JPS5854019A - Deeply dyeable polyester fiber and its production - Google Patents

Abstract

PURPOSE:A polyester containing SO3M groups is melt spun, heat treated and drawn under specific conditions to produce deeply dyeable polyester fiber with a combination of high dyeability and soft touch. CONSTITUTION:A polyester containing ethylene terephthalate as the major recurring units as well a -SO3M groups (M is alkali metal) is melt spun to give an undrawn yarn with an orientation degree (DELTAn) of 0.02-0.08. The undrawn yarn is heat-treated under relax until the crystallinity (xrho) becomes 30-55% and the crystallized fiber is drawn at low temperatures so that the finess increases at a rate of +0.1-1.7 times to give the objective fiber with xrho of 30-55%, DELTAn of 0.06-0.12 and xrho/DELTAn of 350-550. The above -SO3M is preferably -SO3Na.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polynisglu fiber having both high dyeability and soft texture, and an M-week method thereof.

In general, polyester fibers have excellent physical properties and are therefore widely used in clothing and industrial applications.

However, polynisual fibers have the disadvantage that boil dyeing cannot be carried out under normal pressure. In order to improve the dyeability of polyester fibers, it is well known to use polyester copolymerized or mixed with a third component. It has also been reported that heat treatment at 200° C. or higher after stretching improves the affinity of polyester fibers for dyes (British Patent No. 735.171).

However, since polyester fiber has a relatively stiff texture,
It is difficult to obtain products with a soft texture that is most suitable for spring/summer clothing, men's clothing, fall/winter clothing, and women's clothing using the above-mentioned method, especially for fall/winter clothing. The current situation is υ), which is not used.

Therefore, an object of the present invention is to make a deep-dyed polyester fiber that can be dyed by normal pressure boiling from light to deep colors while maintaining the excellent physical properties of polyester fiber, and that has a soft texture. Our goal is to provide the following.

In general, when looking at the structure and performance of polyester fiber over time, spun undrawn yarn has a borrowed orientation, a low crystal structure, is darkly dyed by normal pressure boiling, has a soft texture, but is easy to stretch. There is no functionality at all. However, the so-called drawn yarn obtained by drawing and heat-treating the undrawn yarn has a highly oriented, highly crystalline structure, excellent functionality, and a stiff, hard texture. enhance physical properties,
It is also used for high-performance applications such as tire cords. However, these conventional drawn yarns have problems in that they have poor dyeability and lack the soft texture required for autumn/winter woven and knitted fabrics.

Therefore, the present inventors have discovered that the undrawn yarn has excellent dyeability,
In order to provide a drawn yarn that has a soft texture and the excellent functionality and physical properties of a drawn yarn, we have conducted various studies, and as a result, we have developed a fiber structure that is completely different from that of conventional polyxstel drawn yarn.

The inventors have discovered that the above objects can be achieved by using low-orientation, highly crystalline fibers.

Thus, according to the present invention, fi+ is a polyester fiber whose main repeating unit is ethylene terephthalate and which contains 18O,M groups (M is an alkali metal), and whose crystallinity (χ) is 30 to 5.
5%, an orientation degree (△n) of 006 to 012, and a χμ horse of 350 to 550, and a method for producing the same: (2) The main repeating unit is Hind limb obtained by melt-spinning a polyester which is ethylene terephthalate and contains one 8O, M group (M is an alkali metal) -6= to obtain an undrawn yarn with an orientation degree (△n) of 002 to 0.08. The undrawn fibers are heat treated in an untensioned state to have a crystallinity (χp) of 30 to 55, and then the crystallized fibers are heated at a low temperature and at a magnification of +1.0 to 17 times the fineness increase rate during the heat treatment. Provided is a method for producing deep dyeable polyester fibers, which is characterized by stretching the fibers.

Furthermore, in this regard, in order to obtain a polyester fiber that exhibits easy dyeability in normal pressure boiling water and exhibits a soft texture, the main repeating unit must be ethylene terephthalate and -80,M (M is an alkali). It has been found that fibers having the following properties (al (b) and (c)) can be obtained by melt-spinning a polymer containing metals.

