Odorless antimicrobial polymer-based composite and method of making the same

Abstract

The present application relates to a kind of odorless antibacterial polymer-based composite and its preparation method.The odorless antibacterial polymer-based composite includes the following components, by weight parts:20~30 parts modified waterborne epoxy resin, 5~20 parts waterborne epoxy resin curing agent, 5~10 parts dispersing agent, 5~10 parts defoaming agent, 5~10 parts leveling agent, 5~10 parts film forming aid, 5~10 parts modified glass fiber, 20~30 parts filler, 5~10 parts antibacterial agent, 3~8 parts antioxidant, 20~30 parts water.The present application has excellent performance, such as good adhesion, corrosion resistance, good mechanical properties, good antibacterial property, good weather resistance, water resistance, etc.Because modified four acicular zinc oxide whisker is compounded with zinc ethylene bisdithiocarbamate, the problem of poor compatibility with odorless antibacterial polymer-based composite when modified four acicular zinc oxide is added alone is also changed, and the surface hardness is also increased, thereby increasing the service life.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antibacterial composite materials, in particular to a non-odor antibacterial polymer-based composite material and a preparation method thereof. BACKGROUND

[0002] Polymer-based composite material is a material composed of polymer matrix and other reinforcing materials, which has the advantages of light weight, high strength, corrosion resistance, etc., and is widely used in various fields. However, with the continuous expansion of application fields, the antibacterial property of polymer-based composite material has become an important index.

[0003] Epoxy floor paint has good water and oil resistance, chemical corrosion resistance, high hardness, high wear resistance, superior adhesion, etc., and is color beautiful and easy to maintain, with superior overall comprehensive performance, and is widely used in modern buildings such as factories, shopping malls, garages, home decoration, etc., and has an important position in the floor industry.

[0004] Traditional water-based epoxy floor paint is deficient in weather resistance except for outdoor use, and needs to be further improved in construction process. For example, in some construction environments with frequent rain, a water-based epoxy floor paint with fast curing speed, good hardness, scratch resistance within 24 hours, and moderate pot life is needed. However, the traditional water-based epoxy floor paint has the disadvantages of slow drying speed and long recoat time, etc., and further improving the drying speed (such as lower surface drying time) and hardening time of water-based epoxy floor paint while ensuring the product's wear resistance, hardness, adhesion, scratch resistance and chemical resistance, etc. has become another development direction of water-based epoxy floor paint.

[0005] Tetrapod-shaped zinc oxide whisker, referred to as T-ZnO whisker, is a special form of zinc oxide, which has a regular tetrapod-shaped three-dimensional structure, i.e. the whisker has a core, and four needle-shaped crystals extend radially from the core. It is due to its unique three-dimensional structure that it has many special functions, such as heat conduction, piezoelectricity, pressure sensitivity, wave absorption, sound absorption, vibration reduction, antibacterial, algae prevention, catalysis, etc. Using the nano activity of the tip of tetrapod-shaped zinc oxide, bacteria and their debris can be efficiently killed and eliminated. The composite antibacterial agent and antibacterial material made by adding an appropriate amount of needle-shaped zinc oxide has a killing rate of more than 99% for common bacteria such as Staphylococcus aureus, Escherichia coli, Candida albicans and Salmonella.

[0006] The T-ZnO whisker tip is in the nanometer level or finer level, and the nanometer active component can effectively kill and remove bacteria and their residues, and can also decompose the toxins secreted by the bacteria, and has a significant antibacterial effect. Meanwhile, the atomic oxygen with strong oxidation activity in the T-ZnO whisker lattice can destroy the biological activity and metabolic reproduction function of most bacteria, so as to achieve the antibacterial purpose. The zinc oxide whisker samples doped with iron, copper and silver have good antibacterial and formaldehyde decomposition effects. The killing rate of the T-ZnO whisker resin-based composite material on Escherichia coli and Pseudomonas aeruginosa is 99%.

[0007] The T-ZnO whisker has good wear resistance and can improve the anti-skid performance of materials. Tests show that the T-ZnO whisker applied to rubber, paint and plastic can achieve satisfactory anti-skid effect. Meanwhile, the T-ZnO whisker can effectively convert the absorbed mechanical energy into heat energy and be lost, thereby playing a significant damping role. Meanwhile, the T-ZnO whisker can also absorb sound vibration and convert it into heat energy, so that the material has sound absorption function and achieves sound insulation effect. Finally, the T-ZnO whisker can also be used for air freshening and deodorizing agent.

[0008] CN106811006B discloses a water-based epoxy floor paint composition and preparation method which can be used outdoors. The water-based epoxy floor paint composition comprises two components A and B, and the mass ratio of A to B is 80-150:100. The A component is an acrylic resin hybrid modified water-based epoxy resin, and the epoxy equivalent weight of the acrylic resin hybrid modified water-based epoxy resin is 800-1500. The water-based epoxy floor paint of the invention belongs to a water-based system and does not contain VOC, and is a green and environmentally friendly water-based epoxy floor paint. However, the water-based epoxy floor paint of the invention does not have antibacterial function and has poor comprehensive performance.

[0009] CN102578148B discloses a method for improving the antibacterial performance of four needle-shaped zinc oxide whiskers. The synthesis steps of the invention are as follows: A, add white powder-shaped four needle-shaped zinc oxide whiskers to a potassium sodium tartrate aqueous solution to form a paste or suspension, stir for 10-30 minutes, the molar ratio of potassium sodium tartrate to four needle-shaped zinc oxide whiskers is (0.1-1):100, then slowly add an aqueous solution of copper chloride with the same molar amount of potassium sodium tartrate under stirring; then continue stirring for 30-60 minutes; finally, filter, wash and dry to obtain four needle-shaped zinc oxide whisker composite powder with nano copper tartrate deposited on the surface in situ; B, heat the composite powder to 270-300℃ in a hydrogen atmosphere, keep warm for 15-60 minutes, and cool to room temperature. Although the antibacterial performance of the four needle-shaped silver oxide whiskers is improved by surface modification, the preparation process may not meet the purification standard and may leave toxic and harmful substances such as copper oxide. SUMMARY

[0010] The present application provides a non-odor antibacterial polymer-based composite material, and the preparation steps are as follows, in parts by weight:

[0011] Step 1, first add 20-30 parts of water in a container, continue to add 5-10 parts of dispersing agent, 5-10 parts of defoaming agent, stir for 3-5 min, the stirring speed is 200-300 rpm; continue to add 20-30 parts of filler, 5-10 parts of modified glass fiber, stir for 40-60 min, the stirring speed is 900-1000 rpm; until the slurry fineness is less than 40 μm, continue to add 5-20 parts of water-based epoxy resin curing agent, 5-10 parts of leveling agent, 5-10 parts of antibacterial agent, 3-8 parts of antioxidant, stir for 10-20 min, the stirring speed is 200-300 rpm, to obtain component A;

[0012] Step 2, mix and stir 20-30 parts of modified water-based epoxy resin with 5-10 parts of film-forming aid, the stirring time is 30-40 min, the stirring speed is 800-900 rpm, to obtain component B;

[0013] Step 3, mix and stir component A and component B, the mixing mass ratio of component A to component B is (100-180):100, the stirring time is 30-40 min, the stirring speed is 800-900 rpm; to obtain the non-odor antibacterial polymer-based composite material.

