Thermoplastic polyester elastomer composition, microcellular foam molded body composed thereof having high rebound elasticity, and manufacturing method thereof

Abstract

This invention relates to the field of thermoplastic polyester elastomer foaming technology, and more particularly to a thermoplastic polyester elastomer (TPEE) composition, a highly resilient microporous foamed body composed therefrom, and its manufacturing method and uses.

Description

Technical Field

[0001] This invention relates to a thermoplastic polyester elastomer composition, a highly resilient microporous foamed molded body composed therefrom, its manufacturing method, and its uses. Prior Technology

[0002] With advancements in materials science, thermoplastic polyester elastomers (TPEEs) have been widely applied across various industries due to their excellent elasticity and mechanical properties. However, traditional TPEE foam materials often face numerous challenges during production, including uneven foaming, unstable physical properties, and high costs. Especially in achieving high resilience and high heat resistance, existing technologies often fall short of the demands of high-end applications.

[0003] In existing technologies, TPEE foamed products mostly employ physical or chemical foaming methods. However, these methods often lead to inhomogeneity in the foamed molded body, affecting the overall performance of the product. For example, uncontrollable factors in the physical foaming process (such as temperature and pressure fluctuations) and inaccurate chemical dosages in chemical foaming can both result in uneven density, decreased elasticity, and shortened service life of the foamed product.

[0004] Republic of China Patent I713856B discloses a thermoplastic polyester elastomer resin foamed molded body, comprising a resin phase and a foam layer. This foam layer is composed of independent foamed cells with an average cell diameter of 10-400 μm and a maximum cell diameter of 10-500 μm. However, due to the large diameter distribution range of the cells, the physical properties of the overall foamed molded body are not uniform, potentially leading to localized damage during use.

[0005] Republic of China Patent I793366B discloses a thermoplastic polyester elastomer resin composition for foaming molding, wherein the soft segment content of the thermoplastic polyester elastomer is 20-80% by mass, and the melt tension at melting point +10°C is 0.1-45 cN. However, because it cannot simultaneously improve its impact absorption characteristics, its rebound and compression ratio are not adequately addressed, thus limiting its applications.

[0006] Republic of China Patent I770285B discloses a thermoplastic polyester elastomer resin composition for foaming molding, wherein the thermoplastic polyester elastomer contains an alkali metal salt crystallizing nucleating agent of an organic carboxylic acid with 3 to 40 carbon atoms, which is suitable for lightweight materials and exhibits high resilience and softness. However, while improving its resilience, its tensile strength and tear strength are insufficient, making it unsuitable for high-strength applications.

[0007] Therefore, there is an urgent need for a new foaming technology that can provide more uniform and stable high-rebound thermoplastic polyester elastomer foamed products to meet the market demand for high-performance lightweight materials. Summary of the Invention

[0008] This invention provides a thermoplastic polyester elastomer composition and a microporous foamed article formed from the thermoplastic polyester elastomer resin composition, wherein the thermoplastic polyester elastomer composition comprises: (A) 100 parts by weight of a thermoplastic polyester elastomer, which is composed of a block copolymer consisting of about 30-70% by weight of hard segments (a) of aromatic diacids, aliphatic diacids, or sulfonic diacids and their derivatives, and about 70-30% by weight of polyesters or polyethers of aliphatic diols, which constitute soft segments (b); (B) Approximately 0.1 to 5 parts by weight of heat stabilizer; (C) Approximately 0.01 to 5 parts by weight of foaming agent; (D) Approximately 0.01 to 5 parts by weight of crosslinking agent; (E) Approximately 0.01 to 5 parts by weight of UV stabilizer; and (F) Approximately 0.01 to 5 parts by weight of nucleating agent; The microporous foamed body has a foaming density of about 0.01~0.4 cm3, a rebound of about 50~80%, a pore diameter of about 100~500 μm, and is a closed-cell structure with a closed-cell rate of 1~60%.

[0009] Microcellular foamed moldings composed of thermoplastic polyester elastomers with the above components have excellent physical properties, including hardness, tensile strength, tear strength and other performance indicators that meet the requirements. In addition, they can also have important human factors engineering indicators such as rebound, peel rate and compression ratio, and can be combined with other materials to form a variety of highly reliable functional parts needed in daily life.

