CN109096915A - Coating composition and coating and coating and silica coating and the method for having cated product and forming coating in substrate surface - Google Patents
Coating composition and coating and coating and silica coating and the method for having cated product and forming coating in substrate surface Download PDFInfo
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- CN109096915A CN109096915A CN201810670365.3A CN201810670365A CN109096915A CN 109096915 A CN109096915 A CN 109096915A CN 201810670365 A CN201810670365 A CN 201810670365A CN 109096915 A CN109096915 A CN 109096915A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention discloses a kind of coating composition and coating and coating and the method for having cated product and forming coating in substrate surface, the coating composition contains Perhydropolysilazane, fluorochemical, siloxanes, inorganic particle, optional catalyst and optional silane coupling agent, and the substituent group in the siloxanes on silicon atom is each independently alkyl, aryl or hydrogen atom.The coating that the coating formed by coating composition of the invention is formed in substrate surface not only has excellent adhesion property, but also has good heat resistance and scraping and wiping resistance performance, while also showing low-energy surface characteristic, easy to clean.
Description
Technical field
The present invention relates to technical field of coatings.In particular it relates to a kind of coating composition and by the coating group
The coating that object is formed is closed, the invention further relates to the coating formed by the coating, the present invention further relates to a kind of silica coating, this
Invention has cated product and a kind of method for forming coating in substrate surface further to a kind of.
Background technique
With the development of economy and society, living standards of the people increasingly improve, performance requirements of the people to household electrical appliance
Also higher and higher, more and more careful, the demand to material basic physical properties and specific functionality is growing day by day.Coating is as material function
The main carriers of energy property, receive more and more attention and attention.
Household electrical appliance it is different degrees of in environment such as high/low temperature, greasy dirts, to the resistant of high or low temperature of coating, wearability, resistance to
The performances requirements all with higher such as corrosivity, hardness, surface energy, compactness and transparency.For example, micro-wave oven, oven, oil
The kitchen appliances class product such as smoke machine, kitchen range, high temperature resistant, low surface due to working environments such as its high temperature, high greasy dirts, to material
The performance of energy, wear-resisting, compactness and high-temperature oxidation resistant has high requirement；Refrigerator, air-conditioning etc. are in low temperature environment for a long time,
It is high for antifrost (ice) performance requirement of material；Water heater, refrigerator etc. have the product of metal tubes, for a long time using easily out
Situations such as now corroding, long-term effect and safety to product all have a certain impact, and how to realize golden under high/low temperature, high humidity environment
The corrosion-resistant protection for belonging to pipeline becomes a challenge.
In low-surface-energy material technical aspect, household electric appliances master material to be used includes: organosilicon and Teflon at present
(PTFE) the non-sticky material of two quasi-traditions, and it is emerging in recent years using polysiloxanes as presoma hybrid organic silicon
SiO2/ organic-silicon hybridization system material.But above-mentioned three classes material exists that hardness is low, scraping and wiping resistance performance is poor, adheres to substrate
The performance issues such as performance difference, especially Teflon, be constantly subjected in recent years it is various denounce, food-safety problem be even more perplex it is all
More household appliances manufacturers.
In terms of high abrasion, high hardness material, the most widely used material of household electric appliances is enamel material at present, but its
It is technology barrier that enamel material is difficult to go beyond that brittleness great Yi burst porcelain, complex process, yields be low, and the prosperities such as Europe in recent years
Many researchs and law making of the country for enamel material food touch-safe, even more make enamel material answering in field of household appliances
Caused anxiety with prospect.
Stainless steel material is always the most popular material of household electric appliances mid- to high-end product with its high-grade appearance, but
It easily adheres to cleaning difficulty caused by greasy dirt or makes its surface scratching problem using cleaning material, and being always consumption appliance, person exists
Maximum pain spot when using product, and at applied at elevated temperature environment (oven, microwave oven, kitchen range etc.), easily there is height in stainless steel
The problem of temperature oxidation turns yellow, seriously affects the appearance of stainless steel product.
The following table 1 lists the performance data of the coating of above-mentioned material formation.
Table 1
In conclusion there is also many urgent problems to be solved for current household electric appliances Material Field, wherein provide with resistance to
High temperature, wear-resisting, anticorrosive, high-compactness, high rigidity, the coating technology of (including antifrost) property anti-oxidant, easy to clean are mesh
Preceding entire industry has to the technology captured, and the important support of entire industry development.
Summary of the invention
It is an object of the invention to overcome the coating for household electric appliances be difficult to obtain have both high temperature resistant, wear-resisting, high rigidity,
The technical issues of coating of anti-oxidant and easy to clean (including antifrost) performance, a kind of coating is provided, which has good
Comprehensive performance.
According to the first aspect of the invention, the present invention provides a kind of coating composition, which contains entirely
Hydrogen polysilazane, fluorochemical, siloxanes, inorganic particle, optional catalyst and optional silane coupling agent, it is described
Substituent group in siloxanes on silicon atom is each independently alkyl, aryl or hydrogen atom.
According to the second aspect of the invention, the present invention provides a kind of coating, the coating contain liquid dispersant and
Coating composition described in first aspect of the present invention, each component in the coating composition are dispersed in the liquid dispersant
In.
According to the third aspect of the present invention, the present invention provides a kind of coatings, and the coating is by the second aspect of the present invention
The coating is formed.
According to the fourth aspect of the present invention, the present invention provides a kind of silica coating, which contains
Fluorine compounds, in the silica coating, the molar ratio of fluorine element and element silicon is 0.01-1:1, and the hardness of the silica coating is
6H-9H, heatproof are 300-450 DEG C, and water contact angle is 90 ° -120 °.
According to the fifth aspect of the present invention, the present invention provides a kind of cated product of tool, which contains substrate
And it is attached to the coating on at least partly surface of the substrate, wherein the coating is described in third aspect of the present invention
Silica coating described in the 4th aspect of coating or the present invention.
According to the sixth aspect of the invention, the present invention provides a kind of method for forming coating in substrate surface, the party
Method includes that coating described in the second aspect of the present invention is applied at least partly surface for overlaying on substrate, forms dope layer；To have
The substrate of the dope layer is solidified in the presence of water and oxygen.
The coating for overlaying on substrate surface and being formed is applied by the coating that coating composition of the invention is formed, and is not only had excellent
Adhesion property, and there is good heat resistance and scraping and wiping resistance performance, while also showing low-energy surface characteristic, it is easy to clean
(including antifrost performance).Specifically, the adhesive force of the coating formed by coating composition of the invention can achieve 0 grade, resistance to
Temperature is up to 400 DEG C or more, and for hardness up to 9H or more, the contact angle with water is 105 ° or more.
Detailed description of the invention
Fig. 1 is used to illustrate to be formed by Perhydropolysilazane the transformation mechanism of silica coating.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of coating composition, which contains entirely
Hydrogen polysilazane, fluorochemical, siloxanes, inorganic particle, optional catalyst and optional silane coupling agent.
Coating composition according to the present invention, in the Perhydropolysilazane, SiH1And SiH2Molar ratio can be 1-
40, preferably 4-20, more preferably 8-18, further preferably 10-15.In the present invention, SiH1And SiH2Molar ratio use core
The measurement of magnetic resonance hydrogen spectrometry.
The average molecular weight of the Perhydropolysilazane (PHPS) can be 300-10000, preferably 500-2000, it is more excellent
It is selected as 600-1500, such as can be 600-1000.The average molecular weight is measured using gel permeation chromatography method.
The Perhydropolysilazane is commercially available, and can also be prepared using conventional method, such as: with H2SiCl2As
Raw material, by H2SiCl2Dispersion forms reaction solution in a solvent, and NH is passed through into reaction solution3Gas carries out ammonolysis reaction, by ammonolysis
It reacts obtained reaction mixture to be filtered, filtrate is concentrated, to obtain Perhydropolysilazane.Wherein, NH3With
H2SiCl2Molar ratio can be 5-50, preferably 8-15.The solvent can for chloroform, methylene chloride, tetrahydrofuran,
Petroleum ether, butyl oxide, dimethylbenzene, toluene, hexane, octane, heptane, decane, ethyl acetate, amyl acetate, isoamyl acetate, third
One or more of ketone, espeleton and methylisobutylketone.The ammonolysis reaction can be in -80 DEG C to 0 DEG C of temperature
Lower progress, preferably -40 DEG C to -10 DEG C at a temperature of carry out.The duration of the ammonolysis reaction can be 4-60 hours, excellent
It is selected as 20-30 hours.The filtering carries out in inert atmosphere, such as the gas that can be formed in zero group gas and/or nitrogen
It is carried out in atmosphere.The concentration is preferably vacuum decompression distillation.
