JP4700336B2 - Copolyester composition, method for producing the same, and fiber - Google Patents

Description

  The present invention relates to a copolymerized polyester composition, a method for producing the same, and a fiber. More specifically, a copolyester composition having the performance that the content of a metal element having a true specific gravity of 5.0 or more, particularly antimony and germanium, is extremely small, excellent in hue, and excellent in moldability during fiber production. The manufacturing method and fiber are related.

  Polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate are widely used in fibers, films or other molded products because of their excellent mechanical, physical and chemical performance. ing. In particular, polyethylene terephthalate is used in a very wide range of applications because of its characteristics and price.

  Polyesters typified by polyethylene terephthalate have been modified in various ways depending on the application, and copolyesters obtained by copolymerizing various components are widely known. Polyethylene terephthalate usually used for obtaining such a copolyester is usually obtained by directly esterifying terephthalic acid and ethylene glycol, for example, or by reacting a lower alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol. Transesterification is performed, or terephthalic acid and ethylene oxide are reacted to produce an ethylene glycol ester of terephthalic acid and / or a low polymer thereof. Next, this reaction product is produced by heating under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a predetermined degree of polymerization is reached. At any stage of this production process, terephthalate, which is a copolymerization component, is produced. Copolyesters are produced by adding dicarboxylic acid components other than acids, glycol components other than ethylene glycol, and the like.

  In these polyesters, it is well known that the reaction rate and the quality of the resulting polyester greatly depend on the type of catalyst used in the polycondensation reaction stage. As a result of conventional studies on this point, as a polycondensation catalyst for polyethylene terephthalate, an antimony compound is most widely used because it has excellent polycondensation catalyst performance and a polyester having a good hue. .

  However, when a polyester using an antimony compound as a polycondensation catalyst is continuously melt-spun for a long time to obtain a fiber, foreign matter (hereinafter sometimes referred to simply as a base foreign matter) adheres to the periphery of the base hole. Accumulation and bending of the molten polymer flow (bending) may occur. As a result, there is a problem of formability that fluff and / or yarn breakage occurs in the spinning and drawing processes.

  In addition, germanium compounds are generally used as polyester catalysts for PET bottles, but germanium is a rare metal and is expensive, so the price of the resulting product becomes high. Yes.

It has also been proposed to use a titanium compound such as titanium tetrabutoxide as a polycondensation catalyst other than such antimony compounds and germanium compounds. When such a titanium compound is used, the above-described problem of formability due to the accumulation of foreign matter in the die can be solved. However, there is a new problem that the obtained polyester itself is colored yellow and that the heat stability of the melt is poor. In order to solve this coloring problem, it is a common practice to suppress yellowishness by adding a cobalt compound to polyester. Certainly, the hue (b ^* value) of the polyester can be improved by adding a cobalt compound. However, the addition of a cobalt compound further lowers the melt heat stability of the polyester and tends to cause degradation of the polymer. There is a problem.

In addition, it is disclosed that titanium hydroxide or α-titanic acid is used as a polyester production catalyst as another titanium compound (see, for example, Patent Document 1 and Patent Document 2). However, in the former method, powdering of titanium hydroxide is not easy, whereas in the latter method, α-titanic acid is likely to be altered, so that storage and handling are not easy. Accordingly, none of them are suitable for industrial use, and it is also difficult to obtain a polymer having a good hue (b ^* value).

  In order to solve such a problem, a product obtained by reacting a titanium compound with a specific phosphorus compound (see, for example, Patent Document 3 and Patent Document 4), or a titanium compound and a specific phosphorus compound are used. It is disclosed that an unreacted mixture or a reaction product (see, for example, Patent Document 5) is used as a catalyst for polyester production. Certainly, this method improves the melt heat stability of the polyester and greatly improves the hue of the resulting polymer. However, in these methods, the polymerization reaction rate during the production of the polyester is slow, so that the productivity of the polyester is slightly higher. Has the problem of being inferior.

  In order to improve the molding stability of the polyester, it is effective to not use an antimony compound as a catalyst as described above. However, in the method not using an antimony compound, the color (hue) of the yarn is lowered. Therefore, it could not be used in the past. Accordingly, there has been a demand for a polyester that does not use an antimony compound as a catalyst and is excellent in hue.

  On the other hand, a polyester kneaded with a dye has been disclosed as an attempt to improve the hue of the polyester (see, for example, Patent Documents 6 to 8), but the level of hue improvement has not been sufficient.

Japanese Patent Publication No. 48-2229 Japanese Patent Publication No. 47-26597 International Publication No. 01/00706 Pamphlet International Publication No. 03/008479 Pamphlet International Publication No. 03/027166 Pamphlet JP-A-3-231918 Japanese Patent Laid-Open No. 11-158257 Japanese Patent Laid-Open No. 11-158361

  An object of the present invention is to provide a copolymerized polyester composition having excellent hue and generating very little deposits on the die even when spinning continuously for a long time and having excellent moldability. Another object is to provide a copolyester composition having a clear appearance and capable of obtaining fibers with improved dyeability.

