JP2002161436A - Polytrimethylene terephthalate fiber dyeable with cationic dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a CD-PTT(cation-dyeable polytrimethylene terephthalate) fiber capable of providing a fabric having both a soft touch feeling and an excellent strength because of having high breaking energy and free from excessively shrinking in after processings such as a dye and a method for producing the CD-PTT fiber. SOLUTION: This fiber having high intrinsic viscosity [η], high amorphous compactibility and low shrinkage percentage is produced and the method for producing the fiber is provided by obtaining an undrawn fiber having low degree of orientation, low degree of crystallinity and good drawability by extruding a CD-PTT polymer having a specific region of high polymerization degree from a spinneret set to a specified region of a surface temperature thereof and taking up at a low speed and drawing the undrawn fiber at a specific region of draw ratio. The fabric difficult to be split and having the soft touch feeling can be obtained by using the fiber because the fiber has the high breaking energy and doesn't excessively shrink in after processes such as the dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cationically dyeable polytrimethylene terephthalate fiber and a method for producing the same. More specifically, the present invention provides a cationic dye-dyeable polytrimethylene terephthalate fiber which has a high fiber breaking energy, a small shrinkage during post-processing such as dyeing, a high strength, and a fabric having a soft texture. It relates to the manufacturing method.

[0002]

2. Description of the Related Art Fibers using polytrimethylene terephthalate (hereinafter abbreviated as "PTT") include polyamide fibers and polyethylene terephthalate (hereinafter abbreviated as "PET").
Many features such as low elastic modulus (soft texture), excellent stretchability, easy dyeing, light resistance, heat setting, dimensional stability, and low water absorption that were not found in existing synthetic fibers such as fibers It is an epoch-making fiber having

[0003] By combining PTT fiber with other various materials, PTT fiber has excellent characteristics inherent to PTT fiber,
It can be used as a new material that also takes advantage of the characteristics of the mating material, and is expected to greatly expand use in fabrics. However, with the conventional PTT fiber, there is a possibility that a problem relating to dyeing may occur depending on the type of the composite partner material. For example, since PTT fibers can be substantially dyed only with a disperse dye, when a PTT fiber is combined with a polyurethane elastic fiber or a PTT fiber fabric is processed with a polyurethane resin, the disperse dye is a urethane elastic fiber or Transfer to the processed resin may cause problems such as deterioration in washing fastness, sweat fastness, dry cleaning fastness, and the like.

On the other hand, the present inventors have solved PTT fibers as a means for solving the above problems relating to dyeing and taking advantage of the excellent features of PTT fibers (hereinafter referred to as “CD-PTT fibers”). ) Has already been proposed (WO99 / 09238 published pamphlet). CD
-When dyeing the PTT fiber, the cationic dye is ionically bonded to a dyeing seat such as a sulfonate introduced into the PTT fiber, so that the above-mentioned problem of dye transfer does not occur, and high dyeing fastness is achieved. . In addition, a feature that the sharpness of the dyed fabric is enhanced is also exhibited.

[0005] Generally, copolymerization of a sulfonate-containing compound to enable dyeing with a cationic dye is carried out by PE
A large number of T-based fibers have been used (Japanese Patent Publication No. 34-1049).
No. 7). However, in the case of a polyester obtained by copolymerizing a sulfonate-containing compound, the degree of polymerization is lower than that of a homopolymer due to a thickening effect, that is, a polymer having an intrinsic viscosity [η] of about 0.4 to 0.6 is usually used. Cannot be spun with equipment. As a result, the resulting fibers are brittle and the fabric is easily torn. According to the study of the present inventors, a phenomenon similar to that of the PET fiber occurs in the case of the PTT fiber. In order to make the fabric difficult to tear, not only simply increase the tensile strength of the fiber, but also collectively refer to the energy required to break the fiber structure when applying tension, compression, bending, shearing, etc. to the fiber It is necessary to increase the breaking energy of the cut fiber.

[0006] WO99 / 09238 discloses a PTT polymer having an intrinsic viscosity [η] of 0.6 obtained by copolymerizing sodium sulfoisophthalate at 265 ° C.
A CD-PTT fiber obtained by spinning at a spinning temperature of 0.10 to 1.05 is disclosed. According to the study of the present inventors, since the publication uses a polymer having a relatively high degree of polymerization such as intrinsic viscosity [η] of 0.6, the tensile strength can be relatively high, but the molecule is forcibly stretched. Therefore, the shrinkage of the fiber increases. For this reason, when the fabric is made into a fabric and subjected to post-processing such as dyeing, the fibers largely shrink, and as a result, the fabric becomes hard, and the soft texture expected from the low elastic modulus of PTT may not be sufficiently exhibited.

[0007] Unlike PET, PTT has a helical molecular structure, and if a molecule is forcibly stretched, a new problem such as an increase in fiber shrinkage is considered to occur. Even if a polymer with a higher degree of polymerization is spun using a special spinning machine that can extrude a polymer with a higher melt viscosity, the breaking energy cannot be sufficiently increased because the molecules are forced to be stretched. In addition, the shrinkage rate increases. On the other hand, if the contraction is suppressed by lowering the draw ratio at the time of drawing, the tensile strength and breaking energy of the fiber will not be satisfactory, and a fabric having a strength that can be practically used cannot be obtained.

[0008] WO 99/27168 discloses a PTT polymer having an intrinsic viscosity [η] of 0.7 obtained by copolymerizing sodium sulfoisophthalate.
A CD-PTT fiber obtained by melting at 75 ° C. and spinning is disclosed. However, according to our study, although the fiber has a low boiling water shrinkage of 11%, the peak temperature of the dynamic loss tangent indicating the regularity of the amorphous part of the fiber is as low as 102 ° C. Has a low regularity, the fiber breaking energy is not satisfactory, and a cloth having a satisfactory strength may not be obtained in some cases.

In order to obtain a tear-resistant fabric, PET fibers are copolymerized with an isophthalic acid component having a quaternary phosphonium salt of sulfonic acid (Japanese Patent Publication No. 47-22334), or by copolymerizing a metal sulfonic acid salt. Polyoxyalkylene glycol may be compounded (Japanese Unexamined Patent Publication No.
No. 45812), copolymerization of a metal sulfonic acid salt and addition of a cyclic polyether (Japanese Unexamined Patent Publication No.
No. 4727), and it has been proposed to use a polymer having a high degree of polymerization in which the thickening action is suppressed. However, the substances used in these proposals have low heat resistance in any case, and cannot be obtained by decomposing themselves in a polymerization reaction process or a melt spinning process to obtain a fiber having a sufficient degree of polymerization. Alternatively, there is a disadvantage that the obtained polymer or fiber is colored. Even if the above technology is applied to CD-PTT fiber as it is, the same problem occurs, and at present, satisfactory fiber cannot be obtained.

[0010]

As a result of the study by the present inventors, it has been found that the conventional CD-PTT fiber has the following problems. (1) The breaking energy is low, and the obtained fabric is easily torn. (2) When the fabric is subjected to post-processing such as dyeing, the fibers largely shrink, resulting in a hard and stiff texture, and the soft texture inherent in PTT fibers does not appear. In order to increase the breaking energy, the degree of polymerization of the fiber is increased, and the orientation of the crystal part and the amorphous part is increased, and the denseness of the crystal part and the amorphous part is increased, thereby increasing the regularity of the molecule. It is possible. However, if the orientation and the denseness are too high, the fibers become brittle, and the breaking energy is rather lowered.

In general, when the degree of polymerization of the polymer is increased in order to increase the degree of polymerization of the fiber, the melt viscosity becomes high, so that it cannot be extruded uniformly and spinning becomes difficult. When the melt viscosity is high, the obtained undrawn yarn has a structure that is difficult to be oriented by drawing. It is considered that this is because the extruded polymer is not completely melted, so that the entanglement that hinders stretching cannot be sufficiently unraveled. In such a state, no matter how much stretching is performed, not only can the breaking energy be hardly increased, but also the molecules are excessively strained and greatly shrink during heat treatment performed during post-processing such as dyeing. is there.
If the draw ratio is reduced to suppress shrinkage, the crystallinity and orientation of the fiber will be reduced, and a fiber that can be used practically cannot be obtained. Even if a fiber is produced using a polymer having a higher intrinsic viscosity [η] by a spinning method similar to that disclosed in WO99 / 09238, the melt viscosity of the polymer becomes excessively high. In addition, it is not possible to make both the breaking energy and the shrinkage of the fiber within a range that can be satisfied.

In order to lower the melt viscosity, it is conceivable to raise the melting temperature. However, when the melting temperature is increased, the thermal decomposition becomes severe, and not only does the degree of polymerization of the fiber not rise as expected, but also the decomposition product As a result, the fibers are colored, and fibers having excellent whiteness cannot be obtained. An object of the present invention is to provide a fabric having both a soft texture and excellent strength because the fiber has a high breaking energy, is excellent in whiteness, and does not excessively shrink during post-processing such as dyeing.
An object of the present invention is to provide a D-PTT fiber and a method for producing the same. Problems to be solved in order to achieve the object of the present invention are:
In response to the above problem (1), the degree of polymerization of the fiber is increased, and
By increasing the crystallinity and the orientation, a CD-PTT fiber having a high breaking energy is obtained. In response to the above-mentioned problem (2), while maintaining a high orientation, excessive tension of the molecule is suppressed, and excessive shrinkage is caused. Is to suppress.

