TPU material, preparation method and application thereof

Abstract

The application provides a TPU material and a preparation method and application thereof, and a preparation method of a TPU material, which comprises the following steps: S1, surface cleaning pretreatment of a polyurethane material; S2, surface activation of the polyurethane material after the pretreatment in S1 by using plasma to obtain the activated polyurethane material; S3, grafting reaction of the activated polyurethane material in S2 by immersing the activated polyurethane material in a polyvinylpyrrolidone aqueous solution, the concentration of the polyvinylpyrrolidone aqueous solution is 1wt.%-25wt.%, the temperature of the grafting reaction is 40-80 DEG C, and the grafted polyurethane material is obtained. The TPU material prepared by the application is a polyester thermoplastic polyurethane with certain toughness and thickness, and the surface thereof usually presents strong hydrophobic characteristics; by using the method of low-temperature plasma surface activation and induced grafting, the surface of the TPU material can be strongly modified to be hydrophilic, and the stability can be maintained for a long time.

Description

Technical Field

[0001] This invention relates to the field of materials surface engineering technology, and in particular to a highly stable and hydrophilic TPU material, its preparation process, and its applications. Background Technology

[0002] With the development of science and technology and the improvement of people's living standards, the aging of the population is accelerating, and the number of patients with various intractable diseases is increasing day by day. The demand for health is increasing, which makes the application of biomedical materials in clinical medicine more and more widespread.

[0003] Due to advancements in biomedical engineering, materials science, and biotechnology, medical polymer materials and their products are gaining increasing acceptance in clinical medicine due to their unique biocompatibility and non-toxicity. Polyurethane, in particular, is involved in various aspects of the medical field, including medical catheters, wearable blood glucose monitoring devices, oxygen masks, artificial hearts, artificial blood vessels, drug delivery systems, blood pressure monitor cuffs, and topical wound dressings. However, polyurethane is a non-polar material with low surface energy, resulting in poor surface hydrophilicity, which significantly limits its application in the biomedical field. Currently, hydrophilic modification of polymer materials mainly involves two methods: bulk modification and surface modification. Bulk hydrophilic modification involves complex chemical incorporations, making it difficult to guarantee biocompatibility. Surface hydrophilic modification involves introducing polar functional groups onto the surface of a hydrophobic matrix to improve its hydrophilicity, which is also a very effective method. However, further research has revealed that some surface-modified polyurethane materials gradually lose their hydrophilicity after a period of time, becoming hydrophobic, exhibiting a significant time-dependent effect.

[0004] Significant progress has been made in the research of hydrophilization of some polymers both domestically and internationally. For example, Aleksandra... In "Polyvinylpyrrolidone (PVP) hydrogel coating for cylindrical polyurethane scaffolds," a method for preparing cylindrical polyurethane scaffolds using a polyvinylpyrrolidone hydrogel coating was described. This polyurethane exhibits improved surface wettability and good biocompatibility. However, the hydrogel coating has a certain thickness and mass, and the dried hydrogel coating has low resistance to mechanical damage, leading to surface cracking and the risk of coating peeling off.

[0005] Surface grafting involves activating the surface of a polymer material to form active sites with initiation functions, then mixing it with a polymer containing functional groups, and grafting the functional groups onto the surface using a catalyst (or without a catalyst). P. Alves et al., in their paper "Surface modification of polyurethane films by plasma and ultraviolet light to improve haemocompatibility for artificial heart valves," proposed a method of hydrophilic modification of polyurethane films using plasma and ultraviolet radiation combined with HEMA grafting. However, this method only recorded results up to 30 days, after which the lowest contact angle was around 60°. For example, the patent application number (201810658973.2) for "A method for surface hydrophilic modification of polyurethane" proposed two plasma treatments of polyurethane, which reduced the contact angle from 92° to 27°, and after one week, the contact angle became 36°, but no further tracking of stability was conducted. For example, the patent application number (201710154493.8) entitled "A Method for Hydrophilic Modification of Polyurethane Based on Polystyrene Diazonium Salt" proposes directly immersing a polyurethane carrier in a solution of polystyrene diazonium salt for a certain period of time, reducing the contact angle from 92° to 45-55°. Although the contact angle is reduced, the hydrophilicity is not strong, and the hydrophilic stability is not described. Furthermore, the biosafety of polystyrene diazonium salt needs further investigation. The above methods and techniques only improve hydrophilicity to a certain extent, and the modified materials still have certain "hydrophobic recovery" and biocompatibility issues, which still fall short of their practical clinical applications. To enable modified hydrophilic polyurethane materials to be used in the biomedical field, the grafting reagents should ideally be non-toxic, harmless, safe, and healthy. Therefore, there is an urgent need in the biomedical field to develop a hydrophilic polyurethane with good stability and strong biosafety. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a TPU material and its preparation method in view of the shortcomings of the prior art. The TPU material prepared by the present invention has excellent biocompatibility and strong surface hydrophilicity.

