JP2007284598A - Copolymer polyester composition and fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester composition having extremely slight generation amount of deposit to a spinneret and excellent moldability even when continuously spinning for a long time and a polyester composition capable of obtaining a fiber having clear appearance, improved in dyeing property and excellent in alkali reduction processability. <P>SOLUTION: The invention provides a copolyester in which 0.1-10 mass% glycol component represented by general formula (I) (wherein a functional group R is a 2-6C alkylene group which may be branched; n is an integer of 2-22) is copolymerized with a polyester containing ethylene terephthalate as main recurring units, a copolyester composition having 0.1-5 mass% content of inert particles, in which frequency fraction of particles having 0.01-0.5 μm average particle diameter and >0.5 μm particle diameter is ≤20 mass%, not substantially containing a metal element having ≥5.0 true specific gravity, and a fiber obtained by carrying out melt molding of the copolyester composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to copolyester compositions and fibers. More specifically, the content of metal elements having a true specific gravity of 5.0 or more, particularly antimony and germanium, is extremely small, has excellent properties of hue, and excellent moldability during fiber production. The present invention relates to a polyester composition and fibers that exhibit deep color dyeability and are excellent in alkali weight loss.

  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. In particular, polyethylene terephthalate is used in a very wide range of applications because of its characteristics and price. However, polyester cannot be said to have good dyeability as a fiber for clothing, and is inferior in color depth.

  Conventionally, in order to make up for such drawbacks, fine particles are contained in the polyester, or particle types insoluble in the polyester are precipitated during the polymerization reaction, and then the resulting polyester composition is knitted to produce an alkali weight loss, etc. As a method, a method of forming irregularities on the fiber surface to obtain a deep-colored polyester fiber is known (see, for example, Patent Document 1 and Patent Document 2).

  Polyethylene terephthalate, which is usually used to obtain such a deep color dyeing polyester composition, is usually obtained by directly esterifying terephthalic acid and ethylene glycol, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate. Ethylene glycol is transesterified or terephthalic acid and ethylene oxide are reacted to produce an ethylene glycol ester of terephthalic acid and / or a low polymer thereof. Next, the 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.

  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.

  In order to solve the problem at the time of producing such a deep-colored polyester fiber, a technique that does not use a polycondensation catalyst such as antimony or germanium has been proposed (see Patent Document 3). According to this method, the yarn breakage in the process of producing the deep-colored polyester fiber is certainly reduced, and the process is stabilized. However, on the other hand, the polyester fiber obtained by this method has a problem in that the weight reduction rate in the alkali weight reduction processing applied to improve the texture and dyeability of the fiber is slow and it takes time in the weight reduction processing step. .

Japanese Examined Patent Publication No. 62-28229 JP-A-57-139118 JP 2006-22241 A

  An object of the present invention is to provide a polyester composition that has excellent hue and generates a very small amount of deposits on the die even when spinning continuously for a long time, and has excellent moldability. Another object is to provide a polyester composition having a clear appearance, improved dyeability, and capable of obtaining a fiber excellent in alkali weight loss.

［上記式中、官能基Ｒは分岐していてもよい炭素数２〜６のアルキレン基であり、ｎは２から２２の整数を表す。］ 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 relates to a polyester obtained by copolymerizing a polyester having ethylene terephthalate as a main repeating unit with 0.1 to 10% by mass of a glycol component represented by the following general formula (I) based on the polyester composition, and A metal element having an average particle size in the range of 0.01 to 0.5 μm and a frequency fraction of particles having a particle size exceeding 0.5 μm is 20% by mass or less and has a true specific gravity of 5.0 or more. A polyester composition comprising inactive particles not included, wherein the content of the inactive particles is 0.1 to 5% by mass with respect to the polyester composition, and melt molding this These fibers can be obtained, and these can solve the above problems.

[In the above formula, the functional group R is an optionally branched alkylene group having 2 to 6 carbon atoms, and n represents an integer of 2 to 22. ]

  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. In addition, the amount of deposits on the die is very small, and it is possible to provide a polyester having excellent moldability. As a result, it has excellent hue, deep dyeability, and alkali weight reduction processing. A polyester fiber having excellent properties can be provided.

