JP2007063713A - Undrawn polyester yarn having excellent dyeability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an undrawn polyester yarn having excellent dyeability and made of a polyester having excellent dyeability and free from the problems of the degradation of color, staining of spinneret, increase of filtering pressure and yarn breakage in the fiber production process. <P>SOLUTION: The undrawn polyester yarn is composed of a polyester compounded with a specific titanium compound and a specific phosphorus compound and containing 0.4-5.0 wt.% colloidal silica particles having an average primary particle diameter of 0.02-0.10μm and the yarn has a birefringence (Δn) of 30.0×10<SP>-3</SP>to 50.0×10<SP>-3</SP>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an undrawn polyester yarn excellent in dyeability. More specifically, in the production of polyester, there is no increase in the filtration pressure during melt spinning due to foreign matter caused by the catalyst used during polymerization, the spinning property is good, and the thermal stability, color tone, Polyester that is excellent in dyeability, and that can satisfy both color development and high-passability that cannot be achieved by conventional surface modification alone due to the synergistic effect of fiber surface condition modification and fiber orientation suppression. It relates to undrawn yarn.

  Polyester is used for various purposes because of its useful functionality, and is used for clothing, materials, and medical use, for example. Among them, polyethylene terephthalate is excellent in terms of versatility and practicality and is preferably used.

  In general, polyethylene terephthalate is produced from terephthalic acid or an ester-forming derivative thereof and ethylene glycol. However, 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 causes a defect in the filament, so that it is important to remove it 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 becomes a foreign substance, causing an increase in the filtration pressure of the filter during molding, causing yarn breakage during spinning or film tearing during film formation, etc. It has undesirable characteristics and contributes to a decrease in operability.

  In view of the above background, there is a demand for polyesters that contain little or no antimony. Thus, germanium compounds are known when the role of the polycondensation catalyst is required for compounds other than antimony compounds. However, germanium compounds are difficult to use for general purposes because they have a small reserve and rare value.

  Therefore, in the present invention, as a result of improving the above-mentioned problems and intensively studying a polyester having little yarn breakage, the inventors have found that the object of the present invention can be achieved by using a titanium compound as a polymerization catalyst.

  On the other hand, the proposal which uses the titanium complex which consists of a titanium compound and a phosphorus compound as a polymerization catalyst as a catalyst for polyester polymerization is made (refer patent documents 1-5). Although this method can reduce foreign matters caused by the catalyst, the color tone of the obtained polymer is not sufficient. Accordingly, there is a need for further improvements in titanium compounds.

  In addition, in a copolyester having an isophthalic acid component or a polyether component containing a metal sulfonate group as a copolymerization component, a proposal has been made to use a titanium complex composed of a titanium compound and a phosphorus compound as a polymerization catalyst (patent) Reference 6-10). Certainly, according to this method, an antistatic or moisture-absorbing / water-absorbing polyester having less color caused by the catalyst and having an improved color tone can be obtained, but the above-mentioned problems are very significant. That's not enough.

  Moreover, in the copolymer polyester which uses phenylene dioxydiacetic acid as a copolymerization component, the proposal which uses an organic phosphite compound as a polymerization catalyst and a phosphorus compound is made (refer patent document 11). According to this method, phenylenedioxydiacetic acid, which is a copolymerization component, is added as an essential component for imparting gas barrier properties, and color tone is improved by adding an organic phosphite compound. However, the specific polycondensation catalyst described in Patent Document 11 is only an antimony compound, which eliminates the cause of increased filter pressure during molding, yarn breakage during spinning, or film breakage during film formation. Not supposed to be. Moreover, although the organic acid etc., such as titanium, are mentioned as a polycondensation catalyst described in embodiment of this invention, The specific titanium compound mentioned in this invention is not necessarily mentioned.

  Therefore, in the present invention, it has been obtained that the above improvement can be achieved by a polyester composition characterized in that at least a specific titanium compound and a phosphorus compound are catalysts for polyester polymerization.

