JP5216971B2 - Method for producing cationic dyeable polyester fiber - Google Patents

Description

  The present invention relates to a method for producing a cationic dyeable polyester fiber. More specifically, a cationic dyeable polyester obtained by blending and spinning a polyester chip having a large amount of cationic dyeable monomer copolymerization and a polyester chip substantially not copolymerized with a cationic dyeable monomer. The present invention relates to a fiber manufacturing method.

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

  Polyesters typified by polyethylene terephthalate have been variously modified depending on the application, and copolyesters obtained by copolymerizing various components are widely known. Among these, cationic dyeable polyesters obtained by copolymerizing components having cationic dyeability are widely known mainly for clothing applications.

  Polyethylene terephthalate which is usually used to obtain such a cationic dyeable polyester is usually obtained by directly esterifying terephthalic acid and ethylene glycol, for example, or lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol. Are 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, this reaction product is produced by heating under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a predetermined degree of polymerization is obtained. At any stage of this production process, sulfone, which is a copolymerization component, is produced. A method has been adopted in which a cationic dyeable polyester is obtained by copolymerizing 2 to 3 mol% of a cationic dyeable monomer typified by a metal salt of isophthalic acid and dyed at a high temperature and high pressure (for example, (See Patent Document 1).

  However, since typical cationic dyeable monomers such as 5-sodium sulfoisophthalic acid and derivatives thereof, which are typical cationic dyeable monomers, are ionic components, ionic bonds are formed in the polyester polymerization stage. Since the intermolecular force acts and the melt viscosity increases, it is difficult to produce a high molecular weight cationic dyeable polyester, and the polyester fiber obtained by melt spinning has a low strength. It was.

In order to solve such a problem, a technique for copolymerizing a cationic dyeable monomer having a small ion binding intermolecular force has been disclosed (for example, see Patent Documents 2 and 3). The small cation dyeable monomers having ionic bonding intermolecular force, 5-sulfo the like isophthalate tetrabutoxytitanate phosphonium are illustrated, these cationic dyeable monomers copolymerized polyester has poor thermal stability, the polymerization step It is well known that the quality of polyester depends greatly on the type of catalyst used. Further, strength of the resulting yarn, although is improved than when using 5-sodium sulfoisophthalic acid and its derivatives of the foregoing, 5-sulfoisophthalic acid tetrabutoxytitanate phosphonium used is very expensive, as a result There was a problem that the cost of the resulting cationic dyeable polyester increased significantly.

Japanese Patent Publication No.34-10497 Japanese Patent Laid-Open No. 01-162822 JP 2006-176628 A

  The objective of this invention is providing the polyester fiber by the manufacturing method of the cationic dyeable polyester fiber which can obtain a polyester fiber with high intensity | strength, and its manufacturing method.

As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention. That is, the present invention provides a polyester B which Poriesu Te Le A as the main repeating unit main repeating unit consists of ethylene terephthalate comprising ethylene terephthalate, after each polymerized in a state satisfying the following requirements, melt spinning a mixture of these The content of the aromatic dicarboxylic acid component having a sulfoisophthalate group in the polyester fiber is 2 with respect to the total acid components constituting the polyester fiber. the fraction of less than .5 mole% to 3.0 mole%, 285 ° C., a melt viscosity of Poriesu Te Le a and polyester B were measured at a shear rate of 1000 / s is, by satisfying the following general formula (I) This is a method for producing a cationic dyeable polyester fiber, which can solve the above-mentioned problems.
(Polyester A)
The aromatic dicarboxylic acid component having a sulfoisophthalic acid group is a copolymerized polyester copolymerized in an amount of 10 to 20 mol% with respect to all the acid components constituting the polyester A, and the diethylene glycol contained in the polyester A is 5 Copolyester characterized by being not more than% by weight.
(Polyester B)
A polyester having an ethylene terephthalate component of 95 mol% or more in all repeating units constituting the polyester and an intrinsic viscosity in the range of 0.50 to 1.00 dL / g.
0.8 ≦ A / B ≦ 2.5 (I)
[In the above formula, A and B represent the melt viscosities of polyester A and polyester B measured at 285 ° C. and a shear rate of 1000 / s, respectively. ]

  ADVANTAGE OF THE INVENTION According to this invention, a high intensity | strength cationic dyeable polyester fiber can be provided with the copolyester of a metal salt of sulfoisophthalic acid.

