JPS63159537A - Spun like false twisted two-layerd structural yarn - 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] <Industrial Application Field> The present invention provides a false twisted two-layer structured yarn (composite wound yarn) having a spun-like appearance with a natural-like heathered color effect and ff1 go.
It is related to.

<Prior art> Generally, when two or more types of yarns with different elongations are combined, fed to a supply roller, and twisted with a false twisting spindle, the yarns with lower elongation are difficult to stretch, so the yarn Since the yarns that make up the core and have a high elongation are easy to stretch, they are twisted so as to surround the outer layer of the yarn.

This twisted yarn state is heat-set and then untwisted to obtain a false-twisted two-layer structured yarn in which yarns with low elongation act as a core and yarns with high elongation surround the core in an alternately twisted manner. . Spunlike false-twisted two-layer structured yarn obtained by such a method has already been described in Japanese Patent Publication No. 59-21970, for example.
No. 61-19733.

On the other hand, with the recent return to fashion for natural materials, there has been a demand for materials that have a texture closer to that of natural materials. In particular, there is a high demand for the heathered color effect of natural materials. By the way, in accordance with the above-mentioned proposal by Tokkosho, the core is composed of a polyester filament yarn dyeable with cationic dyes copolymerized with the conventionally used 5-sodium sulfoisophthalic acid, which is not dyeable with ordinary cationic dyes (for example, with disperse dyes). The two-layer yarn with a sheath of polyester filament yarn (which can only be dyed) has a spun-like appearance that is very similar to natural heather.
I have 1!1 go. However, this two-layer structure yarn
The strength is weak, such as the strength of multifilament,
Not only does it require very careful handling when knitting 6-knit fabrics of less than 1 g/denier, but the tear strength of the fabrics produced in this way is low, making them difficult to put into practical use. It turned out that it wasn't.

<Purpose of the invention> The present invention is a heathered color in which the 8th side is cationically dyeable.

To provide a polyester two-layer structure yarn having a spun-like appearance and feel and having sufficient strength to withstand practical use.

<Structure of the Invention> As a result of various studies aimed at achieving the above object, the inventors of the present invention have found that: ・In place of the conventional sodium sulfoisophthalic acid, phosphonium sulfonate salt was copolymerized on the 8 side of the two-layer yarn. The inventors have discovered that the desired effects can be achieved when using modified polyester filament yarns, and have arrived at the present invention.

Thus, according to the present invention, in a spunlike false twisted two-layer structured yarn in which a core filament yarn is covered with a sheath yarn, the core filament is composed of the following cationic dyeable polyester. A heathered, spunlike, false-twisted two-layer structured yarn [cationic dye dyeable polyester] characterized by or different ester-forming functional groups, R+, R2, R
3 and R4 are the same or different groups selected from a hydrogen atom, an alkyl group, an aryl group, and a hydroxyalkyl group, n
represents a positive integer] A polyester having an intrinsic viscosity of 0.5 or more, which is obtained by copolymerizing a sulfonic acid phosphonium salt represented by the following is provided.

The polyester referred to in the present invention has terephthalic acid as the main acid component and at least one glycol, preferably at least one fullkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as the main glycol component. The main target is polyester.

It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/
Alternatively, it may be a polyester in which part of the glycol component is replaced with the above-mentioned glycol or other diol component other than the main component.

Examples of the difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarbonate diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid. Adipic acid. Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as sebacic acid and 1,4-cyclohexane dihruboxylic acid. Further, in the 8-side polyester, as long as the effects of the present invention are substantially achieved, isophthalic acid having a metal sulfonate group such as 5-s]-lium sulfoisophthalic acid may be used as a copolymerization component; In this case, it is desirable to keep the amount used to less than 1.8 mol% based on the terephthalic acid component.

Examples of diol compounds other than the above-mentioned glycols include cyclohexane-1,4-dimetatool, neopentyl glycol, and bisphenol A.

