JP2011063646A - Method for producing polyester composition for production of polyester fiber having high vividness - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a method for producing a polyester composition that can produce a fiber showing improved color depth and vividness when the fiber is dyed and to provide the fiber. <P>SOLUTION: In a method for producing a polyester composition produced by the production process having a step of producing an oligomer from a dicarboxylic acid component composed mainly of terephthalic acid and a diol component composed mainly of ethylene glycol by performing esterification reaction and a step of subjecting the oligomer to polycondensation reaction, the method for producing a polyester composition includes adding an alkali metal compound and/or an alkaline earth metal compound and a specific phosphorus compound such that the alkali metal atom and/or the alkaline earth metal atom are contained in the range of 0.1-2.0 mol% based on the dicarboxylic acid component; and that the phosphorus compound satisfies following formula (1): 0.5≤P/M≤2.0. In numerical formula (1), P represents a molar quantity of phosphorus atom by addition of the phosphorus compound and M represents a molar quantity of an alkali metal atom and/or alkaline earth metal atom by addition of the alkali metal compound and/or the alkaline earth metal compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a polyester composition. More specifically, when a fiber shape is imparted to the polyester composition, a fine fiber can be easily formed on the fiber surface, and when this is dyed, the polyester fiber can exhibit improved color depth and sharpness. About.

  Polyester is widely used as a synthetic fiber because it has many excellent properties. However, polyester fibers have the disadvantage that they have no color depth when dyed with a dye and are inferior in color developability and sharpness compared to natural fibers such as wool and silk, rayon, acetate, and acrylic fibers. In order to eliminate this defect, attempts have been made to chemically modify polyesters to improve dyes, but none of them has been able to obtain sufficient effects.

  In order to eliminate such disadvantages, for example, in Patent Document 1 and Patent Document 2, fine particles of an inert substance are contained in the fiber and treated with an acid or alkali in which the fine particle of the inert substance is dissolved without being affected by the fiber. A method of removing the inert substance and making the fiber surface uneven is known. Further, for example, Patent Document 3 discloses a polyester in which a random uneven surface is irregularly formed on a fiber surface using silica sol or the like, and a finer uneven structure is formed in the unevenness forming the random surface. It has been.

  As an example of using an organic compound as the micropore forming agent, for example, in Patent Documents 4 to 5, a phosphorus compound or a sulfonic acid compound having a carboxylic acid metal salt in the molecule is used as the micropore forming agent, and the alkali weight loss. A method of forming micropores on the fiber surface and inside by treatment is known.

  However, in any known technique, it is possible to give the fiber surface an uneven shape by solvent treatment of the fiber, but the effect of improving the color depth is insufficient, and because of the complicated uneven structure There are problems such as easy fibrillation, and the problem has not been solved in view of high-speed spinning, technical stability, and industrial productivity.

  In order to eliminate such drawbacks, for example, in Patent Document 6, in the stage before the polyester synthesis reaction is completed, a specific phosphorus compound and an alkaline earth of 0.5 to 1.2 times mol of the phosphorus compound. There has been proposed a method for producing a synthetic fiber having fine pores by adding a metal, then completing the synthesis of the polyester, melt-spinning the obtained polyester, and subjecting it to an alkali reduction treatment. According to this method, a polyester fiber having an excellent color depth can be obtained.

  Certainly, according to the present method, it is possible to generate inert particles in a uniform ultrafine particle dispersed state in the polyester during the reaction. However, this method is very effective in a so-called transesterification method using an organic carboxylic acid ester as an acid component. On the other hand, in a direct esterification reaction method using a dicarboxylic acid as a raw material which has become the mainstream in recent years, Since the compound is added to the oligomer in which the solubility of the phosphorus compound is very low, the phosphorus compound is precipitated in the reaction system during the addition, and a large amount of coarse coarse particles are generated. For this reason, it is impossible to carry out molding processing such as melt spinning, and it has been a fact that such a composition can only be produced using a so-called organic carboxylic acid ester as a raw material.

