Mildew-proof antibacterial halogen-free flame-retardant PVC composite material and preparation method and application thereof

Abstract

The application belongs to the technical field of PVC composite materials, and provides a mildew-proof and antibacterial halogen-free flame-retardant PVC composite material and a preparation method and application thereof. The material is prepared from the following raw materials in parts by mass: 20-70 parts of PVC resin, 10-60 parts of modified Mg(OH)2 micro powder, 1-5 parts of modified inorganic compound mildew-proof and antibacterial agent, 1-2 parts of plasticizer, 0.2-1 part of antioxidant, and 0.5-1 part of stabilizer. The modified Mg(OH)2 micro powder is prepared from Mg(OH)2 micro powder, interface modification compound agent and lubricant. The modified inorganic compound mildew-proof and antibacterial agent is prepared from inorganic compound mildew-proof and antibacterial agent and surface modifier. The dispersibility of the inorganic compound mildew-proof and antibacterial agent and Mg(OH)2 in the PVC resin is effectively improved by modifying the Mg(OH)2 micro powder and the inorganic compound mildew-proof and antibacterial agent, so that the mildew-proof and antibacterial property and the flame-retardant property of the PVC composite material are improved.

Description

Technical Field

[0001] This invention relates to the field of PVC composite material technology, and in particular to a mildew-resistant, antibacterial, halogen-free flame-retardant PVC composite material, its preparation method, and its application. Background Technology

[0002] With the development of the automotive industry, higher requirements have been placed on the safety, flame retardancy, functionality, and comfort of automotive interior materials. The market demand for interior materials with halogen-free flame retardancy, high safety, and anti-mildew and antibacterial properties is increasing daily. PVC (polyvinyl chloride) is a widely used material in automotive interiors, possessing good wear resistance, chemical stability, and cost-effectiveness. However, traditional PVC is a flammable material; when exposed to flames or high temperatures, it burns rapidly, releasing large amounts of toxic fumes and gases. Simultaneously, PVC products are prone to mold growth, odor, and performance degradation when exposed to bacterial environments for extended periods, significantly limiting its application in automotive interiors such as synthetic leather, seats, seat covers, door seals, window seals, panels, and thermal and sound insulation composite materials, making it difficult to meet the demands of modern automotive interior materials. Therefore, modifying PVC to improve its flame retardancy and anti-mildew and antibacterial properties, and using it to prepare automotive interior products that meet the requirements of flame retardancy, safety, environmental protection, and anti-mildew and antibacterial properties, is of great significance.

[0003] In recent years, among the various modification measures for PVC materials, the addition of small-molecule organic flame retardants and antibacterial agents is often used to modify PVC to achieve flame retardancy and antibacterial properties in PVC products. However, small-molecule organic flame retardants have poor heat resistance and are prone to migration, precipitation, and decomposition in products, posing a risk to human health. Furthermore, long-term exposure of small-molecule organic flame retardants and antibacterial agents to high temperatures, humidity, light, or oxidation conditions can reduce the antibacterial and flame retardant effects of products, failing to meet the requirements for long-lasting flame retardancy and mildew-proof and antibacterial properties in automotive interior products. Therefore, inorganic compound mildew-proof and antibacterial agents are antibacterial materials combining multiple inorganic components. They effectively inhibit microbial growth and prevent mold growth, exhibiting high-temperature resistance, environmental friendliness, broad spectrum, and long-lasting antibacterial properties. Magnesium hydroxide (Mg(OH)2) is a novel halogen-free filled flame retardant. When heated, it releases bound water and absorbs a large amount of latent heat to reduce the surface temperature of the filled material in a flame. It inhibits polymer decomposition and cools the generated flammable gases, making it an excellent flame retardant. However, Mg(OH)2 and inorganic compound antifungal and antibacterial agents are prone to agglomeration in PVC, which leads to a reduction in the mechanical properties of the composite material and even affects the antifungal, antibacterial and flame-retardant properties of the PVC composite material.

