CN115072775A - Composite sol, coating, preparation method and application thereof - Google Patents
Composite sol, coating, preparation method and application thereof Download PDFInfo
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- CN115072775A CN115072775A CN202210866059.3A CN202210866059A CN115072775A CN 115072775 A CN115072775 A CN 115072775A CN 202210866059 A CN202210866059 A CN 202210866059A CN 115072775 A CN115072775 A CN 115072775A
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- coating
- zirconium
- sol
- composite sol
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- 238000000576 coating method Methods 0.000 title claims abstract description 209
- 239000011248 coating agent Substances 0.000 title claims abstract description 198
- 239000002131 composite material Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 57
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 54
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 25
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 56
- 230000032683 aging Effects 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 44
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 37
- 229910000077 silane Inorganic materials 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 29
- 229960000583 acetic acid Drugs 0.000 claims description 28
- 239000012362 glacial acetic acid Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000080 wetting agent Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 13
- 238000005299 abrasion Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 9
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 6
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 6
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000013007 heat curing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 4
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 4
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 3
- BMTKGBCFRKGOOZ-UHFFFAOYSA-K cyclopenta-1,3-diene;zirconium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1 BMTKGBCFRKGOOZ-UHFFFAOYSA-K 0.000 claims description 3
- DWCMDRNGBIZOQL-UHFFFAOYSA-N dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C DWCMDRNGBIZOQL-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims 1
- 239000013618 particulate matter Substances 0.000 claims 1
- CAINCDLPPXCEEZ-UHFFFAOYSA-L zirconium(2+);dihydroxide Chemical compound O[Zr]O CAINCDLPPXCEEZ-UHFFFAOYSA-L 0.000 claims 1
- 238000005524 ceramic coating Methods 0.000 abstract description 34
- 239000000654 additive Substances 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 238000013329 compounding Methods 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 235000021168 barbecue Nutrition 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a composite sol and a preparation method and application thereof. According to the composite sol disclosed by the invention, the preparation raw materials comprise the zirconium compound, the silicon compound, the pH regulator and water, and when the composite sol is used as an additive for a coating, the composite sol prepared by modifying the silica sol through the zirconium sol achieves the purpose of toughening, and the toughness of the ceramic coating is increased while the better hardness and the wear resistance of the ceramic coating are maintained. The invention also provides a method for preparing the composite sol, a coating containing the composite sol, a method for preparing the coating, a wear-resistant hydrophobic coating and a household appliance with the wear-resistant hydrophobic coating on the surface.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a composite sol, and a preparation method and application thereof.
Background
The ceramic coating is different from any traditional synthetic resin organic coating and is a brand new water-based inorganic coating. It uses nano inorganic compound as main component, and after coating it is solidified by means of low-temp. heating so as to form a coating film whose performance is similar to that of ceramic.
The ceramic coating inherits the advantages of organic coating and inorganic coating, integrates the advantages of high temperature resistance, high hardness, super weather resistance, non-combustion, no smoke, environmental protection, no toxicity, rich colors, simple and convenient coating and the like, and is suitable for various occasions with high requirements. Its unique properties solve many problems that traditional organic coatings cannot solve. The ceramic coating can be applied to: the coating of curtain walls of commercial buildings, antistatic coatings of medical machinery, anti-aging coatings of outdoor large natural gas and petroleum storage tanks, high-temperature resistant non-stick coatings of kitchenware, high-temperature oxidation resistant coatings of metal heating equipment and the like.
Although the ceramic coating has outstanding performance, at present, a plurality of technical bottlenecks such as poor toughness, easy cracking of thick films, high pretreatment requirement on metal substrates, poor adhesion on the substrates and the like still exist, and the technical bottlenecks seriously restrict the further development of the ceramic coating industry.
In the related art, the toughening effect is generally achieved by adding an organic component to the ceramic coating, however, the addition of the organic component causes the overall hardness of the coating to be reduced, the wear resistance to be reduced, and the specific properties of the ceramic coating to be reduced.
Therefore, it is necessary to develop a new additive capable of increasing the toughness of the ceramic coating while maintaining the better hardness and wear resistance of the ceramic coating.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, when the composite sol is used for a coating, the toughness of the ceramic coating can be improved while the better hardness and the wear resistance of the ceramic coating are maintained.
The invention also provides a method for preparing the composite sol.
The invention also provides a coating containing the composite sol.
The invention also provides a method for preparing the coating.
The invention also provides a hydrophobic wear-resistant coating.
The invention also provides a preparation method of the hydrophobic wear-resistant coating.
The invention also provides a household appliance with the hydrophobic wear-resistant coating on the surface.
The first aspect of the invention provides a composite sol, which is prepared from a zirconium compound, a silicon compound, a pH regulator and water, wherein the mass ratio of the zirconium compound to the silicon compound is 0.1-10: 1.
The invention relates to one of the technical schemes of the composite sol, which at least has the following beneficial effects:
according to the composite sol, the preparation raw materials comprise a zirconium compound, a silicon compound, a pH regulator and water, the zirconium compound and the silicon compound are respectively prepared into the zirconium sol and the silicon sol, and after the zirconium sol is modified by the silicon sol to prepare the composite sol, the composite sol can play a role in toughening a coating when being used for the coating, so that the better hardness and the wear resistance of the ceramic coating are maintained, and meanwhile, the toughness of the ceramic coating is increased.