(al Crystallinity (χp) 30~55chi (bl
Birefringence (△n) O,'06~0.12tel
χ, /△n 350-550 (preferably 400-5(
l o ) Here, if χ2 or Δn is less than 006 and #30%, the mechanical properties of the fiber are insufficient and high-order processing is not possible.
On the other hand, when χ2 exceeds 55 or Δn exceeds 012, the crystallization time is prolonged, which is not only disadvantageous in the manufacturing process, but also eliminates the deep dyeing effect. Even more important (
, the above (a) (even if the condition of bl is satisfied, χ, /Δ
If the value of n is less than 350, the functionality of the fiber (handlability, durability, 1 strength elongation) is poor and it cannot be put to practical use. On the other hand, if the value exceeds 550, the wrinkle resistance and dimensional stability of the fiber will deteriorate, and problems such as energy loss and fluffing will also occur.

Hereinafter, the present invention will be explained in detail by giving specific examples. In FIG. 1, undrawn fiber tow 1 (De of 20' x 104.
Δn or 004) is δ-relaxed between two sets of rollers 2 and 4 at a relaxation rate of 10%, and then subjected to relaxation heat treatment by a heater 3.

As a result, the tow 1 becomes a low-oriented, highly crystalline, undrawn tow with a thickness of 22×10' de and a crystallinity χ of 41% (denier increase ratio is 01). In this case, the unstretched tow 1 used has a degree of orientation expressed by birefringence (C) of (+, o2 ~
It is necessary to be in the range of 008. If the degree of orientation of the tow is less than 0.02, there are no nuclei that can crystallize when heat treated, so no crystals will form even when exposed to high temperatures, and the single fibers that make up the tow will fuse together. do,
It becomes unusable. On the other hand, if the degree of orientation of the tow exceeds 008, the degree of crystallinity after heat treatment will be large, exceeding 1, and in this case, even if it can be drawn continuously, the fiber will have a hard texture. And the price of partially oriented rice is 11 tons!
In heat treatment for crystallizing fibers, the following facts must be kept in mind. That is, if the fibers are heat treated during drawing to become highly crystalline and highly oriented fibers, the resulting fibers will not have a soft texture. In this sense, the relaxation heat treatment of the fibers must be carried out under no tension so that the molecular chains are folded and folded. Therefore, the relaxation rate is preferably 5
% or more, more preferably 10% or more. Further, during this heat treatment, fibers with a crystalline temperature χ of 30'% l:J are obtained. For this, at least 130? : A temperature of 150° C. or higher is required. □ In the present invention, it is important that K is distributed evenly in order for the undrawn fibers to crystallize without being fused to each other under high temperature and stress-free conditions.

This slight orientation can be provided by the following method.

These methods include a method in which high-speed spinning is performed and the fibers are oriented during spinning as in this specific example, a method in which the fibers are spun at a low speed and then quenched to achieve orientation, and a method in which the fibers are spun at a low speed and then oriented with a slight stiffening motion.

The unstretched 4II fibers with low orientation and high crystals obtained in this manner and subjected to relaxation heat treatment on the heater 3 are stretched at a stretching ratio of at most 14 by a first pair of rollers 6 while passing through a shade 5 of warm water at 40°C. Stretched. Particular attention must be paid to temperature control during stretching.

If the undrawn fibers are plasticized at high temperatures and stretched as in the drawing process for ordinary polyvarnish fibers, the crystals formed in the process described above will be broken. When stretched, the molecular chains are highly oriented.Then, such polyester fibers exhibit a hard texture like that of ordinary yarn.In order to prevent such texture hardening, in the present invention, the molecular chains are The folding process is carried out at a low temperature that does not cause the folding process to occur.

For this purpose, it is better to carry out the stretching at room temperature, but in cases where lamps are generated due to the cutting of the single fibers, a slight heat may be applied using the aforementioned hot water bath. Even when using this hot water bath, to prevent molecular rearrangement,
The temperature of the bath is preferably below the glass transition point of the polyester fiber. Also, if the stretching ratio is too high, molecular rearrangement occurs to an undesirable extent. If the fiber shrinks during heat treatment before stretching, it is necessary to adopt a stretching ratio that corresponds to the increase in shrinkage rate.

However, even in this case, it is preferable that the stretching ratio is not more than the increase rate of fineness due to shrinkage during heat treatment +17, preferably not more than the increase rate +15.

