JP2008231625A - Cation-dyeable polyester moire fancy yarn - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester moire fancy yarn (uneven yarn) suitable for obtaining a fabric exhibiting natural appearance and improved moire and having excellent dye clarity by cation dyeability and adequate fineness unevenness in fiber length direction and a combined filament conjugate yarn, woven or knitted fabric, etc., each containing the yarn. <P>SOLUTION: The cation-dyeable polyester moire fancy yarn comprises cation-dyeable polyester filaments composed of a modified polyester having ≥0.6 intrinsic viscosity in which 0.1-6.0 mol% specific sulfonic acid phosphonium salt is copolymerized and has 2-25% Uster irregularity and has thick and thin unevenness in the fiber length direction. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyester-tone-designed yarn provided with an appropriate dyeing fineness so as to exhibit excellent dyeing clarity by dyeing with a cationic dye and a natural tone-like appearance at the time of forming a fabric, and a mixed fiber containing the same The present invention relates to a composite yarn and its woven or knitted fabric.

  As a problem inherent to synthetic fibers, particularly polyester fibers, compared to conventional natural fibers, there is an industrial product appearance due to the uniformity of quality by the industrial manufacturing method. As a method for solving this problem, it is possible to produce spotted yarn (thick and thin yarn) intentionally imparted with fineness spots on a polyester filament, and to impart a natural appearance to the product by using it for forming a fabric. (See, for example, Patent Document 1 and Patent Document 2 below).

  On the other hand, polyester fiber has many demands as a synthetic fiber for clothing due to its characteristic whiteness and clearness of dyeing, and it is a representative synthetic fiber that is produced in large quantities even today. In order to differentiate products with the expansion, a number of methods for improving the dyeability during dyeing have been proposed (for example, see Patent Document 3 below). Among them, disperse dyes used for general purposes Giving dyeability with cationic dyes (referred to as “cationic dyeing” in the present invention), which is required for different dyeing with dyeable polyester fibers, is a representative example, and fibers made of cationic dyeable polyester are produced. ing. In particular, dyeing with a cationic dye can provide a vivid appearance because it is superior in vividness and color development after dyeing as compared with that using a disperse dye. In addition, using a general-purpose polyester yarn dyed with disperse dyes and cationic dyeable polyester yarns, after forming a living machine by knitting and weaving, dyeing different colors in the same bath using disperse dyes and cationic dyes is a productive efficiency. Above all, it is gaining importance as an excellent processing technique.

  In these technical backgrounds, natural tone appearance and clearness due to cationic dyeing are both issues that must be addressed in order to promote the recent development of individuality in the fashion clothing field and a bright image in the sports clothing field.

  However, in the conventional production technology of cationic dyeable polyester yarn and the production technology of silk-tone design yarn having a good chic and thin structure (hereinafter sometimes referred to as “spotted yarn”), a simulated cationic gray-tone appearance fabric is used. Although it can be obtained, it is still impossible to obtain a fabric with a high level of design that can be said to be a sufficient practical level. In the case of cationic dyeable polyester fibers, this is due to the fact that it is extremely difficult to provide thickness spots in the fiber length direction. For this reason, there is no cationic dyeable polyester spot yarn having practically and commercially sufficient performance, and its realization is desired.

Japanese Patent Publication No. 01-43045 Japanese Patent Publication No. 03-79450 Japanese Patent Publication No.58-38550

  The present invention has been made in view of the above-mentioned background art. The first object of the present invention is to provide a cationic dye that exhibits an improved artificial appearance, excellent dyeing colorability, a natural appearance like natural fibers, and tone. Another object is to provide a mixed fiber composite yarn and a woven or knitted fabric using the same.

  According to the present invention, the above-described problems are achieved by the following cationic dyeable polyester-tone design yarn, cationic dyeable polyester blended composite yarn, and woven or knitted fabric including the same.

