JPH02272055A - Polyetherester block copolymer composition - Google Patents

Abstract

PURPOSE:To provide the subject composition giving elastic fibers having reduced permanent strain, excellent elastic performance, excellent light resistance and excellent durability against dry heat treatment, etc., by simultaneously compounding a hindered amine compound, a hindered phenol compound, etc., in specific amounts, respectively. CONSTITUTION:A polyetherester block copolymer comprising aromatic polyester units as hard segments and poly(alkylene oxide) glycol units as soft segments is compounded with (A) 0.1-5wt.%, preferably 1-3wt.%, of a hindered amine compound, (B) 0.02-2wt.%, preferably 0.1-0.5wt.%, of a hindered phenol compound, (C) 0.02-2wt.%, preferably 0.1-0.5wt.%, of a sulfur-containing ester compound and (D) 0.1-1wt.%, preferably 0.1-0.5wt.%, of a titanium compound, in a ratio simultaneously satisfied with equations I-III (A-D are the wt.% of the components, A-D, respectively).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to polyetherester block copolymer compositions. More specifically, the polyether ester blocks are suitable for producing durable elastic yarns that have excellent elastic performance and light resistance, and whose elastic performance and light resistance do not deteriorate even after dry heat treatment, wet heat treatment, etc. The present invention relates to polymer compositions.

<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 luminosity. .

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 elongation recovery rate, and also has the advantage of being melt-spun. However, unlike polyurethane, polyether ester block copolymer type elastic yarns have the disadvantages of high permanent deformation and poor elastic performance because the molecular chains are connected by hard segment crystals. be.

In addition, polyetherester block copolymers are extremely susceptible to photodegradation; for example, when used outdoors under conditions such as being exposed to black ink, their elastic performance deteriorates in a relatively short period of time and they become discolored. There are practical problems such as:

As a method for improving the performance of elastic yarns to improve such drawbacks, for example, a method of increasing the degree of crystallinity by adding a crystal nucleating agent (Japanese Patent Application Laid-Open No. 59-45349).

Publication No. 59-45350) is being 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, such as deterioration of elastic performance and light resistance during these treatments.

On the other hand, in order to improve the light resistance of polyether ester block copolymers, methods of adding ultraviolet absorbers have been used. For example, hindered phenol compounds, hindered amines, etc. Method of adding thread compounds, etc. (Special Publication No. 52-2
2744) and a method of blending a hindered amine compound and titanium dioxide (Japanese Patent Laid-Open No. 192450/1983). However, with these methods, the improvement effect is still small and there are practical problems.

<Problems to be Solved by the Invention> The present inventors have solved the inherent disadvantages of conventional elastic yarns made of polyetherester block copolymers, namely, large permanent deformation, poor elastic performance, and poor light resistance. As a result of intensive studies to overcome durability problems such as deterioration of elastic performance and light resistance due to post-processing treatments such as dry heat treatment and wet heat treatment, we found that hindered amine compounds, hindered phenol compounds, sulfur-containing ester compounds, and inert An elastic thread made of a polyetherester block copolymer obtained by blending specific amounts of particles.

Low permanent deformation, excellent elastic performance, dry heat treatment,
It has been found that an elastic yarn can be obtained which is durable against heat treatment and has significantly improved light resistance.

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

<Configuration of the Invention> That is, the present invention provides a polyether ester block copolymer having an aromatic polyester unit as a hard segment and a poly(alkylene oxide) glycol unit as a soft segment, (A) a hindered amine compound 0 .1 to 5% by weight (B) Hindered phenol compound 0.02 to 2-i1Ji double oxide; (C) Sulfur-containing ester compound 0302 to 2% by weight 5(0) Titanium compound <1.1 to 1% by weight % of the polyether ester block copolymer composition.

In the present invention, the polyether ester block copolymer includes 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, a low molecular weight glycol, Molecular weight 400-6000, preferably 600-35
1f with 00 poly(alkylene oxide) glycol
Co obtained by fi combination reaction! ■It means an association.

Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, and 44°-diphenyl ether dicarboxylic acid. Known materials can be used as raw materials for polyester.

Among these dicarboxylic acids, terephthalic acid and isophthalic acid are preferably used from the viewpoint of moldability of the resulting polyether ester block copolymer.

As the ester-forming derivative, lower alkyl esters of the above acids, particularly methyl esters, are preferably used.