On the other hand, many technical disclosures related to polyester fibers whose color developability has been improved by modifying the fiber surface state (see Patent Documents 12 to 14). Conventionally, an antimony compound is converted to 30 ppm in terms of antimony. When colloidal silica fine particles are added to the above-mentioned polymer, the antimony catalyst residue alone can cause foreign matter and base stains, and even the colloidal silica fine particles can act as foreign matters and have a significant adverse effect on operability. It has been confirmed. However, by using the polyester of the present invention, it is possible to solve all the problems such as the contamination of the mouthpiece and the foreign matter so far, and when the surface state is modified by adding colloidal silica fine particles to the polyester of the present invention, the polymer and the surface modification Further improvement in color developability was confirmed by the synergistic effect. In view of the above, as a result of diligent improvement in production and quality of polyester, improvement in color developability, and further development application, at least a specific titanium compound and a phosphorus compound are polyester polymerization catalysts, It was found that a polyester undrawn yarn excellent in color developability and having an excellent feel such as dryness and swell can be obtained from the polyester.
JP 2001-524536 A (Claims) Japanese translation of PCT publication No. 2002-512267 (Claims) JP 2002-293909 A (Claims) JP 2003-040991 A (Claims) JP 2003-040994 A (Claims) JP 2003-128769 A (Claims) JP 2003-128770 A (Claims) JP 2003-119273 A (Claims) JP 2003-147633 A (Claims) JP 2003-129336 A (Claims) JP 2003-147060 A (Claims) JP 52-099400 A (Claims) Japanese Patent Application Laid-Open No. 55-107512 (Claims) JP 2003-105630 A (Claims)

  The object of the present invention is to solve the above-mentioned conventional problems, and at the time of molding a copolyester composition having a copolymer component of an isophthalic acid component containing a metal sulfonate group and a polyoxyalkylene glycol component, there is no increase in filtration pressure, Polyester with good yarn-making and film-forming properties and superior polymer color tone and dyeability compared to conventional products, has high black color development that could not be achieved with conventional technology, and has yarn-making and processing properties Another object of the present invention is to provide a polyester unstretched yarn having excellent texture characteristics such as a dry feeling and a swelling feeling.

The object of the present invention is to copolymerize an isophthalic acid component containing 0.1 to 10 mol% of a metal sulfonate group and a polyoxyalkylene glycol component having a weight average molecular weight of 400 to 6000 of 0.1 to 5.0 wt%. The antimony compound is not contained or the content in terms of antimony atoms relative to the polyester is 30 ppm or less, contains a titanium compound and a phosphorus compound, and further has an average primary particle size of 0.02 to 0.1 μm. A polyester undrawn yarn containing 0.4 to 5% by weight of colloidal silica fine particles, and having a birefringence (Δn) of 30 × 10 ⁻³ to 50 × 10 ⁻³ This can be achieved by the undrawn polyester yarn.

  The polyester composition comprising the specific titanium compound and phosphorus compound of the present invention is excellent in molding processability, and in the production of fibers, can solve problems such as deterioration of color tone, base stain, increased filtration pressure, thread breakage, By using a polyester undrawn yarn, it has high color developability and can improve texture characteristics such as dry feeling and swell feeling.

  The polyester 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. Specific examples of such polyester include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2- And bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate. The present invention is suitable for polyethylene terephthalate or polyester copolymers mainly containing ethylene terephthalate units, which are most commonly used.

  The polyester of the present invention is copolymerized with 0.1 to 10 mol% of isophthalic acid containing a metal sulfonate group and 0.1 to 5.0 wt% of polyoxyalkylene glycol having a weight average molecular weight of 400 to 6000. ing. If the copolymerization amount of isophthalic acid containing a metal sulfonate group is too large, the viscosity at the time of molding becomes abnormally high, causing problems such as an increase in filtration pressure. On the other hand, if the amount is too small, the dyeability is poor. If the weight average molecular weight of the polyoxyalkylene glycol is too large, no copolymerization occurs and a lump is easily formed in the polyester, and if it is too small, the dyeability is poor. When the copolymerization amount of polyoxyalkylene glycol is too large, the heat resistance and polymer color tone are deteriorated, and when it is too small, the dyeability is poor. The copolymerization amount of isophthalic acid containing a metal sulfonate group is preferably 0.6 to 5 mol%, and more preferably 1.0 to 2.0%. The weight average molecular weight of the polyoxyalkylene glycol is preferably 2000 to 5000, and the copolymerization amount is preferably 0.5 to 2.0% by weight.

  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 polyester comprising at least a specific titanium compound and a phosphorus compound of the present invention, the titanium compound that can be used as a polymerization catalyst is a functional group whose substituent is represented by the following formulas 1 to 5 And at least one titanium compound containing at least a carbonyl group, a carboxyl group or an ester group selected from the group consisting of:

(In Formula 1 to Formula 5, R _{1 to} R ₂ 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.)
As Formula 1 of this invention, the functional group which consists of hydroxy polyhydric carboxylic acid type compounds, such as lactic acid, malic acid, tartaric acid, and a citric acid, is mentioned.

