JPS584814A - Easily dyeable polyester raw material for spinning and spun yarn - Google Patents

Abstract

PURPOSE:Spun yarns, containing polyester fibers, having a specific structure in amorphous regions, and consisting of a homopolymer of polyethylene terepthalate, having enough mechanical characteristics for practical use, dyeable under ordinary pressure, and having improved color fastness. CONSTITUTION:A polymer consisting of substantially polyethylene terephthalate is spun at a spinning speed >=4,000m/min and heat-treated under dry heat conditions at 220-300 deg.C or under wet heat conditions at 180-240 deg.C to give polyester fibers having an initial modulus at 30 deg.C >=50g/d, a peak value of dynamic loss tangent (tandelta) >=0.135, preferably >=0.14, at a measuring frequency of 110Hz, a peak temperature (Tmax) <=105 deg.C, and dyeable with a disperse dye under ordinary pressure. At least 5wt% fibers are contained in spun yarns to give easily dyeable spun yarns. The heat treatment can be carried out in any form ranging from the continuous treatment in the spinning step to the treatment of the spun yarns.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a spun raw material or a spun yarn containing easily dyeable bori ester fiber, more specifically, a spun raw material or a spun yarn containing easily dyeable bori ester fiber, which has practically sufficient mechanical properties and good dyeability. In particular, the present invention relates to a spun raw material and a spun yarn having an IJ ester fiber that can be dyed under normal pressure and has an excellent dyeing fastness of 1i.

In this specification, "spinning raw material" refers to as-spun fiber bundles, tows made by gathering dozens to thousands of these fiber bundles, staples cut from tows to appropriate lengths, and staples made from staples cut into appropriate lengths. It refers to slivers that are opened and collected into a cylindrical shape, as well as raw materials or intermediate products during the spinning process to produce spun yarns such as sliver, sewage, sewage, and slivers. "
The term "spun yarn" refers to a yarn spun using a known spinning method from a spinning raw material such as first grade.

In addition, the table "Can be dyed with disperse dyes under normal pressure" is as follows:
Disperse dye C.I.Diff4's Sol-56 (C
, 1, Dlsperms Blue 55: For example, using Resolin Blue FBL (Federal Republic of Germany/Product name of Mother Inil), the amount of dye used is 3% ovf, the bath ratio is 50 times,
P) (6 (adjusted with acetic acid), dispersant (e.g. Dis/
#-T L (Meiho Kagaku Kogyo Co., Ltd. product name) Containing Mu II
After dyeing for 120 minutes at 100°C in an i/l dyebath, the exhaustion rate of the dye dyed on the fiber is 80 or more, and the dye exhaustion rate is expressed by the following formula: .

Does the easily dyeable polyester fiber used in the present invention substantially? It is made of a homopolymer of polyethylene terephthalate and can be obtained by a known polymerization method. (9) Additives commonly used in polyester fibers, such as matting agents, stabilizers, antistatic agents, etc., may also be included. There is no particular restriction on the i9 degree of polymerization as long as it is within the range for normal fiber formation.

In general, polyester fibers, especially polyethylene terephthalate fibers, have many excellent properties such as mechanical properties and thermal and mechanical dimensional stability, and are used for various purposes.On the other hand, -lyethylene terephthalate fibers are dyed. 130 tll when dyeing: A special pressure-resistant dyeing machine is required because it is dyed at high temperature and pressure in the vicinity, and it is mixed with fibers whose chemical properties deteriorate due to high-temperature dyeing such as acrylic fibers. It has drawbacks such as limitations.

Several proposals have already been made for improving the dyeability of polyethylene terephthalate fibers and for dyeing them under normal pressure.For example, during dyeing. - Methods using so-called carriers such as phenylphenol, trichlorobenzene, and methylnaphthalene are known. However, many of the carriers have a pungent odor and are harmful to the human body, making the working environment worse.

There are disadvantages such as difficulty in wastewater treatment after dyeing, and carrier remaining in the dyeing tank, which may lead to a decrease in the waxiness of the dyed layer.

9. Modified polyester fibers copolymerized with a metal sulfonate group-containing compound, Yabori ether, are known as polyester fibers with improved dyeability, but although these modified polyesters have improved dyeability, they are difficult to polymerize and spin. There were drawbacks such as difficulty in producing the polyethylene terephthalate (4-reproduced ethylene terephthalate), which deteriorated its original excellent mechanical properties), and furthermore, the dyeing fastness returned. In the end, the above-mentioned chemical modification of lrimer to make it easier to dye does not preserve the desirable properties of polyethylene terephthalate fiber, such as K, heat resistance, mechanical properties, etc., because it mixes a third component that can serve as a dyeing seat. Change is inevitable.

The purpose of the present invention is to overcome the drawbacks of such conventional methods, have poor dyeing properties, enable normal pressure dyeing with disperse dyes in particular, and have excellent dyeing fastness, while maintaining the original desirable properties. Homo I of 4-lyethylene terephthalate with
To provide a spinning* raw material and a spun yarn containing polyester fibers made of rimers.As a result of conducting research from the microstructural aspect of diliester, the present inventors discovered a specific amorphous structure that was previously unknown. The present invention was completed by investigating the spun raw materials and spun yarns containing fibers having the above-mentioned properties.

