CN113292925A - Coating composition, coating, preparation method and application thereof, and coating - Google Patents
Coating composition, coating, preparation method and application thereof, and coating Download PDFInfo
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- CN113292925A CN113292925A CN202110556402.XA CN202110556402A CN113292925A CN 113292925 A CN113292925 A CN 113292925A CN 202110556402 A CN202110556402 A CN 202110556402A CN 113292925 A CN113292925 A CN 113292925A
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- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 54
- 239000008199 coating composition Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920001709 polysilazane Polymers 0.000 claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 26
- 239000011737 fluorine Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- -1 perfluoroalkyl phosphate esters Chemical class 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 claims description 2
- PCNOVTUXOVNDAS-UHFFFAOYSA-N 3,3-dichlorooxepane Chemical compound ClC1(COCCCC1)Cl PCNOVTUXOVNDAS-UHFFFAOYSA-N 0.000 claims description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 239000005341 toughened glass Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of coatings, and discloses a coating composition, a coating, a preparation method and application thereof, and a coating. The coating composition contains the following components which are stored independently or in a mixed manner: fluorine-silicon resin, polyether modified polysilazane, a fluorine surfactant, a silane coupling agent and a solvent; based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the polyether modified polysilazane is 1-30 mass%, the content of the fluorinated surfactant is 0.01-0.5 mass%, the content of the silane coupling agent is 0.05-0.5 mass%, and the content of the solvent is 30-85 mass%. According to the invention, a specific amount of fluorosilicone resin, polyether modified polysilazane, a fluorine surfactant, a silane coupling agent and a solvent are compounded to obtain the coating composition, and the coating composition can be used for preparing a coating with excellent hydrophobic and oleophobic properties.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a coating composition, a coating, a preparation method and application thereof, and a coating.
Background
Surfaces with special wetting properties, i.e. water repellent surfaces, are widely used in various industries, such as the textile industry, the construction industry, the electrical industry, the automotive industry, and are of great interest to these various industries. Meanwhile, it is becoming a popular research field to make the surface of various natural or synthetic substrates, such as metal, glass, wood, ceramic, etc., have such characteristics using surface modification technology.
In the electrical appliance industry, especially kitchen appliances, oil stains are easy to adhere to the surfaces of the kitchen appliances in the heavy oil stain use environment for a long time and are difficult to clean. At present, a layer of coating is usually sprayed on the surface of an electric appliance in the prior art to isolate oil stains from the surface of the electric appliance, and only the surface of the coating needs to be cleaned.
Therefore, there is a need to develop a coating that adheres well to glass substrates while having easy cleaning and excellent hydrophobic properties.
Disclosure of Invention
The invention aims to solve the problems of poor hydrophobicity and difficult cleaning of the coating on the surface of the electrical product in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a coating composition comprising the following components stored independently of each other or in a mixture of two or more of them:
fluorine-silicon resin, polyether modified polysilazane, a fluorine surfactant, a silane coupling agent and a solvent;
the structural general formula of the polyether modified polysilazane is F (C)xF2xO)mCyF2y-CzH2z-(R1Si-NR2)nIn the formula, x, y and z are each independently an integer selected from 1 to 10, m and n are each independently an integer selected from 1 to 100, R1、R2Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy and C1-20alkyl-NH-;
based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the polyether modified polysilazane is 1-30 mass%, the content of the fluorinated surfactant is 0.01-0.5 mass%, the content of the silane coupling agent is 0.05-0.5 mass%, and the content of the solvent is 30-85 mass%.
In a second aspect, the present invention provides a method of preparing a coating, the method comprising: mixing the components of the coating composition of the first aspect.
In a third aspect, the present invention provides a coating prepared by the method of the second aspect.
A fourth aspect of the invention provides the use of a coating as described by the third aspect in an appliance.
A fifth aspect of the invention provides the use of a coating as described by the third aspect in a kitchen appliance.
The sixth aspect of the present invention provides a coating obtained by spraying the coating material of the third aspect onto a surface of a substrate, followed by drying and curing in this order.