The present invention will be described in detail below.
As the polyester in the present invention, a polyester having an ethylene terephthalate unit obtained by a polycondensation reaction of terephthalic acid and ethylene glycol as a main repeating unit is preferably used. Here, “mainly” means that 70 mol% or more of all repeating units are ethylene terephthalate units. Other copolymer components that may occupy 30 mol% or less are unsubstituted or substituted isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, succinic acid, adipic acid, Examples include sebacic acid, cyclohexanedicarboxylic acid, or lower alkyl esters or lower aryl esters thereof, ester-forming derivatives such as acid halides, trimethylene glycol, tetramethylene glycol, or hexamethylene glycol.

  The polyester composition of the present invention has an average particle diameter in the range of 0.01 to 0.5 μm, and a frequency fraction of particles having a particle diameter exceeding 0.5 μm is 20% by mass or less and has a true specific gravity of 5. It is necessary to contain 0.1 to 5% by mass of inert particles substantially free of zero or more metal elements, based on the total mass of the polyester composition. Here, the inert particles are those that do not cause a chemical reaction with the polyester raw material or the polyester precursor (oligomer) in the polyester production process, do not cause a catalytic action of the chemical reaction, or are simply melted or stored in solid form. It refers to a substance that does not change the physical properties of the polyester polymer when it is in use.

  Examples of the inert particles include calcium carbonate, calcium phosphate (including all primary to tertiary calcium phosphates), calcium silicate, silicon dioxide, aluminum oxide, silicone powder, kaolinite, barium sulfate, titanium dioxide, and the like. Preferably at least one from the group. Further, the inert particles may be a single type or a combination of multiple types. Furthermore, among these, silica sol which is one of calcium carbonate, calcium phosphate and silicon dioxide is preferably used. As calcium phosphate, tricalcium phosphate having no active hydrogen atom is particularly preferably used.

  Further, it is necessary that the inert particles do not substantially contain a metal element having a true specific gravity of 5.0 or more. 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, barium, calcium, magnesium, sodium, potassium, or the like does not correspond to a metal element having a true specific gravity of 5.0 or more. The characteristics and properties of the polyester composition vary depending on the type of metal element contained. For example, when the content of antimony metal is large, it becomes a foreign substance during melt spinning or film formation, and adheres to the periphery of the die or die, which adversely affects long-term continuous formability. When the germanium metal is included, it is expensive per se, which is not preferable because the price of the resulting polyester composition increases when the content increases. In addition, when a metal such as lead or cadmium is contained, the metal element itself is toxic, so that it is not preferable that it is contained in a large amount in the polyester composition. In addition to this, when a metal element having a true specific gravity of 5.0 or more is contained, the obtained polyester may have a poor hue, and when the polyester is melted, the intrinsic viscosity is greatly reduced. In particular, these defects may be easily manifested in polyesters mainly composed of polyethylene terephthalate. Here, the fact that a metal element having a true specific gravity of 5.0 or more is not substantially contained does not mean that the corresponding metal element is absolutely contained, but normal detection accuracy such as an ICP emission analysis method described later. This means that a metal element having a true specific gravity of 5.0 or more cannot be detected even using an analytical evaluation method having

  The inert particles in the present invention need to have an average particle size in the range of 0.01 to 0.5 μm. If the average particle diameter exceeds 0.5 μm, these inert particles are likely to settle during the production process such as in the sol or polyester reaction stock solution, and cannot be stably supplied and dispersed. On the other hand, if the average particle size is less than 0.01 μm, the specific surface area of the particles is too large, and aggregated particles are easily formed during the polymerization reaction of the polyester, and the yarn breakage during yarn production increases. The average particle diameter of the inert particles is preferably in the range of 0.02 to 0.4 μm, and more preferably in the range of 0.03 to 0.3 μm.

