JP2008303476A - Polyester fiber and fabric using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide synthetic fibers which hardly deteriorate a water-repelling performance, even when repeatedly washed, have an excellent water-repelling performance, and have practically durable sufficient mechanical physical properties such as strength and elongation. <P>SOLUTION: Polyester fibers including a polyester composition containing a modified silicone compound having two functional groups at one end contain 2.0 to 20.0 wt.% of the silicone compound based on the weight of the polyester composition, and the polyester composition has an intrinsic viscosity of ≥0.61 dl/g. A fabric using the polyester fibers is provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyester fiber containing a modified silicone compound, and particularly to a polyester fiber having excellent water repellency and mechanical properties and a fabric using the same.

  Conventionally, it has been widely practiced to treat a fabric with a dispersion containing a fluorine-based resin or a silicone-based resin and attach the resin to the surface of the fabric to perform a water repellent treatment. 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, Japanese Patent Laid-Open No. 62-238822 (Patent Document 1) proposes a fiber obtained by melt-kneading a fluororesin, and Japanese Patent Laid-Open No. 2-26919 (Patent Document 2). A fiber obtained by kneading fluoropolymer fine particles has been proposed. In JP-A-9-302523 (Patent Document 3) and JP-A-9-302524 (Patent Document 4), a copolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride is used as a water repellent component in polyester. Containing fibers are provided. However, since a fluororesin generally has a melting point and a decomposition point close to each other, it is difficult to obtain a fiber having a stable and good yarn quality due to the influence of a polymer that has undergone decomposition heat degradation during long-term running. Further, there is a risk that the apparatus is deteriorated due to generation of hydrogen fluoride by heating.

  In JP-A-3-74459 (Patent Document 5), when a modified silicone compound and a polyester oligomer are prepared and contained in polyester, a film excellent in flatness and running property can be obtained. It is disclosed that such polyesters can be used for fibers as well as films. However, if an attempt is made to develop sufficient water repellency by forming into fibers, yarn breakage may occur in the spinning process, further in the weaving and knitting of the fabric, further in the process after making the fabric, and in actual use. , Turned out to be unbearable.

JP-A-62-238822 JP-A-2-26919 JP-A-9-302523 JP-A-9-302524 Japanese Patent Laid-Open No. 3-74459

  The present invention provides a polyester fiber having a high level of water repellency and mechanical properties such as strength and elongation, and a fabric using the same.

［上記式（１）中、Ｒ_１、Ｒ_２、Ｒ_３は同一若しくは異なっても良く、一部若しくは全部がハロゲン原子で置換されていても良い炭素数１８個以下のアルキル基、アルケニル基、アリール基、アラルキル基又はアルキルアリール基を表す。Ｒ_４、Ｒ_５、Ｒ_７は同一若しくは異なっても良い炭素数１０個以下のアルキレン基、アリーレン基、アラルキレン基又はアルキルアリーレン基を表す。Ｒ_６は炭素数１０個以下のアルキル基、アルケニル基、アリール基、アラルキル基又はアルキルアリール基を表わし、Ｘはカルボキシル基及び水酸基よりなる群から選ばれた少なくとも１種の基であり、ｎは１〜１００である。］で示される変性シリコーン化合物を含有するポリエステル組成物からなる繊維であって、ポリエステル組成物の重量を基準として、シリコーン化合物の含有量が２．０〜２０．０重量％の範囲にあり、ポリエステル組成物の固有粘度が０．６１ｄｌ／ｇ以上であるポリエステル繊維およびそれを用いた布帛が提供される。 Thus, according to the present invention, the following general formula (1)

[In the above formula (1), R _1, R _{2 and} R ₃ may be the same or different, and part or all of them may be substituted with a halogen atom, an alkyl group having 18 or less carbon atoms, an alkenyl group, Represents an aryl group, an aralkyl group or an alkylaryl group; R ₄ , R ₅ and R ₇ may be the same or different and each represents an alkylene group having 10 or less carbon atoms, an arylene group, an aralkylene group or an alkylarylene group. R ₆ represents an alkyl group having 10 or less carbon atoms, an alkenyl group, an aryl group, an aralkyl group or an alkylaryl group, X is at least one group selected from the group consisting of a carboxyl group and a hydroxyl group, and n is 1-100. In which the content of the silicone compound is in the range of 2.0 to 20.0% by weight, based on the weight of the polyester composition, and the polyester. A polyester fiber having a composition having an intrinsic viscosity of 0.61 dl / g or more and a fabric using the same are provided.