That is, the present invention provides a spun raw material or a spun yarn characterized in that it contains at least 5 weight polyester fibers which are substantially composed of homopoly(i) of ethylene terephthalate and can be dyed with a disperse dye under normal pressure. .

In order for polyester fibers made of homo I reamer of polyethylene terephthalate to maintain mechanical performance as clothing fibers, the initial mono-lath temperature at 30°C must be 50 F/d.
Must be above. In addition, in order to be able to dye with disperse dye under normal pressure, the measurement frequency is usually 110Hz.
The peak temperature (T
The inventors of the present invention have found that it is preferable that the peak value of tarlδ (max) exceeds 0.135.

The characteristic value expressing the structure of the amorphous region is "m" in 1 above.
Values of aw and (tan)@ax are appropriate.

``ff1aK'' is normally located at a high temperature of 50° C., which is the glass transition temperature, and (tana)max is related to the amount of molecular chains in the amorphous region with activated thermal motion at the temperature TmaX.

In the present invention, T'max, (tana)rfl, and x refer to values related to mechanical absorption (α, absorption) caused by the cycloderange motion of molecular chains inside the amorphous region.

(It comes from c // Liethylene terephthalate) 111M T
max is 130°C or higher, (t mm') max is 0.
It is 13 or less.

Consists of spinning raw materials and yarn. N Reethylene telef! As a result of examining the relationship between the structure of the amorphous region of rate single fibers and dyeability, we found that, as mentioned above, in order for normal pressure dyeing to be possible,
■(jan')max) O-135 and ■T
It is preferable that o□<:105C. Conventionally, with unmodified polyethylene terephthalate, there were no spinning raw materials or single fibers constituting the spun yarn that satisfied the above three-strand property, and atmospheric pressure dyeing was impossible. "Can be dyed with dye under normal pressure", that is, the dye exhaustion rate is so
n or more, whereas in the conventional 4-lyethylene terephthalate iron fiber, the dye exhaustion rate under the above conditions is 30 to 45 h. In addition, in order to further improve the dyeability of the pressure-dyeable I-lyethylene terephthalate single fibers constituting the spinning raw material and spun yarn of the present invention, (jan')m□ should be 0.14.
It is particularly preferable that it is above.

In the present invention, in order to impart satisfactory mechanical properties to the pressure-dyeable ethylene terephthalate single fibers constituting the spinning raw material and the spun yarn, the initial modulus at 30°C is 501/d as described above. It is preferable that it is above. Here, the initial modulus and ras at 30℃ are 3
The dynamic elastic modulus (E'30) at 0°C is estimated.

As (tana)rn□ becomes larger, E'30 generally needs to be larger in order to maintain shape retention. If E'30 is less than 5ON/d, the fiber'sm
Thermal stability is reduced, dimensional stability is poor, and the fiber becomes soft.

Regarding the pressure-dyeable polyethylene terephthalate fibers constituting the spun raw materials and spun yarns of the present invention, which have special properties such as ), and the relationship with stainability.As a result, the following points were clarified.9.

The crystallinity (
X6), the size of microcrystals in the (010) plane (AC8), and the degree of crystal orientation (CO) in the (010) plane are all related to the mechanical properties of the fiber. has sufficient strength as a raw material fiber for spinning (
Xc to have a
It is preferable that X is 301 or more, AC8 is 351 or more, and CO is 8591 or more. More preferably, X is 7
○ or more, Acs is io1 or more, CO is 9091 or more. These are the values measured by the methods described below using ζ-te X0, AC8, and CoFiXll diffraction. In addition, the polyethylene terephthalate fibers used for conventional spinning raw materials and spun yarns have xeaso to 70 degrees, AC8 of 301 or less, and co of 85 to 95.

Next, in the I-lyethylene terephumerate monofilament which can be dyed under normal pressure and which constitutes the spinning raw material and spun yarn of the present invention, the central average refractive index (re 4o) of polarized light having an electric field vector in the fiber axis direction is 1.70. If it is smaller and has a value of 1.65 or more, it has appropriate elongation (20-70) and dyeability, making it more preferable as a clothing fiber. Optimal (n/(.

)) ranges from 1.65 to 1.68.

In addition, the average birefringence (Δn) is 35×10 when the single ethylene terephthalate single fibers that can be dyed under normal pressure and which constitute the spinning raw material and spun yarn of the present invention have an initial modulus of 50 g/d or more at 30°C. 'While more is preferred.

From the viewpoint of structural stability against heat, it is desirable that it be 50xlO' or more. First, from the viewpoint of dyeability and color fastness, it is preferably 120xlO-3 or less, more preferably 85x10-s or less. of.

is less than 120X10', the reduction rate of dynamic elastic modulus (E') in the temperature range of 150 to 220℃ (150
℃, E at 220℃? ) bonds at E'160. E'
220 and expressed as E'220/Etlso) is small, E'220/Et15o is 0.75
Become bigger. That is, the structure becomes stable against heat. It also improves dye fastness. Further Δ. 8!5
Those smaller than XIO-' have extremely excellent atmospheric dyeability.

