JP2009280943A - Water-repellent polyester fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a combined filament having excellent water-repellent performance and capable of giving fabrics low in decrease of initial water repellency which decrease is caused by long term use or repeated washing. <P>SOLUTION: Provided is a water-repellent polyester fiber consisting of a flat section polyester fiber wherein the section form of the single fiber is a flat section which section has a form provided by bonding 3-6 round section single fibers in the longitudinal direction, and which water-repellent polyester fiber contains specific ester-reactive silicone of 2-20 pts.wt. per 100 pts.wt. polyester and is loaded with a metal-containing phosphorus compound and 0.5-1.2 molar times alkaline-earth metal compound based on the metal-containing phosphorus compound without previously reacted and, thereafter, treated by caustic reduction. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a water-repellent polyester fiber having a flat cross-sectional shape that can be suitably used for various apparel and material applications that have no deterioration in water repellency even when used for a long period of time and have excellent texture, permeation resistance, and low air permeability. .

  Conventionally, polyester fibers have been widely used as synthetic fibers because they have many excellent properties. Many proposals have been made on the shape of the single yarn in order to improve the soft feeling and touch feeling when touching while having the excellent characteristics of polyester fiber, especially for sports and casual use in recent years. There is an increasing demand for not only the texture side but also the functional side such as water repellent function and antifouling property.

  Among them, the flat cross-section yarn has anisotropy in the bending characteristics of the raw yarn compared to the round cross-section yarn, and a soft texture is obtained when used as a woven or knitted fabric. It is known that functional effects can be easily obtained. However, the flat cross-section yarn has a larger contact area when touched than the round cross-section yarn, and a specific sticky feeling is developed, which is desired to be improved.

  In order to solve such a problem, it is possible to form a shape in which a round cross-section yarn is joined to the flat cross section in the longitudinal direction of the cross section, as disclosed in JP-A-60-9942 and JP-A-10-96136. JP-A-2004-225180. Improvements in texture, low air permeability, and permeation resistance when fabrics are made by these methods are observed.

  Certainly, the flat cross-section yarn has improved softness, low breathability, and permeation resistance, but in recent years it has become more sophisticated, such as providing water repellency and more sliminess for sports and casual use. There is a need for improved texture.

  As a method for imparting a water repellent function, it has been widely practiced to apply a water repellent treatment by treating a fabric with a dispersion containing a fluorine-based resin or a silicone-based resin and attaching these resins to the surface of the fabric. It has been broken. However, although the fabrics obtained by these processing treatments have water repellency, they have low durability, and the resin treated with the use of the fabric is liable to fall off the surface and easily lose water repellency. is doing. On the other hand, there is a problem that if the amount is sufficient to give sufficient water repellency durability, the texture of the fabric becomes hard. For this reason, the application of polyester fibers to sportswear such as fields where water repellency and texture are both required is greatly limited.

  In contrast, attempts have been made to make the fibers themselves water-repellent fibers rather than post-water-repellent treatments. For example, Japanese Patent Laid-Open No. 62-238822 discloses a fiber obtained by melt-kneading a fluororesin, Japanese Patent Laid-Open No. 2-26919 discloses a fiber obtained by kneading fluoropolymer fine particles, Kaihei 9-302523 and JP-A-9-302524 propose water-repellent polyester fibers containing a copolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride as a water-repellent component. Although the water repellency is certainly good, the fluororesin generally has a melting point and a decomposition point that are close to each other. is there. In addition, there is a problem that the apparatus is deteriorated due to generation of hydrogen fluoride by heating, and there is a problem of an increase in environmental load due to the use of a fluorine compound.

On the other hand, as a method that does not use a fluorine-based compound, Japanese Patent Application Laid-Open No. 2005-105424 discloses a core-sheath type composite fiber using polyester obtained by copolymerizing a specific reactive silicone as a sheath component. This method can make the water repellency durable to some extent, but the degree of water repellency is not enough, and in order to achieve high water repellency, it is necessary to increase the content of reactive silicone, so the strength decreases There was a conflicting problem.
As described above, a water-repellent polyester fiber excellent in process stability, which has an excellent texture surface and has sufficient water repellency and durability even if the fabric is not subjected to post-water repellent processing, is currently desired.