In the case of ordinary polyester filaments, it is well known that when the stretching ratio is low, the functionality is poor and it is not suitable for practical use. On the contrary, even when the fibers according to the invention are drawn at low magnification, the resulting fibers have a high primary yield point,
Since it is highly crystallized before stretching, it retains its functionality. Considering this meaning, it is better to stretch the fibers of the present invention at a fairly low magnification [7].The lower limit of the stretching magnification should be +101, preferably about 1.1, the rate of increase in denier due to shrinkage during heat treatment. It is. Next, the drawn tow with a total denier of 16 x 10' de drawn under the above-mentioned draw ratio of 14 is crimped in a stuffing box, and then canted to become a fluffy 5°. , because it is stretched at a low temperature, the structure of the tow after stretching is disordered and exhibits high shrinkage. Therefore, if a tow with low shrinkage is required, heat setting after stretching is sufficient. At this time, if the tow is pulled more than necessary, the fibers will be significantly oriented, so it is desirable to set the drawn tow at a constant length or in a relaxed state. Specifically, before the crimp is curled, the length may be set using a hot roller, or after the crimp is curled, it may be allowed to freely shrink under dry heat. It is also possible to steam set the cloth made by cutting the crimped tow.

The fabric obtained by pressing in this way is then processed into ordinary spun yarn,
It is made into yarn using the same method as worsted yarn and woolen yarn. In this case, a blend of high shrinkage yarn (unset yarn) and low shrinkage yarn (set yarn) exhibits a bulky texture and soft texture.

Therefore, it can be said that such a blended fabric exhibits a more preferable hand. The best results are obtained when the ratio of high shrinkage yarn to low yield yarn is 03 to 05. Of course, the fiber according to the present invention can also be blended with wool or acrylic.
In particular, when the blending ratio exceeds so%, the effects of the present invention become noticeable.

The spun and yarns obtained in this way are made into woven or knitted fabrics, but especially when fabrics with a relatively loose structure of thick fabric such as soil weave, baguette weave, and pile fabric are made, The effect of the present invention (soft texture) is fully exhibited. The fabric is then scoured, preferably in a highly relaxed state.

In other words, instead of performing jigger scouring, which is performed with the sheath wire in a gently relaxed state, a jet dyeing machine or similar is used to stir and circulate the scouring liquid and the fabric to give a sufficient kneading effect and to dye the fabric. It is preferable to remove such tension and sufficiently relax. By carrying out such relaxation N-green, the fabric has a fluffy and soft texture similar to wool.

When a product is made, the ends of the fabric rise up on the surface of the fabric, and these raised areas are extremely soft, so they have the effect of accentuating the soft feel of the fabric as a whole. In addition, the fabrics themselves intertwine with each other due to their softness, and this intertwining gives the fabric a sense of volume, giving it a more desirable texture.

Polymers useful in the present invention are polyesters in which the main repeating units are ethylenethenephthanate and -8O,M groups (M is alkali gold R), and in small amounts, especially when KM is Na. results. 5-Sodium sulfoisophthalic acid is suitable for introducing 18O,Na groups into polyester. This is used in ranges.

When this amount is less than 1 molty, the texture is hard and the normal pressure dyeability is satisfactory for disperse dyes, but is insufficient for cationic dyes. If the amount exceeds 5 mol, the strength of the fibers will be significantly lowered, resulting in poor processability in spinning and post-processing.From this point of view, good results can be obtained if the amount is preferably in the range of 2 to 35 mol.

As mentioned above, the present invention has been described using Sufu as an example, but
This effect is the same for filaments, which exhibit a soft texture that cannot be obtained with ordinary polyester, so textiles and silk fabrics made using them exhibit a unique texture.

The various properties of the fibers described in the present invention were measured by the following methods.

The degree of orientation, or birefringence, is t#! It is expressed as the difference in refractive index between the direction perpendicular to the fiber axis and the direction parallel to it. The measurement is tricrea
The analysis was carried out using a polarizing microscope equipped with a Pellec compensator using yl phosphate.

Crystallinity χ2 Specific gravity ρ of polyester fibers was determined using an n-hebutane-carbon tetrachloride density gradient tube at 25°C in a conventional manner.

The crystallinity was calculated using the following formula.