  In order to solve these problems, for example, Patent Documents 7 to 8 propose methods for adjusting the addition conditions and reducing the amount of precipitation. However, even with this method, it is difficult to completely suppress precipitates, and it is necessary to add a large amount of ethylene glycol in the middle of the reaction in order to improve solubility. There was also.

Japanese Patent Publication No. 43-014186 Japanese Patent Publication No. 43-016665 JP-A-55-107512 Japanese Patent Laid-Open No. 08-158157 JP 2000-027032 A JP 58-104215 A JP-A-01-068568 Japanese Patent Laid-Open No. 05-132855

  The objective of this invention is providing the manufacturing method of the polyester composition from which the fiber which exhibits the depth of a color improved and the clearness when dyeing was solved, and the fiber is solved.

In view of the above problems, the present inventors have intensively studied, and as a result, have completed the present invention.
That is, the present invention is a production process comprising a step of performing an esterification reaction from a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol, and a step of performing a polycondensation reaction on the oligomer. In the manufacturing method of the polyester composition manufactured in,
An alkali metal atom and / or an alkaline earth metal compound and a phosphorus compound represented by the following general formula (I) are used in an amount of 0.1 to 2 with respect to the dicarboxylic acid component. It is a method for producing a polyester composition characterized in that it is added so as to be contained in a range of 0.0 mol%, and a phosphorus compound is added so as to satisfy the following formula (1). Can be solved.

[In the above formula (I), Ar represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, and R ¹ represents a hydrogen atom or an OR ² group. R ² is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an unsubstituted or substituted 7 to 20 carbon atoms A benzyl group having a carbon atom is represented. ]
0.5 ≦ P / M ≦ 2.0 (1)
[In the above formula (1), P represents the molar amount of phosphorus atom by addition of phosphorus compound, M is the molar amount of alkali metal atom and / or alkali metal atom by addition of alkali metal compound and / or alkaline earth metal compound. Represents. ]

  According to the present invention, since unique micropores can be easily formed on the surface of the fiber, it is possible to exhibit improved color depth and clarity when dyed, and excellent strength and elongation. It is possible to provide a polyester composition suitable for the polyester fiber. In addition, the polyester composition has a low copolymerization amount of by-products such as diethylene glycol and good heat resistance, and also has good productivity when producing polyester fibers from the polyester composition.

2 is a scanning electron micrograph of the polyester fiber surface obtained in Example 1. FIG. 6 is a scanning electron micrograph of the surface of a polyester fiber obtained in Comparative Example 6. 6 is a scanning electron micrograph of the surface of a polyester fiber obtained in Comparative Example 8. 2 is a scanning electron micrograph of the polyester fiber surface obtained in Reference Example 1. FIG.

  Hereinafter, the production method of the present invention will be described in detail. The method for producing a polyester composition of the present invention comprises a step of esterifying a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol to form an oligomer, and a polycondensation reaction on the oligomer. It is a manufacturing method of the polyester composition manufactured at the manufacturing process which has the process to perform.

(Raw material: Acid component)
As the dicarboxylic acid used in the present invention, terephthalic acid is mainly used, but other components may be copolymerized depending on the purpose within a range not losing physical properties. Components other than terephthalic acid include isophthalic acid, phthalic acid, phthalic anhydride, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid, 4,4′-biphenyldicarboxylic acid, p-hydroxybenzoic acid, adipine Acid, sebacic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexyldicarboxylic acid, etc. can be mentioned, but in order to maintain the basic quality of the resulting polyester composition It is preferable that 80 mol% or more, more preferably 90 mol% or more of the dicarboxylic acid component is terephthalic acid.

