Thermoplastic vulcanizate material, article formed by the same and method for forming the same

Abstract

A thermoplastic vuicanizate material comprises: a continuous phase comprising polyester, wherein a melting point of the polyester is less than or equal to 180° C., a dispersant phase comprising cross-linked rubber, wherein an average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

Claims

1. A thermoplastic vulcanizate material, comprising: a continuous phase comprising polyester, wherein a melting point of the polyester is less than or equal to 180° C.; and a dispersant phase comprising cross-linked rubber, wherein an average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

2. The thermoplastic vulcanizate material of claim 1, wherein the polyester has a repeating unit represented by the following formula (1): ##STR00003## wherein R.sub.1 is —(C.sub.2H.sub.4O).sub.z—, —(C.sub.4H.sub.8O).sub.z—, —(C.sub.6H.sub.12O).sub.z—, ##STR00004## z is an integer of 1 to 25; and R.sub.2 is H or a substituent.

3. The thermoplastic vulcanizate material of claim 1, wherein the polyester is co-polyester elastomer (COPE).

4. The thermoplastic vulcanizate material of claim 3, wherein the polyester is at least one selected from the group consisting of: thermoplastic polyester elastomer (TPEE) and polyethylene terephthalate glycol-co-ethylene vinyl acetate (PETG-co-EVA).

5. The thermoplastic vulcanizate material of claim 1, wherein the cross-linked rubber comprises a vinyl group, a styrene group or a combination thereof a content of the vinyl group is in a range from 10 wt % to 90 wt % based on a total weight of the cross-linked rubber when the cross-linked rubber comprises the vinyl group, and a content of the styrene group is in a range from 0.1 wt % to 70 wt % based on the total weight of the cross-linked rubber when the cross-linked rubber comprises the styrene group.

6. The thermoplastic vulcanizate material of claim 5, wherein the content of the vinyl group is in a range from 25 wt % to 60 wt % based on the total weight of the cross-linked rubber.

7. The thermoplastic vulcanizate material of claim 1, wherein the cross-linked rubber is at least one selected from the group consisting of: cross-linked styrene-butadiene rubber (SBR), cross-linked natural rubber (NR), cross-linked butadiene rubber (BR), cross-linked nitrile butadiene rubber (NBR) and cross-linked ethylene vinyl acetate rubber (EVM).

8. The thermoplastic vuicanizate material of claim 1, wherein a weight ratio of the polyester to the cross-linked rubber is in a range from 3:7 to 9:1.

9. The thermoplastic vulcanizate material of claim 8, wherein a weight ratio of the polyester to the cross-linked rubber is in a range from 4:6 to 6:4.

10. The thermoplastic vulcanizate material of claim 1, further comprising processing oil, wherein a content of the processing oil is in a range from 1 wt % to 100 wt % based on a total weight of the cross-linked rubber.

11. The thermoplastic vulcanizate material of claim 1, further comprising elastomer selected from the group consisting of hydrogenated styrene block copolymer (HSBC), thermoplastic polyurethane (TPU) and polyolefin elastomer (POE).

12. The thermoplastic vulcanizate material of claim 1, wherein the average particle diameter of the cross-linked rubber is less than or equal to 30 μm.

13. An article, which is formed by a thermoplastic vulcanizate material, wherein the thermoplastic vulcanizate material comprises: a continuous phase comprising polyester, wherein a melting point of the polyester is less than or equal to 180° C.; and a dispersant phase comprising cross-linked rubber, wherein an average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

14. A method for forming a thermoplastic vulcanizate material, comprising the following steps: providing polyester and crosslinkable rubber, wherein a melting point of the polyester is less than or equal to 180° C.; and performing a dynamic vulcanization process on a mixture comprising the polyester and the crosslinkable rubber with a crosslinking agent to obtain a thermoplastic vulcanizate material, wherein the thermoplastic vulcanizate material comprises: a continuous phase comprising the polyester, wherein a melting point of the polyester is less than or equal to 180° C.; and a dispersant phase comprising a cross-linked rubber, wherein an average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

15. The method of claim 14, further comprising a step of performing a melt blending process on the mixture comprising the polyester and the crosslinkable rubber before the dynamic vulcanization process.

16. The method of claim 14, wherein the mixture further comprises a co-agent, and a sum of a content of the co-agent and a content of the crosslinking agent is in a range from 0.1 wt % to 6 wt % based on a total weight of the mixture and the crosslinking agent.

17. The method of claim 14, wherein the mixture further comprises a co-agent, and a sum of a content of the co-agent and a content of the crosslinking agent is in a range from 0.1 wt % to 5 wt % based on a total weight of the mixture and the crosslinking agent.

18. The method of claim 14, wherein the mixture further comprises a co-agent, and a sum of a content of the co-agent and a content of the crosslinking agent is in a range from 0.1 wt % to 3.6 wt % based on a total weight of the mixture and the crosslinking agent.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0048] FIG. 1 is a TEM photo of a thermoplastic vulcanizate material prepared in Example 1-7 of the present disclosure.

[0049] FIG. 2 is a SEM photo of a thermoplastic vulcanizate material prepared in Example 1-7 of the present disclosure.

