CN110294860B - Process for producing elastic composite material and product thereof - Google Patents
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- CN110294860B CN110294860B CN201810234157.9A CN201810234157A CN110294860B CN 110294860 B CN110294860 B CN 110294860B CN 201810234157 A CN201810234157 A CN 201810234157A CN 110294860 B CN110294860 B CN 110294860B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The elastic composite material is produced with thermoplastic polyamide elastomer and thermoplastic polyurethane elastomer in certain proportion, and through mixing, mixing and foaming, and the small air bubble holes distributed inside the elastomer make the elastomer possess light weight and certain structural strength.
Description
Technical Field
The invention relates to a process for preparing thermoplastic elastomer and a finished product, which are prepared by mixing and foaming, the structure of the prepared elastic composite material has good characteristic performance, and particularly, the elastic composite material has good rebound resilience and light weight when being applied to soles by foaming, and the manufacturing cost is reduced.
Background
Common materials for shoe soles include polyvinyl chloride (PVC), rubber, Ethylene Vinyl Acetate (EVA), Polyurethane (PU), and the like. Among them, EVA foam is most widely used, but EVA foam has high compression set and poor resilience. The PU foaming material has simple processing process, is beneficial to realizing automatic production and is widely concerned, but has the defects of easy yellowing, poor aging resistance and the like.
With the rapid development of material science and the breakthrough of technology, thermoplastic elastomers have been widely used in shoe soles. Thermoplastic Polyamide elastomers (TPA, TPAE, TPE-A, PEBA) are block copolymers of rigid Polyamide (nylon) segments and flexible polyether or polyester segments. Has wider application temperature range and hardness than other thermoplastic elastomers, is mainly applied to low-temperature environments in which other thermoplastic elastomers are not applicable, has excellent mechanical and dynamic properties, good chemical resistance and wear resistance and high temperature resistance, does not contain volatile or migratory plasticizers, and is widely used. But has the defects of easy hydrolysis by boiling water, high price, easy color change of recycled materials and the like, so that the method still has room for improvement. Thermoplastic Polyurethane elastomer (TPU for short) also has excellent wear resistance, better tensile strength and elongation and oil resistance, lower price than Thermoplastic polyamide elastomer and good compatibility, so the Thermoplastic Polyurethane elastomer is the preferred material for modifying Thermoplastic polyamide elastomer. Prior arts relating to material modification are known, such as amide elastomer foamed particles, a method for producing the same, a foamed molded article and a method for producing the same, of taiwan patent No. 1564326.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art, and provides a process for producing an elastic composite material and a product thereof, wherein the elastic composite material is produced by mixing, kneading and foaming a thermoplastic polyamide elastomer and a thermoplastic polyurethane elastomer in a specific ratio, and fine bubble holes distributed in the thermoplastic polyamide elastomer and the thermoplastic polyurethane elastomer are used to reduce the overall structure weight and maintain the effect of a certain structural strength, thereby contributing to control the manufacturing cost of the subsequent shoe sole, and improving the application of the single thermoplastic polyamide elastomer.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a process for preparing elastic composite material includes such steps as mixing, pugging and foaming. Wherein: mixing, namely stirring and mixing the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorbent in a mixer; the first mixture is thermoplastic polyamide elastomer (TPAE), the density of the TPAE is 1-1.01 g/cm3, the hardness of the TPAE is Shore A80-A95, and 40-80 PHR (parts per hundred of the total composition) is added; the second mixture is thermoplastic polyurethane elastomer (TPU), the density of the second mixture is 1.1g/cm 3-1.2 g/cm3, the hardness is Shore A80-A95, and the added weight is 20-60 PHR; the addition weight of the antioxidant yellowing resistant agent is 0.5-1 PHR, the addition weight of the hydrolysis resistant agent is 0.5-1.5 PHR, and the addition weight of the ultraviolet absorbent is 0.5-1 PHR: mixing, namely uniformly mixing the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorbent, and then putting the mixture into a mixing roll for granulation to prepare composite particles; the setting temperature of the mixing roll is 150-170 ℃; a foaming step, namely putting the composite particles, the aqueous dispersion and the entrainer into an autoclave, stirring and mixing, inputting high-pressure fluid into the autoclave, heating the autoclave to ensure that the composite particles and the high-pressure fluid are dissolved and balanced, releasing pressure through the autoclave, and filling steam and high-pressure air into the autoclave to obtain a foamed elastic composite material; the high-pressure fluid is CO2 and N2, the pressure of CO2 is 8-9 MPa, and the pressure of N2 is 5-7 MPa; the heating autoclave temperature is 110 ℃ to 150 ℃ and the heating autoclave time is 0.5hr (hour) to 2 hr.