[0010] One aspect of the present invention is a method for manufacturing a microporous foamed molded body, characterized in that the foamed body is obtained from a thermoplastic polyester elastomer composition, wherein the thermoplastic polyester elastomer composition contains at least one of a UV stabilizer (E) and a nucleating agent (F).

[0011] Another aspect of the present invention provides a functional component of a microporous foamed molded body, which is formed by molding the foamed molded body described in the present invention, and can be used in the fields of automotive interior and exterior parts, sports equipment, medical devices, etc. Simple Explanation of the Diagram

[0012] The foregoing and other features and advantages of the invention will become more apparent from the following more detailed description of preferred embodiments of the invention, as shown in the accompanying drawings.

[0013] Figure 1 is a flowchart of the manufacturing method and equipment for microporous foamed molded articles.

[0014] Figure 2 is a flowchart of the testing procedures and equipment for microporous foamed molded articles.

[0015] Figure 3 is a cross-sectional photograph of the microporous foamed article of Example 1.

[0016] Figure 4 is a cross-sectional photograph of the microporous foamed molded article of Example 2.

[0017] Figure 5 is a cross-sectional photograph of the microporous foamed article of Example 6.

[0018] Figure 6 is a cross-sectional photograph of the microporous foamed molded article of Example 8.

[0019] Figure 7 is a cross-sectional photograph of the microporous foamed molded article of Example 9.

[0020] Figure 8 is a cross-sectional photograph of the microporous foamed article of Example 10.

[0021] Figure 9 is a cross-sectional photograph of the microporous foamed article of Example 11.

[0022] Figure 10 is a cross-sectional photograph of the microporous foamed article of Example 12.

[0023] Figure 11 is a cross-sectional photograph of the microporous foamed article of Example 13.

[0024] Figure 12 is a cross-sectional photograph of the microporous foamed article of Comparative Example 1.

[0025] Figure 13 is a cross-sectional photograph of the microporous foamed article of Comparative Example 2.

[0026] Figure 14 is a cross-sectional photograph of the microporous foamed article of Comparative Example 3. Implementation

[0027] The following description will focus on the various embodiments and other aspects of the present invention. The invention claimed herein may be embodied in different forms and should not be construed as limited to the embodiments described herein. Rather, the invention claimed herein is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the embodiments as defined in the appended claims.

[0028] Any numerical values ​​described herein, such as concentrations or concentration ranges, should be understood to be modified in all cases by the term "about." "About" means within an acceptable margin of error for a particular value, as determined by one of ordinary skill in the art, which will depend in part on how the value was measured or determined, i.e., the limitations of the measurement system. Unless otherwise expressly stated elsewhere in the examples or specification in the context of a particular test, result, or embodiment, "about" means within one standard deviation, or at most 5%, whichever is greater, according to practice in the art.

[0029] The terms "one embodiment," "an embodiment," and "some embodiments" indicate that the described embodiment may include a particular feature, structure, appearance, or characteristic, but each embodiment may not necessarily include that particular feature, structure, or characteristic. Furthermore, such phrases do not necessarily refer to the same embodiment. Moreover, when a particular feature, structure, or characteristic is described with respect to an embodiment, it is assumed herein that, whether explicitly described or not, it falls within the knowledge of those skilled in the art and can therefore be implemented with respect to other embodiments.

[0030] All technical and scientific terms used in this specification and claims, unless otherwise defined, are those known to a person skilled in the art to which this disclosure pertains. The singular terms "a," "an," "the," or similar terms, unless otherwise stated, refer to more than one object. The terms "or," "and," and "and," unless otherwise stated, refer to "and / or." Furthermore, the terms "comprising" and "including" are not restrictive open-ended conjunctions. The foregoing definitions are illustrative only and should not be construed as limiting the subject matter. Unless otherwise stated, all materials used in this disclosure are commercially available and readily accessible.

[0031] This invention discloses a microporous foamed body composed of thermoplastic polyester elastomer and other components. The microporous foamed body has a foaming density of about 0.01~0.5 cm3, a rebound of about 50~75%, a cell diameter of about 100~500 μm and a closed-cell structure, and a closed-cell rate of about 1~60%.