  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 polyethylene terephthalate low polymer is depolymerized to increase the degree of polymerization. Therefore, titanium oxide particles generally used as inorganic particles in fiber matting agents and the like are It 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 polyester of the present invention preferably contains 0.1 to 400 ppm of phosphorus together with the titanium compound in terms of phosphorus atoms with respect to the polyester. 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 hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxy group, and has two or more with respect to the benzene ring. The hydrocarbon group may include 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 It may represent 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 may be an alkoxy group that is —OR ₂ or —OR ₃ with respect to a phosphorus atom. 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 0-2 In is.)
Examples of the phosphorus compound represented by the above formula 6 include phosphites, alkyl diarylphosphites, aryl diarylphosphites, dialkyl arylphosphonites, diaryl arylphosphonites, and the like. 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 of the following formula 8 is preferable. This compound is available as ADK STAB 2112 (Asahi Denka Co., Ltd.) or IRGAFOS 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 7 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 relative 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 available from Asahi Denka Co., Ltd. as ADK STAB PEP-36, ADK STAB PEP-24G, and ADK STAB HP-10, respectively, and formula 10 is available from Ciba Specialty Chemicals as IRGAFOS 126. Is possible. These compounds may be used alone or in combination.

  In the present invention, when a phosphorus compound is added, the phosphorus compound is preferably dissolved or dispersed in the 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 (MES; pH = 5.6-6.8), N- (2-acetamido) iminodiacetic acid (ADA; pH = 5.6-7.5) or the above Phosphorus compounds may be used.

  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.

  It is important that the polyester 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, it is possible to obtain a polymer that is less likely to cause contamination of the die during molding and is relatively inexpensive. More preferably, it is preferably 10 ppm or less, and particularly not substantially contained.

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.

  In the polyester production method of the present invention, the manganese compound is contained at 1 to 400 ppm in terms of manganese atom relative to the polyester at an arbitrary time, and the ratio of manganese compound to phosphorus compound is Mn / P = 0 as the molar ratio of manganese atom to phosphorus atom. Addition of 0.1 to 200 is preferable because the decrease in polymerization activity can be suppressed, and the resulting polymer has good color tone. 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, it is preferable to add 1 to 400 ppm of a cobalt compound at an arbitrary time in terms of cobalt atom relative to the polyester because the color tone of the resulting polymer is good. 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.

  Further, in the method for producing the polyester of the present invention, it is preferable to add a blue color adjusting agent and / or a red color adjusting agent as a color tone adjusting agent at an arbitrary time, because the color tone of the obtained polymer becomes 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. Red color adjusting agents, DESPERSE VIOLET 26, SOLVENT VOLTET 37 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 resulting polyester is particularly preferable when the ratio of the blue-based regulator is 50% by weight or more with respect to the total amount of the color-tone regulator to be added.

  Finally, the total amount of the color tone adjusting agent added to the polyester is preferably 30 ppm or less. If it exceeds 30 ppm, the transparency of the polyester may be lowered or the color may become dull.

  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 or more and 10 or less from the viewpoint of color tone.

  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.

  Further, for the purpose of improving the thermal stability and color tone of the obtained polymer, an alkali metal compound, an alkaline earth metal compound, an aluminum compound, a zinc compound, a tin compound, or the like may be added.

  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.

  In the polyester of the present invention, the color tone in the chip shape is a Hunter value, the L value is 50 or more, the a value is in the range of -5 to 1, and the b value is in the range of -0.5 to 7, such as fibers and films. From the viewpoint of the color tone of the molded product. More preferably, the L value is 65 or more, the a value is −3 to 0.5, and the b value is 1 to 6. Especially about b value, the range of 3-5 is more preferable.

  By using the polyester of the present invention as a constituent of a fiber-forming polymer, a synthetic fiber having unprecedented high dyeing characteristics and not impairing the fiber properties of the fiber-forming polymer can be obtained.

  In the present invention, examples of the fiber-forming polymer include, but are not limited to, polyesters such as 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.

  In order to obtain practically good dyeability, the dyeing exhaustion rate of the synthetic fiber is preferably as high as possible, 30% or more, more preferably 40% or more, and particularly preferably 50% or more.

  In addition to the pigments such as titanium oxide and carbon black, conventionally known antioxidants, anti-coloring agents, anti-lighting agents, anti-static agents and the like may be added to the fiber-forming polymer.

