JPS584835A - Atmospheric pressure dyeable blended yarn containing easily dyeable polyester fober - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel spinning system consisting of one or two of acrylic fibers and wool fibers and certain /rie, -chill fibers.

Traditionally, ester fibers, especially pre-ethylene tere-7 tallate fibers, have been blended with natural fibers such as rounded cotton, hemp, recycled cellulose fibers, and wool, or chemical fibers, which have excellent mechanical and thermal performance. The fiber mte compensates for the lack of mechanical properties of chemical fibers and the lack of water absorption, which is the drawback of %-lyester fibers, and has a practical performance far superior to that of spun yarns made from these fibers alone. A spun yarn is made with.

However, conventional/reethylene teleph! Rate fiber is
For the manufacture of round fibers, which are difficult-to-dye fibers that can only be dyed under high temperature and high pressure conditions of 120 to 130 degrees Celsius, and in particular blends with delicate fibers such as wool and acrylic fibers, whose mechanical properties deteriorate dramatically under high temperature and high pressure conditions. There was a system @. That is, when wool and polyethylene terephthalate fibers are blended, conventionally, the polyethylene terephthalate fibers are dyed at 120 to 130°C in a stable state, and the wool is dyed separately. The so-called yarn dyeing method was used, in which the yarns were dyed at 100 degrees Celsius in the ``G'' and ``D'' states, and then mixed in a nerishino-koho to create a blended yarn. Rare Ka, after spinning non-yarn-dyed double-stranded embroidery using a conventional method, -lyethylene tere 7 talate fiber - phenylphenol, methylnaphthalene, lyo
V1 Organic substances called carriers such as benzene and methyl naltylate are added to the dye bath containing the disperse dye and heated at 100°C.
After dyeing at temperatures around 1000 ml, the wool was dyed with acid dyes, metal-containing dyes, etc. Among these conventional methods, the former yarn-dying method is economically disadvantageous because the spinning machine gets dirty during the first spinning cycle, requires time to clean when changing colors, and has a large amount of fiber O loss. When using the superior carrier dyeing method, use high-temperature, high-pressure dyeing! The working environment of the dyeing factory is worsened because the dyestuff has a irritating odor which is harmful to the human body and is harmful to the human body. It is difficult to process the dyeing water, the carrier remains in K1m during weaving and is difficult to remove, and it may reduce the light fastness of the dyed product. There are many disadvantages such as emitting a pungent odor, the risk of skin damage when worn, and changes in the mechanical properties of 4-lyethylene terephthalate fibers due to carry dyeing, such as a decrease in strength and an increase in elongation. there were. The drawbacks of the prior art technology of blended yarns of wool and 4-liester fibers were also the same in the case of acrylic fibers, 4-liester fibers, and O blended yarns.

In addition, it is known that 4-lyester fibers with O-modified dyeability are copolymerized with metal sulfonate group-containing compounds or I-lyethers, but although these modified esters improve the ceramic color properties, polymerization and spinning are difficult. It is difficult to produce, the production cost increases significantly, or - it reduces the excellent mechanical properties inherent in lyethylene terephthalate, and it also has drawbacks such as poor dye fastness. K, which dyes ester in a dark color, is inside] 105
Because it is necessary to carry out the process at a temperature of ~110°C, deterioration of acrylic fibers and wool fibers due to high temperature and high pressure is still unavoidable in deep color dyeing of blended yarns with acrylic fibers and wool fibers. Spun yarns used together with acrylic fibers and wool fibers tend to have many of the drawbacks of modified 4-esters, so it is not worth the effort to blend them with esters.

The present inventors completed the present invention as a result of research into a new spun yarn that can be dyed under normal pressure and improves the above-mentioned drawbacks of conventional spun yarns.

The S-spun yarn that can be dyed under normal pressure according to the present invention uses one or two types of acrylic fibers and wool Il fibers of 95 to 5 weight
A corner-spun yarn containing 5 to 95% by weight of 4-lyester fibers, characterized in that the -lyester fibers consist essentially of small polymers of polyethylene terephthalate and are capable of being pressure-dyed with disperse dyes. .

"Can be dyed at normal pressure with disperse dyes" means disperse dye C.I.D./Mother's Sol-56 (C, 1, Dla
psrs+@Bin・56; For example, Resolin Blue F
Using BL (product name of I4 Inil, Federal Republic of Germany), dye usage amount B N owf , bath ratio 50 times, P) 1
6 (adjusted with acetic acid), dispersant (e.g. Disno and -T
L (product name of Meisei Kagaku Kogyo Co., Ltd.)) After dyeing in a ZtO dye bath with a content of 1 at 100°C for 120 minutes, the fiber was 111 iecI.
It means that the dyed @O exhaustion rate is 80 or more,
lI in ζζ! The exhaustion rate is expressed by the following formula.