[0014] The modified water-based epoxy resin is made of emulsifier and epoxy resin, the epoxy resin is at least one of bisphenol A type epoxy resin, E51 epoxy resin, E44 epoxy resin, alicyclic epoxy resin, bisphenol F type epoxy resin, and phenolic epoxy resin; more preferably, the epoxy resin is bisphenol A type epoxy resin.

[0015] The emulsifier is at least one of pure acrylic emulsion, vinyl acetate acrylic emulsion, and styrene acrylic emulsion; more preferably, the emulsifier is styrene acrylic emulsion.

[0016] The mass ratio of the epoxy resin and the emulsifier is 100: (10-20); more preferably, the mass ratio of the epoxy resin and the emulsifier is 100:15.

[0017] The water-based epoxy resin curing agent is at least one of polyamide, isophorone diamine, cyclohexanediamine, methylcyclopentadienyl diamine, polyoxypropylene triamine, and polyoxyethylene diamine; more preferably, the water-based epoxy resin curing agent is polyamide.

[0018] The dispersant is at least one of DISPERS-188A, BYK-180, BYK-190, EFKA-4560, W-511, FA-182, EFKA-4550, and W-518; more preferably, the dispersant is BYK-190.

[0019] The defoaming agent is at least one of HS-334, LG-20GB, SXP-120, LG-10, CF-328, CF-698, Foamex 1488, and BYK-020; more preferably, the defoaming agent is Foamex 1488.

[0020] The leveling agent is at least one of BYK-346, BLD-533, BLD-511, Sancure 621N, TEGO Twin 4100, W-77, W-461, BYK-333, and TEGO Twin 4000; more preferably, the leveling agent is BYK-333.

[0021] The film-forming aid is at least one of ethanol, methoxybutanol, and benzyl alcohol; more preferably, the film-forming aid is benzyl alcohol.

[0022] The modified glass fiber is prepared as follows, in parts by weight:

[0023] S1: immerse 5-10 parts of glass fiber in 10-20 parts of a 3-5% mass fraction hydrofluoric acid aqueous solution for 20-50 seconds, continue to clean and dry, and reserve;

[0024] S2: mix 2-3 parts of alkoxysilane, 1-2 parts of a capping agent, 20-30 parts of an organic solvent, and 1-2 parts of a catalyst at 40-80°C, and react for 2-3 hours to obtain modified glass fiber.

[0025] The glass fiber has a diameter of 20-60 μm and a length of 50-300 mm; more preferably, the glass fiber has a diameter of 30 μm and a length of 100 mm.

[0026] The alkoxysilane is at least one of dimethoxymethylvinylsilane, vinyltriethoxysilane, propenyltriethoxysilane, and phenyltriethoxysilane; more preferably, the alkoxysilane is dimethoxymethylvinylsilane.

[0027] The end-capping agent is at least one of hexamethyldisiloxane, methyltriethoxysilane, and tetramethyldivinyl disiloxane; more preferably, the end-capping agent is methyltriethoxysilane.

[0028] The organic solvent is at least one of tetrahydrofuran, methanol, toluene, n-hexane, and chloroform; more preferably, the organic solvent is toluene.

[0029] The catalyst is at least one of sulfuric acid, phosphoric acid, hydrochloric acid, and perchloric acid; more preferably, the catalyst is phosphoric acid.

[0030] The mass fraction of the phosphoric acid is 3-5%; more preferably, the mass fraction of the phosphoric acid is 5%.

[0031] The filler is at least one of rutile titanium dioxide, talc powder, mica, quartz powder, and nano-alumina; more preferably, the filler is rutile titanium dioxide.

[0032] The antibacterial agent is at least one of suberic acid modified four-needle zinc oxide whiskers, nano-zinc oxide, zinc ethylene bis-dithiocarbamate, and zinc pyrithione; preferably, the antibacterial agent is a mixture of zinc ethylene bis-dithiocarbamate and suberic acid modified four-needle zinc oxide whiskers in a mass ratio of (1-3):1.

[0033] The suberic acid modified four-needle zinc oxide whiskers are prepared as follows, by weight:

[0034] X1 adds 5-10 parts of suberic acid to 30-50 parts of anhydrous ethanol, and performs ultrasonic oscillation at a frequency of 20-50 KHz for 30-50 min, so that the suberic acid is completely dissolved and dispersed in the anhydrous ethanol;

[0035] X2 adds 5-10 parts of dried four-needle zinc oxide whiskers to X1, and performs ultrasonic oscillation at a frequency of 20-50 KHz for 30-50 min, and then continues to stir at 40-50℃ for 30-60 min at a stirring speed of 500-800 r / min, and then filters to obtain suberic acid modified four-needle zinc oxide whiskers.

[0036] The antioxidant is at least one of antioxidant 1010, antioxidant 168, 2,6-di-tert-butyl-p-cresol, N,N'-di-sec-butyl-p-phenylenediamine, and trisnonylphenyl phosphite; more preferably, the antioxidant is trisnonylphenyl phosphite.

[0037] The roles of the main raw materials in the present application are introduced as follows:

[0038] The waterborne epoxy resin curing agent: the mechanism of the waterborne epoxy curing agent in the role of the odorless antibacterial polymer-based composite material mainly includes curing reaction and crosslinking reaction. 1. First, the waterborne epoxy curing agent and the epoxy group in the epoxy resin occur ring-opening reaction to generate hydroxyl group, and further react with the epoxy group to generate ether bond. This process makes the curing agent and the epoxy resin closely combined together to form a network structure; 2. Secondly, the multifunctional groups in the waterborne epoxy curing agent and the active groups such as hydroxyl group and ether bond in the epoxy resin occur crosslinking reaction to generate three-dimensional network structure, so that the physical properties and chemical properties of the coating film are improved. The crosslinking reaction can improve the hardness, toughness, wear resistance, corrosion resistance and other properties of the coating film; 3. In addition, the waterborne epoxy curing agent can also improve the construction performance and drying performance of the coating. The waterborne epoxy curing agent can accelerate the drying speed of the coating, reduce the construction waiting time, and improve the chemical property stability of the coating. At the same time, it can also strengthen the physical properties of the material, improve the resistance of the material, make the floor more clean and more durable.

[0039] In summary, the mechanism of the waterborne epoxy curing agent in the role of the odorless antibacterial polymer-based composite material is to improve the performance and construction performance of the coating through curing reaction and crosslinking reaction, and to improve the hardness, toughness, wear resistance, corrosion resistance and other properties of the coating film.

