TW201938683A - Elastic composite material process and product produced therefrom enabling the overall structure to be light-weighted and having an effect of maintaining a certain structural strength - Google Patents

Abstract

Disclosed is an elastic composite material process and a product produced therefrom, in which the elastic composite material is obtained by mixing, kneading and foaming a thermoplastic polyamide elastomer and a thermoplastic polyurethane elastomer at a specific ratio, and the fine pores distributed inside the elastic composite material are used to enable the overall structure to be light-weighted, thereby having an effect of maintaining a certain structural strength, moreover, beneficial to the control of subsequent manufacturing costs for producing shoe soles.

Description

Process of elastic composite material and its finished product

The invention relates to a process and a finished product of a thermoplastic elastomer, which are prepared by mixing and foaming, and the structure of the obtained elastic composite material has good characteristics, especially it is retained in the application of the sole through foaming. Those with good resilience, light material, and reduced production costs.

Materials commonly used in shoe soles are roughly polyvinyl chloride (PVC), rubber, ethylene-vinyl acetate copolymer (EVA), polyurethane (PU), and the like. Among them, EVA foam material is the most widely used, but EVA foam material has high compression deformation and poor resilience. However, PU foaming materials have attracted much attention due to their simple processing process and help to realize automated production, but they have defects such as easy yellowing and poor aging resistance.

With the rapid development of materials science and technological breakthroughs, existing thermoplastic elastomers are widely used in shoe soles on products. Thermoplastic Polyamide Elastomer (Thermoplastic Polyamide Elastomer, abbreviated as TPA, TPAE, TPE-A, PEBA) is a block copolymer composed of rigid polyamide (nylon) segments and flexible polyether or polyester segments. It has a wider application temperature range and hardness than other thermoplastic elastomers. It is mainly used in low temperature environments where other thermoplastic elastomers are not suitable. It also has excellent mechanical and dynamic properties, good chemical and abrasion resistance, and high temperature resistance. And it does not contain volatile or migrating plasticizers, so it is widely used. But its disadvantage is that it has The disadvantages of easy boiling water hydrolysis, high price, and easy discoloration of recycled materials, so there is still room for improvement. The thermoplastic polyurethane elastomer (Thermoplastic Polyurethane abbreviation TPU) also has excellent abrasion resistance, better tensile strength and elongation, and oil resistance. It is cheaper than thermoplastic polyamide elastomers and has good compatibility. Therefore, it is the material of choice for modified thermoplastic polyamide elastomers. It is currently known that related materials have been modified from the prior art, such as the Taiwanese Patent No. I564326, the amidine-based elastomer foamed particles, a manufacturing method thereof, a foamed molded body, and a manufacturing method thereof.

The invention provides an elastic composite material manufacturing process and a finished product thereof, which are prepared by mixing, kneading, and foaming a thermoplastic polyamide elastomer and a thermoplastic polyurethane elastomer through a specific ratio, and distribute the fine bubble cells inside the same. The utility model has the effect of reducing the weight of the overall structure, maintaining a certain structural strength, and helping to control the manufacturing cost of subsequent production of soles. At the same time, it improves the application of the thermoplastic polyamine elastomer alone which still has the aforementioned problems.

