TWI656169B - Elastic composite process and its finished products - Google Patents

Abstract

An elastic composite material process and a finished product thereof, which are obtained by mixing, kneading and foaming a thermoplastic polyimide elastomer and a thermoplastic polyurethane elastomer through a specific ratio, and making the whole by a fine bubble hole distributed therein The structure is lightweight, maintains the effectiveness of a certain structural strength, and helps control the cost of making subsequent shoe soles.

Description

Elastic composite process and its finished products

The invention relates to a process and a finished product of a thermoplastic elastomer, which are prepared by kneading and foaming, and the structure of the elastic composite material has good characteristic performance, in particular, the foaming is applied to the sole for use. Good resilience, light weight, and reduced production costs.

Commonly used materials for the sole are polyvinyl chloride (PVC), rubber, ethylene-vinyl acetate (EVA), polyurethane (PU), and the like. Among them, EVA foaming materials are the most widely used, but EVA foaming materials have high compression deformation and poor resilience. The PU foaming material has been widely concerned with the simple processing process and contributes to the automatic production, but has defects such as easy yellowing and poor aging resistance.

With the rapid development of materials science and technological breakthroughs, thermoplastic elastomers have been widely used in shoe soles. Thermoplastic Polyamide Elastomer (abbreviated as TPA, TPAE, TPE-A, PEBA) is a block copolymer composed of a rigid polyamine (nylon) segment and a flexible polyether or polyester segment. 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 resistance and wear resistance, and high temperature resistance. It is not widely used because it does not contain volatile or migratory plasticizers. But its shortcoming is The boiling water is hydrolyzed, the price is expensive, and the recycled material is easily discolored, so there is still room for improvement. Thermoplastic Polyurethane (TPU) also has excellent wear resistance, good tensile strength, elongation and oil resistance, and is cheaper than thermoplastic polyamine elastomers, and its compatibility is good. It is therefore the material of choice for modified thermoplastic polyamide elastomers. Prior art materials have been known to be modified, such as the amide-based elastomer-expanded particles of Taiwan Patent No. I564326, a method for producing the same, a foamed molded article, and a method for producing the same.

The invention provides an elastic composite material process and a finished product thereof, which are prepared by mixing, kneading and foaming a thermoplastic polyimide elastomer and a thermoplastic polyurethane elastomer through a specific ratio, and the fine bubble holes distributed therein The overall structure is lightweight, maintains the effectiveness of a certain structural strength, and helps to control the cost of manufacturing the subsequent shoe soles, while improving the problems associated with the single use of thermoplastic polyimide elastomers.

The elastic composite process of the present invention comprises a mixing step, a mixing step and a foaming step. Wherein: a mixing step, mixing the first mixture, the second mixture, the anti-oxygen yellowing resistance agent, the hydrolysis resistance agent, and the ultraviolet absorber in a mixer; the first mixture is a thermoplastic polyamide elastomer (TPAE), The density is 1~1.01g/cm ³ , the hardness is A80~A95, and the weight is 40~80PHR (the number of parts per 100 parts of the composition); the second mixture is thermoplastic polyurethane elastomer ( TPU), its density is 1.1g/cm ³ ~1.2g/cm ³ , hardness is A80~A95, the weight is 20~60PHR; anti-oxygen and yellowing agent is added 0.5~1PHR, hydrolysis resistance added The weight is 0.5~1.5PHR, the weight of the ultraviolet absorber is 0.5~1PHR; in the mixing step, the first mixture, the second mixture, the anti-yellowing agent, the hydrolysis resistance agent and the ultraviolet absorber are uniformly mixed and then mixed. The granule is granulated to obtain composite particles; the temperature of the kneading machine is set to 150 ° C to 170 ° C; in the foaming step, the composite particles and the aqueous dispersion and the entraining agent are placed in an autoclave, and after mixing and mixing, input High pressure fluid to the autoclave and heating the autoclave so that the composite particles and the 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 5-7 MPa; the temperature of the heating autoclave is 110 ° C ~ 150 ° C, and the heating autoclave time is 0.5 hr (hours) ~ 2 hr.

An elastic composite material, wherein the first mixture and the second mixture are mixed and foamed into solid particles; the elastic composite material comprises a skin layer, and an inner layer is completely covered by the skin layer. The inner layer has a plurality of cells, and the plurality of cells are in communication and partially non-connected; the first mixture is a thermoplastic polyimide elastomer; and the second mixture is a thermoplastic polyurethane elastomer; The percentage of the first mixture contained in the elastic composite is greater than the percentage of the second mixture contained therein.