［上記式中、Ｒは水素又は炭素数１〜１０のアルキル基を表し、Ｘは水素、炭素数１〜１０のアルキル基又はスルホン酸アルカリ金属塩基を表し、Ｙは炭素数２〜１０のアルキレン基を表す。］ As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention. That is, the present invention provides a copolyester having a content of a metal element having a true specific gravity of 5.0 or more and 0 to 10 mass ppm or less, and having ethylene terephthalate repeating units of 50 mol% or more and less than 99.5 mol% in all repeating units. And a color coordinating polyester composition containing 0.1 to 10 mass ppm of the color adjusting agent based on the total mass of the copolyester composition, and the color adjusting agent is in a nitrogen atmosphere. A color-decreasing dye having a mass decrease starting temperature of 250 ° C. or higher when measured with a thermobalance at a temperature rising rate of 10 ° C./min is selected. When a visible light absorption spectrum in a wavelength range of 380 to 780 nm was measured for a chloroform solution having a mass ratio of 90:10 to 40:60 and an optical path length of 1 cm with respect to a chloroform solution having a concentration of 20 mg / L. There the maximum absorption wavelength in the range of 540～600Nm, and the ratio of absorbance at each of the following wavelength for absorbance at said maximum absorption wavelength satisfies all the following formulas (1) to (4),
A copolymer polyester composition in which the component copolymerized with the copolymer polyester corresponds to at least one of the dicarboxylic acids described in the following general formulas (I) to (III) , and fibers obtained by melt-molding the composition Thus, the above problem can be solved.
0.00 ≦ A ₄₀₀ / A _max ≦ 0.20 (1)
0.10 ≦ A ₅₀₀ / A _max ≦ 0.70 (2)
0.55 ≦ A ₆₀₀ / A _max ≦ 1.00 (3)
0.00 ≦ A ₇₀₀ / A _max ≦ 0.05 (4)
[In the above formula, A ₄₀₀ , A ₅₀₀ , A ₆₀₀ and A ₇₀₀ are the absorbance in the visible light absorption spectrum at wavelengths of 400 nm, 500 nm, 600 nm and 700 nm, respectively, and A _max is the absorbance in the visible light absorption spectrum at the maximum absorption wavelength. Represents. ]

[In the above formula, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, X represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkali metal sulfonate group, and Y represents an alkylene having 2 to 10 carbon atoms. Represents a group. ]

  According to the present invention, it is possible to eliminate the deterioration of hue, which is a drawback of polyesters that do not use Sb or Ge catalyst, while maintaining the excellent properties of polyesters. Further, it is possible to provide a polyester having a very small amount of deposits on the die and having excellent moldability.

  The present invention will be described in detail below. The copolymerized polyester in the present invention is an ethylene terephthalate repeating unit obtained by a polycondensation reaction of terephthalic acid or an ester-forming derivative thereof and an ethylene glycol component, with 50 mol% or more and less than 99.5 mol% in all repeating units. It is a certain polyester. That is, with the copolymerized polyester of the present invention, components other than the ethylene terephthalate repeating unit must be copolymerized in an amount of 0.5 mol% or more and less than 50 mol%.

  The metal element having a true specific gravity of 5.0 or more in the present invention is derived from a metal compound usually contained in a catalyst, a metal color adjuster, a matting agent and the like contained in a polyester. Specifically, antimony, germanium, manganese, cobalt, cerium, tin, zinc, lead, cadmium, and the like are applicable. On the other hand, titanium, aluminum, calcium, magnesium, sodium, potassium, and the like do not correspond to a metal having a true specific gravity of 5.0 or more.

  In the copolymerized polyester composition of the present invention, the content of a metal element having a true specific gravity of 5.0 or more needs to be 0 to 10 ppm by mass or less. The characteristics and properties vary depending on the type of metal contained. For example, when the content of antimony metal is more than 10 ppm by mass, it becomes a foreign substance during melt spinning or film formation and adheres to the periphery of the die or die. This will adversely affect the continuous formability of the period. In the case of germanium metal, since it is expensive per se, the content of the copolyester is undesirably increased when the content is increased. Further, in the case of metals such as lead and cadmium, since the metal element itself is toxic, it is not preferable that it is contained in a large amount in the copolyester. The content of the metal element having a true specific gravity of 5.0 or more is preferably 0 to 7 mass ppm or less, and more preferably 0 to 5 mass ppm or less.

The copolymerized polyester composition of the present invention needs to contain 0.1 to 10 mass ppm of the color adjusting agent based on the total mass. The color adjusting agent represents an organic polyaromatic ring dye or pigment. Specific examples thereof include a blue color adjusting dye, a purple color adjusting dye, a red color adjusting dye, and an orange color adjusting dye as described later. These may be used alone or in combination of two or more. It is preferable to use a plurality of types in combination in terms of easily satisfying the requirements regarding the visible light absorption spectrum as described later. Further, when the visible light absorption spectrum in the wavelength range of 380 to 780 nm was measured for a chloroform solution having a concentration of 20 mg / L at a light path length of 1 cm, the color adjusting agent had a maximum absorption wavelength in the range of 540 to 600 nm and the maximum absorption. The ratio of the absorbance at each wavelength below to the absorbance at the wavelength needs to satisfy all of the following formulas (1) to (4).
0.00 ≦ A ₄₀₀ / A _max ≦ 0.20 (1)
0.10 ≦ A ₅₀₀ / A _max ≦ 0.70 (2)
0.55 ≦ A ₆₀₀ / A _max ≦ 1.00 (3)
0.00 ≦ A ₇₀₀ / A _max ≦ 0.05 (4)
[In the above formula, A ₄₀₀ , A ₅₀₀ , A ₆₀₀ and A ₇₀₀ are the absorbance in the visible light absorption spectrum at wavelengths of 400 nm, 500 nm, 600 nm and 700 nm, respectively, and A _max is the absorbance in the visible light absorption spectrum at the maximum absorption wavelength. Represents. ]

  Here, the visible light absorption spectrum is a spectrum usually measured by a spectrophotometer, but the maximum absorption wavelength of the visible light absorption spectrum of the color matching agent solution contained in the copolymerized polyester composition of the present invention is less than 540 nm. In the case of, the redness of the obtained copolymerized polyester composition becomes strong, and when it exceeds 600 nm, the blueness of the obtained copolymerized polyester composition becomes strong, which is not preferable. The range of the maximum absorption wavelength is preferably 545 to 595 nm, and more preferably 550 to 590 nm.