The zirconium compound, the silicon compound, the pH regulator and the water in the raw materials for preparing the composite sol are common reagents, and the raw materials are easy to obtain and prepare and are beneficial to production and preparation.
According to some embodiments of the invention, the zirconium compound comprises at least one of zirconium oxychloride, zirconyl nitrate, zirconium propionate, zirconium silicate, zirconium ethoxide, zirconium tert-butoxide, zirconium acetylacetonate, zirconium hexafluoroacetylacetonate, cyclopentadienyl zirconium trichloride, dicyclopentadiene zirconium dihydride, tetrakis (dimethylamino) zirconium, and tetrabutylzirconate.
According to some embodiments of the invention, the silicon compound comprises at least one of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, and dodecyltrimethoxysilane.
According to some embodiments of the invention, the pH adjusting agent comprises at least one of glacial acetic acid, hydrochloric acid, formic acid, sulfuric acid, nitric acid, ammonia, sodium hydroxide, and potassium hydroxide.
A second aspect of the present invention provides a method for preparing a composite sol, comprising the steps of: respectively dissolving the zirconium compound and the silicon compound in water, adding the pH regulator to regulate the pH value, then carrying out first aging to obtain zirconium sol and silica sol, adding the zirconium sol into the silica sol, adding the pH regulator again to regulate the pH value, and then carrying out second aging to obtain the composite sol.
The invention relates to a technical scheme for preparing composite sol, which at least has the following beneficial effects:
in the preparation method of the composite sol, firstly, a zirconium compound is dissolved in water, and the zirconium compound is added with the pH regulator to regulate the pH value and then is aged for the first time to prepare the zirconium sol. Dissolving a silicon compound in water, adding the pH regulator to regulate the pH value, and performing first aging to obtain the silica sol. And adding the zirconium sol into the silica sol, adding the pH regulator to regulate the pH, and then performing secondary aging to obtain the composite sol. After the zirconium sol modified silica sol is prepared into the composite sol, when the composite sol is used for a coating, the aim of toughening the coating can be fulfilled, and the toughness of the ceramic coating is increased while the better hardness and wear resistance of the ceramic coating are maintained.
In the preparation method of the composite sol, the purpose of adjusting the pH is to catalyze the hydrolysis of the zirconium compound and the silicon compound, thereby condensing to form the sol.
The aging aims to ensure that the prepared colloid molecular chain is subjected to rearrangement, chain extension and molecular weight increase, and the performance of the coating can be regulated and controlled when the colloid molecular chain is used in the coating.
Dissolving a zirconium compound in water, adding a pH regulator to regulate the pH to 4-10, and aging (first aging) for 12-72 h.
Dissolving a silicon compound in water, adding a pH regulator to regulate the pH to 4-10, and aging (first aging) for 12-72 h.
When the zirconium sol is added into the silica sol, the zirconium sol can be added dropwise, so as to promote the dissolution of the zirconium sol in the silica sol and improve the stability of the silica-zirconium sol.
Adding zirconium sol into silica sol, adding a pH regulator to regulate the pH to 4-10, and aging (aging for the second time) for 24-72 h. The pH adjustment here serves to promote the secondary reaction of the silicozirconium sol to form a stable silicozirconium sol.
In a third aspect of the invention, a coating is provided, and the preparation raw materials comprise composite sol, silane oligomer and water.
The invention relates to one of the technical schemes of the coating, which at least has the following beneficial effects:
in the preparation raw materials of the coating, the composite sol is used as an additive of the coating, the composite sol prepared by modifying the silica sol with the zirconium sol achieves the aim of toughening, and the silane oligomer is used as a film forming substance to provide non-adhesiveness for the coating. Therefore, under the combined action of the composite sol, the silane oligomer and water, the ceramic coating is formed, and the ceramic coating has better toughness while maintaining better hardness and wear resistance.
According to some embodiments of the present invention, the raw materials for preparing the coating comprise the following components in parts by weight:
compounding sol: 10 to 40 portions of the mixture of the components,
silane oligomer: 10 to 45 portions of the mixture of the components,
water: 10 to 80 portions.
According to some embodiments of the invention, the silane oligomer comprises at least one of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, and dodecyltrimethoxysilane.
According to some embodiments of the invention, the preparation raw material further comprises 0.01 to 5 parts by weight of an auxiliary agent.
According to some embodiments of the invention, the adjuvant comprises at least one of a coating pH adjuster, a leveling agent, a wetting agent, a defoamer, a thickener.
A fourth aspect of the present invention provides a method of preparing a coating, comprising the steps of: and dissolving the silane oligomer in water, and adding the silane oligomer into the composite sol to obtain the coating.
The technical scheme of the preparation method of the coating at least has the following beneficial effects:
the preparation method of the coating of the invention comprises the steps of adding the silane oligomer into the composite sol, and mixing the silane oligomer with water to obtain the coating. The preparation method is simple and easy to operate, does not need expensive equipment or complex process control, is favorable for ensuring the stability of the quality of the coating product, and is easy for large-scale batch production.
According to some embodiments of the present invention, the method for preparing a coating material further comprises adjusting the particle size of particles generated by the reaction of the silane oligomer and the composite sol by adjusting pH after adding the silane oligomer dissolved in water to the composite sol.
The particle size of the particles generated by the reaction of the silane oligomer and the composite sol is adjusted, so that the performance of the coating is ensured, and when the particle size of the particles in the coating is less than 1000nm, the comprehensive performance of the coating is better.