[0004] Therefore, there is an urgent need to provide a mildew-proof, antibacterial, halogen-free, flame-retardant PVC composite material to solve the problem of poor flame retardancy and mildew-proof and antibacterial properties of existing modified PVC composite materials. Summary of the Invention

[0005] In view of this, the present invention provides a mildew-resistant, antibacterial, halogen-free flame-retardant PVC composite material, its preparation method and application, to solve the problem of poor flame retardancy and mildew-resistant and antibacterial properties of existing modified PVC composite materials.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a mildew-resistant, antibacterial, halogen-free, flame-retardant PVC composite material, comprising the following components in parts by weight: 20-70 parts PVC resin, 10-60 parts modified Mg(OH)2 micro powder, 1-5 parts modified inorganic compound mildew-resistant and antibacterial agent, 1-2 parts plasticizer, 0.2-1 part antioxidant, and 0.5-1 part stabilizer; wherein the modified Mg(OH)2 micro powder is prepared from Mg(OH)2 micro powder, an interface modifying compound agent, and a lubricant; and the modified inorganic compound mildew-resistant and antibacterial agent is prepared from an inorganic compound mildew-resistant and antibacterial agent and a surface modifier.

[0008] Preferably, the preparation method of the modified Mg(OH)2 micro powder includes the following steps: mixing Mg(OH)2 micro powder, interface modifier compound and lubricant, and heating to obtain modified Mg(OH)2 micro powder.

[0009] Preferably, the mass ratio of the Mg(OH)2 micro powder, the interface modifier compound, and the lubricant is 100:1-2.5:0.5-2.

[0010] Preferably, the interface-modifying compound agent includes two or more of the following: silane coupling agent, isocyanate, titanate, stearic acid, oleic acid, sodium oleate, and sodium dodecyl sulfonate; the lubricant includes one or more of the following: N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, PE wax, and zinc stearate.

[0011] Preferably, the heating temperature during the preparation of the modified Mg(OH)2 micro powder is 70-110℃, and the heating time is 6-15 min.

[0012] Preferably, the preparation method of the modified inorganic compound antifungal and antibacterial agent includes the following steps: mixing the inorganic compound antifungal and antibacterial agent and the surface modifier, and heating them to obtain the modified inorganic compound antifungal and antibacterial agent.

[0013] Preferably, the mass ratio of the inorganic compound antifungal and antibacterial agent to the surface modifier is 100:0.5 to 1.5.

[0014] Preferably, the inorganic compound antifungal and antibacterial agent includes two or more of nano silver, silver oxide, copper oxide, cuprous oxide, copper sulfate, zinc oxide, zinc iodide, calcium phosphate, titanium dioxide, and tin dioxide; the surface modifier includes one or more of silane coupling agent, titanate, aluminate, zinc stearate, and PE wax.

[0015] Preferably, the heating temperature during the preparation of the modified inorganic compound antifungal and antibacterial agent is 60-100℃, and the heating time is 6-15 minutes.

[0016] Preferably, the plasticizer comprises one or more of phthalates, fatty diesters, phosphate esters, tricarboxylic acid esters, diol esters, and polyesters; the antioxidant comprises phosphite antioxidants and / or hindered phenolic antioxidants; and the stabilizer comprises one or more of octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, pentaerythritol tetrakis(4-hydroxy-3,5-di-tert-butylphenylpropionate), triphenyl phosphite, 2,6-tert-butyl-4-methylphenol, and 2-hydroxy-4-methoxybenzophenone.

[0017] The present invention also provides a method for preparing a mildew-proof, antibacterial, halogen-free flame-retardant PVC composite material, comprising the following steps: mixing PVC resin, modified Mg(OH)2 micro powder, modified inorganic compound mildew-proof and antibacterial agent, plasticizer, antioxidant and stabilizer, extruding and granulating to obtain a halogen-free flame-retardant PVC composite material.

