Thermoplastic polyurethane foam material as well as preparation method and application thereof
By combining organic photo-induced luminescence materials into thermoplastic polyurethane foaming materials, the problems of the existing anti-counterfeiting technology being easily copied and poor stability are solved, and anti-counterfeiting sole materials with photo-induced luminescence performance are realized, which are suitable for industrial applications of high-end shoes.
Patent Information
- Application Number
- CN202510551229.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-29
- Publication Date
- 2025-08-15
AI Technical Summary
Existing anti-counterfeiting technologies for footwear such as laser anti-counterfeiting, fluorescent anti-counterfeiting and QR code anti-counterfeiting are problems such as easy to be copied, high cost and poor stability, and it is difficult to meet the anti-counterfeiting needs of high-end shoes.
Thermoplastic polyurethane foaming material is used to combine with organic photo-afterglow luminescence materials, and the photo-afterglow luminescence material is concentrated in the hard phase area of the polyurethane by using the similar principle of similarity, and is formed by supercritical carbon dioxide foaming to form a sole material with photo-afterglow luminescence properties.
It realizes unique photo afterglow luminescence performance, has high recognition and uniqueness, is difficult to replicate, and continues to emit light in dark environments, providing reliable anti-counterfeiting functions, and is suitable for large-scale industrial production.
Smart Images
Figure CN120484482A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of foaming materials, and in particular to a thermoplastic polyurethane foaming material and a preparation method and application thereof. Background Art
[0002] Thermoplastic polyurethane (TPU) boasts advantages such as high elasticity, excellent wear resistance, good chemical resistance, and good processability. It has been widely used in footwear, particularly in the manufacture of soles. As we all know, high-end footwear is often susceptible to counterfeiting by unscrupulous vendors, which not only harms the legitimate interests of consumers but also directly affects the manufacturer's brand image. Therefore, high-end footwear materials must not only possess exquisite design and superior quality, but also possess certain anti-counterfeiting features.
[0003] Currently, common anti-counterfeiting technologies include laser anti-counterfeiting, fluorescent anti-counterfeiting, and QR code anti-counterfeiting. These technologies have all exposed some problems in actual application. For example, laser anti-counterfeiting labels are easy to copy, and their anti-counterfeiting effect will be greatly reduced over time or due to wear and tear of the anti-counterfeiting labels. Fluorescent anti-counterfeiting requires a specific excitation light source, and the hardware cost required for detection is relatively high. In addition, some fluorescent materials are unstable, and the fluorescence intensity will gradually weaken under the influence of light or other environmental factors, making it difficult to achieve a long-term and stable anti-counterfeiting effect. QR codes have certain advantages in information storage and query, but they are easily scanned and cracked by malicious means, resulting in the leakage of anti-counterfeiting information. In summary, existing anti-counterfeiting technologies all have obvious problems and cannot fully meet the anti-counterfeiting requirements of products.
[0004] Therefore, it is of great significance to develop a TPU foam material that has anti-counterfeiting function, is easy to detect, difficult to copy, has a long-lasting anti-counterfeiting effect, and is suitable for use in footwear. Summary of the Invention
[0005] The purpose of the present invention is to provide a thermoplastic polyurethane foam material and a preparation method and application thereof.
[0006] The technical solution adopted by the present invention is:
[0007] A thermoplastic polyurethane foam material comprises thermoplastic polyurethane and an organic photoluminescent material; the hard segment of the thermoplastic polyurethane and the organic photoluminescent material contain similar segment structures.
[0008] Preferably, the organic photopersistence luminescent material is at least one of phenyl phenylcarbamate (PAPE), (2-chloro-4-hydroxyphenyl) phenylcarbamate (PCHPC), methyl phenylcarbamate (MAPE), dimethyl phenylcarbamate (DMAPE), methylethyl phenylcarbamate (MEAPE), methyl N-phenylcarbamate (MHPC), and methoxycarbonylaminonaphthalene (MCAN).
[0009] Note: The structural formula of the above-mentioned organic photoluminescent material is as follows:
[0010]
[0011] Preferably, the mass ratio of the thermoplastic polyurethane to the organic photoluminescent material is 1:0.001-0.03.
[0012] Preferably, the density of the cells in the thermoplastic polyurethane foam material is 10 9 pieces / cm 3 ~10 12 pieces / cm 3 The average diameter of the bubbles is 10μm to 70μm.