[0013]

The present inventors have conducted intensive studies and, surprisingly, have surprisingly found that a specific range of a high polymerization degree CD-PTT polymer which can be extruded uniformly can be converted into a specific range of the spinning surface temperature. An unstretched yarn having low orientation and low crystallinity and good stretchability, obtained by extruding from a spinneret and drawing at a low speed, was drawn in a specific range at a draw ratio, and has a high intrinsic viscosity [η] and a high non-stretchability. Fibers with high crystallinity and low shrinkage have high breaking energy and do not excessively shrink during post-processing steps such as dyeing, so that it is difficult to tear and obtain a fabric having a soft texture. The inventors have found out that they can do so and have accomplished the present invention.

That is, the present invention is as follows. 1. PTT fiber (I) Polytrimethylene terephthalate in which the ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% with respect to the total dicarboxylic acid component, and the following (A) to (C)
A PTT fiber that satisfies the following. (A) Intrinsic viscosity [η]: 0.65 to 1.4 (B) Peak temperature of dynamic loss tangent: 105 ° C. or higher (C) Boiling water shrinkage: 0 to 16% (II) In the above (I), A PTT fiber satisfying the following (D) and (E). (D) Elongation at break: 20-70% (E) Toughness: 16-27 [Here, toughness is a value calculated from the following equation (a). Toughness = strength (cN / dtex) × √elongation (%) (a)] (III) In any of the above (I) or (II), the ester-forming sulfonate is 5-sodium sulfoisophthalic acid A PTT fiber, characterized in that:

2. Unstretched yarn (I) Polytrimethylene terephthalate having an intrinsic viscosity [η] of 0.65 to 1.4 in which an ester-forming sulfonate is copolymerized in an amount of 0.5 to 5 mol% based on all dicarboxylic acid components. Characterized by having a breaking elongation of 150 to 600% and a crystallization peak temperature of 64 to 80 ° C.
T undrawn yarn.

3. Method for Producing PTT Fiber (I) From PTT having an intrinsic viscosity [η] of 0.65 to 1.4, in which an ester-forming sulfonate is copolymerized in an amount of 0.5 to 5 mol% with respect to all dicarboxylic acid components. The elongation at break is 150-600%, and the crystallization peak temperature is 64-80 ° C.
The unstretched yarn is characterized by the maximum draw ratio of 3
P is stretched at a stretch ratio of 0 to 99%.
Method for producing TT fiber. (II) A method of melt-spinning a PTT having an intrinsic viscosity [η] of 0.65 to 1.4 in which an ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% based on all dicarboxylic acid components. Then, the molten polymer extruded from the spinneret was cooled and solidified by setting the spinneret surface temperature to 250 to 295 ° C.
The undrawn yarn drawn at a speed of ~ 3000 m / min
A method for producing a PTT fiber, comprising stretching at a temperature of from 90 to 90 ° C at a stretching ratio of 30 to 99% of the maximum stretching ratio and heat-treating at a temperature of from 100 to 200 ° C. (III) In the above (I), a length of 20 to
A method for producing a PTT fiber, comprising installing a heating tube having a temperature of 500 mm and a temperature of 150 to 350 ° C. (IV) In any one of the above (I) to (III),
A method for producing a PTT fiber, comprising: winding a drawn undrawn yarn once and then drawing it. (V) The method for producing a PTT fiber according to any one of the above (I) to (III), wherein the drawn undrawn yarn is continuously drawn without being wound once.

4. PTT short fiber (I) Consisting of any of the above PTT fibers (I) to (III), having a fiber length of 3 to 200 mm and a degree of crimp of 5 to 35%
A PTT short fiber, characterized in that: 5. Fabric containing PTT fiber (I) PTT fiber (I) to (III) above or PTT
A fabric using at least a part of any of the short fibers (I).

Hereinafter, the present invention will be described in detail. (1) Polymer raw material, etc. The PTT used in the present invention is such that the ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% based on all dicarboxylic acid components. Polytrimethylene terephthalate.
Here, PTT is a polyester containing terephthalic acid as an acid component and trimethylene glycol (also referred to as 1,3-propanediol) as a diol component. The ester-forming sulfonate serves as a seat for dyeing a cationic dye, and is an essential copolymer component for achieving the object of the present invention. Examples of the ester-forming sulfonic acid salt used in the present invention include a sulfonic acid salt-containing compound represented by the following general formula, provided that it is copolymerized with PTT and has a sulfonate group moiety, There is no particular limitation.

[0019]

Embedded image Here, R ¹ and R ² are -COOH, -COOR, -OC
OR (R is an alkyl group having 1 to 10 carbon atoms),
R ¹ and R ² may be the same group or different groups. Z
Is a trivalent organic group having 1 to 30 carbon atoms, and is preferably a trivalent aromatic group. M may be any compound that forms a salt with a sulfonic acid group, but is preferably a metal, more preferably an alkali metal or an alkaline earth metal.

Specific examples of preferred ester-forming sulfonic acid salts include 5-sodium sulfoisophthalic acid,
-Potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 2-
Potassium sulfoterephthalic acid, 4-sodium sulfo-
Examples thereof include 2,6-naphthalenedicarboxylic acid, 2-sodium sulfo-4-hydroxybenzoic acid, and ester derivatives thereof such as methyl and dimethyl esters. In particular, these ester derivatives such as methyl and dimethyl esters are preferable in that the whiteness of the polymer is excellent.

The copolymerization ratio of the ester-forming sulfonic acid salt needs to be 0.5 to 5 mol% based on the total number of moles of all dicarboxylic acid components constituting the polyester. When the copolymerization ratio of the ester-forming sulfonate is 0.5
If the amount is less than mol%, the number of dyeing seats is small, so that sufficient coloring cannot be obtained even by dyeing with a cationic dye. On the other hand, when the copolymerization ratio of the ester-forming sulfonate exceeds 5 mol%, the melt viscosity of the polymer becomes too high or the heat resistance is deteriorated, so that the spinnability is deteriorated or the fiber is liable to yellow. Or become. The copolymerization ratio is preferably 1 to 3 mol%, more preferably 1.2 to 2.5 mol%.
It is.

The CD-PTT of the present invention may contain other copolymer components as long as the object of the present invention is not impaired.
Such copolymer components include 1,4-butanediol, neopentyl glycol, 1,6-hexamethylene glycol, 1,4-cyclohexanediol, 1,4
Ester-forming monomers such as cyclohexane dimethanol, isophthalic acid, adipic acid, dodecane diacid, 1,4-cyclohexane dicarboxylic acid, and polyethylene glycol having a molecular weight of 400 to 100,000. The polymer used in the present invention may contain, if necessary, various additives such as a matting agent, a heat stabilizer, an antifoaming agent, a tinting agent, a flame retardant, an antioxidant, an ultraviolet absorber, and an infrared absorber. , A nucleating agent, a fluorescent whitening agent, and the like may be copolymerized or mixed. In particular, in order to suppress fluff and yarn breakage during spinning and post-processing, titanium oxide having an average particle size of 0.01 to 2 μm is used in an amount of 0.01
It is preferable that the content be contained in an amount of 3 to 3% by weight.

The intrinsic viscosity [η] of the polymer used in the present invention.
Needs to be 0.65 to 1.6, more preferably 0.68 to 1.4, and particularly preferably 0.7 to 1.2. It is possible to obtain a fiber having a high breaking energy for the first time by using a polymer in this range. When the intrinsic viscosity [η] is less than 0.65, it is difficult to develop a sufficient breaking energy. On the other hand, if the intrinsic viscosity [η] exceeds 1.6, the melt viscosity is too high, so that a melt fracture or the like occurs and it becomes difficult to extrude the polymer uniformly. The b * value of the CD-PTT polymer of the present invention is preferably -7 to 15 in order to exhibit excellent color developability when formed into a fabric. The b * value is more preferably -5 to 10, and particularly preferably -2 to 6. Further, the L value is preferably 70 or more, more preferably 80 or more, and particularly preferably 85 or more.

The polymer used in the present invention can be produced by a known method. For example, using terephthalic acid or dimethyl terephthalate, ester-forming sulfonate and trimethylene glycol as raw materials, titanium tetrabutoxide, calcium acetate, magnesium acetate, cobalt acetate, manganese acetate, titanium dioxide, a mixture of titanium dioxide and silicon dioxide One or more metal salts are added and subjected to an esterification reaction or a transesterification reaction under normal pressure or under pressure, and then a catalyst such as titanium tetrabutoxide, antimony trioxide, antimony acetate is added, and The polymer can be obtained by a polycondensation reaction at 270 ° C. under reduced pressure.

It is also preferable to add a stabilizer at any stage of the polycondensation, preferably before the polycondensation reaction, to improve whiteness, improve melt stability, and reduce the molecular weight of oligomers, acrolein, allyl alcohol to 300. It is preferable from the viewpoint of controlling the generation of the following organic substances. In order to increase the degree of polymerization of the polymer, it is preferable to perform solid-state polymerization under nitrogen or under reduced pressure after performing the above-described melt polymerization. The temperature at which the solid-phase polymerization is performed is preferably in the range of 190 to 220 ° C. from the viewpoint of suppressing the polymerization rate, the coloring of the polymer, and the fusion.