[0032] The thermoplastic polyester elastomer composition disclosed in this invention specifically comprises: (A) 100 parts by weight of thermoplastic polyester elastomer, (B) about 0.1 to 5 parts by weight of heat stabilizer, (C) about 0.01 to 5 parts by weight of foaming agent, (D) about 0.01 to 5 parts by weight of crosslinking agent, (E) about 0.01 to 5 parts by weight of UV stabilizer, and (F) about 0.01 to 5 parts by weight of nucleating agent. The thermoplastic polyester elastomer (A) is composed of a hard segment (a) composed of aromatic diacid / aliphatic diacid / sulfonic diacid and its derivatives and a soft segment (b) composed of polyester or polyether of aliphatic diol. The hard segment accounts for 30 to 70% by weight and the soft segment accounts for 70 to 30% by weight, based on the total weight of the elastomer.

[0033] In one specific example, the thermoplastic polyester elastomer composition of the present invention comprises: ● Thermoplastic polyester elastomer (A): 100 parts by weight, which is a block copolymer of polyester hard segments and polyether (or polyester) soft segments; ● Heat stabilizer (B): 0.1 to 5 parts by weight, including pentaerythritol tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and other high-efficiency heat stabilizers to improve the thermal stability of the material during processing; ● Foaming aid (C): 0.01 to 5 parts by weight, including surfactants such as stearic acid and, if applicable, supercritical fluid, to help improve the uniformity of bubble distribution and microporous structure; ● Crosslinking agent (D): 0.01 to 5 parts by weight, including epoxy or anhydride-based polymeric crosslinking agents, which enhance the mechanical strength and dimensional stability of the foam through crosslinking reactions; ● UV stabilizer (E): 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, including aromatic amine or hindered phenolic antioxidants, etc., to improve the UV resistance of the molded article and extend its service life; and ● Nucleating agent (F): 0.01 to 5 parts by weight, including organic carboxylic acid alkali metal salts, used to control the nucleation and growth of bubbles and optimize the size and distribution of the foam structure.

[0034] In one specific example, the thermoplastic polyester elastomer (A) described in this invention is composed of a block copolymer of hard segments and soft segments; wherein, the polyester hard segments are selected from one or more of high-hardness crystalline polybutylene terephthalate (PBT), polyethylene terephthalate (PET), or polytrimethylene terephthalate (PTT), poly(phenylene sulfonate) (CDP), and isophthalic acid (PIA); and the polyether soft segments are selected from polyethylene glycol ether (PEG), polypropylene glycol ether (PPG), or polybutylene ether (PEG). The thermoplastic polyester elastomers are composed of one or more of polyethers such as polyether (PTMG), polylactide (PLLA), polyglycolide (PGA), or polycaprolactone (PCL), with a number average molecular weight of 500-4000, preferably 1000-3000. The thermoplastic polyester elastomers polymerized from the hard and soft segments disclosed above are all within the scope of this invention.

[0035] In one specific example, the heat stabilizer (B) of the present invention may be selected from the group consisting of pentaerythritol tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (CAS No.: 6683-19-8), tris(2,4-di-tert-butylphenyl) phosphite (CAS No.: 31570-04-4) or tetrakis(2,4-di-tert-butylphenyl)[1,1'-biphenyl]-4,4'-dimethylbis(phosphonite) (CAS No.: 38613-77-3). Preferably, the heat stabilizer is selected from the group consisting of antioxidants Irganox® 1098 (Ciba Specialty Chemicals), antioxidants Irganox® 1010 (Ciba Specialty Chemicals), antioxidants Irgafos® 168 (Ciba Specialty Chemicals), antioxidants Ultranox® 626 (Ciba Specialty Chemicals), and combinations thereof.

[0036] In one specific example, the foaming agent (C) described in this invention may be selected from the group consisting of stearic acid, dodecylbenzene-disulfonic acid, dinaphthylmethane-disulfonic acid, siloxane-alkyl copolymers, other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols and cell regulators, fatty alcohols, or dimethylpolysiloxanes. Preferably, the foaming agent is selected from organopolysiloxanes or polysiloxane-free surfactants, including organopolysiloxanes from products under the trade name Dabco® (purchased from Air Products) or Tegostab® (purchased from Evonik), and polysiloxane-free surfactants from the trade name Ortegol® (purchased from Evonik).

[0037] In one specific example, the crosslinking agent (D) of the present invention is selected from the group consisting of one or more of the following types of crosslinking agents: epoxy compounds, carbodiimides, isocyanates, acid anhydrides, silicones, melamine resins, metal salts, metal chelates, amine resins, etc.

