Polyamide copolymer mixture, polyamide copolymer film with high light transmittance and high haze, and preparation method and application of polyamide copolymer film

Abstract

The invention discloses a polyamide copolymer mixture, a polyamide copolymer film with high light transmittance and high haze as well as a preparation method and application of the polyamide copolymer film. Raw materials of the polyamide copolymer film comprise a polyamide copolymer mixture; the polyamide copolymer mixture comprises the following components: a polyamide copolymer, an antioxidant, a heat stabilizer, an antistatic agent, a nucleating agent and inorganic particles. The polyamide copolymer film provided by the invention has high light transmittance and high haze, and by adding the nucleating agent, the inorganic particles and the like into the polyamide copolymer, under the condition of not changing the mechanical properties of the polyamide copolymer, not only are the microphase separation structure and crystallization behavior of polyamide changed, but also the light transmittance of the film is improved. The light transmittance and haze of the polyamide copolymer are improved, so that the polyamide copolymer is applied to the fields of electronics, solar cells, optics and the like.

Description

Technical Field

[0001] This invention belongs to the field of polymer material processing, specifically, it relates to a polyamide copolymer mixture, a polyamide copolymer film with high light transmittance and high haze, its preparation method and application. Background Technology

[0002] Thin films made from highly transparent, high-haze materials possess both high transmittance and high haze, making them highly promising for applications in electronics, solar cells, and optics. For example, these films can serve as anti-glare protective films for displays, preventing direct sunlight; they can be used as surface films on solar cells to capture visible light at different incident angles, improving the cell's photoelectric conversion efficiency; and they can act as optical diffusion films in LED lighting, converting point and line light sources into line and surface light sources, creating a uniform and soft secondary light source. Current technologies typically improve the transparency of films made from highly transparent, high-haze materials by reducing impurities and increasing the refractive index, but this leads to a significant reduction in haze. However, when the haze increases, the internal structure of the highly transparent, high-haze material appears blurred, resulting in reduced transmittance. Therefore, obtaining polymer materials that possess both high haze and high transparency presents a significant challenge.

[0003] Currently, known high-transparency, high-haze films are often prepared using cellulose. For example, Chinese patent CN202210389577 describes a high-transmittance, high-haze cellulose film prepared by adjusting parameters in the traditional pulping and papermaking film-forming process, specifically by regulating the length and width of cellulose fibers through beating degree. The research group of Yu Shuhong at the University of Science and Technology of China has also developed an ultra-strong, ultra-flexible, transparent cellulose fiber film with ultra-fine nanoscale and microscale structures. This film is prepared by introducing micron-scale cellulose fibers into a cellulose nanofiber network, resulting in a multi-scale film with high transmittance and high haze.

[0004] Polyamide copolymers typically contain hard polyamide segments and soft polyether segments, linked by ester or amide bonds. The hard polyamide segments possess high melting points and high crystallinity, enabling the elastomer to maintain good dimensional and thermal stability. The soft polyether segments exhibit good low-temperature flexibility and impact resistance, resulting in excellent elasticity. Therefore, polyamide copolymers have wide applications in medical devices, electrical components, mechanical parts, and high-end sportswear and apparel. However, there are no existing reports on the use of polyamide copolymers to prepare highly transparent, high-haze films. Summary of the Invention

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A polyamide copolymer mixture comprising the following components: polyamide copolymer, antioxidant, heat stabilizer, antistatic agent, nucleating agent, and inorganic particles.

[0007] The inventors discovered that using the above-mentioned polyamide copolymer mixture can improve the crystalline structure of the polyamide copolymer, thereby improving the heat and oxygen stability, antistatic effect, light transmittance, and haze of the polyamide copolymer film.

[0008] According to an embodiment of the present invention, the mass percentage of each component in the polyamide copolymer mixture is as follows:

[0009]

[0010] According to a preferred embodiment of the present invention, the mass percentage of each component in the polyamide copolymer mixture is as follows:

[0011]

[0012]

[0013] According to an embodiment of the present invention, the polyamide copolymer comprises polyamide hard segment structural units and polyether soft segment structural units, wherein the polyamide hard segment structural units and the polyether soft segment structural units are linked by ester bonds or amide bonds. Preferably, the polyamide hard segment structural units are selected from structural units with high melting points and high crystallinity, enabling the polyamide copolymer to maintain good dimensional stability and thermal stability. Preferably, the polyether soft segment structural units are selected from structural units with good low-temperature flexibility and impact resistance, enabling the polyamide copolymer to have good elasticity.

