KR20160123473A - Thermoplastic elastomer composition - Google Patents

Abstract

The present invention relates to a resin composition comprising a matrix resin comprising one or both of Bio EPDM (Ethylene Propylene Diene Monomer) rubber and polypropylene and bio-polyethylene; Peroxide crosslinking agents; Crosslinking auxiliary; Antioxidants; Inorganic fillers; Polypropylene wax; And UV stabilizers. ≪ Desc / Clms Page number 2 >

Description

THERMOPLASTIC ELASTOMER COMPOSITION [0001]

The present invention relates to a thermoplastic elastomer composition using a biomaterial.

Rubber has a disadvantage in that it can not be used for recycling and productivity is low, and the need for replacement thereof has been greatly increased recently. A thermoplastic elastomer (TPE) has been developed as a material to solve the problem of such a rubber.

The thermoplastic elastomer is recognized as a recyclable rubber material between plastic and rubber, and has been used as a substitute for rubber in automobile parts. Recently, as the environment problem of PVC has emerged, it is more promising as a substitute material of soft PVC It is becoming.

Currently, it is actively promoting the use of biomaterials as a policy of national / corporations that encourages the use of various environmental regulations and environmentally friendly materials.

Korean Patent Laid-Open Publication No. 2005-0020003 (Mar. 4, 2005)

The present invention provides an eco-friendly thermoplastic elastomer composition capable of enhancing the bio-derived portion of the composition while maintaining physical properties equivalent to or superior to those of conventional petroleum-based PP / EPDM thermoplastic elastomers, do.

The present invention relates to a bio-EPDM (Ethylene Propylene Diene Monomer) rubber, and a matrix resin comprising one or both of polypropylene and bio-polyethylene; Peroxide crosslinking agents; Crosslinking auxiliary; Antioxidants; Inorganic fillers; Polypropylene wax; And UV (ultraviolet light) stabilizer, wherein the thermoplastic elastomer composition comprises:

The content of the bio EPDM rubber is 20 to 50% by weight based on the total weight of the thermoplastic elastomer composition,

The content of the peroxide crosslinking agent is 0.25 to 0.70 parts by weight based on 100 parts by weight of the matrix resin,

The content of the crosslinking aid is 0.1 to 0.5 parts by weight based on 100 parts by weight of the matrix resin,

The content of the antioxidant is 0.1 to 0.5 parts by weight based on 100 parts by weight of the matrix resin,

The content of the inorganic filler is 10 to 20 parts by weight based on 100 parts by weight of the matrix resin,

The content of the polypropylene wax is 0.5 to 1.0 part by weight based on 100 parts by weight of the matrix resin,

Wherein the content of the UV stabilizer is 0.5 to 10 parts by weight based on 100 parts by weight of the matrix resin.

The bio thermoplastic elastomer composition according to the present invention can be used as an environmentally friendly thermoplastic elastomer composition while replacing the petroleum EPDM with an existing eco-friendly thermoplastic elastomer by replacing the existing petroleum EPDM.

Hereinafter, the thermoplastic elastomer composition according to the present invention will be described in detail.

In the present invention, the bio EPDM rubber means an EPDM rubber derived from ethylene produced by using a biomaterial such as sugar cane, corn, soybean, and the like.

The thermoplastic elastomer composition according to the present invention contains the bio EPDM rubber in an amount of 20 to 50% by weight based on the total weight of the thermoplastic elastomer composition. When the content of the bio EPDM rubber is less than 20% by weight, If the content of the bio EPDM rubber exceeds 50% by weight, the viscosity of the product increases and the extrusion molding operation becomes difficult, and the production cost of the product increases.

In one embodiment of the present invention, the bio EPDM rubber has a Mooney viscosity of at least 55 at 125 占 폚.

In the present invention, the Mooney viscosity is measured through a Mooney viscometer. When the material to be measured is put into a die heated at a specific temperature and rotated, the torque value of a rotating spindle it means.

In one embodiment of the present invention, the bio EPDM rubber includes 5-ethylidene-2-norbornene (ENB).

In one embodiment of the present invention, the content of the 5-ethylidene-2-norbornene is 4 to 9% by weight based on the total weight of the bio EPDM rubber. If the content of the polypropylene is less than 4% by weight, there may be a problem in extrusion / injection molding. If the content of the polypropylene exceeds 9% by weight, the hardness and strength of the product may increase, and cutting during extrusion / injection molding may be difficult.