Coating composition according to the present invention, the fluorochemical can be selected from fluorine containing silane, flucride siloxane, contain
Fluorine clicyclic hydrocarbon, fluorine-containing aliphatic hydrocarbon, fluorine-containing ether, fluorine-containing alcohol ether, fluorochemical polyether, fluorine-containing aromatic hydrocarbons, fluorine-containing epoxyalkane, fluorine-containing sulphur
One or more of acid, sulfonic fluoropolymer salt, fluorine-containing alcohol, fluorinated ketones contained and fluorine-containing pyrrolidones.
It is described containing fluorination from the angle for the performance for further increasing the coating formed by coating composition of the invention
It closes object and is preferably selected from silane shown in siloxanes, Formula II shown in Formulas I, C4-C15Fluorine-containing clicyclic hydrocarbon, C3-C30It is fluorine-containing
Aliphatic hydrocarbon, C4-C30Fluorine-containing ether, C4-C20Fluorine-containing alcohol ether, fluorochemical polyether, C6-C16Fluorine-containing aromatic hydrocarbons, ring shown in formula III
Sulfonic fluoropolymer shown in oxygen alkane, formula IV, C shown in sulfonic fluoropolymer salt, Formula IV shown in Formula V6-C20Fluorine-containing alcohol, Formula VII institute
The C shown4-C12Ketone and C5-C12One or more of fluorine-containing pyrrolidones.
The siloxanes as shown in following formula I,
In Formulas I, n R1, n R3、R2、R4、R5And R6It is identical or different, it is each independently C1-C6Alkyl (preferably
C1-C3Alkyl), C1-C12Fluoro-alkyl (preferably C5-C10Fluoro-alkyl) or hydrogen atom, and n R1, n R3、R2、
R4、R5And R6At least one of be C1-C12Fluoro-alkyl.N can be in the range of 1-500, preferably in the range of 2-100
It is interior, more preferably in the range of 2-50, further preferably in the range of 2-20, still more preferably in the range of 2-10,
It such as can be 2,3,4,5,6,7,8,9 or 10.
In the present invention, in fluoro-alkyl, the quantity of fluorine atom can be 1 or more, and the part hydrogen that can be in alkyl is former
Son is replaced by fluorine atoms, and the whole hydrogen atoms being also possible in alkyl are replaced by fluorine atoms.
The silane as shown in Formula Il,
In Formula II, R7、R8、R9And R10It is identical or different, it is each independently fluorine atom, C1-C20Containing fluoroalkyl (preferably
For C5-C20Contain fluoroalkyl, more preferably C10-C18Contain fluoroalkyl), R11-O-R12-、C6-C12Fluorinated aryl, C1-C8's
Alkyl (preferably C1-C4Alkyl), C1-C5Alkoxy (preferably C1-C3Alkoxy) or hydrogen atom, and R7、R8、R9
And R10At least one of be fluorine atom, C1-C20Contain fluoroalkyl, R11-O-R12Or C6-C12Fluorinated aryl, R11For C1-
C8Fluoro-alkyl (preferably C3-C5Fluoro-alkyl), R12For C1-C6Alkylidene (preferably C2-C5Alkylidene).
Shown in the following formula III of epoxyalkane,
In formula III, R13、R14、R15And R16It is identical or different, it is each independently C1-C8Alkyl, fluorine atom, R17-
CH2Or R18-O-CH2, and R13、R14、R15And R16At least one of be fluorine atom, R17-CH2Or R18-O-CH2, R17
For C3-C12Fluoro-alkyl or C6-C12Containing fluoro aryl (preferably contain fluorophenyl), R18For C3-C12Fluoro-alkyl or
C6-C12Containing fluoro aryl (preferably contain fluorophenyl).
In the present invention, in fluorinated aryl, at least partly hydrogen atom that can be on aryl is replaced by fluorine atoms, and is also possible to
At least partly hydrogen atom on aryl is replaced by fluorine-containing substituent group (as contained fluoroalkyl), can also be that the two combines.
Shown in the following formula IV of sulfonic fluoropolymer,
R19-SO3H (formula IV)
In formula IV, R19For C4-C10Fluoro-alkyl.
Shown in the following Formula V of sulfonic fluoropolymer salt,
R20-SO3M (Formula V)
In Formula V, R20For C4-C10Fluoro-alkyl, M is alkali metal, preferably sodium or potassium.
Shown in the following Formula IV of fluorine-containing alcohol,
R21- OH (Formula IV)
In Formula IV, R21For C6-C20Fluoro-alkyl, preferably C10-C18Fluoro-alkyl.
Shown in the following Formula VII of fluorinated ketones contained,
In Formula VII, R22And R23It is identical or different, it is each independently C1-C5Alkyl or C3-C9Fluoro-alkyl it is (excellent
It is selected as C4-C6Fluoro-alkyl), and R22And R23At least one of be C3-C9Fluoro-alkyl.
Two end groups of coating composition according to the present invention, the fluorochemical polyether are identical or different, respectively can be hydroxyl
Base, carboxyl or acrylate-based.The number-average molecular weight of the fluorochemical polyether can be 1500-100000.The equal molecule of number
Amount is measured using gel permeation chromatography (GPC).
The specific example of coating composition according to the present invention, the fluorochemical can include but is not limited to: three second
Oxygroup [4- (trifluoromethyl) phenyl] silane, methyl perfluoro amyl ketone, 1- methyl -3- trifluoromethyl -2-Pyrrolidone, three ethoxies
The fluoro- n- octyl silane of base -1H, 1H, 2H, 2H- 13,1H, 1H- perfluor -1- tetradecyl alchohol, 1- fluorine heptane, the bis- (3,3,3- tri- of 1,3-
Fluoropropyl) -1,1,3,3- tetramethyl disiloxane, ten trifluorohexane -1- potassium sulfonates, three ethoxy of 3- (seven fluorine isopropoxies) propyl
Base silane, pentafluorophenyl group triethoxysilane, perfluor pentane, [(4- fluorophenoxy) methyl] ethylene oxide, 1H, 1H, 2H,
2H- perfluoro decyl triethoxysilane, six oxa- 20 of 2H- perfluor -5,8,11,14,17- pentamethyl -3,6,9,12,15,18-
One alkane, a fluorine triethoxysilane, trifluoromethyl tetrafluoro phenyl triethoxysilane, 2- (trifluoromethyl) -3- ethyoxyl 12
Fluorine hexane, ten fluoro- 4- (pentafluoroethyl group) oxepane potassium sulfonates, the fluoro- 3,4- bis- of 1,1,1,2,2,3,4,5,5,6,6,6- 12
(trifluoromethyl) hexane, perfluor eicosane, 1H, 6H- perflexane, 1H, 1H, 2H, 2H- perfluor dodecyl triethoxysilane,
It is 1,7- difluoro heptane, ten trifluorohexane of 1,1,1,2,2,3,3,4,5,5,6,6,6-, the pungent fluorine hexane of 1,1,2,2,5,5,6,6-, complete
Fluorine is to terpane, heptafluoro-propane, PF 5070, perfluor (methyl decahydronaphthalenes), perfluoropolyether (including perfluoropolyether alcohol, perfluor
Polyether acrylate and perfluoropolyether carboxylic acid), perfluor -1- butane sulfonic acid, perflenapent, perfluor (hexahydrotoluene), perfluor (2,
2,3,3- 4-methyl-butane), perfluor -1- octane, perflexane, perfluor n-decane, perfluor -1,2- dimethyl cyclohexane, perfluor
Pentadecane, Perfluorononane, Sonazoid, perfluor dodecane, the perfluor tetradecane, perfluor -2,7- dimethyl octane, perfluor 16
Alkane, perfluor -2,3,5,6- tetramethyl-ring hexane, perfluor tridecane, trifluoromethyl-cyclopentane, perfluoro-2-methyl cyclobutane, (perfluor
Hexyl) benzene, perfluor-(1,3,5- trimethylbenzene), perfluorobutyl ethane, perfluorobutyl ether, perfluorotetracosane, perfluoro hexyl second
Alkane, perfluor tetraethyleneglycol dimethyl ether, perfluorooctylethyl group trisiloxanes, perfluor -2- methybutane, perfluor are to terpane, perfluor
