JP2007063714A - Ultrafine polyester fiber and cloth - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultrafine polyester fiber having excellent stability in a yarn-making process and mechanical properties, exhibiting soft and good touch, and satisfying mild and high color development to form a unique pearl-tone milky appearance, excellent opacity and UV-shielding effect and provide a high-quality stretch cloth free from flaws such as fluffs and warp streaks on a warp knit fabric with an elastic fiber such as textured yarn, crimped yarn and polyurethane yarn. <P>SOLUTION: The invention provides a cation-dyeable ultrafine polyester fiber having an L value of 90-95 in Lab color specification system and a residual elongation of 36-50%, made of a polyester containing no or ≤30 ppm antimony in terms of antimony atom and 1-2 wt.% titanium oxide particle and copolymerized with 0.1-6 mol% 5-sulfoisophthalic acid metal salt and 0.1-5 wt.% polyethylene glycol having a weight-average molecular weight of 200-6,000, and consisting of a multifilament yarn having a single fiber fineness of ≤1.1 dtex. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyester ultrafine fiber and fabric having high color developability. More specifically, it has an unprecedented pearly milky feel, high color developability, excellent anti-peeling property, UV-cutting effect, excellent physical properties such as mechanical properties, yarn-making property, and texture, processed yarn and crimped The present invention relates to a polyester extra-fine fiber and a fabric capable of obtaining a high-quality stretch fabric without generating fuzz and warp in a knitted fabric through an elastic fiber such as yarn and polyurethane.

  Polyesters are excellent in durability such as dimensional stability and chemical resistance, and are used for various purposes because of their useful functionality. For example, polyesters are widely used for clothing, industrial use, materials use, medical use and the like.

  On the other hand, in the market, the demand for specialization of synthetic fibers is increasing year by year, and among them, the demand for high color development fibers is strong, and various studies have been made mainly by synthetic fiber companies. Conventionally, polyester obtained by copolymerizing 5-sodium sulfoisophthalic acid alone in order to obtain cationic dyeability (see Patent Documents 1 and 2) and 5-sodium sulfoisophthalic acid in order to obtain atmospheric pressure cationic dyeability. A polyester copolymerized with adipic acid (see Patent Documents 3 and 4) is known. However, the polyesters obtained by these methods contain a large amount of diol components produced in the transesterification and polycondensation reaction steps, and not only mechanical properties and heat stability are significantly reduced, but also by ordinary methods. When spinning, stable spinning is difficult due to the high melt viscosity of the polymer. In order to solve this problem, a technique of copolymerizing an isophthalic acid component containing a metal sulfonate group and a glycol has been disclosed (see Patent Documents 5, 6, and 7). Certainly, this method made it possible to suppress the thickening effect of the cationic dyeable polymer.

  On the other hand, polyester fibers generally have a high Young's modulus, and it has been pointed out that the texture of the woven or knitted fabric is soft, and it is known to reduce the single yarn fineness to give a soft and good texture. It has been. In particular, when the single yarn fineness is 1.1 dtex or less, a unique soft feeling can be obtained. Therefore, there is an increasing need for fine fibers having a single yarn fineness of 1.1 dtex or less and woven or knitted fabrics using them.

  From such a background, a technique of an ultrafine fiber made of polyester obtained by copolymerizing an isophthalic acid component containing a metal sulfonate group and a glycol has been disclosed (see Patent Document 8). Although it is possible to obtain both high color developability, dyeing fastness and soft and good texture by this technology, the improvement of mechanical characteristics and heat stability is still insufficient, not to mention the deterioration of operability in the yarn making process. In addition, fluff and yarn breakage frequently occur in the high-order processing step, which is not satisfactory in terms of productivity.

  In addition, as a recent major application of cationic dyeable fibers, sportswear such as swimwear, leotards and wet suits, and inner uses such as shirts, shorts and lingerie are increasing. In addition to stretch resistance and UV-blocking effect, stretch properties are required. As a means for imparting stretch properties to polyester fiber, false twisting method or a method of imparting crimp characteristics to the original yarn itself by composite spinning of polymers with different shrinkage characteristics into side-by-side type, other types with different shrinkage characteristics Examples of the method include composite blending with fibers, mixed use with processed fibers, crimped yarns, and elastic fibers such as polyurethane. Among them, knitting with elastic fibers is the most versatile and suitable for raw yarns and higher orders. Can be used. However, the elastic yarn has a large variation in the residual elongation of the raw yarn, so it induces tension spots during knitting and easily deteriorates the quality of the warp and the like, so the mechanical properties are inferior. When a cationic dyeable polyester fiber having a lower elongation than normal polyester was used for the other, the quality was significantly lowered, and it could not be commercialized.

  Furthermore, in recent years, there is an increasing tendency for cationic dyeable fibers to be required to have a composite function such as sheer permeability and UV cut. In general, a method of adding inorganic particles having high light reflectivity is known as a means for imparting anti-penetration properties and UV-cutting properties. Among these, titanium oxide particles can be suitably used because of their high light reflectivity, ease of handling and low cost.

  On the other hand, polyester is produced from terephthalic acid or an ester-forming derivative thereof and alkylene glycol, and in a commercial process for producing a high molecular weight polymer, an antimony compound is widely used as a polycondensation catalyst. However, polymers containing antimony compounds have some undesirable properties as described below.

  For example, when a polymer obtained using an antimony catalyst is melt-spun into a fiber, it is known that an antimony catalyst residue is deposited around the die hole.

  As this deposition progresses, it becomes a cause of defects in the filament, so that it needs to be removed in a timely manner. The deposition of the antimony catalyst residue is considered to be due to the antimony compound in the polymer being transformed in the vicinity of the die and partially vaporizing and dissipating, and then a component mainly composed of antimony remains in the die.

  In addition, the antimony catalyst residue in the polymer tends to be relatively large particles, and it has undesirable properties such as becoming a foreign substance and increasing the filter pressure of the filter during molding and causing yarn breakage during spinning. This contributes to a decrease in operability.

  In particular, when the above-described titanium oxide particles or isophthalic acid component containing a metal sulfonate group is used as the antimony catalyst residue, foreign particles are formed using the isophthalic acid component as a nucleus, and the degree thereof increases. Moreover, when they are used in combination, the degree of deterioration is inevitably deteriorated, and not only the yarn breakage and the filtration pressure increase, but also the workability and quality of the obtained fiber product are reduced. It was impossible to obtain a polyester fiber that has both good properties, UV-cutting properties and high color development properties, particularly an ultrafine fiber having a single yarn fineness of 1.1 dtex or less.

In recent years, a polyester fiber technology using a polyester having a low or no antimony content even in a copolyester having a copolymerized component of an isophthalic acid component or a polyether component containing a metal sulfonate group has been disclosed. In particular, there has been proposed one in which the role of the polycondensation catalyst is aluminum and / or a compound thereof and a phenol compound (see Patent Documents 9 and 10). According to this method, although foreign substances resulting from the catalyst can be reduced, it is not sufficient, and the mechanical properties, in particular, the residual elongation sufficient to suppress the deterioration of quality are not maintained. Further, the color tone of the obtained polymer is not sufficient, and further improvement of the polycondensation catalyst is demanded.
JP 34-010497 A (1 page) Japanese National Patent Publication No. 11-506484 (1 page) JP 61-239015 (1 page) JP 11-093020 A (1 page) JP 59-026521 A (1 page) JP-A-63-048353 (1 page) JP 63-120111 A (1 page) JP-A-53-152814 (1 page) JP 2002-212278 A (1 page) JP 2002-227033 A (1 page)

  An object of the present invention is to solve the above-mentioned conventional problems, and has a high color developability with a pearl-like milky feeling and a soft and good texture, which are unprecedented, and has excellent transparency and UV resistance. It has a cutting effect at the same time, is excellent in the stability of the yarn production process, and does not generate fuzz or warp in the knitted fabric through processed yarn, crimped yarn, and elastic fiber, so that a high-quality fabric can be obtained. Polyester microfibers and fabrics are provided.

