Textile accessory and preparation method thereof

Abstract

The invention discloses a textile accessory and a preparation method thereof, and belongs to the technical field of textile accessories. The textile accessory comprises the following raw materials in percentage by mass: 70%-94.5% of polyhydroxyalkanoate, 5%-25% of calcium carbonate and 0.5%-5% of talcum powder. The textile accessory disclosed by the invention not only has relatively high rigidity, but also has certain toughness, and can meet the required mechanical property.

Description

Technical Field

[0001] The present invention relates to the technical field of textile accessories, and in particular to a textile accessory and a preparation method thereof. Background Art

[0002] Textile accessories such as buttons are consumed daily in significant quantities. Traditionally, they are manufactured using petroleum-based plastics (such as polyester, polyamide, ABS, and polypropylene) or natural materials (such as wood and shells). Petroleum-based plastics pose environmental risks, while some natural materials face resource, cost, or processing limitations.

[0003] Polyhydroxyalkanoates (PHA), as a bio-based, biodegradable material, offer a potential alternative to traditional plastics. However, PHA's low mechanical properties make it unsuitable for textile accessories. Summary of the Invention

[0004] The main purpose of the present invention is to provide a textile accessory and a preparation method thereof, aiming to improve the rigidity and toughness of the bio-based textile accessory.

[0005] In a first aspect, the present invention provides a textile accessory comprising the following raw materials in percentage by mass: 70%-94.5% polyhydroxyalkanoate, 5%-25% calcium carbonate, and 0.5%-5% talc.

[0006] In one embodiment, the polyhydroxyalkanoate includes at least one of a P3HB3HP copolymer and a P3HB4HB copolymer.

[0007] In one embodiment, the content of 3-hydroxypropionate units in the P3HB3HP copolymer is 3 mol%-10 mol%; and / or the content of 4-hydroxybutyrate units in the P3HB4HB copolymer is 3 mol%-10 mol%.

[0008] In one embodiment, the weight average molecular weight of the P3HB3HP copolymer and the P3HB4HB copolymer are both 500 kDa-1000 kDa.

[0009] In one embodiment, the calcium carbonate includes at least one of silane coupling agent modified calcium carbonate, stearic acid modified calcium carbonate, and stearate modified calcium carbonate.

[0010] In one embodiment, the average particle size of the calcium carbonate is 0.1 μm-5 μm.

[0011] In one embodiment, the average particle size of the talc is 1 μm-10 μm.

[0012] In one embodiment, the textile accessories include at least one of buttons, zippers, and hangers.

[0013] In a second aspect, the present invention provides a method for preparing a textile accessory, comprising: providing polyhydroxyalkanoate, calcium carbonate and talc, wherein the moisture content of the polyhydroxyalkanoate, calcium carbonate and talc is less than 0.1wt%; melt-blending and granulating the polyhydroxyalkanoate, calcium carbonate and talc to obtain composite material particles, wherein the mass percentage of the polyhydroxyalkanoate is 70%-94.5%, the mass percentage of the calcium carbonate is 5%-25%, and the mass percentage of the talc is 0.5%-5%; and processing and shaping the composite material particles to obtain a textile accessory.

[0014] In one embodiment, the step of melt-blending and granulating the polyhydroxyalkanoate, calcium carbonate and talc comprises: melting and stirring the polyhydroxyalkanoate, calcium carbonate and talc at 160-185° C. at a stirring speed of 100-250 rpm.

[0015] The raw materials of the textile accessory of the present invention include calcium carbonate and talc. Calcium carbonate, as a reinforcing phase, enhances the flexural modulus and hardness of the textile accessory through a rigid particle effect, stress transfer, and nucleation. Talc, as an auxiliary agent, further improves the flexural modulus and hardness of the textile accessory through its unique flaky structure, efficient nucleation, and rigid particle effect. Furthermore, by limiting the addition amounts of calcium carbonate and talc, the present application achieves a balance between the rigidity and toughness of the textile accessory, thereby improving both the rigidity and toughness of the textile accessory.