Perfluorooctyl ethane, 3- (perfluoro hexyl) propylene oxide, 3- (perfluoro hexyl) propylene oxide, 3- (2- perfluoro hexyl ethyoxyl) -1,2-
Propylene oxide, 3- (Sonazoid) -1,2 epoxy prapane, 3- (perfluoro-n-octane) -1,2 epoxy prapane, 1H, 1H, 2H, 2H-
Perfluoro decyl triethoxysilane, 1H, the 1H- perfluor -1- tetradecane, 1H, 1H, 2H, 2H- perfluor heptadecane dimethylsilane, 2H-
Perfluor (5- methyl -3,6- dioxanonane), 3- (perfluor -5- methylhexyl) -1,2 epoxy prapane, 1H, 1H, 2H, 2H- perfluor
Octyl trimethoxy silane, 1H- perflenapent, 1- (perfluor-n- hexyl) dodecane, 1- (perfluor-n- octyl) tetradecane, 1H,
6H- perflexane, 1- (perfluor-n- hexyl) decane, 1- (perfluor-n- octyl) silane, 1H- perfluor -2,4,4- trimethylpentane,
1H, 10H- perfluoro decane, 1H- perfluor -2,6- dimethyl heptane, 1,1,2,2- tetrahydro perfluoro capryl silane, 1- methyl -4- are (complete
Fluoro ethyl) toluene, 1H, 1H, 2H, 2H- perfluor dodecyl triethoxysilane, 2H- perfluor (2- methylpentane), ethylperfluoro fourth
Base ether, 8- perfluoro decyl octane, perfluor iso-butane, perfluorobutyl methyl ethers, perfluoro propene oxid, 1H, 1H, 2H, the 2H- perfluor last of the ten Heavenly stems
Base trimethoxy silane, 2- trifluoromethyl perflenapent, 2H, 3H- perflenapent, trimethoxy (1H, 1H, 2H, 2H- perfluor oneself
Base) silane, trimethyl (perfluoro-ethyl) silane, diisopropyl-(1H, 1H, 2H, 2H- perfluoro capryl) silane and diisopropyl-
(1H, 1H, 2H, 2H- perfluoro hexyl) silane.The fluorochemical is preferably 1H, 1H, 2H, 2H- perfluor heptadecane dimethyl-silicon
Alkane, perfluor -2,3,5,6- tetramethyl-ring hexane, perfluor -1- butane sulfonic acid, methyl perfluoro amyl ketone, [(4- fluorophenoxy) first
Base] ethylene oxide, 1H, 1H- perfluor -1- tetradecyl alchohol, 3- (seven fluorine isopropoxies) propyl-triethoxysilicane, perfluor 24
Alkane, perfluorooctylethyl group trisiloxanes, perfluor hexadecane, pentamethyl -3,6,9,12,15 2H- perfluor -5,8,11,14,17-,
Six oxa- heneicosane of 18-, perfluor -1,2- dimethyl cyclohexane, 1H, 1H, 2H, 2H- perfluor dodecyl triethoxysilane or
One or more of person's 1H, 1H, 2H, 2H- perfluoro decyl trimethoxy silane.The fluorochemical is more preferably
1H, 1H, 2H, 2H- perfluor heptadecane dimethylsilane, perfluor -2,3,5,6- tetramethyl-ring hexane, perfluorotetracosane, perfluor
Octyl ethyl trisiloxanes, perfluor hexadecane, six oxa- of 2H- perfluor -5,8,11,14,17- pentamethyl -3,6,9,12,15,18-
One or more of heneicosane or perfluor -1,2- dimethyl cyclohexane.
Coating composition according to the present invention, relative to 100 parts by weight Perhydropolysilazanes, the fluorochemical contains
Amount can be 0.1-70 parts by weight.Preferably, relative to 100 parts by weight Perhydropolysilazanes, the content of the fluorochemical
For 0.5-40 parts by weight, such as can be with are as follows: 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 weight
Part, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight,
7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight, 11 parts by weight,
11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 14.5 parts by weight, 15 parts by weight, 15.5 parts by weight, 16 weight
Part, 16.5 parts by weight, 17 parts by weight, 17.5 parts by weight, 18 parts by weight, 18.5 parts by weight, 19 parts by weight, 19.5 parts by weight or
20 parts by weight.
Coating composition according to the present invention, the substituent group in the siloxanes on silicon atom is identical or different, respectively solely
It is on the spot alkyl, aryl or hydrogen atom.Substituent group in the siloxanes on silicon atom is former selected from alkyl, aryl and hydrogen
Son is avoided that siloxanes is chemically reacted with remaining component in coating composition, influences the function of each component.
Preferably, the substituent group in the siloxanes on silicon atom is each independently alkyl, aryl or hydrogen atom, excellent
It is selected as C1-C22Alkyl, C6-C12Aryl or hydrogen atom.
The C1-C22Alkyl include C1-C22Straight chained alkyl and C3-C22Branched alkyl, specific example can wrap
Include but be not limited to: methyl, ethyl, propyl (isomers including propyl), butyl (isomers including butyl), amyl (including
The isomers of amyl), hexyl (isomers including hexyl), heptyl (isomers including heptyl), octyl is (including the different of octyl
Structure body), nonyl (isomers including nonyl), decyl (isomers including decyl), undecyl is (including the different of undecyl
Structure body), dodecyl (isomers including dodecyl), tridecyl (isomers including tridecyl), myristyl
(isomers including myristyl), pentadecyl (isomers including pentadecyl), cetyl are (including cetyl
Isomers), heptadecyl (isomers including heptadecyl), octadecyl (isomers including octadecyl), nonadecane
Base (isomers including nonadecyl), eicosyl (isomers including eicosyl), heneicosyl (including 21
The isomers of alkyl) and docosyl (isomers including docosyl).
The C6-C12The specific example of aryl can include but is not limited to: phenyl, naphthalene, aminomethyl phenyl are (such as: 2- first
Base phenyl, 3- aminomethyl phenyl, 4- aminomethyl phenyl) and ethylphenyl (such as: 2- ethylphenyl, 3- ethylphenyl, 4- ethylphenyl).
In a preferred embodiment, the siloxanes is shown in siloxanes, Formula IX shown in the Formula VIII
One or more of cyclosiloxane shown in silane and Formula X.
Siloxanes shown in Formula VIII is as follows,
In Formula VIII, p is indicatedRepetition number, can be in the range of 1-500, preferably in 2-100
In the range of, more preferably in the range of 2-50, further preferably in the range of 2-20, still more preferably in the model of 2-10
It in enclosing, such as can be 2,3,4,5,6,7,8,9 or 10.
In Formula VIII, p R24, p R27、R25And R26It is identical or different, it is each independently C1-C22Alkyl (preferably
C1-C10Alkyl), C6-C12Aryl, hydrogen atom orR30、R31And R32It is identical or different, it is respectively independent
Ground is C1-C22Alkyl (preferably C1-C10Alkyl), C6-C12Aryl or hydrogen atom.
In Formula VIII, R28And R29It is identical or different, it is each independently selected from C1-C22Alkyl (preferably C1-C10Alkane
Base), C6-C12Aryl or hydrogen atom.
Shown in the following Formula IX of silane,
In Formula IX, R33、R34、R35And R36It is identical or different, it is each independently C1-C22Alkyl, C6-C12Aryl, hydrogen
Atom orAnd R33、R34、R35And R36At least one of beR37、R38And R39It is identical
Or it is different, it is each independently C1-C22Alkyl, C6-C12Aryl or hydrogen atom.In Formula IX, R33、R34、R35And R36In
One, two, three or four is
Shown in the following Formula X of cyclosiloxane,
In Formula X, q can in the range of 2-500, preferably in the range of 2-100, more preferably in the range of 2-50,
It still more preferably in the range of 2-10, such as can be 2,3,4,5,6,7,8,9 further preferably in the range of 2-20
Or 10.
In Formula X, q R40With q R41It is identical or different, it is each independently C1-C22Alkyl (preferably C1-C10Alkane
Base, more preferably C1-C5Alkyl), C6-C12Aryl or hydrogen atom.
