A kind of TPU fabric

Abstract

The present invention provides a TPU fabric. The TPU fabric includes a base fabric layer, an adhesive layer, and a TPU layer that are sequentially stacked; the raw materials for preparing the TPU layer include a non-flame-retardant polyol, a flame-retardant polyol, a diisocyanate, a fluorine-containing chain extender, and a flame retardant. The TPU fabric provided in the present invention has good flame retardancy, good hydrophobicity, and good mechanical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane materials, and in particular relates to a TPU cloth material. Background Art

[0002] As an emerging polymer material with broad development prospects, polyurethane has excellent comprehensive performance and wide applications, and is known as the "fifth plastic". As a member of the polyurethane family, polyurethane elastomers can be divided into the following according to different product processing methods: thermoplastic polyurethane elastomers (TPU for short), because their synthetic raw materials are all difunctional, there is basically no chemical cross-linking between their molecular chains, so their processing performance, mechanical properties and low-temperature performance are all very outstanding; cast polyurethane elastomers (CPU for short), unlike thermoplastic polyurethane, have cross-linked molecular chains, large molecular weight, and cannot be processed repeatedly. It is one of the most widely used and largest-yield members in the polyurethane elastomer family, and is also known as "liquid rubber"; polyurethane compound rubber (MPU for short), its raw rubber raw material is polyurethane elastomer, and it is processed and formed through processes such as internal mixing, open mixing, and molding. As a new type of polymer material with better performance than rubber, polyurethane compound rubber has very broad application prospects.

[0003] Polyurethane elastomer is a high molecular block polymer with a large number of carbamate groups on the main chain. It has a unique structure of soft and hard segment block copolymers. The synthesis method of polyurethane elastomer is flexible and should be selected as needed. Its synthesis method is mainly divided into a relatively simple one-step method and a relatively complex two-step method. The relatively complex two-step method can be divided into a relatively simple prepolymer method and a relatively complex semi-prepolymer method. The one-step method is relatively simple, that is, all raw materials are put into the reaction container at one time, and the mixture is uniformly mixed by manual or mechanical stirring and then solidified to form the synthesis of thermoplastic polyurethane elastomer materials. The one-step method takes a short time to produce, has a high output, and can save a lot of time and cost, but its reaction process is difficult to control, and the molecular structure of the prepared polyurethane elastomer is irregular, and the hard segment and soft segment are unevenly distributed; the two-step method refers to a large prepolymer that first reacts the polyol with the curing agent, and then the prepolymer reacts with the chain extender again to finally obtain the polyurethane elastomer. The molecular structure of the elastomer prepared by the two-step method is relatively regular, and the hard segment and soft segment are evenly distributed, but the process is relatively complex and time-consuming.

[0004] Polyurethane elastomers have excellent comprehensive mechanical properties, especially wear resistance, so polyurethane elastomers have broad application and development prospects. Due to their excellent performance, polyurethane elastomer materials have been widely used in transportation, agricultural production, construction materials, medical equipment and other fields. However, due to the poor flame retardancy and water resistance of polyurethane elastomers, how to improve the flame retardancy and water resistance of polyurethane materials has become a hot topic in current research.

[0005] CN112226068A discloses a superhydrophobic and wear-resistant TPU film and a preparation method thereof. The raw materials for preparing the superhydrophobic and wear-resistant TPU film include the following raw materials in parts by mass: 6-10 parts of superhydrophobic nano-silica, 0.1-0.2 parts of flame retardant, 0.4-0.6 parts of cross-linking agent, 0.5-1.6 parts of antioxidant, 70-82 parts of thermoplastic polyurethane TPU particles, and 12-18 parts of polyether polyol. The preparation method includes the following steps: (1) preparation of polydopamine-nano-silica; (2) preparation of superhydrophobic nano-silica; (3) melt blending of superhydrophobic TPU. This technical solution uses dopamine to self-polymerize into a film, uses nano-silica as a matrix, and introduces hydrophobic organic substances to prepare a TPU material with superhydrophobic properties. However, its preparation method is relatively cumbersome, the preparation process of superhydrophobic nano-silica is relatively complex, and the flame retardancy of the prepared TPU film is poor.