  In addition, as a preferred embodiment of the present invention, there are also provided polyester fibers and fabrics in which a modified silicone compound copolymerized with polyester is in the range of 20 to 50% by weight based on the weight of the modified silicone. .

  According to the present invention, there are provided a polyester fiber having high water repellency and mechanical properties such as strength and elongation, and a fabric using the polyester fiber. Even if it is repeated, the water-repellent performance is hardly deteriorated, and the mechanical properties such as strength are sufficient, so that it can be excellent in durability which is difficult to break.

The polyester fiber of the present invention comprises a polyester composition containing 2.0 to 20.0% by weight of a modified silicone compound having the structure of the formula (1) based on the weight of the polyester composition. If the content is less than the lower limit, sufficient water repellency is hardly expressed when the obtained polyester fiber is used as a fabric, and if the content exceeds the upper limit, the strength of the obtained polyester fiber becomes poor and yarn breakage is likely to occur. . The content of the preferred modified silicone compound is in the range of 5.0 to 15.0% by weight, more preferably 7.0 to 12.0% by weight. In addition, the modified silicone in the present invention means that the modified silicone compound is incorporated into the molecular chain by chemical bonding to the polyester and copolymerized, and the polyester is blended without chemical bonding. It means both states that exist in the state. The modified silicone compound used in the present invention is represented by the above formula (1). In the above formula (1), R _1, R _{2 and} R ₃ may be the same or different, It represents an alkyl group, alkenyl group, aryl group, aralkyl group or alkylaryl group having 18 or less carbon atoms, all of which may be substituted with a halogen atom. R _4, R ₅ and R ₇ may be the same or different and each represents an alkylene group having 10 or less carbon atoms, an arylene group, an aralkylene group or an alkylarylene group. R ₆ represents an alkyl group having 10 or less carbon atoms, an alkenyl group, an aryl group, an aralkyl group or an alkylaryl group, X represents a carboxyl group or a hydroxyl group, and n is 1 to 100.

  Known modified silicone compounds include polyester raw materials such as one carboxyl group or hydroxyl group at each of both ends of a siloxane structure extending in a long chain, in addition to the above-mentioned one-end direactive functional group-modified structure. Both-end modified type having a functional group capable of reacting with one side, one-end one-reactive functional group-modified type having one of the above functional groups at one end of the siloxane structure, side having a plurality of functional groups in the side chain There are chain-modified types, but both end-modified types are incorporated into the polyester main chain in a straight line, so that the functional group having a water-repellent function is unlikely to appear on the surface of the polyester molded product when it is molded. Can't get. In addition, the one-terminal monoreactive functional group-modified type and the side chain-modified type react with the functional group involved in the polycondensation reaction and the terminal or side chain of the modified silicone compound, which may inhibit the polycondensation reaction. In addition, since the compatibility with the polyester is poor and it is difficult to blend uniformly, it is not preferable because it causes the occurrence of yarn breakage during yarn production and causes fluff. Further, it is not preferable because it has a problem that it tends to bleed out.

Further, when R _{1 to} R ₇ in the general formula (1) are not functional groups as described above, the desired water repellency cannot be obtained, or the modified silicone compound may not be sufficiently mixed with the polyester. is there. Even if they can be mixed, the modified silicone compound may bleed out from the polyester composition while dyeing, heating, or washing the fibers obtained by spinning the polyester composition, which is not preferable. Among these functional groups, R _{1 to} R ₃ are unsubstituted alkyl groups having 1 to 6 carbon atoms, and R ₄ , R ₅ , and R ₇ are unsubstituted alkylene groups having 1 to 4 carbon atoms. R ₆ is preferably an alkyl group having 4 or less carbon atoms.

  By the way, the number average molecular weight of the modified silicone compound is preferably 10,000 or less, more preferably 300 or more and 8000 or less, and particularly preferably 500 or more and 6000 or less. If the number average molecular weight is larger than the upper limit, the compatibility with the polyester deteriorates, making it difficult to blend uniformly in the polyester, and there are problems such as broken yarn, fluff, and bleed out when the polyester fiber is used. This is not preferable.

  Moreover, it is preferable that 20 to 50 weight% of the modified silicone compound contained in the polyester composition is copolymerized with the polyester based on the weight of the modified silicone compound. If the amount of the copolymerized modified silicone compound is less than the lower limit, the dispersibility of the modified silicone compound blended in the polyester composition tends to deteriorate, whereas if it exceeds the upper limit, mechanical strength such as the strength of the resulting polyester is obtained. The physical properties tend to be low when compared with the same content. A preferred ratio of the copolymerized modified silicone compound is in the range of 20 to 50% by weight.