  In the inert particles in the present invention, the frequency fraction of particles having a particle size exceeding 0.5 μm needs to be 20% by mass or less. When the frequency fraction of particles having a particle size exceeding 0.5 μm exceeds 20% by mass, fine pores formed on the fiber surface become large even after alkali reduction after the obtained polyester composition is made into yarn, and dyeing is performed. Since the deep color effect at the time cannot be obtained, it is not preferable. The frequency fraction of particles having a particle size exceeding 0.5 μm in the inert particles is preferably in the range of 15% by mass or less, and more preferably in the range of 10% by mass or less.

  These inactive particles having a specific average particle size and particle size distribution can be obtained by purchasing commercially available products or appropriately adjusting the particle size by the method described below. That is, there is a method in which a slurry in which inert particles are dispersed in a dispersion medium is once adjusted, and supplied to a sand grinder together with a crushing medium as necessary, and then pulverized. In this pulverization step, it is possible to prepare finely according to the flow rate of the slurry, the pulverization time / number of times, the presence / absence / type of the pulverization media, and further filtered through a filter with a predetermined opening after pulverization.

  Inert particle content in this invention needs to exist in the range of 0.1-5 mass% on the basis of the mass of a polyester composition. When the content is less than 0.1% by mass, the deep color dyeability of the finally obtained polyester fiber becomes insufficient, and when it exceeds 5% by mass, the strength, heat resistance and light resistance of the obtained polyester fiber are insufficient. This is not preferable because the properties deteriorate. The particle content is preferably in the range of 0.15 to 3% by mass, more preferably in the range of 0.2 to 1.0% by mass.

［上記式中、官能基Ｒは分岐していてもよい炭素数２〜６のアルキレン基であり、ｎは２から２２の整数を表す。］ The polyester composition of the present invention needs to be a polyester composition containing a copolyester obtained by copolymerizing 0.1 to 10% by mass of a glycol component represented by the following general formula (I) with respect to the polyester composition. There is.

[In the above formula, the functional group R is an optionally branched alkylene group having 2 to 6 carbon atoms, and n represents an integer of 2 to 22. ]

  Here, when the copolymerization amount of the compound represented by the general formula (I) is less than 0.1% by mass, the alkali weight loss processability of the obtained polyester fiber becomes insufficient, and when the amount exceeds 10% by mass, In addition to a decrease in heat resistance, the light resistance of the resulting polyester fiber is also unfavorable. The copolymerization amount of the compound represented by the general formula (I) is preferably in the range of 0.5 to 9% by mass, and more preferably in the range of 1 to 8% by mass.

  Examples of the compound represented by the general formula (I) include diethylene glycol, triethylene glycol, polyethylene glycol having a number average molecular weight of 1000 or less, dipropylene glycol, tripropylene glycol, polypropylene glycol having a number average molecular weight of 1200 or less, and ditetramethylene glycol. , Tritetramethylene glycol, or polytetramethylene glycol having a number average molecular weight of 1600 or less. Among these, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol having a number average molecular weight of 1000 or less is preferable, and polyethylene glycol, polypropylene glycol, or polytetramethylene glycol having a number average molecular weight of 200 to 1000 is more preferable.

  It is preferable that the polyester composition of this invention contains 0.1-10 mass ppm of color adjusting agents on the basis of the total mass. When content of a color adjusting agent is less than 0.1 mass ppm, the yellowishness of the obtained polyester composition may become strong. On the other hand, when the content exceeds 10 ppm by mass, the lightness of the polyester composition is weakened and the appearance is sometimes dark, which is not preferable. The content is preferably in the range of 0.3 to 9 ppm by mass, and more preferably in the range of 0.5 to 8 ppm by mass. The color adjusting agent represents an organic polyaromatic ring dye or pigment, and is preferably an anthraquinone dye, specifically, a blue color adjusting dye, a purple color adjusting dye, a red color dye. Examples thereof include color adjusting dyes and orange color adjusting dyes. These may be used singly or in combination of a plurality of types, but a blue color adjusting dye and a purple color adjusting dye may be used in a mass ratio of 90:10 to 40:60. preferable.

  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. 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.