[0006] CN112724656A discloses a halogen-free flame-retardant TPU cable material, a preparation method thereof, and an application. The raw materials for preparing the halogen-free flame-retardant TPU cable material include the following components in parts by weight: 54-79 parts of thermoplastic polyurethane elastomer, 7-11 parts of A flame retardant, 7-18 parts of B flame retardant, 5-10 parts of compatibilizer, and 1-5 parts of smoke suppressant; the A flame retardant is a phosphorus-based flame retardant, and the B flame retardant is a modified phosphorus-nitrogen composite flame retardant. Although the TPU material provided by this technical solution has good flame retardancy, its water resistance is poor.

[0007] In the prior art, usually, the flame retardancy and water resistance of polyurethane materials are improved by using flame retardants or hydrophobic additives. However, too much use of additives will affect the mechanical properties of polyurethane materials and may cause migration, resulting in poor performance; while too little addition cannot achieve good results. Therefore, how to provide a TPU fabric with good flame retardancy and water resistance with less or even no additional additives has become an urgent technical problem to be solved at present. Summary of the Invention

[0008] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a TPU fabric. In the present invention, through the design of the raw materials for preparing the TPU layer, and further by using flame-retardant polyols, fluorine-containing chain extenders, and flame retardants, the prepared TPU fabric has good flame retardancy, hydrophobicity, and good mechanical properties.

[0009] To achieve this purpose, the present invention adopts the following technical solutions:

[0010] The present invention provides a TPU fabric, which includes a base fabric layer, an adhesive layer, and a TPU layer stacked in sequence;

[0011] The raw materials for preparing the TPU layer include non-flame-retardant polyol, flame-retardant polyol, diisocyanate, fluorinated chain extender and flame retardant.

[0012] In the present invention, through the reaction of the flame-retardant polyol, the fluorinated chain extender with the non-flame-retardant polyol and the curing agent, flame-retardant substances and fluorine atoms are introduced into the molecular chain of the polyurethane elastomer. Without adding a large amount of additives or even without adding any additives, a TPU fabric material with good flame retardancy, good hydrophobicity and good mechanical properties can be prepared, avoiding the problem of the decline of the mechanical properties of the TPU layer caused by the use of excessive flame retardants and water repellents. At the same time, it avoids the problem of the decline of the flame retardancy and hydrophobicity of the TPU layer caused by the easy precipitation when using excessive flame retardants and water repellents.

[0013] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0014] As a preferred technical solution of the present invention, the raw materials for preparing the TPU layer include the following components in parts by weight:

[0015] 20-50 parts of non-flame-retardant polyol, 10-20 parts of flame-retardant polyol, 25-40 parts of diisocyanate, 15-20 parts of fluorinated chain extender and 1-3 parts of flame retardant.

[0016] In the present invention, by using the fluorinated chain extender, fluorine atoms are introduced into the molecular chain of the polyurethane elastomer to form a TPU layer with a lower free energy surface, so that the TPU fabric has good hydrophobicity. At the same time, in the present invention, through the synergistic effect of the fluorinated chain extender, the flame-retardant polyol and the flame retardant, a TPU fabric with good flame retardant effect can be prepared with a small amount of flame retardant added, avoiding the problem of the decline of the mechanical properties of the TPU caused by too high an addition amount of the flame retardant, and achieving a good flame retardant effect.

[0017] In the present invention, by controlling the content of the flame-retardant polyol within a specific range, the prepared TPU fabric not only has good flame retardancy, but also has the advantages of low production cost and being suitable for industrial production. If the content of the flame-retardant polyol is too small, the flame retardancy of the prepared TPU fabric is poor; if the content of the flame-retardant polyol is too large, the production cost of the TPU fabric is too high, and the use of too much flame-retardant polyol will not further improve the flame retardancy of the TPU fabric, which is not conducive to industrial production.

[0018] In the present invention, the weight parts of the non-flame-retardant polyol can be 20 parts, 22 parts, 25 parts, 27 parts, 30 parts, 33 parts, 36 parts, 39 parts, 42 parts, 45 parts, 47 parts, 50 parts, etc.

[0019] The weight parts of the flame-retardant polyol can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.

[0020] The weight parts of the diisocyanate can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, etc.

[0021] The weight parts of the fluorinated chain extender can be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.

[0022] The weight parts of the flame retardant can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, etc.

[0023] As a preferred technical solution of the present invention, the non-flame-retardant polyol is selected from polyether polyol and / or polyester polyol.