[0014] According to an embodiment of the present invention, the molar ratio of the polyamide hard segment structural unit to the polyether soft segment structural unit is in the range of 95:5-5:95, for example, 95:5, 75:25, 65:35, 55:45, 45:55, 35:65, 25:75, 5:95.

[0015] According to an embodiment of the present invention, the structural units of the polyamide hard segment are provided by AABB-type polyamides and / or AB-type polyamides. Preferably, the AABB-type polyamides have better molecular chain symmetry, better hydrogen bond density, and higher modulus.

[0016] According to an embodiment of the present invention, the AABB-type polyamide is preferably a polyamide material formed from an aliphatic diamine and an aliphatic diacid, such as an even-even, odd-even, even-odd, or odd-odd polyamide material.

[0017] According to an embodiment of the present invention, the AABB type polyamide is preferably selected from at least one or more of polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 1010, polyamide 1012, polyamide 1014, polyamide 1013, polyamide 1212, polyamide 1213, and polyamide 1214; most preferably, it is selected from at least one, two, or three of polyamide 1010, polyamide 1012, and polyamide 1212.

[0018] According to an embodiment of the present invention, the AB-type polyamide is selected from at least one or more of polyamide 6, polyamide 8, polyamide 10, polyamide 11 or polyamide 12, preferably polyamide 12.

[0019] According to an embodiment of the present invention, the structural unit of the polyether soft segment is provided by at least one of the following polyether materials: polyoxyethylene ether, polypropylene ether, polytetramethylene oxide ether; preferably polytetramethylene oxide ether.

[0020] According to an embodiment of the present invention, the antioxidant is selected from at least one or two or more of antioxidant 168, antioxidant 1010, antioxidant 264, antioxidant 1076, and antioxidant 2264.

[0021] According to an embodiment of the present invention, the heat stabilizer is selected from at least one or two or more of zinc stearate, barium stearate, calcium stearate, dibutyltin dilaurate, dibutyltin maleate, dialkyl maleate, and dibutyltin dithioacetate.

[0022] According to an embodiment of the present invention, the antistatic agent is selected from at least one or more of the following: fatty alcohol sulfate or its sodium salt, (alkoxy polyoxyethylene ether sulfate) triethanolamine salt, monoalkyl phosphate salt, dialkyl phosphate salt, alkyl imidazoline, dodecyl dimethyl quaternary ammonium hydantoin, alkyl amino dicarboxylic acid metal salt, glycerol monofatty acid ester, fatty acid ethylene oxide adduct, and carbon black.

[0023] According to embodiments of the present invention, the nucleating agent is selected from at least one or more of polyamide compounds and acylhydrazide compounds. Preferably, the nucleating agent is selected from at least one of TMC-328, TMB-5, TMC-300, TMC-306, N,N-ethylenebis(12-hydroxystearamide), N,N-ethylenebisstearamide, and N,N'-dicyclohexyl-2,6-naphthalenediamide.

[0024] According to an embodiment of the present invention, the inorganic particles are selected from silicon dioxide, glass microspheres, titanium dioxide, aluminum oxide, etc. Preferably, the particle size of the inorganic particles is 0.5-3 micrometers, for example, 1 micrometer, 2 micrometers, or 3 micrometers.

[0025] The present invention also provides a polyamide copolymer film, wherein the raw material of the polyamide copolymer film includes the above-mentioned polyamide copolymer mixture.

[0026] According to an embodiment of the present invention, the polyamide copolymer film has at least one of the following properties:

[0027] 1) Melting point is 100-250℃, for example, 180-200℃;

[0028] 2) The tensile strength can reach 30MPa, for example, 35MPa, 40MPa, 50MPa;

[0029] 3) The elongation at break can reach more than 500%, for example, 600%, 700%, 800%, or 900%;

[0030] 4) Haze level is above 70%, for example, 50%, 60%, 70%, or 80%;

[0031] 5) The light transmittance is above 90%, for example, 91%, 92%, 93%, 94%, or 95%;

[0032] 6) The heat shrinkage rate is 0.9-1.5, for example, 1, 1.1, 1.2.

[0033] According to an embodiment of the present invention, the polyamide copolymer film has good resistance to chemical immersion.

[0034] The present invention also provides a method for preparing the above-mentioned polyamide copolymer film, the method comprising: mixing the above-mentioned polyamide copolymer mixture uniformly, and then preparing the polyamide copolymer film by casting method.