[0007] This invention also provides an application of TPU material in medical polymer materials and their products.

[0008] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0009] A TPU material, wherein the surface water contact angle of the TPU material is less than or equal to 21°, and after being placed in a normal temperature and pressure environment for 60 days, the surface water contact angle of the TPU material is still less than 42°; preferably, the surface water contact angle of the TPU material is less than or equal to 10°, and after being placed in a normal temperature and pressure environment for 60 days, the surface water contact angle of the TPU material is still less than 20°.

[0010] Ideally, the surface water contact angle of the TPU material is less than or equal to 9°, and after being placed under normal temperature and pressure for 60 days, the surface water contact angle of the TPU material is still less than 20°.

[0011] The TPU material of this invention has good biocompatibility, strong cell adhesion, and strong surface hydrophilicity.

[0012] The surface water contact angle refers to the angle between the solid-liquid interface, through the liquid interior, and the gas-solid-liquid interface at the solid-liquid junction. It is usually denoted by θ (see...). Figure 4 ).

[0013] TPU stands for Thermoplastic Urethane, and its Chinese name is thermoplastic polyurethane elastomer.

[0014] In a preferred embodiment of the present invention, the surface carbon content of the TPU material is 70-80%, the surface oxygen content is 15-25%, and the surface nitrogen content is 4-5%. Preferably, the surface carbon content of the TPU material is 75-80%, the surface oxygen content is 15-20%, and the surface nitrogen content is 4.8-5%.

[0015] The surface carbon content of the hydrophilically modified sample decreased, while the oxygen and nitrogen content increased. It also exhibited excellent biocompatibility and enhanced cell adhesion ability.

[0016] This invention also discloses a method for preparing TPU material, characterized by comprising the following steps:

[0017] S1. The surface of the polyurethane material is cleaned and pretreated to obtain the pretreated polyurethane material.

[0018] S2. The surface of the pretreated polyurethane material in S1 is activated by plasma to obtain the activated polyurethane material.

[0019] S3. The activated polyurethane material in S2 is immersed in a polyvinylpyrrolidone aqueous solution for grafting reaction. The heating temperature of the grafting reaction is 40-80℃ to obtain the grafted polyurethane material.

[0020] S4. Clean and dry the grafted polyurethane material from S3.

[0021] This invention uses plasma to activate the polyurethane material, and then grafts polyvinylpyrrolidone onto the surface of the activated polyurethane material at 40-80°C, so that the surface of the obtained TPU material becomes a hydrophilic polyurethane with strong stability and long hydrophilic duration, which is beneficial to cell adhesion.

[0022] The grafting reaction temperature of the present invention is 40–80°C. Preferably, the grafting reaction temperature of the present invention is 50–70°C. Within this temperature range, the grafting speed of polyvinylpyrrolidone is fast and the grafting stability is strong. Below this temperature range, the grafting time of polyvinylpyrrolidone is longer, and the hydrophilic aging time of the obtained TPU material is shorter.

[0023] Above this temperature range, the TPU film will soften under prolonged high temperatures, and the resulting TPU film will not meet the required performance.

[0024] In a preferred embodiment of the present invention, the mass concentration of polyvinylpyrrolidone in S3 is 1% to 25%, and preferably, the mass concentration of polyvinylpyrrolidone in S3 is 10% to 20%.

[0025] Within this mass concentration range, the contact angle between the polyurethane surface and water is significantly reduced, resulting in good hydrophilicity and a longer aging period.