[0024] Preferably, the number-average molecular weight of the polyether polyol is 1000 - 6000, for example, it can be 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, etc.

[0025] Preferably, the polyether polyol is selected from polytetrahydrofuran ether diol and / or polytetramethylene ether diol.

[0026] Preferably, the number-average molecular weight of the polyester polyol is 1000 - 4000, for example, it can be 1000, 1500, 2000, 2500, 3000, 3500, 4000, etc.

[0027] Preferably, the polyester polyol is selected from any one or a combination of at least two of polybutylene adipate diol, polyethylene adipate diol, polyhexylene adipate diol, or polycaprolactone diol.

[0028] As a preferred technical solution of the present invention, the flame-retardant polyol is selected from flame-retardant polyether polyol POP-290E and / or flame-retardant polyester polyol PF-2011.

[0029] As a preferred technical solution of the present invention, the diisocyanate is selected from any one or a combination of at least two of dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or cyclohexyl diisocyanate.

[0030] As a preferred technical solution of the present invention, the fluorinated chain extender is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

[0031] Preferably, the flame retardant is selected from phosphorus-based flame retardants and / or nitrogen-based flame retardants.

[0032] Preferably, if the flame-retardant polyol is only the flame-retardant polyether polyol POP-290E, the flame retardant is preferably a phosphorus-based flame retardant; if the flame-retardant polyol is only the polyester polyol PF-2011, the flame retardant is preferably a nitrogen-based flame retardant.

[0033] Preferably, the phosphorus-based flame retardant is selected from pentaerythritol-based phosphate flame retardants and / or low-polymerization phosphate flame retardants.

[0034] Preferably, the nitrogen-based flame retardant is selected from melamine and / or melamine phosphate.

[0035] As a preferred technical solution of the present invention, the raw materials for preparing the TPU layer further include 0.1 to 2 parts of an antioxidant, such as 0.1 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part or 2 parts, etc.

[0036] Preferably, the antioxidant is selected from any one or a combination of at least two of 2,6-di-tert-butyl-4-methylphenol, antioxidant lU1U, triphenyl phosphite, tris(isodecyl) phosphite, phenyl diisodecyl phosphite or dioctyl phosphite.

[0037] As a preferred technical solution of the present invention, the raw materials for preparing the TPU layer further include 0.1 to 0.5 part of a catalyst, such as 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part, etc.

[0038] Preferably, the catalyst is selected from any one or a combination of at least two of triethanolamine, N,N-dimethylpyridine, N,N-dimethylcyclohexylamine, triethylenediamine, dibutyltin dilaurate or stannous octoate.

[0039] As a preferred technical solution of the present invention, the thickness of the glue layer is 0.1 to 0.3 mm, such as 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm or 0.3 mm, etc.

[0040] It should be noted that there are no special limitations on the material of the glue layer in the present invention, and commonly used glues in the art are applicable, including but not limited to hot melt adhesives, polyurethane water-based adhesives, etc.

[0041] As a preferred technical solution of the present invention, the thickness of the TPU layer is 0.5 - 1 mm, for example, it can be 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1 mm, etc.

[0042] In the present invention, the preparation method of the TPU fabric includes the following steps:

[0043] (1) Coating glue on either side of the base fabric to form a base fabric layer and a glue layer that are adhered to each other;

[0044] (2) After vacuum dehydrating non-flammable polyol and flame-retardant polyol at 110 - 130 °C for 1.5 - 2.5 h, mixing them evenly with the remaining raw material components of the TPU layer, and extruding and granulating at 170 - 200 °C through a twin-screw extruder to obtain the mixture particles;

[0045] Placing the mixture particles in an extruder and extruding them from the die head of the extruder to form a TPU film, and placing the TPU film on the side of the glue layer away from the base fabric layer obtained in step (1), and calendering to form the TPU fabric;

[0046] Among them, the twin-screw extruder includes a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone and a seventh zone connected in sequence;

[0047] The working temperature of the first zone is 110 - 115 °C, the working temperature of the second zone is 140 - 160 °C, the working temperature of the third zone is 160 - 180 °C, the working temperature of the fourth zone is 165 - 185 °C, the working temperature of the fifth zone is 170 - 190 °C, the working temperature of the sixth zone is 170 - 190 °C, and the working temperature of the seventh zone is 155 - 175 °C;

