KR101481224B1 - Thermoplastic Polyetherester Elastomer Composition with Improved Heat Resistance and Flowability and Product Prepared by Composition - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a thermoplastic polyetherester elastomer resin composition having improved heat resistance and fluidity and a molded article produced from the composition. More particularly, the present invention relates to a thermoplastic polyetherester elastomer resin composition having improved heat stability and fluidity, And a thermoplastic polyetherester elastomer resin composition which can be applied to fields requiring an excellent surface property, and a molded article produced from the composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic polyetherester elastomer resin composition having improved heat resistance and fluidity, and a molded article produced from the composition. [0002] Thermoplastic polyetherester elastomer composition,

TECHNICAL FIELD The present invention relates to a thermoplastic polyetherester elastomer resin composition having improved heat resistance and fluidity and a molded article produced from the composition. More particularly, the present invention relates to a thermoplastic polyetherester elastomer resin composition having improved heat stability and fluidity, And a thermoplastic polyetherester elastomer resin composition which can be applied to a field where an excellent surface property is required, and a molded article produced from the composition.

Vulcanized rubber, which is a conventional elastic material, is formed by vulcanization of a low-viscosity rubber raw material produced by natural or artificial synthesis, and is excellent in flexibility and resilience, but has problems of recycling due to complicated molding process, poor stability, And so on.

Various thermoplastic elastomers (TPE) such as styrene type, urethane type, olefin type and amide type have been developed to solve these problems, The polyester thermoplastic elastomer which has been developed relatively recently is a thermoplastic elastic material having an ester-type chain structure. It is excellent in flexibility, resilience and stability, and is free from vulcanization. It is a general thermoplastic material such as polyethylene, polypropylene, (polyamide), polyester (polyester), and the like, and is applied to various fields.

In general, polymeric materials including polyester thermoplastic elastomers are decomposed into low-molecular-weight chains through a chain reaction by thermal oxidation reaction when external energy such as heat or light is lost due to a lack of thermal stability, and the mechanical properties of the resin are degraded.

The stability of these polymers is related to the structure of the polymers and the action of radicals caused by heat, light and stress. Considering these factors, the thermostabilizers (UV stabilizers), stabilizers Additives such as hydrolysis stabilizers have been developed.

For example, U.S. Patent No. 3,723,427 discloses stabilizers of the tris (hydroxybenzyl) cyanurate type, hindered phenolic primary heat-resistant agents currently known in the art, and U.S. Patent No. 3,758,579 A method of mixing a phenol-based primary heat-resistant agent with a secondary heat-resistant agent in the form of a thioester has been disclosed. However, since these methods have merely effected the effect of improving the thermal stability of the resin in the processing step, they have not obtained high heat resistance enough to be applied to a long time exposure at high temperature.

In addition, U.S. Patent No. 4,405,749 discloses that 1,3,5-tris- (2-hydroxyethy1) -s-triazine-2,4,6- (1H, 3H, 5H) trion and 3,5- discloses a method for improving the stability of a polyester resin by using an esterified product of buty1-4-hydroxy hydrocinnamic acid. However, this method also improves the stability of the resin by using a primary heat resistant agent alone or a secondary heat resistant agent , The degree of improvement in heat resistance is insignificant, and the restriction of fluidity limits the application of various products such as automobile products. In particular, the thioester-based secondary heat-resistant agent has problems such as poor color quality and poor flowability during molding, and it has been disadvantageous in that a manufacturing cost is increased due to the addition of an excessive heat stabilizer.

As described above, various thermoplastic polyester elastomer resins have been proposed in order to solve the problems caused by heat stability and inadequate fluidity during molding. However, these methods have only limited heat resistance, Of the population.

Accordingly, the present inventors have made intensive efforts to develop a thermoplastic polyester elastomer resin having excellent heat resistance and excellent flow properties, and as a result, it has been found that an oxazoline compound, an amine compound and cyclic butylene terephthalate are specified in a polyetherester block copolymer By weight, the thermal stability of the resin is satisfied, and the flow characteristics are remarkably improved, thereby completing the present invention.

The main object of the present invention is to provide a thermoplastic polyurethane foam which is suitable for a product which is required to have a high temperature and a long time heat resistance since it has excellent heat resistance and a remarkable flow characteristic, To provide an ester elastomer resin composition.

The present invention also provides a molded article produced from the thermoplastic polyester elastomer resin composition.

In order to achieve the above objects, the present invention provides a polyetherester block copolymer; Oxazoline compounds; Amine-based compounds; And a thermoplastic polyetherester elastomer resin composition comprising cyclic butylene terephthalate.