(2) PTT fiber (I) The PTT fiber of the present invention comprises PTT in which an ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% with respect to all dicarboxylic acid components. (A) ~
It is necessary to satisfy (C). (A) Intrinsic viscosity [η]: 0.65 to 1.4 (B) Peak temperature of dynamic loss tangent: 105 ° C. or higher (C) Boiling water shrinkage: 0 to 16% The first object of the present invention. In order to increase the breaking energy, it is important that the fibers have a high degree of polymerization in a specific range and a high amorphous density. Further, in order to suppress excessive shrinkage, which is the second problem of the present invention, it is important to have a fiber having a high amorphous compactness and a structure in which molecules are not excessively strained. is there.

As an index of the degree of polymerization, intrinsic viscosity [η] is suitable. The peak temperature of the dynamic loss tangent (hereinafter, abbreviated as “Tmax”) is suitable as an index of the amorphous denseness. Further, a boiling water shrinkage rate (hereinafter abbreviated as “BWS”) is suitable as an index of the molecular tension state. Therefore, when the intrinsic viscosity [η], Tmax, and BWS of the fiber satisfy the above ranges, the breaking energy is high for the first time, and
Since it does not excessively shrink in a post-processing step such as dyeing, it becomes a CD-PTT fiber that is hard to tear and that can obtain a fabric having a soft texture.

(I) Intrinsic viscosity [η] (A) The intrinsic viscosity [η] of the fiber must be 0.65 to 1.4. When the intrinsic viscosity [η] is within this range, the fiber has a high breaking energy for the first time. When the intrinsic viscosity [η] is less than 0.65, the degree of polymerization is too low, so that the breaking energy is not satisfactory. On the other hand, when the intrinsic viscosity [η] exceeds 1.4, the melt viscosity is too high to cause melt fracture and the like, and it is impossible to extrude uniformly. Further, even if the spinning conditions are adjusted, it is difficult to lower the tension of the molecules, and the BWS becomes high.
The intrinsic viscosity [η] of the fiber is preferably 0.68 to 1.3,
Particularly preferably, it is 0.7 to 1.2.

(Ii) Peak temperature of dynamic loss tangent (Tmax) (B) Tmax needs to be 105 ° C. or more. Tmax
Is a value obtained from the dynamic viscoelasticity measurement and corresponds to the denseness of the molecule in the amorphous part. As this value increases, it indicates that the amorphous portion has a dense structure. Tmax
If it is less than 105 ° C., the breaking energy of the fiber will be small due to the low density of the amorphous part. On the other hand, the upper limit is not particularly limited, but the CD-PTT of the present invention is not limited.
It is difficult to exceed 130 ° C. for fibers. Tmax
Is more preferably 110 ° C. or higher, particularly preferably 115 ° C. or higher.

(Iii) Boiling water shrinkage (BWS) (C) BWS needs to be 0 to 16%. 16% BWS
If it exceeds, the molecules are in an excessively strained state, and when the obtained fabric is heat-treated by post-processing such as dyeing, it shrinks greatly, resulting in a hard, stiff texture, and PTT fibers The original soft texture does not appear. On the other hand, when the fiber is less than 0%, that is, when the fiber is stretched in the boiling water, it is not possible to obtain a wrinkle-free fabric even after post-treatment such as heat setting. BWS is preferably 3 to 15%, and more preferably 5 to 14%.

(II) Physical Properties of PTT Fiber (i) Elongation at Break (D) The elongation at break is preferably from 20 to 70%. If the elongation at break is less than 20%, the elongation is too low, so that not only is it difficult to increase the breaking energy of the fiber, but also fluff and yarn breakage are likely to occur during stretching and post-processing. On the other hand, if the elongation at break exceeds 70%, it becomes difficult not only to increase the breaking energy of the fiber, but also to draw uniformly, and the fiber tends to have large thickness unevenness. A more preferable range of the elongation at break is 25 to 65%, further preferably 30 to 60%, and particularly preferably 35 to 55%.

(Ii) Toughness (E) The toughness is preferably from 16 to 40. Here, the toughness is a value calculated by the equation (a). The breaking energy of the fiber greatly correlates with the value represented by the product of the strength and the square root of the elongation in the equation (a), which is generally called toughness. When the toughness is 16 or more, the obtained fabric is difficult to tear. If the toughness is less than 16, the resulting fabric tends to tear. The upper limit of the toughness is not particularly limited, and the higher the better, the better. The toughness is more preferably 17 or more, even more preferably 19 or more. The toughness of the CD-PTT fiber is difficult to manufacture beyond 40 due to manufacturing difficulties.

(Iii) Breaking strength The breaking strength is preferably 2.2 cN / dtex or more. If it is less than 2.2 cN / dtex, the strength is low. Therefore, when trying to increase the toughness, it is necessary to increase the elongation, and when a fabric is formed, the portion to which the force is applied remains deformed. Mold release easily occurs.
The breaking strength is more preferably at least 2.4 cN / dtex, further preferably at least 2.6 cN / dtex, particularly preferably at least 2.8 cN / dtex. The upper limit of the breaking strength is determined by the stretching conditions, but it is difficult to manufacture the material at a strength exceeding 7 cN / dtex.

(Iv) Elastic recovery rate (at 20% elongation) The elastic recovery rate at 20% elongation is preferably 60% or more. It is more preferably at least 65%, particularly preferably at least 70%. If the elastic recovery is less than 60%, PT
No longer exhibits the excellent stretch properties inherent to T. Of course, 100% is most preferable.

(V) Birefringence The birefringence is preferably 0.04 to 0.07.
The birefringence is an index indicating the degree of orientation of molecules. When the birefringence of the fiber exceeds 0.07, the degree of orientation of the fiber becomes too high, and the molecule is excessively strained, so that the elongation becomes low and the breaking energy decreases, or the BWS becomes high. It is easy to become too much. On the other hand, if the birefringence of the fiber is 0.0
If it is less than 4, it is not easy to increase the breaking energy of the fiber due to low orientation. The birefringence of the fiber is preferably from 0.043 to 0.068, more preferably from 0.045 to 0.065.

(Vi) Density The fiber preferably has a density of 1.330 g / cm ³ or more. The density is an index indicating the crystallinity of the fiber. The higher the density, the higher the crystallinity. 1.33 density
If it is less than 0 g / cm ³ , it indicates that the crystallinity is not sufficiently high, and it is difficult to exhibit the excellent stretch property unique to PTT fiber. In addition, since the molecules are not sufficiently fixed by crystallization, BWS is also likely to fall outside the scope of the present invention. The upper limit of the density is as follows.
431 g / cm ³ (Materials, Vol. 35, No. 396, 10
67 (published in 1986), it is considered that even if the copolymerized CD-PTT does not exceed this value. The density is more preferably 1.335 g / c
m ³ , and more preferably 1.340 g / cm ³ or more.

(Vii) U% The U% of the fiber is preferably 0 to 3%. U% is USTER TESTER manufactured by Zellbeger Worcester Co., Ltd.
3 is a value obtained from the variation in the mass of the fiber sample.
In this apparatus, a change in mass can be measured by a change in dielectric constant when a fiber sample is passed between electrodes. When passing through the apparatus at a constant speed, an uneven curve as shown in FIG. 1 is obtained. From this result, U% can be obtained according to equation (1) in FIG. When U% exceeds 3%, fluff and yarn breakage frequently occur during post-processing, and fibers having large mechanical property unevenness and dyeing unevenness tend to be formed. U% is preferably 2% or less, more preferably 1.5% or less. Of course, the lower the U%, the better.

(Viii) Color of Fiber The fiber of the present invention is a spectrophotometer (Sakata Inx Co., Ltd.)
Manufactured by Macbeth CE-3000)
It is preferable that the value (yellowness) is -30 to 5, and the WI value (whiteness) is 50 to 150. By setting the color in this range, it becomes easy to obtain a fabric of a desired color when dyeing a light color, or to obtain excellent color developing properties. In order to achieve such a color range, the whiteness of the polymer is set to the b * value and the L value in the range used in the present invention, and melting, extrusion temperature and the like are within the range of the present invention, and coloring by thermal decomposition is performed. It is important to control. The YI value is more preferably from -20 to 4.5, and still more preferably from -10 to 3. Further, the WI value is more preferably 60 to 100, and further preferably 70 to 90.

(Ix) Fiber Form The fiber of the present invention may be a multifilament or a monofilament. When used for applications such as innerwear, it is preferable that the filament is a multifilament. In the case of a multifilament, the total fineness is not particularly limited, but is usually 5
~ 500 dtex, preferably 10-300 dtex,
The single yarn fineness is not particularly limited, but is usually 0.1 to 20 d.
tex, preferably 0.5 to 10 dtex, more preferably 1 to 5 dtex. In the case of a monofilament, it is desirable to appropriately select from 5 to 10,000 d according to the application. The cross-sectional shape of the fiber is not limited, such as round, triangular, other polygonal, flat, L-shaped, W-shaped, cross-shaped, well-shaped, dogbone-shaped, and may be a solid fiber or a hollow fiber. Good. In addition, as long as the object of the present invention is not impaired, a sheath core, a side-by-side, a laminated structure using two or more kinds of polymers having different matting agent contents and intrinsic viscosities [η] within the scope of the present invention. Or a composite fiber having a different cross-sectional shape or polymer type by a single yarn.

