JPH04337349A - Polyether ester block copolymer composition - Google Patents

Abstract

PURPOSE:To provide a polyether ester block copolymer composition suitable for the production of an elastic fiber having excellent elastic property, light- resistance and chlorine-resistance and high durability to dry-heat treatment, wet-heat treatment and use in chlorine water. CONSTITUTION:A polyether ester block copolymer containing an aromatic polyester unit as a hard segment and a poly(alkylene oxide) glycol unit as a soft segment is compounded with (A) 0.1-5wt.% of a phenolic compound hindered at both terminals, (B) 0.02-2wt.% of a phenolic compound hindered at one terminal, (C) 0.1-5wt.% of a hindered amine compound and (D) 0.02-2wt.% of a thioether compound.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to polyetherester copolymer compositions. More specifically, it is a highly durable elastic yarn that has excellent elastic performance, light resistance, and chlorine resistance, and whose elastic performance and light resistance do not deteriorate when subjected to dry heat treatment, wet heat treatment, or use in chlorinated water. The present invention relates to a polyetherester block copolymer composition suitable for production.

0002

[Prior Art] Rubber, polyurethane, etc. have traditionally been used as elastic threads, but while these have excellent properties in terms of elastic recovery, they have problems such as excessive elongation, heat resistance, and light resistance. be. 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 threads have the drawbacks of high permanent deformation and poor elastic performance because the molecular chains are held together by hard segment crystals. .

In addition, polyether ester block copolymers are extremely susceptible to photodegradation, and when used under conditions such as being exposed outdoors, their elastic performance deteriorates over a relatively long period of time and they become discolored. There are practical problems such as: In order to improve the performance of elastic yarns, methods for improving the performance of elastic yarns include, for example, adding a crystal nucleating agent to increase the degree of crystallinity (Japanese Unexamined Patent Publication Nos. 59-45349 and 45350-1989). ) 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, when elastic yarns are used for part or all of woven or knitted fabrics, there is a problem in terms of durability, such as deterioration of elastic performance and light resistance during these treatments.

On the other hand, in order to improve the light resistance of polyetherester block copolymers, a method of adding an ultraviolet absorber has been proposed. For example, a method of adding a hindered phenol compound, a hindered amine compound, etc. to a polyether ester block copolymer (
Japanese Patent Publication No. 52-22744), a method of blending a hindered amine compound and titanium dioxide (Japanese Patent Publication No. 62-2274),
-192450) is shown. However, with these methods, the improvement effect is still small and there are practical problems.

In order to solve this problem, the present inventor first proposed a method in which a hindered amine compound, a hindered phenol compound, a sulfur-containing ester compound, and a titanium compound are used in combination (Japanese Unexamined Patent Publication No. 2-272055);
Alternatively, a method in which a benzotriazole compound, a hindered amine compound, a hindered phenol compound, and a sulfur-containing ester compound are used together (Japanese Patent Application No. 2-25956
The proposal was made regarding the following: Although it is true that these methods yield elastic yarns that have improved the above-mentioned problems, the improvement effect is still small when used in chlorinated water, and there is also the problem of coloring of the elastic yarns, making them impractical for practical use. Problems were recognized.

[0006]

[Problems to be Solved by the Invention] The present invention addresses disadvantages peculiar to conventional elastic yarns made of polyether ester block copolymers, namely, large permanent deformation, poor elastic performance, and poor light resistance and chlorine resistance. disadvantages and dry heat treatment,
The objective is to overcome durability problems such as deterioration of elastic performance and light resistance due to post-processing such as moist heat treatment.

[0007] The present invention provides a polyether ester block copolymer having aromatic polyester units as hard segments and poly(alkylene oxide) glycol units as soft segments, (A) both compounds represented by the following formula (I). Hindered phenol compound 0.1-5% by weight

[
embedded image (B) 0.02 to 2% by weight of a single hindered phenol compound having a structural unit represented by the following formula (II)

[
[In the formula, R3 represents a hydrogen atom, a methyl group or an ethyl group, and t-Bu is the same as defined in formula (I)] (C) hindered amine compound 0.1 to 5% by weight and (
D) A polyetherester block copolymer composition containing 0.02 to 2% by weight of a thioether compound is provided.