[0016] In addition, calcium carbonate and talc as inorganic fillers can reduce the shrinkage and hygroscopicity of textile accessories, that is, help improve the dimensional stability of textile accessories, which is beneficial for the size maintenance of textile accessories such as buttons after multiple washings or in different humidity environments. DETAILED DESCRIPTION

[0017] It should be noted that if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of technical features indicated. Therefore, the features specified as "first" and "second" may explicitly or implicitly include at least one of such features. In addition, if "and / or" or "and / or" appears in the full text, its meaning includes three parallel schemes. Taking "A and / or B" as an example, it includes scheme A, or scheme B, or a scheme in which A and B are satisfied at the same time. "At least one" appearing in the embodiments of the present invention refers to one or more, and "more" refers to two or more.

[0018] The "ranges" disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range.

[0019] In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the fact that ordinary technicians in this field can implement them. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0020] Commonly used textile accessories include buttons, disposable hangers, etc. Buttons need to withstand daily wear and tear, washing and a certain ironing temperature, and disposable hangers need to meet a certain load-bearing capacity. However, polyhydroxyalkanoate (PHA) raw materials cannot meet the mechanical properties required by textile accessories.

[0021] Although in some embodiments, two or more hydroxy fatty acid monomers are copolymerized to obtain polyhydroxy fatty acid esters to improve their mechanical properties, they still cannot meet the requirements of textile accessories.

[0022] In order to solve the above problems, the present invention provides a textile accessory, comprising the following raw materials in percentage by mass: 70%-94.5% polyhydroxyalkanoate, 5%-25% calcium carbonate, and 0.5%-5% talc.

[0023] Polyhydroxyalkanoate (PHA) as a matrix provides biodegradability, biocompatibility and renewability, and its content can be any value between 70% and 94.5%. Exemplarily, the mass percentage of polyhydroxyalkanoate can be 70%, 72%, 74%, 76%, 78%, 80%, 83%, 85%, 88%, 90%, 93% or 94.5%.

[0024] Calcium carbonate is the primary reinforcing filler. On the one hand, the calcium carbonate particles themselves have an elastic modulus (rigidity) far higher than that of the PHA matrix. When the rigid calcium carbonate particles are evenly dispersed in the PHA matrix, they limit the matrix's ability to deform when subjected to stress, thereby enhancing the flexural modulus of the textile accessory. On the other hand, when the textile accessory material is subjected to external force, the stress is effectively transferred from the PHA matrix to the more rigid calcium carbonate particles. The rigid calcium carbonate particles bear a greater proportion of the load, helping to increase the hardness of the textile accessory. Therefore, calcium carbonate can enhance the flexural modulus and hardness of textile accessories through the rigid particle effect and stress transfer.

[0025] The amount of calcium carbonate added can be any value between 5% and 25%. For example, the amount of calcium carbonate added can be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22% or 25%.

[0026] On the one hand, talc powder can serve as an auxiliary reinforcing agent and can also help improve the mechanical properties of textile accessories through the rigid particle effect. On the other hand, talc powder can serve as a nucleating agent and can significantly increase the crystallization rate and crystallization temperature of polyhydroxyalkanoates, thereby shortening the production time of textile accessories. This can effectively improve production efficiency and reduce energy consumption for mass production of textile accessories.

[0027] The amount of talc added can be any value between 0.5% and 5%. For example, the amount of talc added can be 0.5%, 0.8%, 1%, 1.3%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.

[0028] The present application can balance the rigidity and toughness of the textile accessories by limiting the addition amount of calcium carbonate and talcum powder, thereby improving the rigidity of the textile accessories while improving the toughness of the textile accessories.