  In order to solve the above problems, the present invention employs the following configuration. That is, 0.1-6 mol% of 5-sulfoisophthalic acid metal salt and 0.1-5 wt% of polyethylene glycol having a polymerization average molecular weight of 200-6000 are copolymerized and do not contain antimony or the content in terms of atoms Is a multi-yarn having a single yarn fineness of 1.1 dtex or less, a color tone L value of 90 to 95, and a residual elongation. A cationic dyeable polyester microfiber characterized by a degree of 36 to 50%.

  According to the present invention, it has a soft and good texture, a UV-cutting effect and anti-transparency, and a new textured polyester extra fine texture with mild high color development due to an unprecedented pearly milky feeling. In the fiber, fuzz and warp are not generated in the knitted fabric through the elastic fiber or the like, and the fiber can be obtained stably and with high quality.

  Hereinafter, the polyester microfiber of the present invention will be described in detail.

  The cationic dyeable polyester ultrafine fiber of the present invention is copolymerized with 0.1 to 6 mol% of 5-sulfoisophthalic acid metal salt and 0.1 to 5 wt% of polyethylene glycol having a weight average molecular weight of 200 to 6000. This is very important. When 0.1 to 6 mol% of the metal salt of 5-sulfoisophthalic acid is 0.1 mol% or more, the dyeing amount of the cationic dye is increased, and the color developability is improved. On the other hand, when the amount of copolymerization becomes too large, the melt viscosity of the polymer increases greatly, which is accompanied by an increase in filtration pressure and a decrease in spinnability. For this reason, it is important that the copolymerization amount of 5-sulfoisophthalic acid metal salt is 6 mol% or less. Furthermore, it is preferable that it is 0.5-2 mol%. At the same time, the copolymerization amount of polyethylene glycol having a weight average molecular weight of 200 to 6000 is 0.1% by weight or more, so that the dyeing amount of the cationic dye is increased. Suppresses the thickening effect of salt. On the other hand, if the amount of copolymerization is too large, the heat resistance of the polymer is reduced, the strength and elongation of the fiber is lowered, and the color tone is deteriorated. Preferably it is 0.5-4 weight%, and 1-2 weight% is more preferable especially. In addition, when the weight average molecular weight of polyethylene glycol is too large, it is easy to form a lump in polyester without copolymerization, and when it is too small, the dyeability is poor. Therefore, the weight average molecular weight of polyethylene glycol is preferably 2000 to 4000.

  The metal salt of 5-sulfoisophthalic acid metal salt defined in the present invention includes sodium salt and lithium salt, among which sodium salt is preferable.

  Other dicarboxylic acids such as adipic acid, isophthalic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, cyclohexanedicarboxylic acid, and ester-forming derivatives thereof, diethylene glycol, hexamethylene glycol, neopentyl Dioxy compounds such as glycol and cyclohexanedimethanol, oxycarboxylic acids such as p- (β-oxyethoxy) benzoic acid, and ester-forming derivatives thereof may be copolymerized.

  In the cationic dyeable polyester ultrafine fiber of the present invention, it is important that the antimony compound is not contained or the content in terms of antimony atom relative to the polyester is 30 ppm or less. By setting it within this range, the generation of foreign particles can be suppressed, and a relatively inexpensive polymer can be obtained with less generation of base stains during molding processing, less filtration pressure, lower workability, and the like. More preferably, it is 10 ppm or less.

  In addition, a titanium compound is preferable as a polymerization catalyst in place of antimony, and the substituent is at least one selected from the group consisting of functional groups represented by the following formulas 1 to 5 and containing at least a carbonyl group, a carboxyl group, or an ester group. A titanium compound is mentioned.

(In Formula 1 to Formula 5, R _{1 to} R ₃ each independently have hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. This represents a hydrocarbon group having 1 to 30 carbon atoms, and the titanium compound contains at least a carbonyl group, a carboxyl group or an ester group.)
Formula 1 includes functional groups composed of hydroxy polyvalent carboxylic acid compounds such as lactic acid, malic acid, tartaric acid, and citric acid.

  Formula 2 includes a functional group composed of a β-diketone compound such as acetylacetone and a ketoester compound such as methyl acetoacetate and ethyl acetoacetate.

  Moreover, as Formula 3, the functional group which consists of phenoxy, cresylate, salicylic acid, etc. is mentioned.

  Formula 4 includes acylate groups such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacin Polycarboxylic acid compounds such as acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or their anhydrides, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid And functional groups composed of nitrogen-containing polyvalent carboxylic acids such as triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid.

  Formula 5 includes functional groups composed of aniline, phenylamine, diphenylamine, and the like.

  Among these, the inclusion of Formula 1 and / or Formula 4 is preferable from the viewpoint of the thermal stability and color tone of the polymer.

  Examples of the titanium compound include titanium diisopropoxybisacetylacetonate and titanium triethanolamate isopropoxide containing two or more of the substituents represented by formulas 1 to 5.

  It should be noted that conventionally known alkoxytitanium compounds containing no carbonyl group, carboxyl group and ester group, such as tetraisopropoxytitanium and tetrabutoxytitanium, are not included in Formula 1 of the present invention.

The catalyst used in the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, or all or some of the following reactions (1) to (3): A compound that substantially contributes to the promotion of the reaction can be used.
(1) Esterification reaction which is reaction of dicarboxylic acid component and diol component (2) Transesterification reaction which is reaction of ester-forming derivative component of dicarboxylic acid and diol component (3) Substantially ester reaction or transesterification Polycondensation reaction in which the reaction is completed and the resulting polyalkylene terephthalate low polymer is depolymerized to increase the degree of polymerization. Accordingly, titanium oxide particles generally used as inorganic particles in fiber matting agents, etc. Has substantially no catalytic action on the above reaction and is different from the titanium compound that can be used as the catalyst of the present invention.

  The titanium compound (excluding titanium oxide particles) used in the present invention is preferably contained in an amount of 0.5 to 150 ppm in terms of titanium atom with respect to the obtained polymer. When it is 1 to 100 ppm, the thermal stability and color tone of the polymer become better, and it is more preferably 3 to 50 ppm.

  The cationic dyeable polyester ultrafine fiber of the present invention preferably contains 0.1 to 400 ppm of phosphorus in terms of phosphorus atoms with respect to the polyester together with the titanium compound. The phosphorus content is preferably 1 to 200 ppm, more preferably 3 to 100 ppm from the viewpoint of thermal stability and color tone of the polyester during yarn production.

  In the polyester obtained by adding at least a specific titanium compound and a phosphorus compound of the present invention, the specific phosphorus compound used is represented by the following formula 6.