[0008] The polyether ester block copolymer in the present invention refers to an acid component in which 60 mol% or more, preferably 80 mol% or more of the dicarboxylic acid component is an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a low molecular weight Glycol and poly(alkylene oxide) having a molecular weight of 400 to 6,000, preferably 600 to 3,500
It means a copolymer obtained by a polycondensation reaction with glycol.

Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, 4,4'- Known raw materials for polyester can be used, such as diphenyl ether dicarboxylic acid. Among these dicarboxylic acids, terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid are preferably used from the viewpoint of moldability of the resulting polyetherester block copolymer.

[0010] As the ester-forming derivative, lower alkyl esters of the above acids, particularly methyl esters, are preferably used. In addition, acid components other than the above acids used in an amount of 40 mol% or less include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid, and fatty acids such as 1,4-cyclohexanedicarboxylic acid. Examples include cyclic dicarboxylic acids and ester-forming derivatives thereof.

The low molecular weight glycol is a glycol containing 70 mol %, preferably 80 mol % or more of 1,4-butanediol, and other glycols include ethylene glycol, 1,3-propanediol, 1
, 5-pentanediol, 1,6-hexanediol,
Examples include diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like.

[0012] Poly(alkylene oxide) glycols include polyethylene glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide)
Glycol, etc., preferably a homopolymer of poly(tetramethylene oxide) glycol, or a random copolymer or block copolymer in which two or more types of repeating units constituting the homopolymer are copolymerized in random or block form. A combination or a mixed polymer in which two or more of the above homopolymers or copolymers are mixed is used.

Poly(alkylene oxide) used here
The molecular weight of glycol is preferably 400 to 6,000. If the average molecular weight is less than 400, the blockability of the resulting polyether ester block copolymer will decrease, resulting in poor elastic performance, and the polymer melting point will also become low, causing problems in durability against dry heat treatment and wet heat treatment. Undesirable. On the other hand, when the molecular weight of the poly(alkylene oxide) glycol exceeds 6,000, it is not preferable because the resulting polymer is difficult to phase separate and form a block copolymer, resulting in poor elastic performance.

[0014] Such a polyether ester block copolymer can be produced according to a conventional method for producing a copolyester. Specifically, aromatic dicarboxylic acids and/or
Alternatively, the alkyl ester, low molecular weight glycol and poly(alkylene oxide) glycol are placed in a reactor, transesterification or esterification is carried out in the presence or absence of a catalyst, and then polycondensation is carried out in a high vacuum. This is a method of increasing the degree of polymerization to a desired degree.

The content of poly(alkylene oxide) glycol in the polyether ester block copolymer obtained by the polycondensation reaction is preferably in the range of 50 to 80% by weight. If this content exceeds 80% by weight, an elastic yarn with excellent elastic performance can be obtained, but since the melting point of the copolymer becomes too low, the elastic performance may be deteriorated by dry heat treatment, wet heat treatment, or use in chlorinated water. The elasticity decreases rapidly, resulting in an elastic yarn with poor durability. On the other hand, 50
If the amount is less than % by weight, permanent deformation will be large and only elastic yarns with poor elastic properties will be obtained.

In the present invention, the polyether ester block copolymer contains (A) a specific double hindered phenol compound, (B) a single hindered phenol compound,
It is important to include (C) a hindered amine compound and (D) a thioether compound as essential components.

Both hindered phenol compounds (A) used in the present invention are compounds represented by the following formula (I).

[C5]

The blending amount of both hindered phenol compounds in the polyether ester block copolymer is 0% relative to the polyether ester block copolymer.
．． It is necessary to set it to 1-5 weight%. The content is preferably 1 to 3% by weight, and within this range, (B)
By using the components (C) and (D) in combination, light resistance and durability against use in chlorinated water are particularly improved. If the amount of component (A) exceeds 5% by weight, the elastic properties and heat resistance will decrease, and there will be a significant decrease in durability, especially against dry heat, wet heat treatment, or use in chlorinated water. The elastic performance deteriorates significantly during processing. On the other hand, if it is less than 0.1% by weight, the effect of improving light resistance is insufficient.

Next, examples of the singly hindered phenol compound (B) used in the present invention include compounds having a structural unit represented by the following formula (II).

embedded image (In the formula, R3 represents a hydrogen atom, a methyl group, or an ethyl group, and t-Bu represents a tert-butyl group.)

