阅读说明：本技术 一种生物基水性涂料及其制备方法和应用 (Bio-based water-based paint and preparation method and application thereof ) 是由 李勇 裴道海 徐志新 李金钟 于 2020-06-08 设计创作，主要内容包括：本发明提供一种生物基水性涂料及其制备方法和应用,所述生物基水性涂料包括生物基树脂乳液和抗菌抗病毒复合填料；所述抗菌抗病毒复合填料包括无机非金属矿物载体,以及负载于所述无机非金属矿物载体上的纳米二氧化钛和纳米银。所述生物基水性涂料以生物基树脂乳液为成膜物质,具有绿色、可再生和可降解的特性,能够充分满足涂料的环保要求；同时,所述抗菌抗病毒复合填料为多组分协同的具有光催化氧化抗菌性能的无机抗菌填料,赋予漆膜高效、广谱、持久的抗菌抗病毒性能。所述生物基水性涂料在满足环保和抗菌抗病毒要求的同时,成膜后的耐水性、耐碱性和耐污渍性良好,尤其适于作为建筑涂料应用于建筑外墙或室内的涂装中。(The invention provides a bio-based water-based paint and a preparation method and application thereof, wherein the bio-based water-based paint comprises a bio-based resin emulsion and an antibacterial and antiviral composite filler; the antibacterial and antiviral composite filler comprises an inorganic nonmetallic mineral carrier, and nano titanium dioxide and nano silver loaded on the inorganic nonmetallic mineral carrier. The bio-based water-based paint takes bio-based resin emulsion as a film forming substance, has the characteristics of green, regenerability and degradability, and can fully meet the environmental protection requirement of the paint; meanwhile, the antibacterial and antiviral composite filler is an inorganic antibacterial filler with multiple components and synergistic photocatalytic oxidation antibacterial property, and a paint film is endowed with efficient, broad-spectrum and lasting antibacterial and antiviral properties. The bio-based water-based paint meets the requirements of environmental protection, antibiosis and antivirus, has good water resistance, alkali resistance and stain resistance after film formation, and is particularly suitable for being used as building paint to be applied to the coating of building outer walls or indoor.)

1. The bio-based water-based paint is characterized by comprising a bio-based resin emulsion and an antibacterial and antiviral composite filler; the antibacterial and antiviral composite filler comprises an inorganic nonmetallic mineral carrier, and nano titanium dioxide and nano silver loaded on the inorganic nonmetallic mineral carrier.

2. The bio-based water-based paint as claimed in claim 1, wherein the bio-based water-based paint comprises the following components in parts by weight:

30-35 parts by weight of bio-based resin emulsion

1.5-5 parts by weight of antibacterial and antiviral composite filler

15-25 parts of water.

3. The bio-based waterborne coating according to claim 1 or 2, wherein the bio-based resin emulsion comprises a bio-based acrylate emulsion and/or a bio-based polyurethane emulsion;

preferably, the content of C14 in the bio-based resin emulsion is 25-50%.

4. The bio-based water-based paint according to claim 1 or 2, wherein the inorganic non-metallic mineral carrier comprises any one or a combination of at least two of kaolin, heavy calcium, light calcium, talc, wollastonite powder or barium sulfate, preferably a combination of kaolin and talc;

preferably, the particle size of the inorganic nonmetallic mineral carrier is 10-45 μm;

preferably, the loading mass percentage of the nano titanium dioxide on the inorganic nonmetallic mineral carrier is 20-40%;

preferably, the particle size of the nano titanium dioxide is 50-500 nm;

preferably, the loading mass percentage of the nano silver on the inorganic nonmetallic mineral carrier is 15-30%;

preferably, the particle size of the nano silver is 50-500 nm;

preferably, the mass ratio of the nano titanium dioxide to the nano silver is 1 (0.5-1.2).

5. The bio-based water-based paint according to claim 1 or 2, wherein the inorganic nonmetallic mineral carrier is further loaded with silicon oxide;

preferably, the loading mass percentage of the silicon oxide on the inorganic nonmetallic mineral carrier is 5-15%;

preferably, the inorganic nonmetallic mineral carrier is also loaded with alumina;

preferably, the loading mass percentage of the alumina on the inorganic nonmetallic mineral carrier is 5-15%;

preferably, the antibacterial and antiviral composite filler comprises an inorganic nonmetallic mineral carrier, and nano titanium dioxide, nano silver, silicon oxide and aluminum oxide which are loaded on the inorganic nonmetallic mineral carrier;

preferably, the particle size of the antibacterial and antiviral composite filler is 13-50 μm.

