JP2015143314A - Cationic dyeable polyester composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester composition capable of manufacturing fiber consisting of a cationic dyeable polyester composition having reduced spinning initial filtration pressure during melting spinning by using the cationic dyeable polyester composition and suppressed filtration pressure increase during melting spinning.SOLUTION: There is provided a cationic dyeable polyester composition having ethylene terephthalate as a main repeating unit and containing an isophthalic acid component having a sulfonic acid base of 1.0 to 3.0 mol% to the total dicarboxylic acid component and polyethylene glycol of 0.5 to 2.0 wt.% to the polyester composition.

Description

  The cationic dyeable polyester composition of the present invention is an excellent cationic dyeable dye having a reduced initial filtration pressure at the time of melt spinning due to a viscosity-reducing action based on the polymer composition, and an increase in the filtration pressure at the time of melt spinning is suppressed. The present invention relates to a polyester composition that can provide a fiber comprising a conductive polyester composition.

  Polyesters, especially polyesters based on polyethylene terephthalate, have excellent mechanical, mechanical and chemical properties, so that they are fibers for clothing, industrial use, films for magnetic tape, surface coating, etc., and tires. Widely used in industrial applications such as cords and nets. In the case of using as a fiber for clothing, in order to supplement the dyeability of the polyester, a modified polyester obtained by copolymerizing an isophthalic acid component having a sulfonate group represented by 5-sodium sulfoisophthalic acid, or a sulfonate group is used. There is known a modified polyester in which polyethylene glycol or the like is copolymerized in addition to the isophthalic acid component possessed to easily increase the viscosity of the polyester.

  However, when melt spinning is performed using a polyester obtained by copolymerizing an isophthalic acid component having a sulfonate group, the filtration pressure at the time of spinning tends to increase, and there is a fundamental problem that stable production is difficult.

  In order to solve such a problem, the cationic dyeable polyester has been improved.

  For example, by using a direct heavy oligomer mainly composed of terephthalic acid and ethylene glycol, an isophthalic acid component having polyethylene glycol and a sulfonate group is copolymerized, and an isophthalic acid component having a sulfonate group in the modified polyester There is exemplified a modified polyester composition that suppresses the rate of increase in the filtration pressure during melt spinning by defining the material amount ratio of lithium atoms and the material amount ratio of lithium atoms and phosphorus atoms (Patent Document 1). However, this method can suppress substances that cause an increase in the filtration pressure derived from lithium and phosphorus, but cannot completely suppress the oligomer of the isophthalic acid component having a sulfonate group. It was not enough. In addition, there has been a problem with increasing the initial filtration pressure accompanying the thickening of the isophthalic acid component having a sulfonate group.

  Further, in a transesterification reaction system using dimethyl terephthalate and ethylene glycol as raw materials, 1.3 to 2.5 mol% of isophthalic acid having a sulfonate group, 0.01 to hindered phenol antioxidant There is also known a method for producing a basic dye-dyed modified polyester by adding 2.0 to 3% by weight of polyethylene glycol of 2.0% by weight and molecular weight of 300 to 4000 (Patent Document 2). . However, even with this method, the oligomer of the isophthalic acid component having a sulfonate group cannot be sufficiently suppressed, and the effect of reducing the filtration pressure is not sufficient. In addition, there has been a problem with respect to an increase in the initial filtration pressure accompanying the thickening of the isophthalic acid component having a sulfonate group.

  On the other hand, with respect to the copolymerized polycaproamide resin composition, there is also known a method in which white foreign substances derived from an isophthalic acid component having a sulfonate group are finely dispersed by using a surfactant together to suppress the generation of white foreign substances. (Patent Document 3). In this method, it is possible to suppress a certain amount of white foreign substances derived from the isophthalic acid component having a sulfonate group, but the surfactant to be used in combination may change into a causative substance of increased filtration pressure. Further improvements were needed. In addition, there has been a problem with respect to an increase in the initial filtration pressure accompanying the thickening of the isophthalic acid component having a sulfonate group.

  That is, in the above background art, a cationic dyeable polyester composition in which the initial filtration pressure during melt spinning is reduced and the increase in filtration pressure during melt spinning is compatible is not known.

JP 2006-45696 A (Claims) JP-A-61-126131 (Claims) JP 2008-31322 A (Claims)

  An object of the present invention is to provide a cationic dyeable polyester composition in which an initial filtration pressure generated during melt spinning is reduced and an increase in filtration pressure during melt spinning can be suppressed.

  The above-described problem is a polyester whose main repeating unit is ethylene terephthalate, containing 1.0 to 3.0 mol% of an isophthalic acid component having a sulfonate group with respect to all dicarboxylic acid components, and containing 0 to polyethylene glycol for the polyester composition. It can be solved by a cationic dyeable polyester composition characterized by containing .5 to 2.0% by weight.

