CN112126298A - Water-based acrylic resin coating with intelligent mildew-proof function and preparation method thereof - Google Patents
Water-based acrylic resin coating with intelligent mildew-proof function and preparation method thereof Download PDFInfo
- Publication number
- CN112126298A CN112126298A CN202011007328.8A CN202011007328A CN112126298A CN 112126298 A CN112126298 A CN 112126298A CN 202011007328 A CN202011007328 A CN 202011007328A CN 112126298 A CN112126298 A CN 112126298A
- Authority
- CN
- China
- Prior art keywords
- water
- parts
- soluble starch
- acrylic resin
- mildew
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
Abstract
The invention relates to the field of coatings, and discloses a water-based acrylic resin coating with an intelligent mildew-proof function and a preparation method thereof, wherein the water-based acrylic resin coating comprises the following components in parts by weight: 30-50 parts of water-based acrylic resin emulsion with the solid content of 30-50 wt%, 1-15 parts of intelligent mildew-proof microcapsule particles, 20-30 parts of filler, 1-5 parts of dispersing agent, 0-2 parts of flatting agent, 0-2 parts of defoaming agent and 20-40 parts of water. 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.
Description
Technical Field
The invention relates to the field of coatings, in particular to a water-based acrylic resin coating with an intelligent mildew-proof function and a preparation method thereof.
Background
Compared with the traditional organic solvent-based coating, the water-based coating has the advantages of low price, safe use, resource and energy conservation, environmental pollution and public nuisance reduction, and the like, thereby becoming the main direction for developing the coating industry at present. The water-based acrylic resin coating is the pollution-free coating which is the fastest in development and the most in variety in the water-based coatings.
In a humid environment, particularly in southern China regions 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 also 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 moisture absorbing component or an antibacterial component to the paint, which respectively absorb moisture and inhibit the growth of microorganisms. For example, the Chinese invention patent CN201410268287.6 discloses a nontoxic water-based microcapsule mildew-proof heat-insulating coating and a preparation method thereof, wherein the mildew-proof heat-insulating coating mainly comprises organic silicon modified acrylate self-emulsifying emulsion, a nontoxic mildew-proof agent microcapsule, a filler, an auxiliary agent and deionized water. The nontoxic mildew inhibitor microcapsule takes lipophilic antifouling agents such as menadione epoxide and the like as a capsule core and polyacrylate as a capsule wall, ensures that the mildew inhibitor uniformly and effectively seeps out for a long time, has obvious mildew-proof and heat-preservation effects, and has longer service life than the traditional mildew-proof coating.
However, the mildew-proof coating disclosed in the above patents is only added with an additive having an antibacterial and mildew-proof or moisture-absorbing effect, and does not have a function of intelligently adjusting the mildew-proof capability thereof according to the ambient humidity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a water-based acrylic resin coating with an intelligent mildew-proof function and a preparation method thereof. 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.
The specific technical scheme of the invention is as follows: a water-based acrylic resin coating with an intelligent mildew-proof function comprises the following components in parts by weight:
30-50 parts of water-based acrylic resin emulsion with the solid content of 30-50 wt%,
1-15 parts of intelligent mildew-proof microcapsule particles,
20-30 parts of a filler,
1-5 parts of a dispersing agent,
0-2 parts of a leveling agent,
0-2 parts of a defoaming agent,
20-40 parts of water.
The coating disclosed by the invention takes the water-based acrylic resin as a film forming material, takes water as a solvent, 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 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 water-based acrylic resin coating comprises the following components in parts by weight:
35-45 parts of water-based acrylic resin emulsion with the solid content of 30-50 wt%,
5-10 parts of intelligent mildew-proof microcapsule particles,
20-25 parts of a filler,
1-3 parts of a dispersing agent,
0.5 to 1 portion of flatting agent,
0.5 to 1 portion of defoaming agent,
25-30 parts of water.
Preferably, the filler is one or more of diatomite, silicate, calcium carbonate, talcum powder and white carbon black. The defoaming agent is a polydimethylsiloxane defoaming agent; the leveling agent is a polyether siloxane type leveling agent.
Preferably, the dispersing agent is sodium hexametaphosphate and sodium tripolyphosphate.