[0050] FIG. 3 is a TEM photo of a thermoplastic vulcanizate material prepared in Example 1-10 of the present disclosure.

[0051] FIG. 4 is a SEM photo of a thermoplastic vulcanizate material prepared in Example 1-10 of the present disclosure.

DETAILED DESCRIPTION OF EMBODIMENT

[0052] Different embodiments of the present disclosure are provided in the following description. These embodiments are meant to explain the technical content of the present disclosure, but not meant to limit the scope of the present disclosure. A feature described in an embodiment may be applied to other embodiments by suitable modification, substitution, combination, or separation.

[0053] It should be noted that, in the present specification, when a component is described to have an element, it means that the component may have one or more of the elements, and it does not mean that the component has only one of the element, except otherwise specified.

[0054] In the present specification, except otherwise specified, the feature A “or” or “and/or” the feature B means the existence of the feature A, the existence of the feature B, or the existence of both the features A and B. The feature A “and” the feature B means the existence of both the features A and B. The term “comprise(s)”, “comprising”, “include(s)”, “including”, “have”, “has” and “having” means “comprise(s)/comprising but is/are/being not limited to”.

[0055] In the present disclosure, except otherwise specified, the terms “almost”, “about” and “approximately” usually mean the acceptable error in the specified value determined by a skilled person in the art, and the error depends on how the value is measured or determined. In some embodiments, the terms “almost”, “about” and “approximately” mean within 1, 2, 3 or 4 standard deviations. In some embodiments, the terms “almost”, “about” and “approximately” mean within ±20%, within ±15%, within ±10%, within ±9%, within ±8%, within ±7%, within ±6%, within ±5%, within ±4%, within ±3%, within ±2%, within ±1%, within ±0.5%, within ±0.05% or less of a given value or range. The quantity given here is an approximate quantity, that is, without specifying. “almost”, “about” and “approximately”, it can still imply “almost”, “about” and “approximately”. In addition, the terms “in a range from a first value to a second value” and “in a range between a first value and a second value” mean the said range comprises the first value, the second value and other values between the first value and the second value.

[0056] In addition, the features in different embodiments of the present disclosure can be mixed to form another embodiment.

Material

A: Rubber

[0057] A-1: ESBR styrene-butadiene rubber), Zeon Corp., NIPOL® 1502

[0058] A-2: SSBR (Solution-polymerized styrene-butadiene rubber), JSR Corp., SL563R

[0059] A-3: IIR (Poly(isobutylene-isoprene), MB Fuller, KALAR® 5246

[0060] A-4: BR (Butadiene rubber), Kumho Petrochemical Co., Ltd, KBR-01

[0061] A-5: NR (Natural rubber), Hoang Dung Co., Ltd, SVR 3L

[0062] A-6: NBR (Acrylonitrile butadiene rubber), Arlanxeo Corp., PERBUNAN® 1846 F

[0063] A-7: EVM (Ethylene vinyl acetate rubber), Arlanxeo Corp., Levapred® 800

B: Plastic

[0064] B-1: TPEE (Thermoplastic polyester elastomer), T.sub.m: 145° C., Shinkong Synthetic Fibers Co., 4000-DL

[0065] B -2: PBS (Polybutylene succinate), T.sub.m: 115° C.

[0066] B -3: COPE (Co-polyester elastomer), T.sub.m: 120° C.

[0067] B-4: COPE, T.sub.m: 1.49° C.

[0068] B-5: COPE, T.sub.m: 151° C.

[0069] B-6: COPE, T.sub.m: 140° C.

[0070] B-7: COPE, T.sub.m: 140° C.

[0071] B-8: TPEE, shore A: 45, T.sub.m: 150° C., Mitsubishi Chemical Co., TEFABLOC A1400N

[0072] B-9: TPEE, shore A: 61, T.sub.m: 150° C., Mitsubishi Chemical Co., TEFABLOC A1500N

[0073] B-L10: TPEE, shore A: 67, T.sub.m: 160° C., Mitsubishi Chemical Co., TEFABLOC A1606C

[0074] B-11: PETG (Poly(ethylene terephthalate-co-1,4-cyclohexylene dimethylene terephthalate), T.sub.m: 260° C., SK Chemicals Co., SKYGREEN® K2012

[0075] B-12: EVA (Ethylene-vinyl acetate copolymers), T.sub.m: 84° C., USI Corp., POLYMER-E ®EV-103

C: Processing Oil

[0076] C-1: Naphthenic and paraffinic oils, Ergon Inc., HyPrene L2000

[0077] C-2: Naphthenic oils, Eneos Corporation, BUENO GR 500

[0078] C-3: Paraffinic Oil, Michang Oil Ind. Co., Fomi 550

D: Compatibilizer

[0079] D-1: Ethylene-glycidyl metharylate polystyrene copolymer, NOF Corp., MOMPER® A4100

[0080] D-2: Aromatic water-based resin, Mitsui Chemicals Co., FTR™ 6100

[0081] D-3: EAA (Ethylene acrylic acid copolymers), Dow Chemicals Co., PRIMACOR® 5980I