(In the above formula 6, R ₁ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms, and has two or more with respect to the benzene ring. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl, and R ₂ and R ₃ are each independently An alkoxy group that represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, or an alkoxy group and that is —OR ₂ or —OR ₃ with respect to a phosphorus atom may be used. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl, L + M + N = 3, and L is an integer of 1 to 3. , M and N are integers from 0 to 2 .)
Examples of the phosphorus compound represented by the above formula 6 include phosphites, alkyl diarylphosphites, aryl diarylphosphites, dialkyl arylphosphonites, and arylarylphosphonites. It is preferable that it is a phosphite from a viewpoint of heat stability and a color tone improvement. Specifically, as a phosphorus compound having no cyclic structure, triphenyl phosphite, tris (4-monononylphenyl) phosphite, trimethyl phosphite as a compound of L = 3, M = 0, and N = 0 in formula 6 (Monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, etc., and monooctyl diphenyl phosphite as a compound of L = 2, M = 1, and N = 0 Monodecyldiphenyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′- Biphenylene diphosphite and the like, and dioctyl monophenyl phosphite, di = 1 as a compound of L = 1, M = 1 and N = 1 Examples include decyl monophenyl phosphite. Among them, tris (2,4-di-tert-butylphenyl) phosphite represented by the following formula 7 is preferable. This compound is available as “ADK STAB” (registered trademark) 2112 (Asahi Denka Co., Ltd.) or “IRGAFOS” (registered trademark) 168 (Ciba Specialty Chemicals).

  Moreover, it is preferable that the phosphorus compound represented by Formula 6 is a compound which has a 6-membered ring structure or more containing a phosphorus atom from a viewpoint of thermal stability and a color tone improvement. Specific phosphorus compounds include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2) as compounds of L = 1, M = 1, and N = 1. 2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite, 3,9-bis (2,4-dicumylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5,5] undecane, phenyl-neopentylene glycol phosphite, etc., and 2,2-methylenebis (4,6-di-tert-butyl as a compound of L = 2, M = 1 and N = 0 Phenyl) octyl phosphite and the like. Furthermore, the compound described in the following formula 8 is preferable from the viewpoint of thermal stability and color tone improvement.

R ₁ and R ₂ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxy group, and two or more of them are present with respect to the benzene ring. It may be a different group. The hydrocarbon group in this case may contain an alicyclic structure such as cyclohexyl, an aliphatic branched structure, and an aromatic ring structure such as phenyl or naphthyl. Specific examples of the compound include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite represented by the following formula 9 and bis (2 , 4-di-tert-butylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite represented by Formula 11 is preferred. These compounds of formulas 9 to 11 are “Adekastab” (registered trademark) PEP-36, “Adekastab” (registered trademark) PEP-24G, and “Adekastab” (registered trademark) HP-10, respectively. Formula 10 is available from Ciba Specialty Chemicals as “IRGAFOS” ® 126. These compounds may be used alone or in combination.

  In the present invention, when a specific phosphorus compound is added, it is preferable that the phosphorus compound is dissolved or dispersed in a diol component such as ethylene glycol.

  In addition, the phosphorus compound contained in the polyester of this invention may add phosphorus compounds other than Chemical formula 6 from a viewpoint of heat stability and a color tone improvement. Examples of such phosphorus compounds include one or two of phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid, phosphinic acid, and phosphine compounds. It is preferable. Specifically, for example, phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate and the like phosphoric acid series, phosphorous acid, trimethyl phosphite, triethyl phosphite, triphenyl phosphite and the like. Phosphate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthryl Phosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5-dicarboxy Phenylphosphonic acid, 2,6-dicarboxyl Nylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2,3,5-tricarboxyphenylphosphonic acid, 2,3 , 6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, methylphosphonic acid diethyl ester, ethylphosphonic acid dimethyl ester, ethyl Phosphonic acid diethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, benzylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester, benzylphosphonic acid diester Phenyl ester, lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), sodium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), magnesium bis (3 Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate), diethylphosphonoacetic acid, methyl diethylphosphonoacetate, Phosphonic acid compounds such as ethyl diethylphosphonoacetate, hypophosphorous acid, sodium hypophosphite, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid Xylylphosphinic acid, Biphenylylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditolylphosphinic acid, dixylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, Anthrylphosphinic acid, 2-carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphinic acid, 2,4-dicarboxyphenylphosphinic acid, 2,5- Dicarboxyphenylphosphinic acid, 2,6-dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid, 3,5-dicarboxyphenylphosphinic acid, 2,3,4-trica Boxyphenylphosphinic acid, 2,3,5-tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid, 2,4,6-tricarboxy Phenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2,3-dicarboxylphenyl) phosphinic acid, bis ( 2,4-dicarboxyphenyl) phosphinic acid, bis (2,5-dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, Bis (3,5-dicarboxyphenyl) phosphinic acid, bis (2,3 4-tricarboxyphenyl) phosphinic acid, bis (2,3,5-tricarboxyphenyl) phosphinic acid, bis (2,3,6-tricarboxyphenyl) phosphinic acid, bis (2,4,5-tricarboxyphenyl) ) Phosphinic acid and bis (2,4,6-tricarboxyphenyl) phosphinic acid, methylphosphinic acid methyl ester, dimethylphosphinic acid methyl ester, methylphosphinic acid ethyl ester, dimethylphosphinic acid ethyl ester, ethylphosphinic acid methyl ester, Diethylphosphinic acid methyl ester, ethylphosphinic acid ethyl ester, diethylphosphinic acid ethyl ester, phenylphosphinic acid methyl ester, phenylphosphinic acid ethyl ester, phenylphosphinic acid phenyl ester, diphenyl Nylphosphinic acid methyl ester, diphenylphosphinic acid ethyl ester, diphenylphosphinic acid phenyl ester, benzylphosphinic acid methyl ester, benzylphosphinic acid ethyl ester, benzylphosphinic acid phenyl ester, bisbenzylphosphinic acid methyl ester, bisbenzylphosphinic acid ethyl ester, Phosphinic acids such as bisbenzylphosphinic acid phenyl ester, trimethylphosphine oxide, triethylphosphine oxide, tripropylphosphine oxide, triisopropylphosphine oxide, tributylphosphine oxide, phosphine oxides such as triphenylphosphine oxide, methylphosphonous acid, ethyl Phosphonous acid, propylphosphonous acid, isopropyl phosphite Phosphonic acid series such as phonic acid, butylphosphonous acid, phenylphosphonous acid, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, dimethyl Phosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid and other phosphinic acid systems, methylphosphine, dimethylphosphine, trimethylphosphine, methylphosphine, diethylphosphine, Examples include phosphines such as triethylphosphine, phenylphosphine, diphenylphosphine, and triphenylphosphine, and these phosphorus compounds may be used alone or in combination.

  In the present invention, specific solvents for the polyester polymerization catalyst include water, methanol, ethanol, ethylene glycol, propanediol, butanediol, benzene, and xylene, and any one or two of these may be used. preferable. Further, from the viewpoint of thermal stability and color tone, an acidic compound such as hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, 2- (N- Good buffer such as (morpholino) ethanesulfonic acid (pH = 5.6 to 6.8), N- (2-acetamido) iminodiacetic acid (pH = 5.6 to 7.5) or the above phosphorus compound is used. May be.