(X) Form of Wound Yarn The fiber of the present invention may be wound in any form such as a pan or cheese-like package. In the case of a cheese-like package, the bulge rate is preferably 20% or less.
FIG. 2- (a) shows a cheese-like package (100) in which the yarn is wound into a desired shape. The yarn is wound on a core (10
3) Wound on a cylindrical thread layer (104) with a flat end surface (102) formed on it. The bulge is a bulging end face (102a) of the cheese-like package (100) which is generated when the winding thread slides due to a strong tightening force due to the contraction of the winding thread as shown in FIG. What is the bulge rate?
The winding width Q of the innermost layer and the winding width R of the most bulged portion shown in FIG.
This is a value calculated using the following equation. Bulge rate = {(RQ) / Q} x 100%

A cheese-like package having a bulge ratio within the above range can be easily achieved by setting the intrinsic viscosity [η], the peak temperature of the dynamic loss tangent, and the BWS within the range of the present invention. If the bulge ratio of the cheese-like package exceeds 20%, the winding yarn collapses during transportation and cannot be unwound, and yarn breakage, fluff, and stain spots due to uneven unwinding tension tend to occur. In the worst case, the end face protrudes from the thread tube, so that it cannot be transported. Further, the tightening of the winding is large, and it often does not come off the spindle of the winding machine. The bulge ratio is preferably 15% or less, more preferably 1%.
0% or less. Of course, 0% is most preferable. In the cheese-like package, the winding width Q is set to 40 to 3 in order to reduce the tension at the time of releasing the fiber and suppress the fluctuation of the tension.
It is preferable that the diameter is 00 mm and the diameter of the yarn tube is 50 to 250 mm.

(3) Method for Producing PTT Fiber Next, a method for obtaining the CD-PTT fiber of the present invention will be described.
Basically, PTT having an intrinsic viscosity [η] of 0.65 to 1.6 in which an ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% with respect to all dicarboxylic acid components, After the molten polymer extruded from the spinneret is cooled and solidified at a surface temperature of 250 to 295 ° C., an undrawn yarn taken at a speed of 100 to 3000 m / min is drawn at a drawing temperature of 30 to 90 ° C.
Stretching at a stretching ratio of 30 to 99% of the maximum stretching ratio, 1
It is obtained by heat treatment at a temperature of 00 to 200 ° C. In the present invention, any of a so-called conveyor method, in which the drawn undrawn yarn is once wound and then drawn, and a so-called spin draw take-up method (hereinafter, abbreviated as “SDTU method”) in which the undrawn yarn is stretched continuously without winding. But it is good.

1) First, a method of drawing an undrawn yarn will be described. Withdrawing undrawn yarn refers to winding by the winding machine 12 shown in FIG. 3 in the conveyor method, and refers to winding up to the first roll 18 shown in FIG. 5 in the SDTU method. From drying to undrawing the undrawn yarn, the conveyor method is also S
Since the DTU method is the same, it will be described with reference to FIG. The PTT pellets dried to a predetermined moisture content in the dryer 1 are supplied to the extruder 2 and melted. The molten PTT is sent to the spin head 4 and measured by a gear pump. Thereafter, the mixture is extruded from a spinneret 6 having a plurality of holes attached to the spinneret pack 5. The water content of the PTT pellet supplied to the extruder is preferably 100 ppm or less, more preferably 50 ppm or less, and still more preferably 3 ppm or less, from the viewpoint of suppressing a decrease in the degree of polymerization of the polymer.
The content is preferably set to 0 ppm or less.

The first important factor for producing the fiber of the present invention is
The point is to obtain an undrawn yarn having a high degree of polymerization, low orientation and crystallinity, and good stretchability. In order to achieve a high degree of polymerization, it is desirable to increase the degree of polymerization of the polymer to be used and to suppress the decomposition by lowering the melting temperature so that the degree of polymerization does not decrease. When the decomposition is severe, there is also an undesired problem that the fibers are colored. On the other hand, in order to obtain an undrawn yarn having good drawability, it is necessary to raise the melting temperature to completely melt the polymer and sufficiently unravel the entanglement that hinders drawing. In particular, it is desirable to increase the melting temperature because the entanglement is severe in a high polymerization degree polymer.

In order to make these both compatible, it is desirable to select a temperature condition in a specific range. That is, the temperature of the extruder is preferably 245 to 290 ° C, more preferably 250 to 280 ° C, and still more preferably 255 to 270 ° C.
And the temperature of the spin head is preferably 255-295.
° C, more preferably 260 to 290 ° C, still more preferably 265 to 285 ° C, and the temperature of the spin head is preferably higher than that of the extruder, more preferably 5 ° C or more. Since the temperature of the spin head is closely related to the spinning surface temperature described later, it is desirable to select from the above range so that the spinning surface temperature is in an appropriate range.

Since the polymer having a high degree of polymerization as used in the present invention has a strong interaction between molecules, the molecules tend to be oriented from the time when the polymer is extruded to the time when the polymer is cooled and solidified and the fiber is drawn. In the present invention, suppressing the orientation of the undrawn yarn is a very important point. In order to suppress the orientation of the undrawn yarn, the polymer under the spinneret is reduced in the state of intermolecular interaction by raising the surface temperature of the spinnerer, and at the same time, the extruded polymer is slowly solidified and the polymer thinning rate is reduced. It is necessary to suppress the sudden deformation of the molecule by lowering.

Therefore, in the present invention, it is one of the important points to keep the spinning surface temperature in a specific temperature range of 250 to 295 ° C. Spout surface temperature of 250 ° C
If it is less than 1, not only the orientation of the undrawn yarn cannot be suppressed, but also problems such as yarn breakage, frequent fluffing, and yarn unevenness occur. If the spinning surface temperature exceeds 295 ° C., thermal decomposition becomes severe, and the degree of polymerization of the undrawn yarn becomes low or the undrawn yarn is colored. Spout surface temperature is 255-
290 ° C is preferred, and 260 to 285 ° C is more preferred.

To achieve such a spinning surface temperature,
It is preferable to set the temperature of the spin head appropriately and to install a heating cylinder immediately below the spinneret. If the spin head temperature is set too high in order to increase the spinning surface temperature, thermal decomposition will be severe and the resulting fibers will be colored or the degree of polymerization will be reduced. By using the heating tube, the spin head temperature can be lowered, so that the thermal decomposition of the polymer can be suppressed, and the extruded polymer is rapidly cooled and solidified by increasing the temperature of the spinning surface and the atmosphere under the spinning hole. This can be easily suppressed. Heating cylinder temperature is 100-350
C., preferably 150 to 300 C., more preferably 20 to 300.degree.
0-250 ° C is particularly preferred. The length of the heating cylinder is preferably from 50 to 300 mm, more preferably from 100 to 250 mm, from the viewpoint of the effect of loosening the entanglement of the polymer and the workability of spinning.

In order to reduce the rate of thinning of the polymer, the draft at the time of spinning is preferably set in a low range of 10 to 2000. Here, the spinning draft is a value represented by the following equation. Spinning draft = V ₂ / V _1, however, V _1: the linear velocity of the polymer when extruded from the spinning nozzle (m / min) V _2: first roll peripheral speed (m / min) (without the first roll If the draft is less than 10, the spinning diameter becomes too small and the extrusion pressure increases, so that melt fracture and the like occur, making it difficult to extrude uniformly. If the draft exceeds 2,000, the thinning rate of the polymer increases, and the degree of orientation of the undrawn yarn tends to increase. The spinning draft is more preferably 50 to 1500, and 100 to 1000.
Is more preferable, and 150 to 500 is particularly preferable.

The spinner used in the present invention has a diameter of 0.2 to 0.2.
Preferably, the diameter is 0.7 mm, and the ratio of the diameter to the length is 1: 0.25 to 1: 3. If the diameter is less than 0.2 mm, or if the ratio of the diameter to the length exceeds 3, the extrusion pressure will increase and melt fracture will occur, making it difficult to extrude uniformly. On the other hand, the diameter is 0.7mm
If the ratio exceeds, the fiber unevenness tends to increase, or the draft becomes high, whereby the fiber is oriented, and the drawability may decrease. If the ratio of diameter to length is less than 0.25,
The spout may be deformed or chipped after using the spout for a long time. Spout diameter 0.25-0.6mm
Is more preferable, and 0.3 to 0.5 mm is further preferable.
Further, the ratio of the diameter to the length is more preferably 1: 0.5 to 1: 2, and still more preferably 1: 0.75 to 1: 1.5. The polymer extruded from the spinneret is cooled and solidified into fibers.
Cooling is preferably performed by blowing cold air of 0 to 40 ° C. onto the polymer. Although the cooled and solidified fiber may be directly wound up, it may be wound up by a winder using a first take-up roll shown in FIG. 3 or taken up by a first roll shown in FIG.
It is preferable to perform stretching continuously.

