JP2895252B2 - Polyetherester block copolymer elastic yarn - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyetherester block copolymer elastic yarn. More specifically, the present invention relates to a polyetherester block copolymer elastic yarn having excellent elastic performance and light resistance, and particularly excellent in durability without lowering elastic performance and light resistance due to dry heat treatment, wet heat treatment and the like.

[0002]

2. Description of the Related Art Conventionally, rubber, polyurethane, and the like have been used as elastic yarns, but they exhibit excellent characteristics in terms of elastic recovery, but have problems such as excessive elongation, heat resistance, and light resistance.

On the other hand, elastic materials of polyetherester block copolymer type have recently been used as resins. When this polymer is formed into a yarn, it has an elongation recovery ratio that is inferior to that of polyurethane, but has relatively good recoverability under low elongation, and has the advantage that it can be melt-spun. However, unlike the polyurethane, the polyetherester block copolymer type elastic yarn has a disadvantage that the permanent chain is large and the elastic performance is inferior because the molecular chains are anchored by the crystal of the hard segment. .

[0004] Further, polyetherester block copolymers are susceptible to photodegradation. For example, when used under conditions where they are exposed to the outdoors, their elastic performance deteriorates in a relatively short time, and There are practical problems such as coloring.

As a method for improving the performance of the elastic yarn in order to improve such a defect, for example, a method of increasing the crystallinity by blending a crystal nucleating agent (JP-A-59-45349, JP-A-59-45350). Gazette) has been proposed. However, the performance of the elastic yarn cannot be significantly improved by such a method, and the performance is still insufficient for use as an elastic yarn. In particular, when the elastic yarn is used for part / or the whole of the woven or knitted fabric, a problem is recognized in terms of durability such that elastic performance and light resistance are deteriorated during these treatments.

On the other hand, in order to improve the light resistance of the polyetherester block copolymer, a method of adding an ultraviolet absorber has been proposed. For example, a method of adding a hindered phenol compound, a hindered amine compound or the like to a polyetherester block copolymer (Japanese Patent Publication No. 52-22744), a method of blending a hindered amine compound and titanium dioxide (Japanese Patent Application Laid-open No. Sho 62-62). 19
2450). However, these methods still have a small improvement effect and pose practical problems.

[0007] In order to improve such a problem, the present inventor previously obtained a poly (hindered amine) compound, a hindered phenolic compound, a sulfur-containing ester compound, and a polystyrene obtained by combining a specified amount of inert particles. An elastic yarn made of ether ester block copolymer was proposed.
This elastic yarn has low permanent distortion, excellent elastic performance, and is durable to dry heat treatment, wet heat treatment, etc., and at the same time, light resistance is greatly improved. I do.

However, further improvements in elastic performance and light resistance,
In particular, there is a demand for an elastic yarn that can withstand dry heat treatment, wet heat treatment, and the like.

[0009]

DISCLOSURE OF THE INVENTION The present inventors have found that the drawbacks inherent in elastic yarns made of conventional polyetherester block copolymers are that they have large permanent set, poor elastic performance, and poor light resistance. As a result of intensive studies to overcome the drawbacks and the problems of durability such as deterioration of elastic performance and light resistance due to post-processing such as dry heat treatment and wet heat treatment, the intrinsic viscosity IV of the polyetherester block copolymer forming the elastic yarn was determined. When the terminal carboxyl group concentration, melting point, and molecular weight distribution are within a specific range, an elastic yarn having a durable elastic performance especially in dry heat treatment, wet heat treatment and the like is obtained, and at the same time, light resistance is greatly improved. It was found that it could be obtained.

The present inventor has conducted further studies based on such findings, and as a result, has completed the present invention.

[0011]