In addition, when a visible light absorption spectrum was measured at a light path length of 1 cm for a chloroform solution having a concentration of 20 mg / L of the color adjusting agent contained in the copolymerized polyester composition of the present invention, each wavelength shown above relative to the absorbance at the maximum absorption wavelength. When the ratio of the absorbance at 1 is out of any one of the above formulas (1) to (4), the resulting copolymerized polyester composition is unfavorably colored. It is more preferable to satisfy the above formulas (1) to (4), and more preferably to satisfy any one or more of the following formulas (5) to (8), and further satisfy all the following formulas (5) to (8). Preferably it is.
0.00 ≦ A ₄₀₀ / A _max ≦ 0.15 (5)
0.30 ≦ A ₅₀₀ / A _max ≦ 0.60 (6)
0.60 ≦ A ₆₀₀ / A _max ≦ 0.95 (7)
0.00 ≦ A ₇₀₀ / A _max ≦ 0.03 (8)
[In the above formula, A ₄₀₀ , A ₅₀₀ , A ₆₀₀ and A ₇₀₀ are the absorbance in the visible light absorption spectrum at wavelengths of 400 nm, 500 nm, 600 nm and 700 nm, respectively, and A _max is the absorbance in the visible light absorption spectrum at the maximum absorption wavelength. Represents. ]

  Furthermore, when content of the above-mentioned color adjusting agent contained in the copolymerized polyester composition of the present invention is less than 0.1 mass ppm, the yellowness of the copolymerized polyester composition becomes strong. On the other hand, if it exceeds 10 ppm by mass, the brightness becomes weak and the blackness becomes strong visually, which is not preferable. The content of the color adjusting agent is preferably in the range of 0.3 mass ppm to 9 mass ppm, and more preferably in the range of 0.5 mass ppm to 8 mass ppm.

The color adjusting agent used in the present invention is selected from color adjusting dyes having a mass decrease starting temperature of 250 ° C. or higher when measured with a thermobalance in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. It is preferable. Here, the mass decrease start temperature when measured with a thermobalance is the mass decrease start temperature (T ₁ ) described in JIS K-7120, and is a heat resistance index possessed by the color adjuster. Become. When the mass decrease starting temperature is less than 250 ° C., the heat resistance of the color adjusting agent is insufficient, which is not preferable because it causes coloring of the finally obtained copolymer polyester composition. The mass decrease starting temperature is more preferably 300 ° C. or higher. More preferably, the copolymerized polyester composition does not decompose at a temperature at which it is in a molten state.

  As described above, the copolymerized polyester of the present invention requires that components other than the ethylene terephthalate repeating unit be copolymerized in an amount of 0.5 mol% or more and less than 50 mol% in all repeating units. Here, the components other than the ethylene terephthalate repeating unit copolymerized with the copolymerized polyester of the present invention are preferably compounds represented by the following general formulas (I) to (VI). Preferably, the copolymerization component corresponds to at least one of the dicarboxylic acids described in the following general formulas (I) to (III). Moreover, it is also preferable that the copolymerization component corresponds to at least one of glycols described in the following general formulas (IV) to (VI).

［上記式中、Ｒは水素又は炭素数１〜１０のアルキル基を表し、Ｘは水素、炭素数１〜１０のアルキル基又はスルホン酸アルカリ金属塩基を表し、Ｙは炭素数２〜１０のアルキレン基を表す。］

[In the above formula, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, X represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkali metal sulfonate group, and Y represents an alkylene having 2 to 10 carbon atoms. Represents a group. ]

［上記式中、Ｚは炭素数３〜１０の脂肪族基を表し、ｌは２から５の整数、ｍ、ｎはそれぞれ独立した１から５の整数を表し、Ａｒはｐ，ｍ，ｏ−フェニレン基、４，４’−イソプロピリデンジフェニレン基、４，４‘−スルホニルジフェニレン基を表す。］

[In the above formula, Z represents an aliphatic group having 3 to 10 carbon atoms, l represents an integer of 2 to 5, m and n represent independent integers of 1 to 5, and Ar represents p, m, o- A phenylene group, a 4,4′-isopropylidenediphenylene group, and a 4,4′-sulfonyldiphenylene group are represented. ]

Here, the compounds represented by the above general formula (I) include isophthalic acid, isophthalic acid dimethyl ester or isophthalic acid diethyl ester, sodium sulfoisophthalic acid, sodium sulfoisophthalic acid dimethyl ester or sodium sulfoisophthalic acid diethyl ester, lithium sulfone Preferred examples include isophthalic acid, lithium sulfoisophthalic acid dimethyl ester or lithium sulfoisophthalic acid diethyl ester.

Examples of the compound represented by the general formula (II) include 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid dimethyl ester, and 2,6-naphthalenedicarboxylic acid diethyl ester.