According to the invention, a specific amount of fluorosilicone resin, polyether modified polysilazane, a fluorine surfactant, a silane coupling agent and a solvent are compounded to obtain the coating composition, and a coating prepared from the coating composition has very good hydrophobic and oleophobic properties, so that the defect that the surface of a traditional kitchen electrical product is difficult to clean can be effectively improved.
The inventors have found that coatings prepared using the compositions of the present invention exhibit significantly better adhesion and hydrophobicity when used to toughen glass substrates.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It should be noted that, in various aspects of the present invention, the present invention is described only once in one aspect thereof without repeated description with respect to the same components in the aspects, and those skilled in the art should not be construed as limiting the present invention.
In the case where no explanation is given to the contrary, the room temperature in the present invention is 25. + -. 2 ℃.
Said C is1-20The alkyl group of (A) means an alkyl group having a total number of carbon atoms of 1 to 20, and includes straight-chain alkyl groups and branched-chain alkyl groups, and may be, for example, C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkyl group of (1). "C1-10The alkyl group of (1) has a similar explanation to this, only the total number of carbon atoms is different.
Said C is2-20The alkenyl group means an alkenyl group having 2 to 20 carbon atoms in total, and includes a straight-chain alkenyl group and a branched-chain alkenyl group, and may be, for example, C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkenyl groups of (a). "C2-10The "alkenyl group" has similar explanations as above, only the total number of carbon atoms is different.
Said C is6-20The aryl group of (2) means an aryl group having 6 to 20 carbon atoms in total, and may be, for example, a phenyl group, an alkyl-substituted phenyl group, a naphthyl group, an alkyl-substituted naphthyl group, a biphenyl group, an alkyl-substituted biphenyl group or the like. "C6-12The aryl group of (1) has a similar interpretation to this, only differing in the total number of carbon atoms.
Said C is1-20The alkoxy group (C) means an alkoxy group having 1 to 20 carbon atoms in total, and may be, for example, C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkoxy group of (2). "C1-10The "alkoxy group" of (a) has a similar explanation to this, only the total number of carbon atoms is different.
Said C is1-20alkyl-NH-means: one substituent on N is C1-20Alkyl, illustratively, C1-20alkyl-NH-may be, for example, CH3-NH-, the "CH3"may be substituted by C1-20Any group of alkyl groups. "C1-10alkyl-NH- "has a similar interpretation, only differing in the total number of carbon atoms.
The first aspect of the present invention provides a coating composition containing the following components stored independently of each other or in a mixture of two or more of them:
fluorine-silicon resin, polyether modified polysilazane, a fluorine surfactant, a silane coupling agent and a solvent;
the structural general formula of the polyether modified polysilazane is F (C)xF2xO)mCyF2y-CzH2z-(R1Si-NR2)nIn the formula, x, y and z are each independently an integer selected from 1 to 10, m and n are each independently an integer selected from 1 to 100, R1、R2Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy and C1-20alkyl-NH-;
based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the polyether modified polysilazane is 1-30 mass%, the content of the fluorinated surfactant is 0.01-0.5 mass%, the content of the silane coupling agent is 0.05-0.5 mass%, and the content of the solvent is 30-85 mass%.
According to a particularly preferred embodiment, the content of the fluorosilicone resin is 10 to 30 mass%, the content of the polyether-modified polysilazane is 4 to 15 mass%, the content of the fluorine surfactant is 0.01 to 0.1 mass%, the content of the silane coupling agent is 0.05 to 0.3 mass%, and the content of the solvent is 60 to 85 mass%, based on the total mass of the coating composition. The inventors have found that with the preferred embodiment a more hydrophobic coating can be obtained.
Preferably, the weight average molecular weight of the fluorosilicone resin is 100-10000, preferably 300-3000, and the relative density (20 ℃) of the fluorosilicone resin is 1.05-1.2g/cm3。
More preferably, the fluorosilicone resin is RF-901 fluorosilicone resin purchased from Fuxin Ruifeng fluorochemicals, Inc. In this preferred case, the coating composition obtained enables the preparation of coatings of very high hardness which adhere better to the surface of the kitchen appliance.