6. The bio-based water-based paint as claimed in claim 5, wherein the preparation method of the antibacterial and antiviral composite filler comprises the following steps:

(1) mixing an inorganic nonmetallic mineral carrier, an inorganic acid, water and a dispersant I to obtain a dispersion liquid I; mixing titanium tetrachloride, water and a dispersing agent II to obtain titanium tetrachloride hydrolysate;

(2) mixing and reacting the dispersion liquid I obtained in the step (1) with titanium tetrachloride hydrolysate to obtain a sample loaded with nano silicon dioxide;

(3) mixing and reacting the sample obtained in the step (2), silver salt and a reducing agent to obtain the antibacterial and antiviral composite filler;

preferably, the dispersant I and the dispersant II in the step (1) respectively and independently comprise any one or a combination of at least two of alkali metal phosphate, polyacrylamide, polyacrylate, sodium dodecyl sulfate, sodium lignin sulfonate, polyvinyl alcohol, polyester dispersant or polyether dispersant;

preferably, the mass percentage of the inorganic nonmetallic mineral carrier in the dispersion liquid I in the step (1) is 5-50%;

preferably, the mass percentage of the inorganic acid in the dispersion liquid I in the step (1) is 2-30%;

preferably, the mass percentage of the dispersing agent I in the dispersion liquid I in the step (1) is 0.02-10%;

preferably, the mass ratio of titanium tetrachloride to water in the titanium tetrachloride hydrolysate in the step (1) is 1 (1-10);

preferably, the mass ratio of the titanium tetrachloride to the dispersant II in the step (1) is 1 (0.005-0.3);

preferably, the mixing method in step (2) is as follows: dripping titanium tetrachloride hydrolysate into the dispersion liquid I;

preferably, the reaction time in the step (2) is 2-6 h;

preferably, the silver salt of step (3) comprises silver nitrate;

preferably, the reducing agent in step (3) comprises sodium borohydride, sodium citrate or glucose;

preferably, the reaction temperature in the step (3) is 40-100 ℃;

preferably, the reaction time in the step (3) is 5-60 min;

preferably, the reaction in step (3) is completed and then a step of loading silica and/or alumina is included;

preferably, the method for supporting silicon oxide is as follows: mixing the system obtained after the reaction in the step (3) with a silicate solution, and reacting to obtain a sample loaded with silicon oxide;

preferably, the method for supporting alumina is as follows: mixing and reacting the system obtained in the step (3) with a tetrahydroxy aluminum sodium silicate solution to obtain an alumina-loaded sample;

preferably, the preparation method of the antibacterial and antiviral composite filler comprises the following steps:

(1) mixing an inorganic nonmetallic mineral carrier, an inorganic acid, water and a dispersant I to obtain a dispersion liquid I; mixing titanium tetrachloride, water and a dispersing agent II to obtain titanium tetrachloride hydrolysate;

(2) mixing and reacting the dispersion liquid I obtained in the step (1) with titanium tetrachloride hydrolysate to obtain a sample loaded with nano silicon dioxide;

(3) mixing the sample obtained in the step (2), silver nitrate and a reducing agent, and reacting for 5-60 min at 40-100 ℃; and after the reaction is finished, adding a silicate solution into the system to carry out a silicon oxide loading reaction, and then adding a tetrahydroxy sodium aluminum alloy solution to carry out an aluminum oxide loading reaction to obtain the antibacterial and antiviral composite filler.