That is, the present invention provides:
Polycarboxylic acid component mainly composed of 2,6-naphthalenedicarboxylic acid, glycol component mainly composed of 1,4-butanediol, and poly (alkylene oxide) glycol component having an average molecular weight of about 400 to 4000 An elastic yarn comprising an ether ester block copolymer, wherein said polyether ester block copolymer simultaneously satisfies the following formulas (I) to (IV): Is provided. (I) 1.2 ≦ IV ≦ 1.7 (II) 170 ≦ Tm (III) 5 ≦ Mw / Mn ≦ 25 (IV) CV ≦ 30 [However, IV is intrinsic viscosity, Tm is melting point (° C.), Mw Indicates a weight average molecular weight, Mn indicates a number average molecular weight, and CV indicates a terminal carboxy group concentration (equivalent / 10 ⁶ g). The polyetherester block copolymer in the present invention is defined as an acid component in which 80 mol% or more, preferably 90 mol% or more of a dicarboxylic acid component is 2,6-naphthalenedicarboxylic acid or an ester-forming derivative thereof, and a glycol. Ingredient 8
0 mol% or more, preferably 90 mol% or more, is a low molecular weight glycol component which is 1,4-butanediol or an ester-forming derivative thereof, and has a molecular weight of 400 to 4000;
Preferably, it means a copolymer obtained by a polycondensation reaction with 600 to 3500 poly (alkylene oxide) glycol.

2,6- used in an amount of less than 20 mol%
Acid components other than naphthalenedicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,7-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, and 4,4′-diphenyletherdicarboxylic acid. Dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid and 1,4
-Cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and ester-forming derivatives thereof.

The low molecular weight glycol components other than 1,4-butanediol used in an amount of less than 20 mol% include ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6 -Hexanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like.

As the poly (alkylene oxide) glycol, polyethylene glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide)
And a homopolymer of poly (tetramethylene oxide) glycol, or a random copolymer or a block copolymer in which two or more of the repeating units constituting the homopolymer are copolymerized in random or block form. A polymer, or a mixed polymer obtained by mixing two or more of the above homopolymers and copolymers is used. The molecular weight of the poly (alkylene oxide) glycol used here is 400 to 4000. Average molecular weight of 4
If it is less than 00, the resulting polyetherester block copolymer has poor elasticity due to reduced blockability,
Further, it is not preferable because the melting point of the polymer becomes low, which causes a problem in durability against dry heat treatment and wet heat treatment.
On the other hand, when the molecular weight of the poly (alkylene oxide) glycol exceeds 4,000, it is not preferable because the resulting polymer is unlikely to phase-separate into a block copolymer and has poor elasticity.

The poly (alkylene oxide) glycol content in the polyetherester block copolymer is 5
It is preferably in the range of 0 to 80% by weight, and if it exceeds 80% by weight, an elastic yarn having excellent elastic performance is obtained, but the melting point of the copolymer becomes too low. In this case, the elastic performance is rapidly reduced, resulting in an elastic yarn having poor durability. If the content is less than 50% by weight,
Only an elastic yarn having a large permanent set and inferior elastic properties can be obtained.

The present inventors have studied the heat resistance of elastic yarns made of such polyetherester block copolymers, that is, the prevention of deterioration in elastic performance against dry heat treatment (160 ° C. × 1 minute). Investigations on elastic yarns made of various polyetherester block copolymers have revealed that the heat resistance of the elastic yarns does not always correspond to the melting point. Similarly, it was found that the intrinsic viscosity of the polyetherester block copolymer did not correspond simply. These findings were completely unpredictable. Therefore, as a result of a detailed analysis of the relationship between the degree of deterioration of the elastic performance to dry heat treatment and the characteristics of the polyetherester block copolymer constituting the elastic yarn, the durability of the elastic performance to dry heat treatment indicates that the elastic yarn has Viscosity (IV), melting point (Tm), molecular weight distribution (Mw / M) of the polyetherester block copolymer
n) and terminal carboxyl group concentration (CV).

Further, such a result can be obtained by the wet heat treatment (13).
It was also found that the elastic performance durability of the elastic yarn with respect to (0 ° C. × 60 minutes) and the maintenance of the light resistance of the elastic yarn with respect to the dry heat treatment and / or the wet heat treatment also exist.

In addition, as a result of quantitative analysis of these results, it was found that a polyetherester block copolymer elastic yarn having excellent durability without decreasing its elastic performance and light resistance by dry heat treatment and wet heat treatment was obtained. They have found that they can be obtained by simultaneously satisfying the following (I) to (IV). (I) 1.2 ≦ IV ≦ 1.7 (II) 170 ≦ Tm (III) 5 ≦ Mw / Mn ≦ 25 (IV) CV ≦ 30 IV of the polyetherester block copolymer constituting the elastic yarn is 1 If less than 2, the elastic yarn has a large permanent set before the dry heat treatment and the wet heat treatment, and the elastic yarn has a low elongation recovery rate and is inferior in performance as an isoelastic yarn, and the elasticity after the dry heat treatment and / or the wet heat treatment is low. Properties and light resistance are extremely low and cannot be practically used as an elastic yarn. this is,
Even if a polyetherester block copolymer satisfying the formulas (II), (III) and (IV) is used, no improvement effect is observed.