Preferably, in the structural general formula of the polyether modified polysilazane, x, y and z are respectively and independently selected from integers of 1-20, m and n are respectively and independently selected from integers of 1-10, R1、R2Each independently selected from hydrogen and C1-10Alkyl of (C)2-10Alkenyl of, C6-12Aryl of (C)1-10Alkoxy and C1-10alkyl-NH-.
Preferably, the polyether-modified polysilazane has a weight average molecular weight of 100-1000, preferably 500-1000.
More preferably, the polyether modified polysilazane is a polyether modified polysilazane IOTA-455 available from yota, inc. The inventors have found that in this preferred case, the coating obtained from the coating composition has the advantage of being easier to clean.
Preferably, the fluorosurfactant is selected from at least one of perfluoroalkyl phosphate ester, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl amine oxide compound, fluorine-containing aliphatic amine oxide, fluorine-containing aliphatic sodium sulfosuccinate, fluorine-containing aliphatic stearate, fluorine-containing aliphatic phosphate ester, fluorine-containing aliphatic quaternary ammonium salt, and fluorine-containing aliphatic polyethylene oxide.
Preferably, the fluorosurfactant is selected from at least one of FC-129 from 3M, FC-170C from 3M, FC-430 from 3M, FC-4430 from 3M, FSO from DuPont, FSO-100 from DuPont, FSN-100 from DuPont, FS-63 from DuPont, FS-3100 from DuPont, FS-300 from DuPont, PF-136A from OMNOVA, PF-151N, OMNOVA, and PF-156A from OMNOVA.
More preferably, the fluorosurfactant is selected from at least one of FS-63 from DuPont, FS-3100 from DuPont, and PF-156A from OMNOVA. The inventor finds that the coating prepared by adopting the preferable fluorine surfactant composition can obviously improve the hydrophobic and oleophobic effects of the coating.
Preferably, the solvent is selected from at least one of n-hexane, n-octane, n-decane, chloroform, dichloromethane, dichloroethylene, diethyl ether, petroleum ether, toluene, xylene, m-ditrifluorotoluene, acetone, methyl ethyl ketone, cyclohexanone, butyl acetate, diethylene glycol dimethyl ether, hydrofluoroether, perfluoroheptane, perfluoromethylcyclohexane, propylene glycol monomethyl ether acetate, and tetrahydrofuran.
Preferably, the m-ditrifluorotoluene has the structural formula
Preferably, the solvent is selected from at least one of toluene, xylene and ethyl acetate.
Preferably, the silane coupling agent is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, isobutyltriethoxysilane, 3-aminopropyltriethoxysilane, and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane.
More preferably, the silane coupling agent is at least one selected from the group consisting of gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane. In this preferred case, the coating produced using the coating composition has superior adhesion properties.
In a second aspect, the present invention provides a method of preparing a coating, the method comprising: mixing the components of the coating composition of the first aspect.
According to a particularly preferred embodiment, the mixing of the components of the coating composition comprises the following steps:
(1) in the presence of a solvent, carrying out a first contact reaction on fluorosilicone resin, a fluorine surfactant and a silane coupling agent to obtain a diluent;
(2) and carrying out a second contact reaction on the diluent and the polyether modified polysilazane to obtain the coating.
Preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 100-800rpm, the temperature is 20-40 ℃, and the time is 10-60 min.
More preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 500-800rpm, the temperature is 23-25 ℃, and the time is 15-30 min.
Preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1000-2000rpm, the temperature is 20-40 ℃, and the time is 10-30 min.
More preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1000-1500rpm, the temperature is 23-25 ℃, and the time is 10-20 min.
In a third aspect, the present invention provides a coating produced by the method of the second aspect.
A fourth aspect of the invention provides the use of a coating as described by the third aspect in an appliance.
A fifth aspect of the invention provides the use of a coating as described by the third aspect in a kitchen appliance.
The sixth aspect of the present invention provides a coating obtained by spraying the coating material of the third aspect onto a surface of a substrate, followed by drying and curing in this order.
Preferably, the substrate is a glass substrate.
