KR102006842B1 - Thermoplastic elastomer composition using bio-based material - Google Patents

Abstract

The present invention is a matrix resin consisting of bio ethylene propylene diene monomer (EPDM) rubber, polypropylene and bio polyethylene; Peroxide crosslinking agents; Crosslinking aids; Antioxidants; Inorganic fillers; Polypropylene waxes; And UV stabilizer; relates to a thermoplastic elastomer composition comprising.

Description

Thermoplastic elastomer composition using a bio material {THERMOPLASTIC ELASTOMER COMPOSITION USING BIO-BASED MATERIAL}

The present invention relates to thermoplastic elastomer compositions using biomaterials.

Rubber has a disadvantage in that it is not recycled and has low productivity, and the need for replacement thereof has recently been greatly increased. Thermoplastic elastomer (TPE) has been developed as a material for solving the problems of the rubber.

Thermoplastic elastomer has been used as a substitute material for rubber in automobile parts as it is recognized as a recyclable rubber material as an intermediate material between plastic and rubber, and as the environmental problem of PVC has recently emerged, it is becoming more promising as a substitute for soft PVC. have.

At present, the government is actively promoting the use of bio-materials as a policy of a country / company that encourages various environmental regulations and the use of eco-friendly materials.

Korean Patent Publication No. 2005-0020003 (2005.03.04.)

The present invention is to provide an environmentally friendly thermoplastic elastomer composition that can increase the bio-derived portion in the composition to highlight the environmentally friendly aspect while maintaining the same or superior properties of the existing petroleum-based PP / EPDM thermoplastic elastomer.

The present invention is a matrix resin consisting of bio ethylene propylene diene monomer (EPDM) rubber, polypropylene and bio polyethylene; Peroxide crosslinking agents; Crosslinking aids; Antioxidants; Inorganic fillers; Polypropylene waxes; And UV stabilizer; Thermoplastic elastomer composition comprising,

The content of the bio EPDM rubber is 60% by weight based on the total weight of the matrix resin,

The content of the polypropylene is 20% by weight relative to the total weight of the matrix resin,

The content of the bio polyethylene is 20% by weight based on the total weight of the matrix resin,

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 parts by weight based on 100 parts by weight of the matrix resin,

The content of the UV stabilizer provides a thermoplastic elastomer composition, characterized in that 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 may be usefully applied as an eco-friendly thermoplastic elastomer composition while replacing petroleum-based EPDM by replacing the existing petroleum-based EPDM and manufacturing petroleum-based thermoplastic elastomer.

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

In the present invention, the bio EPDM rubber refers to EPDM rubber derived from ethylene produced using bio raw materials such as sugar cane, corn and soybeans.

The thermoplastic elastomer composition according to the present invention contains 60% by weight of bio EPDM rubber with respect to the total weight of the matrix resin. When the content of bioEPDM rubber is less than 60% by weight, the elasticity of the product may be lowered and the sensitivity may be reduced.

In one embodiment of the present invention, the bio EPDM rubber has a Mooney viscosity of 55 or more at 125 ℃.

In the present invention, the Mooney viscosity is measured through a Mooney viscometer, the torque value of the rotating spindle (torque) when rotating the material to be measured in the die heated to a specific temperature (die) it means.

In an exemplary 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 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 during extrusion / injection molding, and when the content of the polypropylene exceeds 9% by weight, the hardness and strength of the product may increase, which may cause difficulty in cutting during extrusion / injection molding.

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

In one aspect of the first embodiment of the present invention, the content of the polypropylene is 20% by weight based on the total weight of the matrix resin. If the content of the polypropylene is less than 20% by weight there may be a problem in extrusion / injection molding.

In one aspect of the first exemplary embodiment of the present invention, the polypropylene has a melt index (MI) of 0.2 to 0.5 g / 10 min at 230 ° C. and 2.16 kg. When the melt index of the polypropylene is less than 0.2 g / 10 min at 230 ° C. and 2.16 kg, it is disadvantageous in extrusion / injection molding, and when it exceeds 0.5 g / 10 min, it is difficult to control the extrusion / injection molding due to the decrease in viscosity. Occurs.

In a 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 using bio raw materials such as sugar cane, corn and soybeans.

In one aspect of the second embodiment of the present invention, the content of the bio polyethylene is 20% by weight based on the total weight of the matrix resin. If the content of the bio polyethylene is less than 20% by weight there may be a problem in extrusion / injection molding.

In one aspect of the second embodiment of the present invention, the bio-polyethylene has a melt index (MI) of 0.2 ~ 0.5 g / 10min at 190 ℃, 2.16 kg. If the melt index of the bio polyethylene is less than 0.2 g / 10 min at 190 ° C. and 2.16 kg, it is disadvantageous for extrusion / injection molding, and if the melt index of the bio polyethylene exceeds 0.5 g / 10 min, the extrusion / injection molding due to high flow Problems can arise in the control of flow.

