JP4673054B2 - Polyester composition and method for producing the same - Google Patents

Description

  The present invention relates to a matte polyester composition, a method for producing the same, and fibers. More specifically, the matte polyester composition has 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. About.

  Polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate are widely used in fibers, films and other molded products because of their excellent mechanical, physical and chemical performance. Yes.

  Polyesters typified by polyethylene terephthalate have been variously modified depending on the application. For example, by dispersing a matting agent typified by titanium oxide (see, for example, Patent Document 1), fibers, woven fabrics, etc. Reduce excess gloss. Furthermore, since the polyester fiber obtained by using this has functions such as soft texture, anti-permeability, anti-visibility, and ultraviolet transmission prevention, it is widely known mainly for clothing and interior use.

  In order to obtain such a matte polyester, a commonly used technique is, for example, a direct esterification reaction of an aromatic dicarboxylic acid and an alkylene glycol, or a lower alkyl ester of an aromatic dicarboxylic acid such as dimethyl aromatic dicarboxylate. And an alkylene glycol are transesterified or an aromatic dicarboxylic acid and ethylene oxide are reacted to produce an alkylene glycol ester of an aromatic dicarboxylic 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 polymerization degree is reached. A matting agent is added at any stage of this production process. It is manufactured by dispersing.

  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 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 an antimony compound is used as a polycondensation catalyst, if the polyester is melt-spun continuously for a long time, foreign matter (hereinafter, sometimes referred to simply as a base foreign matter) adheres and accumulates around the mouthpiece hole, resulting in a molten polymer. Flow bending phenomenon (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 expensive, so the problem is that the price of the resulting product increases. Yes.

Although it has been proposed to use a titanium compound such as titanium tetrabutoxide as a polycondensation catalyst other than the antimony compound, when such a titanium compound is used, the above-described molding caused by the deposition of foreign matter in the die However, there is a new problem that the obtained polyester itself is discolored in yellow and that the heat stability of the melt is poor. In order to solve the above-mentioned coloring problem, it is generally performed to add a cobalt compound to polyester to suppress yellowing. Certainly, the hue of the polyester (color b ^* value) can be improved by adding a cobalt compound, but by adding a cobalt compound, the thermal stability of the polyester is lowered and the polymer is easily decomposed. There is a problem.

Further, as other titanium compounds, it is disclosed that titanium hydroxide (for example, see Patent Document 2) or α-titanic acid (for example, see Patent Document 3) is used as a catalyst for polyester production. . However, in the former method, it is not easy to powder titanium hydroxide. On the other hand, in the latter method, α-titanic acid is easily altered, so that its storage and handling are not easy. In addition, it is difficult to obtain a polymer having a good hue (color b ^* value).

In addition, a product obtained by reacting a titanium compound and trimellitic acid (see, for example, Patent Document 4), and a product obtained by reacting a titanium compound and a phosphite (for example, patents). Reference 5)), each of which is disclosed as a catalyst for producing polyester. Certainly, according to this method, although the melt heat stability of polyester is improved to some extent, the hue (color b ^* value) of the obtained polymer is not sufficient, and therefore the polymer hue (color b ^* value) is not sufficient. Further improvement is desired.

  As described above, it is effective to use antimony as a catalyst in order to suppress the foreign matter from the die. However, in the method not using antimony, the color (hue) of the yarn is lowered, so that it is conventionally used. Could not be used. Therefore, there has been a demand for a polyester fiber that does not use antimony as a catalyst and is excellent in hue.

  On the other hand, as an attempt to improve the hue of the polyester, a polyester kneaded with a dye has been disclosed (see, for example, Patent Documents 6 to 10), but the level of hue improvement has not been sufficient.

JP-A-55-133431 Japanese Patent Publication No. 48-2229 Japanese Patent Publication No. 47-26597 Japanese Patent Publication No.59-46258 JP 58-38722 A JP-A-3-231918 Japanese Patent Laid-Open No. 11-158257 Japanese Patent Laid-Open No. 11-158361 JP 2004-204136 A JP 2004-204137 A

  The object of the present invention is to solve the above-mentioned problems of the prior art, excellent in hue, and generate very little amount of deposits (foreign matter foreign matter) even when spinning continuously through a spinneret for a long time. Another object of the present invention is to provide a matte polyester composition and fibers having an improved hue and having excellent performance of excellent moldability.