JP 60-9942 A Japanese Patent Laid-Open No. 10-96136 JP 2004-225180 A JP-A-62-238822 JP-A-2-26919 JP-A-9-302523 JP-A-9-302524 JP-A-2005-105424

  An object of the present invention is to provide a polyester cross-sectionally water-repellent yarn having a flat cross-sectional shape that has excellent water-repellent performance that overcomes the problems of the prior art and has a low initial water repellency due to long-term use or repeated washing. It is to provide.

  As a result of investigations to solve such problems, the present inventors have found that this is achieved by using a specific water-repellent polyester in the flat cross-sectional shape fiber.

That is, according to the present invention,
The cross-sectional shape of the single yarn is a flat shape, and the flat shape is a flat cross-sectional fiber having a shape such that 3 to 6 single yarns having a round cross section are joined in the longitudinal direction, and constitutes the fiber. A water-repellent polyester fiber containing 2 to 20 parts by weight of an ester-reactive silicone represented by the following formula (1) as a polymer with respect to 100 parts by weight of the polymer is provided.

（上記式中、Ｒはアルキル基を表し、ｎは１〜１００の整数である。）

(In the above formula, R represents an alkyl group, and n is an integer of 1 to 100.)

  Furthermore, 0.1 to 3 mol% of the metal-containing phosphorus compound (a) represented by the following formula (2) with respect to the acid component constituting the polyester and 0.5 to 1 with respect to the metal-containing phosphorus compound A polyester fiber formed by adding 2 times mole of alkaline earth metal compound (b) without previously reacting (a) and (b) and then reducing the amount of alkali, rich in deep color and improving tactile sensation A flat cross-section water-repellent polyester fiber is preferably provided.

（式中、Ｒ１及びＲ２は一価の有機基であってＲ１及びＲ２は同一でも異なってもよく、Ｍはアルカリ金属又はアルカリ土類金属であって、ｍはＭがアルカリ金属の場合は１、Ｍがアルカリ土類金属の場合は１／２である。）

(Wherein R1 and R2 are monovalent organic groups, R1 and R2 may be the same or different, M is an alkali metal or alkaline earth metal, and m is 1 when M is an alkali metal. , M is 1/2 when alkaline earth metal.)

  A water-repellent polyester fiber having a specific cross-sectional shape containing a specific ester-forming silicone, and by adding a phosphorus compound to the polyester and forming fine pores by weight loss with an alkali. Excellent texture, unique touch, and durable water repellency A water-repellent polyester fiber having both color depth and vividness when colored.

Hereinafter, the water-repellent polyester fiber of the present invention will be described in detail.
The polymer constituting the water-repellent polyester fiber of the present invention is a polyester mainly composed of polyester and mainly composed of components formed from aromatic dicarboxylic acid and alkylene glycol. A polyester having an aromatic dicarboxylic acid and an alkylene glycol as a repeating unit is a polyester synthesized from a corresponding aromatic dicarboxylic acid and / or an ester-forming derivative thereof and a diol, and as long as the physical properties are not impaired as a general-purpose resin. Other components may be copolymerized depending on the purpose. Examples of the ester-forming derivative include lower alkyl esters having 1 to 6 carbon atoms, lower aryl esters having 6 to 12 carbon atoms, and acid halides. The main repeating unit means that 70 mol% of all repeating units constituting the polyester is composed of a component formed from the aromatic dicarboxylic acid and alkylene glycol.

  The aromatic dicarboxylic acid and / or ester-forming derivative thereof includes terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, 1,4-cyclohexyl dicarboxylic acid, adipic acid, sebacic acid, phthalic acid, phthalic anhydride , 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid, dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl adipate, dimethyl sebacate Dimethyl phthalate, dimethyl 5-sodium sulfoisophthalate, or dimethyl 5-tetrabutylphosphonium sulfoisophthalate. In addition to the dimethyl ester and other lower alkyl esters as described above, acid chlorides may be used as the ester-forming derivative. Among these, it is particularly preferable to use terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, or dimethyl 2,6-naphthalenedicarboxylate.

  As diols, ethylene glycol, 1,4-butanediol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, dipropylene glycol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol, dimethylolpropionic acid, poly (ethylene oxide) glycol, or poly (tetramethylene oxide) glycol can be mentioned, particularly ethylene glycol, 1,3-propylene glycol or It is preferable to use 1,4-butanediol.

