JP2008174861A - Cation-dyeable ultrafine polyester combined filament yarn - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a combined filament yarn having excellent softness, touch feeling, dyeability, color fastness and mechanical characteristics and good combined filament processing conditions and comprising a cation-dyeable ultrafine polyester multifilament yarn as one component. <P>SOLUTION: A highly oriented undrawn polyester multifilament yarn has the cation-dyeable ultrafine polyester multifilament yarn composed of a modified polyester copolymerized with a specific sulfonic acid quaternary phosphonium salt and having an intrinsic viscosity of more than 0.6. The cation-dyeable ultrafine polyester multifilament yarn has dtex a single filament fineness of not more than 0.7 and a birefringence (Δn) of 0.03 to 0.08. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a blended yarn including an ultrafine cationic dyeable (hereinafter referred to as cationic dyeable) polyester fiber yarn.

Polyester fibers have the advantages of high strength, chemical stability, excellent dimensional stability, pleat retention, and anti-wrinkle properties. Studies have been made to obtain color development after natural fiber-like dyeing.
Of these, dye dyes and cationic dyes disclosed in Japanese Patent Publication No. 34-10497, Japanese Patent Publication No. 47-22334, and Japanese Patent No. 2915045, which are particularly aimed at color clarity after dyeing, are particularly polyester fibers. It was an epoch-making invention that brought new possibilities and industrial development.

  In recent years, there is a wide variety of needs related to polyester dyeing technology, and there is a need for specialized differentiating materials that have a strong visual impression, for example, marbling and tone. In response to such needs, two types of polymers having different dyeability are used and blended yarns are used. For example, Japanese Patent Application Laid-Open Nos. 9-241938 and 2003-336136 propose the use of entangled mixed yarns composed of cationic dyeable polyester yarns and non-dyeable polyester yarns. Certainly, this method can be used to dye the blended yarn as a woven or knitted fabric, but the desired tone can be obtained. Recently, the needs of the blended yarn are becoming increasingly diversified, and a softer and more flexible texture of the blended yarn is required. It has become like this. In order to meet these demands, a fiber having a fineness of the fiber constituting the mixed yarn and an improved dyeability is required.

  JP-A-2-19528, JP-A-2002-249941 and the like have proposed a mixed yarn composed of two types of polyester fiber having a difference in thermal shrinkage, but it is flexible with a fineness of 1 dtex or less and It was not possible to meet the demand for blended yarn with deep dyeability.

In response to these market demands, there is the cationic dyeing technology described above as a conventional polyester thickening technology, but it does not have a reactive dyeing seat. There is a method in which a monomer containing a functional group to be seated (for example, a metal salt of sulfoisophthalic acid) is copolymerized in a polymer skeleton, and molecular design is performed so that coloring property at dyeing is sufficient. However, these methods have a fatal problem that the polymerization viscosity does not increase and the degree of polymerization does not increase. This has been able to cover and use this property in the clothing field that places importance on fashionability, but is a field that requires mechanical strength such as tear resistance, abrasion resistance, and burst resistance as a fabric, The use for sports clothing and wiping cloth was hindered. In addition, since the conventional cationic dyeable ultrafine fiber has low strength, the processing tone at the time of blending processing is lowered, and it is actually impossible to produce a cationic dyeable ultrafine mixed yarn.
Various studies have been made to solve the problems of these cationic dyeable polyester blended yarns, but none of the fineness, mechanical strength, and dyeing clarity have been achieved at a practical level.

Japanese Patent Publication No.34-10497 Japanese Patent Publication No. 47-22334 Japanese Patent No. 2915045 Japanese Patent Laid-Open No. 9-241938 JP 2003-336136 A

  The object of the present invention is to solve the above-mentioned problems in the cationic dyeable ultrafine mixed yarn, and was made in response to market demands, and is excellent in softness, texture, dyeability, dyeing fastness, and It is an object of the present invention to provide a polyester extra fine mixed yarn that satisfies the mechanical characteristics, yarn forming property, workability and unwinding property at the same time.