[0038] In one specific example, the UV stabilizer (E) described in this invention is selected from the group consisting of aromatic amine antioxidants, hindered phenol antioxidants, sulfur antioxidants, hindered amine light stabilizers, benzotriazole light stabilizers, benzophenone light stabilizers, benzoate light stabilizers, and triazole light stabilizers.

[0039] In one specific example, the nucleating agent (F) of the present invention is selected from alkali metal salts of organic carboxylic acids having carbon numbers of 3 to 40, wherein the metal is lithium, sodium, potassium, zinc, magnesium, calcium, barium, or an organosilicone nucleating agent, or an inorganic nucleating agent, wherein the nucleating agent is composed of talc powder and intercalated mica.

[0040] The embodiments provided by this invention demonstrate the performance of foamed molded articles under different component ratios and preparation conditions. The preparation, mixing, foaming, and testing steps of the materials are recorded in detail, along with a detailed performance evaluation of the resulting products, such as resilience, hardness, tensile strength, and tear strength. The experimental data described below show that the foamed molded articles of this invention outperform existing technologies in all performance tests, verifying the superiority and practicality of this invention.

[0041] [Manufacturing method of thermoplastic polyester elastomer composition]:

[0042] Thermoplastic polyester elastomer particles (selected from Shin Kong Corporation) with a hardness range of approximately 60-95 Shore A and an intrinsic viscosity of approximately 0.8-2.5 dL / g were pre-dried at 100°C for approximately 4 hours. Approximately 0.5 parts by weight of heat stabilizer (0.25 parts by weight each of hindered phenolic antioxidant Irganox® 1010 and phosphite antioxidant Irgafos® 168), approximately 1.0-2.5 parts by weight of foaming agent (Ortegol), approximately 0.5 parts by weight of nucleating agent (talc), approximately 2.0 parts by weight of crosslinking agent formulation (epoxy crosslinking agent Daicel Celloxide 2021P), and approximately 0.5-1.0 parts by weight of functional additive (2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole) were mixed with approximately 100 parts by weight of the dried thermoplastic polyester elastomer particles to obtain the midsole mixture. The midsole mixture is fed into a twin-screw extruder (26ψ, L / D=44) via a loss-in-weight meter for mixing (screw temperature approximately 150~220℃, speed 250~300rpm). The mixed midsole mixture is then pelletized to obtain shoe midsole particles.

[0043] Table 1: Composition of the thermoplastic elastomer components in Examples 1-13 (parts by mass): Composition Element Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 A1 100 100 100 100 A2 100 100 100 B1 0.5 0.5 0.25 0.5 0.5 0.5 B2 0.25 C1 2.0 2.0 1.7 1.5 0.1 C2 1.9 1.9 D1 0.5 0.8 0.3 D2 1.0 0.3 0.5 E1 0.3 0.5 E2 0.8 F1 0.2 0.2 0.2 F2 0.5 0.3 Composition Element Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 A1 100 100 100 100 100 A2 100 B1 0.5 0.5 0.5 0.5 0.5 0.5 C1 2.2 2.0 1.5 C2 2.0 1.2 2.5 D1 0.8 1.5 1.5 D2 1.2 1.5 1.5 E3 1.2 1.2 1.2 1.2 1.2 1.2 F3 0.3 0.5 0.3

[0044] Table 2. Composition of the thermoplastic elastomers in Comparative Examples 1-3 (parts by mass): Composition Comparative Example 1 Comparative Example 2 Comparative Example 3 A1 100 100 A2 100 B1 0.5 D1 1.0 F1 0.5

[0045] In Tables 1 and 2, A1 is TPEE from Hechuang brand, MFR=25, melting point 195℃; A2 is TPEE from CE brand, MFR=15, melting point 180℃; B1 is IR1010; B2 is IR1098; C1 is Tegostab; C2 is Ortegol; D1 is epoxy crosslinking agent Daicel Celloxide 2021P; D2 is an anhydride crosslinking agent (pyromellitic dianhydride); E1 is UV 326; E2 is UV 328; E3 is 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole; F1 is intercalated mica; F2 is barium sulfate; and F3 is talc.

[0046] The melt flow rate (MFR) test of thermoplastic polyester elastomer compositions for foaming is conducted according to the test method described in ASTM D1238, with a load of 2,160 g and a test temperature of 230 °C.