As will be described later, the amount and structure of the copolymerized modified silicone compound and the modified silicone compound in a blended state can be distinguished and specified by ¹ H-NMR measurement. Moreover, it is described in Unexamined-Japanese-Patent No. 2002-48777 that it is the above-mentioned one terminal bireactive functional group modified type, ie, the structure which has two reactive functional groups in the one terminal of the siloxane structure of a modified silicone compound. Thus, it can be confirmed that a polyurethane resin reaction product obtained by reacting a polyisocyanate having three isocyanate groups in the molecule is analyzed by gel permeation chromatography.

  As the polyester constituting the polyester fiber of the present invention, aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate can be preferably exemplified, and among these, mechanical properties, moldability and the like are balanced. Polyethylene terephthalate and polybutylene terephthalate are preferred. These polyesters may be copolymerized with other components according to the purpose within a range not impairing the effects of the present invention. For example, examples of the copolymer component include isophthalic acid, 5-sodium isophthalic acid, adipic acid, trimellitic acid, diethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, and pentaerythritol. In addition, polycarboxylic acids such as trimellitic acid, trimesic acid, trimellitic anhydride, pyromellitic acid, trimellitic acid monopotassium salt, polyvalent hydroxy such as glycerin, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, etc. You may copolymerize compounds, hydroxycarboxylic acids, such as p-hydroxybenzoic acid.

  What is necessary is just to synthesize | combine by the well-known arbitrary methods as a manufacturing method of polyester in this invention. For example, when the dicarboxylic acid component is terephthalic acid, a method of directly esterifying terephthalic acid and alkylene glycol, a method of transesterifying a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and alkylene glycol, or terephthalic acid The first stage reaction is performed to produce a glycol ester of terephthalic acid by a method of reacting an acid and an alkylene oxide, followed by heating under reduced pressure in the presence of a polymerization catalyst to polycondensate until a desired degree of polymerization is obtained. It can be produced by a stage reaction. In addition, it is preferable to perform the addition time of the above-mentioned modified silicone compound before the end of the polycondensation reaction before the end of the polycondensation reaction from the viewpoint of satisfying the copolymerization ratio as described above. It may be added separately. The proportion of the knitted silicone compound copolymerized can be adjusted by the addition timing and addition amount.

  When the first stage reaction is a transesterification reaction, the reaction temperature is 180 to 230 ° C., the reaction pressure is preferably in the range of normal pressure to 0.3 MPa, and the second stage reaction (polycondensation reaction) The reaction temperature is preferably 200 to 260 ° C. and the reaction pressure is preferably 60 to 0.1 kPa. Such transesterification reaction and polycondensation reaction may be performed in one step or may be performed in multiple steps.

  As the transesterification catalyst used in these reaction steps, an alkali metal salt such as sodium, an alkaline earth metal salt such as magnesium or calcium, or a metal compound such as titanium, zinc or manganese is preferably used. As the polycondensation catalyst, germanium compounds, antimony compounds, titanium compounds, cobalt compounds or tin compounds are preferably used. The amount of the catalyst used is not particularly limited as long as it is an amount necessary for proceeding the transesterification reaction and polycondensation reaction, and a plurality of catalysts can be used in combination. Further, when the first stage reaction is a direct esterification reaction, the esterification reaction can proceed directly without using a catalyst, but the above catalyst may be used if necessary.

  It is also preferable to add a stabilizer either during the first stage reaction, during the second stage reaction, or after completion of the reaction. As the stabilizer, phosphate esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphites such as triphenyl phosphate, acid phosphate esters such as methyl acid phosphate, dibutyl phosphate, monobutyl phosphate Phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, or polyphosphoric acid, hindered phenol antioxidants, sulfur antioxidants, and amine antioxidants are preferred.