  Examples of the compound represented by the general formula (III) include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, or dimethyl ester or diethyl ester thereof, and particularly adipic acid, sebacic acid, or These dimethyl esters are preferably exemplified.

  Examples of the compound represented by the general formula (IV) include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and decamethylene glycol, and particularly preferably trimethylene glycol or tetramethylene glycol.

  Examples of the compound represented by the general formula (V) include diethylene glycol, triethylene glycol, tetraethylene glycol and the like, and particularly preferred is diethylene glycol. Here, about 0.7 to 4.5 mol% of diethylene glycol is usually copolymerized in polyethylene terephthalate by side reaction during the polymerization reaction, but when diethylene glycol is copolymerized as the copolymerized polyester of the present invention. Uses the total amount of diethylene glycol produced by this side reaction as a copolymerization component.

  Examples of the compound represented by the general formula (VI) include 1,4-bis (2-hydroxyethoxybenzene), 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, 4,4 ′. Preferred examples include -bis (2-hydroxyethoxy) diphenyl sulfone.

  These copolymer components are usually copolymerized in an appropriate amount according to the purpose in order to improve the disadvantages of polyethylene terephthalate. However, if the copolymerization amount is less than 0.5 mol%, the effect of sufficient improvement is not manifested. If it is at least mol%, the characteristics such as high heat resistance, light resistance and solvent resistance inherent to polyethylene terephthalate are lost, which is not preferable.

  The preferred copolymerization amount of the copolymer component varies depending on the component, but among the compounds represented by the general formula (I), the compound having an alkali metal sulfonate group and the general formula (III). In the case of a compound, the range of 1.0 mol% or more and 20 mol% or less is preferable, and the range of 1.5 mol% or more and 10 mol% or less is more preferable. About other compounds, the range of 3 mol% or more and 40 mol% or less is preferable, and the range of 5 mol% or more and less than 20 mol% is still more preferable.

  The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the copolymerized polyester composition of the present invention is not particularly limited, but can be usually used in resin molded products such as fibers, films, and bottles. Preferably, it is in the range, specifically in the range of 0.40 to 1.00. In addition, it is also preferable to increase the intrinsic viscosity of the copolyester composition by solid phase polymerization.

The hue of the copolyester composition of the present invention is not particularly limited, but if the color adjusting agent to be used in the present invention is not added, the hue of the copolyester composition obtained is yellowish. Unfavorable hue. The color of the copolyester composition is such that the color a ^* value in the L ^* a ^* b ^* color system after crystallization proceeds by heat treatment at 140 ° C. for 2 hours is −9 to 0, and the color b ^* value is − It is preferable that it exists in the range of 2-10. The color value varies depending on the amount of the color adjusting agent to be contained. When the color a ^* value is smaller than −9, the copolyester composition has a strong green taste, and when it is larger than 0, the redness is red. It becomes strong and is not preferable. Further, when the color b ^* value is less than −2, the copolyester composition is not preferable because the blueness is strong and when it is more than 10, the yellowness becomes strong.

  The copolymerized polyester composition according to the present invention contains a small amount of additives as necessary, for example, an antioxidant, a solid phase polymerization accelerator, a fluorescent whitening agent, an antistatic agent, an antibacterial agent, an ultraviolet absorber, a light stabilizer Further, a heat stabilizer, a light shielding agent, a matting agent, or the like may be included.

  As a method for producing a copolyester in the present invention, a conventionally known polyester production method is used. That is, first, terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of a terephthalic acid component such as dimethyl terephthalate (hereinafter sometimes referred to as DMT) is transesterified with ethylene glycol to produce a dicarboxylic acid. A glycol ester of an acid and / or a low polymer thereof is produced. As for the copolymer component, when a lower alkyl ester of a dicarboxylic acid component is used, it can be used when it is added at the same time as the lower alkyl ester of terephthalic acid to cause an ester exchange reaction. In the case of a free dicarboxylic acid component or glycol component as a copolymer component, it may be added either directly before the esterification reaction or transesterification reaction, or after the completion of the reaction, but the free dicarboxylic acid component is transesterified. When using for reaction, it is better to add after completion | finish of transesterification. Then, the reaction product is heated under reduced pressure in the presence of a polycondensation catalyst and subjected to a polycondensation reaction until a predetermined polymerization degree is obtained, thereby producing a desired copolymerized polyester.

  More specifically, the polycondensation catalyst used in producing the copolyester is preferably a titanium compound and / or an aluminum compound. Here, it does not specifically limit as a titanium compound, A titanium compound common as a polycondensation catalyst of polyester, for example, titanium acetate, tetra-n-butoxy titanium, etc. are mentioned. More preferable as the titanium compound is a titanium compound represented by the following general formula (VII), or a titanium compound represented by the general formula (VII) and an aromatic polyvalent carboxylic acid represented by the following general formula (VIII) or anhydride thereof. The product obtained by reacting the product is used.

［上記式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ互いに独立に、炭素数１〜１０のアルキル基又はフェニル基を示し、ｍは１〜４の整数を示し、かつｍが２、３又は４の場合、２個、３個又は４個のＲ^２及びＲ^３は、互いに異なっていてもよい。］

[In the above formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, m represents an integer of 1 to 4, and m is 2 In the case of 3 or 4, 2, 3 or 4 R ² and R ³ may be different from each other. ]

［上記式中、ｑは２〜４の整数を表わす。］

[In the above formula, q represents an integer of 2 to 4. ]

  On the other hand, the aluminum compound is not particularly limited, but is preferably an organoaluminum compound from the viewpoint of catalytic activity. Among them, aluminum acetylacetonate is preferable because it is stable and easy to handle. In addition, these titanium compounds and aluminum compounds may be used alone or in combination of both compounds, or two or more of each compound may be used in combination. It is particularly preferable to use it. Among them, the most preferable is a compound represented by the above general formula (VII), or a compound represented by the above general formula (VII) and an aromatic polyvalent carboxylic acid represented by the above general formula (VIII) or an anhydride thereof. The reacted product is used alone.