[0026] In a preferred embodiment of the invention, the grafting reaction in S3 is heated in a water bath.

[0027] In a preferred embodiment of the present invention, the grafting reaction time in S3 is 0.1 to 1 hour.

[0028] Grafting time is less than 0.1 hours, resulting in a low grafting rate. The grafted PVP membrane shows significant aging at high temperatures, with the contact angle increasing rapidly.

[0029] In a preferred embodiment of the present invention, the plasma gas in S2 is one or both of nitrogen and argon, and the total gas flow rate is 10-70 sccm; preferably, the plasma gas in S2 is a mixture of nitrogen and argon with a volume ratio of 1:1-3, and the total gas flow rate is 50-70 sccm.

[0030] The mixed gas plasma exhibits better activation effects, generating more polar groups and grafting sites. The system pressure is 40–60 Pa, and the total power is 80–120 W.

[0031] In a preferred embodiment of the present invention, the plasma pressure in S2 is 20-80 Pa, the plasma activation time is 0.5-10 min, and the power of the plasma processing device is 100-400 W; preferably, the plasma pressure in S2 is 40-80 Pa, the plasma activation time is 2-10 min, and the power of the plasma processing device is 250-400 W.

[0032] Above this power range, surface etching intensifies, roughness increases, and hydrophilicity decreases. Below this power range, the number of activated grafting sites is small, resulting in poor grafting performance.

[0033] In a preferred embodiment of the present invention, in step S1, the polyurethane material is immersed in a solvent and deionized water for ultrasonic cleaning, and then dried for later use. Ethanol is preferred as the solvent.

[0034] In a preferred embodiment of the present invention, the total cleaning time in S1 is 2 to 10 minutes.

[0035] In a preferred embodiment of the present invention, the solvent in S1 is one or more of methanol, ethanol, and acetone.

[0036] The present invention also discloses the application of the TPU material in medical polymer materials and their products.

[0037] The grafting reagent of this invention uses PVP (polyvinylpyrrolidone) reagent that is already used in clinical medicine, thereby solving the problem of the current clinical application of some medical TPU materials requiring a hydrophilic, stable and safe surface. Its surface modification method briefly includes: (1) surface cleaning and drying; (2) surface low-temperature radio frequency plasma-induced activation; (3) grafting with polyvinylpyrrolidone solution; (4) surface residual liquid cleaning and drying. In addition, radio frequency in low-temperature radio frequency plasma refers to radio frequency, but it does not belong to the band division in radio communication, because the radiation performance is very low in such a frequency range, so it is rarely used in communication equipment. Its effect on biological organisms is mainly thermal. When the radio frequency current frequency is high enough (>100kHz), it causes the movement of charged ions in the tissue, i.e., frictional heat generation (60~100℃). The commonly used frequency of plasma radio frequency equipment is 200~500kHz, and the output power is 100~400W. Low temperature refers to the operating temperature being room temperature.

[0038] The purpose of this invention is to transform hydrophobic polyurethane into a highly stable hydrophilic polyurethane through surface modification. Medical devices using surface-hydrophilic polyurethane materials achieve high surface lubricity in clinical applications, reducing damage to the interface between organs and devices, and alleviating patient suffering. Furthermore, this hydrophilic polyurethane exhibits excellent biocompatibility, thus the hydrophilic polyurethane of this invention also has significant potential applications in medical implant materials.

[0039] The polyurethane material obtained by this invention is a thermoplastic polyurethane with certain toughness and thickness. The original contact angle is greater than 100°. After the surface is treated with low-temperature plasma-induced grafting, the optimal contact angle can be less than 10°. After being placed in a normal temperature and pressure environment for 60 days, the contact angle is still less than 20°. The carbon content on the surface of the sample after hydrophilic modification decreases, while the oxygen and nitrogen content increases. It also has excellent biocompatibility and enhanced cell adhesion ability.

[0040] The specific surface modification technology for obtaining superhydrophilic polyurethane materials is as follows:

[0041] (1) Surface cleaning and pretreatment of polyurethane materials. The polyurethane materials were immersed in ethanol and deionized water for ultrasonic cleaning for 5 minutes respectively, and then dried by blowing air for later use.