〔２〕上記〔１〕のカチオン可染ポリエステル杢調意匠糸とポリエステル杢調意匠糸との沸水収縮率差が２％以上のポリエステルフィラメントを引き揃えて混繊したことを特徴とするカチオン可染ポリエステル混繊複合糸。
〔３〕上記〔１〕のカチオン可染ポリエステル杢調意匠糸及び／又は上記〔２〕のポリエステル混繊複合糸を構成糸として含むことを特徴とする織編物。 [1] A cationic dyeable polyester filament yarn comprising a modified polyester having an intrinsic viscosity of 0.6 or more obtained by copolymerizing 0.1 to 6.0 mol% of a sulfonic acid phosphonium salt represented by the following general formula (I). In addition, a cationic dyed polyester-tone design yarn characterized in that it is composed of a patchy thread having thick spots in the fiber length direction in which the Worcester spot of each filament is 2 to 25%.

[2] Cationic dyeing characterized in that polyester filaments having a difference in boiling water shrinkage of 2% or more between the cationic dyeable polyester yarn-like design yarn and polyester yarn-like design yarn of [1] above are mixed and mixed. Polyester blended composite yarn.
[3] A woven or knitted fabric comprising the cationic dyeable polyester-tone design yarn of [1] and / or the polyester blended composite yarn of [2] as constituent yarns.

According to the polyester spotted yarn having cationic dyeability according to the present invention, it is possible to provide a fabric exhibiting excellent dyeing colorability, natural fiber-like natural appearance and tone. Further, a composite yarn obtained by mixing this and a polyester filament yarn having a difference in boiling water shrinkage of 2% or more becomes a fabric having a suitable texture with an appropriate swelling when heat is applied in a dyeing process or the like using this as a woven or knitted fabric. .
Therefore, the woven fabric and the knitted fabric containing the cationic dyeable polyester spotted yarn and / or the mixed fiber composite yarn containing the cationic dyeable yarn according to the present invention as a constituent yarn are particularly useful as a material in the clothing field where design properties are required.

  Hereinafter, embodiments of the present invention will be described in detail by dividing into polyester spotted yarn having cationic dyeability, mixed fiber composite yarn and woven / knitted fabric using the same.

<Cation dyeable polyester spotted yarn>
The polyester dyed yarn having cationic dyeability of the present invention is copolymerized with 0.1 to 6.0 mol% of a sulfonic acid quaternary phosphonium salt described later, and has an intrinsic viscosity (measured with a 25 ° C. orthochlorophenol solution). ) Is made of a modified polyester polymer having a value of 0.60 or more, preferably 0.64 to 0.80, and each filament has a Wooster degree of 2 to 25%, preferably 6 to 13%. It is characterized by having thick and thin spots in the fiber length direction.

  The polyester in the present invention mainly includes a polyester whose main repeating unit is ethylene terephthalate or trimethylene terephthalate. Such a polyester may be copolymerized with other components such as phthalic acid, isophthalic acid, adipic acid, sebacic acid, naphthalenedicarboxylic acid, butylene glycol, etc., as long as the object of the present invention is not impaired. Further, if necessary, an antioxidant, an ultraviolet absorber, a flame retardant, a fluorescent thickening agent, a matting agent, a color adjusting agent, an antifoaming agent and other additives may be contained.

  Such polyester is synthesized by any method. For example, when describing polyethylene terephthalate, usually, terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol are transesterified, or terephthalic acid and ethylene. The first stage reaction in which a glycol ester of terephthalic acid and / or its low polymer is produced by reacting with oxide and the reaction product in the first stage is heated under reduced pressure until the desired degree of polymerization is reached. It is produced by a second stage reaction that undergoes a polycondensation reaction.

  In the present invention, it is important to use a modified polyester having an intrinsic viscosity of 0.6 or more obtained by copolymerizing 0.1 to 6.0 mol% of a sulfonic acid quaternary phosphonium salt with the above polyester as a patch forming polymer. is there. Here, the sulfonic acid quaternary phosphonium salt as a copolymerization component is a compound represented by the following general formula (I).

