JPH0120248B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing modified polyester fibers dyeable with basic dyes. More specifically, it has good dyeability, high yarn strength,
The present invention relates to a method for producing modified polyester fibers that can be dyed with basic dyes and have excellent alkali resistance and light fastness of dyed products. [Prior Art] Basic dye-dyeable polyester has been known in Japanese Patent Publication No. 10497/1983, but
In this method, a large amount of isophthalic acid component (hereinafter referred to as S component) containing a metal sulfonate group is included in order to satisfy the dyeability, so if the polymer is spun using the normal method, the melt viscosity of the polymer will be high and spinning will be difficult. Become. Therefore, in order to spin a polymer containing a large amount of the S component by a conventional method, it is necessary to lower the degree of polymerization of the polymer and lower the melt viscosity to a range that allows normal spinning. As a result, the yarn strength decreases, and the alkali resistance decreases due to the addition of a large amount of S component, which limits the uses of the resulting polyester fibers. Furthermore, if a large amount of the S component is added, the cost of raw materials will naturally increase significantly. In order to improve the above-mentioned problems, a method is known in which the S component is reduced, and in order to compensate for the resulting decrease in dyeability, a method is known in which a glycol component, such as an acid component such as isophthalic acid or adipic acid, is copolymerized. For example, Japanese Patent Publication No. 55-17806 describes an example in which 1 to 10% by weight of polyalkylene glycol is copolymerized with a copolymer obtained by copolymerizing the S component.
In such examples, the dyeability is certainly improved by the copolymerization of the glycol component, but the yarn strength is insufficient and a yarn quality that can withstand alkali treatment cannot be obtained. [Problems to be Solved by the Invention] The present inventors have discovered that the following becomes possible by copolymerizing a glycol component in an S component copolymerization system. One of them is that by copolymerizing the glycol component, it is possible to obtain satisfactory dyeing properties with a small amount of S component copolymerized, and this means that the glycol component increases the effective utilization rate of the S component in the polymer for basic dyes. This is because it has a function (dying property improvement effect). Secondly, by copolymerizing the glycol component, a polymer with the same melt viscosity and high degree of polymerization can be obtained in the S component copolymerization system, which means that the glycol component can be used in the S component copolymerization system without lowering the polymerization degree. This is because it has the effect of lowering the melt viscosity of the polymer (thinning effect). Therefore, by copolymerizing the glycol component with the S component copolymerization system, it is possible to achieve satisfactory dyeing properties within the range of melt viscosity that allows normal spinning without using special equipment such as a heating cylinder, and Polymers with the necessary degree of polymerization to obtain fibers with a degree of 80 to 100 are obtained. This can only be obtained when the melt viscosity is lowered by reducing the amount of S component copolymerized by copolymerizing the glycol component, and by lowering the melt viscosity by copolymerizing the glycol component. However, in order to lower the melt viscosity to a range that allows normal spinning, it is necessary to increase the amount of copolymerized glycol component. On the other hand, when the amount of copolymerized glycol component increases, the light fastness of the dyed product decreases. Therefore, in order to satisfy the light fastness of the dyed product, the amount of copolymerized glycol component must be below a certain level. By the way, as mentioned above, the glycol component has the function of increasing the effective utilization rate of the S component for basic dyes (dying property improvement effect), so if the copolymerization amount of the glycol component is kept below a certain amount, the dyeing In order to satisfy the properties, the copolymerized amount of the S component must be a certain amount or more. On the other hand, in order to satisfy the yarn strength, the degree of polymerization cannot be made too low, so it is necessary to determine the amount of copolymerization of the S component and glycol component so as to satisfy the dyeability and light fastness of the dyed product. The viscosity of a polymer with a degree of polymerization that satisfies yarn strength is 1.8 to 3.0 times that of ordinary polyester. However, if this highly viscous polymer is spun using a normal method without using special equipment such as a heating tube, there is a problem in that only yarn with low strength and elongation can be obtained. Therefore, the present inventors conducted intensive studies regarding the polymer composition and spinning conditions, and as a result, they arrived at the present invention. That is, the object of the present invention is to achieve a drawn yarn strength of 4 g/