Average refractive index (n/(o)) at the center of the fiber and refractive index f at a distance of 0.8 times the radius from the center of the fiber
l / (α8) or "/(-(L8) difference [Δ/(
When α8-0) is 10X10-s to 80X10, it has sufficient strength and has few streaks and strong elongation. The fact that the local average refractive index distribution is symmetrical with respect to the center of the fiber means that the minimum value of the average refractive index n/ is (n/Co
)-10xlO') or more and the difference between n/(-DJ) and 1/(118) is 50 x 10-s or less, preferably 10 x 10-5 or less.As mentioned above, Values such as n(O), n/(C8)/(-is)%Δbe(α8-0)1Δn, etc. were measured by the method described later using an interference mold analyzer.

In addition, in the pressure-dyeable I-lyethylene terephthalate single fiber constituting the spinning raw material and spun yarn of the present invention, 2
20tl: Mechanical loss tangent (tan' 220
) is preferably smaller; initial warping due to temperature rise,
The decrease in lath is small.

If tan6220 is less than 0.25, # initial modifier. The amount of lath reduction becomes significantly smaller. In other words, the fiber has a structure that is extremely stable against heat.

The 4-polyethylene terephthalate single fibers that can be dyed under normal pressure and which constitute the spinning raw materials and spun yarns of the present invention are, for example, as shown in the Examples later, ethylene terephthalate fibers spun at a spinning speed of 4,000 g @ / min or more. 22
It can be obtained by performing heat treatment by dry heat at a temperature within the range of 0'C to 30°C.Also, 180°C
It can also be obtained by subjecting it to superheated steam, saturated steam or hot water within a temperature range of ~240C, or by heat-moisture treatment.

During MA of the pressure-dyeable I-polyethylene terephthalate fibers constituting the spinning raw materials and spun yarns of the present invention, the polymer viscosity, spinning temperature, atmospheric condition under the spinneret, gradation method, take-up speed, etc. are adjusted as appropriate. In particular, by controlling cooling solidification and thinning deformation of the polymer stream spun from the spinneret, fibers with good spinnability and desired properties can be obtained. 4IK, control of cooling and solidification of spun fibers is important, ensuring good spinnability and obtaining desired properties.
Rapid cooling assimilation, especially cooling and solidification by low-temperature cooling air perpendicular to the fibers from one direction, is not very good. The speed of the drive roller at which the fiber is withdrawn after it has been subjected to further oil treatment, if necessary.

Illus IwJK An example of an apparatus for producing 4-polyethylene tere 7/rate fibers that can be dyed under normal pressure, which constitute the spun raw materials and spun yarns of the present invention, is shown. Molten polyethylene terephthalate is spun through 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 a round fluid suction device 4 for cooling and suctioning the fiber bundle 1 is provided below it. ing.

The fiber bundle that has passed through the tubular heating zone and the fluid suction device passes through the oil application device 5 and is then taken off by the take-up roller 6.
means surface velocity. The pulled fiber bundle is continuously
Preferably, the fiber bundle is once wound around the take-up roller 6 and then passed through a pair of fiber bundle feeding rollers 5-7. ) drawn out, 220-300
It passes through a heating cylinder 8 whose temperature is adjusted to an appropriate temperature within the range of 11 degrees t, is guided by a pair of edge fiber bundles a--ra 9, and is wound up by a winding roller 10. At this time, adjust the rotational speed of the fiber bundle feed rollers 7 and 9,
The fiber bundle 1 is elongated to a suitable elongation rate in the heating cylinder 8 and subjected to heat treatment.

The heat treatment method for obtaining the pressure-dyeable /17 ethylene terephthalate fiber of the present invention can be carried out continuously during the spinning process as exemplified above, or by once winding it around the take-up roller 6 and then rolling it up. In addition to the subsequent heat treatment method, the following method may also be used. That is, after winding with the take-up roller 6 at a spinning speed of 4,000 steel/min or more,
These polyethylene terephthalate fiber bundles are gathered together to form a tow-like fiber bundle, and then heat treated or crimped and cut into staples. After opening,
A method of heat-treating the yarn in the form of a sliver, a yarn, a yarn, a yarn, etc., and a method of heat-treating the yarn in the form of a spun yarn after spinning are also adopted.

Of course, the heat treatment method may be either a method using dry heat or a method using warm heat, as described above.

FIG. 2 shows an example of an apparatus for subjecting a tow or sliver of ethylene terephthalate fibers spun on a spinning plate at a spinning speed of 4,000 m/split to wet heat treatment with superheated steam. In FIG. 2, the tow or sliver 11 is pulled up by a pair of feed rollers 12 and reaches the guide roller 139.
be led to.

