CN112175425A - Powder coating with negative ion releasing, moisture absorbing and mildew preventing functions and preparation method thereof - Google Patents
Powder coating with negative ion releasing, moisture absorbing and mildew preventing functions and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of coatings, and discloses a powder coating with negative ion releasing, moisture absorbing and mildew preventing functions and a preparation method thereof, wherein the powder coating comprises the following components: 30-50 parts of diatomite, 10-20 parts of sepiolite, 5-15 parts of tourmaline, 1-10 parts of mica powder, 1-10 parts of zeolite powder, 5-15 parts of intelligent mildew-proof microcapsule particles, 1-5 parts of carboxymethyl cellulose, 5-10 parts of silica sol, 1-5 parts of a dispersing agent, 0-1 part of a leveling agent and 0-1 part of a defoaming agent. The powder coating disclosed by the invention takes an inorganic material as a main raw material, and simultaneously contains a material capable of emitting far infrared rays and releasing negative ions and intelligent mildew-proof microcapsule particles capable of intelligently adjusting the mildew-proof capability of the coating according to the environmental humidity.
Description
Technical Field
The invention relates to the field of coatings, in particular to a powder coating with negative ion releasing, moisture absorbing and mildew preventing functions and a preparation method thereof.
Background
The inorganic powder coating is a novel environment-friendly coating which can be used after being added with water and is easy to scrape. The inorganic powder coating is prepared by compounding natural inorganic mineral materials and the like serving as main materials with a polymer additive, and has the advantages of high hardness, good air permeability and hygroscopicity, environmental friendliness and the like.
However, since natural inorganic mineral materials such as diatomaceous earth, sepiolite, bentonite, and the like have good hygroscopicity in the inorganic powder coating, mildew stains are highly likely to occur when the inorganic powder coating is exposed to a high humidity environment for a long period of time. Particularly, in southern areas of China with humid and hot climate, the humidity in the air is high, the wall coating is easy to absorb moisture in a long-time high humidity environment, so that the wall surface is easy to dewfall, and the coating is easy to become a hotbed for breeding microorganisms in the humid and hot environment, thereby causing mildew. On one hand, the mildew is difficult to remove, which causes great negative influence on the beauty of the wall surface. On the other hand, the microorganisms erode the coating, so that the coating is faded and falls off.
At present, in order to solve the above technical problems, a common solution is to add a mildewproof component to the paint to play a role in inhibiting the growth of microorganisms. For example, chinese invention patent CN201710589027.2 discloses a waterproof and mildewproof interior wall powder coating and a production process thereof, wherein the powder coating comprises the following raw materials in parts by weight: 60-80 parts of diatomite, 70-90 parts of fly ash, 15-30 parts of montmorillonite, 20-30 parts of talcum powder, 8-20 parts of aluminum hydroxide powder, 5-10 parts of bamboo charcoal fiber, 1-5 parts of antimony trioxide, 0.6-2 parts of sodium hypochlorite, 1-3 parts of nano zinc oxide, 0.2-0.6 part of kasong, 0.1-0.5 part of dispersing agent, 0.2-0.8 part of wetting agent and 0.1-0.3 part of defoaming agent. The preparation method comprises the steps of diatomite purification and mixed ball milling.
Although the powder coating contains antibacterial and bacteriostatic components, the powder coating has a mildew-proof function. However, the mildew-proof powder coating disclosed in the above patents is only added with an additive having an antibacterial and mildew-proof effect, and does not have a function of intelligently adjusting the mildew-proof capability according to the ambient humidity.
On the other hand, the inorganic powder products in the current market have single function, serious homogenization phenomenon and low added value of the products.
Disclosure of Invention
In order to solve the technical problems, the invention provides a powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew and a preparation method thereof. The powder coating disclosed by the invention takes an inorganic material as a main raw material, and simultaneously contains a material capable of emitting far infrared rays and releasing negative ions and intelligent mildew-proof microcapsule particles capable of intelligently adjusting the mildew-proof capability of the coating according to the environmental humidity.
The specific technical scheme of the invention is as follows: the powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
30-50 parts of diatomite,
10-20 parts of sepiolite, and a mixture of sepiolite,
5-15 parts of tourmaline, and the like,
1-10 parts of mica powder,
1-10 parts of zeolite powder, wherein,
5-15 parts of intelligent mildew-proof microcapsule particles,
1-5 parts of carboxymethyl cellulose,
5-10 parts of silica sol,
1-5 parts of a dispersing agent,
0-1 part of a leveling agent,
0-1 part of defoaming agent.
The coating provided by the invention is mainly made of inorganic materials, uses water as a solvent when in use, and does not contain an organic solvent, so that VOC (volatile organic compounds) is not generated, and the coating is green and environment-friendly. The inorganic materials mainly comprise diatomite and sepiolite, and have excellent hygroscopicity and harmful gas adsorption capacity.
