JPH0362808B2 - - Google Patents

Description

[Detailed description of the invention]

<Field of Application> The present invention relates to a method for producing processed polyester yarn. More specifically, the present invention relates to a method for producing polyester processed yarn that can be dyed with basic dyes, has excellent mechanical properties, and has a high crimp rate. <Prior art> Polyester fibers dyeable with basic dyes take advantage of their excellent color development, high color fastness, etc.
It has come to be widely used in training wear, etc. By the way, conventional basic dye-dyable polyesters are mainly copolymerized with sodium sulfoisophthalic acid components, but this copolymer has a higher melting point and physical properties than ordinary homopolyesters such as polyethylene terephthalate (PET). For this reason, the processing temperature during false twisting of filament yarns made of this copolymer must be 20 to 30°C lower than that of PET. In this issue, it is a woven or knitted fabric with a voluminous feel and no stiffness. On the other hand, in an attempt to obtain a high crimp rate, the heater temperature was increased,
If false twisting is carried out at the same temperature as the processing temperature of PET fibers, the strength will be reduced and in some cases fusion will occur, making the fibers stiffer. <Purpose of the invention> The present invention solves the above-mentioned problems in basic dye-dyeable polyester processed yarns, has mechanical properties, volume and stiffness comparable to those of woven and knitted fabrics of PET fibers, and has An object of the present invention is to provide a method for producing polyester processed yarn with excellent color fastness. <Structure of the Invention> As a result of various studies aimed at achieving the above object, the present inventors have found that when using a modified polyester filament yarn copolymerized with a sulfonic acid phosphonium salt instead of the conventional sodium sulfoisophthalic acid, the desired result can be achieved. The inventors have discovered that this is effective and have arrived at the present invention. Thus, according to the invention, the following general formula [Wherein 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, n is a positive integer] A polyester copolymerized with a sulfonic acid phosphonium salt represented by 1. A method for producing a polyester processed yarn, which comprises false twisting a filament yarn comprising: a False twisting number T (t/m) (20000/√)≦T≦(36000/√) Here, De is the denier of the filament yarn when passing through the false twisting tool b False twisting processing temperature H (℃) 180≦H≦ 220 is provided. The polyester in the present invention is a polyester having terephthalic acid as the main acid component and at least one type of glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as the main glycol component. The main target is It may also be a polyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/or a part of the glycol component is replaced with the above-mentioned glycol or other diol component other than the main component. It may also be polyester. The difunctional carboxylic acids other than terephthalic acid used here include, for example, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid. ，
Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. Furthermore, isophthalic acid having a metal sulfonate group such as 5-sodium sulfoisophthalic acid may be used as a copolymerization component within the range where the effects of the present invention can be substantially achieved. It is desirable to suppress the amount to less than 1.8 mol%. In addition, examples of diol compounds other than the above-mentioned glycols include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycols. I can give it to you. Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as the polyester is substantially linear. Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, usually terephthalic acid and ethylene glycol are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are transesterified. The first stage reaction is to react with terephthalic acid to produce a glycol ester and/or its low polymer, and the first stage reaction product is heated under reduced pressure until the desired degree of polymerization is achieved. It is produced by a second stage reaction of polycondensation. In the present invention, the following general formula is present in the polymer chain of the polyester. It is necessary that the sulfonic acid phosphonium salt represented by is copolymerized. In the above general formula, A is an aromatic group or an aliphatic group, and an aromatic group is preferable. X ₁ and X ₂ are ester-forming functional groups,
Examples include carboxyl group, chlorocarboxyl group, hydroxyl group, acyloxy group, etc. Preferred specific examples include