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 Is small and exhibits a green color, and when the mass ratio of the blue color adjusting dye is smaller than 40:60, the color a ^* value increases and a red color is exhibited, which may not be preferable. The color adjusting dye is more preferably a blue color adjusting dye and a purple color adjusting dye used in a mass ratio of 80:20 to 50:50.

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 polyester composition. The mass decrease starting temperature is more preferably 300 ° C. or higher. More preferably, the polyester does not decompose at a temperature at which it is in a molten state.

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

The hue of the polyester composition of the present invention is not particularly limited, but if the above-described color adjusting agent is not added, the hue of the obtained polyester tends to be a yellowish hue. 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 color adjusting agent contained. 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 becomes strong. It is not preferable. Further, when the color b ^* value is less than −2, the polyester composition has a strong bluish color.

  As the method for producing the polyester in the present invention, a conventionally known polyester production method is used. That is, first, a dicarboxylic acid component such as terephthalic acid is directly esterified with a glycol component such as ethylene glycol, or a lower alkyl ester of a dicarboxylic acid component such as dimethyl terephthalate (hereinafter sometimes referred to as DMT) and ethylene. A glycol component such as glycol is transesterified to produce a glycol ester of dicarboxylic acid and / or a low polymer thereof. 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. Also in the case of including other polyesters other than polyester, a method of copolymerizing with the polyester, or a method of blending with polyester after polycondensation, etc., using a production method generally known for other polyesters other than polyester is adopted. be able to.

  More specifically, the polycondensation catalyst used in producing the polyester 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. 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. 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.

  As described above, the polyester composition of the present invention preferably uses a titanium compound and / or an aluminum compound as a polycondensation catalyst, but further uses a phosphorus compound as a stabilizer in order to further improve heat resistance and hue. It is 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.

  In addition, the inert particles and the glycol component represented by the general formula (I) may be added in any production process as long as the physical properties of the polyester are not impaired in the production process. Preferably, the esterification reaction or transesterification reaction is completed from the initial point of the esterification reaction or transesterification reaction, and the glycol ester of dicarboxylic acid and / or its low polymer is produced and the polycondensation reaction starts. It is preferable to be added up to. More preferably, it is added immediately after completion of the esterification reaction or transesterification reaction.

  Further, the polyester composition in 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, a heat stabilizer. A stabilizer, a light-shielding agent, a matting agent, or the like may be included. In particular, an antioxidant is preferably added in order to improve the thermal stability and oxidation resistance deterioration of the copolymer component. As the antioxidant, a hindered phenol-based antioxidant is preferably added, and the addition amount is preferably in the range of 0.05 to 1% by mass with respect to the entire polyester composition.

  There is no limitation in particular as a manufacturing method when manufacturing the polyester fiber of this invention, A conventionally well-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 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, the polyester fiber of the present invention is preferably subjected to an alkali weight reduction treatment in order to improve the texture and dyeability. In particular, the polyester fiber is made into a woven or knitted fabric using the obtained polyester fiber and then subjected to the alkali weight loss treatment. It becomes possible to improve the dyeability which is the subject of the present invention.

  Here, the alkali weight loss rate of the polyester fiber of the present invention is preferably in the range of 2.5 to 5.0 mass% / hour in a sodium hydroxide aqueous solution having a concentration of 10 g / L and 100 ° C. When the alkali weight loss rate is less than 2.5% by mass / hour, the alkali weight loss processing step takes a long time, and when it is greater than 5.0% by mass / hour, it is difficult to adjust the final alkali weight loss rate. The alkali weight loss rate is more preferably in the range of 3.0 to 4.5% by mass / hour. In order to make the alkali weight loss rate in the range of 2.5 to 5.0% by mass / hour, as described above, a specific glycol component whose main repeating unit is ethylene terephthalate and represented by the formula (I) Can be realized by a polyester composition in which a predetermined amount of inert particles having an average particle size and a particle frequency fraction exceeding 0.5 μm in the above-described range are blended with polyester.

  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 a polyester composition chip in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer.