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 relates to a polyester composition containing 0.1 to 10 mass ppm of an organic color adjuster, wherein the polyester composition is ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, ethylene naphthalate, trimethylene naphthalate. A matting agent containing at least one polyester selected from the group consisting of phthalate and tetramethylene naphthalate and having an average particle size of 1.0 μm or less, based on the mass of the polyester composition, is 0. The content of the metal element that is contained in the range of 1 to 20.0 mass% and has a true specific gravity of 5.0 or more is 0 to 10 mass ppm or less based on the mass of the polyester composition ,
The organic color adjusting agent has a maximum absorption wavelength in a visible light absorption spectrum in a range of 380 to 780 nm measured in a chloroform solution at a concentration of 20 mg / L and an optical path length of 1 cm, and a maximum absorption wavelength. The ratio of the absorbance at each wavelength below with respect to the absorbance at the above satisfies all of the following formulas (1) to (4), and measured with a thermobalance at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. A matte polyester composition characterized by being selected from color-setting dyes having a mass reduction starting temperature of 250 ° C. or higher , and polyester fibers obtained by melt-molding the composition. The above-described problems can be solved by the present invention.
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. ]

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

The present invention will be described in detail below.
The polyester in the present invention includes a polyester having at least one main repeating unit selected from the group consisting of ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, ethylene naphthalate, trimethylene naphthalate and tetramethylene naphthalate. Polyester. The “main repeating unit” preferably represents at least 70 mol% or more, more preferably 90 mol% or more of all repeating units. The polyester may be a copolymer polyester obtained by copolymerizing a third component other than the component constituting the alkylene glycol ester unit of the aromatic dicarboxylic acid. The third component (copolymerization component) may be either a dicarboxylic acid component or an alkylene glycol component. Dicarboxylic acid components preferably used as the third component include aromatic dicarboxylic acids such as isophthalic acid and phthalic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid, and cyclohexanedicarboxylic acid. Examples thereof include alicyclic dicarboxylic acids such as acids and the like, and these can be used alone or in combination of two or more.

  The metal element having a true specific gravity of 5.0 or more in the present invention is usually derived from a metal compound contained in a catalyst, a metal color adjuster, a matting agent or the like contained in a polyester or a polyester composition. is there. 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 polyester composition of the present invention, the content of the 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, an increase in the content increases the price of the resulting polyester composition, which is not preferable. Further, in the case of metals such as lead and cadmium, since the metal element itself is toxic, it is not preferable to contain a large amount in the polyester composition. 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.

In the present invention, the matting agent is a compound containing at least one of sodium, potassium, magnesium, calcium, barium, titanium, and aluminum as a metal. Specifically, titanium oxide (TiO ₂ ), barium sulfate ( BaSO _4), include the aluminum oxide, which may be used alone, or may be used in combination. In particular, titanium oxide having three types of crystal systems has been widely used, and among the three types of crystal systems, the anatase type has excellent hue because the absorption wavelength is not visible, and the polyester composition at the time of kneading. Since the deterioration is small, it is used very suitably.

  The polyester composition in the present invention needs to contain inorganic fine particles as a matting agent in the range of 0.1 to 20.0% by mass based on the mass of the polyester composition. If the content is less than 0.1% by mass, the matte effect is reduced, which is not preferable. On the other hand, if the content exceeds 20.0%, the spinning (spinning) process becomes unstable, which is not preferable. The addition amount of the matting agent is preferably in the range of 0.1 to 5.0% by mass, and more preferably in the range of 0.3 to 3.0% by mass.