In a first embodiment of the present invention, the matrix resin comprises a thermoplastic elastomer composition wool characterized by comprising bio EPDM rubber and polypropylene.

In one aspect of the first aspect of the present invention, the content of the polypropylene is 30 to 40% by weight based on the total weight of the thermoplastic elastomer composition. If the content of the polypropylene is less than 30% by weight, there may be a problem in extrusion / injection molding. If the content of the polypropylene is more than 50% by weight, the hardness may increase and there may be a sensitivity problem of the product.

In one aspect of the first embodiment of the present invention, the polypropylene has a melt index (MI) of 0.2 to 0.5 at 230 占 폚 and 2.16 kg. If the melt index of the polypropylene is less than 0.2 at 230 캜 and at 2.16 kg, it is disadvantageous in extrusion / injection molding. If the melt index is higher than 0.5, control becomes difficult during extrusion / injection molding due to a decrease in viscosity.

In the second embodiment of the present invention, the matrix resin includes bio EPDM rubber and bio-polyethylene.

In the present invention, bio-polyethylene refers to polyethylene produced by using biomaterials such as sugar cane, corn, soybeans and the like.

In one aspect of the second aspect of the present invention, the content of the bio-polyethylene is 20 to 30% by weight based on the total weight of the thermoplastic elastomer composition. If the content of the bio-polyethylene is less than 20% by weight, there may be a problem in the extrusion / injection molding. If the content is more than 30% by weight, the hardness may increase and the product may have sensitivity problems.

In one aspect of the second embodiment of the present invention, the bio-polyethylene has a melt index (MI) of 0.2 to 0.5 at 190 占 폚 and 2.16 kg. If the melt index of the bio-polyethylene is less than 0.2 at 190 ° C and less than 0.2 at 2.16 kg, if the melt index of the bio-polyethylene exceeds 0.5, problems in control of flow during extrusion / May occur.

The thermoplastic elastomer composition according to the present invention contains a peroxide crosslinking agent in an amount of 0.25 to 0.70 part by weight based on 100 parts by weight of the matrix resin. When the content of the crosslinking agent is less than 0.25 part by weight, And when it is more than 0.70 part by weight, the polypropylene chain is severed by the peroxide crosslinking agent, resulting in an open cell.

In one embodiment of the present invention, the peroxide crosslinking agent has a half-life temperature of 170 DEG C and a molecular weight of 290 or more, preferably 2,5-dimethyl-2,5-di- (tertiarybutylperoxy) hexane 2,5-Dimethyl-2,5-di- (tert-butylperoxy) -hexane).

The thermoplastic elastomer composition according to the present invention contains a crosslinking aid in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the matrix resin. When the content of the crosslinking agent is less than 0.1 parts by weight, If the amount is more than 1 part by weight, cross-linking may cause fish eye on the surface of the product, which may cause problems in the appearance of the product.

In one embodiment of the present invention, the crosslinking assistant is N, N'-m-phenylenedimaleimide, 1,2-polybutadiene, or a mixture thereof.

The thermoplastic elastomer composition according to the present invention contains the antioxidant in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the matrix resin. When the content of the antioxidant is less than 0.1 parts by weight, the physical properties of the composition are deteriorated. There may be a problem of performance deterioration. If the amount is more than 0.5 part by weight, a problem may occur that a product is blooming.

In one embodiment of the present invention, the antioxidant has a melting point of 120 ° C or higher and a whiteness of 95% or higher, preferably tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) Tetrakis- (3-dodecylthiopropionate), or a mixture thereof. The term " tetrakis (3,5-di-tert-butylphenyl) propionate " have.

The thermoplastic elastomer composition according to the present invention contains an inorganic filler in an amount of 10 to 20 parts by weight based on 100 parts by weight of the matrix resin. If the content of the inorganic filler is less than 10 parts by weight, the material ratio increases and its role as a filler becomes insignificant If it exceeds 20 parts by weight, the specific gravity of the product increases, and the extrusion molding operation becomes difficult due to the increase of the hardness and the flowability of the inorganic filler.

In one embodiment of the present invention, the inorganic filler has a particle size of 10 mu m or less and a whiteness of 95% or more.