7. The bio-based water-based paint as claimed in claim 1 or 2, further comprising 0.2-0.3 part by weight of a bactericidal and mildewproof agent;

preferably, the fungicidal agent comprises an isothiazolinone fungicide;

preferably, the bio-based water-based paint further comprises 0.2-2.5 parts by weight of a water-retaining agent;

preferably, the water retaining agent comprises a cellulose ether;

preferably, the bio-based water-based paint further comprises 0.4-1.0 part by weight of a dispersant;

preferably, the bio-based water-based paint further comprises 0.2-0.3 part by weight of a wetting agent;

preferably, the bio-based water-based paint further comprises 0.1-0.3 part by weight of a pH regulator;

preferably, the bio-based water-based paint further comprises 0.2-0.4 part by weight of an antifreezing agent;

preferably, the bio-based water-based paint further comprises 1.0-2.0 parts by weight of a film-forming assistant;

preferably, the boiling point of the film-forming assistant is more than or equal to 290 ℃;

preferably, the bio-based water-based paint further comprises 0.2-0.4 part by weight of a defoaming agent;

preferably, the defoamer comprises a high plant-based defoamer;

preferably, the bio-based water-based paint further comprises 1.0-2.0 parts by weight of a thickening agent;

preferably, the thickener comprises any one of polyurethane thickener, cellulose or alkali swelling thickener or a combination of at least two thereof;

preferably, the bio-based water-based paint also comprises 35-45 parts by weight of other pigments and fillers;

preferably, the other pigment and filler comprises any one or at least two of titanium dioxide, kaolin, talcum powder, white carbon black or calcium carbonate;

preferably, the titanium dioxide is rutile type titanium dioxide.

8. The bio-based water-based paint as claimed in claim 7, wherein the bio-based water-based paint comprises the following components in parts by weight:

the antibacterial and antiviral composite filler comprises an inorganic nonmetallic mineral carrier, and nano titanium dioxide, nano silver, silicon oxide and aluminum oxide which are loaded on the inorganic nonmetallic mineral carrier.

9. The preparation method of the bio-based water-based paint as claimed in any one of claims 1 to 8, characterized in that the preparation method comprises the following steps: mixing and uniformly dispersing bio-based resin emulsion, antibacterial and antiviral composite filler, water, optional paint auxiliary agent and optional other pigments and fillers to obtain the bio-based water-based paint;

preferably, the coating auxiliary agent comprises any one or a combination of at least two of a bactericidal and mildew-proof agent, a water-retaining agent, a dispersing agent, a wetting agent, a pH regulator, an antifreezing agent, a film-forming auxiliary agent, a defoaming agent or a thickening agent.

10. Use of the bio-based water-based paint according to any one of claims 1 to 8 in building exterior wall paint or interior paint.

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a bio-based water-based coating as well as a preparation method and application thereof.

Background

With the rapid development of the building industry and the housing industry, the proportion of the building coating in the coating is increased day by day, and meanwhile, people also continuously put forward new requirements on the product performance of the building coating, thereby accelerating the product optimization and the updating of the building coating. At present, the building coating can be divided into two categories of solvent type and water type according to a dispersion medium, the water-based building coating is a system taking water as the dispersion medium, the content of harmful substances in the water-based coating is less than one eighth of that of the traditional solvent type coating, and the water-based building coating has the characteristics of low VOC, no toxicity and no pollution, and better meets the requirements of the current environmental protection regulations and environmental protection consciousness of people, so the water-based building coating becomes an important development trend of the building coating and has a very wide application prospect.

In the development process of coating water-based paint, people gradually find that the film-forming substance of the water-based paint is a water-soluble polymer or a polymer emulsion, and the water-based paint is polymerized by using monomers in petroleum as starting materials, and the petroleum belongs to non-renewable resources, so that the petroleum-based water-based paint still cannot meet the currently advocated environmental protection concept. With the increasing shortage of petroleum resources and the rising prices, the market is calling for the use of renewable resources instead of traditional petroleum-based products more and more. Products containing biobased functional groups perform similarly to petroleum-based products, with all or part of the raw materials being biobased, renewable agricultural (e.g., plant, animal, or microbial, etc.) or forestry raw materials; these raw materials, in addition to having the advantages of low odor, low VOC and being renewable, contribute to reducing carbon emissions. Therefore, the development of aqueous paint formulations using bio-based aqueous resins as film-forming materials for paints is a new direction.

CN105462426A discloses an efficient weather-resistant, water-resistant and stain-resistant water-based bio-based paint and a preparation method thereof, wherein the water-based bio-based paint is composed of the following raw materials: 17-20 parts of water, 0.15-0.3 part of cellulose, 25-40 parts of emulsion, 0.2-0.4 part of sterilization mildew preventive, 3-10 parts of precipitated barium sulfate, 14-20 parts of titanium dioxide, as well as a pH regulator, a wetting agent, a dispersing agent, heavy calcium, calcined kaolin, a film-forming auxiliary agent, a thickening agent, an adhesion force enhancer, an antifreezing agent and an antifoaming agent; wherein the emulsion is formed by polymerizing dibutyl itaconate and acrylate monomers. The water-based bio-based paint adopts emulsion taking bio-based as a raw material, and has the characteristics of environmental protection, weather resistance, water resistance and contamination resistance.