[0029] Furthermore, calcium carbonate and talc, as inorganic fillers, help reduce shrinkage and hygroscopicity in textile accessories, improving their dimensional stability. This is beneficial for buttons and other textile accessories to maintain their dimensions after repeated washing or in varying humidity environments. Furthermore, calcium carbonate and talc, as fillers, form a good interfacial bond with the PHA matrix, allowing them to be evenly dispersed within the PHA matrix, further enhancing the strength of the fabric.

[0030] Furthermore, the calcium carbonate and talc fillers selected in the present invention are low-cost and widely available. This significantly improves the rigidity, hardness, and molding efficiency of textile accessories while effectively controlling production costs, enabling them to economically meet the requirements of both disposable and large-scale textile accessories. Furthermore, the polyhydroxyalkanoate, the primary material of the present invention, is a biodegradable material, and the calcium carbonate and talc are both natural minerals, making the resulting textile accessories environmentally friendly and promising for future applications.

[0031] According to some embodiments of the present invention, the polyhydroxyalkanoate includes at least one of a P3HB3HP copolymer and a P3HB4HB copolymer.

[0032] P3HB3HP copolymer refers to a polymer obtained by copolymerization of 3-hydroxybutyrate (3HB) and 3-hydroxypropionate (3HP), and P3HB4HB refers to a polymer obtained by copolymerization of 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB).

[0033] The crystallinity of traditional P3HB (homopolymer of 3HB) is between 60% and 80%, and it has certain rigidity and crystallinity. By introducing an appropriate amount of 3HP or 4HB monomer, the high crystallinity of P3HB can be reduced, making the composite material extremely rigid and having improved flexibility.

[0034] According to some embodiments of the present invention, the content of 3-hydroxypropionate units in the P3HB3HP copolymer is 3 mol%-10 mol%; and / or the content of 4-hydroxybutyrate units in the P3HB4HB copolymer is 3 mol%-10 mol%.

[0035] In the P3HB3HP copolymer, a 3-hydroxypropionate unit content of 3 mol% to 10 mol% means that in the molecular chain of P3HB3HP, the amount of 3HP monomer units accounts for 3% to 10% of the total monomer units (3HB + 3HP). The same applies to the 4-hydroxybutyrate unit content of P3HB4HB copolymer, which is 3 mol% to 10 mol%.

[0036] When the content of 3-hydroxypropionate units is 3 mol%-10 mol% or the content of 4-hydroxybutyrate units is 3 mol%-10 mol%, the crystallinity of pure P3HB can be reduced from 60%-63% to 45%-55%, which can not only ensure the rigidity of the textile accessories, but also give the textile accessories a certain toughness.

[0037] According to some embodiments of the present invention, the weight average molecular weight of the P3HB3HP copolymer and the P3HB4HB copolymer are both 500 kDa-1000 kDa.

[0038] The weight-average molecular weight (Mw) of the P3HB3HP copolymer or the P3HB4HB copolymer is 500 kDa-1000 kDa. The high molecular weight ensures that the material itself has sufficient cohesive strength, avoiding insufficient strength of the composite material due to too low a molecular weight. In addition, the appropriate molecular weight range ensures moderate viscosity of the melt during processing, facilitating melt blending with other components.

[0039] According to some embodiments of the present invention, the calcium carbonate includes at least one of silane coupling agent-modified calcium carbonate, stearic acid-modified calcium carbonate, and stearate-modified calcium carbonate.

[0040] Silane coupling agent-modified calcium carbonate refers to a material obtained by surface-treating calcium carbonate with a silane coupling agent. The hydrolyzable groups in the silane coupling agent molecules (such as methoxy-OCH3 and ethoxy-OC2H5) hydrolyze in the presence of water to form silanols (Si-OH). These silanols react with hydroxyl groups (-OH) on the calcium carbonate surface to form stable Si-O-Ca chemical bonds, firmly adsorbing the silane coupling agent to the calcium carbonate surface. The organophilic groups (such as amino and vinyl groups) on the silane coupling agent molecules interact physically or chemically with the polyhydroxyalkanoate (PHA) matrix, improving the interfacial compatibility between the PHA and the matrix, thereby facilitating the uniform dispersion of the calcium carbonate within the matrix. Stearic acid-modified calcium carbonate and stearate-modified calcium carbonate are similarly designed to enhance compatibility with the PHA matrix.