Examples include aliphatic, alicyclic, and aromatic diol compounds such as bisphenol S, and polyoxyalkylene glycols.

Additionally, polycarboxylic acids such as trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane to the extent that the polyester is substantially linear.

Polyols such as pentaerythritol can be used.

Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, it is usually a direct esterification reaction between terephthalic acid and ethylene glycol, a transesterification reaction between a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or a transesterification reaction between terephthalic acid and ethylene glycol. A first step reaction involves reacting with ethylene oxide to produce a glycol ester of terephthalic acid and/or a low amount polymer thereof, and a desired degree of polymerization is achieved by heating the first step reaction product under reduced pressure. It is produced by a second stage reaction of polycondensation.

In the present invention, it is necessary that a sulfonic acid phosphonium salt represented by the following general formula % is copolymerized into the polymer chain of the polyester filament on the 8 side of the two-layer yarn. In the above general formula, A is an aromatic group or an aliphatic group, and an aromatic group is preferable. x1 and x2 are ester-forming functional groups, examples of which include carboxyl group, chlorocarboxyl group, hydroxyl group, acyloxy group, etc., and a preferred specific example is (C)uOH.

0(C112±1-10〇(CH2s1-Land OH.

C [0 (CH2 - 1 "-yunhro to 1 (however, R
represents a lower alkyl group or a phenyl group, 1 represents an integer of 1 or more, and m represents an integer of 2 or more. This X+ and x2 may be the same or different. R+ + R2*R3 and R4 are hydrogen atoms, an alkyl group, an aryl group, a hydroxyalkyl group,
Alkyl groups are preferred, and butyl groups are particularly preferred. R+, R2, R3, and R4 may be the same or different. Also, n is a positive integer, usually 1
Or 2.

Such sulfonic acid phosphonium salts can generally be easily synthesized by reacting the corresponding sulfonic acid with phosphines or by reacting the corresponding sulfonic acid metal salt with phosphonium halides. When synthesizing from a sulfonic acid and a phosphine, it is not necessarily necessary to isolate the salt, and the corresponding sulfonic acid and phosphine may be added to the polyester to be modified to generate a salt within the polyester reaction system. However, when synthesizing from a sulfonic acid metal salt and a phosphonium halide, the inorganic salts produced have negative effects, such as lowering the softening point due to excessive side reactions and making it impossible to increase the degree of polymerization. It must be added to the polyester after sufficient salt removal.

A specific example of the sulfonic acid phosphonium salt is 3.5
-Dicarbomethoxybenzenesulfonic acid tetramethylphosphonium salt, 3.5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3.5-dicarbomethoxybenzenesulfonic acid tributylmethylphosphonium salt, 2.6-dicarbomethoxynaphthalene - 4-
Sulfonic acid tetra, butylphosphonium salt, 2,6-
Examples include dicarbomethoxybenzenesulfonic acid tetramethylphosphonium salt.

In order to copolymerize the sulfonic acid bosphonium salt into the main chain of the polyester, the above-mentioned bosphonium salt can be copolymerized at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the first stage reaction is completed. Just add the compound. In this case, if the amount used is too small, there will be insufficient dyeing seat in the polyester fiber obtained in terms of Rfn, resulting in insufficient dyeability for basic dyes, and conversely, if it is too large, the softening point of the obtained polymer will be 0.5 to 3.5 mol % based on the bifunctional carboxylic acid component constituting the polyester fiber, as this results in a decrease in the fiber properties such as mechanical properties of the polyester rata ultimately obtained.
, preferably in a range of 0.7 to 2.8 mol%.

In order to make a fiber from the basic dye-dyeable modified polyester obtained in this way, it is not necessary to employ any special method, and a normal melt-spinning method for polyester IN can be arbitrarily employed. The fibers spun here may be circular or irregularly shaped.

