JP2928574B2 - Polyetherester block copolymer elastic yarn - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyetherester block copolymer elastic yarn. More specifically, the present invention relates to a polyester ether block copolymer elastic yarn having excellent elastic performance and light fastness, and particularly excellent in durability without deteriorating elastic performance and light fastness due to dry heat treatment and wet heat treatment.

<Prior 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, an elastic body of a polyetherester block copolymer type has recently been used as a resin application,
When formed into a yarn, this polymer has an elongation recovery ratio that is inferior to that of polyurethane, but has relatively good recovery properties 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 drawback that the permanent chains are large and the elastic performance is inferior because the molecular chains are anchored by hard segment crystals. .

In addition, the polyetherester block copolymer is extremely susceptible to light degradation, for example, when used under conditions such as outdoor exposure, the elastic performance is reduced in a relatively short time, and coloration occurs. There are practical problems.

As a method of 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 and JP-A-59-45350) is known. 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, conventionally, a method of adding an ultraviolet absorber has been proposed in order to improve the light resistance of the polyetherester block copolymer. 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. 52-22)
744) and a method of blending a hindered amine compound and titanium dioxide (Japanese Patent Application Laid-Open No. 62-192450). However, these methods still have a small improvement effect and pose practical problems.

The present inventor has sought to improve such a problem by previously blending a specific amount of a hindered amine compound, a hindered phenol compound, a sulfur-containing ester compound, and inert particles, and a polyether ester block obtained by blending in a specific amount. An elastic yarn composed of a 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, there is a demand for an elastic yarn that can be further improved in elastic performance and light resistance, especially resistant to dry heat treatment, wet heat treatment and the like.

<Problems to be Solved by the Invention> The present inventors have found that a drawback inherent in elastic yarns made of a conventional polyetherester block copolymer, namely, large permanent strain, poor elastic performance, and poor light resistance. As a result of extensive studies to overcome the disadvantages of durability, such as the deterioration of elastic performance and light resistance due to post-processing such as dry heat treatment and wet heat treatment, the polyetherester block copolymer constituting the elastic yarn is formed. When the molecular weight distribution of the poly (alkylene oxide) glycol component is in a specific range and the concentration of terminal carboxyl groups of the polyetherester block copolymer is lower than a specific value, particularly when the dry heat treatment or the wet heat treatment is performed. It has been found that a durable elastic performance can be obtained, and at the same time, an elastic yarn having significantly improved light resistance can be obtained.

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

<Means for Solving the Problem> That is, the present invention provides a dicarboxylic acid component mainly composed of terephthalic acid, a glycol component mainly composed of 1,4-butanediol, and a poly (number average molecular weight of about 1,000 to 3,000). An alkylene oxide) glycol component as a component, and a poly (alkylene oxide) glycol component having a content of
In an elastic yarn comprising 50 to 80% by weight of a polyetherester block copolymer, the number average molecular weight and the weight average molecular weight of the poly (alkylene oxide) glycol component satisfy the following formula (I), and 1.8 ≦ w / n + 2 × 10 ⁻⁴ n ≦ 2.0 (I) [where, w represents a weight average molecular weight, and n represents a number average molecular weight. At the same time, of the polyetherester block copolymer,
An object of the present invention is to provide a polyetherester block copolymer elastic yarn having a terminal carboxyl group concentration of 25 equivalents / 10 ⁶ g or less.

The polyetherester block copolymer in the present invention is at least 80 mol% of the dicarboxylic acid component, preferably
An acid component in which 90 mol% or more is terephthalic acid or an ester-forming derivative thereof, and a low molecular weight in which 80 mol% or more, preferably 90 mol% or more of a glycol component is 1,4-butanediol or an ester-forming derivative thereof. It means a copolymer obtained by a polycondensation reaction with a glycol component and a poly (alkylene oxide) glycol having a number average molecular weight of 1,000 to 3,000.

Acid components other than terephthalic acid used in an amount of less than 20 mol% include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecane diacid and alicyclic dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid and the like; And an ester-forming derivative thereof.

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-hexane. Examples thereof include diol, diethylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol.

Examples of the poly (alkylene oxide) glycol include polyethylene glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, and the like, and preferably poly (tetramethylene oxide) glycol is used. The poly (alkylene oxide) glycol used here has a number average molecular weight of 1,000 to 30.
00. If the number average molecular weight is less than 1,000, the resulting polyetherester block copolymer will have poor blockability, resulting in inferior elasticity, and will have a low polymer melting point, causing a problem in durability against dry heat treatment and wet heat treatment. Therefore, it is not preferable. On the other hand, if the molecular weight of the poly (alkylene oxide) glycol exceeds 3,000, the resulting polymer is unlikely to be phase-separated into a block copolymer,
It is not preferable because of poor elastic performance.

The content of poly (alkylene oxide) glycol in the polyetherester block copolymer is 50 to 80% by weight.
When the content exceeds 80% by weight, an elastic yarn having excellent elastic performance can be obtained, but the melting point of the copolymer is too low. Decreases rapidly, resulting in an elastic yarn having poor durability. On the other hand, if it is less than 50% by weight, only an elastic yarn having a large permanent strain and inferior elastic properties can be obtained.