Hereinafter, the present invention will be described in detail. The polyester constituting the cationic dyeable polyester fiber of the present invention is a polyester comprising a polyester having ethylene terephthalate as a main repeating unit obtained by polycondensation reaction of terephthalic acid or an ester-forming derivative thereof and an ethylene glycol component. and Te Le a, also the polyesters B containing ethylene terephthalate as the main repeating unit, after each polymerized in a state satisfying the following requirements, a polyester obtained by melt spinning a mixture of these. Here, “to be the main repeating unit” means that 80 mol% or more of all repeating units constituting the polyester is composed of ethylene terephthalate repeating units. Furthermore, 285 ° C., a melt viscosity of Poriesu Te Le A and polyester B were measured at a shear rate of 1000 / s is a cationic dyeable polyester fiber characterized by satisfying the following formula (I), polyester fibers The content of the aromatic dicarboxylic acid component having a sulfoisophthalic acid group in the polyester fiber is a ratio of 1.1 mol% or more and less than 3.0 mol% with respect to the total acid component in the polyester fiber.

(Polyester A)
The aromatic dicarboxylic acid component having a sulfoisophthalic acid group is a copolymerized polyester copolymerized in an amount of 7 to 20 mol% based on the total acid components constituting the polyester A, and the diethylene glycol contained in the polyester A is 5 Copolyester characterized by being not more than% by weight.

(Polyester B)
A polyester having an ethylene terephthalate component of 95 mol% or more in all repeating units constituting the polyester and an intrinsic viscosity in the range of 0.50 to 1.00 dL / g.
0.8 ≦ A / B ≦ 2.5 (I)
[In the above formula, A and B represent the melt viscosities of polyester A and polyester B measured at 285 ° C. and a shear rate of 1000 / s, respectively. ]

  As an aromatic dicarboxylic acid component having a sulfoisophthalate group copolymerized with the polyester A used in the present invention, a metal salt of 5-sulfoisophthalic acid (specifically, lithium salt, sodium salt, potassium salt), Examples are quaternary phosphonium salts of 5-sulfoisophthalic acid or quaternary ammonium salts of 5-sulfoisophthalic acid. These ester-forming derivatives are also preferably exemplified. Examples of ester-forming derivatives include lower dialkyl esters having 1 to 6 carbon atoms, lower diaryl esters having 6 to 8 carbon atoms, and dicarboxylic acid halides (dicarboxylic acid chlorides and dicarboxylic acid bromides). Specific examples include dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester or diphenyl ester. More specific quaternary phosphonium salts and quaternary ammonium salts include tetramethylphosphonium salt (or tetramethylammonium salt), tetraethylphosphonium salt (or tetraethylammonium salt), tetrapropylphosphonium salt (or tetrapropylammonium salt), List tetrabutylphosphonium salt (or tetrabutylammonium salt), trimethylbenzylphosphonium salt (or trimethylbenzylammonium salt), triethylbenzylphosphonium salt (or triethylbenzylammonium salt) or tributylbenzylphosphonium salt (or tributylbenzylammonium salt) Can do. Among these groups, a metal salt of 5-sulfoisophthalic acid is preferably exemplified from the viewpoints of thermal stability, cost, etc., and in particular, 5-sulfoisophthalic acid which is a sodium salt of 5-sulfoisophthalic acid or a dimethyl ester thereof. The sodium salt of acid dimethyl ester is particularly preferred.