  The cationic dyeable polyester composition of the present invention has a reduced initial filtration pressure during melt spinning and can suppress an increase in filtration pressure during melt spinning. This makes it possible to reduce costs such as reducing the loss associated with filter filter replacement.

  The main component of the cationic dyeable polyester composition of the present invention is a polyester composition obtained after an esterification reaction or a transesterification reaction of a dicarboxylic acid or an ester derivative thereof and a diol.

  The cationic dyeable polyester of the present invention comprises ethylene terephthalate as a main repeating unit of 70 mol% or more, more preferably 80 mol% or more.

  The cationic dyeable polyester of the present invention has an isophthalic acid component having a sulfonate group based on the total dicarboxylic acid component in an amount of 1.0 to 3.0 mol%, and a polyethylene glycol content in the polyester composition of 0.5 to 2. The inclusion of 0% by weight is essential for reducing the initial filtration pressure generated when melt spinning using the cationic dyeable polyester composition and for suppressing the increase in filtration pressure during melt spinning. If either the content of the isophthalic acid component having a sulfonate group or the content of polyethylene glycol is out of the range, the thickening action due to the isophthalic acid component having a sulfonate group cannot be suppressed. And the increase in the filtration pressure during melt spinning becomes faster, and the object of the present application cannot be achieved. Preferably, a cationic dyeable polyester comprising 1.5 to 2.5 mol% of an isophthalic acid component having a sulfonate group relative to the total dicarboxylic acid component and 0.8 to 1.5 wt% of polyethylene glycol based on the total polyester composition. It is a composition.

  As the isophthalic acid component having a sulfonate group with respect to all the dicarboxylic acid components contained in the cationic dyeable polyester composition of the present invention, a known one may be used. Specifically, 5-sodium sulfoisophthalic acid, 5 -Sodium sulfoisophthalic acid dimethyl ester, 5-sodium sulfoisophthalic acid diethyl ester, 5-sodium sulfoisophthalic acid glycol ester, 5-lithium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid dimethyl ester, 5-lithium sulfoisophthalic acid diethyl ester And 5-lithium sulfoisophthalic acid diglycol ester and the like, and a mixture of these may be used. However, from the viewpoint of availability, methyl 5-sodium sulfoisophthalate, glyceryl 5-sodium sulfoisophthalate Ruesuteru is preferable.

  As the polyethylene glycol contained in the cationic dyeable polyester composition of the present invention, those having a number average molecular weight of 400 to 10,000 are preferably used from the viewpoint of availability. More preferably, the number average molecular weight is 600 to 5000, which has a high viscosity reducing effect due to interaction with the hydrophilic portion of the surfactant.

  The diethylene glycol (hereinafter referred to as “DEG amount”) of the cationic dyeable polyester composition of the present invention is preferably 1.7 to 8.0% by weight with respect to the polyester composition. When an isophthalic acid component having a sulfonate group is added during the ester reaction, the amount of diethylene glycol produced as a by-product increases, so that it is more preferably 2.5 to 4.0% by weight. More preferably, it is 2.9 to 3.5% by weight. When added during the ester reaction, although the amount of diethylene glycol is certainly increased, the production of foreign substances derived from the isophthalic acid component having a sulfonate group is suppressed, and an increase in filtration pressure can be suppressed, which is preferable.

  The surfactant contained in the cationic dyeable polyester of the present invention is preferably 0.03 to 0.6 mol%, more preferably 0.04 to 0.55 mol%, based on the polyester composition. is there. Since the surfactant has a hydrophilic group and a hydrophobic group in its structure, the hydrophobic group of the surfactant has a sulfonate group by controlling the ratio of the isophthalic acid component having the sulfonate group and the surfactant. In addition to suppressing the thickening action of the polyester by the isophthalic acid component, the hydrophilic group of the surfactant can more effectively express the thinning action of polyethylene glycol. By these effects, the initial filtration pressure at the time of melt spinning can be reduced, and further, the increase in the filtration pressure at the time of melt spinning can be suppressed.