The specific example of coating composition according to the present invention, the siloxanes can include but is not limited to: 1,1,5,5-
Tetramethyl -3,3- diphenyl trisiloxanes, 1,1,1,3,5,5,5,-heptamethyltrisiloxane, 3- (dimethylsilyl bis) -1,1,
5,5- tetramethyl -3- phenyl trisiloxanes, 1,1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes, 1,1,3,3- tetramethyl
Disiloxane, 1,3,5- trimethyl -1,3,5- triphenyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, 1,1,3,3,5,5- six
Methyl trisiloxanes, methyl-three (dimethylsilyl bis) silane, ten diformazan basic rings, six siloxanes, tetramethyl -2,4 2,4,6,8-,
6,8- tetraphenyl cyclotetrasiloxane, 1,1,3,3,5,5,7,7- octamethylcyclotetrasiloxane, 1,1,3,3- tetramethoxy -1,3- diformazan
Base disiloxane, 1,3,5,7- tetramethyl-ring tetrasiloxane, 1,1,3,3,5,5,7,7- octaethyl cyclotetrasiloxane, four (diformazans
Base siloxy) silane, 1,1,3,3,5,5,7,7,9,9- decamethylcyclopentaandoxane, octamethylcy-clotetrasiloxane, pentamethyl two
Siloxanes, hexaethyldisiloxane, 1,1,5,5- tetraphenyl -1,3,3,5- tetramethyl trisiloxanes, 1,1,3,5,5- pentamethyl -
3- phenyl trisiloxanes, seven methyl -3- phenyl trisiloxanes of 1,1,1,3,5,5,5-, dodecyl heptamethyltrisiloxane, 1,
3- bis- (4- aminomethyl phenyl) -1,1,3,3- tetramethyl disiloxane, 3,3- diphenyl-hexam ethylcyclotrisiloxane, 2,4,6- front three
Base-cyclotrisiloxane, 2,4,6,8- tetramethyl -2- (trimethoxysilyl) ethyl cyclotetrasiloxane, ten dimethyl, five silicon
Oxygen alkane, decamethyl tetrasiloxane, hexaphenyldisiloxane, 1,3,5,7- tetramethyl -1,1,3,5,7,7- hexaphenyl tetrasiloxane,
Methyl three (trimethylsiloxy group) silane, 1,3- diethoxy -1,1,3,3- tetramethyl disiloxane, three (trimethyl silicane of phenyl
Oxygroup) silane, octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane, ethyl three (dimethylsilyl bis) silane, ethyl three
(trimethylsiloxy group) silane, 1,1,1,5,5,5- hexam ethylcyclotrisiloxane, 1,3,5,7- tetraethyl cyclotetrasiloxane, 3,5- bis-
Phenyl octamethylcyclotetrasiloxane, tetradecamethylhexasiloxane, 1,3- dimethyl -1,1,3,3- tetraphenyl disiloxane, 1,3- are pungent
Base tetramethyl disiloxane, 2,2,4,4- tetramethyl -6,6,8,8- tetraphenyl cyclotetrasiloxane, 2,4,6- triethyl group -2,4,6-
Trimethyl cyclotrisiloxane, 1,1,3,3- tetramethoxy -1,3- diphenyl disiloxane, 3- ethyl heptamethyltrisiloxane, 1,
1,1,5,5,5- Hexaethyl -3- methyl trisiloxanes, 1,1,1- triethyl group -3,3,3- trimethyl trisiloxanes, 1,1,1,3,5,
7,7,7- prestox -3,5- two (trimethylsiloxy group) tetrasiloxane, six (2- ethyl-butoxy) disiloxane, 1,1,3,3- tetra-
Ethyl -1,3- dimethyldisiloxane, 1,1,1,5,5,5- hexamethyl -3- octyl -3- [(trimethyl silicon substrate) oxygroup] three silicon oxygen
Alkane, 1,1,1,5,5,5- hexamethyl -3- (2- phenylethyl) -3- [(trimethyl silicon substrate) oxygroup] trisiloxanes, polyphenyl methyl
Siloxanes, ten hexamethyls, seven siloxanes, three decamethyl rings, 15 siloxanes, 20 prestox ring tetradecane siloxanes, 32
16 siloxanes of methyl ring, 30 prestox ring, 19 siloxanes, four silicon oxygen of 2,2,4,4,6,6- hexamethyl -8,8- hexichol basic ring
Alkane, 20 diformazan basic ring, 11 siloxanes, two decamethyl rings, ten siloxanes, 20 tetramethyl-ring, ten disiloxane, 1,3,3,5,
5,7- vegolysen, 1,7,7- tetraphenyl tetrasiloxane, ten pregnancy basic rings, eight siloxanes, ten prestox rings, nine siloxanes, 20
Methyl nonyl siloxanes, 20 dimethyl, ten siloxanes, 20 hexamethyl, ten disiloxane, 20 prestox, ten trisiloxanes, three
Ten hexamethyls, 17 siloxanes, 2,5- diphenyl hexamethyl cyclotetrasiloxane, ten monomethyls, five siloxanes, 30 tetramethyls-ten
Six siloxanes, hexam ethylcyclotrisiloxane, 1,3,5- trimethyl -1,1,3,5,5- pentaphenyltrisiloxane, 1,1,3,3- tetramethyl -
1,3- diphenyl disiloxane, 1,1,1,3,3,5,5- heptamethyltrisiloxane, four silicon oxygen of 1,1,3,3,5,5,7,7- prestox
Bis- [(trimethylsilyl) oxygen of alkane, decamethylcyclopentaandoxane, diethyldiethoxysilane, 1,1,1,5,5,5- hexamethyl -3,3-
Base]-trisiloxanes, five phenyl -1,3,5- trimethicone of 1,1,3,5,5-, bis- (dimethylsilyl bis) -1,1,7 3,5-,
7- tetramethyl -3,5- diphenyl tetrasiloxane, nine methyl of 3,5,7- triphenyl, five siloxanes, tetramethyl -6,6,8 2,2,4,4-,
8- tetraphenyl cyclotetrasiloxane, 1,1,3,3- tetramethyl disiloxane, polydiethylsiloxane, one in dimethyl silicone polymer
Kind is two or more.The siloxanes is preferably 1,1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes, ten hexamethyls seven
Siloxanes, 1,1,1,3,5,5,5,-heptamethyltrisiloxane, 20 prestox ring tetradecane siloxanes, diethoxy -1 1,3-,
1,3,3- tetramethyl disiloxane, octadecyl heptamethyltrisiloxane, 3,5- diphenyl octamethylcyclotetrasiloxane, 2,4,6- tri-
One or more of six siloxanes of ethyl -2,4,6- trimethyl cyclotrisiloxane or ten diformazan basic rings.
Coating composition according to the present invention, relative to 100 parts by weight Perhydropolysilazanes, the content of the siloxanes can
Think 0.01-150 parts by weight, preferably 0.1-80 parts by weight.It is described more preferably, for 100 parts by weight Perhydropolysilazanes
The content of siloxanes is 2-60 parts by weight, such as can be with are as follows: 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7
Parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight,
16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 weights
Measure part, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight,
33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 weights
Measure part, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight,
50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 weights
Measure part, 59 parts by weight or 60 parts by weight.
Coating composition according to the present invention, in a preferred embodiment, the fluorochemical be 1H, 1H,
2H, 2H- perfluor heptadecane dimethylsilane, perfluor -2,3,5,6- tetramethyl-ring hexane, perfluorotetracosane, perfluoro capryl second
Base trisiloxanes and pentamethyl -3,6, one or more of 9,12,15,18- six oxa- heneicosanes, the siloxanes
It is 1,1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes, ten hexamethyls, seven siloxanes, 20 prestox ring tetradecane silicon
One of oxygen alkane, 1,3- diethoxy -1,1,3,3- tetramethyl disiloxane and octadecyl heptamethyltrisiloxane or two
Kind or more.In the preferred embodiment, the weight ratio of the fluorochemical and the siloxanes is preferably 1:0.1-4,
More preferably 1:0.5-2.
Coating composition according to the present invention, the inorganic particle can be conventional selection as filler.Preferably, institute
Stating inorganic particle is one or both of silica dioxide granule, Zinc oxide particles, alumina particle and diboron trioxide particle
More than.It is highly preferred that the inorganic particle is silica dioxide granule.It is further preferred that the inorganic particle is gas phase dioxy
Silicon carbide particle.The average grain diameter of the inorganic particle is preferably 2-50nm, more preferably 5-30nm, further preferably
10-20nm。
Coating composition according to the present invention, relative to 100 parts by weight Perhydropolysilazanes, the content of the inorganic particle
It can be 0.1-50 parts by weight, preferably 1-40 parts by weight, such as can be with are as follows: 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 weight
Part, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 weight
Part, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22
Parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 weight
Part, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39
Parts by weight or 40 parts by weight.
Coating composition according to the present invention, preferably also contains catalyst, to promote the poly- silicon of the perhydro in coating composition
Azane and siloxanes ceramic form coating.The catalyst can be amines catalyst and/or metal-based catalysts.The amine
Class catalyst can be one or more of aliphatic amine, cycloaliphatic amines, hydramine and aromatic amine.The metal class catalysis
Agent can be organotin catalysts and/or palladium catalyst.The specific example of the catalyst can include but is not limited to: diethyl
Amine, triethylamine, triethylene tetramine, triethylenediamine, piperazine, piperidines, morpholine, N, N- dimethylethanolamine, diisopropanolamine (DIPA),
N, N- diethyl ethylene diamine, aniline, o-phenylenediamine, benzidine, N, accelerine, dibutyltin dilaurate, octanoic acid
One of stannous, stannous methide, triphenyltin, palladium charcoal, palladium chloride, palladium propionate, acid chloride and four (triphenyl phosphorus) palladiums or two
Kind or more.
Coating composition according to the present invention, relative to 100 parts by weight Perhydropolysilazanes, the content of the catalyst can
Think 0-8 parts by weight, preferably 1-6 parts by weight, such as can be with are as follows: 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight,
3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight or 6 parts by weight.