  In the polycondensation stage, the polycondensation reaction is carried out under the above conditions until it can be confirmed that the degree of polymerization (molecular weight, intrinsic viscosity) of the target polyester is obtained by a technique such as monitoring the melt viscosity. Then, after confirming that the target molecular weight has been reached, the polycondensation reaction is terminated, and the polyester is obtained by discharging from the reaction vessel and cutting into chips after cooling. After the chip is dried, it can be used for the production of polyester fibers and the like described later. Moreover, you may manufacture a polyester fiber as it is from the polyester after completion | finish of a polycondensation reaction, without once shape | molding in chip shape. By the way, the polyester fiber of the present invention has an intrinsic viscosity (solvent: mixed solvent of 40% by weight of 1,1,2,2-tetrachloroethane and 60% by weight of phenol) in a fiber state of 0.61 or more. It is necessary. A preferable lower limit of the intrinsic viscosity is 0.63 dl / g or more. On the other hand, the upper limit of the intrinsic viscosity is not particularly limited, but is preferably 0.80 dl / g or less from the viewpoint of spinning stability, and further, the step of increasing the intrinsic viscosity such as solid phase polymerization is omitted or time-consuming. Is preferably 0.70 dl / g or less. One of the characteristics of the present invention is that the intrinsic viscosity is set to the lower limit or more, so that deterioration of mechanical properties such as strength due to the inclusion of the modified silicone compound described above can be suppressed, which is sufficient for practical use. This is because the fiber has sufficient strength to prevent the yarn breakage during the manufacturing process or use. In order to satisfy the intrinsic viscosity in the state of such a fiber, in part, the temperature in the melt extruder when extruding into a fiber is made as low as possible, and the residence time there is shortened, so that the polymer However, even if such conditions are adopted, the decrease in the intrinsic viscosity of 0.2 to 0.3 dl / g cannot be avoided. It is preferable that the viscosity be 0.3 dl / g or more higher than the intrinsic viscosity in the fiber state.

  The polyester fiber according to the present invention can be produced by a method known per se. For example, the spinning method is not particularly limited. For example, the polyester composition obtained as described above is extruded into a fiber form in a molten state, melt-spun at a speed of 500 to 3500 m / min, and stretched and heat-treated. , A method in which melt spinning is performed at a speed of 1000 to 5000 m / min and stretching and false twisting are performed simultaneously or subsequently, a method in which melt spinning is performed at a high speed of 5000 m / min or more, and a stretching process is omitted depending on the use. It is done. Further, the fiber thus obtained may be cut into a desired length to form a short fiber, and a method such as spunbonding or melt blow spinning can be preferably employed. The cross-sectional shape of the fiber is not particularly limited, and may be an elliptical cross section, a triangular cross section, or a star cross section in addition to a circular cross section. Further, the polyester fiber of the present invention is not limited to the fiber spun using only the polyester composition containing the above-mentioned modified silicone compound, and is arranged on the surface of the fiber from which the polyester composition containing the modified silicone compound is obtained. For example, a composite fiber having a core-sheath structure in which the polyester composition containing the modified silicone compound is disposed in the sheath and the polyester composition not containing the modified silicone compound or having a lower content than the polyester composition of the sheath is disposed in the core. It may be a sea-island type composite fiber having many cores. Such a composite fiberization is preferable because the mechanical properties of the fiber can be further easily maintained.

  By the way, the polyester fiber of this invention has the outstanding water repellency by containing a modified silicone compound as above-mentioned. However, from the viewpoint of developing sufficient water repellency when the fabric is used, the contact angle of the surface of the polyester fiber with water is preferably 110 ° or more, more preferably 115 ° or more. By providing the polyester fiber itself with such a high contact angle, excellent water repellency can be exhibited when it is made into a fabric.

  The polyester fiber of the present invention has a single yarn fineness in the range of 0.5 to 5.0 dtex, more preferably in the range of 1.0 to 3.0 dtex, from the viewpoint of water repellency and handling properties such as subsequent processing steps. Preferably there is. Moreover, when using as a long fiber, it is preferable for the same reason that the fineness (single filament fineness x number of single yarns) as a fiber bundle is in the range of 30 to 150 dtex, more preferably 50 to 100 dtex.

  By the way, the polyester fiber of this invention has the outstanding water repellency by containing a modified silicone compound. In particular, when a fabric is used, the contact angle of the surface of the polyester fiber with water is preferably 110 ° or more, more preferably 115 ° or more, from the viewpoint of developing sufficient water repellency. By providing the polyester fiber itself with such a high contact angle, excellent water repellency can be exhibited when it is made into a fabric.

  Next, the fabric of the present invention is formed from the above-described polyester fiber of the present invention, and may be in any form of woven fabric, knitted fabric, and nonwoven fabric. Preferably, it is a woven fabric because water repellency when it is made into a fabric is more easily expressed. In addition, in order to make the fabric of the present invention more easily exhibit water repellency when it is made into a fabric, one surface of the fabric has a projected area of all fibers when the area of the fibers on the surface is viewed in the projected area. As a reference, it is preferable that 50% or more, more than 70%, be occupied by the polyester fiber of the present invention.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.
(1) Intrinsic viscosity:
A sample was dissolved in a mixed solvent of 40% by weight of 1,1,2,2-tetrachloroethane and 60% by weight of phenol and measured at 35 ° C. according to a conventional method.