  In the present invention, a method for synthesizing a polyester polymerization catalyst is as follows: (1) A titanium compound is mixed in a solvent, and a part or all of the titanium compound is dissolved in the solvent. Dripping. (2) When using a ligand of a titanium compound such as the hydroxycarboxylic acid compound or the polyvalent carboxylic acid compound, the titanium compound or the ligand compound is mixed in a solvent and a part or all of the mixture is in the solvent. In this mixed solution, the ligand compound or titanium compound is dissolved and diluted in a stock solution or solvent and added dropwise. In addition, it is preferable from the viewpoint of thermal stability and color tone improvement that a phosphorus compound is further dissolved and diluted in a stock solution or a solvent and added dropwise to the mixed solution. Said reaction conditions are performed by heating at the temperature of 0-200 degreeC for 1 minute or more, Preferably it is 2-100 minutes at the temperature of 20-100 degreeC. The reaction pressure at this time is not particularly limited, and may be normal pressure. The mixed solvent is charged into a reaction apparatus equipped with a thermometer and a stirring blade, and is stirred and mixed at a temperature of 0 to 200 ° C. for 1 minute or longer, preferably at a temperature of 10 to 100 ° C. for 2 to 60 minutes.

  In the present invention, the polyester polymerization catalyst may be added to the polyester reaction system as it is, but the compound is mixed in advance with a solvent containing a diol component that forms a polyester such as ethylene glycol or propylene glycol, to obtain a solution. Alternatively, it is preferable to prepare a slurry and, if necessary, remove low-boiling components such as alcohol used at the time of synthesizing the compound and then add it to the reaction system, since foreign matter generation in the polymer is further suppressed. As the esterification reaction catalyst and the transesterification reaction catalyst, there are a method of adding a catalyst immediately after the addition of the raw material and a method of adding the catalyst together with the raw material. In addition, when added as a polycondensation reaction catalyst, it may be substantially before the start of the polycondensation reaction, before the esterification reaction or transesterification reaction, or after the completion of the reaction, before the polycondensation reaction catalyst is started. You may add to. Further, a phosphorus compound may be additionally added from the viewpoint of improving thermal stability and color tone. In this case, in order to suppress the deactivation of the catalyst due to the contact between the polyester polymerization catalyst of the present invention containing the titanium compound and the phosphorus compound, a method of additional addition to different reaction vessels or the same reaction vessel There are a method in which the addition interval between the polyester polymerization catalyst of the invention and the phosphorus compound is set to 1 to 15 minutes and a method in which the addition position is separated.

  Further, when the molar ratio of Ti / P is 0.1 to 20 as phosphorus atoms with respect to the titanium atoms of the titanium compound, the thermal stability and color tone of the polyester are favorable, which is preferable. More preferably, it is Ti / P = 0.2-10, More preferably, Ti / P = 0.3-5.

  The cationic dyeable polyester ultrafine fiber of the present invention contains 1 to 400 ppm of manganese compound in terms of manganese atom relative to polyester, and the ratio of manganese compound to phosphorus compound is Mn / P = 0.1 as the molar ratio of manganese atom to phosphorus atom. It is preferable that it is -200 since light resistance becomes favorable. The manganese compound used in this case is not particularly limited. Specifically, for example, manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, manganese acetate tetrahydrate, manganese acetate dihydrate Etc.

  Moreover, in the cationic dyeable polyester extra fine fiber of this invention, when a cobalt compound is further contained in 1-400 ppm in conversion of the cobalt atom with respect to polyester, a color tone becomes favorable and it is preferable. The cobalt compound used in this case is not particularly limited, and specific examples include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate.

  In addition, it is preferable that the cationic dyeable polyester ultrafine fiber of the present invention further contains a blue color adjusting agent and / or a red color adjusting agent as a color tone adjusting agent because the color tone is good.

  As the color tone adjusting agent used in the present invention, a dye used for a resin or the like can be used. Specifically, in COLOR INDEX GENERIC NAME, blue color tone such as SOLVENT BLUE 104, SOLVENT BLUE 122, SOLVENT BLUE 45, etc. Adjusting agents, SOLVENT RED 111, SOLVENT RED 179, SOLVENT RED 195, SOLVENT RED 135, PIGMENT RED 263, VAT RED 41, etc. And a purple color tone adjusting agent. Among them, SOLVENT BLUE 104, SOLVENT BLUE 45, SOLVENT RED 179, SOLVENT RED 195, SOLVENT RED 135, which do not contain halogen that is likely to cause corrosion of equipment, have relatively good heat resistance at high temperatures and excellent color developability, SOLVENT VIOLET 49 is preferably used.

  Further, one or more of these color tone adjusting agents can be used depending on the purpose. In particular, it is preferable to use one or more blue-type adjusting agents and red-type adjusting agents, since the color tone can be finely controlled. Furthermore, in this case, the color tone of the polyester obtained is particularly preferable when the ratio of the blue-based adjusting agent is 50% by weight or more with respect to the total amount of the color adjusting agent to be contained.

  Finally, the content of the color tone adjusting agent with respect to the polyester is preferably 30 ppm or less in total.

  In order to balance the polymer color tone, it is preferable that the contents of cobalt and the color tone adjusting agent satisfy the formula (1).

2 ≦ CL + CO / 10 ≦ 15 (1)
[However, CL in the formula represents the content (ppm) of the color adjusting agent with respect to the polyester, and CO represents the content (ppm) of the cobalt compound in terms of cobalt atom with respect to the polyester. ]
The value of the formula (1) is more preferably 4 to 10 from the viewpoint of color tone.

  Moreover, you may contain an alkali metal compound, an alkaline-earth metal compound, an aluminum compound, a zinc compound, a tin compound etc. in order to improve the thermal stability and color tone of the polymer obtained.

  It is important that the cationic dyeable polyester ultrafine fiber of the present invention contains 1-2% by weight of titanium oxide particles. By containing 1% by weight or more of titanium oxide particles, anti-penetration properties and UV cut properties are exhibited. On the other hand, when the content of titanium oxide particles exceeds 2% by weight, the occurrence of secondary agglomeration and the generation of foreign particles are promoted, leading to an increase in filtration pressure, process failure, and deterioration in quality. In addition, since the titanium oxide particles inhibit color development, it is important that the content is 2% by weight or less. The amount is preferably 1.3 to 1.7% by weight, and particularly preferably 1.4 to 1.6% by weight in order to develop a novel texture with a milky feeling. Further, the titanium oxide particles used in the present invention have an average secondary particle size of 1.0 μm or less, and an integral ratio of particles of 2.0 μm or more in the particle size frequency distribution is 5% or less in the spinning process. From the viewpoint of reducing the wear of each guide and the like, anatase-type titanium oxide particles are particularly preferable in terms of color tone.

  In addition to particles such as silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin and carbon black, additives such as anti-coloring agents, stabilizers and antioxidants may be contained.

  Examples of the polyester component of the present invention include, but are not limited to, polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. Polyester mainly composed of polyethylene terephthalate, which is the most versatile as a synthetic fiber for clothing, is preferable.

  The intrinsic viscosity IV of the cationic dyeable polyester ultrafine fiber of the present invention is preferably 0.6 to 1. When the intrinsic viscosity is 0.6 or more, the fiber strength and elongation becomes high, so that it is possible to reduce the fineness of single yarn for the purpose of improving clothes comfort. Further, it is preferable that the intrinsic viscosity is 1 or less because the spinnability is improved.

  The cationic dyeable polyester ultrafine fiber of the present invention has a single yarn fineness of 1.1 dtex or less in order to obtain a soft and good texture when it is made into a woven or knitted fabric. Further, in order to obtain a unique soft feeling, 0.7 dtex or less is preferable.

  In addition, the total fineness of the cationic dyeable polyester ultrafine fiber in the present invention is preferably 20 dtex or more from the viewpoint of high-processability and fabric practicality, and cooling spots in the spinning process accompanying an increase in the number of filaments. Is preferably 200 dtex or less.