In the present invention, the undrawn yarn is wound up.
Alternatively, the speed of taking the roll into a roll or the like is 100 to 3000.
It is also important to set m / min (hereinafter, "drawing speed" means both the speed at which the undrawn yarn is wound and the speed at which the undrawn yarn is taken up by a roll or the like). By setting the take-up speed within this range, it becomes easy to suppress the orientation of the undrawn yarn. Since the extruded polymer falls by its own weight, it is difficult to make the take-off speed less than 100 m / min. On the other hand, when the take-off speed exceeds 3000 m / min, the thinning speed of the polymer increases, and
Since the air resistance increases, it becomes difficult to suppress the orientation of the undrawn yarn. Pickup speed is 300-2000m /
Min, more preferably from 600 to 1600 m / min, particularly preferably from 800 to 1200 m / min.

The undrawn yarn used in the present invention has a breaking elongation of 1
It is desirable that the crystallization peak temperature is 50 to 600% and the crystallization peak temperature is 64 to 80 ° C. If the elongation at break is less than 150%, since the molecules are entangled with each other, it is difficult to orient the fibers by stretching and increase the breaking energy. On the other hand, if the elongation at break exceeds 600%, the undrawn yarn becomes brittle, and the yarn is liable to break, making it difficult to draw stably. The elongation at break is more preferably from 180 to 500%, particularly preferably from 200 to 400%.

On the other hand, the crystallization peak temperature is 2 DSC.
This is the temperature of the peak top of the crystallization peak observed when the thermal analysis of the undrawn yarn is performed at 0 ° C./min. As the regularity of the undrawn yarn increases, the crystallization peak temperature decreases due to crystallization at a lower temperature. In the present invention, the lower the regularity such as the orientation of the undrawn yarn, the better. Therefore, the crystallization peak temperature is preferably as high as possible. Further, the stretching is preferably performed by softening the undrawn yarn at a temperature higher than the glass transition point (around 40 to 50 ° C. for the undrawn yarn of the present invention),
If the crystallization peak temperature is low, crystallization starts simultaneously with softening, and the stretchability deteriorates. From such a viewpoint, the crystallization peak temperature is preferably as high as possible. If the crystallization peak temperature is lower than 64 ° C., crystallization will occur immediately upon stretching, making it impossible to stretch at a high magnification. CD
With -PTT, the crystallization peak temperature does not exceed 80 ° C. The crystallization peak temperature is more preferably 66 to 80.
° C, more preferably 68-80 ° C.

It is preferable that the finishing agent is applied by the finishing agent applying device 9 before the cooled and solidified fiber is taken out. By providing the finishing agent, the fiber convergence, antistatic properties, slipperiness, and the like are improved, and the generation of fluff and yarn breakage during winding or post-processing can be suppressed. Here, the finishing agent is a water emulsion obtained by emulsifying an oil agent using an emulsifier, a solution in which the oil agent is dissolved in a solvent, or the oil agent itself, and is used to improve fiber convergence, antistatic properties, slipperiness, and the like. is there. Here, the oil agent is an aliphatic ester, a mineral oil, a molecular weight of 1,000 to 200.
A mixture containing at least one of the polyethers of No. 00 and having a sum of 40 to 90% by weight is preferable, and the components are preferably selected as necessary.

In the present invention, the oil agent is preferably applied to the fiber as a water emulsion having a concentration of 1 to 50% by weight. By using a water emulsion liquid, it becomes easy to suppress uneven adhesion of the oil agent and to improve the form of the wound yarn. The concentration of the water emulsion is more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight. When the concentration of the oil agent is low, it is necessary to apply a large amount of finish to the fiber in order to attach a preferable amount of the oil agent to the fiber. When the concentration is less than 1% by weight, the amount of the finish is too large, and it is difficult to give the finish to the fiber. On the other hand, if the concentration exceeds 50% by weight, the viscosity of the finishing agent is high, and the amount of the finishing agent decreases when a certain amount of the oiling agent is applied to the fibers. It becomes difficult.

It is preferable that the oil agent is applied in an amount of 0.2 to 3% by weight based on the weight of the fiber. If it is less than 0.2% by weight,
The effect of the oil agent is small, and the yarn breaks down due to static electricity, and the yarn breaks or fuzzes due to friction. 3% by weight
If the ratio exceeds the above range, the resistance of the fibers during running becomes too large, and the oil agent adheres to the rolls, hot plates, guides, etc., and contaminates them. Oil agent is 0.25 to fiber weight
It is preferable to adhere 2.5% by weight, particularly preferably 0.3 to 2% by weight. Of course, a part of the oil agent may permeate into the fiber. As a method of applying the finishing agent, a method using a known oiling roll or a method using a guide nozzle described in, for example, JP-A-59-116404 can be used. A method using a guide nozzle is preferable in order to suppress the occurrence of yarn breakage and fluff due to the above.

In the conveyor method, it is preferable to take up the undrawn yarn by controlling the winding tension using two or more pairs of take-up rolls such as the first take-up roll 10 and the second take-up roll 11 shown in FIG. . In this way, since the winding shape of the undrawn yarn can be improved, the fluctuation of the tension for unwinding the undrawn yarn during drawing is reduced, and a uniform, high-quality fiber with less fluff and yarn breakage is produced. It is easy to obtain.
The winding tension of the undrawn yarn is 0.04 to 0.3 cN / dt.
ex is preferable, 0.05 to 0.2 cN / dtex is more preferable, and 0.06 to 0.15 cN / dtex is particularly preferable. The SDTU method will be described later, including the taking together with the stretching.

2) Next, a method for drawing an undrawn yarn will be described. A second important point for producing the fiber of the present invention is to draw the undrawn yarn having a low degree of orientation at an appropriate range of magnification. For this purpose, it is necessary to perform stretching at a stretching ratio of 30 to 99% of the maximum stretching ratio. Here, the maximum draw ratio refers to the highest draw ratio at which the fiber is not broken when drawing is performed under the same drawing equipment and conditions as those for actually producing the fiber. When the stretching ratio exceeds 99% of the maximum stretching ratio, it is difficult to perform stable stretching because yarn breakage occurs. If the stretching ratio is less than 30% of the maximum stretching ratio, it is difficult to stretch uniformly, and the fiber tends to have large thickness unevenness. The stretching ratio is preferably 50 to 95% of the maximum stretching ratio, and 60 to 9%.
0% is more preferred.

The temperature at which such stretching is performed is 30 to
90 ° C. is preferred. Here, the temperature at which the drawing is performed is a temperature at which the fiber is heated before drawing, and corresponds to the temperature of the first drawing roll in the conveyor method and the temperature of the first roll in the SDTU method.
By setting the temperature within this range, it is easy to perform high-magnification stretching while suppressing the occurrence of yarn breakage and fluff during stretching, and it is easy to obtain a fiber having a high breaking energy, which is the object of the present invention. Stretching temperature is 40 to 80 ° C by the conveyor method.
Is more preferably 55 to 70 ° C., and SDT
In the U method, the temperature is more preferably from 50 to 85 ° C, and particularly preferably from 60 to 80 ° C. The drawn fiber is preferably subjected to a heat treatment in order to crystallize and reduce the shrinkage and increase the strength. The heat treatment may be performed in a step different from the stretching, but is preferably performed after the stretching in order to simplify the step.

The heat treatment temperature is preferably 50 to 200 ° C., and the heat treatment time is preferably 0.001 to 1 second. Temperature 50
If the temperature is less than ℃ or the time is less than 0.001 second, the fiber cannot be sufficiently crystallized and the structure cannot be fixed.
It may be difficult to reduce the shrinkage or increase the breaking energy of the fiber. On the other hand, when the temperature exceeds 200 ° C., yarn breakage or fluff occurs, and it becomes difficult to continuously draw the fiber. The temperature of the heat treatment is more preferably 60-18.
The temperature is 0 ° C, more preferably 80 to 160 ° C. The heat treatment time may be long, but when the fiber is continuously drawn and heat treated, it is preferably 1 second or less in view of productivity and equipment size. Since the crystallinity is determined by the heat treatment temperature and the heat treatment time, it is more preferable to select the heat treatment temperature and the heat treatment time according to the stretching speed.

When producing fibers by the conveyor method, usually
Stretching can be performed using a draw-twisting machine or a roll stretching machine used when producing ET or nylon fiber by the conveyor method. An example of a method of drawing an undrawn yarn by the conveyor method will be described with reference to FIG. The undrawn yarn 13 obtained by the conveyor method is drawn between the first drawing roll 14 and the second roll 16 heated to the above-mentioned drawing temperature, and after being heat-treated by the hot plate 15 heated to the above-mentioned heat treatment temperature. Is wound up by a winder 17. A drawing pin for fixing the drawing point, a device for entangled fibers, and rolls and guides for deflecting the fibers may be provided on the way. In addition, it is also preferable to twist at the same time as winding.

Next, an example of a method for producing a fiber by the SDTU method will be described with reference to FIG. The undrawn yarn drawn by the first roll 18 heated to the above-mentioned drawing temperature is then
After being wound around the second roll 19 heated to the above-mentioned heat treatment temperature and stretched between the first roll 18 and the second roll 19 having a higher peripheral speed than the first roll 18, the second roll 19 is stretched.
Heat treatment, and the winding machine 2 having a lower speed than the second roll 19.
1 and wound up. Here, reference numeral 20 denotes a free roll that is not driven by itself. It is important that the peripheral speed of the first roll 18 be in the range of the aforementioned undrawn yarn take-up speed. The peripheral speed of the second roll 19 is determined by the stretching ratio, but is usually 600 to 6000 m / min.