【formula】 【formula】

[Formula] (-CH ₂ ) _l OH, -O(CH ₂ )- _n -[[O(CH ₂ )- _n ]- _l OH,

[Formula] (However, R is a lower alkyl group or a phenyl group, _l
is an integer of 1 or more, m is an integer of 2 or more), etc. X ₁ and X ₂ may be the same or different. R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, alkyl groups, aryl groups,
It is a hydroxyalkyl group, preferably an alkyl group, and particularly preferably a butyl group. this
R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. Further, 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 sulfonic acid and 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. Specific examples of the sulfonic acid phosnium salts include 3,5-dicarbomethoxybenzenesulfonic acid tetramethylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, and 3,5-dicarbomethoxybenzenesulfonic acid. Tributylmethylphosphonium salt, 2,6
-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt, 2,6-dicarbomethoxybenzenesulfonic acid tetramethylphosphonium salt, and the like. In order to copolymerize the sulfonic acid phosphonium salt into the main chain of the polyester, the above-mentioned phosphonium 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 seats in the final polyester fiber, resulting in insufficient dyeability with basic dyes, and conversely, if it is too large, the softening point of the resulting polymer will be As a result, the yarn physical properties such as the mechanical properties of the final polyester fiber will deteriorate.
It is used in a range of 0.5 to 3.5 mol%, preferably 0.7 to 2.0 mol%. In order to make fibers from the basic dye-dyeable modified polyester thus obtained, it is not necessary to employ any special method, and any ordinary melt-spinning method for polyester fibers may be employed. The fibers spun here may be circular or irregularly shaped. What is important here is the intrinsic viscosity [η] _f of the filament yarn, which should be at least 0.50, more preferably at least 0.55; if it is below this, fusion will occur even at a false twisting temperature of 180°C. easy to do,
Mechanical properties tend to deteriorate significantly. Also, the occurrence of fuzz is large. On the other hand, the higher the intrinsic viscosity, the higher the crimp rate, which is preferable. 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 of the yarn obtained above is T (t/m) (20000/√)≦T≦(36000/
√) (Here, De represents the denier of the filament when it passes through the false twister.) False twisting is performed.
If the number of false twists T (t/m) is less than 20,000/√, the woven or knitted fabric obtained by weaving and knitting this will not have firm texture, while if the number of false twists T exceeds 36,000/√, fuzz will occur during false twisting. This causes the strength of the processed yarn to decrease, making it unusable for practical use. Furthermore, if the false twisting temperature is less than 180℃, the crimpability of the processed yarn will be low, while if it exceeds 220℃,
The strength decreases significantly, the fusion between the fibers becomes severe, fluffing tends to occur, and dyeing spots tend to occur, making it unusable for practical use. <Action/Effect> The reason why the crimp rate of the basic dye-dyeable polyester yarn obtained in this manner is higher than that of the conventional polyester yarn copolymerized with a sodium sulfoisophthalic acid component. Although the full details have not been elucidated, it is presumed that this is due to the following mechanism. That is, when a sodium sulfoisophthalic acid component is copolymerized into polyester as a modifier, the interaction between the modifiers is high, and therefore the melt viscosity decreases despite the low degree of polymerization (low intrinsic viscosity). tends to increase, and spinnability tends to deteriorate. Generally, in most cases of copolyester polyester containing sodium sulfoisophthalic acid component, the intrinsic viscosity is less than 0.5. In the case of polyester with such a low degree of polymerization, there is a large amount of low molecular weight components such as oligomers, which act as plasticizers when exposed to high temperatures, and tend to cause plasticization and fusion of fibers. In particular, the sodium sulfoisophthalic acid component, which has strong intermolecular interactions, is polymerized while still associated during polyester polymerization, so oligomers containing a large amount of the sodium sulfoisophthalic acid component are likely to be generated, leading to plasticization and fusion. Easy to progress. On the other hand, in this polymer, since the ionic components are covered with sublime groups, namely R ₁ , R ₂ , R ₃ , and R ₄ , it is possible to greatly reduce the ionic properties, and the melt viscosity It is possible to avoid the phenomenon of an abnormal increase in the amount of the polymer, a polymer with a high degree of polymerization can be obtained, and therefore the amount of the oligomer component can be significantly reduced. On the other hand, the generation of oligomers containing a large amount of cationic dyes, which tends to occur with the sodium sulfoisophthalic acid component, is also suppressed.
Even if the number of moles of the modifier required for cationic dyeability is set to a low value, the dyeing density can be maintained.
For these reasons, the polymer in the present invention is
A sufficiently high degree of polymerization is ensured with few oligomers,
Uniform characteristics can be obtained. Therefore, even in the false twisting process, it is presumed that the deformation caused by false twisting does not undergo plastic deformation entirely, but that the deformation can be partially retained, resulting in a high crimp rate. This mechanism can also be estimated from the limit temperature of woolly processing temperature. For example, even when polyester is copolymerized with an equal amount of modifier, strength deterioration occurs only at a higher woolly processing temperature of 10°C to 30°C than when copolymerizing with sodium sulfoisophthalic acid. The phenomenon also supports the above estimation. That is, although there is a difference in the crimp rate between the two even under the same woolly processing conditions, the polyester of the present invention has the advantage that the processing temperature can be further increased, and as a result, a higher crimp rate can be obtained. Therefore, using the polyester processed yarn according to the method of the present invention, it is possible to produce polyester products having innovative performance in the clothing field or the interior decoration field. <Examples> Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples. Note that the intrinsic viscosity [η] _f is measured as follows. The intrinsic viscosity [η] is given by lim ^c → ⁰ {ln(ηrel)}/c and is a value obtained by measuring as follows. That is, ηrel is the ratio of the viscosity of a dilute polyester solution using orthochlorophenol as a solvent to the viscosity of the above-mentioned molten resin measured at the same temperature and in the same units, and c is
100c.c. is the number of grams of polyester in the mixture. Examples 1 to 6 and Comparative Examples 1 to 7 100 parts of dimethyl terephthalate, 66 parts of ethylene glycol, 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt in the amounts listed in Table 1 (range 0 to 4.3 parts) It was carried out by changing the amount.
The range of this amount is 0 for dimethyl terephthalate.
This corresponds to a range of ~3.5 mol%. ), 0.03 parts of manganese acetate tetrahydrate (based on dimethyl terephthalate)
0.024 mol %) was charged into a transesterification tank, and the temperature was raised from 140°C to 230°C over 4 hours under a nitrogen gas atmosphere, and the transesterification reaction was carried out while the methanol produced was distilled out of the system. Subsequently, 0.03 part of a 56% aqueous solution of orthophosphoric acid (0.033 mol% relative to dimethyl terephthalate) and 0.04 part of antimony trioxide (0.027 mol%) were added to the obtained product, and the mixture was transferred to a polymerization vessel. Then 1mm from 760mmHg over 1 hour
The pressure was reduced to Hg, and at the same time the temperature was raised from 230°C to 280°C over 1 hour and 30 minutes. Polymerization was carried out under reduced pressure of 1 mmHg or less at a polymerization temperature of 280° C. until the intrinsic viscosity shown in Table 1 was reached. Table 1 shows the intrinsic viscosity of the obtained polymer. The obtained polymer is dried by a conventional method, and the pore diameter is
The material was melted at 300°C using a spinneret with 24 circular spinning holes of 0.25 mm, drawn at a drawing speed of 1500 m/min, and drawn in a conventional manner to obtain a raw yarn of 75 denier and 24 filaments. Ta. Next, the original yarn was false-twisted at a number of 3380t/m using a false-twisting machine.
False twisting was carried out by adjusting the tension at the entrance of the false twisting tool to approximately 20 g and varying the false twisting temperature. On the other hand, for comparison, a polymer copolymerized with a sodium sulfoisophthalic acid component was used, and spinning-drawing-false twisting was performed in the same manner as above.