  Each of these dicarboxylic acids and / or ester-forming derivatives thereof and diols may be used alone or in combination of two or more. Polyesters obtained from these preferred combinations are polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polytrimethylene terephthalate, polytrimethylene-2,6-naphthalate, polytetramethylene-2,6- Naphthalate is preferably used in the polyester of the present invention. Of these, polyethylene terephthalate and polybutylene terephthalate having particularly well-balanced mechanical properties and moldability are particularly preferable.

  In order to impart water repellency to the polymer constituting the water-repellent polyester fiber of the present invention, it is necessary to use a polyester containing an ester-reactive silicone represented by the following formula (1) in the above-described polyester.

（上記式中、Ｒはアルキル基を表し、ｎは１〜１００の整数である。）

(In the above formula, R represents an alkyl group, and n is an integer of 1 to 100.)

  The alkyl group of R has 18 or less carbon atoms, and the number average molecular weight of the ester-reactive silicone is 10,000 or less, preferably 300 or more and 6000 or less. When the number average molecular weight is larger than 10,000, the compatibility with the polyester is lowered, and it is difficult to make the polyester uniformly exist in the polyester.

  Further, the ester reactive silicone needs to be contained in an amount of 2 to 20% by weight based on the polyester. If it is less than 2% by weight, sufficient water repellency cannot be obtained as a fiber. If it exceeds 20% by weight, the physical properties of the polyester are impaired, the strength as a fiber is lowered, and the production becomes difficult. Or, stable production becomes difficult during long-term running.

  Here, including ester-reactive silicone means that the ester-reactive silicone is incorporated into the molecular chain by chemical bonding to the polyester and copolymerized, and the polyester does not chemically bond and exists in a blended state. It means that both are included. The non-copolymerized component is stably present in the polyester in the blended state and does not adversely affect the fiberization. This reason is presumed that the polyester copolymerized with the ester reactive silicone may stabilize the unreacted ester reactive silicone moiety.

  In this invention, it is preferable that what is copolymerized with polyester among the ester reactive silicone contained in polyester is 20 to 50 weight% with respect to the total weight of ester reactive silicone. If it is less than 20%, the dispersibility of the ester-reactive silicone in a blend state deteriorates in the polyester, and the spinning property is lowered. If it exceeds 50%, the physical properties are impaired, the spinning property is lowered, and fluff is generated. Cause. The copolymerization amount of the ester reactive silicone is preferably 25 to 40% by weight based on the total weight of the ester reactive silicone.

  What is necessary is just to synthesize | combine by the well-known arbitrary methods as a method of obtaining the ester reactive silicone containing polyester of this invention. For example, when the dicarboxylic acid component is terephthalic acid, a method of directly esterifying terephthalic acid and alkylene glycol, and a transesterification reaction between a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and alkylene glycol, or terephthalic acid In the first stage, in which a glycol ester of terephthalic acid is produced by a method of reacting with an alkylene oxide, followed by polycondensation until the desired degree of polymerization is achieved by heating under reduced pressure in the presence of a polymerization catalyst. However, either method is possible. From the viewpoint of satisfying the copolymerization ratio, the ester-reactive silicone compound is preferably added before the end of the polycondensation reaction and before the end of the polycondensation reaction. good. And the ratio of the said ester reactive silicone compound copolymerized can be adjusted with this addition time and addition amount.

  As another embodiment of the water-repellent polyester composite fiber of the present invention, the polymer constituting the polymer is 0.1 to 3 mol% of the following formula (2) with respect to the acid component constituting the polyester in addition to the ester-reactive silicone. ) And the metal-containing phosphorus compound (a) and 0.5 to 1.2 moles of the alkaline earth metal compound (b) with respect to the metal-containing phosphorus compound (a) and (b) What is added without making it react and is carrying out the alkali weight reduction can also be mentioned as a preferable aspect.

（式中、Ｒ１及びＲ２は一価の有機基であってＲ１及びＲ２は同一でも異なってもよく、Ｍはアルカリ金属又はアルカリ土類金属であって、ｍはＭがアルカリ金属の場合は１、Ｍがアルカリ土類金属の場合は１／２である。）

(Wherein R1 and R2 are monovalent organic groups, R1 and R2 may be the same or different, M is an alkali metal or alkaline earth metal, and m is 1 when M is an alkali metal. , M is 1/2 when alkaline earth metal.)