The intelligent mildew-proof microcapsule particles have hydrophobic surfaces, so the intelligent mildew-proof microcapsule particles have poor dispersibility in water-based paint and are easy to agglomerate, and the dispersant is required to be added to uniformly disperse the intelligent mildew-proof microcapsule particles in the paint.
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 a coating taking water as a solvent, 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 disclosed by the invention takes the water-based acrylic resin as a film forming material, takes water as a solvent, 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 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
An aqueous acrylic resin coating with intelligent mildew-proof function comprises:
40 parts of water-based acrylic resin emulsion with the solid content of 40 weight percent,
10 parts of intelligent mildew-proof microcapsule particles,
25 parts of a filler (diatomite),
3 parts of a dispersing agent (sodium hexametaphosphate),
1 part of leveling agent (polyether siloxane type leveling agent),
1 part of defoaming agent (polydimethylsiloxane),
and 20 parts of water. 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
A water-based acrylic resin coating with an intelligent mildew-proof function comprises the following components in parts by weight:
50 parts of water-based acrylic resin emulsion with the solid content of 30 weight percent,
1 part of intelligent mildew-proof microcapsule particles,
25 parts of a filler (silicate),
1 part of a dispersing agent (sodium tripolyphosphate),
2 parts of flatting agent (polyether siloxane type flatting agent),
1 part of defoaming agent (polydimethylsiloxane),
and 20 parts of water.
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 1:0.01:1, and obtaining the water-soluble starch microcapsule wrapped by the roasted crab shell powder after ball milling.
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 3
A water-based acrylic resin coating with an intelligent mildew-proof function comprises the following components in parts by weight:
30 parts of water-based acrylic resin emulsion with the solid content of 50 weight percent,
15 parts of intelligent mildew-proof microcapsule particles,
30 parts of a filler (calcium carbonate),
5 parts of a dispersing agent (sodium hexametaphosphate),
and 20 parts of water.
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 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 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
A water-based acrylic resin coating with an intelligent mildew-proof function comprises the following components in parts by weight:
35 parts of water-based acrylic resin emulsion with the solid content of 40 weight percent,
5 parts of intelligent mildew-proof microcapsule particles,
25 parts of a filler (talcum powder),
3 parts of a dispersing agent (sodium hexametaphosphate),
0.5 part of flatting agent (polyether siloxane type flatting agent),
0.5 part of defoaming agent (polydimethylsiloxane),
31 parts of water.
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 5
A water-based acrylic resin coating with an intelligent mildew-proof function comprises the following components in parts by weight:
45 parts of water-based acrylic resin emulsion with the solid content of 40 weight percent,
10 parts of intelligent mildew-proof microcapsule particles,
20 parts of a filler (white carbon black),
1 part of dispersant (sodium hexametaphosphate),
1 part of flatting agent (polyether siloxane type flatting agent),
1 part of defoaming agent (polydimethylsiloxane),
and 22 parts of water.
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 N, P, K elements in an amount of 1 wt%) and the water-soluble starch microcapsule in a high-energy ball mill for 1-3h according to the mass ratio of 1.5:0.05:1, and obtaining the water-soluble starch microcapsule wrapped by the roasted crab shell powder after ball milling.
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
An aqueous acrylic resin coating comprising:
40 parts of water-based acrylic resin emulsion with the solid content of 40 weight percent,
35 parts of a filler (diatomite),
3 parts of a dispersing agent (sodium hexametaphosphate),
1 part of flatting agent (polyether siloxane type flatting agent),
1 part of defoaming agent (polydimethylsiloxane),
and 20 parts of water.
Comparative example 2
An aqueous acrylic resin coating comprising:
40 parts of water-based acrylic resin emulsion with the solid content of 40 weight percent,
10 parts of mildew-proof microcapsule particles,
25 parts of a filler (diatomite),
3 parts of a dispersing agent (sodium hexametaphosphate),
1 part of flatting agent (polyether siloxane type flatting agent),
1 part of defoaming agent (polydimethylsiloxane),
and 20 parts of water.
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 3
An aqueous acrylic resin coating comprising:
40 parts of water-based acrylic resin emulsion with the solid content of 40 weight percent,
10 parts of mildew-proof microcapsule particles,
25 parts of a filler (diatomite),
3 parts of a dispersing agent (sodium hexametaphosphate),
1 part of flatting agent (polyether siloxane type flatting agent),
1 part of defoaming agent (polydimethylsiloxane),
and 20 parts of water.