The coating of the invention simultaneously contains tourmaline, mica powder and zeolite powder. Wherein, the mica powder and the tourmaline have the functions of emitting far infrared rays and releasing negative ions, and the zeolite powder has developed pores inside and can absorb moisture and harmful gases. In addition, the invention can effectively enhance the negative ion release capacity after combining the tourmaline, the mica powder, the zeolite powder, the diatomite and the sepiolite. The reason for this is that: the mica and the tourmaline generate potential difference under the change of the external temperature, so that the air is ionized, and the electrons convert water molecules around the mica and the tourmaline into negative oxygen ions. In a high humidity environment, the negative oxygen ions can be generated far continuously because the water molecules in the air are sufficient, but in a low environment humidity environment, the negative oxygen ion generating capacity is limited because the number of molecules which can act around the negative oxygen ions is greatly reduced. In the present invention, since a large amount of inorganic material having excellent moisture absorption ability is contained, water molecules in the air can be effectively adsorbed, and thus, it is possible to ensure that negative oxygen ions are continuously generated and released. Therefore, the coating can realize the effective release of negative oxygen ions in a low-humidity environment.
In addition, the coating contains intelligent mildew-proof microcapsule particles, and has the function of intelligently adjusting the moisture absorption capacity and mildew-proof capacity of the coating according to the environmental humidity.
Preferably, the particle size of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 1-100 microns.
Preferably, the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder are subjected to heat treatment at 250-350 ℃ for 1-2h in advance.
Preferably, the dispersant is selected from polyethylene glycol, sodium dodecyl benzene sulfonate and polyacrylamide.
Preferably, the defoaming agent is selected from polydimethylsiloxane and polyoxypropylene glycerol ether.
Preferably, the leveling agent is a polydimethylsiloxane-type leveling agent.
Preferably, the preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a water-soluble starch solution with the weight percent of 5-10, adding 0.5-1 wt% of silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 3-5, heating in a 70-80 ℃ water bath for 1-2h under the dark condition, then adding excessive sodium borohydride into the solution, adding alkali to adjust the pH value of the solution to 7-9, reacting for 1-3h, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
In the step 1), the water-soluble starch is used as a coating wall material of the intelligent mildew-proof microcapsule particles, and the water-soluble starch is subjected to silver-carrying treatment, so that the water-soluble starch has a certain antibacterial property, and the growth of microorganisms is inhibited.
2) Adding the silver-loaded water-soluble starch into water, and then adding tween into the water under the stirring condition of 400-600r/min at the temperature of 50-60 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 5-10 wt%.
3) Dripping the volatile plant oil phase extract into the silver-loaded water-soluble starch solution according to the mass ratio of 1:5-10 under the stirring condition of 100-200r/min to form an oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
The water-soluble starch has a hydrophilic surface and a hydrophobic inner cavity, so that the water-soluble starch can be used as an ideal carrier of the volatile vegetable oil phase extract to prepare the water-soluble starch microcapsule loaded with the volatile vegetable oil phase extract.
4) Taking crab shells, rough grinding, carrying out anaerobic roasting at the temperature of 350-450 ℃ for 1-3h, and then carrying out anaerobic roasting at the temperature of 900-950 ℃ for 2-4h, and fine grinding to obtain roasted crab shell powder.
The crab shell is mainly made of calcium carbonate and partial organic matters, the crab shell is coarsely ground to a certain particle size, anaerobic roasting is carried out at the temperature of 350-plus-450 ℃, the organic matters can be carbonized, then anaerobic roasting is carried out at the temperature of 900-plus-950 ℃, the organic matters are further carbonized, the calcium carbonate is gradually pyrolyzed into calcium oxide and carbon dioxide, a large number of capillary pores can be generated in crab shell powder in the two-step roasting process, and the obtained roasted crab shell powder is a mixed material which has certain adsorbability, takes the calcium oxide as a main material and takes the biochar as an auxiliary material.
5) Mechanically milling the roasted crab shell powder, the photodegradation catalyst and the water-soluble starch microcapsule in a high-energy ball mill for 1-3h according to the mass ratio of 1-2:0.01-0.05:1, and obtaining the water-soluble starch microcapsule wrapped by the roasted crab shell powder after ball milling.
The roasted crab shell powder and the photodegradation catalyst can be coated on the surface of the water-soluble starch microcapsule in a micro particle shape (without forming a complete coating layer) under the action of mechanical force.
6) Adding the water-soluble starch microcapsule wrapped by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:0.5-1.5 for modification treatment, and taking out.
The silane coupling agent is used for carrying out surface modification treatment on the water-soluble starch microcapsule wrapped by the roasted crab shell powder, so that the compatibility of the water-soluble starch microcapsule and an organic polymer can be improved, and conditions are provided for subsequent treatment.
7) Adding the product obtained in the step 6) into an organic solution of the ethylene-carbon monoxide copolymer in batches under the condition of keeping out of the sun for uniform dispersion, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain the intelligent mildew-proof microcapsule particles for later use in the absence of the sun.