E. Peroxide

[0082] E-1: 80% of polypropylene and 20% 2,5-Dimethyl-2,5-bis(tert-butylperoxy)hexane, MannTek Co., Ltd, CR PP-20X

F. Co-Agent

[0083] F-1: 75% N, N′-m-phenylene bismaleimide and 25% ethylene propylene terpolymer, Attnan Co., Ltd, Atnen PDM-75

[0084] F-2: Syndiotactic-1,2-polybutadiene, JSR Corp., RB-830

G: Anti-Scorch Agent

[0085] G-1: 2,2,6,6-Tetramethylpiperidinooxy, Merck Chemical Co., TEMPO

H: Filler

[0086] H-1: Silica, Sibelco Group, Silverbond 925

I: Additive

[0087] I-1: Plasticizer, UPC Group, UN640

[0088] I-2: Tetra isopropyl titanate, catalyst, Borica Co., Ltd., TYTAN-TIPT

[0089] I-3: Lithium Neodecanoate, catalyst, EGE KIMYA Sanayive Ticaret A.S., EGECat® 1D6121

J: Anti-Oxidant

[0090] J-1: Benzeneproanole acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diylbis(2,2-dimethyl-2,1-ethaned iyl)ester), Chemicals, AO20

[0091] J-2: Bis(2,4-dicumylphenyl)pentaeryythritol diphosphate, Dover Chemical Corporation, S9228

[0092] J-3: Tetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenyldiphosphonite, Clariant International Ltd, AddWorks LXR 568

[0093] J-4: Tetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenyldiphosphonite, Clariant International Ltd, VN 125949

K: Wax

[0094] K-1: Polar modified wax, Clariant International Ltd, RBW 102

[0095] K-2: Waxy amide, Kao Chemicals Global, KAO WAX EB-FF

[0096] K-3: Zinc 12-hydroxystearate, Sakai Chemical Industry Co., Ltd, SZ-120H

L: Elastomer

[0097] L-1: SEBS (StyTene-ethylene-butylene-styrene), LCY, SEBS 7533

[0098] L-2: HSBC (Hydrogenated styrene block copolymer), Kraton, MD6951

[0099] L-3: TPU (Thermoplastic polyurethane), Okada Engineering Co. Ltd., Gumthane AKX-550

[0100] L-4: PBE (Propylene-based elastomer), ExxonMobil Corp., Vistamaxx 6202

M: Anti-Wear Agent

[0101] M-1: Polyester modified polysiloxane, Evonik Industries AG., TEGOMER H-Si 6441P

Processing Method

Twin-Screw Extruder

[0102] The processing method using the twin-screw extruder is known in the art. Briefly, the polyester, the crosslinkable rubber and the additives were added and melted at 180° C., the processing oil was selectively added and mixed at 180° C., and the crosslinking agent (optionally with the co-agent) was added and mixed at 180° C. Then, the dynamic vulcanization process was performed at 190° C., followed by conveying out at 190° C. to obtain the thermoplastic vulcanizate material.

Banbury Mixer

[0103] The processing method using the banbury mixer is known in the art. Briefly, the crosslinkable rubber was mixed with the processing oil at 180° C. if it was needed, followed by adding the additives. Then, the polyester and the crosslinking agent (optionally with the co-agent) were sequentially added at 180° C. The dynamic vulcanization process was performed at 180° C. for 20 to 30 minutes to obtain the thermoplastic vulcanizate material.

Testing Method

[0104] The Shore A hardness of the obtained thermoplastic vulcanizate material was measured according to ASTM D2240. The dry and wet slip resistance of the obtained thermoplastic vulcanizate material was measured according to SATRA TM144-2011. The microstructures of the obtained thermoplastic vulcanizate material were observed with the transmission electron microscope (TEM) or scanning electron microscope (SEM).

Example 1

[0105] The components of the thermoplastic rubber composition, the processing method and the test results of thermoplastic vulcanizate material are shown in the following Tables 1-1 and 1-2.

TABLE-US-00001 TABLE 1-1 Processing method Twin-screw extruder Banbury mixer Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 Plastic:Rubber 3:7 4:6 5:5 7:3 4:6 6:4 7:3 Oil Filling (phr) 50 50 50 50 50 50 50 Rubber (wt %) A-1 46 39 35 23 39 31.4 25 Plastic (wt %) B-1 20 27 35 53 27 48.1 58.2 Processing Oil C-1 73 19.5 11.5 11.5 19.5 15.7 12.5 (wt %) Compatibilizer D-1 — 3.3 — — 3.3 — — (wt %) Peroxide (wt %) E-1 1.15 0.6 0.875 0.575 0.6 0.785 0.625 Co-agent (wt %) F-1 3.07 1.6 2.34 1.54 1.6 2.1 1.67 F-2 — 1.2 — — 1.2 — — Anti-scorch G-1 0.083 0.04 0.063 0.042 0.04 0.056 0.045 agent (wt %) Filler (wt %) H-1 4.197 6.66 5.672 5.533 6.66 0.759 0.86 Anti-oxidant J-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (wt %) J-2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Wax K-1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 K-2 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Anti-wear agent M-1 1.4 — 2.45 3.71 — — — Shore A 45.0 ± 54.8 ± 60.5 ± 72.3 ± 65.0 ± 73.8 ± 75.5 ± hardness 2.2 0.8 0.4 0.9 0.2 0.8 0.7 Dry slip 0.81 ± 0.99 ± 0.66 ± 0.58 ± 0.93 ± 0.77 ± 0.74 ± resistance 0.01 0.02 0.01 0.0 0.01 0.01 0.0 Wet slip 0.29 ± 0.23 ± 0.27 ± 0.27 ± 0.24 ± 0.38 ± 0.4 ± resistance 0.02 0.0 0.01 0.01 0.0 0.0 0.01