(Raw material: Glycol component)
As the diol component used in the present invention, ethylene glycol is mainly used, but other components may be copolymerized depending on the purpose within a range not losing physical properties. As components other than ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,2-propylene glycol, 2,2-dimethyl-1,3-propanediol (neopentylene glycol), Examples include dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dimethylolpropionic acid, poly (ethylene oxide) glycol, and poly (tetramethylene oxide) glycol. In order to maintain the basic quality of the obtained polyester composition, 80 mol% or more, more preferably 90 mol% or more of the diol component is preferably ethylene glycol.

(Ingredients: other)
Polyesters in the present invention include trimellitic acid, trimesic acid, trimellitic anhydride, pyromellitic acid, trimellitic acid monopotassium salt and other polycarboxylic acids, glycerin, pentaerythritol, sodium dimethylolethylsulfonate, dimethyl A polyvalent hydroxy compound such as potassium methylolpropionate may be copolymerized within 1 mol% of the acid component as long as the object of the present invention is achieved.

(Oligomer)
The process for producing an oligomer by carrying out an esterification reaction from a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol contains the method for producing a polyester composition of the present invention. Here, the oligomer means that the dicarboxylic acid component and the diol component are terephthalic acid and ethylene glycol, respectively, and in addition to bis (2-hydroxyethyl) terephthalate, the molecule contains two or more repeating units of ethylene terephthalate. Intrinsic viscosity, molecular weight, and degree of polymerization are not so high that it can be called terephthalate, and it represents a compound whose terminal is a carboxyl group or a hydroxyethyl group. The esterification reaction is performed until such an oligomer is formed. The reaction rate of the esterification reaction can be detected by measuring the amount of water produced.

(Intrinsic viscosity)
The polyester composition in the present invention preferably has an intrinsic viscosity of 0.60 dL / g or more. When the intrinsic viscosity is less than 0.60 dL / g, the physical properties of the fiber molded product obtained by melt spinning the polyester are lowered and the practicality is poor. The upper limit of the intrinsic viscosity is not particularly limited, but is preferably 1.2 dL / g or less from the viewpoint of ease of production of the polyester composition and ease of molding of a fiber molded article obtained therefrom. By appropriately adjusting the polycondensation conditions of the polyester, a polyester composition having an intrinsic viscosity within this range can be produced.

(Internal precipitation particles)
The polyester composition of the present invention is individually added to the polyester composition production stage without previously reacting the phosphorus compound represented by the following general formula (I) with the alkali metal compound and / or alkaline earth metal compound. And it is preferable to contain the microparticles | fine-particles formed when an alkali metal compound and / or an alkaline-earth metal compound and a phosphorus compound react during the synthesis | combination reaction of a polyester composition. Since these are fine particles formed by reacting inside the reaction vessel, they may be hereinafter referred to as “internal precipitation particles”.

(Alkali metals and alkaline earth metals)
Regarding the alkali metal element and alkaline earth metal element according to the present invention, Li, Na, Mg, Ca, Sr, and Ba are preferable, and Ca, Sr, and Ba are particularly preferably used. Of these, Ca is most preferably used. The alkali metal compound and / or alkaline earth metal compound according to the present invention is not particularly limited as long as it reacts with the phosphorus compound to form a metal-containing phosphorus compound. Specifically, a salt with an organic carboxylic acid is preferable, and acetate is particularly preferable because acetate can be easily removed as a by-product by reaction. The alkali metal and / or alkaline earth metal compounds may be used alone or in combination of two or more.

  The alkali metal compound and / or alkaline earth metal compound is desirably used in a state dissolved in a solvent. As the solvent at this time, an appropriate solvent can be selected from known solvents, but it is most preferable to use glycol used as a raw material of the target polyester. That is, in the present invention, as is apparent from the above description, ethylene glycol is used.

