JPH0336934B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel spun yarn comprising one or two of acrylic fibers and wool fibers and specific polyester fibers. Conventionally, polyester fibers, especially polyethylene terephthalate fibers, have been blended with natural fibers or chemical fibers such as cotton, hemp, recycled cellulose fibers, and wool for their superior mechanical and thermal performance. A spun yarn is produced that compensates for the lack of mechanical properties and the lack of water absorption, which is a drawback of polyester fibers, and has practical performance far superior to yarns spun from these individual fibers alone. However, because conventional polyethylene terephthalate fibers are dye-resistant fibers that can only be dyed under high temperatures and pressures of 120 to 130°C, their mechanical properties are significantly degraded under high temperatures and pressures, especially when used with wool and acrylic fibers. There were restrictions on the production of blended yarns with fibers. That is, when wool and polyethylene terephthalate fibers are blended, conventionally the polyethylene terephthalate fibers are dyed at 120 to 130°C in the form of tows or staples, and the wool is separately dyed at 100°C in the form of loose wool or tops. The so-called yarn dyeing method was used, in which the two were mixed in a kneading process to create a blended yarn. In rare cases, after spinning the non-pre-dyed fibers using a conventional method, the polyethylene terephthalate fibers are treated with an organic substance called a carrier such as o-phenylphenol, methylnaphthalene, chlorobenzene, or methyl salicylate in a dyebath containing a disperse dye. After dyeing at a temperature of around 100°C, the wool was dyed with acid dyes, metal-containing dyes, etc. Among these conventional methods, the former dyeing method is economically disadvantageous because the spinning machine gets dirty during the spinning process, requires time to clean when changing colors, and also causes a large amount of fiber loss. When using the latter carrier dyeing method, the dyeing density is inferior to high-temperature and high-pressure dyeing, staining spots called carrier spots caused by insufficient emulsification of the carrier may occur, and the carrier has a pungent odor. It is harmful to the human body, which worsens the working environment of dyeing factories; it is difficult to treat dyeing waste water; and the light fastness of dyed products decreases because the carrier remains in the fibers and is difficult to remove. residual carrier may emit a pungent odor;
Also, there is a risk of skin damage when worn.
Carrier dyeing has had many disadvantages, including changes in the mechanical properties of polyethylene terephthalate fibers, such as a decrease in strength and an increase in elongation. These drawbacks of the prior art in blended yarns of wool and polyester fibers also apply to blended yarns of acrylic fibers and polyester fibers. In addition, polyester fibers with improved dyeability are known that are copolymerized with metal sulfonate group-containing compounds or polyether, but although these modified polyesters improve dyeability, they are difficult to polymerize and spin. There were drawbacks such as a significant increase in manufacturing costs, a deterioration of the excellent mechanical properties inherent to polyethylene terephthalate, and poor color fastness. In addition, dyeing modified polyester to a high density requires dyeing at a temperature of 105 to 110°C.
In the density dyeing of blended yarns with acrylic fibers and wool fibers, deterioration of the acrylic fibers and wool fibers due to high temperature and pressure is still unavoidable. Therefore,
Spun yarns using modified polyester together with acrylic fibers and wool fibers have the disadvantages of modified polyesters, so there is little point in going to the trouble of blending polyesters. The present inventors completed the present invention as a result of research on a new spun yarn that can be dyed under normal pressure and improves the above-mentioned drawbacks of conventional spun yarns. The blended yarn that can be dyed under normal pressure according to the present invention contains one or two types of acrylic fibers and wool fibers.
A spun yarn containing ~5% by weight and 5% to 95% by weight of polyester fiber, wherein the polyester fiber is substantially composed of a homopolymer of polyethylene terephthalate, and the initial modulus of the polyester fiber at 30°C is 50 g/d or more. Yes, measurement frequency
The peak temperature (T _nax ) of mechanical loss tangent (tan δ) at 110 Hz is 105°C or less, the peak value of tan δ [(tan δ) _nax ] is 0.14 or more, and the crystallinity (Xc) is 30% or more. Yes, the size of microcrystals (ACS) on the (010) plane is 35 Å or more, the degree of crystal orientation (CO) on the (010) plane is 85% or more, and it is possible to dye with a disperse dye at atmospheric pressure. It is characterized by "Can be dyed at normal pressure with disperse dye" means disperse dye C.I. Disperse Blue 56 (CI Disperse Blue 56)
Disperse Blue 56; e.g. Resolin Blue FBL
[Product name of Bayer AG, Federal Republic of Germany])
100 in a dye bath with a dye usage of 3% owf, a bath ratio of 50 times, a pH of 6 (adjusted with acetic acid), and a dispersant (for example, Disper TL [product name of Meisei Chemical Industry Co., Ltd.]) content of 1 g/.