The important thing here is that the intrinsic viscosity of the core filament yarn [
η'If (measured at 30°C in ortho-chlorophenol), the value is 0.50 or more (more preferably 0.5
If it is less than this, the strength of the two-layered yarn remains at a low level, and when it is made into a woven or knitted fabric, its tear strength will not be suitable for practical use. On the other hand, there is no particular limitation on the intrinsic viscosity of the sheath filament yarn as it does not contribute to the strength of the multifilament, but in order to prevent it from falling off due to friction etc. after becoming a two-layered yarn, the intrinsic viscosity should be 0.
45 or more, more preferably 0.5 or more. Furthermore, in the present invention, the polyester is a matting agent 9 coloring agent.

It may contain additives such as flame retardants.

A typical example of the false twisted two-layer structured yarn according to the present invention has a core yarn 1 surrounded by two sheath yarns (wound yarns) as shown in FIG.
Refers to those in which the threads are wound alternately in the form of twisted threads. Such a false-twisted two-layer structured yarn has a portion in which the constituent filaments of the core yarn and the wound yarn are intertwined with each other, thereby stably maintaining the alternately twisted yarn-like wound structure. There is a characteristic that

By the way, such a false twisted two-layer structured yarn (composite yarn) is produced by a process of intertwining raw yarns (filament yarns) with different elongations, a process of creating a 21111'!5 yarn structure by heating the intertwined yarns, and a process of unraveling it. It consists of a step of twisting the material into a two-layered structure with alternating twisting and winding.

This embodiment will be explained with reference to FIG. 2. Two yarns 3 and 3' having different elongations are combined in a guide 4 and then placed in a tension adjustment device @5. The yarn is fed through a feed roller 6 to an air jet nozzle 7 for interlacing, where it is turned into an interlaced yarn having 20 or more interlacing points. Next, this intertwined yarn is supplied to a drawing false twisting zone by a first delivery roller 8, passes through a heater 9° false twisting tool 10, is taken off by a second delivery roller 11, and is then wound up as cheese 13. In the above example, a circumferential friction false twisting tool is shown as the false twisting tool, but with this false twisting tool, a uniform double-layered false twisted yarn can be obtained at high speed.

A typical combination of two or more types of filament yarns in the present invention is that the yarn with lower elongation has at least 1.0
Use a yarn that can be stretched and false-twisted five times or more, and a yarn with a high elongation that can be further elongated by 80% or more compared to the original yarn. Most preferably, the less elongated yarn is 100%
A partially oriented filament yarn having an elongation of 1.4 f8 or more and a draw ratio of 1.4 f8 or more is used in combination with an undrawn yarn having a high elongation of more than 250%.

Further, although the undrawn yarn and the partially oriented yarn may have the same filament cross-sectional shape, the content of the matting agent, the presence or absence of the coloring agent, etc., at least one of these may be made different.

The denier of the undrawn yarn and the partially oriented yarn should be selected depending on the intended use, but it is generally preferable that the total denier be greater than or equal to the core yarn.

The raw yarn to be subjected to the false twisting process may be a drawn yarn that has undergone a melt-spinning-drawing process, or may be an intermediately oriented yarn (POY) wound at a spinning speed of about 3000 m/min.

When this intermediately oriented yarn is used, drawing and false twisting can be performed simultaneously, which is advantageous in reducing costs.

Next, the yarn thus obtained is subjected to false twisting or stretching false twisting. In other words, the number of false twists T (t/
g) (20,ooO/r■τ)≦T≦(36,0
False twisting is performed using (TfT). False twist number T (t/l) is 20,000/F
If the number of false twists T exceeds 36,000/fl, fuzz will occur during the false twisting process, and the strength of the textured yarn will deteriorate. and becomes unusable for practical use.

Furthermore, if the false twisting temperature is less than 160°C, the crimpability of the processed yarn will be low, while if it exceeds 220°C, fusion between fibers will occur and the texture will become hard, which is not preferable.