[0018] Preferably, the extrusion granulation temperature is 110–165°C, the current is 100–160A, and the pressure is ≤10MPa.

[0019] The present invention also provides a method for preparing anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material and the application of the prepared anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material in automotive interiors.

[0020] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] This invention modifies Mg(OH)₂ micropowder and an inorganic compound antifungal and antibacterial agent, improving the interfacial compatibility between Mg(OH)₂ micropowder and the inorganic compound antifungal and antibacterial agent and PVC resin, and forming a stable interfacial bond force. This effectively improves the dispersibility of the inorganic compound antifungal and antibacterial agent and Mg(OH)₂ micropowder in PVC resin, thereby enhancing the antifungal, antibacterial, and flame-retardant properties of the antifungal, antibacterial, and halogen-free flame-retardant PVC composite material. Furthermore, the antifungal, antibacterial, and halogen-free flame-retardant PVC composite material of this invention can be widely used in automotive interior synthetic leather, seats, seat covers, door seals, window seals, panels, and thermal and sound insulation composite materials, greatly improving the flame retardancy and antifungal and antibacterial properties of automotive interior products, resulting in immeasurable economic and social benefits. Detailed Implementation

[0022] This invention provides a mildew-resistant, antibacterial, halogen-free, flame-retardant PVC composite material, comprising the following components in parts by weight: 20-70 parts PVC resin, 10-60 parts modified Mg(OH)2 micro powder, 1-5 parts modified inorganic compound mildew-resistant and antibacterial agent, 1-2 parts plasticizer, 0.2-1 part antioxidant, and 0.5-1 part stabilizer; wherein the modified Mg(OH)2 micro powder is prepared from Mg(OH)2 micro powder, an interface modifying compound agent, and a lubricant; and the modified inorganic compound mildew-resistant and antibacterial agent is prepared from an inorganic compound mildew-resistant and antibacterial agent and a surface modifier.

[0023] In this invention, the PVC resin is preferably 30-60 parts, more preferably 40-55 parts, and even more preferably 45 parts; the modified Mg(OH)2 micro powder is preferably 20-50 parts, more preferably 30-40 parts, and even more preferably 35 parts; the modified inorganic compound antifungal and antibacterial agent is preferably 1.5-4.5 parts, more preferably 2-4 parts, and even more preferably 2.5 parts; the plasticizer is preferably 1.2-1.8 parts, more preferably 1.4-1.6 parts, and even more preferably 1.5 parts; the antioxidant is preferably 0.3-0.8 parts, more preferably 0.4-0.6 parts, and even more preferably 0.5 parts; and the stabilizer is preferably 0.6-0.9 parts, more preferably 0.7-0.8 parts, and even more preferably 0.75 parts.

[0024] In this invention, the preparation method of the modified Mg(OH)2 micro powder includes the following steps: mixing Mg(OH)2 micro powder, interface modifier compound and lubricant, and heating to obtain modified Mg(OH)2 micro powder.

[0025] In this invention, the mass ratio of the Mg(OH)2 micro powder, the interface modifier compound and the lubricant is 100:1~2.5:0.5~2, preferably 100:1.2~2:0.8~1.5, and more preferably 100:1.5~1.6:1~1.2.

[0026] In this invention, the particle size of the Mg(OH)2 micro powder is preferably 400-6000 mesh, more preferably 1000-5000 mesh, and even more preferably 2000-4000 mesh.

[0027] In this invention, the interface-modifying compound agent includes two or more of the following: silane coupling agent, isocyanate, titanate, stearic acid, oleic acid, sodium oleate, and sodium dodecyl sulfonate; the lubricant includes one or more of the following: N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, PE wax, and zinc stearate.

[0028] In this invention, the stirring rate during the preparation of the modified Mg(OH)2 micro powder is preferably 400-800 r / min, more preferably 500-700 r / min, and even more preferably 600 r / min.

