KR101423609B1 - Thermoplastic elastomer composition comprising polyamide and method for preparating the same - Google Patents

Abstract

Disclosed is a polyamide thermoplastic elastomer composition. According to the present invention, a polyamide thermoplastic elastomer composition includes 5-95 wt% of a polyolefin elastomer and 5-95 wt% of polyamide and is cross-linked by electron beam irradiation, or the like. The polyamide thermoplastic elastomer composition can have an excellent mechanical property and a heat-resisting property due to electron beam irradiation and thus can be used as a raw material in various engineering fields, such as automobile and aviation, and so on. Also, since the composition is reformable, has an excellent elastic restoring force and does not require a large number of reinforcing materials during forming, the composition is eco-friendly and is capable of saving energy upon manufacturing.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic elastomer composition and a method for producing the thermoplastic elastomer composition,

TECHNICAL FIELD The present invention relates to an elastomer composition, and more particularly, to a polyamide thermoplastic elastomer composition comprising a polyamide and a polyolefin elastomer.

Rubber, which is often called Rubber, is a material that has inherent properties such as high elongation, flexibility, resilience and high frictional force that other materials can not have. It is widely used in daily necessities, automobile and electrical and electronic parts, medical supplies, It is one of the main materials used in all industries ranging from civil engineering to civil engineering. In contrast, thermoplastic elastomer (TPE) material has a physical crosslinking structure unlike a thermosetting rubber which forms a permanent chemical crosslinking, and exhibits rubber elasticity such as a general thermosetting rubber at a temperature range of use. However, in the condition that physical crosslinking is dissociated, It has melt processability like plastic. Due to these characteristics, TPE material is easy to rework, energy is reduced during product molding, scrap is scarcely generated, and it is an eco-friendly material that is much lighter than general thermosetting rubber which is applied in the form of adding a large amount of reinforcing agent. Demand is growing at a rapid pace. With this trend, interest in TPE materials as eco-friendly materials is increasing in various engineering fields as well as in automobile and aviation fields. However, the conventional TPE materials have problems in that they can not be used due to low heat resistance and low mechanical properties for use as engineering materials requiring high temperature conditions and excellent mechanical properties such as automobile and aviation fields.

An object of the present invention is to provide a resin composition which is excellent in mechanical properties and heat resistance and can be used as materials for various engineering fields such as automobiles and aviation while being thermoplastic and can be re-molded, has a low permanent strain, And to provide a thermoplastic elastomer composition capable of reducing energy.

According to an aspect of the present invention, there is provided a polyolefin elastomer composition comprising 5 to 95% by weight of a polyolefin elastomer; And 5 to 95% by weight of a polyamide; and the polyamide-based thermoplastic elastomer composition is a crosslinked polyamide-based thermoplastic elastomer composition.

The polyamide thermoplastic elastomer composition may further comprise 1 to 50 parts by weight of a maleic polyolefin elastomer based on 100 parts by weight of the total of the polyolefin elastomer and the polyamide.

The crosslinking may be formed by electron beam irradiation.

The crosslinking may be formed by irradiating 1 kGy to 300 kGy of electron beams.

The polyolefin-based elastomer may be at least one selected from the group consisting of EPDM (ethylene propylene diene rubber), EPR (ethylene propylene rubber) and polyolefin copolymer.

The crosslinking may be formed of at least one selected from the polyolefin-based elastomer and the maleated polyolefin-based elastomer.

The polyamide-based elastomer composition may be a polyamide-based thermoplastic elastomer composition having a permanent tensile strain (%) of 0% to 50%.

The polyamide-based elastomer composition may have a flow property by being deformed at a melting point or higher of the polyamide.

The polyamide may be at least one selected from the group consisting of aliphatic polyamide, polyphthalamide, and aromatic polyamide.

According to another aspect of the present invention, there is provided a process for producing a polyolefin elastomer comprising the steps of: (a) preparing a mixture comprising a polyolefinic elastomer and a polyamide; And a step of crosslinking the mixture to prepare a thermoplastic elastomer composition (step b), wherein the polyamide-based thermoplastic elastomer composition is a thermoplastic elastomer composition.