The elastic composite material manufacturing process of the present invention includes a mixing step, a kneading step, and a foaming step. In the mixing step, the first mixture, the second mixture, the anti-yellowing and anti-yellowing agent, the hydrolysis resistance agent, and the ultraviolet absorber are mixed in a mixer, and the first mixture is a thermoplastic polyamide elastomer (TPAE). Its density is 1 ~ 1.01g / cm ³ , hardness is Shaw A80 ~ A95, added weight is 40 ~ 80PHR (parts per hundred parts of total composition); the second mixture is thermoplastic polyurethane elastomer ( TPU), the density is 1.1g / cm ³ ~ 1.2g / cm ³ , the hardness is Shaw A80 ~ A95, the weight is 20 ~ 60PHR; the anti-oxidation and yellowing resistance agent is 0.5 ~ 1PHR, the hydrolysis resistance is added The weight is 0.5 to 1.5 PHR, and the ultraviolet absorber is added to the weight of 0.5 to 1 PHR. In the mixing step, the first mixture, the second mixture, the anti-yellowing agent, the hydrolysis resistance agent, and the ultraviolet absorber are mixed uniformly and then put into the mixture. The granulator is granulated to obtain composite particles. The mixing machine is set to a temperature of 150 ° C to 170 ° C. In the foaming step, the composite particles, the water dispersion liquid, and the entrainer are placed in an autoclave, and after mixing, input High pressure fluid to the autoclave and heat the autoclave so that the composite particles and high pressure fluid To dissolve the balance, and then poured into the autoclave and the pressure release of water vapor and air through a high pressure in an autoclave, the resulting elastic composite foam; the high pressure fluid CO ₂ and N _2, and the CO ₂ pressure of 8 ~ 9MPa, and N _{2 The} pressure is 5 to 7 MPa; the aforementioned heating autoclave temperature is 110 ° C to 150 ° C, and the heating autoclave time is 0.5hr (hour) to 2hr.

An elastic composite material is a solid particle mixed with a first mixture and a second mixture in proportion and foamed. The elastic composite material includes a skin layer and an inner and inner layer completely covered by the skin layer. The inner layer has a plurality of air cells, and the plurality of air cells are partially connected and partially disconnected; the first mixture is a thermoplastic polyamide elastomer; the second mixture is a thermoplastic polyurethane elastomer; and The percentage of the first mixture contained in the elastic composite is greater than the percentage of the second mixture contained therein.

1‧‧‧ Elastic Composite

2‧‧‧ epidermis

3‧‧‧ inner layer

31‧‧‧ bubble hole

The first diagram is a flowchart of the present invention.

The second figure is a comparison table of the composition ratio and material characteristics of the embodiment of the present invention and the control group.

The third figure is a schematic perspective view of the elastic composite material of the present invention.

The fourth figure is a schematic sectional view of the elastic composite material of the present invention.

The fifth diagram is a partially enlarged diagram of the A block in the fourth diagram.

Please refer to the first diagram of the figure. The elastic composite material manufacturing process of the present invention includes a mixing step, a kneading step, and a foaming step.

In the mixing step, the first mixture, the second mixture, the anti-yellowing resistance agent, the hydrolysis resistance agent, and the ultraviolet absorber are stirred and mixed in a mixer; the first mixture is a thermoplastic polyamide elastomer (TPAE), and its density It is 1 ~ 1.01g / cm ³ , hardness is Shaw A80 ~ A95, and the weight is 40 ~ 80PHR (corresponding parts per 100 parts of total composition); the second mixture is thermoplastic polyurethane elastomer (TPU) , Its density is 1.1g / cm ³ ~ 1.2g / cm ³ , hardness is Shaw A80 ~ A95, added weight is 20 ~ 60PHR; antioxidant added yellowing resistance agent is added 0.5 ~ 1PHR, hydrolysis resistant agent is added as 0.5 ~ 1.5PHR, UV absorber added weight is 0.5 ~ 1PHR.

In the mixing step, the first mixture, the second mixture, the anti-yellowing and anti-yellowing agent, the hydrolysis resistance agent, and the ultraviolet absorber are mixed uniformly, and then put into a kneading machine to granulate to obtain composite particles. The preset temperature of the kneading machine is 150 ° C ~ 170 ° C; in the foaming step, the aforementioned composite particles, water dispersion and entrainer are placed in an autoclave, and after stirring and mixing, a high-pressure fluid is input to the autoclave and the autoclave is heated, so that the composite particles and the high-pressure fluid reach Dissolve and balance, then release pressure from the autoclave and pour water vapor and high-pressure air into the autoclave to obtain a foamed elastic composite material; the aforementioned high-pressure fluid is CO ₂ and N ₂ , and the CO ₂ pressure is 8 to 9 MPa, and N ₂ The pressure is 5 to 7 MPa; the temperature of the aforementioned heating autoclave is 110 ° C to 150 ° C, and the heating autoclave time is 0.5hr to 2hr.