After dyeing at ℃ for 120 minutes, the exhaustion rate of the dye attached to the fiber is 80% or more. Here, the dye exhaustion rate is expressed by the following formula. Dye exhaustion rate (%) = Amount of dye dyed on the fiber (weight) / Amount of dye added to the dye bath (weight) x 100 The dye used in the present invention is made of a homopolymer of polyethylene terephthalate and is dispersed at normal pressure. Dyeable polyester fiber is a new fiber,
The spun yarn of the present invention made of such novel polyester fibers, acrylic fibers, and/or wool fibers has extremely remarkable operational efficiency that was completely unexpected from conventionally known spun yarns. Specifically, spun yarns using conventionally known polyethylene terephthalate fibers suffer from the above-mentioned drawbacks that occur because the polyethylene terephthalate fiber itself has a dye exhaustion rate of only 30 to 45% under the same dyeing conditions as above. In contrast, in the present invention,
In addition to solving all of these drawbacks, the disadvantages of spun yarns using modified polyester fibers, such as decreased mechanical properties, decreased heat resistance, and decreased color fastness, are also resolved. In particular, the spun yarn of the present invention has an extremely low shrinkage rate in hot water. For example, 40% by weight of conventional polyethylene terephthalate fiber, 30% by weight of acrylic fiber (Cashmilon)
100℃ of No. 48 twin yarn consisting of weight% and wool 30%
x 40% by weight of ethylene terephthalate copolyester fiber, which has a shrinkage rate of about 8-10% after hot water treatment for 30 minutes and contains 3% by weight of isophthalic acid/sodium sulfonate components, and 30% by weight of similar acrylic fiber. % and 30% by weight of wool, the shrinkage rate after similar hot water treatment is about 10 to 13%, whereas the conventional polyethylene terephthalate fiber or copolyester fiber of the present invention is 48 with a composition substituted with fibers
The shrinkage rate of double-ply yarn after similar hot water treatment is only about 2 to 3%. The spun yarn of the present invention contains 95 to 5% by weight of one or both of acrylic fibers and wool fibers, substantially consists of a homopolymer of polyethylene terephthalate, and contains 5 to 95% of polyester fibers that can be dyed under atmospheric pressure with disperse dyes. It is essential to contain % by weight.
When the content is outside this range, problems arise such as the excellent mechanical properties of the blended yarn are considerably inferior. Polyester fibers made of homopolymer of polyethylene terephthalate are combined with acrylic fibers and/or
Or, in order to achieve the intended purpose of the present invention when mixed with wool fiber and used as a spun yarn, it is necessary to
The initial modulus at is 50 g/d or more (meaning dynamic elastic modulus [E′ ₃₀ ] at 30°C),
Mechanical loss tangent (tanδ) at measurement frequency 110Hz
The peak temperature (T _nax ) of is below 105℃,
Use one with an equal value of (tan δ) [(tan δ) _nax ] of 0.14 or more. As the characteristic values expressing the structure of the amorphous region, the above values of T _nax and (tanδ) _nax are appropriate, as detailed in the specification of Japanese Patent Application No. 1983-46408 filed by the same applicant. be. T _nax is usually 50℃, which is the glass transition point.
Located on the high temperature side, (tan δ) _nax is related to the amount of molecular chains in the amorphous region activated by thermal motion at the temperature T _nax . In the present invention, T _nax and (tan δ) _nax refer to values related to mechanical absorption (αa absorption) caused by micro-Brownian motion of molecular chains inside the amorphous region. Conventional polyethylene terephthalate fiber has a T _nax of 130°C or higher and a (tan δ) _nax of 0.13 or lower. (tan δ) In general, it is desired that E′ ₃₀ be large because the larger _{the nax} , the better the shape retention. If E' ₃₀ is less than 50 g/d, the thermal stability of the fiber structure will decrease, the dimensional stability will be poor, and the fiber will become soft. The fibers made of a polyethylene terephthalate homopolymer that can be dyed under atmospheric pressure with disperse dyes and which constitute the blended yarn of the present invention have sufficient strength (3 g/d or more) and initial modulus (50
crystallinity (Xc) in order to have a
is 30% or more, (010) crystallite size (ACS)
is 35 Å or more, and the degree of crystal orientation (CO) of the (010) plane is 85
% or more. More preferably,
Xc is 70% or more, ACS is 50Å or more, and CO is 90% or more. In addition, polyethylene terephthalate fibers used for conventional spinning raw materials and spun yarns have Xc.