CN109762447A discloses a bio-based antibacterial coating and a preparation method thereof, wherein the bio-based antibacterial coating comprises the following components: antibacterial macromolecules, water-based epoxy emulsion, a defoaming agent, an antioxidant, a water-based curing agent and deionized water; the antibacterial macromolecule is formed by covalently bonding sulfaguanidine, DL-tartaric acid and glycitin, and then grafting the sulfaguanidine, DL-tartaric acid and glycitin on an epoxy resin matrix to form the bio-based antibacterial coating. The bio-based antibacterial coating integrates sterilization and bacteriostasis, and has better heat resistance.

CN110041829A discloses an environment-friendly plant-based interior wall water paint and a preparation method thereof, wherein the plant-based interior wall water paint comprises the following components: the coating comprises water-based plant-based odor-removing resin, a defoaming agent, a preservative, an antibacterial agent, a bio-based wetting agent, a dispersing agent, pigment and filler, a plant cellulose thickening agent, a flatting agent, water-based silicone resin and water; the plant-based interior wall water paint is formaldehyde-free, odorless and fresh in smell, and has mildew resistance and antibacterial property.

Because bacteria and hidden viruses are easy to breed in the environment where the building coating is located, and the bacteria belong to vegetative propagation, the propagation speed is very high, and the building coating has potential harm to human bodies; therefore, the antibacterial property of the architectural coating is very important. The antibacterial agent applied to the building coating in the prior art comprises a natural organic antibacterial agent and a synthetic organic antibacterial agent, wherein the natural organic antibacterial agent has poor heat resistance, selectivity to virus and bacteria and short service life; the synthetic organic antibacterial agent has certain toxicity; and the organic antibacterial agent can generate drug resistance after long-term use, is easy to generate super bacteria, and is not suitable for long-acting antibiosis in building coatings.

Therefore, the development of a bio-based water-based paint with long-acting antibacterial property is the focus of research in the field.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a bio-based water-based paint, a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a bio-based water-based paint, which comprises a bio-based resin emulsion and an antibacterial and antiviral composite filler; the antibacterial and antiviral composite filler comprises an inorganic nonmetallic mineral carrier, and nano titanium dioxide and nano silver loaded on the inorganic nonmetallic mineral carrier.

The bio-based water-based paint provided by the invention takes the bio-based resin emulsion as a film forming substance, has the characteristics of greenness, reproducibility and degradability, and can fully meet the environmental protection requirement of the paint.

Different from the strategy of using an organic antibacterial agent to realize the antibacterial property of the coating in the prior art, the invention introduces an inorganic antibacterial and antiviral composite filler to realize the high-efficiency lasting antibacterial property of the coating, wherein the antibacterial and antiviral composite filler comprises an inorganic non-metallic mineral carrier, nano titanium dioxide and nano silver, and the inorganic non-metallic mineral carrier effectively avoids the agglomeration of nano particles, so that the nano titanium dioxide and the nano silver are dispersed in the coating system in a nano scale to better exert the antibacterial and antiviral activity of the coating. The nano titanium dioxide can absorb ultraviolet light and generate charged particles with strong oxidizing property under the excitation of the ultraviolet light, so that the nano titanium dioxide directly acts on bacteria and viruses to realize inhibition and killing; meanwhile, toxic substances generated by bacteria can be degraded, and the broad-spectrum sterilization and antivirus effects are achieved; the nano silver has strong inhibiting and killing effects on harmful microorganisms, and does not generate drug resistance. According to the antibacterial and antiviral composite filler disclosed by the invention, the nano titanium dioxide and the nano silver are combined, and the antibacterial and antiviral activity of the nano titanium dioxide and the nano silver is synergistic, so that the broad-spectrum and efficient antibacterial performance is realized; more importantly, the nano titanium dioxide has stronger photooxidation catalytic antibacterial activity under the excitation of ultraviolet light with short wavelength, the utilization rate of visible light is extremely low, the introduction of nano silver can influence the energy band structure of the nano titanium dioxide, the photocatalytic oxidation activity of the nano titanium dioxide is improved, and the antibacterial performance of the nano titanium dioxide is further enhanced. The antibacterial and antiviral composite filler of the invention endows the bio-based water-based paint with high-efficiency and broad-spectrum antibacterial and antiviral properties through the synergistic effect of the inorganic non-metallic mineral carrier, the nano titanium dioxide and the nano silver, and meanwhile, the antibacterial and antiviral composite filler does not cause drug resistance and is not consumed, so that the antibacterial and antiviral composite filler has long-acting property and can meet the continuous antibacterial requirement of the paint in the service life.

