CN112300643A - Fireproof and insect-proof interior wall coating and preparation method thereof - Google Patents
Fireproof and insect-proof interior wall coating and preparation method thereof Download PDFInfo
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- CN112300643A CN112300643A CN202011228738.5A CN202011228738A CN112300643A CN 112300643 A CN112300643 A CN 112300643A CN 202011228738 A CN202011228738 A CN 202011228738A CN 112300643 A CN112300643 A CN 112300643A
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- 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
- C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
-
- 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
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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a fireproof and insect-proof interior wall coating which is characterized by comprising the following components in parts by weight: 40-80 parts of aqueous synthetic resin emulsion; 50-100 parts of silica sol; 100 portions and 200 portions of potassium silicate; 15-30 parts of methylsiloxane derivatives; 40-80 parts of insect-proof mixed liquid; wherein, in the aqueous synthetic resin emulsion, the aqueous synthetic resin is a copolymer of ethylene and vinyl acetate; the size of the silica sol is 10-20 nm. The invention has the advantages of good compatibility, no APEO, no VOC, and independence from raw materials of film forming additives, antifreezing agents and other additives; and the characteristics of fire resistance, good air permeability of a paint film and high water vapor transmission rate of the inorganic material are utilized, and the effect of the mosquito-proof mixed liquid is combined, so that the mosquito-proof mixed liquid can play a role for a long time.
Description
Technical Field
The invention relates to the field of coatings, in particular to a fireproof and insect-proof interior wall coating and a preparation method thereof.
Background
The interior wall coating has the characteristics of convenient construction, outstanding performance, safety and environmental protection, occupies the domination in domestic interior wall decoration, and has the market share of more than 70 percent. However, with the improvement of living standard and concept of people, the decoration requirement is only considered by consumers, more consumers begin to pursue the performance of the interior wall coating in terms of functionality and environmental protection, the existing common interior wall coating does not have the fireproof performance due to the use of organic film-forming substances, and part of inorganic coatings have poor formula stability and are easy to crack.
The humid and sultry climate in summer is more suitable for the reproduction and activity of mosquitoes, so that the mosquitoes are more, and the mosquito bites are always unhappy. Researches show that the folium artemisiae argyi contains eudesmane, cineole, 4-terpineol and other components and has the effects of expelling insects and preventing mosquitoes; the special odor of herba Menthae and Lavender has effects of tranquilizing and repelling mosquito.
The potassium silicate paint prepared with the alkali metal potassium silicate solution and silica sol has the features of water resistance, fire resistance, wear resistance, contamination resistance, etc. and its poor stability is still one great disadvantage. Therefore, it is highly desirable to find an interior wall coating that has fire and insect protection efficacy, while having formulation stability and compatibility.
Disclosure of Invention
The invention aims to provide a fireproof and insect-proof interior wall coating which comprises the following components in parts by weight:
wherein, in the aqueous synthetic resin emulsion, the aqueous synthetic resin is a copolymer of ethylene and vinyl acetate;
the size of the silica sol is 10-20 nm.
Furthermore, the content of the vinyl acetate in the ethylene and vinyl acetate copolymer is 75-85 wt%.
Further, the solid content of the aqueous synthetic resin emulsion is 48 to 52% by weight.
Further, the insect-proof mixed liquor comprises folium artemisiae argyi, lavender, mint and water.
Further, the insect-proof mixed solution comprises the following components in parts by weight:
2-3 parts of folium artemisiae argyi, 1-2 parts of lavender, 1-2 parts of mint and 14-20 parts of water.
Furthermore, the fireproof and insect-proof interior wall coating also comprises a pH regulator, a wetting agent, a defoaming agent, a dispersing agent, a thickening agent, a leveling agent and pigment and filler.
Further, the pH regulator is organic silanol;
the wetting agent is selected from alkyl polyoxyethylene or polyoxyethylene fatty alcohol ether;
the defoaming agent is selected from polysiloxane-polyether copolymer emulsion or mineral oil;
the dispersant is a sodium polycarboxylate dispersant;
the thickening agent is selected from one or two of attapulgite and hydroxyethyl cellulose;
the flatting agent is polyurethane;
the pigment and filler is selected from one or more of rutile titanium dioxide, calcium carbonate, precipitated barium sulfate and kaolin.
Another object of the present invention is to provide a method for preparing the fireproof and insect-proof interior wall coating, which comprises the following steps:
(1) mixing folium Artemisiae Argyi, Lavender, and herba Menthae, air drying, and pulverizing to obtain mixture;
(2) the mixture was mixed with deionized water, sonicated, and then filtered.
Further, the mixture was pulverized to 150-200 mesh.
Further, the temperature of the ultrasound is 50-80 ℃.