Of course, the spun-like two-layer structure yarn that is the subject of the present invention is not limited to the above-mentioned yarns, but may also include materials known as two-layer structure yarns that similarly exhibit a spun-like texture, such as Japanese Patent Application Laid-Open No. 55 -76128 publication.

Special Publication No. Sho 61-19728, Special Publication No. Sho 59-2197
Publication No. 0.

As shown in Japanese Patent Publication No. 59-39526, (a) a filament yarn with a low elongation is used as a core component, and filament yarns with a higher elongation than the filament yarn are wound around the filament yarn as a sheath component in an alternately twisted form; The winding portion forming the outer layer portion and the intertwined core portion formed by mixing and intersecting both yarns are alternately arranged along the yarn axis direction, and there are no loops or slacks on the yarn surface. Existing spun-like two-layer structured yarn [0] Alternately twisted yarn-like wrapped yarn in which the core component and sheath component are not entangled (/ Furthermore, by post-entangling the processed yarn of (0), the core component and False twist 2 with a cross section formed between the sheath component
Layer Structure Yarn [Function] According to the invention, the desired false-twisted two-layer structure yarn can be obtained as a result of the interlacing treatment applied to the raw yarn, in combination with the characteristics of the raw yarn used. In other words, it is clear that the strength of the multifilament depends mainly on the core fibers in order to obtain yarns with sufficient elongation differences. By the way, most conventional polyesters dyeable with cationic dyes are copolymerized with 5-sodium sulfoisophthalic acid as a modifier, but this modifier has a large ionic interaction, so When the degree of polymerization increases, the melt viscosity rapidly increases, making melt spinning difficult. Therefore, in cationic dye-dyeable polyester copolymerized with 5-sodium sulfoisophthalic acid, the degree of polymerization (i.e., intrinsic viscosity) must be kept at a low value, and the intrinsic viscosity is generally 0.4 to 0.4. 0.5 is adopted. Therefore, when such polymers are used to form filament yarns, only low strength ilM can be obtained. Furthermore, when this is used as the core yarn of the above-mentioned false twisted 21i structured yarn, the strength of the entire false twisted yarn depends on the core yarn, so only a false twisted yarn with even lower strength can be obtained, making it unsuitable for practical use. It becomes a thing. On the other hand, in the present invention, no abnormal increase in melt viscosity was observed in the modified polyester copolymerized with sulfonic acid phosphonium salt,
Therefore, it is possible to sufficiently increase the intrinsic viscosity even with a melt viscosity that can be melt-spun, and therefore it is possible to make a false-twisted yarn with sufficient strength even in a heathered two-layer structure yarn with core IIN, which has both strength and texture. It is possible to obtain heathered spun-like yarn that satisfies both of the following.

Furthermore, it was surprisingly found that in modified polyester copolymerized with sulfonic acid phosphonium salt having such a high intrinsic viscosity, no strength deterioration occurred even if the processing temperature was set high during false twisting. . The reason for this is not fully elucidated, but it is thought to be as follows. Polyester is produced by an ester condensation polymerization reaction, and contains components ranging from low molecular weight to high molecular weight components. By the way, low molecular weight components, such as dimers.

It is obvious that an oligomer component with a low degree of polymerization, such as a trimer, acts as a plasticizer for the polymer component. When conventional sodium sulfoisophthalate is copolymerized,
The intrinsic viscosity is kept low, and this cationic dye-dyed polyester contains a low molecular weight substance, that is, a plasticizer component.

Furthermore, since sodium sulfoisophthalate has a large interaction between ions, it is likely that the agent exists in an associated state, and therefore contains multiple oligomers containing a large amount of the agent. This can be easily confirmed by an oligomer extraction test using a poor solvent.

Therefore, even if a sufficiently high value is obtained, the polymer melting temperature of this polyester (i.e., the polymer melting temperature measured in a static state without polymer flow) is
In dynamic deformation such as false twisting, that is, deformation in which temperature is applied while twisting, plasticization by the plasticizer component becomes significant, and flow deformation occurs from a relatively low temperature, resulting in strength deterioration.