[0041] According to some embodiments of the present invention, the average particle size of calcium carbonate is 0.1 μm-5 μm.

[0042] The average particle size of calcium carbonate can be any value between 0.1 μm and 5 μm. For example, the average particle size of calcium carbonate can be 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm. In some embodiments, the average particle size of calcium carbonate can be a volume median particle size Dv50. Calcium carbonate with an average particle size of 0.1 μm-5 μm has significant advantages in improving the flexural modulus and hardness of the finished product through its own stiffness, stress transfer, nucleation and optimization of the polymer microstructure, while also taking into account impact performance, processing convenience and cost-effectiveness.

[0043] According to some embodiments of the present invention, the average particle size of talc is 1 μm-10 μm.

[0044] The average particle size of talc can be any value between 1 μm and 10 μm. For example, the average particle size of talc can be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.

[0045] According to some embodiments of the present invention, the textile accessory includes at least one of a button, a zipper, and a hanger.

[0046] According to some embodiments of the present invention, the present invention provides a method for preparing a textile accessory, comprising: providing polyhydroxyalkanoate, calcium carbonate and talc, wherein the moisture content of the polyhydroxyalkanoate, calcium carbonate and talc is less than 0.1wt%; melt-blending and granulating the polyhydroxyalkanoate, calcium carbonate and talc to obtain composite material particles, wherein the mass percentage of the polyhydroxyalkanoate is 70%-94.5%, the mass percentage of the calcium carbonate is 5%-25%, and the mass percentage of the talc is 0.5%-5%; and processing and shaping the composite material particles to obtain a textile accessory.

[0047] A polyhydroxyalkanoate with a moisture content below 0.1 wt% can avoid molecular weight loss that may result from excessively high moisture content. In some embodiments, to obtain polyhydroxyalkanoate, calcium carbonate, and talc with a moisture content below 0.1 wt%, the polyhydroxyalkanoate, calcium carbonate, and talc can be vacuum dried at 80°C-100°C for 4-6 hours. Drying in a vacuum environment can effectively control the moisture content of the raw materials and avoid high-temperature hydrolysis of the polyhydroxyalkanoate. Furthermore, limiting the drying time can reduce thermal oxidative degradation of the polyhydroxyalkanoate.

[0048] Polyhydroxyalkanoate, calcium carbonate, and talc can be blended using a twin-screw extruder. The three materials experience longitudinal and transverse shear between the screws, resulting in a more uniform mixing. After mixing, the materials are extruded from the extruder head to produce a molten strand. After cooling in a water tank or air, the pelletizer forms uniform composite pellets.

[0049] The composite material particles can be processed into textile accessories using processes such as injection molding, compression molding, and extrusion molding. In some embodiments, the composite material particles can be vacuum-dried at 70°C-90°C for 2-4 hours before molding. This can reduce moisture absorption by the composite material particles during storage, avoid bubbles and surface defects during injection molding, and ensure the surface finish of the product. During injection molding, the temperature of the injection mold can be set at 40°C-80°C.

[0050] According to some embodiments of the present invention, the step of melt-blending and granulating polyhydroxyalkanoate, calcium carbonate and talc comprises: melting and stirring the polyhydroxyalkanoate, calcium carbonate and talc at 160-185° C. at a stirring speed of 100-250 rpm.

[0051] Blending at 160°C-185°C can keep the polyhydroxyalkanoate in a molten state, which helps disperse the calcium carbonate and talc fillers. When using a twin-screw extruder to melt blend the raw materials, the temperature of each section of the extruder can be set between 160°C-185°C, and the screw speed can be set between 100rpm-250rpm. This can ensure uniform dispersion of calcium carbonate and talc in the polyhydroxyalkanoate matrix and good interfacial bonding.