（式中、Ａは芳香族基又は脂肪族基、Ｘ_１はエステル形成性官能基、Ｘ_２はＸ_１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、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４はアルキル基及びアリール基より選ばれた同一又は異なる基、ｎは正の整数を示す）
ｂ）カチオン可染ポリエステルマルチフィラメントが、第４級オニウム塩を上記式（Ｉ）で表されるスルホン酸４級ホスホニウム塩に対して、０．１〜２０モル％含むこと。
ｃ）該カチオン可染ポリエステルマルチフィラメントの複屈折率（Δｎ）が０．０３〜０．０８の範囲である高配向ポリエステル未延伸マルチフィラメントであること。
ｄ）該カチオン可染ポリエステルマルチフィラメントの単糸繊度が０．７ｄｔｅｘ以下であること。
ｅ）交絡数が６０ケ／ｍ以上である混繊糸であること。 Cationic dyeable extra fine polyester blend yarn that satisfies the following requirements.
a) The cationic dyeable polyester multifilament is copolymerized with a sulfonic acid quaternary phosphonium salt represented by the following formula (I) in an amount of 0.1 to 10 mol% based on the total acid components in the cationic dyeable polyester multifilament. The modified polyester has an intrinsic viscosity of 0.6 or more.

(In the formula, A is an aromatic group or aliphatic group, X ₁ is an ester-forming functional group, X ₂ is the same or different ester-forming functional group or hydrogen atom as X ₁ , R ₁ , R ₂ , R ₃ and R ₄ represents the same or different group selected from an alkyl group and an aryl group, and n represents a positive integer)
b) The cationic dyeable polyester multifilament contains 0.1 to 20 mol% of a quaternary onium salt with respect to the sulfonic acid quaternary phosphonium salt represented by the above formula (I).
c) A highly oriented polyester unstretched multifilament in which the birefringence (Δn) of the cationic dyeable polyester multifilament is in the range of 0.03 to 0.08.
d) The single yarn fineness of the cationic dyeable polyester multifilament is 0.7 dtex or less.
e) A blended yarn having an entanglement number of 60 / m or more.

  When using a cationic dyeable polyester multifilament composed of a modified polyester having a specific viscosity as a constituent component of a blended yarn and a specific polyester having a specific viscosity, birefringence, and fineness, softness, It is possible to obtain a cationic dyeable polyester ultrafine mixed yarn excellent in texture, dyeability and dyeing fastness, and satisfying mechanical properties, yarn forming properties, processability and unwinding properties at the same time. In particular, when blending and processing with other components of the blended yarn, it is possible to greatly reduce the cut yarn, fluff, etc., and the process tone is greatly improved.

  The polyester used in the present invention is a polyester having terephthalic acid as a main acid component and at least one glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as a main glycol component. Is the main target.

  Here, the acid component may be a polyester in which a part of the terephthalic acid component is replaced with another bifunctional carboxylic acid component, and / or a part of the glycol component is the glycol other than the main component or other Polyester substituted with a diol component may be used.

  Examples of the bifunctional carboxylic acid other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and adipic acid. Aromatic, aliphatic and alicyclic bifunctional carboxylic acids such as, sebacic acid and 1,4-cyclohexanedicarboxylic acid. Further, isophthalic acid having a sulfonic acid metal base such as 5-sodium sulfoisophthalic acid may be used as a copolymerization component as long as the effect of the present invention is substantially exhibited.

  Examples of the diol compound other than the glycol include aliphatic, alicyclic and aromatic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A and bisphenol S, and polyoxyalkylene glycol. Can give.

  Furthermore, a polycarboxylic acid such as trimellitic acid and pyromellitic acid, and a polyol such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as the polyester is substantially linear.

  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 to produce a glycol ester of terephthalic acid and / or its low polymer by reacting with an oxide, etc., and heating the reaction product of the first stage 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, a sulfonic acid quaternary phosphonium salt represented by the following general formula (I) is used as a copolymerization component as a cationic dye for the above polyester.

In the formula, A represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. X ₁ represents an ester-forming functional group, and specific examples thereof include dicarboxylic acids such as terephthalic acid. X ₂ represents an ester-forming functional group or a hydrogen atom that is the same as or different from X _1, and among them, an ester-forming functional group is preferable. R ₁ , R ₂ , R ₃ and R ₄ represent the same or different groups selected from the group consisting of alkyl groups and aryl groups. n is a positive integer. Such a sulfonic acid quaternary phosphonium salt can be easily synthesized by a reaction between a corresponding sulfonic acid and a phosphine or a reaction between a corresponding metal salt of a sulfonic acid and a phosphonium halide.