  In order to obtain the above metal-containing phosphorus compound, it is usually easy to heat normal phosphoric acid or a corresponding normal phosphoric acid ester (mono, di, or tri) and a predetermined amount of the corresponding metal compound in the presence of a solvent. can get. It is preferable to use glycol used as a raw material for the target polyester as the solvent at this time.

  The addition amount of the metal-containing phosphorus compound needs to be 0.1 to 3 mol% with respect to the polyester acid component. If it is less than 0.1 mol%, the color depth and sharpness are not expressed, and if it exceeds 3 mol%, the strength of the obtained fiber is not sufficient, and the fiber product is stable in the subsequent weaving and knitting process. Manufacturing becomes difficult.

  Examples of the alkaline earth metal compound used in combination with the metal-containing phosphorus compound include alkaline earth metal organic carboxylates such as calcium acetate, calcium oxalate, benzoate, phthalate, and stearate.

  The metal-containing phosphorus compound and the alkaline earth metal compound need to be added to the reaction system of the ester-reactive silicone-containing polyester without being reacted in advance. By doing so, insoluble particles can be produced in a uniform ultrafine particle state in the polyester. If the above metal-containing compound and alkaline earth metal compound are reacted externally in advance to form insoluble particles and then added to the polyester reaction system, the dispersibility of the insoluble particles in the polyester deteriorates and the color of the polyester fiber finally obtained It is difficult to obtain depth and clarity.

  The water-repellent polyester fiber of the present invention has a flat cross-sectional shape of a single yarn, and the flat shape is a flat cross-sectional fiber having a shape in which 3 to 6 single yarns having a round cross section are joined in the longitudinal direction. It is. Here, “as joined” does not mean that the members are actually joined at the melt spinning stage, but means that they have a “joined” shape as a result.

  The cross-sectional shape of the flat cross-section fiber of the present invention will be described with reference to FIG. 1 (a) to 1 (e) schematically show the cross-sectional shape of a flat cross-section fiber, where (a) is three, (b) is four, and (c) is five round cross-section singles. It shows the shape as if the yarn were joined.

  That is, the cross-sectional shape of the water-repellent polyester fiber of the present invention is such that a round cross-section single yarn is joined in the longitudinal direction (major axis direction), and the convex part and convex part (mountain and mountain) with the major axis as the axis. The concave portions and the concave portions (valleys and valleys) are symmetrically overlapped with each other, and the number of round cross-section single yarns is 3 to 6 as described above.

  When the number of single yarns with a round cross section is two, only softness similar to that obtained when a round cross-section fiber is used as a fabric can be obtained, and permeation resistance, low air permeability, and water absorption are also deteriorated. On the other hand, when the number of round cross-section single yarns exceeds 7, the fibers are easily broken and the wear resistance is lowered.

  The polyester fiber of the present invention having the above-described cross-sectional shape is a combination of a low yarn stress and a low bending rigidity of a flat cross-sectional yarn, and can provide a unique soft feeling and touch when used as a fabric.

  The fineness of the water-repellent polyester fiber of the present invention is particularly preferably a single yarn fineness of 0.1 to 2.5 dtex in order to make the softness of the woven or knitted fabric stand out. It is practically difficult to produce a composite fiber of less than 0.1 dtex, and if it exceeds 2.5 dtex, the single yarn becomes thick, so that a soft texture cannot be obtained and the water repellency is also lowered. A preferred range is 0.3-2 dtex.

  As a method for producing the water-repellent polyester fiber of the present invention, it is possible to produce a yarn using a die apparatus that can obtain a flat fiber that satisfies the above-mentioned requirements. For example, a method of extruding into a fiber in a molten state, melt spinning at a speed of 500 to 3500 m / min, and then directly stretching and heat-treating without winding once. Other preferred methods include melt spinning and stretching at a speed of 1000 to 5000 m / min, melt spinning at a high speed of 5000 m / min or more, and a method for omitting the stretching step depending on the application. It can be excellent in stability.

  In order to remove a part of the metal-containing phosphorus compound and the like from the polyester fiber obtained in this way, the film is subjected to a drawing heat treatment or false twisting as necessary, or further applied to the fabric by a known knitting machine. Then, it can be easily performed by treating with an aqueous solution of an alkali compound (decreasing the alkali).