The step (a) is a step of adding a maleic polyolefin-based elastomer to the polyamide and mixing (step a-1); And a step (a-2) of preparing a mixture by mixing the polyolefin-based elastomer with the product of step a-1.

The crosslinking may be performed by electron beam irradiation.

The crosslinking can be carried out by irradiating 1 kGy to 300 Kgy of an electron beam.

The step (a) may be carried out by stirring at a temperature set at a temperature higher than the melting temperature of the polyamide.

According to another aspect of the present invention, an elastomeric material including the polyamide-based thermoplastic elastomer composition may be provided.

According to another aspect of the present invention, there is provided a component including the elastic material used in any one selected from the fields of life, sports, architecture, civil engineering, automobile, aviation, medical and electric and electronic technology.

The thermoplastic elastomer composition of the present invention is excellent in mechanical properties and heat resistance and can be used as a material for various engineering fields such as automobile and aviation. It is thermoplastic and can be re-formed, has a low permanent strain and does not require a large amount of reinforcing material It is environmentally friendly and has the effect of saving energy in manufacturing.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the mechanism by which a thermoplastic elastomer composition is produced. Fig.
Fig. 2 shows the result of measurement of mechanical properties according to the composition ratio of the thermoplastic elastomer composition material in Test Example 1. Fig.
Fig. 3 shows the stress-strain curves of the thermoplastic elastomer composition in Test Example 2 in accordance with the electron beam irradiation amount.
4 shows changes in the permanent set of tension according to the irradiation dose of the thermoplastic elastomer composition in Test Example 3. Fig.
Fig. 5 is a photograph showing the result of the reformation test according to the electron beam irradiation amount of the thermoplastic elastomer composition in Test Example 4. Fig.

After the polyamide-based thermoplastic elastomer composition of the present invention is described, the production method thereof will be described.

The polyamide-based thermoplastic elastomer composition of the present invention comprises a polyolefin-based elastomer and a polyamide.

In some cases, the thermoplastic elastomer composition may further include a maleic polyolefin-based elastomer. At this time, the maleic polyolefin-based elastomer can function as a compatibilizer of the composition.

Specifically, the thermoplastic elastomer composition may include 5 to 95% by weight of a polyolefin elastomer and 5 to 95% by weight of a polyamide.

In some cases, the thermoplastic elastomer composition may further comprise 1 to 50 parts by weight of the maleated polyolefin elastomer based on 100 parts by weight of the thermoplastic elastomer, that is, the total of the polyolefin elastomer and the polyamide.

The polyolefin-based elastomer may be an ethylene propylene diene rubber (EPDM), an ethylene propylene rubber (EPR), or various other polyolefin-based copolymers.

The thermoplastic elastomer composition may be crosslinked, and it is preferable that the crosslinking is formed in a polyolefin-based elastomer, in a maleated polyolefin-based elastomer, or in a polyolefin-based elastomer and a maleated polyolefin-based elastomer. If crosslinking is formed on the polyamide, reworkability may be lowered.

The polyolefin-based elastomer including the polyolefin elastomer and the maleated polyolefin elastomer can act as a factor for increasing the tensile strength and the elongation at break of the composition by the chemical cross-linking structure. The above-mentioned chemical cross-linking structure can be realized by electron beam irradiation treatment, and other possible methods within the scope of the present invention may be used.

The maleic polyolefin elastomer is preferably contained in an amount of 1 to 50 parts by weight, more preferably 3 to 20 parts by weight, still more preferably 3 to 20 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic elastomer composition 5 to 15 parts by weight may be further included

When the amount of the maleic polyolefinic elastomer is less than 1 part by weight based on the weight of the thermoplastic elastomer composition 100, the effect of increasing the compatibility of the polyamide and the polyolefinic elastomer may not be sufficient, It is undesirable because the flexibility may be lowered or the process cost may be increased.

The polyamide may be an aliphatic polyamide such as a polyamide p represented by the following structural formula 1, a polyamide q represented by the structural formula 2 or the like, and may be an aromatic polyamide such as polyphthalamide, aromatic polyamide polyamide) may be applied.