The entrance to the heat treatment II device 150 is S! Jy) 14, there is a slot at the exit, and ) 14' has a groove so that the temperature inside the moist heat treatment apparatus 15 is not influenced by the temperature of the outside atmosphere. In addition, the heat-and-moisture treatment device 15 is provided with a large number of grooves 16 on the upper and lower sides of the inner wall so that the superheated steam is simultaneously applied from the upper and lower surfaces of the heat treatment device 9-. Further, heaters 17 are provided on the upper and lower sides of the wet heat treatment apparatus 15, so that the temperature of the superheated steam can be controlled. On the other hand, one error 24
The saturated steam with an r-di pressure of about 10 ky/cm" is input into the heating device 21 through the loop 23, heated by the heater 22, and becomes superheated steam with a temperature of 180 to 240°C. This superheated steam is heated to the pulp 20. It is sent to a moist heat treatment device 15, and is heated by a heater 17 so that the temperature does not drop and the temperature distribution does not become large.
The tow or sliver 11 is subjected to a wet heat treatment through the slit 16. The tow or sliver that has been subjected to moist heat treatment is passed through the slit 14' to the guide roller 18.
and is wound up by a winding device 19.

Among the heat-treated polyethylene terephthalate fibers obtained as described above, those that have been heat-treated immediately after spinning or in the form of thick fibers can be stuffed with a stuffer by a conventional method.
is crimped in a box and spun by a tow spinner 11, or it is cut into a systable shape 11 by a conventional method and spun by itself, or it is mixed with other fibers. Ru. In addition, the heat-treated sea urchin, f, and In some cases, the spun yarn is heat treated. When heat-treated in the form of Kuep 1 sliver 1-spun yarn, it may be mixed with fibers that can withstand heat treatment, such as cotton, hemp, recycled cellulose fibers, and nylon 66 fibers, but wool, acrylic fibers, etc. When blended with fibers that do not have good heat resistance, such as polyethylene terephthalate fibers, a method in which only the I-lyethylene terephthalate fibers are heat-treated is used.

As mentioned above, ethylene terephthalate fibers that are spun at a spinning speed of 4,000 m/min or more and subjected to heat treatment have an initial modulus of 50 JF/d or more and a mechanical loss tangent at a measuring number of scissors of 11011 m. The peak value of (tana) [(tana)□8] exceeds 0.135, the peak temperature ("rnax) is 105°C or less, and it can be dyed under normal pressure.

The spun raw material and spun yarn of the present invention are the above-mentioned pressure dyeable I
It contains at least 5% polyethylene terephthalate fiber by weight, but the spinning raw material and the method for producing the spun yarn vary somewhat depending on the heat treatment method. When a spun raw material or a spun yarn is made only from I-lyethylene phthalate rutted fibers that can be dyed under normal pressure, the heat treatment step may be performed in any of the above-mentioned steps. When blending with other fibers or materials with poor heat resistance such as wool or acrylic fibers, the spinning rate is 4.0.
The ethylene terephthalate fibers spun at 00 m/min can be heat-treated in the tow or staple state before being blended with other fibers, that is, immediately after spinning, and then blended in the cotton blending or drawing process. Desirable ° Since the spun raw materials and spun yarns of the present invention thus obtained contain polyethylene terephthalate fibers that can be dyed under normal pressure, they are dyed at 130° C.
The dyeing temperature, which used to rise to around 100°C, can be held down to 100°C, resulting in significant energy savings. Also, since high-pressure dyeing equipment is not required, equipment costs can be reduced, and at the same time, stable management can be achieved! ! The cost involved is low and the economic effect is great. At the same time, blended yarns with wool and acrylic fibers have the advantage that yarn-dyed yarns with no deterioration in mechanical properties can be obtained. Furthermore, in the case of wool and acrylic blended yarn, it is possible to expand the application to fields that were previously impossible, such as dyeing in the state of woven or knitted products after weaving or knitting. A method for measuring the structural properties of is described.

Dynamic loss tangent (-) and dynamic elastic modulus (Etsu) manufactured by Toyo Goldwyn Co., Ltd., Leono arm Idelon (Rh@ov%b
ran) DD'/-me type dynamic viscoelasticity determination device, sample approximately 01cm, measurement frequency 110Hz, heating rate 1
-1 and E at each temperature in dry air at 0°C/min
'Measure gh t1ml' from the temperature curve -1 peak temperature (Tm, x) (C) and the same peak height (-),
You can get more. FIG. 3(1) and FIG. 3(b) show −δ-temperature curves, E′, respectively, of the fiber mass of the present invention, the conventional drawn yarn (B), the undrawn yarn (0), and the partially oriented yarn (9). One temperature -
90 typical examples are schematically illustrated.

<Average refractive index (nz, n□), and average birefringence> Observe from the side of the fiber by the interference fringe method using a transmission quantitative interference microscope (for example, Interfaco, an interference microscope manufactured by Carl Zeiss Jena, East Germany). The uniform refractive index distribution 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 JL K for polarized light with an electric field vector perpendicular to the fiber axis.

All measurements explained here were performed using green light (wavelength λ-549m).
μ) is used.

The fiber uses an optically flat slide glass and cover glass, has a refractive index that provides a shift of the interference fringes within the range of 0.2 to 2 wavelengths, and is inert to the fiber. immersed in the agent. 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. The mother turn of this interference fringe is photographed, magnified approximately 1,500 times, and analyzed.

