JPH02175719A - Polyether ester block copolymer - Google Patents

Abstract

PURPOSE:To provide the title copolymer which can give an elastic yarn free from compression set and excellent in elastic properties, durability to heat treatment, etc., by using a terephthalic acid-based dicarboxylic acid component and a specified glycol component. CONSTITUTION:A polyether ester block copolymer is prepared from a terephthalic acid-based dicarboxylic acid (esterifiable derivative) (A), an ethylene glycol (esterifiable derivative) (B), a 1,4-cyclohexanedimethanol (esterifiable derivative) (C) and a polyoxyalkylene glycol (D) of an average MW of 400-6000 as essential components. This copolymer is constituted so that it can simultaneously satisfy the relations I and II (wherein X is the molar % of component C based on the sum of components B and C; and D is the wt.% of component D based on the total polymer weight) and has an m.p. >=220 deg.C, an intrinsic viscosity >=1.1 and a half-crystallization time at 50 deg.C<=10sec.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an elastic body. More specifically, it has low permanent distortion, excellent elastic performance, and is dry heat treated.

<Prior art> Concerning a polyetherester elastic body suitable for producing durable elastic threads that do not deteriorate in permanent set 1 elastic performance due to wet heat treatment etc. Conventionally, rubber, polyurethane, etc. have been used as elastic threads. Although these exhibit excellent properties in terms of elastic recovery, they have problems such as excessive elongation, heat resistance, and light resistance.

On the other hand, polyether ester block copolymer type elastomers have recently come into use as resin applications. When made into yarn, this polymer exhibits relatively good recovery under low elongation, although it is not as good as polyurethane in terms of elongation recovery, and also has the advantage of being melt-spun. However, unlike polyurethane, polyether ester block copolymer type elastic yarns have disadvantages such as large permanent deformation and poor elastic performance because the molecular chains are held together by hard segment crystals. be.

In order to improve the performance of elastic threads, methods for improving the performance of elastic threads include, for example, increasing the degree of crystallinity by orienting a crystal nucleating agent (Japanese Patent Laid-Open No. 59-45349).

No. 59-45350) has been proposed. However, such methods cannot significantly improve the performance of the elastic yarn, and the performance is still insufficient for use as an elastic yarn. In particular, elastic yarn is used as part of woven or knitted fabrics.
Or, when used as a whole, there is a problem in terms of durability in that the elastic performance deteriorates during these treatments.

<Problems to be Solved by the Invention> The present inventor has conducted extensive studies in order to overcome the drawbacks inherent to elastic yarns made of conventional polyetherester block copolymers, namely, large permanent deformation and poor elastic performance. As a result, surprisingly, a polyether ester copolymer was obtained by using ethylene glycol and 1,4-cyclohexalinemethanol in appropriate ratios as glycol components and by selecting the copolymerization ratio of polyoxyalkylene glycol. The elastic yarn made of 200% has low permanent deformation and excellent elastic performance, and is dry heat treated.

It has been found that elastic yarns that are durable against moist heat treatment can be obtained.

As a result of further studies based on this knowledge, the present inventors have completed the present invention.

<Configuration of the Invention> That is, the present invention provides dicarboxylic acids mainly including terephthalic acid and/or ester-forming derivatives thereof (component A), ethylene glycol and/or ester-forming derivatives thereof (component B), and 1,4- Cyclohexaline methanol and/or its ester-forming derivative (component C) is the main component, low-molecular m-glycol and/or its ester-forming derivative, polyoxyalkylene glycol with an average molecular weight of 400 to 6,000 (component C) are the constituent components. A polyether ester block copolymer which satisfies the following formulas (I) and (II) at the same time: 70'l;
C<95...(I>50';D<
, 80...(It) (wherein, C and D represent component C and the amount of copolymerization of component C, respectively, C is mol% of component C with respect to the total amount of component B and component C, and D is the total polymer % by weight of component C), and the melting point of the copolymer is 220°C or higher, and the intrinsic viscosity is 1
．． The object of the present invention is to provide a polyether ester block copolymer characterized by having a crystallization time of 1 or more and a 1/2 crystallization time at 50° C. of 10 seconds or less.