In the polyester composition of the present invention, the average particle size of the matting agent to be added needs to be 1.0 μm or less. When the average particle diameter exceeds 1.0 μm, the amount of coarse particles described below may increase, which is preferable because the frequency of polyester filter replacement increases, the quality of the polyester composition deteriorates, and the rate of yarn breakage in the yarn making process increases. Absent. The average particle size is more preferably 0.05 to 0.60 μm. More specifically, the number of coarse particles of 0.5 μm or more is preferably less than 5 particles / mm ² . When it is 5 pieces / mm ² or more, the rate of increase in the filtration pressure when the polyester composition is filtered increases, the frequency of filter replacement increases, and the quality of the polyester composition deteriorates. ) Unfavorable increase in yarn breakage rate in the process. The content of coarse particles is preferably less than 3 particles / mm ^{2, and} more preferably not found at all. In particular, by using a matting agent having few coarse particles, it is possible to obtain a polyester composition that is extremely good, that is, having few coarse particles. More specifically, in order to obtain a matting agent with few coarse particles, a conventionally known method, that is, a method such as classification or pulverization may be used, and the method may be either wet or dry. The surface treatment may be performed by a known method. It is often preferable to treat the particle surface with a silane, aluminate or titanate surface treatment agent or a water-soluble polymer. The content of coarse particles is 50 mg of a polyester composition sandwiched between two cover glasses, melt-pressed at 280 ° C., rapidly cooled, observed using a phase-contrast microscope, and analyzed using an image analyzer Luzex 500. It can be evaluated by doing.

  There is no particular limitation on the method for adding the above-described matting agent contained in the polyester composition of the present invention, and it may be added at any stage in the transesterification reaction, esterification reaction or polycondensation reaction process. Well, furthermore, a method of supplying a matting agent quantitatively from a side feeder or the like as a powder, solution or slurry after melting a polyester produced by a known method in advance using an extruder or the like, including a matting agent in advance A method of producing a master polyester with a high amount and mixing it with a polyester with a low matting agent content and an extruder, or an extruder after blending the polyester composition chip and the matting agent in powder form. The method of mixing with is used.

The polyester composition of the present invention has a maximum absorption wavelength in a visible light absorption spectrum of 380 to 780 nm measured in a chloroform solution at a concentration of 20 mg / L and an optical path length of 1 cm, and has a maximum absorption. It is preferable that the ratio of the light absorbency in the following each wavelength with respect to the light absorbency in a wavelength contains 0.1-10 mass ppm of the organic color adjusting agent satisfying 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 organic colorant solution contained in the polyester composition of the present invention is less than 540 nm. In the case of, the redness of the obtained polyester composition becomes strong, and when it exceeds 600 nm, the blueness of the obtained polyester composition becomes strong. The range of the maximum absorption wavelength is more preferably in the range of 545 to 595 nm. Further, when a visible light absorption spectrum is measured at an optical path length of 1 cm for a chloroform solution having a concentration of 20 mg / L of an organic color adjusting agent contained in the polyester composition of the present invention, each wavelength shown above with respect to the absorbance at the maximum absorption wavelength. When the ratio of the absorbance at is out of any one of the above formulas (1) to (4), the resulting 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). More preferably.
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 organic color adjusting agent contained in the polyester composition of the present invention is less than 0.1 ppm by mass, the yellowness of the 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 organic color adjusting agent is more preferably in the range of 0.3 mass ppm to 9 mass ppm.

The organic color adjusting agent used in the present invention is a color adjusting dye 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 to be selected. 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 the heat resistance of the organic color adjusting agent. It becomes an indicator. When the mass decrease starting temperature is less than 250 ° C., the heat resistance of the organic color adjusting agent is insufficient, which is not preferable because it causes coloring of the finally obtained polyester composition. The mass decrease starting temperature is more preferably 300 ° C. or higher. More preferably, the polyester composition does not decompose at a temperature at which it is in a molten state.

The hue of the polyester composition of the present invention is not particularly limited, but if the organic color adjusting agent used in the present invention is not added, the hue of the resulting polyester composition becomes a yellowish hue. It may be undesirable. The hue of the polyester composition is such that the color a ^* value is −9 to 0 and the color b ^* value is −2 to 2 in the L ^* a ^* b ^* color system after crystallizing by heat treatment at 140 ° C. for 2 hours. A range of 10 is preferable. The color value varies depending on the amount of the organic color adjusting agent contained, but when the color a ^* value is less than −9, the polyester composition has a strong green color, and when the color value is greater than 0, the red color has a red color. It becomes strong and is not preferable. Further, when the color b ^* value is less than −2, the polyester composition has a strong bluish color.

  Further, the polyester composition in the present invention may further contain 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, A heat stabilizer or a light-shielding agent may be included.