The object of the present invention is to produce a basic dyeable modified polyester fiber which has a high yarn strength of d or more, has excellent alkali resistance, and has excellent light fastness of dyed products. [Means for Solving the Problems] The object of the present invention described above is to provide an isophthalic acid component containing 1.3 to 1.8 mol% of metal sulfonate groups.
A modified polyester copolymerized with 0.5-1.9% by weight of a glycol component with a molecular weight of 400-6000 and a degree of polymerization of 82-105 is spun under conditions that satisfy the following formulas and then stretched. , manufacturing method of modified polyester fiber characterized by producing fibers with a degree of polymerization of 85 to 100 Shear rate (γ〓) ≦10 ⁴ sec ^-1 Draft ≦250 Back pressure of die (p) ≧40 Kg/cm ² Shear stress This can be achieved by (τ)≦(Q+0.7)×10 ⁷ dyne/cm ² (Q is the discharge amount per single hole g/min.hole). In the present invention, the S component is a compound represented by the following formula, specifically dimethyl (5-sodium sulfo) isophthalate, bis-2-hydroxyethyl (5-sodium sulfo) isophthalate, bis-4-hydroxy Examples include butyl (5-sodium sulfo) isophthalate. (However, M represents an alkali metal such as Na, Li, K, etc., and A and A' represent -CH ₃ or -(CH ₂ ) nOH. n represents an integer of 2 or more.) A preferred S component is dimethyl (5-sodium sulfo) isophthalate and bis-2-hydroxyethyl (5-sodium sulfo) isophthalate. The S component needs to be 1.3 to 1.8 based on the polyester obtained. If the S component is less than 1.3 mol%, satisfactory dyeing properties cannot be obtained even if the amount of glycol copolymerized is increased or the dyeing temperature is raised. This is due to the lack of S component in the polymer that reacts with the basic dye. On the other hand, S
If the amount of the component exceeds 1.8 mol%, if you try to obtain a polymer with the degree of polymerization necessary to obtain fibers with a degree of polymerization of 80 or higher, the melt viscosity of the polymer will increase significantly due to the copolymerization of a large amount of the S component. Therefore, polyester fibers with high strength and elongation cannot be obtained. The S component can be added at any time until the polyester manufacturing reaction is completed, but it is recommended to add it before the beginning of the polycondensation reaction in order for the added S component to be sufficiently copolymerized into the polyester chain. is preferred. When the S component is a glycol ester, it is preferably added between the end of the transesterification reaction or the esterification reaction and the start of the polycondensation reaction. The glycol component must have a molecular weight of 400 to 6,000. If the molecular weight is less than 400, the effect of improving dyeing properties will be small, and due to the low boiling point of glycol, it will be difficult to use during the polycondensation reaction. Glycol scatters out of the system, making it difficult to copolymerize a certain amount. On the other hand, a glycol component with a molecular weight exceeding 6000 deteriorates the oxidative decomposition resistance of the copolymerized polymer, and also makes it difficult to uniformly copolymerize the glycol component. The anti-frosting properties of the fabric are reduced. The molecular weight of the glycol component is more preferably 400 to 2000, particularly preferably 400 to 900. A typical example of the glycol component having a molecular weight of 400 to 6000 is the formula HO-( _CH2 - _CH2 -O)m-R