In the present invention, the Δ component constituting the polyether ester block copolymer (a dicarboxylic acid component mainly composed of terephthalic acid, specifically, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenoxy ethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, adipic acid,
Sebacin 11. 1. Aromatic, fatty acid, alicyclic difunctional carboxylic acid such as 4-cyclohexanedicarboxylic acid r!
Examples thereof include lower dialkyl esters having 1 to 4 carbon atoms, phenyl esters, and the like.

In the polyether ester block copolymer of the present invention, the B component (ethylene glycol and/or its ester-forming derivative) is an ethylene glycol component and the C component (1,4-cyclohexaline methanol and/or its ester-forming derivative ), and the total of component B and component C must be 80 mol % or more of the low molecular weight glycol component constituting the polyether ester block copolymer.

Here, the low molecular weight glycol components other than component B and component C are glycols with a molecular weight smaller than 250, and specifically include 1.2- or 1.3-propylene glycol, 1,4-butane aliphatic diols such as diol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, alicyclic diols such as 1,1-cyclohexalinemethanol, tricyclodecane dimethol, xylylene glycol, bis( p-hydroxy)diphenyl,
Bis(p-hydroxyphenyl)propane.

2.2-Bis[4-(2-hydroxyethoxy)phynylcoproban, bis[4-(2-hydroxyethoxy)
Examples include diols containing aromatic groups such as phenyl]sulfone and 1,1-bis[4-(2-hydroxyethoxy)phenylcocyclohexane.

Component C (1,4-cyclohexalinemethanol component) used in the present invention is usually a trans isomer.

Consists of a mixture of cis isomers. The proportion of this trans isomer in the total 1,4-cyclohexaline methanol may be 60 to 70% of the commercially available 1,4-cyclohexaline methanol, but preferably this proportion is 80% or more. By doing so, the heat resistance and elastic properties of the polyether ester copolymer elastic yarn finally obtained are further improved.

Component D (polyoxyalkylene glycol having an average molecular weight of 400 to 6,000) constituting the polyether ester copolymer of the present invention includes polyethylene glycol,
Examples include polypropylene glycol, polytetramethylene glycol, and copolymers thereof, and particularly polyoxyalkylene glycol copolymers containing polytetramethylene glycol and tetramethylene oxide units as main components are preferably used. The average molecular weight of the polyoxyalkylene glycol is preferably 400 to 6,000. If the average molecular weight is less than 400, the blockability of the resulting polyether ester polymer will decrease, resulting in poor elastic performance, and the melting point of the polymer will become low, causing problems in durability against dry heat treatment and wet heat treatment, which is undesirable. . On the other hand, the molecular weight of polyoxyalkylene glycol is 6
If it exceeds 000, it is not preferable because the resulting polymer is difficult to undergo phase separation and block copolymerization, resulting in poor elastic performance.

In the polyether ester block copolymer of the present invention, the amounts of component C and component D are as follows (I) and (I).
It is necessary to simultaneously satisfy formula I).

70<C<95...(I)50<, D
<80...(It) (wherein, C3D represents the amount of copolymerization of component C and component D, respectively, C is the mol% of component C relative to the total amount of component B and component C, and D is the amount of D relative to the total polymer. If the amount C of component C shown in formula (I) is less than 70 mol%, the melting point of the polyetherester copolymer will be too low and the crystallization rate will also be low. In particular, the durability of elastic performance against dry heat treatment and wet heat treatment is insufficient. In addition, the crystallization rate of the polyether ester copolymer is slow, making it difficult to pelletize the polymer after the polymerization reaction is completed, and at the same time, problems such as sticking in IIi miscellaneous parts occur during spinning. In this case, if an attempt is made to reduce the amount of component D in order to prevent a decrease in the melting point of the copolymer and to improve the crystallization rate, it becomes difficult to obtain an elastic thread with excellent elastic performance as originally intended. .

On the other hand, if the content of the C component exceeds 95 mol%, the polymerization reaction rate slows down, making it difficult to obtain a copolymer with an intrinsic viscosity of 1.2 or more, which is necessary to obtain excellent elastic performance. Become.