The particle size of the particles generated by the reaction of the silane oligomer and the composite sol can be adjusted by adjusting the pH, and the mechanism is that the reaction speed can be controlled by adjusting the pH so as to control the particle size of the particles generated by the reaction of the silane oligomer and the composite sol.
The fifth aspect of the invention provides a hydrophobic wear-resistant coating prepared from the coating.
The invention relates to a technical scheme of a hydrophobic wear-resistant coating, which at least has the following beneficial effects:
the hydrophobic wear-resistant coating is formed by the coating, the coating takes the composite sol as an additive of the coating, the composite sol prepared by modifying the silica sol with the zirconium sol plays a toughening role, and the silane oligomer is taken as a film forming substance to provide non-adhesiveness for the coating. Therefore, under the combined action of the composite sol, the silane oligomer and water, the ceramic coating is formed, and after a coating is formed by the ceramic coating, the ceramic coating has better toughness while maintaining better hardness and wear resistance.
According to some embodiments of the invention, the hydrophobic abrasion resistant coating has a thickness of 10 μm to 100 μm.
The sixth aspect of the present invention provides a preparation method of a hydrophobic wear-resistant coating, wherein the preparation method comprises: and (3) after the coating is constructed on the surface of the base material, carrying out thermosetting treatment.
According to some embodiments of the invention, the temperature of the thermal curing process is 60 ℃ to 300 ℃.
According to some embodiments of the invention, the temperature of the thermal curing process is between 80 ℃ and 280 ℃.
According to some embodiments of the invention, the heat curing process is performed for a time period of 10min to 60 min.
The seventh aspect of the invention provides a household appliance, and the surface of the household appliance is provided with the hydrophobic wear-resistant coating.
The invention relates to one of the technical schemes of the household appliances, which at least has the following beneficial effects:
the hydrophobic wear-resistant coating is arranged on the surface of the household appliance, and the coating has better toughness while maintaining better hardness and wear resistance of the ceramic coating, so that after the hydrophobic wear-resistant coating is arranged, the surface of the household appliance has higher hardness, better wear resistance and better toughness, the service life of the household appliance is prolonged, the surface quality of the household appliance is higher, and the problems of scratches, coating falling and the like on the surface of the household appliance are not easy to occur in the use process and in a high-temperature environment.
According to some embodiments of the invention, the household appliance comprises a pot, a stove, a baking utensil, a range hood, and a kitchen range.
According to some embodiments of the invention, the pot comprises a rice cooker, a frying pan or a stir pan.
According to some embodiments of the invention, the oven comprises an induction cooker.
According to some embodiments of the invention, a rotisserie apparatus includes an oven and a barbecue grill.
Drawings
FIG. 1 is a surface topography map of a coating prepared from the coating of example 1 before high temperature resistance testing.
FIG. 2 is a surface topography of a coating prepared from the coating of example 1 after a high temperature resistance test.
FIG. 3 is a surface topography after high temperature resistance testing of coatings prepared from the coatings of comparative example 1.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
In some embodiments of the invention, the invention provides a composite sol, the preparation raw materials comprise a zirconium compound, a silicon compound, a pH regulator and water, and the mass ratio of the zirconium compound to the silicon compound is 0.1-10: 1.
It can be understood that, the composite sol of the invention is prepared by the raw materials comprising the zirconium compound, the silicon compound, the pH regulator and the water, and when the composite sol is used as an additive in a coating, the composite sol prepared by the zirconium sol modified silica sol achieves the aim of toughening, and the toughness of the ceramic coating is increased while the better hardness and the wear resistance of the ceramic coating are maintained.
In addition, the zirconium compound, the silicon compound, the pH regulator and the water in the raw materials for preparing the composite sol are common reagents, and the raw materials are easy to obtain and prepare, so that the composite sol is beneficial to production and preparation.
In some embodiments of the invention, the zirconium compound comprises at least one of zirconium oxychloride, zirconyl nitrate, zirconium propionate, zirconium silicate, zirconium ethoxide, zirconium tert-butoxide, zirconium acetylacetonate, zirconium hexafluoroacetylacetonate, cyclopentadienyl zirconium trichloride, dicyclopentadiene zirconium dihydride, tetrakis (dimethylamino) zirconium, and tetrabutylzirconate.
In some embodiments of the invention, the silicon compound comprises at least one of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, and dodecyltrimethoxysilane.
In some embodiments of the invention, at least one of glacial acetic acid, hydrochloric acid, formic acid, sulfuric acid, nitric acid, ammonia, sodium hydroxide, and potassium hydroxide is included.
In still other embodiments of the present invention, the present invention provides a method for preparing a composite sol, comprising the steps of: respectively dissolving a zirconium compound and a silicon compound in water, adding a pH regulator to regulate the pH, then carrying out first aging to obtain zirconium sol and silica sol, adding the zirconium sol into the silica sol, adding the pH regulator again to regulate the pH, and then carrying out second aging to obtain the composite sol.
Specifically, in the method for preparing the composite sol of the present invention, the zirconium compound is dissolved in water, and the zirconium sol is prepared by first aging after adjusting the pH by adding the pH adjuster. Dissolving a silicon compound in water, adding a pH regulator to regulate the pH value, and performing first aging to obtain the silica sol. And adding the zirconium sol into the silica sol, adding a pH regulator to regulate the pH, and performing secondary aging to obtain the composite sol. After the zirconium sol modified silica sol is prepared into the composite sol, when the composite sol is used for a coating, the aim of toughening the coating can be fulfilled, and the toughness of the ceramic coating is increased while the better hardness and the wear resistance of the ceramic coating are maintained.