0
The compound having the structural unit represented by formula (II) is preferably a compound having a molecular weight of 500 or more, and specific examples include the following compounds. 3,9
-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1
-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 2-t-butyl-6-(
3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenylacrylate, 4,4'-butylidene-bis-(3-methyl-6-t-butylphenol), triethylene glycol-bis-3 -(3-t-
Butyl-4-hydroxy-5-methylphenyl) propionate and the like can be preferably used.

In the composition of the present invention, such (B)
The partially hindered phenol compound is blended in an amount of 0.02 to 2% by weight, preferably 0.1 to 0.5% by weight, based on the polyether ester block copolymer. As the amount of component (B) increases, the light resistance of the elastic yarn obtained from the composition is significantly improved, and at the same time, the elastic performance and light resistance for use in dry heat treatment, wet heat treatment, etc. or in chlorinated water are improved. The durability improvement effect is recognized. However, if the blending amount exceeds 2% by weight, the elastic performance will deteriorate significantly. In particular, the elastic performance decreases significantly after dry heat treatment, wet heat treatment, etc.

The hindered amine compound (C) used in the present invention is preferably a compound represented by the following formula (III).

embedded image In formula (III), R4 , R5 , R6 and R7
are the same or different and represent an alkyl group having 1 to 6 carbon atoms.

Examples of the hindered amine compound represented by formula (III) include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis-(
2,2,6,6-tetramethyl-4-piperidinyl)adipate, bis-(2,2,6,6-tetramethyl-4
-piperidinyl) suberate, bis-(2,2,6,6
-tetramethyl-4-piperidinyl) sebacate, bis-(2,2,6,6-tetramethyl-4-piperidinyl) phthalate, bis-(2,2,6,6-tetramethyl-4-piperidinyl) isophthalate , bis-(2,2
, 6,6-tetramethyl-4-piperidinyl) terephthalate, bis-(1,2,2,6,6-pentamethyl-
4-piperidinyl) sebacate, N,N'-bis-(2
,2,6,6-tetramethyl-4-piperidinyl)adipamide, bis-(1,2,2,6,6-pentamethyl-
4-piperidinyl)-n-butyl (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis-(
1,2,2,6,6-pentamethyl-4-piperidinylbenzyl) malonate, bis-(1,2,2,6,6-
Pentamethyl-4-piperidinyl) diethylmalonate, bis-(2,2,6,6-tetramethyl-4-piperidinyl)dibenzylmalonate, bis-(2,2,6,
6-tetramethyl-4-piperidinyl)benzylethylmalonate, bis-(2,2,6,6-tetramethyl-
4-piperidinyl)-n-butyl (3,5-di-t-butyl-4-hydroxybenzyl) malonate, tetra-(2,2,6,6-tetramethyl-4-piperidinyl) ester of butanetetracarboxylic acid , 1-[2-{3-
(3,5-di-t-butyl-4-hydroxyphenyl)
propionyloxy}ethyl]-4-[3-(3,5-
di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3 ,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidinyl)imino} compound with a molecular weight of 2,000 or more, dimethyl succinate/1-(2-hydroxyethyl)-4-
Examples include polyesters of hydroxy-2,2,6,6-tetramethylpiperidine having a molecular weight of 2,000 or more.

The amount of the hindered amine compound (C) in the polyether ester block copolymer composition must be 0.1 to 5% by weight based on the polyether ester block copolymer. The blending amount is preferably 1 to 3% by weight, and if the blending amount exceeds 5% by weight, the elastic properties and heat resistance of the resulting elastic yarn will decrease, and the durability against dry heat treatment, wet heat treatment, etc. will deteriorate. The deterioration of elastic performance during these treatments becomes large. On the other hand, if it is less than 0.1% by weight, the effect of improving light resistance is insufficient.

Further, the thioether compound (D) of the present invention is a compound having at least one sulfur atom in the molecule, and preferably has a structure represented by the following general formula (IV) or (V). . S-(R'COOR'')2...(IV)(
R″SR′COOCH2 )4 C...(V) However, in formula (IV) and formula (V), R' has 1 to 1 carbon atoms.
10 alkylene group, and R'' represents an alkyl group having 3 to 40 carbon atoms.

In formulas (IV) and (V), preferred examples of R' include methylene group, ethylene group, propylene group, butylene group, hexylene group, etc., and preferred examples of R'' include , octyl group, decyl group, tridecyl group, dodecyl group, myristyl group, stearyl group, etc.