$4 of f-lyethylene terephthalate used in the present invention
19 w- and can be dyed under normal pressure with disperse dyes''&-
Liester fiber is a new power fiber, and is this new? The spun yarn of the present invention made of ester fibers, acrylic fibers and/or wool fibers has extremely remarkable effects that were completely unexpected from conventionally known spinning systems.

Specifically, in a spun yarn using a conventionally known I-lyethylene terephthalate fiber, the I-lyethylene terephthalate fiber itself has a dye exhaustion rate of 30 to 30 under the same dyeing conditions as above.
While only 45X has the above-mentioned drawbacks caused by the dangerous nature of the fiber, the present invention eliminates all such drawbacks and improves the mechanical properties of the spun yarn using modified I-liester fibers. Disadvantages such as decreased heat resistance and decreased color resistance are determined. Special feature: The spun yarn of the present invention has an extremely low shrinkage rate in hot water.
Acrylic fiber (cassia 0n) 30 weight and sheep @3
No. 48 twin yarn made of ON has a shrinkage rate of 8 to 10Xm after hot water treatment at 100℃ for 30 minutes, and is an ethylene terephthalate copolymer containing 3X by weight of isophthalic acid and sodium sulfonate components. 40% by weight of ester fiber,
The shrinkage rate of No. 48 twin yarn made of similar acrylic fiber 30 weight x and wool 30 weight x after similar hot water treatment is 10~
Similar hot water treatment of 4811 twin yarn with a composition of 13 N@degrees, but with the above-mentioned conventional single ethylene terephthalate fiber or copolymerized I polyester fiber replaced with the single ester fiber of the present invention! The O shrinkage rate after 1 hour is only about 2 to 3 inches.

The spun yarn of the present invention contains one or both of acrylic fibers and wool fibers with a substantial KyJ of 95 to 5 weight-1? 9 made from homolymer of polyethylene terephthalate, and a delicate l-lyester that can be dyed under normal pressure with disperse dyes! S~9B weight-
It is essential to contain it.

If the content deviates from the range of tIxζOS, there will be problems such as poor mechanical properties as a blended yarn.

4 consisting of homo I remer of ethylene terephthalate
Lyester fibers, acrylic fibers and/or sheep fibers
In order to effectively achieve the intended purpose of the present invention when used as a spinning system, the initial modulus and lath at 30°C must be SOF/4 or more (dynamic modulus of elasticity at 30°C). [1!Means black ◎])), measurement frequency 110
The peak temperature of the mechanical loss tangent (-δ) in Is (
``Il&!) is 108 (-1) is 0.14 or more.

m a! The characteristic values expressing the structure of the amorphous region include the above T, □ and (imJl)m, xo values, as detailed in the specification of Japanese Patent Application No. 56-46408 filed by the same applicant. is appropriate e'rm, xF1 is normally 50
℃ is located on the high temperature side, (-ri, □ is temperature T, .KThff
In the present invention, 11! and (-δ)wax means a value related to mechanical absorption (aa absorption) caused by Ot Klobrown motion of molecular chains inside the amorphous region. Conventional 4 rie ≠ “m1kX” of lenterephthalate fiber is 1
30°C [, (-)□8 is 0.13 or less.

As (-δ)11x becomes larger, the shape retention property of the fiber decreases.In general, it is desired that "so" becomes larger.

If 1 is less than SOP/d, the fiber structure has poor thermal stability, poor dimensional stability, and becomes soft as a fiber.

Due to the disperse dye constituting the newly developed W14011I+# yarn, the fiber m is made of a homolymer of ethylene terephthalate that can be dyed under normal pressure and has sufficient strength (SJ
In order to have initial modulus (P/d or higher) and initial modulus (SOJP/d or higher), X@ must be 30- or higher, and MuC1 must be ss1.
As mentioned above, CO is preferably 85 or more, more preferably Xs is 70 or more, ACI is so1 or more,
CO is 901s or more. In addition, the single ethylene terephthalate fiber used for conventional spinning raw materials and spun yarns has an X-mo~ton, AC11H301 or less, and a co of 85
Furthermore, in the 4-lyethylene tere7-talate fiber constituting the blended yarn of the present invention, the central refractive index (my(o)) of polarized light having an electric field vector in the fiber axis direction is n ~ 9s-.
is 1. If the γO is small and 1.65 or more, it has suitable O elongation (20 to 70) and dyeability, making it highly desirable as a clothing fiber.

The optimal range of (a, (.)) is 1.65 to 1.68.

Also, the average birefringence ()m)tlj, 35 x 1G
It is preferable that the value is above, but on the other hand, it is preferably 50X10 or more from the viewpoint of structural stability against heat, and tL< is preferably 1!0XIO or less from the point of view of improving dyeability and arbitrary color change. , more preferably 8!
5XIO or less. When the proverb becomes 120X10 or less, the dynamic elastic modulus (
V reduction rate (the values of E' at 150°C and 220°C are respectively "'1801 E'tzo"'220/I
'1110) is small, g/, 20/
g/, 50 is larger than 0.75 t, is.