(Metal compound addition amount)
Said alkali metal compound and / or alkaline earth metal compound is in the range of 0.1 to 2.0 mol% of the alkali metal atom and / or alkali metal atom in terms of metal atom with respect to the above-mentioned dicarboxylic acid component. It is necessary to add so that it may contain. When the addition amount is less than 0.1 mol%, the amount of particles formed from the phosphorus compound and the alkali metal compound and / or alkaline earth metal compound described later decreases, so the resulting polyester composition is melt-spun, The formation of the surface uneven structure of the polyester fiber obtained by reducing the weight becomes insufficient, and sufficient sharpness cannot be expressed. On the other hand, if it exceeds 2.0 mol%, the particles formed from these phosphorus compounds and alkali metal compounds and / or alkaline earth metal compounds form coarse particles, so the resulting polyester is melt-spun, The formation of the uneven surface structure of the polyester fiber obtained by reducing the alkali becomes insufficient, and the spinning property in the melt spinning process is remarkably deteriorated. The addition amount of these alkali metal compounds and / or alkaline earth metal compounds is preferably in the range of 0.2 to 1.8 mol%, more preferably in the range of 0.5 to 1.5 mol% in terms of metal element. .

(Metal compound addition time)
The timing of addition of the alkali metal compound and / or alkaline earth metal compound during the production process of the polyester composition can be selected from any stage of the esterification reaction process and the polycondensation reaction process. From the influence on the esterification reaction and the polycondensation reaction, it is desirable to add during the esterification reaction or after the end of the esterification reaction, in the first half of the polycondensation reaction (within 30 minutes).

(Phosphorus compound)
The phosphorus compound according to the present invention needs to be a compound represented by the following general formula (I).

[In the above formula (I), Ar represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, and R ¹ represents a hydrogen atom or an OR ² group. R ² is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an unsubstituted or substituted 7 to 20 carbon atoms A benzyl group having a carbon atom is represented. ]

Specific examples of the functional group represented by R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl. Group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, phenyl group, naphthyl group, biphenyl group, benzyl group, methylphenyl group, ethylphenyl group, propyl group A phenyl group, a dimethylphenyl group, etc. can be mentioned. Further, one or more hydrogen atoms in these hydrocarbon groups may be substituted with a carboxyl group, an ester group, a halogen group, an alkyloxy group or the like.
Examples of the functional group represented by Ar include a phenyl group, a mono- (di- or tri-) halogenated phenyl group, a methoxyphenyl group, a mono- (di- or tri-) carboxyphenyl group, and a 1- (2-) naphthyl group. Mono- (di- or tri-) halogenated-1- (2-) naphthyl group, 1- (2- or 9-) anthranyl group, 4- (2- or 3-) biphenyl group Can be mentioned.

  Examples of the compound of the general formula (I) include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, normal propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid. , Naphthylphosphonic acid, anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid 2,5-dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenyl Phosphonic acid, 2, , 5-tricarboxyphenylphosphonic acid, 2,3,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, Of these, phenylphosphonic acid is most preferably used. The above phosphorus compound is desirably used in a state dissolved in a solvent. As the solvent at this time, an appropriate solvent can be selected from known solvents, but it is most preferable to use glycol used as a raw material of the target polyester. That is, in the present invention, as is apparent from the above description, ethylene glycol is used.

(When phosphorus is added)
The timing of adding the phosphorus compound to the polyester may be before or after the addition of the alkali metal compound and / or alkaline earth metal compound. The phosphorus compound reacts with the alkali metal compound and / or the alkaline earth metal compound to form particles insoluble in the polyester, but the same particles are formed regardless of which is added first. However, since addition of a phosphorus compound in the early stage of the esterification reaction may inhibit the esterification reaction, it is desirable that the latter half of the esterification reaction or the first half of the polycondensation reaction after the esterification reaction is completed (30 minutes). It is desirable to add within