[0052] Example 1

[0053] Raw materials: 83% P3HB4HB (4HB 5 mol%, Mw 700 kDa), 15% stearic acid-modified calcium carbonate, and 2% talc. The P3HB4HB is marketed as Hengtan Z2501; the stearic acid-modified calcium carbonate has an average particle size (Dv50) of 1 μm and is marketed as Jiangxi Baiyanhua CC series; and the talc has an average particle size (Dv50) of 5 μm and is marketed as Liaoning Aihai FT-3000.

[0054] Preparation method:

[0055] P3HB4HB, calcium carbonate, and talc were dried under vacuum at 90 °C for 5 h;

[0056] The dried raw materials were added to a twin-screw extruder (Coperion ZSK-26, L / D=40), and the barrel temperature (from feed port to die head) was set to 165°C / 170°C / 175°C / 180°C / 175°C, and the screw speed was 150 rpm.

[0057] The extrudate is water-cooled and then pelletized to obtain composite material particles;

[0058] After the composite material particles were vacuum dried at 80°C for 3 h, they were injection molded into standard strips, buttons, and hanger samples using an injection molding machine (Haitian MA series) at a mold temperature of 60°C.

[0059] Example 2

[0060] Different from Example 1, the raw materials of this example are: P3HB4HB (4HB 5 mol%, Mw 700 kDa) 90%, stearic acid-modified calcium carbonate 5%, and talc 5%.

[0061] Example 3

[0062] Different from Example 1, the raw materials of this example are: 94.5% of P3HB4HB (4HB 5 mol%, Mw 700 kDa), 5% of stearic acid-modified calcium carbonate, and 0.5% of talc.

[0063] Example 4

[0064] Different from Example 1, the raw materials of this example are: P3HB4HB (4HB 5 mol%, Mw 700 kDa) 74%, stearic acid-modified calcium carbonate 25%, and talc 1%.

[0065] Example 5

[0066] Different from Example 1, the raw materials of this example are: P3HB4HB (4HB 5 mol%, Mw 700 kDa) 70%, stearic acid-modified calcium carbonate 25%, and talc 5%.

[0067] Example 6

[0068] Different from Example 1, the weight average molecular weight Mw of the P3HB4HB copolymer in this example is 1000 kDa.

[0069] Example 7

[0070] Different from Example 1, the polyhydroxyalkanoate in this example is a P3HB3HP copolymer (3HP 5 mol%, Mw 700 kDa).

[0071] Comparative Example 1

[0072] The difference from Example 1 is that the raw material of the textile accessories in this comparative example is: P3HB4HB (4HB 5 mol%, Mw 700 kDa) 100%.

[0073] Comparative Example 2

[0074] Different from Example 1, the raw materials of the textile accessories in this comparative example are: P3HB4HB (4HB 5 mol%, Mw 700 kDa) 98% and talc 2%.

[0075] Comparative Example 3

[0076] Different from Example 1, the raw materials of the textile accessories in this comparative example are: P3HB4HB (4HB 5 mol%, Mw 700 kDa) 68%, stearic acid-modified calcium carbonate 30%, and talc 2%.

[0077] Performance Testing

[0078] Flexural modulus: Refer to ISO 178, use a universal material testing machine to test standard injection molded specimens at 23°C, 50% RH, and a test rate of 2 mm / min.

[0079] Shore D hardness: Refer to standard ISO 868 and use a Shore D hardness tester to test the surface hardness of injection molded specimens.

[0080] Heat Deflection Temperature (HDT): The heat deformation temperature of standard injection molded specimens was tested in a silicone oil bath at a heating rate of 120 K / h and a bending stress load of 0.45 MPa, according to ISO 75-1 / -2, method B (edge).

[0081] Charpy notched impact strength: The impact strength of injection molded specimens with V-notch was tested according to ISO 179-1 method 1eA.