Specifically, the purpose of the pH adjustment is to catalyze the hydrolysis of the zirconium compound and the silicon compound, thereby condensing into a sol.
Further, the aging aims to ensure that the prepared colloidal molecular chain is rearranged, subjected to chain extension and subjected to molecular weight increase, and the performance of the coating can be regulated and controlled when the colloidal molecular chain is used in a coating.
Dissolving a zirconium compound in water, adding a pH regulator to regulate the pH to 4-10, and aging (first aging) for 12-72 h.
Dissolving a silicon compound in water, adding a pH regulator to regulate the pH to 4-10, and aging (first aging) for 12-72 h.
When the zirconium sol is added into the silica sol, the zirconium sol can be added dropwise, so as to promote the dissolution of the zirconium sol in the silica sol and improve the stability of the zirconium silica sol.
And adding the zirconium sol into the silica sol, adding a pH regulator to regulate the pH to 4-10, and aging (secondary aging) for 24-72 h. The pH is adjusted here to promote the secondary reaction of the silica-zirconium sol to form a stable silica-zirconium sol.
In some other embodiments of the present invention, the present invention provides a coating prepared from raw materials including a composite sol, a silane oligomer, and water.
Specifically, the preparation raw materials comprise the following components in parts by weight:
compounding sol: 10 to 40 portions of the mixture of the components,
silane oligomer: 10 to 45 portions of the weight portion of the mixture,
water: 10 to 80 portions.
It can be understood that in the preparation raw materials of the coating, the composite sol is used as an additive of the coating, the zirconium sol is used for modifying the silica sol to achieve the toughening purpose, and the silane oligomer is used as a film forming substance to provide non-adhesiveness for the coating. Therefore, under the combined action of the composite sol, the silane oligomer and water, the ceramic coating is formed, and has better toughness while maintaining better hardness and wear resistance of the ceramic coating.
In some embodiments of the invention, the silane oligomer includes at least one of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, and dodecyltrimethoxysilane.
In some embodiments of the invention, the preparation raw material further comprises 0.01-5 parts by weight of an auxiliary agent.
In some embodiments of the invention, the adjuvant comprises one or more of a pH adjuster, a leveling agent, a wetting agent, a defoamer, a thickener.
It can be understood that, in the auxiliary agent, the pH regulator is used for regulating the pH of the coating, thereby controlling the reaction speed and the particle size of particles in the coating, and further regulating and controlling the performance of the coating.
It will also be appreciated that the levelling agent, among the adjuvants, acts to promote the formation of a smooth, even and homogeneous coating film on the coating material during the drying process. Can effectively reduce the surface tension of the finishing liquid and improve the leveling property and uniformity of the finishing liquid. Can improve the permeability of the coating liquid, reduce the possibility of generating spots and stains during the brush coating, increase the coverage and ensure that the formed film is uniform and natural. Mainly surfactant, organic solvent, etc.
It is also understood that, among the additives, the wetting agent is divided into a substrate wetting agent and a wetting dispersant, wherein the substrate wetting agent is used for improving the surface tension and permeability of the coating, so that the substrate can be better wetted, and the adhesion of the coating is improved.
It can also be understood that the foaming of the coating is a common phenomenon, and is influenced by various surfactants, and the coating can generate a large amount of bubbles in the production or painting process, so that the original filler is dispersed, the utilization rate of equipment is reduced, the production period is prolonged, and even the coating film has defects, pinholes and shrinkage cavities. The function of the defoamer is to reduce or eliminate bubbles in the coating.
It will also be appreciated that, among the adjuvants, the thickener thickens the paint, prevents sagging during application, and imparts excellent mechanical properties and storage stability to the paint.
In some embodiments of the present invention, the present invention provides a method of preparing a coating comprising the steps of: and dissolving the silane oligomer in water, and adding the solution into the composite sol to obtain the coating.
It is understood that the coating of the present invention can be prepared by adding the silane oligomer to the composite sol and mixing with water. The preparation method is simple and easy to operate, does not need expensive equipment or complex process control, is favorable for ensuring the stability of the quality of the coating product, and is easy for large-scale batch production.
In some embodiments of the present invention, the method for preparing the coating further comprises adjusting the particle size of the particles formed by the reaction of the silane oligomer and the composite sol by adjusting the pH after adding the silane oligomer dissolved in water to the composite sol.
Specifically, the particle size of the particles generated by the reaction of the silane oligomer and the composite sol is adjusted to ensure the performance of the coating, and when the particle size of the particles in the coating is less than 1000nm, the comprehensive performance of the coating is better.
The particle size of the particles generated by the reaction of the silane oligomer and the composite sol can be adjusted by adjusting the pH, and the mechanism is that the reaction speed can be controlled by adjusting the pH so as to control the particle size of the particles generated by the reaction of the silane oligomer and the composite sol.
In other embodiments of the present invention, the present invention provides a hydrophobic abrasion resistant coating prepared from the coating of the present invention.
It is easy to understand that the hydrophobic wear-resistant coating is formed by a coating, the coating takes the composite sol as an additive of the coating, the zirconium sol in the coating is used for modifying the silica sol to achieve the toughening purpose, and the silane oligomer is used as a film forming substance to provide non-adhesiveness for the coating. Therefore, under the combined action of the composite sol, the silane oligomer and water, the ceramic coating is formed, and after a coating is formed by the ceramic coating, the ceramic coating has better toughness while maintaining better hardness and wear resistance.