Preferably, the thickness of the coating is 0.1-100 μm, preferably 1-20 μm.
Preferably, the drying conditions at least satisfy: the temperature is 20-40 ℃ and the time is 0.5-2 h.
More preferably, the drying conditions at least satisfy: the temperature is 23-25 ℃ and the time is 0.5-1 h.
Preferably, the curing conditions at least satisfy: the temperature is 90-250 ℃ and the time is 0.5-5 h.
More preferably, the curing conditions at least satisfy: the temperature is 100 ℃ and 200 ℃, and the time is 0.5-2 h.
In the following examples, unless otherwise specified, the laboratory instruments and raw materials are commercially available.
Laboratory apparatus
Full-automatic water contact angle tester: model Bolede BLD-D1, Bolede instruments, Inc., Dongguan;
spraying an instrument: model number spray gun W-71, Japan rock field company;
raw materials
Fluorosilicone resin-1: the number average molecular weight was 1000 and the relative density (20 ℃ C.) was 1.1g/cm3The designation RF-901, available from Fuxin Ruifeng fluorochemical, Inc.;
fluorosilicone resin-2: the number average molecular weight was 800 and the relative density (20 ℃ C.) was 1.1g/cm3A designation RF-902, available from funiren fluorochemicals ltd;
fluorine-silicon resin-3: the number average molecular weight was 2400 and the relative density (20 ℃ C.) was 1.1g/cm3RF-903, available from funiren fluorochemicals ltd;
silicone resin: polysiloxane resin, designation H201, Shenzhen Jipeng silicon fluorine materials Limited;
polyether modified polysilazane-1: number average molecular weight of 600, under the designation IOTA-455, available from yota, inc, Anhui;
polyether modified polysilazane-2: number average molecular weight 800, mark IOTA-555, available from Aiyota, Anhui, Inc.;
polyether modified polysilazane-3: number average molecular weight 900, mark IOTA-655, available from Aiyota, Anhui, Inc.;
organic polyborosilazane: number average molecular weight of 700, number IOTA-9120, available from ai xiao ta silicone oil ltd, Anhui;
fluorine surfactant: FS-63, available from DuPont;
fluorine surfactant: FS-3100, from DuPont;
fluorine surfactant: PF-156A, available from OMNOVA;
fluorine surfactant: PF-136A, available from OMNOVA;
fluorine surfactant: FC-430, available from 3M company;
fluorine surfactant: FS-300, available from DuPont;
fluorine surfactant: FC-4430, available from 3M;
solvent: acetone, purchased from southbound tomb petrochemicals ltd;
solvent: toluene, purchased from southbound tomb petrochemical company;
solvent: butyl acetate, purchased from southbound tomb petrochemicals ltd;
solvent: xylene, available from jonan yuno chemical co;
solvent: petroleum ether, available from jonan yuno chemical co;
solvent: acetone, available from jonan yuno chemical co;
silane coupling agent: gamma-aminopropyltrimethoxysilane, available from Sanfu silicon industries, Inc. of Tangshan;
silane coupling agent: gamma-glycidoxypropyltrimethoxysilane, available from Sanfu silicon, Inc., Tangshan;
silane coupling agent: gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, available from Sanfu silicon, Inc., Tang mountain;
silane coupling agent: 3-aminopropyltriethoxysilane, available from Sanfu silicon industries, Inc. of Tang mountain;
silane coupling agent: gamma-methacryloxypropyltrimethoxysilane, available from Sanfu silicon, Inc., Tang mountain;
a toughened glass substrate: available from Dongguan Tai glass Co., Ltd;
the amounts of the components in the following examples are all expressed in "% by mass" based on the total mass of the coating composition, and the total mass of the coating composition is 1000 g.
Example 1
This example illustrates the formulation and processing parameters of the coating composition of the present invention according to Table 1, and the preparation of the coating according to the method described below.
The method for preparing the coating comprises the following steps:
(1) under the condition of room temperature, adding toluene, fluorosilicone resin and a fluorine surfactant into a reaction kettle, and stirring at 500rpm for 20min to obtain a diluent;
(2) and adding polyether modified polysilazane and gamma-aminopropyltrimethoxysilane into the diluent at room temperature, and stirring at 1100rpm for 20min to obtain the coating.