Please refer to the second figure of the drawing, which shows a control group and first to third embodiments. The first embodiment adopts a first mixture (thermoplastic polyamide elastomer) of 80 PHR and a second mixture (thermoplastic polyurethane elastomer) of 20 PHR. The second embodiment uses a first mixture of 60 PHR (thermoplastic polyamide elastomer) and a second mixture of 40 PHR (thermoplastic polyurethane elastomer). The third embodiment uses a first mixture of 40 PHR (thermoplastic polyamide elastomer) and a second mixture of 60 PHR (thermoplastic polyurethane elastomer). The second mixture (thermoplastic polyurethane elastomer, TPU) of the foregoing first to third embodiments has a hardness of Xiao A85, a density of 1.2 g / cm ³ , a softening point of 120 ° C., and a melting point of 155 ° C. In contrast, the thermoplastic polyamide elastomer of the control group used PEBAX 4533, hardness was Shaw A92, density was 1.01 g / cm ³ , soft point was 111 ° C, and melting point was 147 ° C. The first mixture also uses PEBAX 4533 as an example. In addition, the first mixture can also be mixed with UBESTA XAP or VESTAMID E and TPU, which also has the same effect.

Special attention is paid to the elastic composites produced in the first to third examples. The experimentally measured elongation is much greater than the elongation of the group, and the tensile strengths measured in the first and second examples are also higher than To build groups. For the rest of the material characteristics such as hardness, density, tear strength, rebound, etc., the first to third embodiments have substantially no difference compared to the fabrication group. It can be seen that the present invention improves the softening point and melting point of the original first mixture after the second mixture (thermoplastic polyurethane elastomer, TPU) is mixed with the first mixture through chain foaming, and the material extension is greatly improved. Rate, tensile strength and other characteristics.

The aforementioned elastic composite material process includes the following technical features.

The aforementioned mixing step further includes a slip agent and a nucleating agent, and is mixed with the first mixture, the second mixture, an anti-yellowing agent, a hydrolysis resistance agent, and an ultraviolet absorber in a mixer, and the weight of the slip agent is 0.5 ~ 1PHR, nucleating agent added weight is 2 ~ 5PHR.

The mixer in the aforementioned 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 to 2 mm.

The aqueous dispersion of the aforementioned foaming step includes water and a surfactant, and the entrainer is any of 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. The dissolution balance of the foaming step includes immersion for 0.5 ~ 2hr. The particle size of the foamed elastic composite is 3mm ~ 7mm.

As shown in the third to fifth figures, the finished product obtained according to the foregoing elastic composite material manufacturing process includes an outer skin layer 2 and an inner inner layer 3 which is completely covered by the outer skin layer 2, and the inner inner layer 3 There are a plurality of bubble cells 31, and the plurality of bubble cells 31 are partially connected and partially disconnected. The elastic composite material 1 has a particle size of 3 mm to 7 mm, the skin layer 2 has a thickness of 100 μm to 200 μm, and the cell 31 has a diameter of 100 to 400 μm. The outer surface of the skin layer 2 is smooth. The elastic composite material 1 can be made into an oval shape or a spherical shape.