Specific examples of these thioether compounds include dioctylthiodipropionate, didodecylthiodipropionate, dodecylstearylthiodipropionate, distearylthiodipropionate, dimyristylthiodipropionate, and dipropionate. Decyl thiodipropionate, didodecyl-β,β'-thiodibutyrate, distearyl-β,β'-thiodibutyrate, pentaerythritol-tetrakis (dodecylthiopropionate), pentaerythritol-tetrakis (dodecylthioacetate) , pentaerythritol-tetrakis (dodecylthiobutyrate), pentaerythritol-tetrakis (octadecylthiopropionate), pentaerythritol-tetrakis (laurylthiopropionate), and the like.

Among these, didodecyl thiodipropionate, distearyl thiodipropionate, distearyl-β,β'-thiodibutyrate, pentaerythritol-tetrakis (dodecylthiopropionate), pentaerythritol-tetrakis (Laurylthiopropionate) is preferred.

In the composition of the present invention, the amount of the thioether compound (D) blended is 0.02 to 2% by weight, preferably 0.02% by weight, based on the polyetherester block copolymer.
It is 1 to 0.5% by weight. As the amount of the compound increases, the light resistance of the elastic yarn obtained from the composition increases (A)
Greatly improved by the synergistic action with both hindered phenol compounds, (B) single hindered phenol compound, and (C) hindered amine compound, and at the same time dry heat treatment,
Durability improvement effects on elastic performance and light resistance are recognized when used in moist heat treatment or in chlorinated water. However, if the blending amount exceeds 2% by weight, the elastic performance will deteriorate significantly. In particular, the elastic performance is significantly reduced after dry heat treatment and wet heat treatment.

[0030] In the composition of the present invention, component (A);
The blending proportions of component (B), component (C), and component (D) greatly affect light resistance, elastic performance against dry heat treatment, wet heat treatment, or use in chlorinated water, and durability of light resistance. In order to maximize the synergistic effect of components (A), (B), (C), and (D), it is preferable to blend them within the range of formula (1) below. 2≦(a+c)/(b+d)・・・(1) [However, a, b, c, d are (A) component, (B) component, (C
The amounts (% by weight) of component ) and component (D) relative to the polyether ester block copolymer are shown. ]

0031
] Furthermore, it is preferable that the blending ratios of component (B) and component (D) be approximately the same, as shown by the following formula (2), as this is particularly effective in improving elastic performance and light resistance. 0.5≦d/b≦2.5 (2)

[0032]
The compounding agents detailed above (A) component, (B) component, (C)
The method of adding the components and component (D) to the polyetherester block copolymer is not particularly limited. That is,
During the polycondensation reaction process of the polyether ester block copolymer, components (A) to (D) are added or melted using a single screw extruder, twin screw extruder, roll mixer, Banbury mixer, etc. Any method may be employed, such as adding components (A) to (D) to the polyether ester block copolymer.

The intrinsic viscosity (IV) (orthochlorophenol, 35°C) of the polyether ester block copolymer of the present invention is 1.1 or more, and the higher the better, but if it is too high, melt spinning may be difficult. It becomes difficult and also impractical in terms of cost, so preferably those with a value of 1.3 to 1.7 are used.

[0034]

[Examples] The present invention will be explained in more detail with reference to Examples below. In the examples, "parts" and "%" are by weight. Further, the properties of the polyether ester block copolymer were measured by the following method. 1. Intrinsic viscosity (IV) Calculated from the viscosity measured at 35°C of a 0.6 g/50 ml orthochlorophenol solution of polymer.

2. Elongation recovery ■ Instantaneous elongation recovery rate Apply a load corresponding to 200% elongation to a 10 cm sample, quickly elongate it by 200%, remove the load after 5 seconds, quickly read the sample length L cm, and calculate using the following formula (3). did. {[20-(L-10)]/20}×100(
%)...(3)

■ Apply a load equivalent to 100% elongation to a sample with a permanent strain length of 10 cm and leave it for 4 hours, then remove the load and measure the length L'cm of the sample after leaving it for 4 hours. It was calculated using the following formula (4). Permanent strain = {[(L'-10)]/10}×10
0...(4) ■Strength and elongation A sample with a length of 5 cm was stretched at a tensile rate of 1000%/min, and the strength and elongation at break were measured.