Among the titanium compounds represented by the general formula (VII), tetraalkoxide titanium and / or tetraphenoxide titanium are particularly limited as long as R ^{1 to} R ⁴ are alkyl groups or phenyl groups having 1 to 10 carbon atoms. Although not, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetraethoxy titanium, tetraphenoxy titanium, or the like is preferably used. In addition, as the aromatic polyvalent carboxylic acid represented by the general formula (VIII) to be reacted with such a titanium compound or an anhydride thereof, phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid, or an anhydride thereof may be used. Preferably used. When the titanium compound and the aromatic polyvalent carboxylic acid or anhydride thereof are reacted, all or part of the aromatic polyvalent carboxylic acid or anhydride thereof is dissolved in a solvent, and the titanium compound is dropped into this. What is necessary is just to make it react for 30 minutes or more at the temperature of 0-200 degreeC. Moreover, what is necessary is just to add the remaining aromatic polyhydric carboxylic acid or its anhydride after dripping a titanium compound as needed.

As described above, the copolyester composition of the present invention preferably uses a titanium compound and / or an aluminum compound as a polycondensation catalyst. However, in order to further improve heat resistance and hue, a phosphorus compound is used as a stabilizer. It is preferable to use together. Although there is no restriction | limiting in particular as this phosphorus compound, Preferably phosphoric acid, phosphorous acid, phosphonic acid, or phosphinic acid or these alkyl, aryl ester, and a phosphono acetate type compound are especially preferable. The phosphorus compound may be added to the copolymerized polyester composition at any time after the transesterification or esterification reaction is substantially completed, but usually the esterification reaction or transesterification reaction is completed. It is preferable to add immediately afterward and to carry out polycondensation reaction thereafter.

  Furthermore, it is preferable that the manufacturing method of the copolyester composition of this invention is manufactured by adding a color adjusting agent in the arbitrary steps of the copolyester manufacturing process mentioned above. Among them, it is more preferable that the color adjusting agent is added at an arbitrary stage until the polycondensation reaction step in the copolymer polyester production step is completed. In particular, it is most preferable to add the color adjusting agent after completion of the esterification reaction or transesterification reaction.

In the method for producing a copolyester composition of the present invention, a blue color adjusting dye and a purple color adjusting dye are used in combination in a mass ratio of 90:10 to 40:60, or blue as a color adjusting agent. It is preferable to use the system color adjusting dye and the red or orange color adjusting dye in a mass ratio of 98: 2 to 80:20. Here, the blue color-modifying dye is generally indicated as “Blue” among commercially available color-adjusting dyes, and specifically, the maximum absorption in the visible light absorption spectrum in the solution. The wavelength is about 580 to 620 nm. Similarly, the purple color-modifying dye is the one described as “Violet” among commercially available color-adjusting dyes. Specifically, the maximum absorption wavelength in the visible light absorption spectrum in the solution is The thing in about 560-580 nm is shown. The red color-modifying dyes are those listed as “Red” among commercially available color-adjusting dyes. Specifically, the maximum absorption wavelength in the visible light absorption spectrum in the solution is 480 to 480. It is about 520 nm. The orange color-modifying dyes are those listed as “Orange” among commercially available color-adjusting dyes.

  As these color adjusting dyes, oil-soluble dyes are particularly preferable. As specific examples, blue color adjusting dyes include C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 45 (Telasol Blue RLS), C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 87, C.I. I. Solvent Blue 94 and the like. Examples of purple color adjusting pigments include C.I. I. Solvent Violet 8, C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Violet 21, C.I. I. Solvent Violet 27, C.I. I. Solvent Violet 28, C.I. I. Solvent Violet 36 etc. are mentioned. Examples of red color adjusting pigments include C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27, C.I. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Solvent Red 100, C.I. I. Solvent Red 109, C.I. I. Solvent Red 111, C.I. I. Solvent Red 121, C.I. I. Solvent Red 135, C.I. I. Solvent Red 168, C.I. I. Solvent Red 179 etc. are illustrated. Examples of the orange color adjusting dye include C.I. I. Solvent Orange 60 etc. are mentioned.

Here, when the blue color adjusting dye and the purple color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than the mass ratio 90:10, the color a of the copolymer polyester composition to be obtained is a. ^{* If the} value is small and green, and the mass ratio of the blue color - modifying dye is smaller than 40:60, the color a ^* value becomes large and red is not preferable. Similarly, in the case where a blue color adjusting dye and a red or orange color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than 98: 2, the resulting copolymerized polyester composition exhibit green color a ^* value becomes small, 80: If the mass ratio of the blue orthochromatic dye than 20 is small, undesirably coming exhibiting red color a ^* value becomes large. The color adjusting dye is a combination of a blue color adjusting dye and a purple color adjusting dye in a mass ratio of 80:20 to 50:50, or a blue color adjusting dye and a red or orange color. It is more preferable to use the color adjusting dye in a mass ratio of 95: 5 to 90:10.

