JP2008247930A - Water-repellent polyester composition and fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic fiber having excellent water-repellency hardly reduced by repeated laundry, and also having good texture and dye affinity. <P>SOLUTION: The polyester composition comprises a polyester composed of a main repeating unit formed out of an aromatic dicarboxylic acid and an alkylene glycol, and a silicone compound. The silicone compound is a modified silicone compound represented by general formula (1) [wherein, X is one group selected from the group consisting of a carboxy group and a hydroxy group; and n is 1-100], and the content of the modified silicone compound based on the weight of the composition is 1.0-20.0 wt.%. The modified silicone of 0.2-5.0 wt.% based on the weight of the polyester composition is copolymerized with the polyester, and the remainder thereof is compounded in the polyester composition. The polyester fiber comprises the polyester composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyester composition containing a modified silicone compound, and particularly to a polyester composition having excellent water repellency and low wear characteristics, and a polyester fiber using the same.

As a water repellent processing method for a fabric, a method of coating the surface of a fabric with a fluorine water repellent or a silicone water repellent is well known. As a problem of water repellent processing, there is a problem that the water repellency performance is lowered due to the influence of friction or washing during use and the influence of peeling of the water repellent coating the surface. On the other hand, a water-repellent fabric having improved washing durability using a silicone-based water repellent has been proposed (for example, see Patent Document 1). Further, it is disclosed that a durable water-repellent fabric can be obtained by applying a thermoplastic resin modified with a silicone-based water repellent or a fluorine-based water repellent to the fabric surface (see, for example, Patent Document 2). .) Further, it is disclosed that a durable water-repellent fabric can be obtained by forming fine convex portions on the surface of the fabric (see, for example, Patent Document 3).
However, these methods have a problem in that the water repellency is deteriorated when the film is cracked or peeled off due to rubbing or itching during wearing or washing.

  In addition, a method has been proposed in which a water-repellent layer is formed on the fiber surface constituting the fabric by low-temperature plasma polymerization of a fluorine-based monomer or a silicon-based monomer (see, for example, Patent Document 4). On the other hand, a core-sheath composite fiber (see, for example, Patent Document 5) using a fluororesin as a sheath, a polyester fiber and a core-sheath composite fiber (for example, see Patent Documents 6 to 8) in which fluororesin is mixed and dispersed are disclosed. ing. However, even with these methods, the decrease in water repellency performance due to washing and dry cleaning cannot be suppressed, and there is a problem in durability. Further, the water repellency function is lowered due to the particles kneaded and dispersed during alkali weight reduction processing. There was a problem. Furthermore, synthetic fibers made of fluorine-containing polymers such as polytetrafluoroethylene and copolymers thereof are also known, but this fiber has a high Young's modulus and has a hard texture and cannot be used for general clothing and is dyed. There was a problem that things couldn't be done.

Japanese Patent Publication No. 61-9432 JP 09-195169 A JP 2004-256939 A Japanese Patent Laid-Open No. 04-343762 Japanese Unexamined Patent Publication No. 53-31851 JP-A-62-238822 Japanese Patent Laid-Open No. 06-136616 Japanese Patent Laid-Open No. 06-220718

  An object of the present invention is to provide a synthetic fiber having excellent water repellency, little deterioration in water repellency even after repeated washing, and good texture and dyeability.

［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。］
で表される数平均分子量が１０，０００以下である変性シリコーン化合物であって、得られるポリエステル組成物重量に対し１．０〜２０．０重量％含有されており、該ポリエステル組成物に含有されている変性シリコーン化合物のうち、ポリエステル組成物重量に対して０．２〜５．０重量％が該ポリエステルに共重合されており、残りの変性シリコーン化合物がポリエステル組成物中に配合されており、該ポリエステルに共重合されている変性シリコーン化合物の重量が該ポリエステル組成物に含有されている変性シリコーン化合物の重量に対して５０重量％以下であることを特徴とするポリエステル組成物により解決されることを見出し、本発明を完成させた。 An object of the present invention is a polyester composition comprising a polyester and a silicone compound, the main component of which is a component formed from an aromatic dicarboxylic acid and an alkylene glycol, the silicone compound having the following general formula (1)

[In the above formula (1), R ₁ , R ₂ and R ₃ may be the same or different, and a 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 represent the same or different 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. ]
Is a modified silicone compound having a number average molecular weight of 10,000 or less, and is contained in an amount of 1.0 to 20.0% by weight based on the weight of the obtained polyester composition. Of the modified silicone compound, 0.2 to 5.0% by weight of the polyester composition is copolymerized with the polyester, and the remaining modified silicone compound is blended in the polyester composition. To be solved by the polyester composition, wherein the weight of the modified silicone compound copolymerized with the polyester is 50% by weight or less based on the weight of the modified silicone compound contained in the polyester composition The present invention was completed.