Furthermore, since the obtained polyether ester copolymer has poor heat resistance, dry heat treatment is particularly necessary.

The durability of the elastic performance against moist heat treatment will be insufficient.

When the D component in the polyether ester block copolymer of the present invention exceeds 80% by mass, an elastic yarn with excellent elastic performance can be obtained, but the melting point of the copolymer becomes too low, so dry heat treatment, wet The elastic properties during heat treatment deteriorate rapidly, resulting in an elastic yarn with poor durability. Also,
If the D component is less than 50% by weight, only elastic yarns with large permanent set and poor elastic properties can be obtained. To improve this B
If a large number of components are copolymerized, as described above, the melting point of the copolymer will be significantly lowered and the durability of the elastic properties will be poor.

Furthermore, in the present invention, in order to obtain an elastic thread with good elastic performance, the 1/2 crystallization time of the polyether ester block copolymer at 50°C must be at least 10 seconds or less, preferably 7 seconds or less. be. That is, in the case of a polyether ester block copolymer whose 1/2 crystallization time at 50°C exceeds 10 seconds,
Even with melt spinning or subsequent ordinary drawing treatment, it is not possible to increase the size of the microcrystals in the resulting elastic yarn. As a result, the force that holds the molecular chains together becomes insufficient, resulting in increased permanent strain and poor elastic properties. The 1/2 crystallization time at 50°C is at least 10
In order to achieve this within seconds, in addition to adjusting the constituent components and contents of each of the polyether ester block copolymers of the present invention as described above, the intrinsic viscosity IV of an orthochlorophenol solution of the polymer measured at 35°C It is necessary that the melting point of the polymer be 1.1 or more and the melting point of the polymer be 220°C or more.

IV of the polyetherester block copolymer of the present invention
If it is less than 1.1, the 1/2 crystallization time at 50° C. will exceed 10 seconds, and the mechanical properties of the finally obtained elastic thread will be insufficient. Iv is 1.1 or more, and the higher the value, the better; however, if it is too high, melt spinning becomes difficult, and it is not practical from a cost standpoint, so it is preferably 1.3.
~1.7 is used.

In addition, when the melting point of the copolymer is lower than 220°C, the durability of the elastic yarn to dry heat and wet heat treatment is insufficient, and the 1/2 crystallization time at 50°C is 10 seconds. As a result, only elastic yarns with significantly inferior elastic properties can be obtained.

A polyether ester block copolymer having components A, B, Ca, and D as constituent components can be produced according to a conventional method for producing copolymerized polyester. in particular,
Aromatic dicarboxylic acids and/or their alkyl esters (
Component A), ethylene glycol (component B), 1,4-cyclohexaline methanol (component C), and polyoxyalkylene glycol (component D) are placed in a reactor and esterified directly in the presence or absence of a catalyst. In this method, a transesterification reaction is carried out, and then a polycondensation reaction is carried out in a high vacuum to raise the degree of polymerization to a desired degree.

Like ordinary polyester, the polyether ester block copolymer contains matting agents, pigments such as carbon black, antioxidants such as hindered phenol compounds and hindered amine compounds, and ultraviolet absorbers such as benzophenone compounds and benzophenone compounds. triazole compound,
There is no problem even if it contains salicylate compounds.

<Effects of the Invention> The elastic thread made of the polyether ester copolymer of the present invention has little permanent deformation, excellent elastic performance, and is resistant to dry heat treatment.
It also shows excellent durability against moist heat treatment. therefore,
It can be used in woven and knitted fabrics that require elastic performance, and its effects are extremely large.

Furthermore, the polyether elastomer of the present invention provides an elastic body with excellent heat resistance and can be extrusion blow molded or profile extrusion molded, so it is particularly suitable for use in fields where it is used at high temperatures, such as tubes.

It can also be used in fields such as hoses, belts, electrical parts, wire covering materials, and automobile parts.

<Example> The present invention will be specifically described below with reference to Examples. In the Examples, all "parts" refer to weight products.

The properties of the polyether ester copolymer were measured by the following method.