As shown in Fig. 4, the refractive index of the fiber encapsulant is N, the refractive index between the points 81 on the outer periphery of the fibers is
The thickness between G and S is t, the wavelength of the light beam used is λ, the distance between the parallel interference fringes of the pack ground (1λ), and the fiber #l.
! If the deviation of the interference fringes is d, the optical path difference is R-
It is expressed as fiλ-(n7 (or ayo)-N)t.

If the radius of the fiber is R, then from the center R8 of the fiber to the outer circumference R1
From the optical path difference at each position, the refractive index nz of the fiber at each position is
(Also, Fi mouth □) distribution can be obtained. When r is the distance from the center of the fiber to each position, x = r /R
0, that is, the refractive index at the center Km of the fiber is called the average refractive index (nz(+))t or n□(.)).

X is 1 on the outer circumference and #iθ~1 in other parts
For example, the refractive index at the point of X W 0.8 is "/ (Q, s) (t or "□ ((18)
Also, the average refractive index is expressed as ``/(O) and n (.), and the average birefringence is expressed as Δ!
In FIG. 4, 31 indicates fibers, 32 indicates interference fringes caused by the mounting medium, and 33 indicates interference fringes caused by fibers.

FIG. 5 shows the n7 distribution of the conventional drawn yarn (a) and the fiber of the present invention (4). In the figure, the horizontal axis is the distance z x r/R from the center, and the vertical axis is n7. be.

<Size of microcrystals AC5I)> The size of microcrystals AC8) can be determined by determining the OX-ray diffraction intensity in the direction of the arrowhead using the equatorial reflection method.

The X-diffraction intensity was measured using an X,1 generator (Rυ-2) manufactured by Rigaku Denki Co., Ltd.
00PL) and an f-niometer (8G-98), scintillation and countermeasures were used for the meter, and a pulse height analyzer was used for the counter.
Measured at a wavelength of 15,418 cm), the fiber sample was made of aluminum so that the fiber axis of the fiber sample was -1 with respect to the X-ray diffraction plane. place it in the holder. At this time, the thickness of the sample will be 0.5 parts! 5 +W), 30kV, 30m
Operate the X-ray generator at A and set the scanning speed to 10/
Minutes, Char) speed jllllOw/minute, time constant 1 second, May/day, Susuri, To 1/2°, Receiver Dasuri, To α3-, Scan, Tallings IJ, )
2# records the diffraction intensity from 35° to 7° at 1/2°. Set it so that it is within the full scale of the recorder.

Ethylene terephthalate fibers generally have three major reflections in the range of equatorial diffraction angles 2θ-17° to 26° ((100), (010) from the low-angle ventral side).

(110) plane). Figure 6 shows an example of the x11 diffraction intensity curve of polyethylene tere-7 tallate fiber (in the figure, the dots indicate crystalline parts and b indicates amorphous parts). To find ACg,
For example, E. Alexander wears "Polymer X-ray diffraction"
Kagaku Doujin Publishing, Chapter 7 Sheller (8@b@rr@r
) Diffraction intensity between 020-7° and 20=35° - Connect the lines with a straight line and use it as the baseline. Draw a line from the apex of the 0 diffraction peak to the baseline and calculate the distance between the peak and the baseline. Enter the midpoint. Draw a horizontal line through the midpoint of the diffraction intensity curve between the diffraction peaks, intersecting two shoulders of the peaks of the curve if the major reflections are well separated, but only one shoulder if the separation is poor. intersect with 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 III constant values are converted into radians and used as the line width. Furthermore, this line width is corrected using the following formula.

β-mea [iJ B is the measured line width, b is the broadening constant of 8%
Single crystal 0 (111) The size of the microcrystal is A, which is expressed in radians at the peak of surface reflection and is 9 line width (half width).
Cg) is given by the following formula % formula % (2). Here, K is 1 and λ is the wavelength of the X-ray (
1,5418 The XIIa diffraction intensity curve thus obtained is connected with a straight line between the diffraction intensities between 2-7° and 2#-35° to form a baseline. 2#
The valley near -20' is set as the apex, connected with a straight line along the low-angle side and the high-angle side O base, separated into a crystalline part and an amorphous part, and determined by the area method according to the following formula.

Crystal part 0*1w degree Generator (R[J-200P1.
), a fiber sample measuring device (FB-3), a co-9niometer (SG-9), a scintillation counter for the counter, a pulse height analyzer for the counting section, and two, Cu monochromatized with a Kel filter. - to α@ (wavelength λ latitude 1.54181)
Measure with. /Liethylene terephthalate fibers generally have three main reflections on the equatorial line, but the degree of crystal orientation (
(010) plane reflection is used for Co)0 measurement. 20 of the (01G) surface reflection used is the diffraction intensity in the equatorial direction -
Determined from the line.

The X-ray generator operates at 30 kV and 80 mA.