  Examples of the alkali compound used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate and the like. Of these, sodium hydroxide and potassium hydroxide are particularly preferred.

  The concentration of the aqueous solution of the alkali compound varies depending on the type of the alkali compound and the processing conditions, but is usually preferably in the range of 0.01 to 40% by weight, particularly preferably in the range of 0.1 to 30% by weight. The treatment temperature is preferably in the range of room temperature to 100 ° C., and the treatment time is usually in the range of 1 to 4 hours. Further, the amount of elution and removal by the treatment of the aqueous solution of the alkali compound should be in the range of 2% by weight or more with respect to the fiber weight.

When the metal-containing phosphorus compound is added to the polymer, by treating with the aqueous solution of the alkali compound in this way, the polymer is arranged in the fiber axis direction, and the maximum value of the frequency distribution is the width in the direction perpendicular to the fiber axis. A large number of micropores having a size in the range of 0.1 to 0.3 μm and a length in the fiber axis direction of 0.1 to 5 μm can be formed on the fiber surface and in the vicinity thereof, and dyed. In particular, it has an excellent color depth.
In addition, the polyester fiber of the present invention may contain any additive such as a catalyst, an anti-coloring agent, a heat-resistant agent, a flame retardant, a fluorescent brightening agent, a matting agent, and a coloring agent as necessary. good.

The woven or knitted fabric using the fibers thus obtained has excellent water repellency, no deterioration in water repellency due to long-term use, repeated washing, etc., and the color depth and vividness when colored. Exhibits sex.
The water-repellent polyester fiber of the present invention can be a core-sheath type composite fiber, for example.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples. Each item in the examples was measured by the following method.

(1) Under an atmosphere of strength 20 ° C. and 65% RH, the strength at break was measured with a tensile tester under the conditions of a sample length of 20 cm and a speed of 20 cm / min. The number of measurements was 10, and the average was taken as each intensity.

(2) Softness Using the polyester fibers obtained in each Example and Comparative Example for warp and weft, weaving a plain fabric with a basis weight of 75 g / m ² , refining and drying by a conventional method, and then heating at 180 ° C. I set it. Further, a part of this was used to reduce the alkali so that the weight loss rate was 25%, thereby obtaining a fabric. Using this fabric, sensory evaluation was performed by five panelists, 3: all were judged to be very good, 2: three or more were judged to be good, and 1: 3 were judged to be bad Was ranked as (bad) in three stages.

(3) Sensory evaluation by five panelists using a fabric equivalent to that used for the slime feeling softness evaluation, 3: All judged extremely good, 2: Three or more judged good The ones that were judged as defective by 1: 3 or more were ranked as (bad) in three stages.

(4) Contact angle (fiber repellency)
Polyester fibers are extracted from the same fabric used for softness, and then a single yarn is collected and distilled water is used using an automatic micro contact angle measuring device “MCA-2” manufactured by Kyowa Interface Science Co., Ltd. Then, the contact angle between the fiber and the water droplet when 500 pl of distilled water was dropped onto the surface of the single yarn of the fiber was measured by the θ / 2 method, and it was determined that the larger the contact angle, the better the water repellency.

(5) Water repellency (water repellency of fabric)
Using a cloth equivalent to that used for the softness evaluation, evaluation was performed by displaying the score on the wetness of the cloth in accordance with the spray test method of JIS L-1092, except that the time was 10 minutes.
100 points: No wet or water droplets on the surface 90 points: No wet surface, but small water droplets 80 points: Small individual water droplets on the surface 70 points: Surface More than half of the surface is wet and small individual wetness penetrates the cloth 50 points: The entire surface is wet 0 points: The front and back surfaces are wet throughout

(6) Spinnability:
The spinnability in the spinning process was expressed by the following four-step evaluation.
A: There is no fluff generation or yarn breakage, and it is very good.
○: Slightly fluffy but good without thread breakage.
Δ: Slightly fluffed and thread breakage occurred (1-2 times / hr)
X: Fluff occurs and yarn breakage occurs frequently (3 times / hr or more)
Among these evaluations, ◯ or higher is an evaluation result that can be used practically.