(Pre-reaction of phosphorus compounds and alkali metal compounds is prohibited)
However, in the method of adding to a polyester a compound obtained by reacting a phosphorus compound with an alkali metal compound and / or an alkaline earth metal compound in advance before adding to the polyester, the phosphorus compound and alkali metal compound and / or adjusted in advance The size of the particles formed from the alkaline earth metal compound is increased. Therefore, the surface uneven structure of the polyester fiber obtained by melt spinning the polyester obtained by adding it to the polyester and then reducing the alkali cannot form the desired finely textured structure. It is not possible to obtain a polyester fiber that exhibits the sharpness of the above. Therefore, in the method for producing a polyester composition of the present application, an alkali metal compound and / or an alkaline earth metal compound and a phosphorus compound are reacted before being added to the step of forming an oligomer and / or the step of performing a polycondensation reaction. However, it is possible to preferably employ a method of individually adding to the polyester production process. However, it is within the scope of the present invention to add it as a simple mixture of both compounds as required.

(Phosphorus atom / metal atom ratio)
The addition amount of the phosphorus compound and the alkali metal compound and / or the alkaline earth metal compound needs to be added at a ratio represented by the following formula (1).
0.5 ≦ P / M ≦ 2.0 (1)
When the P / M in the above formula (1) is less than 0.5, the amount of particles formed from the phosphorus compound and the alkali metal compound and / or alkaline earth metal compound is decreased. The formation of the surface uneven structure of the polyester fiber obtained by reducing the alkali becomes insufficient, and sufficient sharpness cannot be expressed, and the amount of the alkali metal compound and / or alkaline earth metal compound in the polyester becomes excessive, and excessive The metal atom component is not preferable because it accelerates the thermal decomposition of the polyester and significantly impairs the thermal stability. On the other hand, when P / M exceeds 2.0, the phosphorus compound becomes excessive and the excessive phosphorus compound inhibits the polymerization reaction of the polyester. P / M is preferably in the range of 0.8 to 1.8, more preferably 0.9 to 1.5.

(Polymerization catalyst, other additives)
The polyester composition of the present invention includes a metal compound catalyst for compounds such as antimony, germanium, and titanium, which are usually used in the production of polyester, a phosphorus compound as an anti-coloring agent, an antioxidant, an optical brightener, and an antistatic agent. An agent, an antibacterial agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a light-shielding agent, a matting agent, and the like may be contained within the scope of the object of the present invention.

(Production method of polyester composition)
Next, an example of the preferable manufacturing method for obtaining the polyester composition of this invention is demonstrated in detail. That is, after the polyester is prepared, the above phosphorus compound, alkali metal compound and / or alkaline earth metal compound are mixed by a method such as blending to obtain a polyester composition. This is a method for producing a polyester composition by adding a phosphorus compound and an alkali metal and / or alkaline earth metal compound according to the invention to carry out a polymerization reaction of the polyester. Internal precipitation particles can be generated by this method. Furthermore, the polyester production reaction conditions in the method of the present invention are not particularly limited, but the polycondensation reaction is generally performed at a temperature of 230 to 320 ° C. under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa), or It is preferable to carry out polycondensation for 15 to 300 minutes by combining these conditions.

(Melt spinning, alkali weight loss)
A conventional polyester fiber melt spinning method can be arbitrarily adopted as the method of melt spinning the fiber obtained by the above method to obtain a fiber. The fiber spun here may be a solid fiber having no hollow part or a hollow fiber having a hollow part. A sea-island type composite fiber or a side-by-side type composite fiber having a multilayer structure of two or more layers may be used.

  As a method for imparting a fine concavo-convex structure to the surface of the polyester fiber thus obtained, a method of reducing the weight by contacting with a basic compound is preferable. The contact with the basic compound is facilitated by, for example, treating the fiber with an aqueous solution of the basic compound after subjecting the fiber to a treatment such as stretching heat treatment or false twisting as necessary, or further forming a fabric. Can be done.

  Examples of the basic compound used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, and potassium carbonate. Of these, sodium hydroxide and potassium hydroxide are particularly preferred. The concentration of the basic compound aqueous solution varies depending on the type of the basic compound, processing conditions, and the like, but is preferably in the range of 0.1 to 30% by weight. The treatment temperature is preferably in the range of room temperature to 100 ° C.