  When the amount of copolymerization of the aromatic dicarboxylic acid component having a sulfoisophthalic acid group copolymerized with the polyester A of the present invention is less than 7 mol% based on the total acid components constituting the polyester, Unless the mixing ratio of polyester A in the polyester fiber is increased, the content of the aromatic dicarboxylic acid component containing sulfoisophthalic acid in the polyester fiber after blend spinning cannot be set to a desired concentration. Therefore, the strength of the obtained polyester fiber becomes insufficient. On the other hand, when the copolymerization amount exceeds 20 mol% with respect to the total acid component constituting the polyester, it becomes difficult to form a chip after melt polymerization of polyester A, and the resulting polyester fiber is subjected to alkali weight reduction processing. When the polyester A component in the polyester fiber is eluted, sufficient cationic dyeability cannot be obtained, which is not preferable. The copolymerization amount is preferably 7 mol% or more and 15 mol% or less, and more preferably 8 mol% or more and less than 10 mol%. The total acid component includes, of course, an aromatic dicarboxylic acid having the 5-sulfoisophthalic acid group, but includes terephthalic acid and other dicarboxylic acid components constituting polyethylene terephthalate.

  Furthermore, the diethylene glycol component contained in the polyester A of the present invention needs to be 5% by weight or less. When the content exceeds 5% by weight, the strength of the resulting polyester fiber is lowered, which is not preferable. In order to reduce the diethylene glycol component to 5% by weight or less, it is a matter of course that diethylene glycol is not used in a large amount as a copolymerization component, but the esterification reaction, transesterification reaction, polycondensation reaction, and one reaction thereof to the next reaction. It should be noted that the conditions under which diethylene glycol is produced as a by-product are not adopted in each step of shifting to (1). The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of polyester B used in the present invention needs to be 0.50 to 1.00 dL / g. When the intrinsic viscosity is less than 0.50 dL / g, the strength of the resulting polyester fiber is insufficient. On the other hand, when it exceeds 1.00 dL / g, polyester B is produced by the solid phase polymerization method following the melt polymerization method. This is not preferable because the production cost in the polycondensation step of polyester B is greatly increased and the melt viscosity of polyester B is increased, so that the spinnability in the spinning step is deteriorated. A more preferable range of intrinsic viscosity is 0.60 to 0.90 dL / g.

  Furthermore, the polyester B needs to have 95 mol% or more of ethylene terephthalate components in all repeating units constituting the polyester. If it is less than 95 mol%, the strength of the resulting polyester fiber may be insufficient. Furthermore, it is preferable that the polyester B does not substantially contain an aromatic dicarboxylic acid component having a sulfoisophthalate group. The term “substantially” means that it is several hundred ppm or less in weight when it is erroneously included due to contamination in the manufacturing process, for example. If the polyester B contains an aromatic dicarboxylic acid having a sulfoisophthalic acid group, it may be difficult to increase the intrinsic viscosity to the above value.

  The manufacturing method of the polyester A and the polyester B in this invention is not specifically limited, As long as said requirements are satisfy | filled, the manufacturing method of the polyester generally known is used. That is, a low polymer is produced by a direct polycondensation reaction between terephthalic acid and ethylene glycol, or an ester exchange reaction between an ester-forming derivative of terephthalic acid typified by dimethyl terephthalate and ethylene glycol. 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. As a method of copolymerizing an aromatic dicarboxylic acid having a sulfoisophthalate group and / or an ester-forming derivative thereof, a generally known production method can be used. In general, when a cationic dyeable polyester is produced, it is preferable to add a small amount of alkali metal salt or alkaline earth metal salt in order to suppress the amount of diethylene glycol by-produced in the polyester polymerization step. By this method, the diethylene glycol content in the polyester A can be within the above range.

  Further, the polyester A and the polyester B in the present invention contain a small amount of additives as necessary, for example, an antioxidant, a fluorescent whitening agent, an antistatic agent, an antibacterial agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, It may contain a light-shielding agent or a matting agent. In particular, antioxidants and matting agents are particularly preferably added.