As the surfactant contained in the cationic dyeable polyester composition of the present invention, a known surfactant having a hydrophilic group and a hydrophobic group is used, but an isophthalic acid component having a sulfonate group or polyethylene glycol, and a molecular structure or molecular weight. Since those having relatively close to each other exhibit a synergistic effect, the surfactant is preferably a compound having an aromatic ring. More preferred are sodium dodecylbenzenesulfonate and sodium salt of β-naphthalenesulfonate formalin condensate. The β-naphthalenesulfonic acid formalin condensate is available as “Demol N” manufactured by Kao Corporation. In particular, sodium dodecylbenzenesulfonate has the same structure as isophthalic acid having a sulfonate group in the hydrophilic group portion, an aromatic ring substituted by the sulfonate group, and an alkyl group in the side chain having a structure different from that of polyethylene glycol. Since it is easy to exhibit interaction, it is preferably used.
It is preferable that the lithium atom contained in the cation dyeable polyester composition of this invention is 0.03-0.4 mol% in conversion of lithium element with respect to a polyester composition. More preferably, it is 0.1-0.4 mol%. When the lithium atom is within this range, salt exchange occurs with the metal salt portion of the isophthalic acid component having a sulfonate group, so that ionic impurities that are the cause of increased filtration pressure during melt spinning are easily dissolved in the polymer. This is preferable because an increase in filtration pressure is suppressed. When a surfactant is used in combination, if the lithium atom is within this range, the surfactant has a sulfonate group by causing salt exchange with the metal salt portion of the isophthalic acid component having the surfactant and the sulfonate group. Coordinates with isophthalic acid component. The reason why coordination is facilitated is considered to be because the atomic radius of the lithium atom is the smallest. When the surfactant is easily coordinated to the isophthalic acid component having a sulfonate group, the initial filtration pressure at the time of melt spinning is reduced, and an increase in filtration pressure can be suppressed. As the lithium atom, a known lithium compound can be used. Lithium acetate dihydrate is preferred because of its availability.

  It is preferable that the phosphorus atom contained in the cation dyeable polyester composition of this invention is 0.005-0.08 mol% in conversion of phosphorus element with respect to a polyester composition. More preferably, it is 0.03-0.05 mol%. The phosphorus atom does not act directly on the surfactant, but the lithium atom and the phosphorus atom are likely to react, so the lithium atom reacted with the phosphorus atom is the metal salt part of the isophthalic acid component having a sulfonate group or It becomes difficult to cause salt exchange with the surfactant. From this, it is possible to improve the heat resistance of the polyester composition by optimizing the amount of phosphorus atoms, and when the surfactant is used in combination, the effect of the lithium atom on the surfactant is easily expressed. I can do it. As the phosphorus atom, a known phosphorus compound can be used. Preferred are trimethyl phosphate and phosphoric acid.

  The silicone compound contained in the cationic dyeable polyester composition of the present invention is preferably used in order to suppress foaming properties such as antioxidants and surfactants. It is preferable that it is 25 ppm or more and 250 ppm or less as a silicone compound with respect to all the polyester compositions. More preferably, it is 25 ppm or more and 100 ppm or less. As the silicone compound, a known ricone compound can be used. Polymethylphenylsiloxane is preferred. The polymethylphenylsiloxane can be purchased as TSF433 from Momentive Performance Materials Japan GK.

  The cationic dyeable polyester composition of the present invention may use a basic compound such as an aqueous solution containing 20% by weight of tetraethylammonium hydroxide (hereinafter referred to as EAH20) or potassium hydroxide in order to suppress by-production of diethylene glycol. These basic compounds may be used in combination. In particular, EAH20 is preferably used because interaction with other additives hardly occurs. EAH20 is preferably 125 ppm or less, more preferably 40 ppm or less in terms of nitrogen.

  The amount of carboxyl end groups of the cationic dyeable polyester composition of the present invention is preferably 25 to 50 equivalents / ton. More preferably, it is 30-45 equivalent / ton.

  In addition, a well-known additive can be included in the range which does not impair the objective of this invention. For example, a transesterification catalyst represented by metal acetates such as cobalt acetate, manganese acetate, and magnesium acetate, a radical scavenger represented by Irganox 1010, and a matting agent represented by titanium oxide. The content of cobalt acetate is preferably 5 to 50 ppm in terms of the amount of cobalt element. The content of manganese acetate is preferably 20 to 80 ppm in terms of the amount of manganese element.

  Specifically, the cationic dyeable polyester composition of the present invention can be produced as follows.

  The cationic dyeable polyester composition of the present invention undergoes an esterification reaction or a transesterification reaction of dicarboxylic acid or its ester-forming derivative with ethylene glycol, and provides an isophthalic acid component having a sulfonic acid for all dicarboxylic acid components as 1. Polyester composition by adding 0 to 3.0 mol%, adding polyethylene glycol to the polyester composition to 0.5 to 2.0 wt%, and performing polycondensation in the presence of a polycondensation catalyst. Can be manufactured.

  In the esterification reaction as a method for producing the cationic dyeable polyester composition of the present invention, the molar ratio of ethylene glycol or terephthalic acid is 1.05-1. The ester reaction can be carried out while continuously supplying 50 slurries to the ester reaction vessel. Alternatively, the esterification reaction may be performed after adding a total amount of ethylene glycol and terephthalic acid to the ester reaction tank before starting the esterification reaction in the state where the low polymer is present in the ester reaction tank in advance.