In order to produce a thermoplastic polyester elastomer resin having improved heat resistance and flow characteristics, the thermoplastic polyetherester elastomer resin composition preferably contains 0.1 to 1.5 parts by weight of an oxazoline compound based on 100 parts by weight of the polyetherester block copolymer, 0.3 to 2.0 parts by weight of an amine compound and 1.0 to 7.0 parts by weight of cyclic butylene terephthalate.

In order to produce a thermoplastic polyester elastomer resin having improved heat resistance and flow characteristics, the polyetherester block copolymer is characterized in that its surface hardness is SHORE 30D to 75D.

In order to produce a thermoplastic polyester elastomer resin having improved heat resistance and flow characteristics, the oxazoline compound is a compound represented by the following formula (1).

[Chemical Formula 1]

In order to produce a thermoplastic polyester elastomer resin having improved heat resistance and flow characteristics, the amine compound is preferably 4,4'-bis (α, α-dimethylbenzyl-disphenylamine), N, N ' Phenyl-p-phenylenediamine, N, N (N, N'-diphenyl- -Di- (1,4-dimethyl-pentyl) -p-phenylenediamine, 1,3-dibutylthiourea, p, p-dioctyldiphenylamine, 2,2,4- Dihydroquinoline and N, N'-trimethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl-propionamide).

The present invention in a further preferred form is characterized in that the weight average molecular weight of the cyclic butylene terephthalate is from 100,000 g / mol to 1,000,000 g / mol in order to produce a thermoplastic polyester elastomer resin having improved heat resistance and flow characteristics.

The present invention also provides an elastomer molded article produced from the thermoplastic polyetherester elastomer resin composition.

INDUSTRIAL APPLICABILITY The thermoplastic polyetherester elastomer resin composition according to the present invention is remarkably improved in heat resistance and fluidity, and significantly improved in thermal stability and fluidity, and can be used for a long time at a high temperature, in an injection molding of a complicated structure, .

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The present invention, in one aspect, relates to a polyetherester block copolymer; Oxazoline compounds; Amine-based compounds; And cyclic butylene terephthalate. BACKGROUND ART [0002] The present invention relates to a thermoplastic polyetherester elastomer composition.

Hereinafter, the thermoplastic polyetherester elastomer resin composition according to a specific embodiment of the present invention will be described in detail.

The thermoplastic polyetherester elastomer resin composition according to the present invention comprises a polyetherester block copolymer, an oxazoline compound, an amine compound and cyclic butylene terephthalate, so that each component has a synergistic effect and the thermoplastic polyether The ester elastomer resin composition and the molded article obtained therefrom have remarkably elevated heat resistance and flow characteristics. Accordingly, according to one embodiment of the present invention, the thermoplastic polyetherester elastomer resin composition is remarkably improved in thermal stability and fluidity, and is suitable for applications requiring high temperature and long-time heat resistance, and is suitable for molding various products And can be used in many applications without limitation.

In the present invention, the polyetherester block copolymer may have a surface hardness of SHORE 30D to 75D in terms of strength and heat resistance. If the surface hardness of the polyetherester block copolymer is less than SHORE 30D, the amount of soft segments may increase relatively, which may cause problems in strength and heat resistance. If the surface hardness exceeds SHORE 75D, the amount of hard segments increases The impact resistance may be lowered by brittle. At this time, the surface hardness can be measured according to ASTM D-2240. The polyetherester block copolymer may have a melting point of about 150 to 215 DEG C in the above range of surface hardness.

The polyetherester block copolymer may include a structure in which a hard segment represented by the following general formula (2) and a soft segment represented by the following general formula (3) are alternately repeated, and the structure is such that the hard segment and the soft segment are regularly or It can be repeated irregularly alternately. Such a polyetherester block copolymer may contain a repeating unit represented by the following formula (4).

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4, D may be a radical in which two hydroxyl groups are removed in a saturated aliphatic diol having 2 to 8 carbon atoms, a cyclic diol or a mixed structure thereof, and G is a radical having 2 to 8 carbon atoms having a molecular weight of 400 to 4000, An aromatic, aliphatic, cyclic dicarboxylic acid having 2 to 12 carbon atoms, or a mixed structure thereof having a molecular weight of 500 or less, and R may be a radical in which two hydroxyl groups have been removed from the polyether glycol or polyester glycol And n may be an integer of 7 or more.

In the present invention, the oxazoline-based compound is a 2,2-m-phenylene-bis (2-oxazoline) do.

[Chemical Formula 1]

2,2-m-phenylene-bis (2-oxazoline)] represented by the above formula (1) acts to trap the active radical, It exhibits heat resistance and hardly deteriorates the initial color. In addition, the oxazoline-based compound acts as a decomposing agent for peroxide generated in the aging process, and can act as a capturing agent for formic acid generated in the decomposition of the soft segment, so that the volatile substances can be prevented from being dispersed to the outside have.