In other words, the structure becomes stable against heat. The tenacity of heavy nine dyeing is also improved. Furthermore, those with a size smaller than 85×10 2 have excellent atmospheric dyeability and are acceptable.

The average refractive index at the center of the fiber (n, ((1)) and the refractive index at a distance of 0.8 times the radius from the center of the fiber - # (o, s) t or "# (-0,11 ) difference [
)#(0,8-0)) is 10XIO to 80X10, it has sufficient strength and has few striations and strong elongation unevenness, where the local average refractive index distribution is at the center of the fiber. It is said that it is symmetrical with respect to the minimum value of the average refractive index n, (
m, ((1)-10xlO) or more], and m, (-
0,8) and m#(0,suO) is less than 15OxlO, and lf is less than 10XIG.

1+, 22G'CKTh = mechanical loss tangent (tsm#
226) is better as it is smaller, which reduces the decrease in initial modulus 1las due to temperature rise. When I' 21Q is 0.25 or less, the initial 4 degrees and glitter becomes significantly smaller.

Is it possible to dye under normal pressure with disperse dye? For example, as will be shown later in the Examples, the fiber made of polyethylene tere-7 tallate medium molymer is a fiber made of a polyethylene tere-7 tallate umbrella molymer spun at a spinning speed of 4,000 m/min or more. By performing heat treatment using dry heat at a temperature within the range of 220℃ to 300℃! Take, 1
Superheated steam, tempered steam, and the like within the temperature range of 80 to 240'C can also be obtained by heat treatment using hot water.

In addition, fiber 114D, which is a raw material of fiber 114D made of homof-rimer of stream ethylene terephthalate, which constitutes the blended yarn of the present invention.
Homoly 1- of polyethylene terephthalate can be obtained by known polymerization methods. ★T-normal? It may also contain additives used in liester fibers, such as matting agents, stabilizers, and antistatic agents.

Further, there is no particular restriction on the degree of polymerization as long as it is within the range of 01111 for ordinary fiber formation.

FIG. 1 shows an example of an apparatus for producing fibers that can be dyed under normal pressure using a disperse dye made of ethylene terephthalate, which constitutes the blended yarn of the present invention. Melting? Liethylene terephthalate is spun out from a spinneret (not shown) in a heated spinning head 2 and cooled in the atmosphere to form a fiber bundle 1.

Below this spinneret, there is provided a heating area 3 that surrounds the nine fiber bundles 1 that have been spun, and further below that, a 108-body pulling device 4 is provided for cooling and suctioning the fiber bundles 1. It is being After passing through the oil application device 5, the fiber bundle is taken off by a take-off roller 6.The "spinning speed" in the present invention means the surface speed of this take-off roller 60.Next, a pair of iron fiber bundles are fed.] Pulled out by roller 7, 220~
The fiber bundle is passed through a heating tube 8 adjusted to an appropriate bottle temperature within a range of 300 degrees, guided by a pair of fiber bundle feeders 90 and 9, and wound up by a winding roller 10.

At this time, by adjusting the rotational speeds of the fiber bundle feeding shear rollers 7 and 90, the fiber bundle 1 is elongated in the heating cylinder 8 to an extremely low elongation rate and subjected to heat treatment.

In addition to the above-mentioned O heat #1l11 method, the following method can also be used to heat the heated part. That is, the spinning speed is set to 4. After winding at a density of more than 10 minutes, these polyethylene terephthalate fiber bundles are gathered together to form a tow O-type 11.
After K, it is heat treated or crimped, cut into staples, placed in a can and heat treated, or after the staples are opened, they are made into urchin, f, sly/arm, to, and de cape shapes. A method of heat treatment is also adopted. Of course, the heat treatment can be carried out either by dry heat or warm heat, as described above.

Figure 2 shows the results of spinning at a spinning speed of 4,000 m/no.
An example of an apparatus for thermally treating tows of polyethylene tele-7 tallate fibers with superheated steam was shown. In FIG. 2, 1 is a tow or sliver, which is pulled up by a pair of feed rollers 12, reaches an idle roller 13, and is guided to a heat treatment device 15. The entrance of the III processing device 18 is pickpocketed,)14. The outlet is slotted and grooved so that the temperature inside the heat treatment equipment f15 is not influenced by the temperature of the outside atmosphere. In addition, the moist heat treatment apparatus 15 has a large number of slots 16 located above and below so that superheated steam is simultaneously applied to the top and bottom surfaces of the sliver or sliver. It is provided for. In addition, heaters 17 are installed at the top and bottom of the thermal treatment device 15 so that the temperature of the superheated steam can be controlled. on the other hand? Itsu-2
The saturated steam with an r-di pressure of about 10 to #/c/ generated in step 4 is input to the heating device 21 by the /4 lude 23 and heated by the heater 2, and becomes near-hot steam at a temperature of 180 to 24 OcO. This superheated steam is sent to the thermal treatment device 15 by the Pal F20, and is controlled to lower the temperature by the heater 17 so that the temperature distribution does not fluctuate greatly. The sliver 11 is subjected to a high humidity heat treatment. II The tow or sliver that has been heated for 461 m is passed through the flat 14' and the winding guide roller 18 and wound up in the winding device 19. Of the f-lyethylene tele7 tallate heat-treated as described above, the tow or sliver is spun directly. If the product is heat-treated in the form of a tow or a tow, it will be processed using the usual method. , Roll up in the box S-a
The fibers are cut into staples and blended with acrylic fibers, wool fibers, or both acrylic fibers and wool fibers in the spinning process. Tatsu8. ! , sliver, ) heat-treated VFO shape is part 1.
1. A blended yarn is made by mixing wool G and F and acrylic fiber G and F by a conventional method.