Further, the production method for producing the copolyester fiber of the present invention is not particularly limited, and a conventionally known melt spinning method is used. For example, it is preferable to produce the dried copolyester composition by melt spinning at a temperature in the range of 270 ° C. to 300 ° C., and the spinning speed of the melt spinning is preferably 400 to 5000 m / min. When the spinning speed is in this range, the strength of the obtained fiber is sufficient, and the winding can be stably performed. Further, the shape of the die used at the time of spinning is not particularly limited, and any of circular, irregular, solid and hollow can be adopted. Further, the drawn yarn can be obtained by drawing the undrawn polyester fiber once or by continuously drawing it without winding. Furthermore, since the copolymerized polyester composition of the present invention has characteristics not found in conventional polyesters due to various copolymerization components, it can also be used as a composite fiber.

The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. The intrinsic viscosity, hue, titanium content, and the layer of deposits generated on the spinneret were measured by the methods described below.
(A) Intrinsic viscosity:
A dilute solution obtained by dissolving the copolyester composition chip in orthochlorophenol at 100 ° C. for 60 minutes was determined from the value measured at 35 ° C. using an Ubbelohde viscometer.
(A) Diethylene glycol (DEG) content:
The copolymerized polyester composition chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was measured using gas chromatography (HP Hewlett-Packard (HP 6850)). .
(C) Copolymerization component content (copolymerization ratio)
A sample of the copolyester composition is dissolved in a deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent, and then subjected to nuclear magnetic resonance spectrum using JEOL A-600 superconducting FT-NMR manufactured by JEOL Ltd. ( ¹ H-NMR) was measured, and the copolymerization component content was quantified from the spectrum pattern according to a conventional method.
(D) Hue (L ^* value, a ^* value, b ^* value):
・ Chip:
The copolymerized polyester composition chip was melted at 285 ° C. under vacuum for 10 minutes, and after this was formed into a plate having a thickness of 3.0 ± 1.0 mm on an aluminum plate, it was immediately cooled in ice water, and the plate was cooled to 140 ° C. Dry crystallization treatment was performed for 2 hours. Then, it placed on the white standard plate for color difference adjustment, and measured Hunter L ^* and b ^* of the plate surface using Minolta Co., Ltd. Hunter type color difference meter (CR-200 type). L ^* indicates lightness, and the larger the value, the higher the lightness, and b ^{* the} greater the value, the greater the degree of yellowing. Other detailed operations were performed according to JIS Z-8729.
·fiber:
After making the fiber into a tubular knitting by a conventional method, four knitted fabrics were overlapped and measured using a Hunter type color difference meter (CR-200 type) manufactured by Minolta Co., Ltd.
(E) Qualitative analysis of metal components with true specific gravity of 5.0 or more:
The copolymer polyester composition sample was mixed with ammonium sulfate, sulfuric acid, nitric acid, and perchloric acid, wet-decomposed at about 300 ° C. for 9 hours, diluted with distilled water, and then an ICP emission spectrometer (JY170 ULTRACE) manufactured by Rigaku Corporation. Qualitative analysis was conducted to confirm the presence or absence of a metal element having a true specific gravity of 5.0 or more. About the metal element by which presence of 1 mass ppm or more was confirmed, the element content was shown.
(F) Titanium, aluminum, antimony, phosphorus, manganese, calcium content:
The amount of aluminum element, antimony element, manganese element, and phosphorus element in the copolymerized polyester composition is a test molded body having a flat surface with a compression press machine after a granular polyester composition sample is heated and melted on a steel plate. Was prepared using a fluorescent X-ray apparatus (ZSX100e type, manufactured by Rigaku Corporation). Regarding the amount of titanium element soluble in the polyester in the copolymerized polyester composition, the sample in the copolymerized polyester composition was dissolved in orthochlorophenol, and then extracted with 0.5 N 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, even if the copolyester composition contains titanium oxide, it is possible to determine the amount of titanium element soluble in the polyester.
(G) Deposited layer generated on the spinneret (the height of foreign matter deposit):
The copolyester composition is made into a chip, melted at 290 ° C., discharged from a spinneret with a hole diameter of 0.15 mmφ and 12 holes, spun at 600 m / min for 2 days, and generated at the outer edge of the discharge outlet of the base The height of the deposit layer was measured. As the height of the adhered layer increases, bending tends to occur in the filamentous flow of the melted polyester composition, and the moldability of the polyester decreases. That is, the height of the deposit layer generated in the spinneret is an index of the moldability of the polyester.
(H) Mass reduction start temperature of color adjusting agent:
Using a TAS-200 thermobalance manufactured by Rigaku Denki Kogyo Co., Ltd., the temperature was measured in a nitrogen atmosphere at a heating rate of 10 ° C./min according to JIS K7120.

[Reference Example 1] Synthesis of Titanium Catalyst A Tetra-n-butoxytitanium is added to an ethylene glycol solution (0.2% by mass) of trimellitic anhydride in an amount of ½ mol with respect to trimellitic anhydride, and under normal pressure in air. And kept at 80 ° C. for 60 minutes. Thereafter, it was cooled to room temperature, and the produced catalyst was recrystallized with 10 times the amount of acetone. The precipitate was filtered through filter paper and dried at 100 ° C. for 2 hours to obtain the target compound. This is designated as titanium catalyst A.