Claims (10)

An elastic composite material manufacturing process includes a mixing step of mixing a first mixture, a second mixture, an anti-yellowing agent, a hydrolysis-resistant agent, and an ultraviolet absorber in a mixer; the first mixture is a thermoplastic polymer. Amine elastomer, its density is 1 ~ 1.01g / cm ³ , hardness is Shaw A80 ~ A95, weight is 40 ~ 80PHR (parts per hundred total components of the composition); the second mixture is thermoplastic Polyurethane elastomer, its density is 1.1g / cm ³ ~ 1.2g / cm ³ , hardness is Shaw A80 ~ A95, added weight is 20 ~ 60PHR; anti-oxidation and yellowing resistance agent is added 0.5 ~ 1PHR, hydrolysis resistance Add 0.5 to 1.5 PHR and UV absorber to 0.5 to 1 PHR. In the mixing step, mix the first mixture, the second mixture, the anti-yellowing agent, the hydrolysis resistance agent, and the ultraviolet absorber, and place them in the mixture. Kneading machine to obtain composite particles; the above-mentioned kneading machine is set to a temperature of 150 ° C to 170 ° C; in the foaming step, the aforementioned composite particles, an aqueous dispersion liquid, and an entrainer are placed in an autoclave, and after mixing, the pressure is input Fluid to the autoclave and heat the autoclave so that the composite particles The high pressure fluid to reach equilibrium was dissolved, and then poured into the autoclave and the pressure release of water vapor and air through a high pressure in an autoclave, the resulting elastic composite foam; the high pressure fluid CO ₂ and N _2, and the CO ₂ pressure of 8 ~ 9MPa, The N ₂ pressure is 5 to 7 MPa; the aforementioned heating autoclave temperature is 110 ° C. to 150 ° C., and the heating autoclave time is 0.5 hr to 2 hr. In the elastic composite material manufacturing process according to claim 1, the mixing step further includes a slip agent, a nucleating agent, and a first mixture, a second mixture, an anti-yellowing agent, The hydrolysis-resistant agent and ultraviolet absorber are mixed in a mixer, and the weight of the lubricant is 0.5 to 1 PHR, and the weight of the nucleating agent is 2 to 5 PHR. The elastic composite material manufacturing process according to claim 2, wherein the water dispersion in the foaming step includes water and a surfactant, and the entraining agent is any of cyclopentane, butane, ethanol, or methanol, and water and the surface The ratio of active agent and entrainer is 1: 0.002: 0.02 to 1: 0.01: 0.05. The elastic composite material manufacturing process according to claim 3, wherein the dissolution balance of the foaming step includes immersion for 0.5 to 2 hours. The elastic composite material manufacturing process according to claim 4, wherein the kneader in the kneading step is an internal mixer, a single screw extruder or a twin screw extruder, and the particle size of the composite particles is 1 to 2 mm. The elastic composite material manufacturing process according to any one of claim 1 to claim 5, wherein a particle size of the foamed elastic composite material is 3 mm to 7 mm. An elastic composite material is a solid particle mixed with a first mixture and a second mixture in proportion and foamed. The elastic composite material includes a skin layer and an inner and inner layer completely covered by the skin layer. The inner layer has a plurality of bubble cells, and the plurality of bubble cells are partially connected and partially disconnected. Among them, the connection ratio of the plurality of bubble cells is less than 5% and the disconnection ratio is more than 95%. The mixture is a thermoplastic polyamide elastomer; the second mixture is a thermoplastic polyurethane elastomer; and the percentage of the first mixture contained in the elastic composite material is greater than the second mixture contained therein Thing percentage. The elastic composite material according to claim 7, wherein the first mixture is 40 to 80 phr (parts per hundred total components of the composition), and the second mixture is 10 to 40 phr. The elastic composite material according to claim 8, wherein the elastic composite material has a hardness of 92A to 94A; the elastic composite material has a density of 1.01g / cm ³ to 1.07g / cm ³ ; the elastic composite material has a tensile strength of 183.5kg / cm2 to 243.9kg / cm2; the elongation of the elastic composite is 529.83% to 727.19%; the tear strength of the elastic composite is 140kg / cm to 149kg / cm; the rebound rate of the elastic composite is 52% to 54% . The elastic composite material according to claim 9, wherein the elastic composite material has a particle size of 3 mm to 7 mm, and the thickness of the skin layer is 100 μm to 200 μm. The outer surface of the epidermal layer is smooth.