In some embodiments of the invention, the hydrophobic abrasion resistant coating has a thickness of 10 μm to 100 μm.
In some embodiments of the invention, the hydrophobic abrasion resistant coating is prepared by: after the coating is applied to the surface of the base material, heat curing treatment is carried out.
In some embodiments of the invention, the temperature of the thermal curing process is 60 ℃ to 300 ℃.
Further, the temperature of the heat curing treatment is 80 ℃ to 280 ℃.
In some embodiments of the present invention, the time of the heat-curing treatment is 10min to 60 min.
In further embodiments of the present invention, the present invention provides a household appliance having a surface provided with a hydrophobic, abrasion resistant coating according to the present invention.
The hydrophobic wear-resistant coating is arranged on the surface of the household appliance, and the coating has better toughness while maintaining better hardness and wear resistance of the ceramic coating, so that after the hydrophobic wear-resistant coating is arranged, the surface of the household appliance has higher hardness, better wear resistance and better toughness, the service life of the household appliance is prolonged, the surface quality of the household appliance is higher, and the problems of scratches, coating falling and the like on the surface of the household appliance are not easy to occur in the use process and in a high-temperature environment.
In some embodiments of the invention, the household appliance comprises a pot, a stove, a roaster, a range hood, and a cooker.
In some embodiments of the invention, the pot includes a rice cooker, a frying pan or a wok.
In some embodiments of the invention, the oven comprises an induction cooker.
In some embodiments of the invention, the roaster includes an oven and a barbecue grill.
It is easy to understand that cookware, stoves, baking tools, smoke exhaust machines and cooking utensils which are used daily are frequently used in people's life, so that if the surface coating is not high in hardness and poor in wear resistance, scratches are easy to occur, the coating is easy to fall off, the surface appearance quality of the utensil is poor, and after the hydrophobic wear-resistant coating is used, the wear resistance is better, the scratches are not easy to occur, and the surface quality is improved. Meanwhile, the coating has a hydrophobic function, so that the coating is easier to clean. In addition, the hydrophobic coating disclosed by the invention is high-temperature resistant, and is suitable for utensils which are often used in a high-temperature environment, such as pots, stoves, baking tools, smoking tools, stoves and the like.
The technical solution of the present invention will be better understood with reference to the following specific examples.
Example 1
The embodiment prepares the composite sol, and the specific preparation method comprises the following steps:
dissolving zirconium oxychloride in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 12h to obtain zirconium sol;
dissolving methyltrimethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 24h to obtain silica sol;
slowly dripping 2 parts of zirconium sol into 1 part of silica sol according to the mass part, adding 20% glacial acetic acid to adjust the pH value to 5, and aging for 24 hours to prepare the composite sol.
Further, using the prepared composite sol, this example prepares a coating, and the preparation raw materials include:
dimethyl dimethoxy silane oligomer: 10 percent of the total weight of the mixture,
compounding sol: 30 percent of the total weight of the mixture,
water: 59.95 percent of the total weight of the steel,
other auxiliary agents: 0.05 percent.
The preparation method of the coating comprises the following steps:
dissolving dimethyl dimethoxy silane in water, adding 20% glacial acetic acid to adjust the pH value of a system to be 5, then adding the mixture into the composite sol, adjusting the pH value by adding glacial acetic acid to adjust the particle size of particles generated by the reaction of the composite sol and the dimethyl dimethoxy silane to be 10-500 nm, then adding 0.01% of a flatting agent BYK333 and 0.04% of a wetting agent BYK346, and uniformly mixing to obtain the composite sol.
Example 2
The embodiment prepares the composite sol, and the specific preparation method comprises the following steps:
dissolving zirconyl nitrate in water, adding ammonia water to adjust the pH value of the system to 8, and aging for 12h to obtain zirconium sol;
dissolving methyltrimethoxysilane in water, adding ammonia water to adjust the pH value of the system to 8, and aging for 24h to obtain silica sol;
slowly dripping 1 part of zirconium sol into 1 part of silica sol according to the mass part, adding ammonia water to adjust the pH value of the system to 8, and aging for 24 hours to prepare the composite sol.
Further, using the prepared composite sol, this example prepares a coating, and the preparation raw materials include:
methyltrimethoxysilane oligomer: 25 percent of the total weight of the mixture,
compounding sol: 20 percent of the total weight of the mixture,
water: 54.95 percent of the total weight of the steel,
other auxiliary agents: 0.05 percent.
The preparation method of the coating comprises the following steps:
dissolving methyltrimethoxysilane in water, adding ammonia water to adjust the pH value of a system to be 8, then adding the methyltrimethoxysilane into the composite sol, adjusting the pH value by adding ammonia water to adjust the particle size of the particles generated by the reaction of the composite sol and methyltrimethoxysilane oligomer to be 500-700 nm, then adding 0.01% of flatting agent BYK333 and 0.04% of wetting agent BYK346, and uniformly mixing to obtain the composite sol.
Example 3
The embodiment prepares the composite sol, and the specific preparation method comprises the following steps:
dissolving zirconium propionate in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 12h to obtain zirconium sol;
dissolving gamma- (2, 3-epoxypropoxy) propyl silane in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 24h to obtain silica sol;
slowly dripping 2 parts of zirconium sol into 1 part of silica sol according to the mass part, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 48 hours to prepare the composite sol.