  In the present invention, it is important that the colloidal silica fine particles contained in the polyester have an average primary particle diameter of 0.02 to 0.1 μm. When the average primary particle diameter is larger than 0.1 μm, the void diameter on the surface of the polyester fiber formed after the alkali weight loss treatment becomes too large, and the reflected light on the fiber surface cannot be sufficiently suppressed, and sufficient black color developability. Cannot be obtained. Further, the silica fine particles cause wear of the yarn path guides, which causes a problem in industrial production. On the other hand, when the average primary particle diameter is less than 0.02 μm, the colloidal silica particles are likely to aggregate, which causes an increase in back pressure during spinning, which hinders stable industrial production. It is preferable that it is 0.04-0.08 micrometer from the point of black coloring property.

  In order to develop the excellent color developability that is the object of the present invention, it is important that the amount of colloidal silica fine particles added is 0.4 to 5% by weight. If the amount of colloidal silica particles added exceeds 5% by weight, the above-mentioned guides will be worn, the spinning quality will be deteriorated and the quality of the obtained fibers will be deteriorated, and the internal pressure of the pack will increase due to particle aggregation. Productive problems occur. On the contrary, when the added amount is less than 0.4% by weight, the wear and productivity of the yarn guides are improved, but the black color developability is greatly deteriorated. In consideration of the yarn forming property and the color developability, the amount of colloidal silica particles added is more preferably 1 to 4% by weight.

  The colloidal silica in the present invention refers to one in which fine particles present as a single particle are mainly composed of silicon oxide and are present as a colloid using water or a unitary alcohol or diol or a mixture thereof as a dispersion medium.

  As a method for adding colloidal silica to the polymer, it may be mixed at any stage before esterification or transesterification of the polyester, during the polycondensation reaction, after the polycondensation reaction, and before melt molding.

It is important that the polyester undrawn yarn of the present invention has a birefringence of 30 × 10 ⁻³ to 50 × 10 ⁻³ . When the birefringence is less than 30 × 10 ⁻³ , it is substantially important to stretch at a high magnification in the processing stage, and as a result, the orientation of the obtained fiber becomes high and it becomes difficult to obtain excellent color development. Become. The reason why excellent color developability cannot be obtained is that the fiber is highly oriented, the surface refractive index is increased, the amount of reflected light on the fiber surface is increased, and the dye exhaustion rate is decreased. In addition, there are problems such as unstable yarn processing due to changes in physical properties of undrawn yarn over time, and quality variations. On the other hand, if the birefringence is larger than 50 × 10 ⁻³ , the applicable yarn processing method is limited and general versatility is lost. In addition, since high-speed spinning is substantially important, stable yarn production becomes difficult.

  The intrinsic viscosity of the undrawn polyester yarn of the present invention is more preferably 0.57 to 0.63 in order to obtain good color developability and stable spinning operability.

  Moreover, the cross-sectional shape of the polyester undrawn yarn of the present invention is not particularly defined, and may be round or other irregular cross-sections.

  The polyester undrawn yarn of the present invention can be used as an undrawn yarn, but by applying to various yarn processing methods exemplified by normal drawing, false twisting, fluid processing, relaxation heat treatment, etc. The texture characteristics such as swell can be improved.

  These high-order processing techniques may be applied solely with the polyester undrawn yarn of the present invention, or may be combined with other yarns. Even in the case of producing a woven or knitted fabric using a processed yarn obtained by applying a higher-order processing technique to the polyester undrawn yarn of the present invention, there is no restriction on the knitting machine, the woven or knitted structure, and the like.

The polyester undrawn yarn of the present invention can be obtained by the prior art by adding a specific amount of colloidal silica having a specific particle diameter and setting the birefringence of the undrawn yarn to 30 × 10 ⁻³ to 50 × 10 ^−3. As a result, it has become possible to obtain an unstretched polyester yarn having significantly improved color developability compared to the above. This is because the birefringence of the undrawn yarn is 30.0 in addition to the suppression of reflected light by the fiber surface irregularities formed by eluting the colloidal silica fine particles added to the polymer by a technique such as alkali weight loss treatment. × with ^{10 -3} ~50.0 × 10 -3, by the synergistic action of substantially present invention undrawn yarn fiber orientation drawn yarn-yarn with is suppressed to improve the coloring effect It is.

  A method for producing the polyester of the present invention will be described. 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. 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 is as follows. Titanium oxide as a matting agent is applied to the low polymer obtained in any stage of the series of reactions (1) or (2), preferably in the first half of the series of reactions (1) or (2). After adding particles and additives such as a cobalt compound, the above-mentioned titanium compound is added as a polycondensation catalyst and a polycondensation reaction is performed to obtain a high molecular weight polyethylene terephthalate.