  Preferred examples of the sulfonic acid quaternary phosphonium salt include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, 3,5-dicarboxybenzenesulfone. Benzyltributylphosphonium acid 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 ethyltributylphosphonium 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 polyester, it may be added at any stage before the completion of the above-described polyester synthesis, preferably at any stage before the completion of the first stage reaction. Good. The proportion of the sulfonic acid phosphonium salt copolymerized with the polyester is suitably in the range of 0.1 to 10 mol%, more preferably with respect to the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester. The range of 0.5-6 mol% is 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 cationic dyeability is no longer significantly improved. On the contrary, the physical properties of the polyester are lowered, making it difficult to achieve the object of the present invention.

  When the modified polyester is produced, when a small amount of the sulfonic acid quaternary phosphonium salt represented by the general formula (I) and a small amount of the sulfonic acid tertiary phosphonium salt represented by the following general formula (II) are used together, The decomposition reaction in the polymerization process is suppressed, and the resulting modified polyester and the molded product made thereof are very good in color, which is preferable.

  The sulfonic acid tertiary phosphonium salt is represented by the following general formula (II), and the 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.

（式中、Ｂは前記一般式（Ｉ）におけるＡと同様に定義され、Ｘ_３は前記一般式（Ｉ）におけるＸ１と同様に定義され、Ｘ_４は前記一般式（Ｉ）におけるＸ_２と同様に定義され、Ｒ_５、Ｒ_６、Ｒ_７は前記一般式（Ｉ）におけるＲ_１、Ｒ_２及びＲ_３と同様に定義され、ｎは正の整数である）

(In the formula, B is defined in the same manner as A in the general formula (I), X ₃ is defined in the same manner as X ₁ in the general formula (I), and X ₄ is X ₂ in the general formula (I). R ₅ , R ₆ and R ₇ are defined in the same manner as R ₁ , R ₂ and R ₃ in the general formula (I), and n is a positive integer.

  Preferred 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 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. Further, 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 producing the modified polyester, it is necessary to add a quaternary onium salt. The quaternary onium salts include quaternary ammonium salts, quaternary phosphonium salts, and the like. Specifically, the quaternary ammonium salts include tetramethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium hydroxide, and chloride. Tetraethylammonium, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetraisopropylammonium hydroxide, tetraisopropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetraphenylhydroxide Examples include ammonium and tetraphenylammonium chloride.

  If the amount of the quaternary onium salt used is too small, the effect of improving the heat resistance becomes insufficient. On the other hand, if the amount is too large, the heat resistance deteriorates. The tendency to color brown becomes remarkable. For this reason, the amount of the quaternary onium salt used is preferably in the range of 0.1 to 20 mol%, particularly preferably in the range of 1 to 10 mol%, based on the sulfonic acid phosphonium salt.

  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 synthetic 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 quaternary phosphonium salt of the raw material is used. It may remain in the phosphonium salt of sulfonic acid that is a reaction product. In such a case, it is not necessary to use a quaternary phosphonium salt, and the remaining quaternary phosphonium salt can be used.

By satisfying the above conditions, a modified polyester excellent in whiteness with little yellow having an intrinsic viscosity necessary for high strength of 0.60 or more, more preferably 0.64 or more can be obtained.
The modified polyester thus obtained is melt-spun. A normal spinning method is adopted for this melt spinning. Generally, in melt spinning, a polymer is melted at a temperature 30 to 50 ° C. higher than its melting point and discharged from a spinneret. When this spinning method is applied to the modified polyester, it may be decomposed and colored during spinning or the degree of polymerization may be reduced. In such a case, it is preferable to perform spinning at a temperature below 280 ° C.

  As described above, by adding the quaternary onium salt, more preferably by adding the quaternary onium salt and employing the above low temperature spinning method, the degree of polymerization of the modified polyester is reduced or yellowed. For the first time, it is possible to provide a cationic dye-modified modified polyester fiber having an intrinsic viscosity of 0.6 or more, particularly preferably 0.63 or more, and the fiber has a silk factor of 15 or more. Preferably, it can exhibit a high strength of 20 or more, exhibits high whiteness, and exhibits excellent sharpness when dyed.

  Recently, in sports clothing, polyester fibers that are vividly dyed and excellent in light fastness are required, and further, high tear strength in fabrics is required. The tear strength of a fabric largely depends on the intrinsic viscosity and further on the silk factor, although there is a portion depending on the woven or knitted structure of the fabric. In sports apparel, a high silk factor is required, as can be seen from its use, and a silk factor of 15 or more, preferably 20 or more is required. This is the first cationic dye having a high silk factor and excellent heat resistance according to the present invention. A dyeable polyester fiber can be obtained.