50-70%, ACS less than 30 Å, CO 85%-95%. Furthermore, in the polyethylene terephthalate fibers constituting the blended yarn of the present invention, the central refractive index (n ₍₀₎ ) of polarized light having an electric field vector in the fiber axis direction is
If it is smaller than 1.70 and 1.65 or more, it has appropriate elongation (20 to 70%) and dyeability, and is more preferable as a clothing fiber. optimal (n ₍₀₎ )
ranges from 1.65 to 1.68. Further, the average birefringence (Δn) is preferably 35×10 ⁻³ or more, but desirably 50×10 ⁻³ or more from the viewpoint of structural stability against heat. Further, from the viewpoint of improving dyeability and color fastness, it is preferably 120×10 ⁻³ or less, more preferably 85×10 ⁻³ or less. When Δn _is less _than ¹²⁰ (expressed as E′ ₂₂₀ /E′ ₁₅₀ ) becomes smaller, and E′ ₂₂₀ /E′ ₁₅₀ becomes larger than 0.75. In other words, the structure becomes stable against heat. The color fastness is also improved. Furthermore, Δn is 85×10 ^-3
Smaller ones have extremely good atmospheric dyeability. The difference between the average refractive index (n ₍₀₎ ) at the center of the fiber and the refractive index n _(0.8) or n _(-0.8) at a distance of 0.8 times the radius from the center of the fiber [Δ _(0.8-0) ] is
When it is 10×10 ⁻³ to 80×10 ⁻³ , it has sufficient strength and has few staining spots, strong elongation spots, etc. The fact that the local average refractive index distribution is symmetrical with respect to the fiber center means that the minimum value of the average refractive index n is (n ₍₀₎
-10×10 ^-3 ) or more, and n _(-0.8) and n _(0.8)
The difference is 50×10 ^-3 or less, more preferably 10×10 ^-3
This refers to the following cases. Furthermore, the smaller the mechanical loss tangent (tan δ ₂₂₀ ) at 220° C. is, the better, and the decrease in the initial modulus due to temperature rise is reduced. tanδ ₂₂₀
is less than 0.25, the initial modulus becomes significantly smaller. For example, fibers made of homopolymer of polyethylene terephthalate that can be dyed with disperse dyes at normal pressure can be dyed at 4000 m/min as shown in the examples later.
Fibers made of polyethylene terephthalate homopolymer spun at a spinning speed of 220°C or more
It can also be obtained by dry heat heat treatment at a temperature in the range of 180 to 240 °C, or by moist heat heat treatment with superheated steam, saturated steam, or hot water in the temperature range of 180 to 240 °C. Can be done. The homopolymer of polyethylene terephthalate, which is the raw material for the fiber made of the homopolymer of polyethylene terephthalate constituting the blended yarn of the present invention, can be obtained by a known polymerization method. Also,
Additives commonly used in polyester fibers, such as matting agents, stabilizers, antistatic agents, etc., may also be included. Further, there is no particular restriction on the degree of polymerization as long as it is within the range for normal fiber formation. FIG. 1 shows an example of an apparatus for manufacturing a fiber made of a polyethylene terephthalate homopolymer constituting the blended yarn of the present invention and capable of being dyed under normal pressure with a disperse dye. Molten polyethylene terephthalate is spun from a spinneret (not shown) in a heated spinning head 2 and cooled in the atmosphere to form a fiber bundle 1.
A tubular heating area 3 surrounding the spun fiber bundle 1 is provided below the spinneret, and further below it a fluid suction device 4 for cooling and suctioning the fiber bundle 1. There is. After passing through the oil application device 5, the fiber bundle is taken off by a take-off roller 6. The "spinning speed" used in the present invention means the surface speed of the take-up roller 6. Next, the fiber bundle is pulled out by a pair of fiber bundle feeding rollers 7, passed through a heating tube 8 adjusted to an appropriate temperature within the temperature range of 220 to 300°C, and guided by a pair of fiber bundle feeding rollers 9. It is wound up by a winding roller 10. At this time, by adjusting the rotational speeds of the fiber bundle feed rollers 7 and 9, the fiber bundle 1 is elongated to an appropriate elongation rate in the heating cylinder 8 and subjected to heat treatment. In addition to the above-mentioned heat treatment method, the following method is also used for heat treatment. That is, after winding the polyethylene terephthalate fiber bundles at a spinning speed of 4,000 m/min or more using the take-up roller 6, the polyethylene terephthalate fiber bundles are assembled into a tow, which is then heat-treated or crimped, and then cut and stapled. Alternatively, the staple may be heated in the form of a web, sliver, top, etc. after being opened. Of course, the heat treatment method may be carried out by either a dry heat method or a moist heat method as described above. FIG. 2 shows an example of an apparatus for subjecting tow or sliver of polyethylene terephthalate fibers spun at a spinning speed of 4000 m/min or higher to wet-heat heat treatment with superheated steam. In FIG. 2, 11 is a tow or sliver, which is pulled up by a pair of feed rollers 12 and guided by a guide roller 1.
3 and is led to the moist heat treatment device 15. A slit 14 is provided at the entrance of the wet heat treatment apparatus 15, and a slit 14' is provided at the outlet, so that the temperature inside the wet heat treatment apparatus 15 is not influenced by the temperature of the outside atmosphere. Further, the moist heat treatment apparatus 15 is provided with a large number of slits 16 on the upper and lower sides in the inner wall so that the tow or sliver is simultaneously exposed to superheated steam from the upper and lower surfaces. Further, heaters 17 are provided on the upper and lower sides of the wet heat treatment apparatus 15 so as to control the temperature of the superheated steam. On the other hand, saturated steam with a gauge pressure of about 10 Kg/cm ² generated in the boiler 24 enters the heating device 21 through the valve 23 and is heated by the heater 22 to become superheated steam at a temperature of 180 to 240°C. This superheated steam is sent to a moist heat treatment device 15 by a valve 20, adjusted by a heater 17 so that the temperature does not drop and the temperature distribution does not become large, and hits the tow or sliver 11 through a slit 16 to perform a moist heat heat treatment. The tow or sliver that has undergone the moist heat treatment passes through the guide roller 18 through the slit 14' and is taken to the winding device 1.