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
The water-based acrylic resin coatings of example 1 and comparative examples 1 to 3 were subjected to a mold 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). Wherein the coatings of example 1 and comparative example 3 were subjected to 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 example 2, so that the mildew-proof effect can be effectively achieved, and the mildew-proof grade is grade 1; in contrast, comparative example 1 has a lower grade of 3 because it does not contain a mildewproof component; although the comparative example 3 contains the mildew-proof component, the polymer layer on the surface of the mildew-proof particle cannot be rapidly degraded after being coated with ultraviolet radiation because the mildew-proof particle does not contain a photodegradation catalyst, so that the mildew-proof component cannot be released in time, and certain influence is caused on the mildew-proof performance of the mildew-proof 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 2, 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 water-based acrylic resin coating with the intelligent mildew-proof function is characterized by comprising the following components in parts by weight:
30-50 parts of water-based acrylic resin emulsion with the solid content of 30-50 wt%,
1-15 parts of intelligent mildew-proof microcapsule particles,
20-30 parts of a filler,
1-5 parts of a dispersing agent,
0-2 parts of a leveling agent,
0-2 parts of a defoaming agent,
20-40 parts of water.
2. The aqueous acrylic resin coating according to claim 1, comprising the following components in parts by weight:
35-45 parts of water-based acrylic resin emulsion with the solid content of 30-50 wt%,
5-10 parts of intelligent mildew-proof microcapsule particles,
20-25 parts of a filler,
1-3 parts of a dispersing agent,
0.5 to 1 portion of flatting agent,
0.5 to 1 portion of defoaming agent,
25-30 parts of water.
3. The aqueous acrylic resin coating according to claim 1 or 2, wherein: the filler is one or more of diatomite, silicate, calcium carbonate, talcum powder and white carbon black; the defoaming agent is a polydimethylsiloxane defoaming agent; the leveling agent is a polyether siloxane type leveling agent.
4. The aqueous acrylic resin coating according to claim 1 or 2, wherein: the dispersant is sodium hexametaphosphate and sodium tripolyphosphate.
5. The aqueous acrylic resin coating according to claim 1 or 2, 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.
6. The aqueous acrylic resin coating according to claim 5, wherein: in the step 2), the adding amount of the Tween is 0.5-1.5 wt% of the water.
7. The aqueous acrylic resin coating according to claim 5, wherein: in the step 3), the dropping speed of the volatile vegetable oil phase extract is 0.05-0.2 mL/s.
8. The aqueous acrylic resin coating according to claim 5, wherein: 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.
9. The aqueous acrylic resin coating according to claim 5, 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 aqueous acrylic resin coating according to claim 5, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011007328.8A CN112126298A (en) | 2020-09-23 | 2020-09-23 | Water-based acrylic resin coating with intelligent mildew-proof function and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011007328.8A CN112126298A (en) | 2020-09-23 | 2020-09-23 | Water-based acrylic resin coating with intelligent mildew-proof function and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112126298A true CN112126298A (en) | 2020-12-25 |
Family
ID=73842755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011007328.8A Withdrawn CN112126298A (en) | 2020-09-23 | 2020-09-23 | Water-based acrylic resin coating with intelligent mildew-proof function and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112126298A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114891405A (en) * | 2022-01-24 | 2022-08-12 | 海南大学 | Intelligent antifouling microcapsule particle, preparation method thereof and environment-friendly marine antifouling coating with intelligent antifouling function |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030013551A1 (en) * | 2001-06-22 | 2003-01-16 | Harris Kevin M. | Golf ball compositions with microencapsulated healing agent |
| CN103468066A (en) * | 2013-08-13 | 2013-12-25 | 三棵树涂料股份有限公司 | Antimicrobial and mildewproof paint and preparation method thereof |
| US20180333515A1 (en) * | 2016-06-24 | 2018-11-22 | The Procter & Gamble Company | Absorbent articles comprising encapsulating agents |