A method of measuring the structure of a single yso fiber will be described below.

<Mechanical loss tangent (-J) and dynamic elastic modulus (E')> Toyo? - Made by Ludwin, Leono Isolon (Rh@ev
Using a DDV-MS type dynamic viscoelasticity measuring device, the bllr at each temperature was measured in dry air at a sample size of 0.1 mm, a measurement frequency of 110 HI, and a heating rate of 10°C/min.
's and E' are measured. -a -1 temperature white line to -1 peak temperature (TffI,,XC) and the same peak height ((t+
+a′)max) is obtained. Figure 3 (1) and Figure 3) show the fibers of the present invention (1), the conventional abrasive drawn yarn (8),
-δ-@ of undrawn yarn (b) and partially oriented yarn (b), respectively
A typical example of E'-temperature-IIO is schematically illustrated.

The average refractive index (ny * m□) and the average birefringence are measured from the side of the fiber by the interference fringe method using a transmission quantitative interference microscope (for example, an interference mirror Inter 7 Aco manufactured by Karl Zeiss Jena, East Germany). The observed average 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 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 performed here are performed using green light 41 (wavelength λ = 54
981J11) using f;b.

The fibers were immersed in an optically flat glass slide and cover lath, with a refractive index axis that gave an interference fringe shift within the range of 042 to 2 wavelengths, and inert to the fibers. be done. Several fibers are immersed in this encapsulant so that the single threads do not touch each other. Furthermore, the fiber axis of ##I should be perpendicular to the optical axis of the interference microscope and the interference fringes. Photograph each turn of this interference fringe and magnify it approximately 1500 times. To analyze.

As shown in Fig. 4, the refractive index of the fiber encapsulant is N, and the refractive index between oAs' and s' on the outer circumference of the delicate O is (or is),
The thickness between B"-8" is t, the wavelength of the light beam used is λ, t4
Determine the distance between the parallel interference fringes of the y fugland (Aishima at 1λ),
If the deviation of the interference fringes on the fiber is d, then the optical path difference is
It is expressed by the metaphor λ-(su(t wa ayo)-N) t.

If the fiber O radius is 凇, the outer circumference R1 from the center R6 of the fiber
From the optical path difference at each position, the refractive index of the fiber at each position (
Or -1) distribution can be obtained. When r is the distance from the center of the fiber to each position, X m yAw Q
, that is, the refractive index at the center of the fiber O is the average refractive index (
”, (0) 19 #11 (.p).

X is 1 on the outer circumference and 0 to l on other parts
For example, the refractive index at x wm O, 110 points is expressed as ``, (0, @) (t or tortoise (., su), t and average refractive index 1'# From (0) and 1 (0), the average multilayer refractive index ()n) is noa=-ri(.)-nko(.

).

In addition, in Figure 4, it is 31t! 32a shows interference fringes due to fibers, 32a shows interference fringes due to the mounting medium, and 33 shows interference fringes due to fibers, respectively.

Fig. 5 shows the conventional Stretching Thread) and the O-fiber IIm of the present invention (2).
In the diagram showing the distribution of Ori, the horizontal axis is the distance from the center z xry /R1, and the vertical axis is the turtle, but zwm (
J is the center of delicateness! 41 and x! -1 is a point on the outer periphery of the fiber.

(Size of microcrystals e11)) Determine the size of fine crystals (ACII) by measuring the X-ray diffraction intensity in the equatorial direction using the equatorial reflection method.
The folding strength was measured using the xIs generating scissors device RU-100P manufactured by Rigaku Denki Co., Ltd.
L) and f niometer (liG-9R), scintillation counter for the counter, tl liquid high analysis for the counter, 2. monochromatization with a Kel filter, 90w -Km II
(Wavelength! = 1.54181) Measure. Set the textile sample O in an aluminum bracket so that the fiber axis is perpendicular to the X diffraction surface. At the time of Jin,
Set the sample so that the thickness is around 0.5-3.
Continuously rotate the X-ray generator at 0 kV -30 mA, scan speed 107 minutes, chart speed [10 / minute, time constant 1 second, ts-y wing speed, ) 1/2
°, Receiver slit 0.3■, Sukya, Talinda slit, To1 /l'K Th I? '! 1 # # S
5O-1) - Record the rough angle. Set it so that it is within the full scale of the recorder.