  The amount by which the polyester fiber is reduced by the treatment with the basic compound aqueous solution or the like is preferably 2% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more based on the fiber weight. By treating with an aqueous solution of the basic compound in this way, a large number of micropores arranged in the fiber axis direction can be formed on the fiber surface and its vicinity, so that excellent color depth and sharpness are exhibited when dyed. become.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples. The analysis items in the examples were measured by the methods described below.

(A) Intrinsic viscosity:
A dilute solution obtained by dissolving the polyester composition in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer.

(A) Diethylene glycol content:
The polyester sample chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was measured using gas chromatography (manufactured by Hewlett-Packard (HP 6850)).

(C) Tensile strength / elongation of fiber:
Measurement was performed in accordance with the method described in JIS-L-1070.

(D) Uneven structure on fiber surface:
The fabric after alkali weight reduction was observed at 4000 times with a scanning electron microscope. Based on the fiber surface structure obtained by the method of Reference Example 1, the formation state of the concavo-convex structure was evaluated.

(E) Deep chromaticity:
Deep chromaticity (K / S) was used as a measure of color depth. The spectral reflectance of the sample fabric was measured with an RC-330 self-recording spectrophotometer manufactured by Shimadzu Corporation, and obtained under the direction of Kubelka Munch below. A larger value indicates a greater deep color effect.
K / S = (1-R) ² / 2R
Here, R represents reflectance, K represents an absorption coefficient, and S represents a scattering coefficient.

(F) Repeating unit of polyester fiber (polyester composition), chemical structure of contained compound A polyester composition sample was dissolved in deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent, and then the precipitate was removed by filtration. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of the obtained solution was measured using JEOL A-600 superconducting FT-NMR manufactured by JEOL Ltd. The chemical structure of the repeating unit of the polyester was identified from the spectrum pattern according to a conventional method. Further, methanol was added to the polyester composition solution to precipitate the polyester component, and then the supernatant liquid was concentrated and subjected to nuclear magnetic resonance spectrum analysis to identify the chemical structure of the phosphonic acid compound such as an alkali metal compound.

(G) Phosphorus atom and metal atom content in the polyester composition:
The phosphorus metal atom content in the polyester composition and the metal atom content were obtained by heating and melting a granular polyester composition (fiber) sample on a steel plate, and then preparing a test molded body having a flat surface with a compression press. Using this test molded body, it was determined using a fluorescent X-ray apparatus (Model 3270E manufactured by Rigaku Corporation). About what used the titanium compound as a catalyst, after dissolving a sample in orthochlorophenol, extraction operation was performed with 0.5N hydrochloric acid. The extract was quantified using a Hitachi Z-8100 atomic absorption spectrophotometer. Here, when dispersion of titanium oxide was confirmed in the extract after extraction with 0.5 N hydrochloric acid, titanium oxide particles were precipitated using a centrifuge. Next, only the supernatant was recovered by the gradient method, and the same operation was performed. By these operations, the titanium element soluble in the polyester added as a catalyst can be quantified even if the sample contains titanium oxide. Moreover, when content was less than the measurement limit of less than 1 ppm, it described as "ND".

(H) Yarn-making property, pack pressure increase during filtration:
In order to evaluate coarse particles in the polyester composition, the filtration pressure increase rate was evaluated as follows. A polymer quantitative supply device was attached to the molten polymer outlet side of a small single screw type extruder, and two 2400 mesh wire mesh filters with an inner diameter of 64 mmφ were attached to the outlet side. Next, the temperature of the molten polyester is controlled to be constant at 290 ° C., and the polymer is continuously filtered for 10 hours so that the polyester flow rate is 33.3 g / min. The average value of the pressure increase values on the filter entrance side at this time was defined as the filtration pressure increase rate (pack pressure increase).

