Low-odor antibacterial skin-touch polypropylene composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a low-odor antibacterial skin-touch polypropylene composite material, a preparation method and application. The low-odor antibacterial skin-touch polypropylene composite material is prepared from the following components in percentage by mass: 48 to 73 percent of polypropylene, 0 to 6 percent of Si-ZnO particles, 15 to 30 percent of thermoplastic composite elastomer master batch, 5 to 40 percent of slipping agent, 0.1 to 1 percent of antioxidant, 0.1 to 1 percent of lubricant and 0.4 to 1 percent of light stabilizer. The Si-ZnO particles are obtained by modifying the surfaces of ZnO particles with a silane coupling agent; the mass ratio of the silane coupling agent to the ZnO particles is (4-5): 1. The invention also discloses a preparation method of the low-odor antibacterial skin-touch polypropylene composite material. The polypropylene composite material prepared by the invention has the advantages of good touch feeling, softness, low odor and antibacterial effect, and can be widely used in the fields of household articles, automotive interiors, building materials and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a low-odor, antibacterial, skin-feel polypropylene composite material, a preparation method and an application thereof. Background Art

[0002] With the development of polypropylene (PP) industry, PP has been widely used in household appliances, automobiles, building materials and other fields in people's lives due to its advantages of high chemical stability, good heat resistance, easy processing, safety, environmental protection and low price. However, as the quality of human production and life gradually develops, consumers have higher and higher requirements for the appearance quality and health and safety of various products in life.

[0003] At present, the surface hardness of products injection molded by polypropylene materials is extremely hard, and in different climates, direct contact with human skin will make people feel extremely uncomfortable, such as cold, hard and odor, etc. In addition, the previous related technical solutions are to add a layer of skin-friendly paint film material, fabric or leather on the surface of the product to improve the consumer experience, but they have not solved the substantive problems, but may cause scratches, spots and odor, etc. Patent CN 112538218 B discloses a low-hardness, low-friction coefficient and good-touch polypropylene composition. The present invention is based on reducing the hardness of the material and enhancing the mechanical properties of the material, and adding an external lubricant with dissolving properties can effectively reduce the friction coefficient of the composition and overcome the deterioration effect of the rubber phase elastomer on the material. Patent CN 118638423 A discloses a skin-friendly material for a one-piece toilet seat. The skin-friendly material in the present invention uses white carbon black as a reinforcing filler and includes polysiloxane materials and modified hollow glass microspheres, wherein the surface-modified hollow glass microspheres can be well bonded to fill the micropores on the surface of silica gel (polysiloxane materials), thereby making the product surface smoother and flatter and improving the anti-fouling and wear-resistant properties. The above solutions have not been able to completely solve the problem of one-time injection molding of materials, including low odor, skin feel, anti-fouling and antibacterial properties. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a low-odor, antibacterial, skin-feel polypropylene composite material, a preparation method and an application thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A low-odor antibacterial skin-feel polypropylene composite material, characterized in that the raw materials for preparing the low-odor antibacterial skin-feel polypropylene composite material include, by mass percentage: 48-73% polypropylene, 0-6% Si-ZnO particles, 15-30% thermoplastic composite elastomer masterbatch, 5-40% lubricant, 0.1-1% antioxidant, 0.1-1% lubricant, and 0.4-1% light stabilizer; the sum of the mass percentages of each component is 100%;

[0007] The Si-ZnO particles are obtained by surface modification of ZnO particles with a silane coupling agent; the mass ratio of the silane coupling agent to the ZnO particles is (4-5):1.

[0008] Furthermore, the melt index of the polypropylene at 230° C. and 2.16 kg is 1 to 100 g / 10 min; and the polypropylene is copolymer polypropylene, homopolypropylene or a combination thereof.

[0009] Furthermore, the preparation method of the Si-ZnO particles is as follows: zinc acetate and lithium hydroxide in a molar ratio of 1:2 are added to ethanol, placed in a water bath at 0°C, stirred for reaction for 1.5 hours, then transferred to a water bath at 60°C, stirred for reaction for 5 hours, and after the reaction is completed, filtered, washed, and vacuum dried to obtain ZnO particles with a particle size of 100 to 200 nm; ZnO particles are mixed with vinyltriethoxysilane in a mass ratio of 1:5, fully stirred at room temperature for 1.5 hours, and filtered to obtain Si-ZnO particles.

[0010] Furthermore, the preparation of the ZnO particles includes: adding zinc salt and lithium hydroxide into ethanol at a molar ratio of 1:2, placing in a water bath and stirring to react, filtering, washing and drying after the reaction is completed.

[0011] Furthermore, the preparation of the thermoplastic composite elastomer masterbatch includes: melting and extruding styrene copolymers, polyolefin copolymers, antioxidants and silicones through an internal mixer; the mass ratio of the styrene copolymers to the polyolefin copolymers is (1-9):(1-9).

[0012] Furthermore, the silicones are silicone masterbatches and silicone liquids; the polyolefin copolymers are ethylene-ethylene copolymers and ethylene-octene copolymers; and the melting temperature of the internal mixer is 150-180°C.