上記一般式（Ｉ）中、Ａは芳香族基又は脂肪族基を示し、なかでも芳香族基、特ににベンゼン環が好ましい。Ｘ１はエステル形成性官能基を示し、その具体例としてカルボキシル基又はその誘導体等をあげることができる。Ｘ２はＸ１と同一もしくは異なるエステル形成性官能基又は水素原子を示し、なかでもエステル形成性官能基であることが好ましい。そして、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれアルキル基及びアリール基よりなる群から選ばれた同一又は異なる基を示す。ｎは正の整数であり、好ましくは１又は２である。

In the above general formula (I), A represents an aromatic group or an aliphatic group, and among them, an aromatic group, particularly a benzene ring is preferable. X1 represents an ester-forming functional group, and specific examples thereof include a carboxyl group or a derivative thereof. X2 represents an ester-forming functional group or a hydrogen atom that is the same as or different from X1, and is preferably an ester-forming functional group. R1, R2, R3, and R4 each represent the same or different group selected from the group consisting of an alkyl group and an aryl group. n is a positive integer, preferably 1 or 2.

  Such a sulfonic acid quaternary phosphonium salt can generally be easily synthesized by a reaction between a corresponding sulfonic acid and a phosphine or a reaction between a corresponding sulfonic acid metal salt and a phosphonium halide.

  Preferred examples of the sulfonic acid quaternary phosphonium salt include tetrabutylphosphonium salt of 3,5-dicarboxybenzenesulfonic acid, ethyltributylphosphonium salt of 3,5-dicarboxybenzenesulfonic acid, and 3,5-dicarboxybenzenesulfone. Acid benzyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3 , 5-Dicarboxybenzenesulfonic acid butyltriphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid benzyltriphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid Trabutylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid ethyl tributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid benzyltributylphosphonium salt, 3-carbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carbohydrate Methoxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonic acid tetrabutylphosphonium salt, 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonic acid tetraphenylphosphonium salt, 3 -(Β-hydroxyethoxycarbonyl) benzenesulfonic acid tetrabutylphosphonium salt, 3- (β-hydroxyethoxycarbonyl) benzenesulfonic acid tetraphenylphosphonium salt, 4 Examples thereof include -hydroxyethoxybenzenesulfonic acid tetrabutylphosphonium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt, α-tetrabutylphosphonium sulfosuccinic acid, and the like. The sulfonic acid phosphonium salts may be used alone or in combination of two or more.

  In order to copolymerize the sulfonic acid quaternary phosphonium salt with the polyester, it is added at any stage before the completion of the synthesis of the polyester described above, preferably at any stage before the completion of the first stage reaction. That's fine.

  The proportion of the sulfonic acid quaternary phosphonium salt copolymerized with the polyester is suitably in the range of 0.1 to 10 mol% with respect to the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester, The range of 0.5-10 mol% is particularly preferable. If the copolymerization ratio is less than 0.1 mol%, the dyeability of the resulting copolymerized polyester with respect to the cationic dye tends to be insufficient, and if it exceeds 10 mol%, the dyeability with the cationic dye no longer shows a significant improvement. On the contrary, the physical properties of the polyester fiber are lowered, so that it is difficult to achieve the object of the present invention.

  In the present invention, when the modified polyester is produced, a small amount of the sulfonic acid tertiary phosphonium salt represented by the following general formula (II) is used together with the sulfonic acid quaternary phosphonium salt represented by the general formula (I). The decomposition reaction in the polymerization process is suppressed, and the resulting modified polyester and the color tone of the resulting polyester are extremely preferable.

上記一般式（II）式中、Ｂは上記一般式（Ｉ）におけるＡと同様に、芳香族基又は脂肪族基を示し、なかでも芳香族基が好ましい。Ｘ３は上記一般式（Ｉ）におけるＸ１と同様に、エステル形成性官能基を示し、その具体例としてカルボキシル基又はその誘導体等をあげることができる。Ｘ４は上記一般式（Ｉ）におけるＸ２と同様に、Ｘ３と同一もしくは異なるエステル形成性官能基又は水素原子を示し、なかでもエステル形成性官能基であることが好ましい。また、Ｒ５、Ｒ６及びＲ７は、上記一般式（Ｉ）におけるＲ１、Ｒ２及びＲ３と同様に、それぞれアルキル基及びアリール基よりなる群から選ばれた同一又は異なる基を示す。そして、ｎは正の整数である。

In the general formula (II), B represents an aromatic group or an aliphatic group as in A in the general formula (I), and among them, an aromatic group is preferable. X3 represents an ester-forming functional group in the same manner as X1 in the above general formula (I), and specific examples thereof include a carboxyl group or a derivative thereof. X4 represents an ester-forming functional group or a hydrogen atom that is the same as or different from X3, similarly to X2 in the general formula (I), and is preferably an ester-forming functional group. R5, R6 and R7 represent the same or different groups selected from the group consisting of an alkyl group and an aryl group, respectively, similarly to R1, R2 and R3 in the general formula (I). N is a positive integer.