Attach the sample to the fiber sample measuring device so that the single yarns are parallel to each other. It is appropriate to heat the sample so that the thickness of the sample becomes O, S-. The goniometer is set to the 2# value determined from the equatorial diffraction intensity curve. Using the symmetrical transmission method, the azimuthal direction is scanned from -30° to +30° and the diffraction intensity in the azimuthal direction is recorded. Further -180° and +
The diffraction intensity in the 1800 azimuth direction is recorded. At this time, the scan speed is 4°/min, the chart speed is 10/min,
The time constant is 1 second, the collimator is 2 mm, the receiving pin is 19 mm long, and the width is 3.5 mm.

To determine CO from the obtained diffraction intensity curve in the azimuthal direction, the average value of the diffraction intensity obtained at +1800 is taken, and a horizontal line is drawn to use it as a 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 passing through the midpoint, measure the distance between the two intersections of this and the diffraction intensity curve, and convert this value to the angle f(0).The orientation angle H(') is the crystal orientation FIlFi. It is given by the following equation.

color Dyeability was evaluated by equilibrium industrial wear rate.

Disperse dye resolindel- (R*m@l1m@81w・)
Using FBL (product name of 4 Inil Co., Ltd.), 3X @
vf.

Dl as a zero dispersant dyed at 100 °C in a bath ratio of 1:50
Add 1f/ of sp@r TL and further dilute with acetic acid.
=6. The dyeing rate is determined after the specified time (2 hours) has passed.
The dye solution was collected, the amount of dye in the residual solution was calculated based on the absorbance, and the amount subtracted from the amount of dye used for dyeing was used as the amount of dyeing to calculate the dyeing rate (conversion). In addition, test Na score roll F
Scouring at 60°C for 20 minutes using C2P/l, drying, vI
Il (20° C. x 65 XRH) was used.

Dyeing fastness> A sample was stained using method O in the same manner as in the dyeability evaluation except that the dye concentration was set to IX@wf and the staining time was 90 minutes.
, using a surfactant (tonmol RC-700) IP/l, and photowashing for 20 minutes at a bath ratio of 1:50.80°C was evaluated.

The dyeing sensitivity year is light resistance/(J+l1SL-1044K
(according to JI8L-0849), frictional retention (according to JI8L-0849)
, E, Togre, and Cinda harshness (according to JI8L-0850) were evaluated.

<Initial modulus, lath> The value of Bi at 30° C. in the dynamic viscoelasticity test described above was taken as the initial modulus.

<Strong elongation> Toyo No. 1 1k l' TEN81LON manufactured by U4
[UTM-n-20 type tensile tester] 5cIR
Measurement was performed at a tensile rate of 2°/rm5n.

<Diving shrinkage rate> When the length of the sample under a load of 0.1 JP/d is L, and after the load is removed and treated in water for 30 minutes, the length measured again under the same load is L. The shrinkage rate is expressed as L·-L Diving shrinkage rate (trans)electron □X100.

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 78nol/tetrachloroethane.
At 100°C, the pore diameter was 0.35 wmφ, the number of holes was 6000, and the spinning machine was spun with a 20°C air flow supplied from the entire periphery of IIR #I in parallel to the running direction of the fibers.
After cooling and solidifying, add oil and heat for 4 minutes to 9 minutes.
．． 000 m Winding at a speed of 7 minutes, 1,800 d/6
A fiber bundle of 00f was obtained.

These fiber bundles were bundled into 100 tows of 180,000 denier each, made into a flat plate through a comb-shaped id, and the internal temperature was adjusted to 247°C using the dry heat treatment device 8 shown in Fig. 1. Then, heat treatment was performed for 1 second while applying tension of denier S, 6O, and osiP.

Also, for comparison, 1 spun at a spinning speed of 3,000 m/min
A tow of 80,000 denier was spun at a spinning speed of 1,200 m for 7 minutes, then stretched to 3.3 times at 30°C, and a tow of 9,180,000 denier was similarly heat-treated.

From the tow thus obtained as a spinning raw material, single fibers were extracted and their physical property values were determined and shown in Table 1.

Margin number 1 below! g! According to the results of the method of the present invention, 4,000
- Spun at a spinning speed of 247 DEG C. and subjected to dry heat treatment at 247 DEG C., Kutou becomes dyeable under normal pressure, and is found to have sufficient mechanical properties and thermal stability as a spinning raw material. On the other hand, tow spun at a spinning speed of 3.000 rv' minutes outside the scope of the present invention and tow spun at a spinning speed of 1,200 m/min and drawn 3.3 times do not have any of the above characteristics. It is insufficient.

Example 2 Polyethylene terephthalate with [η] of 0.65) t-1
A fiber bundle of 1,800 d/600 f was obtained by spinning at a spinning speed of 4,500 m/min using the same spinning method as in Example 1.
lf this fiber bundle! Using the thermal treatment equipment shown in Figure 2,
．． Moisture heat treatment was performed for 0.6 seconds in superheated steam at 206° C. while applying a tension of 1 jl/d 2 . Table 2 shows the measured values of the physical properties of the fiber bundles before and after heat treatment. .

From the results in Table 2 in the margin below, 1. It can be seen that the spouted bundles that have been heat-treated with ffi heat are much more ink-dyed than the fiber bundles before treatment, and can be dyed under normal pressure. The mechanical performance also indicates that it is sufficient as a spinning raw material.