[Structural formula 1]

In the above formula 1,

n is an integer of 10 to 10000,

p is an integer from 2 to 50;

[Structural formula 2]

In the above formula 2,

n is an integer from 5 to 5000,

q is an integer from 2 to 50,

r is an integer from 2 to 50;

The polyamide p is exemplified by polyamide 6, polyamide 11, polyamide 12, and the like. The polyamide q, r may be polyamide 6,6, polyamide 6,10, polyamide 6,12, or the like.

The polyamide may be contained in the thermoplastic elastomer composition in an amount of 5 to 95 wt%, more preferably 10 to 90 wt%, and still more preferably 15 to 80 wt%, as described above.

When the content of the polyamide is less than 5% by weight, the proportion of the solid phase is too small, which is not preferable for the physical properties and reprocessability. When the content exceeds 95% by weight, the proportion of the polyolefin flexible phase is too small.

The polyamide thermoplastic elastomer composition of the present invention preferably has a permanent set (%) in a range of 0% to 50%, and has a flow property that is deformed at a temperature higher than the melting temperature of the polyamide contained in the elastomer composition desirable.

Hereinafter, a method for producing the polyamide thermoplastic elastomer composition of the present invention will be described.

First, the polyolefin elastomer and the polyamide are mixed to prepare a mixture (step a).

Preferably, the step (a) comprises adding a maleic polyolefin elastomer to the polyamide and mixing the polyolefin elastomer (step a-1), and then mixing the product of step a-1 with a polyolefin elastomer (step a- 2). ≪ / RTI >

It is preferred that the mixtures prepared in the mixture step a-1 and step a-2 are stirred for a predetermined time so as to be sufficiently mixed, and the total stirring time in step a is carried out for 5 minutes to 30 minutes, depending on the case .

Next, the mixture is crosslinked to prepare a thermoplastic elastomer composition (step b).

The crosslinking is preferably performed by electron beam irradiation, and the electron beam irradiation can be performed in the range of 1 to 300 kGy, preferably 1 to 250 kGy, more preferably 1 to 100 kGy have.

The electron beam irradiation treatment can cause a cross-linking reaction between polymers included in the thermoplastic elastomer composition of the present invention, preferably between polyolefin elastomers, that is, between maleated polyolefin elastomers and polyolefin elastomers, between polyolefin elastomers Or maleic polyolefin elastomer, and the degree of crosslinking may be varied depending on the electron beam irradiation amount. Therefore, depending on the material to which the thermoplastic elastomer is applied, the electron beam dose may be varied to control its characteristics.

The mechanism by which the thermoplastic elastomer composition is produced according to the above-described method is schematically shown in Fig. According to FIG. 1, a crosslinked reaction occurs between polyolefin elastomers by irradiating the produced composition with an electron beam to prepare a thermoplastic elastomer composition having improved mechanical properties.

The polyamide-based thermoplastic elastomer composition produced by the above method can be applied to various industrial fields such as electric and electronic parts, construction, civil engineering, high-performance engineering, sports goods and the like that simultaneously require elasticity and durability.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

Manufacturing example  One

22.5 g of polyamide 12 (number average molecular weight 25,000 g / mol, Arkema) was added to HAAKE Internal Mixer (600 QC) set at 190 ° C. and stirred for 2 minutes. Then, maleated EPDM (malated EPDM, mepDM (Royaltuf 498, maleic anhydride to 1 wt%, number average molecular weight 110,000 g / mol, Chemtura) was added and stirred for 2 minutes. Thereafter, 22.5 g of EPDM (570 F grade, molecular weight 190,000 g / mol, manufactured by Kumhopolychem) was added and stirred for 6 minutes to prepare a composition.

Manufacturing example  2

A composition was prepared in the same manner as in Production Example 1, except that 18 g of polyamide 12 and 27 g of EPDM were used.

Manufacturing example  3

A composition was prepared in the same manner as in Production Example 1, except that 13.5 g of polyamide 12 and 31.5 g of EPDM were used.

Manufacturing example  4

A composition material was prepared in the same manner as in Production Example 1 except that 9 g of polyamide 12 and 36 g of EPDM were used.

Example  One

The composition material prepared according to Preparation Example 1 was cooled, finely chopped and made into a sheet (150x150x1 mm3) 1 mm thick using a hot press (QM900M), and dumbbell shaped specimen was prepared according to ASTM D412 standard Respectively. The specimen was irradiated with electron beam of 25 kGy in a nitrogen atmosphere at 10 MeV and 1 mA using an electron beam accelerator (EB-tech) to prepare a thermoplastic elastomer composition.