The invention has the beneficial effects that:
1. an organic-inorganic compounding mode is adopted, the advantages of organic coatings and inorganic coatings are integrated, silica sol with the size of 10-20nm is mixed with potassium silicate, methylsiloxane derivatives, preferably r-glycidyl ether propyl trimethyl siloxane are used as a stabilizer, and a high-stability inorganic bonding material is obtained through compounding, and inorganic components in the coatings can enable the formula to have excellent fire-resistant property;
2. the inorganic binding material is selected and compounded with the ethylene and vinyl acetate copolymer-based aqueous synthetic resin emulsion, so that the brittleness of a paint film is improved, and the flexibility and the film forming effect of the paint film are improved;
3. due to the special effects of the folium artemisiae argyi, the mint and the lavender, the characteristics of inorganic materials are combined, the air permeability of a paint film is good, the water vapor transmission rate is high, and the anti-mosquito mixed liquid can play a role for a long time.
Detailed Description
In the description of the examples of the present invention, all the components are commercially available materials unless otherwise specified.
Among the raw materials referred to in the examples of the present invention,
the folium artemisiae argyi, the lavender and the mint are common traditional Chinese medicine raw materials;
the silica sol is purchased from Nolon and has the model number of NYACOLM 30;
r-glycidyl Ether propyl Trimethylsiloxane is purchased from Hemician 306;
the method for testing the fineness of the paint paste is carried out according to the national standard GB/T1724-79;
the viscosity was measured using a stormer viscometer.
Example 1
The fireproof and insect-proof interior wall coating comprises the following components in parts by weight:
wherein, in the aqueous synthetic resin emulsion, the aqueous synthetic resin is a copolymer of ethylene and vinyl acetate, and the content of the vinyl acetate of the ethylene and the vinyl acetate is 75 wt%;
the solid content of the aqueous synthetic resin emulsion was 48% by weight;
the insect-proof mixed liquid comprises the following components in parts by weight:
3 parts of folium artemisiae argyi; 2 parts of lavender; 1 part of mint; and 20 parts of deionized water.
The preparation method of the fireproof and insect-proof interior wall coating comprises the following steps:
(1) adding 10-20nm silica sol into a reaction kettle according to the mass parts, stirring at the speed of 400r/min, heating to 30 ℃, slowly adding r-glycidyl ether propyl trimethyl siloxane, and stirring at the speed of 400r/min for 20 min;
(2) slowly adding potassium silicate into the reaction kettle, stirring at the speed of 600r/min for 20min, and obtaining an inorganic bonding material in the reaction kettle for later use;
(3) mixing folium artemisiae argyi, lavender and mint according to the mass parts, air-drying, crushing to obtain a mixture, crushing the mixture to 150 meshes, blending with deionized water according to the mass parts, ultrasonically dispersing for 3 hours in a water bath at 50 ℃, and filtering residues through a filter cloth of 300 meshes to obtain an anti-mosquito mixed solution for later use;
(4) sequentially adding deionized water, potassium methyl siliconate, dodecyl polyoxyethylene ether, polyether modified siloxane and attapulgite into a small kettle according to the mass parts, and stirring at 900r/min for 5 min;
(5) according to the mass parts, the rutile type titanium dioxide, the kaolin and the calcium carbonate are added into a small kettle and dispersed for 30min at 1300r/min, and the fineness of the tested paint paste is less than or equal to 50 mu m.
(6) Slowly adding the components in the reaction kettle into a small kettle, stirring for 5min at the speed of 1000r/min, adding the aqueous synthetic resin emulsion, the mosquito-proof mixed liquid and the polyurethane according to the mass parts, stirring for 10min at the speed of 1000r/min, testing the viscosity, and slightly adjusting the viscosity to 105-.
Example 2
The fireproof and insect-proof interior wall coating comprises the following components in parts by weight:
wherein, in the aqueous synthetic resin emulsion, the aqueous synthetic resin is a copolymer of ethylene and vinyl acetate, and the content of the vinyl acetate of the ethylene and the vinyl acetate is 85 wt%;
the solid content of the aqueous synthetic resin emulsion was 52% by weight;
the insect-proof mixed liquid comprises the following components in parts by weight:
2 parts of folium artemisiae argyi; 1 part of lavender; 2 parts of mint; 14 parts of deionized water.