The product obtained in the step 6) is a water-soluble starch microcapsule coated by roasted crab shell powder subjected to surface treatment by a silane coupling agent, the core material of the microcapsule is a volatile plant oil phase extract with excellent antibacterial property and fragrance, the coating can be endowed with a mould-proof effect, the first wall material is silver-loaded water-soluble starch, the volatile plant oil phase extract can be effectively coated and a slow release function is realized, and the first wall material also has antibacterial property. The second wall material is roasted crab shell powder which takes calcium oxide as a main material and biochar as an auxiliary material, and is coated on the surface of the silver-loaded water-soluble starch in a micro-particle shape. And a large amount of heat can be generated in the water absorption reaction process of the calcium oxide, so that the release of the volatile vegetable oil phase extract can be promoted, and the mildew-proof effect is further enhanced. The advantage of this effect is that different degrees of mould-proof effect can be achieved depending on the ambient humidity: when the environmental humidity is lower, the roasted crab shell powder hardly absorbs water, so that reaction heat is not generated, the volatile plant oil phase extract is normally and slowly released, and the release period is prolonged as much as possible; along with the improvement of different degrees of the environmental humidity, the water absorption of the roasted crab shell powder is increased to different degrees, so the reaction heat is increased to different degrees, and the release of the volatile vegetable oil phase extract is enhanced to different degrees. Furthermore, the antibacterial activity of silver can be further activated at a temporarily higher temperature. As is known, the higher the environmental humidity, the more easily the microorganisms grow, and a stronger mold-proof effect is required. Therefore, the coating can adjust the mildew-proof effect according to the ambient humidity.
The reason why the microcapsule is further coated with the ethylene-carbon monoxide copolymer in the step 7) is that the intelligent mildew-proof microcapsule particles are finally added into the coating taking water as a solvent (when in use), and the roasted crab shell powder reacts with the water before extraction. Therefore, the invention firstly coats a layer of hydrophobic ethylene-carbon monoxide copolymer on the surface of the intelligent mildew-proof microcapsule particles as a protective film to isolate the external moisture. The ethylene-carbon monoxide copolymer has excellent photodegradable property. In the invention, a small amount of photodegradation catalyst is added into intelligent mildew-proof microcapsule particles. When the coating is coated on a wall surface, the coating is dried and cured, and the ethylene-carbon monoxide copolymer can be rapidly degraded by manually irradiating the coating by using an ultraviolet lamp tube or a common visible light source; or the ethylene-carbon monoxide copolymer can be naturally and slowly degraded by light under natural illumination according to actual needs.
Preferably, in the step 2), the tween is added in an amount of 0.5 to 1.5 wt% of the water.
Preferably, in the step 3), the dropping speed of the volatile vegetable oil phase extract is 0.05-0.2 mL/s.
Preferably, in the step 3), the volatile plant oil phase extract is perilla essential oil and lavender essential oil in a mass ratio of 1-2: 1.
Preferably, in the step 4), the grain diameter of the crab shell after coarse grinding is 0.5-2mm, and the grain diameter after fine grinding is 0.1-0.5 μm.
Preferably, in step 7), the concentration of the ethylene-carbon monoxide copolymer organic solution is 5 to 20 wt%; the addition amount of the product obtained in the step 6) is 10-20 wt% of the mass of the ethylene-carbon monoxide copolymer.
Compared with the prior art, the invention has the following technical effects:
(1) the coating provided by the invention is mainly made of inorganic materials, uses water as a solvent when in use, and does not contain an organic solvent, so that VOC (volatile organic compounds) is not generated, and the coating is green and environment-friendly.
(2) The inorganic material in the coating is mainly diatomite and sepiolite, and has excellent hygroscopicity and harmful gas adsorption capacity.
(3) The coating of the invention simultaneously contains tourmaline, mica powder, zeolite powder, diatomite and sepiolite. Wherein, the mica powder and the tourmaline have the functions of emitting far infrared rays and releasing negative ions, and the zeolite powder, the diatomite and the sepiolite have the capabilities of absorbing moisture and harmful gases. The invention can effectively enhance the negative ion release capacity by combining the tourmaline, the mica powder, the zeolite powder, the diatomite and the sepiolite.
(4) The coating disclosed by the invention takes the water-based acrylic resin as a film forming material, contains intelligent mildew-proof microcapsule particles, and has the function of intelligently adjusting the mildew-proof capability of the coating according to the ambient humidity.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
40 parts of diatomite, namely 40 parts of diatomite,
15 parts of sepiolite,
10 parts of tourmaline, 10 parts of,
5 parts of mica powder, namely 5 parts of mica powder,
5 parts of zeolite powder, namely 5 parts of zeolite powder,
10 parts of intelligent mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
8 parts of silica sol, namely 8 parts of silica sol,
3 parts of a dispersing agent (polyethylene glycol),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 300 ℃ for 1.5 hours in advance.
The preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a water-soluble starch solution with the weight percent of 8, adding 0.8 percent by weight of silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 4, heating in a 75 ℃ water bath for 1.5 hours under the light-proof condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 8, reacting for 2 hours, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1 wt% of tween into the water under the stirring condition of 500r/min at 55 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 8 wt%.