Further, using the prepared composite sol, this example prepares a coating, and the preparation raw materials include:
gamma- (2, 3-glycidoxy) propyl silane oligomer: 16 percent of the total weight of the mixture,
compounding sol: 25 percent of the total weight of the mixture,
water: 58.95 percent of the total weight of the mixture,
other auxiliary agents: 0.05 percent.
The preparation method of the coating comprises the following steps:
dissolving gamma- (2, 3-epoxypropoxy) propyl silane in water, adding 20% of glacial acetic acid to adjust the pH value of a system to be 5, then adding the system into the composite sol, adjusting the pH value by adding the glacial acetic acid to adjust the particle size of particles generated by the reaction of the composite sol and gamma- (2, 3-epoxypropoxy) propyl silane oligomer to be 800nm, then adding 0.01% of flatting agent BYK333 and 0.04% of wetting agent BYK346, and uniformly mixing to obtain the composite material.
Example 4
The embodiment prepares the composite sol, and the specific preparation method comprises the following steps:
dissolving zirconium silicate in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 12h to obtain zirconium sol;
dissolving methyltrimethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 24h to obtain silica sol;
slowly dripping 3 parts of zirconium sol into 1 part of silica sol by mass, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 48 hours to prepare the composite sol.
Further, using the prepared composite sol, this example prepares a coating, and the preparation raw materials include:
the embodiment prepares a coating, and the preparation raw materials comprise:
methyltriethoxysilane oligomer: 40 percent of the total weight of the mixture,
compounding sol: 10 percent of the total weight of the mixture,
water: at a rate of 59%,
other auxiliary agents: 1 percent.
The preparation method of the coating comprises the following steps:
dissolving methyltriethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of a system to 5, then adding the mixture into the composite sol, adjusting the pH value by adding glacial acetic acid to adjust the particle size of particles generated by the reaction of the composite sol and methyltriethoxysilane oligomer to 300-600 nm, then adding 0.5% of a flatting agent BYK333 and 0.5% of a wetting agent BYK346, and uniformly mixing to obtain the composite sol.
Example 5
The embodiment prepares the composite sol, and the specific preparation method comprises the following steps:
dissolving zirconium tert-butoxide in water, adding hydrochloric acid to adjust the pH value of the system to 4, and aging for 72h to obtain zirconium sol;
dissolving vinyl trimethoxy silane in water, adding hydrochloric acid to adjust the pH value of a system to 4, and aging for 24 hours to obtain silica sol;
slowly dripping 1 part of zirconium sol into 1 part of silica sol according to the mass part, adding hydrochloric acid to adjust the pH value of the system to 4, and aging for 48 hours to prepare the composite sol.
Further, using the prepared composite sol, this example prepares a coating, and the preparation raw materials include:
vinyl trimethoxy silane oligomer: 45 percent of the total weight of the mixture,
compounding sol: 40 percent of the total weight of the mixture,
water: 10 percent of the total weight of the mixture,
other auxiliary agents: 5 percent.
The preparation method of the coating comprises the following steps:
dissolving vinyl trimethoxy silane in water, adding hydrochloric acid to adjust the pH value of a system to be 4, then adding the mixture into the composite sol, adjusting the pH value by adding hydrochloric acid to adjust the particle size of particles generated by the reaction of the composite sol and vinyl trimethoxy silane oligomer to be 700-900 nm, then adding 4% of a flatting agent BYK333 and 1% of a wetting agent BYK346, and uniformly mixing to obtain the vinyl trimethoxy silane/vinyl trimethoxy silane composite sol.
Example 6
The embodiment prepares the composite sol, and the specific preparation method comprises the following steps:
dissolving zirconium ethoxide in water, adding sodium hydroxide to adjust the pH value of the system to 10, and aging for 48 hours to obtain zirconium sol;
dissolving ethyl trimethoxy silane in water, adding sodium hydroxide to adjust the pH value of a system to 10, and aging for 48 hours to obtain silica sol;
slowly dripping 1 part of zirconium sol into 2 parts of silica sol according to the mass parts, adding sodium hydroxide to adjust the pH value of the system to 4, and aging for 48 hours to prepare the silicon-zirconium composite sol.
Further, using the prepared composite sol, this example prepares a coating, and the preparation raw materials include:
ethyl trimethoxysilane oligomer: 40 percent of the total weight of the mixture,
compounding sol: 40 percent of the total weight of the mixture,
water: 19.9 percent of the total weight of the steel,
other auxiliary agents: 0.1 percent.
The preparation method of the coating comprises the following steps:
dissolving ethyl trimethoxy silane in water, adding sodium hydroxide to adjust the pH value of a system to 10, then adding the system into the silicon-zirconium composite sol, adjusting the pH value by adding sodium hydroxide to adjust the particle size of particles generated by the reaction of the composite sol and vinyl trimethoxy silane oligomer to 900-1000 nm, then adding 0.05% of a flatting agent BYK333 and 0.05% of a wetting agent BYK346, and uniformly mixing to obtain the silicon-zirconium composite sol.
Comparative example 1
The preparation method of the silica sol comprises the following steps:
dissolving methyltrimethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 24h to obtain silica sol.