An elastic composite material is solid particles formed by mixing a first mixture and a second mixture in proportion and foaming; the elastic composite material comprises a surface layer and an inner lining completely covered by the surface layer, wherein the inner lining is provided with a plurality of bubble holes, and the bubble holes are partially communicated and partially not communicated; the first mixture is a thermoplastic polyamide elastomer; the second mixture is thermoplastic polyurethane elastomer; the elastic composite material also contains a first mixture in a percentage greater than a second mixture in a percentage.
The invention has the advantages that the sole is prepared by mixing, mixing and foaming the thermoplastic polyamide elastomer and the thermoplastic polyurethane elastomer according to a specific proportion, the overall structure has light weight by virtue of the fine bubble holes distributed in the thermoplastic polyamide elastomer and the thermoplastic polyurethane elastomer, the effect of maintaining certain structural strength is maintained, the manufacturing cost of the subsequent sole is controlled, and the problems in the application of the single-use thermoplastic polyamide elastomer are solved.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a flow chart of the present invention.
FIG. 2 is a table comparing the composition ratio and material properties of examples of the present invention with those of a control group.
Fig. 3 is a perspective view of the elastic composite of the present invention.
FIG. 4 is a schematic cross-sectional view of an elastic composite of the present invention.
Fig. 5 is a partially enlarged view of block a of fig. 4.
The reference numbers in the figures illustrate:
1 elastic composite material
2 epidermal layer
3 inner lining
31 bubble hole
Detailed Description
Referring to fig. 1, the process of the present invention for producing elastic composite material includes a mixing step, a mixing step and a foaming step.
Mixing, namely stirring and mixing the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorbent in a mixer; the first mixture is thermoplastic polyamide elastomer (TPAE), the density of the TPAE is 1-1.01 g/cm3, the hardness of the TPAE is Shore A80-A95, and 40-80 PHR (parts per hundred of the total composition) is added; the second mixture is thermoplastic polyurethane elastomer (TPU), the density of the second mixture is 1.1g/cm 3-1.2 g/cm3, the hardness is Shore A80-A95, and the added weight is 20-60 PHR; the addition weight of the antioxidant yellowing resistant agent is 0.5-1 PHR, the addition weight of the hydrolysis resistant agent is 0.5-1.5 PHR, and the addition weight of the ultraviolet absorbent is 0.5-1 PHR.
Mixing, namely uniformly mixing the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorbent, and then putting the mixture into a mixing roll for granulation to prepare composite particles; the setting temperature of the mixing roll is 150-170 ℃; a foaming step, namely putting the composite particles, the aqueous dispersion and the entrainer into an autoclave, stirring and mixing, inputting high-pressure fluid into the autoclave, heating the autoclave to ensure that the composite particles and the high-pressure fluid are dissolved and balanced, releasing pressure through the autoclave, and filling steam and high-pressure air into the autoclave to obtain a foamed elastic composite material; the high-pressure fluid is CO2 and N2, the pressure of CO2 is 8-9 MPa, and the pressure of N2 is 5-7 MPa; the temperature of the heating autoclave is 110-150 ℃, and the heating autoclave time is 0.5-2 hr.
Please refer to fig. 2, which shows a control group and the first to third embodiments. Wherein the first embodiment employs a first blend of 80PHR (thermoplastic polyamide elastomer) and a third blend of 20PHR (thermoplastic polyurethane elastomer). The second embodiment employs a first blend of 60PHR (thermoplastic polyamide elastomer) and a second blend of 40PHR (thermoplastic polyurethane elastomer). The third embodiment employs a first blend of 40PHR (thermoplastic polyamide elastomer) and a second blend of 60PHR (thermoplastic polyurethane elastomer). The second blend (thermoplastic polyurethane elastomer, TPU) of the foregoing first through third embodiments had a hardness of Shore A85, a density of 1.2g/cm3, a softening point of 120 deg.C, and a melting point of 155 deg.C. The thermoplastic polyamide elastomer of the control was PEBAX 4533, Shore A92 hardness, density 1.01g/cm3, soft point 111 ℃ and melting point 147 ℃ as in the first mixture of the first to third examples. In addition, the first mixture may be compounded with TPU using UBESTA XAP or VESTAMID E with the same effect.