[0013] Furthermore, the lubricant is at least one of calcium carbonate, talc, glass fiber, and white carbon black; the antioxidant is a hindered phenol antioxidant, a phosphite antioxidant, or a combination thereof; the lubricant is at least one of stearate, white oil, TAF, and EBS; and the light stabilizer is at least one of hindered amines, hindered benzoates, benzotriazoles, o-hydroxybenzophenones, and benzylmalonates.

[0014] A method for preparing a low-odor antibacterial skin-feel polypropylene composite material comprises: weighing polypropylene, Si-ZnO particles, thermoplastic composite elastomer masterbatch, slip agent, antioxidant, lubricant and light stabilizer according to their respective mass percentages, then mixing them evenly, and then using a twin-screw extruder to melt, extrude and granulate to obtain the low-odor antibacterial skin-feel polypropylene composite material.

[0015] Furthermore, the screw temperature of the twin-screw extruder is 170-230° C., and the rotation speed is 200-1000 rpm.

[0016] The low-odor, antibacterial, skin-feel polypropylene composite material described above is used as a skin-friendly material in automotive interior products.

[0017] Beneficial effects of the present invention: The low-odor antibacterial skin-feel polypropylene composite material of the present invention can effectively improve the compatibility between polypropylene resin and Si-ZnO material by preparing Si-ZnO particles by self-made method, so that the mechanical properties of polypropylene composite material can meet industrial requirements, and ZnO can slowly release zinc ions, which can effectively kill bacteria and exert the antibacterial property of polypropylene composite material. And Si-ZnO material has the advantages of being non-toxic and tasteless, having good biocompatibility and low cost. At the same time, the thermoplastic composite elastomer is compatible with silicones in the form of high shear to be more evenly dispersed, so that the surface roughness of the material is reduced, so as to solve the problem of forming a typical "island" structure after the polypropylene, filler, Si-ZnO particles and composite elastomer are melt-extruded, giving the polypropylene composite material a soft skin feel and antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0019] Figure 1 This is a SEM image of Si-ZnO particles prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] The technical solution of the present invention is described in detail below through specific embodiments.

[0022] In the following examples and comparative examples:

[0023] The copolymer polypropylene is Hainan PP K8009, with a melt index of 8-11g / cm3;

[0024] Homopolymer polypropylene is Beihai Refining PP Z30S, with a melt index of 20-26 g / cm3;

[0025] The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1;

[0026] The lubricant is at least one of talcum powder, calcium carbonate, glass fiber and white carbon black;

[0027] The lubricant is ethylene bis stearamide;

[0028] Light stabilizers are hindered amines;

[0029] The preparation method of Si-ZnO particles is as follows:

[0030] Zinc acetate and lithium hydroxide in a molar ratio of 1:2 were added to ethanol, placed in a water bath at 0°C, stirred for reaction for 1.5 hours, then transferred to a water bath at 60°C, stirred for reaction for 5 hours, and after the reaction was completed, filtered, washed, and vacuum dried to obtain ZnO particles with a particle size of 100 to 200 nm; ZnO particles were mixed with vinyl triethoxysilane in a mass ratio of 1:5, fully stirred at room temperature for 1.5 hours, and filtered to obtain Si-ZnO particles;

[0031] The preparation method of thermoplastic composite elastomer masterbatch is as follows:

[0032] Different proportions of styrene copolymers and polyolefin copolymers, antioxidants, and silicones are melted and high-sheared in an internal mixer; the product obtained by the mass ratio of the styrene copolymer to the polyolefin copolymer being 10:90 is recorded as a thermoplastic composite elastomer A; the product obtained by the mass ratio of the styrene copolymer to the polyolefin copolymer being 30:70 is recorded as a thermoplastic composite elastomer B; the product obtained by the mass ratio of the styrene copolymer to the polyolefin copolymer being 50:50 is recorded as a thermoplastic composite elastomer C; the product obtained by the mass ratio of the styrene copolymer to the polyolefin copolymer being 70:30 is recorded as a thermoplastic composite elastomer D; the product obtained by the mass ratio of the styrene copolymer to the polyolefin copolymer being 90:10 is recorded as a thermoplastic composite elastomer E;

[0033] The component formulas of Examples 1 to 16 and Comparative Examples 1 to 4 are shown in Table 1 and Table 2:

[0034] Table 1

[0035]

[0036]

[0037] Table 2

[0038]

[0039]

[0040] According to the formulas in Table 1 and Table 2, the raw materials were weighed and put into a high-speed mixer for mixing at a mixing speed of 400 rpm / min for 2 to 3 minutes. Then, the raw materials were transferred to the main feeding hopper of a twin-screw extruder and melt-extruded and granulated at a temperature of 180-220° C. to obtain pellets.