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

  As a method of obtaining the polyester undrawn yarn of the present invention, for example, terephthalic acid, ethylene glycol and colloidal silica are mixed to obtain a polyester by a usual polymerization method, and the polyester is spun by a usual method to obtain an undrawn yarn. Obtainable.

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 manganese element in polyester It was determined using 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 performing the above pretreatment was analyzed for titanium element, phosphorus element, antimony element and manganese element.
(2) Solution haze After dissolving 2.0 g of the sample to be measured in 20 mL of orthochlorophenol and performing the same pretreatment as (1), using a haze meter (Suga Test Instruments, HGM-2DP type), Analysis was carried out by integrating sphere photoelectric photometry.

If the solution haze is less than 2%, the content of foreign matter is small, and it can be said that the polymer has excellent yarn-making properties.
(3) Color tone of polymer Using a color difference meter (SM color computer model SM-3, manufactured by Suga Test Instruments Co., Ltd.), it was measured as a Hunter value (L, a, b value).
(4) Observation of deposits in the die The amount of deposits around the die holes 72 hours after spinning of the fibers was observed using a long focus microscope. The state in which deposits were hardly recognized was judged as ◯, the state in which deposits were recognized but operable was judged as Δ, and the state in which deposits were found and yarn breakage frequently occurred was judged as ×.
(5) Dye exhaust rate The processed yarn obtained by the various processing methods described in the examples was used as a knitted fabric, the cylindrical knitted fabric was malachite green (manufactured by Kanto Chemical) 5% Owf, acetic acid 0.5 ml / l, sodium acetate 0. Dyeing was carried out for 60 minutes in a 120 ° C. hot water solution with a bath ratio of 1: 100 consisting of 2 g / l, and the dye exhaust rate of the tubular knitted fabric was determined from the dye concentration difference before and after dyeing.

In addition, if this value is larger than 40%, it can be said that the polymer is excellent in dyeability.
(6) Evaluation of coloring property After using the processed yarn obtained by the various processing methods described in the examples as a knitted fabric, and treating the knitted fabric so that the alkali weight loss rate is 20%, Diax Black BG-FS (Mitsubishi) is used as a dye. Chemical product, disperse dye) 15% owf aqueous dispersion was used and dyed for 60 minutes at a bath ratio of 1:30 and 130 ° C., and the L value was measured 3 times with a colorimeter (CM-3700D, manufactured by Minolta). The average value was obtained by measurement.
(7) Intrinsic viscosity The polyester undrawn yarn was dissolved in O-chlorophenol and measured at 25 ° C.
(8) Average primary particle diameter The average primary particle diameter of the colloidal silica particles was measured with a particle size analyzer (LA-700) manufactured by HORIBA.
(9) Birefringence index The birefringence index of the polyester undrawn yarn was measured with a polarizing microscope (XTP-11) manufactured by NIKON.
(10) Spinning operability Spinning operability is determined from the number of yarn breaks during spinning.
Special: XX (Spinning yarn breakage less than 0.7 times / ton)
Excellent: ○ (Spinned yarn breakage 0.7 or more and less than 1.5 times / ton)
Normal: △ (Spun yarn breakage 1.5 or more and less than 2.0 times / ton)
Defect: × (Spring yarn breakage 2.0 times / ton or more)
The four grades were evaluated.
(11) Texture characteristics (dryness, swelling)
A sensory test was conducted by 5 panelists in a paired comparison with the reference sample, and the evaluation was made in four stages: special: OO, excellent: ◯, normal: △, defective: X. As a reference sample, an undrawn yarn having a 90 dtex / 48f round cross section made of polyethylene terephthalate obtained under the same spinning conditions as in Example 1 was subjected to yarn processing in the same manner as in each Example, and knitting and processing were performed. What was done was used.

Example 1
About 100 kg of bis (hydroxyethyl) terephthalate is charged in advance with a slurry of 82.5 kg of high-purity terephthalic acid (Mitsui Chemicals) and 35.4 kg of ethylene glycol (Nippon Shokubai Co., Ltd.), temperature 250 ° C., pressure 1.2 × The esterification reaction tank maintained at 10 ⁵ Pa was sequentially supplied over 4 hours, and after the completion of the supply, the esterification reaction was continued for another 1 hour, and 101.5 kg of this esterification reaction product was put into the polycondensation tank. Transferred.

