CN112759967A - Inorganic paint for water-based mineral interior wall and preparation method thereof - Google Patents
Inorganic paint for water-based mineral interior wall and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 30
- 239000011707 mineral Substances 0.000 title claims abstract description 29
- 239000003973 paint Substances 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title description 6
- 238000000576 coating method Methods 0.000 claims abstract description 69
- 239000011248 coating agent Substances 0.000 claims abstract description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000839 emulsion Substances 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical class [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 15
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012764 mineral filler Substances 0.000 claims abstract description 12
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 24
- 239000002518 antifoaming agent Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000000080 wetting agent Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 230000008719 thickening Effects 0.000 claims description 10
- 229920000388 Polyphosphate Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000001205 polyphosphate Substances 0.000 claims description 9
- 235000011176 polyphosphates Nutrition 0.000 claims description 9
- 239000003755 preservative agent Substances 0.000 claims description 9
- 230000002335 preservative effect Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- -1 2,2, 4-trimethyl-1, 3-pentanediol isobutyrate diester Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 230000002528 anti-freeze Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 3
- 229920006321 anionic cellulose Polymers 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000004078 waterproofing Methods 0.000 claims description 3
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 claims description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 claims description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 238000005201 scrubbing Methods 0.000 abstract description 9
- 238000013329 compounding Methods 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000004111 Potassium silicate Substances 0.000 description 8
- 238000005034 decoration Methods 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- 229910052913 potassium silicate Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009396 hybridization Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000212376 Ammi Species 0.000 description 1
- 235000007034 Carum copticum Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009500 colour coating Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an inorganic coating for water-based mineral interior walls, which mainly comprises components such as nano modified silicon dioxide, modified potassium silicate, emulsion, titanium dioxide, kaolin, other mineral fillers, cellulose ether, water and the like. The inorganic coating for the water-based mineral interior wall disclosed by the invention has the advantages that the main bonding material is nano modified silicon dioxide, the auxiliary bonding material is modified potassium silicate and emulsion, the coating of titanium dioxide, kaolin and other mineral fillers by the bonding material can reach the standard of high-quality interior wall coating, the grade A fire resistance can be achieved, the mandatory requirements in GB 50222-. In addition, by compounding and hybridizing the modified nano silicon dioxide aqueous solution and the silicone-acrylate emulsion RS-996AD, the scrubbing resistance of the coating is high, and the strength of the coating is obviously increased in age.
Description
Technical Field
The invention relates to an inorganic coating for an aqueous mineral inner wall and a preparation method thereof, belonging to the technical field of coatings.
Background
With the implementation of the specification of GB50222 and 2017 'building interior decoration design fire prevention' in 2018, civil residences, industrial plants and special places are compulsorily regulated, such as: a class A fireproof decorative material is required to be used for ceilings and wall surfaces and partitions of buildings with the building area exceeding a certain scale, and it is pointed out that 3.0.6 inorganic decorative paint applied on a class A base material can be used as a class A decorative material.
The majority of interior wall coatings in the current market use acrylic emulsion as a film forming substance, the emulsion is a petroleum-based synthetic product, all the emulsion is carbon chain compounds, almost all the emulsion is carbon-containing and high-carbon organic products, the content of organic matters is 45-55%, meanwhile, certain VOC and APEO exist, the adding amount in the coating is often 9-45%, and the coating cannot meet the requirements of A-grade decoration materials in GB50222-2017 'architectural interior decoration design fire protection code'. The coatings also require the addition of large amounts of organic adjuvants, such as film-forming aids, preservatives, and the like, and sometimes introduce formaldehyde and VOCs.
In recent years, some inorganic coatings are on the market, but most of the inorganic coatings have high organic content of 8-12%, so that although the coating performance is improved, the grade A fire resistance cannot be achieved. The paint has low organic content (0-5%) and can reach A-grade fireproof inorganic paint, but the bonding material is mainly modified potassium silicate, and the paint is a high-activity water-soluble inorganic mineral salt, so the finished product of the paint has poor stability and is accompanied with serious post-thickening gelation phenomenon and water diversion phenomenon after long-term storage, and the pH value of the paint is more than 12, so many raw materials in the common paint can not be used for a long time under the high-alkaline condition of the inorganic paint, and even water-based color paste in the common interior wall paint can not be used, so that the paint has single color which is mostly white or extremely light, and can hardly meet the daily decoration requirement.