[0029] In this invention, the heating temperature during the preparation of the modified Mg(OH)2 micro powder is 70-110℃, preferably 80-105℃, and more preferably 100℃; the heating time is 6-15 min, preferably 8-12 min, and more preferably 10 min.

[0030] In this invention, the preparation method of the modified inorganic compound antifungal and antibacterial agent includes the following steps: mixing the inorganic compound antifungal and antibacterial agent and the surface modifier, and heating them to obtain the modified inorganic compound antifungal and antibacterial agent.

[0031] In this invention, the mass ratio of the inorganic compound antifungal and antibacterial agent to the surface modifier is 100:0.5 to 1.5, preferably 100:0.7 to 1.2, and more preferably 100:0.8 to 1.

[0032] In this invention, the inorganic compound antifungal and antibacterial agent includes two or more of nano silver, silver oxide, copper oxide, cuprous oxide, copper sulfate, zinc oxide, zinc iodide, calcium phosphate, titanium dioxide, and tin dioxide; the surface modifier includes one or more of silane coupling agent, titanate, aluminate, zinc stearate, and PE wax.

[0033] In this invention, the stirring rate during the preparation of the modified inorganic compound antifungal and antibacterial agent is preferably 400-800 r / min, more preferably 500-700 r / min, and even more preferably 600 r / min.

[0034] In this invention, the heating temperature during the preparation of the modified inorganic compound antifungal and antibacterial agent is 60-100°C, preferably 75-95°C, more preferably 80-90°C, and even more preferably 85°C; the heating time is 6-15 min, preferably 8-13 min, and even more preferably 11 min.

[0035] In this invention, the plasticizer includes one or more of phthalates, fatty diesters, phosphate esters, tricarboxylic acid esters, diol esters, and polyesters. The phthalates preferably include dioctyl phthalate and / or dibutyl phthalate. The fatty diesters include one or more of di(2-ethylhexyl) adipate, di(2-ethylhexyl) sebate, and dibutyl sebate. The phosphate esters preferably include one or more of tricresyl phosphate, triphenyl phosphate, and tri(2-ethylhexyl) phosphate.

[0036] In this invention, the antioxidants include phosphite antioxidants and / or hindered phenolic antioxidants. Preferably, the phosphite antioxidants include one or more of triphenyl phosphite, diisooctyl phenyl phosphite, and diphenyl octyl phosphite. Preferably, the hindered phenolic antioxidants include one or more of 2,6-di-tert-butyl-4-methylphenol, tea polyphenols, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), and 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246).

[0037] In this invention, the stabilizer includes one or more of the following: octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, pentaerythritol tetrakis(4-hydroxy-3,5-di-tert-butylphenylpropionate), triphenyl phosphite, 2,6-tert-butyl-4-methylphenol, and 2-hydroxy-4-methoxybenzophenone.

[0038] The present invention also provides a method for preparing the above-mentioned anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material, comprising the following steps: mixing PVC resin, modified Mg(OH)2 micro powder, modified inorganic compound anti-mildew and antibacterial agent, plasticizer, antioxidant and stabilizer, extruding and granulating to obtain halogen-free flame-retardant PVC composite material.

[0039] In this invention, the extrusion granulation temperature is 110–165°C, preferably 120–160°C, more preferably 130–150°C, and even more preferably 140°C; the current is 100–160A, preferably 110–150A, more preferably 120–140A, and even more preferably 130A; the pressure is ≤10MPa, preferably 8–9MPa, more preferably 7–8MPa, and even more preferably 6–7MPa.

[0040] In this invention, the mixing time during the preparation of the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material is preferably 8 to 30 minutes, more preferably 10 to 20 minutes, and even more preferably 15 minutes. The mixing stirring rate is preferably 400 to 800 r / min, more preferably 500 to 700 r / min, and even more preferably 600 r / min.

[0041] The present invention also provides an application of the anti-mildew, antibacterial, halogen-free, flame-retardant PVC composite material prepared by the above-mentioned method in automotive interiors, wherein the automotive interiors include one of synthetic leather, seats, seat covers, door seals, window seals, panels, and heat and sound insulation composite materials.