On the other hand, when the IV of the polyetherester block copolymer exceeds 1.7, the elongation of the elastic yarn is considerably reduced, and the original function of the elastic yarn to be expanded is reduced.
Further, when the IV exceeds 1.7, the Young's modulus increases, and the processing tension increases in the processing such as the warping step, which causes problems such as thread breakage. Further, when such a dry heat treatment and a wet heat treatment of the elastic yarn are performed, the elastic performance and light resistance are remarkably deteriorated, which causes a problem in practical use.

The Tm of the polyetherester block copolymer elastic yarn must be 170 ° C. or higher. Dry processing is 15 for normal polyester fiber processing.
0 to 160 ° C x 1 to 5 minutes, wet heat treatment is 110 to 135 ° C
× 40 to 60 minutes. In order to withstand such dry heat treatment and wet heat treatment and to maintain elastic performance and light resistance, the polyetherester block copolymer elastic yarn must satisfy the formulas (I), (III) and (IV). , Tm
Should be 170 ° C. or higher. When Tm is lower than 170 ° C., performance deterioration due to dry heat treatment and / or wet heat treatment is undesirably large.

The most characteristic feature of the polyetherester block copolymer constituting the elastic yarn of the present invention is that it has a more specific molecular weight distribution. That is, when the molecular weight distribution is expressed by Mw / Mn, the most important point in the present invention is to satisfy the above formula (III). When the polyetherester block copolymer elastic yarn is subjected to a dry heat treatment or a wet heat treatment, the molecular chain is more or less cut to cause deterioration. The molecular weight distribution changes with this deterioration, and Mw /
Mn increases. Therefore, the smaller the Mw / Mn, the better. However, when it is less than 5 (a polyetherester block copolymer elastic yarn having a sharp molecular weight distribution).
Although they have excellent durability against dry heat treatment and wet heat treatment, and particularly have good light resistance, they have a drawback that their elastic performance as elastic yarn is insufficient. on the other hand,
If Mw / Mn exceeds 25, the elastic performance is very good, but the durability against dry heat treatment and wet heat treatment is inferior.

In the present invention, in addition to the intrinsic viscosity, melting point, and molecular weight distribution of the polyetherester block copolymer constituting the elastic yarn, the terminal carboxyl group concentration (CV) is determined by the dry heat treatment and / or the wet heat treatment of the elastic yarn. This is an important factor for improving the durability of the elastic performance and the light resistance of the glass.
(CV) of the polyetherester block copolymer is 3
If it exceeds 0, the durability of the elastic performance against the dry heat treatment and / or the wet heat treatment decreases, and the light resistance also deteriorates.

Such a polyetherester block copolymer can be produced according to a usual method for producing a copolymerized polyester. Specifically, a dicarboxylic acid component mainly composed of 2,6-naphthalenedicarboxylic acid, a glycol component mainly composed of 1,4-butanediol, and poly (alkylene oxide) glycol are put into a reactor, and the mixture is placed in the presence of a catalyst. Alternatively, a transesterification reaction or an esterification reaction is carried out in the absence, and a polycondensation reaction is further carried out under a high vacuum to raise the degree of polymerization to a desired degree.

In the present invention, the IV, Tm, Mw / M of the polyetherester block copolymer constituting the elastic yarn
It is necessary to set n and CV within the above ranges. For that purpose, it is necessary to appropriately set the conditions of the above-mentioned polymerization reaction and use a copolymer having physical properties in consideration of a ratio which varies depending on the spinning method. IV depends on polymerization time, polymerization temperature, stirring speed, type of catalyst, addition amount, etc., the longer the polymerization time, the higher the polymerization temperature, the faster the stirring speed, and the larger the catalyst addition amount, the larger the IV. Can be.

The melting point (Tm) depends on the composition and the copolymerization amount of the hard segment, the molecular weight, the composition and the copolymerization amount of poly (alkylene oxide) glycol. Tm can be increased by forming the hard segment portion into a homopolyester or by reducing the copolymerization amount of poly (alkylene oxide) glycol.