[0041] The pellets prepared in the above-mentioned comparative examples were injection molded and tested for performance under the same conditions according to the following standards:

[0042] Tensile properties: tested according to GB / T 1040-2006 standard, the tensile rate is 50mm / min;

[0043] Odor level: tested according to Volkswagen PV3900 standard;

[0044] Antibacterial performance test: Determined according to the method of GB / T 31402-2015;

[0045] Skin feel test: The test method includes the tester touching a 100mm*120mm large board with his hands to evaluate the smoothness (delicate and smooth feeling): to see whether it has a delicate and smooth feeling. The large board with good skin-friendliness feels very delicate and smooth. Multiple groups of parallel experiments are used, and 6 people are selected in each group for testing. The skin feel evaluation is scored and the average score is calculated. The full score for each person is 10 points. The higher the score, the better the skin feel effect / elasticity.

[0046] The test results are shown in Table 3 and Table 4:

[0047] Table 3

[0048]

[0049]

[0050] Table 4

[0051]

[0052] It can be seen from the results in the table that the polypropylene composite materials of various embodiments prepared by the present invention have the characteristics of good touch, softness, low odor, antibacterial, etc., which improves the competitiveness of the products.

[0053] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0054] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A low-odor antibacterial skin-feel polypropylene composite material, characterized in that: The raw materials for preparing the low-odor antibacterial skin-feel polypropylene composite material include, by mass percentage, 48-73% polypropylene, 0-6% Si-ZnO particles, 15-30% thermoplastic composite elastomer masterbatch, 5-40% lubricant, 0.1-1% antioxidant, 0.1-1% lubricant, and 0.4-1% light stabilizer; the sum of the mass percentages of each component is 100%; The Si-ZnO particles are obtained by surface modification of ZnO particles with a silane coupling agent; the mass ratio of the silane coupling agent to the ZnO particles is (4-5):

1.

2. The low-odor antibacterial skin-feel polypropylene composite material according to claim 1, characterized in that: The melting index of the polypropylene at 230° C. and 2.16 kg is 1 to 100 g / 10 min; the polypropylene is copolymer polypropylene, homopolymer polypropylene or a combination thereof.

3. The low-odor antibacterial skin-feel polypropylene composite material according to claim 1, characterized in that: The preparation method of the Si-ZnO particles is as follows: zinc acetate and lithium hydroxide in a molar ratio of 1:2 are added to ethanol, placed in a water bath at 0°C, stirred for reaction for 1.5 hours, then transferred to a water bath at 60°C, stirred for reaction for 5 hours, and after the reaction is completed, filtered, washed, and vacuum dried to obtain ZnO particles with a particle size of 800-1200 nm; ZnO particles and vinyl triethoxysilane are mixed in a mass ratio of 1:5, fully stirred at room temperature for 1.5 hours, and filtered to obtain Si-ZnO particles.

4. The low-odor antibacterial skin-feel polypropylene composite material according to claim 3, characterized in that: The preparation of the ZnO particles comprises: adding zinc salt and lithium hydroxide into ethanol at a molar ratio of 1:2, placing in a water bath and stirring to react, filtering, washing and drying after the reaction is completed, to obtain the ZnO particles.

5. The low-odor antibacterial skin-feel polypropylene composite material according to claim 1, characterized in that: The preparation of the thermoplastic composite elastomer masterbatch comprises: melting and extruding a styrene copolymer, a polyolefin copolymer, an antioxidant and a silicone through an internal mixer; the mass ratio of the styrene copolymer to the polyolefin copolymer is (1-9):(1-9).

6. The low-odor antibacterial skin-feel polypropylene composite material according to claim 5, characterized in that: The silicones are silicone masterbatches and silicone liquids; the polyolefin copolymers are ethylene-ethylene copolymers and ethylene-octene copolymers; and the melting temperature of the internal mixer is 150-180°C.

7. The low-odor antibacterial skin-feel polypropylene composite material according to claim 1, characterized in that: The lubricant is at least one of calcium carbonate, talc, glass fiber, and white carbon black; the antioxidant is a hindered phenol antioxidant, a phosphite antioxidant, or a combination thereof; the lubricant is at least one of stearate, white oil, TAF, and EBS; the light stabilizer is at least one of hindered amines, hindered benzoates, benzotriazoles, o-hydroxybenzophenones, and benzylmalonates.

8. A method for preparing a low-odor antibacterial skin-feel polypropylene composite material, characterized in that: include: The raw materials of polypropylene, Si-ZnO particles, thermoplastic composite elastomer masterbatch, slip agent, antioxidant, lubricant and light stabilizer are weighed according to the mass percentage of claim 1, then mixed evenly, and then melted, extruded and granulated by a twin-screw extruder to obtain a low-odor antibacterial skin-feel polypropylene composite material.

9. The method for preparing a low-odor antibacterial skin-feel polypropylene composite material according to claim 8, characterized in that: The screw temperature of the twin-screw extruder is 170-230° C., and the rotation speed is 200-1000 rpm.

10. Use of the low-odor, antibacterial, skin-feel polypropylene composite material as claimed in any one of claims 1 to 7 as a skin-friendly material in automotive interior products.

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