  The strength of the cationic dyeable polyester ultrafine fiber of the present invention is preferably 3 to 5 cN / dtex. Since the cationic dyeable polyester ultrafine fiber of the present invention is developed mainly for sports applications, it is desirable to be able to withstand impacts such as scratches and severe stretching movements.

  It is important that the residual elongation of the cationic dyeable polyester microfiber of the present invention is 36 to 50%. When the residual elongation is 36% or more, the variation in the breaking elongation of the elastic yarn when knitted with the elastic yarn is absorbed, and the shape variation of the fabric is suppressed, so that the quality is improved. On the other hand, when the residual elongation exceeds 50%, the dyeing spots and the physical properties of the yarn are changed over time due to the decrease in oriented crystallinity. A more preferable range of residual elongation is 36 to 45%. Furthermore, it is more preferable that the difference in elongation when the fiber is loaded with 50 cN is 0.8% or less. A method for measuring the difference in elongation will be described later.

  The shrinkage characteristics of the cationic dyeable polyester ultrafine fiber of the present invention are preferably a boiling water shrinkage of 6 to 10% and a dry heat shrinkage of 8 to 14% from the viewpoint of fabric form and dimensional stability. The boiling water shrinkage and the dry heat shrinkage in the present invention are mainly controlled by the crystal orientation, and are particularly set by the draw ratio and the heat setting temperature. For example, the draw ratio is set so that the residual elongation of the yarn after drawing is 36 to 50%, and the heat set temperature is set in the range of 115 to 155 ° C., thereby achieving the above boiling water shrinkage rate. can do.

  The content of the dimer of the diol component in the cationic dyeable polyester ultrafine fiber of the present invention, that is, the raw material glycol component of the polyester, is preferably 1.5 to 1.8% by weight. When the content of the diol component is 1.5% by weight or more, the dyeing property of the dye is improved, but when the content is too large, dyeing spots and dyeing differences are generated, and therefore, 1.8% by weight or less is preferable. .

  The amount of carboxyl end groups of the cationic dyeable polyester ultrafine fiber of the present invention is preferably 30 to 55 equivalent / ton. Since heat resistance falls when the carboxyl end group amount increases, it is preferably 30 to 45 equivalent / ton, more preferably 30 to 40 equivalent / ton.

  In addition, although it does not specifically limit as a means to change content of a diol component and the amount of carboxyl terminal groups, it adjusted suitably by changing polymerization catalysts, such as superposition | polymerization temperature, the raw material preparation amount of superposition | polymerization, and an alkali metal. In particular, lithium acetate is preferably used as a means for changing the content of the diol component, and the addition amount is preferably 50 to 150 ppm.

  It is important that the color tone L value of the cationic dyeable polyester extra fine fiber of the present invention is 90-95. This color tone L value can be appropriately changed depending on the polymer composition, polymerization conditions, polymerization catalyst, contained particle type and compound, but imparting anti-penetration property and UV-cutting property when the color tone L value is 90 to 95. At the same time, it is possible to achieve color development with a new milky feeling for the first time. Moreover, it is preferable that the color tone b value of the cation dyeable polyester hollow fiber of this invention is 0-8, the breadth of dye selection spreads at the time of dyeing | staining a fabric, and versatility becomes high. When the color tone b value is 0 to 8, the process passability of the dyeing process is stabilized and the quality is improved. Further preferable color tone b value is 0-5.

  The FYL of the cationic dyeable hollow fiber of the present invention is preferably 0.8 or less. FYL measures the dyeing difference variation in the fiber longitudinal direction.

  As an example of means for optimizing FYL, stretching temperature can be mentioned. Particularly, in a polyester component not containing antimony of the present invention or having an atomic conversion content of 30 ppm or less, a polyester contrast using an antimony catalyst of 100 ppm or more- It is preferable to set the temperature at 2 ° C. By doing so, it is possible to suppress the variation in the stretching point. Specifically, although it depends on the stretching heat treatment time and the fineness configuration, the stretching temperature is preferably 85 to 89 ° C.

  The cationic dyeable polyester ultrafine fiber of the present invention may be subjected to false twisting or the like.

  The fabric obtained from the cationic dyeable polyester ultrafine fiber of the present invention can be suitably used for both woven fabrics and knitted fabrics, but the characteristics of the present invention are most manifested particularly when knitted through knitting.

  The cationic dyeable polyester ultrafine fiber of the present invention can be blended and blended with other types of fibers. A plurality of functionalities (water absorption, moisture absorption, cool feeling, warm feeling, etc.) can be imparted by blending or mixing with other types of fiber yarns. Examples of other types of fiber yarns include, but are not limited to, synthetic fibers such as polyester and polyamide, and natural fibers such as silk and cotton. Among them, the mixing ratio of the cationic dyeable polyester ultrafine fiber is preferably 30% by weight or more. More preferably, it is 50 to 100% by weight.

  The cationic dyeable polyester ultrafine fiber of the present invention can be used to give various functionalities to the fiber by exhausting the resin and the functional agent after forming the fabric.

  In general, in order to obtain practically good dyeability, the higher the dye exhaustion rate of the synthetic fiber, the better. However, the dye exhaustion rate of the cationic dyeable polyester ultrafine fiber of the present invention is 30% or more, more preferably It is 40% or more, particularly preferably 50% or more.

  In addition to the pigments such as carbon black, conventionally known antioxidants, anti-coloring agents, light-proofing agents, antistatic agents and the like may be added to the cationic dyeable polyester ultrafine fibers of the present invention.

  The oil used in the cationic dyeable polyester of the present invention is preferably a fatty acid ester or a polyether oil. In particular, the cationic dyeable polyester is preferably provided with an oil agent that is particularly prone to have static electricity and that can be expected to improve smoothness and prevent fluff. Moreover, you may use together fatty acid ester and a polyether-type oil agent as needed.

  The manufacturing method of the raw material resin of the cationic dyeable polyester extra fine fiber of this invention is demonstrated. Although the example of a polyethylene terephthalate is described as a specific example, it is not limited to this.

Polyethylene terephthalate is usually produced by one of the following processes.
(1) A process in which terephthalic acid and ethylene glycol are used as raw materials, a low polymer is obtained by direct esterification reaction, and a high molecular weight polymer is obtained by subsequent polycondensation reaction, and (2) dimethyl terephthalate and ethylene glycol are used as raw materials. In this process, a low polymer is obtained by a transesterification reaction, and a high molecular weight polymer is obtained by a subsequent polycondensation reaction. Among these, direct esterification reaction by transesterification of terephthalic acid and ethylene glycol is preferable in terms of cost. Here, the esterification reaction proceeds even without a catalyst, but the aforementioned titanium compound may be added as a catalyst. In the transesterification reaction, a catalyst such as manganese, calcium, magnesium, zinc, lithium or the above titanium compound is used as a catalyst, and the catalyst used in the reaction after the transesterification reaction is substantially completed. In order to inactivate, a phosphorus compound is added.

  The method for producing a resin of the present invention described above is a method in which the low polymer obtained in the first half of the series of optional reactions of (1) or (2), preferably (1) or (2) is matted. Add additives such as titanium oxide particles, cobalt compounds and manganese compounds as agents, add 5-sodium sulfoisophthalic acid metal salt and polyethylene glycol as copolymer components, then add the above-mentioned titanium compounds as polycondensation catalysts A polycondensation reaction to obtain a high molecular weight polyethylene terephthalate.

  Further, the above reaction can be applied to a batch, semi-batch, or continuous system.