Therefore, the research and development of an interior wall decoration material which can meet the A-level fire resistance, has good decoration, various colors and good storage performance is a problem to be solved urgently by technical personnel at present.
Disclosure of Invention
Aiming at the prior art, the invention provides an inorganic coating for a water-based mineral interior wall, which can meet the A-level fire resistance, and has the advantages of good decoration, various colors and good storability. The inorganic coating for the water-based mineral interior wall takes the modified nano-silica aqueous solution as a main bonding material, is matched with emulsion and modified potassium silicate with a certain content, and controls the total content of organic matters to be 0-5 percent, so that the inorganic coating not only meets the A-grade fireproof requirement, but also has the characteristics of good storability, good matching property with color paste, good decoration and various colors because the activity of the modified nano-silica is weaker than that of the potassium silicate.
The invention is realized by the following technical scheme:
an inorganic coating for water-based mineral interior walls is composed of the following components in parts by weight:
18-25 parts of deionized water
10.1-0.2 parts of defoaming agent
0.1 to 0.2 portion of thickening powder
2-4 parts of anti-settling agent pre-solution
2.5-3 parts of cellulose ether
15-25 parts of modified nano silicon dioxide aqueous solution
0.3-0.5 part of stabilizer
1-2 parts of antifreezing agent
0.2 to 0.5 part of dispersant
0.1 to 0.2 portion of wetting agent
2.5-18 parts of titanium dioxide
5-10 parts of kaolin
15-35 parts of other mineral fillers
0-0.3 part of film forming auxiliary agent
0-6 parts of emulsion
20.05-0.1 part of defoaming agent
0.1-0.3 part of environment-friendly preservative
0.3-1 part of multifunctional additive
0-5 parts of modified potassium silicate
0-2 parts of organosilicon waterproofing agent
0-3 parts of color paste for the water-based paint.
Preferably, the defoaming agent 1 is selected from SN 321-C of St.John & Poaceae, is a foam inhibitor mainly comprising paraffin and hydrophobic silica, has excellent initial and sustained foam inhibition, good alkali resistance and high efficiency.
Preferably, the thickening powder is selected from YT-10 of the excellent chemical union, is a polymer of high molecular weight anions refined by a scientific method, is high-efficiency in thickening, and has high pseudoplasticity in super shear rate and large concentration range.
Preferably, the anti-settling agent pre-solution is selected from a high-purity polyphosphate water solution, and is a 5% pre-dispersion prepared by dispersing polyphosphate in water at a high speed, wherein the selected polyphosphate is SW of Suzhou province. Can be prepared by the following method: starting a dispersion machine, adjusting the rotating speed to 400-500 r/min, adding 95 parts of deionized water into a container, slowly adding 5 parts of polyphosphate SW, adjusting the rotating speed to 1700-2500 r/min, dispersing for 1-2 h until the viscosity is stable, and prefabricating for later use.
Preferably, the cellulose ether is selected from modified anionic cellulose ethers, hydroxyethyl methyl cellulose ethers.
Preferably, the modified nano-silica aqueous solution is an aqueous dispersion of nano-silica with organically modified surface, and the main component of the modified nano-silica aqueous solution is SiO2. The modified nano-silica aqueous solution is a product existing in the prior art, and can be obtained by conventional purchase, such as: GHS1368 of the river-yin and Chinese Union, the pH value is 9-10, the solid content is 28 +/-1 percent, and the stabilizer is Na2The content of O is less than or equal to 0.3 percent, the average grain diameter is 10-20 nanometers, and the adhesive property is better. The modified nano silicon dioxide is coupled with the silanol bond on the surface of the dispersion body of the modified nano silicon dioxide through an organic silicon modifier, so that a steric hindrance and charge repulsion dual stabilizing mechanism is achieved to improve the stability of the nano dispersion body; the organic modification of the surface also improves the compatibility with emulsion, has certain functions of dispersing powder and color spreading, and also improves the water resistance of the coating; at the same time, the residual silanol bonds on the surface of the dispersion can also be driedThe self-polycondensation reaction can also generate chemical crosslinking with emulsion, a base layer, pigments, fillers and the like to form a complete space three-dimensional network skeleton structure, thereby coating other powder to enhance the mechanical property of the coating. The coating is a grade A fireproof material, is inorganic and non-combustible, can resist high temperature of over 1000 ℃, is different from potassium silicate, does not belong to salts, has low alkali content, does not salt out color of a color coating, and has a certain effect of improving color saturation.