[0106] FIG. 1 is a TEM photo of a thermoplastic vulcanizate material prepared in Example 1-7 of the present disclosure, wherein the black portion is the cross-linked rubber, and the white portion is the polyester. FIG. 2 is a SEM photo of a thermoplastic vulcanizate material prepared in Example 1-7 of the present disclosure, wherein the black portion is the polyester, and the white portion is the cross-linked rubber.

[0107] As shown in FIG. 1 and FIG. 2, it can be found that the obtained thermoplastic vulcanizate materials have the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

[0108] Even not shown in the figure, the TEM or SEM photos of the thermoplastic vuicanizate materials prepared in Examples 1-1 to 1-6 also show that the obtained thermoplastic vuicanizate materials have similar structures shown in FIG. 1 or FIG. 2.

TABLE-US-00002 TABLE 1-2 Processing method Banbury mixer Example 1-8 1-9 1-10 1-11 1-12 1-13 1-14 Plastic:Rubber 3:7 4:6 5:5 6:4 7:3 8:2 9:1 Oil filling (phr) 50 50 50 50 50 50 50 Rubber (wt %) A-1 49.5 44.3 38.6 32.3 25.5 17.88 9.46 Plastic (wt %) B-1 21.2 29.5 38.6 48.5 59.4 71.54 85.11 Processing Oil C-1 24.7 22.1 19.3 16.2 12.7 8.94 4.73 (wt %) Peroxide (wt %) E-1 1.237 1.107 0.965 0.809 0.637 0.45 0.08 Co-agent (wt %) F-1 3.30 2.95 2.57 2.16 1.70 1.19 0.63 Shore A 54.7 ± 61.3 ± 67.2 ± 71 ± 76 ± 82.7 ± 84.5 ± hardness 0.5 0.5 0.8 0.8 0.0 0.2 0.4 Dry slip 1.05 ± 0.96 ± 0.89 ± 0.84 ± 0.77 ± 0.73 ± 0.61 ± resistance 0.02 0.01 0.01 0.01 0.0 0.01 0.01 Wet slip 0.37 ± 0.35 ± 0.36 ± 0.35 ± 0.36 ± 0.47 ± 0.41 ± resistance 0.02 0.02 0.01 0.01 0.02 0.0 0.01 Cross-linked 0.5~ 0.5~ 0.3~ 0.3~ 0.2~ — — rubber average 6.0 8.0 4.0 4.0 3.0 particle diameter (μm)

[0109] FIG. 3 is a TEM photo of a thermoplastic vulcanizate material prepared in Example 1-10 of the present disclosure, wherein the black portion is the cross-linked rubber, and the white portion is the polyester. FIG. 4 is a SEM photo of a thermoplastic vulcanizate material prepared in Example 1-10 of the present disclosure, wherein the black portion is the polyester, and the white portion is the cross-linked rubber.

[0110] As shown in FIG. 3 and FIG. 4, it can be found that the obtained thermoplastic vulcanizate materials have the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is about 0.3 μm to 4.0 μm.

[0111] Even not shown in the figure, the TEM or SEM photos of the thermoplastic .sup.-vulcanizate materials prepared in Examples 1-8, 1-9, 1-11 to 1-14 also show that the obtained thermoplastic vulcanizate materials have similar structures shown in FIG. 3 or FIG. 4.

[0112] The results of Examples to 114 show that the thermoplastic vulcanizate materials with the desired structure can be obtained when the weight ratio of the polyester to the crosslinkable rubber is in a range from 3:7 to 9:1.

Example 2

[0113] The components of the thermoplastic rubber composition, the processing method and the test results of the thermoplastic vulcanizate material are shown in the following Tables 2-1 to 2-3.