The molecular weight distribution (Mw / Mn) can be adjusted by controlling the polymerization conditions, polymerization time, polymerization temperature, stirring speed, catalyst addition amount, catalyst type, additive, poly (alkylene oxide) as well as IV control. ) Depends on the molecular weight, copolymerization amount, etc. of the glycol. The polymerization time under a high vacuum of 1 mmHg or less is long, the polymerization time under a low vacuum of up to 30 mmHg is short, the polymerization temperature is high, the stirring speed is high, and the amount of catalyst added is large, the Mw / Mn becomes large. As the polymerization catalyst for the polyetherester block copolymer, compounds such as titanium, niobium, germanium, and antimony are usually used. Particularly, aromatic organic acid salts such as benzoic acid and trimellitic acid of titanium are used. Alternatively, the use of fatty acid salts such as oxalates and acetates is preferable because Mw / Mn can be increased. When an alkali metal compound or an alkaline earth metal compound is further added as an additive during the polymerization reaction, Mw / Mn
Can be reduced.

The alkali metal compound or alkaline earth metal compound used herein is not particularly limited, and any of the generally known compounds can be used. For example, talc, magnesium oxide, magnesium silicate, sodium stearate, stearin Barium acid, potassium benzoate, sodium terephthalate, sodium monomethyl terephthalate, sodium monomethyl isophthalate, sodium benzoate, sodium orthochlorobenzoate,
Acetates such as sodium, calcium, magnesium, potassium, etc., montanic acid and montanates composed of metals such as lithium, sodium, potassium, magnesium, calcium, aluminum, etc., and montanic acid as ethylene glycol, 1,2- or 1,3- Propanediol, 1,3
-Or a montanic acid ester salt composed of the above metal partially neutralized with an aliphatic diol such as 1,4-butanediol or the following general formula:

[0028]

Embedded image [In the formula, A is an alkyl group or an aryl group, which may contain a substituent, and M is an alkali metal or an alkaline earth metal. And a metal salt of an alkyl sulfonic acid or an aryl sulfonic acid. Among them, acetate salts of sodium and potassium, sodium, potassium, lithium or calcium salts of alkylsulfonic acids having an alkyl group having 1 to 20 carbon atoms, or sodium, potassium, lithium or calcium salts of benzenesulfonic acid and benzene nuclei thereof Preferred are those in which a reactive group such as a carboxyl group, a hydroxyl group or an amino group is substituted, those in which an alkyl group is substituted, and those in which the substituted alkyl group is substituted by the above-mentioned reactive group. Even if these alkali metal compounds and alkaline earth metal compounds are used alone,
More than one species may be used in combination.

By combining such various means, a desired Mw / Mn can be obtained.

The CV depends on the polymerization time, the polymerization temperature, the type and amount of the catalyst, the IV and other additives. The longer the polymerization time and the higher the polymerization temperature, the higher the CV. When an alkali metal compound or an alkaline earth metal compound is added as an additive during the polymerization reaction, the CV can be reduced.

The polyetherester block copolymer constituting the elastic yarn of the present invention may include a matting agent, a pigment (for example, carbon black), an antioxidant (for example, a hindered phenol type) as in the case of ordinary polyester. Compounds, hindered amine compounds, etc.), ultraviolet absorbers (for example, benzophenone compounds, benzotriazole compounds, sacylate compounds) and the like.

The polyetherester block copolymer described above can be melt-spun very easily without special means, and can be spun in accordance with a general thermoplastic polymer melt-spinning method. That is, unlike the polyurethane elastic yarn, the yarn and the single yarn denier can be arbitrarily set similarly to the ordinary polyester fiber.

The yarn obtained by melt-spinning the above block copolymer has sufficient elasticity as it is, but may be further stretched and / or heat-treated in accordance with the intended use of the elastic yarn. May be any of elongation heat treatment, fixed length heat treatment and relaxation heat treatment.