  As the method for producing the polyester 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. The reaction product is then heated under reduced pressure in the presence of a polycondensation catalyst to cause a polycondensation reaction until a predetermined degree of polymerization is obtained, thereby producing the desired polyester.

  The polycondensation catalyst used when producing the polyester of the present invention 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 (I), a titanium compound represented by the following general formula (I) and an aromatic polyvalent carboxylic acid represented by the following general formula (II) or The product obtained by reacting with an anhydride 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、ｎは２〜４の整数を表わす。］

[In the above formula, n 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 excellent in terms of stability and easy handling. Moreover, these titanium compounds and aluminum compounds may be used alone, in combination or in combination of two or more, but it is particularly preferable to use the titanium compound alone. Of these, the compound represented by the above general formula (I) or the compound represented by the above general formula (I) and the aromatic polyvalent carboxylic acid represented by the above general formula (II) or an anhydride thereof is most preferable. The reacted product is used alone.

Among the titanium compounds represented by the general formula (I), 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, the aromatic polyvalent carboxylic acid represented by the general formula (II) to be reacted with the titanium compound or the anhydride thereof includes terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, hemimellitic acid, or pyromellitic acid. Or these anhydrides are used preferably. 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 polyester 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 may be used in combination as a stabilizer. preferable. 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 polyester composition at any time after the ester exchange reaction or the esterification reaction is substantially completed, but usually immediately after the esterification reaction or the ester exchange reaction is completed. The polycondensation reaction is preferably carried out thereafter.

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

In the method for producing a polyester 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 as an organic color adjusting agent, or blue. 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 pigments, oil-soluble dyes are particularly preferable. Specific examples of blue color adjusting pigments 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 ^* value of the obtained polyester composition exhibits green becomes small, 40: If the mass ratio of the blue orthochromatic dye than 60 is small, undesirably coming exhibiting red color a ^* value becomes large. 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 color of the resulting polyester composition exhibited green a ^* value is smaller, 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 polyester 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 polyester 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 within this range, the strength of the obtained fiber is sufficient, and the winding can be performed stably. The drawn yarn can be drawn by winding the undrawn polyester fiber or by continuously drawing the undrawn polyester fiber without winding it once. Furthermore, in order to enhance the texture of the polyester fiber of the present invention, an alkali weight loss treatment is also preferably performed. The shape of the base used for spinning is not particularly limited, and any of round, irregular, solid and hollow can be adopted. It can also be used as one component of these composite fibers.

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 polyester 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 content:
The polyester composition chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposed product was measured using gas chromatography (manufactured by Hewlett-Packard (HP 6850 type)).
(C) Hue (L ^* value, b ^* value):
The polyester composition chip was melted at 285 ° C. under vacuum for 10 minutes, formed into a plate having a thickness of 3.0 ± 1.0 mm on an aluminum plate, and immediately cooled in ice water. A time dry crystallization treatment was performed. 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.
(D) Metal component qualitative analysis with true specific gravity of 5.0 or more:
A polyester composition chip sample is 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 an ICP emission analyzer (JY170 ULTRACE) manufactured by Rigaku Corporation. Qualitative analysis was performed and the presence or absence of a metal element having a true specific gravity of 5.0 or more was confirmed. About the metal element by which presence of 1 mass ppm or more was confirmed with respect to the polyester composition chip | tip mass, the metal element content was quantified by the following operation.
(E) Titanium, phosphorus, aluminum, calcium, manganese, antimony content:
The amount of phosphorus element, aluminum element, calcium element, manganese element, and antimony element in the polyester composition chip has a flat surface with a compression press machine after a granular polyester composition sample is heated and melted on a steel plate. A test molded body was prepared and determined using a fluorescent X-ray apparatus (ZSX100e type, manufactured by Rigaku Corporation). Regarding the amount of titanium element soluble in the polyester in the polyester composition, the sample in the 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 polyester composition contains titanium oxide derived from inorganic fine particles as a matting agent, it is possible to determine a titanium element soluble in polyester as a catalyst.