  ADVANTAGE OF THE INVENTION According to this invention, the synthetic fiber which shows the outstanding water repellency with few fall of water repellency even if it wears and wash | cleans repeatedly, and has a favorable feel and dyeability can be obtained.

  The present invention is described in detail below. The first of the present invention is a polyester composition containing 1.0 to 20.0% by weight based on the weight of the polyester composition from which a modified silicone compound having specific characteristics can be obtained.

The modified silicone compound used in the present invention is represented by the general formula (1) shown above, and in the above formula (1), R ₁ , R ₂ and R ₃ may be the same or different, An alkyl group, alkenyl group, aryl group, aralkyl group or alkylaryl group having 18 or less carbon atoms which may be partially or entirely substituted with a halogen atom is represented. R ₄ , R ₅ and R ₇ represent the same or different 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 It is a modified silicone compound having a molecular weight of 1 to 100 and an average number molecular weight of 10,000 or less.

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. Furthermore, 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 is not adequately and sufficiently miscible with the polyester. There is a thing. Even if they can be mixed, the modified silicone compound may bleed out from the polyester composition during the dyeing process, other heat processing process, or the washing process of the fiber obtained by spinning the polyester composition. It 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.

  Further, the number average molecular weight of the modified silicone compound needs to be 10,000 or less, preferably 300 or more and 6,000 or less, more preferably 500 or more and 1,000 or less. When the number average molecular weight is greater than 10,000, the compatibility with the polyester deteriorates, and it is difficult to uniformly blend in the polyester. When the polyester fiber is used, problems such as yarn breakage, fluff, and bleed out occur. It is not preferable.

  Furthermore, the modified silicone compound needs to be contained in an amount of 1.0 to 20.0% by weight based on the obtained polyester composition. It is preferable to contain 4.0 to 19.0 weight%. When the amount is less than 1.0% by weight, the modified silicone compound-containing polyester composition cannot exhibit sufficient water repellency, and when the amount is more than 20.0% by weight, the silicone compound in the blended state is converted into the polyester composition. This is not preferable because it cannot uniformly disperse in the material, which causes yarn breakage during yarn production and fluff. “Contained” means that the modified silicone compound is incorporated into the molecular chain by chemical bonding to the polyester and copolymerized as described later, and the polyester is present in a blended state without chemical bonding. It refers to including both states.

  Further, the modified silicone compound contained in the polyester composition needs to be 0.2 to 5.0% by weight copolymerized with the polyester with respect to the weight of the polyester composition. And the remainder needs to be mix | blended with the polyester composition. That is, the remainder is present in a blended state, indicating that it is not bonded to the polyester main chain by a chemical bond. It is preferable that 1.5 to 3.0% by weight is copolymerized. If the amount of the copolymerized modified silicone compound is less than 0.2% by weight, the dispersibility of the modified silicone compound blended in the polyester deteriorates. This is not preferred because the physical properties of the resulting polyester are significantly reduced.

  Furthermore, it is necessary that the weight of the modified silicone compound copolymerized with the polyester is 50% by weight or less based on the weight of the modified silicone compound contained in the polyester composition. In the polyester composition, when the weight of the modified silicone compound copolymerized with the polyester exceeds 50% by weight based on the weight of the modified silicone compound contained in the polyester composition, the modified silicone compound becomes more uniform. Even if it is dispersed in the polyester composition and the content is increased, the desired water-repellent performance cannot be achieved. More preferably, the weight of the copolymerized modified silicone compound is 10 to 45% by weight based on the weight of the modified silicone compound contained.

As a result of intensive studies to achieve both washing-resistant and water-repellent properties, we used a modified silicone compound having a specific chemical structure represented by the above general formula (1) and put it into a normal polyester manufacturing process. Surprisingly, it was found that a part of the copolymer was copolymerized with the polyester main chain, and the remaining components were present in the polyester composition in a blended state. Furthermore, it has been confirmed that this state can be maintained even if the polyester composition is made into a fiber by melt spinning or the like, and then subjected to a treatment such as dyeing. 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, as described later. 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 also confirm by analyzing the polyurethane resin reaction material obtained by making it react with the polyisocyanate which has three isocyanate groups in a molecule | numerator by gel permeation chromatography.