Bori ethylene terephthalate fibers are generally equatorial ll0I
I'm at a loss! #-17' ~ 26°Cl1illK3x0 Main 11 reflections (from low angle (Zoo), (
010).

(110) plane), Figure 6 shows an example of the X@diffraction strong line of an ethylene terephthalate fiber (a in the figure shows the crystalline part and b shows the amorphous part).To find the ACS , For example, 1. The formula of "Polymer X#Il Folding" by Alexander, Kagaku Doujin Publishing, Chapter m7 0''59-(8@h@rr@r) is used.

The sinusoidal intensity lines between 2#-70 and 2#-35' are directly connected to form a baseline. Drop a line from the apex of the a-fold peak to the baseline and mark the midpoint between the baselines at the peak. A horizontal diffraction image that passes through the midpoint
The main reflection drawn during the 11HFt♂-reduction intersects two shoulders of the Ka-line peak when well separated, but only one shoulder when the separation is poor. The width of this peak is kept constant.

If it intersects only one shoulder, keep the distance between the intersecting point and the midpoint constant and double it. If it crosses two shoulders, measure the distance between the two 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-Me J Ding J la measurement The line width measured, b is! The line width (half width) expressed in radians of the (111) plane reflection peak of a single crystal using the Rodninder constant, the size of the microcrystal (CS)
is given by the following equation (2). In ζζ, K is 1, λ is
1,54181), β is the corrected line width, eFif
Well, there is an r angle "t'2#01/2-t'.

<Crystallization m1 (X・)> XIII obtained in the same manner as microcrystal O size O constant
I#f strongly variable self-line], a bend between intensity -70 and 20s 35°! Connect them once with a direct line and use it as a baseline. The valley near 81m2G' is the apex, connected with a straight line along the lower and higher angle sides, separated into crystalline and non-crystalline parts, and determined by the area method according to the following formula.

<Crystal orientation (CO)> Rigaku Densachi Co., Ltd. X-ray generator (RU-200PL), fiber sample measurement system @ (ys-s), -f:#l-1-(8G
-9) Measurement is carried out using Cvi-1@Main (wavelength λ 1.5418X) monochromatized with a Kel filter, using a pulse height analyzer as the counter and a pulse height analyzer as the counter. /Liethylene terephthalate binding generally has three main reflections on the equatorial line, but the degree of crystal orientation (Co
) Use (010) IN reflection for Cam determination. 2 of the stone (010) surface reflection used is determined from the diffraction intensity curve in the direction of the road.

The xI1 generator is operated on SOHV, SOHIA. Attach the sample to the delicate sample measuring device so that the single threads are parallel to each other. It is appropriate to adjust the thickness of the sample to about 0.5 mm, and set the goniometer to the 2# value determined from the diffraction intensity curve in the s-direction. The azimuthal direction is scanned from -300 to +30' using the symmetrical transmission method, and the diffraction intensity in the azimuth direction is recorded. Furthermore, the diffraction intensities in the azimuth directions of −180° and +180° are recorded. At this time, the scan ender speed was 74°/min, the chart speed was 10/min, the Maym instant was 1 second, the collimator was 2-1, the receiving pick-up was 19-1, the vertical width was 19-1, and the horizontal width was 3.5-.

K to calculate CO from the obtained diffraction intensity curve in the azimuth direction
The average value of the diffraction intensities obtained at a, ±1800 is taken, and a horizontal line is drawn to form the baseline. Drop the baseline K11ll from the peak point 011 and find the midpoint of its height. Draw a horizontal line passing through the midpoint, measure the distance between the two intersections of this line and the diffraction intensity, and convert this value into an angle (0), which is given by the orientation angle H.

<Dyeability of I-lyethylene 7-melate fiber> Dyeability was evaluated based on the wear rate.

Disperse dye resolinol (R-esolla* B11
1@) Using FIIL (/? Inil company product name),
3-.vf, bath ratio l to sO at 100°C. Dlsp@r as a dispersant? Add IP/ to L and adjust to -16 with acetic acid. The dyeing rate is determined by collecting the dye solution after a specified period of time (2 hours), calculating the amount of dye in the remaining solution based on the absorbance, subtracting this from the amount of dye used for dyeing, and calculating the amount of dyeing. Dyeing rate (- was calculated.The sample was scoured for 20 minutes at 6G'C using a score roll FC2jj/A,
It was dried and conditioned at ff1 (20° C. x 6511 RH).