It is wound up at 9. Among the polyethylene terephthalates heat-treated as described above, those heat-treated immediately after spinning or in the form of tow are crimped and cut into staples in a stuffer box by a conventional method, and then processed into acrylic fibers and wool in the spinning process. fiber,
Or it is blended with a mixture of acrylic fiber and wool fiber. Further, the heat-treated yarns in the form of webs, slivers, and tops are directly mixed with wool tops and acrylic fiber tops to produce blended yarns by conventional methods. Below, a measurement method specific to the structure of the fiber of the present invention will be described. <Mechanical loss tangent (tanδ) and dynamic elastic modulus (E′)
> Using a Rheovibron DDV-c type dynamic viscoelasticity measurement device manufactured by Toyo Baldwin Co., Ltd., approximately 0.1 mg of sample was measured at each temperature in dry air at a measurement frequency of 110 Hz and a heating rate of 10°C/min. go
Measure tanδ and E′. From the tanδ-temperature curve, tanδ
The same peak height [(tanδ) _nax ] as the peak temperature (T _nax ) (°C) is obtained. Figures 3a and 3b show the tan δ-temperature curves of the fiber A of the present invention, the conventional drawn yarn B, the undrawn yarn C, and the partially oriented yarn D, respectively.
A typical example of the E'-temperature curve is schematically illustrated. <Average refractive index (n, n⊥) and average birefringence> Observation from the side of the fiber by the interference fringe method using a transmission quantitative interference microscope (for example, interference microscope Interfaco manufactured by Karl Zeiss Jena, East Germany) The distribution of the average refractive index can be measured. This method applies to fibers with a circular cross section. The refractive index of a fiber is characterized by the refractive index n for polarized light with an electric field vector parallel to the fiber axis and the refractive index n⊥ for polarized light with an electric field vector perpendicular to the fiber axis. All measurements described here are performed using green light (wavelength λ =
549mμ) is used. The fibers are made using optically flat glass slides and cover glasses, which have a refractive index (N) that provides a shift of the interference fringes within the range of 0.2 to 2 wavelengths, and are placed in a mounting medium that is inert to the fibers. immersed. Several fibers are immersed in this encapsulant so that the single threads do not touch each other. Furthermore, the fibers should have their fiber axes perpendicular to the optical axis of the interference microscope and the interference fringes. This interference fringe pattern is photographed, magnified approximately 1,500 times, and analyzed. As shown in Figure 4, the refractive index of the fiber encapsulant is N, the refractive index n (or n⊥) between points S' and S'' on the outer periphery of the fiber, and the thickness between S' and S'' is t. , the wavelength of the light beam used is λ, the distance between parallel interference fringes in the background (corresponding to 1λ) is D, and the deviation of the interference fringes due to the fiber is d, then the optical path difference R is R=d/Dλ=(n (or n⊥) −N)t. When the radius of the fiber is R, the distribution of the refractive index n (or n⊥) of the fiber at each position can be determined from the optical path difference at each position from the fiber center R ₀ to the outer periphery R. When r is the distance from the fiber center to each position, x=r/R=0, that is, the refractive index at the fiber center is the average refractive index (n ₍₀₎ or n⊥ ₍₀₎ )
That's what it means. x is 1 on the outer circumference and takes a value between 0 and 1 on the other parts, for example x = 0.8
The refractive index at the point is expressed as n _(0.8) (or n⊥ _(0.8) ). Furthermore, from the average refractive index n ₍₀₎ and n⊥ ₍₀₎ , the average birefringence (Δn) is expressed as Δn=n ₍₀₎ −n⊥ ₍₀₎ . In FIG. 4, reference numeral 31 indicates fibers, 32 indicates interference fringes due to the mounting medium, and 33 indicates interference fringes due to fibers. FIG. 5 shows the conventional drawn yarn B and the fiber A of the present invention.
The distribution of n is shown. In the figure, the distance from the center x=r/R is plotted on the horizontal axis, and n is plotted on the vertical axis, but x=
0 is the center of the fiber, x=1 and x=-1 are points on the outer periphery of the fiber. <Size of Microcrystals (ACS)> The size of microcrystals (ACS) can be determined by measuring the X-ray diffraction intensity in the equator direction using an equatorial reflection method. The X-ray diffraction intensity was measured using a Rigaku Denki X-ray generator (RU-200PL) and a goniometer (SG-9R), a scintillation counter for the counter, a pulse height analyzer for the counting section, and was converted into a monochromatic color using a nickel filter. Measured using Cu-Kα radiation (wavelength λ = 1.5418 Å). The fiber sample was placed in an aluminum sample holder so that the fiber axis was perpendicular to the X-ray diffraction plane. At this time, set the sample thickness to about 0.5 mm. The X-ray generator was operated at 30 kV and 30 mA, scanning speed 1°/min, charting speed 10 mm/min, time constant 1 second, divergence slit 1/2°, receiving slit 0.3 mm, scattering slit. Diffraction intensity is recorded from 35° to 7° in 2θ at 1/2°.