  Subsequently, 5 g of silicon (manufactured by Toshiba Silicone Co., Ltd., 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- (G-t-butyl-4-hydroxyphenol) propionate) (Ciba Geigy Co., Ltd., Irganox 1010) 75 g, lithium acetate 45 g, blue color tone regulator SOLVENT BLUE 104 (Clariant, Polysynthlen Blue RBL) 0.4 g ethylene A glycol solution, an ethylene glycol solution (catalyst A) composed of a citric acid chelate titanium compound equivalent to 10 ppm in terms of titanium atom and phosphoric acid with respect to the polymer, and a 70 ppm (7 ppm in terms of phosphorus atom) phase with respect to the polymer Bis (2,6-di -tert- butyl-4-methylphenyl) pentaerythritol - di - phosphite (Asahi Denka Co., Ltd., Adekastab PEP-36) was added a mixture of ethylene glycol slurry. 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 stirring for another 5 minutes, an 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, the reaction system was heated from 250 ° C. to 290 ° C. while containing 2.0% by weight of colloidal silica fine particles having an average primary particle size of 0.05 μm with respect to the polymer and then stirring the low polymer at 30 rpm. While gradually raising the temperature to 0 ° C., 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 obtained polymer had 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.

This polyester was spun from a 48-hole round hole cap, entangled with 5 pieces / m, and then taken up at a take-up speed of 3700 m / min to obtain a 90 dtex / 48 f polyester undrawn yarn. In the melt spinning process, deposits around the mouthpiece holes during spinning and an increase in filtration pressure were hardly observed, and there was almost no yarn breakage during stretching, and the polymer had good moldability. The polyester undrawn yarn obtained had an intrinsic viscosity of 0.610 and a birefringence of 43 × 10 ⁻³ .

  The polyester undrawn yarn was subjected to drawing false twisting at a draw ratio of 1.6 times and a false twisting temperature of 180 ° C. to obtain false twisted yarn.

  The false twisted yarn is knitted with a FAX knitting machine, refined with hot water at 98 ° C, treated with a 3% aqueous sodium hydroxide solution to give a knitted fabric with a weight loss rate of 20%, and dyed at 130 ° C. It was.

  The L value of the obtained knitted fabric was 10.7, and the color development was extremely excellent. Furthermore, the obtained knitted fabric had a good texture and was excellent in quality.

Examples 2-12
Spinning, yarn processing and knitting were carried out under the same production conditions as in Example 1 except that the copolymerization amount of the isophthalic acid component containing a metal sulfonate group and the weight average molecular weight and copolymerization amount of polyethylene glycol were changed. Almost no deposits and no increase in filtration pressure were observed around the nozzle holes during spinning, and the color tone, color developability and texture were good.

Examples 13-19
Content of titanium compound as catalyst, phenyl phosphite, tris (monononylphenyl) phosphite, bis instead of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite Point of using (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite, content of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite Spinning, yarn processing, and knitting were performed under the same manufacturing conditions as in Example 1 except that was changed. Almost no deposits and no increase in filtration pressure were observed around the nozzle holes during spinning, and both color tone and color development were good.

Examples 20-32
Same as Example 1 except that 15 ppm antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.) in terms of metal is mixed with the titanium compound and added, and the type and content of the cobalt compound, manganese compound, and color modifier are changed. Spinning, yarn processing, and knitting were performed under manufacturing conditions. Almost no deposits and no increase in filtration pressure were observed around the nozzle holes during spinning, and both color tone and color development were good.

Examples 33-41
Spinning, yarn processing and knitting were performed under the same production conditions as in Example 1 except that the catalyst B composed of a citrate chelate titanium compound, phenylphosphonic acid and phosphoric acid was used as the catalyst. Almost no deposits and no increase in filtration pressure were observed around the nozzle holes during spinning, and both color tone and color development were good.

Examples 42-50
Spinning, yarn processing and knitting were performed under the same production conditions as in Example 1 except that the catalyst C composed of a lactic acid chelate titanium compound and phosphoric acid was used as the catalyst. Almost no deposits and no increase in filtration pressure were observed around the nozzle holes during spinning, and both color tone and color development were good.

Examples 51-59
Spinning, yarn processing and knitting were performed under the same production conditions as in Example 1 except that the catalyst D consisting of a lactic acid chelate titanium compound, phenylphosphonic acid and phosphoric acid was used as the catalyst, and the addition amount of the phosphorus compound 1 was changed. Almost no deposits and no increase in filtration pressure were observed around the nozzle holes during spinning, and both color tone and color development were good.