The winding speed is determined by the stretching ratio and the relaxing ratio, but is usually from 600 to 6000 m / min.
It is. In the SDTU method, it is preferable that the speed of the winder 21 is lower than that of the second roll 19, that is, the fiber is relaxed and wound. The CD-PTT fiber of the present invention is wound on the second roll 1 at the speed of the winder 21.
When manufactured at the same peripheral speed of 9, the wound fiber shrinks, and the shrinkage force tightens the yarn tube, so that even with a small winding amount of 1 kg or less, the cheese-like package can be wound from the spindle of the winder. A phenomenon that the bulge cannot be removed or has a bulge ratio of 20% or more, that is, a so-called tight tightening is likely to occur. As a result, the fibers cannot be obtained, or the unwinding tension is high and varies greatly, so that it is difficult to stably perform post-processing. On the other hand, when the speed of the winder is lower than that of the second roll, tightness of the obtained cheese-like package can be suppressed.

The relaxation ratio (winding machine speed / second roll peripheral speed) is preferably 0.8 to 0.999, more preferably 0.83 to 0.99, and further preferably 0.85 to 0.95.
0.95. However, even if such a relaxation magnification is applied, if the winding amount is increased, the tightening of the winding may occur. In this case, by using a high-strength yarn tube made of resin, metal, or thick paper to prevent deformation of the yarn tube due to tight tightening, the yarn tube can be easily removed from the spindle of the winder. Winding with a small winding amount of, for example, 2 kg or less is also an effective method for suppressing tightening.

In order to suppress the tightening of the winding, it is preferable that the fiber is cooled to (glass transition point of polymer + 20) ° C. or less before winding. CD-PTT is, for example, PET
Since the molecule has a bent structure as compared with the above, it is easy to move even at a relatively low temperature, contracts while being wound, and is very likely to be tightly wound. Therefore, by performing such cooling, it becomes possible to suppress the molecular motion, and as a result, it is possible to suppress the tightening of the winding. The lower the yarn temperature after cooling, the better, but it is usually -5 to 70C, preferably 0 to 50C. As a method for cooling the yarn, a method such as blowing cold air, immersing in a cooling liquid such as water or an organic solvent, or sliding on a low-temperature plate or roll can be used. Most preferably, a roll is provided between the second roll 19 and the winder 21. With such a method, it is easy to increase the winding amount.

The tension between the second roll 19 and the winder 21 is preferably 0.02 to 0.20 cN / dtex. It is preferable to adjust the speed of the winder so that the tension is in this range. If it is attempted to wind with such a low tension in the conventional PET or nylon melt spinning, the running of the yarn is not stable, and the yarn comes off the traverse of the winder, and the yarn breaks, A switching error occurs when the winding yarn is automatically switched to the next yarn tube. However, surprisingly, in the case of CD-PTT fiber, such a problem does not occur even when wound at an extremely low tension as in the present invention, and the cheese having a good winding shape is not tightly wound at a low tension. It becomes easy to obtain a shape package.
PT can be wound stably with such low tension.
This is considered to be due to the low elastic modulus and the high elastic recovery rate, which are characteristics of the T fiber.

If the tension is less than 0.02 cN / dtex, the tension is too weak, so that the traverse with the traverse guide of the winding machine cannot be made good, the winding form becomes poor, the yarn comes off from the traverse, and the yarn is removed. Cutting is easy to occur.
On the other hand, if the tension exceeds 0.20 cN / dtex, even if the fiber is cooled and wound up, it becomes easy to cause tightness. The tension at the time of winding is preferably 0.0
25 to 0.15 cN / dtex, more preferably 0.0
It is 3 to 0.10 cN / dtex. In the present invention, entanglement treatment may be performed as necessary in the spinning process. The entanglement treatment may be performed before or after the finish is applied, before winding, or at a plurality of locations.

The winding machine 21 used in the present invention may be any of a spindle driving system, a touch roll driving system, and a system in which both the spindle and the touch roll are driven. It is preferable that a winder of a type in which both are driven winds a large amount of yarn. When only one of the touch roll and the spindle is driven, the other is rotated by friction from the drive shaft, so that the surface speed differs between the thread tube attached to the spindle and the touch roll due to slippage. For this reason, when the thread is wound from the touch roll to the spindle, the thread is stretched or loosened, the tension is changed, the winding appearance is deteriorated, or the thread is easily rubbed and damaged. By driving both the spindle and the touch roll, it is possible to control the difference in surface speed between the touch roll and the yarn tube, reduce slippage, and improve the yarn quality and winding appearance. Can be.

It is preferable that the twill angle at the time of winding the fiber is 3.5 to 8 °. If the angle is less than 3.5 °, the yarns do not intersect with each other so much that the yarns are slippery. On the other hand, when the angle exceeds 8 °, the diameter of the end portion becomes larger than that of the central portion because the amount of yarn wound around the end portion of the yarn tube increases. For this reason, when winding, only the end comes into contact with the touch roll and the yarn quality deteriorates, and the tension fluctuation when unwinding the wound yarn increases, causing fluff and yarn breakage. It is easy to occur frequently.
The helix angle is more preferably 4 to 7 °, particularly preferably 5 °.
〜6.5 °.

The CD-PTT fiber obtained as described above can be used as a short fiber. When short fibers are used, the fiber length is preferably 3 to 300 mm, and the degree of crimp is preferably 5 to 35% or more. By using such a short fiber, it can be suitably used in the field of materials such as inner materials made of spun yarn, materials for clothing such as sports, wadding, and nonwoven fabric. The fiber length is less than 3 mm or the crimp degree is 5
%, It becomes difficult to entangle the fibers. On the other hand, if the fiber length exceeds 300 mm or the crimp degree is 35
%, The processability of the spinning process and the like deteriorates. The fiber length is more preferably from 5 to 200 mm, and from 10 to 1
50 mm is more preferred. The degree of crimp is more preferably 8 to 30%.

The short fibers have an elastic recovery of 8% at 10% elongation.
It is preferably at least 0%, more preferably at least 90%. If the elastic recovery is less than 80%, the stretchability tends to be poor. Further, the short fiber preferably has a flexural recovery of 80% or more, more preferably 90% or more. If the flexural recovery rate is less than 80%, when used for wadding and the like, it lacks restorability and tends to set. Such short fibers can be obtained by crimping the long fibers obtained in the present invention using a method such as stuffer box crimping, steam jet or other thermal fluid crimping, gear crimping, and then cutting. be able to. The fiber may be crimped without preconditioning, but it is preferable to crimp it after heat treatment in order to increase the elastic recovery and the bending recovery. The heat treatment is preferably performed under a constant length or under tension. Further, the heat treatment temperature is preferably 100 to 160 ° C., and the heat treatment time is preferably 0.01 to 90 minutes.

The CD-PTT fiber of the present invention can also be used as a false twisted yarn. By performing the false twisting, a false twisted yarn having a very soft and good elastic recovery property and a good dyeing property can be obtained. As the method of false twisting, any method such as a pin type, a friction type, a nip belt type, and an air twisting type, which are generally used, may be used, but a friction type and a nip belt type which can increase the processing speed are preferable.
Processing conditions are not particularly limited, and can be appropriately selected from a known condition range.

The CD-PTT fiber of the present invention is used alone,
Or, by using it for a part of the fabric, the fabric becomes excellent in softness, stretchability, and color development. In particular, since the fiber of the present invention has a small shrinkage and a large breaking energy,
Even after subjecting the woven or knitted fabric used alone or in part of the fabric to a post-processing such as dyeing, the fabric does not excessively shrink,
A very soft hand can be maintained, and a fabric having excellent burst strength and tear strength can be obtained. Other fibers used in a part of the fabric are not particularly limited. In particular, by mixing with fibers such as stretch fibers represented by polyurethane elastic yarn, cellulose fibers, wool, silk, and acetate, nylon fibers are used. And characteristics that cannot be obtained with a fabric using PET fibers. That is, the fabric can be dyed at normal pressure using, for example, a cationic dye and / or a disperse dye, and has a unique texture with softness and stretchability that has not existed conventionally.

The form and knitting and weaving method of the fabric of the present invention are not particularly limited, and known methods can be used. For example, plain fabrics using the fiber of the present invention for warp or weft, fabrics such as reversible fabrics, warp knitting, weft knitting, knitted fabrics such as circular knitting, and the like can be mentioned. good. The fiber of the present invention can be used for clothing such as outerwear, innerwear, lining, and sports, as well as for materials such as raw yarn for carpet, interlining, and flocky, by taking advantage of its properties.

[0075]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below using examples and the like. Needless to say, the present invention is not limited by the examples and the like. The main measured values in the examples were measured by the following methods. (1) Intrinsic viscosity [η] Intrinsic viscosity [η] was measured using an Ostwald viscometer, 35
° C, specific viscosity ηsp in o-chlorophenol and concentration C
The ratio ηsp / C of (g / 100 ml) was extrapolated to zero concentration and determined according to the following equation. [Η] = lim (ηsp / C) C → 0

(2) Hue (L value, b * value) of polymer Measured using a color computer of Suga Test Instruments Co., Ltd. (3) Peak temperature of dynamic loss tangent (Tmax) Dynamic loss tangent (tan δ) at each temperature using a Leo vibron manufactured by Orientec Co., Ltd. in dry air at a measurement frequency of 110 Hz and a heating rate of 5 ° C./min. And the dynamic modulus of elasticity were measured. From the result, a dynamic loss tangent-temperature curve was obtained, and the peak temperature (T
max) (° C.). (4) Boiling water shrinkage (BWS) It was determined as the skein shrinkage based on JIS-L-1013.