Such a sulfonic acid tertiary phosphonium salt can be easily synthesized, for example, by a reaction between a corresponding sulfonic acid metal salt and a tertiary phosphonium halide.
Preferable specific examples of the sulfonic acid tertiary phosphonium salt include tributylphosphonium salt of 3,5-dicarboxybenzenesulfonic acid, triethylphosphonium salt of 3,5-dicarboxybenzenesulfonic acid, and triethylphosphonium salt of 3,5-dicarboxybenzenesulfonic acid. Propylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid triphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tribenzylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid trihexylphosphonium salt, 3,5- Examples thereof include dicarboxybenzenesulfonic acid trioctylphosphonium salt and 3,5-dicarboxybenzenesulfonic acid tricyclohexylphosphonium salt.

  If the amount of the sulfonic acid tertiary phosphonium salt used is too small, the effect of preventing the modified polyester from being colored yellowish brown becomes insufficient. Since the heat resistance may be deteriorated, the range of 0.5 to 10 mol% is suitable with respect to the sulfonic acid quaternary phosphonium salt, and the range of 1 to 4 mol% is particularly preferable. The sulfonic acid tertiary phosphonium salt may be added at any stage before the synthesis of the polyester is completed in the same manner as the sulfonic acid quaternary phosphonium salt. May be added separately. In the production stage of the sulfonic acid quaternary phosphonium salt, a sulfonic acid tertiary phosphonium salt may be by-produced and partially remain in the produced sulfonic acid quaternary phosphonium salt. In this case, if the amount of the remaining sulfonic acid tertiary phosphonium salt is controlled within the above range by controlling the purification conditions, it may not be used separately.

  In the present invention, it is preferable to add a quaternary onium salt in producing the modified polyester. Examples of such quaternary onium salts include quaternary ammonium salts and quaternary phosphonium salts. Specifically, examples of the quaternary ammonium salts include tetramethylammonium hydroxide, tetramethylammonium chloride, and tetraethylammonium hydroxide. , Tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetraisopropylammonium hydroxide, tetraisopropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium chloride, hydroxylated Examples thereof include tetraphenylammonium and tetraphenylammonium chloride. Examples of the quaternary phosphonium salt include tetra-n-butylphosphonium bromide.

A range of 0.1 to 20 mol% is preferable with respect to the amount of the quaternary onium salt used and a total of the phosphonium sulfonate salt, and a range of 1 to 10 mol% is particularly preferable.
The quaternary onium salt may be added at any stage until the synthesis of the polyester is completed. For example, the quaternary onium salt may be added to the polyester raw material or during the first stage reaction. It may be added after the end of the stage reaction until the start of the second stage reaction or during the second stage reaction.

  The addition order of the quaternary onium salt and the sulfonic acid phosphonium salt may be arbitrary, and may be added after mixing both in advance. Further, in the production of phosphonium sulfonate, a synthesis method by reaction of a quaternary phosphonium salt such as a quaternary phosphonium halide and a sulfonic acid metal salt may be employed, in which case the raw material quaternary phosphonium salt is used. May remain in the phosphonium salt of sulfonic acid which is a reaction product. In such a case, it is not necessary to add a quaternary phosphonium salt, and this remaining quaternary phosphonium salt can be used.

  The polyester polymer represented by the general formula (I) is copolymerized with 0.1 to 6.0 mol%, preferably 0.5 to 3.0 mol% of a sulfonic acid phosphonium salt, and has an intrinsic viscosity ( (Measured with a 25 ° C. orthochlorophenol solution) is 0.60 or more, preferably 0.64 to 0.80.