Coating composition according to the present invention, preferably also contains silane coupling agent, to further increase by the Coating material composition
In the coating that object is formed, the dispersion degree of inorganic particle in the base, and it is strong to further increase the combination of inorganic particle in the base
Degree.The silane coupling agent can be conventional selection.Preferably, the silane coupling agent is triethoxy -3- thiocyanogen propyl
Silane, tetraethoxysilane, bis- [3- (trimethoxy silicon substrate) propyl] ethylenediamines, triethoxy octyl silane, (trimethoxy silicon
Alkyl) ethylene, N- phenylaminomethyl triethoxysilane, bis- [3- (triethoxy silicon substrate) propyl] disulphide, trimethoxy
Methyl-monosilane, 3- glycidylpropyl trimethoxy silane, 3- (trimethoxysilyl) propyl -2- methyl -2- acrylic acid
Ester, four oxa- -6- sila hendecane of 6- ethyl -6- (2- methoxy ethoxy) -2,5,7,10- and 3- r-chloropropyl trimethoxyl first
One or more of silane.
Coating composition according to the present invention, relative to 100 parts by weight Perhydropolysilazanes, the silane coupling agent contains
Amount can be 0-40 parts by weight, preferably 1-20 parts by weight, such as can be with are as follows: 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 weight
Part, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 weight
Part, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight or 20 parts by weight.
According to the second aspect of the invention, the present invention provides a kind of coating, the coating contain liquid dispersant and
Coating composition described in first aspect of the present invention, each component in the coating composition are dispersed in the liquid dispersant
In.
The liquid dispersant can be the liquids that can dissolve dispersion Perhydropolysilazane, fluorochemical and siloxanes
Matter, such as can be C3-C10Alkane, C1-C5Halogenated alkane, C4-C10Ether, C3-C10Ketone, C7-C12Aromatic hydrocarbons, C6-C12
Halogenated aryl hydrocarbon and C4-C20One or more of ester.The specific example of the liquid dispersant may include but
It is not limited to: hexane (the various isomers including hexane, such as n-hexane), heptane (the various isomers including heptane, such as positive heptan
Alkane), octane (the various isomers including octane, such as normal octane), nonane (the various isomers including nonane, such as n -nonane),
Decane (the various isomers including decane, such as n-decane), chloroform, methylene chloride, dichloroethylene, ether, petroleum ether, two
Butyl ether, acetone, 1- butanone, cyclohexanone, isophorone, toluene, dimethylbenzene (such as paraxylene and ortho-xylene), chlorobenzene, second
Acetoacetic ester, butyl acetate, ethylene acetate, two glycerol dipropionates, trimethylolpropane dicaprylate, glycol dinitrate
Acid esters, 2- ethylpentanoic phenyl ester, 2- methyl butyl capronate, 3,3- dimethyl -1- butyl acid esters, cinnamyl valerate, second two
Alcohol dibutyrate, 3- methoxybutyl -3- methoxy propyl alkanoic acid ester, 2- ethoxyethyl group capronate, 1- methyl amyl valerate,
One or more of 3M7100,3M7200 and trifluoromethyl benzyl chloride.Preferably, the liquid dispersant contains
One or more of 3M7100,3M7200 and trifluoromethyl benzyl chloride, on the basis of the total amount of the liquid dispersant, choosing
It can be 0.5-50 parts by weight, preferably 1-45 from the content of 3M7100,3M7200 and the liquid dispersant of trifluoromethyl benzyl chloride
Parts by weight, more preferably 1.5-25 parts by weight, further preferably 1.6-10 parts by weight.
The amount of the liquid dispersant, which is subject to, can make each component in coating composition form uniform dispersion liquid.It is excellent
Selection of land, relative to 100 parts by weight Perhydropolysilazanes, the content of the liquid dispersant can be 50-10000 parts by weight, excellent
It is selected as 60-5000 parts by weight, more preferably 70-3000 parts by weight.
Coating according to the present invention can also contain other auxiliary agents, such as: in levelling agent, defoaming agent and viscosity modifier
One or more.The defoaming agent can for it is common it is various be able to suppress formation of foam, destroy the foams formed and/
Or the substance for deviating from the foam of formation from system, such as can be organopolysiloxane system defoamer, polyether system defoaming agent
With higher alcohol system defoaming agent.The levelling agent for promote coating formed during dry solidification one it is more smooth, smooth
And uniform coating, it can be polyacrylate system levelling agent.The viscous regulator is used for the viscosity of adjusting coating, Ke Yiwei
Polyamide wax, organobentonite, rilanit special, metallic soap, hydroxy alkyl cellulose and its derivative, polyvinyl alcohol and polypropylene
One or more of hydrochlorate.
Coating according to the present invention, can by the coating composition each component and optional auxiliary agent be dispersed in liquid
It is obtained in body dispersing agent.Preferably, Perhydropolysilazane is dissolved at least partly liquid dispersant, forms the poly- silicon of perhydro
Azane dilution forms precursor dispersion liquid by fluorochemical and inorganic particle dispersion in the dilution；In the coating
When composition contains catalyst and/or silane coupling agent, catalyst and/or silane coupling agent are dissolved in remainder liquid point
In powder, catalyst and/or coupling agent solution are formed.The precursor dispersion liquid is mixed with catalyst and/or coupling agent solution,
Obtain coating according to the present invention.
According to the third aspect of the present invention, the present invention provides a kind of coatings, and the coating is by the second aspect of the present invention
The coating is formed.
The thickness of the coating can be selected according to specifically used occasion.Generally, the thickness of the coating can be with
It is 0.1-15 microns, preferably 0.5-10 microns.
The coating that the coating as described in the second aspect of the present invention is formed not only has good adhesion property, but also shows
The hardness and heat resistance improved out, while also showing low-surface-energy characteristic.
Specifically, coating described in third aspect, the hardness of the coating can be 6H-9H according to the present invention, preferably
8H-9H；Heatproof can be 300-450 DEG C, preferably 400-450 DEG C；Water contact angle can be 90 ° -120 °, preferably 105 ° -
115°。
Coating described in third aspect according to the present invention, high-temperature oxidation resistance Δ E can be 0.5 hereinafter, generally
0.2-0.4；Wearability can be 3500 times or more, generally 4000-5000 times.
According to the fourth aspect of the present invention, the present invention provides a kind of silica coating, contain fluorochemical.The oxygen
In SiClx coating, the molar ratio of fluorine element and element silicon can be 0.01-1:1, preferably 0.02-0.6.The silica coating
In, the molar ratio of fluorine element and element silicon is measured using X-ray photoelectron spectroscopy.
Silica coating described in the 4th aspect, the hardness of the silica coating are 6H-9H according to the present invention, preferably
8H-9H；Heatproof can be 300-450 DEG C, preferably 400-450 DEG C；Water contact angle can be 90 ° -120 °, preferably 105 ° -
115°。
Silica coating described in 4th aspect according to the present invention, high-temperature oxidation resistance Δ E can be for 0.5 hereinafter, one
As be 0.2-0.4；Wearability can be 3500 times or more, generally 4000-5000 times.
Silica coating described in 4th aspect according to the present invention, in the silica coating, nitrogen and element silicon
Molar ratio can be 0.01-10:100, preferably 0.1-5:100, more preferably 0.1-1:100, further preferably 0.1-
0.5:100.In the silica coating, the molar ratio of nitrogen and element silicon is measured using X-ray photoelectron spectroscopy.
The thickness of the silica coating can be selected according to specifically used occasion.Generally, the silica applies
The thickness of layer can be 0.1-15 microns, preferably 0.5-10 microns.
Silica coating described in 4th aspect according to the present invention, the silica coating can be first using the present invention
Coating described in coating composition described in aspect or the second aspect of the present invention is formed.
According to the fifth aspect of the present invention, the present invention provides a kind of cated product of tool, which contains substrate
And it is attached to the coating on at least partly surface of the substrate, wherein the coating is described in third aspect of the present invention
Silica coating described in coating or the 4th aspect.
The thickness of the coating can be selected according to specifically used requirement.Generally, the thickness of the coating can be with
It is 0.1-15 microns, preferably 0.5-10 microns.
The material of article according to the invention, the substrate is not particularly limited, can for metallic substrates, substrate of glass,
Two or more composite substrates in ceramic bases, enamel substrate, polymeric substrates or above-mentioned substrate.The metallic substrates
Specific example can include but is not limited to: stainless steel base, aluminium substrate, plating aluminium substrate, zinc-plated substrate and cast iron substrate.It is described poly-
The specific example of polymer substrates can include but is not limited to: polycarbonate (PC) substrate, acrylonitrile-butadiene-styrene (ABS) ternary
Copolymer (ABS) substrate, polypropylene (PP) substrate, polyformaldehyde (POM) substrate, polybutylene terephthalate (PBT) (PBT) substrate
One or more of with polyethylene terephthalate (PET) substrate.
Article according to the invention, coating are high to the adhesive force of substrate, and usually 0 grade.