[Reference Example 2] Visible light absorption spectrum measurement of color-adjusting agent (color-adjusting dye), preparation of color-adjusting agent The color-adjusting dye shown in Table 1 was made into a chloroform solution at a concentration of 20 mg / L at room temperature, and quartz having an optical path length of 1 cm. The cell was filled, and the control cell was filled with chloroform alone, and a visible light absorption spectrum in a visible light region of 380 to 780 nm was measured using a Hitachi spectrophotometer U-3010 type. In the case of mixing the two color adjusting dyes, the total concentration was 20 mg / L. The ratio of the absorbance at each wavelength of 400, 500, 600, and 700 nm to the maximum absorption wavelength and the absorbance at that wavelength was measured. Further, the thermal mass decrease start temperature of the powder color adjusting dye was measured. The results are shown in Table 1. In addition, when adding these color adjusters in the polyester production process in the Examples and Comparative Examples, the solution is dissolved or dispersed at a temperature of 100 ° C. so as to have a concentration of 0.1% by mass with respect to the glycol solution used as a raw material. Prepared.

[Example 1]
-Manufacture of copolymerized polyester composition chip In a mixture of 90 parts by mass of dimethyl terephthalate, 10 parts by mass of dimethyl isophthalate and 70 parts by mass of ethylene glycol, 0.016 parts of titanium catalyst A prepared in Reference Example 1 was subjected to a pressure reaction. Charged into a possible SUS container. The ester exchange reaction was performed while increasing the pressure from 140 ° C. to 240 ° C. under a pressure of 0.07 MPa, and then 0.023 parts by mass of triethylphosphonoacetate was added to complete the ester exchange reaction.
Thereafter, 0.3 parts of a 0.1% by weight ethylene glycol solution of the color adjusting agent A shown in Table 1 and 1.5 parts by weight of 20% by weight ethylene glycol of titanium dioxide were added to the reaction product and transferred to a polymerization vessel. The temperature was raised to 0 ° C., and a polycondensation reaction was performed in a high vacuum of 30 Pa or less to obtain a copolyester composition having an intrinsic viscosity of 0.65 and a diethylene glycol content of 1.7 mol%. Furthermore, it was made into a chip according to a conventional method. The results are shown in Tables 2 and 3.
-Manufacture of copolyester fiber After the chip is dried at 140 ° C for 5 hours, a raw yarn of 333 dtex / 36 fil is produced at a spinning temperature of 285 ° C and a winding speed of 400 m / min, and is stretched 4.0 times to 83.25 dtex / A 36 fil drawn yarn was obtained. The obtained drawn yarn was further knitted into a cylinder by a conventional method. The results are shown in Table 4.

[ Reference Example 2, Example 3-5 , Comparative Example 1]
In Example 1, it implemented like Example 1 except having changed the copolymerization component and the color adjusting agent so that it might become the kind and quantity which are shown in Table 2. The results are shown in Tables 3 and 4.

[Example 6]
In Example 1, 100 parts by mass of dimethyl terephthalate is used, dimethyl isophthalate is not used, 60 parts by mass of ethylene glycol is used, and the compounds shown in Table 2 are used as copolymerization components. The same procedure as in Example 1 was performed except that the amount was adjusted to be a copolymerization amount. The results are shown in Tables 3 and 4.

[Example 7-9]
In Example 6, it implemented like Example 6 except having changed the copolymerization component and the color adjusting agent so that it might become the kind and quantity which are shown in Table 2. The results are shown in Tables 3 and 4.

[ Example 10 ]
To a mixture of 90 parts by mass of dimethyl terephthalate, 10 parts by mass of dimethyl isophthalate and 70 parts by mass of ethylene glycol, 0.063 parts by mass of calcium acetate monohydrate was provided with a stirrer, a rectifying column and a methanol distillation condenser. The ester exchange reaction was carried out while charging the reactor and gradually raising the temperature from 140 ° C. to 240 ° C. while distilling methanol generated as a result of the reaction out of the system. Then, 0.045 mass part of 56 mass% phosphoric acid aqueous solution was added, and the transesterification reaction was terminated. Thereafter, 0.3 parts by mass of a 0.1% by mass ethylene glycol solution of the color adjusting agent A shown in Table 2 in the reaction product, 0.033 parts by mass of aluminum acetylacetonate, 1.5% by mass of 20% ethylene glycol of titanium dioxide. To a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation device, heated to 285 ° C., and subjected to a polycondensation reaction at a high vacuum of 30 Pa or less to obtain a copolymer polyester composition I got a thing. The obtained chip produced fibers in the same manner as in Example 1. The results are shown in Tables 2-4.

[Comparative Example 2]
To a mixture of 90 parts by weight of dimethyl terephthalate, 10 parts by weight of dimethyl isophthalate and 70 parts by weight of ethylene glycol, 0.032 parts by weight of manganese acetate tetrahydrate was provided with a stirrer, a rectifying column and a methanol distillation condenser. The ester exchange reaction was carried out while charging the reactor and gradually raising the temperature from 140 ° C. to 240 ° C. while distilling methanol generated as a result of the reaction out of the system. Thereafter, 0.02 part by mass of trimethyl phosphate was added to complete the transesterification reaction. Subsequently, the obtained reaction product was transferred to a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation apparatus, and 0.045 parts by mass of diantimony trioxide, 20% by mass of ethylene dioxide, 1.5% of ethylene glycol. Mass parts were added, the temperature was raised to 290 ° C., and a polycondensation reaction was performed in a high vacuum of 30 Pa or less to obtain a copolymerized polyester composition. The obtained chip produced fibers in the same manner as in Example 1. The results are shown in Tables 2-4.