  The color tone adjusting agent is preferably added to the polyester at any time after completion of the esterification reaction or transesterification reaction until the polycondensation reaction is completed. In particular, it is preferably added after completion of the esterification reaction or transesterification reaction and before the start of the polycondensation reaction, because the dispersion in the polyester is good.

  It is also possible to add the color tone adjusting agent to the polyester after the polycondensation reaction is substantially completed. In this case, a method of directly melting and kneading the color tone adjusting agent on the chip using a single screw or twin screw extruder, or preparing a polyester containing the color tone adjusting agent at a high concentration separately in advance, You may blend with the chip which does not contain.

  The cationic dyeable polyester ultrafine fiber of the present invention is obtained by melt spinning the polyester of the present invention from a spinneret, applying an oil agent to obtain an unstretched yarn, and winding it once or by subsequent stretching. It is done.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.
(1) Content of catalyst-derived titanium element, phosphorus element, antimony element, and cobalt element in polyester It was determined with a fluorescent X-ray elemental analyzer (manufactured by Horiba, Ltd., MESA-500W type). X-ray fluorescence analysis was performed after the following pretreatment. That is, polyester is dissolved in orthochlorophenol (5 g of polymer per 100 g of solvent), and after adding the same amount of dichloromethane as this polymer solution to adjust the viscosity of the solution, a centrifuge (rotation speed 18000 rpm, 1 hour) To settle the particles. Thereafter, only the supernatant liquid is collected by the gradient method, and the polymer is reprecipitated by adding the same amount of acetone as the supernatant liquid, and then filtered through a 3G3 glass filter (manufactured by IWAKI). After washing with acetone, the acetone was removed by vacuum drying at room temperature for 12 hours. The polymer obtained by the above pretreatment was analyzed for titanium element, phosphorus element, antimony element, and cobalt element.
(2) Intrinsic viscosity IV of fiber
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
(3) Fineness and single yarn fineness The total fineness of the multifilament was calculated from the weight of 100 m of polyester cation dyeable ultrafine fiber and calculated from the weight using the following equation. The single yarn fineness was calculated by dividing the total fineness by the number of filaments.

Fineness (dtex) = (100 m long weight) × 100
Single yarn fineness (dtex) = (fineness) / (number of filaments)
(4) Strength, residual elongation, and elongation difference at 50 cN load Using a Tensilon tensile tester manufactured by Toyo Baldwin Co., Ltd., measuring conditions were a sample length of 20 cm and a tensile speed of 40 cm / min, and the number of measurements was 25 times. The average value was evaluated. Further, the difference in elongation at the time of 50 cN weighting was read from the strong elongation curve of the number of measurements 25 times, and obtained from the maximum elongation-minimum elongation.
(5) FYL
Using FYL-500SR manufactured by Toray Engineering Co., Ltd., measurement was performed at a yarn speed of 60 m / min, a measurement time of 5 minutes, and a dyeing temperature of 90 ° C., and the standard deviation values of 10 samples were averaged and evaluated.
(6) Boiling water shrinkage rate Wet heat treatment was performed in a bath at 99 ° C. for 15 minutes, and the yarn length before and after that was evaluated by an average value of two measurements.
(7) Dry heat shrinkage rate Dry heat treatment was performed in an oven at 150 ° C. for 15 minutes, and the yarn length before and after the heat treatment was evaluated by an average value of two measurements.
(8) Color tone The fiber was wound on a metal plate and measured twice with a Hunter value (L, a, b value) using an SM color computer model SM-3 (manufactured by Suga Test Instruments Co., Ltd.). Obtained from the value.
(9) Spinnability Continuous spinning was performed for 168 hours (7 days), and the spinnability was determined according to the following determination method.
◯: Thread breakage rate is less than 3.0% ○: Thread breakage rate is 3.0% or more and less than 5.0% △: Thread breakage rate is 5.0% or more and less than 7.0% ×: Thread breakage rate is 7.0% or more-: Evaluation not possible (10) Color developability A three-step determination method by five experts for comparison evaluation with a standard sample treated in the same manner as a sample obtained by winding a fiber on a metal plate and dyeing with a red dye. It was evaluated with.
○ ○: Excellent ○: Good ×: Equivalent (11) Permeability The transmittance of 5 knitted samples of 5 cm × 5 cm was measured using SM color computer model SM-3 (manufactured by Suga Test Instruments Co., Ltd.) The average value was evaluated (n = 5).
○○: Transmittance less than 10% ○: Transmittance 10-20%
×: Transmittance 20% or more (12) Texture (soft feeling)
The overall evaluation was evaluated by a three-step evaluation method with five skilled workers.
○ ○: Excellent ○: Good ×: Impossible (13) Quality Texture (pearly tone, silky feeling, etc.), surface quality uniformity, and overall evaluation of stained spots were evaluated by five experts using a four-step evaluation method. .
○○: Excellent ○: Good Δ: Acceptable ×: Impossible “Phosphorus compound 1” described in Tables 1 to 12 is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di- Phosphite (Asahi Denka Co., Adeka Stub PEP-36)
“B1” is a blue color tone adjusting agent, SOLVENT BLUE 104 (manufactured by Clariant, Polysynthren Blue RBL)
“Phosphorus compound 2” described in Table 4 is phenyl phosphite (manufactured by Aldrich).
“Phosphorus compound 3” means tris (monononylphenyl) phosphite (manufactured by Aldrich)
“Phosphorus compound 4” is bis (2,4-di-tert-butylphenyl) pentaerythritol di-phosphite (Asahi Denka Co., Adeka Stub PEP24G).
“R1” described in Table 5 is a red color adjuster SOLVENT RED 135 (manufactured by Clariant, Polysynthren Red GFP).
In addition, the synthesis | combining method of catalyst AC is described below.

Catalyst A. Synthesis Method of Lactic Acid Chelate Titanium Compound (Phosphate Mixture) Titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer from a dropping funnel to ethylene Glycol (218 g, 3.51 mol) was added. The rate of addition was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and an 85 wt / wt% aqueous solution of ammonium lactate (252 g, 2.00 mol) was added to the reaction flask to give a clear pale yellow product (Ti content 6.54 wt. %). A 85 wt / wt% aqueous solution of phosphoric acid (114 g, 1.00 mol) was added to this mixed solution to obtain a titanium compound containing a phosphorus compound (P content 4.23 wt%).

Catalyst B. Method of synthesizing citric acid chelate titanium compound (phosphoric acid mixture) Citric acid monohydrate (532 g, 2.52 mol) was added to hot water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Dissolved. To this stirred solution was slowly added titanium tetraisopropoxide (288 g, 1.00 mol) from the addition funnel. The mixture was heated to reflux for 1 hour to produce a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to a temperature below 70 ° C., and a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) was slowly added via a dropping funnel to the stirred solution. The resulting product was filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove isopropanol / water and a slightly cloudy light yellow product (Ti content 3 .85% by weight). A 85 wt / wt% aqueous solution of phosphoric acid (114 g, 1.00 mol) was added to this mixed solution to obtain a titanium compound containing a phosphorus compound (P content: 2.49 wt%).

Catalyst C. Synthesis method of lactate chelate titanium compound (phenylphosphonic acid, phosphoric acid mixed) To titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer Ethylene glycol (218 g, 3.51 mol) was added from the dropping funnel. The rate of addition was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and an 85 wt / wt% aqueous solution of ammonium lactate (252 g, 2.00 mol) was added to the reaction flask to give a clear pale yellow product (Ti content 6.54 wt. %). To this mixed solution, phenylphosphonic acid (158 g, 1.00 mol) and an aqueous 85 wt / wt% phosphoric acid solution (39.9 g, 0.35 mol) were added to obtain a titanium compound containing a phosphorus compound. Obtained (P content 5.71% by weight).