[0048] The extruder includes: a first feeding zone with a temperature of 165 - 175 °C; a second mixing zone with a temperature of 175 - 185 °C; a third mixing zone with a temperature of 180 - 190 °C; a fourth high mixing zone with a temperature of 185 - 195 °C; a fifth calculation zone with a temperature of 190 - 200 °C; a sixth discharging zone with a temperature of 195 - 205 °C;

[0049] The temperature at the connection between the die head and the extruder is 195 - 210 °C;

[0050] When the die head works, it includes 15 temperature zones. Among them, the temperature of the first zone is 190 - 205 °C, the temperature of the second to twelfth zones is 185 - 200 °C, and the temperature of the thirteenth to fifteenth zones is 190 - 205 °C;

[0051] The pressure of the calendering is 30 - 50 kgf.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] In the present invention, through the design of the raw materials for preparing the TPU layer, further by using a flame - retardant polyol, a fluorine - containing chain extender, and a flame retardant, and controlling the content of the flame - retardant polyol within a specific range, without the need to additionally add a water - repellent agent and with a small amount of flame retardant used, the prepared TPU fabric has good flame retardancy, good hydrophobicity, and good mechanical properties. Its flame - retardant grade is V - 0, the oxygen index is 28.2 - 31, the water contact angle > 107°, specifically 107.3 - 110.3°, and the tensile strength is 53.1 - 54.2 MPa. Detailed implementation manners

[0054] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the said examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0055] The sources of some components in the examples and comparative examples are as follows:

[0056] Polytetrahydrofuran ether glycol: BASF, PTMG1000;

[0057] Polytetramethylene ether glycol: DuPont, USA, with a number - average molecular weight of 1000;

[0058] Polybutylene adipate glycol: Jining Huakai Resin Co., Ltd., with a number - average molecular weight of 2000;

[0059] Polyethylene adipate glycol: Yantai Huada Chemical Industry Co., Ltd., with a number - average molecular weight of 3500;

[0060] Polyhexylene adipate glycol: Yantai Synthetic Leather Factory, with a number - average molecular weight of 2000;

[0061] Polycaprolactone diol: Daicel Corporation, Japan, CAPA7201A;

[0062] Flame - retardant polyether polyol POP - 290E: Huzhou Innovation Polyurethane Technology Co., Ltd.;

[0063] Flame - retardant polyester polyol PF - 2011: Qingdao Ruinuo Chemical Co., Ltd.;

[0064] Pentaerythritol-based phosphate flame retardant: Great Lake, USA, CN-1197;

[0065] Low-polymer phosphate flame retardant: Supersta, Fyrol PN.

[0066] Example 1

[0067] This example provides a TPU fabric, which includes a base fabric layer, an adhesive layer, and a TPU layer stacked in sequence;

[0068] Among them, the base fabric layer is a nylon fabric with a thickness of 0.4 mm;

[0069] The adhesive layer is a polyurethane water-based adhesive with a thickness of 0.2 mm;

[0070] The raw materials for preparing the TPU layer include the following components in parts by weight:

[0071] 20 parts of polytetrahydrofuran ether glycol, 20 parts of polybutylene adipate glycol, 15 parts of flame-retardant polyether polyol POP-290E, 30 parts of hexamethylene diisocyanate, 18 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 parts of pentaerythritol-based phosphate flame retardant, 1 part of 2,6-di-tert-butyl-4-methylphenol, and 0.3 part of triethanolamine;

[0072] The thickness of the TPU layer is 0.8 mm.

[0073] The preparation method of the above TPU fabric includes the following steps:

[0074] (1) Coat the polyurethane water-based adhesive on either side of the nylon fabric to form a base fabric layer and an adhesive layer that fit together;

[0075] (2) After vacuum dehydrating polytetrahydrofuran ether glycol, polybutylene adipate glycol, and flame-retardant polyether polyol POP-290E at 120°C for 2 h, mix them evenly with the remaining raw material components of the TPU layer, and extrude and pelletize them at 180°C through a twin-screw extruder to obtain the mixture particles;

[0076] Place the mixture particles in an extruder, extrude them from the die head of the extruder to form a TPU film, and place the TPU film on the side of the adhesive layer obtained in step (1) away from the base fabric layer, and calender it to form the TPU fabric;