[0042] (2) Low-temperature plasma is used to activate the polyurethane surface. The system pressure in the plasma treatment device is 20-80 Pa, the plasma activation time is 0.5-10 min, the power of the plasma treatment device is 100-400 W, the gas flow rate is 10-40 sccm, and the gas types are nitrogen and argon and their mixture.

[0043] (3) The surface-plasma-activated polyurethane material is immersed in a polyvinylpyrrolidone aqueous solution for grafting treatment. The concentration of polyvinylpyrrolidone is 1 wt.% to 25 wt.%, the water bath temperature is 40 to 80℃, and the water bath time is 0.1 to 1 h.

[0044] (4) The grafted polyurethane material is cleaned with a large amount of deionized water, dried in a forced-air drying oven, and stored in an exposed atmospheric environment.

[0045] The above-described solution of the present invention has the following beneficial effects:

[0046] (1) Compared with the original unmodified polyurethane material, the hydrophilic polyurethane material of the present invention has a significantly reduced contact angle between the polyurethane surface and water, good hydrophilicity and long aging time.

[0047] (2) Compared with the original unmodified polyurethane material, the hydrophilic polyurethane material of the present invention is more conducive to cell adhesion than the hydrophobic polyurethane material.

[0048] (3) Compared with other methods or other grafting reagents, the hydrophilic polyurethane of the present invention introduces polyvinylpyrrolidone, which has been used in medical clinical practice. Therefore, the modified polyurethane material has strong biocompatibility and no cytotoxicity. Attached Figure Description

[0049] Figure 1a represents the surface contact angle between the unmodified sample and deionized water.

[0050] Figure 1 b represents the surface contact angle between sample 1 prepared in Example 1 and deionized water.

[0051] Figure 1 c represents the contact angle between sample 3 prepared in Example 3 and the surface of deionized water.

[0052] Figure 1 d represents the surface contact angle between sample 4 prepared in Example 4 and deionized water.

[0053] Figure 1 e represents the surface contact angle between sample 5 prepared in Example 5 and deionized water.

[0054] Figure 1 f is the surface contact angle between sample 6 prepared in Example 6 and deionized water.

[0055] Figure 2 a represents the XPS plots of the unmodified sample, sample 3, and sample 5.

[0056] Figure 2 b is a graph showing the change of contact angle between samples 5 and 6 over time.

[0057] Figure 3 a represents the cell metabolic intensity diagram of sample 5 prepared in Example 5 and the unmodified sample.

[0058] Figure 3 b is an electron micrograph of cells on the surface of the unmodified sample.

[0059] Figure 3 c is an electron micrograph of cells on the surface of sample 5 prepared in Example 5.

[0060] Figure 4 A schematic diagram of the surface water contact angle. Detailed Implementation

[0061] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.

[0062] Comparative Example 1

[0063] The polyurethane was ultrasonically cleaned with large amounts of anhydrous ethanol and deionized water for 5 minutes. After absorbing the residual liquid with lint-free paper, it was placed in a forced-air drying oven and dried for later use.

[0064] The polyurethane thickness is 0.3 mm. High-purity N2 is used as the working gas. The vacuum chamber is evacuated to a background vacuum. The ion source gas switch is turned on, and high-purity N2 is introduced. The gas flow rate is 10 sccm, and the system gas pressure is 50 Pa. The radio frequency voltage and current power supplies are turned on in sequence. The total power is 100 W. The polyurethane surface is activated by ion beam at room temperature (15-25℃) for 2 min. Then the ion source is turned off.

[0065] After completing the plasma activation process on the polyurethane surface, the gas filling valve was immediately opened to introduce the atmosphere and obtain sample 1.

[0066] Contact angle tests were performed on the surface of sample 1 (using deionized water as the reagent), with five points tested each time (the same method applies to other examples). The average contact angle was 51.5°, which is significantly lower than the 109.2° contact angle of the unmodified sample. Figure 1 a and Figure 1 b represents the contact angle measurement results for the unmodified sample and sample 1, respectively.

[0067] Comparative Example 2

[0068] The pre-cleaning process and parameters were exactly the same as those in Comparative Example 1. High-purity N2 was used as the working gas. The vacuum chamber was evacuated to a background vacuum. The ion source gas switch was turned on, the Ar gas flow rate was 20 sccm, the system gas pressure was 70 Pa, and the radio frequency voltage and current power supplies were turned on in sequence. The total power was 300 W. The polyurethane surface was activated by ion beam at room temperature (15-25℃) for 5 min. Then the ion source was turned off.