〈-liethylene tele7 tallate fiber ll: color 11 cell 1
＞Test hydrosulfite stained in the same manner as in the dyeability evaluation except that the dye concentration was 1-wfKL and the staining time was 90 minutes (at hydrosulfite) 11P/L, sodium hydroxide 1jl
/4. Surfactant (Sunmol RC-700) IP/L
using a bath ratio of 1:1! Evaluation was made after reduction cleaning at 50.80'C for 20 minutes.

Colorfastness: Light resistance (according to JI8L-1044), abrasion fastness (according to JI8L-0849), medium, Tode l' y '/7ri II observance (JI8L-08)
50) was evaluated.

<Initial modulus and lath> Let the value of E' at 30°C in the dynamic viscoelasticity test mentioned above be the initial modulus and lath.

(Strong elongation) TlCN81LON UT manufactured by Toyo Nkl”tsu4n Co., Ltd.
M-Rin-20m tensile testing machine initial length 51, tensile speed *i
.

Measured at ■/waim.

<Water production shrinkage rate> α1 #/d The length of the sample under load is L, and after removing the load and treating it in boiling water for 30 minutes, it is measured again under the same load, and the length is L. The water production shrinkage rate is expressed as o -L water production shrinkage rate (-Teng□X 100 ).

The present invention will be described below with reference to specific examples.

Example 1 In the 271 mixed solvent of phenol/tetrachloroethane, 4-lyethylene terephthalate having an intrinsic viscosity [η] (hereinafter referred to as [da]) of 0.63 at 35°C is spun at a temperature [
Spun at 300℃ from a spinneret with a hole diameter of 0.35 φ and 600 holes, the entire circumference of the fiber is #! After being cooled and solidified by a flow of air at 22°C supplied parallel to the direction of the rectangular fibers, the fibers were coated with oil and wound at a speed of 4,600WV% for 5oOd/t. A fiber bundle of 600 f was obtained. This fiber bundle was bundled into a 180,000 denier tow, passed through a comb-shaped guide to form a flat plate, and was processed using the drying machine 8 shown in Figure 1. Internal temperature ['t246℃
The denier Q, 0811 tension was applied and the hot part was exposed for 1 second.
The results of LtI extraction and measurement of physical property 9IL' are shown in Table 1 together with the measured values of the leather fiber before heat treatment. - The keratin tow' was crimped in a staff 1-bix by the usual method. Next, it was cut into 16-length pieces using a Guruguru cutter, and Nistert and De were made by worsted spinning in a conventional manner. This top and undyed wool top are mixed with ester 50,
A 60-handed twin yarn with a blending ratio of 501s wool was obtained. This spun yarn was made into a yarn with a frame circumference of iW@ and a yarn weight of 150#4Dtt, and was placed under normal pressure in a liquid circulation type dyeing machine under normal pressure.
rs@R@dl13) 0.8% (against the dyed material), and acid dye Kayanol-ken Lindaret R8 (Nippon Kayaku Co., Ltd. product name C, 1, Mu e1m R@4114) 0.4% (against the dyed material) , acetic acid Q, 5ILL, in a dye bath with a bath ratio of 1:60, the temperature was gradually raised from 25°C to 19°C over 50 minutes, and 9
After staining at 9°C for 70 minutes, the staining solution was discarded and the dye was stained in a bath of 1117t of sodium alkylbenzenesulfonate for 70 minutes.
Wash at 0℃ for 20 minutes, rinse with water twice, dehydrate, and remove
It was dried at 0°C for 40 minutes. The dyed yarn obtained is dark red K.
・From the results shown in Table 1, the heat-treated Kutou was much easier to dye than the untreated one, could be dyed under normal pressure, and had sufficient mechanical performance. It turns out that.

Table 1 Example 2 (IF) (0.66 IDyl) ethylene terephthalate, spinning temperature [298°C, pore diameter 0.35-φ, number of holes 60
The fibers are spun from a spinneret of 5.100Wv5+, cooled and solidified by a flow of 20°C air WcL supplied parallel to the running direction of the fibers from the entire periphery of the fibers, and then an oil agent is applied.
A fiber bundle of 1,800 d/600 f was obtained by winding at a speed of After applying it, it was cut to a length of 6 gm using a Guruguru cutter to form a staple.The staple was packed in a can with many holes on the side at an apparent density of f1.8 and 9/m, and placed in an autoclave. The pressure of the autoclave-like pot was reduced to 1 g using a vacuum pump, the air was removed, and superheated steam at 188° C. was blown into the tube for intense aging heat treatment for 45 seconds. Once again, after removing the steam O from inside i by depressurization, super-aged steam at 188°C was blown in and heat treatment was performed using fl heat for 4 seconds. As shown in Table 2, the second
From the results in the table, it can be seen that the staples subjected to the moist heat 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 Nystelt is an undyed acrylic product made from 34.76mm staples of acrylic short fibers using a conventional method! , and undyed wool dog t-warm yarn to obtain a blended yarn of 48 knuckle twin yarns.