[0040] Wetting dispersant BYK-190: If the pigment is dispersed in the epoxy resin, the dispersion efficiency will not be high due to the viscosity of the resin. If the curing agent contains a surface active segment, it has a certain wetting dispersing ability, and theoretically it can be used without dispersant. Considering the compatibility of conductive pigments with other ingredients and striving to disperse good conductive pigments in a short time, it is necessary to choose the right wetting dispersant. The mechanism of action of wetting dispersant BYK-190 in odorless antibacterial polymer-based composites mainly includes wetting, dispersing and stabilizing effects. 1. First, BYK-190 can help odorless antibacterial polymer-based composites wet the pigment and filler better through its wetting effect, improving the leveling and application performance of the coating; 2. Secondly, the dispersing effect of BYK-190 can prevent pigment flocculation, keep the color and tinting strength of the coating and pigment paste stable, and reduce the floating color and flower phenomenon in the pigment mixture, which helps to improve the color strength and hiding power of the coating film; 3. In addition, BYK-190 also has a stabilizing effect, which can increase the storage stability of the system. It can make the pigment deflocculate through steric hindrance stabilization, and due to the small particle size of the deflocculated pigment, high gloss and color strength can be obtained, and the hiding power of transparent pigments will also be improved. In addition, due to the reduction of viscosity, the flowability can also be improved, and the content of pigments can be increased.

[0041] In summary, the mechanism of action of wetting dispersant BYK-190 in odorless antibacterial polymer-based composites is to improve the performance and application performance of the coating through wetting, dispersing and stabilizing effects, and to improve the gloss, color strength and hiding power of the coating film and other properties.

[0042] Defoamer Foamex 1488: Defoamers should be considered because some ingredients have surface-active effects and can easily form foam; air can be entrained during application; the film density is not sufficient, with micropores; film thickness affects the speed of bubble discharge. The combination of antifoam and defoamer will be better. The mechanism of defoamer Foamex 1488 in odorless antibacterial polymer-based composites is mainly to reduce the surface tension of foam and destroy the stability of foam, thereby eliminating foam. During the production and application of odorless antibacterial polymer-based composites, bubbles or foam are easily generated due to the involvement of various chemicals and complex reaction processes. These bubbles can seriously affect the flowability, application performance, and film quality of the paint. Defoamer Foamex 1488 is an organic silicone polymer with low surface tension and good defoaming performance. It can effectively eliminate bubbles in odorless antibacterial polymer-based composites and improve the flowability and application performance of the paint. The mechanism of defoamer Foamex 1488 includes the following aspects: 1. Reducing surface tension: defoamer Foamex 1488 has a low surface tension that can effectively wet the surface of the foam, reducing the elasticity of the foam and making it easy to break; 2. Destroying foam stability: defoamer Foamex 1488 can penetrate into the interior of the foam, changing the local surface tension of the foam and causing it to break; 3. Preventing foam regeneration: defoamer Foamex 1488 can inhibit the regeneration of foam, thereby maintaining the stability and application performance of the paint.

[0043] In summary, the mechanism of defoamer Foamex 1488 in odorless antibacterial polymer-based composites is to eliminate bubbles by reducing surface tension, destroying foam stability, and inhibiting foam regeneration, thereby improving the flowability and application performance of the paint and enhancing the film quality.

[0044] Leveling agent BYK-333: The surface tension of water is relatively high, and the wetting of the substrate is weak. At the same time, the film can be fully leveled within a limited time, ensuring that the gloss is not compromised. The mechanism of leveling agent BYK-333 in odorless antibacterial polymer-based composites mainly includes reducing surface tension, improving wettability, and eliminating orange peel or Benard vortex caused by surface tension differences during the drying process. 1. Reducing surface tension: leveling agent BYK-333 needs to have certain compatibility with the system, and its surface tension needs to be lower than the system. This way, migration can occur on the surface of the paint film, and then the leveling effect can be achieved; 2. Improving wettability: leveling agent BYK-333 can reduce the surface tension of paints and printing inks, improve substrate wetting, and prevent shrinkage. In water-based systems, it can improve anti-blocking properties; 3. Eliminating orange peel or Benard vortex caused by surface tension differences during the drying process: this is mainly achieved by reducing the surface tension of the film and improving the consistency of the surface tension of each part, thereby eliminating orange peel or Benard vortex caused by surface tension differences.

[0045] In addition, the leveling agent BYK-333 can also improve the leveling property of the coating system, make the coating film surface smooth, and improve the gloss.

[0046] In summary, the mechanism of action of the leveling agent BYK-333 in the odorless antibacterial polymer-based composite material is to improve the leveling property of the coating and the surface quality of the coating film by reducing the surface tension, improving the wettability, and eliminating the orange peel or Bernhard vortex caused by the difference in surface tension during the drying process.

[0047] The film-forming aid benzyl alcohol: The role of the film-forming aid is to reduce the MFFT, adjust the system viscosity, and is beneficial to the apparent, etc. A good film-forming aid should meet the following points: 1. Good hydrolytic stability; 2. Low freezing point; 3. Appropriate volatility; 4. Good coagulation efficiency; 5. Environmental type.

[0048] The film-forming aid benzyl alcohol in the odorless antibacterial polymer-based composite material mainly plays a role in plasticizing the epoxy resin and reducing the brittleness of the low molecular weight epoxy resin after film formation. 1. As a solvent for salicylic acid, benzyl alcohol can participate in the curing reaction of the epoxy resin. In this process, benzyl alcohol can play a role in plasticizing the epoxy resin and reducing the brittleness of the low molecular weight epoxy resin after film formation. This can improve the flexibility and durability of the coating, thereby prolonging its service life; 2. In addition, benzyl alcohol can also improve the construction performance and drying speed of the coating. It can accelerate the drying speed of the coating, reduce the waiting time for construction, and improve the chemical stability of the coating.

[0049] It should be noted that the use of film-forming aids must strictly follow the principles of product and environmental suitability to ensure their stability in coatings and not cause adverse effects on the environment and human body. At the same time, attention should be paid to the addition amount of benzyl alcohol to avoid excessive use and cause performance degradation.

[0050] In general, the film-forming aid benzyl alcohol in the odorless antibacterial polymer-based composite material plays a role in improving the flexibility and durability of the coating, improving the construction performance and drying speed, etc. to improve its quality and service life.

[0051] Glass fiber: The mechanism of action of glass fiber in odorless antibacterial polymer-based composites mainly includes enhancing its strength and hardness, improving temperature resistance, and enhancing wear resistance. 1. First, glass fiber has high strength and hardness, which can effectively increase its compressive strength and wear resistance. Adding an appropriate amount of glass fiber to odorless antibacterial polymer-based composites can make them more solid and durable, and not easily damaged by external forces; 2. Second, glass fiber has a high melting point and temperature resistance, which can effectively improve the temperature resistance of odorless antibacterial polymer-based composites. In a high-temperature environment, the glass fiber in odorless antibacterial polymer-based composites can play a role in reinforcing materials, preventing them from deforming or breaking due to high temperature; 3. In addition, glass fiber can also improve the construction performance and drying speed of coatings. It can speed up the drying speed of coatings, reduce the waiting time for construction, and improve the chemical stability of coatings.

[0052] In summary, the mechanism of action of glass fiber in odorless antibacterial polymer-based composites is to enhance its strength and hardness, improve temperature resistance, and enhance wear resistance to improve quality and service life.