χ, = (0,7491-1/ρ) / 0.061
78 dye adsorption rate dyeing is 5% o, w, f, Aizen Cathi
The dyeing was carried out using lon Red GTLH (manufactured by Hodogaya Chemical Industry Co., Ltd.) under the conditions of a bath ratio of 100, a temperature of 100° C., and a dyeing time of 60 minutes.

The dye adsorption rate was calculated from the dye concentration in the remaining bath.

As mentioned above, the polyester fiber according to the present invention has extremely good dyeability, so it can be dyed not only in light to medium colors under normal pressure boiling water, but also in deep to very dark colors, which were difficult to achieve with conventional polyester fibers. Deep dyeing is also possible, and the dyed yarn has a very soft texture, which is necessary for thick autumn/winter textiles.

Example 1 An ethylene terephthalate copolymer polyvarnish with an intrinsic viscosity of 055, obtained by copolymerizing 26 moles of 5-sodium sulfoisophthalic acid component with respect to the total acid component, was prepared with a single fiber denier under the conditions shown in Table 1. The fibers were spun to obtain a yarn of 3 de. The polymer of Experiment 43 in Table 1 contained 1.9 moles of 5-sodium sulfoisophthalic acid and PL3 moles of isophthalic acid instead of 26 moles of 5-sodium sulfoisophthalic acid.

The experimental results are shown in Table 2, and the dyeing rate and χ5, △n,
The relationship between χp/lsn is shown in FIG.

Figure 2 shows experimental rot, and ◎ indicates dyeing rate of 90% or more, O indicates 80-90%, Δ indicates 60-80%, and X indicates 60%.
It represents 0chi or less.

17-IC Example 2 A polyester with an intrinsic viscosity of 0.59 made by copolymerizing 5-sodium sulfoisophthalic acid component with an aftershock component was melt-spun to form a filament with an orientation degree of 004. This filament was crystallized at a relaxation rate of 10% and a temperature of 200°C to a crystallinity of about 41%, and then cold-stretched 1.4 times at 40°C. Subsequently, the drawn yarn was
It was brought into contact with a roller at 0° C. and heat set for a fixed length. Furthermore,
The fibers were crimped using a Stuffing Bonox type crimping machine, dried, and then cut to obtain a cloth having a length of 51 fi. Separately, it was directly crimped without heat setting, dried and then cut. The former was blended at a weight ratio of 60% and the latter was blended at a weight ratio of 40% and spun into a No. 30 twin yarn to produce a twill fabric.The fabric was relaxed in a Sumoto jet, dyed at 100°C, and finished. The resulting fabric had a texture that was completely different from conventional polyester fabrics; it had the softness of melton made from natural wool, and was also extremely darkly dyed.

Comparative Example 1 Spun at a spinning speed of 1200 lm, orientation degree △n is 001
When the tow with a low temperature was heat-treated at 200° C. in the same manner as in Example 2, the tow was fused and spinning became impossible. In order to prevent this fusion, the temperature was lowered to 110° C., but sufficient crystallization did not occur, and no improvement in softness was observed when the material was made into a woven material. Further, when the tow was stretched 15 times and then heat-treated, no fusion occurred even at 200°C, but only a hard texture was obtained when it was made into a woven fabric.

Example 3 A modified polyester containing 26 moles of 5-sodium sulfoisophthalic acid was spun at a spinning speed of 1 [100 m/fm to obtain a tow with an orientation degree Δn of 0008, and the tow was passed through a hot water bath at 80°C. The film was then semi-stretched to 15 times and slightly oriented. The obtained tow had a Δn22- of 005. This tow has a relaxation rate of 5% and a temperature of 180
The tow was crystallized at 150°C to have a crystallinity (χ) of 37 degrees, and the crystallized tow was cold-stretched 1.4 times, crimped using a crimp machine, and then set in an air glow at 150°C. The tow was then bias cut to a 64/89.0 staple. The fabric is blended with wool at a ratio of 30 nia 0 weight 8%, 24
I made it into a spun yarn of double yarn. The yarn was plain woven, then relaxed and dyed. Furthermore, when the fabric was brushed after dyeing, it became a very soft fabric that resembled a flannelette and had excellent napping properties. Also, the dyeability was extremely high and the dyeing was deep.