Example  2

A thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that the electron beam was irradiated at an irradiation dose of 50 kGy.

Example  3

A thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that the electron beam was irradiated with an irradiation dose of 100 kGy.

Example  4

A thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that the composition material prepared according to Preparation Example 2 was used.

Example  5

A thermoplastic elastomer composition was prepared in the same manner as in Example 4, except that the electron beam was irradiated at an irradiation dose of 50 kGy.

Example  6

A thermoplastic elastomer composition was prepared in the same manner as in Example 4 except that the electron beam was irradiated with an irradiation dose of 100 kGy.

Example  7

A thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that the composition material prepared according to Preparation Example 3 was used.

Example  8

A thermoplastic elastomer composition was prepared in the same manner as in Example 7, except that the electron beam was irradiated with an irradiation dose of 50 kGy.

Example  9

A thermoplastic elastomer composition was prepared in the same manner as in Example 7, except that the electron beam was irradiated at an irradiation dose of 100 kGy.

Example  10

A thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that the composition material prepared in Preparation Example 4 was used.

Example  11

A thermoplastic elastomer composition was prepared in the same manner as in Example 10, except that the electron beam was irradiated with an irradiation dose of 50 kGy.

Example  12

A thermoplastic elastomer composition was prepared in the same manner as in Example 10, except that the electron beam was irradiated with an irradiation dose of 100 kGy

Example  13

A thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that maleated EPDM was not included in the composition material prepared according to Preparation Example 1.

Example  14

A thermoplastic elastomer composition was prepared in the same manner as in Example 4, except that maleated EPDM was not included in the composition material prepared according to Preparation Example 2.

Example  15

A thermoplastic elastomer composition was prepared in the same manner as in Example 7, except that maleated EPDM was not included in the composition material prepared according to Preparation Example 3.

Example  16

A thermoplastic elastomer composition was prepared in the same manner as in Example 10, except that maleated EPDM was not included in the composition material prepared according to Production Example 4.

Comparative Example  One

A thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that the electron beam irradiation treatment was not performed.

Comparative Example  2

A thermoplastic elastomer composition was prepared in the same manner as in Example 4, except that the electron beam irradiation treatment was not performed.

Comparative Example  3

A thermoplastic elastomer composition was prepared in the same manner as in Example 7, except that the electron beam irradiation treatment was not performed.

Comparative Example  4

A thermoplastic elastomer composition was prepared in the same manner as in Example 10, except that the electron beam irradiation treatment was not performed.

Comparative Example  5

A thermoplastic elastomer composition was prepared in the same manner as in Example 13, except that the electron beam irradiation treatment was not performed.

Comparative Example  6

A thermoplastic elastomer composition was prepared in the same manner as in Example 14 except that the electron beam irradiation treatment was not performed.

Comparative Example  7

A thermoplastic elastomer composition was prepared in the same manner as in Example 15, except that the electron beam irradiation treatment was not performed.

Comparative Example  8

A thermoplastic elastomer composition was prepared in the same manner as in Example 16, except that the electron beam irradiation treatment was not performed.

Table 1 below summarizes the components constituting the compositions of Examples 1 to 16 and Comparative Examples 1 to 8 and the dose of electron beam irradiation.

EPDM (g) Polyamide 12 (g) mPDM (g) Electron beam (e-beam) dose, (kGy) Example 1 22.5 22.5 4.5 25 Example 2 22.5 22.5 4.5 50 Example 3 22.5 22.5 4.5 100 Example 4 27.0 18.0 4.5 25 Example 5 27.0 18.0 4.5 50 Example 6 27.0 18.0 4.5 100 Example 7 31.5 13.5 4.5 25 Example 8 31.5 13.5 4.5 50 Example 9 31.5 13.5 4.5 100 Example 10 36.0 9.0 4.5 25 Example 11 36.0 9.0 4.5 50 Example 12 36.0 9.0 4.5 100 Example 13 22.5 22.5 - 25 Example 14 27.0 18.0 - 25 Example 15 31.5 13.5 - 25 Example 16 36.0 9.0 - 25 Comparative Example 1 22.5 22.5 4.5 - Comparative Example 2 27.0 18.0 4.5 - Comparative Example 3 31.5 13.5 4.5 - Comparative Example 4 36.0 9.0 4.5 - Comparative Example 5 22.5 22.5 - - Comparative Example 6 27.0 18.0 - - Comparative Example 7 31.5 13.5 - - Comparative Example 8 36.0 9.0 - -