[0053] Filler rutile titanium dioxide: The mechanism of action of filler rutile titanium dioxide in odorless antibacterial polymer-based composites mainly includes improving hiding power, enhancing white color retention, and increasing wear resistance. 1. First, rutile titanium dioxide has high hiding power, which can effectively hide surface defects and unevenness. This makes the surface smoother and more even, improving aesthetics and user comfort; 2. Second, rutile titanium dioxide has excellent weather resistance and stability, which can enhance its white color retention. Even in harsh environmental conditions such as ultraviolet light, humidity, etc., rutile titanium dioxide can maintain stable color and performance; 3. Finally, rutile titanium dioxide can also increase its wear resistance, effectively resisting friction and wear, which makes it more durable and less prone to wear and tear.

[0054] In summary, the mechanism of action of filler rutile titanium dioxide in odorless antibacterial polymer-based composites is to improve hiding power, enhance white color retention, and increase wear resistance to improve its quality and performance.

[0055] Antibacterial agent suberic acid surface modified tetrapod-shaped zinc oxide whisker: 1. The properties and application characteristics of tetrapod-shaped zinc oxide whisker are similar to those of silicon carbide whisker, potassium titanate whisker and the like, but relevant reports are very few. The tetrapod-shaped zinc oxide whisker is a three-dimensional tetrapod, that is, the whisker has a core, and four needle-shaped crystals extend radially from the core. Each needle-shaped body is a single crystal microfiber, and the included angle between any two needle-shaped bodies is 109°. The center body diameter of the whisker is 0.7-1.4 µm, the needle-shaped body root diameter is 0.5-14 µm, and the needle-shaped body length is 3-200 µm. It is the only crystal with a three-dimensional spatial structure ever discovered; 2. The T-ZnO whisker also has high strength, high modulus (its elastic modulus is 350 Gpa), and high temperature (can withstand 1720°C) performance. Due to these unique properties, when the T-ZnO whisker is used as a reinforcing material for composite materials or an additive for coatings, it is easy to achieve three-dimensional uniform distribution and isotropy of the material, which is an advantage that one-dimensional whiskers cannot have; 3. Related research has found that the T-ZnO whisker also has excellent properties such as shock absorption, noise reduction, wave absorption, antistatic, antibacterial, etc. The T-ZnO whisker has the characteristics of a three-dimensional tetrahedral structure, while general whiskers are needle-shaped or rod-shaped, such as silicon carbide whisker, potassium titanate whisker, etc., which are one-dimensional fiber-like, similar to glass fiber and carbon fiber, and their main use is as reinforcing materials; 4. Studies have shown that this general one-dimensional fiber-like whisker is difficult to achieve three-dimensional uniform distribution in the matrix material, thereby causing anisotropy of the properties of the composite material. The T-ZnO whisker can achieve three-dimensional uniform distribution in the matrix material, thereby making the composite material isotropic in mechanical properties, thereby eliminating or reducing the anisotropy of the composite material; improving the sliding fit performance; can be used as a reinforcing material for plastics, rubbers, coatings and adhesives; 5. A considerable part of the T-ZnO whisker tip is at the nanometer level or finer, and its nanometer active ingredients can efficiently kill and remove bacteria and their debris, and also decompose toxins secreted by bacteria, with significant antibacterial effect. At the same time, a considerable part of the atomic oxygen in the T-ZnO whisker lattice has very strong oxidation activity, which can destroy the biological activity and metabolic reproduction function of most bacteria, achieving the purpose of antibacterial. Zinc oxide whisker samples doped with iron, copper and silver show good antibacterial and formaldehyde decomposition effects. Detection shows that the T-ZnO whisker resin-based composite material has a 99% killing rate on Escherichia coli and Pseudomonas aeruginosa.

[0056] The mechanism of action of antioxidant trisnonylphenyl phosphite in the odorless antibacterial polymer-based composite is mainly to inhibit the generation of free radicals and terminate chain reactions, thereby preventing the aging and discoloration of the coating film. 1. During the construction process of the odorless antibacterial polymer-based composite, free radicals are easily generated due to the involvement of various chemicals and complex reaction processes, which in turn leads to the aging and discoloration of the coating film. Antioxidant trisnonylphenyl phosphite can effectively inhibit the generation of free radicals and terminate chain reactions, thereby preventing the aging and discoloration of the coating film; 2. In addition, antioxidant trisnonylphenyl phosphite can also improve the weather resistance and yellowing resistance of the coating film. It can enhance the chemical stability of the coating film, so that it can maintain stable performance in harsh environments such as ultraviolet light and humidity.

[0057] In summary, the mechanism of action of antioxidant trisnonylphenyl phosphite in the odorless antibacterial polymer-based composite is to prevent the aging and discoloration of the coating film by inhibiting the generation of free radicals and terminating chain reactions, improving the weather resistance and yellowing resistance of the coating film, and prolonging its service life.

[0058] Advantages of the present application:

[0059] 1. The antibacterial agent of the present application is an inorganic zinc antibacterial agent, namely, a modified four-needle-shaped zinc oxide whisker compounded with an organic zinc antibacterial agent, zinc ethylene bisdithiocarbamate. The antibacterial performance of the antibacterial agent is superior to that of general antibacterial agents, and the ring is maintained for a long time. Moreover, the problem of poor compatibility of the modified four-needle-shaped zinc oxide whisker with the odorless antibacterial polymer-based composite is solved. In addition, the surface hardness of the odorless antibacterial polymer-based composite is also improved, and the service life thereof is increased.

[0060] 2. The odorless antibacterial polymer-based composite disclosed by the present application does not contain VOC in the whole system, and is a green and environmentally friendly odorless antibacterial polymer-based composite.

[0061] 3. The odorless antibacterial polymer-based composite of the present application has a compatibility between materials, so that the odorless antibacterial polymer-based composite of the present application has a pencil hardness of ≥1 H after curing for 24 h, and has higher mechanical properties than traditional odorless antibacterial polymer-based composites.

[0062] 4. The odorless antibacterial polymer-based composite of the present application further improves the toughness of the paint film while basically not reducing the hardness of the paint film, and has good scratch resistance after curing for 1 day. The balance between the hardness and toughness of the paint film is achieved, the water resistance of the odorless antibacterial polymer-based composite is improved by reducing the amount of organic thickening agent, and the weather resistance and comprehensive performance of the odorless antibacterial polymer-based composite are further improved. DETAILED DESCRIPTION

[0063] For a further understanding of the present application, a non-odorous antibacterial polymer-based composite material and a preparation method thereof provided by the present application are described in detail below in conjunction with examples.

[0064] In the following each of the following:

[0065] Bisphenol A type epoxy resin: Model: E-03, from Hubei Shisun Biotechnology Co., Ltd.

[0066] Styrene-acrylic emulsion: Item No.: Y17677, from Shanghai Yuanye Biotechnology Co., Ltd.

[0067] Polyamide: Item No.: TB07339, from Hubei Taibang Chemical Co., Ltd.

[0068] Dispersant: Model: DISPERBYK-190, from BYK (Germany).