In one embodiment of the present invention, the inorganic filler is calcium carbonate.

The thermoplastic elastomer composition according to the present invention contains the polypropylene wax in an amount of 0.5 to 1.0 part by weight based on 100 parts by weight of the matrix resin. When the content of the polypropylene wax is less than 0.5 part by weight, the scratch resistance The improvement effect is insufficient and it is not effective in improving the abrasion resistance. When the amount is 1.0 part by weight or more, the polypropylene wax is transferred to the product surface of the finished product, which may cause problems in implementation of product characteristics. When the content of the polypropylene wax is 0.5 parts by weight or more and 1.0 parts by weight or less, the surface slip property of the finished product is improved and the abrasion resistance is increased.

In one embodiment of the present invention, the propylene-based wax has a specific gravity of 0.90 or less and a melting point of 160 ° C or more.

The thermoplastic elastomer composition according to the present invention contains 0.5 to 10 parts by weight of a UV stabilizer per 100 parts by weight of the matrix resin. When the content of the UV stabilizer is less than 0.5 parts by weight, surface whitening and micro cracks If the amount is more than 10 parts by weight, a UV stabilizer having a low molecular weight may be migrated to the surface, resulting in a problem of blooming in appearance of the product.

In one embodiment of the present invention, the UV stabilizer is a benzotriazole type UV absorber, an Oligomeric Hindered Amine Light Stabilizer type UV stabilizer, or a mixture thereof.

In the third embodiment of the present invention, the thermoplastic elastomer composition further comprises a process oil, and the process oil does not limit the process oil so far as it serves to improve the processability of the composition.

In one aspect of the third aspect of the present invention, the process oil is paraffin oil, and the thermoplastic elastomer composition contains the paraffin oil in an amount of 20 to 50 parts by weight based on 100 parts by weight of the matrix resin. If the content is less than 20 parts by weight, the flowability during extrusion molding is poor, which may cause defective molding and defective work. If the content is more than 50 parts by weight, the melt strength may be lowered.

In one aspect of the third embodiment of the present invention, the paraffin oil has a kinematic viscosity at 40 DEG C of 170 or more. When the kinematic viscosity of the paraffin oil is 170 or more, the melt strength may be lowered due to viscosity increase of the product.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to examples. However, these examples are provided for illustrative purposes only in order to facilitate understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.

( Manufacturing example  One) EPDM  Thermoplastics including mattress resins composed of rubber and polypropylene Erastomeric  Produce

Constituent Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Petroleum-based EPDM rubber (% by weight) 60 70 80 - - - Bio EPDM rubber
(weight%) - - - 60 70 80 Polypropylene (% by weight) 40 30 20 40 30 20 Peroxide crosslinking agent (parts by weight) 0.25 0.25 0.25 0.25 0.25 0.25 Crosslinking aid (parts by weight) 0.25 0.25 0.25 0.25 0.25 0.25 Antioxidant
(Parts by weight) 0.2 0.2 0.2 0.2 0.2 0.2 Inorganic filler
(Parts by weight) 10 10 10 10 10 10 UV stabilizer
(Parts by weight) 5 5 5 5 5 5 Polypropylene wax
(Parts by weight) One One One One One One Highly viscous paraffin oil
(Parts by weight) 40 40 40 40 40 40

In Table 1, the weight% is a content ratio of the thermoplastic elastomer composition to the total weight, and the weight ratio is a content ratio with respect to 100 weight ratio of the matrix resin comprising petroleum-based or bio EPDM rubber and polypropylene.

In Table 1, trade names and manufacturers of each component are as follows.

Petroleum-based EPDM rubber: [KEP-2480, KEP Corporation]

Bio-based EPDM rubber: [KELTAN 5470,9950 ECO, LANXESS]

General-Purpose Polypropylene: [RP2400, Korean Oil Company]

Peroxide crosslinking agent: 2,5-dimethyl-2,5-di- (tertiarybutylperoxy) hexane [Luperox 101-50D, Atochem]

Crosslinking aid: N, N'-m-phenylene dimaleimide [TAC-50, DEGUSA]

Antioxidant: tetrakis (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate [SEENOX 412, Shipro Kasei]

Inorganic filler: calcium carbonate [SF, Dongho Calcium]

Polypropylene wax: [500 series, Lion Chemtech]

UV stabilizer: Benzotriazole type UV absorber, Oligomeric HALS type UV stabilizer [BASF]

Paraffin oil: [KL900B, SJC]

The thermoplastic elastomer compositions of Comparative Examples 1 to 3 and Examples 1 to 3 in the composition as shown in Table 1 were prepared by an extrusion molding method according to a general manufacturing method known in the art.