(A) Diethylene glycol (DEG) 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, a ^* value, b ^* value):
・ Evaluation method in chip form:
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.
-Evaluation method in fiber form:
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.

(D) Metal component qualitative analysis with true specific gravity of 5.0 or more:
A polyester (PES) 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 analyzer (JY170 ULTRACE) manufactured by Rigaku Corporation. ) Was used 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.

(E) Titanium, aluminum, antimony, phosphorus content:
In the polyester (PES) composition, the amount of titanium element soluble in the polyester, the amount of aluminum element, the amount of antimony element, and the amount of phosphorus element are obtained by heating and melting a granular polyester composition sample on a steel plate, and then using a compression press machine. A test molded body having the above was prepared and obtained using a fluorescent X-ray apparatus (ZSX100e type, manufactured by Rigaku Corporation).

(F) Layer of deposits generated on the spinneret:
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 melted polyester composition, and the moldability of the polyester becomes lower. That is, the height of the deposit layer generated in the spinneret is an index of the moldability of the polyester.

(G) Alkaline weight loss rate:
A test piece in which fibers are formed on a fabric is immersed in an aqueous solution of sodium hydroxide at a concentration of 10 g / L and 100 ° C. at a bath ratio of 300, and subjected to an alkali reduction treatment until the mass reduction rate of the fabric reaches 20%. Was plotted against time to determine the alkali weight loss rate.

上記数式中、Ｋは吸収係数、Ｓは散乱係数である。Ｒは分光反射率を示し、このスペクトルを測定し、最大値を深色度とする。本発明においては２３以上を良好と判断した。 (H) Deep color dyeability evaluation:
The fabric subjected to the above-described alkali weight reduction treatment was washed with water, then prepared with a 2% owf solution of a disperse dye Sumikaron Navy Blue S-2GL manufactured by Sumitomo Chemical Co., Ltd. at a bath ratio of 1:50, and dyed at 130 ° C. for 1 hour. The dyed cloth was measured with a colorimetric color difference meter (CE-3000 type) manufactured by Greta Macbeth Co., and the deep chromaticity (K / S) was determined by the following Kubelka-Munk equation.

In the above formula, K is an absorption coefficient and S is a scattering coefficient. R indicates spectral reflectance, this spectrum is measured, and the maximum value is defined as deep chromaticity. In the present invention, 23 or more was judged good.

(K) 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.

(Co) Type of glycol component and copolymerization rate After dissolving the polyester composition sample in deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent, the precipitate was removed by filtration, and the resulting solution was JEOL A nuclear magnetic resonance spectrum ( ¹ H-NMR) was measured using JEOL A-600 superconducting FT-NMR. From the spectrum pattern, the kind of glycol and the amount of copolymerization were quantified according to a conventional method.

(C) Properties relating to inert particles The content of inert particles in the polyester composition was calculated from the mass of the precipitate obtained by the above method. Furthermore, the average particle diameter and frequency fraction of the inert particles were measured with the DLS-7000 manufactured by Otsuka Electronics Co., Ltd., and the frequency fraction of the particles having a particle size exceeding 0.5 μm was calculated from the particle size distribution.