  In the polyester composition of this invention, it consists of the polyester which uses as a main repeating unit the component formed from aromatic dicarboxylic acid and alkylene glycol, and the said modified silicone compound. 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, 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 ester-forming derivatives 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 derivatives thereof include 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, in particular ethylene glycol, 1,3-propylene glycol or 1, It is preferable to use 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. Polyethylene terephthalate, polyethylene-2,6-naphthalate, polytrimethylene terephthalate, polytrimethylene-2,6-naphthalate, polytetramethylene terephthalate, polytetramethylene-2,6-polyester obtained from these preferred combinations. Naphthalate is preferred as the polyester constituting the polyester composition of the present invention.

  The polyester in the present invention includes trimellitic acid, trimesic acid, trimellitic anhydride, pyromellitic acid or trimellitic acid monopotassium salt or a polyvalent carboxylic acid or derivative thereof, glycerin, sodium dimethylolethylsulfonate or dimer. A polyvalent hydroxy compound such as potassium methylolpropionate or a derivative thereof, or a hydroxycarboxylic acid such as p-hydroxybenzoic acid may be copolymerized as long as the object of the present invention is achieved.

  The polyester composition of the present invention is usually a metal compound catalyst such as lithium, sodium, calcium, magnesium, manganese, zinc, antimony, germanium, or titanium, which is usually used in the production of polyester, and a phosphorus compound as a coloring inhibitor / antioxidant. In addition, inert particles and organic compounds used for modifying titanium dioxide or other polyester as a matting agent may be included within the scope of the object of the present invention.

  What is necessary is just to synthesize | combine by the well-known arbitrary methods as a manufacturing method of polyester in this invention. When the aromatic dicarboxylic acid or the like is terephthalic acid or the like, usually, 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 Alternatively, the first stage reaction for producing a glycol ester of terephthalic acid and / or a low polymer thereof by the method of reacting terephthalic acid and alkylene oxide is performed, followed by heating under reduced pressure in the presence of a polymerization catalyst. It is produced by a second stage reaction in which polycondensation is performed until the degree of polymerization is reached. The reactive-modified silicone compound described above may be supplied into the reaction tank at an appropriate stage before the completion of polyester production before the polycondensation process starts. Within this range, the supply stage is supplied at an earlier stage when it is desired to increase the amount of copolymerized polyester, and at a later stage when it is desired to increase the blending (blend state) amount. preferable. In addition, as a result of continual research on compounds that can be produced under normal production conditions and have the desired water repellency without significantly changing the production conditions of the normal polyester production process, the above general formula It came to discover the compound represented by (1).

  When the first stage reaction is a transesterification reaction, the reaction temperature is usually 180 to 230 ° C., and the reaction pressure is normal pressure to 0.3 MPa. The reaction temperature during the second stage reaction (polycondensation reaction) is usually 200 to 260 ° C., and the reaction pressure is usually 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, it is preferable to use an alkali metal salt such as sodium, an alkaline earth metal salt such as magnesium or calcium, and a metal compound such as titanium, zinc or manganese. As the polycondensation catalyst, it is preferable to use a germanium compound, an antimony compound, a titanium compound, a cobalt compound or a tin compound. 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.

  When the first stage reaction is a direct esterification reaction, the aromatic dicarboxylic acid as a raw material itself can serve as an esterification catalyst without using a catalyst, so that the esterification reaction proceeds directly without using a catalyst. . Even in the case of direct esterification reaction, the above-mentioned catalyst can be added as necessary, and the use of a catalyst is not excluded.

  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. The intrinsic viscosity of the polyester composition of the present invention (solvent: mixed solvent of 1,1,2,2-tetrachloroethane 40% by weight and phenol 60% by weight) is not particularly limited. It is preferable that it is the range which can be normally used in this resin molded product, and specifically, it is preferable to exist in the range of 0.40-1.00 dL / g. More preferably, it is 0.50 to 0.80 dL / g. In addition, it is also preferable to increase the intrinsic viscosity of the polyester composition by solid phase polymerization.

  The polyester fiber and the composite fiber according to the second aspect of the present invention can be produced by the same method as that applied to the polyester fiber and the composite fiber that are usually known using the above-described polyester composition. 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. Although any known method can be employed for the conjugate fiber in the present invention, it is preferably used as a “sheath” of a so-called “core-sheath structure”, in particular, in order to develop water repellency. At this time, a single core structure or a sea-island type multi-core structure may be used.

