JP4613639B2 - Polyester fiber and fabric - Google Patents

Description

  The present invention relates to a polyester fiber satisfying unprecedented pearly-like milky feeling, high color developability, excellent anti-peeling property and UV-cutting effect, and is knitted with elastic fibers such as processed yarn, crimped yarn and polyurethane. Thus, no fluff or warp is generated, and a high-quality stretch fabric can be obtained.

  Polyester is excellent in durability such as dimensional stability and chemical resistance, and is used for various purposes from the usefulness of its functionality. For example, it is suitably used for clothing, industrial use, materials use, medical use, etc. .

  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. However, in recent years, there has been a demand for not only high color developability but also composite function with anti-transparency, UV cut and the like. 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 become relatively large particles, which can be a foreign matter, resulting in increased filter filtration pressure during molding, thread breakage during spinning, or film breakage during film formation, etc. It has undesirable characteristics and 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.

Recently, as the main use of cationic dyeable fibers, sportswear such as swimwear, leotards, wet suits, and inner use such as shirts, shorts, lingerie, etc. are attracting attention. Stretch characteristics are required in addition to the see-through property and UV cut effect. 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, since the elastic yarn has a large variation in the residual elongation of the original yarn, it causes tension unevenness during knitting, and tends to deteriorate the quality of the warp and the like. When dyeable polyester fibers were used for the other, the quality was particularly deteriorated and could not be commercialized.
JP 34-10497 A (page 1) Japanese National Patent Publication No. 11-506484 (1 page) JP 61-239015 (1 page) Japanese Patent Laid-Open No. 11-93020 (1 page) JP 59-26521 A (1 page) JP 63-48353 (1 page) JP 63-120111 A (1 page)

  Accordingly, an object of the present invention is to solve the above-mentioned problems and to stably obtain a polyester fiber satisfying both a high color developability with an unprecedented pearl-like milky feeling, excellent anti-peeling property, and UV cut effect. The object of the present invention is to obtain a high quality without knitting, warp or the like, and knitting with elastic fibers.

The present invention achieves the above object, and comprises 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. copolymerized, it is 30ppm or less content of either atomic terms not containing antimony, consisting further of titanium oxide particles 1-2 wt%, poly ethylene terephthalate containing the diol component 1.5 to 1.8 wt% color L value of 90-95, a cationic dyeable poly ethylene terephthalate fibers, wherein the residual elongation is 36-50%.

  According to the present invention, a new textured polyester fiber having a mild and high color developability due to an unprecedented pearl-like milky feeling can be obtained by knitting with an elastic fiber or the like. Also, no fluff or vertical muscles are generated, and stable and high quality can be obtained.

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

Cationic dyeable polyester 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 Weight Average polyethylene glycol having a molecular weight of 200 to 6,000 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 Weight average for copolymerization amount of polyethylene glycol having a molecular weight of 200 to 6,000 is dyeing of cationic dyes is increased by 0.1 wt% or more, the improved color developability simultaneously 5-sulfoisophthalic acid Suppresses the thickening effect caused by metal salts. 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.

  The cationic dyeable polyester fiber of the present invention does not contain an antimony compound, or the content of the polyester in terms of antimony atoms 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.

  Although not particularly limited as a polymerization catalyst in place of antimony, a titanium compound is preferable, and at least a carbonyl group, a carboxyl group or an ester group selected from the group consisting of functional groups represented by the following formulas 1 to 5 The titanium compound which is at least 1 type to contain 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 of 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. All or some of the following reactions (1) to (3) Refers to a compound that substantially contributes to the promotion of the reaction.
(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) 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 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, dialkylarylphosphonites, and arylarylphosphonites. A phosphite is preferable from the viewpoint of stability and 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.

  When adding the specific phosphorus compound of this invention, it is preferable to make it the state which dissolved or disperse | distributed the phosphorus compound in diol components, such as said ethylene glycol.

  In addition, you may add phosphorus compound other than Chemical formula 6 from the viewpoint of thermal stability and a color tone improvement to the phosphorus contained in the polyester of this invention. 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. Phosphoric acid, 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.

  Specific solvents for the polyester polymerization catalyst of the present invention 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.

  The method for synthesizing a catalyst for polyester polymerization of the present invention is as follows. (1) A titanium compound is mixed with a solvent, and a part or all of the titanium compound is dissolved in the solvent. To do. (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.

  The polyester polymerization catalyst of the present invention may be added to the polyester reaction system as it is, but the compound is mixed with a solvent containing a diol component that forms a polyester such as ethylene glycol or propylene glycol in advance, If it is made into a slurry and, if necessary, low boiling components such as alcohol used at the time of synthesizing the compound are removed and then added to the reaction system, foreign matter formation in the polymer is further suppressed, which is preferable. 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 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. A light resistance of 200 is preferable because of good light resistance. 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 fiber of this invention, when a cobalt compound is further contained 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 fiber of the present invention further contains a blue-based adjusting agent and / or a red-based adjusting agent as a color tone adjusting agent, because the color tone is good.