It is noted that the elongation of the elastic composite material obtained in the first to third embodiments is much higher than that of the opposite group, and the tensile strength of the elastic composite material obtained in the first and second embodiments is higher than that of the opposite group. The remaining material properties of hardness, density, tear strength, rebound, etc. are substantially less different in the first through third embodiments than in the case of the manufacturing. Therefore, the second mixture (thermoplastic polyurethane elastomer, TPU) with higher melting point is mixed with the first mixture for foaming, so that the softening point and the melting point of the original first mixture are improved, and the characteristics of elongation, tensile strength and the like of the material are greatly improved.
The process for manufacturing the elastic composite material comprises the following technical features.
The mixing step further comprises a lubricant and a nucleating agent, and the lubricant, the nucleating agent, the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorbent are stirred and mixed in a mixer, wherein the adding weight of the lubricant is 0.5-1 PHR, and the adding weight of the nucleating agent is 2-5 PHR.
The mixing machine in the mixing step is an internal mixer, a single-screw extruder or a double-screw extruder, and the particle size of the composite particles is 1-2 mm.
The aqueous dispersion of the foaming step comprises water and a surfactant, the entrainer is any one of cyclopentane, butane, ethanol or methanol, and the ratio of the water to the surfactant and the entrainer is 1: 0.002: 0.02-1: 0.01: 0.05. The dissolution balance of the foaming step comprises soaking for 0.5-2 hr. The particle size of the foamed elastic composite material is 3-7 mm.
Referring to fig. 3 to 5, the elastic composite material 1 includes a skin layer 2 and an inner layer 3 completely covered by the skin layer 2, wherein the inner layer 3 has a plurality of bubble holes 31, and the plurality of bubble holes 31 are partially connected and partially not connected. The elastic composite material 1 has a particle size of 3mm to 7mm, the thickness of the skin layer 2 is 100 micrometers to 200 micrometers, and the diameter of the bubble holes 31 is 100 micrometers to 400 micrometers. The outer surface of the skin layer 2 is smooth. The elastic composite material 1 can be made into an oval shape or a round ball shape.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications made to the above embodiment according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A process for producing an elastic composite material, comprising:
mixing, namely stirring and mixing the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorbent in a mixer;
the first mixture is thermoplastic polyamide elastomer, the density of the first mixture is 1-1.01 g/cm3, the hardness of the first mixture is Shore A80-A95, and 40-80 parts by weight of PHR (parts per hundred of the total composition) are added; the second mixture is thermoplastic polyurethane elastomer, the density of the second mixture is 1.1g/cm 3-1.2 g/cm3, the hardness is Shore A80-A95, and the weight of the second mixture is 20-60 PHR;
the addition weight of the antioxidant yellowing resistant agent is 0.5-1 PHR, the addition weight of the hydrolysis resistant agent is 0.5-1.5 PHR, and the addition weight of the ultraviolet absorbent is 0.5-1 PHR;
mixing, namely uniformly mixing the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorbent, and putting the mixture into a mixing roll to prepare composite particles; the setting temperature of the mixing roll is 150-170 ℃;
a foaming step, namely putting the composite particles, the aqueous dispersion and the entrainer into an autoclave, stirring and mixing, inputting high-pressure fluid into the autoclave, heating the autoclave to ensure that the composite particles and the high-pressure fluid are dissolved and balanced, releasing pressure through the autoclave, and filling steam and high-pressure air into the autoclave to obtain a foamed elastic composite material; the high-pressure fluid is CO2 and N2, the pressure of CO2 is 8-9 MPa, and the pressure of N2 is 5-7 MPa; the temperature of the heating autoclave is 110-150 ℃, and the heating autoclave time is 0.5-2 hr.
2. The process of claim 1, wherein the mixing step further comprises mixing the lubricant and the nucleating agent with the first mixture, the second mixture, the antioxidant yellowing-resistant agent, the hydrolysis-resistant agent and the ultraviolet absorber in a blender under stirring, wherein the weight of the lubricant is 0.5 to 1PHR and the weight of the nucleating agent is 2 to 5 PHR.
3. The process of claim 2, wherein the aqueous dispersion of the foaming step comprises water and a surfactant, the entrainer is cyclopentane, butane, ethanol or methanol, and the ratio of water to the surfactant and the entrainer is 1: 0.002: 0.02 to 1: 0.01: 0.05.
4. The process of claim 3, wherein the solution balance of the foaming step comprises soaking for 0.5-2 hr.
5. The process of claim 4, wherein the mixing roll in the mixing step is an internal mixer, a single screw extruder or a twin screw extruder, and the particle size of the composite particles is 1-2 mm.
6. The process of any one of claims 1 to 5, wherein the particle size of the foamed elastic composite is between 3mm and 7 mm.