Preferably, the stabilizer is selected from SPS of Craine, is quaternary ammonium salt with a gemini star structure, and can slow down various curing reactions in the inorganic coating and improve the viscosity stability of the coating. The concrete structure is shown in figure 1.
Preferably, the antifreeze is selected from imported environmentally friendly low temperature antifreeze, such as YT-BM6 from the UK Union, zero VOC.
Preferably, the dispersant is selected from Coadis 123K of Gaotai France, is a hydrophobic modified potassium salt acrylic copolymer, has good water resistance and pigment and filler dispersibility, and can reduce the phenomenon of coating film blooming caused by salting out due to the fact that the potassium salt structure is very suitable for being used in an inorganic coating system containing potassium silicate.
Preferably, the wetting agent is selected from the group consisting of colaine EO/PO block copolymers, alkyl polyoxyethylene ethers. The paint does not contain APEO, has good water resistance, does not influence color development, and has the function of improving freeze thawing resistance.
Preferably, the titanium dioxide is selected from chloride rutile type titanium dioxide R-895 with better weather resistance and higher whiteness.
Preferably, the kaolin is selected from artificially treated calcined kaolin having a mesh size of 1250 mesh and a type C-60.
Preferably, the other mineral filler is one or more selected from heavy calcium carbonate, air separation mica powder, silica micropowder, talcum powder and wollastonite powder. The purity of the main compounds in the ore should be more than 99%.
Preferably, the film forming aid is selected from 2,2, 4-trimethyl-1, 3 pentanediol isobutyrate diester with higher boiling point, which has better alkali resistance, does not generate odor of low molecular alcohol due to hydrolysis when used as a film forming aid in inorganic coating, and has better film forming auxiliary effect.
Preferably, the emulsion is selected from silicone acrylic emulsion RS-996AD of Badful company, the content of organic silicon of the emulsion is up to 8 percent, and the emulsion has good hardness, water resistance, water permeability and color development. The organic silicon branched chain contained in the emulsion can be coupled with the residual silanol bonds on the surface of the nano silicon dioxide in the drying process, so that the wrapping property of the mineral powder is improved, and the mechanical property of the coating film is further improved.
Preferably, the defoaming agent 2 is selected from SN 1311 of Santa Nuo Puke, Japan, is a modified silicone-based defoaming agent, and has continuous defoaming performance.
Preferably, the environment-friendly preservative is selected from YT-BM6 with good alkali resistance, and is a mixture of Bit and Mit.
Preferably, the multifunctional auxiliary agent is selected from 881 of Jiangyin couplet of China, is alkyl sylvite, and has the effects of adjusting pH, and improving the waterproof performance and the stability of the inorganic coating. The structural formula is HO- [ SiR (OX) -O-]n-H, wherein R is a carbon alkyl group and X is a cation.
Preferably, the modified potassium silicate is selected from GHS1378A of Jiangyin Union of China, is a bonding material which is obtained by chemically modifying pure potassium silicate with silane or is called organic-inorganic hybridization, reduces the reaction activity of the potassium silicate by properly reducing the number of active silanol groups of the potassium silicate by connecting organic groups to silicon atoms in the potassium silicate, and can further improve the stability of the potassium silicate through the steric hindrance of the organic groups. The residual silanol bonds can also be subjected to polycondensation reaction with the main bonding substance nano silicon dioxide in the drying process, so that the powder is more densely coated to enhance the mechanical property of the coating. The pH value is 11-12, the solid content is 28 +/-1%, and the stabilizing agent is K2O, modulus is 3.9, and has certain film forming property.
Preferably, the organic silicon waterproof agent is 208 of Jiangyin national Union, is an alkyl polydimethylsiloxane water-based emulsion, can improve the hydrophobicity, the water resistance and the air permeability of the inorganic silicate coating, and can also effectively improve the scrubbing resistance.
Preferably, the color paste for the water-based paint is selected from one or more of iron oxide black, iron oxide yellow, iron oxide red, ultramarine, phthalocyanine green, scarlet, phthalocyanine blue, medium yellow and permanent violet.