[0042] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0043] Example 1

[0044] Preparation of modified Mg(OH)2 micro powder: 1 kg of Mg(OH)2 micro powder with a particle size of 2000-3000 mesh was dried at 105℃ for 2 hours for later use. The dried Mg(OH)2 micro powder was added to a temperature-controlled high-speed mixer with stearic acid, silane coupling agent KH570 and N,N'-ethylenebisstearamide in a mass ratio of 25:0.2:0.2:0.3. The mixture was reacted at a stirring rate of 600 r / min and a reaction temperature of 100℃ for 15 min to obtain modified Mg(OH)2 micro powder.

[0045] Preparation of modified inorganic compound antifungal and antibacterial agent: 0.2 kg of inorganic compound antifungal and antibacterial agent (silver oxide and titanium dioxide in a mass ratio of 3:1) and 0.002 kg of silane coupling agent KH570 were added to a temperature-controlled high-speed mixer and reacted at a stirring rate of 600 r / min and a reaction temperature of 85℃ for 11 min to obtain the modified inorganic compound antifungal and antibacterial agent.

[0046] Preparation of anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material: 55 parts by weight of PVC resin, 3 parts by weight of modified inorganic compound anti-mildew and antibacterial agent, 38 parts by weight of modified Mg(OH)2 micro powder, 1.5 parts by weight of dioctyl phthalate, 0.5 parts by weight of diisooctyl phenyl phosphite, and 1.0 part by weight of octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate were added to a high-speed mixer and stirred at 600 r / min for 15 min until uniformly mixed. The uniformly mixed material was then added to a twin-screw extruder and extruded and granulated under the conditions of 160℃, 130A current, and 7MPa pressure to obtain the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material.

[0047] Example 2

[0048] Modified Mg(OH)2 micro powder was prepared using the method described in Example 1.

[0049] Preparation of modified inorganic compound antifungal and antibacterial agent: 0.2 kg of inorganic compound antifungal and antibacterial agent (silver oxide and titanium dioxide in a mass ratio of 1:1) and 0.002 kg of silane coupling agent KH570 were added to a temperature-controlled high-speed mixer and reacted at a stirring rate of 600 r / min and a reaction temperature of 85℃ for 11 min to obtain the modified inorganic compound antifungal and antibacterial agent.

[0050] Preparation of anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material: 55 parts by weight of PVC resin, 3 parts by weight of modified inorganic compound anti-mildew and antibacterial agent, 38 parts by weight of modified Mg(OH)2 micro powder, 1.5 parts by weight of dioctyl phthalate, 0.5 parts by weight of diisooctyl phenyl phosphite, and 1.0 part by weight of octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate were added to a high-speed mixer and stirred at 600 r / min for 15 min until uniformly mixed. The uniformly mixed material was then added to a twin-screw extruder and extruded and granulated under the conditions of 160℃, 130A current, and 7MPa pressure to obtain the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material.

[0051] Example 3

[0052] Modified Mg(OH)2 micro powder was prepared using the method described in Example 1.

[0053] Preparation of modified inorganic compound antifungal and antibacterial agent: 0.2 kg of inorganic compound antifungal and antibacterial agent (silver oxide and titanium dioxide in a mass ratio of 1:3) and 0.002 kg of silane coupling agent KH570 were added to a temperature-controlled high-speed mixer and reacted at a stirring rate of 600 r / min and a reaction temperature of 85℃ for 11 min to obtain the modified inorganic compound antifungal and antibacterial agent.

[0054] Preparation of anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material: 55 parts by weight of PVC resin, 3 parts by weight of modified inorganic compound anti-mildew and antibacterial agent, 38 parts by weight of modified Mg(OH)2 micro powder, 1.5 parts by weight of dioctyl phthalate, 0.5 parts by weight of diisooctyl phenyl phosphite, and 1.0 part by weight of octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate were added to a high-speed mixer and stirred at 600 r / min for 15 min until uniformly mixed. The uniformly mixed material was then added to a twin-screw extruder and extruded and granulated under the conditions of 160℃, 130A current, and 7MPa pressure to obtain the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material.