[0047] The melting point was measured using a Seiko Electronics Industries, Ltd. (DSC220) differential scanning calorimeter. Specifically, 5 mg of the sample was placed in an aluminum pan, covered and sealed, and melted at 250°C for 2 minutes in nitrogen atmosphere. The temperature was then reduced to 50°C at a rate of 20°C / min, and subsequently increased back to 250°C at a rate of 20°C / min. The temperature curve was recorded. The endothermic peak generated during melting was determined from the obtained temperature curve and defined as the melting point.

[0048] [Manufacturing Method of Microporous Foamed Molded Articles]:

[0049] The aforementioned midsole particles are dried at approximately 80-100°C for about 6-8 hours, and then a shoe midsole foam is obtained by chemical or physical foaming. There is no particular limitation on the foaming method for the foamed molded body of the present invention; a foaming method that involves impregnating the resin composition with high-pressure gas and then depressurizing (releasing pressure) is preferable. In terms of molding cycle time or cost, a molding method that can obtain homogeneous foam is preferable, where the volume of the mold cavity is expanded during injection molding of the foaming agent and the polyester elastomer composition of the present invention. Specifically, the method is as follows: As shown in Figure 1, the molten polyester elastomer composition, along with a chemical foaming agent and, where appropriate, a supercritical inert gas (N2 or CO2), is injected and filled into a mold cavity formed by multiple molds to obtain the foamed molded body.

[0050] Using the polyester elastomer resin composition obtained above, a foamed molded body is produced by the above-described mold expansion method. Regarding the mold, a flat plate-making mold (width 200 mm, length 200 mm, thickness 20 mm) consisting of a fixed mold and a movable mold is used. Specifically, in the plasticizing zone of an electric injection molding machine with a mold sealing force of 1800 kN and a screw diameter of 40 mm and a screw stroke of 180 mm, nitrogen gas in a supercritical state is injected and injected into the mold, which has been heated to a surface temperature of 50°C. During the stage where a non-foamed surface layer of 100~800 μm is formed by the injection external pressure and the foaming pressure from within, the movable mold is moved in the mold opening direction by the length shown in Table 2 (core-pulling amount (mm)) to expand the volume of the mold cavity, thereby obtaining a foamed molded body. At this point, by appropriately adjusting the molding temperature, the time from filling the resin to core pulling (core pulling delay time), and the time from the start to the end of core pulling (core pulling transfer time) according to the material, a foamed molded body with the target air chamber size is obtained. The test results of the physical properties of the foamed molded bodies composed of thermoplastic polyester elastomer compositions of Examples 1-13 and Comparative Examples 1-3 are shown in Table 3 below.

[0051] Table 3: Physical properties of the foamed articles prepared in Examples 1-7 and Comparative Example 1 physical properties unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 hardness Asker C 46-50 51-66 53-68 45-51 45-52 45-55 45-53 49-62 Tensile strength kg / cm2 19 26 twenty two 20 twenty two twenty three 29 11 Tear strength kg / cm twenty three twenty three 13 26 29 27 19 11 Rebound % 62 62 63 65 68 70 62 58 Peeling rate kg / cm 3.16 2.36 1.9 1.5 1.9 2.7 2.0 1.8 Compression ratio % 35 26 33 30 28 25 twenty three 49 Property retention rate % 3.2 66.3 2.2 56.6 54.6 1.3 2.0 0.3

[0052] Table 4: Physical properties of the foamed articles prepared in Examples 8-13 and Comparative Examples 2-3 physical properties unit Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 2 Comparative Example 3 density g / cm3 0.18 0.18 0.18 0.18 0.18 0.16 0.18 0.16 Average aperture M-means 299 283 252 233 211 223 380 321 Closed porosity % 40.6 30.3 33.2 44.2 53.5 50.1 1.2 1.9 hardness Asker C 54-59 46-50 47-50 43-50 45-52 45-53 45-50 55-60 Tensile strength kg / cm2 twenty two 20 twenty two 26 30 28 11 13 Rebound % 61 65 66 63 68 73 58 58 Property retention rate % 75.2 72.5 69.6 77.3 71.3 80.3 0.3 1.2

[0053] [Physical properties of foamed molded bodies:]

[0054] The physical property measurement methods for foamed molded articles composed of the thermoplastic polyester elastomer compositions of the above examples or comparative examples are as follows:

[0055] hardness

[0056] According to ASTM D2240, the center of a 100mm long / 100mm wide foamed molded body (the foamed molded body obtained above) was measured using an ASKER Type C hardness tester.