In the invention, the bio-based water-based paint comprises the following components in parts by weight:

30-35 parts by weight of bio-based resin emulsion

1.5-5 parts by weight of antibacterial and antiviral composite filler

15-25 parts of water.

The bio-based resin emulsion is contained in an amount of 30 to 35 parts by weight, for example, 30.5 parts by weight, 31 parts by weight, 31.5 parts by weight, 32 parts by weight, 32.5 parts by weight, 33 parts by weight, 33.5 parts by weight, 34 parts by weight or 34.5 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity.

The content of the antibacterial and antiviral composite filler is 1.5 to 5 parts by weight, for example, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight or 4.8 parts by weight, and specific point values therebetween are limited by space and for the sake of brevity, and the specific point values included in the range are not exhaustive.

The water is present in an amount of 15 to 25 parts by weight, such as 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, or 24 parts by weight, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the ranges set forth.

In the present invention, the bio-based resin emulsion includes a bio-based acrylate emulsion and/or a bio-based polyurethane emulsion.

Preferably, the bio-based resin emulsion has a C14 content of 25-50%, such as 27%, 29%, 30%, 32%, 34%, 35%, 37%, 39%, 40%, 42%, 44%, 45%, 47%, or 49%, and specific points therebetween, limited to space and for brevity, the present invention is not exhaustive of the specific points included in the ranges.

In the invention, the bio-based content of the bio-based resin emulsion is measured by C14 content, and the test method of the C14 content is carried out by referring to the international standard ASTM D6866. In a preferable technical scheme of the invention, the content of C14 in the bio-based resin emulsion is 25-50%, if the content exceeds the range, the content of C14 is too low, the renewable and environment-friendly requirements cannot be met, and if the content of C14 is too high, the resistance of the bio-based water-based paint, such as acid and alkali resistance, weather resistance and the like, is reduced, and the service performance of a coating film is affected.

In the invention, the inorganic nonmetallic mineral carrier comprises any one or combination of at least two of kaolin, heavy calcium, light calcium, talcum powder, wollastonite powder or barium sulfate, and preferably the combination of the kaolin and the talcum powder.

Preferably, the particle size of the inorganic non-metallic mineral carrier is 10 to 45 μm, such as 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm or 44 μm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.

Preferably, the loading mass percentage of the nano titanium dioxide on the inorganic nonmetallic mineral carrier is 20-40%, for example, 22%, 24%, 25%, 27%, 29%, 30%, 32%, 34%, 35%, 37% or 39%, and the specific points between the above points are limited to space and for conciseness, and the invention is not exhaustive to list the specific points included in the range.

Preferably, the nano titanium dioxide has a particle size of 50 to 500nm, such as 55nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 130nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm, 470nm or 490nm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.

Preferably, the loading mass percentage of the nano silver on the inorganic nonmetallic mineral carrier is 15-30%, such as 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28% or 29%, and the specific points between the above points are limited by space and for the sake of brevity, and the invention is not exhaustive to list the specific points included in the range.

Preferably, the nano silver has a particle size of 50 to 500nm, such as 55nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 130nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm, 470nm or 490nm, and specific values therebetween are limited by space and for brevity, and the invention does not exhaust the specific values included in the range.

Preferably, the mass ratio of the nano titanium dioxide to the nano silver is 1 (0.5-1.2), such as 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1 or 1: 1.15.

Preferably, the inorganic nonmetallic mineral carrier is also loaded with silicon oxide.