[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] Preparation of color adjusting agent Table 1 shows the results of measuring the thermal mass decrease starting temperature of the powder color adjusting dyes 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 polyester composition chip To a mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol, 0.063 parts by mass of calcium acetate monohydrate (70 mmol% with respect to 1 mol of DMT) was stirred and rectified. A reactor equipped with a tower and a methanol distillation condenser was charged, and the ester exchange reaction was carried out while gradually raising the temperature from 140 ° C. to 240 ° C. while distilling methanol produced as a result of the reaction out of the system. Thereafter, 0.045 parts by mass of a 56% by mass phosphoric acid aqueous solution (50 mmol% with respect to 1 mol of DMT) was added to complete the transesterification reaction. Thereafter, 0.4 parts of a 0.1% by weight ethylene glycol solution of the color adjusting agent A shown in Table 1 (4 ppm by mass with respect to the amount of the polyester composition material) in the reaction product, the titanium catalyst A prepared in Reference Example 1. 032 parts by mass (10 mmol% with respect to 1 mol of DMT) and 2.6 parts by mass of an ethylene glycol slurry of 20 mass% of tribasic calcium phosphate having an average particle size of 0.06 μm (0.5 mass% with respect to the amount of the polyester composition material), Polyethylene glycol having a number average molecular weight of 600, 5.2 parts by mass (5% by mass based on the polyester composition), and ethylene bis (oxyethylene) bis- [3- (3-t-butyl-4-hydroxy-) as an antioxidant 5-methylphenyl) -propionate] (Irganox 245 manufactured by Ciba Specialty Chemicals) 0.2% by mass with respect to the composition), transferred to a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation apparatus, heated to 285 ° C., and heated in a high vacuum of 30 Pa or less. A condensation reaction was performed to obtain a polyester composition having an intrinsic viscosity of 0.65 and a diethylene glycol content of 0.6% by mass, and chipped in accordance with a conventional method, the results of which are shown in Table 3. The polyester composition As a result of analysis, a metal element having a true specific gravity of 5.0 or more was not detected. Therefore, it was judged that the added inert particles did not contain a metal element having a true specific gravity of 5.0 or more.

-Manufacture of polyester fiber A polyester composition chip is dried at 160 ° C for 4 hours, a spinning temperature of 285 ° C and a winding speed of 400 m / min is made to produce a raw yarn of 333 dtex / 36 fil and 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.

[Example 2-10, Comparative Example 1-4]
In Example 1, it implemented like Example 1 except having changed phosphoric acid, the polycondensation catalyst, the inert particle, and the copolymerization component into the kind and quantity which are shown in Table 2. The results are shown in Tables 3 and 4.

  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. In addition, the amount of deposits on the die is very small, and polyester having excellent moldability can be provided. As a result, it has excellent hue, deep dyeability, and alkali weight reduction processability. It is possible to provide a polyester fiber that is excellent in resistance.

Claims (9)

A polyester comprising ethylene terephthalate as a main repeating unit, a copolymer polyester obtained by copolymerizing 0.1 to 10% by mass of a glycol component represented by the following general formula (I) with respect to the polyester composition, and an average particle size of 0 .Inactive particles having a frequency fraction of particles having a particle diameter of more than 0.5 μm in a range of 0.01 to 0.5 μm and containing substantially no metal element having a true specific gravity of 5.0 or more. It is a polyester composition which consists of these, Comprising: The copolyester composition whose content of this inert particle is 0.1-5 mass% with respect to a polyester composition.

[In the above formula, the functional group R is an optionally branched alkylene group having 2 to 6 carbon atoms, and n represents an integer of 2 to 22. ]   The copolymerized polyester composition according to claim 1, wherein the inert particles are at least one selected from the group consisting of calcium carbonate, calcium phosphate, calcium silicate, silicon dioxide, aluminum oxide, silicone powder, kaolinite, barium sulfate, and titanium dioxide. object.   The copolyester composition according to claim 2, wherein the calcium phosphate is tricalcium phosphate.   The copolyester according to any one of claims 1 to 3, wherein the compound represented by the general formula (I) is at least one of polyethylene glycol, polypropylene glycol and polytetramethylene glycol having a number average molecular weight of 1000 or less. Composition.   The copolyester composition according to any one of claims 1 to 4, wherein the polyester composition contains 0.1 to 10 ppm by mass of an anthraquinone color adjuster based on the total mass of the polyester composition.   6. The copolyester composition according to claim 5, wherein the color adjusting agent contains a blue color adjusting pigment and a purple color adjusting pigment in a mass ratio of 90:10 to 40:60.   The copolyester composition according to any one of claims 1 to 6, wherein the polyester contains a titanium compound and / or an aluminum compound as a polycondensation catalyst.   The polyester fiber obtained by melt-spinning the copolyester composition of any one of Claims 1-7.   The polyester fiber according to claim 8, wherein the alkali weight loss rate in a sodium hydroxide aqueous solution having a concentration of 10 g / L and 100 ° C is 2.5 to 5.0 mass% / hour.