[0082] Melt flow rate (MFR): measured in accordance with ISO 1133-1 at 190°C and a load of 2.16 kg.

[0083] Test results

[0084] The test results of Examples 1-7 and Comparative Examples 1-5 are shown in Table 1.

[0085] Table 1 Test results of Examples 1-7 and Comparative Examples 1-5

[0086]

[0087]

[0088] As can be seen from Table 1, the flexural modulus of the samples in Examples 1-7 of the present invention is greater than or equal to 2.0 GPa, the Shore D hardness is greater than or equal to 75, the heat deformation temperature HDT is greater than or equal to 80°C, and the notched impact strength of the simply supported beam is greater than or equal to 2.0 kJ / m 2 , which shows that the textile accessory of the present invention not only has a higher bending modulus and hardness, improved dimensional stability, but also can maintain a certain impact toughness and a certain heat resistance.

[0089] Comparison of Example 1 and Comparative Example 2 shows that when the raw material does not contain calcium carbonate, the flexural modulus and hardness of the sample are not effectively improved, and cannot meet the rigidity requirements of textile accessories. Comparison of Example 1 and Comparative Example 3 shows that when the addition of calcium carbonate is too high, although the rigidity of the sample is enhanced, its impact strength is only 1.8 kJ / m 2 , indicating that the toughness of the sample is insufficient and cannot meet the toughness requirements required for textile accessories.

[0090] The above description is merely an exemplary embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformation made by utilizing the contents of the present invention specification under the technical concept of the present invention, or any direct / indirect application in other related technical fields, is included in the patent protection scope of the present invention.

Claims

1. A textile accessory, characterized in that: The following raw materials are included in mass percentage: Polyhydroxyalkanoate 70%-94.5%, calcium carbonate 5%-25%, talc 0.5%-5%.

2. The textile accessory according to claim 1, characterized in that The polyhydroxyalkanoate includes at least one of a P3HB3HP copolymer and a P3HB4HB copolymer.

3. The textile accessory according to claim 2, characterized in that In the P3HB3HP copolymer, the content of 3-hydroxypropionate units is 3 mol% to 10 mol%; and / or, In the P3HB4HB copolymer, the content of 4-hydroxybutyrate units is 3 mol% to 10 mol%.

4. The textile accessory according to claim 2, characterized in that The weight average molecular weights of the P3HB3HP copolymer and the P3HB4HB copolymer are both 500 kDa-1000 kDa.

5. The textile accessory according to any one of claims 1 to 4, characterized in that The calcium carbonate includes at least one of silane coupling agent modified calcium carbonate, stearic acid modified calcium carbonate, and stearate modified calcium carbonate.

6. The textile accessory according to claim 5, characterized in that The average particle size of the calcium carbonate is 0.1 μm-5 μm.

7. The textile accessory according to any one of claims 1 to 4, characterized in that The average particle size of the talc powder is 1 μm-10 μm.

8. The textile accessory according to any one of claims 1 to 7, characterized in that The textile accessories include at least one of buttons, zippers, and hangers.

9. A method for preparing a textile accessory, characterized in that: include: Providing polyhydroxyalkanoate, calcium carbonate and talc, wherein the water content of the polyhydroxyalkanoate, calcium carbonate and talc is less than 0.1wt%; The polyhydroxyalkanoate, calcium carbonate, and talc are melt-blended and granulated to obtain composite material particles, wherein the mass percentage of the polyhydroxyalkanoate is 70%-94.5%, the mass percentage of the calcium carbonate is 5%-25%, and the mass percentage of the talc is 0.5%-5%; The composite material particles are processed and formed into textile accessories.

10. The method for preparing a textile accessory according to claim 9, characterized in that: The step of melt-blending and granulating the polyhydroxyalkanoate, calcium carbonate and talc comprises: The polyhydroxyalkanoate, calcium carbonate and talc are melted and stirred at 160° C.-185° C., with a stirring speed of 100 rpm-250 rpm.

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