[Test Example]

Test Example  1: composition of the composition not irradiated with electron beam Polyamide and EPDM Analysis of mechanical properties according to weight ratio of polymer

In order to analyze the relationship between the tensile strength and the elongation at break according to the weight ratio of the polyamide and the EPDM polymer in the polyamide-based composition sheet before the electron beam irradiation treatment, tensile stress was applied to the sheet prepared according to Comparative Examples 1 to 8, Tensile test was carried out.

Specifically, the tensile strength was measured at a tensile speed of 10 mm / min (cross head speed) at room temperature by ASTM D412 using a universal testing machine (UTM, United Co, Model STM-1OE) Tensile strength, elongation at break and Young's modulus were obtained.

The tensile test analysis results of the composition specimens according to Comparative Examples 1 to 4 are shown in Fig.

2, the tensile strength and the elongation at break of the EPDM polymer and the polyamide 12 varied depending on the ratio by weight of the mixture. Specifically, the higher the ratio of polyamide 12 to the mixed material, the higher the tensile strength but the tendency of the elongation at break to decrease. On the other hand, the tensile strength decreased as the ratio of EPDM polymer increased, but the elongation at break tended to increase. Also, when comparing Comparative Examples 1 to 4 and Comparative Examples 5 to 8, tensile strength and elongation at break were changed by addition of mEPDM. Specifically, as the mPDM was added to the mixed material, both tensile strength and elongation at break tended to increase. It is considered that the increase of the compatibility through the imidization reaction between mEPDM and polyamide 12 results in a decrease in the interfacial distance between EPDM and polyamide, thereby increasing the physical properties of the composition.

Here, in the composition material before the electron beam irradiation treatment used in the present invention, the EPDM polymer mainly plays a role of increasing the elongation at break, and the mEPDM serves to increase the compatibility of the EPDM polymer with the polyamide, And that it is mainly involved in. It can be understood that optimum mechanical properties can be obtained according to an appropriate combination of the two components, and that the optimum composition material before irradiation with electron beams necessary for the present invention can be selected.

Test Example  2: Analysis of Mechanical Properties of Thermoplastic Elastomer Composition by Electron Beam Irradiation

In order to examine the tensile strength of the thermoplastic elastomer composition according to the dose of electron beam irradiation, the thermoplastic elastomer composition specimens prepared according to Examples 1 to 12 and Comparative Examples 1 to 4 were subjected to tensile test And a stress-strain curve is shown in Fig.

3, in the graphs (c) and (d), the elongation at break decreases and the tensile strength tends to increase as the electron beam dose increases. On the contrary, graphs (a) and (b) show that, unlike the graphs (c) and (d), the tensile strength increases and the elongation at break is not decreased even when the electron beam dose is increased. Rather, in the graph (a), except for the irradiation of 100 kGy (Example 3), the elongation at break increased and the tensile strength decreased with increasing electron beam irradiation.

These results are due to the fact that the EPDM in the composition is selectively crosslinked due to electron beam irradiation. Therefore, in the graphs (c) and (d), the EPDM content is higher than that of the polyamide 12, so that the properties of the EPDM based on the selective crosslinking reaction are more dominant than those of the polyamide 12.

As a result, the graphs (c) and (d) show a tendency that the selective crosslinking reaction of EPDM due to the irradiation of electron beams is relatively large, thereby increasing the tensile strength and decreasing the elongation at break. On the other hand, The graph shows that the content of EPDM is relatively low, which indicates that the properties due to the selective crosslinking reaction of EPDM by the electron beam irradiation and the physical properties represented by the polyamide 12 are complex. It is believed that mEPDM and EPDM can bond with polyamide 12 and EPDM due to partial crosslinking due to electron beam irradiation, in addition to the reaction commercialization of mEPDM and polyamide 12.