  The transesterification reaction as a method for producing the cationic dyeable polyester composition of the present invention is such that the molar ratio of ethylene glycol and dimethyl terephthalate is about 1.5 to 2.5, such as the transesterification reaction rate and diethylene glycol. This is preferable because it is possible to appropriately control by-product formation.

  A known catalyst can be used as the transesterification catalyst used in the method for producing the cationic dyeable polyester composition of the present invention. For example, cobalt, magnesium, manganese, titanium oxides and acetates are preferably used. These may be used as a mixture, or may be used alone or in any way.

  As a method for producing the cationic dyeable polyester composition of the present invention, the addition time of an isophthalic acid component having a sulfonate group is such that the isophthalic acid component having a sulfonate group is easily incorporated into an ethylene terephthalate unit as a main skeleton. Therefore, it is preferable to add during the ester reaction. More preferably, in order to suppress the amount of by-produced dialkylene glycol, the ester reaction rate is preferably 95% or more, and more preferably the ester reaction rate is 98% or more. Although an increase in diethylene glycol is inevitable, a method of adding it together with terephthalic acid or ethylene glycol and adding it before the ester reaction substantially starts is preferably employed.

  As a method for producing the cationic dyeable polyester composition of the present invention, the addition time of polyethylene glycol is preferably just before the start of the polymerization reaction in order to minimize the thermal history.

  As a method for producing the cationic dyeable polyester composition of the present invention, the addition timing of the surfactant is preferably preliminarily mixed with an isophthalic acid component having a sulfonate group and then an isophthalic acid component having a sulfonate group. It is preferable to be the same as the timing of addition. Addition to the reaction system at the same time is preferable because the surfactant is easily coordinated to the isophthalic acid component having a sulfonate group, and as a result, the thickening action is easily suppressed. The mixing time of the surfactant and the isophthalic acid component having a sulfonate group is not particularly limited. However, in order to facilitate the coordination of the surfactant to the isophthalic acid component having a sulfonate group, the mixing time is 15 minutes or more before addition to the reaction system. It is preferable to mix in advance.

  As a method for producing the cationic dyeable polyester composition of the present invention, the lithium compound is preferably added to the reaction system after mixing with an isophthalic acid component having a sulfonate group, and exchange with a metal salt is preferable. Is preferable, because coordination with an isophthalic acid component having a sulfonate group is likely to occur.

  As a manufacturing method of the cation dyeable polyester composition of this invention, the addition time of a phosphorus compound and a silicone compound can be added in the arbitrary steps before a polymerization reaction starts.

  A known polycondensation catalyst can be used as the polycondensation catalyst used as a method for producing the cationic dyeable polyester composition of the present invention. For example, antimony compounds, germanium compounds, titanium compounds and the like are preferably used. These may be used as a mixture or may be used alone.

  The esterification and polycondensation reaction apparatus for producing the cationic dyeable polyester composition of the present invention may be any apparatus as long as it is a commonly used reaction apparatus.

  From the above, the cationic dyeable polyester composition of the present invention has a reduced initial filtration pressure at the time of melt spinning due to a viscosity reducing action based on the polymer composition, and an increase in the filtration pressure at the time of melt spinning is suppressed. The present invention relates to a polyester composition capable of providing a fiber comprising an excellent cationic dyeable polyester. The present invention relates to a polyester composition whose main repeating unit is ethylene terephthalate, comprising 1.0 to 3.0 mol% of an isophthalic acid component having a sulfonate group relative to the total dicarboxylic acid component, and a polyethylene glycol based on the polyester composition Can be achieved for the first time by a cationic dyeable polyester composition characterized by containing 0.5 to 2.0% by weight.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured with the following method.

(1) Intrinsic viscosity of polyester (IV)
The sample was dissolved in orthochlorophenol and measured at 25 ° C. using an Ostwald viscometer.

(2) Color tone of polyester Measured using a color difference meter (SM color computer model SM-T45, manufactured by Suga Test Instruments). Measured as Hunter value (b value).

(3) Diethylene glycol (DEG) content of polyester A sample was hydrolyzed with monomethanolamine and then diluted with 1,6-hexanediol / methanol.
After neutralizing with terephthalic acid, it was determined from the peak area of gas chromatography.

(4) COOH amount of polyester Using orthocresol as a solvent, it was titrated with an automatic titration apparatus (COM-550, manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.02 N aqueous NaOH solution at 25 ° C.

(5) Initial pressure during spinning Using a 15-micron non-woven filter having a diameter of 95 mm, the polyester was melt filtered at a discharge rate of 70 g / min, and the entry pressure of the non-woven fabric filter 2 hours after the start of pouring was used as the initial pressure during spinning.