[Example 1]
In an esterification reaction vessel, 86 parts of terephthalic acid and 40 parts of ethylene glycol were subjected to an esterification reaction according to a conventional method to obtain an oligomer. To this oligomer, 86 parts of terephthalic acid and 40 parts of ethylene glycol were continuously supplied over 65 minutes, and an esterification reaction was carried out at 245 ° C. Then, 0.045 part of antimony trioxide was added and 20 minutes later, an oligomer having an equimolar amount equal to the amount of oligomer produced from the additionally supplied terephthalic acid and ethylene glycol was fed to the polycondensation reaction tank. Immediately after completion of the liquid feeding, 0.5 mol% of calcium acetate with respect to the acid component in the polymer was added to the polycondensation reaction tank. After 5 minutes, 0.6 mol% of phenylphosphonic acid was added to the polycondensation reaction tank based on the acid component in the polymer. Thereafter, the temperature was raised to 290 ° C., and a polycondensation reaction was performed at a high vacuum of 0.03 kPa or less to obtain a polyester chip having an intrinsic viscosity of 0.64 dL / g.
This chip was dried at 140 ° C. for 6 hours, and melt-spun at 290 ° C. using a spinneret having a hole diameter of 0.3 mm (circular) and 36 holes. The obtained undrawn yarn was drawn 3.5 times to obtain a drawn yarn of 83 dtex / 36 fil.

The obtained drawn yarn was subjected to S twist 2500 T / m or Z twist 2500 T / m strong twist, and then subjected to heat treatment at 80 ° C. for 30 minutes to perform twisting to obtain S twist strong twist yarn and Z twist strong twist yarn. . A satin georgette woven fabric was woven by alternately arranging two S twists and two Z twists with a warp density of 47 strands / cm and a weft density of 32 strands / cm. The obtained raw machine was relaxed using a rotary washer at a boiling temperature for 20 minutes and then subjected to embossing, and then subjected to presetting according to a conventional method, and then the boiling temperature in a sodium hydroxide aqueous solution having a concentration of 3.5% by weight. To obtain a fabric having a weight loss rate of 20% by weight. The fiber surface of the weight-reduced fabric has a large number of micropores arranged in the fiber axis direction and having a minor axis of 0.1 to 0.5 μm and a major axis of 0.5 to 1.5 μm. Confirmed with a microscope.
The fabric after the alkali weight reduction is dyed for 60 minutes at 130 ° C. using Dianix Black HG-FS (Mitsubishi Chemical) 15% owf, and then an aqueous solution containing 1 g / L of sodium hydroxide and 1 g / L of hydrosulfite. Then, it was reduced and washed at 70 ° C. for 20 minutes to obtain a black dyed fabric. The results are shown in Table 1.

[Examples 2 to 5, Comparative Examples 1 to 4]
In Example 1, it carried out like Example 1 except having changed the addition amount of calcium acetate and phenylphosphonic acid into the quantity of Table 1. The results are shown in Table 1.

[Comparative Examples 5 and 6]
In Example 1, it carried out similarly to Example 1 except having changed into manganese acetate and zinc acetate instead of calcium acetate. The results are shown in Table 1.

[Comparative Examples 7 and 8]
In Example 1, it implemented like Example 1 except having changed into the regular phosphoric acid and the trimethyl phosphate instead of phenylphosphonic acid. The results are shown in Table 1.