  The color tone adjusting agent of the present invention is a dye used for a resin or the like. Specifically, in COLOR INDEX GENERIC NAME, blue color tone adjusting agents such as SOLVENT BLUE 104, SOLVENT BLUE 122, SOLVENT BLUE 45, SOLVENT RED 111, SOLVENT RED 179, SOLVENT RED 195, SOLVENT RED 135, PIGMENT RED 263, VAT RED 41, etc. Examples thereof include system color adjusting agents. Among them, SOLVENT BLUE 104, SOLVENT BLUE 45, SOLVENT RED 179, SOLVENT RED 195, SOLVENT RED 135, which do not contain halogen that tends to cause corrosion of equipment, have relatively good heat resistance at high temperatures and excellent color development, 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 of the present invention contains 1 to 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 the integral ratio of particles of 2.0 μm or more in the frequency distribution is 5% or less. From the viewpoint of reducing wear of guides 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.

The The polyester component of the present invention, of the most versatile clothing synthetic fibers, a polyester mainly composed of polyethylene terephthalate.

  The intrinsic viscosity of the cationic dyeable polyester fiber of the present invention is preferably 0.6-1. 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 strength of the cationic dyeable polyester fiber of the present invention is preferably 3 to 5 cN / dtex. Since the cationic dyeable polyester fiber of the present invention is developed mainly for sports applications, it is desirable that the cationic dyeable polyester fiber can withstand impacts such as rubbing and severe stretching motion.

  It is important that the residual elongation of the cationic dyeable polyester fiber 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.

  The shrinkage characteristics of the cationic dyeable polyester fiber of the present invention are preferably a boiling water shrinkage of 6 to 10% and a dry heat shrinkage of 8 to 14% in view of the form and dimensional stability of the fabric. 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 diol component in the cationic dyeable polyester fiber of the present invention is 1.5 to 1.8% by weight . If the content of the diol component is 1.5% by weight or more, the dyeing property of the dye is improved. However, if the content is too large, dyeing spots and dyeing differences are generated, so that the content is 1.8% by weight or less . . The diol component indicates a dimer and is measured using GC-14B (manufactured by Shimadzu Corporation).

  The amount of carboxyl end groups of the cationic dyeable polyester 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 fiber of the present invention is 90 to 95. The color tone can be appropriately changed depending on the polymer composition, the polymerization conditions, the polymerization catalyst, the contained particle type and the compound, and the color tone L value is from 90 to 95, thereby imparting anti-penetration properties and UV-cutting properties. 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 fiber of this invention is 0-8, the range 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.

  As the cross-sectional shape of the cationic dyeable polyester fiber of the present invention, it is also possible to impart functionality to the fiber by forming a cross-sectional shape such as a hollow, three-leaf, six-leaf, or the like.

  The FYL of the cationic dyeable 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.

  Further, the polymer used for the cationic dyeable polyester fiber of the present invention is not only used alone, but may be combined with other polymers. The composite ratio is preferably 3 to 95% by weight based on the total polymer amount. The lower limit of the composite ratio is for the purpose of developing the characteristics of the cationic dyeable polyester fiber of the present invention, and the upper limit of the composite ratio is for developing the characteristics of the composite fiber. Examples of these embodiments include laminated types such as core-sheath type, sea-island type, side-by-side type, and composite fibers such as blended fibers.

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

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

  The cationic dyeable polyester 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 fiber is preferably 30% by weight or more. More preferably, it is 50 to 100% by weight.

  The cationic dyeable polyester 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 exhaust rate of the synthetic fiber, the better. However, the dye exhaust rate of the cationic dyeable polyester fiber of the present invention is 30% or more, more preferably 40. % Or more, particularly preferably 50% or more.

  The cationic dyeable polyester fiber of the present invention may of course contain conventionally known antioxidants, anti-coloring agents, light-proofing agents, antistatic agents and the like in addition to pigments such as carbon black.

  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 cationic dyeable polyester resin 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 production method of the present invention is a matte agent for the low polymer obtained in the first stage of the series of optional reactions of (1) or (2), preferably in the series of reactions of (1) or (2). After adding additives such as titanium oxide particles, cobalt compound, manganese compound and the like, 5-sodium sulfoisophthalic acid metal salt and polyethylene glycol are added as copolymerization components, the above-mentioned titanium compound is added as a polycondensation catalyst and heavy. A condensation reaction is performed to obtain 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.