  In particular, the intrinsic viscosity has a strong influence on the patch processing property after spinning, and if it is less than 0.60, sufficient Wooster spots cannot be obtained. In order to obtain Wooster spots with sufficient level of design for clothing, it is preferable that the intrinsic viscosity is 0.64 or more at the polymer stage of the raw material for yarn production. If the intrinsic viscosity is 0.64 or more, in the processing step after the yarn production and weaving, an excellent shade difference can be expressed by dyeing, and a fabric excellent in mottled feeling can be obtained.

  It is necessary that the speckle dyeable polyester patch of the present invention has a Wortester tester spot (Wooster spot) in the range of 2 to 25%, preferably 6 to 13%. If the Worcester spot is less than 2%, the feeling of wrinkle after the formation of the fabric is insufficient, and the spot feel exhibits different color tone spots in various places of the fabric, and the fabric quality is remarkably lowered. On the contrary, when Wooster spots exceed 25%, the boiling water shrinkage ratio of the cationic dyeable polyester yarn itself increases, and shrinkage spots due to the large width in the fabric formation and subsequent processing steps are expressed on the fabric surface. Easy to handle and difficult to handle.

  The method for producing the cationic dyeable polyester spotted yarn of the present invention is arbitrary, and a conventionally known method for producing spotted yarn may be appropriately employed. For example, a method of stretching an undrawn yarn made of a cationic dyeable modified polyester as described above at a draw ratio below its natural draw ratio, a method of forcibly changing the draw ratio, and a non-uniform heat treatment during drawing Examples thereof include a method of performing the above, a method of blowing compressed air or the like at the time of stretching, and the like. Moreover, the thickness unevenness | corrugation of a fiber length direction can also be effectively generated by making unstretched (partial orientation) thread | yarn before extending | stretching pass over on appropriate conditions.

  In addition, the single yarn fineness of the polyester spotted yarn having cationic dyeability of the present invention is suitably in the range of 1.0 to 9.0 dtex, and the total total fineness is not particularly limited unless there is a problem in the yarn production and processing steps. It is not limited. Moreover, the single yarn cross-sectional shape is not limited to a circle, and may be an ellipse, a flat shape, a trilobal (trilobal), a multilobal (multilobal), or a hollow fiber having a hollow portion. .

<Mixed fiber composite yarn>
Although the polyester dyed yarn having cationic dyeability of the present invention can be used as it is, it is used as a polyester filament yarn having a boiling water shrinkage different from that, in particular, as a composite yarn blended together with a high shrinkage polyester filament yarn. It is preferable to do this. When producing a mixed fiber composite yarn by aligning the polyester dyed yarn having cationic dyeability of the present invention and the highly shrinkable polyester filament yarn having a boiling water shrinkage different from that of the patch yarn, the cationic dyeable polyester yarn of the present invention and The boiling water shrinkage difference with the counterpart polyester filament yarn is 2% or more, preferably 5% or more. When the difference in boiling water shrinkage is less than 2%, the shrinkage difference from the partner fiber constituting the mixed fiber composite yarn is insufficient, and the resulting fabric is insufficiently swollen to obtain the desired good texture. I can't. If the difference in boiling water shrinkage is 2% or more, it is possible to realize a feeling of swelling in the fabric, and if it is 5% or more, it is possible to impart a feeling of swelling that is excellent for use in clothing, and a fabric with a good texture. It can be produced.

  The single yarn fineness of the counterpart high-shrinkage polyester filament yarn is suitably in the range of 0.5 to 3.5 dtex. Moreover, the single yarn cross-sectional shape is not limited to a circle, and may be an ellipse, a flat shape, a trilobal (trilobal), a multilobal (multilobal), or a hollow fiber having a hollow portion. .

In the different shrinkage mixed fiber composite yarn of the present invention, low shrinkage fibers are stretched on the yarn surface by heat treatment. Therefore, the smaller the single yarn fineness, the better the feeling of swelling and the soft touch of the surface. Therefore, when using a cation dyeable polyester spotted yarn as the low shrinkage fiber, the single yarn fineness is particularly preferably 0.1 to 2 dtex.
The composite ratio of the above-mentioned cationic dyeable polyester patch yarn and the highly shrinkable polyester filament yarn having a boiling water shrinkage of 2% or more is preferably in the range of 15/85 to 85/15.