(5) Strength (rupture strength), elongation (elongation at break), toughness Using Tensilon manufactured by Orientec Co., Ltd., which is a constant-speed elongation type tensile tester based on JIS-L-1013,
The measurement was performed at a grip interval of 20 cm and a tensile speed of 20 cm / min. The toughness was calculated from the following equation using the strength and elongation measured by the above methods. Toughness = strength (cN / dtex) x √ elongation (%)

(6) Elastic recovery The elastic recovery was obtained as an elastic recovery obtained by the following method. The fiber is attached to a tensile tester with a distance between chucks of 20 cm, stretched to a predetermined stretching rate (L ₀ ) at a stretching speed of 20 cm / min, and left for 1 minute. Thereafter, the material is contracted again at the same speed, and a stress-strain curve is drawn. During the contraction, the elongation when the stress becomes zero is defined as the residual elongation (La). The elastic recovery was determined according to the following equation. Elastic recovery _{= (L 0 -La) / L} 0 × 100 (%) (7) birefringence fiber Handbook - raw ed, p. 969 (5th printing, Maruzen Co., Ltd., 1978), using an optical microscope and a compensator, from the retardation of polarized light observed on the fiber surface.

(8) Density According to JIS-L-1013, carbon tetrachloride and n-
The measurement was performed by a density gradient tube method using a density gradient tube prepared with heptane. (9) U% U% is USTER · T manufactured by Zellbeger Worcester Co., Ltd.
It was determined by measuring with ESTER3 under the following conditions. Measurement speed: 100m / min Measurement time: 1 minute Measurement times: 2 Twist type: S twist

(10) Fiber Color The WI value, which is the whiteness, according to the method according to ASTM-E-313-73, and the YI value, which is the yellowness, according to the method according to ASTM-D-1925-70 The measurement was carried out under the following conditions using the evaluation cloth prepared by the following method. Preparation method of evaluation fabric 1) A sample is used as a single-knit fabric. 2) Scouring is performed in 70 ° C. warm water containing 2 g / l of score roll FC-250 for 20 minutes. 3) Heat set at 180 ° C. for 30 seconds using a tenter. Measuring method Apparatus: Spectrophotometer: Macbeth CE-3000 (manufactured by Sakata Inx Co., Ltd.) Condition: Field of view: 2 ° Light source: C (CIE 1964) Specular gloss: Included UV light: Included Calculation: Calculate according to the following formula, calculate YI value, The WI value was calculated. YI = 100 × (1.28X-1.06Z) / Y WI = 4 × 0.847Z-3Y Here, X, Y, and Z are tristimulus values of the sample in the XYZ color system.

(11) Bulge ratio The yarn layer (104) shown in FIG. 3- (A) or FIG. 3- (B)
The winding width Q of the innermost layer and the winding width R of the bulging portion were measured and calculated according to the following formula. Bulge rate = {(RQ) / Q} × 100% (12) Crystallization peak temperature of undrawn yarn The crystallization peak temperature of undrawn yarn is Perkin Elm.
The measurement was carried out under the following conditions using a Pyris1 DSC (input compensation type differential calorimeter) manufactured by ER Co., Ltd., and the peak value of the exothermic peak derived from crystallization was defined as the crystallization peak temperature. The peak value was determined using the attached analysis software. Measurement temperature: 0 to 280 ° C Heating rate: 20 ° C / min

(13) Adhesion rate of oil agent Based on JIS-L-1013, the fiber was washed with diethyl ether, diethyl ether was distilled off, and the amount obtained by dividing the amount of pure oil agent adhering to the fiber surface by the fiber weight was calculated. The oil agent adhesion rate was used. (14) Degree of Crimp The length when a sample was subjected to an initial load of 0.01764 cN / dtex was defined as a, and the length when a load of 0.265 cN / dtex was applied was defined as b. The test was performed 10 times, and the average value was used as the value of the degree of crimp. Crimping degree (%) = (ba) / b × 100 (15) Bending recovery rate The fiber before cutting was prepared by dividing the fiber having a width of 30 mm, a length of 40 mm and a thickness of 40.
The fiber is wound five times around a μm plate so that the fibers do not overlap with an initial load of 0.0294 cN / dtex, and a load of 1 kg is applied to the bent portion of the fiber. After 30 seconds, the load was removed, the fiber was cut at the center of the plate, the recovery angle after 10 minutes was measured, and the recovery rate was calculated.

[0083]

Examples 1 to 4 1300 g of dimethyl terephthalate
(6.7 mol), 1,3-propanediol 1144
g (15 mol), 40.5 g (0.14 mol) of dimethyl 5-sodium sulfoisophthalate, 2.4 g (0.014 mol) of calcium acetate monohydrate, 1.0 g (0.01 mol) of lithium acetate dihydrate Was charged into a 3 liter autoclave, and transesterification was carried out at 220 ° C. while distilling off methanol. Subsequently, 0.65 g of trimethyl phosphate and 1.3 of titanium tetrabutoxide were used.
4g, titanium dioxide 0.05% by weight of theoretical polymer amount
After the addition, a polycondensation reaction was performed at 270 ° C. for 2 hours at a vacuum of 0.1 to 0.5 torr while distilling off 1,3-propanediol. The obtained polymer was further subjected to solid-state polymerization at 210 ° C. under a nitrogen stream to obtain a polymer having an intrinsic viscosity [η] shown in Table 1. All of the obtained chips had b * values in the range of -2 to 6, and L values of 85 or more, and were excellent in whiteness.

The obtained polymer was dried by a conventional method using the apparatus shown in FIG.
After being melted by an extruder set at 65 ° C., the solution was sent to a spin head having a temperature shown in Table 1 and had a diameter of 0.35 mm.
It was extruded from a single-array spinneret having 36 holes with a length of 0.35 mm. The spinning draft at this time was as shown in Table 1. Under the spout, length 100m at the temperature shown in Table 1
m heating cylinder was installed. The spinning surface temperature at this time is shown in Table 1. Next, a temperature of 20 ° C. was applied to the extruded polymer.
After cooling and solidifying by applying a cool air at a wind speed of 0.4 m / min, using a guide nozzle, octyl stearylate 60% by weight,
An oil agent containing 15% by weight of polyoxyethylene alkyl ether and 3% by weight of potassium phosphate was applied as a water emulsion finish having a concentration of 20% by weight so that the oil agent adhesion rate to the fiber was 1.0% by weight. .

The fiber to which the oil agent was applied passed through the first take-up roll having the peripheral speed shown in Table 1 and then passed through the second take-up roll so that the tension became 0.1 cN / dtex. At a speed shown in Table 2 to obtain an undrawn yarn. Table 1 shows the physical properties of the wound undrawn yarn. Each of the undrawn yarns had a preferred range of elongation and crystallization peak temperature. The wound undrawn yarn was drawn by a drawing machine shown in FIG. 4 with the first drawing roll at 60 ° C. and the hot plate at 140 ° C. at the draw ratio shown in Table 1 to obtain 56 dtex / 24 filaments. Fiber was obtained.
Table 3 shows the physical properties of the obtained fiber. In each case, generation of fluff was not observed during spinning and stretching. In addition, any fibers correspond to the scope of the present invention, and BW
The fiber was low in S and high in toughness.

[0086]

Comparative Examples 1-4 Conveying method In the same manner as in Example 1, fibers were produced under the conditions shown in Table 1. Table 3 shows the physical properties of the obtained fiber. In Comparative Example 1, since the degree of polymerization of the polymer used was low, the degree of polymerization of the obtained fiber was low, the toughness was low, and the BWS was high. In Comparative Example 2, since there was no heating tube, the obtained undrawn yarn had a low crystallization peak temperature. When the obtained undrawn yarn was drawn, the peak temperature of the dynamic loss tangent was less than 105 ° C., and the BWS exceeded 16%, which was out of the range of the present invention. Further, the toughness of the fiber was low, and the fiber was not satisfactory.

In Comparative Example 3, the temperature of the spinning surface was increased by increasing the SH temperature without installing a heating cylinder, and the orientation of undrawn yarn was suppressed. However, since the SH temperature was too high, the polymer was decomposed, the intrinsic viscosity [η] of the fiber was out of the range of the present invention, and the b * value was high, resulting in a yellow colored fiber. Further, the fiber had low toughness. In Comparative Example 4, the elongation of the undrawn yarn and the crystallization peak temperature were both low because the take-up speed was high. The obtained undrawn yarn was drawn,
Peak temperature of dynamic loss tangent is less than 105 ° C, BWS is 1
It exceeded 6% and was out of the range of the present invention. Further, the fiber had low toughness.