[0055] Example 4

[0056] The only difference between Example 4 and Example 1 is that, in the process of preparing the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material, the PVC resin is 45 parts and the modified Mg(OH)2 micro powder is 48 parts.

[0057] Example 5

[0058] The only difference between Example 5 and Example 2 is that, in the process of preparing the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material, the PVC resin is 45 parts and the modified Mg(OH)2 micro powder is 48 parts.

[0059] Example 6

[0060] The only difference between Example 6 and Example 3 is that, in the process of preparing the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material, the PVC resin is 45 parts and the modified Mg(OH)2 micro powder is 48 parts.

[0061] Example 7

[0062] The only difference between Example 7 and Example 1 is that, in the process of preparing the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material, the amount of PVC resin is 35 parts and the amount of modified Mg(OH)2 micro powder is 58 parts.

[0063] Example 8

[0064] The only difference between Example 8 and Example 2 is that, in the process of preparing the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material, the PVC resin is 35 parts and the modified Mg(OH)2 micro powder is 58 parts.

[0065] Example 9

[0066] The only difference between Example 9 and Example 3 is that, in the process of preparing the mildew-proof, antibacterial, halogen-free flame-retardant PVC composite material, the PVC resin is 35 parts and the modified Mg(OH)2 micro powder is 58 parts.

[0067] Example 10

[0068] The only difference between Example 10 and Example 1 is that: in the process of preparing the modified inorganic compound antifungal and antibacterial agent, the amount of silane coupling agent KH570 added is 0.0018 kg; in the process of preparing the antifungal, antibacterial, halogen-free flame-retardant PVC composite material, the amount of modified inorganic compound antifungal and antibacterial agent is 2 parts.

[0069] Example 11

[0070] The only difference between Example 11 and Example 2 is that: in the process of preparing the modified inorganic compound antifungal and antibacterial agent, the amount of silane coupling agent KH570 added is 0.0022 kg; in the process of preparing the antifungal, antibacterial, halogen-free flame-retardant PVC composite material, the amount of modified inorganic compound antifungal and antibacterial agent is 2 parts.

[0071] Example 12

[0072] The only difference between Example 12 and Example 3 is that: in the process of preparing the modified inorganic compound antifungal and antibacterial agent, the amount of silane coupling agent KH570 added is 0.0018 kg; in the process of preparing the antifungal, antibacterial, halogen-free flame-retardant PVC composite material, the amount of modified inorganic compound antifungal and antibacterial agent is 4 parts.

[0073] Example 13

[0074] The only difference between Example 13 and Example 4 is that: in the process of preparing the modified inorganic compound antifungal and antibacterial agent, the amount of silane coupling agent KH570 added is 0.0022 kg; in the process of preparing the antifungal, antibacterial, halogen-free flame-retardant PVC composite material, the amount of modified inorganic compound antifungal and antibacterial agent is 4 parts.

[0075] Example 14

[0076] The only difference between Example 14 and Example 5 is that, in the process of preparing modified Mg(OH)2 micro powder, the mass ratio of Mg(OH)2 micro powder to stearic acid, silane coupling agent KH570 and N,N'-ethylenebisstearamide is 100:0.8:0.7:1.2.

[0077] Example 15

[0078] The only difference between Example 15 and Example 6 is that, in the process of preparing modified Mg(OH)2 micro powder, the mass ratio of Mg(OH)2 micro powder to stearic acid, silane coupling agent KH570 and N,N'-ethylenebisstearamide is 100:0.8:0.9:1.2.

[0079] Example 16

[0080] The only difference between Example 16 and Example 7 is that, in the process of preparing modified Mg(OH)2 micro powder, the mass ratio of Mg(OH)2 micro powder to stearic acid, silane coupling agent KH570 and N,N'-ethylenebisstearamide is 100:0.8:0.7:1.5.