Note that acid components other than the above acids used in an amount of 40 mol% or less include adipic acid, sebacic acid, azelaic acid,
Examples include aliphatic dicarboxylic acids such as dodecanoic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 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-
Bentanediol, 1,6-hexanediol, diethylene glycol and 1,4-cyclohexanediol,
Examples include 1,4-cyclohexane dimetatool.

Examples of the poly(alkylene oxide) glycol include polyethylene glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, etc., and preferably a homopolymer of poly(tetramethylene oxide) glycol or the above homopolymer. A random copolymer or block copolymer in which two or more constituent repeating units are copolymerized in a random or block form,
Alternatively, a mixed polymer in which two or more of the above-mentioned homopolymers or copolymers are mixed is used.

The molecular weight of the poly(alkylene oxide) glycol used here is preferably 400 to 6,000. Average molecular weight is 4
If the groove is not 00, the blockiness of the polyether ester block copolymer obtained is reduced, resulting in poor elastic performance.
This is undesirable because the melting point of the polymer becomes low, causing problems in durability against heat treatment and wet heat treatment.
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.

Such a polyether ester block copolymer can be produced according to a conventional method for producing a copolyester.

Specifically, an aromatic dicarboxylic acid and/or its alkyl ester, a low molecular weight glycol, and a poly(alkylene oxide) glycol are placed in a reactor, and a transesterification or esterification reaction is carried out in the presence or absence of a catalyst. This is a method in which a polycondensation reaction is carried out under high vacuum to increase the degree of polymerization to a desired degree.

The content of poly(alkylene oxide) glycol in the polyether ester block copolymer obtained by the above polycondensation reaction is preferably in the range of 50 to 80% by weight. However, since the melting point of the copolymer becomes too low, the elastic performance during dry heat treatment and wet heat treatment decreases rapidly, resulting in an elastic yarn with poor durability.
If it is less than 50% by weight, only elastic yarns with large permanent set and poor elastic properties can be obtained.

In the present invention, a specific hindered amine compound (component (A)) is added to the polyether ester block copolymer.
, hindered phenolic hOJ (component (B)), sulfur-containing ester compound (component (C)), and titanium compound (component (O)) are important to be blended as essential components.

The hindered amine compound (component (A)) used in the present invention includes 4-benzoyloxy-2,2,6,8
-tetramethylpiperidine), bis-(2,2,6,6
-tetramethyl-4-piperidinyl) suberate, bis-(2,2,6,6-tetramethyl-4-piperidinyl) sepagate, bis-(2,2,G6-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-bentamethyl-4-piperidinyl) sebacate,
N,N"-bis-(22,6,6-tetramethyl-4-
piperidinyl)adipamide, bis-(1,2,2,6,
8-pentamethyl-4-piperidinyl)-n-butyl(
3,5-ditert-butyl-4-human 0-1r dibenzyl)
malonate, bis-(1,2,2,6,6-bentamethyl-4-piperidinylbenzyl)malonate, bis-(
1,2,2,6,6-bentamethyl-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-tert-butyl-4-hydroxybenzyl) malonate, butanetetracarboxylic acid Detler (2,2
,6,6-tetramethyl-4-piperidinyl) ester, 1-[2-[3-H,S-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,
6-titramethylbiperidine, 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 molecules of 12,000 or more Dimethyl succinate/1-<2-
hydroxyethyl)-4-hydroxy-2,2,6,6
- Molecule Ik2 with polyester of titramethyl biveridine
000 or more are given as examples, and the following (IV)
It is a hindered amine compound having one or more structures represented by the formula.

In the formula, R1, R2, R3, and R4 are alkyl groups having 1 to 6 carbon atoms, and may be different or the same.

The amount of the hindered amine compound (component (8)) in the polyether ester block copolymer is 0.1 to the polyether ester block copolymer.
It is necessary to set it to 5% by weight.

Preferably, it is 1 to 3 fflffi%, and within this range, light resistance is particularly improved. but,
If it exceeds 5% by weight, the elastic properties and heat resistance will deteriorate, and in particular, the durability against dry heat treatment, warm heat treatment, etc. will be greatly reduced, and the elastic performance will deteriorate significantly during these treatments.

On the other hand, if it is less than 0.1% by weight, (2) the optical properties improvement effect is insufficient.

Hindered phenol compound 'kNB used in the present invention
Examples of component) include those having a structural unit represented by the following (V).

In the formula (V), R represents a hydrogen atom, a methyl group, or an ethyl group) Those having a structural unit of the formula (V) preferably have a molecular weight of 500 or more, and specifically, those having a molecular weight of 500 or more are preferable. Examples of such compounds include:

3.9-bis[2-+3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,8i0-tetraoxasbio[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)1 triethylene glycol-bis-
3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate and the like can be preferably used.