Comparing Comparative Examples 5 to 8 with Examples 13 to 16, it can be seen that there is a change in physical properties even only by the electron beam irradiation treatment of 25 kGy. In detail, due to the electron beam irradiation of 25 kGy, the elongation at break was decreased but the tensile strength was increased as shown in Examples 15 and 16 in Comparative Examples 7 and 8. In Comparative Example 6, both tensile strength and elongation at break Whereas in Comparative Example 5, as shown in Example 13, the tensile strength was decreased, but the elongation at break was increased. As described above, in Examples 14 and 15 in which EPDM content was high due to the difference in selective crosslinking due to electron beam irradiation according to the content of EPDM, the selective crosslinking reaction was relatively increased, and tensile strength was increased and elongation at break was decreased , Whereas Examples 13 and 14 are relatively low in EPDM content, so that it is considered that the properties due to the selective crosslinking reaction of EPDM and the physical properties exhibited by polyamide 12 are manifested in a complex manner. Therefore, it can be understood that an elastomer composition having various physical properties can be manufactured by controlling the EPDM content and the electron beam irradiation amount in the EPDM / mEPDM / polyamide 12 composition.

Test Example  3: Analysis of Elastic Restoration Characteristic of Thermoplastic Elastomer Composition According to Electron Beam Irradiation

In order to analyze the elastic restoration characteristics of the thermoplastic elastomer composition according to the dose of electron beam irradiation, the thermoplastic elastomer composition sheets of Examples 1 to 16 and Comparative Examples 1 to 8 were tested for the permanent set of strain (E (%)) ) Were measured.

The permanent tensile strain may be defined by the following equation. Permanent elongation strain values are useful for measuring the elastic recovery of elastomers. The smaller the measured value, the higher the elastic restoration rate.

E (%) = 100 [L-L (0) / L (0)

In this formula,

L is the final length of the specimen after the permanent tensile strain test,

L (0) is the length of the specimen before the permanent strain test.

Specifically, an external force was applied to the specimen to change the length to 100%, and then the specimen was held for 10 minutes while maintaining the external force. Thereafter, the external force was removed, the length (L) of the specimen was waited until there was no change in length, and the permanent strain was measured according to the above equation. The results are shown in FIG.

According to FIG. 4, in the case of (a), there is no measurement value from 0 to 50 kGy because the sample is not stretched to 100% and the sample is broken during external force application. In addition, when irradiated with electron beams of 50 kGy or more, the change was slight. (b) showed a tendency of permanent stretching to decrease from 0 to 50 kGy and a slight decrease at 50 to 100 kGy. In the cases of (c) and (d), the elongation at break was similar to that of electron beam irradiation. This is because the selective crosslinking reaction of EPDM is almost entirely extended by electron beam irradiation. (b), it can be concluded that the crosslinking reaction between mEPDM and EPDM, which form a copolymer with polyamide 12, binds the entire composition components as the electron beam irradiation amount increases. In addition, it was found that the permanent stretching strain of Comparative Example 8 and Example 16, which was irradiated with 25 kGy by electron beam irradiation, was reduced due to irradiation of 25 kGy electron beam.

Likewise, it was found through comparison examples 6 to 8 and comparative examples 2 to 4 that the permanent elongation strain due to the increase in compatibility of mEPDM was decreased. It can be concluded that the selective crosslinking reaction due to electron beam irradiation and the increased compatibility of EPDM and polyamide due to mEPDM exhibit a more effective elastic recovery rate by reducing the permanent elongation strain as described above.

Test Example  4: Influence of electron irradiation on thermoplastic elastomer composition Reformation  Character analysis

In order to analyze the reformation forming properties of the thermoplastic elastomer composition of the present invention upon irradiation with electron beams, a small amount of the specimen of the thermoplastic elastomer composition sheet produced according to Examples 1, 4, 7, and 10 was peeled off and hot pressed (QM900M) Under a temperature condition of 180 ° C, a pressure of 5 MPa was applied to check whether deformation occurred.

The thermoplastic elastomer compositions prepared according to Examples 1, 4, 7, and 10 were compared with photographs after deformation and shown in Fig.

According to FIG. 5, it was found that deformation due to heat occurred in the specimen subjected to electron beam irradiation.