Set it so that it is within the full scale of the recorder. Polyethylene terephthalate fibers generally have three main reflections in the range of equatorial diffraction angle 2θ = 17° to 26° (from the low angle side (100), (010), (11
0) side). An example of an X-ray diffraction intensity curve of a polyethylene terephthalate fiber is shown in FIG. 6 (in the figure, a indicates a crystalline portion, and b indicates an amorphous portion). To obtain the ACS, for example, the Scherrer equation in "Polymer X-ray Diffraction" by LE Alexander, Kagaku Dojin Publishing, Chapter 7 is used. A straight line connects the diffraction intensity curves between 2θ = 7° and 2θ = 35° to form the baseline. Draw a perpendicular line from the top of the diffraction peak to the baseline and draw the midpoint between the baselines at the peak. A horizontal line through the midpoint is drawn between the diffraction intensity curves and the diffraction peaks. While the major reflections are well separated, they intersect two shoulders of the peak of the curve, while when the separation is poor, they intersect only one shoulder. Measure the width of this peak. If it only intersects one shoulder, measure the distance between the intersecting point and the midpoint and double it. If it crosses two shoulders, measure the distance between both shoulders. These measured values are converted into radians and used as the width of the line. Furthermore, this line width is corrected using the following formula. β=√ ² − ² B is the measured line width, and b is the broadening constant, which is the line width (half width) expressed in radians of the peak of (111) plane reflection of the Si single crystal. The size of the crystallite (ACS) is given by the following formula: ACS(Å)=K·λ/β _cps θ. Here, K is 1, λ is the X-ray wavelength (1.5418 Å), β is the corrected line width, and θ
is the Bragg angle and is 1/2 of 2θ. <Crystallinity (Xc)> X obtained in the same way as measuring the size of microcrystals
From the line diffraction intensity curve, connect the diffraction intensity curves between 2θ = 7° and 2θ = 35° with a straight line to form the baseline. The valley around 2θ = 20° is set as the apex, connected with a straight line along the base of the low angle side and the high angle side, and separated into the crystalline part and the subcrystalline part, and calculated by the area method according to the following formula. Xc = Scattering intensity of crystal part / Total scattering intensity x 100 <Crystal orientation (CO)> Rigakudenso X-ray generator (RU-200PL), fiber sample measuring device (FS-3), goniometer (SG- 9), a scintillation counter is used as the counter, a pulse height analyzer is used as the counting part, and Cu-Kα rays (wavelength λ =
1.5418Å). Polyethylene terephthalate fibers generally have three main reflections on the equatorial line, but for the measurement of crystal orientation (CO), (010)
Use surface reflection. (010) surface reflection used
2θ is determined from the diffraction intensity curve in the equatorial direction. The X-ray generator operates at 30kV and 80mA. Attach the sample to the fiber sample measuring device so that the single yarns are parallel to each other. It is appropriate that the thickness of the sample be approximately 0.5 mm. Set the goniometer at the 2θ value determined from the equatorial diffraction intensity curve. The azimuthal direction is scanned from −30° to +30° using the symmetrical transmission method, and the diffraction intensity in the azimuthal direction is recorded. Furthermore, the diffraction intensity in the azimuth directions of −180° and +180° is recorded. At this time, the scanning speed is 4°/
minutes, chart speed 10mm/min, time constant 1 second, collimator 2mmφ, receiving slit length 19mm, width 3.5mm. To determine CO from the obtained diffraction intensity curve in the azimuthal direction, take the average value of the diffraction intensities obtained at ±180°, draw a horizontal line, and use it as the baseline. Draw a perpendicular line from the top of the peak to the baseline and find the midpoint of its height. Draw a horizontal line through the midpoint,
The distance between the two intersection points of this and the diffraction intensity curve is measured, and this value is converted into an angle (°), and the value is defined as the orientation angle H (°). The degree of crystal orientation is given by the following formula: CO (%) = 180° - H/180° x 100. <Dyeability of polyethylene phthalate fiber> Dyeability was evaluated based on the equilibrium dyeing rate. Disperse dye Resoline Blue
Using FBL (Bayer product name), 3% owf,
Dyeing was carried out at 100°C in a bath ratio of 1:50. as a dispersant
Add 1g of DisperTL and further add acetic acid.
Adjust to PH=6. The dyeing rate is determined by the specified time (2 hours)
After the lapse of time, the dye solution was collected, the amount of dye in the remaining solution was calculated from the absorbance, and the amount subtracted from the amount of dye used for dyeing was used to calculate the dyeing rate (%).
In addition, the sample was heated at 60℃ using a score roll FC2g/
The material was scoured for 20 minutes, dried, and humidity-controlled (20°C x 65% RH). <Dyeing fastness of polyethylene terephthalate fiber> A sample was dyed in the same manner as in the dyeability evaluation, except that the dye concentration was 1% owf and the dyeing time was 90 minutes. Hydrosulfite 1g/, sodium hydroxide 1g/, Surfactant (Sunmol RC-
700) 1 g/, and was subjected to reduction cleaning at 80° C. for 20 minutes at a bath ratio of 1:50. Color fastness is light fastness (based on JISL-1044), rubbing fastness (based on JISL-0849), and hot pressing fastness (based on JISL-0850).
was evaluated. <Initial Modulus> The value of E' at 30°C in the dynamic viscoelasticity test mentioned above was taken as the initial modulus. <Strong elongation> TENSILON UTM− manufactured by Toyo Baldwin Co., Ltd.