In addition, the sulfur-containing ester compound ((C)
As component), it is an ester compound having at least one sulfur atom in the molecule, and specifically, an ester compound having the structure of the following formula (Vl) or (■) is preferable. “ )z
(Vl) (R# SR' C00CHz +h
C(Vi) (However, in the formula, R' represents an alkylene 1 having 1 to 10 carbon atoms, and R'' represents an alkyl group having 3 to 40 carbon atoms.) Preferred examples of R' include a methylene group, an ethylene group, Examples include a propylene group, a butylene group, a hexylene group, and preferred examples of R' include an octyl group, a decyl group, a tridecyl group, a dodecyl group, a myristyl group, and a stearyl group.

Specific examples of these sulfur-containing ester compounds include:
Dioctylthiodipropionate, didodecylthiodipropionate, dodecylstearylthiodipropionate, disterarylthiodipropionate, simyristylthiodipropionate, didecylthiodipropionate, didodecyl-β, β′-thio Dibutyrate, distearyl-β, β′-thiodibutyrate, pentaerythol-tetrakis (dodecylthiopropionate), pentaerythol-tetrakis (dodecylthioacetate), pentaerythol-tetrakis (dodecylthiobutyrate) , pentaerythritol-tetrakis (octadecylna 10 bionate), pentaerythritol-
Examples include tetrakis (laurylthiopropionate). Among these, didodecylthiodipropionate, disterialylthiodipropionate, distearyl-β,β′-thiodibutyrate, pentaerythritol-tetrakis (dodecylthiopropionate), pentaerythritol-tetrakis ( laurylthiopropionate) is preferred.

The blending amount of the hindered phenol compound (component (8)) and the sulfur-containing ester compound (compound (C)) in the polyether ester block copolymer is 0.02~ It is necessary to set the content to 2% by weight, and it is particularly preferable to set the content to 0.1 to 0.5% by weight. As the amount of these components (B) and (C) increases during the copolymerization, the light resistance of the elastic thread obtained from the copolymer increases due to the synergistic effect with the hindered amine compound (A) component. At the same time, the durability improvement effect of elastic performance and light resistance against dry heat treatment, warm heat treatment, etc. is recognized. However, if the blending amount is too large, hindered amine compounds
1 (component (A)), the elastic performance decreases conversely. Especially dry heat treatment.

The elastic performance after moist heat treatment etc. is significantly reduced.

Therefore, it is important to balance the blending amounts of component (A), component (8), and component (C), and it is preferable to blend them so as to satisfy the following formula (I).

1.0≦A/(B10)≦5.0...CI)
In addition, when the proportions of component (8) and component (C) are approximately the same as shown in the range of formula (n) below, the effect of improving elastic performance and light resistance is particularly high. Largely desirable.

1.5≦B/C≦2.0...
(■) Compounding agent used in the present invention, titanium compound ((D)
Ingredients) include fatty acid salts such as titanium oxalate and acetate, tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, organic acid salts such as aromatic acids such as benzoic acid and monotrimellitic acid, titanium oxides,
Alternatively, composite oxides with metal elements such as zirconium may be mentioned, but tetraalkyl titanate titanium oxides are particularly preferred.Among titanium oxides, anatase type is preferred, and rutile type is preferred. Due to surface activity, light resistance and heat resistance are reduced, which is not preferable.

The amount of component (D) added to the polyether ester block copolymer must be 0.1 to 1.0% by weight, particularly 0.1 to 0. Preferably, the amount is .5% by weight.
By blending component (D) into the copolymer, the elastic properties of the resulting elastic thread are improved; ) and sulfur-containing ester compounds ((
Even in the presence of component (C), if the amount of component (D) is too large, the light resistance and heat resistance will decrease. In addition, the occurrence of foreign substances 11 increases in the copolymer, and the spinning properties tend to deteriorate. Therefore, it is preferable that the blending amount of the DJ acid component be within the range of formula (1m) below.

0.02≦D/A≦0.5...
(lit) The method of adding the above-described compounding agents (A) component, (8) component, (C) component, and (D) component to the polyether ester block copolymer is not particularly limited. A method of adding components FA) to ([1) into one culm of polycondensation reaction of an ester block copolymer, or - a screw extruder, a twin screw extruder, an 0-lumixer.
Any method may be employed, such as adding the components (A) to fD) to the molten polyetherester block copolymer using a Banbury mixer or the like.