[0013] Preferably, the thermoplastic polyurethane foam material has an afterglow luminescence of 3s to 5s after being irradiated by ultraviolet rays.
[0014] Preferably, the wavelength of the ultraviolet light is 240nm to 365nm.
[0015] A method for preparing the thermoplastic polyurethane foam material as described above comprises the following steps: uniformly mixing thermoplastic polyurethane and an organic photoluminescent material, and then foaming and molding with supercritical carbon dioxide to obtain the thermoplastic polyurethane foam material.
[0016] Preferably, a method for preparing the thermoplastic polyurethane foam material as described above comprises the following steps: adding thermoplastic polyurethane and an organic photoluminescent material into a screw extruder for mixing until microstructural analysis confirms that the organic photoluminescent material is concentrated in the hard segment of the polyurethane, and then performing supercritical carbon dioxide foaming to obtain the thermoplastic polyurethane foam material.
[0017] Preferably, the processing temperature of the screw extruder is 190°C to 220°C.
[0018] Preferably, the microstructure analysis method is at least one of transmission electron microscopy observation, scanning electron microscopy observation, and atomic force microscopy observation.
[0019] Preferably, the supercritical carbon dioxide foaming molding has a molding pressure of 2 MPa to 6 MPa, a molding temperature of 80° C. to 160° C., and a holding time of 3 min to 7 min.
[0020] An anti-counterfeiting material comprises the above-mentioned thermoplastic polyurethane foam material.
[0021] A shoe, the sole of which comprises the above-mentioned thermoplastic polyurethane foam material.
[0022] Principle of the Invention: The present invention cleverly utilizes the structural similarity between the hard segments of thermoplastic polyurethane (TPU) and the organic photoluminescent material. Based on the principle of like dissolves like, the organic photoluminescent material is spontaneously and highly concentratedly distributed in the hard segment phase of the TPU. The hard segment phase of the TPU not only provides a rigid environment for the organic photoluminescent material, inhibiting "non-radiative transitions," but also blocks oxygen, preventing oxygen quenching of excitons. Under ultraviolet irradiation, the organic photoluminescent material absorbs photon energy and transitions from the ground state to an excited state. After the ultraviolet irradiation ceases, the excited organic photoluminescent material reaches the triplet state through "intersystem crossing," and then gradually releases energy in a relatively slow process, presenting itself as light. This achieves the photoluminescence phenomenon of the TPU foam material, allowing the TPU foam material to continuously emit light visible to the naked eye in a dark environment. The intensity and duration of the afterglow can be precisely controlled by adjusting the type and amount of the organic photoluminescent material and the mixing process with the TPU.
[0023] The beneficial effects of the present invention are as follows: the thermoplastic polyurethane foam material of the present invention not only has the structure and characteristics of traditional foam materials, but also has unique photoluminescence performance, can be used to make footwear products with anti-counterfeiting functions, and is suitable for large-scale industrial production and application.
[0024] Specifically:
[0025] 1) The thermoplastic polyurethane foam material of the present invention has the structure and characteristics of traditional foam materials and can be used to prepare soles. At the same time, the thermoplastic polyurethane foam material also has unique photoinduced afterglow luminescence properties, which can give the product anti-counterfeiting properties. For example: when the thermoplastic polyurethane foam material is used as a sole material, when a specific light source is used to illuminate the sole, the sole can still continue to emit a unique afterglow light for a long period of time even after the light source is removed. This afterglow luminescence feature has extremely high recognition and uniqueness, and is difficult to imitate and copy by conventional means. Whether after a short exposure in a daylight environment or in a dark environment such as at night, the thermoplastic polyurethane foam material can stably exert its anti-counterfeiting effect. Therefore, the thermoplastic polyurethane foam material of the present invention can provide a reliable, durable and easy-to-identify method for authenticity identification of high-end shoes;
[0026] 2) The thermoplastic polyurethane foam material of the present invention is prepared by a supercritical foaming molding process. Carbon dioxide in a supercritical state has both high diffusivity of a gas and high solubility of a liquid. Under set pressure and temperature conditions, supercritical carbon dioxide can quickly and evenly penetrate into the interior of the thermoplastic polyurethane to form a large number of tiny and evenly distributed bubble nuclei. With the subsequent precise regulation and release of pressure, these bubble nuclei will continue to expand, ultimately forming a stable and uniform foam structure within the thermoplastic polyurethane. Of particular importance is that the distribution of the organic photoluminescent material in the hard segment phase region of the polyurethane is not significantly affected during the entire foaming process and can still remain highly concentrated, thereby ensuring that the foamed material can fully retain the photoluminescent properties. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 This is the SEM image of the thermoplastic polyurethane foam material in Example 1.