The preparation method of the inorganic coating for the water-based mineral interior wall comprises the following steps:
(1) and (3) slowly adding the defoaming agent 1, the thickening powder, the anti-settling agent pre-solution and the cellulose ether into the deionized water in sequence, adjusting the rotating speed of a dispersion machine to 400-500 r/min, and dispersing until no obvious particles exist in the water.
(2) And (3) adding the modified nano silicon dioxide aqueous solution, the stabilizing agent, the antifreezing agent, the dispersing agent and the wetting agent in sequence, and dispersing for 3-5 min until the dispersion is uniform.
(3) Titanium dioxide, kaolin and other mineral fillers are sequentially added, and are dispersed at a high speed of 1800-2000 r/min for 30-40 min, and the detection fineness is 40-50 microns.
(4) And (3) sequentially adding the defoaming agent 2, the emulsion and the film forming additive, stirring at a medium speed of 600-1000 r/min for 5min, and slowly defoaming.
(5) Sequentially adding an environment-friendly preservative, a multifunctional additive, modified potassium silicate and an organic silicon waterproof agent, and dispersing at a medium speed for 10min to obtain the white water-based mineral inorganic coating for the interior wall.
(6) Adding the color paste for the water-based paint according to the required color, dispersing at medium speed for 10min to obtain the inorganic paint for the inner wall of the color water-based mineral, sieving and discharging, and packaging after the detection is qualified.
The inorganic coating for the water-based mineral interior wall disclosed by the invention has the advantages that the main bonding material is nano modified silicon dioxide, the auxiliary bonding material is modified potassium silicate and emulsion, the coating of titanium dioxide, kaolin and other mineral fillers by the bonding material can reach the standard of high-quality interior wall coating, the grade A fire resistance can be achieved, the mandatory requirements in GB 50222-.
The various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art. To the extent that the terms and phrases are not inconsistent with known meanings, the meaning of the present invention will prevail. The components related to the invention are all products existing in the prior art and can be purchased in the conventional market.
Drawings
FIG. 1: structural schematic diagram of quaternary ammonium salt with gemini star structure, wherein R5、R6、R7Is alkyl, M1、M2Is alkenyl, X1、Y1Being covalently bonded organic radicals, D-Is an anion.
FIG. 2: graph of scrub resistance times.
FIG. 3: reaction mechanism schematic, wherein M2+Is Ca2+，Mg2+；
Is a modified nano silicon dioxide colloid surface and a silanol group at the tail end of an organic silicon chain segment contained in the silicone-acrylic emulsion.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The present invention has been described generally and/or specifically with respect to materials used in testing and testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
The "parts" or "%" described in the present application are by mass unless otherwise specified.
The raw materials used in this application are as follows:
antifoam agent 1 (SN 321-C of Saint Pachylomaceae, Japan).
Thickening powder (Youtou alliance YT-10).
An anti-settling agent pre-solution (5% water solution of SW of Jiangsu national construction).
Cellulose ethers (modified anionic cellulose ethers of the Shanghai Mitsu-shi row S30000YP2, hydroxyethyl methyl cellulose ether SH30000YP2 of Germany Kelain).
Modified nano-silica aqueous solution (GHS 1368 of Jiangyin Union of China).
Stabilizers (SPS, clariant, germany).
Antifreeze (bolt friend chemical HT 904).
Dispersant (Coadis 123K from Gaotai, France).
Wetting agents (ED 3060, german, kraine, 2070, german).
Titanium dioxide (R-895 of herboria python).
Kaolin (Jinkun C-60).
Other mineral fillers (the dry mica powder GB-3, the heavy calcium carbonate GY-716 of the widely-sourced chemical industry, 800 meshes of Ammi micro-nano silica powder, and 800 meshes of Excellent coating union wollastonite powder ultra-fine white).
Film-forming aid (RTC-16 of Runtai chemical).
Emulsion (Bardefy silicone acrylic emulsion RS-996 AD).
Antifoam agent 2 (SN 1311, Saint Pachylomaceae, Japan).
Environmental protection type antiseptic (Excellent alliance YT-BM 6).
Multifunctional additive (881 of Jiangyin couplet of China).
Modified potassium silicate (GHS 1378A, Union of Jiangyin China).
An organosilicon waterproofing agent (209 of Jiangyin national Union).