Note that the ultra-thinning viscosity 'r■ of the polyether ester block copolymer used in the present invention is preferably 1.1 or more.
If it is less than 1.1, the mechanical properties of the finally obtained elastic system will be insufficient. The higher the IV, the higher the IV is 1.1 or more, the better, but if it is too high, melt spinning becomes difficult, and
Not realistic from a cost perspective, preferably 1.3 to 1.7
are used.

<Effects of the Invention> The elastic thread made of the polyether ester block copolymer composition of the present invention has low permanent deformation, excellent elastic performance and light resistance, and is also excellent against dry heat treatment, hot heat treatment, etc. It can be used for woven or knitted fabrics that exhibit durability and therefore require elastic performance and light resistance, and the effect is extremely large.

In addition, the polyether ester block copolymer composition of the present invention provides an elastic body with excellent heat resistance and light resistance, and can be extrusion blow molding or profile extrusion molding, so it is particularly suitable for use at high temperatures. areas such as tubes, hoses and belts.

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

<Example> The present invention will be specifically described below with reference to Examples. In the Examples, all parts r and j indicate a heavy state part.

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

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

2. Elongation recovery (1) Instant 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, and quickly reduce the sample length to 1 cm. Read it and calculate it using the following formula.

Instantaneous elongation recovery rate = ([10-(r-10)] /101 xloo
(%) (2) Elongation elastic modulus The elongation elastic modulus was determined by the measuring method specified in the JIS L 1073 (1977) Synthetic Fiber System Test Method, Yoshiyoshi Elastic Modulus Method.

(31 Permanent deformation length 10) A load equivalent to 100% elongation was applied to 10 samples and left for 4 hours, then the load was removed and the length of the sample 1'■ after being left for 4 hours was measured. , was calculated using the following formula.

Permanent strain = ([(f' -10) 1 /101 x
lQO (2) Strength and elongation Using a sample with a length of 5 cm, stretch it at a tensile rate of 1000%/min, and determine the strength and elongation at break by DI.

3. The tensile strength retention rate (%) of the light-resistant elastic yarn sample after irradiation for 40 hours was measured using a fade meter and expressed as X.

Examples 1-9. Bikyo Examples 1 to 8 167.3 parts of dimethyl terephthalate, 105 parts of tetramethylene glycol, 275 parts of polytetramethylene glycol with a number average molecular weight of 2000, and 0.2 parts of tetrabutyl titanate were charged into a reactor, and transesterification was carried out at 190°C in an inner hot water. The reaction was carried out. When about 70% of the methanol of theory 1 was distilled off, component (0) listed in Table 1 was added as a 20% slurry or solution of tetramethylene glycol, and a condensation reaction was started at 21°C by increasing temperature and reducing pressure. . The m-condensation reaction took about 30 minutes to make 301] 1 g, then took another 30 minutes to make 3 parts/ml 1 g, and then 111 g! ) 19 or less vacuum at an internal temperature of 245 °C for 200 minutes, add the components (A), FB), and (C) listed in Table 1, and further react for 20 minutes at 245 °C in a vacuum of 1ffi11 (J or less). The reaction was carried out.

After forming the polyether ester block copolymer into a pellet, the pellet was dried and then melted at 265°C.
Discharge J13.9g from a cap with 3-hole nozzle
The polymer was extruded at /min. This polymer was wound through two body rolls at a speed of 1500 m/min to obtain an elastic yarn. The performance of this elastic yarn is shown in Table 2.

(T)c:+shiro5-” l middle Procedural amendment Heisei 1 year

Claims (1)

[Scope of Claims] (1) For a polyether ester block copolymer having aromatic polyester units as hard segments and poly(alkylene oxide) glycol units as soft segments, (A) a hindered amine compound of 0.1 -5% by weight (B) 0.02-2% by weight of a hindered phenol compound (C) 0.02-2% by weight of a sulfur-containing ester compound (D) 0.1-1% by weight of a titanium compound Characteristic polyetherester block copolymer composition. (2) The amounts of compounding agents (A) to (D) are as follows (I)
The polyetherester block copolymer composition according to claim (1), which simultaneously satisfies formulas (III) to (III). 1.0≦A/(B+C)≦5.0 (I) 0.5≦B/C≦2.0...(II) 0.02≦D/A≦0.5...(III) (However, A, B, C, and D indicate the blending amount (% by weight) of the hindered amine compound, hindered phenol compound, sulfur-containing ester compound, and titanium compound, respectively.)