The mixing ratio (weight %) of this blended yarn was 40!6 ester, 35% acrylic, and 2591 wool. In Pt production, liquid circulation dyeing, disperse dyes Guiyani, Kuszora, Ri(
Dianix Black B G -F Ss Mitsubishi Kasei Corporation product name) 496 (for dyed material), -6 (adjusted with vinegar IIK), with a bath ratio of 1 to 0, gradually raise the temperature from 20℃ to 99℃ for 35 minutes , dyed at 99℃ for 90 minutes, cooled to 70℃ for 20 minutes, drained the dye solution, washed with water,
Next, it was washed for 15 minutes at 70° C. in a bath of 20% ammonia water 1/1 and nohydrosulfite 0.5 fl/1. After that, wash with water twice (b) to make sure, then cationic dye Eisenkachironpla, RiBXH (product name of Hodogaya Chemical Co., Ltd.)
1.8% (to dyed material), PH3.5 (adjusted with 4# acid)
, the temperature was gradually raised from 70°C in a bath with a bath ratio of 1 to 0 to 99.
℃ for 30 minutes, dyed at 99℃ for 80 minutes, then dyed at 90°C.
The dye bath was cooled to 5°C and dyed with rim dye Eriochrome Black Erl...hrom 1k P2B (Ciba Geigy, Switzerland product name C, 1, M@rlant Black).
k7) 1.4% (for dyed material) K-containing amount,
A quantity of the anti-settling agent Dydes T4- (D (product name of Ichisha Yushisha Co., Ltd.) 296 (for dyed objects) was added to the dye bath and the temperature was raised to 99°C for 10 minutes.The temperature was raised in a 99°C trench. After 70
After staining for 30 minutes, adding sodium dichromate 'tO, 691 (to the dyed object) and dyeing for 30 minutes, staining solution t7
After cooling to 0℃ for 30 minutes and discharging, rinse with water.
Then add 0 sodium alkylbenzenesulfonate,
Wash in a bath containing SIA at 75°C for 15 minutes, then wash with water?
The zero-order rcgt was removed and dehydrated three times, and then dried at 80° C. for 35 minutes. The obtained dyed yarn was colored black, had an intensity of 403I, and had a pleasant texture.

For comparison, a 3d x 76 m staple of conventional I-lyethylene terephthalate fiber and a 3d x 76 staple of an easily dyed 4-liester prepared by copolymerizing sodium isophthalate sulfonate in place of the lθ molar ratio of terephthalic acid in 4-lyethylene terephthalate were used. The same acrylic short fibers and wool toddye were used under the same conditions and at the same blending rate.
I made a blended yarn of double-count yarn and made each tube with a final length of 1 m and a weight of 200#O#. Only when dyeing the 4-lyester fiber side with a disperse dye, I dyed the conventional polyethylene terephthalate fiber in a pressure-resistant liquid jet ground dyeing machine. The temperature of the blend was raised to 130°C, and the temperature of the blend of sodium isophthalate sulfone copolyester fiber was raised to 110°C, and all other dyeing conditions were the same. Compared to the dyed yarn of the present invention, the obtained Tomo dyed yarns have a coarser and harder texture, and the strength of the yarn dyed at 130°C is 302I, and the strength of the yarn dyed at 110°C is 357jI, which is higher than the yarn of the present invention. 25 fights each, 11
It was in a slow decline.

The shrinkage wheel after dyeing was 2.8% for the blended yarn of the present invention and 2.8% for the conventional I
The concentration was 9.711 for the one using polyethylene terephthalate, and 12.5 for the one using colimer ester.Example 3: Table 2 in the margin Example 1 A fiber bundle of 1,800d/600f was obtained by spinning at a spinning speed of 4,7004 minutes using the same spinning method as in the case of ＃／
, +i tension [from a hanging bottle to 0 in superheated steam at 205℃
．． Table 3 shows the measured values of various physical properties of the fiber bundles that were subjected to thermal heat treatment for S seconds before and after the heat treatment. According to the results of the GS table] The fiber bundles that were subjected to thermal heat treatment for ] It can be seen that the material can be dyed with ink to a large extent and can be dyed under normal pressure, and that its mechanical performance is also sufficient as a spinning raw material.

Next, 100 of the above fiber bundles were bundled to a total weight of 61,800 yen, crimped using a conventional method, and cut into 76 pieces. Undyed atarilt used in Example 2,
Mixed with f, ester 40gI, acrylic SOS blending rate 0
609 double yarn blended yarn tll9 ,1,Disp@rs@Bl
ue 56) 1.5% (to dyed material), cationic dye Kayacryl Blue GRL (Nippon Kayaku Co. product name C, 1, B
a5is! I1we41) 2嗟 (for dyed objects), saponification prevention agent Maydes/Mana-CD (Ipposha Yushisha product name) 211
(for the dyed object), PH4 (adjusted with acetic acid), bath ratio 1:65
The temperature was gradually raised from 70°C in a dye bath, and dyeing was carried out at 99°C for 41 S minutes and 60 minutes at 99°C. Staining after staining*t'y.