[0069] Defoamer: Model: Foamex 1488, from Digo.

[0070] Leveling agent: Model: DISPERBYK-333, from BYK (Germany).

[0071] Rutile titanium dioxide: particle size of 300 mesh.

[0072] Glass fiber: diameter of 30 μm, length of 100 mm.

[0073] Nano zinc oxide: Model: ZT-J20, average particle size of 20 nm, from Zhejiang Zhiti Nano New Material Co., Ltd.

[0074] Ethylene bis-dithiocarbamic acid zinc: CAS No.: 12122-67-7.

[0075] Four acicular zinc oxide whiskers: Model: JC-07-01, from Chengdu Tianyou Jingchuang Technology Co., Ltd. Example 1

[0076] A non-odorous antibacterial polymer-based composite material, the preparation steps are as follows:

[0077] Step 1 first add 20.0 g water in 500 mL beaker, continue to add 5.0 g dispersant BYK-190, 5.0 g antifoaming agent Foamex 1488, stirring 5 min, stirring speed is 300 rpm; continue to add 20.0 g filler rutile titanium dioxide, 6.0 g modified glass fiber, stirring 40 min, stirring speed is 900 rpm; to slurry fineness is 20 μm, continue to add 5.0 g polyamide, 5.0 g leveling agent BYK-333, 6.0 g octanedioic acid modified four acicular zinc oxide, 3.0 g antioxidant trisnonylphenyl phosphite, stirring 10 min, stirring speed is 200 rpm, to obtain component A;

[0078] Step 2 mix 20.0 g modified waterborne epoxy resin with 5.0 g film forming aid benzyl alcohol, stirring time is 30 min, stirring speed is 800 rpm, to obtain component B;

[0079] Step 3 mix component A 37.5 g with component B 25.0 g, stirring time is 30 min, stirring speed is 800 rpm, to obtain the odorless antibacterial polymer-based composite material.

[0080] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, and the mass ratio of the two is 100:15.

[0081] The epoxy resin is bisphenol A type epoxy resin.

[0082] The emulsifier is styrene-acrylic emulsion.

[0083] The modified glass fiber is prepared as follows:

[0084] S1 immerse 6 g glass fiber in 15 g mass fraction 3% hydrofluoric acid aqueous solution for 30 seconds, continue to clean and dry for standby;

[0085] S2 mix the glass fiber treated in step S1 with 3 g dimethoxymethyl vinyl silane, 2 g methyl triethoxysilane, 25 g toluene, 2 g mass fraction 5% phosphoric acid aqueous solution at 70℃, and react for 2 h to obtain modified glass fiber.

[0086] The octanedioic acid modified four acicular zinc oxide whisker is prepared as follows:

[0087] X1 add 6 g octanedioic acid to 50 mL anhydrous ethanol, ultrasonic oscillation, ultrasonic oscillation frequency is 35 KHz, ultrasonic time is 40 min, so that it is completely dissolved and dispersed in anhydrous ethanol;

[0088] X2: 6 g of dry tetrapod-like zinc oxide whiskers were added to X1, and ultrasonic oscillation was performed at a frequency of 30 KHz for 50 min, and then stirring was continued at 45℃ for 40 min at a stirring speed of 600 r / min, and then suberic acid-modified tetrapod-like zinc oxide whiskers were obtained by filtration. Example 2

[0089] An odorless antibacterial polymer-based composite material was prepared by the following steps:

[0090] Step 1: 20.0 g of water was first added to a 500 mL beaker, and then 5.0 g of dispersant BYK-190 and 5.0 g of defoaming agent Foamex 1488 were added, and stirring was performed at a stirring speed of 300 rpm for 5 min; then 20.0 g of filler rutile titanium dioxide and 6.0 g of modified glass fiber were added, and stirring was performed at a stirring speed of 900 rpm for 40 min; until the slurry fineness was 20 μm, and then 5.0 g of polyamide, 5.0 g of leveling agent BYK-333, 6.0 g of nano zinc oxide, and 3.0 g of antioxidant trisnonylphenyl phosphite were added, and stirring was performed at a stirring speed of 200 rpm for 10 min;

[0091] Step 2: 20.0 g of modified waterborne epoxy resin was mixed with 5.0 g of film-forming aid benzyl alcohol and stirred for 30 min at a stirring speed of 800 rpm;

[0092] Step 3: 37.5 g of component A was mixed with 25.0 g of component B and stirred for 30 min at a stirring speed of 800 rpm, to obtain the odorless antibacterial polymer-based composite material.

[0093] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, and the mass ratio of the two is 100:15, and the modified waterborne epoxy resin is prepared by mixing;

[0094] The epoxy resin is a bisphenol A type epoxy resin;

[0095] The emulsifier is a styrene-acrylic emulsion;

[0096] The modified glass fiber is prepared by the same method as in Example 1, which will not be repeated here. Example 3

[0097] An odorless antibacterial polymer-based composite material was prepared by the following steps:

[0098] Step 1 first add 20.0 g water in 500 mL beaker, continue to add 5.0 g dispersant BYK-190, 5.0 g antifoaming agent Foamex 1488, stir 5 min, stirring speed is 300 rpm;Continue to add 20.0 g filler rutile titanium dioxide, 6.0 g modified glass fiber, stir 40 min, stirring speed is 900 rpm;To slurry fineness is 20 μm, continue to add 5.0 g polyamide, 5.0 g leveling agent BYK-333, 6.0 g zinc ethylene bisdithiocarbamate, 3.0 g antioxidant trisnonylphenyl phosphite, stir 10 min, stirring speed is 200 rpm;

[0099] Step 2 20.0 g modified waterborne epoxy resin is mixed with 5.0 g film forming aid benzyl alcohol stirring, stirring time is 30 min, stirring speed is 800 rpm;

[0100] Step 3 component A 37.5 g and component B 25.0 g are mixed and stirred, the stirring time is 30 min, the stirring speed is 800 rpm, to obtain the odorless antibacterial polymer based composite material.

[0101] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, and the mass ratio of the two is 100:15, and the modified waterborne epoxy resin is prepared by mixing;

[0102] The epoxy resin is bisphenol A type epoxy resin;

[0103] The emulsifier is styrene acrylic emulsion;

[0104] The modified glass fiber is prepared by the same method as in example 1, which is not described here. Example 4

[0105] An odorless antibacterial polymer based composite material, the preparation steps are as follows:

[0106] Step 1 first add 20.0 g water in 500 mL beaker, continue to add 5.0 g dispersant BYK-190, 5.0 g antifoaming agent Foamex 1488, stir 5 min, stirring speed is 300 rpm;Continue to add 20.0 g filler rutile titanium dioxide, 6.0 g modified glass fiber, stir 40 min, stirring speed is 900 rpm;To slurry fineness is 20 μm, continue to add 5.0 g polyamide, 5.0 g leveling agent BYK-333, 6.0 g zinc pyrithione, 3.0 g antioxidant trisnonylphenyl phosphite, stir 10 min, stirring speed is 200 rpm;

[0107] Step 2: 20.0 g of modified waterborne epoxy resin was mixed with 5.0 g of film forming aid benzyl alcohol under stirring for 30 min at a stirring speed of 800 rpm.