3) Dripping volatile plant oil phase extract (mixture of Perilla frutescens essential oil and Lavender essential oil at a mass ratio of 1.5: 1) into silver-loaded water-soluble starch solution at a speed of 0.15mL/s under stirring at 150r/min at a mass ratio of 1:8 to form oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 1.5mm, carrying out anaerobic roasting at 400 ℃ for 2h, then carrying out anaerobic roasting at 925 ℃ for 3h, and finely grinding until the average grain diameter is 0.3 mu m, thus obtaining roasted crab shell powder.
5) Mechanically milling the roasted crab shell powder, the photodegradation catalyst (nano titanium dioxide doped with 1 wt% of N, P, K elements respectively) and the water-soluble starch microcapsule in a high-energy ball mill for 2 hours according to the mass ratio of 1.5:0.03:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule coated by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:1 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of an ethylene-carbon monoxide copolymer with the concentration of 15 wt% and the mass of 8 times of that of the product under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Example 2
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
30 parts of diatomite for treating the surface of the soil,
20 parts of sepiolite, namely 20 parts of sepiolite,
5 parts of tourmaline, namely, a mixture of the raw materials,
10 parts of mica powder, namely 10 parts of mica powder,
10 parts of zeolite powder, namely 10 parts of zeolite powder,
10 parts of intelligent mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
5 parts of silica sol, namely adding 5 parts of silica sol,
5 parts of a dispersing agent (sodium dodecyl benzene sulfonate),
1 part of polydimethylsiloxane type flatting agent,
1 part of defoaming agent (polyoxypropylene glycerol ether).
Wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 250 ℃ for 2 hours in advance.
The preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a water-soluble starch solution with the weight percent of 8, adding 0.5 weight percent of silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 3.5, heating in a 75 ℃ water bath for 1.5h under the light-shielding condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 8.5, reacting for 2.5h, cooling to separate out a solid, centrifugally separating, washing and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1 wt% of tween into the water under the stirring condition of 550r/min at the temperature of 55 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 8 wt%.
3) Dripping volatile plant oil phase extract (mixture of perilla essential oil and lavender essential oil with a mass ratio of 1: 1) into silver-carrying water-soluble starch solution at a speed of 0.1mL/s under stirring at 200r/min at a mass ratio of 1:6 to form an oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 1mm, firstly roasting in an anaerobic environment at 400 ℃ for 1.5h, then roasting in an anaerobic environment at 950 ℃ for 2.5h, and finely grinding until the average grain diameter is 0.2 mu m to obtain roasted crab shell powder.
5) Mechanically ball-milling the roasted crab shell powder, the photodegradation catalyst (nano titanium dioxide doped with 1 wt% of N, P, K elements respectively) and the water-soluble starch microcapsule in a high-energy ball mill for 1.5h according to the mass ratio of 2:0.05:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule coated by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:1 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of 10-time mass of 10 wt% ethylene-carbon monoxide copolymer under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Example 3
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
50 parts of diatomite, namely adding 50 parts of diatomite,
10 parts of sepiolite, namely 10 parts of sepiolite,
15 parts of tourmaline, 15 parts of,
1 part of mica powder, namely 1 part of mica powder,
5 parts of zeolite powder, namely 5 parts of zeolite powder,
5 parts of intelligent mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
10 parts of silica sol, namely 10 parts of silica sol,
1 part of a dispersant (polyacrylamide),
wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 250 ℃ for 2 hours in advance.
The preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a 10 wt% water-soluble starch solution, adding 1 wt% silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 3, heating in a water bath at 80 ℃ for 1h under the light-proof condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 7, reacting for 3h, cooling to separate out a solid, and carrying out centrifugal separation, washing and vacuum drying to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1.5 wt% of Tween into the water under the stirring condition of 600r/min at the temperature of 60 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 10 wt%.
3) Dripping volatile plant oil phase extract (mixture of perilla essential oil and lavender essential oil with a mass ratio of 2: 1) into silver-carrying water-soluble starch solution at a speed of 0.2mL/s under stirring at 200r/min at a mass ratio of 1:10 to form an oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 2mm, firstly roasting in anaerobic condition at 450 ℃ for 1h, then roasting in anaerobic condition at 950 ℃ for 2h, and finely grinding until the average grain diameter is 0.5 mu m to obtain roasted crab shell powder.
5) Mechanically milling the roasted crab shell powder, the photodegradation catalyst (nano titanium dioxide doped with 1 wt% of N, P, K elements respectively) and the water-soluble starch microcapsule in a high-energy ball mill for 3 hours according to the mass ratio of 1:0.01:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule wrapped by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:1.5 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of 10 times of the ethylene-carbon monoxide copolymer with the mass concentration of 5 wt% under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain the intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Example 4
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
35 parts of diatomite, namely adding 35 parts of diatomite,
10 parts of sepiolite, namely 10 parts of sepiolite,
15 parts of tourmaline, 15 parts of,
10 parts of mica powder, namely 10 parts of mica powder,
1 part of zeolite powder, namely 1 part of zeolite powder,
15 parts of intelligent mildew-proof microcapsule particles,
5 parts of carboxymethyl cellulose, namely 5 parts of,
5 parts of silica sol, namely adding 5 parts of silica sol,
3 parts of a dispersant (polyacrylamide),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 350 ℃ for 1h in advance.
The preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a 5 wt% water-soluble starch solution, adding 0.5 wt% silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 5, heating in a 70 ℃ water bath for 2 hours under the light-proof condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 9, reacting for 1 hour, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 0.5 wt% of tween into the water under the stirring condition of 400r/min at 50 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 5 wt%.
3) Dripping volatile plant oil phase extract (mixture of perilla essential oil and lavender essential oil with a mass ratio of 1: 1) into silver-carrying water-soluble starch solution at a speed of 0.05mL/s under stirring at 100r/min at a mass ratio of 1:5 to form an oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 0.5mm, carrying out anaerobic roasting at 350 ℃ for 3h, then carrying out anaerobic roasting at 900 ℃ for 4h, and finely grinding until the average grain diameter is 0.1 mu m to obtain roasted crab shell powder.
5) Mechanically milling the roasted crab shell powder, the photodegradation catalyst (nano titanium dioxide doped with 1 wt% of N, P, K elements respectively) and the water-soluble starch microcapsule in a high-energy ball mill for 1h according to the mass ratio of 1.5:0.02:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule wrapped by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:0.5 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of an ethylene-carbon monoxide copolymer with the concentration of 20 wt% and the mass of 5 times of that of the product under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Example 5
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
45 parts of diatomite, namely adding 45 parts of diatomite,
10 parts of sepiolite, namely 10 parts of sepiolite,
10 parts of tourmaline, 10 parts of,
5 parts of mica powder, namely 5 parts of mica powder,
5 parts of zeolite powder, namely 5 parts of zeolite powder,
10 parts of intelligent mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
7 parts of silica sol, namely adding 7 parts of silica sol,
4 parts of a dispersing agent (polyethylene glycol),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 10 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 350 ℃ for 2 hours in advance.
The preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a 6 wt% water-soluble starch solution, adding 0.5 wt% silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 4.5, heating in a water bath at 80 ℃ for 2 hours under the light-shielding condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 7.5, reacting for 2.5 hours, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1 wt% of tween into the water under the stirring condition of 500r/min at the temperature of 60 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 6 wt%.
3) Dripping volatile plant oil phase extract (mixture of perilla essential oil and lavender essential oil with a mass ratio of 1: 1) into the silver-carrying water-soluble starch solution at a speed of 0.15mL/s under stirring at 200r/min at a mass ratio of 1:6 to form an oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 1.5mm, firstly roasting in an anaerobic environment at 400 ℃ for 2h, then roasting in an anaerobic environment at 900 ℃ for 3h, and finely grinding until the average grain diameter is 0.4 mu m to obtain roasted crab shell powder.
5) Mechanically milling the roasted crab shell powder, the photodegradation catalyst (nano titanium dioxide doped with 1 wt% of N, P, K elements respectively) and the water-soluble starch microcapsule in a high-energy ball mill for 1-3h according to the mass ratio of 2:0.05:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule coated by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:1 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of an ethylene-carbon monoxide copolymer with the concentration of 10 wt% and the mass of 8 times of that of the product under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Comparative example 1
The powder coating capable of releasing negative ions comprises the following components in parts by weight:
45 parts of diatomite, namely adding 45 parts of diatomite,
20 parts of sepiolite, namely 20 parts of sepiolite,
10 parts of tourmaline, 10 parts of,
5 parts of mica powder, namely 5 parts of mica powder,
5 parts of zeolite powder, namely 5 parts of zeolite powder,
3 parts of carboxymethyl cellulose, namely 3 parts of,
8 parts of silica sol, namely 8 parts of silica sol,
3 parts of a dispersing agent (polyethylene glycol),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 300 ℃ for 1.5 hours in advance.
Comparative example 2
A powder coating with moisture absorption and mildew prevention functions comprises the following components in parts by weight:
50 parts of diatomite, namely adding 50 parts of diatomite,
20 parts of sepiolite, namely 20 parts of sepiolite,
5 parts of zeolite powder, namely 5 parts of zeolite powder,
10 parts of intelligent mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
8 portions of silica sol
3 parts of a dispersing agent (polyethylene glycol),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average grain diameter of the diatomite, the sepiolite and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 300 ℃ for 1.5 hours in advance.
The preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a water-soluble starch solution with the weight percent of 8, adding 0.8 percent by weight of silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 4, heating in a 75 ℃ water bath for 1.5 hours under the light-proof condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 8, reacting for 2 hours, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1 wt% of tween into the water under the stirring condition of 500r/min at 55 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 8 wt%.