In the invention, the silicon oxide loaded on the inorganic nonmetallic mineral carrier can be used as an intermediate connecting component, and the tight combination of the nano titanium dioxide, the nano silver and the inorganic nonmetallic mineral carrier is realized through the chemical bond effect, so that the stability of the antibacterial and antiviral composite filler is obviously improved, and the structural stability of the antibacterial and antiviral composite filler is still not damaged in a high-speed dispersion state.

Preferably, the silica is supported on the inorganic nonmetallic mineral carrier at a mass percent of 5 to 15%, such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or 14%, and the specific values therebetween are limited in space and for the sake of brevity and are not exhaustive of the invention to include the specific values within the stated ranges.

Preferably, the inorganic nonmetallic mineral carrier is also loaded with alumina.

In the invention, the alumina loaded on the inorganic nonmetallic mineral carrier is used as an intermediate to play a connecting role, and the nano titanium dioxide, the nano silver and the inorganic nonmetallic mineral carrier are tightly combined through the chemical bond effect, so that the stability of the antibacterial and antiviral composite filler is obviously improved, and the structural stability of the antibacterial and antiviral composite filler is still not damaged in a high-speed dispersion state.

Preferably, the loading mass percentage of the alumina on the inorganic non-metallic mineral carrier is 5-15%, such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.

Preferably, the antibacterial and antiviral composite filler comprises an inorganic nonmetallic mineral carrier, and nano titanium dioxide, nano silver, silicon oxide and aluminum oxide which are loaded on the inorganic nonmetallic mineral carrier.

Preferably, the particle size of the antibacterial and antiviral composite filler is 13 to 50 μm, such as 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm or 48 μm, and specific points therebetween are limited in space and for the sake of brevity, and the present invention is not exhaustive enumeration of the specific points included in the range.

The particle size of the antibacterial and antiviral composite filler is 13-50 mu m, and the antibacterial and antiviral composite filler cannot meet the paint film performance requirement of the bio-based water-based paint due to the overlarge particle size; the excessively small particle size thereof results in an increase in complexity of the preparation process, an increase in cost, and a decrease in antibacterial efficiency of the antibacterial and antiviral composite filler.

In the invention, the preparation method of the antibacterial and antiviral composite filler comprises the following steps:

(1) mixing an inorganic nonmetallic mineral carrier, an inorganic acid, water and a dispersant I to obtain a dispersion liquid I; mixing titanium tetrachloride, water and a dispersing agent II to obtain titanium tetrachloride hydrolysate;

(2) mixing and reacting the dispersion liquid I obtained in the step (1) with titanium tetrachloride hydrolysate to obtain a sample loaded with nano silicon dioxide;

(3) and (3) mixing and reacting the sample obtained in the step (2), silver salt and a reducing agent to obtain the antibacterial and antiviral composite filler.

Preferably, the dispersant I and the dispersant II in the step (1) respectively and independently comprise any one of alkali metal phosphate, polyacrylamide, polyacrylate, sodium dodecyl sulfate, sodium lignin sulfonate, polyvinyl alcohol, polyester dispersant or polyether dispersant or a combination of at least two of the alkali metal phosphate, the polyacrylamide, the polyacrylate, the sodium dodecyl sulfate, the sodium lignin sulfonate.

Preferably, the content of the inorganic nonmetallic mineral carrier in the dispersion liquid I in the step (1) is 5 to 50% by mass, for example, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.

Preferably, the content of the inorganic acid in the dispersion liquid I in the step (1) is 2 to 30% by mass, for example, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.

Preferably, the dispersion I in the dispersion liquid I in the step (1) is 0.02-10% by mass, such as 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 9.5%, and the specific values therebetween are limited by space and for brevity, and the invention is not exhaustive of the specific values included in the range.

Preferably, the mass ratio of titanium tetrachloride to water in the titanium tetrachloride hydrolysate in the step (1) is 1 (1-10), such as 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9 or 1: 9.5.

Preferably, the mass ratio of the titanium tetrachloride and the dispersant II in the step (1) is 1 (0.005-0.3), for example, 1:0.008, 1:0.01, 1:0.02, 1:0.04, 1:0.06, 1:0.08, 1:0.1, 1:0.11, 1:0.13, 1:0.15, 1:0.17, 1:0.19, 1:0.2, 1:0.21, 1:0.23, 1:0.25, 1:0.27, 1:0.29, or the like.