(6) Spinning ΔP
Based on the number of days elapsed until the pressure on the entry side of the nonwoven fabric filter reached 25 MPa, it was calculated in terms of MPa / day according to Formula 1, and was determined according to the following criteria.
(25.0-Initial pressure during spinning) / Elapsed days [MPa / day] Formula 1
○: Less than 2.5 MPa / day
X: 2.5 MPa / day or more.

(7) Dyeability (L value)
A cylindrical knitted fabric was produced with two gauge yarns (150 dtex) from the obtained drawn yarn at 22 gauge. I. Staining was carried out for 60 minutes in a 95 ° C. hot water solution of 5% owf of Basic Blue 66, 0.5 ml / l of acetic acid, 0.2 g / l of sodium acetate and a bath ratio of 1: 100, and the measurement method of (2) above. The color tone L value was determined and judged according to the following criteria.

○: Less than 45
X: 45 or more.

[Reference example]
(Transesterification reaction)
Ethylene glycol and dimethyl terephthalate are added to a reaction vessel equipped with a rectifying column so that the molar ratio of ethylene glycol / dimethyl terephthalate is 2.0, and cobalt acetate tetrahydrate is added as a transesterification catalyst. It added so that it might contain in 400 ppm in the obtained low polymer. Then, while raising the temperature of the reaction vessel from 140 ° C. to 235 ° C., methanol was distilled off to conduct a transesterification reaction, thereby obtaining a low polymer of bishydroxyethyl terephthalate. The transesterification rate at this time was 98%.

[Example 1]
After adding 700 ppm of EAH20 to the low polymer in an ester reaction vessel in which 1750 kg of the low polymer of bishydroxyethyl terephthalate is present, a slurry having an ethylene glycol / terephthalic acid molar ratio of 1.15 is added over 3 hours. The reaction was continued until the esterification reaction rate reached 98% while keeping the reaction vessel temperature at 245 ° C. by distilling off only water generated during the ester reaction from the upper stage of the rectifying column. Next, 1.8 mol% of lithium acetate and lithium acetate obtained with respect to the polyester obtained by replacing both ends of 5-sodium sulfoisophthalic acid with ethylene glycol (hereinafter referred to as 5-sodium sulfoisophthalic acid diEG ester) -0.30 mol% with respect to the polyester which can obtain a dihydrate was previously mixed for 30 minutes, and it added to the ester reaction tank over about 10 minutes, and was then heat-mixed for about 30 minutes. The obtained low polymer containing 5-sodium sulfoisophthalic acid diEG was 3185 kg. Of these, 1435 kg was transferred to the polymerization reactor while being filtered through a 10 micron filter.

  Add to the low polymer transferred to the polymerization reaction tank so that the silicone compound (product name: TSF-433, Momentive Performance Materials Japan LLC) can be obtained to 50 ppm, based on the addition. It added so that it might become 0.040 mol% with respect to polyester which can obtain phosphoric acid after 1 minute. Seven minutes after the addition of phosphoric acid, it is 900 ppm for the polyester from which Irganox 1010 is obtained, 40 ppm in terms of cobalt for the polyester from which cobalt acetate is obtained, and 225 ppm in terms of antimony element for the polyester from which antimony trioxide is obtained. Add to. 3 minutes after the end of the addition, 1.0% by weight is added to the polyester composition from which polyethylene glycol having a number average molecular weight of 1000 can be obtained. Three minutes after the end of the addition, titanium oxide (ethylene glycol slurry of titanium oxide, titanium oxide concentration in ethylene glycol concentration of 13.0% by weight) is added to 0.07% by weight with respect to the obtained polyester. After 2 minutes from the end of the addition, the pressure is reduced from normal pressure to 0.1 kPa over 40 minutes, the temperature is raised from 235 ° C. to 290 ° C., and a high vacuum of 0.1 kPa or less is maintained. The polycondensation reaction was performed until the intrinsic viscosity (IV) became 0.69 dl / g. The polyester obtained had a b value of 12.8, a DEG amount of 3.3% by weight, and a COOH amount of 41.0 eq / ton, which were excellent in quality.

(Spinning method)
After drying this polyester, it was subjected to a spinning machine, filtered at a spinning temperature of 293 ° C. with a 15-micron non-woven filter having a diameter of 95 mm, and a molten polyester having a discharge rate of 70 g / min, a discharge port diameter of 0.25 mm and a hole depth of 0.35 mm. Is discharged from a nozzle nozzle having 96 round holes, and the discharged yarn is cooled and solidified by a cooling chimney with a cooling air of 0.5 m / second, and converged by an oil supply device at a position 2 m below the nozzle. An oil agent is applied (applied as 1% by weight with respect to the fiber weight as a pure oil component), pre-entangled at a working pressure of 0.25 MPa using compressed air as a fluid with an entanglement nozzle, a first godet roll with a peripheral speed of 2750 m / min, The cheese package was wound with 12 kg of undrawn yarn of 130 dtex and 48 filaments. The peripheral speed of the winder was 2720 m / min. The initial spinning pressure at this time was 11.0 MPa, and the spinning ΔP was 2.2 MPa / day, and stable operation was possible.