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 of yarn IV
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
(3) 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.
(4) 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.
(5) 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 the heat treatment was evaluated by an average value of two measurements.
(6) 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.
(7) 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.
(8) Spinnability Continuous spinning was performed for 168 hours (7 days), and the spinnability was determined according to the following determination method.
○: Yarn breakage rate less than 3.0% ○: Yarn breakage rate of 3.0% or more and less than 5.0% Δ: Yarn breakage rate of 5.0% or more and less than 7.0% ×: Yarn breakage rate 7.0% or more-: Evaluation not possible (9) Color developability Three-step judgment method by five skilled workers for comparative evaluation with a standard sample treated in the same manner as a sample dyed with a red dye on a metal plate. It was evaluated with.
○ ○: Excellent ○: Good ×: Equivalent (10) 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%
X: Transmittance 20% or more (11) Quality The 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 was added 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 supplied to a spinning machine, and a molten polymer is discharged from a nozzle nozzle (φ0.25 mm, 24 holes) at a spinning speed of 290 ° C. at a spinning speed of 1500 m / min. Spinning was performed, and an oil agent containing 40% by weight of a fatty acid ester and 9% by weight of a polyether was applied to the fiber by 1% by weight to obtain an undrawn yarn having 140 dtex-24 filaments and a residual elongation of 300%. The obtained undrawn yarn was drawn and heat-set at a drawing temperature of 87 ° C., a heat setting temperature of 145 ° C. and a magnification of 2.5 times to obtain a drawn yarn of 56 dtex-24 filament. 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 (Example 1) had both excellent anti-peeling property and color developability and had a pearly milky feeling.

Examples 4 and 6, Comparative Examples 1 and 2

Examples 4 and 6 and Comparative Examples 1 and 2 were tested in the same manner as in Example 1 except that the amount of 5-sulfoisophthalic acid metal salt was changed.

Examples 4 and 6 were excellent in process stability and obtained both a color development property and an anti-penetration property.

  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
Weight average molecular weight of polyethylene glycol, except that the copolymerization amount were respectively changed experimented in the same manner as in Example 1.

  In Examples 7 to 14, there were few yarn breaks, excellent anti-peeling properties and color developability, and a novel milky feeling was obtained.

Although Comparative Examples 3-4 are experiments Weight average molecular weight of the polyethylene glycol was used of 100,7000, although satisfying the coloring property and anti-transparent property, there is fuzz, texture was poor.

  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.

Example 1 6-19, 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.

Both Example 1 6-19 is excellent in color developing property and anti-transparent property, quality was 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 and 22 to 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) Example 1 is used except that tris (monononylphenyl) phosphite (phosphorus compound 3) and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (phosphorus compound 4) are used instead. A knitted fabric was obtained in the same manner. 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 obtained woven fabric was a high-quality knitted fabric that achieved both a waterproof property and a coloring property. 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 38-42, 45-48
Change the polymerization temperature of the polymer, the intrinsic viscosity and terminal carboxyl group content, the content of the diol component was changed respectively. All experiments were excellent in process stability and were high quality and high quality knitted fabrics. Table 7 shows the evaluation results.

Example 49-5 2, Comparative Examples 11-12
A knitted fabric was obtained in the same manner as in Example 1 except that the stretching conditions were changed.

  Examples 49 to 51 and Comparative Examples 11 to 12 are experiments in which the draw ratio was changed and the residual elongation was changed. However, although Examples 49 to 51 were good in quality and quality, the residual elongation was In Comparative Examples 11 to 12 with 34% and 52%, warp was generated in the knitted fabric, and the quality was poor.

Example 52 a experiment was 89 ° C. The stretching temperature but both were excellent in color developing property and anti-transparent property. The evaluation results are shown in Table 8.

Example 5 5-56
The experiment was performed in the same manner as in Example 1 except that the stretching heat setting temperature was changed.

Example 5 5-56 it respectively 130 ° C. The oriented heat-set temperature was changed to 110 ° C., although an experiment of changing the boiling water shrinkage percentage and the dry heat shrinkage ratio, any process stability is good, The quality was excellent. Table 9 shows the evaluation results.

Examples 57-60, Comparative Examples 13-14
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 57 was excellent in yarn production and stable in quality. On the other hand, Comparative Example 13 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 14 was a knitted fabric with low color developability and a dull color.

  Examples 58 to 60 were experiments in which the spinning temperatures were 285 ° C., 295 ° C., and 298 ° C., respectively, and all of the quality of the anti-peeling property and the color developing property were good. Table 10 shows the evaluation results.

Examples 61-62
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 good color quality. The evaluation results are shown in Table 11.

Example 63 to 65,67～ 70
A knitted fabric was obtained in the same manner as in Example 1 except that composite spinning was performed with polyethylene terephthalate having an ethylene terephthalate repeating unit of 99 mol%.

Examples 63 to 65, 67 to Example 70 use a composite spinning base to dispose polyethylene terephthalate as the other component in the sheath component of the core-sheath composite, the island component of the sea-island composite, and the side-by-side type one component, and the discharge ratio However, the knitted fabric satisfying the effects of the present invention and having both the anti-peeling property and the color developing property was obtained. The evaluation results are shown in Table 12.

Claims (3)

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. hereinafter, further titanium oxide particles 1-2 wt%, the color tone L value of poly ethylene terephthalate containing the diol component 1.5 to 1.8 wt% 90-95, residual elongation is 36 to 50% cationic dyeable poly ethylene terephthalate fibers, characterized in that. 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. hereinafter, further oxidize the particulate titanium 1-2% by weight, a composite fiber with poly ethylene terephthalate containing the diol component 1.5 to 1.8 wt% whereas the component, the color tone L value 90 to 95, cationic dyeable poly ethylene terephthalate fibers residual elongation is characterized in that it is a 36 to 50%. A fabric comprising the polyester fiber according to claim 1 or 2 as at least a part thereof.