[0057] Tensile strength

[0058] According to the standard measurement method of ASTM D412, the maximum tensile stress applied when a foamed molded body with a length of 140 mm and a thickness of 3 to 14 mm is stretched to the breaking point is determined using a universal tensile testing machine.

[0059] Tear strength

[0060] According to the standard measurement method of ASTM D624, the foamed molded body was foamed and cut to a size of 2x25x110mm (cut: 0.5mm), and the maximum tensile stress applied when stretched to the breaking point was measured using a universal tensile testing machine.

[0061] Rebound

[0062] The test was conducted according to the method described in ASTM D2632. Using a manual measuring tester, a steel ball was dropped from a specified height onto the test piece, and the maximum rebound height was recorded. Three measurements were performed within one minute, and the median was calculated to determine the resilience.

[0063] Peeling rate

[0064] According to the standard measurement method of ASTM D3574, the dimensions are 152.4 mm x 25.4 mm, with a 40 mm notch cut along its edge, and the maximum tensile stress (section tear strength) applied when stretched to the breaking point is determined using a universal tensile testing machine.

[0065] Compression ratio

[0066] Compression tests were performed on foamed molded bodies with a diameter of 29 mm and a thickness of 12.5 mm according to ASTM D395. The samples were compressed by 50% at 60°C for 6 hours. The result is the percentage of the material sample that failed to recover its original height.

[0067] Closed porosity

[0068] According to the standard test method of ASTM D6226, Boyle's Law states that for a fixed quantity of gas in a closed container at constant temperature, the pressure and volume of the gas are inversely proportional. The apparatus consists of two chambers of known volume connected by a valve. The test sample is placed in one chamber and connected to high-purity nitrogen. The pressure in the sample chamber is increased to a predetermined pressure, and this value P1 is recorded. Then, the valve between the two chambers is opened, and the second lower pressure P2 is recorded again. The pressure change P1 / P2 can be used to calculate the volume ratio (Vspec), and then the open volume percentage (Ov) can be calculated.

[0069] The closed-cell volume percentage (Cv) is obtained by taking 100% of the sample volume and subtracting the open-cell volume percentage (Ov) / unfoamed area of ​​the sample (Wv).

[0070] Because the formula includes the unfoamed area of ​​the sample (Wv), the percentage of open-cell volume plus the percentage of closed-cell volume is not 100%.

[0071] The test steps are shown in Figure 2:

[0072] Step 1: First, inject the sample into the sample chamber at a pressure of 20 kPa. Close the two-way valve and open the pressure relief valve to remove the air from the sample, at least twice.

[0073] Step 2: After the sample air is removed, close the pressure relief valve and inject it into the sample chamber at a pressure of 20 kPa for 10-15 seconds. Record the pressure P1. Then open the two-way valve for 10-15 seconds and record the pressure P2.

[0074] Test environment: The sample was placed at 23℃±3℃ / 50% relative humidity under the valve for 24 hours.

[0075] Test conditions: Gas: N2, pressure 20 kPa.

[0076] Sample size: 2.5 x 2.5 x 2.5 cm cube or 6.25 cm² x 2.5 cm cylinder.

[0077] Due to the requirements of various molding tools for microporous foamed moldings, the optimal hardness is approximately 45-70°C, with an optimal hardness of approximately 50-60°C. Tensile strength primarily affects the ability to maintain shape during use; the optimal tensile strength is approximately 15-35 kg / cm², with an optimal hardness of approximately 20-30 kg / cm². Tear strength primarily affects ensuring the material is not easily damaged or broken during processing and production, thereby improving production efficiency and product quality; the optimal tear strength is approximately 15-35 kg / cm², with an optimal hardness of approximately 20-30 kg / cm². Rebound properties primarily provide considerations for the comfort, physical impact energy absorption, and durability of the specific product; the optimal rebound property is approximately 50-80%, with an optimal rebound property of approximately 70-80%. Peel rate primarily affects the adhesion between the material and other materials, maintaining the product's structural performance; the optimal peel rate is approximately 1.9-3.5 kg / cm², with an optimal peel rate of approximately 2-3 kg / cm². kg / cm; as for the compression ratio, it is based on the needs of convenient transportation, space saving and improved efficiency, and can provide more convenience and economy in transportation, storage and use. The optimal compression ratio is about 40% or less, and the best is about 30% or less.