(7) Amount of contained silicone compound:
The amount of modified silicone contained in the polyester composition was quantified by 1H-NMR method. Furthermore, the polyester sample was dissolved in an appropriate solvent, a poor solvent was added to perform reprecipitation operation, and 1H-NMR measurement was also performed on the solid matter obtained by filtration. The amount of the modified silicone compound copolymerized in the polyester is quantified from the value of the measurement result after the latter reprecipitation operation, and the difference between the value of the measurement result before the former reprecipitation and the value of the latter measurement result. The amount of the silicone compound blended was quantified. In addition, in the chemical structure of the modified silicone compound, for the blended component, the component in the solvent for reprecipitation operation is the recovered component, and for the copolymerized component, the residual component after hydrolysis of the reprecipitated polyester is used. This can be done by measuring.

(8) Deep color property L * described in JIS Z 8729 (color display method-L * a * b * color system and -L * u * v * color system) is a value representing deep color property, The light source D65 and the viewing angle were determined as 10 °.

[Example 1]
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 10 parts by weight of an ester-reactive silicone compound (a compound in which R in the general formula (1) is an ethyl group, n = 9, FM-DA11 manufactured by Chisso), manganese acetate 0.031 part of tetrahydrate was charged into the reactor, and the temperature was raised from 140 ° C. to 240 ° C. over 3 hours in a nitrogen gas atmosphere, and transesterification was performed while removing methanol to be purified out of the system. After the transesterification reaction is completed, 0.024 part of phosphoric acid as a stabilizer and 0.04 part of antimony trioxide as a polycondensation reaction catalyst are added, then the temperature is raised to 285 ° C., and the polycondensation reaction is performed under reduced pressure. To obtain a silicone-containing polyester. The polyester obtained had an intrinsic viscosity of 0.65 (35 ° C. in orthochlorophenol).

  This polyester is dried to a moisture content of 70 ppm or less, and then melted by an extruder at a melting temperature of 300 ° C., and a spinneret having 36 discharge holes having a single yarn cross-sectional shape shown in FIG. Was spun off and taken up at a spinning speed of 1000 m / min after applying the oil to obtain an undrawn yarn. The undrawn yarn is drawn and heat set at a preheating temperature of 90 ° C., a draw ratio of 3.0 times, and a heat setting temperature of 180 ° C., and consists of a flat cross-section yarn having a single yarn fineness of 1.2 dtex and a total fineness of 43 dtex. A multifilament was obtained.

  After making a taffeta fabric using the obtained fiber and dyeing it using a disperse dye, the weight was reduced at a rate of 30% by treating with 80 ° C. and 3.5% sodium hydroxide aqueous solution. . The obtained fabric was excellent in water repellency and deep color, and had a supple and slimy texture. Table 1 shows the physical properties of the obtained multifilament.

[Example 2, Example 3, Comparative Example 1, Comparative Example 4, Comparative Example 5]
The same procedure as in Example 1 was carried out except that the ester-reactive silicone was changed to 2, 20, 0, 1, 1 and 23 parts in Example 1. Table 1 shows the physical properties of the obtained multifilament.

  In Examples 2 and 3, which are within the scope of the present invention, it was possible to obtain both water repellency and texture. However, in Comparative Example 1 containing no ester-reactive silicone and in Comparative Example 4 having a small amount, water repellency was obtained. In Comparative Example 5 having too much content, the spinning performance was poor but the spinnability was poor.

[Comparative Example 2, Comparative Example 3]
In Example 1, the same procedure as in Example 1 was performed except that the discharge nozzle at the time of spinning was a circular shape and a flat shape without constriction. Table 1 shows the physical properties of the obtained multifilament.
Comparative Example 2 having a round cross section was inferior in soft feeling, and Comparative Example 3 having a flat cross section without constriction was too poor in terms of sliminess due to excessive contact between fibers.