-O-(CH ₂ -CH ₂ -O)n-H (R is a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, a divalent aromatic carbonization group such as a phenyl group, a bisphenyl group, a naphthalene group, etc.) Hydrogen groups, m and n are the same or different integers and 1≦m+n≦100), bisphenol A-ethylene oxide adducts, and polyalkylene glycols represented by the following formulas. A( _CnH2nO )mH (A is _ClH2l + _1O or OH, l is 1 to 10, n is 2 to 5, and m is 3 to 100) Furthermore, as the glycol component, polyalkylene glycol is more preferable. This is because polyalkylene glycol has a greater viscosity-reducing effect than other glycols, so it is more advantageous than other glycols in obtaining a polymer having the degree of polymerization necessary to obtain fibers with a degree of polymerization of 85 to 100. As the polyalkylene glycol, polyethylene glycol having OH groups at both ends is more preferable. This is because the shorter the alkylene oxide unit is, or the more randomly the glycol is copolymerized, the greater the effect of improving dyeability and reducing the viscosity. The copolymerized amount of the glycol component needs to be in the range of 0.5 to 1.9% by weight based on the resulting polyester. If the amount is less than this range, the effect of improving dyeability will be small, and if it is more than this range, the properties, especially the light fastness of the dyed product and the oxidative decomposition resistance will be greatly reduced. Therefore, the copolymerization of glycol component is 0.7 to 1.5% by weight.
is more preferable. The glycol component may be added at any stage until the polyester production reaction is completed, but it is preferably added at a stage before the initial stage of the polycondensation reaction. Furthermore, upon addition, the S component may be added at the same time as the S component, or may be added separately in any order. The degree of polymerization of the modified polyester fiber obtained in the present invention is 85-100. Usually, when a polymer is melted during spinning, the degree of polymerization decreases, so in order to obtain fibers with the above degree of polymerization, the degree of polymerization of the polymer needs to be 82 to 105. If the degree of polymerization of the polymer is less than 82, it will not be possible to satisfy the yarn strength of the polyester fiber (4.0 g/d or more) aimed at in the present invention, and if the degree of polymerization of the polymer exceeds 105, the melt viscosity of the polymer will decrease. The fibers become extremely large, making it impossible to obtain the desired fibers with high strength and elongation. A modified polyester having a degree of polymerization of 82 to 105 may be obtained by polycondensation reaction alone, or by a combination of solid phase polymerization reaction. In the present invention, it is necessary to spin the modified polyester under specific spinning conditions. Among the spinning conditions, it is particularly important to keep the flow and deformation behavior in the molten state within a specific range, and specifically, the conditions shown below need to be adopted. Shear speed (γ〓)≦10 ⁴ sec ^-1 draft≦250 Back pressure of mouthpiece (p)≧40Kg/cm ² Shear stress (τ)≦(Q+0.7) ×10 ⁷ dyne/cm ² (Q is per single hole Discharge rate (g/min.hole) Here, the values of shear velocity and shear stress represent the flow characteristics at the spinneret, and are calculated by the following formula. γ = 32q/πD ³ ρ (sec ^-1 ) D: Mouth hole diameter (cm) q: Discharge amount per single hole (g/sec・hole) ρ: Molten polymer density (g/cm ³ ) τ=9.8×10 ⁵ PD/4L (dyn/cm ² ) P: Mouth back pressure (Kg/cm ² ) L: Mouth hole depth (cm) When γ and τ exceed the above upper limit values, the polymer of the present invention has a high melt viscosity. Therefore, the flow behavior at the mouth part is not uniform, and the strength and elongation characteristics of the yarn are reduced. The back pressure (P) of the mouthpiece must be 40 kg/cm ² or more. When P is less than 40 Kg/cm ² , the flow between the discharge holes in the die becomes uneven, and the strength and elongation decreases due to unevenness between single yarns and unevenness between single yarns.
The back pressure of the mouthpiece is preferably 50Kg/ ^cm2 or more, and 60
Kg/cm ² or more is more preferable. The spinning draft must be 250 or less, and if the spinning draft exceeds 250, the strength and elongation will decrease due to increased unevenness in yarn fineness. Further, the fineness unevenness appears as large waves in the measurement of Worcester's spots, and when the fineness unevenness becomes large, staining spots occur. In addition, the polyester referred to in the present invention is one in which at least 80 mol% of the constituent units are ethylene terephthalate or butylene terephthalate, and other components other than the S component and the glycol component are copolymerized with 10 mol% or less, preferably 5 mol% or less. You may do so. In addition to the above-mentioned copolymerization components, it also contains ordinary transesterification catalysts, polymerization catalysts, side reaction inhibitors such as phosphorus compounds and alkali metal salts, matting agents such as titanium dioxide, coloring inhibitors, and oxidative decomposition inhibitors. You can stay there. In particular, alkali metal salts have the effect of suppressing the amount of by-product diethylene glycol, and oxidative decomposition inhibitors have the effect of suppressing deterioration of the oxidative decomposition properties of the polymer due to glycol copolymerization, so it is preferable to use them. The modified polyester fiber of the present invention has excellent dyeability with basic dyes, and the dyeing temperature can be changed as appropriate depending on the polymer composition constituting the fiber.