Example 1
A slurry of 82.5 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 35.4 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) was previously charged with about 100 kg of bis (hydroxyethyl) terephthalate, and the temperature was 250 ° C. The esterification reaction vessel maintained at a pressure of 1.2 × 10 ⁵ Pa was sequentially supplied over 4 hours, and after the completion of the supply, the esterification reaction was further performed over 1 hour. 5 kg was transferred to a polycondensation tank.

  Subsequently, 5 g of silicon (manufactured by Toshiba Silicone Co., TSF433) was added to the polycondensation reaction tank into which the esterification reaction product was transferred. After stirring for 5 minutes, 11.5 g of cobalt acetate (30 ppm in terms of cobalt atom relative to the polymer), 15 g of manganese acetate (33 ppm in terms of manganese atom relative to the polymer), pentaerythritol-tetrakis (3- (3,5- Di-t-butyl-4-hydroxyphenol) propionate) (Ciba Geigy, Irganox 1010) 75 g, Lithium acetate 45 g, Blue color tone adjuster SOLVENT BLUE 104 (Clariant, Polysynthren Blue RBL) 0.4 g of ethylene An ethylene glycol solution (catalyst A) consisting of a lactic acid chelate titanium compound equivalent to 10 ppm in terms of titanium atom and a phosphoric acid equivalent to 6 ppm in terms of phosphorus atom with respect to the glycol solution and the polymer, 70 ppm (phosphorus atom with respect to the polymer) A mixture of ethylene glycol slurry of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite (Asahi Denka Co., Adeka Stub PEP-36) equivalent to 7 ppm in total was added. . After further stirring for 5 minutes, 1 kg of polyethylene glycol having a weight average molecular weight of 4000 (manufactured by Sanyo Chemical Industries, Ltd.) was added. After further stirring for 5 minutes, ethylene glycol solution of 5-sodium sulfoisophthalic acid hydroxyethyl ester (manufactured by Takemoto Yushi Co., Ltd., ES-740) was added so that the sulfur content relative to the polymer was 0.3%. . After further stirring for 5 minutes, ethylene glycol slurry of titanium oxide particles was added to the polymer so that the amount was 1.5% by weight in terms of titanium oxide particles, and then the reaction was conducted while stirring the low polymer at 30 rpm. The system was gradually heated from 250 ° C. to 290 ° C., and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, discharged into cold water in a strand form, and immediately cut to obtain polymer pellets. The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours.

  The polymer obtained had an IV of 0.7, a color tone of L = 72, a = −2.5, b = 4.5, and a solution haze of 0.7%. Also, it was confirmed that the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 13 ppm, Ti / P = 0.50, and the content of antimony atoms was 0 ppm. did.

  Further, after drying this polyester, it is subjected to a spinning machine, and a molten polymer with a discharge rate of 17 g / min is discharged from a nozzle nozzle having 72 discharge holes under the condition of a spinning temperature of 290 ° C. and spun at a spinning speed of 1800 m / min. The oil agent was applied at 1% by weight with respect to the fiber weight to obtain an undrawn yarn having 94 dtex-72 filaments and a residual elongation of 300%. The obtained undrawn yarn was drawn and heat set at a drawing temperature of 90 ° C., a heat setting temperature of 140 ° C. and a magnification of 2.1 times to obtain a drawn yarn of 44 dtex-72 filaments. A 28-gauge half tricot was knitted using the obtained drawn yarn at the front and 44 dtex polyurethane elastic yarn at the back at a 15% mixing ratio. Next, after relaxing setting at 90 ° C. × 30 seconds, heat setting was performed at 190 ° C. × 40 seconds. Subsequently, malachite green (manufactured by Kanto Chemical Co., Inc.) 5% owf, acetic acid 0.5 g / L, bath ratio 1: 100, dyed at 125 ° C. for 30 minutes, and heat set at 160 ° C. for 40 seconds. It was. The obtained knitted fabric had both excellent anti-peeling property and color developability, an excellent soft feeling and a texture, and a pearly milky feeling.

Examples 2-6, Comparative Examples 1-2
In Example 2, a knitted fabric was obtained in the same manner as in Example 1 except that lithium 5-sulfoisophthalate was used as the metal salt of 5-sulfoisophthalic acid. The obtained knitted fabric was excellent in quality and quality.

  In Examples 3 to 6 and Comparative Examples 1 and 2, experiments were conducted in the same manner as in Example 1 except that the amount of 5-sulfoisophthalic acid metal salt was changed.

  Examples 3 to 6 were excellent in soft feeling, texture, and process stability, and those having both color developability and anti-peeling property were obtained.

  Comparative Example 1 was an experiment in which the copolymerization amount of the metal salt of 5-sulfoisophthalic acid was 0.05 mol%, but the color developability was inferior because the copolymerization amount was small.

  Comparative Example 2 was an experiment in which the copolymerization amount of the metal salt of 5-sulfoisophthalic acid was 7 mol%. However, since the copolymerization amount was too high, the increase in the filtration pressure was large and yarn breakage was sporadic. Further, the obtained knitted fabric was conspicuous and had poor quality. The evaluation results are shown in Table 1.

Examples 7-14, Comparative Examples 3-6
An experiment was conducted in the same manner as in Example 1 except that the weight average molecular weight and the copolymerization amount of polyethylene glycol were changed.

  In Examples 7 to 14, there were few yarn breaks, excellent anti-peeling properties and coloring properties, and a soft feeling, a texture and a novel milky feeling were obtained.

  Comparative Examples 3 to 4 are experiments using polyethylene glycol having a weight average molecular weight of 100, 7000. Although satisfying color development, sheerness, and soft feeling, they were fuzzy and had a poor texture.

  Comparative Example 5 was an experiment in which the copolymerization amount of polyethylene glycol was 6% by weight, but the yarn forming property was moderately stable, but fluff was generated during warping and knitting because the copolymerization amount was too high.

  Comparative Example 6 was an experiment in which polyethylene glycol was not added, but some thread breakage was observed and the color development was inferior. The evaluation results are shown in Table 2.

Examples 15-19, Comparative Examples 7-8
Implemented except changing the type and content of catalyst titanium compound (catalyst B), content of antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.), content of phosphoric acid, content of color modifier A knitted fabric was obtained in the same manner as in Example 1.

  Examples 15 to 19 were all excellent in color developability and transparency, and both soft feeling and quality were good.

  Comparative Example 7 was an experiment in which 50 ppm of antimony trioxide was added, but the increase in the filtration pressure was large and yarn breakage was sporadic. Moreover, the obtained knitted fabric was fuzzy and had poor quality.

  Comparative Example 8 was an experiment in which 334 ppm of antimony trioxide and 26 ppm of phosphoric acid were added. However, since the amount of extraneous polymer increased, the filtration pressure increased and the thread breakage was remarkable, and the process stability was inferior. The evaluation results are shown in Table 3.

Examples 20-23
The point of using the catalyst C which consists of a lactic acid chelate compound, phenylphosphonic acid, and phosphoric acid for a catalyst, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite (phosphorus compound 1) Instead, phenyl phosphite (phosphorus compound 2), tris (monononylphenyl) phosphite (phosphorus compound 3), bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite (phosphorus compound 4) A knitted fabric was obtained in the same manner as in Example 1 except that was used. The obtained knitted fabric was excellent in quality and quality as in Example 1, and the yarn-making property was stable. The evaluation results are shown in Table 4.