The present inventor has determined that the heat resistance of the elastic yarn made of such a polyetherester block copolymer, that is, the dry heat treatment (16
(0 ° C x 1 minute) and to prevent the deterioration of elastic performance against wet heat treatment (130 ° C hot water x 60 minutes), especially the molecular weight of poly (alkylene oxide) glycol constituting the polyetherester block copolymer As a result of analyzing the relationship between the distribution and the properties of the polyetherester block copolymer, the durability of the elastic performance to dry heat treatment and wet heat treatment is determined by the concentration of terminal carboxyl groups of the polyetherester block copolymer constituting the elastic yarn. And poly (alkylene oxide) glycol were found to be closely related to the molecular weight distribution. As a result of further detailed examination, the light resistance (strength retention) after dry heat treatment and wet heat treatment was 40%.
% Or more, the molecular weight distribution index w / n of the poly (alkylene oxide) glycol is such that the terminal carboxyl group concentration of the polyetherester block copolymer is 25 equivalents / 1.
Under 0 ⁶ g or less, and finding that there is a need to reduce as much as n is higher w / n, further result of quantitative analysis of this relationship, in order to obtain a good elastic yarn in light resistance,
It has been found that it is important to satisfy the following expression (I).

1.8 ≦ w / n + 2 × 10 ⁻⁴ n ≦ 2.0 (I) Further, the result of the analysis of the relationship between the result of the formula (I) and the terminal carboxyl group concentration of the polyetherester block copolymer was also analyzed. A durable polyetherester block copolymer elastic yarn without lowering of elastic performance and light resistance due to wet heat treatment can further control the carboxyl group concentration of the polyetherester block copolymer. a important, it was also found that this should be less than or equal to 25 equivalents / 10 ⁶ g.

Such a polyetherester block copolymer can be produced according to a usual method for producing a copolymerized polyester. Specifically, a dicarboxylic acid component mainly containing terephthalic acid, a glycol component mainly containing 1,4-butanediol, and a poly (alkylene oxide) glycol satisfying the above-mentioned formula (I) are put into a reactor, and a catalyst is placed therein. In this method, a transesterification reaction or an esterification reaction is carried out in the presence or absence of a compound, 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, as described above, the carboxyl group concentration of the polyether ester block copolymer (CV) is it is necessary to set the following 25 eq / 10 ⁶ g, this value is polymerized in the above process It can be controlled by appropriately setting the time, polymerization temperature, type of catalyst and its addition amount, intrinsic viscosity, and other additives. For example, CV can be reduced by shortening the polymerization time as much as possible and lowering the polymerization temperature as much as possible, or adding an alkali metal compound or an alkaline earth metal compound as an additive during the polymerization reaction.

The polyetherester block copolymer according to the present invention thus produced preferably has an intrinsic viscosity (value in an elastic yarn) in the range of 1.2 to 1.7.

When the IV of the polyetherester block copolymer constituting the elastic yarn is less than 1.2, the elastic yarn has a large permanent strain or a low elongation recovery rate before the dry heat treatment and the wet heat treatment. As well as the elastic properties and light resistance after dry heat treatment and / or wet heat treatment may be reduced.

On the other hand, IV of the polyetherester block copolymer is
If it exceeds 1.7, the elongation of the elastic yarn is considerably reduced, and the original elongation function of the elastic yarn is reduced, or the Young's modulus is increased, and the processing tension is increased during the processing such as a warping process. It may cause a problem such as cutting. Moreover, when such an elastic yarn is subjected to dry heat treatment or wet heat treatment, the elastic performance and light resistance tend to decrease.

Further, the Tm of the polyetherester block copolymer elastic yarn is preferably set to 170 ° C. or higher. In the processing process of ordinary polyester fiber, dry heat treatment is 150-160 ° C x 1
The heat treatment for 5 minutes is performed at 110 to 135 ° C. for 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 Tm of the polyetherester block copolymer elastic yarn may be 170 ° C. or more. Tm 170
When the temperature is lower than ℃, the performance deterioration due to the dry heat treatment and / or the wet heat treatment tends to increase.

The polyetherester block copolymer constituting the elastic yarn of the present invention includes a matting agent, a pigment (for example, carbon black, etc.), an antioxidant (for example, a hindered phenol compound, a hindered amine) in the same manner as ordinary polyester. Even if it contains an ultraviolet absorber (for example, a benzophenone-based compound, a benzotriazole-based compound, or a sacylate-based compound).

Since the polyetherester block copolymer described above can be melt-spun very easily without requiring any special means, it can be carried out according to 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 subjected to further stretching and / or heat treatment according to the purpose of use of the elastic yarn. Any of heat treatment, quantitative heat treatment and relaxation heat treatment may be used.