  Also, the spinning method is not particularly limited, and any method of long fiber, short fiber, spun bond, and melt blow spinning can be employed. The spinning speed is not particularly limited, and stretching and false twisting may be performed following spinning. For example, a method in which melt spinning is performed at a speed of 500 to 3500 m / min, stretching and heat treatment, 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, and a high speed of 5000 m / min or more. For example, a method of omitting the stretching step may be employed depending on the use.

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) Contact angle:
A single yarn was collected from the test piece, and the contact angle on the surface of the single yarn was measured using distilled water using an automatic micro contact angle measuring device “MCA-2” manufactured by Kyowa Interface Science Co., Ltd. It was judged that 115 deg or more was a level that could achieve the object of the present invention.
(3) Water repellency:
It 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.
(4) Washing durability:
Washing | cleaning prescribed | regulated to JIS-L-0271-103 was repeated 10 times. After the washing, the above water repellency was evaluated. A score of 80 or more after washing was judged to be a level that could achieve the object of the present invention.
(5) Spinnability:
The spinning performance 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) Amount of contained silicone compound:
^The amount of modified silicone contained in the polyester composition was quantified by ¹ H-NMR method. Furthermore, after dissolving the polyester sample in a suitable solvent, a poor solvent was added to perform reprecipitation operation, and the solid matter obtained by filtration was also subjected to ¹ H-NMR measurement. 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.

[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 = about 9 compound: manufactured by Chisso Corporation, trade name FM-DA11 average molecular weight = 1,000) 10 parts by weight, manganese acetate tetrahydrate 0.031 weight The reactor was charged into a reactor, heated from 140 ° C. to 240 ° C. over 3 hours in a nitrogen gas atmosphere, and transesterification was performed while distilling the produced methanol out of the system. After the transesterification reaction is completed, 0.024 parts by weight of phosphoric acid as a stabilizer and 0.04 parts by weight of antimony trioxide as a polycondensation reaction catalyst are added, and then the temperature is raised to 285 ° C. A condensation reaction was carried out to obtain a polyester composition. It was 0.62 dL / g when the intrinsic viscosity of this polyester composition was measured. The amount of the modified silicone compound contained in the polyester composition was 8.5 wt%. After the polyester composition was dried, it was melted at 285 ° C. in a single screw extruder, and discharged from a spinneret having 24 round hole extrusion nozzle holes with a hole diameter of 0.2 mmΦ at a spinning extrusion temperature of 290 ° C. And a heated godet roll set at 90 ° C. and a stretched heated godet roll set at 3800 m / min and 120 ° C. to obtain a polyester base yarn of 75 denier / 24 filaments. Next, a plain woven fabric was woven using the obtained polyester yarn for 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 a conventional method so that the weight loss rate was 30%. A single yarn was extracted from the raw yarn and the alkali-reduced fabric, and the contact angle was measured. The woven fabric was evaluated for water repellency by the method described above. The results are shown in Table 1. In Table 1, in the modified silicone compound, a compound having a hydroxyl group, a carboxyl group or the like only on one side of the chain of the siloxane structure as represented by the general formula (1) is represented as “one end”, and a compound on both sides of the chain is represented by “both ends”. A compound having no hydroxyl group or carboxyl group in the molecule was represented as “non-modified”. The number of reactive functional groups represents the number of hydroxyl groups, carboxyl groups, etc. in one molecule of the modified silicone compound.

[Examples 2 and 3]
It implemented by the method similar to Example 1 except having adjusted the addition amount of the modified silicone compound (FM-DA11) so that modified silicone compound content might become the quantity of Table 1. The results are shown in Table 1.

[Examples 4 and 5]
The modified silicone compound used is trade name FM-DA21 (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, and n = about 63 compound: manufactured by Chisso Corporation, average molecular weight 5,000), and the addition amount was adjusted so that the content is the amount described in Table 1, The same method as in Example 1 was performed. The results are shown in Table 1.

[Example 6]
A reactor was charged with 100 parts by weight of dimethyl terephthalate, 70 parts by weight of trimethylene glycol, 10 parts by weight of a modified silicone compound (FM-DA11), and 0.053 parts by weight of tetra-n-butyl titanate. The temperature was raised from 140 ° C. to 210 ° C. over the course of the reaction, and the ester exchange reaction was carried out while distilling the produced methanol out of the system. After the transesterification reaction was completed, the temperature was raised to 265 ° C., and a polycondensation reaction was performed under reduced pressure to obtain a polyester.