Color paste for water-based paint (color paste for water-based paint of the world, iron oxide red SM8805, iron oxide yellow SM8810, carbon black SM6800, bright red SM9811 and medium yellow SM 9806).
Examples preparation of inorganic coating materials for aqueous mineral interior walls
The compositions of examples 1 to 5 are shown in Table 1.
The preparation method comprises the following steps:
(1) and (3) slowly adding the defoaming agent 1, the thickening powder, the anti-settling agent pre-solution and the cellulose ether into the deionized water in sequence, adjusting the rotating speed of a dispersion machine to 400-500 r/min, and dispersing until no obvious particles exist in the water.
(2) And (3) adding the modified nano silicon dioxide aqueous solution, the stabilizing agent, the antifreezing agent, the dispersing agent and the wetting agent in sequence, and dispersing for 3-5 min until the dispersion is uniform.
(3) Titanium dioxide, kaolin and other mineral fillers are sequentially added, and are dispersed at a high speed of 1800-2000 r/min for 30-40 min, and the detection fineness is 40-50 microns.
(4) And (3) sequentially adding the defoaming agent 2, the emulsion and the film forming additive, stirring at a medium speed of 600-1000 r/min for 5min, and slowly defoaming.
(5) Sequentially adding an environment-friendly preservative, a multifunctional additive, modified potassium silicate and an organic silicon waterproof agent, and dispersing at a medium speed for 10min to obtain the white water-based mineral inorganic coating for the interior wall.
(6) Adding the color paste for the water-based paint according to the required color, dispersing at medium speed for 10min to obtain the inorganic paint for the inner wall of the color water-based mineral, sieving and discharging, and packaging after the detection is qualified.
TABLE 1 coating formulation ratios of examples 1-5
In example 1, the coating is a white inorganic coating, modified nano-silica aqueous solution GHS1368 is used as a main binder, modified potassium silicate GHS1378A and a small amount of emulsion RS-996AD are matched, and the stability of a finished product is improved through a stabilizing agent SPS, a multifunctional additive 881, a wetting agent ED3060, cellulose ether and the like.
In example 2, the coating is a white inorganic coating, modified nano-silica aqueous solution GHS1368 is used as a main binder, and a small amount of emulsion RS-996AD, scaly mica powder and fibrous wollastonite powder are matched, so that the mechanical properties of the coating are improved.
In example 3, the black-gray inorganic paint uses modified nano-silica aqueous solution GHS1368 as main binder, and matches with a small amount of emulsion RS-996AD and scaly mica powder with color retention, and the perfect color is achieved by adjusting titanium dioxide and carbon black color paste.
In the embodiments 4 and 5, the color inorganic paint uses modified nano-silica aqueous solution GHS1368 as a main binder, a small amount of emulsion RS-996AD as an auxiliary film forming material, and is matched with scaly mica powder with color retention function to achieve the required color through the adjustment of titanium dioxide and color paste.
The results of the overall performance tests are shown in table 2.
TABLE 2
It can be seen from examples 2 to 5 that the viscosity of the coating is increased with the addition of the color paste, slight floating water occurs after 30 days of hot storage, which indicates that the dispersant and wetting agent in the color paste have influence on the state of the inorganic coating, but the scrub resistance and the A-level fireproof performance have little influence, the overall fineness is not changed, and the large-area coating effect is good after the research test, and the coating is tried by customers at present.
Meanwhile, the originally unexpected technical effect is also found by actually detecting the scrubbing resistance of the coating film. Through the compound hybridization of the modified nano silicon dioxide aqueous solution and the silicone-acrylic emulsion RS-996AD, the scrubbing resistance of the coating film is far higher than that of the common A2-grade fireproof inorganic coating in the market, and the strength of the coating film is obviously increased in age.
The compound hybridization scrub resistant times of the modified nano-silica aqueous solution and the silicone-acrylate emulsion RS-996AD along with the change of the curing age are shown in Table 3 and figure 2.