[0069] After completing the plasma activation process on the polyurethane surface, the gas filling valve was immediately opened to introduce the atmosphere, and sample 2 was obtained.

[0070] A contact angle test was performed on the surface of sample 2 (using deionized water as the reagent), and the measured contact angle was 47.6°.

[0071] Comparative Example 3

[0072] The pre-cleaning process and parameters were exactly the same as those in Comparative Example 1. High-purity Ar and N2 were used as working gases. The vacuum chamber was evacuated to a background vacuum. The ion source gas switch was turned on, and the flow rates of Ar and N2 were 20 sccm and 40 sccm, respectively. The vacuum chamber pressure was 50 Pa. The RF voltage and current power supplies were turned on in sequence, with a total power of 300 W. The polyurethane surface was ion-beam etched and activated at room temperature (15-25℃) for 3 min. Then the ion source was turned off.

[0073] After completing the plasma activation process on the polyurethane surface, the gas filling valve was immediately opened to introduce the atmosphere, and sample 3 was obtained.

[0074] A contact angle test was performed on the surface of sample 3 (using deionized water as the reagent), and the measured contact angle was 39.6°. Figure 1 As shown in c.

[0075] Comparative Example 4

[0076] Using the same pre-cleaning and surface plasma process and parameters as Comparative Example 3, after completing the plasma activation process on the polyurethane surface, the gas valve was immediately opened to allow atmospheric air inflow. The sample was then removed, and the surface-plasma-activated polyurethane was immersed in a 3 wt.% aqueous solution of polyvinylpyrrolidone (K30) for 9 hours at room temperature (15–25°C) to carry out the grafting reaction. After the grafting reaction was completed, excess grafting solution was rinsed off with deionized water, and the sample was dried in a drying oven to obtain Sample 4.

[0077] A contact angle test was performed on the surface of sample 4 (using deionized water as the reagent), and the measured contact angle was 21.0°. The contact angle further decreased, as... Figure 1 As shown in d.

[0078] Example 1

[0079] Using the same pre-cleaning and surface plasma process and parameters as Comparative Example 3, after completing the plasma etching activation process on the polyurethane surface, the gas valve was immediately opened to allow atmospheric air in. The sample was then removed, and the surface-plasma-activated polyurethane was placed in a 3 wt.% polyvinylpyrrolidone aqueous solution and subjected to a 50°C water bath for 15 minutes for grafting. After the grafting reaction was completed, excess grafting solution was rinsed off with deionized water, and the sample was dried in a drying oven to obtain Sample 5.

[0080] A contact angle test was performed on the surface of sample 5 (using deionized water as the reagent), and the measured contact angle was 16.7°. Figure 1 As shown in e. Compared with Example 4, this process exhibits superior grafting performance and more stable hydrophilicity. After being placed in an atmospheric environment for 60 days, the contact angle remains at 34.0°, as... Figure 2 As shown in b, the C content on the surface decreases after modification, while the contents of O and N increase. The surface functional groups change after modification, leading to a change in surface hydrophilicity. Figure 2 The XPS results for sample a and the data in Table 1 are shown. The cellular metabolic intensity on the sample surface was tested. The results showed that on the first day, sample 5 was not significantly different from the unmodified sample, but on the third day, sample 5 showed a certain degree of improvement compared to the unmodified sample (e.g., ...). Figure 3 a) This indicates that sample 5 grafted with PVP did not cause cytotoxicity or inhibit cell proliferation; on the contrary, it had a certain promoting effect. Furthermore, the cells on the surface of sample 5 showed better integration with the substrate and stronger adhesion. Figure 3 As shown in b and 3c.

[0081] Table 1. Surface elemental analysis results of the samples before and after modification.