(2) Strength and elongation The strength and elongation at break were measured with a tensile tester in an atmosphere of 20 ° C. and 65% RH 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 strength and elongation.

(3) Contact angle:
In (6) water repellency test described later, a single yarn was collected from a test piece before alkali weight reduction, and distilled water was used using an automatic micro contact angle measuring device “MCA-2” manufactured by Kyowa Interface Science Co., Ltd. The contact angle of the single yarn surface was measured using 500 picoliters. The larger the contact angle, the better the water repellency.

(4) Amount of contained silicone compound:
^The amount of modified silicone contained in the polyester composition was quantified by ¹ H-NMR method. Furthermore, the polyester sample was dissolved in an appropriate solvent, a poor solvent was added to perform reprecipitation, and ¹ H-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.

(5) 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.

(6) Water repellency:
A plain fabric was woven using the polyester fibers obtained in each Example and Comparative Example as warp and weft, and this fabric was refined and dried by a conventional method, and then heat-set at 180 ° C. Further, a part of the alkali was reduced by an ordinary method so that the weight loss rate was 30% by weight. The fabric after the alkali weight reduction thus obtained was measured according to JIS-L-1092 (spray method) (1992). From the state of the fabric after the measurement, evaluation was performed with a score of 0 to 100 points according to the following criteria described in the JIS standard.
100 points: No wetness or water droplet adhesion on the surface.
90 points: those which do not get wet on the surface, but show adhesion of small water droplets.
80 points: those showing small individual water droplets on the surface.
70 points: Shows wetness in more than half of the surface, and shows that small individual wetness penetrates the fabric.
50 points: Wet on the entire surface.
0 point: The front and back surfaces are all wet.

[Example 1]
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, modified silicone compound (shown by general formula (1), X is a hydroxyl group, R _{1 to} R ₃ are methyl groups, R ₄ is a trimethylene group, R ₅ and R ₇ Is a methylene group, R ₆ is an ethyl group, n = 9 compound: manufactured by Chisso Corporation, trade name: FM-DA11, average molecular weight: 1000) 2 parts by weight, manganese acetate tetrahydrate 0.031 parts The mixture was heated from 140 ° C. to 240 ° C. in a nitrogen gas atmosphere over 3 hours, and the ester exchange reaction was carried out while distilling the produced methanol 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 polyester composition. When the intrinsic viscosity of this polyester composition was measured, it was 0.654 dl / g. The amount of the modified silicone compound contained in the polyester composition was 2% by weight. After the polyester composition was dried, it was melted at 285 ° C. in a single-screw extruder, and a spin extrusion temperature of 290 ° C. from a spinneret having 24 round hole extrusion nozzle holes with a hole diameter of 0.3 mmφ and a land length of 0.6 mm. Were discharged under the condition of a total discharge amount of 24 g / min and taken up at a speed of 1000 m / min to obtain an undrawn yarn. The obtained undrawn yarn was drawn 3.3 times at 80 ° C. and heat-treated at 180 ° C. to obtain polyester fibers of 77.6 dtex / 24 filaments.
Properties of the obtained polyester composition, polyester fiber and fabric are shown in Table 1.

[Examples 2 and 3, Comparative Examples 1 and 2]
The same operation as in Example 1 was repeated except that the amount of the modified silicone compound (FM-DA11) was adjusted so that the content of the modified silicone compound was the amount shown in Table 1.
Properties of the obtained polyester composition, polyester fiber and fabric are shown in Table 1.

[Comparative Example 3]
In Example 1, the modified silicone compound was changed to a modified silicone compound having a monofunctional carboxylic acid group at the end of the molecular chain (trade name: X22-3710, manufactured by Shin-Etsu Chemical Co., Ltd.), and its content was 10% by weight. The same operation as in Example 1 was repeated except that the addition amount was changed so that
Properties of the obtained polyester composition, polyester fiber and fabric are shown in Table 1.

[Comparative Example 4]
In Example 1, the modified silicone compound was changed to a modified silicone compound having a bifunctional carboxylic acid at both ends of the molecule of the molecular chain (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-162C), and its content was 10 wt. The same operation as in Example 1 was repeated except that the addition amount was changed to be%.