  The cationic dyeable polyester fiber of the present invention needs to have a birefringence in the range of 0.03 to 0.08. If it is less than 0.03, the yarn becomes brittle in the mixed fiber processing, resulting in frequent yarn breakage, making it difficult to process, and if it exceeds 0.08, fluffing occurs frequently in the spinning and mixed fiber processing step, and in the fabric making process after Since production efficiency is inhibited, it is not preferable.

  In order to make the birefringence within this range, for example, the modified polyester is melt-spun at a take-up speed of 3000 m / min or more to obtain a multifilament yarn having an average fineness of a single yarn of 1.0 dtex or less, preferably 0.7 dtex or less. It is preferable.

  The fineness of the fiber of the present invention is preferably 0.7 dtex or less, and preferably 0.1 to 0.7 dtex. When it is less than 0.1, the productivity is extremely lowered, and when it exceeds 0.7, the softness and the texture are lowered, which is not preferable.

The cationic dyeable highly oriented polyester unstretched multifilament of the present invention is mixed with other raw yarns. Although any filament can be used as the other raw yarn, it is preferable to use a polyester multifilament or the like. For example, a polyester multifilament having a larger hot water shrinkage than the cationic dyeable highly oriented polyester unstretched multifilament can be used.
Further, the mixed yarn is preferably subjected to an entanglement treatment of about 60 / m by an air entanglement nozzle such as an interlace.

  A typical process of the present invention will be described with reference to the accompanying drawings (FIG. 1). Cationic dyeable highly oriented polyester unstretched multifilament (A) and polyester multifilament (B) are fed together and supplied to the supply roller (1), and then the yarn is entangled with an air jet nozzle for entanglement. Then, it preheats with a preheating roller (2), and extends | stretches to a predetermined magnification with a take-off roller (4). At this time, these mixed yarns are heat-set by a set heater (5) provided between the preheating roller and the take-up roller. Further, the yarn taken up by the take-up roller is continuously wound up by a take-up device arranged on the rear side to obtain a target mixed yarn package (6).

  Here, when the cationic dyeable ultrafine highly oriented polyester unstretched multifilament (A) of the present invention is not used, the conventional cationic dyeable ultrafine yarn of 0.7 dtex or less cannot take strength, and frequent occurrence of yarn breakage and fluff occurs. As a result, the mixed fiber processing tone is lowered, yield, productivity is poor, and the production cannot be practically performed.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The part and% in an Example show a weight part and weight%, respectively.
The measuring method is as follows.

Intrinsic viscosity [η] of the polymer: It was determined from a value obtained by measuring a sample with a 25 ° C. orthochlorophenol solution.
Softening point (SP): Measured by the penetration method.
Polymer hue: indicated by L value and b value by Hunter type color difference meter. The larger the value, the better the whiteness, and the greater the b value, the stronger the yellowness.
Number of carboxyl group terminals of polymer: The sample was dissolved by heating in benzyl alcohol and titrated with a sodium hydroxide solution. The larger the number of carboxyl group terminals, the more thermal decomposition occurs.
Diethylene glycol content (DEG content) in the polymer: A polyester sample was thermally decomposed with hydrazine hydrate, and the supernatant was quantified by gas chromatography (1,4-butanediol was used as an internal standard).
Polymer heat resistance: After completion of the polymerization reaction of the copolymerized polymer, the polymer extrusion nitrogen gas pressure from the polymerization can is adjusted, the time required for polymer removal is set to 60 minutes or more, and the polymer 10 minutes and 60 minutes after the start of polymer removal The intrinsic viscosity [η] was evaluated based on the difference.
Mixing process condition Evaluated by the occurrence of broken yarn and fluff.
○: Thread breakage Good without fluff ×: Thread breakage

[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 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt in an amount of 1.7 mol% with respect to dimethyl terephthalate as the cationic dyeing agent and 4 As a class onium salt, tetra-n-butylphosphonium bromide in an amount of 0.050 mol% with respect to dimethyl terephthalate was charged into a transesterification can and heated from 140 ° C to 220 ° C over 3 hours in a nitrogen gas atmosphere. The transesterification reaction was carried out while distilling off the methanol produced. Subsequently, 0.03 part of a 56% aqueous solution of normal phosphoric acid (0.003 mol% with respect to dimethyl terephthalate) was added as a stabilizer to the obtained product, and at the same time, excessive ethylene glycol was purged from the temperature. Started. 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. When the polymerization was carried out at a polymerization temperature of 280 ° C. for 2 hours under a reduced pressure of 1 mmHg or less, the vacuum was broken with nitrogen gas to terminate the polymerization reaction, and the polymer was discharged at 280 ° C. under nitrogen gas pressurization.