[0108] Step 3: Component A 37.5 g was mixed with Component B 25.0 g under stirring for 30 min at a stirring speed of 800 rpm to obtain the odorless antibacterial polymer-based composite material.

[0109] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier with a mass ratio of 100:15, and the modified waterborne epoxy resin is prepared by mixing.

[0110] The epoxy resin is a bisphenol A type epoxy resin.

[0111] The emulsifier is a styrene-acrylic emulsion.

[0112] The modified glass fiber is prepared by the same method as in Example 1, which is not repeated here. Example 5

[0113] An odorless antibacterial polymer-based composite material is prepared by the following steps:

[0114] Step 1: 20.0 g of water was first added to a 500 mL beaker, followed by 5.0 g of dispersant BYK-190 and 5.0 g of defoamer Foamex 1488, stirring for 5 min at a stirring speed of 300 rpm; then 20.0 g of filler rutile titanium dioxide and 6.0 g of modified glass fiber were added, stirring for 40 min at a stirring speed of 900 rpm; until the slurry fineness was 20 μm, then 5.0 g of polyamide, 5.0 g of leveling agent BYK-333, 4.0 g of zinc ethylene bisdithiocarbamate, 2.0 g of octanedioic acid modified tetrapod-shaped zinc oxide, and 3.0 g of antioxidant trisnonylphenyl phosphite were added, stirring for 10 min at a stirring speed of 200 rpm.

[0115] Step 2: 20.0 g of modified waterborne epoxy resin was mixed with 5.0 g of film forming aid benzyl alcohol under stirring for 30 min at a stirring speed of 800 rpm.

[0116] Step 3: Component A 37.5 g was mixed with Component B 25.0 g under stirring for 30 min at a stirring speed of 800 rpm to obtain the odorless antibacterial polymer-based composite material.

[0117] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier with a mass ratio of 100:15, and the modified waterborne epoxy resin is prepared by mixing.

[0118] The epoxy resin is a bisphenol A type epoxy resin.

[0119] The emulsifier is a styrene-acrylic emulsion.

[0120] The modified glass fiber is prepared in the same manner as in Example 1, which is not repeated here.

[0121] The suberic acid modified tetrapod-shaped zinc oxide is prepared in the same manner as in Example 1, which is not repeated here.

[0122] Test item 1: basic performance test of odorless antibacterial polymer-based composite material

[0123] The test is carried out according to the standard "GB / T 22374-2018 Floor Coating Materials".

[0124] Table 1 Basic performance test of odorless antibacterial polymer-based composite material

[0125]

[0126] From the performance test of odorless antibacterial polymer-based composite material of Examples 1-5 in Table 1, it can be found that the performance of Example 5 is the best, and it also shows that adding suberic acid modified tetrapod-shaped zinc oxide compounded with organic zinc antibacterial agent zinc ethylene bisdithiocarbamate to odorless antibacterial polymer-based composite material can improve its surface hardness, which can be seen from the hardness size in the above test; from the adhesion size in the above table, it can be seen that adding inorganic antibacterial agent suberic acid modified tetrapod-shaped zinc oxide compounded with organic zinc antibacterial agent zinc ethylene bisdithiocarbamate to odorless antibacterial polymer-based composite material can improve its compatibility problem in odorless antibacterial polymer-based composite material, so that the compatibility of the compounded antibacterial agent in odorless antibacterial polymer-based composite material is better than that of suberic acid modified tetrapod-shaped zinc oxide alone.

[0127] The possible reasons for the above changes are: 1. Suberic acid modified tetrapod-shaped zinc oxide and zinc ethylene bisdithiocarbamate can be compatible with water-based epoxy resin, improving the stability of the system; 2. Suberic acid modified tetrapod-shaped zinc oxide and zinc ethylene bisdithiocarbamate can react with water-based epoxy resin to form a network structure, thereby improving the surface hardness of odorless antibacterial polymer-based composite material; 3. Suberic acid modified tetrapod-shaped zinc oxide and zinc ethylene bisdithiocarbamate can enhance the wear resistance and weather resistance of odorless antibacterial polymer-based composite material, thereby improving its service life; 4. Suberic acid modified tetrapod-shaped zinc oxide and zinc ethylene bisdithiocarbamate can reduce the surface tension of odorless antibacterial polymer-based composite material coating, improve the wettability and flowability of the coating, and thereby improve the surface smoothness and hardness of the odorless antibacterial polymer-based composite material coating.

[0128] In summary, the inorganic antibacterial agent suberic acid modified four needle-shaped zinc oxide is compounded with the organic zinc antibacterial agent zinc ethylene bisdithiocarbamate to be added into the odorless antibacterial polymer-based composite material, which can improve the compatibility problem of suberic acid modified four needle-shaped zinc oxide added alone into the odorless antibacterial polymer-based composite material, and improve the surface hardness, wear resistance and weather resistance of the odorless antibacterial polymer-based composite material.

[0129] Test item 2: scratch resistance test of odorless antibacterial polymer-based composite material

[0130] The test is carried out according to the standard “GB / T 9279.1-2015 Determination of resistance to scratching of paints and varnishes Part 1 Constant load method”. The corresponding paint film is prepared from the odorless antibacterial polymer-based composite materials of the above-mentioned examples 1-5, and then the scratch test is carried out.

[0131] The substrate should be a steel plate with a thickness of 0.8 mm and meet the requirements of ISO 1514, and the size of the substrate is 200 mm×100 mm;

[0132] Substrate treatment and coating: the substrate is treated according to ISO 1514, and then the material prepared in the above examples is coated according to the specified method.

[0133] Drying and conditioning: the painted test panel should be dried (or baked) and maintained under the specified conditions for the specified time. The painted test panel is conditioned at a temperature of (23±2)℃ and a relative humidity of (50±5)℃ (according to the provisions in ISO 3270) for at least 16 h before testing.

[0134] The thickness of the dry coating is determined by a method specified in ISO 2808, calculated in μm.

[0135] A painted test panel is clamped on the test panel holder with the test face upward. The position of the test panel is fixed to ensure that the distance between the scratches is at least 5 mm, and the distance between the scratches and the edge of the test panel is at least 10 mm.

[0136] Table 2 Scratch resistance test of odorless antibacterial polymer-based composite material

[0137]

[0138] As can be seen from Table 2, the scratch resistance of the prepared odorless antibacterial polymer-based composite of Example 5 is the best. The possible reasons are as follows: 1. The octanedioic acid modified tetrapod-like zinc oxide and zinc ethylene bisdithiocarbamate both have antibacterial properties, which can effectively inhibit the growth of bacteria, thereby improving the antibacterial properties of the odorless antibacterial polymer-based composite. At the same time, these antibacterial agents can form a network structure, enhance the hardness and wear resistance of the coating film, and thus improve the scratch resistance; 2. The octanedioic acid modified tetrapod-like zinc oxide and zinc ethylene bisdithiocarbamate can reduce the surface tension of the coating film, improve the wettability and flowability of the coating film, and thus improve the surface smoothness and scratch resistance of the coating film; 3. The octanedioic acid modified tetrapod-like zinc oxide and zinc ethylene bisdithiocarbamate can enhance the chemical corrosion resistance of the odorless antibacterial polymer-based composite, thereby improving its durability and scratch resistance.