The preparation method of the fireproof and insect-proof interior wall coating comprises the following steps:
(1) adding 10-20nm silica sol into a reaction kettle according to the mass parts, stirring at the speed of 600r/min, heating to 40 ℃, slowly adding r-glycidyl ether propyl trimethyl siloxane, and stirring at the speed of 600r/min for 20 min;
(2) slowly adding potassium silicate into the reaction kettle, stirring at the speed of 800r/min for 20min, and obtaining an inorganic bonding material in the reaction kettle for later use;
(3) mixing folium artemisiae argyi, lavender and mint according to the mass parts, air-drying, crushing to obtain a mixture, crushing the mixture to 200 meshes, blending with deionized water according to the mass parts, ultrasonically dispersing for 3 hours in 80 ℃ water bath, and finally filtering residues through 300-mesh filter cloth to obtain an anti-mosquito mixed solution for later use;
(4) sequentially adding deionized water, potassium methyl siliconate, sodium polycarboxylate, dodecyl polyoxyethylene ether, polyether modified siloxane and hydroxyethyl cellulose into a small kettle according to the mass parts, and stirring at 1100r/min for 5 min;
(5) according to the mass parts, the rutile type titanium dioxide, the kaolin and the calcium carbonate are added into a small kettle and dispersed for 30min at 1500r/min, and the tested fineness of the paint paste is less than or equal to 50 mu m.
(6) Slowly adding the components in the reaction kettle into a small kettle, stirring for 5min at the speed of 1000r/min, adding the aqueous synthetic resin emulsion, the mosquito-proof mixed liquid and the polyurethane according to the mass parts, stirring for 10min at the speed of 1200r/min, testing the viscosity, and slightly adjusting the viscosity to 105-.
Example 3
The fireproof and insect-proof interior wall coating comprises the following components in parts by weight:
wherein, in the aqueous synthetic resin emulsion, the aqueous synthetic resin is a copolymer of ethylene and vinyl acetate, and the content of the vinyl acetate of the ethylene and the vinyl acetate is 80 wt%;
the solid content of the aqueous synthetic resin emulsion was 50% by weight;
the insect-proof mixed liquid comprises the following components in parts by weight:
3 parts of folium artemisiae argyi; 2 parts of lavender; 1 part of mint; 16 parts of deionized water.
The preparation method of the fireproof and insect-proof interior wall coating comprises the following steps:
(1) adding 10-20nm silica sol into a reaction kettle according to the mass parts, stirring at the speed of 500r/min, heating to 35 ℃, slowly adding r-glycidyl ether propyl trimethyl siloxane according to the mass parts, and stirring at the speed of 500r/min for 20 min;
(2) slowly adding potassium silicate into the reaction kettle, stirring at the speed of 700r/min for 20min, and obtaining an inorganic bonding material in the reaction kettle for later use;
(3) mixing folium artemisiae argyi, lavender and mint according to the mass parts, air-drying, crushing to obtain a mixture, crushing the mixture to 170 meshes, blending with deionized water according to the mass parts, ultrasonically dispersing for 3 hours in 70 ℃ water bath, and finally filtering residues through 300-mesh filter cloth to obtain an anti-mosquito mixed solution for later use;
(4) sequentially adding deionized water, potassium methyl siliconate, sodium polycarboxylate, dodecyl polyoxyethylene ether, polyether modified siloxane and hydroxyethyl cellulose into a small kettle according to the mass parts, and stirring at 1000r/min for 5 min;
(5) according to the mass parts, the rutile type titanium dioxide, the kaolin and the calcium carbonate are added into a small kettle and dispersed for 30min at the speed of 1400r/min, and the tested fineness of the paint paste is less than or equal to 50 mu m.
(6) Slowly adding the components in the reaction kettle into a small kettle, stirring for 5min at the speed of 1100r/min, adding the aqueous synthetic resin emulsion, the mosquito-proof mixed liquid and the polyurethane according to the mass parts, stirring for 10min at the speed of 1100r/min, testing the viscosity, and slightly adjusting the viscosity to 105-.
Test example
The samples obtained in examples 1-3 and conventional latex paints were tested for relevant technical effects.
Wherein the common latex paint is an interior wall paint taking styrene-acrylic emulsion as a film forming substance.
And (3) fire prevention test: constructing according to the normal construction mode of the latex paint to prepare a 30 x 40cm test board, roasting the test board by aiming at an alcohol blast lamp, and observing the condition of a paint film;
insect prevention test: five surfaces of a cuboid of 20X 30X 40cm are respectively coated with the product and the common emulsion paint, one surface is capped by transparent glass, equal amount of mosquitoes are put in the closed space, and the mosquito prevention effect is determined by observing the stopping position of the mosquitoes.
The results obtained are shown in table 1 below.
TABLE 1 technical Effect of samples from examples 1-3 and general latex paints
| Fire protection | Insect prevention | |
| Example 1 | No open fire and no obvious combustion | The mosquito mainly stops on the glass surface |
| Example 2 | No open fire and no open lightApparent combustion phenomenon | The mosquito mainly stops on the glass surface |
| Example 3 | No open fire and no obvious combustion | The mosquito mainly stops on the glass surface |
| Common latex paint | Has open fire and is easy to ignite | The mosquitoes are evenly distributed |
The above results demonstrate the advancement of the examples over conventional latex paints.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the foregoing description only for the purpose of illustrating the principles of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims, specification, and equivalents thereof.