  After the polyester composition was dried, it was melted at 260 ° C. in a single screw extruder, and discharged at a spinning extrusion temperature of 265 ° C. from a spinneret having 24 round hole extrusion nozzle holes with a hole diameter of 0.2 mmΦ, and 1200 m / And wound through a heated godet roll set at 60 ° C. and a stretched heated godet roll set at 3800 m / min and 160 ° C. to obtain a polyester base yarn of 77 denier / 24 filaments. Next, a plain woven fabric was woven using the obtained polyester yarn for warp and weft, and this fabric was refined and dried by a conventional method, and then heat-set at 160 ° C. Further, a part of the alkali was reduced by a conventional method so that the weight loss rate was 30%. A single yarn was extracted from the raw yarn and the alkali-reduced fabric, and the contact angle was measured. The woven fabric was evaluated for water repellency by the method described above. The results are shown in Table 1.

[Comparative Example 1]
It implemented by the method similar to Example 1 except having adjusted the addition amount of the modified silicone compound (FM-DA11) so that modified silicone compound content might become the quantity of Table 1. Many yarn breaks occurred in the yarn making process, and stable production was difficult, and it was not possible to secure a raw yarn sample. The results are shown in Table 1.

[Comparative Example 2]
It implemented by the method similar to Example 1 except having adjusted the addition amount of the modified silicone compound (FM-DA11) so that modified silicone compound content might become the quantity of Table 1. The results are shown in Table 1.

[Comparative Examples 3 to 9]
The modified silicone compound was changed to the silicone compound having the structure described in the following and Table 1, and the amount was adjusted so that the content would be the amount described in Table 1. Carried out. The results are shown in Table 1. The silicone compounds used in each example are as follows.
The compound used in Comparative Example 3 is the same as the compound used in Example 1 except that n = about 200. The compound used in Comparative Example 4 is a compound represented by the general formula (1), and R _{1 to} Compound in which R ₃ is a methyl group, R ₄ is a trimethylene group, -R ₅ -CR ₆ (R ₇ -X) ₂ is -C ₂ H ₄ OH, and n is about 10, a compound used in Comparative Example 5 : A compound represented by the general formula (1), wherein R _{1 to} R ₃ are methyl groups, -R ₄ —O—R ₅ —CR ₆ (R ₇ —X) ₂ is —C ₂ H ₄ COOH, n = about 10 compound / compound used in Comparative Example 6: compound represented by general formula (1), wherein R _{1 to} R ₃ are methyl groups, R ₄ is trimethylene group, —R ₅ —CR ₆ ( R _{7 -X) 2} portions _{-OOCC (CH 3) = CH 2} , n = reduction used in compound Comparative example 7 is about 10 Compound: a compound represented by the general formula (1), wherein R ₁ and R ₂ are methyl groups, R ₃ and —R ₄ —O—R ₅ —CR ₆ (R ₇ —X) ₂ are —C ₃ H ₆ —O—C ₂ H ₄ OH, n = about 9 compound / compound used in Comparative Example 8: compound represented by the general formula (1), wherein R ₁ and R ₂ are methyl groups, R ₃ and Compounds in which —R ₄ —O—R ₅ —CR ₆ (R ₇ —X) ₂ is C ₂ H ₄ COOH, n = about 10 or more are all used in Comparative Example 9 manufactured by Chisso Corp. : Polydimethylsiloxane represented by the following formula (2), wherein m = about 65

[Comparative Example 10]
It implemented by the method similar to Example 1 except not adding a modified silicone compound. The results are shown in Table 1.

  From the results in Table 1, it was confirmed that the fibers obtained from the polyester compositions of Examples 1 to 6 had excellent water repellency even after weight reduction with alkali and high washing durability.

  According to the present invention, it is possible to obtain a synthetic fiber having excellent water repellency with little deterioration in water repellency even after repeated wearing and washing, and having a good texture and dyeability, and durable water repellency is required. It is useful as a material for clothing and industrial materials.

Claims (2)

A polyester composition comprising a polyester and a silicone compound, the main component of which is a component formed from an aromatic dicarboxylic acid and an alkylene glycol, wherein the silicone compound is represented by the following general formula (1)

[In the above formula (1), R ₁ , R ₂ and R ₃ may be the same or different, and a 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 represent the same or different 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. ]
Is a modified silicone compound having a number average molecular weight of 10,000 or less, and is contained in an amount of 1.0 to 20.0% by weight based on the weight of the obtained polyester composition. Of the modified silicone compound, 0.2 to 5.0% by weight of the polyester composition is copolymerized with the polyester, and the remaining modified silicone compound is blended in the polyester composition. A polyester composition, wherein the weight of the modified silicone compound copolymerized with the polyester is 50% by weight or less based on the weight of the modified silicone compound contained in the polyester composition.   A polyester fiber comprising the polyester composition according to claim 1.