[0078] Examples 1-7 show that the compression ratio after foaming is approximately 40% or less, and the resilience is excellent. Furthermore, high-ratio foaming is possible, resulting in lightweight material with excellent foaming properties. The compression ratio is significantly reduced due to the simultaneous use of UV stabilizers and nucleating agents.

[0079] As shown in Example 1 of Figure 3, compared with the cross-section of the microporous foamed body of Example 2 of Figure 4, the terminal acid group of CDP TPEE reacts more completely with the epoxy crosslinking agent, resulting in higher tensile strength. However, if the epoxy crosslinking agent is excessive, the viscosity will be too high, making it impossible to foam at a high ratio. The lightweight properties are poor, and the physical properties tend to decrease.

[0080] As shown in Figure 3, comparing the cross-sections of the microporous foamed bodies of Example 1 and Comparative Example 1 in Figure 12, the use of anhydrides and the high melt strength of the polyester elastomer resin resulted in better maintenance of the cell morphology and superior physical properties. Weather resistance was evaluated by comparing Examples 4-5 with Comparative Example 1, and both examples showed excellent weather resistance.

[0081] As shown in Figure 5, the foaming density of Example 6 is compared with the cross-section of the microporous foamed body of Comparative Example 1 in Figure 12. After the acid anhydride crosslinking agent opens the ring, it will form an interface with the foaming aid, making the foam cells more uniformly dispersed and improving the physical properties.

[0082] As shown in Tables 3-4, compared with Comparative Examples 1-3, the examples within the scope of this invention use epoxy-based polyester elastomer resins with higher melt strength, better maintenance of cell morphology, and better physical properties. Comparing Examples 11-13 with Comparative Example 2, their weather resistance also shows excellent performance.

[0083] Compared with Comparative Examples 2-3, Examples 8-10 show that after the anhydride crosslinking agent opens its ring, it forms an interface with the foaming agent, making the foam cells more uniformly dispersed and improving the physical properties.

[0084] Compared with Comparative Examples 2-3, Examples 11-13 show that the terminal acid groups of the polyester elastomer react more completely with the epoxy crosslinking agent, resulting in higher tensile strength and excellent resilience. Furthermore, it allows for high-ratio foaming, is lightweight, and exhibits excellent foaming and molding properties.

[0085] The microporous foamed molded articles manufactured in the above embodiments are particularly suitable for molding highly reliable functional parts, such as automotive interior and exterior trim parts, sports equipment (grips / yoga mats / cushions), medical devices, running shoe midsoles / tongues / insoles, and building sound insulation / heat insulation materials.

[0086] For purposes of explanation, the foregoing description uses specific nomenclature to provide a thorough understanding of the described embodiments. However, those skilled in the art will understand that many specific details are not required to implement the described embodiments. Therefore, the foregoing description of the specific embodiments described herein is for illustrative and descriptive purposes only, and is not intended to be exhaustive or to limit the embodiments to the precise forms disclosed. Those skilled in the art will understand that many modifications and variations are possible in light of the foregoing teachings.

[0087] The summary and abstract paragraphs may set forth one or more, but not all, exemplary embodiments of the invention as contemplated by the present invention, and are therefore not intended to limit the invention and the scope of the appended claims in any way.

[0088] The foregoing description of the specific embodiments fully reveals the general nature of the invention, enabling others to easily modify and / or adapt them for various applications of such specific embodiments by applying knowledge in the relevant art, without excessive experimentation and without departing from the general concept of the invention. Therefore, based on the teachings and guidance presented herein, such adjustments and modifications are intended to be within the meaning and scope of equivalent examples of the disclosed embodiments. It should be understood that the terminology used herein is for illustrative purposes and not limiting, and is to be interpreted by one of ordinary skill in the art based on the teachings and guidance. The breadth and scope of the invention should not be limited to any of the foregoing illustrative embodiments, but should be defined only according to the following claims and their equivalents.