  In addition, the phosphorus compound 1 described in Tables 1 to 6 is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite (Asahi Denka Co., Ltd., ADK STAB PEP-36). , B1 is a blue color tone adjusting agent SOLVENT BLUE 104 (Clariant Polysythlen Blue RBL), and R1 in Tables 3 to 6 is a red color tone adjusting agent SOLVENT RED 135 (Clariant Red Polythren Red GFP). The phosphorus compound 2 described in Table 2 is phenyl phosphite (manufactured by Aldrich), the phosphorus compound 3 is tris (monononylphenyl) phosphite (manufactured by Aldrich), and the phosphorus compound 4 is bis (2 , 4-Di-tert-butylphenyl) pentaerythrito -Di-phosphite (Asahi Denka Co., Adeka Stub PEP24G).

  In addition, the synthesis | combining method of catalyst A-F is described below.

Catalyst A. 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 B. Method for synthesizing citric acid chelate titanium compound (mixed of phenylphosphonic acid and phosphoric acid) In a 3 L flask equipped with a stirrer, a condenser and a thermometer, warm water (371 g) was mixed with citric acid / monohydrate (532 g, 2. 52 mol) was 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). 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 2.49% by weight).

Catalyst C. 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 D. 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).

Comparative Examples 1 and 2
Spinning, yarn processing, and knitting were performed under the same production conditions as in Example 1 except that the copolymerization amount of the isophthalic acid component containing a metal sulfonate group was changed. Table 7 shows the results of evaluating the spinning operability, the L value after the alkali weight reduction treatment of the obtained knitted fabric, and the texture.

  In Comparative Example 1, deposits around the mouthpiece hole during spinning and an increase in filtration pressure were hardly observed, and the color tone was good, but the dye exhaustion rate of the obtained polyester yarn was as low as 25%, and the dyeability was high. It was inferior.

  On the other hand, in Comparative Example 2, although the dyeability was excellent, deposits around the mouthpiece holes during spinning and an increase in filtration pressure occurred, and yarn breakage during stretching also occurred frequently. In addition, the polyester had a b value of 7.4 and a poor color tone.

Comparative Examples 3 and 4
Spinning, yarn processing, and knitting were performed under the same production conditions as in Example 1 except that the weight average molecular weight of polyethylene glycol was changed. Table 7 shows the results of evaluating the spinning operability, the L value after the alkali weight reduction treatment of the obtained knitted fabric, and the texture.

  In Comparative Example 3, there was almost no deposit around the nozzle hole during spinning and an increase in filtration pressure, and the color tone was good, but the dye exhaustion rate of the obtained polyester yarn was as low as 19% and inferior in dyeability. It was. On the other hand, in Comparative Example 4, deposits around the die hole during spinning and an increase in filtration pressure occurred, and yarn breakage during stretching frequently occurred, resulting in poor moldability.

Comparative Examples 5 and 6
Spinning, yarn processing, and knitting were performed under the same production conditions as in Example 1 except that the copolymerization amount of polyethylene glycol was changed. Table 7 shows the results of evaluating the spinning operability, the L value after the alkali weight reduction treatment of the obtained knitted fabric, and the texture.

  In Comparative Example 5, deposits around the nozzle holes during spinning and an increase in filtration pressure were hardly observed, and the color tone was good, but the dye exhaustion rate of the obtained polyester yarn was as low as 22% and dyeability was low. It was inferior.

  On the other hand, in Comparative Example 6, although the dyeability was excellent, deposits around the mouthpiece hole during spinning and an increase in filtration pressure occurred, and yarn breakage during stretching frequently occurred. In addition, the b value was 8.5 and the yellow polyester was inferior in color tone.

Comparative Example 7
Instead of catalyst A, antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.), 334 ppm in terms of antimony atom, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di, with respect to the obtained polyester -Phosphoric acid instead of phosphite was polymerized in the same manner as in Example 1 except that 26 ppm in terms of phosphorus atom was added to the obtained polyester and no color tone modifier was added, and melt spinning was performed. Even if the catalyst is changed, the polymerization reactivity can change well, and there is no problem with the color tone of the polyester and the dyeability of the polyester yarn, but the polymer solution haze is as high as 3.4%. Thread breakage occurred and the spinning operability was poor.