[0077] Among them, the twin-screw extruder includes a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone, and a seventh zone connected in sequence; the working temperature of the first zone is 110°C, the working temperature of the second zone is 14°C, the working temperature of the third zone is 170°C, the working temperature of the fourth zone is 180°C, the working temperature of the fifth zone is 185°C, the working temperature of the sixth zone is 190°C, and the working temperature of the seventh zone is 160°C;

[0078] The extruder includes: a first feeding zone with a temperature of 170°C; a second mixing zone with a temperature of 180°C; a third mixing zone with a temperature of 185°C; a fourth high-mixing zone with a temperature of 190°C; a fifth calculation zone with a temperature of 195°C; a sixth discharging zone with a temperature of 200°C;

[0079] The temperature at the connection between the die head and the extruder is 200°C;

[0080] When the die head is working, it includes 15 temperature zones. Among them, the temperature of the first zone is 190°C, the temperature of the second to twelfth zones is 195°C, and the temperature of the thirteenth to fifteenth zones is 200°C;

[0081] The pressure of the calendering forming is 35 kgf.

[0082] Example 2

[0083] This example provides a TPU fabric, which includes a base fabric layer, an adhesive layer, and a TPU layer stacked in sequence;

[0084] Among them, the base fabric layer is a nylon fabric with a thickness of 0.5 mm;

[0085] The adhesive layer is a polyurethane water-based adhesive with a thickness of 0.3 mm;

[0086] The preparation raw materials of the TPU layer include the following components in parts by weight:

[0087] Polytetramethylene ether glycol 25 parts, polyhexamethylene adipate glycol 25 parts, flame-retardant polyether polyol POP-290E 10 parts, cyclohexyl diisocyanate 40 parts, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 15 parts, low-polymerization phosphate flame retardant 1 part, antioxidant lU1U 2 parts, and dibutyltin dilaurate 0.5 part;

[0088] The thickness of the TPU layer is 0.7 mm;

[0089] The preparation method of the above TPU fabric is the same as that of Example 1.

[0090] Example 3

[0091] This embodiment provides a TPU fabric, which includes a base fabric layer, an adhesive layer, and a TPU layer stacked in sequence;

[0092] Among them, the base fabric layer is a nylon fabric with a thickness of 0.5 mm;

[0093] The adhesive layer is a polyurethane aqueous adhesive with a thickness of 0.2 mm;

[0094] The raw materials for preparing the TPU layer include the following components in parts by weight:

[0095] 10 parts of polytetrahydrofuran ether glycol, 10 parts of polyhexylene adipate glycol, 20 parts of flame-retardant polyester polyol PF-2011, 25 parts of cyclohexyl diisocyanate, 20 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 parts of melamine phosphate, 0.1 part of tris(isodecyl) phosphite, and 0.1 part of stannous octoate;

[0096] The thickness of the TPU layer is 1 mm;

[0097] The preparation method of the above TPU fabric is the same as that of Example 1.

[0098] Example 4

[0099] This embodiment provides a TPU fabric, which includes a base fabric layer, an adhesive layer, and a TPU layer stacked in sequence;

[0100] Among them, the base fabric layer is a nylon fabric with a thickness of 0.5 mm;

[0101] The adhesive layer is a polyurethane aqueous adhesive with a thickness of 0.1 mm;

[0102] The raw materials for preparing the TPU layer include the following components in parts by weight:

[0103] 20 parts of polytetramethylene ether glycol, 25 parts of polyethylene adipate glycol, 20 parts of flame-retardant polyester polyol PF-2011, 40 parts of dicyclohexylmethane diisocyanate, 18 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3 parts of melamine, 1 part of tris(isodecyl) phosphite, and 0.3 part of triethanolamine;

[0104] The thickness of the TPU layer is 0.5 mm;

[0105] The preparation method of the above TPU fabric is the same as that of Example 1.

[0106] Example 5

[0107] This embodiment provides a TPU fabric, which is only different from that of Embodiment 1 in that the weight fraction of the flame-retardant polyether polyol POP-290E in the raw materials for preparing the TPU layer is 10 parts, and other conditions are the same as those in Embodiment 1.

[0108] Embodiment 6

[0109] This embodiment provides a TPU fabric, which is only different from that of Embodiment 1 in that the weight fraction of the flame-retardant polyether polyol POP-290E in the raw materials for preparing the TPU layer is 20 parts, and other conditions are the same as those in Embodiment 1.