[Examples 4 and 5]
In Example 2, the same operation as in Example 2 was repeated except that the intrinsic viscosity of the polymer was 0.672 dl / g and 0.615 dl / g.

[Example 6]
In Example 2, a modified silicone compound having an average molecular weight of 5000 (manufactured by Chisso Corporation, trade name: FM-DA21 (shown by general formula (1), X is a hydroxyl group, and R _{1 to} R ₃ are methyl groups) , R ₄ is a trimethylene group, R ₅ and R ₇ are methylene groups, R ₆ is an ethyl group, and n = about 63 compound: manufactured by Chisso Corp., average molecular weight 5,000)) The same operation as in Example 2 was repeated.

[Example 7]
In Example 2, the same operation as in Example 2 was repeated except that the amount of the modified silicone compound added was 5 parts by weight.

[Comparative Example 5]
In Example 2, the same operation as in Example 2 was repeated except that the intrinsic viscosity of the polymer was 0.602 dl / g.

[Comparative Example 6]
A reactor is charged with 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 0.031 part of manganese acetate tetrahydrate, and the temperature is raised from 140 ° C. to 240 ° C. over 3 hours in a nitrogen gas atmosphere. The transesterification was carried out while distilling methanol 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 polyester composition. When the intrinsic viscosity of this polyester composition was measured, it was 0.641 dl / g. After the polyester composition was dried, it was melted at 285 ° C. in a single-screw extruder, and a spin extrusion temperature of 290 ° C. from a spinneret having 24 round hole extrusion nozzle holes with a hole diameter of 0.3 mmφ and a land length of 0.6 mm. Were discharged under the condition of a total discharge amount of 24 g / min and taken up at a speed of 1000 m / min to obtain an undrawn yarn. The obtained undrawn yarn was drawn 3.3 times at 80 ° C. and heat-treated at 180 ° C. to obtain 81.1 dtex / 24 filament polyester fiber.

[Comparative Example 7]
In Comparative Example 6, the same operation as in Comparative Example 6 was repeated except that the intrinsic viscosity of the polymer was 0.605 dl / g.

In Table 1, in the column of the type of modified silicone compound, A is a modified silicone compound (shown by general formula (1), X is a hydroxyl group, R _{1 to} R ₃ are methyl groups, R ₄ is a trimethylene group, R ₅ and R ₇ are methylene groups, R ₆ is an ethyl group, n = about 9 compound: manufactured by Chisso Corporation, trade name: FM-DA11, average molecular weight: 1000), B is monofunctional at the end of the molecular chain Modified silicone compound having a carboxylic acid group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-3710), C is a modified silicone compound having a bifunctional carboxylic acid at both ends of the molecular chain (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-162C), D is a modified silicone compound (shown by general formula (1), X is a hydroxyl group, R _{1 to} R ₃ are methyl groups, R ₄ is a trimethylene group, R ₅ and R ₇ are methylene groups, R ₆ Is ethyl , N = about 63 compound: manufactured by Chisso Corporation, trade name: FM-DA21, average molecular weight: 5000) means.

  According to the present invention, it is possible to obtain a synthetic fiber that exhibits excellent water repellency with little deterioration in water repellency even after repeated wearing and washing, and has sufficient mechanical properties such as strength and elongation that can withstand practical use. It is useful as a material for clothing and industrial materials that require durable water repellency.

Claims (3)

A fiber comprising a polyester composition containing a modified silicone compound represented by the following general formula (1), wherein the silicone compound content is 2.0 to 20.0% by weight based on the weight of the polyester composition A polyester fiber having a polyester composition having an intrinsic viscosity of 0.61 dl / g or more.

[In the above formula (1), R _1, R _{2 and} R ₃ may be the same or different, and part or all of them may be substituted with a halogen atom, an alkyl group having 18 or less carbon atoms, an alkenyl group, Represents an aryl group, an aralkyl group or an alkylaryl group; R ₄ , R ₅ and R ₇ may be the same or different and each represents an alkylene group having 10 or less carbon atoms, an arylene group, an aralkylene group or an alkylarylene group. R ₆ represents an alkyl group having 10 or less carbon atoms, an alkenyl group, an aryl group, an aralkyl group or an alkylaryl group, X is at least one group selected from the group consisting of a carboxyl group and a hydroxyl group, and n is 1-100. ]   2. The polyester fiber according to claim 1, wherein among the modified silicone compounds, the polyester copolymer is in the range of 20 to 50% by weight based on the weight of the modified silicone.   A fabric using the polyester fiber according to claim 1.