[0035] According to an embodiment of the present invention, the casting process is carried out in equipment known in the art, such as a casting extruder.

[0036] According to an embodiment of the present invention, the process conditions of the casting method include: a temperature of 150 to 250°C, a screw speed of 30 to 150 rpm, and a cooling roller speed of 1 to 10 m / s.

[0037] Preferably, the twin-screw extruder has an extrusion temperature of 180–240°C, a screw speed of 60–100 rpm, and a cooling roller speed of 2–5 m / s.

[0038] The present invention also provides the application of the above-mentioned polyamide copolymer mixtures or polyamide copolymer films in the fields of electronics, solar cells, and optics.

[0039] Compared with the prior art, the present invention has the following advantages:

[0040] This invention utilizes the aforementioned polyamide copolymer mixture to prepare polyamide copolymer films via a casting method. By controlling the microphase separation structure within the polyamide copolymer, the crystalline structure of the polyamide copolymer can be improved, thereby enhancing the heat and oxygen stability, electrostatic effect, light transmittance, and haze of the polyamide copolymer film. The preparation method provided by this invention is simple, easy to implement, and has wider applications.

[0041] The polyamide copolymer film provided by this invention has high light transmittance and high haze. By adding nucleating agents, inorganic particles, etc. to the polyamide copolymer, without changing the mechanical properties of the polyamide copolymer, not only is the microphase separation structure and crystallization behavior of the polyamide copolymer changed, but the light transmittance and haze of the polyamide copolymer are also improved, thereby enabling the polyamide copolymer to be used in the fields of electronics, solar cells, and optics. Attached Figure Description

[0042] Figure 1 A photograph showing the appearance of the polyamide copolymer film prepared in Example 1;

[0043] Figure 2 This is a photograph of the polyamide copolymer film prepared in Example 1 under natural light. Detailed Implementation

[0044] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0045] Example 1

[0046] By mass percentage, 98.55 wt% polyamide copolymer (KHX7025), 0.1 wt% antioxidant 618, 0.1 wt% heat stabilizer dibutyltin dilaurate, 0.3 wt% nucleating agent TMC-300, 0.05 wt% antistatic agent glycerol monofatty acid ester, and 0.5 wt% inorganic particles SiO2 (1 micrometer) were mixed evenly to obtain a blend. The blend was then cast using an extrusion casting machine at a temperature of 180–200 °C, a screw speed of 80 rpm, and a cooling roller speed of 3.5 m / s to obtain a polyamide copolymer film with a thickness of 90 μm.

[0047] Comparative Example 1

[0048] By mass percentage, 99.35 wt% of polyamide copolymer (KHX7025), 0.1 wt% of antioxidant 618, 0.1 wt% of heat stabilizer dibutyltin dilaurate, 0.05 wt% of antistatic agent glycerol monofatty acid ester, and 0.05 wt% of SiO2 (1 micrometer) were mixed evenly to obtain a mixture. The blend was then cast using an extrusion casting machine at a temperature of 180–200 °C, a screw speed of 80 rpm, and a cooling roller speed of 3.5 m / s to obtain a polyamide copolymer film with a thickness of 90 μm.

[0049] Comparative Example 2

[0050] The method for preparing polyamide copolymer films in this comparative example is basically the same as in Example 1, except that the blend prepared in Example 1 is cast using an extrusion casting machine at a temperature of 220°C, a screw speed of 80 rpm, and a cooling roller speed of 3.5 m / s to obtain a polyamide copolymer film with a thickness of 90 μm.

[0051] Comparative Example 3

[0052] The method for preparing polyamide copolymer films in this comparative example is basically the same as in Example 1, except that the polyamide copolymer in Example 1 is replaced with polyamide 1012, which does not contain polyether structural units; the casting process conditions are the same as in Example 1, and a polyamide copolymer film with a thickness of 90 μm is obtained.

[0053] The test results of the polyamide copolymer films prepared in Example 1 and Comparative Examples 1-3 are shown in Table 1 below. Tensile strength and elongation at break were tested according to national standard GB / T1040.3-2006. Optical properties were measured according to national standard GB / T 2410-2008. Thermal shrinkage was measured according to national standard GB / T 13519-2017.

[0054] Table 1

[0055]

[0056] Examples 2-7

[0057] The preparation method of the polyamide copolymer films in Examples 2-7 is the same as that in Example 1, except that the formulation of their blends is different from that in Example 1. The types and contents of additives in the specific formulations are shown in Table 2. The amount of additives in Table 2 is by mass percentage, and the rest are polyamide copolymers.