1. Intrinsic viscosity (IV) Calculated from the value measured at 35°C of a solution of 0.6 g of polymer in 150-orthochlorophenol.

2. Melting point The melting peak temperature was determined using an implicit difference analyzer model 900 manufactured by DuPont at a heating rate of 20° C./min.

3. Crystallization rate Depolarization intensity method Crystallization rate measurement method (New Experimental Chemistry Course 19
Polymer Chemistry ■Page 917, edited by the Chemical Society of Japan, published by Maruzen ■).

Approximately 20 q of polymer was placed on a slide glass and melted at 250° C. for 1 minute to prepare a slide. Next, the polymer in the preparation was melted by heating at 250°C for 2 minutes, immediately cooled to 50°C, and then the crystallization rate was measured.

Further, the performance of the elastic yarn was measured by the following method.

4. Elongation recovery (1) Instantaneous elongation recovery rate A load corresponding to 100% elongation was applied to sample 10α, and the sample was quickly elongated to 100%.After 5 seconds, the load was removed and the length log of the sample was quickly read. Calculated using the formula.

Instantaneous elongation recovery rate = ([10-(1-10> Ko/10) x 1
00 (%) (2 Elongation Modulus JIS L 1073 (1977) Synthetic Fiber Yarn Test Method Elongation Elasticity Modulus It was determined as the elongation elasticity modulus by the measuring method specified in Method B.

(3) Apply a load equivalent to 100% elongation to a sample with a permanent set length of 10 cm, leave it for 4 hours, then remove the load, measure the length of the sample after leaving it for 4 hours, and calculate the following formula: Calculated by.

Permanent deformation - ((dan'-10> /10) x 100
(4) Using a sample with strength and elongation length of 5 CIR, tensile speed of 1000%/
The strength and elongation at break were measured.

Examples 1-6. Comparative Examples 1 to 6 Dimethyl terephthalate as component A and ethylene glycol as component B in the amounts listed in Table 1.

As component C, 1,4-cyclohexaline methanol (
The ratio of trans and cis isomers is listed in Table 1),
A reaction vessel was charged with polytetramethylene glycol having a number average molecular weight of 1fi 2000 as component D and 0.35 parts of tetrabutyl titanate as a transesterification and polymerization catalyst.
The transesterification reaction was carried out at an internal temperature of 200°C. About 95% of the theoretical amount of methanol was distilled out of the system. then 255
The temperature was raised to ℃ and the pressure started to be reduced.

It took about 30 minutes to reach 301MH9, and then another 30 minutes to reach 3.
Am1, vacuum below 11M89, internal temperature 265℃
It became unresponsive for 240 minutes. The properties of the obtained polymer are listed in Table 1.

After drying the polymer, it was melted at 265° C. and extruded through a cap with a three-hole nozzle at a rate of 13.9 g/min. This polymer was wound through two body rolls at a speed of 150 f)m/min to obtain an elastic yarn. The performance of this elastic yarn is shown in Table 1.

Claims (2)

[Claims] (1) Dicarboxylic acids mainly including terephthalic acid and/or their ester-forming derivatives (component A), ethylene glycol and/or their ester-forming derivatives (component B), and 1,4-cyclohexaline methanol and/or its ester-forming derivatives A polyether ester block copolymer whose constituent components are a low molecular weight glycol and/or its ester-forming derivative mainly consisting of an ester-forming derivative (component C), and a polyoxyalkylene glycol having an average molecular weight of 400 to 6,000 (component D). The copolymer satisfies the following formulas (I) and (II) at the same time, and 70≦C≦95...(
I) 50≦D≦80...(II) (In the formula, C and D indicate the copolymerization amount of component C and component D, respectively, and C is the mol% of component C with respect to the total amount of component B and component C.
, D is the weight% of component D based on the total polymer) and the melting point of the copolymer is 220°C or higher and the intrinsic viscosity is 1
．． 1. A polyether ester block copolymer having a crystallization time of 1 or more and a 1/2 crystallization time at 50° C. of 10 seconds or less. (2) The polyether ester block copolymer according to claim 1, wherein the C component is a mixture of a trans isomer and a cis isomer, and the proportion of the trans isomer is 80% or more.