Article according to the invention can exist in a variety of manners, can be various plates and profile, or it is various at
The utensil of type, such as various household electrical appliance, the specific example of the household electrical appliance can include but is not limited to: micro-wave oven, oven,
Kitchen ventilator, kitchen range, dust catcher, dish-washing machine, air-conditioning, refrigerator, water heater and washing machine.
According to the sixth aspect of the invention, the present invention provides a kind of method for forming coating in substrate surface, the party
Method includes that coating described in the second aspect of the present invention is applied at least partly surface for overlaying on substrate, forms dope layer；To have
The substrate of the dope layer is solidified in the presence of water and oxygen.
The coating can be applied using conventional method and overlay on at least partly surface of substrate and (need to form the table of coating
Face), such as: the combination of one or more of spraying, spin coating, showering, dip-coating, roller coating.It, can be with before applying and covering coating
The substrate is subjected to cleaning treatment using conventional method, such as: carry out degreasing and/or washing.
The coating can be carried out in the coating thickness of the substrate surface according to the thickness requirement of finally formed coating
Selection.Generally, the coating the coating thickness of the substrate surface make finally formed coating with a thickness of 0.1-15
Micron, preferably 0.5-10 microns.
According to the present invention the 6th aspect described in method, by the substrate with the dope layer water and oxygen presence
Under solidified.As shown in Figure 1, Perhydropolysilazane is converted under the action of water and oxygen in the presence of water and oxygen
For silica, and then silica coating is formed in substrate surface.
The cured condition is subject to and Perhydropolysilazane can be made to transform into silica.Preferably, the solidification
Condition make in finally formed coating, the molar ratio of nitrogen and element silicon is 0.1-10:100, preferably 0.1-5:
100, more preferably 0.1-1:100, further preferably 0.1-0.5:100.
Generally, the solidification can carry out in the atmosphere containing oxygen that relative humidity is 45-90%.It is described containing
Oxygen atmosphere can be pure oxygen atmosphere, can also form atmosphere, such as oxygen and non-active gas for oxygen and other gases
The atmosphere of formation, the non-active gas for example can be zero group gas (such as helium and/or argon gas) and/or nitrogen.Preferably,
Described be solidificated in the air atmosphere that relative humidity is 60-80% carries out.It is highly preferred that the relative humidity that is solidificated in is 60-
It is carried out in 70% air atmosphere.It is further preferred that it is described be solidificated in relative humidity be 60-65% air atmosphere in into
Row.
The solidification can carry out under conditions of being heated or not heated, and can also carry out under the irradiation of ultraviolet light.One
As, the solidification can 25-350 DEG C at a temperature of carry out, preferably 50-320 DEG C at a temperature of carry out, more preferably exist
Carried out at a temperature of 100-300 DEG C, further preferably 200-280 DEG C at a temperature of carry out.The cured duration can
By according in a manner of cured and cured temperature is selected, can convert Perhydropolysilazane completely or almost completely
Subject to silica.Preferably, the cured duration is 0.5-10 hours.It is highly preferred that described cured lasting
Time is 1-8 hours.It is further preferred that the cured duration is 2-4 hours.
Method described in 6th aspect according to the present invention, the substrate with the dope layer is before being solidified, preferably
It is dried, to remove the volatile components in the dope layer.The drying can 20-100 DEG C of room temperature at a temperature of into
Row.
Method described in 6th aspect according to the present invention, it can be metal that the material of the substrate, which is not particularly limited,
Two or more composite substrates in substrate, substrate of glass, ceramic bases, enamel substrate, polymeric substrates or above-mentioned substrate.
The specific example of the metallic substrates can include but is not limited to: stainless steel base, aluminium substrate, plating aluminium substrate, zinc-plated substrate and
Cast iron substrate.The specific example of the polymeric substrates can include but is not limited to: polycarbonate (PC) substrate, acrylic nitrile-butadiene
Styrene terpolymer (ABS) substrate, polypropylene (PP) substrate, polyformaldehyde (POM) substrate, poly terephthalic acid fourth
One or more of diol ester (PBT) substrate and polyethylene terephthalate (PET) substrate.
The substrate can be various plates or profile, also can be set in various molding tools, be preferably provided at
In household electrical appliance, the household electrical appliance be preferably micro-wave oven, oven, kitchen ventilator, kitchen range, dust catcher, dish-washing machine, air-conditioning, refrigerator,
Water heater or washing machine.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, the Perhydropolysilazane of use is purchased from Institute of Chemistry, Academia Sinica.Below
It is total using nuclear-magnetism using the average molecular weight of gel color infiltration spectral method measurement Perhydropolysilazane in embodiment and comparative example
The hydrogen spectrometry that shakes measures SiH in Perhydropolysilazane1And SiH2Molar ratio.
In following embodiment and comparative example, in coating, the molar ratio of fluorine element and element silicon uses x-ray photoelectron spectroscopy
The molar ratio of method measurement, nitrogen and element silicon is measured using X-ray photoelectron spectroscopy.
In following embodiment and comparative example, the hardness of coating is using the measurement of method specified in GB/T6739-2006；Coating
Adhesive force use cross-hatching, measured according to method specified in GB/T9286-1998；The water contact angle of coating, which uses, is purchased from moral
The full-automatic water contact angle instrument of the model DSA100 of state measures under conditions of 25 DEG C and 1 standard atmospheric pressure.
In following embodiment and comparative example, the heat resistance of coating is measured using water contact angle method, i.e., by prepared painting
After layer is heated to different temperatures in an oven and is kept for 2 hours at such a temperature, its water contact angle is tested, if water contact angle is lower than
90 °, it is determined as that temperature tolerance is lost, and using the temperature as the maximum temperature of heatproof, the temperature is higher, then the heat resistance of coating
Better.
In following embodiment and comparative example, the high-temperature oxidation resistance of coating is measured using chromatic aberration test method, test
Template after high-temperature oxydation and the color difference between template is not aoxidized, value of chromatism is smaller, then the high-temperature oxidation resistance of coating is better, tool
Body test method is when prepared coating being heated to 400 DEG C in an oven and keeping 2 at such a temperature, to measure the coating in oxygen
Change the chromatic value of front and back, and calculates the difference of the two.
In following embodiment and comparative example, the wear-resisting property of coating is measured using the method for 3M sand paper reciprocating friction, if applying
Layer appearance is show-through, falls off, then to there are data of the Rubbing number of this phenomenon as wearability, and is taken according to nearby principle
Whole to obtain wearability, abrasion resistance value is higher, and the wearability of coating is better.
Embodiment 1-21 is for illustrating the present invention.
Embodiment 1
(1) by 40 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 11) be added
Into 37 parts by weight butyl acetates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) by 1 parts by weight (3- trimethoxy silicon propyl) diethyl ethylenediamine, 2 parts by weight dibutyltin dilaurates
It is added in 15 parts by weight butyl acetates and 1 parts by weight 3M7200, in room temperature (for 25 DEG C), stirring forms uniform coupling agent and urges
Agent solution.
(3) by 1 parts by weight 1,1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes are (purchased from the limited public affairs of lark prestige science and technology
Department, similarly hereinafter), 1 parts by weight 1H, 1H, 2H, 2H- perfluor heptadecane dimethylsilane (be purchased from lark prestige Science and Technology Ltd., similarly hereinafter)
It is added in PHPS dilution with 2 parts by weight fumed silicas (average particle size particle size 12nm), step (2) system is then added
Standby coupling agent catalyst solution stirs evenly in room temperature (for 25 DEG C), obtains coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to 304 stainless steel bases using spraying method, forms coating
Layer.Substrate with dope layer is dried in vacuo at 60 DEG C, removes the solvent in dope layer.It then, is 60% in relative humidity
Air atmosphere in, in 200 DEG C solidify 2 hours, obtain the substrate with coating (with a thickness of 6 microns).To the performance of coating into
Row test, is as a result listed in table 2.
Comparative example 1
Have cated substrate using method preparation same as Example 1, unlike, in step (3), do not use
1H, 1H, 2H, 2H- perfluor heptadecane dimethylsilane (that is, the coating of preparation is free of fluorochemical).To the performance of coating into
Row test, is as a result listed in table 2.
Comparative example 2
Have cated substrate using method preparation same as Example 1, unlike, in step (3), 1 is not used,
1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes (that is, coating not silicone-containing of preparation).The performance of coating is carried out
Test, is as a result listed in table 2.
Comparative example 3
Have cated substrate using method preparation same as Example 1, unlike, in step (3), 1 is not used,
1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes and 1H, 1H, 2H, 2H- perfluor heptadecane dimethylsilane are (that is, preparation
Coating not silicone-containing and fluorochemical).The performance of coating is tested, is as a result listed in table 2.
Comparative example 4
Have cated substrate using method preparation same as Example 1, unlike, in step (3), 1,1,1,3,
5,5,5,-seven methyl -3- octyl trisiloxanes with etc. the diphenyl dichlorosilanes of weight replace.The performance of coating is surveyed
Examination, is as a result listed in table 2.