−20 type tensile testing machine, initial length 5cm, tensile speed 20
Measured in mm/min. <Boiling water shrinkage rate> When the length of the sample under a load of 0.1 g/d is L ₀ , the load is removed and the sample is treated in boiling water for 30 minutes, the length measured again under the same load is L, and the boiling water shrinkage is The rate is expressed as boiling water shrinkage rate (%)=L ₀ -L/L×100. The present invention will be described below with reference to Examples. Example 1 Polyethylene terephthalate having an intrinsic viscosity [η] (hereinafter referred to as [η]) of 0.63 at 35°C was spun in a 2/1 mixed solvent of phenol/tetrachloroethane at a temperature of 300°C, with a pore diameter of 0.35 mmφ and a pore diameter of 0.35 mmφ. number
The fibers are spun from a 600 spinneret, cooled and solidified by a flow of air at 22°C that is supplied from all around the fibers in parallel to the running direction of the fibers, and then an oil agent is applied.
A fiber bundle of 1800d/600f was obtained by winding at a speed of 4600m/min. These fiber bundles are bundled into 100 fiber bundles each to form a tow of 180,000 denier, passed through a comb-shaped guide, and made into a flat plate. Using the dry heat treatment device 8 shown in Fig. 1,
Adjust the internal temperature to 246℃, per denier
Heat treatment was performed for 1 second while applying a tension of 0.08 g. Single fibers were extracted from this tow, and the physical properties were measured. The results are shown in Table 1 together with the measured values for the single fibers before heat treatment. This tow was crimped in a staff box in a conventional manner, then cut to a length of 76 mm using a Guruguru cutter, and an ester top was made by worsted spinning in a conventional manner. This top was mixed with an undyed wool top to obtain a 60 count twin yarn with a blend ratio of 50% ester and 50% wool. The weight of this spun yarn with a frame circumference of 1m
A skein of 150g was made and dyed with disperse dye Miketone polyester red in a liquid circulation type skein dyeing machine under normal pressure.
FN (Mitsui Chemicals product name CIDisperse Red113) 0.8
% (to dyed material), and acid dye Kayanol Millinglet RS (Nippon Kayaku Co., Ltd. product name: CIAcid Red)
114) Gradually raise the temperature from 25℃ to 99℃ using a dye bath with 0.4% (based on the dyed material) and 0.5g of acetic acid/bath ratio of 1:60.
It took 50 minutes and was stained at 99°C for 70 minutes. Next, discard the staining solution, wash in a bath containing 1 g of sodium alkylbenzenesulfonate at 70°C for 20 minutes, and rinse with water for 2 times.
It was dehydrated several times and dried at 80°C for 40 minutes. The obtained dyed yarn was colored deep red and had a good texture. From the results in Table 1, it can be seen that the heat-treated tow is much easier to dye than the tow before treatment, can be dyed under normal pressure, and has sufficient mechanical performance.

【table】

[Table] Example 2 Polyethylene terephthalate with [η] of 0.65 was spun at a spinning temperature of 298°C from a spinneret with a hole diameter of 0.35 mmφ and 600 holes, and was fed from all around the fiber in parallel to the running direction of the fiber. After being cooled and solidified by a flow of air at 20℃, an oil agent is applied and the
A fiber bundle of 1800d/600f was obtained by winding at a speed of 1800d/600f.
After converging 200 of these fiber bundles into a 360,000 denier tow, it was crimped using a standard method using a staff box, and then cut to 76 mm using a Guruguru cutter.
It was cut to length and stapled. The apparent density of this staple is attached to a can with many holes on the side.
It was packed at 1.8Kg/m ³ and placed in an autoclave-like pot. Next, the pressure inside the autoclave-like pot was reduced to 10 mmHg using a vacuum pump to remove air.
Superheated steam at 188°C was blown into the sample for 45 seconds of moist heat treatment. After removing the steam in the pot by reducing the pressure again,
Heat treatment was performed by blowing superheated steam at 188°C for 45 seconds using moist heat. Table 2 shows the measured values of various physical properties of the staple before and after the heat treatment using moist heat. From the results in Table 2, it can be seen that the staples subjected to the moist heat treatment are dyeable under normal pressure and have sufficient mechanical properties as a spinning raw material. Next, using this staple, an ester top was made by worsted spinning in a conventional manner. This ester top is blended with an undyed acrylic top made from acrylic short fiber 3D, 76mm staples using a conventional method, and an undyed wool top.
A blended yarn of 48 count double yarn was obtained. The blending rate (weight%) of this blended yarn is 40% ester, 35% acrylic, and wool.
It was 25%. Next, the weight of this blended yarn with a skein circumference of 1m
A skein of 200g is made and dyed with disperse dye Dianix Black in a liquid circulation dyeing machine.