[Example 4]
Transesterify 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (0.066 mol% with respect to dimethyl terephthalate), and 10 parts of ester-reactive silicone (FM-DA11 manufactured by Chisso) The can was charged, and the ester exchange reaction was carried out while distilling out the ethanol produced by raising the temperature from 140 ° C. to 230 ° C. over 4 hours in a nitrogen gas atmosphere. Subsequently, 0.5 parts of trimethyl phosphate (0.693 mol% with respect to dimethyl terephthalate) and 0.31 part of calcium acetate monohydrate (1 with respect to trimethyl phosphate) were added to the reaction product obtained. / 2 moles) was prepared by reacting in 8.5 parts of ethylene glycol at 120 ° C. for 60 minutes under a total reflux for 9.31 parts of a transparent solution of phosphoric ester calcium salt and 0.57 parts at room temperature. 9.88 parts of a mixed clear solution of calcium phosphate diester calcium salt and calcium acetate obtained by dissolving 1 mg of calcium acetate monohydrate (0.9 moles with respect to trimethyl phosphate) was added to the polymerization vessel. did. Subsequently, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time, the temperature was raised from 230 ° C. to 285 ° C. over 1 hour 30 minutes. Thereafter, polymerization was further carried out under a reduced pressure of 1 mmHg or less at a polymerization temperature of 285 ° C. for 3 hours for a total of 4 hours and 30 minutes to obtain a polyester having an intrinsic viscosity of 0.62 (35 ° C. in orthochlorophenol).

  The polyester is dried to a moisture content of 70 ppm or less, and then melted in an extruder at a melting temperature of 300 ° C., so that the discharge hole has a single yarn cross-sectional shape as shown in FIG. Was spun from a spinneret having 36 holes, and after application of an oil, it was taken out at a spinning speed of 1000 m / y to obtain an undrawn yarn. The undrawn yarn is drawn and heat set at a preheating temperature of 90 ° C., a draw ratio of 3.0 times, and a heat setting temperature of 180 ° C., and consists of a flat cross-section yarn having a single yarn fineness of 1.2 dtex and a total fineness of 42 dtex. A multifilament was obtained.

  After making a taffeta fabric using the fiber obtained here and dyeing it using a disperse dye, the weight loss is reduced by 30% by treating with 80 ° C, 3.5% sodium hydroxide aqueous solution. went. The obtained fabric was excellent in water repellency and further in deep color, and had a supple and slimy texture.

[Example 5]
In Example 4, 3.0 parts of trimethyl phosphate (4.16 mol% with respect to dimethyl terephthalate) and 1.9 parts of calcium acetate monohydrate (1/2 times mol with respect to trimethyl phosphate) were added. The same procedure as in Example 1 was performed except that it was used. Table 1 shows the physical properties of the obtained multifilament.
The fabric produced using this multifilament has a very excellent appearance not only in water repellency and texture but also in deep color.

  Polyester fabric with high durability, water repellency, excellent color depth and sharpness, useful for materials such as tents and surgical clothing, and for clothing such as sports, casual, and men's and women's suits It is.

The schematic diagram of the single yarn section of the polyester flat section fiber of the present invention is shown. (A) Cross-sectional view of the single yarn constituting the polyester flat cross-section fiber of the present invention (b) Cross-sectional view of the single yarn constituting the polyester flat cross-section fiber of the present invention (c) Single unit constituting the polyester flat cross-section fiber of the present invention Cross section of yarn (d) Cross section of flat yarn having two ridges outside of the present invention (e) Cross section of flat yarn having seven ridges outside of the present invention (f) Cross section of flat cross section yarn outside of the present invention Figure

Claims (3)

The cross-sectional shape of the single yarn is a flat shape, and the flat shape is a flat cross-sectional polyester fiber having a shape such that 3 to 6 single yarns having a round cross section are joined in the longitudinal direction. 2) to 20 parts by weight of ester-reactive silicone represented by 100) by weight of polyester.

(In the above formula, R represents an alkyl group, and n is an integer of 1 to 100.) 0.1 to 3 mol% of the metal-containing phosphorus compound (a) represented by the following formula (2) with respect to the acid component constituting the polyester and 0.5 to 1.2 times the metal-containing phosphorus compound The water-repellent polyester fiber according to claim 1, which is a polyester fiber obtained by adding a molar alkaline earth metal compound (b) without previously reacting (a) and (b) and then reducing the alkali.

(Wherein R1 and R2 are monovalent organic groups, R1 and R2 may be the same or different, M is an alkali metal or alkaline earth metal, and m is 1 when M is an alkali metal. , M is 1/2 when alkaline earth metal.)   The water-repellent polyester according to any one of claims 1 to 2, wherein the ester-reactive silicone is copolymerized with the polyester in an amount of 20 to 50% by weight based on the total weight of the ester-reactive silicone. fiber.

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