[0089] none

Claims

1. A thermoplastic polyester elastomer composition comprising: (A) 100 parts by weight of a thermoplastic polyester elastomer, which is a block copolymer composed of about 30-70% by weight of hard segments (a) of aromatic diacids, aliphatic diacids, or sulfonic diacids and their derivatives, and about 70-30% by weight of soft segments (b) of polyesters or polyethers of aliphatic diols, wherein... The polyester hard segment is selected from the group consisting of high-hardness crystalline poly(terephthalic acid) butadiene glycol (PBT), polyethylene terephthalate (PET), or poly(terephthalic acid) butadiene glycol (PTT), poly(terephthalate) sulfonates (CDP), and isophthalic acid (PIA); the polyether soft segment is selected from polyethylene glycol ether (PEG), polypropylene glycol ether (PPG), polybutylene glycol ether (PTMG), polylactide (PLLA), and polyglycolic acid (PEG). (A) The group consisting of PGA and polycaprolactone (PCL); (B) about 0.1 to 0.5 parts by weight of a heat stabilizer selected from: pentaerythritol tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1'-biphenyl]-4,4'-dimethylbis(phosphonite), antioxidant Irganox® 1098, antioxidant Irganox® 1010, antioxidant Irgafos® 168 and antioxidant Ultranox® Group 626; (C) about 0.01 to 2.2 parts by weight of a foaming agent, wherein the foaming agent is selected from the group consisting of: stearic acid, dodecylbenzene-disulfonic acid, dinaphthylmethane-disulfonic acid, siloxaneoxyalkylene copolymers, other organic polysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols and cell regulators, fatty alcohol dimethyl polysiloxanes and combinations thereof; (D) about 0.01 to 1.5 parts by weight of a crosslinking agent, wherein the crosslinking agent is selected from the group consisting of: epoxy compounds, carbodiimides, isocyanates, acid anhydrides, silicone alcohols, melamine resins, metal salts, metal chelates, amine resins and combinations thereof; (E) about 0.01 to 1.2 parts by weight of a UV stabilizer, and The UV stabilizer is selected from the group consisting of: aromatic amine antioxidants, hindered phenol antioxidants, sulfur antioxidants, hindered amine light stabilizers, benzotriazole light stabilizers, benzophenone light stabilizers, benzoate light stabilizers, triazole light stabilizers, nickel light stabilizers, salicylic acid light stabilizers, and combinations thereof; (F) about 0.01 to 0.5 parts by weight of a nucleating agent, wherein the nucleating agent is selected from the group consisting of: organic carboxylic acid alkali metal salts with 3 to 40 carbon atoms and inorganic nucleating agents, wherein the metal in the organic carboxylic acid alkali metal salt is selected from the group consisting of lithium, sodium, potassium, zinc, magnesium, calcium, and barium, and the inorganic nucleating agent is selected from the group consisting of talc and intercalated mica.

2. A microporous foamed body comprising a thermoplastic polyester elastomer composition as described in claim 1, wherein the microporous foamed body has a foaming density of about 0.01 to 0.4 cm3, a rebound of about 50 to 99%, and a cell diameter of about 100 to 500 μm.

3. The microporous foamed article as described in claim 2, wherein the foam is a closed-cell structure and the closed-cell ratio is about 1 to 60%.

4. The microporous foamed molded article as described in claim 2, characterized in that its hardness is 45~70C.

5. The microporous foamed molded body as claimed in claim 2, characterized in that it has a tensile strength of 15~35 kg / cm2 and / or a tear strength of 15~35 kg / cm.

6. The microporous foamed molded article as described in claim 2, characterized in that its resilience is 50-75%.

7. The microporous foamed molded body as described in claim 2, characterized in that it has a peeling rate of 1.9~3.5 kg / cm.

8. The microporous foamed molded article as claimed in claim 2, characterized in that it has a compression ratio of less than 40%.

9. A method for manufacturing a microporous foamed molded article, characterized in that the microporous foamed molding system is obtained by foaming a thermoplastic polyester elastomer composition as described in claim 1.

10. A functional component of a microporous foamed molded body, which is formed by molding a microporous foamed molded body as described in any one of claims 2 to 8.

11. The functional component as described in claim 10, wherein the functional component is an automotive interior or exterior trim, sports equipment, medical device, shoe component, building sound insulation material, or thermal insulation material.

12. The functional component as described in claim 11, wherein the sports equipment is a grip, yoga mat, or seat, and the shoe component is a midsole, tongue, or insole.

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