TABLE-US-00003 TABLE 2-1 Banbury Processing method Twin-screw extruder mixer Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 Plastic:Rubber 3.5:6.5 3.5:6.5 3.5:6.5 3.5:6.5 5:5 6:4 6:4 Oil filling (phr) 80 80 80 80 80 50 50 Rubber (wt %) A-1 39 40 40 40 32 31 31.00 Plastic (wt %) B-2 2 — — — 32 — — B-3 — 21.6 — — — — — B-4 — — 21.6 — — — — B-5 — — — 21.6 — — — B-6 — — — — — 46 — B-7 — — — — — — 36.80 Processing Oil C-1 — — — — 25.6 15.5 15.50 (wt %) C-2 31.2 32 32 32 — — — Compatibilizer D-1 3 — — — 3.2 — — (wt %) Peroxide (wt %) E-1 0.98 1 1 1 0.8 1.55 0.78 Co-agent (wt %) F-1 0.52 0.54 0.54 0.54 2.14 4.14 2.080 Anti-scorch G-1 0.07 0.07 0.07 0.07 0.06 0.12 0.12 agent (wt %) Filler (wt %) H-1 3.575 4.135 4.135 4.135 3.1 0.59 3.42 Anti-oxidant J-1 0.021 0.022 0.022 0.022 0.1 0.1 0.10 (wt %) J-3 — — — — 0.2 — — J-2 — — — — 0.2 0.20 J-4 0.032 0.033 0.033 0.033 — — — K-3 — — — — 0.2 — — Wax (wt %) K-1 0.2 0.2 0.2 0.2 — 0.2 0.20 K-2 0.4 0.4 0.4 0.4 0.6 0.6 0.60 Shore A — — — — — 77 ± 77.3 ± hardness 0.4 1.2 Dry slip — — — — — 0.64 ± 0.66 ± resistance 0.01 0.01 Wet slip — — — — — 0.4 ± 0.39 ± resistance 0.01 0.02

TABLE-US-00004 TABLE 2-2 Processing method Banbury mixer Example 2-8 2-9 2-10 2-11 2-12 2-13 2-14 Plastic:Rubber 7:3 7:3 7:3 7:3 7:3 7:3 7:3 Oil filling (phr) 50 50 50 50 50 50 50 Rubber (wt %) A-1 25.00 25.00 25.00 — 22.51 25.00 25.00 A-2 — — — 22.00 — — — A-3 — — — 5.50 — — — Plastic (wt %) B-1 58.2 29.10 29.10 51.00 50.91 40.74 29.10 B-8 — 29.10 — — — — — B-9 — — 29.10 — 5.66 17.46 — B-10 — — — — — — 29.10 Processing Oil C-1 12.5 12.50 12.50 15.20 11.26 12.50 12.50 (wt %) Compatibilizer D-2 — — — 2.19 — — — (wt %) Peroxide (wt %) E-1 0.625 0.625 0.625 0.69 0.56 0.625 0.625 Co-agent (wt %) F-1 1.67 1.67 1.67 1.840 1.501 1.67 1.67 Anti scorch G-1 0.045 0.045 0.045 0.05 0.04 0.045 0.045 agent (wt %) Filler (wt%) H-1 0.86 0.86 0.86 0.43 0.84 0.86 0.86 Plasticizer I-1 — — — — 5.657 — — (wt %) Anti-oxidant J-1 0.1 0.10 0.10 0.10 0.10 0.10 0.10 (wt %) J-2 0.2 0.20 0.20 0.20 0.19 0.20 0.20 Wax K-1 0.2 0.20 0.20 0.20 0.19 0.20 0.20 K-2 0.6 0.60 0.60 0.60 0.58 0.60 0.60 Shore A 75.5 ± 62.3 ± 64.0 ± 72.0 ± 74.7 ± 69.7 ± 68.0 ± hardness 0.7 0.5 0.0 0.0 0.5 0.9 0.0 Dry slip 0.74 ± 0.9 ± 0.92 ± 0.82 ± 0.77 ± 0.89 ± 0.83 ± resistance 0.0 0.01 0.02 0.01 0.01 0.01 0.02 Wet slip 0.4 ± 0.28 ± 0.27 ± 0.28 ± 0.3 ± 0.29 ± 0.26 ± resistance 0.01 0.01 0.01 0.01 0.02 0.01 0.0

TABLE-US-00005 TABLE 2-3 Twin-screw extruder Processing method Comparative Example example 2-1 2-15 2-16 Plastic:Rubber 3.3:6.7 4:6 4:6 Oil filling (phr) 50 50 51 Rubber (wt %) A-1  42 40 40 Plastic (wt %) B-11 21 22.4 22.4 B-12 — 5.6 5.60 Processing Oil (wt %) C-3  21 20 20.57 Compatibilizer (wt %) D-3  3.2 — — Peroxide (wt %) E-1  0.65 0.65 0.65 Co-agent (wt %) F-2  1.3 1.30 1.3 F-1  1.75 1.75 1.75 Anti-scorch agent (wt %) G-1  0.05 0.05 0.05 Filler (wt %) H-1  8.25 7.44 6.85 Catalyst (wt %) I-2 — 0.01 — I-3 — — 0.03 Wax K-2  0.8 0.8 0.8

[0114] Even not shown in the figure, the TEM or SEM photos of the thermoplastic vulcanizate materials prepared in Examples 2-1 to 2-16 show that the obtained thermoplastic vulcanizate materials have the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

[0115] In addition, in Examples 2-15 to 2-16, PETG-co-EVA with the melting point of 81° C. was formed, and the obtained thermoplastic vulcanizate materials have the structure that the continuous phase is constituted by the polyester, and the dispersant phase is constituted by the cross-linked rubber. However, in Comparative example 2-1, PETG with the melting point of 260° C. was used, and the obtained thermoplastic materials have the structure that the dispersant phase is constituted by the polyester, and the continuous phase is constituted by the cross-linked rubber. Thus, the structure obtained in Examples 2-15 to 2-16 cannot be obtained in Comparative example 2-1.