3. The tensile strength retention rate (%) of the light-resistant elastic yarn sample after irradiation for 40 hours was measured using a fade meter. 4. The chlorine-resistant elastic yarn sample was soaked in chlorinated water (effective chlorine concentration 100 ppm).
, pH 7) at room temperature, and the tensile strength retention rate (%) was measured after 5 hours.

Examples 1 to 9, Comparative Examples 1 to 7 167.3 parts of dimethyl terephthalate, 1 part of tetramethylene glycol
05 parts of polytetramethylene glycol having a number average molecular weight of 2,000, and 0.2 parts of tetrabutyl titanate were charged into a reactor, and a transesterification reaction was carried out at an internal temperature of 190°C. When about 70% of the theoretical amount of methanol had been distilled off, the polycondensation reaction was started by raising the temperature and reducing the pressure. The polycondensation reaction took about 30 minutes to bring the pressure to 30 mmHg, then another 30 minutes to bring it to 3 mmHg, and then the temperature was lowered to 2 mm in a vacuum of 1 mmHg or less.
The reaction was carried out at 45°C for 200 minutes, and (A) and (
B), (C), (D) components are added in the proportions listed in Table 2,
The reaction was further carried out for 20 minutes at 245° C. under a vacuum of 1 mmHg or less. Table 1 shows the compound name of each component, and Table 2 shows its type, blending amount, and limiting viscosity of the polymer.

After pelletizing the produced polyetherester block copolymer and drying the pellet,
The polymer was melted at 5° C. and extruded through a cap with a three-hole nozzle at a discharge rate of 3.9 g/min. This polymer was wound through two Godet rolls at a speed of 1,500 m/min to obtain an elastic yarn. Table 3 shows the performance of this elastic yarn. In Table 3, "after dry heat treatment" refers to the performance after treatment at 160℃ for 1 minute, and "after wet heat treatment" refers to the performance after treatment in 130℃ hot water for 6 minutes.
The performance after 0 minute processing is shown.

Example 10, Comparative Examples 8 to 11 160 parts of 2,6-naphthalene dicarboxylic acid dimethyl ester, 100 parts of tetramethylene glycol, number average molecular weight 2,000
A polyether ester block copolymer was obtained by adding each component listed in Table 2 in the proportions listed in Table 2 under the same conditions as in Example 1 except that 310 parts of polytetramethylene glycol was used as a raw material. Example 1 from the obtained polymer
Elastic yarn was manufactured in the same manner as above and its performance was measured. The results are shown in Table 3.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

Effects of the Invention: The elastic yarn made of the polyether ester block copolymer composition of the present invention has low permanent deformation, excellent elastic performance and light resistance, and is resistant to dry heat treatment, wet heat treatment, use in chlorinated water, etc. It also shows excellent durability. Therefore, it can be used in woven or knitted fabrics that require elastic performance, light resistance, and chlorine resistance, and its effects are extremely large. In addition, the polyether ester block copolymer composition of the present invention can provide an elastic body with excellent heat resistance and light resistance, and can also be extrusion blow molded or profile extrusion molded, so it can be used particularly at high temperatures. field,
For example, it can be used in fields such as tubes, hoses, belts, electrical parts, wire covering materials, and automobile parts.

Claims (2)

[Claims] Claim 1: A polyether ester block copolymer having aromatic polyester units as hard segments and poly(alkylene oxide) glycol units as soft segments, (A) both hindered molecules represented by the following formula (I); Phenol compound 0.1 to 5% by weight [Formula 1] (B) Single hindered phenol compound having a structural unit represented by the following formula (II) 0.02 to 2% by weight [
[In the formula, R3 represents a hydrogen atom, a methyl group or an ethyl group, and t-Bu is the same as defined in formula (I)] (C) hindered amine compound 0.1 to 5% by weight and (
D) A polyetherester block copolymer composition containing 0.02 to 2% by weight of a thioether compound. Claim 2: Claim 1 in which the amounts of component (A), component (B), component (C), and component (D) in the polyether ester block copolymer satisfy the following formula (1).
The polyetherester block copolymer composition described. 2≦(a+c)/(b+d)...(1) [However, a, b, c, and d are (A) component, (B) component, (
The amounts (wt%) of component C) and component (D) relative to the polyether ester block copolymer are shown. ]