[0058] In the copolymer formulations, Examples 2-3 used the polyamide copolymer prepared in Preparation Example 1; Examples 4-5 used commercially available Vestamid E47 as the polyamide copolymer; Examples 6-7 used commercially available Pebax 3533 as the polyamide copolymer.

[0059] The performance test results of the prepared polyamide copolymer film are shown in Table 3.

[0060] Table 2

[0061]

[0062] Table 3

[0063]

[0064] The exemplary embodiments of the present invention have been described above. However, the scope of protection of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A polyamide copolymer mixture, characterized in that, The polyamide copolymer mixture comprises the following components: polyamide copolymer, antioxidant, heat stabilizer, antistatic agent, nucleating agent, and inorganic particles.

2. The polyamide copolymer mixture according to claim 1, characterized in that, The mass percentage of each component in the polyamide copolymer mixture is as follows:

3. The polyamide copolymer mixture according to claim 1 or 2, characterized in that, The polyamide copolymer comprises structural units of polyamide hard segments and polyether soft segments, wherein the structural units of polyamide hard segments and polyether soft segments are connected by ester bonds or amide bonds. Preferably, the molar ratio of the polyamide hard segment structural unit to the polyether soft segment structural unit is in the range of 95:5-5:

95.

4. The polyamide copolymer mixture according to any one of claims 1-3, characterized in that, The structural units of the polyamide hard segment are provided by AABB type polyamide and / or AB type polyamide. Preferably, the AABB-type polyamide is a polyamide material formed from an aliphatic diamine and an aliphatic diacid. Preferably, the AABB type polyamide is selected from at least one or more of polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 1010, polyamide 1012, polyamide 1014, polyamide 1013, polyamide 1212, polyamide 1213, and polyamide 1214. Preferably, the AB-type polyamide is selected from at least one or more of polyamide 6, polyamide 8, polyamide 10, polyamide 11 or polyamide 12.

5. The polyamide copolymer mixture according to any one of claims 1-4, characterized in that, The structural unit of the polyether soft segment is provided by at least one of the following polyether materials: polyoxyethylene ether, polyoxypropylene ether, and polytetramethylene oxide ether.

6. The polyamide copolymer mixture according to any one of claims 1-5, characterized in that, The antioxidant is selected from at least one or more of antioxidant 168, antioxidant 1010, antioxidant 264, antioxidant 1076, and antioxidant 2264. Preferably, the heat stabilizer is selected from at least one or more of zinc stearate, barium stearate, calcium stearate, dibutyltin dilaurate, dibutyltin maleate, dialkyl maleate, and dibutyltin dithioacetate. Preferably, the antistatic agent is selected from at least one or more of the following: fatty alcohol sulfate or its sodium salt, (alkoxy polyoxyethylene ether sulfate) triethanolamine salt, monoalkyl phosphate salt, dialkyl phosphate salt, alkyl imidazoline, dodecyl dimethyl quaternary ammonium hydantoin salt, alkyl amino dicarboxylic acid metal salt, glycerol monofatty acid ester, fatty acid ethylene oxide adduct, and carbon black. Preferably, the nucleating agent is selected from at least one or two or more of polyamide compounds and acylhydrazine compounds. Preferably, the inorganic particles are selected from at least one of silicon dioxide, glass microspheres, titanium dioxide, and aluminum oxide.

7. A polyamide copolymer film, characterized in that, The raw material for the polyamide copolymer film includes the polyamide copolymer mixture according to any one of claims 1-6; Preferably, the polyamide copolymer film has at least one of the following properties: 1) Melting point is 100-250℃; 2) The tensile strength can reach 30MPa; 3) The elongation at break can reach over 500%; 4) Haze level is above 70%; 5) Light transmittance is over 90%; 6) The thermal shrinkage rate is 0.9-1.

5. Preferably, the polyamide copolymer film has good resistance to chemical immersion.

8. The method for preparing the polyamide copolymer film according to claim 7, characterized in that, The preparation method includes: uniformly blending a polyamide copolymer mixture and then preparing the polyamide copolymer film by casting.

9. The preparation method according to claim 8, characterized in that, The process conditions for the casting method include: a temperature of 150–250°C, a screw speed of 30–150 rpm, and a cooling roller speed of 1–10 m / s.

10. The application of the polyamide copolymer film according to claim 7 in the fields of electronics, solar cells, and optics.

Images