[0028] Figure 2 This is the SEM image of the thermoplastic polyurethane foam material in Example 2.
[0029] Figure 3 This is the SEM image of the thermoplastic polyurethane foam material in Example 3.
[0030] Figure 4 This is the SEM image of the thermoplastic polyurethane foam material in Example 4.
[0031] Figure 5 This is the SEM image of the thermoplastic polyurethane foam material in Example 5.
[0032] Figure 6 This is the SEM image of the thermoplastic polyurethane foam material in Example 6.
[0033] Figure 7This is the SEM image of the thermoplastic polyurethane foam material in Example 7.
[0034] Figure 8 This is the SEM image of the thermoplastic polyurethane foam material in Example 8.
[0035] Figure 9 This is the SEM image of the thermoplastic polyurethane foam material in Example 9.
[0036] Figure 10 This is the SEM image of the thermoplastic polyurethane foam material in Example 10.
[0037] Figure 11 This is the SEM image of the thermoplastic polyurethane foam material in Example 11.
[0038] Figure 12 These are luminous effect diagrams of the thermoplastic polyurethane foam material in Example 1 when excited by an ultraviolet lamp with a wavelength of 254 nm and when the ultraviolet lamp is turned off.
[0039] Figure 13 These are luminous effect diagrams of the thermoplastic polyurethane foam material in Example 3 when excited by an ultraviolet lamp with a wavelength of 254 nm and when the ultraviolet lamp is turned off.
[0040] Figure 14 These are luminous effect diagrams of the thermoplastic polyurethane foam material in Example 5 when excited by an ultraviolet lamp with a wavelength of 254 nm and when the ultraviolet lamp is turned off.
[0041] Figure 15 These are luminous effect diagrams of the thermoplastic polyurethane foam material in Example 7 when excited by an ultraviolet lamp with a wavelength of 254 nm and when the ultraviolet lamp is turned off.
[0042] Figure 16 These are luminous effect diagrams of the thermoplastic polyurethane foam material in Example 10 when excited by an ultraviolet lamp with a wavelength of 254 nm and when the ultraviolet lamp is turned off. DETAILED DESCRIPTION
[0043] The present invention will be further explained and illustrated below with reference to specific embodiments.
[0044] Example 1:
[0045] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0046] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and phenyl phenyl carbamate (PAPE) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to PAPE of 1:0.005. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that PAPE was concentrated in the hard segment phase of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 3.5 MPa and the temperature was set to 90°C for 5 minutes. The mixture was then rapidly depressurized for foaming to obtain a thermoplastic polyurethane foam material.
[0047] The scanning electron microscope (SEM) image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 1 shown.
[0048] Depend on Figure 1 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 11 pieces / cm 3 The average diameter of the bubbles is 35 μm.
[0049] Example 2:
[0050] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0051] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and phenyl phenyl carbamate (PAPE) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to PAPE of 1:0.01. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that PAPE was concentrated in the hard segment phase of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 3.5 MPa and the temperature was set to 90°C for 5 minutes. The mixture was then rapidly depressurized for foaming to obtain a thermoplastic polyurethane foam material.
[0052] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 2 shown.
[0053] Depend on Figure 2 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 11 pieces / cm 3 The average diameter of the bubbles is 38 μm.
[0054] Example 3:
[0055] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0056] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and phenyl phenyl carbamate (PAPE) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to PAPE of 1:0.02. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that PAPE was concentrated in the hard segment phase of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4 MPa and the temperature was 100°C. The mixture was maintained for 5 minutes, and the pressure was then rapidly reduced for foaming to obtain a thermoplastic polyurethane foam material.
[0057] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 3 shown.
[0058] Depend on Figure 3 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 10 pieces / cm 3 The average diameter of the bubbles is 25 μm.
[0059] Example 4:
[0060] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0061] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and phenyl phenyl carbamate (PAPE) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to PAPE of 1:0.01. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that PAPE was concentrated in the hard segment phase of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4 MPa and the temperature was 120°C. The mixture was maintained for 5 minutes, and the pressure was then rapidly reduced for foaming to obtain a thermoplastic polyurethane foam material.
[0062] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 4 shown.
[0063] Depend on Figure 4 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 9 pieces / cm 3 The average diameter of the bubbles is 50 μm.