<Effects of the Invention> As described above, according to the present invention, the carboxyl group concentration of the polyetherester block copolymer constituting the elastic yarn is set to a specific range, and at the same time, the polyetherester block copolymer is used. Since the molecular weight distribution of the poly (alkylene oxide) glycol constituting is set to a specific range, it is excellent in elastic properties and light resistance, and in particular, elastic performance and light resistance are deteriorated even by dry heat treatment, wet heat treatment and the like. It is possible to provide a highly durable elastic yarn that does not suffer from the problem. 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.

<Example> Hereinafter, the present invention will be specifically described with reference to examples. In the examples, all “parts” indicate parts by weight.

The properties of the polyetherester block copolymer were measured by the following methods.

1. Intrinsic viscosity (IV) 35 of polymer 0.6g / 50ml orthochlorophenol solution
Calculated from the value measured at ° C.

2. Melting point (Tm) Using a thermal differential analyzer Model 990, manufactured by Du Pont,
The measurement was performed at 20 ° C./min to determine the melting peak temperature.

3. Terminal carboxyl group concentration (CV) Dissolve 0.1 g of polymer in 10 ml of benzyl alcohol,
After addition of ml of chloroform, the mixture is titrated with sodium hydroxide-benzyl alcohol. Use phenol red as an indicator.

4. Elongation recoverability (1) Instantaneous elongation recovery rate Apply a load corresponding to 100% elongation to a sample 10cm quickly and elongate it 100%. After 5 seconds, remove the load and quickly read the length lcm of the sample. Was calculated by

Instantaneous elongation recovery rate = {[10- (l-10)] / 10} x 100 (%) (2) Strength, elongation Using a 5cm long sample, elongate at a pulling speed of 1000% / min. Was measured for strength and elongation.

5. Light resistance Tensile strength retention (%) after irradiating the elastic yarn sample with a fade meter for 40 hours was measured and calculated.

Examples 1 and 2, Comparative Examples 1 to 3 167.3 parts of dimethyl terephthalate, 105 parts of tetramethylene glycol, weight average molecular weight (w) described in Table 1
275 parts of polytetramethylene glycol having a number average molecular weight (n) of 2000 and 0.2 of tetrabutyl titanate
The reactor was charged into a reactor, and a transesterification reaction was performed at an internal temperature of 190 ° C. After about 80% of the theoretical amount of methanol was distilled off, the polycondensation reaction was started by raising the temperature and reducing the pressure. The polycondensation reaction is performed while gradually reducing the pressure, and the pressure is reduced to 30 mmHg over 30 minutes.
The reaction was carried out at a temperature of 3 mmHg over a period of 1 minute and a vacuum of 1 mmHg or less at the internal temperature and time shown in Table 1.

After pelletizing the resulting polyetherester block copolymer, the pellets were dried and melted at 245 ° C.
The polymer was extruded from a cap having a hole nozzle at a discharge rate of 3.9 g / min. This polymer was wound through two godet rolls at a speed of 1000 m / min to obtain an elastic yarn. Table 1 shows the characteristics and performance of this elastic yarn.

Example 3 and Comparative Example 4 The number average molecular weight was 1000 in the weight average molecular weight described in Table 1.
Was carried out in the same manner as in Example 1 except that polytetramethylene glycol was used and the polymerization reaction conditions were changed as shown in Table 1. Table 1 shows the results.

Example 4, Comparative Example 5 The number average molecular weight of the weight average molecular weight shown in Table 1 was 3000.
Was carried out in the same manner as in Example 1 except that polytetramethylene glycol was used and the polymerization reaction conditions were changed as shown in Table 1. Table 1 shows the results.

Comparative Example 6 167.3 parts of dimethyl terephthalate, 105 parts of tetramethylene glycol, the weight average molecular weight was 2800 and the number average molecular weight was 2
Into a reactor were charged 275 parts of 000 parts of polytetramethylene glycol and 0.2 parts of tetrabutyl titanate, and an ester exchange reaction was performed at an internal temperature of 210 ° C. After about 95% of the theoretical amount of methanol was distilled off, the temperature was raised to 245 ° C., and the polycondensation reaction was started under reduced pressure. The polycondensation reaction was performed while gradually reducing the pressure, and the pressure was adjusted to 0.2 mmHg over 50 minutes, and the reaction was performed under these conditions for 240 minutes.

The obtained copolymer was formed into an elastic yarn in the same manner as in Example 1. The properties and performance of this elastic yarn are shown in Table 1.

Claims (1)

(57) [Claims] 1. A dicarboxylic acid component mainly containing terephthalic acid, a glycol component mainly containing 1,4-butanediol,
And an elasticity comprising a poly (alkylene oxide) glycol component having a number average molecular weight of about 1,000 to 3,000 and a poly (alkylene oxide) glycol content of 50 to 80% by weight. In the yarn, the number average molecular weight and weight average molecular weight of the poly (alkylene oxide) glycol component satisfy the following formula (I), and 1.8 ≦ w / n + 2 × 10 ⁻⁴ n ≦ 2.0 (I) Indicates a weight average molecular weight, and n indicates a number average molecular weight. At the same time, a polyetherester block copolymer elastic yarn, wherein the terminal carboxyl group concentration of the polyetherester block copolymer is 25 equivalents / 10 ⁶ g or less.