BG-FS, Mitsubishi Kasei product name) 4% (for dyed material),
At pH 6 (adjusted with acetic acid) and a bath ratio of 1:70, the temperature was gradually raised from 20°C to 99°C for 35 minutes, and dyeing was carried out at 99°C for 90 minutes. Cool to 70℃ for 20 minutes, drain the dye solution, wash with water, and then add 1g/20% ammonia water.
, 70℃ in a bath of 0.5g/hydrosulfite.
Washed for 15 minutes. After that, after repeating the washing with water twice, the cationic dye Eisenkatyron Black was applied.
BXH (Hodogaya Chemical Co., Ltd. product name) 1.8% (to dyed material),
PH3.5 (adjusted with formic acid), 70 in a bath with a bath ratio of 1:70
Gradually raise the temperature from ℃ to 99℃ for 30 minutes at 99℃
Stained for 80 minutes. Next, the dye bath is cooled to 95℃ and dyed with chrome dye Eriochrome Black.
P2B (Switzerland Ciba Geigy product name CI
Mordant Black 7) Add an amount equivalent to 1.4% (based on the dyed material) and an amount equivalent to 2% (based on the dyed material) of the anti-settling agent Daidesper CD (product name of Ichisha Yushisha Co., Ltd.) to the dye bath for 10 minutes. The temperature was raised to 99℃. After heating to 99℃, stain for 70 minutes, and remove sodium dichromate.
After adding 0.6% (to the dyed object) and chroming for 30 minutes, the staining solution was cooled to 70°C over 30 minutes and discharged. Next, wash with water, then at 75℃ in a bath containing 0.5g/sodium alkylbenzenesulfonate.
Washed for 15 minutes and repeated water washing three times. Next, the skeins were taken out, dehydrated, and then dried at 80°C for 35 minutes. The obtained dyed yarn was colored black and had a strength of 403g.
Moreover, it had a good texture. For comparison, a 3D x 76 mm staple of conventional polyethylene terephthalate fiber and a 3D x 76 mm staple of easily dyeable polyester made by copolymerizing sodium isophthalate sulfonate instead of 10 mol% of terephthalic acid in polyethylene terephthalate were used. Using the same acrylic short fibers and wool tops under the same conditions and with the same blending ratio, a blended yarn of 48 count twin yarn was made, and each skein with a skein circumference of 1 m and a weight of 200 g was made. Only when dyeing the polyester fiber side with disperse dyes, in a pressure-resistant liquid jet skein dyeing machine, for dyeing conventional polyethylene terephthalate fiber blends, the dyeing temperature is 130℃.
The temperature is raised to 110℃ for the blended polyester fibers copolymerized with sodium isophthalate sulfonate.
The temperature was increased to Compared to the dyed yarn of the present invention, the dyed yarns obtained have a coarser and harder texture and a strength of 302 g for the yarn dyed at 130°C, and 357 g for the yarn dyed at 110°C.
, which were 25% and 11% lower than those of the present invention, respectively. The shrinkage rate after dyeing is 2.8% for the blended yarn of the present invention, and that for the conventional yarn using polyethylene terephthalate.
9.7%, 12.5% with copolymer ester
It was hot.

【table】

[Table] Example 3 Polyethylene terephthalate having [η] of 0.67 was spun using the same spinning method as in Example 1 at a spinning speed of 4700 m/min to obtain a fiber bundle of 1800 d/600 f. This fiber bundle is treated using a mixed heat treatment device shown in Fig. 2.
Moisture heat treatment was performed for 0.5 seconds in superheated steam at 205° C. while applying a tension of 0.1 g/d. Table 3 shows the measured values of various physical properties of the fiber bundle before and after heat treatment. From the results in Table 3, the fiber bundles subjected to heat treatment by moist heat are:
It can be seen that the fiber bundle is much easier to dye than the fiber bundle before treatment and can be dyed under normal pressure, and its mechanical performance is also sufficient as a spinning raw material. Next, 100 of the above fiber bundles were bundled into a tow of 180,000 d, which was crimped by a conventional method and cut into 76 mm pieces. Next, an ester top was made from this staple by worsted spinning according to a conventional method, and mixed with the undyed acrylic top used in Example 2 to create an ester top with 40% ester.
A blended yarn of No. 60 twin yarn with a blending ratio of 60% acrylic was obtained.
This blended yarn was made into a skein with a frame circumference of 1 m and a weight of 250 g, and dispersed dye Resolin Blue FBL (product name of Bayer AG, Federal Republic of Germany, product name CIDisperse Blue 56) 1.5% (based on the dyed material) under normal pressure in a liquid circulation type skein dyeing machine.
Cationic dye Kayacryl Blue GRL (Nippon Kayaku Co., Ltd. product name CIBasic Blue 41) 2% (for the dyed material), anti-settling agent Dydesper CD (Ichipsha Yushi Co. product name)
2% (based on the dyed material), PH4 (adjusted with acetic acid), bath ratio 1:65, gradually increasing the temperature from 70℃ to 99℃.