The ratio of the melt viscosity of polyester A and polyester B in the present invention needs to be in the range of the following general formula (I).
0.8 ≦ A / B ≦ 2.5 (I)
[In the above formula, A and B represent the melt viscosities of polyester A and polyester B measured at 285 ° C. and a shear rate of 1000 / s, respectively. ]

  When A / B is less than 0.8, the molecular weight of the polyester A is remarkably reduced, and a polyester fiber having sufficient strength cannot be obtained. On the other hand, when A / B exceeds 2.5, uniform mixing and dispersion of polyester A and polyester B in the spinning process are not sufficient. Therefore, large spots of polyester A and polyester B are generated in the obtained polyester fiber, which is not preferable because the strength of the resulting polyester fiber is lowered. Furthermore, in order to satisfy the above range of the melt viscosity ratio, both polyester A and polyester B are polymerized so as to satisfy the above requirements, and there is an acid that may greatly affect other melt viscosity fluctuations. This can be achieved by copolymerizing the component or glycol component, or by not blending an organic or inorganic compound having such properties.

  Among these, setting the value of the intrinsic viscosity of polyester B within the above range can be considered as one of the effective means. Since polyester A has an aromatic dicarboxylic acid component having a sulfoisophthalate group copolymerized, as described in the background art section, the melt viscosity increases even at a low intrinsic viscosity. It has been difficult to produce a polyester, for example, a polyester having an intrinsic viscosity of 0.5 dL / g or more as defined in the polyester B of the present invention. In order to increase the melt viscosity of polyester B so as to satisfy the above formula (I) for polyester A having a high melt viscosity even at such a relatively low intrinsic viscosity, it is compared with increasing the intrinsic viscosity. This is because it can be implemented easily. The intrinsic viscosity of the polyester B can be increased by performing melt polymerization and then solid phase polymerization. In addition, as described later, raising the intrinsic viscosity of polyester B can be said to be a preferable embodiment for solving the problems of the present invention because the intrinsic viscosity of polyester after blending polyester A and polyester B can be kept high. .

  The manufacturing method of the high intensity | strength cationic dyeable polyester fiber in this invention is the method of melt-spinning the polyester, after mixing the polyester A and the polyester B. FIG. When the content of the aromatic dicarboxylic acid component having a sulfoisophthalate group in the polyester fiber after blending is less than 1.1 mol%, the dyeing after the cationic dyeing is poor, and a polyester fiber having a clear color development is obtained. Since it is not, it is not preferable. On the other hand, when the content is 3.0 mol% or more, the strength of the resulting polyester fiber is lowered, which is not preferable. As described above, the polyester A obtained by copolymerizing an aromatic dicarboxylic acid having a sulfoisophthalate group may have difficulty in increasing its intrinsic viscosity. Accordingly, the aromatic dicarboxylic acid having a sulfoisophthalic acid group is not copolymerized and blended with the polyester B having a relatively high intrinsic viscosity, whereby the aromatic polyester having the sulfoisophthalic acid group in the polyester after blending is blended. Even if the amount of copolymerization is large, a relatively high intrinsic viscosity can be maintained, and good atmospheric pressure cationic dyeability and high breaking strength can be realized simultaneously.