[0139] In summary, the combination of the inorganic zinc antibacterial agent octanedioic acid modified tetrapod-like zinc oxide and the organic zinc antibacterial agent zinc ethylene bisdithiocarbamate can improve the antibacterial properties, surface hardness, wear resistance, and durability of the odorless antibacterial polymer-based composite, thereby improving its scratch resistance. This may be because these antibacterial agents can form a network structure, reduce the surface tension of the coating film, enhance the hardness and wear resistance of the coating film, and the like.

[0140] Test item 3: Aging resistance test of odorless antibacterial polymer-based composite

[0141] The test was carried out in accordance with the standards "GB / T 1865-2009 Color Paint and Varnish - Artificial Climate Aging and Artificial Radiation Exposure Filtered Xenon Arc Radiation" and "GB / T-1766-2008 Color Paint and Varnish - Rating Method for Coating Aging".

[0142] This standard uses a numerical rating of 0 to 5 to evaluate the degree and amount of damage, with "0" indicating no damage and "5" indicating severe damage. The determination of the four levels of numbers 1, 2, 3, and 4 should be such that the entire rating range is best distinguished, and if necessary, intermediate half levels can be taken to make more detailed records of all observed phenomena.

[0143] Table 3: Aging resistance test of odorless antibacterial polymer-based composite

[0144]

[0145] As can be seen from Table 3, the anti-aging performance test of the prepared odorless antibacterial polymer-based composite material in Example 5 is the best, the comprehensive performance evaluation reaches 0 level, and the anti-aging performance is far superior to Examples 1-4. The possible reasons are as follows: 1. The octanedioic acid modified tetrapod-like zinc oxide and the zinc ethylene bisdithiocarbamate have antibacterial properties, thereby improving the antibacterial properties of the odorless antibacterial polymer-based composite material. At the same time, these antibacterial agents can form a network structure, enhance the hardness and wear resistance of the coating film, and thus improve the anti-aging performance; 2. The octanedioic acid modified tetrapod-like zinc oxide and the zinc ethylene bisdithiocarbamate can reduce the surface tension of the coating film, improve the wettability and flowability of the coating film, and thus improve the surface smoothness and anti-aging performance of the coating film; 3. The octanedioic acid modified tetrapod-like zinc oxide and the zinc ethylene bisdithiocarbamate can capture free radicals and inhibit oxidation reactions, thereby slowing down the aging process of the coating film and improving the anti-aging performance; 4. The octanedioic acid modified tetrapod-like zinc oxide and the zinc ethylene bisdithiocarbamate can enhance the chemical corrosion resistance of the odorless antibacterial polymer-based composite material, thereby improving its durability and anti-aging performance.

[0146] In summary, the combination of the inorganic zinc antibacterial agent octanedioic acid modified tetrapod-like zinc oxide and the organic zinc antibacterial agent zinc ethylene bisdithiocarbamate added to the odorless antibacterial polymer-based composite material can improve its antibacterial properties, surface hardness, wear resistance, and durability, and thus improve its anti-aging performance. This may be because these antibacterial agents can form a network structure, reduce the surface tension of the coating film, capture free radicals, and enhance the hardness and wear resistance of the coating film.

[0147] Test Example 4: Anti-mold test of odorless antibacterial polymer-based composite material

[0148] The antibacterial rate of 50% meets the national standard. The test bacteria used are Escherichia coli (E. coli) ASI.90 and Staphylococcus aureus (S. aureus) ASI.89. Escherichia coli Staphylococcus aureus

[0149] The antibacterial properties are determined according to the standard "GB / T 21866-2008 Antibacterial Coatings (Paint Film) Determination of Antibacterial Properties and Antibacterial Effect".

[0150] This method quantitatively inoculates bacteria on the sample to be tested, uses the film sticking method to make the bacteria uniformly contact the sample, after a certain period of culture, detects the number of viable bacteria in the sample, and calculates the antibacterial rate of the sample. The antibacterial test should be carried out in a laboratory that meets the requirements of laboratory biosafety management and facility conditions specified in GB 19489.

[0151] ​​Main equipment: constant temperature incubator (37±1) °C, refrigerator (0~5) °C, clean bench, pressure steam sterilization pot, electric heating drying box, balance (precision 0.01 g), sterilized plate, sterilized test tube, sterilized pipette, inoculation ring, alcohol lamp.

[0152] Preparation of paint sample board: sampling according to GB / T 3186. The substrate used for the prepared test board should generally be the actual use substrate (such as cement, wood board, metal plate, plastic plate). The coating film is made according to GB / T 1727, and the coating is generally applied twice, the second time after the first time is dry, the total thickness of the coating film is less than 100 μm, the sample board should be flat, no rust, etc. The painted test board is cut into 10 pieces of 50 mm×50 mm size, and sterilized before the experiment.

[0153] Bacterial resistance calculation formula: R =( B - C ) / B ×100

[0154] In the formula, R —bacterial resistance, expressed in (%) and the value is taken to four significant figures, according to the provisions of GB / T 1250;

[0155] B —average number of recovered bacteria (cfu / piece) of blank control sample board after 24 h;

[0156] C —average number of recovered bacteria (cfu / piece) of antibacterial coating sample board after 24 h.

[0157] The qualitative method is used to observe the size of the transparent circle formed by the growth of bacteria around the transparent circle, which can indicate the resistance of the mold-resistant antibacterial agent to bacterial growth.

[0158] This test method is to apply the antibacterial agent to the surface of the original culture medium in a specific way, and the culture medium contains bacterial culture agar for test use. After the antibacterial agent is applied, it is diffused in a three-dimensional manner in the specific culture medium. If the antibacterial agent can inhibit the growth and reproduction of the bacteria used for testing, it can form a transparent circle around it. By observing the size of the transparent circle, the ability of the mold-resistant antibacterial agent to inhibit bacterial growth can be evaluated; the standard of “Antibacterial Plastic (Composite) Flexible Packaging” (T / SHBX 012—2021) is that the size of the transparent circle is greater than 99%, indicating that the mold-resistant antibacterial agent has strong resistance to bacterial generation, and the transparent circle is greater than 90%, indicating that the antibacterial agent has a certain resistance to bacterial generation.