[Table] *Fusion between single yarns Comparative Example 1 has no basic dye deposition and is not dyeable. In Comparative Example 2, the amount of the agent added was as high as 4 mol %, there was slight fusion between the single yarns, and the crimp rate and yarn strength were insufficient. Comparative example 3 has a low intrinsic viscosity;
Even at the woolly processing temperature of 210°C, fusion between single yarns occurred, and both yarn strength and crimp rate were significantly reduced. Comparative Example 4 has an insufficient crimp rate due to insufficient processing temperature. On the other hand, in Examples 1 to 6, the yarn strength of the processed yarns is high, the crimp rate is over 20%, and the dyeability with basic dyes is also sufficient. Comparative Examples 5 to 7 show examples in which sodium dimethyl sulfoisophthalate, which has been conventionally used as a cationic dye agent, is copolymerized, but the crimp rate and yarn strength are insufficient.

Claims (1)

[Claims] 1. The following general formula [wherein A is an aromatic or 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 is a positive integer.] A method for producing a polyester processed yarn, which comprises false twisting a filament yarn having an intrinsic viscosity of 0.5 or more under the following processing conditions a and b. a False twisting number T (t/m) (2000/√)≦T≦(36000/√) Here, De is the denier of the filament yarn when passing through the false twisting tool b False twisting processing temperature H (℃) 180≦H≦ 220 2 Claim 1, wherein the copolymerized amount of the sulfonic acid phosphonium salt is 0.5 to 3.5 mol% based on the bifunctional carboxylic acid component constituting the polyester.
A method for producing polyester processed yarn as described in Section 1. 3. The method for producing a polyester textured yarn according to claim 1 or 2, wherein R ₁ , R ₂ , R ₃ and R ₄ in the general formula representing the sulfonic acid phosphonium salt are butyl groups. 4. The method for producing a processed polyester yarn according to any one of claims 1 to 3, wherein the polyester is a polyester whose main constituent unit is ethylene terephthalate.