A range of 140°C is preferred, and a range of 120 to 135°C is more preferred. [Example] The present invention will be specifically explained with reference to Examples below. Note that the characteristic value measurement method in the example is as follows. (Amount of copolymerized glycol component) After decomposing the polymer with amines, it is determined by gas chromatography or Calibol titration. (Degree of Polymerization) The degree of polymerization is calculated by determining the number of terminal groups per unit weight using a commonly used method and using the following formula. Degree of polymerization = 2 × 10 ⁶ / Number of terminal groups (co / 10 ⁶ g) × M (M means the average value of the molecular weight of repeating units in the polymer (or thread).) (Intrinsic viscosity) Orthochloro dissolved in phenol,
Displayed as measured value at 25℃. (Method for creating tubular knitted fabric) A tubular knitted fabric is knitted using the filament yarn to be evaluated using a 27-gauge sock knitting machine (manufactured by Koike Kikai Seisakusho Co., Ltd.). (Scouring method) The cylindrical knitted fabric to be evaluated was treated with 0.2% nonionic activator [Sandet G-900 (manufactured by Sanyo Kasei Co., Ltd.)] using a conventional method.
and scouring by boiling in boiling water containing 0.2% soda ash for 5 minutes, then washing and drying. (Light fastness) The refined tubular knitted fabric obtained from the filament to be evaluated was treated with Estrol Blue N-3RL (trade name manufactured by Sumitomo Chemical) 1.5% owf, acetic acid 0.5ml/, and sodium acetate.
After staining for 60 minutes in a 120°C aqueous solution containing 0.15g/1:100, dyeing was carried out in an 80°C aqueous solution containing 2g/hydrosulfite, 2g NaOH/2g Sundetsu G-900, according to a conventional method. 20
Perform reduction cleaning for a minute, wash with water, and dry. The dyed tubular knitted fabric is photobleached using a fade meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-LI1044, and measured using a blue scale standard. (Dyeability) The tube knitted fabric after scouring obtained from the filament to be evaluated was dyed with malachite green (trade name: Kanto Kagaku) 5%Owf, acetic acid 0.5ml/, acetic acid soda 0.2
Dyeing is carried out for 60 minutes in a hot aqueous solution at 120 DEG C. in a bath ratio of 1:100 consisting of g/g/ml. Next, the dyeing concentration in the residual dyeing solution after pulling up this tubular knitted fabric is measured, and the dye exhaustion rate of the tubular knitted fabric is determined. (Alkali resistance) In an aqueous solution with a concentration of 50g/NaOH at a temperature of 95℃,
The yarn was treated at a bath ratio of 1:100, resulting in a weight loss rate of 20%.
Determined from the yarn strength characteristics when . (Oxidative decomposition resistance) Using differential thermal analysis, measure the oxidative decomposition initiation temperature and calculate from that value. Example 1 4 kg of dimethyl (5-sodium sulfo)isophthalate (1.7 mol% copolymerization) was added to a mixture of 150 kg of dimethyl terephthalate, 94 kg of ethylene glycol, 210 g of lithium acetate dihydrate, 30 g of manganese acetate tetrahydrate, and 60 g of antimony trioxide. The transesterification reaction was completed by raising the temperature from 140°C to 235°C under atmospheric pressure over 4 hours with stirring. Next, add 64.5g of trimethyl phosphate and titanium dioxide.
Ethylene glycol slurry containing 16% by weight
After adding 810 g and 150 g of Irganox 1010 (manufactured by Ciba Geigy), which is an oxidative decomposition inhibitor,
The pressure inside the can was reduced to 500 mmHg, and 25 kg of ethylene glycol was distilled off. Thereafter, the glycol components listed in Table 1 were added, the temperature was raised from 240°C to 280°C over 2 hours, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and the reduced pressure was maintained at 1 mmHg or less until the temperature reached 280°C.
The polycondensation reaction was continued for an additional 1.5 hours, for a total of 3 hours and 30 minutes. The properties of the obtained polymer are shown in Table 1.