[0116] The results of Examples 2-1 to 2-16 show that the thermoplastic vulcanizate materials with the desired structure can be obtained when the polyester has the melting point less than or equal to 180° C.

Example 3

[0117] The components of the thermoplastic rubber composition, the processing method and the test results of the thermoplastic vulcanizate material are shown in the following Tables 3-1 and 3-2.

TABLE-US-00006 TABLE 3-1 Processing method Banbury mixer Example 3-1 3-2 3-3 3-4 3-5 3-6 Plastic:Rubber 7:3 7:3 7:3 7:3 5.5:4.5 7:3 Oil tilling (phr) 50 50 50 50 0 50 Rubber (wt %) A-1 25.0 — — — — 75.0 A-2 — — — 25.0 — — A-4 — 25.0 — — — — A-5 — — 25.0 — — — A-6 — — — — 39.0 — A-7 — — — — — 5.8 Plastic (wt %) B-1 58.2 58.2 58.2 58.20 46.5 52.4 Processing Oil C-1 12.5 12.5 12.5 12.50 — 12.5 (wt %) Compatibilizer D-1 — — — — 3.3 — (wt %) Peroxide (wt %) E-1 0.625 0.625 0.625 0.625 0.6 0.63 Co-agent (wt %) F-1 1.67 1.67 1.67 1.67 1.6 1.67 F-2 — — — — 1.2 — Anti-scorch G-1 0.045 0.045 0.045 0.045 0.04 0.05 anent (wt %) Filler (wt %) H-1 0.86 0.86 0.86 0.86 6.66 0.86 Anti-oxidant J-1 0.1 0.1 0.1 0.10 0.1 0.10 (wt %) J-2 0.2 0.2 0.2 0.20 0.2 0.20 Wax K-1 0.2 0.2 0.2 0.20 0.2 0.20 K-2 0.6 0.6 0.6 0.60 0.6 0.60 Shore A 76.3 ± 79.3 ± 78.3 ± 74.8 ± 81.3 ± 77 ± hardness 0.5 0.5 0.5 0.2 0.5 0.0 Dry slip 0.78 ± 0.5 ± 0.73 ± 0.84 ± 0.77 ± 0.8 ± resistance 0.02 0.01 0.02 0.0 0.01 0.01 Wet slip 0.33 ± 0.31 ± 0.23 ± 0.28 ± 0.24 ± 0.28 ± resistance 0.02 0.02 0.02 0.0 0.02 0.02

TABLE-US-00007 TABLE 3-2 Processing method Banbury mixer Example 3-7 3-8 3-9 3-10 3-11 Plastic:Rubber 7:3 7:3 7:3 7:3 7:3 Oil filling (phr) 50 50 50 50 50 Rubber and A-1 25.0 25.0 25.0 75.0 25.0 Elastomer L-1 8.3 16.6 — — — (wt %) L-2 — — 16.6 — — L-3 — — — — 17.46 L-4 — — — 29.10 — Plastic (wt %) B-1 49.9 41.6 41.6 29.10 40.74 Processing Oil C-1 12.5 12.5 12.5 12.50 2.5 (wt %) Peroxide (wt %) E-1 0.625 0.625 0.625 0.625 0.625 Co-agent (wt %) F-1 1.67 1.67 1.67 1.67 1.67 Anti-scorch G-1 0.045 — — 0.045 0.045 agent (wt %) Filler (wt %) H-1 0.86 0.86 0.86 0.86 0.86 Anti-oxidant J-1 0.1 0.1 0.1 0.10 0.1 (wt %) J-2 0.2 0.2 0.2 0.20 0.2 K-1 0.2 0.2 0.2 0.20 0.2 Wax K-2 0.6 0.6 0.6 0.60 0.6 Shore A 71.5 ± 68.2 ± 64.2 ± 62.5 ± 69.3 ± hardness 0.4 0.2 0.2 1.1 0.9 Dry slip 0.82 ± 0.89 ± 0.88 ± 0.92 ± 0.89 ± resistance 0.02 0.01 0.02 0.01 0.01 Wet slip 0.32 ± 0.78 ± 0.37 ± 0.38 ± 0.3 ± resistance 0.02 0.0 0.02 0.0 0.01

[0118] Even not shown in the figure, the TEM or SEM photos of the thermoplastic vulcanizate materials prepared in Examples 3-1 to 3-12 show that the obtained thermoplastic vulcanizate materials have the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

[0119] The results of Examples 34 to 3-6 show that the thermoplastic vulcanizate materials with the desired structure can be obtained by using different types of crosslinkable rubber. The results of Examples 3-7 to 3-12 show that the thermoplastic vulcanizate materials with the desired structure can be obtained when elastomer was added.

Example 4

[0120] The components of the thermoplastic rubber composition, the processing method and the test results of the thermoplastic vulcanizate material are shown in the following Table 4.