[0034]

As described above, according to the present invention,
By simultaneously setting the IV, Tm, Mw / Mn, and CV of the polyetherester block copolymer constituting the elastic yarn within a specific range, it is excellent in elastic properties and light resistance,
In particular, it is possible to provide an elastic yarn excellent in durability without deteriorating elastic performance and light resistance even by dry heat treatment, wet heat treatment and the like. Therefore, the elastic yarn of the present invention can be used for a woven or knitted fabric in which elastic performance and light resistance are important factors, and the effect is extremely large.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, all “parts” indicate parts by weight. The properties of the polyetherester block copolymer are as follows:
It was measured by the following method. 1. Intrinsic viscosity (IV) Calculated from the value measured at 35 ° C. in a 0.6 g / 50 ml orthochlorophenol solution of a polymer. 2. Melting point (Tm) The melting peak temperature was determined by measuring the temperature at a heating rate of 20 ° C./min using a thermal differential analyzer Model 990 manufactured by Du Pont. 3. Add 5 mg of Mw / Mn polymer to 0.2 of hexafluoroisopropanol.
After dissolving with 0.2 ml of chloroform and 0.2 ml of chloroform, and further diluting the total amount to 10 ml with chloroform, measurement was performed using a GPC (Waters ALC / GPC 244 type) manufactured by Waters Corporation in the range of 50 to 1,000,000 in terms of polystyrene molecular weight.
Mw and Mn were calculated. Column is MSTY manufactured by Waters
RAGEL and detector used UV254nm. This Mw and M
The molecular weight distribution index Mw / Mn was calculated from n. 4. Terminal carboxyl group concentration (CV) 0.1 g of the polymer is dissolved in 10 ml of benzyl alcohol, 10 ml of chloroform is added, and the solution is titrated with sodium hydroxide-benzyl alcohol. Use phenol red as an indicator. 5. Elongation recovery (1) Instantaneous elongation recovery rate Apply a load corresponding to 100% elongation to a 10 cm sample, quickly elongate it by 100%, remove the load after 5 seconds, quickly read the length Lcm of the sample, and use the following formula. Was calculated by Instantaneous elongation recovery rate = {[10− (L−10)] / 10} ×
100 (%) (2) Permanent strain A 10 cm long sample was left to stand for 4 hours under a load corresponding to 100% elongation, then the load was removed and the length of the sample after leaving for 4 hours L ′ cm Was measured and calculated by the following equation. Permanent strain = {(L'-10) / 10} x 100 (%) (3) Strength and elongation Using a 5 cm long sample, elongate at a pulling speed of 1000% / min. Was measured. 6. Light Resistance Tensile strength retention (%) after irradiating the elastic yarn sample with a fade meter for 40 hours was measured and calculated.

[0036]

EXAMPLES 1-10, COMPARATIVE EXAMPLES 1-9 160 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester, 100 parts of tetramethylene glycol, polytetramethylene glycol described in (Table 1), additives, and a catalyst were placed in a reactor. The transesterification reaction was carried out at an internal temperature of 190 ° C. About 80 of theoretical amount
% Of methanol was distilled off, and then a polycondensation reaction was started by raising the temperature and reducing the pressure. The polycondensation reaction was carried out while gradually reducing the pressure, and was adjusted to 30 mmHg over the time described in (Table 1).
The pressure was reduced to 3 mmHg over 0 minutes, and thereafter, the reaction was carried out under the vacuum of 1 mmHg or less at the internal temperature and time described in (Table 1).

After pelletizing with the produced polyetherester block copolymer, the pellets were dried and then dried.
C. and the polymer was extruded at a discharge rate of 3.9 g / min from a cap having a three-hole nozzle. This polymer was wound through two godet rolls at a speed of 1000 m / min to obtain an elastic yarn. The properties and performance of this elastic yarn are shown in (Table 2).

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

Claims (1)

(57) [Claims] 1. A dicarboxylic acid component mainly containing 2,6-naphthalenedicarboxylic acid, a glycol component mainly containing 1,4-butanediol, and an average molecular weight of about 400 to 400.
An elastic yarn comprising a polyetherester block copolymer having a poly (alkylene oxide) glycol component of 0 as a constituent component, wherein the polyetherester block copolymer simultaneously satisfies the following formulas (I) to (IV): A polyetherester block copolymer elastic yarn characterized by comprising: (I) 1.2 ≦ IV ≦ 1.7 (II) 170 ≦ Tm (III) 5 ≦ Mw / Mn ≦ 25 (IV) CV ≦ 30 [However, IV is intrinsic viscosity, Tm is melting point (° C.), Mw Indicates a weight average molecular weight, Mn indicates a number average molecular weight, and CV indicates a terminal carboxy group concentration (equivalent / 10 ⁶ g). ]