[0159] Table 4 Antimicrobial test of odorless antimicrobial polymer-based composite materials

[0160] Test item Antibacterial rate (Escherichia coli) / % Antibacterial rate (Staphylococcus aureus) / % Example 1 91.51 92.13 Example 2 90.32 91.35 Example 3 85.53 90.18 Example 4 90.51 91.34 Example 5 99.42 99.83

[0161] From the above table 4, it can be seen that the antibacterial effect of example 5 is the best, followed by example 1. This shows that the inorganic zinc antibacterial agent suberic acid modified four needle-shaped zinc oxide is compounded with the organic zinc antibacterial agent zinc ethylene bisdithiocarbamate, and the antibacterial performance is the best. The possible reason is that: 1. The synergistic effect of suberic acid modified four needle-shaped zinc oxide and zinc ethylene bisdithiocarbamate. After the compounding of the two antibacterial agents, the synergistic effect can be produced, and the antibacterial effect is enhanced; 2. The mechanism of suberic acid modified four needle-shaped zinc oxide and zinc ethylene bisdithiocarbamate is more comprehensive. They can inhibit the growth of bacteria and mold at the same time, and have a wider antibacterial spectrum; 3. The stability of suberic acid modified four needle-shaped zinc oxide and zinc ethylene bisdithiocarbamate is higher. They have better compatibility with waterborne epoxy resin, and are not easy to separate and precipitate, so as to maintain the durability of the antibacterial performance; 4. The antibacterial effect of suberic acid modified four needle-shaped zinc oxide and zinc ethylene bisdithiocarbamate is more rapid. They can rapidly inhibit the growth of bacteria and prevent microorganisms from causing damage to the odorless antibacterial polymer-based composite material.

[0162] In summary, the antibacterial performance of the inorganic zinc antibacterial agent suberic acid modified four needle-shaped zinc oxide compounded with the organic zinc antibacterial agent zinc ethylene bisdithiocarbamate is better than that of nano zinc oxide, inorganic zinc antibacterial agent suberic acid modified four needle-shaped zinc oxide, organic zinc antibacterial agent zinc ethylene bisdithiocarbamate and zinc pyrithione. The main reason is that they have synergistic effect, comprehensive antibacterial spectrum, high stability and rapid antibacterial effect.

[0163] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Modifications, replacements and improvements made within the principles of the present application should be included in the protection scope of the present application.

Claims

1. A process for the preparation of an odorless antimicrobial polymer-based composite material, characterized in that, Comprising the following steps, in parts by weight: Step 1 first add 20~30 parts of water in the container, continue to add 5~10 parts of dispersing agent, 5~10 parts of defoaming agent, stirring 3~5 min, stirring speed is 200~300 rpm; continue to add 20~30 parts of filler, 5~10 parts of modified glass fiber, stirring 40~60 min, stirring speed is 900~1000 rpm; to slurry fineness less than 40 μm, continue to add 5~20 parts of water-based epoxy resin curing agent, 5~10 parts of leveling agent, 5~10 parts of antibacterial agent, 5~8 parts of antioxidant, stirring 10~20 min, stirring speed is 200~300 rpm, get component A; Step 2, 20~30 parts of modified water-based epoxy resin and 5~10 parts of film forming aid are mixed and stirred, the stirring time is 30~40 min, and the stirring speed is 800~900 rpm, to obtain component B; Step 3, component A and component B are mixed and stirred, the mixing mass ratio of component A to component B is (100~180):100, the stirring time is 30~40 min, and the stirring speed is 800~900 rpm; to obtain the odorless antibacterial polymer-based composite material; The modified water-based epoxy resin is made of emulsifier and epoxy resin, the epoxy resin is at least one of bisphenol A type epoxy resin, E51 epoxy resin, E44 epoxy resin, alicyclic epoxy resin, bisphenol F type epoxy resin, and phenolic epoxy resin; the emulsifier is at least one of pure acrylic emulsion, acetone acrylic emulsion, and benzene acrylic emulsion; the mass ratio of the epoxy resin to the emulsifier is 100:(10~20); the water-based epoxy resin curing agent is at least one of polyamide, isophorone diamine, cyclohexanediamine, methylcyclopentadienyl diamine, polypropylene triamine, and polyethylene diamine; The antibacterial agent is a mixture of ethylene bisdithiocarbamic acid zinc and octanedioic acid modified four needle-shaped zinc oxide whiskers in a mass ratio of (1~3):1; The octanedioic acid modified four needle-shaped zinc oxide whisker is prepared by the following method, in parts by weight: X1 add 5~10 parts of octanedioic acid to 30~50 parts of anhydrous ethanol, ultrasonic oscillation, ultrasonic oscillation frequency is 20~50 KHz, ultrasonic time is 30~50 min, make it completely dissolved and dispersed in anhydrous ethanol; X2 add 5~10 parts of dry four needle-shaped zinc oxide whisker to X1, ultrasonic oscillation, ultrasonic oscillation frequency is 20~50 KHz, ultrasonic time is 30~50 min, continue to stir at 40~50℃ for 30~60 min, stirring speed is 500~800 r / min, filter to obtain octanedioic acid modified four needle-shaped zinc oxide whisker; The preparation method of the modified glass fiber is as follows, in parts by weight: S1 immerse 5~10 parts of glass fiber in 10~20 parts of 3~5% mass fraction hydrofluoric acid aqueous solution for 20~50 seconds, continue to clean and dry for standby; S2 mixing the glass fiber treated in step S1 with 2-3 parts of alkoxy silane, 1-2 parts of capping agent, 20-30 parts of organic solvent, 1-2 parts of catalyst at 40-80℃ for 2-3 h to obtain modified glass fiber.

2. The process for the preparation of tasteless antimicrobial polymer-based composites according to claim 1, characterized in that: The dispersant is at least one of BYK-180, BYK-190, EFKA-4560, W-511, FA-182, EFKA-4550, and W-518; the defoaming agent is at least one of HS-334, LG-10, CF-328, BYK-011, Foamex 1488, and BYK-020; the leveling agent is at least one of BYK-346, Sancure 621N, TEGO Twin 4100, W-77, W-461, BYK-333, and TEGO Twin 4000; and the film-forming aid is at least one of ethanol, methoxybutanol, and benzyl alcohol.

3. The method of preparing an odorless antimicrobial polymer-based composite material according to claim 1, characterized in that: The glass fiber has a diameter of 20-60 μm and a length of 50-300 mm.

4. The method of preparing an odorless antimicrobial polymer-based composite according to claim 1, characterized in that: The alkoxy silane is at least one of dimethoxymethylvinylsilane, vinyltriethoxysilane, propenyltriethoxysilane, and phenyltriethoxysilane; the capping agent is at least one of hexamethyldisiloxane, methyltriethoxysilane, and tetramethyldivinyl disiloxane; the organic solvent is at least one of tetrahydrofuran, methanol, toluene, n-hexane, and chloroform; the catalyst is at least one of sulfuric acid, phosphoric acid, hydrochloric acid, and perchloric acid; and the mass fraction of the catalyst is 3-5%.

5. The method of preparing an odorless antimicrobial polymer-based composite material according to claim 1, characterized in that: The filler is at least one of rutile titanium dioxide, talc, mica, quartz powder, and nano-alumina; and the antioxidant is at least one of antioxidant 1010, antioxidant 168, 2,6-di-tert-butyl-p-cresol, N,N'-di-sec-butyl-p-phenylenediamine, and trisnonylphenyl phosphite.

6. A tasteless antimicrobial polymer-based composite material, characterized by: The tasteless antibacterial polymer-based composite material is prepared by the method of any one of claims 1-5.

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