( Experimental Example  One) Comparative Example  1 to 3 and Example  1 to 3 < / RTI > Erastomeric  Basic property measurement

The basic properties of the thermoplastic elastomers of Comparative Examples 1 to 3 and Examples 1 to 3 prepared in Preparation Example 1 were measured according to KS M 6518, and the hardness and tensile specimen [dumbbell triangle], tear specimen [Tear A type] was used. The measurement results are shown in Table 2 below.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 basic
Properties Hardness (Shore A) 90 88 86 90 88 86 Tensile strength (kgf / cm3) 180 170 160 180 170 160 Elongation at break (%) 680 660 640 680 660 640 Tear strength (kgf / cm) 72 60 54 70 61 53

As shown in Table 2 above, when the bio EPDM rubber other than the petroleum EPDM rubber was included as the mattress resin in Examples 1 to 3, the physical properties of the EPDM rubber with the existing thermoplastic elastomer compositions as in Comparative Examples 1 to 3 were equivalent . ≪ / RTI > Therefore, compared to the conventional thermoplastic elastomer compositions as in Comparative Examples 1 to 3, the bio-derived portion in the thermoplastic elastomer can be increased to highlight the environment-friendly aspect.

( Manufacturing example  2) polypropylene, bio-polyethylene, or mixtures thereof and EPDM  Thermoplastics including mattress resins made of rubber Erastomer  Preparation of composition

The thermoplastic elastomer compositions of Comparative Examples 1, 4 and 5 and Examples 1, 4 and 5 were prepared in the same manner as in Production Example 1, respectively, with the compositions shown in Table 3 below.

Constituent Comparative Example 1 Comparative Example 4 Comparative Example 5 Example 1 Example 4 Example 5 Petroleum-based EPDM rubber (% by weight) 60 60 60 - - - Bio EPDM rubber
(weight%) - - - 60 60 60 Polypropylene (% by weight) 40 20 - 40 20 - Bio-polyethylene (% by weight) - 20 40 - 20 40 Crosslinking agent (parts by weight) 0.25 0.25 0.25 0.25 0.25 0.25 Crosslinking aid (parts by weight) 0.25 0.25 0.25 0.25 0.25 0.25 Antioxidant
(Parts by weight) 0.2 0.2 0.2 0.2 0.2 0.2 Inorganic filler
(Parts by weight) 10 10 10 10 10 10 UV stabilizer
(Parts by weight) 5 5 5 5 5 5 Polypropylene wax
(Parts by weight) One One One One One One Highly viscous paraffin oil
(Parts by weight) 40 40 40 40 40 40

In Table 3, the weight% of the constituent components is the content ratio of the thermoplastic elastomer composition with respect to the total weight, and the weight ratio of the thermoplastic elastomer composition to the thermoplastic elastomer composition is in a weight ratio of 100 to the weight ratio of the mattress resin composed of petroleum or polypropylene, .

In Table 3, the trade name of the bio-polyethylene and its manufacturer are [SGM9450F, EcoMax Korea Co., Ltd.], and the trade names and manufacturers of the remaining components are shown in Table 1.

( Experimental Example  2) Comparative Example  1, 4, 5, Example  1, 4, and 5, Erastomeric  Basic property measurement

The basic properties of the thermoplastic elastomers of Comparative Examples 1, 4, 5 and Examples 1, 4 and 5 prepared in Preparation Example 2 were measured according to KS M 6518, and the hardness and tensile specimen ] And tear specimen [Tear A type] were used. The measurement results are shown in Table 4 below.

division Comparative Example 1 Comparative Example 4 Comparative Example 5 Example 1 Example 4 Example 5 basic
Properties Hardness (Shore A) 90 87 84 90 85 81 Tensile strength (kgf / cm3) 180 170 160 180 163 150 Elongation at break (%) 680 670 650 680 660 630 Tear strength (kgf / cm) 70 67 62 70 64 55

As shown in Table 4, when the content of bio-polyethylene was increased in Example 5, the physical properties due to the compatibility problem were partially reduced, but the hardness, tensile strength, elongation at break and tear strength were not significantly decreased , It can be seen that when the polypropylene and bio-polyethylene are used in appropriate combination as in Example 4, the physical properties and the physical properties with the existing thermoplastic elastomer composition are equivalent. Thus, in comparison with conventional thermoplastic elastomer compositions such as Comparative Examples 1, 4, and 5, the thermoplastic elastomer composition includes the bio EPDM rubber, and the content of bio-polyethylene is increased to increase the bio-derived portion in the thermoplastic elastomer The environmentally friendly aspect can be highlighted.