(F) Layer of deposits generated on the spinneret (the height of the foreign matter deposit):
The polyester composition is made into chips, melted at 290 ° C., discharged from a spinneret having 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 kimono layer was measured. As the height of the adhered layer increases, bending tends to occur in the filamentous flow of the discharged polyester composition melt, and the moldability of the polyester composition decreases. That is, the height of the deposit layer generated in the spinneret is an index of the moldability of the polyester composition.
(G) Mass reduction start temperature of organic 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.
(H) Average particle size of matting agent:
It measured using Shimadzu Corporation CP-50 type Centrifugal Particle Size Analyzer. Then, the particle size corresponding to 50 Mass Percent is read from the cumulative curve of the particles of each particle size calculated based on the centrifugal sedimentation curve obtained by this measuring instrument and the abundance thereof, and this value is taken as the average particle size. To do.
(K) Coarse particles in the polyester composition:
50 mg of the polyester composition is sandwiched between two cover glasses, melt-pressed at 280 ° C., rapidly cooled, and observed with a phase-contrast microscope. Inside the microscope image with an image analyzer Luzex 500 (manufactured by Nireco Corporation) The number of particles having a maximum length of 5.0 μm or more is counted, and the following determination is made.
Special grade: 5.0 .mu.m primary particles can not find at all beyond: more than 5.0 .mu.m particle count 5 / mm ² under a is secondary: the number of particles exceeding 5.0 .mu.m is at 5 to 10 / mm ² A grade 3: The number of particles exceeding 5.0 μm exceeds 10 particles / mm ² Note that only the special grade and the first grade are provided for practical use.
(Ko) Degree of matting:
A sample (one single fiber) was sampled on a preparation and the reflected light was observed at 200 times using a stereomicroscope (“AFX-IIA” manufactured by Nikon). A sample that was partially whitened was indicated by Δ, and a sample that was almost entirely transparent was indicated by ×.
(C) Yarn breakage rate:
In the spinning process, 100 spools of 100 minutes / wind were manufactured, and the number of spools in which breakage occurred was expressed as a percentage of the number of manufactured spools.

[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 organic color adjusting agent (color adjusting dye), preparation of organic color adjusting agent The color adjusting dye shown in Table 1 was made into a chloroform solution having a concentration of 20 mg / L at room temperature, A quartz cell with an optical path length of 1 cm was filled, and a 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 organic color adjusting agents in the polyester production process in Examples and Comparative Examples, the solution is dissolved or dissolved at a temperature of 100 ° C. with respect to a glycol solution used as a raw material at a concentration of 0.1% by mass. Prepared by dispersing.

[Example 1]
-Manufacture of polyester composition chip In a mixture of 100 parts of dimethyl terephthalate and 70 parts of ethylene glycol, 0.016 part of titanium catalyst A prepared in Reference Example 1 was charged into a SUS container capable of pressure reaction. 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 part of triethylphosphonoacetate was added to complete the ester exchange reaction. Thereafter, 12.5 parts by mass of an ethylene glycol slurry containing 20% by mass of titanium dioxide adjusted to an average particle size of 0.32 μm prepared as a matting agent was added, and the color adjusting agent A prepared in Reference Example 2 was further added. 0.2 part of 0.1 mass% ethylene glycol solution was added, it moved to the polymerization container, it heated up to 290 degreeC, and the polycondensation reaction was performed in the high vacuum of 30 Pa or less, and the polyester composition was obtained. Furthermore, it was made into a chip according to a conventional method. The results are shown in Table 2.
・ Manufacture of polyester fiber After the chip was dried at 140 ° C. for 5 hours, a raw yarn of 333 dtex / 36 fil was produced at a spinning temperature of 285 ° C. and a winding speed of 400 m / min. A drawn yarn was obtained. The results are shown in Table 2.

[Example 2]
In Example 1, it implemented similarly to Example 1 except having changed the organic type color adjusting agent into the kind and quantity which are shown in Table 2. The results are shown in Tables 2 and 3.