(Extension false twist method)
The obtained undrawn yarn was subjected to drawing false twisting using a disk false twister at a heater temperature of 180 ° C., a drawing speed of 400 m / min, a DY ratio of 1.55 and a draw ratio of 1.7 times, and 75 dtex, 36 filaments The processed yarn was obtained.

(Dyeing method)
A cylindrical knitted fabric was produced using the obtained processed yarn, and dyeing was performed by the method (7). The obtained tubular knitted fabric had an L value of 30.8 and was excellent in dyeability.

[Examples 2 to 6]
A polyester was produced in the same manner as in Example 1 except that the conditions described in Table 1 were used. As shown in Table 1, the quality of the polyester composition was good, and the yarn production evaluation was also good.

[Example 7]
After adding 700 ppm of EAH20 to the low polymer in an ester reaction vessel in which 1750 kg of the low polymer of bishydroxyethyl terephthalate is present, a slurry having an ethylene glycol / terephthalic acid molar ratio of 1.15 is added over 3 hours. The reaction was continued until the esterification reaction rate reached 98% while keeping the reaction vessel temperature at 245 ° C. by distilling off only water generated during the ester reaction from the upper stage of the rectifying column. Next, it becomes 1.8 mol% with respect to the polyester which can obtain what substituted the both terminal of 5-sodium sulfo isophthalic acid by ethylene glycol (henceforth 5-sodium sulfo isophthalic acid diEG ester). Weigh and mix 0.30 mol% with respect to the polyester to obtain lithium acetate dihydrate and 0.06 mol% with respect to the polyester to obtain sodium dodecylbenzenesulfonate (DBS) for 30 minutes in advance. The mixture was added to the reaction vessel over about 10 minutes, and then heated and mixed for about 30 minutes. The obtained low polymer containing 5-sodium sulfoisophthalic acid diEG was 3185 kg. Of these, 1435 kg was transferred to the polymerization reactor while being filtered through a 10 micron filter.

  Add to the low polymer transferred to the polymerization reactor to 100 ppm with respect to the polyester from which the silicone compound (product name: TSF-433, Momentive Performance Materials Japan GK) is obtained. It added so that it might become 0.040 mol% with respect to polyester which can obtain phosphoric acid after 1 minute. 7 minutes after the addition of phosphoric acid, it is 900 ppm for the polyester from which Irganox 1010 is obtained, 40 ppm in terms of cobalt for the polyester from which cobalt acetate is obtained, and 225 ppm in terms of antimony for the polyester from which antimony trioxide is obtained. Add to. 3 minutes after the end of the addition, 1.0% by weight is added to the polyester composition from which polyethylene glycol having a number average molecular weight of 1000 can be obtained. Three minutes after the end of the addition, titanium oxide (ethylene glycol slurry of titanium oxide, titanium oxide concentration in ethylene glycol concentration of 13.0% by weight) is added to 0.07% by weight with respect to the obtained polyester. After 2 minutes from the end of the addition, the pressure is reduced from normal pressure to 0.1 kPa over 40 minutes, the temperature is raised from 235 ° C. to 290 ° C., and a high vacuum of 0.1 kPa or less is maintained. The polycondensation reaction was performed until the intrinsic viscosity (IV) became 0.69 dl / g. The polyester obtained had a b value of 13.3, a DEG amount of 3.3% by weight, and a COOH amount of 41.2 eq / ton, which were excellent in quality.

(Spinning method)
After drying this polyester, it was subjected to a spinning machine, filtered at a spinning temperature of 293 ° C. with a 15-micron non-woven filter having a diameter of 95 mm, and a molten polyester having a discharge rate of 70 g / min, a discharge port diameter of 0.25 mm and a hole depth of 0.35 mm. Is discharged from a nozzle nozzle having 96 round holes, and the discharged yarn is cooled and solidified by a cooling chimney with a cooling air of 0.5 m / second, and converged by an oil supply device at a position 2 m below the nozzle. An oil agent is applied (applied as 1% by weight with respect to the fiber weight as a pure oil component), pre-entangled at a working pressure of 0.25 MPa using compressed air as a fluid with an entanglement nozzle, a first godet roll with a peripheral speed of 2750 m / min, The cheese package was wound with 12 kg of undrawn yarn of 130 dtex and 48 filaments. The peripheral speed of the winder was 2720 m / min. The initial spinning pressure at this time was 10.0 MPa, and the spinning ΔP was 2.1 MPa / day, and stable operation was possible.