【table】

[Table] Next, each of the above polymers was vacuum dried, and the following
Melt spinning was carried out under the conditions shown in the table. In this case, the draft, which is a spinning characteristic, is 94, the shear speed is 5800sec ^-1 ,
The back pressure of the mouthpiece is 60~80Kg/ ^cm2 , and the shear stress is 0.89~
It was 1.2×10 ⁷ dyne/cm ² , which satisfied the spinning conditions specified in the present invention.

[Table] Further, each of the obtained undrawn yarns was subjected to hot roll drawing under the drawing conditions shown in Table 3 below to obtain drawn yarns of 75 denier and 36 filaments. Table 4 shows the yarn physical properties, dyeability, light fastness, and alkali resistance of the obtained drawn yarn.

【table】

[Table] As is clear from Tables 1 and 4, in experiments Nos. 1 to 7 that satisfied the requirements of the present invention, yarn strength, dyeability, light fastness, alkali resistance (strong after alkali treatment), and stability were The polymerizability and oxidative decomposition (ratio of copolymerized amount to added amount) were good. On the other hand, in Comparative Examples 1, 2, and 3, the molecular weight of the glycol was lower than the range of the present invention, so stable copolymerization was poor, and the dyeability was low, so that the effects of the present invention could not be exhibited. Furthermore, in Comparative Example 4, the molecular weight of the glycol exceeded the upper limit specified in the scope of the present invention, so the dyeability and oxidative decomposition properties were poor, and the yarn targeted by the present invention could not be obtained. In addition, in Comparative Examples 5 and 6, the amount of copolymerized glycol exceeded the upper limit specified in the present invention, so the oxidative decomposition properties and light fastness were poor, and the yarns were not satisfactory.
In Comparative Example 7, the amount of glycol copolymerized was below the lower limit specified in the present invention, so dyeability was poor and a satisfactory thread could not be obtained. Example 2 Dimethyl (5-sodium sulfo) isophthalate to be added and copolymerized was added as shown in Table 5, the glycol to be added and copolymerized was polyethylene glycol (molecular weight 600), and the amount of glycol added was 1.0.
Polymerization and yarn spinning were carried out in the same manner as in Example 1 except for the weight percentages. Table 5 shows the properties of the polymer, the spinning properties, the physical properties of the drawn yarn, the dyeability, the fastness to light, and the alkali resistance.