TABLE 3
| |
1 day | 3 days | 7 days | 14 days | 21 days | 28 days | 35 days |
| Scrub resistant (second time) | 120 | 530 | 6500 | 12000 | 17500 | 21000 | 22000 |
As can be seen from Table 3, the scrubbing resistance times of the series of products in 7 days can reach more than 6000 times, and the requirements of the excellent products in GB/T9756-. And the common A2 grade inorganic interior wall coating on the market is sampled and detected to find the common times of scrubbing resistance in the same periodThe paint meets the requirements of first-class products in GB/T9756-2018 synthetic resin emulsion interior wall paint for 1500-3500 times. Through purchasing other types of silicone-acrylate emulsion and matching with the modified nano-silica aqueous solution, the co-period scrubbing resistance times are found to be 2000-4000 times and lower than that of the product of the invention, which shows that the modified nano-silica and the silicone-acrylate emulsion RS-996AD in the product have the mutual hybridization coordination effect, the content of the organic silicon in the silicone-acrylate emulsion is far higher than that of other emulsions, the mass fraction reaches 8%, some nano-micropores exist after the silicone-acrylate emulsion is formed into a film, and the silicone-acrylate emulsion is compounded with the modified nano-silica, so that the tail end of an organic silicon chain segment contained in the silicone-acrylate emulsion
And the modified nano-silica remaining
The crosslinking reaction is carried out to form a three-dimensional hybrid bonding material of a crosslinked mutual transmission network and fully bond the powder, the mechanical strength of the coating is improved, and the scrubbing resistance achieves the effect which is not expected originally.
Meanwhile, as can be seen from fig. 2, the scrub resistance of the product is also improved continuously along with the prolonging of the curing time. The change of the film performance with time is obviously unexpected, but the data show that the scrubbing resistance times can reach more than 75 percent of the whole strength when the film is cured for 21 days; after 28 days of maintenance, the frequency change amplitude tends to be smooth, and the film coating strength is stable; the inorganic coating is different from common latex paint, the inorganic coating is used as a reaction type coating, the strength change of the inorganic coating is more similar to that of cement, the modified nano-silica is used as a main binding substance, and the modified nano-silica can slowly react with CO in the air in a coating film after moisture evaporation2Or calcium ions and magnesium ions in the coating film base layer react, the strength is continuously improved, and the reaction mechanism is shown in figure 3.
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (10)
1. An inorganic coating for water-based mineral interior walls, which is characterized in that: the composition comprises the following components in parts by weight:
18-25 parts of water
10.1-0.2 parts of defoaming agent
0.1 to 0.2 portion of thickening powder
2-4 parts of anti-settling agent pre-solution
2.5-3 parts of cellulose ether
15-25 parts of modified nano silicon dioxide aqueous solution
0.3-0.5 part of stabilizer
1-2 parts of antifreezing agent
0.2 to 0.5 part of dispersant
0.1 to 0.2 portion of wetting agent
2.5-18 parts of titanium dioxide
5-10 parts of kaolin
15-35 parts of other mineral fillers
0-0.3 part of film forming auxiliary agent
0-6 parts of emulsion
20.05-0.1 part of defoaming agent
0.1-0.3 part of environment-friendly preservative
0.3-1 part of multifunctional additive
0-5 parts of modified potassium silicate
0-2 parts of organosilicon waterproofing agent
0-3 parts of color paste for the water-based paint.
2. The inorganic coating material for mineral water-based interior walls according to claim 1, characterized in that: the antifoaming agent 1 is selected from SN 321-C of Santa Nuo family of Japan;
or/and: the thickening powder is selected from YT-10 of the excellent chemical union;
or/and: the anti-settling agent pre-solution is selected from a high-purity polyphosphate water solution, and is a 5% pre-dispersion body prepared by dispersing polyphosphate at a high speed and dissolving the polyphosphate in water, wherein the selected polyphosphate is SW built in Suzhou nations;
or/and: the cellulose ether is selected from modified anionic cellulose ethers, hydroxyethyl methyl cellulose ethers.
3. The inorganic coating material for mineral water-based interior walls according to claim 1, characterized in that: the modified nano-silica aqueous solution is GHS1368 of Jiangyin Union of China;
or/and: the stabilizer is selected from SPS of Craine;
or/and: the antifreeze is selected from YT-BM6 of the excellent path union;
or/and: the dispersant is selected from Coadis 123K of Gaotai France;
or/and: the wetting agent is selected from the group consisting of colaine EO/PO block copolymer and alkyl polyoxyethylene ether.