These results show that the crosslinked reaction of EPDM in the specimens subjected to electron beam irradiation partially shows thermoplastic properties.

The mechanical properties of Examples 1, 4, 7, 10 and 13 to 16 showing the best properties as thermoplastic elastomers are shown in Table 2 below, 8 were summarized.

Referring to Table 2, it can be seen that the thermoplastic elastomer composition irradiated with the electron beam has a higher value of the permanent elongation strain than the thermoplastic elastomer composition not irradiated with the electron beam.

Samples
(25 kGy) Young's modulus
(MPa) The tensile strength
(MPa) Elongation at break
(%) Permanent elongation strain
(%) Example 1 27 3.85 76 - Example 4 8 2.75 256 4 Example 7 9 3.65 312 4 Example 10 4 3.45 547 2.67 Example 13 103 3.74 28 - Example 14 42 2.56 72 - Example 15 7 1.73 79 - Example 16 3 1.58 234 3 Comparative Example 1 76 4.78 62 - Comparative Example 2 21 2.55 131 16 Comparative Example 3 6 1.61 360 4 Comparative Example 4 3 1.91 660 4 Comparative Example 5 148 4.26 21 - Comparative Example 6 51 2.29 38 - Comparative Example 7 4 1.47 97 - Comparative Example 8 2 1.21 310 6

* Permanent elongation: measured after 100% elongation for 10 minutes

* In Examples 1, 13 to 15 and Comparative Examples 1 and 5 to 7, 100% elongation before fracture and no measurement of permanent elongation strain

Claims (14)

5 to 95% by weight of a polyolefin elastomer; And
And 5 to 95% by weight of a polyamide; and the thermoplastic elastomer composition is a polyamide-
The polyamide-based thermoplastic elastomer composition is crosslinked,
Wherein the polyolefin-based elastomer is at least one selected from the group consisting of EPDM (Ethylene Propylene Diene Monomer), EPR (Ethylene Propylene Rubber) and a polyolefin-based copolymer. The method according to claim 1,
Wherein the polyamide-based thermoplastic elastomer composition further comprises 1 to 50 parts by weight of a maleic polyolefin-based elastomer based on 100 parts by weight of the total of the polyolefin-based elastomer and the polyamide. The method according to claim 1,
Wherein the crosslinking is formed by electron beam irradiation. ≪ RTI ID = 0.0 > 18. < / RTI > The method of claim 3,
Wherein the crosslinking is formed by irradiating 1 kGy to 300 kGy of an electron beam. delete 3. The method according to claim 1 or 2,
Wherein the crosslinking is formed of at least one selected from the polyolefin elastomer and the maleated polyolefin elastomer. The method according to claim 1,
Wherein the polyamide-based elastomer composition has a permanent tensile strain (%) of 0% to 50%. The method according to claim 1,
Wherein the polyamide-based elastomer composition has a flow property by being deformed at a melting point or higher of the polyamide. The method according to claim 1,
Wherein the polyamide is at least one selected from the group consisting of an aliphatic polyamide, a polyphthalamide, and an aromatic polyamide. Preparing a mixture comprising a polyolefinic elastomer and a polyamide (step a); And
And crosslinking the mixture to prepare a thermoplastic elastomer composition (step b)
Wherein the polyolefinic elastomer is at least one selected from the group consisting of EPDM (Ethylene Propylene Diene Monomer), EPR (Ethylene Propylene Rubber) and a polyolefin-based copolymer. 11. The method of claim 10,
The step a
Adding a maleic polyolefinic elastomer to the polyamide and mixing (step a-1); And
A process for producing a polyamide-based thermoplastic elastomer composition, which comprises a step (a-2) of mixing a product of step a-1 with a polyolefin-based elastomer to prepare a mixture. 11. The method of claim 10,
Wherein the crosslinking is carried out by electron beam irradiation. ≪ RTI ID = 0.0 > 21. < / RTI > 13. The method of claim 12,
Wherein the crosslinking is carried out by irradiating 1 kGy to 300 kGy of electron beam (Electron beam). 11. The method of claim 10,
Wherein the step (a) is carried out by stirring at a temperature set at a temperature higher than the melting temperature of the polyamide.

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