  As a method for producing cationic dyeable polyester fibers in the present invention, a method of blending and spinning the above two kinds of polyester chips is employed. That is, it is preferable to manufacture by spinning a chip composed of dried polyester A and a chip composed of dried polyester B and then melt spinning in the range of 270 ° C. to 300 ° C., and the melt spinning take-up speed is 400 to 5000 m. It is preferable to spin at a speed of / min. When the spinning speed is in this range, the polyester fiber obtained has sufficient strength and can be wound stably. Moreover, about the blend ratio of polyester A and polyester B, it has the copolymerization rate of the aromatic dicarboxylic acid component which has the sulfoisophthalic acid group copolymerized in the polyester A, and has the sulfoisophthalic acid group in the obtained polyester fiber. In consideration of the content of the aromatic dicarboxylic acid component, it can be easily determined. Further, the cationic dyeable polyester fiber of the present invention preferably has a tensile strength of 3.5 cN / dtex. For that purpose, it is preferable that the undrawn yarn wound by the above-described method is further drawn in a range of about 1.2 times to 6.0 times in a drawing step. This stretching may be performed after winding the unstretched polyester fiber once, or may be performed continuously without winding. Moreover, there is no restriction | limiting in particular also about the shape of the nozzle | cap | die used at the time of spinning.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. In addition, the analysis item etc. in an Example were measured by the method of the following description.

(A) Diethylene glycol (DEG) content The polyester composition chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was determined by gas chromatography (HP6850 type manufactured by Hewlett-Packard Company). )).

(A) Melt viscosity After drying the polyester composition chip at 140 ° C. for 8 hours, the shear rate was 1000 / s from the value measured at 285 ° C. using a flow tester (manufactured by Shimadzu Corporation (CFT-500D)). The value at was obtained.

(U) 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.

(D) Tensile strength (breaking strength) and tensile elongation (breaking elongation) of polyester fiber
The measurement was performed according to the method described in JIS L1013: 1999 8.5.

(E) Cationic dyeing CATHILON BLUE CD-FRL H0 . 1 hour at 130 ° C. in a staining solution of 2 g / L, CD-FBLH 0.2 g / L (both cation dyeable dyes manufactured by Hodogaya Chemical Co., Ltd.), sodium sulfate 3 g / L, acetic acid 0.3 g / L Dyeing was performed at a bath ratio of 1:50, and the dyeing rate was determined by the following formula.
Dyeing rate = (OD ₀ −OD ₁ ) / OD ₀ × 100 (%)
OD ₀ : Absorbance at 576 nm of the dye solution before dyeing OD ₁ : Absorbance at 576 nm of the dye solution after dyeing In the present invention, a dye having a dyeing rate of 95% or more was judged to have good dyeability.

(F) Determination of aromatic dicarboxylic acid having sulfoisophthalic acid group After dissolving the polymer sample in deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent, JEOL A-600 manufactured by JEOL Ltd. A nuclear magnetic resonance spectrum ( ¹ H-NMR) was measured using conduction FT-NMR, and the content was quantified from the spectrum pattern according to a conventional method.

[Example 1]
-Manufacture of polyester A 0.063 weight of calcium acetate is added to a mixture of 100 weight parts of dimethyl terephthalate, 16.7 weight parts of dimethyl 5-sodium sulfoisophthalate (hereinafter referred to as "SIPM") and 60 weight parts of ethylene glycol. And 0.16 parts by weight of sodium acetate trihydrate was added, and the ester exchange reaction was carried out while distilling out the methanol produced as a result of the reaction while gradually raising the temperature from 140 ° C to 240 ° C. It was. Thereafter, 0.25 part by weight of trimethyl phosphate was added to complete the transesterification reaction. To the reaction product, 0.001 part by weight of titanium trimellitic acid and 0.35 part by weight of titanium dioxide as a matting agent are added and transferred to a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation device. The temperature was raised to 285 ° C., and a polycondensation reaction was performed under a high vacuum of 30 Pa or less. The polycondensation reaction was terminated when the stirring power at which the melt viscosity reached 200 Pa · s was reached, and chips were formed according to a conventional method.