TABLE-US-00008 TABLE 4 Processing method Banbury mixer Example 4-1 4-2 4-3 4-4 4-5 4-6 4-7 Plastic:Rubber 3:7 3:7 3:7 4:6 5:5 6:4 7:3 Oil filling (phr) 50 50 50 50 50 50 50 Rubber (wt %) A-1 49.5 49.91 50.84 44.3 38.6 32.3 25.5 Plastic (wt %) B-1 21.2 21.39 21.79 29.5 38.6 48.5 59.4 Processing Oil C-1 24.7 24.9 25.42 22.1 19.3 16.2 12.7 (wt %) Peroxide (wt %) E-1 1.237 0.42 1.27 1.107 0.965 0.809 0.637 Co-agent (wt %) F-1 3.3 3.33 0.68 2.95 2.57 2.16 1.7 Peroxide + Co-agent 4.5 3.8 2.0 4.1 3.5 3.0 2.3 (wt %) Shore A 54.7 ± 55 ± 51 ± 61.3 ± 67.2 ± 71 ± 76 ± hardness 0.5 0.0 0.0 0.5 0.8 0.8 0.0 Dry slip 1.05 ± 1.09 ± 0.99 ± 0.96 ± 0.89 ± 0.84 ± 0.77 ± resistance 0.02 0.01 0.01 0.01 0.01 0.01 0.0 Wet slip 0.37± 0.58± 0.52± 0.35 ± 0.36 ± 0.35 ± 0.36 ± resistance 0.02 0.04 0.01 0.02 0.01 0.01 0.02 Processing method Banbury mixer Example 4-8 4-9 4-10 4-11 4-12 4-13 Plastic:Rubber 8:2 9:1 9:1 9:1 9:1 9:1 Oil filling (phr) 50 50 50 50 50 50 Rubber (wt %) A-1 17.88 9.46 9.44 9.24 9.49 9.38 Plastic (wt % B-1 71.54 85.11 84.97 83.2 85.4 84.44 Processing Oil C-1 8.94 4.73 4.72 4.6'2 4.74 4.69 (wt %) Peroxide (wt %) E-1 0.45 0.08 0.24 2.31 0.24 0.23 Co-agent (wt %) F-1 1.19 0.63 0.63 0.62 0.13 1.25 Peroxide + Co-agent 1.6 0.7 0.9 2.9 0.4 1.5 (wt %) Shore A 82.7 ± 84.5 ± 85.7 ± 83.2 ± 81.8 ± 85 ± hardness 0.2 0.4 0.6 0.8 0.2 0.4 Dry slip 0.73 0.61 ± 0.65 ± 0.62 ± 0.62 ± 0.63 ± resistance 0.01 0.01 0.01 0.01 00.0 0.0 Wet slip 0.47 ± 0.41 ± 0.43 ± 0.44 ± 0.47 ± 0.45 ± resistance 0.0 0.01 0.0 0.01 0.01 0.01

[0121] Even not shown in the figure, the TEM or SEM photos of the thermoplastic vulcanizate materials prepared in Examples 4-1 to 4-13 show that the obtained thermoplastic vuicanizate materials have the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is less than or equal to 100 μm. In addition, the results of Examples 4-1 to 4-13 also show that the sum of the contents of the peroxide and the co-agent less than or equal to 6 wt % based on the total weight of the thermoplastic rubber composition to be treated with the dynamic vulcanization process is a suitable amount for forming the thermoplastic vulcanizate materials of the present disclosure.

Example 5

[0122] The components of the thermoplastic rubber composition, the processing method and the test results of the thermoplastic vulcanizate material are shown in the following Table 5.

TABLE-US-00009 TABLE 5 Processing method Banbury mixer Example 5-1 5-2 5-3 5-4 5-5 Plastic:Rubber 5.5:4.5 7:3 7:3 7:3 7:3 Oil filling (phr) 0 50 60 80 100 Rubber (wt %) A-1 0 25 24.3 23.2 22.1 A-6 39.0 — — — — Plastic (wt %) B-1 46.5 58.2 56.8 54.1 51.7 Processing Oil (wt %) C-1 — 12.5 14.6 18.6 22.1 Compatibilizer (wt %) D-1 3.3 — — — — Peroxide (wt%) E-1 0.6 0.625 0.61 0.58 0.55 Co-agent (wt %) F-1 1.6 1.67 1.62 1.55 1.48 F-2 1.2 — — — — Anti-scorch agent (wt %) G-1 0.04 0.045 0.044 0.042 0.04 Filler (wt %) H-1 6.66 0.86 0.86 0.86 0.86 Anti-oxidant (wt %) J-1 0.1 0.1 0.1 0.1 0.1 J-2 0.2 0.2 0.2 0.2 0.2 Wax K-1 0.2 0.2 0.7 0.7 0.2 K-2 0.6 0.6 0.6 0.6 0.6 Shore A hardness 81.3 ± 75.5 ± 76 ± 75.2 ± 75.2 ± 0.5 0.7 0.0 0.2 0.2 Dry slip resistance 0.77 ± 0.74 ± 0.75 ± 0.74 ± 0.68 ± 0.01 0.0 0.01 0.01 0.02 Wet slip resistance 0.24 ± 0.4 ± 0.34 ± 0.38 ± 0.32 ± 0.02 0.01 0.01 0.01 0.01

[0123] Even not shown in the figure, the TEM or SEM photos of the thermoplastic vulcanizate materials prepared in Examples 5-1 to 5-5 show that the obtained thermoplastic vulcanizate materials have the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

[0124] The results of Examples 5-1 to 5-5 show that the thermoplastic vulcanizate materials with the desired structure can be obtained whether the processing oil is used or not.