Example 3 At a spinning temperature of 302°C, 4-ethylene terephthalate with [da] of 0.63 was passed through a spinning nozzle with a hole diameter of 0.30-φ and a number of holes of 600, and the fiber was run from the entire periphery of the fiber. After being cooled and solidified by a flow of air at 20° C. supplied parallel to the direction, an oil agent was applied and the fiber bundle was wound at a speed of 5.200 rolls/min to obtain 1 fiber bundle of 9004/600 f. This fiber bundle? After concentrating 200 pieces of Li to 80,000 d of tow, the staff d-? After applying the usual KID crimping method using Tux, it was cut to a length of 38 mm using a Guruguru cutter to make it stable. This stable has many hole pipes on the side [J! It was packed with a hanging density of 1.8 mHg and put into an autoclave-like pot. Next, the pressure inside the autoclave-like pot was reduced to 10 mHg using a vacuum pump to remove air, and superheated steam at 187°C was blown. A wet heat treatment was performed for 45 seconds. Once again, the steam in the valley was removed by decompression, and 1
Superheated steam at 87° C. was blown into the sample for 45 seconds to perform heat treatment.

Table 3 shows the physical properties of the staple before and after the heat treatment with moist heat.

From the results shown in Table 3 below, it can be seen that the staples subjected to heat treatment using moist heat become dyeable under normal pressure and have sufficient mechanical properties as a spinning raw material.Example No. Normal pressure dyeing obtained in Example 2 A tow made of possible polyethylene terephthalate fiber is crimped in a star, furge, and box using a conventional method, and then cut into lengths of 76 ridges using a Guruguru cutter, and ester is produced by worsted spinning using a conventional method.
A 7" T-made yarn was made with undyed wool (T and G) to obtain a 60 count twin yarn with a blend ratio of 50% ester and 50% wool. gt
After making, under normal pressure in a liquid circulating dyeing material, disperse dye-based ketonbori ester red FN (Mitsui Chemicals product name C, I, D
lsp*rm* R@d 113) 1% (for the dyed object), and acid dye Kayanol-based red R8C Nippon Kayaku Co., Ltd. product name C, 1, Aaid R@d 114)
0.5% (based on the object to be dyed), vinegar @ 0.5i1μ, bath ratio 1:7 (1) Gradually raise the temperature of the dye bath to 25°C to 99%
℃ for 45 minutes, dyed at 99℃ for 60 minutes, then discarded 1 dye solution - 1 sodium alkylpene sulfonate
Washed in a 1/L bath at 70°C for 15 minutes, rinsed with water twice to dehydrate, and dried in SO'c for 45 minutes. The dyed yarn obtained had a deep red layer color and was in good condition. It had a unique texture.

Example 5 The nine staple tubes which can be dyed under normal pressure obtained in Example 3 were blended with cotton by a conventional cotton spinning method to obtain a 40-count spun At with a blend ratio of 63% dilyester and 3596% cotton. This spun yarn is made into a total weight of 2 SOIt) 714 with a frame circumference of 1, and disperse dyed with a liquid jet dyeing machine. I
G-FS (product name of Mitsubishi Kasei Corporation) a, s% (to dyed material), vinegar rR0,21/9 at 99°C in a bath ratio of 1:80.
The 0-minute ester fiber was dyed and washed with water.Next, the fed yarn was transferred to a dyeing tank and dyed with Ikeslen Direct Black RB (
Mitsubishi Kasei product name C-1, Vat Blaek 13
) The cotton fiber tube was dyed in a conventional manner at 5% (based on the material to be dyed), and the yarn was transferred again to the liquid injection method, washed in a bath of 0.511/L of sodium alkylbenzenesulfonate, and then washed twice with water. After dehydration, it was dried at 90°C for 1 hour. The dyed yarn obtained had a black color and a good texture.

[Brief explanation of the drawing]