[0088]

[Table 1]

[0089]

Examples 5 and 6 SDTU method Using the polymers shown in Table 2 obtained in the same manner as in Example 1, the SDTU spinning apparatus shown in FIG. 5 was used to produce Examples 1 and 2, except for the conditions shown in Table 2. In the same manner as in the above, drying to finish application was performed. The fiber to which the finishing agent has been applied is stretched, heat-treated, and wound under the conditions shown in Table 2 using a first roll, a second roll, and a winder set under the conditions shown in Table 2. A fiber of 86 dtex / 24 filament was obtained. The properties of the obtained fibers are shown in Table 3. In order to measure the physical properties of the undrawn yarn before stretching, the physical properties of the undrawn yarn directly wound at the same speed as the first roll were measured. The results are shown in Table 2.

The physical properties of the undrawn yarn are as follows:
The crystallization peak temperature was in a preferable range. In each case, the obtained fibers did not show any fluff during spinning, and the physical properties of the obtained fibers were also within the scope of the present invention, and were fibers having low shrinkage and high toughness. . The cheese-like package obtained by winding 4 kg of the fiber can be easily taken out from the spindle of the winding machine, the bulge ratio is within the scope of the present invention as shown in Table 3, and the tightening phenomenon is not observed. I couldn't.

Comparative Example 6 SDTU Method Spinning was performed in the same manner as in Example 5 except for the conditions shown in Table 2 to obtain a fiber. Table 3 shows the physical properties of the obtained fiber.

[0091]

[Table 2]

[0092]

[Table 3]

In Comparative Example 6, since there was no heating tube, the peak temperature of the dynamic loss tangent of the obtained fiber was less than 105 ° C., which was out of the range of the present invention. Further, the fiber had low toughness. In addition, when 4 kg of the fiber was wound, the tightness of the winding was so high that the cheese-like package could not be taken out from the spindle of the winder. Also, in order to measure the physical properties of the undrawn yarn before drawing,
The physical properties of the undrawn yarn directly wound at the same speed as the first roll were measured. As shown in Table 2, the undrawn yarn had a crystallization peak temperature lower than the preferred range of the present invention.

[0094]

Example 7 The fiber obtained in Example 1 was heated at 150 ° C. for 5 hours.
After a constant-length moist heat treatment for a minute, crimp was applied by stuffer box crimping and cut to obtain short fibers. The obtained short fiber had a fiber length of 60 mm, a degree of crimp of 14%, and an elastic recovery of 95%. The crimped fiber before the cutting had a good bending recovery rate of 90%. The obtained short fibers had good dyeability, had a soft texture, and were excellent in stretchability, and could be made into spun yarn, wadding, or the like.

[0095]

Example 8 The fiber obtained in Example 1 and 233 dtex
The warp knitted fabric was knitted using Roica (polyurethane-based elastic fiber manufactured by Asahi Kasei Corporation). The knitting gauge is 28
G, loop length is 1080 mm / 48 for polyester fiber
0 course, stretch fiber was 112 mm / 480 course, and driving density was 90 course / inch. The mixing ratio of the polyester fibers was set to 75%. The obtained dough is relaxed and scoured for 2 minutes at 90 ° C.
A dry heat setting was performed at 1 ° C. for 1 minute. Next, Kayacryl Black BS-ED (a cationic dye manufactured by Nippon Kayaku Co., Ltd.) was used as a dye, and Disper TL (a nonionic activator manufactured by Meisei Chemical Co., Ltd.) was used as a dispersant at 1 g / liter. 50 g / l of sodium sulfate and 15 g / l of sodium carbonate are added, and a dye is added to an aqueous solution adjusted to pH 11 to make a dyeing solution. Dyeing is performed at 105 ° C for 1 hour at a dye concentration of 8% owf and a bath ratio of 1:50. Was. After the dyeing, a finishing treatment was performed by a conventional method. The obtained dyed fabric was sufficiently dyed, and was also excellent in dyeing fastness. This dyed knitted fabric did not excessively shrink during dyeing, and was excellent in softness, stretchability, tension, and waist.

[0096]

The CD-PTT fiber of the present invention uses a CD-PTT polymer having a high degree of polymerization in a specific range, is extruded at a spun surface temperature in a specific range, is cooled, and is taken up at a low speed to obtain an orientation property. An unstretched yarn having low crystallinity and good stretchability was obtained by stretching the unstretched yarn at a specific draw ratio. The intrinsic viscosity [η] was high, the amorphous denseness was low, and the BWS was low. In the fiber that had, the breaking energy is high and it does not shrink excessively in post-processing steps such as dyeing, so it is hard to tear,
In addition, the fabric produced using the CD-PTT fiber of the present invention, which can obtain a fabric having a soft texture, is a fiber excellent in tear resistance, having a soft texture, and having a clear dyeing property. Therefore, CD-PTT fiber alone or in combination with urethane elastic fiber or the like is useful for inners, vests, and cross knitting type pantyhose.

[Brief description of the drawings]

FIG. 1 is an uneven curve (mass change of fiber) when the fiber is passed through USTER TESTER3.

FIG. 2 is a schematic view showing a cheese-like package in which the PTT fiber of the present invention is wound around a yarn tube. Figure 2- (a)
FIG. 2 is a schematic view of a desirable cheese-like package. FIG.
(B) is a schematic diagram of a cheese-like package with a bulge.

FIG. 3 is a schematic view showing an outline of an apparatus for obtaining an undrawn yarn when the present invention is carried out by a conveyor method.

FIG. 4 is a schematic view showing an outline of a draw-twisting machine for drawing an undrawn yarn when carrying out the present invention by a conveyor method.

FIG. 5 is a schematic diagram showing an outline of a spinning machine for implementing the present invention by the SDTU method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Dryer 2 Extruder 3 Bend 4 Spin head 5 Spinner pack 6 Spinner 7 Heating cylinder 8 Cooling air 9 Finishing agent application device 10 1st take-up roll 11 2nd take-up roll 12, 17, 21 Winder 13 Unstretched Thread 14 First draw roll 15 Hot plate 16 Second draw roll 18 First roll 19 Second roll 20 Free roll 21a Spindle 21b Touch roll

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) D04B 21/00 D04B 21/00 B F term (reference) 4L002 AA05 AA07 AB01 AC00 DA01 DA04 EA00 FA03 FA06 4L035 BB52 BB60 BB89 BB91 DD19 DD20 EE01 EE08 EE20 4L048 AA22 AA42 AA46 AA48 AA49 AA50 AA55 AB05 AC07 AC09 AC10 CA00 CA01 CA12 DA01

Claims (11)

[Claims] 1. A polytrimethylene terephthalate in which an ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% based on all dicarboxylic acid components, wherein the poly (trimethylene terephthalate) comprises the following (A):
Polytrimethylene terephthalate fibers satisfying the requirements of (C) to (C). (A) Intrinsic viscosity [η]: 0.65 to 1.4 (B) Peak temperature of dynamic loss tangent: 105 ° C. or more (C) Boiling water shrinkage: 0 to 16% 2. The polytrimethylene terephthalate fiber according to claim 1, further satisfying the following requirements (E) and (F). (E) Elongation at break: 20-70% (F) Toughness: 16-40 [Here, toughness is a value calculated by the following equation (a). Toughness = strength (cN / dtex) x elongation (%) 3. The polytrimethylene terephthalate fiber according to claim 1, wherein the ester-forming sulfonate is 5-sodium sulfoisophthalic acid. 4. A polytrimethylene terephthalate having an intrinsic viscosity [η] of 0.65 to 1.4, wherein an ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% based on all dicarboxylic acid components. And the elongation at break is 150-600
%, And a polytrimethylene terephthalate undrawn yarn having a crystallization peak temperature of 64 to 80 ° C. 5. A polytrimethylene terephthalate having an intrinsic viscosity [η] of 0.65 to 1.4, in which an ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% based on all dicarboxylic acid components. And the elongation at break is 150-600
%, And a polytrimethylene terephthalate undrawn yarn characterized by having a crystallization peak temperature of 64 to 80 ° C. is drawn at a draw ratio of 30 to 99% of the maximum draw ratio. A method for producing terephthalate fiber. 6. A polytrimethylene terephthalate having an intrinsic viscosity [η] of 0.65 to 1.6, wherein an ester-forming sulfonic acid salt is copolymerized in an amount of 0.5 to 5 mol% based on all dicarboxylic acid components. This is a method of melt-spinning, in which the molten polymer extruded from the spinneret is cooled and solidified at a spinning surface temperature of 250 to 295 ° C, and the undrawn yarn drawn at a speed of 100 to 3000 m / min is heated to 30 to 90 ° C. At a stretching ratio of 30 to 99% of the maximum stretching ratio at a temperature of
A method for producing polytrimethylene terephthalate fiber, comprising heat-treating at a temperature of 0 to 200C. 7. The method for producing a polytrimethylene terephthalate fiber according to claim 6, wherein a heating tube having a length of 20 to 500 mm and a temperature of 150 to 350 ° C. is provided under the spinneret. 8. The method for producing a polytrimethylene terephthalate fiber according to claim 5, wherein the drawn undrawn yarn is once wound and then drawn. 9. The drawn undrawn yarn is drawn continuously without being wound once.
7. The method for producing a polytrimethylene terephthalate fiber according to any one of 7. 10. A fiber having a fiber length of 3 to 200 mm and a degree of crimp of 5
The polytrimethylene terephthalate staple fiber according to any one of claims 1 to 3, wherein the content is from 35% to 35%. 11. A fabric using the polytrimethylene terephthalate fiber according to claim 1 for at least a part thereof.