[Table] As is clear from Table 5 above, experiment numbers 9-
In No. 11, the copolymerized amount of dimethyl (5-sodium) sulfoisophthalate satisfies the range specified in the present invention, and the yarn physical properties, yarn dyeability, alkali resistance, light fastness, etc. are all satisfactory. It was hot. On the other hand, experiment number 8 was dimethyl (5-
Because the copolymerization amount of sodium) sulfoisophthalate is below the lower limit defined by the present invention, the dyeability is unsatisfactory.In Experiment No. 12, the degree of polymerization of the polymer is below the lower limit of the present invention, so the yarn physical properties (strength, elongation) are unsatisfactory. ), the alkali resistance is unsatisfactory. In addition, in experiment number 13, the amount of copolymerized dimethyl (5-sodium) sulfoisophthalate exceeds the upper limit of the present invention, so if the polymerization degree is set to 82 or more, the polymer melt viscosity increases, and therefore the spinning characteristics do not meet the specifications of the present invention. Out of range. Therefore, the yarn physical properties and alkali resistance of the yarn obtained in Experiment No. 13 were unsatisfactory. Example 3 Everything was the same as Example 1 except that dimethyl (5-sodium sulfo)isophthalate was 1.7 mol%, glycol was polyethylene glycol (average molecular weight 600), and the glycol copolymerization amount was 1.0% by weight.
Polymers with a degree of polymerization of 70, 82, 91, and 100 were produced by changing the polycondensation time using the same method as above, and among these, the polymer with a degree of polymerization of 100 was solid-phase polymerized to obtain a polymer with a degree of polymerization of 113. . Next, each of these polymers was subjected to yarn spinning in the same manner as in Example 1. Polymer properties of the obtained polymer, spinning properties,
The physical properties, dyeability, light fastness, and alkali resistance of the obtained yarn are shown in Table 6.

[Table] Comparative Example A melt polycondensation reaction was carried out in the same manner as in Example 1, except that dimethyl (5-sodium) sulfoisophthalate was 2.0 mol% and no glycol was added. The properties of the obtained polymer were that the intrinsic viscosity was 0.56 and the melting point was 254°C. The physical properties of the yarn obtained by spinning this polymer in the same manner as in Example 1 were a degree of polymerization of 85, a strength of 4.1 g/d, and an elongation of 33%.The dyeability of this yarn was 45%. The light fastness was grade 4 and the alkali resistance was 215 g. The yarn properties, light fastness, and alkali resistance were at a satisfactory level, but the dyeability was unsatisfactory. Example 4 Using the polymer of Example 1 and Experiment No. 2, yarn spinning was carried out by changing the spinning conditions. Note that the stretching conditions were the same as in Table 3. The results of the spinning properties and the properties of the drawn yarn obtained are shown in Table 7. In addition, the drawing excellence ratio in Table 7 is the ratio of the number of drawn yarns that do not have defects such as yarn breakage, single yarn breakage, or fluff during drawing when 10 undrawn yarns of 1 kg are drawn. expressed.

【table】

〔Effect of the invention〕

The present invention strictly controls and combines the polymer composition, degree of polymerization, and spinning conditions, and for the first time, the present invention achieves high yarn strength of 4 g/d or more, as well as alkali resistance, dyeability, and light fastness of dyed products. Modified polyester fibers that can be dyed with basic dyes and have excellent properties can be stably produced industrially.

Claims (1)

[Claims] 1. An isophthalic acid component containing 1.3 to 1.8 mol% of metal sulfonate groups and a molecular weight of 0.5 to 1.9% by weight.
Copolymerized with 400 to 6000 glycol components,
and a modified polyester with a degree of polymerization of 82 to 105,
A method for producing a modified polyester fiber, which comprises spinning the fiber under conditions that satisfy the following formulas and then drawing the fiber to obtain a fiber having a degree of polymerization of 85 to 100. Shear speed (γ〓)≦10 ⁴ sec ^-1 draft≦250 Back pressure of mouthpiece (p)≧40Kg/cm ² Shear stress (τ)≦(Q+0.7) ×10 ⁷ dyne/cm ² (Q is per single hole (discharge rate g/min.hole) 2. The method for producing a modified polyester fiber according to claim 1, wherein the glycol component having a molecular weight of 400 to 6000 is a polyalkylene glycol represented by the following formula. . A (CnH ₂ nO) mH (A is ClH ₂ l+ ₁ O or OH, l is 1 to 10, n is 2 to 5, m is 3 to 100)