[0110] Embodiment 7

[0111] This embodiment provides a TPU fabric, which is only different from that of Embodiment 1 in that the weight fraction of the flame-retardant polyether polyol POP-290E in the raw materials for preparing the TPU layer is 5 parts, and other conditions are the same as those in Embodiment 1.

[0112] Embodiment 8

[0113] This embodiment provides a TPU fabric, which is only different from that of Embodiment 1 in that the weight fraction of the flame-retardant polyether polyol POP-290E in the raw materials for preparing the TPU layer is 25 parts, and other conditions are the same as those in Embodiment 1.

[0114] Embodiment 9

[0115] This embodiment provides a TPU fabric, which is only different from that of Embodiment 1 in that the pentaerythritol-based phosphate flame retardant is replaced with melamine phosphate, and other conditions are the same as those in Embodiment 1.

[0116] Embodiment 10

[0117] This embodiment provides a TPU fabric, which is only different from that of Embodiment 3 in that melamine phosphate is replaced with the pentaerythritol-based phosphate flame retardant, and other conditions are the same as those in Embodiment 3.

[0118] Embodiment 11

[0119] This embodiment provides a TPU fabric, which is only different from that of Embodiment 1 in that the weight fraction of melamine phosphate is 7 parts, and other conditions are the same as those in Embodiment 1.

[0120] Comparative Example 1

[0121] This comparative example provides a TPU fabric, which is only different from that of Embodiment 1 in that the raw materials for preparing the TPU layer do not contain the flame-retardant polyether polyol POP-290E alcohol, the weight fraction of polytetrahydrofuran ether diol is 27 parts, and the weight fraction of polybutylene adipate diol is 28 parts, and other conditions are the same as those in Embodiment 1.

[0122] Comparative Example 2

[0123] A TPU fabric in this comparative example is different from that in Example 1 only in that 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane is replaced by hydroquinone dihydroxyethyl ether, and other conditions are the same as those in Example 1.

[0124] Comparative Example 3

[0125] This comparative example provides a TPU fabric, which is different from that in Example 1 only in that the raw materials for preparing the TPU layer do not contain pentaerythritol-based phosphate flame retardant, and other conditions are the same as those in Example 1.

[0126] The performances of the TPU fabrics provided in the above examples and comparative examples were tested under the following conditions:

[0127] Water contact angle: Tested with a JCZOOOC type contact angle / interface tension measuring instrument produced by Shanghai Zhongchen Equipment Co., Ltd., contact angle measurement range: 0-180°. During the test, the sample to be tested was placed flat on the sample stage.

[0128] Using water as the test liquid, 1 pL of the test liquid was dropped on the surface of the sample (the side of the TPU layer away from the glue layer), and the image was captured immediately, and the contact angle was read by making a tangent. Each sample was tested 3 times, and the difference in readings was within 1°, and the average value was recorded as the finally tested water contact angle.

[0129] Tensile property: The mixture particles obtained in step (2) in the above examples and comparative examples were made into standard dumbbell-shaped specimens according to GB / T528-98, and the mechanical properties were tested at 25°C with a microcomputer-controlled electronic tensile testing machine of SANS Company at a tensile rate of 50 mm / min until the specimen broke.

[0130] Flammability: According to the standard of GB / T 2408-2008, the vertical flammability test was carried out on the TPOU layer material in the TPU fabric.

[0131] Oxygen index: Tested according to the national standard of GB / T 2406-93, and the TPOU layer material in the TPU fabric was tested with an oxygen index tester (Jiangning Analytical Instrument Factory, Nanjing, model JF-3).

[0132] The performance test results of the TPU fabrics provided in the above examples and comparative examples are shown in Table 1 below:

[0133] Table 1

[0134]

[0135]

[0136] As can be seen from the content of Table 1, in the present invention, through the design of the raw materials for preparing the TPU layer, further by using a flame-retardant polyol, a fluorinated chain extender and a flame retardant, and controlling the content of the flame-retardant polyol within a specific range, without the need to additionally add a water repellent and with a small amount of flame retardant used, a TPU fabric material with good flame retardancy, good hydrophobicity and good mechanical properties can be prepared. Its flame retardancy rating is V-0, the oxygen index is 28.2 - 31, the water contact angle > 107°, specifically 107.3 - 110.3°, and the tensile strength is 53.1 - 54.2 MPa.