The oxazoline compound may be added in an amount adjusted as needed to improve the durability of the thermoplastic polyetherester elastomer resin composition. In order to obtain better heat resistance, the oxazoline compound may be added in an amount of 0.1 wt% based on 100 wt. Parts of the polyetherester block copolymer And more preferably 1.5 parts by weight or less in order not to interfere with the inherent properties of the polymer elastomer. Accordingly, the content of the oxazoline compound may be 0.1 to 1.5 parts by weight based on 100 parts by weight of the polyetherester block copolymer in terms of heat resistance and flow characteristics of the resin.

 In the present invention, the amine compound serves as a heat stabilizer of the composition. Specifically, 4,4'-bis (α, α-dimethylbenzyl-diphenylamine), N, N'- Phenyl-p-phenylenediamine, N, N'-di- (1, 3-di-tert-butyl- Dimethyl-pentyl) -p-phenylenediamine, 1,3-dibutylthiourea, p, p-dioctyldiphenylamine, 2,2,4- -Trimethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl-propionamide and the like, phenylene-diamine, quinoline, diphenylamine, naphthylamine, mercaptobenzimidazole and An amine-based heat-resistant agent containing a thiourea functional group, or a mixture of heat-resistant agents composed of the same, and more preferably, from the viewpoint of the radical capturing function of the heat-resistant agent, 4,4'-bis (α, -Disphenylamine) [4,4'-bis (alpha, alpha-dimethylbenzyl diphenylamine).

At this time, the content of the amine compound is preferably 0.3 to 2 parts by weight based on 100 parts by weight of the polyetherester block copolymer. If the amount is less than 0.3 parts by weight based on 100 parts by weight of the polyetherester block copolymer, the effect on heat resistance is insufficient. If the amount is more than 2 parts by weight, it is not economical. There is a possibility that the apparent quality deterioration may occur.

In addition, the thermoplastic polyetherester elastomer resin composition according to the present invention contains cyclic buthylene terephthalate (CBT) in order to improve the fluidity of the resin. At this time, the content of cyclic butylene terephthalate is 1.0 to 7.0 parts by weight based on 100 parts by weight of the polyetherester block copolymer, and when it is used in an amount of less than 1.0 part by weight, the effect of improving the conductivity is insufficient, It may cause deterioration of other mechanical properties.

The cyclic butylene terephthalate contributes to enhancement of the melt flow in processes such as injection molding and extrusion molding and has no influence on the physical properties of the thermoplastic polyetherester elastomer as a base resin It is possible to secure a remarkable quality in a product having a unique and complex structure and a long injection flow by elaborately improving the melt flowability and thinning the mold wall, time and shortening the temperature to the molding temperature / pressure.

The cyclic butylene terephthalate according to the present invention has a weight average molecular weight of 100,000 g / mol to 1,000,000 g / mol. When cyclic butylene terephthalate having a weight average molecular weight of less than 100,000 g / mol is used, And when cyclic butylene terephthalate having a weight average molecular weight exceeding 1,000,000 g / mol is used, the effect of improving the fluidity is insufficient, which is not preferable.

In another aspect, the present invention relates to an elastomer molded article produced from the thermoplastic polyetherester elastomer resin composition.

The elastomer molded article according to the present invention can be produced by using a composition containing an oxazoline compound, an amine compound and cyclic butylene terephthalate in a polyetherester block copolymer and having improved heat resistance and fluidity, The present invention can be applied to a field in which the molded article is exposed to an external environment for a long time. As a concrete example of such an application field, the molded article may be used as an internal and external material of automobile and mechanical parts, a wiper blade cover, an airbag cover, an auto lever slide, Materials and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. It will be apparent to those skilled in the art that these examples are for illustrative purposes only and that the present invention is not construed as being limited by these examples.