[Comparative Example 9]
In an esterification reaction vessel, 86 parts of terephthalic acid and 40 parts of ethylene glycol were subjected to an esterification reaction according to a conventional method to obtain an oligomer. To this oligomer, 86 parts of terephthalic acid and 40 parts of ethylene glycol were continuously supplied over 65 minutes, and an esterification reaction was carried out at 245 ° C. Then, 0.045 part of antimony trioxide was added and 20 minutes later, an oligomer having an equimolar amount equal to the amount of oligomer produced from the additionally supplied terephthalic acid and ethylene glycol was fed to the polycondensation reaction tank. After completion of the liquid feeding, 0.53 parts of calcium acetate (0.5 mol% with respect to terephthalic acid) and 0.57 parts of phenylphosphonic acid (1.2 times mol with respect to calcium acetate) were added to 6.8 parts. A clear solution of calcium phenylphosphonate prepared by reacting in ethylene glycol at a temperature of 120 ° C. for 60 minutes was added. Thereafter, the temperature was raised to 290 ° C., and a polycondensation reaction was performed at a high vacuum of 0.03 kPa or less to obtain a polyester chip having an intrinsic viscosity of 0.64 dL / g.
The obtained polyester was subjected to spinning, weight loss and dyeing treatment in the same manner as in Example 1. The results are shown in Table 1.

[Reference Example 1: Transesterification (described in Patent Document 6)]
Methanol produced by charging 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 0.06 parts by weight of calcium acetate monohydrate in a transesterification reaction tank and raising the temperature from 140 ° C. to 230 ° C. in a nitrogen gas atmosphere. Was transesterified while distilling out of the system. Subsequently, 0.2 parts of trimethyl phosphate (0.25 mol% with respect to dimethyl terephthalate) and 0.35 parts of calcium acetate monohydrate (1/2 mol with respect to trimethyl phosphate) were added. Add a clear solution of calcium phosphate diester calcium salt prepared by reaction for 60 minutes at 120 ° C in 8 parts ethylene glycol, then add 0.04 parts by weight antimony trioxide and transfer to polycondensation reactor. did. Thereafter, the temperature was raised to 290 ° C., and a polycondensation reaction was performed at a high vacuum of 0.03 kPa or less to obtain a polyester chip having an intrinsic viscosity of 0.64 dL / g.
The obtained polyester was subjected to spinning, weight loss and dyeing treatment in the same manner as in Example 1. The results are shown in Table 1. The polyester content is high and the heat resistance of the polyester composition is deteriorated. Was not good.

  The polyester fiber obtained from the polyester composition obtained in the Examples of the present application has a lot of fine pores on the fiber surface by performing a weight loss treatment (alkali weight loss) with an aqueous basic compound solution, and a color depth by performing a dyeing treatment. And it comes to show clarity. However, even if the fibers obtained by the comparative example were subjected to the same treatment, the number of micropores was small, or coarse pores were slightly fewer, fewer, or slightly larger, and the fibers were dyed. However, polyester fibers exhibiting color depth and clarity were not obtained.

  According to the present invention, since unique micropores can be easily formed on the surface of the fiber, a polyester fiber which can exhibit improved color depth and sharpness when dyed is provided.

Claims (2)

Manufactured in a manufacturing process that has an esterification reaction from a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol, and a step of polycondensation reaction on the oligomer. In the method for producing a polyester composition,
An alkali metal atom and / or an alkaline earth metal compound and a phosphorus compound represented by the following general formula (I) are used in an amount of 0.1 to 2 with respect to the dicarboxylic acid component. A method for producing a polyester composition, comprising adding in a range of 0.0 mol% and adding a phosphorus compound so as to satisfy the following formula (1).
[In the above formula (I), Ar represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, and R ¹ represents a hydrogen atom or an OR ² group. R ² is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an unsubstituted or substituted 7 to 20 carbon atoms A benzyl group having a carbon atom is represented. ]
0.5 ≦ P / M ≦ 2.0 (1)
[In the above formula (1), P represents the molar amount of phosphorus atom by addition of phosphorus compound, M is the molar amount of alkali metal atom and / or alkali metal atom by addition of alkali metal compound and / or alkaline earth metal compound. Represents. ]   When producing a polyester composition, an alkali metal compound and / or an alkaline earth metal compound and a phosphorus compound are individually reacted without being added to the step of forming an oligomer and / or the step of performing a polycondensation reaction. It adds to the manufacturing process of polyester to the manufacturing method of the polyester composition of Claim 1 characterized by the above-mentioned.