Preferably, the mixing method in step (2) is as follows: and dripping the titanium tetrachloride hydrolysate into the dispersion liquid I.

Preferably, the reaction time in step (2) is 2-6 h, such as 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 4.8h, 5h, 5.2h, 5.5h or 5.8h, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.

Preferably, the silver salt of step (3) comprises silver nitrate.

Preferably, the reducing agent in step (3) comprises sodium borohydride, sodium citrate or glucose.

Preferably, the reaction temperature in step (3) is 40-100 ℃, for example, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 98 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.

Preferably, the reaction time of step (3) is 5-60 min, such as 8min, 10min, 12min, 15min, 18min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 58min, and the specific values therebetween are limited by space and for simplicity, and the invention is not exhaustive.

Preferably, the reaction in step (3) further comprises a step of loading silica and/or alumina.

Preferably, the method for supporting silicon oxide is as follows: and (4) mixing the system obtained after the reaction in the step (3) with a silicate solution, and reacting to obtain a sample loaded with silicon oxide.

Preferably, the method for supporting alumina is as follows: and (4) mixing the system obtained after the reaction in the step (3) with a tetrahydroxy aluminum sodium silicate solution, and reacting to obtain the sample loaded with the alumina.

Preferably, the preparation method of the antibacterial and antiviral composite filler comprises the following steps:

(1) mixing an inorganic nonmetallic mineral carrier, an inorganic acid, water and a dispersant I to obtain a dispersion liquid I; mixing titanium tetrachloride, water and a dispersing agent II to obtain titanium tetrachloride hydrolysate;

(2) mixing and reacting the dispersion liquid I obtained in the step (1) with titanium tetrachloride hydrolysate to obtain a sample loaded with nano silicon dioxide;

(3) mixing the sample obtained in the step (2), silver nitrate and a reducing agent, and reacting for 5-60 min at 40-100 ℃; and after the reaction is finished, adding a silicate solution into the system to carry out a silicon oxide loading reaction, and then adding a tetrahydroxy sodium aluminum alloy solution to carry out an aluminum oxide loading reaction to obtain the antibacterial and antiviral composite filler.

In the present invention, the bio-based water-based paint further comprises 0.2 to 0.3 parts by weight (for example, 0.21 part by weight, 0.22 part by weight, 0.23 part by weight, 0.24 part by weight, 0.25 part by weight, 0.26 part by weight, 0.27 part by weight, 0.28 part by weight, or 0.29 part by weight) of a fungicide and mildew inhibitor.

Preferably, the fungicidal agent comprises an isothiazolinone fungicide, such as 1, 2-benzisothiazolin-3-one (BIT) and/or Methylisothiazolinone (MIT).

In the invention, the sterilization mildew preventive is an organic auxiliary agent, and plays a role in-tank sterilization mildew prevention during the storage process of the bio-based water-based paint.

Preferably, the bio-based water-based paint further comprises 0.2-2.5 parts by weight (e.g. 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight or 2.4 parts by weight) of a water retention agent.

Preferably, the water retaining agent comprises a cellulose ether.

Preferably, the bio-based water-based paint further comprises 0.4-1.0 parts by weight (for example, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight or 0.78 parts by weight) of a dispersant.

Preferably, the bio-based water-based paint further comprises 0.2-0.3 parts by weight (such as 0.21 parts by weight, 0.22 parts by weight, 0.23 parts by weight, 0.24 parts by weight, 0.25 parts by weight, 0.26 parts by weight, 0.27 parts by weight, 0.28 parts by weight or 0.29 parts by weight) of a wetting agent.

Preferably, the bio-based water-based paint further comprises 0.1-0.3 parts by weight (for example, 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, 0.18 parts by weight, 0.2 parts by weight, 0.22 parts by weight, 0.24 parts by weight, 0.26 parts by weight or 0.28 parts by weight) of a pH regulator.

Preferably, the bio-based water-based paint further comprises 0.2-0.4 parts by weight (for example, 0.22 parts by weight, 0.24 parts by weight, 0.26 parts by weight, 0.28 parts by weight, 0.3 parts by weight, 0.32 parts by weight, 0.34 parts by weight, 0.36 parts by weight or 0.38 parts by weight) of an antifreezing agent.

Preferably, the bio-based water-based paint further comprises 1.0-2.0 parts by weight (such as 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight or 1.9 parts by weight) of a film-forming assistant.