[0137] Compared with Example 1, if the amount of the flame-retardant polyol used is too small (Example 7), the flame retardancy of the prepared TPU layer is poor; if the amount of the flame-retardant polyol used is too large (Example 8), the cost of preparing the TPU is too high, which is not conducive to industrial production.

[0138] Compared with Example 1 or 3, if the flame-retardant polyol is a flame-retardant polyether polyol POP-290E and the flame retardant is a nitrogen-based flame retardant (Example 9), or if the flame-retardant polyol is only a polyester polyol PF-2011 and the flame retardant is a phosphorus-based flame retardant (Example 10), the flame retardancy of the prepared TPU fabric material is poor.

[0139] Compared with Example 1, if the amount of the flame retardant used is too large (Example 11), the mechanical properties of the prepared TPU fabric material are poor.

[0140] Compared with Example 1, if the raw materials for preparing the TPU layer do not contain a flame-retardant polyol (Comparative Example 1), or do not contain a fluorinated chain extender (Comparative Example 2), or do not contain a flame retardant (Comparative Example 3), the flame retardancy of the prepared TPU layer is poor.

[0141] In summary, in the present invention, through the design of the raw materials for preparing the TPU layer, further by using a flame-retardant polyol, a fluorinated chain extender and a flame retardant, and controlling the content of the flame-retardant polyol within a specific range, without the need to additionally add a water repellent and with a small amount of flame retardant used, a TPU fabric material with good flame retardancy, good hydrophobicity and good mechanical properties can be prepared.

[0142] The applicant declares that the present invention uses the above embodiments to illustrate the detailed process flow of the present invention, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A TPU fabric material, characterized in that, The TPU fabric material includes a base fabric layer, an adhesive layer, and a TPU layer which are stacked in sequence; The preparation raw materials of the TPU layer are composed of the following components in parts by weight: 20 - 50 parts of non - flame - retardant polyol, 10 - 20 parts of flame - retardant polyol, 25 - 40 parts of diisocyanate, 15 - 20 parts of fluorine - containing chain extender, 1 - 3 parts of flame retardant, 0.1 - 2 parts of antioxidant, and 0.1 - 0.5 parts of catalyst; The fluorine - containing chain extender is 2,2 - bis[4-(4 - aminophenoxy)phenyl]hexafluoropropane; The flame - retardant polyol is selected from flame - retardant polyether polyol POP - 290E, and the flame retardant is selected from pentaerythritol - based phosphate flame retardant and / or low - polymerization phosphate flame retardant; Or The flame - retardant polyol is selected from flame - retardant polyester polyol PF - 2011, and the flame retardant is selected from melamine and / or melamine phosphate.

2. The TPU fabric material according to claim 1, wherein The non - flame - retardant polyol is selected from polyether polyol and / or polyester polyol.

3. The TPU fabric material according to claim 2, wherein, The number - average molecular weight of the polyether polyol is 1000 - 6000.

4. The TPU fabric material according to claim 2, wherein The polyether polyol is selected from polytetrahydrofuran ether diol and / or polytetramethylene ether diol.

5. The TPU fabric material according to claim 2, wherein The number - average molecular weight of the polyester polyol is 1000 - 4000.

6. The TPU fabric according to claim 2, characterized in that, The polyester polyol is selected from any one or at least two combinations of polybutylene adipate diol, polyethylene adipate diol, polyhexylene adipate diol, or polycaprolactone diol.

7. The TPU fabric material according to claim 1, characterized in that, The diisocyanate is selected from any one or at least two combinations of dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or cyclohexyl diisocyanate.

8. The TPU fabric material according to claim 1, wherein, The antioxidant is selected from any one or at least two combinations of 2,6 - di - tert - butyl - 4 - methylphenol, antioxidant lU1U, triphenyl phosphite, tris(isodecyl) phosphite, phenyl diisodecyl phosphite, or dioctyl phosphite.

9. The TPU fabric material according to claim 1, wherein The catalyst is selected from any one or at least two combinations of triethanolamine, N,N - dimethylpyridine, N,N - dimethylcyclohexylamine, triethylenediamine, dibutyltin dilaurate, or stannous octoate.

10. The TPU fabric material according to claim 1, wherein, The thickness of the adhesive layer is 0.1 - 0.3 mm.

11. The TPU fabric material according to claim 1, characterized in that, The thickness of the TPU layer is 0.5 - 1 mm.

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