3) Dripping volatile plant oil phase extract (mixture of Perilla frutescens essential oil and Lavender essential oil at a mass ratio of 1.5: 1) into silver-loaded water-soluble starch solution at a speed of 0.15mL/s under stirring at 150r/min at a mass ratio of 1:8 to form oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 1.5mm, carrying out anaerobic roasting at 400 ℃ for 2h, then carrying out anaerobic roasting at 925 ℃ for 3h, and finely grinding until the average grain diameter is 0.3 mu m, thus obtaining roasted crab shell powder.
5) Mechanically milling the roasted crab shell powder, the photodegradation catalyst (nano titanium dioxide doped with 1 wt% of N, P, K elements respectively) and the water-soluble starch microcapsule in a high-energy ball mill for 2 hours according to the mass ratio of 1.5:0.03:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule coated by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:1 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of an ethylene-carbon monoxide copolymer with the concentration of 15 wt% and the mass of 8 times of that of the product under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Comparative example 3
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
60 parts of calcium carbonate, namely calcium carbonate,
10 parts of tourmaline, 10 parts of,
5 parts of mica powder, namely 5 parts of mica powder,
10 parts of intelligent mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
8 parts of silica sol, namely 8 parts of silica sol,
3 parts of a dispersing agent (polyethylene glycol),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average particle size of the calcium carbonate, the tourmaline and the mica powder is 5 microns. The tourmaline and the mica powder are subjected to heat treatment at 300 ℃ for 1.5h in advance.
The preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a water-soluble starch solution with the weight percent of 8, adding 0.8 percent by weight of silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 4, heating in a 75 ℃ water bath for 1.5 hours under the light-proof condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 8, reacting for 2 hours, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1 wt% of tween into the water under the stirring condition of 500r/min at 55 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 8 wt%.
3) Dripping volatile plant oil phase extract (mixture of Perilla frutescens essential oil and Lavender essential oil at a mass ratio of 1.5: 1) into silver-loaded water-soluble starch solution at a speed of 0.15mL/s under stirring at 150r/min at a mass ratio of 1:8 to form oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 1.5mm, carrying out anaerobic roasting at 400 ℃ for 2h, then carrying out anaerobic roasting at 925 ℃ for 3h, and finely grinding until the average grain diameter is 0.3 mu m, thus obtaining roasted crab shell powder.
5) Mechanically milling the roasted crab shell powder, the photodegradation catalyst (nano titanium dioxide doped with 1 wt% of N, P, K elements respectively) and the water-soluble starch microcapsule in a high-energy ball mill for 2 hours according to the mass ratio of 1.5:0.03:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule coated by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:1 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of an ethylene-carbon monoxide copolymer with the concentration of 15 wt% and the mass of 8 times of that of the product under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Comparative example 4
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
40 parts of diatomite, namely 40 parts of diatomite,
15 parts of sepiolite,
10 parts of tourmaline, 10 parts of,
5 parts of mica powder, namely 5 parts of mica powder,
5 parts of zeolite powder, namely 5 parts of zeolite powder,
10 parts of mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
8 parts of silica sol, namely 8 parts of silica sol,
3 parts of a dispersing agent (polyethylene glycol),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 300 ℃ for 1.5 hours in advance.
The preparation method of the mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a water-soluble starch solution with the weight percent of 8, adding 0.8 percent by weight of silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 4, heating in a 75 ℃ water bath for 1.5 hours under the light-proof condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 8, reacting for 2 hours, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1 wt% of tween into the water under the stirring condition of 500r/min at 55 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 8 wt%.
3) Dripping volatile plant oil phase extract (mixture of Perilla frutescens essential oil and Lavender essential oil at a mass ratio of 1.5: 1) into silver-loaded water-soluble starch solution at a speed of 0.15mL/s under stirring at 150r/min at a mass ratio of 1:8 to form oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to prepare the water-soluble starch microcapsule loaded with the volatile plant oil phase extract, namely the mildew-proof microcapsule particle.
Comparative example 5
The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew comprises the following components in parts by weight:
40 parts of diatomite, namely 40 parts of diatomite,
15 parts of sepiolite,
10 parts of tourmaline, 10 parts of,
5 parts of mica powder, namely 5 parts of mica powder,
5 parts of zeolite powder, namely 5 parts of zeolite powder,
10 parts of mildew-proof microcapsule particles,
3 parts of carboxymethyl cellulose, namely 3 parts of,
8 parts of silica sol, namely 8 parts of silica sol,
3 parts of a dispersing agent (polyethylene glycol),
0.5 part of polydimethylsiloxane type flatting agent,
0.5 part of defoaming agent (polydimethylsiloxane).
Wherein the average grain diameter of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 5 microns. Diatomite, sepiolite, tourmaline, mica powder and zeolite powder are subjected to heat treatment at 300 ℃ for 1.5 hours in advance.