  The resulting polymer had 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. The intrinsic viscosity ([η] 60) was 0.648.

  This polymer is formed into chips according to a conventional method, dried, melted at a maximum of 310 ° C. using a spinneret having 72 circular discharge holes with a hole diameter of 0.15 mm, and high-speed spinning at a take-up speed of 3200 m / min. An ultrafine yarn having a birefringence of Δn 0.045 was obtained with 36 dtex / 72 filaments (single yarn dtex: 0.5). The intrinsic viscosity [ηF] of the obtained spun yarn was 0.625. The obtained yarn was entangled and mixed in the process shown in FIG.

  The resulting cationic dyeable highly oriented unstretched polyester multifilament and a fully oriented polyester multifilament exhibiting a higher hydrothermal shrinkage (fully oriented polyester multifilament comprising polyethylene terephthalate copolymerized with isophthalic acid) ), The yarns are entangled by an air entanglement device, the preheating roller temperature is 80 ° C., the draw ratio is 0.97, the heater temperature is 190 ° C., the overfeed rate is 1.0%, and the air pressure of the rear interlace nozzle is 1.2 kg / cm 2. And 70 k / m entanglement was applied, and mixed fiber processing was performed at a take-up speed of 600 m / min.

  The physical properties of the mixed yarn thus obtained are as follows: the single yarn fineness of the cationic dyeable yarn in the mixed yarn is 0.5 dtex, the strength is 3.5 g / dtex, the silk factor is 21.7, and the L value is 84.7. The b value was 6.8. Moreover, the mixed fiber finishing tone was good without any yarn breakage.

  A fabric in which this mixed yarn is woven by a conventional method is used as a dye bath (as an auxiliary agent) containing 2% owf of a cationic dye: Cathilon CD-FRLH / Cathillon Blu CD-FBLH = 1/1 (manufactured by Hodogaya Chemical Co., Ltd.). Stained at 120 ° C. for 60 minutes with 3 g / l of mirabilite and 0.3 g / l of acetic acid. As shown in Table 1, the clearness of the dyed fabric exhibited a clear dark blue color, and since the surface was an ultrafine fiber, the touch was soft and the texture was excellent.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that tetra-n-butylphosphonium bromide was not used.
The obtained polymer had a softening point (SP) of 253.5 ° C., a diethylene glycol content (DEG content) of 1.67, an intrinsic viscosity after 10 minutes of discharge ([η] 10) of 0.576, and after 60 minutes of discharge. Has an intrinsic viscosity ([η] 60) of 0.521, an intrinsic viscosity ([η] f) of the spun yarn of 0.480, and a single yarn fineness of the cationic dyeable yarn in the mixed yarn is 0.5 dtex. , The strength is as low as 2.1 g / dtex, the silk factor is 15.5, the L value is 79.8, the b value is 14.9, the coloring is seen, the blending processing is not good, and the ultrafine blended yarn is Caterpillars were generated and lacked in quality (see Table 1). The quality of the dyed fabric was clear but the strength was weak and the practicality was poor.

[Example 2]
Instead of 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt and tetra-n-butylphosphonium bromide used in Example 1, 3 in an amount of 1.7 mol% with respect to dimethyl terephthalate. , 5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt and tetraphenylphosphonium hydroxide in an amount of 0.050 mol% with respect to dimethyl terephthalate are used. The same procedure as in Example 1 was performed except that it was performed before.

  The resulting polymer has a softening point (SP) of 250.4 ° C., a diethylene glycol content (DEG content) of 1.65, an intrinsic viscosity after 10 minutes of discharge ([η] 10) of 0.674, and after 60 minutes of discharge. Has an intrinsic viscosity ([η] 60) of 0.653, an intrinsic viscosity ([η] f) of the spun yarn of 0.630, and a single yarn fineness of the cationic dyeable yarn in the mixed yarn is 0.5 dtex. The strength was 3.8 g / dtex, the silk factor was 23.0, the L value was 84.9, and the b value was 7,6. Moreover, the mixed fiber finishing tone was good without any yarn breakage. As shown in Table 1, the clearness of the dyed fabric exhibited a clear dark blue color, and since the surface was an ultrafine fiber, the touch was soft and the texture was excellent.