7. An elastic composite material is solid particles formed by mixing a first mixture and a second mixture in proportion and foaming;
the elastic composite material comprises a surface layer and an inner lining completely covered by the surface layer, wherein the inner lining is provided with a plurality of bubble holes, the bubble holes are partially communicated and partially not communicated, the communication proportion of the bubble holes is less than 5 percent, and the non-communication proportion is more than 95 percent;
the first mixture is a thermoplastic polyamide elastomer;
the second mixture is thermoplastic polyurethane elastomer;
the elastic composite material also contains a first mixture in a percentage greater than a second mixture in a percentage.
8. An elastic composite, according to claim 7, characterized in that said first mixture is between 40 and 80phr (parts per hundred of total composition) and said second mixture is between 10 and 40 phr.
9. The elastic composite of claim 8, wherein the elastic composite hardness is from 92A to 94A; the elastic composite has a density of 1.01g/cm3 to 1.07g/cm 3; the tensile strength of the elastic composite material is 183.5kg/cm 2-243.9 kg/cm 2; the elastic composite has an elongation of 529.83% to 727.19%; the elastic composite material has a tear strength of 140kg/cm to 149 kg/cm; the elastic composite has a rebound resilience of 52% to 54%.
10. The elastic composite of claim 9, wherein the elastic composite has a particle size of 3mm to 7mm, the skin layer has a thickness of 100 μm to 200 μm, and the outer surface of the skin layer is smooth.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810234157.9A CN110294860B (en) | 2018-03-21 | 2018-03-21 | Process for producing elastic composite material and product thereof |
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| CN201810234157.9A CN110294860B (en) | 2018-03-21 | 2018-03-21 | Process for producing elastic composite material and product thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024089364A1 (en) * | 2022-10-26 | 2024-05-02 | Arkema France | Foam comprising a thermoplastic polyurethane and a copolymer having polyamide blocks and polyether blocks with amine end groups |
| WO2024089365A1 (en) * | 2022-10-26 | 2024-05-02 | Arkema France | Foam comprising a thermoplastic polyurethane and a copolymer with polyamide blocks and polyether blocks |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021068100A1 (en) * | 2019-10-08 | 2021-04-15 | 加久企业股份有限公司 | Manufacturing process of hollow elastomer |
| CN112659442A (en) * | 2019-10-16 | 2021-04-16 | 加久企业股份有限公司 | TPU foamed sole manufacturing process and finished product thereof |
| WO2022162048A1 (en) | 2021-01-28 | 2022-08-04 | Basf Se | Particle foam made of tpe with a shore hardness between 20d and 90d |
| FR3119396B1 (en) * | 2021-02-01 | 2024-04-19 | Arkema France | Copolymer with polyamide blocks and polyether blocks for the manufacture of a foamed article |
| CN115895094A (en) * | 2022-10-27 | 2023-04-04 | 泉州匹克鞋业有限公司 | Composition for ultralight elastic sole and preparation method thereof |
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| CN107556513A (en) * | 2017-09-14 | 2018-01-09 | 四川大学 | A kind of Crystalline plastics expanded particle formed body and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9498927B2 (en) * | 2013-03-15 | 2016-11-22 | Nike, Inc. | Decorative foam and method |
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| JPS6042432A (en) * | 1983-08-18 | 1985-03-06 | Japan Styrene Paper Co Ltd | Foamed particle |
| CN105102518A (en) * | 2013-03-15 | 2015-11-25 | 耐克创新有限合伙公司 | Process for foaming thermoplastic elastomers |
| CN106687511A (en) * | 2014-09-30 | 2017-05-17 | 积水化成品工业株式会社 | Amide elastomer foam particles, method for producing same, foam molded body and method for producing foam molded body |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024089364A1 (en) * | 2022-10-26 | 2024-05-02 | Arkema France | Foam comprising a thermoplastic polyurethane and a copolymer having polyamide blocks and polyether blocks with amine end groups |
| WO2024089365A1 (en) * | 2022-10-26 | 2024-05-02 | Arkema France | Foam comprising a thermoplastic polyurethane and a copolymer with polyamide blocks and polyether blocks |
| FR3141465A1 (en) * | 2022-10-26 | 2024-05-03 | Arkema France | Thermoplastic polyurethane and copolymer foam with polyamide blocks and amine chain-ended polyether blocks |
| FR3141464A1 (en) * | 2022-10-26 | 2024-05-03 | Arkema France | Thermoplastic polyurethane and copolymer foam with polyamide blocks and polyether blocks |
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| CN110294860A (en) | 2019-10-01 |
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