The preparation method of the mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a 6 wt% water-soluble starch solution, adding 0.5 wt% silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 4.5, heating in a water bath at 80 ℃ for 2 hours under the light-shielding condition, then adding excessive sodium borohydride into the solution, adding sodium hydroxide to adjust the pH value of the solution to 7.5, reacting for 2.5 hours, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain the silver-loaded water-soluble starch.
2) Adding the silver-loaded water-soluble starch into water, and then adding 1 wt% of tween into the water under the stirring condition of 500r/min at the temperature of 60 ℃ to obtain a silver-loaded water-soluble starch solution with the concentration of 6 wt%.
3) Dripping volatile plant oil phase extract (mixture of perilla essential oil and lavender essential oil with a mass ratio of 1: 1) into the silver-carrying water-soluble starch solution at a speed of 0.15mL/s under stirring at 200r/min at a mass ratio of 1:6 to form an oil-in-water emulsion; and (3) carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to obtain the water-soluble starch microcapsule loaded with the volatile plant oil phase extract.
4) Taking crab shells, coarsely grinding until the average grain diameter is 1.5mm, firstly roasting in an anaerobic environment at 400 ℃ for 2h, then roasting in an anaerobic environment at 900 ℃ for 3h, and finely grinding until the average grain diameter is 0.4 mu m to obtain roasted crab shell powder.
5) Mechanically ball-milling the roasted crab shell powder and the water-soluble starch microcapsule in a high-energy ball mill for 1-3h according to the mass ratio of 1.5:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder.
6) Adding the water-soluble starch microcapsule coated by the roasted crab shell powder into a silane coupling agent according to the mass ratio of 1:1 for modification treatment, and taking out.
7) Adding the product obtained in the step 6) in batches into a toluene solution of an ethylene-carbon monoxide copolymer with the concentration of 10 wt% and the mass of 8 times of that of the product under the condition of keeping out of the sun, uniformly dispersing, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain intelligent mildew-proof microcapsule particles for later use under the condition of keeping out of the sun.
Performance testing
Firstly, testing the anion release performance:
the powder coatings of example 1 and comparative examples 1 to 5 were subjected to a negative ion release performance test: the method is carried out according to the test method of the anion generation amount of JC/T1016-2006 material. In which the coatings of example 1 and comparative example 5 were subjected to an artificial ultraviolet irradiation for 30min after coating. The detection data are as follows:
| group of | Amount of anion released (ions/cc) |
| Example 1 | 1530 |
| Comparative example 1 | 1556 |
| Comparative example 2 | 321 |
| Comparative example 3 | 893 |
| Comparative example 4 | 1491 |
| Comparative example 5 | 1622 |
From the data in the above table it can be seen that: the tourmaline and the mica powder are contained in the embodiment 1 and the comparative examples 1,4 to 5, so that negative oxygen ions can be effectively released; in the comparative example 2, the release amount of negative oxygen ions is very low because tourmaline and mica powder are not contained; in comparative example 3, although tourmaline and mica powder are contained, compared with example 1, diatomite, sepiolite and zeolite powder with high moisture absorption capacity are replaced by calcium carbonate with poor moisture absorption, so that the diatomite, the sepiolite and the zeolite powder cannot be matched with the tourmaline and mica powder, the release amount of negative oxygen ions is greatly reduced, and the tourmaline, the mica and a high-humidity material are compounded to obviously provide the negative oxygen ion release capacity
Secondly, testing mildew resistance:
the powder coatings of example 1 and comparative examples 1 to 5 were subjected to a mildew resistance test: the test period is 28 days according to the (wet room suspension method) in the national standard GB 1741-2007' determination method of the resistance to mold of paint film) under the environment of normal humidity (80 + -1%, 29 + -1 ℃, and protected from light) and the environment of high humidity (95 + -1%, 29 + -1 ℃, and protected from light). In which the coatings of example 1 and comparative example 5 were subjected to an artificial ultraviolet irradiation for 30min after coating. The detection data are as follows:
grade 0-no significant mold growth under about 50 times magnification;
grade 1-no or very little mold growth is visible to the naked eye, but significant mold growth is visible under a magnifying glass;
grade 2, wherein the mold growth is obviously seen by naked eyes, and the coverage area on the surface of the sample is 10-30%;
grade 3, wherein the mold growth is obviously seen by naked eyes, and the coverage area on the surface of the sample is 30-60%;
grade 4-the mold growth is obviously seen by naked eyes, and the coverage area on the surface of the sample is more than 60%;
from the data in the above table it can be seen that:
under the environment of 80% humidity, the mildew-proof components are contained in the embodiment 1 and the comparative examples 2 to 4, so that the mildew-proof effect can be effectively achieved, and the mildew-proof grade is 0 grade; in contrast, comparative example 1 has a lower grade of 2 because it does not contain a mildewproof component; although the comparative example 5 contains the mildewproof component, the polymer layer on the surface of the mildewproof particle cannot be rapidly degraded after being coated with ultraviolet radiation because the mildewproof particle does not contain the photodegradation catalyst, so that the mildewproof component cannot be released in time, and certain influence is caused on the mildewproof performance of the mildewproof particle.