(Extension false twist method)
The obtained undrawn yarn was subjected to drawing false twisting using a disk false twister at a heater temperature of 180 ° C., a drawing speed of 400 m / min, a DY ratio of 1.55 and a draw ratio of 1.7 times, and 75 dtex, 36 filaments The processed yarn was obtained.

(Dyeing method)
A cylindrical knitted fabric was produced using the obtained processed yarn, and dyeing was performed by the method (7). The obtained tubular knitted fabric had an L value of 32.0 and was excellent in dyeability.

[Examples 8 to 19]
A polyester was produced in the same manner as in Example 7 except that the conditions described in Table 2 were used. As shown in Table 2, the quality of the polyester composition was good, and the yarn production evaluation was also good.

[Comparative Example 1]
After adding 700 ppm of EAH20 to the low polymer in an ester reaction vessel in which 1750 kg of the low polymer of bishydroxyethyl terephthalate is present, a slurry having an ethylene glycol / terephthalic acid molar ratio of 1.15 is added over 3 hours. The water is continuously supplied, and only water generated during the ester reaction is distilled off from the upper stage of the rectification column, and the reaction is performed until the esterification reaction rate reaches 98% while maintaining the reaction vessel temperature at 245 ° C. The low polymer mainly composed of bishydroxyethyl terephthalate obtained at this time was 3185 kg. Of these, 1435 kg was transferred to the polymerization reactor while being filtered through a 10 micron filter.

  It is added to the low polymer transferred to the polymerization reaction tank so that it becomes 50 ppm with respect to the polyester from which the silicone compound (product name: TSF-433, manufactured by Momentive Performance Materials Japan GK) is obtained. 1 minute later, phosphoric acid was added to 0.040 mol% based on the polyester. Seven minutes after the addition of phosphoric acid, 900 ppm for the polyester that can obtain IR1010, 40 ppm in terms of cobalt for the polyester that can obtain cobalt acetate, and 225 ppm in terms of antimony element for the polyester that can obtain antimony trioxide. To do. Three minutes after the end of the addition, 1.0% by weight is added to the polyester from which polyethylene glycol having a number average molecular weight of 1000 can be obtained. Three minutes after the end of the addition, 5-sodium sulfoisophthalic acid diEG ester (1.8 mol% with respect to the obtained polyester) and lithium acetate dihydrate (0 with respect to the obtained polyester) mixed in advance for 30 minutes. .30 mol%) is added to the polymerization reactor over about 15 minutes. Three minutes later, titanium oxide (ethylene glycol slurry of titanium oxide, titanium oxide concentration in ethylene glycol 13.0% by weight) is added to 0.07% by weight with respect to the obtained polyester. After 2 minutes from the end of the addition, the pressure is reduced from normal pressure to 0.1 kPa over 40 minutes, the temperature is raised from 235 ° C. to 290 ° C., and a high vacuum of 0.1 kPa or less is maintained. The polycondensation reaction was performed until the intrinsic viscosity (IV) became 0.69 dl / g. The polyester obtained had a b value of 13.0, a DEG amount of 1.4% by weight, and a COOH amount of 51.0 eq / ton.

  Using the obtained polyester, the evaluation of yarn production was carried out by the method described in Example 1, and the results described in Table 3 were obtained. The obtained tubular knitted fabric had an L value of 30.8 and excellent dyeability, but the spinning ΔP was large and stable production could not be performed.

[Comparative Example 2]
A polyester was produced in the same manner as in Example 1 except that the conditions described in Table 3 were used. As shown in Table 3, the spinning ΔP was small, but the dyeability was poor.

[Comparative Example 3]
A polyester was produced in the same manner as in Example 1 except that the conditions described in Table 3 were used. As shown in Table 3, the spinning ΔP was large and stable production could not be performed.

[Comparative Example 4]
A polyester was produced in the same manner as in Comparative Example 1 except that the conditions described in Table 3 were used, and the yarn production was evaluated. The obtained tubular knitted fabric had an L value of 33.2 and excellent dyeability, but the spinning ΔP was large and stable production could not be performed.

[Comparative Example 5]
Since an isophthalic acid component having a sulfonate group was not added, a polyester was produced in the same manner as in Comparative Example 1 under the conditions described in Table 3 except that lithium acetate dihydrate was added after the addition of antimony trioxide. Yarn evaluation was performed. As shown in Table 3, the spinning ΔP was small, but the dyeability was poor.