1‧‧‧Flexible composite

2‧‧‧ skin layer

3‧‧‧ inner lining

31‧‧‧ bubble holes

The first figure is a flow chart of the present invention.

The second graph is a comparison table of the composition ratio and material properties of the examples of the present invention and the control group.

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

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

The fifth figure is a partial enlarged view of the A block of the fourth figure.

Referring to the first figure of the drawing, the elastic composite process of the present invention comprises a mixing step, a mixing step and a foaming step.

a mixing step of mixing the first mixture, the second mixture, the antioxidant yellowing resistance agent, the hydrolysis resistance agent, and the ultraviolet absorber in a mixer; the first mixture is a thermoplastic polyamide elastomer (TPAE), and the density thereof It is 1~1.01g/cm ³ , the hardness is A80~A95, and the weight is 40~80PHR (the number of parts per 100 parts of the composition); the second mixture is thermoplastic polyurethane elastomer (TPU) The density is 1.1g/cm ³ ~1.2g/cm ³ , the hardness is Xiao A80~A95, the weight is 20~60PHR; the anti-oxygen yellowing agent is added 0.5~1PHR, the hydrolysis resistance is added 0.5~1.5PHR, UV absorber added weight is 0.5~1PHR.

In the mixing step, the first mixture, the second mixture, the anti-oxidation anti-yellowing agent, the hydrolysis-resistant agent, and the ultraviolet absorber are uniformly mixed and placed in a kneader to be granulated to obtain composite particles; the setting temperature of the kneader is 150 ° C ~ 170 ° C; foaming step, the above composite particles and aqueous dispersion, entrainer into the autoclave, and after mixing and mixing, input high pressure fluid to the autoclave and heat the autoclave, so that the composite particles and high pressure fluid Dissolving the equilibrium, and then releasing the pressure in the autoclave and injecting steam and high-pressure air into the autoclave to obtain a foamed elastic composite; the high-pressure fluid is CO ₂ and N ₂ , and the pressure of CO ₂ is 8-9 MPa, and N ₂ The pressure is 5-7 MPa; the temperature of the above heated autoclave is 110 ° C to 150 ° C, and the heating autoclave time is 0.5 hr to 2 hr.

Please refer to the second figure of the drawing, which shows the control group and the first to third embodiments. In the first embodiment, a first mixture of 80 PHR (thermoplastic polyimide elastomer) and a second mixture of 20 PHR (thermoplastic polyurethane elastomer) were employed. The second embodiment employed a second mixture of 60 PHR (thermoplastic polyimide elastomer) and a second mixture of 40 PHR (thermoplastic polyurethane elastomer). The third embodiment is a second mixture of a 40 PHR (thermoplastic polyimide 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 had a hardness of A85, a density of 1.2 g/cm ³ , a softening point of 120 ° C, and a melting point of 155 ° C. The thermoplastic polyamine elastomer of the control group was PEBAX 4533, having a hardness of Xiao A92, a density of 1.01 g/cm ³ , a soft point of 111 ° C, and a melting point of 147 ° C. The same first to third examples. The first mixture is also exemplified by PEBAX 4533. In addition, the first mixture can also be mixed with TPU using UBESTA XAP or VESTAMID E.

It is particularly noted that the elastic composite materials prepared in the first to third embodiments have experimentally measured elongations much greater than those for the formation, and the tensile strengths measured in the first and second examples are also higher. For grouping. Regarding the other material properties such as hardness, density, tear strength, rebound, and the like, the first to third embodiments are substantially different from each other in comparison with the formation. It can be seen that the present invention improves the softening point and the melting point of the original first mixture by foaming the mixed mixture with the first mixture through the second mixture (thermoplastic polyurethane elastomer, TPU) having a higher melting point, and greatly improves the material elongation. Rate, tensile strength and other characteristics.

The foregoing elastic composite process includes the following technical features.

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

The kneading machine in the kneading step is an internal mixer or a single screw extruder or a twin screw extruder, and the particle diameter of the composite particles is 1 to 2 mm.

The aqueous dispersion of the aforementioned foaming step comprises water and a surfactant, and the entrainer is any one of cyclopentane, butane, ethanol or methanol, and the ratio of water to surfactant and 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 to 2 hr. The foamed elastic composite has a particle size of 3 mm to 7 mm.