And (3) spraying the coating (the spraying distance is 200mm, the caliber of a nozzle is 0.8mm, and the air pressure is 0.3MPa) on the surface of the toughened glass substrate to form a coating layer, drying the toughened glass substrate with the coating layer at room temperature for 1h, and then putting the toughened glass substrate with the coating layer into an oven at the temperature of 120 ℃ for curing for 2h to obtain a coating S1.
The remaining examples were carried out using the same procedure as in example 1, except that the coating composition formulation and the process parameters were different, unless otherwise specified, see in particular table 1.
Comparative example 1
This comparative example was carried out using a procedure similar to that of example 1, except that: the formulation does not contain fluorine silicon resin.
Comparative example 2
This comparative example was carried out using a procedure similar to that of example 1, except that: the formula does not contain polyether modified polysilazane.
Comparative example 3
This comparative example was carried out using a procedure similar to that of example 1, except that: the formulation does not contain a fluorinated surfactant.
Comparative example 4
This comparative example was carried out using a procedure similar to that of example 1, except that: the formula adopts organic silicon resin to replace fluorine silicon resin.
Comparative example 5
This comparative example was carried out using a procedure similar to that of example 1, except that: in the formula, organic polyborosilazane is used to replace polyether modified polysilazane.
TABLE 1
Table 1 (continuation 1)
Test example 1
The water contact angle, hardness, adhesion and other properties of the example and comparative products were tested, and the results are shown in Table 2 below.
Wherein, the water contact angle is tested by adopting a full-automatic water contact angle tester;
testing the hardness of the coating according to the national standard GB/T6739-2009;
the adhesion performance of the coating was tested according to the national standard GB/T9286-1998.
TABLE 2
The results in table 2 show that the coating composition is obtained by compounding the fluorosilicone resin, the polyether modified polysilazane, the fluorine surfactant, the silane coupling agent and the solvent according to the specific mixture ratio, and the coating prepared from the coating composition has very good hydrophobic and oleophobic properties, so that the defect that the surface of the traditional kitchen electrical product is difficult to clean is effectively overcome.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (19)
1. A coating composition characterized by containing the following components stored independently of each other or in a mixture of two or more of them:
fluorine-silicon resin, polyether modified polysilazane, a fluorine surfactant, a silane coupling agent and a solvent;
the structural general formula of the polyether modified polysilazane is F (C)xF2xO)mCyF2y-CzH2z-(R1Si-NR2)nIn the structural general formula of the polyether modified polysilazane, x, y and z are respectively and independently integers from 1 to 10, m and n are respectively and independently integers from 1 to 100, R1、R2Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20OfBase, C1-20Alkoxy and C1-20alkyl-NH-;
based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the polyether modified polysilazane is 1-30 mass%, the content of the fluorinated surfactant is 0.01-0.5 mass%, the content of the silane coupling agent is 0.05-0.5 mass%, and the content of the solvent is 30-85 mass%.
2. The coating composition according to claim 1, wherein the content of the fluorosilicone resin is 10 to 30 mass%, the content of the polyether-modified polysilazane is 4 to 15 mass%, the content of the fluorine surfactant is 0.01 to 0.1 mass%, the content of the silane coupling agent is 0.05 to 0.3 mass%, and the content of the solvent is 60 to 85 mass%, based on the total mass of the coating composition.
3. The coating composition according to claim 1 or 2, wherein the weight average molecular weight of the fluorosilicone resin is 100-10000, preferably 300-3000, and the relative density (20 ℃) of the fluorosilicone resin is 1.05-1.2g/cm3。
4. The coating composition according to any one of claims 1 to 3, wherein in the general structural formula of the polyether-modified polysilazane, x, y and z are each independently an integer selected from 1 to 20, m and n are each independently an integer selected from 1 to 10, and R is1、R2Each independently selected from hydrogen and C1-10Alkyl of (C)2-10Alkenyl of, C6-12Aryl of (C)1-10Alkoxy and C1-10alkyl-NH-;
preferably, the polyether-modified polysilazane has a weight average molecular weight of 100-1000, preferably 500-1000.