Preferably, the boiling point of the film-forming aid is greater than or equal to 290 ℃, i.e., the film-forming aid is preferably a high-boiling-point film-forming aid.

Preferably, the bio-based water paint further comprises 0.2-0.4 parts by weight (for example, 0.22 parts by weight, 0.24 parts by weight, 0.26 parts by weight, 0.28 parts by weight, 0.3 parts by weight, 0.32 parts by weight, 0.34 parts by weight, 0.36 parts by weight or 0.38 parts by weight) of an antifoaming agent.

Preferably, the defoamer comprises a high plant based defoamer.

Preferably, the bio-based water-based paint further comprises 1.0-2.0 parts by weight (such as 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight or 1.9 parts by weight) of a thickening agent.

Preferably, the thickener comprises any one of or a combination of at least two of a polyurethane-based thickener, a cellulose or an alkali swelling thickener.

Preferably, the bio-based water-based paint further comprises 35-45 parts by weight (for example, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight or 44 parts by weight) of other pigments and fillers.

Preferably, the other pigment and filler comprises any one or at least two of titanium dioxide, kaolin, talcum powder, white carbon black or calcium carbonate.

Preferably, the titanium dioxide is rutile type titanium dioxide.

Preferably, the bio-based water-based paint comprises the following components in parts by weight:

the antibacterial and antiviral composite filler comprises an inorganic nonmetallic mineral carrier, and nano titanium dioxide, nano silver, silicon oxide and aluminum oxide which are loaded on the inorganic nonmetallic mineral carrier.

In another aspect, the present invention provides a method for preparing the bio-based water-based paint, wherein the method comprises the following steps: and mixing and uniformly dispersing the bio-based resin emulsion, the antibacterial and antiviral composite filler, water, optional paint auxiliary agents and optional other pigments and fillers to obtain the bio-based water-based paint.

Preferably, the coating auxiliary agent comprises any one or a combination of at least two of a bactericidal and mildew-proof agent, a water-retaining agent, a dispersing agent, a wetting agent, a pH regulator, an antifreezing agent, a film-forming auxiliary agent, a defoaming agent or a thickening agent.

Illustratively, the preparation method of the bio-based water-based paint specifically comprises the following steps: mixing water and a water-retaining agent, then sequentially adding a dispersing agent, a wetting agent and a defoaming agent, adding an antibacterial and antiviral composite filler and other pigments according to the formula amount, and uniformly dispersing at a high speed; and sequentially adding other coating additives except the thickening agent and the bio-based resin emulsion, uniformly mixing, and then adding the thickening agent and/or water according to actual requirements to obtain the bio-based water-based coating.

In another aspect, the present invention provides a use of the bio-based water-based paint as described above in building exterior wall paint or interior paint.

Compared with the prior art, the invention has the following beneficial effects:

the bio-based water-based paint provided by the invention takes the bio-based resin emulsion as a film forming substance, has the characteristics of green, regenerability and degradability, and can fully meet the environmental protection requirement of the paint; meanwhile, the antibacterial and antiviral composite filler is an inorganic filler, and the synergistic effect of the inorganic nonmetallic mineral carrier, the nano titanium dioxide and the nano silver enables the I-level antibacterial rate of a paint film to reach more than 99.0, even more than or equal to 99.9 percent, the I-level antiviral rate to reach 90.1-97.3 percent, and the antibacterial and antiviral composite filler has efficient, broad-spectrum and lasting antibacterial and antiviral properties and can meet the requirement of the paint on persistent antibacterial and antiviral in the service life. In addition, the antibacterial and antiviral composite filler also comprises silicon oxide and aluminum oxide, and the tight combination of the nano titanium dioxide, the nano silver and the inorganic nonmetallic mineral carrier is realized through the chemical bond effect, so that the stability of the antibacterial and antiviral composite filler is obviously improved, and the structural stability of the antibacterial and antiviral composite filler is still not damaged in a high-speed dispersion state. The bio-based water-based paint disclosed by the invention meets the requirements of environmental protection, antibiosis and antivirus, has excellent dispersibility and coatability, has good water resistance, alkali resistance and stain resistance after film formation, and is particularly suitable for being used as a building paint to be applied to decoration and protection of building outer walls or interiors.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.