Examples 24-31
Experiments were performed in the same manner as in Example 1 except that the types and contents of the cobalt compound and the color tone adjusting agent were changed. The resulting woven fabric was a high-quality knitted fabric having both softness and color development, soft and good texture. The evaluation results are shown in Table 5.

Examples 32-37, Comparative Examples 9-10
The experiment was performed in the same manner as in Example 1 except that the content of the titanium oxide particles was changed.

  In Examples 32-37, both the anti-penetration property and the color developability were achieved, and the content of titanium oxide particles of 1.4-1.6 was particularly excellent.

  Comparative Example 9 was an experiment in which the content of titanium oxide particles was 0.8% by weight, but was inferior in the anti-penetration property.

  Comparative Example 10 was an experiment in which the content of titanium oxide particles was 2.2% by weight, but coarse polymer foreign matter was formed, the filtration pressure increased greatly, and yarn breakage occurred frequently. Further, the obtained knitted fabric had low color developability. The evaluation results are shown in Table 6.

Examples 38-48
The polymerization temperature of the polymer was changed, and the intrinsic viscosity, the amount of carboxyl end groups, and the type and content of the diol component were changed. All experiments were excellent in process stability and were high quality and high quality knitted fabrics. Table 7 shows the evaluation results.

Examples 49-50, Comparative Example 11
A knitted fabric was obtained in the same manner as in Example 1 except that the single yarn fineness was changed.

  In Examples 49 to 50, both quality and quality were good, but in Comparative Example 11 in which the single yarn fineness was 1.3 dtex, a fabric having a strong fabric tension was not obtained.

Examples 51-54
A knitted fabric was obtained in the same manner as in Example 1 except that the total fineness of the multifilament was changed to 20, 56, 100, and 200 dtex. In all experiments, high-grade knitted fabrics with good high-order passability were obtained.
The evaluation results are shown in Table 8.

Examples 55-59, Comparative Examples 12-13
A knitted fabric was obtained in the same manner as in Example 1 except that the stretching conditions were changed.

  Examples 55 to 57 and Comparative Examples 12 to 13 are experiments in which the draw ratio was changed and the residual elongation was changed. However, although Examples 55 to 57 were good in both quality and quality, the residual elongation was In Comparative Examples 12 to 13 with 34% and 52%, warp was generated in the knitted fabric, and the quality was poor.

  Examples 58 to 59 are experiments in which the stretching temperature was 89 ° C. and 91 ° C., both of which were good in quality and quality. Table 9 shows the evaluation results.

Examples 60-62
The experiment was performed in the same manner as in Example 1 except that the stretching heat setting temperature was changed.

  Examples 60 to 62 are experiments in which the stretching heat set temperature was changed to 155 ° C., 130 ° C., and 110 ° C., respectively, and the boiling water shrinkage rate and the dry heat shrinkage rate were changed. The quality was excellent. Table 10 shows the evaluation results.

Examples 63 to 66, Comparative Examples 14 to 15
An experiment was conducted in the same manner as in Example 1 except that the type and content of the color tone adjusting agent, the content of titanium oxide particles, and the spinning temperature were changed.

  Example 63 was excellent in yarn production and stable in quality. On the other hand, Comparative Example 14 was inferior in see-through property, did not have the pearly milky feeling of the present invention, and a characteristic knitted fabric could not be obtained. Further, Comparative Example 15 was a knitted fabric with low color developability and a dull color.

  Examples 64-66 were experiments in which the spinning temperatures were 285 ° C., 295 ° C., and 298 ° C., respectively, all having a soft and good texture, and good anti-peeling properties and coloring properties. The evaluation results are shown in Table 11.

Examples 67-68
The experiment was conducted in the same manner as in Example 1 except that the spinning speed was changed to 3000 m / min, the draw ratio was changed to 1.25 times, and the draw temperatures were changed to 88 ° C. and 90 ° C., respectively. And color developability, soft and good texture, and good quality. The evaluation results are shown in Table 12.

Claims (12)

  0.1 to 6 mol% of 5-sulfoisophthalic acid metal salt and 0.1 to 5% by weight of polyethylene glycol having a weight average molecular weight of 200 to 6000 are copolymerized to contain no antimony or have an atomic equivalent content of 30 ppm. Further, it is formed of polyester containing 1 to 2% by weight of titanium oxide particles, multi yarn having an average fineness of a single yarn of 1.1 dtex or less, a color tone L value of 90 to 95, and a residual elongation. A cationic dyeable polyester microfiber characterized by a degree of 36 to 50%.   The cationic dyeable polyester microfiber according to claim 1, wherein the polyester is polyethylene terephthalate.   The cationic dyeable polyester microfiber according to claim 1 or 2, wherein the polyester contains 1.5 to 1.8% by weight of a diol component.   The cationic dyeable polyester microfiber according to any one of claims 1 to 3, wherein the polyester contains a titanium compound and a phosphorus compound. The titanium compound substituent is a group selected from the group consisting of functional groups represented by the following formulas 1 to 5, and contains at least a carbonyl group, a carboxyl group or an ester group, and the formula 6 The cationic dyeable polyester microfiber according to claim 4, comprising at least one phosphorus compound.

(In Formula 1 to Formula 5, R _{1 to} R ₃ each independently have hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. Represents a hydrocarbon group having 1 to 30 carbon atoms.)

(In the above formula 6, R ₁ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxy group containing 1 to 50 carbon atoms. R ₂ and R ₃ are each independently selected. Represents a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxy group, L + M + N = 3, and L is an integer of 1 to 3, and M and N are It is an integer from 0 to 2.) In formulas 1 to 3 of the substituent of the titanium compound, at least one of R _{1 to} R ₃ is a hydrocarbon group having 1 to 30 carbon atoms having a carbonyl group, a carboxyl group, or an ester group. Item 6. The cationic dyeable polyester ultrafine fiber according to Item 5. R ₁ in Formula 4 of the substituent of the titanium compound is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, or an ester group. The cationic dyeable polyester microfiber according to claim 5.   The cationic dyeable polyester ultrafine fiber according to any one of claims 5 to 6, wherein the phosphorus compound represented by Formula 6 is a compound having a ring structure of 6 or more members containing a phosphorus atom. The cationic dyeable polyester microfiber according to claim 8, wherein the phosphorus compound is a compound represented by Formula 7.

(In the above formula 7, R ₁ and R ₂ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxy group.)   0.5 to 150 ppm of titanium compound in terms of titanium atom relative to polyester (excluding titanium atom content of titanium oxide particles), 0.1 to 400 ppm of phosphorus compound in terms of phosphorus atom relative to polyester, ratio of titanium compound to phosphorus compound The cationic dyeable polyester microfiber according to any one of claims 4 to 9, wherein Ti / P = 0.1 to 20 as a molar ratio of titanium atom to phosphorus atom.   The manganese compound is contained in an amount of 1 to 400 ppm in terms of manganese atom relative to the polyester, the cobalt compound is contained in an amount of 1 to 400 ppm in terms of cobalt atom, and the ratio of the manganese compound to the phosphorus compound is Mn / P = 0. The cationic dyeable polyester microfiber according to claim 10, which is 1 to 200.   A fabric in which the polyester microfiber according to any one of claims 1 to 11 is used at least in part.