The cells were stained for 60 minutes at 99°C. After staining, add staining solution to 70%
Cool to ℃ over 20 minutes, wash with water, and cool at 70℃ in a bath containing 0.5 g of sodium alkylbenzenesulfonate.
It was washed for 20 minutes in a vacuum cleaner, and then washed with water three times. Next, after dehydration, it was dried at 75°C for 10 minutes. The obtained dyed yarn was colored deep blue, had a strength of 505 g, and had a good texture. For comparison, a 3D x 76 mm staple of conventional polyethylene terephthalate fiber and a 3D x 76 mm staple of easily dyeable polyester copolymerized with sodium isophthalate sulfonate instead of 7 mol% of terephthalic acid in polyethylene terephthalate were used. Each thread is mixed with the same acrylic top to create a blended yarn of No. 60 twin yarn with the same blending ratio and a skein circumference of 1m.
So, I made a skein weighing 250g. When dyeing only the polyester fiber side with disperse dyes, the temperature of conventional polyethylene terephthalate fiber blends is raised to 130°C in a pressure-resistant liquid jet skein dyeing machine, and sodium isophthalate sulfonate copolymerized polyester fibers are blended with polyester fibers. The sample was heated to 110°C, and all other staining conditions were the same. The dyed yarns obtained had a rougher and harder texture than the dyed yarns of the present invention, and the strength of the yarn dyed at 130° C. was 394 g, and the strength of the yarn dyed at 110° C. was 448 g. They were 22% and 11% lower than those of the present invention, respectively. The shrinkage rate after dyeing of the blended yarn of the present invention is 2.5%, and that of the conventional yarn using polyethylene terephthalate fiber is 8.7%.
%, and those using copolymer ester were 10.7%.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a spinning and heat treatment apparatus for raw fibers for producing the blended yarn of the present invention. In the figure, 1 is a fiber bundle, 2 is a spinning head, 3 is a tubular heating area, 4 is a fluid suction device, 5 is an oil application device, 6 is a take-up roller, 7 is a fiber bundle feeding roller, 8 is a heating cylinder for heat treatment, Reference numeral 9 indicates a fiber bundle feeding roller, and reference numeral 10 indicates a fiber bundle winding roller. FIG. 2 is a schematic diagram showing an example of a heat treatment apparatus using superheated steam used in an embodiment of the present invention. In the figure, 11 is a fiber bundle, tow or sliver, 1
2 is a feed roller, 13 is a guide roller,
14 and 14' are slits for preventing excessive leakage of superheated steam in the heat-and-moisture treatment device 15 and suppressing temperature fluctuations, 15 is the heat-and-moisture treatment device, and 16 is a slit for blowing out superheated steam provided on the inner wall of the heat-and-moisture treatment device. 17 is a heater for heating the superheated steam inside the wet heat treatment device 15 to prevent the temperature from decreasing and to reduce the temperature distribution; 18 is a guide roller; 19 is a device for winding a fiber bundle, tow or sliver; 20 is a valve, 21 is a superheated steam generator, 22 is a heater, 23 is a valve, and 24 is a boiler. Figures a and 3b are graphs schematically representing a mechanical loss tangent (tan δ)-temperature curve and a dynamic elastic modulus (E')-temperature curve, respectively. In the figure,
A indicates the fiber used in the present invention, B indicates the conventional drawn fiber, C indicates the undrawn fiber, and D indicates the partially oriented fiber. FIG. 4 is an example of an interference fringe pattern used to measure the radial refractive index (n or n⊥) distribution within the fiber cross section. In the figure, a is a cross-sectional view of the fiber, b
is a diagram of an interference fringe pattern, 31 is a fiber, 32 is an interference fringe due to a mounting medium, and 33 is an interference fringe due to a fiber. Figure 5 shows the refractive index (n) in the radial direction of the polyethylene terephthalate fiber A used in the present invention and the conventional drawn polyethylene terephthalate fiber B.
It is a graph showing an example of distribution. FIG. 6 is a graph showing an example of an X-ray diffraction intensity curve of polyethylene terephthalate fiber.

Claims (1)

[Claims] 1. 95 to 5% by weight of one or two of acrylic fibers and wool fibers and 5 to 5% by weight of polyester fibers.
A spun yarn containing 95% by weight, wherein the polyester fiber is substantially composed of a homopolymer of polyethylene terephthalate, and the polyester fiber is
has an initial modulus of 50 g/d or more,
Mechanical loss tangent (tanδ) at measurement frequency 110Hz
peak temperature (T _nax ) is 105℃ or less, and tanδ
The peak value [(tan δ) _nax ] is 0.14 or more, the crystallinity (Xc) is 30% or more, the (010) crystallite size (ACS) is 35 Å or more, and the (010)
A blended yarn that can be dyed at atmospheric pressure with a disperse dye and has a plane crystal orientation (CO) of 85% or more. 2. A patent claim in which the polyester fiber is spun at a spinning speed of 4000 m/min or more and then subjected to dry heat treatment at a temperature of 220°C to 300°C or wet heat treatment at a temperature of 180°C to 240°C. The blended yarn according to item 1.