Embodiment 2
Have cated substrate using method preparation same as Example 1, unlike, in step (2), do not use
3M7200, the dosage of butyl acetate are 16 parts by weight.The performance of coating is tested, is as a result listed in table 2.
Table 2
Embodiment 3
(1) by 35 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added
Into 49.2 parts by weight butyl oxides, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) by 1.1 parts by weight triethoxy octyl silane, 1.8 parts by weight acid chlorides be added to 6.9 parts by weight butyl oxides and
In 1 parts by weight 3M7100, in room temperature (for 25 DEG C), stirring forms uniform coupling agent catalyst solution.
(3) by 2 parts by weight, ten hexamethyl, seven siloxanes, 1 parts by weight perfluor -2,3,5,6- tetramethyl-ring hexane and 2 weight
Part fumed silica (average particle size particle size 15nm) is added in PHPS dilution, and the idol of step (2) preparation is then added
Connection agent catalyst solution stirs evenly in room temperature (for 25 DEG C), obtains coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to substrate of glass using spraying method, forms dope layer.It will
Substrate with dope layer is dried in vacuo at 60 DEG C, removes the solvent in dope layer.Then, the air for being 50% in relative humidity
In atmosphere, solidify 2 hours in 250 DEG C, obtain the substrate with coating (with a thickness of 10 microns).The performance of coating is surveyed
Examination, is as a result listed in table 3.
Embodiment 4
Have cated substrate using method preparation same as Example 3, unlike, in step (3), ten hexamethyls
The 1,1,1,3,5,5,5 of the weight such as seven siloxanes use ,-heptamethyltrisiloxane replaces.The performance of coating is tested, as a result
It is listed in table 3.
Embodiment 5
Have cated substrate using method preparation same as Example 3, unlike, in step (3), perfluor -2,
3,5,6- tetramethyl-ring hexane with etc. the perfluor -1- butane sulfonic acid of weight replace.The performance of coating is tested, as a result in table
It is listed in 3.
Embodiment 6
Have cated substrate using method preparation same as Example 3, unlike, in step (3), perfluor -2,
3,5,6- tetramethyl-ring hexane with etc. the methyl perfluoro amyl ketones of weight replace.The performance of coating is tested, as a result in table 3
In list.
Embodiment 7
Have cated substrate using method preparation same as Example 3, unlike, in step (3), perfluor -2,
3,5,6- tetramethyl-ring hexane with etc. [(4- fluorophenoxy) methyl] ethylene oxide of weight replace.The performance of coating is surveyed
Examination, is as a result listed in table 3.
Embodiment 8
Have cated substrate using method preparation same as Example 3, unlike, in step (3), perfluor -2,
The 1H of the weight such as 3,5,6- tetramethyl-ring hexane use, 1H- perfluor -1- tetradecyl alchohol replace.The performance of coating is tested, as a result
It is listed in table 3.
Embodiment 9
Have cated substrate using method preparation same as Example 3, unlike, in step (3), perfluor -2,
3,5,6- tetramethyl-ring hexane with etc. 3- (seven fluorine isopropoxies) propyl-triethoxysilicanes of weight replace.To the performance of coating
It is tested, is as a result listed in table 3.
Table 3
Embodiment 10
(1) by 30 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 14) be added
Into 53.1 parts by weight ethylene glycol dibutyrates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 1.3 parts by weight 3- glycidylpropyl trimethoxy silanes, 1.6 parts by weight stannous methides are added to 6.5 weights
It measures in part ether and 1.5 parts by weight trifluoromethyl benzyl chlorides, in room temperature (for 25 DEG C), it is molten that stirring forms uniform coupling agent catalyst
Liquid.
(3) by 2 parts by weight, 20 prestox ring tetradecane siloxanes, 3 parts by weight perfluorotetracosanes and 2 parts by weight gas phases
Silica (average particle size particle size 20nm) is added in PHPS dilution, and the coupling agent that step (2) preparation is then added is urged
Agent solution stirs evenly in room temperature (for 25 DEG C), obtains coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 60 DEG C, removes the solvent in dope layer.Then, the sky for being 60% in relative humidity
In gas atmosphere, solidify 2 hours in 250 DEG C, obtain the substrate with coating (with a thickness of 8 microns).The performance of coating is surveyed
Examination, is as a result listed in table 4.
Embodiment 11
(1) by 25 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added
Into 54 weight part of ethylacetate, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) by 1.4 parts by weight 3- (trimethoxysilyl) propyl -2- methyl -2- acrylate, 1.4 parts by weight two
Phenyltin is added in 9.2 parts by weight paraxylene and 2 parts by weight 3M7100, and in room temperature (for 25 DEG C), stirring forms uniform
Coupling agent catalyst solution.
(3) by 3 parts by weight 1,3- diethoxy -1,1,3,3- tetramethyl disiloxanes, 2 parts by weight perfluorooctylethyl groups three
Siloxanes and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added in PHPS dilution, and step is then added
Suddenly the coupling agent catalyst solution of (2) preparation stirs evenly in room temperature (for 25 DEG C), obtains coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 60 DEG C, removes the solvent in dope layer.Then, the sky for being 60% in relative humidity
In gas atmosphere, solidify 2 hours in 250 DEG C, obtain the substrate with coating (with a thickness of 10 microns).The performance of coating is surveyed
Examination, is as a result listed in table 4.
Embodiment 12
Have cated substrate using method identical with embodiment 11 preparation, unlike, in step (2), do not use
3M7100, but use 10.6 parts by weight paraxylene.The performance of coating is tested, is as a result listed in table 4.
Embodiment 13
Have cated substrate using method identical with embodiment 11 preparation, unlike, in step (3), perfluor is pungent
Base ethyl trisiloxanes with etc. the perfluor hexadecanes of parts by weight replace.The performance of coating is tested, is as a result arranged in table 4
Out.
Table 4
Embodiment 14
(1) by 20 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added
Into 56.2 parts by weight 1- methyl amyl valerates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 1.6 parts by weight N- phenylaminomethyl triethoxysilanes, 1.1 parts by weight palladium chlorides are added to 6.6 parts by weight
In petroleum ether and 2.5 parts by weight 3M7200, in room temperature (for 25 DEG C), stirring forms uniform coupling agent catalyst solution.
(3) by 6 parts by weight octadecyl heptamethyltrisiloxanes, 4 parts by weight 2H- perfluor -5,8,11,14,17-, five first
Six oxa- heneicosane of base -3,6,9,12,15,18- and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added
Into PHPS dilution, the coupling agent catalyst solution that step (2) preparation is then added is stirred evenly in room temperature (for 25 DEG C),
Obtain coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 45 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 4 microns).The performance of coating is surveyed
Examination, is as a result listed in table 5.
Embodiment 15
(1) by 15 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added
Into 56.1 parts by weight ethylene glycol diformates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 1.7 parts by weight trimethoxymethylsila,es, 0.8 parts by weight of octanoic acid stannous are added to 6.4 parts by weight ethylene glycol
In dicarboxylic acid esters and the trifluoromethyl benzyl chloride of 3 parts by weight, in room temperature (for 25 DEG C), it is molten that stirring forms uniform coupling agent catalyst
Liquid.
(3) by 9 parts by weight 3,5- diphenyl octamethylcyclotetrasiloxanes, 6 parts by weight perfluor -1,2- dimethyl cyclohexanes and 2
Parts by weight fumed silica (average particle size particle size 12nm) is added in PHPS dilution, and step (2) preparation is then added
Coupling agent catalyst solution stir evenly in room temperature (for 25 DEG C), obtain coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 50 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 8 microns).The performance of coating is surveyed
Examination, is as a result listed in table 5.
Embodiment 16
(1) by 10 parts by weight Perhydropolysilazane (average molecular weight 800, SiH1And SiH2Molar ratio be 12) be added
Into 50 parts by weight trimethylolpropane dicaprylates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 1.9 parts by weight triethoxy -3- thiocyanogen propyl silanes, 0.5 parts by weight dibutyltin dilaurate are added
Enter into 12.7 parts by weight trimethylolpropane dicaprylates and 3.9 parts by weight 3M7200, in room temperature (for 25 DEG C), stirring is formed
Uniform coupling agent catalyst solution.
(3) by 13 parts by weight 2,4,6- triethyl group -2,4,6- trimethyl cyclotrisiloxane, 6 parts by weight 1H, 1H, 2H, 2H-
Perfluor dodecyl triethoxysilane and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added to PHPS dilution
In liquid, the coupling agent catalyst solution that step (2) preparation is then added is stirred evenly in room temperature (for 25 DEG C), is obtained according to this
The coating of invention.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 45 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 5 microns).The performance of coating is surveyed
Examination, is as a result listed in table 5.