-Production of polyester B 0.063 parts by weight of calcium acetate is added to a mixture of 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, and the temperature is gradually raised from 140 ° C to 240 ° C, and as a result of the reaction. The transesterification reaction was carried out while distilling methanol to be distilled out of the system. Thereafter, 0.25 part by weight of trimethyl phosphate was added to complete the transesterification reaction. To the reaction product, 0.001 part by weight of titanium trimellitic acid and 0.35 part by weight of titanium dioxide as a matting agent are added and transferred to a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation device. The temperature was raised to 285 ° C., and a polycondensation reaction was performed under a high vacuum of 30 Pa or less. The polycondensation reaction was terminated when the stirring power at which the melt viscosity reached 200 Pa · s was reached, and chips were formed according to a conventional method.

-Manufacture of polyester fiber After the polyester A and polyester B chips are dried at 160 ° C for 4 hours, they are continuously fed to the extruder so that the weight ratio of polyester A / polyester B = 0.33 / 1.0. Then, spinning drawing was carried out in a single stage with a direct spinning drawing machine (spin draw) at a spinning temperature of 295 ° C. to obtain a polyester fiber of 44 dtex / 36 filaments. Cylinder knitting was made using the obtained polyester fiber, and after removing the oil agent by scouring at 70 ° C. for 20 minutes, the cation dyeability was evaluated by the above method. The results are shown in Table 1.

[Examples 2 to 4, Comparative Examples 1 to 7]
In Example 1, the melt viscosity and the amount of SIPM copolymerization were changed in the production process of polyester A, the intrinsic viscosity was changed in the production process of polyester B, and the polyester A / polyester B mixing ratio was changed in the production process of polyester fiber. Except for this, the same procedure as in Example 1 was performed. The results are shown in Table 1.

[Comparative Example 8]
In Example 1, when the same procedure as in Example 1 was performed except that the amount of SIPM copolymerization was changed as shown in Table 1 in the production process of polyester A, there was a cutting failure in the step of forming a chip after the polymerization condensation reaction of polyester A. Many occurrences of polyester A non-defective chips could not be obtained.

[Comparative Example 9]
In Example 1, the amount of SIPM copolymerization was changed as shown in Table 1 in the production process of polyester A, and the same procedure as in Example 1 was carried out except that spinning was performed using only polyester A in the production process of polyester fiber. The results are shown in Table 1.

  According to the present invention, it is possible to provide an inexpensive and high-strength cationic dyeable polyester fiber by using a copolymer polyester of sulfoisophthalic acid metal salt. Its industrial significance is great.

Claims (3)

Polyester B that Poriesu Te Le A as a main repeating unit main repeating unit consists of ethylene terephthalate comprising ethylene terephthalate, after each polymerized in a state satisfying the following requirements, cations obtained by melt spinning a mixture of these A method for producing a dyeable polyester fiber, wherein the content of an aromatic dicarboxylic acid component having a sulfoisophthalate group in the polyester fiber is 2.5 mol% or more based on the total acid components constituting the polyester fiber. Cationic dyeing property, wherein the melt viscosity of polyester A and polyester B measured at 285 ° C. and a shear rate of 1000 / s satisfies the following general formula (I): A method for producing polyester fiber.
(Polyester A)
The aromatic dicarboxylic acid component having a sulfoisophthalic acid group is a copolymerized polyester copolymerized in an amount of 10 to 20 mol% with respect to all the acid components constituting the polyester A, and the diethylene glycol contained in the polyester A is 5 Copolyester characterized by being not more than% by weight.
(Polyester B)
A polyester having an ethylene terephthalate component of 95 mol% or more in all repeating units constituting the polyester and an intrinsic viscosity in the range of 0.50 to 1.00 dL / g.
0.8 ≦ A / B ≦ 2.5 (I)
[In the above formula, A and B represent the melt viscosities of polyester A and polyester B measured at 285 ° C. and a shear rate of 1000 / s, respectively. ]   The method for producing a cationic dyeable polyester fiber according to claim 1, wherein titanium trimellitic acid is used in the production process of polyester A and the production process of polyester B.   The cationic dyeable polyester fiber obtained by the production method according to claim 1 or 2, wherein the tensile strength is 3.5 cN / dtex or more.