Further, using the prepared silica sol, this comparative example prepared a coating material prepared by the following raw materials:
dimethyl dimethoxy silane oligomer: 20 percent of the total weight of the mixture,
silica sol: 20 percent of the total weight of the mixture,
water: the content of the waste water is 59.95%,
other auxiliary agents: 0.05 percent.
The preparation method of the coating comprises the following steps:
dissolving dimethyl dimethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of a system to be 5, then adding the dimethyl dimethoxysilane into silica sol, adjusting the pH value by adding glacial acetic acid to adjust the particle size of particles generated by the reaction of the silica sol and dimethyl dimethoxysilane oligomer to be 10-500 nm, then adding 0.01% of flatting agent BYK333 and 0.04% of wetting agent BYK346, and uniformly mixing to obtain the nano-silica sol.
Comparative example 2
The comparative example firstly prepares a composite sol, and the specific preparation method comprises the following steps:
dissolving zirconium oxychloride in water, adding 20% glacial acetic acid to adjust the pH value of the system to 4, and aging for 12h to obtain zirconium sol;
dissolving methyltrimethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 24h to obtain silica sol;
and slowly dripping 2 parts of zirconium sol into 1 part of silica sol according to the mass part to prepare the composite sol.
Further, using the prepared composite sol, a coating was prepared according to this comparative example, and the preparation raw materials included:
dimethyl dimethoxy silane oligomer: 20 percent of the total weight of the mixture,
compounding sol: 20 percent of the total weight of the mixture,
water: 59.95 percent of the total weight of the steel,
other auxiliary agents: 0.05 percent.
The preparation method of the coating comprises the following steps:
dissolving dimethyl dimethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of a system to be 4, then adding the dimethyl dimethoxysilane into the composite sol, adjusting the particle size of particles generated by the reaction of the composite sol and dimethyl dimethoxysilane oligomer by adding glacial acetic acid to adjust the pH value to be 1000-1200 nm, then adding 0.01% of flatting agent BYK333 and 0.04% of wetting agent BYK346, and uniformly mixing to obtain the nano-silver/zinc/.
Comparative example 3
The comparative example firstly prepares a zirconium sol, and the specific preparation method comprises the following steps:
dissolving zirconium tert-butoxide in water, adding 20% glacial acetic acid to adjust the pH value of the system to 5, and aging for 24h to obtain zirconium sol.
Further, using the prepared zirconium sol, this comparative example prepared a coating material prepared by the following raw materials:
dimethyl dimethoxy silane oligomer: 20 percent of the total weight of the mixture,
zirconium sol: 20 percent of the total weight of the mixture,
water: 59.95 percent of the total weight of the steel,
other auxiliary agents: 0.05 percent.
The preparation method of the coating comprises the following steps:
dissolving dimethyl dimethoxysilane in water, adding 20% glacial acetic acid to adjust the pH value of a system to be 5, then adding the system into zirconium sol, adjusting the pH value by adding glacial acetic acid to adjust the particle size of particles generated by the reaction of the zirconium sol and dimethyl dimethoxysilane oligomer to be 10-500 nm, then adding 0.01% of flatting agent BYK333 and 0.04% of wetting agent BYK346, and uniformly mixing to obtain the product.
Test example 1
The coatings of example 1 and comparative examples 1 to 3 were produced according to standard GB/T39688-2020, the substrate material being an aluminized plate and the coating thickness being 30 μm, and the non-stick properties, high temperature resistance, impact strength and abrasion resistance of the paint film were tested.
The coating was tested for non-tackiness according to the standard GB 32095.2-2015.
The standard of the high temperature resistance test of the coating is GB/T1735-2009.
The impact strength of the paint is tested according to the standard GB/T1732-2020.
The abrasion resistance test of the coating is based on the standard GB 32095.2-2015.
The results are shown in Table 1.
TABLE 1 film property test results
According to the test results in table 1, it can be seen that the coating formed by the coating of comparative example 1 has lower high temperature resistance, impact strength and abrasion resistance than the coating formed by the coating of example 1 because the silica sol is used in the coating and the composite sol is not used.
The coating formed by the coating of the comparative example 2 has a high acid value, and under the condition of a long reaction time, the particle size of the coating is 1000 nm-1200 nm, the particle size is too large, particles in the coating agglomerate, the comprehensive performance of the coating is reduced, and the high-temperature resistance, the impact strength and the wear resistance of the coating are lower than those of the coating formed by the coating of the example 1.
The coating formed by the coating of comparative example 3 has lower high-temperature resistance, impact strength and wear resistance than the coating formed by the coating of example 1 because the zirconium sol is used in the coating and the composite sol is not used. Specifically, in the system, on one hand, because the grain diameters of the silicon zirconium sol are different, the two sols are compounded, the coating has better compactness and more excellent performance; on the other hand, silicon zirconium is mixed because the silicon surface energy is lower, so that the silicon zirconium mixed silicon zirconium has better non-stick property. Therefore, the zirconium sol alone does not work well.
Test example 2
The surface morphology of the coating prepared from the coating of example 1 was observed by scanning electron microscopy, and the results are shown in fig. 1. The surface morphologies of the coatings prepared from the coatings of example 1 and comparative example 1 after the high temperature resistance test in test example 1 were also observed, and the results are shown in fig. 2 and 3.
Wherein, FIG. 2 is the surface morphology of the coating prepared by the coating of example 1 after the high temperature resistance test, and it can be seen that the coating surface is dense and flat.