  Other yarns to be combined with the cationic dyeable polyester spotted yarn may be high shrinkage filament yarns made of ordinary polyethylene terephthalate. In such a combination, disperse dyes and cationic dyes should be used in the same bath and dyed in different colors. The composite single yarn is dyed into two colors and combined with the chic and thin effect of the cationic dyeable polyester spotted yarn, it becomes a composite yarn or woven or knitted fabric particularly excellent in design.

  A method for mixing the above-described low-shrinkage fibers and high-shrinkage fibers is not particularly limited, and any conventionally known method can be arbitrarily employed. For example, the aligned yarn may be passed through an air entanglement processing apparatus, and both fibers may be mixed and entangled well to form a composite yarn. The overfeed rate during mixed fiber entanglement processing is preferably 0.1 to 2%.

  In addition, a woven fabric or a knitted fabric containing the cationic dyeable polyester patch yarn and / or the mixed fiber composite yarn containing the same as a constituent yarn is woven and knitted by a method known per se, and further refined as necessary. -Can be produced by dyeing.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by these. In addition, unless otherwise indicated, the part and% in each example mean a weight part and weight%, respectively. Each evaluation item shown in each example was measured by the following method.

<Boiling water shrinkage>
It was measured according to the hot water shrinkage rate A method of JIS L1013 “Test method for chemical fiber filaments”.
<Worcester spots>
The change of the fiber diameter in the fiber length direction was measured by a normal test using an Evenes tester.
<杢 appearance>
With respect to the candy appearance of the dyed fabric, a three-step evaluation of excellent, acceptable, and impossible was performed by a sensory test by five panelists.

[Example 1]
100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.03 part of manganese acetate tetrahydrate (0.024 mol% with respect to dimethyl terephthalate), 0.009 part of cobalt acetate tetrahydrate as a color adjuster (terephthalic acid 0.007 mol% with respect to dimethyl), 1.0 mol% with respect to dimethyl terephthalate, and 0 with respect to 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt and dimethyl terephthalate. While adding 0.050 mol% of tetra-n-butylphosphonium bromide to a transesterification vessel, the temperature was raised from 140 ° C. to 220 ° C. over 3 hours in a nitrogen gas atmosphere, and methanol formed was distilled out of the system. Transesterification was performed. Subsequently, 0.03 part of a 56% aqueous solution of normal phosphoric acid (0.003 mol% with respect to dimethyl terephthalate) was added to the obtained product as a stabilizer, and at the same time, excessive temperature rise of ethylene glycol was started. did. Ten minutes later, 0.04 part of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added as a polycondensation catalyst. When the internal temperature reached 240 ° C., the ethylene glycol purge was terminated, and the reaction product was transferred to a polymerization can.

Next, while the temperature was raised, the reaction was carried out at atmospheric pressure until the internal temperature reached 260 ° C., and then the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time, the internal temperature was raised to 280 ° C. over 1 hour 30 minutes. Under the reduced pressure of 1 mmHg or less, when the polymerization was further carried out at a polymerization temperature of 280 ° C. for 2 hours, the vacuum was broken with nitrogen gas to complete the polymerization reaction, and the polymer was discharged at 280 ° C. under nitrogen gas pressure.
The resulting polymer has a softening point (SP) of 253.5 ° C., a diethylene glycol content (DEG content) of 1.68, an intrinsic viscosity after 10 minutes of discharge ([η] ₁₀ ) of 0.672, and after 60 minutes of discharge. ([Η] ₆₀ ) was 0.648.