5. The coating composition according to any one of claims 1 to 4, wherein the fluorosurfactant is selected from at least one of perfluoroalkyl phosphate esters, perfluoroalkyl betaines, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl amine oxide compounds, fluoroaliphatic amine oxides, fluoroaliphatic sodium sulfosuccinates, fluoroaliphatic stearates, fluoroaliphatic phosphate esters, fluoroaliphatic quaternary ammonium salts, and fluoroaliphatic polyethylene oxide;
preferably, the fluorosurfactant is selected from at least one of FC-129 from 3M, FC-170C from 3M, FC-430 from 3M, FC-4430 from 3M, FSO from DuPont, FSO-100 from DuPont, FSN-100 from DuPont, FS-63 from DuPont, FS-3100 from DuPont, FS-300 from DuPont, PF-136A from OMNOVA, PF-151N, OMNOVA, and PF-156A from OMNOVA.
6. The coating composition according to any one of claims 1 to 5, wherein the solvent is selected from at least one of n-hexane, n-octane, n-decane, chloroform, dichloromethane, dichloroethylene, diethyl ether, petroleum ether, toluene, xylene, m-ditrifluorotoluene, acetone, methyl ethyl ketone, cyclohexanone, butyl acetate, diethylene glycol dimethyl ether, hydrofluoroether, perfluoroheptane, perfluoromethylcyclohexane, propylene glycol monomethyl ether acetate and tetrahydrofuran;
preferably, the solvent is selected from at least one of toluene, xylene and ethyl acetate.
7. The coating composition according to any one of claims 1 to 6, wherein the silane coupling agent is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, isobutyltriethoxysilane, 3-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane.
8. A method of preparing a coating, the method comprising: mixing the components of the coating composition of any one of claims 1 to 7.
9. The method of claim 8, wherein the act of mixing the components of the coating composition comprises the steps of:
(1) in the presence of a solvent, carrying out a first contact reaction on fluorosilicone resin, a fluorine surfactant and a silane coupling agent to obtain a diluent;
(2) and carrying out a second contact reaction on the diluent and the polyether modified polysilazane to obtain the coating.
10. The method of claim 9, wherein in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 100-800rpm, the temperature is 20-40 ℃, and the time is 10-60 min;
preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 500-800rpm, the temperature is 23-25 ℃, and the time is 15-30 min.
11. The process according to claim 9 or 10, wherein in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1000-2000rpm, the temperature is 20-40 ℃, and the time is 10-30 min;
preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1000-1500rpm, the temperature is 23-25 ℃, and the time is 10-20 min.
12. A coating prepared by the method of any one of claims 8 to 11.
13. Use of the coating material as claimed in claim 12 in an electrical appliance.
14. Use of a coating as claimed in claim 12 in a kitchen appliance.
15. A coating which is obtained by spraying the coating material as claimed in claim 12 on the surface of a substrate and then drying and curing the coating material in this order.
16. The coating of claim 15, wherein the substrate is a glass substrate.
17. Coating according to claim 15 or 16, wherein the thickness of the coating is 0.1-100 μ ι η, preferably 1-20 μ ι η.
18. The coating of any one of claims 15-17, wherein the drying conditions at least satisfy: the temperature is 20-40 ℃, and the time is 0.5-2 h;
preferably, the drying conditions at least satisfy: the temperature is 23-25 ℃ and the time is 0.5-1 h.
19. The coating of any one of claims 15-18, wherein the curing conditions at least satisfy: the temperature is 90-250 ℃ and the time is 0.5-5 h;
preferably, the curing conditions at least satisfy: the temperature is 100 ℃ and 200 ℃, and the time is 0.5-2 h.
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| CN119391300A (en) * | 2024-11-26 | 2025-02-07 | 西安得在电力科技有限公司 | A high temperature resistant and heavy corrosion resistant fluorine silicon polymer coating and its preparation method and application |
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