[0082]

[0083] Example 2

[0084] Using the same pre-cleaning and surface plasma process and parameters as Comparative Example 3, after completing the plasma activation process on the polyurethane surface, the gas valve was immediately opened to allow atmospheric air inflow. The sample was then removed, and the surface-plasma-activated modified polyurethane was placed in a 17 wt.% polyvinylpyrrolidone aqueous solution and grafted at 60°C for 15 min. After the grafting reaction, excess grafting solution was rinsed off with deionized water, and the sample was dried in a drying oven to obtain Sample 6.

[0085] A contact angle test was performed on the surface of sample 6 (using deionized water as the reagent), and the measured contact angle was 9.2°. Figure 1 As shown in f, it can be clearly seen that the contact angle of the polyurethane after the above process modification further decreases, and it maintains a strongly hydrophilic state for a considerable period of time, after 60 days ( Figure 2 b) The contact angle is 12.8°.

[0086] Example 3

[0087] Using the same pre-cleaning and surface plasma process and parameters as Comparative Example 3, after completing the plasma activation process on the polyurethane surface, the gas valve was immediately opened to allow atmospheric air in, and the sample was removed. The polyurethane, after surface plasma activation modification, was placed in a 6 wt.% polyvinylpyrrolidone aqueous solution and grafted at 80°C in a water bath for 20 minutes. After the grafting reaction, excess grafting solution was rinsed with deionized water, and the sample was dried in a drying oven to obtain Sample 7. The contact angle of Sample 7 was measured to be 20.1° using deionized water as the reagent.

[0088] Table 2 shows the process parameters and contact angles of the samples obtained for Comparative Examples 1-4 and Examples 1-3.

[0089]

[0090] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles described herein. For example, any modifications to the shape of the thermoplastic polyurethane matrix material (sheet, tubular, granular, etc.), the plasma generation method, the plasma discharge equipment and its mechanical structure, various derivatives of the grafting reagent, and various solvents for the grafting reagent should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a TPU material, characterized in that... Includes the following steps: S1. The surface of the polyurethane material is cleaned and pretreated to obtain the pretreated polyurethane material. S2. The surface of the pretreated polyurethane material in S1 is activated by plasma to obtain the activated polyurethane material. S3. The activated polyurethane material in S2 is immersed in a polyvinylpyrrolidone aqueous solution for grafting reaction. The heating temperature of the grafting reaction is 40~80 ℃ to obtain the grafted polyurethane material. S4. Clean and dry the grafted polyurethane material from S3; The plasma gas in S2 is a mixture of nitrogen and argon with a volume ratio of 1:1~3, and the total gas flow rate is 50~70 sccm; The mass concentration of polyvinylpyrrolidone in S3 is 10%~20%; The plasma pressure in S2 is 20~80 Pa; The grafting reaction time in S3 is 0.1~1 h.

2. The method for preparing TPU material according to claim 1, characterized in that, The grafting reaction in S3 is performed by heating in a water bath.

3. The method for preparing TPU material according to any one of claims 1 to 2, characterized in that, The plasma activation time is 0.5~10 min, and the power of the plasma treatment device is 100~400 W.

4. The method for preparing TPU material according to claim 1, characterized in that, The plasma pressure in S2 is 40~80 Pa, the plasma activation time is 2~10 min, and the power of the plasma treatment device is 250~400 W.

5. The method for preparing TPU material according to any one of claims 1-2, characterized in that, In S1, the polyurethane material is immersed in solvent and deionized water for ultrasonic cleaning, and then dried for later use.

6. A TPU material prepared by the preparation method according to any one of claims 1 to 5, characterized in that, The surface water contact angle of the TPU material is less than or equal to 21°, and after being placed under normal temperature and pressure for 60 days, the surface water contact angle of the TPU material is still less than 42°.

7. The TPU material according to claim 6, characterized in that, The surface water contact angle of the TPU material is less than or equal to 10°, and after being placed under normal temperature and pressure for 60 days, the surface water contact angle of the TPU material is still less than 20°.

8. The TPU material according to claim 7, characterized in that, The TPU material has a surface carbon content of 70-80%, a surface oxygen content of 15-25%, and a surface nitrogen content of 4-5%.

9. The TPU material according to claim 6, characterized in that, The TPU material has a surface carbon content of 75-80%, a surface oxygen content of 15-20%, and a surface nitrogen content of 4.8-5%.

10. The application of the TPU material according to claim 6 or 7 in the preparation of medical polymer materials and their products.

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