It! FIG. 1 is a schematic diagram showing an example of a spinning and heat treatment apparatus for producing the spinning raw material of the present invention. In the figure, 1 is a fiber bundle, 2 is for spinning, 3 is a tubular heating area, 4 is a fluid suction device, 5 is an oil application device, 6 is a take-up row 2-17 is a fiber bundle feed roller, and 8 is for heat treatment. 9 is a heating cylinder, 9 is a fiber bundle feeding roller, and 10 is 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 FIG. 0, 11 is a fiber bundle, tow or sliver, 12 is a feed roller, 13 is a guide row two, 14 and 14' are ninth slits for preventing excessive leakage of superheated steam in the heat-and-moisture treatment equipment fl15 and suppressing temperature fluctuations; 15 is the heat-and-moisture treatment equipment;
6 is a slot provided on the inner wall of the heat-and-moisture treatment device for spouting superheated steam; 17 is a heater for heating the superheated steam inside the heat-and-moisture treatment device 15 to prevent the temperature from decreasing and to reduce the temperature distribution; 1g; Guide row 2-119 is a device for winding fiber bundles, tows or slivers %20 is /4
21 is a superheated steam generator, 22 is a heater, 2
3 is the valve, 24 is? Each error is shown below. Figure 3 (, ) and Figure 3 (Figure 3) are respectively the mechanical loss tangent (-δ) - temperature curved edge and the dynamic elastic modulus (E') - temperature -1I.
In Figure 6, which is a graph schematically representing the graph, 2) indicates the fiber of the present invention, (B) indicates the conventional stretched fiber, 2) indicates the unstretched fiber, and Φ) indicates the value of the partially oriented fiber.・#! Figure 4 is an example of the interference fringes used to measure the cross-sectional radial refractive index (n/) distribution of the fiber. In the diagram, 31 is a fiber, 32 is an interference fringe due to the encapsulant, and 33 is an interference fringe due to the fiber fiK. Figure 5 shows the ethylene terephthalate fiber matrix of the present invention and the conventional stretched polyethylene terephthalate. fiber CB)
FIG. 2 is a graph showing an example of the radial refractive index (n7) distribution of FIG. FIG. 6 is a graph showing an example of the X-ray diffraction intensity curve of the ethylene terephthalate fiber. Patent Applicant: Asahi Kasei Kogyo Co., Ltd. Patent Attorney: Akira Aoki, Patent Attorney: Kazuyuki Nishidate, Patent Attorney: 1) Yukio, Patent Attorney: Akira Yamaguchi, FP, 4 (b) fIIJ5 1,0-0 ,8' OO081,0 6th frame

Claims (1)

[Claims] 1. Substantially made of homo-I remer of polyethylene terephthalate and dyeable with disperse dye under normal pressure/
A spinning raw material or spun yarn characterized by containing at least 14h5 weight of 17 ester fiber. 2. The polyester fiber is substantially made of homo-4 reamer of polyethylene terephthalate with an initial modulus and lath of 50 #/d or more at 30°C, and a mechanical loss tangent (jan') at a constant frequency of 110 Hz. The peak temperature ("rflllK) is 105°C or less, and ja
The peak value of n'[(jan')maX) is 0.13! S
The spun raw material or spun yarn according to claim 1, which has a value exceeding . 3. The spun raw material or spun yarn according to claim 1 or 211, wherein the polyester fiber is spun at a spinning speed of 4,000 m for 7 minutes or more and subjected to dry heat treatment at 220 to 300°C. 4.4 Lyester fiber has a spinning speed of 4. A spun yarn made of the spun raw material according to claim 1XJ or claim 2, which is spun at a speed of ooom/min or more and subjected to a moist heat heat treatment at 180 to 240°C. 5, (t1δ)rna of /lyester fiber! is 0.14
The spun raw material or spun yarn according to claim 2, which is the above. 6./The average birefringence index (Δn) of the ester fiber is 50X
The spun raw material or spun yarn according to claim 2, which has a diameter of 10' to 120 x 10-3. 7./The Twax of the polyester fiber is 100°C or less, the crystallinity (xo) is 3011 or more, the (010) plane microcrystal size (Act) is 35X or more, and (0
10) The spun raw material or spun yarn according to claim 2, wherein the degree of crystal orientation (CO) of the plane is 85- or more. 8, / The crystallinity (Xc) of the ester fiber is 7091 or more, the size of the microcrystals of the (01G) plane AC8) is so1
The spun raw material or spun yarn according to claim 7, wherein the degree of crystal orientation (co) of the (010) plane is 90 or more. 9./The spun raw material or spun yarn according to claim 8, wherein the T'max of the polyester fiber is 100°C or less, and the average refractive index (n401) is 1.65 or more and less than 1.70. . 10.4IJ The difference between the average refractive index (n4o) of the ester fiber and the refractive index of the part at a distance of 0.8 times the radius from the center [Δ/((L8-oj)] is 10 x 10-3 to 8
0x10 The spun raw material or spun yarn according to any one of claims 7 to 9. 11.417 The spun raw material or spun yarn according to any one of claims 7 to 10, wherein the local average refractive index distribution of the ester fibers is symmetrical with respect to the center of the fibers. 12. The initial monopolymer at 30°C has a lath of 50 #/d or more and is not substantially a homopolymer of polyethylene terephthalate, and the peak temperature (T□) of the mechanical loss tangent (tan') at a constant frequency of 110 Hm I)
is below 105℃, and the peak value of tana ((tan
A spun yarn comprising only 4-liester fibers that can be dyed under normal pressure with a disperse dye having a Ba value of more than 0.135. 13.30tl:l (initial modulus, last is 50 #
/d or more, and the peak temperature (T, □) of the mechanical loss tangent (jan') at a measurement frequency of 110 Hz is 105°C or less, and the peak value of jan' [(tana )m, x:l
Contains 5 to 95% by weight of polyester fibers that can be dyed under normal pressure with a disperse dye having a value of more than 0.135, and 95 to 15% by weight of at least one of cotton, hemp, recycled cellulose fiber and nylon 66 fiber. Weight: The spinning raw material according to claim 2 contained herein is a spun yarn. 14. The spinning raw material according to claim 11, wherein the spinning raw material is tow. 15. The spinning raw material according to claim 11, wherein the spinning raw material is stable.