[0081] Example 17

[0082] The only difference between Example 17 and Example 8 is that, in the process of preparing modified Mg(OH)2 micro powder, the mass ratio of Mg(OH)2 micro powder to stearic acid, silane coupling agent KH570 and N,N'-ethylenebisstearamide is 100:0.8:0.8:1.5.

[0083] Example 18

[0084] The only difference between Example 18 and Example 9 is that, in the process of preparing modified Mg(OH)2 micro powder, the mass ratio of Mg(OH)2 micro powder to stearic acid, silane coupling agent KH570 and N,N'-ethylenebisstearamide is 100:0.8:0.9:1.5.

[0085] Comparative Example 1

[0086] The only difference between Comparative Example 1 and Example 1 is that the inorganic compound antifungal and antibacterial agent was not modified.

[0087] Comparative Example 2

[0088] The only difference between Comparative Example 2 and Example 1 is that the Mg(OH)2 micro powder was not modified.

[0089] Forty parts each of the antifungal, antibacterial, halogen-free flame-retardant PVC composite materials prepared in Examples 1-18 and Comparative Examples 1-2 were taken and mixed evenly with 60 parts of PVC. The mixtures were then injection molded at 160°C to prepare standard test strips, and performance tests were performed on the standard test strips. Antibacterial performance, antifungal performance, limiting oxygen index, and vertical flame retardant performance were tested according to national standards GB / T20944.3-2008, GB / T24346-2009, GB / T2046-1993, and UL-94V. The test results are shown in Table 1 below.

[0090] Table 1 Performance test results of anti-mildew, antibacterial, halogen-free flame-retardant PVC composite materials

[0091]

[0092]

[0093] As shown in Table 1, the unmodified Mg(OH)₂ micropowder and inorganic compound antifungal and antibacterial agents (silver oxide and titanium dioxide) in Comparative Examples 1 and 2 did not have ideal effects on improving the antifungal, antibacterial, and flame-retardant properties of PVC products. However, adding the modified Mg(OH)₂ micropowder and inorganic compound antifungal and antibacterial agents (silver oxide and titanium dioxide) to PVC not only improved the antifungal and antibacterial properties of the PVC resin but also effectively improved its flame-retardant rating and limiting oxygen index, while significantly reducing the cost of PVC products. This is because the modified Mg(OH)₂ micropowder and inorganic compound antifungal and antibacterial agents (silver oxide and titanium dioxide) can be uniformly dispersed in the PVC resin, greatly improving the interfacial compatibility between the Mg(OH)₂ micropowder and inorganic compound antifungal and antibacterial agents (silver oxide and titanium dioxide) and the PVC resin, and forming a stable interfacial bond.

[0094] Furthermore, by comparing the performance test results of the antifungal, antibacterial, halogen-free flame-retardant PVC composite materials prepared in Examples 1-18, it can be seen that different amounts of interface modifiers added affect the improvement effect of modified Mg(OH)2 micropowder on the antifungal, antibacterial, and flame-retardant properties of PVC products. Different concentrations of surface modifiers also affect the improvement effect of modified inorganic compound antifungal and antibacterial agents on the antifungal, antibacterial, and flame-retardant properties of PVC products. Specifically, when the mass ratio of Mg(OH)2 micropowder to interface modifier (stearic acid and silane coupling agent KH570 at a mass ratio of 1:1) and lubricant is 100:1.6:1.5, the resulting modified Mg(OH)2 micropowder has the best effect on improving the flame-retardant properties of PVC products; when the mass ratio of inorganic compound antifungal and antibacterial agent to surface modifier is 100:1, the resulting modified inorganic compound antifungal and antibacterial agent has the best effect on improving the antifungal and antibacterial properties of PVC products.