| US20190099335A1 (en) * | 2009-04-27 | 2019-04-04 | Premier Dental Products Company | Buffered microencapsulated compositions and methods |
| CN110055820A (en) * | 2019-03-06 | 2019-07-26 | 浙江工业大学 | A kind of preparation method of the compound fresh-keeping paper base material of functionality for reinforcing sustained release |
| CN110527383A (en) * | 2019-09-10 | 2019-12-03 | 深圳市瑞福联合新材料发展有限公司 | A kind of fungi-proofing interior wall coating of water mildow-proof |
-
2020
- 2020-09-23 CN CN202011007328.8A patent/CN112126298A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030013551A1 (en) * | 2001-06-22 | 2003-01-16 | Harris Kevin M. | Golf ball compositions with microencapsulated healing agent |
| US20190099335A1 (en) * | 2009-04-27 | 2019-04-04 | Premier Dental Products Company | Buffered microencapsulated compositions and methods |
| CN103468066A (en) * | 2013-08-13 | 2013-12-25 | 三棵树涂料股份有限公司 | Antimicrobial and mildewproof paint and preparation method thereof |
| US20180333515A1 (en) * | 2016-06-24 | 2018-11-22 | The Procter & Gamble Company | Absorbent articles comprising encapsulating agents |
| CN110055820A (en) * | 2019-03-06 | 2019-07-26 | 浙江工业大学 | A kind of preparation method of the compound fresh-keeping paper base material of functionality for reinforcing sustained release |
| CN110527383A (en) * | 2019-09-10 | 2019-12-03 | 深圳市瑞福联合新材料发展有限公司 | A kind of fungi-proofing interior wall coating of water mildow-proof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114891405A (en) * | 2022-01-24 | 2022-08-12 | 海南大学 | Intelligent antifouling microcapsule particle, preparation method thereof and environment-friendly marine antifouling coating with intelligent antifouling function |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103289453A (en) | Anti-bacteria deodorizing inorganic functional coating and preparation method thereof | |
| CN102391741B (en) | Ammonia-removing and formaldehyde-removing paint | |
| CN112126336A (en) | Antibacterial and mildew-resistant waterborne polyurethane coating and preparation method thereof | |
| CN112126298A (en) | Water-based acrylic resin coating with intelligent mildew-proof function and preparation method thereof | |
| CN111955478B (en) | Slow-release carbon-based antibacterial and antiviral composite material and preparation method and application thereof | |
| CN107841270B (en) | Preparation method of lignin phenolic resin adhesive | |
| CN104725931A (en) | Preparation method of water-based ink, containing composite antibacterial material, for tipping paper | |
| CN112175425A (en) | Powder coating with negative ion releasing, moisture absorbing and mildew preventing functions and preparation method thereof | |
| CN102134105B (en) | Method for accessorily preparing nanometer cobaltosic oxide granules at room temperature by utilizing amino acids | |
| CN109575726B (en) | Indoor energy-saving brightening functional coating and preparation method thereof | |
| CN109796814B (en) | Antibacterial interior wall coating and preparation method thereof | |
| CN113136127B (en) | Antiviral healthy plant water paint and preparation method thereof | |
| CN109718738B (en) | Zirconia spherical adsorbent and preparation method and application thereof | |
| CN108659587A (en) | A kind of preparation process of the environmentally friendly diatom ooze coating of enhancing | |
| CN111568806B (en) | Essential oil-loaded biological polysaccharide and protein modified boron nitride and preparation method and application thereof | |
| CN111330543B (en) | Hydrophobic activated carbon adsorbent for treating high-humidity VOCs and preparation method thereof | |
| CN112175475A (en) | Bio-based nano negative ion antibacterial water-based paint | |
| CN109593393B (en) | Preparation method of antibacterial agent for interior wall coating | |
| US11732140B2 (en) | Environment-friendly wall paint for building and preparation method thereof | |
| CN109225547A (en) | A kind of preparation method and applications for exempting to grind carbon black | |
| CN112280353B (en) | Antibacterial and ultraviolet-resistant thermochromic wax color paint and preparation method thereof | |
| CN114574046A (en) | Novel biological sound-insulation diatom interior wall coating and preparation method thereof | |
| JP5148994B2 (en) | Method for improving the quality of water-based ink for ballpoint pens | |
| CN110922818A (en) | Multifunctional ecological type negative ion coating and preparation method thereof | |
| CN112121633A (en) | Peculiar smell scavenger and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201225 |