[0064] Example 5:
[0065] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0066] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and (2-chloro-4-hydroxyphenyl)phenyl carbamate (PCHPC) were added to a screw extruder for mixing. The mass ratio of thermoplastic polyurethane to PCHPC was 1:0.005. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that PCHPC was concentrated in the hard segment phase region of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 3.5 MPa and the temperature was set to 100°C. The mixture was maintained for 5 minutes, and the pressure was then rapidly reduced for foaming to obtain a thermoplastic polyurethane foam material.
[0067] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 5 shown.
[0068] Depend on Figure 5 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 9 pieces / cm 3 The average diameter of the bubbles is 55 μm.
[0069] Example 6:
[0070] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0071] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and methyl phenyl carbamate (MAPE) were added to a screw extruder for mixing. The mass ratio of thermoplastic polyurethane to MAPE was 1:0.01. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that MAPE was concentrated in the hard segment phase region of the polyurethane. The material was then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4 MPa and the temperature was 110°C. The mixture was maintained for 5 minutes, and the pressure was then rapidly reduced for foaming to obtain a thermoplastic polyurethane foam material.
[0072] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 6 shown.
[0073] Depend on Figure 6 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 11 pieces / cm 3 The average diameter of the bubbles is 20 μm.
[0074] Example 7:
[0075] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0076] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and phenyl dimethylcarbamate (DMAPE) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to DMAPE of 1:0.015. The processing temperature of the screw extruder was 200°C until scanning electron microscopy confirmed that DMAPE was concentrated in the hard segment phase of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4.5 MPa and the temperature was set to 100°C for 5 minutes. The mixture was then rapidly depressurized for foaming to obtain a thermoplastic polyurethane foam material.
[0077] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 7 shown.
[0078] Depend on Figure 7 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 11 pieces / cm 3 The average diameter of the bubbles is 25 μm.
[0079] Example 8:
[0080] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0081] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and methyl ethyl phenyl carbamate (MEAPE) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to MEAPE of 1:0.01. The processing temperature of the screw extruder was 200°C until scanning electron microscopy confirmed that MEAPE was concentrated in the hard segment phase of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4 MPa and the temperature was 110°C. The mixture was maintained for 5 minutes, and the pressure was then rapidly reduced for foaming to obtain a thermoplastic polyurethane foam material.
[0082] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 8 shown.
[0083] Depend on Figure 8 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 9 pieces / cm 3 The average diameter of the bubbles is 40 μm.
[0084] Example 9:
[0085] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0086] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and methyl ethyl phenyl carbamate (MEAPE) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to MEAPE of 1:0.015. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that MEAPE was concentrated in the hard segment phase region of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4 MPa and the temperature was set to 100°C for 5 minutes. The mixture was then rapidly depressurized for foaming to obtain a thermoplastic polyurethane foam material.
[0087] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 9 shown.
[0088] Depend on Figure 9 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 10 pieces / cm 3 The average diameter of the bubbles is 20 μm.
[0089] Example 10:
[0090] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0091] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and methyl N-phenylcarbamate (MHPC) were added to a screw extruder for mixing at a mass ratio of thermoplastic polyurethane to MHPC of 1:0.02. The processing temperature of the screw extruder was 200°C until it was confirmed by scanning electron microscopy that MHPC was concentrated in the hard segment phase region of the polyurethane. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4 MPa and the temperature was 110°C. The mixture was maintained for 5 minutes, and the pressure was then rapidly reduced for foaming to obtain a thermoplastic polyurethane foam material.
[0092] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 10 shown.
[0093] Depend on Figure 10 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 10 pieces / cm 3 The average diameter of the bubbles is 28 μm.
[0094] Example 11:
[0095] A thermoplastic polyurethane foam material, the preparation method of which is as follows:
[0096] Thermoplastic polyurethane (BASF's Cellasto MH24-60) and methoxycarbonylaminonaphthalene (MCAN) were added to a screw extruder for mixing. The mass ratio of thermoplastic polyurethane to MCAN was 1:0.015. The processing temperature of the screw extruder was 200°C until MCAN was confirmed to be concentrated in the hard segment phase of the polyurethane through scanning electron microscopy observation. The materials were then transferred to a supercritical carbon dioxide foaming equipment, and the pressure was set to 4.5 MPa and the temperature was set to 100°C. The mixture was maintained for 5 minutes, and the pressure was then rapidly reduced for foaming to obtain a thermoplastic polyurethane foam material.