According to the present invention, it is possible to eliminate the deterioration of hue, which has been a drawback of polyesters that do not use Sb or Ge catalyst, while maintaining the excellent properties of the copolyester. Further, it is possible to provide a copolyester composition having an extremely small amount of deposits on the die and having excellent moldability.

Claims (12)

A copolyester having a content of a metal element having a true specific gravity of 5.0 or more and 0 to 10 ppm by mass or less and having an ethylene terephthalate repeating unit of 50 mol% or more and less than 99.5 mol% in all repeating units, and a color adjuster. A copolyester composition comprising 0.1 to 10 ppm by weight of a color adjusting agent based on the total mass of the copolyester composition, and the temperature adjusting rate is 10 ° C. in a nitrogen atmosphere. Selected from color-matching dyes having a mass decrease starting temperature of 250 ° C. or higher when measured with a thermobalance under the conditions of / min., And a weight ratio of 90:10 between the blue color-adjusting dye and the purple color-adjusting dye. When the visible light absorption spectrum in the wavelength region of 380 to 780 nm is measured at a light path length of 1 cm with respect to a chloroform solution having a concentration of 20 mg / L, which is included in the range of ˜40: 60, the maximum absorption wavelength is In the range of 40～600Nm, and the ratio of absorbance at each of the following wavelength for absorbance at said maximum absorption wavelength satisfies all the following formulas (1) to (4),
A copolymerized polyester composition in which the component copolymerized with the copolymerized polyester corresponds to at least one of the dicarboxylic acids described in the following general formulas (I) to (III) .
0.00 ≦ A ₄₀₀ / A _max ≦ 0.20 (1)
0.10 ≦ A ₅₀₀ / A _max ≦ 0.70 (2)
0.55 ≦ A ₆₀₀ / A _max ≦ 1.00 (3)
0.00 ≦ A ₇₀₀ / A _max ≦ 0.05 (4)
[In the above formula, A ₄₀₀ , A ₅₀₀ , A ₆₀₀ and A ₇₀₀ each have a wavelength of 400 nm,
Absorbance in the visible light absorption spectrum at 500 nm, 600 nm and 700 nm, and A _max represents the absorbance in the visible light absorption spectrum at the maximum absorption wavelength. ]

[In the above formula, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, X represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkali metal sulfonate group, and Y represents an alkylene having 2 to 10 carbon atoms. Represents a group. ] The copolymer polyester composition according to claim 1, wherein the component copolymerized with the copolymer polyester corresponds to at least one of the dicarboxylic acids described in the general formula (I) . The compound represented by the general formula (I) is isophthalic acid, isophthalic acid dimethyl ester or isophthalic acid diethyl ester, sodium sulfoisophthalic acid, sodium sulfoisophthalic acid dimethyl ester or sodium sulfoisophthalic acid diethyl ester, lithium sulfoisophthalic acid, Or the copolymer polyester composition of any one of Claims 1-2 which is lithium sulfoisophthalic-acid dimethyl ester or lithium sulfoisophthalic-acid diethyl ester. The copolymerized polyester composition according to any one of claims 1 to 3, wherein the component copolymerized with the copolymerized polyester corresponds to at least one of glycols represented by the following general formulas (IV) to (VI). .

[In the above formula, Z represents an aliphatic group having 3 to 10 carbon atoms, l represents an integer of 2 to 5, m and n each independently represents an integer of 1 to 5, Ar represents o, m, p- A phenylene group, a 4,4′-isopropylidenediphenylene group or a 4,4′-sulfonyldiphenylene group is represented. ] A compound having a sulfonic acid metal base or a compound represented by the above general formula (III) among the compounds represented by the above general formula (I) is copolymerized in an amount of 1.0 to 20 mol%. 5. The copolyester composition according to any one of 4 above. The copolymer polyester composition according to any one of claims 2 to 5, wherein the compound represented by the general formula (II) or (IV) to (VI) is copolymerized in an amount of 3.0 to 40 mol%. Hue copolyester composition 140 ° C., the color ^{a *} value in ^{the L} * ^a * ^{b *} color system after promoting crystallization by 2 hours heat treatment -9～0, color ^{b *} value -2 The copolyester composition according to any one of claims 1 to 6, which is in the range of 10.   The copolymerized polyester is produced by subjecting a dicarboxylic acid component and a glycol component to an esterification reaction or a transesterification reaction and a polycondensation reaction using a polycondensation catalyst containing a titanium compound. The manufacturing method of the copolyester composition of description. The copolymerized polyester according to claim 8, wherein the titanium compound is a product obtained by reacting a compound represented by the following general formula (VII) with an aromatic polycarboxylic acid or an anhydride represented by the following general formula (VIII). A method for producing the composition.

[In the above formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, m represents an integer of 1 to 4, and m is 2 In the case of 3 or 4, 2, 3 or 4 R ² and R ³ may be different from each other. ]

[In the above formula, q represents an integer of 2 to 4. ]   The method for producing a copolyester composition according to any one of claims 8 to 9, wherein the color adjusting agent is added at any stage until the polycondensation reaction step in the copolyester production process is completed.   The production of a copolyester composition according to any one of claims 8 to 10, wherein a blue color adjusting dye and a purple color adjusting dye are used in combination in a mass ratio of 90:10 to 40:60 as the color adjusting agent. Method.   A copolyester fiber obtained by melt spinning the copolyester composition according to any one of claims 1 to 7.