The thermoplastic elastomer composition according to the present invention contains a peroxide crosslinking agent in an amount of 0.25 to 0.70 parts by weight based on 100 parts by weight of the matrix resin, and when the content of the crosslinking agent is less than 0.25 parts by weight, the crosslinked rubber particles are present in a heterogeneous continuous phase. Therefore, it is disadvantageous to realize a uniform appearance, and when it exceeds 0.70 parts by weight, a lot of chain cleavage of polypropylene by a peroxide crosslinking agent may occur, and an open cell may be generated.

In one embodiment of the present invention, the peroxide crosslinking agent has a half-life temperature of 170 ° 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, and when the content of the crosslinking agent is less than 0.1 parts by weight, the beneficial effect of use is insignificant, and 0.5 parts by weight. If it exceeds, fish eye is generated on the surface of the product due to overcrosslinking, which may cause a problem in the appearance of the product.

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

The thermoplastic elastomer composition according to the present invention contains an antioxidant in an amount of 0.1 to 0.5 parts by weight with respect to 100 parts by weight of the matrix resin, and when the content of the antioxidant is less than 0.1 parts by weight, the physical properties of the composition are lowered and performance is reduced when the finished product is used for a long time. Problems may occur, and if the amount exceeds 0.5 parts by weight, a problem may occur in which a blooming occurs in the product.

In an exemplary embodiment of the present invention, the antioxidant has a melting point of 120 ° C. or more and a whiteness of 95% or more, preferably tetrakis (3,5-di-tertiary-butyl-4-hydroxyphenyl) Propionate (tetrakis (3,5-di-tertbutyl-4-hydroxyphenyl) propionate), tetrakis- (3-dodecylthiopropionate), or mixtures thereof 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, and when the content of the inorganic filler is less than 10 parts by weight, the material cost increases and the role as a filler is insignificant. Exceeding the parts by weight increases the specific gravity of the product, making the extrusion difficult due to the hardness increase and flowability of the inorganic filler.

In one embodiment of the present invention, the inorganic filler has a particle size of 10 μm 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 a polypropylene wax in an amount of 0.5 to 1.0 parts by weight based on 100 parts by weight of the matrix resin, and when the content of the polypropylene wax is less than 0.5 parts by weight, the scratch resistance of the finished product is improved. Insignificantly, it is not effective for improving wear resistance, and if it is 1.0 parts by weight or more, polypropylene wax may be transferred to the surface of the finished product, which may cause a problem in implementing product characteristics. In addition, 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 wear resistance is increased.

In one embodiment of the present invention, 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 the present invention contains a UV stabilizer in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the matrix resin, and when the content of the UV stabilizer is less than 0.5 parts by weight, surface whitening and fine cracks are generated by UV attack. If it exceeds 10 parts by weight, a low molecular weight UV stabilizer is transferred to the surface, which may cause a problem of blooming on the exterior of the product.

In one embodiment of the present invention, the UV stabilizer is a benzotriazole type UV absorber, oligomeric HALS type UV stabilizer, or a mixture thereof.

In the third exemplary embodiment of the present invention, the thermoplastic elastomer composition further includes a process oil, and the process oil is not limited so long as it serves to improve processability of the composition.

In one aspect of the third exemplary embodiment of the present invention, the process oil is a paraffin oil, and the thermoplastic elastomer composition contains 20 to 50 parts by weight of the paraffin oil with respect to 100 parts by weight of the matrix resin, wherein the content of the paraffin oil is If the amount is less than 20 parts by weight, the flowability during extrusion may be poor, which may cause mold defects and work defects. If the content exceeds 50 parts by weight, the melt strength may be lowered.

In one aspect of the third exemplary embodiment of the present invention, the paraffin oil has a Kinematic Viscosity in the range of 170 ° C. or higher. If the kinematic viscosity of paraffin oil is 170 or more, the melt strength may be lowered due to an increase in the viscosity 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 only for the purpose of illustration to help the understanding of the present invention is not limited to the scope and scope of the present invention by the following examples.

Preparation Example 1 Preparation of Thermoplastic Elastomers Containing Matrix Resin Consisting of EPDM Rubber and Polypropylene

Composition Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Petroleum EPDM Rubber (wt%) 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 High Viscosity Paraffin Oil
(Parts by weight) 40 40 40 40 40 40

In Table 1, the unit of the component is weight percent based on the total weight of the matrix resin, and the weight ratio is based on the petroleum or bio EPDM rubber and 100 weight ratio of the matrix resin including polypropylene.

In addition, the brand names and manufacturers of each component in Table 1 are as follows.

Petroleum EPDM Rubber: [KEP-2480, KEP Corporation]

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

* Universal polypropylene: [RP2400, Korea Petrochemical Co., Ltd.]

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

Crosslinking aid: N, N'-m-phenylenedimaleimide [TAC-50, DEGUSA Corporation]

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

Inorganic filler: calcium carbonate [SF, Dongho Calcium Co., Ltd.]