Example 4 A polyester obtained by copolymerizing 26 mol of 5-sodium sulfoinphthalic acid component was spun at 4000 yl/II.
Melt spinning with IM, 006.65 de/36
flla, and while shrinking the undrawn yarn by 36%,
Heat treatment was performed at 0° C., and the crystallinity χ2 was set to 46 coefficients. The obtained low-oriented highly crystalline fibers were cold-stretched 16 times at room temperature to a 53 d
a/36 fils, the fibers were knitted into a tricot, and when dyed at 100°C, the dyeing was deep like rayon, and the texture was softer than rayon. In addition, when the de-stretching was carried out by contacting with a plate heater at 180°C, the obtained tricot was not dyed deeply at the dyeing temperature of 100°C and had a hard texture. In addition, even when stretched 2.1 times at low temperatures, satisfactory stiffness was not obtained, and conversely, when stretched only 12 times, elastic recovery was small, and when worn as clothes, the elbow area There was a risk that it would become weaker.

[Brief explanation of drawings]

FIG. 1 is a flow sheet schematically explaining the manufacturing process of the polyester fiber of the present invention. Figure 2 shows the degree of orientation (su) and degree of crystallinity (χ,) for various polyester fibers including the polyester fiber of the present invention.
, χ2/mu, and normal pressure dyeability. 1: Undrawn fiber bundle 1': Stretched fiber bundle 2: Roller 3: Heater 4: Roller 5: Hot water bath 6: Stretched - - roller 25 - Oj bacteria

Claims (1)

[Scope of Claims] (1) A polyester fiber whose main repeating unit is ethylene terephthalate and which contains 18O,M groups (M is an alkali metal), and whose crystallinity (χρ) is from 30 to
55chi, orientation degree (△n) is 006 to 012, and χl1
A deep dyeable polyester fiber characterized by having lAn in the range of 350 to 550. The deep dyeable polyester fiber according to claim 1, wherein the f2+ -8O,M group is an 18O,Na group. The deep dyeable polyester fiber according to claim 1, which contains 1 to 5 mole of 5-sodium sulfoisophthalic acid component based on the total acid component as a component containing +3), -8Q, and M groups. (Deeply dyed polyester fiber according to claim 3, which contains 2 to 35 mol of 5-sodium sulfoisophthalate as a 4+ -SO,M group-containing component based on the total acid component. (5) The deep-dyed polyester fiber according to claim 1, wherein xp/Δn is 400 to 500. (6) The main unit is ethylene terephthalate.
and one 8O, M S (M is an alkali metal)
The degree of orientation (ZΔn
) is O,02-008, the undrawn fibers are heat-treated in a non-tensioned state to have a crystallinity (χ2) of 30-008.
55 inch, and then drawing the crystallized fiber at a low temperature and at a rate of increase in fineness of +1.0 to 17 times during the heat treatment. +71 -8o, M group is 18O, Na group; method for producing deep dyeable polyester fiber θ according to claim 6; +81 -8 The deep dyeable polyester fiber according to claim 6, in which a polyester containing a 5-sodium sulfoinphthalic acid component in an amount of 1 to 5 mol based on the total acid component is used as the O, M group-containing component. Manufacturing method. tt+) -8O,M group-containing component is a polyester containing 2 to 35 molti of 5-sodium sulfoinphthalic acid component based on the total acid component.
A method for producing the deep-dyed polyester fiber as described in Section 1. 7. The method for producing deep dyeable polyester fibers according to claim 6, wherein the OI stressless heat treatment is carried out under an over-eid of 10% or less. (11) The method for producing deep dyeable polyester fibers according to claim 10, wherein the tensionless heat treatment is performed under an overfeed of 5% or less. (12) A method for producing deep dyed (ll-polyester fiber (1)) according to claim 6, wherein the heat treatment is carried out at a temperature of 13'O<0>C or higher. (13) The heat treatment is carried out at a temperature of 150<0>C or above (14) The method for producing a deep dyeable polyester fiber according to claim 6, wherein the drawing is carried out at a temperature below the glass transition point of the polyester fiber. (15) Linearity increase rate during heat treatment for stretching +1.1 to 1
．． A method for producing a deep dyeable polyester fiber according to claim 6, which is carried out at a magnification of 5 times.