Therefore, if the copolymerization of sodium sulfoisophthalic acid is reduced to suppress the increase in melt viscosity and increase the intrinsic viscosity, the crimp properties can be improved, but the copolymerization 1 of the agent must be kept at 1.0 mol% or less. Unavoidably, the dyeability with cationic dyes becomes very low, and the effect of lowering the oligomer is slight, and the false-twisting temperature can only be raised slightly.

In particular, the heathered tone of the thread is due to the m color due to cationic dyes, and the natural tone due to its sharpness, and a decrease in dyeability significantly reduces its commercial value.

On the other hand, in the polymer of the present invention copolymerized with a bosphonium sulfonate salt, the ions are R1+ R2*R3, R4
Because it is covered with groups, its ionic opening force is weak, and it exhibits polymerization behavior similar to that of the terephthalic acid component, resulting in a significant decrease in oligomer trough (oligomer extraction test using a poor solvent). In addition, the intrinsic viscosity can be easily increased, the amount of low molecular weight substances produced can be suppressed, and these effects together prevent plasticization at low temperatures and enable false twisting at high temperatures.
A crimp characteristic, that is, a spun-like property can be obtained.

[Effect] According to the present invention, since the filaments in the outer layer have a loose structure with high elongation, a sulfonic acid phosphonium salt is copolymerized on the 8 side of a spun-like two-layer structure yarn with an extremely flexible texture. By using a modified polyester having a high intrinsic viscosity, it is possible to obtain a vA knitted fabric with a natural-like heather and a sufficient level of strength.

[Example] Actual droplet example-1 Elongation 12 obtained by spinning at a speed of 3500 m/min
Intrinsic viscosity obtained by copolymerizing 2.6 mol% of 0% tetrabutylphosphonium sulfoisophthalic acid [ηconi 0.
61, polyethylene terephthalate filament yarn (116d/24fils) with a softening point of 254°C and a speed of 1
Polyester filament yarn (220d/72f'+I) with an intrinsic viscosity of 0.62 and without copolymer components with an elongation of 350% obtained by spinning at 500 m / min
After aligning them, they are intertwined and stretched and false-twisted in the process shown in Figure 2. One.

Overfeed rate 0.5 due to interlaced nozzle
%, a compressed air pressure of 4 Kg/aA gave 42/711 entanglements, and then the stretching ratio was 1.55 times and the number of false twists was 2500.
T/Jl, heater temperature 170℃, yarn speed 35017L
/ Stretched and false twisted with win. Here, in order to increase the processing speed, a circumferential friction false twisting device was used as the false twisting device.

The processed yarn thus obtained has a uniform alternately twisted two-layer structure as shown in Fig. 2, and the yarn (elongation r!1.
39%, [77] r-o, 57) The yarn had partial entanglement (entanglement points: 28 pieces/M) with the yarn (elongation: 84%) constituting the outer layer. The yarn thus obtained had a strength of 2.5 g/denier, and when it was woven, there were no problems such as neps or yarn breakage during the weaving process. The fabric also had a spun-like and soft texture. The tear strength of the fabric was also sufficient, and a natural-looking heather was obtained.

Comparative Example-1 Elongation 11 obtained by spinning at a speed of 3150 m/min
Intrinsic viscosity [η] = 0.47 obtained by copolymerizing 2.6 mol% of 8% 5-sodium sulfoisophthalic acid.

Polyethylene terephthalate filament yarn (t18d/24filS) with a softening temperature of 254℃ and a speed of 1500℃
Polyester filament yarn (220d/72fil), which does not contain copolymer components and has an intrinsic viscosity of 0.63 and has an elongation of 350% obtained by spinning at m/min, is aligned to form a second
Entanglement treatment and stretching false twisting were performed in the steps shown in the figure.