According to the above-mentioned elastic composite process, as shown in the third to fifth figures, the elastic composite 1 comprises a skin layer 2, and an inner layer 3 is completely covered by the skin layer 2, the inner layer 3 There are a plurality of bubble holes 31, and the plurality of bubble holes 31 are partially connected and partially disconnected. The elastic composite 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 bubble holes 31 have a diameter of 100 to 400 μm. Further, the outer surface of the skin layer 2 is smooth. The elastic composite 1 can be made into an elliptical shape or a spherical shape.

Claims (10)

An elastic composite process comprising: a mixing step of mixing a first mixture, a second mixture, an antioxidant anti-yellowing agent, a hydrolysis resistance agent, and an ultraviolet absorber in a mixer; the first mixture is a thermoplastic poly An amine elastomer having a density of 1 to 1.01 g/cm ³ , a hardness of A80 to A95, and a weight of 40 to 80 PHR (the number of parts per 100 parts of the composition); the second mixture is thermoplastic Polyurethane elastomer with a density of 1.1g/cm ³ ~1.2g/cm ³ , hardness of A80~A95, weight of 20~60PHR, anti-oxygen and yellowing agent added weight of 0.5~1PHR, hydrolysis resistance The weight is 0.5~1.5PHR, the weight of the ultraviolet absorber is 0.5~1PHR, and the mixing step is to mix the first mixture, the second mixture, the anti-yellowing agent, the hydrolysis resistance agent and the ultraviolet absorber. a mixing machine to obtain composite particles; the above-mentioned kneading machine is set at a temperature of 150 ° C to 170 ° C; in the foaming step, the composite particles and the aqueous dispersion and the entraining agent are placed in an autoclave, and after being mixed and mixed, a high pressure is input. Fluid to the autoclave and heating 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 pressure of the N ₂ is 5-7 MPa; the temperature of the heated autoclave is 110 ° C to 150 ° C, and the heating autoclave time is 0.5 hr to 2 hr. The elastic composite process according to claim 1, wherein the mixing step further comprises a slip agent, a nucleating agent, and the first mixture, the second mixture, the anti-oxygen yellowing agent, The hydrolysis resistance agent and the ultraviolet absorber are mixed and mixed in the mixer, the weight of the slip agent is 0.5~1PHR, and the weight of the nucleating agent is 2~5PHR. The elastic composite process of claim 2, wherein the aqueous dispersion of the foaming step comprises water and a surfactant, and the entrainer is any one of cyclopentane, butane, ethanol or methanol, and the water and the surface The ratio of active agent to entrainer is from 1:0.002:0.02 to 1:0.01:0.05. The elastic composite process of claim 3, wherein the dissolution balance of the foaming step comprises immersion for 0.5 to 2 hr. The elastic composite material process according to claim 4, wherein the kneading machine in the mixing step is an internal mixer or a single screw extruder or a twin screw extruder, and the particle diameter of the composite particles is 1 to 2 mm. The elastic composite process according to any one of claims 1 to 5, wherein the foamed elastic composite has a particle size of 3 mm to 7 mm. An elastic composite material, wherein the first mixture and the second mixture are mixed and foamed into solid particles; the elastic composite material comprises a skin layer, and an inner layer is completely covered by the skin layer. The inner layer has a plurality of cells, and the plurality of cells are connected and partially disconnected, wherein the plurality of cells have a communication ratio of 5% or less and a non-connecting ratio of 95% or more; The mixture is a thermoplastic polyamide elastomer; the second mixture is a thermoplastic polyurethane elastomer; and the elastic composite contains a percentage of the first mixture greater than the second mixture Percentage of objects. The elastic composite of claim 7, wherein the first mixture is 40 to 80 phr (the number of parts per hundred parts of the composition), and the second mixture is 10 to 40 phr. The elastic composite according to claim 8, wherein the elastic composite has a hardness of 92A to 94A; the elastic composite has a density of 1.01g/cm ³ to 1.07g/cm ³ ; and the elastic composite has a tensile strength of 183.5kg. /cm2 to 243.9kg/cm2; the elastic composite elongation rate is 529.83% to 727.19%; the elastic composite tear strength is 140kg/cm to 149kg/cm; the elastic composite rebound rate is 52% to 54% . The elastic composite according to claim 9, wherein the elastic composite has a particle size of from 3 mm to 7 mm, the skin layer has a thickness of from 100 μm to 200 μm, and the outer surface of the skin layer is smooth.