Claims (16)

A bio-EPDM (Ethylene Propylene Diene Monomer) rubber, and a matrix resin comprising one or both of polypropylene and bio-polyethylene; Peroxide crosslinking agents; Crosslinking auxiliary; Antioxidants; Inorganic fillers; Polypropylene wax; And a UV stabilizer, wherein the thermoplastic elastomer composition comprises:
The content of the bio EPDM rubber is 20 to 50% by weight based on the total weight of the thermoplastic elastomer composition,
The content of the peroxide crosslinking agent is 0.25 to 0.70 parts by weight based on 100 parts by weight of the matrix resin,
The content of the crosslinking aid is 0.1 to 0.5 parts by weight based on 100 parts by weight of the matrix resin,
The content of the antioxidant is 0.1 to 0.5 parts by weight based on 100 parts by weight of the matrix resin,
The content of the inorganic filler is 10 to 20 parts by weight based on 100 parts by weight of the matrix resin,
The content of the polypropylene wax is 0.5 to 1.0 part by weight based on 100 parts by weight of the matrix resin,
Wherein the content of the UV stabilizer is 0.5 to 10 parts by weight based on 100 parts by weight of the matrix resin. The bio EPDM rubber according to claim 1, wherein the bio EPDM rubber has a Mooney viscosity of at least 55 at 125 ° C, the bio EPDM rubber comprises 5-ethylidene-2-norbornene, Wherein the content of the thermoplastic elastomer composition is 4 to 9% by weight based on the total weight of the bio EPDM rubber. The thermoplastic elastomer composition according to claim 1, wherein the matrix resin comprises bio EPDM rubber and polypropylene. The thermoplastic elastomer composition according to claim 3, wherein the polypropylene content is 30 to 40% by weight based on the total weight of the thermoplastic elastomer composition. The thermoplastic elastomer composition according to claim 1, wherein the polypropylene has a melt index (MI) of from 0.2 to 0.5 at 230 DEG C and 2.16 kg. The thermoplastic elastomer composition according to claim 1, wherein the matrix resin comprises bio EPDM rubber and bio-polyethylene. The thermoplastic elastomer composition according to claim 6, wherein the content of the bio-polyethylene is 20 to 30% by weight based on the total weight of the thermoplastic elastomer composition. The thermoplastic elastomer composition according to claim 1, wherein the bio-polyethylene has a melt index (MI) of 190 ° C or 2.16 kg at 0.2 to 0.5. The thermoplastic elastomer composition according to claim 1, wherein the peroxide crosslinking agent has a half-life temperature of 170 ° C and a molecular weight of 290 or more. The thermoplastic elastomer composition according to claim 1, wherein the antioxidant has a melting point of 120 ° C or higher and a whiteness of 95% or higher. The thermoplastic elastomer composition according to claim 1, wherein the inorganic filler has a particle size of 10 탆 or less and a whiteness of 95% or more. The thermoplastic elastomer composition according to claim 1, wherein the inorganic filler is calcium carbonate. The thermoplastic elastomer composition according to claim 1, wherein the polypropylene wax has a specific gravity of 0.90 or less and a melting point of 160 ° C or more. The thermoplastic elastomer composition according to claim 1, wherein the UV stabilizer is a benzotriazole type UV absorber, a HALS type UV stabilizer (Oligomeric Hindered Amine Light Stabilizer type UV stabilizer), or a mixture thereof. Composition. The thermoplastic elastomer composition of claim 1, wherein the thermoplastic elastomer composition further comprises a paraffin oil. 16. The thermoplastic elastomer composition according to claim 15, wherein the paraffin oil has a kinematic viscosity at 40 DEG C of 170 or more.