Overfeed rate 0.5 due to interlaced nozzle
%, a compressed air pressure of 4 Kg/cd was used to impart 40 entanglements/m, followed by stretching at a stretching ratio of 1.55 times and a number of false twists of 2500 T/m.
The fibers were drawn and false-twisted at a heater temperature of 170° C. and a yarn speed of 350 m/min. Here, in order to increase the processing speed, a circumferential friction false twisting device was used as the false twisting device. The processed yarn thus obtained had a lot of fluff, and yarn breakage occurred frequently during the false twisting process, making it difficult to secure a sample in a jar. The strength of the yarn at this time was very low at 0.64 g/d.

Therefore, when the heater temperature was lowered to 160° C. and false twisting was performed under the same conditions as described above to obtain a processed yarn, there was almost no yarn breakage during false twisting, and the yarn was in good condition with little fuzz. The strength of the thread is 1
．． 1g/de, and when weaving using this thread, %J
I! Problems such as yarn breakage occasionally occurred during the process, and the resulting fabrics also had somewhat insufficient spun-like properties, and the tear strength was low and remained at a level that would pose a practical problem.

Example-2 Intrinsic viscosity [η] = 0.5 obtained by copolymerizing 2.6 mol% of tetrabutylphosphonium sulfoisophthalic acid with an elongation of 122% obtained by a spinning speed of 3600 m/min.
4. Polyester filament yarn (220d/72fi) with an intrinsic viscosity of 0.63 that does not contain copolymer components and has an elongation of 350% obtained by spinning a polyethylene terephthalate yarn (117d/24fils) with a softening temperature of 253°C and a speed of 1500m/min. Example-1 by aligning Is)
False twisting was performed under the same conditions as above.

The processed yarn thus obtained has an alternately twisted two-layer structure as shown in FIG. 2, and constitutes a core portion. Yarn (elongation 35%,
ηf = 0.5), yarn forming the outer layer (elongation 8
The yarn had partial interlacing (interlacing I: 8 degrees, 25 strands/M). The yarn strength thus obtained was 1.7
7/denier, and when weaving using this yarn, there were no problems such as naps or yarn breakage during the weaving process, and the resulting fabric also had a spun-like and soft texture, making it suitable for fabrics. The tear strength was also sufficient, and a natural-looking heather was obtained.

[Brief explanation of the drawing]

FIG. 1 is an enlarged side view showing the yarn structure of the spun-like two-layer yarn of the present invention, and FIG. 2 is a schematic diagram showing one embodiment of the apparatus for producing the two-layer W4 yarn of the present invention. 1: Yarn with lower elongation (core yarn). 2: Thread with higher elongation (sheath thread). 3.3': Raw yarn, 4 guides, 5: Tension device. 6: Feed roller, 7: Interlace nozzle. 8: First delivery roller, 9: Heater. 10: false twisting tool, 11: second delivery roller.

Claims (2)

[Claims] (1) A spun-like false twisted two-layer structured yarn in which a core filament yarn is covered with a sheath yarn, characterized in that the core filament is composed of the following cationic dye-dyable polyester. A heathered spun-like false twisted two-layer structured yarn. [Cationic dye dyeable polyester] The following general formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, A is an aromatic group or an aliphatic group, X_1 and X_2
are the same or different ester-forming functional groups, R_1, R_
2, R_3 and R_4 are the same or different groups selected from a hydrogen atom, an alkyl group, an aryl group, and a hydroxyalkyl group, and n represents a positive integer.] Polyester with a viscosity of 0.5 or more (2) A spun-like false twisted two-layer structured yarn, in which a filament yarn dyeable with a cationic dye with a small elongation constitutes the core, and a filament yarn undyed with a cationic dye and a filament yarn with a higher elongation than the filament yarn. A patent in which the core is surrounded by alternately twisted threads to form an outer layer, and at the boundary between the core and the outer layer, parts of both filament threads are mixed and intertwined with each other to form an intertwined part. A heathered spun-like false twisted two-layer structured yarn according to claim (1).