[ Example  1 to 6 and Comparative Example  1 to 6]

(100 parts by weight of polyetherester block copolymer (surface hardness: SHORE 55D, Kolon)) were mixed in the compositions shown in Table 1 below. In order to maximize the physical properties of the resin composition, an extruder having two inlet ports is used. In order to maximize the physical properties of the resin composition, a polyester knit resin (hereinafter referred to as " Neat Resin), an oxazoline compound / amine compound, and cyclic butylene terephthalate were added to the second inlet. Feeder is used to ensure the quantitativeness of each component, and the input position should be the same as the first injection position. In order to prevent pyrolysis by the shear of the screw, it is desirable to minimize the residence time, and a decompression device called a vent is provided in the vicinity of the discharge part to effectively reduce the pressure to 150 mmHg or less. The resin composition thus prepared was dried in a dehumidifying drier at 90 DEG C for about 4 hours and then subjected to physical property evaluation.

division 2,2-m-phenylene-bis (2-oxazoline)
(Parts by weight) 4,4'-bis (?,? - dimethylbenz
Di-dodecylamine)
(Parts by weight) Cyclic butylene terephthalate (CBT 160 *)
(Parts by weight) Example 1 0.1 0.5 3 Example 2 0.5 1.0 5 Example 3 0.5 0.5 3 Example 4 1.0 1.5 One Example 5 1.0 2.0 7 Example 6 1.5 1.0 3 Comparative Example 1 0.05 1.0 3 Comparative Example 2 1.8 1.0 3 Comparative Example 3 0.5 0.1 5 Comparative Example 4 0.5 2.5 5 Comparative Example 5 1.0 0.5 0.5 Comparative Example 6 1.0 0.5 9 CBT 160: weight average molecular weight of 400,000 g / mol (manufactured by CYCLIC)

Hereinafter, the resin compositions prepared with the compositions exemplified in Examples and Comparative Examples of the present invention were evaluated for their physical properties based on the following evaluation criteria.

1) Heat resistance: A specimen prepared for measuring the tensile strength according to ASTM D638 was aged at 168 ° C for 100 hours, and then the tensile strength retention was calculated, and a value of 50% or less was judged to be defective.

2) Flow Index: Measured according to ASTM D1238, and the value of 30 g / 10 min was judged to be defective.

division Tensile strength retention (%)
(Heat resistance index) Flow Index (g / 10 min) Example 1 51 37 Example 2 58 41 Example 3 55 35 Example 4 67 31 Example 5 69 45 Example 6 72 35 Comparative Example 1 42 34 Comparative Example 2 58 28 Comparative Example 3 40 42 Comparative Example 4 62 27 Comparative Example 5 56 22 Comparative Example 6 48 48

As shown in Table 2, the polyetherester elastomer resin compositions of Examples 1 to 6 exhibited a tensile strength retention ratio of more than 50% and a flow index of not less than 31 g / 10 min. On the contrary, the polyetherester elastomer resin compositions of Comparative Examples 1 to 6 had a flow index of 27 g / 10 min when the tensile strength retention ratio was at most 62% (Comparative Example 4) and a tensile strength retention ratio of 48% when the flow index was 48 g / . In addition, when the oxazoline compound and the amine compound were used in a smaller amount than the reference amount (Comparative Examples 1 and 3), the tensile strength retention ratio was lowered. When the oxazoline compound and amine compound were used in excess (Comparative Examples 2 and 4) (Comparative Example 5), the fluidity was lowered. When the cyclic butylene terephthalate was used in an excess amount (Comparative Example 6), the tensile strength maintenance ratio .

Therefore, it was found that the components of the oxazoline compound, the amine compound and the cyclic butylene terephthalate contained in the polyetherester block copolymer exert synergistic effects to improve the heat resistance and fluidity of the resin.

Having described specific portions of the invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the invention is not limited thereby will be. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (7)

0.1 to 1.5 parts by weight of an oxazoline compound, 0.3 to 2.0 parts by weight of an amine compound and 1.0 to 7.0 parts by weight of cyclic butylene terephthalate based on 100 parts by weight of a polyetherester block copolymer,
Wherein the weight ratio of the oxazoline compound to the amine compound is 1: 0.6 to 1: 5.0.
delete The thermoplastic polyetherester elastomer resin composition according to claim 1, wherein the polyetherester block copolymer has a surface hardness of SHORE 30D to 75D.
The thermoplastic polyetherester elastomer resin composition according to claim 1, wherein the oxazoline compound is a compound represented by the following formula (1).
[Chemical Formula 1]

The method according to claim 1, wherein the amine compound is at least one selected from the group consisting of 4,4'-bis (α, α-dimethylbenzyl-diphenylamine), N, N'- Di-tert-butyl-4-hydrophenyl-propionamide, N-octyl-N'-phenyl- 1,3-dibutylthiourea, p, p-dioctyldiphenylamine, 2,2,4-trimethyl-1,2-dihydroquinoline and N, N'- , 5-di-tert-butyl-4-hydroxyphenyl-propionamide.
The thermoplastic polyetherester elastomer resin composition according to claim 1, wherein the cyclic butylene terephthalate has a weight average molecular weight of 100,000 g / mol to 1,000,000 g / mol.
7. An elastomer molded article produced from the thermoplastic polyetherester elastomer resin composition according to any one of claims 1 to 6.