Cool to ℃ for 20 minutes, wash with water, and soak in a bath of sodium alkylbenzenesulfonate for 70 minutes.
CK for 20 minutes, water washing t3 times, dehydration, and drying at 75° C. for 10 minutes. The obtained dyed yarn was colored deep blue, had a strength of 5 osjFt, and had a good texture.

For comparison, a 3d x 76m staple of copolymerized ink-dyed polyester was used instead of the conventional 3d x 76m staple of 1 polyethylene terephthalate fiber and 7 molar terephthalic fiber of sodium isophthalate sulfone t-4 polyethylene terephthalate. When dyeing only the 4-liester fiber side with the same acrylic todde and mixed yarn of 6OW twin yarn with the same blending ratio and dyeing only the 4-liester fiber side with a 0 disperse dye made at a weight of 250Ii at a circumference of 1m, pressure-resistant liquid injection type dyeing In the dyeing machine, the temperature of the conventional polyethylene terephthalate fiber tube blend is raised to 130'C, and the temperature of the isophthalic acid sulfone sodium copolymerized & IJ ester fiber blend is raised to 110'C. All staining conditions were the same under pressure.

Compared to the dyed yarn of the present invention, the obtained dyed yarns had a coarser and harder texture and a strength of 130'C dyed yarn had a strength of 394J.
11-1, and 11 (1): The dyed one showed 4481, which was 22 and 11 lower than the good 0 inventive one, respectively.

tkShrinkage rate of the blended yarn of the present invention after dyeing #'12. 8.7% using conventional I polyethylene terephthalate fiber, 10.7% using coli mer ester
It was/Table 3 in the margin below

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a spinning machine and a heat treatment apparatus for raw material fibers for producing the blended yarn of the present invention. heating range, 4
is a fluid suction device, 5 is an oil application device, 6#i take-up 90-
7 is a fiber bundle feeding roller, 8 is a heating cylinder for heat treatment,
9 indicates the fiber bundle feed row 2-% IO indicates the fiber end removal roller tube. Figure 2 is a schematic diagram showing an example of a heat treatment device using superheated steam used in the present @O example. 11 is a fiber bundle, tow or sliver, 12 is a tweed roller, 13 is a guide roller, 14 and 14' are slits for preventing excessive leakage of superheated steam in the thermal treatment device 15 and suppressing temperature fluctuations), 18tj thermal treatment equipment, 1
6 is a heater for blowing out superheated steam provided in the moist heat treatment equipment 15; Is 18 a guide low? -119 is a device for taking fiber bundle, tow or sliver 10, 20 is pulp, 21 is a superheated steam generator, 22 is a heater, 23
%24Fi & Itsu respectively. Figure 3 (1) and 3rd opening) are respectively the mechanical loss pressure m
! (-δ) one temperature curve, dynamic elastic modulus (E') one temperature - a
(4)
(B) shows the value of the fiber used in the present invention, (B) shows the conventional drawn fiber, ((') shows the value of the undrawn fiber, and (B) shows the value of the partially oriented fiber. Figure 4 shows the radial direction in the cross section of the fiber. Refractive group (m# or n□
) In figure 0, which is an example of the main turn of the interference fringes used for measuring the distribution, (a) is a cross-sectional view of the fiber, (a) is a diagram of the interference fringe/middle turn, 31 is the fiber, and 32 is the mounting medium KL. The interference fringe 33 is the interference fringe due to fibers. If! FIG. 5 is a graph showing an example of the radial refraction wheel (n〃) distribution of the straight ethylene terephthalate fiber used in the present invention and the conventional drawn 4-polyethylene terephthalate fiber (B). FIG. 6 is a graph showing an example of strong X-ray diffraction lines of 4-lyethylene 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 3rd F (Q) Temperature ('C) 〒4 kan b) Fifth wa

Claims (1)

[Scope of Claims] 1. A spun yarn containing 95 to 5% by weight of one or two of acrylic fibers and wool fibers and 5 to 95% by weight of preester fibers, wherein the -lyester fibers are substantially A blended yarn capable of being dyed under normal pressure, characterized in that it is a homoprimer of 4-lyethylene terephthalate and can be dyed under normal pressure with a disperse dye. 2. When the initial modulus of the ester fiber at 30°C is 509/d or more, the mechanical loss tangent (imJ) at the measurement frequency of 110 Hm is 0.
If the temperature is below 105℃, the -1 lifetime value [(-δ)
] is larger than 0.135. The blended yarn according to claim 1. 3. The blended yarn according to claim 2, wherein (tma) of the ester fiber is 0.14 or more. 4. - After the riester embroidery is spun at a spinning speed of 4,000 m/min or more, it is subjected to dry heat treatment at a temperature of 220°C to 300°C or hot heat treatment at a temperature of 180°C to 2240°C O*W. The blended spinning system according to any one of claims 1 to 3, wherein