[Comparative Example 2]
The same procedure as in Example 2 was performed except that tetraphenylphosphonium hydroxide was not used.
The resulting polymer had a softening point (SP) of 253.1 ° C., a diethylene glycol content (DEG content) of 1.67, an intrinsic viscosity after 10 minutes of discharge ([η] 10) of 0.583, and after 60 minutes of discharge. Has an intrinsic viscosity ([η] 60) of 0.532, an intrinsic viscosity ([η] f) of the spun yarn of 0.495, and a single yarn fineness of the cationic dyeable yarn in the mixed yarn is 0.5 dtex. The strength was 2.2 g / dtex, the silk factor was 14.2, the L value was 78.8, and the b value was 15.5. Further, the mixed fiber processing tone was poor, and as in Comparative Example 1, the practicality was poor.

[Example 3]
Instead of 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt and tetraphenylphosphonium hydroxide used in Example 2, 3,5-dicarboxybenzene in an amount of 1.7 mol% relative to dimethyl terephthalate The same procedure as in Example 2 was conducted except that tetra-n-butylammonium hydroxide in an amount of 0.003 mol% based on tetra-n-butylphosphonium sulfonate and dimethyl terephthalate was used.

The resulting polymer had a softening point (SP) of 253.3 ° C., a diethylene glycol content (DEG content) of 1.63, an intrinsic viscosity after 10 minutes of discharge ([η] 10) of 0.673, and after 60 minutes of discharge. Has an intrinsic viscosity ([η] 60) of 0.651, an intrinsic viscosity ([η] f) of the spun yarn of 0.623, and a single yarn fineness of the cationic dyeable yarn in the mixed yarn is 0.5 dtex. The strength was 3.6 g / dtex, the silk factor was 23.3, the L value was 85.3, and the b value was 7.5. Moreover, the mixed fiber finishing tone was good without any yarn breakage. As shown in Table 1, the clearness of the dyed fabric exhibited a clear dark blue color, and since the surface was an ultrafine fiber, the touch was soft and the texture was excellent.
As shown in Table 1, the clearness of the dyed fabric exhibited a clear dark blue color, and since the surface was an ultrafine fiber, the touch was soft and the texture was excellent.

  High strength, soft surface, good touch, good squeaky feel, and a vivid color tone can be obtained, so in addition to clothing applications, tear resistance, abrasion resistance, burst resistance, etc. It can be used in fields requiring high mechanical strength, sports clothing, wiping cloth, and the like.

It is the schematic which shows an example of the apparatus which enforces the method of this invention.

Explanation of symbols

A: Raw yarn made of cationic dyeable polyester filament,
B ... Raw yarn that gives a characteristic other than A,
1 ... feed roller,
2 ... Preheating roller,
3 …… Air jet nozzle for entanglement,
4 …… Retracting roller
5 …… Set heater,
6 …… Tsumari package (cationic dyed blended yarn of the present invention),

Claims (1)

A cationic dyeable ultrafine polyester mixed yarn characterized by satisfying the following requirements in a mixed yarn comprising two or more component fiber yarns including a cationic dyeable polyester multifilament and a cationic undyed polyester multifilament.
a) The cationic dyeable polyester multifilament is copolymerized with a sulfonic acid quaternary phosphonium salt represented by the following formula (I) in an amount of 0.1 to 10 mol% based on the total acid components in the cationic dyeable polyester multifilament. The modified polyester has an intrinsic viscosity of 0.6 or more.

(In the formula, A is an aromatic group or aliphatic group, X ₁ is an ester-forming functional group, X ₂ is the same or different ester-forming functional group or hydrogen atom as X ₁ , R ₁ , R ₂ , R ₃ and R ₄ represents the same or different group selected from an alkyl group and an aryl group, and n represents a positive integer)
b) The cationic dyeable polyester multifilament contains 0.1 to 20 mol% of a quaternary onium salt with respect to the sulfonic acid quaternary phosphonium salt represented by the above formula (I).
c) A highly oriented polyester unstretched multifilament in which the birefringence (Δn) of the cationic dyeable polyester multifilament is in the range of 0.03 to 0.08.
d) The single yarn fineness of the cationic dyeable polyester multifilament is 0.1 to 0.7 dtex.
e) A blended yarn having an entanglement number of 60 / m or more.

Images