This polymer is made into chips according to a conventional method, dried, melted at a maximum of 300 ° C. using a spinneret having 36 circular discharge holes with a hole diameter of 0.25 mm, and spun at a take-up speed of 2200 m / min. , 126 dtex / 36 fil semi-drawn yarn was obtained. The undrawn yarn was heated and half-drawn at the draw ratio shown in Table 1, and heat-set to be fixed to obtain a target polyester dyed yarn having cationic dyeability.
The obtained cationic dyeable polyester spotted yarn had a total fineness of 84 dtex, a strength of 2.8 cN / dtex, and an elongation of 55%. Further, the process tone in the spinning / drawing process was excellent, and the polyester spotted yarn had no fluff and good quality. The physical properties of this polyester patch were as shown in Table 1.

  This cationic dyeable polyester spotted fabric (plain fabric) is dyed bath (assistant) containing 2% owf of the cationic dye: Catilon CD-FRLH / Catilon Blue CD-FBLH = 1/1 (Hodogaya Chemical Co., Ltd.). (Containing 3 g / L of mirabilite and 0.3 g / L of acetic acid as an agent), and stained at 120 ° C. for 60 minutes. The evaluation results of the fabric after dyeing are shown in Table 1.

[Examples 2-3 and Comparative Example 1]
In the same manner as in Example 1, only the amount of 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt added was changed as shown in Table 1, and the production of polyester spotted yarn was carried out in the same manner. did. Table 1 shows the physical properties of the obtained polyester spotted yarn and the evaluation results on the fabric.

[Comparative Examples 2-3]
In the same production method as in Example 2, the reaction was carried out at normal pressure until the internal temperature reached 260 ° C. while raising the temperature in the polymerization vessel, then the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and simultaneously over 1 hour 30 minutes. The internal temperature was raised to 280 ° C. Polymerization was completed in the middle of polymerization at a polymerization temperature of 280 ° C. under a reduced pressure of 1 mmHg or less, and a polymer having a lower intrinsic viscosity than that of Example 2 was obtained. The subsequent manufacturing method was the same as in Example 1. The results are shown in Table 1.

[Comparative Examples 4 to 5]
In the method of Example 1, instead of 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt and tetra-n-butylphosphonium bromide, sodium dimethyl-5-sulfoisophthalate and benzoic acid were used, Similarly, a polymerization reaction was performed. Table 1 shows the results of spinning the obtained polymer in the same manner as in Example 1 and evaluating the fabric. From these experimental results, it was confirmed that a sufficient thick and thin structure could not be realized when the cationic dye copolymerized with polyester was a sodium salt.

[Example 4]
Cationic dyeable polyester spot yarn of Example 1 (Fineness: 84 dtex / 36 fil, boiling water shrinkage: 13.5%) and normal high-shrinkage polyethylene terephthalate multi-fmented yarn (Fineness: 84 dtex / 24 fil, boiling water shrinkage: 29. 6%) and were mixed and entangled using an air entanglement processing apparatus to produce a composite yarn. A plain woven fabric was prepared using the composite yarn. This fabric was dyed at 120 ° C. for 60 minutes in a dye bath containing both the same cationic dye as in Example 1 and a disperse dye: Kalonon-P / Navy Blue R-SF (manufactured by Nippon Kayaku). As a result, a dyed fabric having a bulging tone and excellent design was obtained.

  According to the polyester spotted yarn having cationic dyeability of the present invention, it is possible to stably provide a woven or knitted fabric (textile product) having a good tone and excellent design while having an appropriate swell feeling. It is particularly useful in these fields.

Claims (3)

A cationic dyeable polyester filament yarn comprising a modified polyester having an intrinsic viscosity of 0.6 or more obtained by copolymerizing 0.1 to 6.0 mol% of a sulfonic acid phosphonium salt represented by the following general formula (I), A cationic dyeable polyester-tone design yarn characterized in that it is composed of patchy yarn having thick spots in the fiber length direction in which the Worcester spot of the filament is 2 to 25%.

  A cationic dyeable dyeing product comprising the cationic dyeable polyester yarn-like design yarn according to claim 1 and a polyester filament yarn having a difference in boiling water shrinkage of 2% or more between the polyester yarn-like design yarn and being mixed together. Polyester blended composite yarn.   A woven or knitted fabric comprising at least one of the cationic dyeable polyester-tone design yarn according to claim 1 or the polyester blended composite yarn according to claim 2 as a constituent yarn.