  The phosphorus compound 1 listed in Table 7 is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite (Asahi Denka Co., Adeka Stub PEP-36), and B1 Is a blue color tone adjusting agent (manufactured by Clariant, Polysynthren Blue RBL).

Comparative Examples 8-10
Spinning, yarn processing, and knitting were performed under the same production conditions as in Example 1 except that the content of colloidal silica fine particles and the average primary particle diameter contained in the polyester were changed as shown in Table 1. Table 7 shows the results of evaluating the spinning operability, the L value after the alkali weight reduction treatment of the obtained knitted fabric, and the texture.

  In Comparative Example 8, since no colloidal silica was contained in the polyester, the fiber surface unevenness was not formed after the alkali weight reduction treatment, and the color developability and the texture were significantly inferior.

  In Comparative Example 9, agglomeration of colloidal silica particles was observed, the void diameter formed on the fiber surface was increased and the color developability was lowered, and the back pressure was attributed to the large amount of colloidal silica particles contained. A rise occurred and the spinning operability deteriorated significantly.

  In Comparative Example 10 having a large primary particle size, the degree of wear of the yarn guides was severe and the spinning operability deteriorated, and the color development and texture were inferior.

Comparative Example 11
The birefringence of the polyester undrawn yarn was changed as shown in Table 2 (specifically, Example 8 was spinning speed 3000, Example 9 was spinning speed 4000, Comparative Example 5 was 2500, Comparative Example 6 was 4500 m / min). Each undrawn yarn was spun) and the obtained undrawn yarn was drawn 1.2 times so that the processed yarn elongation was 35%, and then subjected to relaxation heat treatment at 180 ° C. to obtain a 56T-48F processed yarn. Obtained.

  The processed yarn was mixed with 84 dtex / 12f polyester filament and Taslan in the same manner as in Example 1, and was subjected to weaving, alkali weight loss treatment, and dyeing, and then the color development and texture characteristics of the resulting fabric were evaluated.

  As a reference sample for evaluation of texture characteristics, a processed yarn was used which was obtained by stretching an unstretched yarn made of polyethylene terephthalate having a round cross section of 90dtex / 48f by 1.6 times and then relaxing heat treatment at 180 ° C.

  Comparative Example 11 was excellent in color development, swelling and dry feeling, but the spinning operability deteriorated and stable yarn production could not be performed.

Claims (13)

An antimony compound comprising an isophthalic acid component containing 0.1 to 10 mol% of a metal sulfonate group and a polyoxyalkylene glycol component having a weight average molecular weight of 400 to 6000 of 0.1 to 5.0 wt%; 0.4 or less colloidal silica fine particles containing 30 ppm or less in terms of antimony atom relative to polyester, containing a titanium compound and a phosphorus compound, and having an average primary particle size of 0.02 to 0.1 μm. Polyester undrawn yarn characterized by containing ˜5 wt%, and having a birefringence (Δn) of 30 × 10 ⁻³ to 50 × 10 ⁻³ . 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 polyester undrawn yarn according to claim 1, 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 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 3. An undrawn polyester yarn according to item 2. 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 undrawn polyester yarn according to claim 2, wherein:   The unstretched polyester yarn according to any one of claims 2 to 4, 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 polyester undrawn yarn according to claim 5, wherein the phosphorus compound is a compound represented by Formula 7.

(In 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, including 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 polyester undrawn yarn according to any one of claims 1 to 6, wherein the molar ratio of titanium atom to phosphorus atom is Ti / P = 0.1 to 20.   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. It is 1-200, The polyester undrawn yarn of any one of Claims 1-7 characterized by the above-mentioned.   The polyester undrawn yarn according to any one of claims 1 to 8, comprising a blue-based adjusting agent and / or a red-based adjusting agent as a color adjusting agent. The polyester undrawn yarn according to claim 9, wherein the content of the color tone adjusting agent and the cobalt compound satisfies 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 color adjusting agent is a dye, and its COLOR INDEX GENERIC NAME is SOLVENT BLUE 104, SOLVENT BLUE 122, SOLVENT BLUE 45 in the blue system, and SOLVENT RED 135, SOLVENT RED 111, SOLVENT RED 111, and SOLVENT RED 17 in the red system. The undrawn polyester yarn according to claim 9 or 10.   The color tone is a Hunter value, the L value is 50 or more, the a value is in the range of -5 to 1, and the b value is in the range of -0.5 to 7, respectively. Polyester undrawn yarn.   The unstretched polyester yarn according to claim 1, comprising polyethylene terephthalate having an intrinsic viscosity of 0.57 to 0.63.