Polypropylene Wax: [500 Series, Lion Chemtech]

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

Paraffinic oil: [KL900B, SJC Corporation]

The thermoplastic elastomer composition of Comparative Examples 1 to 3 and Examples 1 to 3 with the same composition as in Table 1 was prepared by an extrusion method according to a general manufacturing method known in the art.

( Experimental Example  One) Comparative example  1 to 3 and Example  Basic Properties of Thermoplastic Elastomers Prepared with Each Composition of 1-3

With respect to the thermoplastic elastomers of Comparative Examples 1 to 3 and Examples 1 to 3 prepared in Preparation Example 1, the basic physical properties were measured based on KS M 6518, and hardness and tensile test specimens [House 3], tear specimens [Tear Type A] 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 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, when Examples 1 to 3 in the bio-epdm rubber, not petroleum-based EPDM rubber in the mattress resin as shown in the physical properties of the same as the existing thermoplastic elastomer composition of Comparative Examples 1 to 3 It can be seen. Therefore, it is possible to increase the bio-derived portion in the thermoplastic elastomer as compared to the existing thermoplastic elastomer composition, such as Comparative Examples 1 to 3 to highlight the environment-friendly aspect.

Preparation Example 2 Preparation of a Thermoplastic Elastomer Composition Comprising a Matrix Resin Consisting of Polypropylene, Bio Polyethylene, or a Mixture thereof and EPDM Rubber

The thermoplastic elastomer compositions of Comparative Examples 1, 4, 5, Examples 1, 4, and 5 were prepared in the same manner as in Preparation Example 1, using the same composition as in Table 3 below.

Composition Comparative Example 1 Comparative Example 4 Comparative Example 5 Example 1 Example 4 Example 5 Petroleum EPDM Rubber (wt%) 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 High Viscosity Paraffin Oil
(Parts by weight) 40 40 40 40 40 40

In Table 3, the unit of the component is weight percent based on the total weight of the matrix resin, and the weight ratio is based on petroleum or polypropylene, bio polyethylene, or a mixture thereof and 100 weight ratio of the matrix resin composed of EPDM rubber. to be.

In addition, the brand name and the manufacturer of the bio polyethylene in Table 3 is [SGM9450F, Ecomass Korea, Inc.], the brand name and manufacturer of the remaining components are shown in Table 1.

( Experimental Example  2) Comparative example  1, 4, 5, Example  Basic Properties of Thermoplastic Elastomers Prepared with Compositions 1, 4, and 5

For the thermoplastic elastomers of Comparative Examples 1, 4, 5, Examples 1, 4, and 5 prepared in Preparation Example 2, basic physical properties were measured based on KS M 6518, and hardness and tensile test specimens [Hard type 3], Tear specimen [Tear A type] was 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 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 increasing the content of the bio polyethylene in Example 5, the physical properties due to compatibility problems are partially reduced, but it can be seen that the hardness, tensile strength, elongation at break and tear strength do not fall significantly. As in Example 4, when using a suitable combination of polypropylene and bio polyethylene, it can be seen that the physical properties of the physical properties and the existing thermoplastic elastomer composition is equivalent. Therefore, compared to the existing thermoplastic elastomer compositions such as Comparative Examples 1, 4 and 5, it is possible to include bio EPDM rubber in the thermoplastic elastomer composition and to increase the content of bio polyethylene to increase the bio-derived portion in the thermoplastic elastomer, thereby highlighting environmentally friendly aspects. have.

Claims (12)

Matrix resins composed of bio ethylene propylene diene monomer (EPDM) rubber, polypropylene and bio polyethylene; Peroxide crosslinking agents; Crosslinking aids; Antioxidants; Inorganic fillers; Polypropylene waxes; And UV stabilizer; Thermoplastic elastomer composition comprising,
The content of the bio EPDM rubber is 60% by weight based on the total weight of the matrix resin,
The content of the polypropylene is 20% by weight relative to the total weight of the matrix resin,
The content of the bio polyethylene is 20% by weight based on the total weight of the matrix resin,
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 parts by weight based on 100 parts by weight of the matrix resin,
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 polyethylene is a thermoplastic elastomer composition characterized in that the melt index (MI) is 0.2 ~ 0.5g / 10min at 190 ℃, 2.16 kg. The method of claim 1, wherein the bio EPDM rubber has a Mooney viscosity of 55 or more at 125 ℃, the bio EPDM rubber comprises 5-ethylidene-2-norbornene, The content of the thermoplastic elastomer composition, characterized in that 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 polypropylene has a melt index (MI) of 0.2 to 0.5 g / 10 min at 230 ° C. and 2.16 kg. delete 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 µm or less and a whiteness of 95% or more. The thermoplastic elastomer composition of 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, an oligomeric HALS type UV stabilizer, or a mixture thereof. . The thermoplastic elastomer composition of claim 1, wherein the thermoplastic elastomer composition further comprises paraffin oil. The thermoplastic elastomer composition according to claim 11, wherein the paraffin oil has a kinematic viscosity in the range of 170 or more.