[0095] This invention combines a modified inorganic compound antifungal and antibacterial agent with Mg(OH)2 micro powder and PVC resin, effectively improving the dispersibility of the inorganic compound antifungal and antibacterial agent and Mg(OH)2 in PVC resin. This enhances the antifungal, antibacterial, and flame-retardant properties of the PVC composite material, thereby improving the antifungal, antibacterial, and flame-retardant properties of PVC products made from this PVC composite material. It can be widely used in automotive interior synthetic leather, seats, seat covers, door seals, window seals, panels, and heat and sound insulation composite materials.

[0096] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A mildew-proof, antibacterial, halogen-free, flame-retardant PVC composite material, characterized in that, The components include the following parts by mass: 20-70 parts PVC resin, 10-60 parts modified Mg(OH)2 micro powder, 1-5 parts modified inorganic compound antifungal and antibacterial agent, 1-2 parts plasticizer, 0.2-1 part antioxidant, and 0.5-1 part stabilizer; The modified Mg(OH)2 micro powder is prepared from Mg(OH)2 micro powder, interface modifier compound and lubricant; The modified inorganic compound antifungal and antibacterial agent is prepared by an inorganic compound antifungal and antibacterial agent and a surface modifier; The plasticizer includes one or more of the following: phthalates, fatty acid diesters, phosphate esters, tricarboxylic acid esters, diol esters, and polyesters; The antioxidants include phosphite antioxidants and / or hindered phenolic antioxidants; The stabilizer includes one or more of the following: octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, pentaerythritol tetrakis(4-hydroxy-3,5-di-tert-butylphenylpropionate), triphenyl phosphite, 2,6-tert-butyl-4-methylphenol, and 2-hydroxy-4-methoxybenzophenone. The preparation method of the modified Mg(OH)2 micro powder includes the following steps: Mg(OH)2 micro powder, interface modifier and lubricant are mixed and heated to obtain modified Mg(OH)2 micro powder; The mass ratio of the Mg(OH)2 micro powder, the interface modifier compound, and the lubricant is 100:1~2.5:0.5~2; The interface-modifying compound agent includes two or more of the following: silane coupling agent, isocyanate, titanate, stearic acid, oleic acid, sodium oleate, and sodium dodecyl sulfonate. The lubricant includes one or more of N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, PE wax, and zinc stearate; The heating temperature during the preparation of the modified Mg(OH)2 micro powder is 70~110℃, and the time is 6~15min; The preparation method of the modified inorganic compound antifungal and antibacterial agent includes the following steps: An inorganic compound antifungal and antibacterial agent and a surface modifier are mixed and heated to obtain a modified inorganic compound antifungal and antibacterial agent. The mass ratio of the inorganic compound antifungal and antibacterial agent to the surface modifier is 100:0.5~1.5; The inorganic compound antifungal and antibacterial agent includes two or more of the following: nano silver, silver oxide, copper oxide, cuprous oxide, copper sulfate, zinc oxide, zinc iodide, calcium phosphate, titanium dioxide, and tin dioxide. The surface modifier includes one or more of silane coupling agents, titanates, aluminates, zinc stearate, and PE wax; The modified inorganic compound antifungal and antibacterial agent is prepared by heating at a temperature of 60-100℃ for 6-15 minutes.

2. The preparation method of the anti-mildew, antibacterial, halogen-free flame-retardant PVC composite material according to claim 1, characterized in that, Includes the following steps: PVC resin, modified Mg(OH)2 micro powder, modified inorganic compound antifungal and antibacterial agent, plasticizer, antioxidant and stabilizer are mixed and extruded to obtain halogen-free flame-retardant PVC composite material.

3. The method for preparing a mildew-resistant, antibacterial, halogen-free flame-retardant PVC composite material according to claim 2, characterized in that, The extrusion granulation temperature is 110~165℃, the current is 100~160A, and the pressure is ≤10MPa.

4. The application of the anti-mildew, antibacterial, halogen-free, flame-retardant PVC composite material prepared by the method of any one of claims 2 to 3 in automotive interiors.

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