FIG. 3 shows the surface morphology of the coating prepared from the coating of comparative example 1 after the high temperature resistance test, the coating prepared from the coating of comparative example 1 has poor toughness, so the coating is easy to crack at high temperature, and the coating has uneven surface and cracks.
The coating is suitable for the surface of a household appliance, and the surface of the household appliance is provided with the hydrophobic wear-resistant coating, and the coating has better toughness while maintaining better hardness and wear resistance of the ceramic coating, so that after the hydrophobic wear-resistant coating is arranged, the surface of the household appliance has higher hardness, better wear resistance and better toughness, the service life of the household appliance is prolonged, the surface quality of the household appliance is higher, and the problems of scratches, coating falling and the like on the surface of the household appliance are not easy to occur in the using process and in a high-temperature environment.
Specifically, the household appliances include a pot, a stove, a roaster, a range hood, and a cooker. Wherein the pot comprises an electric cooker, a frying pan or a frying pan. The stove comprises an induction cooker. The roaster comprises an oven and a barbecue grill.
It is easy to understand that cookware, stoves, baking tools, smoke exhaust machines and cooking utensils which are used daily are frequently used in people's life, so that if the surface coating is not high in hardness and poor in wear resistance, scratches are easy to occur, the coating is easy to fall off, the surface appearance quality of the utensil is poor, and after the hydrophobic wear-resistant coating is used, the wear resistance is better, the scratches are not easy to occur, and the surface quality is improved. Meanwhile, the coating has a hydrophobic function, so that the coating is easier to clean. In addition, the hydrophobic coating disclosed by the invention is high-temperature resistant, and is suitable for utensils which are often used in a high-temperature environment, such as pots, stoves, baking tools, smoking tools, stoves and the like.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (20)
1. The composite sol is characterized in that the preparation raw materials comprise a zirconium compound, a silicon compound, a pH regulator and water, and the mass ratio of the zirconium compound to the silicon compound is 0.1-10: 1.
2. The composite sol according to claim 1, characterized in that the zirconium compound comprises at least one of zirconium oxychloride, zirconyl nitrate, zirconium propionate, zirconium silicate, zirconium ethoxide, zirconium tert-butoxide, zirconium acetylacetonate, zirconium hexafluoroacetylacetonate, cyclopentadienyl zirconium trichloride, dicyclopentadiene zirconium dihydroxide, tetrakis (dimethylamino) zirconium, and tetrabutyl zirconate.
3. The composite sol according to claim 1, wherein the silicon compound comprises at least one of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, γ - (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, and dodecyltrimethoxysilane.
4. The composite sol according to any one of claims 1 to 3, wherein the pH adjusting agent comprises at least one of glacial acetic acid, hydrochloric acid, formic acid, sulfuric acid, nitric acid, aqueous ammonia, sodium hydroxide and potassium hydroxide.
5. A process for preparing the composite sol according to any one of claims 1 to 4, characterized in that it comprises the following steps: respectively dissolving the zirconium compound and the silicon compound in water, adding the pH regulator to regulate the pH value, then carrying out first aging to obtain zirconium sol and silica sol, adding the zirconium sol into the silica sol, adding the pH regulator again to regulate the pH value, and then carrying out second aging to obtain the composite sol.
6. The process according to claim 5, characterized in that the time of the first ageing is between 12 and 72 hours.
7. The process according to claim 5, characterized in that the time of the second ageing is between 24 and 72 hours.
8. A coating material, characterized in that raw materials for preparation comprise the composite sol according to any one of claims 1 to 4, a silane oligomer and water.
9. The coating according to claim 8, wherein the preparation raw materials comprise the following components in parts by weight:
the composite sol of any one of claims 1 to 4: 10 to 40 portions of the mixture of the components,
silane oligomer: 10 to 45 portions of the mixture of the components,
water: 10 to 80 portions.
10. The coating of claim 8 or 9, wherein the silane oligomer comprises at least one of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, and dodecyltrimethoxysilane.
11. The coating according to claim 8 or 9, wherein the preparation raw material further comprises 0.01 to 5 parts by weight of an auxiliary agent.
12. The coating of claim 11, wherein the auxiliary agent comprises at least one of a coating pH adjuster, a leveling agent, a wetting agent, a defoaming agent, and a thickener.
13. A method of preparing a coating according to any one of claims 8 to 12, comprising the steps of: and dissolving the silane oligomer in water, and adding the silane oligomer into the composite sol to obtain the coating.
14. The method of claim 13, further comprising adjusting the particle size of the particulate matter formed by the reaction of the silane oligomer and the composite sol by adjusting the pH after adding the silane oligomer dissolved in water to the composite sol.
15. A hydrophobic abrasion resistant coating, prepared from the coating of any one of claims 8 to 12.
16. The hydrophobic abrasion resistant coating according to claim 15, wherein the hydrophobic abrasion resistant coating has a thickness of 10 μm to 100 μm.
17. A method of preparing the hydrophobic abrasion resistant coating of claim 15 or 16, wherein the method is: and (3) after the coating is constructed on the surface of the base material, carrying out thermosetting treatment.
18. The method according to claim 17, wherein the temperature of the heat curing process is 60 ℃ to 300 ℃.
19. A household appliance, characterized in that the surface of the household appliance is provided with a hydrophobic, wear-resistant coating as claimed in claim 15 or 16.
20. The household appliance of claim 19, wherein the household appliance comprises a pot, a stove, a roaster, a range hood, and a stove.
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