[0097] The SEM image of the thermoplastic polyurethane foam material in this embodiment is as follows: Figure 11 shown.
[0098] Depend on Figure 11 It can be seen that the thermoplastic polyurethane foam material has a uniform cell structure and the cell density is 10 10 pieces / cm 3 The average diameter of the bubbles is 30 μm.
[0099] Photoperiod luminescence performance test:
[0100] The luminous effects of the thermoplastic polyurethane foam materials in Examples 1, 3, 5, 7 and 10 when excited by a UV lamp with a wavelength of 254 nm (UV on; excitation time is 10 s) and after the UV lamp is turned off (UV off) are shown in the figure. Figures 12-16 shown.
[0101] Depend on Figure 12 It can be seen that the thermoplastic polyurethane foam material in Example 1 can continue to emit green afterglow after the ultraviolet lamp is turned off, the duration is about 3 seconds, and the emission wavelength is 495 nm.
[0102] Depend on Figure 13 It can be seen that the thermoplastic polyurethane foam material in Example 3 can continue to emit green afterglow after the ultraviolet lamp is turned off, the duration is about 3 seconds, and the emission wavelength is 495 nm.
[0103] Depend on Figure 14 It can be seen that the thermoplastic polyurethane foam material in Example 5 can continue to emit green afterglow after the ultraviolet lamp is turned off, the duration is about 3 seconds, and the emission wavelength is 503 nm.
[0104] Depend on Figure 15 It can be seen that the thermoplastic polyurethane foam material in Example 7 can continue to emit green afterglow after the ultraviolet lamp is turned off, the duration is about 3 seconds, and the emission wavelength is 491 nm.
[0105] Depend on Figure 16It can be seen that the thermoplastic polyurethane foam material in Example 10 can continue to emit green afterglow after the ultraviolet lamp is turned off, the duration is about 3 seconds, and the emission wavelength is 498 nm.
[0106] In addition, through the same test, it was found that the thermoplastic polyurethane foam materials in Examples 2, 4, 6, 8, 9 and 11 also have unique photo-afterglow luminescence properties.
[0107] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.
Claims
1. A thermoplastic polyurethane foam material, characterized in that: The composition includes thermoplastic polyurethane and an organic photoluminescent material; the hard segment of the thermoplastic polyurethane and the organic photoluminescent material contain similar segment structures.
2. The thermoplastic polyurethane foam material according to claim 1, characterized in that: The organic photopersistence luminescent material is at least one of phenyl phenylcarbamate, (2-chloro-4-hydroxyphenyl) phenylcarbamate, methyl phenylcarbamate, dimethyl phenylcarbamate, methylethyl phenylcarbamate, methyl N-phenylcarbamate, and methoxycarbonylaminonaphthalene.
3. The thermoplastic polyurethane foam material according to claim 1 or 2, characterized in that: The mass ratio of the thermoplastic polyurethane to the organic photo-afterglow luminescent material is 1:0.001-0.
03.
4. The thermoplastic polyurethane foam material according to claim 1 or 2, characterized in that: The density of the cells in the thermoplastic polyurethane foam material is 10 9 pieces / cm 3 ~10 12 pieces / cm 3 The average diameter of the bubbles is 10μm to 70μm.
5. The thermoplastic polyurethane foam material according to claim 1 or 2, characterized in that: The thermoplastic polyurethane foam material has afterglow luminescence of 3s to 5s after being irradiated by ultraviolet rays.
6. The thermoplastic polyurethane foam material according to claim 5, characterized in that: The wavelength of the ultraviolet rays is 240nm to 365nm.
7. A method for preparing a thermoplastic polyurethane foam material according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: uniformly mixing thermoplastic polyurethane and organic photo-afterglow luminescent material, and then foaming and molding with supercritical carbon dioxide to obtain thermoplastic polyurethane foam material.
8. The preparation method according to claim 7, characterized in that: The supercritical carbon dioxide foaming molding has a molding pressure of 2MPa to 6MPa, a molding temperature of 80°C to 160°C, and a pressure holding time of 3min to 7min.
9. An anti-counterfeiting material, characterized in that: The thermoplastic polyurethane foam material comprises the thermoplastic polyurethane foam material according to any one of claims 1 to 6.
10. A shoe, characterized in that: The shoe sole comprises the thermoplastic polyurethane foam material according to any one of claims 1 to 6.