[Example 3]
A mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol was charged with 0.063 parts by mass of calcium acetate monohydrate in a reactor equipped with a stirrer, a rectifying column and a methanol distillation condenser, and 140 ° C. The ester exchange reaction was carried out while distilling out the methanol produced as a result of the reaction while gradually raising the temperature to 240 ° C. Then, 0.045 mass part of 56 mass% phosphoric acid aqueous solution was added, and the transesterification reaction was terminated. Thereafter, 12.5 parts by mass of an ethylene glycol slurry containing 20% by mass of titanium dioxide having an average particle diameter adjusted to 0.32 μm was added to the reaction product, and 0.1 of the color adjusting agent A prepared in Reference Example 2 was further added. Add 0.2 parts by mass of ethylene glycol solution, transfer to a reaction vessel equipped with a stirrer, nitrogen inlet, vacuum port and distillation apparatus, raise the temperature to 290 ° C., and perform polycondensation reaction at a high vacuum of 30 Pa or less To obtain a polyester composition. The obtained chip produced fibers in the same manner as in Example 1. The results are shown in Tables 2 and 3.

[Example 4]
In Example 1, it carried out like Example 1 except having changed the inorganic fine particle added as a matting agent to be added into the substance shown in Table 2. The results are shown in Tables 2 and 3.

[Comparative Example 1]
Manufacture of polyester composition chip A mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol was provided with 0.032 parts by mass of manganese acetate tetrahydrate, 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. Thereafter, 12.5 parts by mass of an ethylene glycol slurry containing 20% by mass of titanium dioxide adjusted to an average particle size of 0.32 μm prepared as a matting agent was added to the reaction product, and then the reaction product obtained Is transferred to a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port, and a distillation apparatus, 0.045 parts by mass of antimony trioxide is added, the temperature is raised to 290 ° C., and polycondensation reaction is performed at a high vacuum of 30 Pa or less. To obtain a polyester composition. Furthermore, it was made into a chip according to a conventional method. The obtained chip produced fibers in the same manner as in Example 1. The results are shown in Tables 2 and 3.

[Comparative Example 2]
In Example 1, it implemented like Example 1 except having changed the titanium dioxide to add into the average particle diameter shown in Table 2. The results are shown in Tables 2 and 3.

[Comparative Example 3, Comparative Example 4]
In Example 1, it implemented like Example 1 except having changed the addition amount of the titanium dioxide into the average particle diameter shown in Table 2. The results are shown in Tables 2 and 3.

  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 matte polyester composition having a very small amount of deposits on the die and having excellent moldability.

Claims (8)

A polyester composition containing 0.1 to 10 ppm by mass of an organic color adjuster, wherein the polyester composition is ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, ethylene naphthalate, trimethylene naphthalate and tetramethylene naphthalate selected from the group consisting of, 0.1 to 20.0 mass at least one comprises a polyester whose main recurring unit, a matting agent average particle diameter of 1.0μm or less based on the weight of the polyester composition %, And the content of the metal element having a true specific gravity of 5.0 or more is 0 to 10 ppm by mass or less based on the mass of the polyester composition ,
The organic color adjusting agent has a maximum absorption wavelength in a visible light absorption spectrum in a range of 380 to 780 nm measured in a chloroform solution at a concentration of 20 mg / L and an optical path length of 1 cm, and a maximum absorption wavelength. The ratio of the absorbance at each wavelength below with respect to the absorbance at the above satisfies all of the following formulas (1) to (4), and measured with a thermobalance at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. A matte polyester composition characterized by being selected from coloring dyes having a mass reduction starting temperature of 250 ° C. or higher .
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. ]   The polyester composition according to claim 1, wherein the matting agent contained in the polyester composition is a compound containing at least one of sodium, potassium, magnesium, calcium, barium, titanium, and aluminum. The polyester composition according to claim 1 , wherein the step of producing the polyester is a step using a polycondensation catalyst, and the polycondensation catalyst is a titanium compound and / or an aluminum compound. The titanium compound is a titanium compound represented by the following general formula (I), or a compound represented by the following general formula (I) and an aromatic polyvalent carboxylic acid represented by the following general formula (II) or an anhydride thereof. The polyester composition according to claim 3 , which is a product obtained by reacting with a polyester.

[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, n represents an integer of 2 to 4. ] The polyester composition according to claim 3 , wherein the aluminum compound is an organoaluminum compound. Furthermore, the polyester composition of any one of Claims 1-5 formed by mix | blending a phosphorus compound. 7. The a value is −9 to 0 and the b value is −2 to 10 in the hue in the L * a * b * color system after heat treatment at 140 ° C. for 2 hours. The polyester composition according to item.   The polyester fiber obtained by melt-spinning the polyester composition of any one of Claims 1-7.