Claims (10)
1. The fireproof and insect-proof interior wall coating is characterized by comprising the following components in parts by weight:
wherein, in the aqueous synthetic resin emulsion, the aqueous synthetic resin is a copolymer of ethylene and vinyl acetate;
the size of the silica sol is 10-20 nm.
2. The fireproof and insect-resistant interior wall coating of claim 1, wherein the vinyl acetate content in the ethylene-vinyl acetate copolymer is 75-85 wt%.
3. A fire and insect resistant interior wall coating material as claimed in claim 1, wherein said aqueous synthetic resin emulsion has a solid content of 48 to 52% by weight.
4. The fireproof and insect-proof interior wall coating of claim 1, wherein the insect-proof mixed solution comprises folium artemisiae argyi, lavender, mint and water.
5. The fireproof and insect-proof interior wall coating as claimed in claim 4, wherein the insect-proof mixed solution comprises the following components in parts by weight:
2-3 parts of folium artemisiae argyi, 1-2 parts of lavender, 1-2 parts of mint and 14-20 parts of water.
6. The fireproof and insect-proof interior wall coating material of claim 1, further comprising a pH regulator, a wetting agent, a defoaming agent, a dispersing agent, a thickening agent, a leveling agent and a pigment and filler.
7. The fireproof and insect-resistant interior wall coating material of claim 6, wherein the pH regulator is silicone alcohol;
the wetting agent is selected from alkyl polyoxyethylene or polyoxyethylene fatty alcohol ether;
the defoaming agent is selected from polysiloxane-polyether copolymer emulsion or mineral oil;
the dispersant is a polyphosphoric acid dispersant;
the thickening agent is selected from one or two of attapulgite and hydroxyethyl cellulose;
the flatting agent is polyurethane;
the pigment and filler is selected from one or more of rutile titanium dioxide, calcium carbonate, precipitated barium sulfate and kaolin.
8. The method for preparing a fireproof and mothproof interior wall coating according to any one of claims 1 to 7, which comprises the following steps:
(1) mixing folium Artemisiae Argyi, Lavender, and herba Menthae, air drying, and pulverizing to obtain mixture;
(2) the mixture was mixed with deionized water, sonicated, and then filtered.
9. The method as claimed in claim 8, wherein the mixture is pulverized to 150-200 mesh.
10. The method for preparing a fireproof and mothproof interior wall coating according to claim 8, wherein the temperature of the ultrasound is 50-80 ℃.
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| CN202011228738.5A CN112300643A (en) | 2020-11-06 | 2020-11-06 | Fireproof and insect-proof interior wall coating and preparation method thereof |
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| CN202011228738.5A CN112300643A (en) | 2020-11-06 | 2020-11-06 | Fireproof and insect-proof interior wall coating and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130369A (en) * | 2015-07-22 | 2015-12-09 | 河北晨阳工贸集团有限公司 | Aqueous internal wall inorganic coating and preparation method thereof |
| CN107083135A (en) * | 2017-04-07 | 2017-08-22 | 河北晨阳工贸集团有限公司 | Organic-inorganic compounding outer wall water-based coating and preparation method thereof |
| CN107418262A (en) * | 2017-07-13 | 2017-12-01 | 福州安晟高索环保材料有限公司 | A kind of environment-friendly type coating containing oyster shell whiting and preparation method thereof |
| CN109997883A (en) * | 2018-01-05 | 2019-07-12 | 立志美丽（南京）有限公司 | A kind of natural plant culicifuge |
| CN110812294A (en) * | 2019-11-22 | 2020-02-21 | 高小军 | Insect-expelling floral water and preparation method thereof |
-
2020
- 2020-11-06 CN CN202011228738.5A patent/CN112300643A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130369A (en) * | 2015-07-22 | 2015-12-09 | 河北晨阳工贸集团有限公司 | Aqueous internal wall inorganic coating and preparation method thereof |
| CN107083135A (en) * | 2017-04-07 | 2017-08-22 | 河北晨阳工贸集团有限公司 | Organic-inorganic compounding outer wall water-based coating and preparation method thereof |
| CN107418262A (en) * | 2017-07-13 | 2017-12-01 | 福州安晟高索环保材料有限公司 | A kind of environment-friendly type coating containing oyster shell whiting and preparation method thereof |
| CN109997883A (en) * | 2018-01-05 | 2019-07-12 | 立志美丽（南京）有限公司 | A kind of natural plant culicifuge |
| CN110812294A (en) * | 2019-11-22 | 2020-02-21 | 高小军 | Insect-expelling floral water and preparation method thereof |
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Application publication date: 20210202 |