In 95% environment, the example 1 still can keep better mildew resistance because of having the intelligent mildew-proof function, while in the comparative example 4, because of not containing calcium oxide, the mildew-proof effect can not be adjusted according to the ambient humidity, therefore the mildew-proof performance can not be effectively enhanced in high humidity environment, therefore the mildew-proof effect is poor.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mildew is characterized by comprising the following components in parts by weight:
30-50 parts of diatomite,
10-20 parts of sepiolite, and a mixture of sepiolite,
5-15 parts of tourmaline, and the like,
1-10 parts of mica powder,
1-10 parts of zeolite powder, wherein,
5-15 parts of intelligent mildew-proof microcapsule particles,
1-5 parts of carboxymethyl cellulose,
5-10 parts of silica sol,
1-5 parts of a dispersing agent,
0-1 part of a leveling agent,
0-1 part of defoaming agent.
2. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 1, wherein: the particle size of the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder is 1-100 microns.
3. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 1, wherein: the diatomite, the sepiolite, the tourmaline, the mica powder and the zeolite powder are subjected to heat treatment for 1-2 hours at the temperature of 250-350 ℃ in advance.
4. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 1, wherein: the dispersing agent is selected from polyethylene glycol, sodium dodecyl benzene sulfonate and polyacrylamide.
5. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 1, wherein: the defoaming agent is selected from polydimethylsiloxane and polyoxypropylene glycerol ether.
6. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 1, wherein: the flatting agent is a polydimethylsiloxane type flatting agent.
7. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 1, wherein: the preparation method of the intelligent mildew-proof microcapsule particle comprises the following steps:
1) preparing silver-loaded water-soluble starch: dissolving water-soluble starch in water to prepare a water-soluble starch solution with the weight percent of 5-10, adding 0.5-1 wt% of silver nitrate into the water-soluble starch solution, uniformly stirring, dropwise adding dilute nitric acid under the stirring condition until the pH value of the solution is 3-5, heating in a 70-80 ℃ water bath for 1-2 hours under the dark condition, then adding excessive sodium borohydride into the solution, adding alkali to adjust the pH value of the solution to 7-9, reacting for 1-3 hours, cooling to separate out a solid, centrifugally separating, washing, and drying in vacuum to obtain silver-loaded water-soluble starch;
2) adding the silver-loaded water-soluble starch into water, and then adding tween into the water under the stirring condition of 50-60 ℃ and 400-;
3) dripping the volatile plant oil phase extract into the silver-loaded water-soluble starch solution according to the mass ratio of 1:5-10 under the stirring condition of 100-200r/min to form an oil-in-water emulsion; carrying out rotary evaporation on the oil-in-water emulsion, and carrying out freeze drying on the obtained concentrated solution to prepare a water-soluble starch microcapsule loaded with the volatile plant oil phase extract;
4) taking crab shells, coarsely grinding, carrying out anaerobic roasting for 1-3h at 350-450 ℃, and then carrying out anaerobic roasting for 2-4h at 900-950 ℃, and finely grinding to obtain roasted crab shell powder;
5) mechanically ball-milling the roasted crab shell powder, the photodegradation catalyst and the water-soluble starch microcapsule in a high-energy ball mill for 1-3h according to the mass ratio of 1-2:0.01-0.05:1 to obtain the water-soluble starch microcapsule wrapped by the roasted crab shell powder;
6) adding the water-soluble starch microcapsule coated by the roasted crab shell powder into a silane coupling agent for modification treatment according to the mass ratio of 1:0.5-1.5, and taking out;
7) adding the product obtained in the step 6) into an organic solution of the ethylene-carbon monoxide copolymer in batches under the condition of keeping out of the sun for uniform dispersion, then carrying out centrifugal treatment, washing the obtained precipitate with water, and drying to obtain the intelligent mildew-proof microcapsule particles for later use in the absence of the sun.
8. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 7, wherein:
in the step 2), the adding amount of the Tween is 0.5-1.5 wt% of the water;
in the step 3), the dropping speed of the volatile vegetable oil phase extract is 0.05-0.2 mL/s; the volatile plant oil phase extract is perilla essential oil and lavender essential oil in a mass ratio of 1-2: 1.
9. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 7, wherein: in the step 4), the grain diameter of the crab shell after coarse grinding is 0.5-2mm, and the grain diameter after fine grinding is 0.1-0.5 μm.
10. The powder coating with the functions of releasing negative ions and absorbing moisture and preventing mold as claimed in claim 7, wherein: in the step 7), the concentration of the ethylene-carbon monoxide copolymer organic solution is 5-20 wt%; the addition amount of the product obtained in the step 6) is 10-20 wt% of the mass of the ethylene-carbon monoxide copolymer.
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Cited By (1)
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| CN113737185A (en) * | 2021-07-26 | 2021-12-03 | 中国南方电网有限责任公司超高压输电公司检修试验中心 | Gas-phase rust-proof humidity-controlling agent and preparation method and application thereof |
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