4. The inorganic coating material for mineral water-based interior walls according to claim 1, characterized in that: the titanium dioxide is selected from rutile titanium dioxide R-895;
or/and: the kaolin is selected from Jinkun C-60;
or/and: the other mineral fillers are selected from one or more of heavy calcium carbonate, air separation mica powder, silica micropowder, talcum powder and wollastonite powder.
5. The inorganic coating material for mineral water-based interior walls according to claim 1, characterized in that: the film-forming auxiliary agent is selected from 2,2, 4-trimethyl-1, 3-pentanediol isobutyrate diester;
or/and: the emulsion is selected from silicone acrylic emulsion RS-996AD of Badelujin company;
or/and: the antifoaming agent 2 is selected from SN 1311 of Santa Nuo Puke.
6. The inorganic coating material for mineral water-based interior walls according to claim 1, characterized in that: the environment-friendly preservative is selected from YT-BM 6;
or/and: the multifunctional auxiliary agent is selected from 881 of Jiangyin couplet;
or/and: the modified potassium silicate is selected from GHS1378A of the Union of Jiangyin China;
or/and: the organic silicon waterproof agent is selected from 208 of Jiangyin Union of China;
or/and: the color paste for the water-based paint is selected from one or more of iron oxide black, iron oxide yellow, iron oxide red, ultramarine, phthalocyanine green, scarlet, phthalocyanine blue, medium yellow and permanent violet.
7. The inorganic coating material for an interior mineral wall according to any one of claims 1 to 6, characterized in that: the components are one of the following components:
8. the method for preparing the inorganic paint for the water-based mineral inner wall according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
(1) sequentially adding the defoaming agent 1, the thickening powder, the anti-settling agent pre-solution and the cellulose ether into water, and dispersing until no obvious particles exist in the water;
(2) adding the modified nano-silica aqueous solution, the stabilizer, the antifreezing agent, the dispersant and the wetting agent in sequence, and dispersing uniformly;
(3) titanium dioxide, kaolin and other mineral fillers are added in sequence and dispersed uniformly;
(4) sequentially adding the defoaming agent 2, the emulsion and the film forming auxiliary agent, and uniformly stirring;
(5) sequentially adding an environment-friendly preservative, a multifunctional additive, modified potassium silicate and an organic silicon waterproof agent, and uniformly dispersing to obtain the water-based paint.
9. The method for preparing the inorganic paint for the water-based mineral interior wall according to claim 8, wherein: further comprising the step (6): adding color paste for the water-based paint according to the required color, and uniformly dispersing to obtain the inorganic paint for the color water-based mineral inner wall;
or/and: the anti-settling agent pre-solution is prepared by the following method: starting a dispersion machine, adjusting the rotating speed to 400-500 r/min, adding 95 parts of deionized water into a container, slowly adding 5 parts of polyphosphate SW, adjusting the rotating speed to 1700-2500 r/min, dispersing for 1-2 h until the viscosity is stable, and prefabricating for later use.
10. The method for preparing the inorganic paint for water-based mineral interior walls according to claim 8 or 9, characterized in that: the method comprises the following specific steps:
(1) sequentially and slowly adding the defoaming agent 1, the thickening powder, the anti-settling agent pre-solution and the cellulose ether into deionized water, adjusting the rotating speed of a dispersion machine to 400-500 r/min, and dispersing until no obvious particles exist in the water;
(2) adding the modified nano-silica aqueous solution, the stabilizer, the antifreezing agent, the dispersant and the wetting agent in sequence, and dispersing for 3-5 min until the nano-silica aqueous solution is uniformly dispersed;
(3) sequentially adding titanium dioxide, kaolin and other mineral fillers, dispersing at a high speed of 1800-2000 r/min for 30-40 min, and detecting the fineness of 40-50 microns;
(4) sequentially adding a defoaming agent 2, an emulsion and a film forming additive, stirring at a medium speed of 600-1000 r/min for 5min, and slowly defoaming;
(5) sequentially adding an environment-friendly preservative, a multifunctional additive, modified potassium silicate and an organic silicon waterproof agent, and dispersing at a medium speed for 10min to obtain the white water-based mineral inorganic coating for the inner wall;
(6) adding the color paste for the water-based paint according to the required color, dispersing at medium speed for 10min to obtain the inorganic paint for the inner wall of the color water-based mineral, sieving and discharging, and packaging after the detection is qualified.
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Application publication date: 20210507 |