filament was obtained in the same manner as in Example 1 except that a base having 40 round single holes with a hole diameter of 0.6 mmφ and a hole length of 0.78 mm was used. .

  Using polyester fibers obtained in Examples 1 to 5, temperature T (max), degree of entanglement, tear value, process passability, flame retardancy when applying fineness, single fiber fineness, shrinkage stress and maximum shrinkage stress Table 1 shows the results of evaluation of heat resistance, matting / color tone, combing property, and curl setting property.

[Comparative Examples 1-3]
The same procedure as in Example 1 was performed except that the base polyester chip and the master polyester chip were prepared by the method described in Example 1 so that the blending ratios shown in Comparative Examples 1 to 3 in Table 1 were obtained. However, for Comparative Example 3, the following evaluation was not performed because the yarn-making property was lowered and polyester fibers were not obtained.

[Comparative Example 4]
Except that the base polyester chip and the master polyester chip were prepared by the method described in Example 1 and the speed was changed to 2DR (180 ° C.) of 2500 m / min so as to have the blending ratio shown in Comparative Example 4 of Table 1. The same procedure as in Example 1 was performed.

[Comparative Example 5]
The base polyester chip and the master polyester chip were prepared by the method described in Example 1 so that the blending ratio shown in Comparative Example 5 in Table 1 was obtained, and the discharge rate was adjusted to 875 g / min with a metering pump. The production of polyester fibers for artificial hair of 3500 dtex-40 filaments in the same manner as in Example 1 except that a base having 40 round single holes with a hole diameter of 0.6 mmφ and a hole length of 0.78 mm was used. However, the following evaluation was not performed because a uniform cooling property could not be obtained in the cooling step, and fluff was frequent and polyester fibers could not be obtained due to deterioration of quality.

[Comparative Example 6]
A base polyester chip and a master polyester chip were prepared by the method described in Example 1 so that the blending ratio shown in Comparative Example 6 in Table 1 was obtained, and an entanglement processing device (PS-1600 parallel jet manufactured by Heberline Co., Ltd.) was 2FR- Installed between 1DR, 1DR-2DR, 2DR-RR, RR-winder, and entangled by injecting high-pressure fluid at 0.6, 0.8, 1.0, and 1.0 MPa settings, respectively The same procedure as in Example 1 was performed except that the treatment was performed.

  As is apparent from the results in Table 1, Comparative Examples 1 and 3 and 5 which are not polyester fibers of the present invention have problems such as inferior matteness and color tone when used as artificial hair, and polyester fibers having low process passability. Cannot be obtained, and Comparative Example 2 has a problem that flame retardancy is impaired. Further, Comparative Examples 4 and 6 each have a problem that the heat resistance is poor and a dimensional change occurs, and there is a problem in handling as artificial hair because combability is extremely poor.

  On the other hand, the polyester fiber for artificial hair that satisfies the scope of the present invention has flame retardancy, is excellent in heat resistance characteristics, and is further subjected to post-processing such as alkali weight loss treatment by modifying the fiber surface, Since it has excellent surface gloss, texture and combability comparable to human hair, it can be used effectively as artificial hair.

  The polyester fiber for artificial hair of the present invention has excellent properties comparable to human hair, and contributes greatly to hair or hair products such as wigs, hair wigs, extensions, hair bands and doll hairs.

a major axis part length b minor axis part length c narrowest part length Y yarn 1 wall surface 2 entanglement processing part 3 compressed air 4 injection nozzle 5 introduction part 6 yarn outlet

Claims (4)

Colloidal silica fine particles having an average primary particle diameter of 0.02 to 0.1 μm are contained in an amount of 0.4 to 5% by weight when the weight of the whole fiber is 100% by weight, and a bifunctional phosphorus compound is copolymerized. A polyester fiber containing polyester, which satisfies the following characteristics (1) to (5):
(1) Total fineness: 560-3300 dtex
(2) Single fiber fineness: 15 to 85 dtex
(3) Shrinkage stress at dry heat of 100 ° C. (F ₍₁₀₀₎ ): 0.01 to 0.06 cN / dtex
Shrinkage stress at 180 ° C. dry heat (F ₍₁₈₀₎ ): 0.03 to 0.1 cN / dtex
Temperature giving maximum shrinkage stress (T _(max) ): 200-240 ° C
(4) Entanglement (l ₁ ): 1 ≦ l ₁ ≦ 5
(5) Tear value (l ₂ ): 0 <l ₂ ≦ 1 2. The polyester fiber according to claim 1, wherein the cross-sectional shape of the single fiber is a glasses-type, and the degree of necking (b / c) is 1.1 to 2.3. The amount of phosphorus atoms is 0.3 to 1.0% by weight when the total weight of the polyester fiber containing polyester obtained by copolymerization of a bifunctional phosphorus compound is 100% by weight. Item 3. The polyester fiber according to Item 1 or 2. The heat treatment temperature is 200 to 250 ° C in a direct spinning drawing method in which a fiber extruded from a spinneret is subjected to a cooling treatment using a cooling device and then subjected to a drawing heat treatment, and the heat treatment temperature is 200 to 250 ° C. The manufacturing method of the polyester fiber of Claim 1.

Images