[Comparative Example 6]
After adding 700 ppm of EAH20 to the low polymer in an ester reaction vessel in which 1750 kg of the low polymer of bishydroxyethyl terephthalate is present, a slurry having an ethylene glycol / terephthalic acid molar ratio of 1.15 is added over 3 hours. The water is continuously supplied, and only water generated during the ester reaction is distilled off from the upper stage of the rectification column, and the reaction is performed until the esterification reaction rate reaches 98% while maintaining the reaction vessel temperature at 245 ° C. The low polymer mainly composed of bishydroxyethyl terephthalate obtained at this time was 3185 kg. Of these, 1435 kg was transferred to the polymerization reactor while being filtered through a 10 micron filter.

  It is added to the low polymer transferred to the polymerization reaction tank so that the silicone compound (product name: TSF-433, manufactured by Momentive Performance Materials Japan Godo Kaisha) can be obtained to 100 ppm. 1 minute later, phosphoric acid was added to 0.040 mol% based on the polyester. Seven minutes after the addition of phosphoric acid, 900 ppm for the polyester that can obtain IR1010, 40 ppm in terms of cobalt for the polyester that can obtain cobalt acetate, and 225 ppm in terms of antimony element for the polyester that can obtain antimony trioxide. To do. Three minutes after the end of the addition, 1.0% by weight is added to the polyester from which polyethylene glycol having a number average molecular weight of 1000 can be obtained. Three minutes after the end of the addition, 5-sodium sulfoisophthalic acid diEG ester (1.8 mol% with respect to the obtained polyester) and lithium acetate dihydrate (0 with respect to the obtained polyester) mixed in advance for 30 minutes. 30 mol%) and sodium dodecylbenzenesulfonate (0.01 mol% relative to the resulting polyester) are added to the polymerization reactor over about 15 minutes. Three minutes later, titanium oxide (ethylene glycol slurry of titanium oxide, titanium oxide concentration in ethylene glycol 13.0% by weight) is added to 0.07% by weight with respect to the obtained polyester. After 2 minutes from the end of the addition, the pressure is reduced from normal pressure to 0.1 kPa over 40 minutes, the temperature is raised from 235 ° C. to 290 ° C., and a high vacuum of 0.1 kPa or less is maintained. The polycondensation reaction was performed until the intrinsic viscosity (IV) became 0.69 dl / g. The polyester obtained had a b value of 13.2, a DEG amount of 1.4% by weight, and a COOH amount of 51.2 eq / ton.

  Using the obtained polyester, the evaluation of yarn production was carried out by the method described in Example 7, and the results described in Table 4 were obtained. The obtained tubular knitted fabric had an L value of 31.2 and excellent dyeability, but the spinning ΔP was large and stable production could not be performed.

[Comparative Example 7]
A polyester was produced in the same manner as in Comparative Example 6 except that the conditions described in Table 4 were used, and the yarn production was evaluated. As shown in Table 4, the spinning ΔP was large and the dyeability was poor.

[Comparative Example 8]
A polyester was produced in the same manner as in Example 7 except that the conditions described in Table 4 were used, and the yarn production was evaluated. As shown in Table 4, the spinning ΔP was small, but the dyeability was poor.

[Comparative Example 9]
A polyester was produced in the same manner as in Example 7 except that the conditions described in Table 4 were used, and the yarn production was evaluated. As shown in Table 4, the spinning ΔP was large and stable production could not be performed.

[Comparative Example 10]
A polyester was produced in the same manner as in Comparative Example 6 except that the conditions described in Table 4 were used, and the yarn production was evaluated. The obtained tubular knitted fabric had an L value of 33.6 and excellent dyeability, but the spinning ΔP was large and stable production could not be performed.

[Comparative Example 11]
Since an isophthalic acid component having a sulfonate group was not added, a polyester was produced in the same manner as in Comparative Example 6 under the conditions described in Table 4 except that lithium acetate dihydrate was added after the addition of antimony trioxide. Yarn evaluation was performed. As shown in Table 4, the spinning ΔP was small, but the dyeability was poor.

Claims (5)

  The main repeating unit is a polyester composed of ethylene terephthalate, which contains 1.0 to 3.0 mol% of an isophthalic acid component having a sulfonate group with respect to the total dicarboxylic acid component, and the content of polyethylene glycol in the polyester composition is 0.00. A cationic dyeable polyester composition comprising 5 to 2.0% by weight.   A cationic dyeable polyester composition characterized in that the main repeating unit is a polyester composed of ethylene terephthalate and contains 1.7 to 8.0% by weight of diethylene glycol content relative to the polyester composition.   The cationic dyeable polyester composition according to claim 1 or 2, wherein the main repeating unit is a polyester composed of ethylene terephthalate and contains 0.03 to 0.6 mol% of a surfactant for the polyester composition. object.   The cationic dyeable polyester composition according to claim 3, wherein the surfactant is a compound having an aromatic ring.   The cationic dyeable polyester composition according to claim 4, wherein the surfactant is sodium dodecylbenzenesulfonate.