Example 6

[0125] The components of the thermoplastic rubber composition, the processing method and the test results of the thermoplastic vulcanizate material are shown in the following Table 6.

TABLE-US-00010 TABLE 6 Processing method Banbury mixer Example 6-1 6-2 6-3 6-4 6-5 6-6 6-7 Plastic:Rubber 3:7 3:7 3:7 5:5 5:5 5:5 9:1 Oil filling (phr) 50 50 50 0 50 100 0 Rubber (wt %) A-1 49.5 49.91 50.84 47.81 38.6 32.35 9.91 Plastic (wt %) B-1 21.2 21.39 21.79 47.81 38.6 32.35 89.18 Processing Oil C-1 24.7 24.95 75.42 — 19.3 32.35 — (wt %) Peroxide (wt %) E-1 1.237 0.42 1.27 1.2 0.965 0.81 0.25 Co-agent (wt %) F-1 3.3 3.33 0.68 3.19 2.57 2.16 0.66 Peroxide + Co-agent 4.5 3.8 2.0 4.4 3.5 3.0 0.9 (wt %) Shore A 54.7 ± 55 ± 51 ± 77.2 ± 67.2 ± 55.2 ± 88 ± hardness 0.5 0.0 0.0 0.2 0.8 0.2 0.8 Dry slip 1.05 ± 1.09 ± 0.99 ± 0.72 ± 0.89 ± 0.87 ± 0.67 ± resistance 0.02 0.01 0.01 0.02 0.01 0.01 0.02 Wet slip 0.37 ± 0.58 ± 0.52 ± 0.35 ± 0.36 ± 0.40 ± 0.36 ± resistance 0.02 0.04 0.01 0.01 0.01 0.01 0 Processing method Banbury mixer Example 6-8 6-9 6-10 6-11 6-12 6-13 Plastic:Rubber 9:1 9:1 9:1 9:1 9:1 9:1 Oil filling (phr) 50 50 50 50 50 100 Rubber (wt %) A-1 9.46 9.44 9.24 9.49 9.38 9.02 Plastic (wt %) B-1 85.11 84.97 83.2 85.4 84.44 81.14 Processing Oil C-1 4.73 4.72 4.62 4.74 4.69 9.02 (wt %) Peroxide (wt %) E-1 0.08 0.24 2.31 0.24 0.23 0.23 Co-agent (wt %) F-1 0.63 0.63 0.62 0.13 1.25 0.6 Peroxide + Co-agent 0.7 0.9 2.9 0.4 1.5 0.8 wt % Shore A 84.5 ± 85.7 ± 83.2 ± 81.8 ± 85 ± 85.2 ± hardness 0.4 0.6 0.8 0.2 0.4 0.2 Dry slip 0.61 ± 0.65 ± 0.62 ± 0.62 ± 0.63 ± 0.59 ± resistance 0.01 0.01 0.01 0.0 0.0 0.02 Wet slip 0.41 ± 0.43 ± 0.44 ± 0.47 ± 0.45 ± 0.35 ± resistance 0.01 0.0 0.01 0.01 0.01 0.01

[0126] Even not shown in the figure, the TEM or SEM photos of the thermoplastic vulcanizate materials prepared in Examples 6-1 to 6-13 show that the obtained thermoplastic vulcanizate materials have the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is less than or equal to 100 μm.

[0127] In addition, the results of Examples 6-1 to 6-13 also show that the sum of the contents of the peroxide and the co-agent less than or equal to 6 wt % based on the total weight of the thermoplastic rubber composition is a suitable amount for forming the thermoplastic vulcanizate materials of the present disclosure.

[0128] In conclusion, the present disclosure provides a novel thermoplastic vulcanizate material which has the structure that the continuous phase is constituted by the polyester, the dispersant phase is constituted by the cross-linked rubber, and the average particle diameter of the cross-linked rubber is less than or equal to 100 μm. In addition, the novel thermoplastic rubber composition or thermoplastic vulcanizate material of the present disclosure can be used to manufacture a variety of articles such as tires, hoses, belts, gaskets, moldings, shoe outsoles, and molded parts. Furthermore, when the article made by the thermoplastic vulcanizate material of the present disclosure is no longer used and recycled, the recycled article can be pulverized into powders or small pieces, and a suitable amount of the powders or small pieces can be added into the fresh thermoplastic rubber composition of the present disclosure to manufacture a new article.

[0129] Although the present disclosure has been explained in relation to its embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the disclosure as hereinafter claimed.