Embodiment 17
(1) by 15 parts by weight Perhydropolysilazane (average molecular weight 1000, SiH1And SiH2Molar ratio be 12) be added
Into 35 parts by weight 2- methyl butyl capronates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 2 parts by weight triethoxy octyl silane, 0.2 parts by weight triphenyltin are added to two fourths of 20.8 parts by weight
In ether and the 3M7100 of 15 parts by weight, in room temperature (for 25 DEG C), stirring forms uniform coupling agent catalyst solution.
(3) by 10 parts by weight, ten diformazan basic ring, six siloxanes, 10 parts by weight 1H, 1H, 2H, 2H- perfluoro decyl trimethoxies
Silane and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added in PHPS dilution, and step is then added
(2) the coupling agent catalyst solution prepared stirs evenly in room temperature (for 25 DEG C), obtains coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 45 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 2 microns).The performance of coating is surveyed
Examination, is as a result listed in table 5.
Embodiment 18
(1) by 40 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added
Into 15 parts by weight butyl acetates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) by 1 parts by weight (3- trimethoxy silicon propyl) diethyl ethylenediamine, 2 parts by weight dibutyltin dilaurates
It is added in the butyl acetate of 5 parts by weight and the 3M7100 of 15 parts by weight, in room temperature (for 25 DEG C), stirring forms uniform coupling
Agent catalyst solution.
(3) by 10 parts by weight, ten diformazan basic ring, six siloxanes, 10 parts by weight 1H, 1H, 2H, 2H- perfluor heptadecane dimethyl
Silane and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added in PHPS dilution, and step is then added
(2) the coupling agent catalyst solution prepared stirs evenly in room temperature (for 25 DEG C), obtains coating according to the present invention.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 45 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 4 microns).The performance of coating is surveyed
Examination, is as a result listed in table 5.
Embodiment 19
(1) by 5 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added to
In 75 parts by weight 2- methyl butyl capronates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 2 parts by weight triethoxy octyl silane, 0.2 parts by weight stannous phenide are added to two fourths of 10.8 parts by weight
In ether, in room temperature (for 25 DEG C), stirring forms uniform coupling agent catalyst solution.
(3) by 1 parts by weight 1,1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes, 1 parts by weight 1H, 1H, 2H, 2H-
Perfluor heptadecane dimethylsilane and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added to PHPS dilution
In, the coupling agent catalyst solution that step (2) preparation is then added is stirred evenly, is obtained according to this hair in room temperature (for 25 DEG C)
Bright coating.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 45 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 5 microns).The performance of coating is surveyed
Examination, is as a result listed in table 5.
Embodiment 20
(1) by 40 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added
Into 37 parts by weight butyl acetates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 1 parts by weight (3- trimethoxy silicon propyl) diethyl ethylenediamine is added in 15 parts by weight butyl acetates,
Room temperature (for 25 DEG C), stirring form uniform coupling agent solution.
(3) by 2 parts by weight 1,1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes, 3 parts by weight 1H, 1H, 2H, 2H-
Perfluor heptadecane dimethylsilane and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added to PHPS dilution
In, the coupling agent solution that step (2) preparation is then added stirs evenly in room temperature (for 25 DEG C), obtains painting according to the present invention
Material.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 45 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 9 microns).The performance of coating is surveyed
Examination, is as a result listed in table 5.
Embodiment 21
(1) by 40 parts by weight Perhydropolysilazane (average molecular weight 600, SiH1And SiH2Molar ratio be 12) be added
Into 35 parts by weight butyl acetates, in room temperature (for 25 DEG C), stirring forms the PHPS dilution of stable homogeneous.
(2) 2 parts by weight dibutyltin dilaurates are added to 15 parts by weight butyl acetates and 1 parts by weight 3M7200
In, in room temperature (for 25 DEG C), stirring forms uniform catalyst solution.
(3) by 2 parts by weight 1,1,1,3,5,5,5,-seven methyl -3- octyl trisiloxanes, 3 parts by weight 1H, 1H, 2H, 2H-
Perfluor heptadecane dimethylsilane and 2 parts by weight fumed silicas (average particle size particle size 12nm) are added to PHPS dilution
In, the catalyst solution that step (2) preparation is then added stirs evenly in room temperature (for 25 DEG C), obtains painting according to the present invention
Material.
(4) surface that the coating of step (3) preparation is applied to stainless steel base using spraying method, forms dope layer.
Substrate with dope layer is dried in vacuo at 45 DEG C, removes the solvent in dope layer.Then, the sky for being 65% in relative humidity
In gas atmosphere, solidify 4 hours in 200 DEG C, obtain the substrate with coating (with a thickness of 0.5 micron).The performance of coating is carried out
Test, is as a result listed in table 5.
Table 5
Embodiment 1-21's as a result, it was confirmed that painting that the coating formed by coating composition of the invention is formed in substrate surface
Layer not only has excellent adhesion property, but also has good heat resistance, corrosion resistance and scraping and wiping resistance performance, together
When also show low-energy surface characteristic, it is (including antifrost performance) easy to clean.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (22)
1. a kind of coating composition, the coating composition contain Perhydropolysilazane, fluorochemical, siloxanes, inorganic particle,
Optional catalyst and optional silane coupling agent, the substituent group in the siloxanes on silicon atom are each independently alkane
Base, aryl or hydrogen atom.
2. coating composition according to claim 1, wherein the fluorochemical is selected from fluorine containing silane, fluorine silicon
Oxygen alkane, fluorine-containing clicyclic hydrocarbon, fluorine-containing aliphatic hydrocarbon, fluorine-containing ether, fluorine-containing alcohol ether, fluorochemical polyether, fluorine-containing aromatic hydrocarbons, fluorine-containing alkylene oxide
One or more of hydrocarbon, sulfonic fluoropolymer, sulfonic fluoropolymer salt, fluorine-containing alcohol, fluorinated ketones contained and fluorine-containing pyrrolidones；
Preferably, the fluorochemical is silane, C shown in siloxanes, Formula II shown in the Formulas I4-C15Fluorine-containing alicyclic ring
Race's hydrocarbon, C3-C30Fluorine-containing aliphatic hydrocarbon, C4-C30Fluorine-containing ether, C4-C20Fluorine-containing alcohol ether, fluorochemical polyether, C6-C16Fluorine-containing virtue
Epoxyalkane shown in hydrocarbon, formula III, C shown in sulfonic fluoropolymer salt, Formula IV shown in sulfonic fluoropolymer, Formula V shown in formula IV6-C20
Fluorine-containing alcohol, C shown in Formula VII4-C12Ketone and C5-C12One or more of fluorine-containing pyrrolidones,
In Formulas I, n R1, n R3、R2、R4、R5And R6It is identical or different, it is each independently C1-C6Alkyl, C1-C12Fluoro
Alkyl or hydrogen atom, and n R1, n R3、R2、R4、R5And R6At least one of be C1-C12Fluoro-alkyl,
N is in the range of 1-500, preferably in the range of 2-100, more preferably in the range of 2-50, further preferably in 2-
In the range of 20, still more preferably in the range of 2-10；
In Formula II, R7、R8、R9And R10It is identical or different, it is each independently fluorine atom, C1-C20Contain fluoroalkyl, R11-O-
R12-、C6-C12Fluorinated aryl, C1-C8Alkyl, C1-C5Alkoxy or hydrogen atom, and R7、R8、R9And R10In at least
One is fluorine atom, C1-C20Contain fluoroalkyl, R11-O-R12Or C6-C12Fluorinated aryl, R11For C1-C8Fluoro-alkyl,
R12For C1-C6Alkylidene；
In formula III, R13、R14、R15And R16It is identical or different, it is each independently C1-C8Alkyl, fluorine atom, R17-CH2Or
R18-O-CH2, and R13、R14、R15And R16At least one of be fluorine atom, R17-CH2Or R18-O-CH2, R17For C3-C12
Fluoro-alkyl or C6-C12Contain fluoro aryl, R18For C3-C12Fluoro-alkyl or C6-C12Contain fluoro aryl；
R19-SO3H (formula IV)
In formula IV, R19For C4-C10Fluoro-alkyl；
R20-SO3M (Formula V)
In Formula V, R20For C4-C10Fluoro-alkyl, M is alkali metal, preferably sodium or potassium；
R21- OH (Formula IV)
In Formula IV, R21For C6-C20Fluoro-alkyl；
In Formula VII, R22And R23It is identical or different, it is each independently C1-C5Alkyl or C3-C9Fluoro-alkyl, and R22With
R23At least one of be C3-C9Fluoro-alkyl.
3. coating composition according to claim 1, wherein in the siloxanes, the alkyl is C1-C22Alkyl,
The aryl is C6-C12Aryl.
4. coating composition according to claim 1, wherein the siloxanes be the siloxanes shown in the Formula VIII,
One or more of cyclosiloxane shown in silane and Formula X shown in Formula IX,
In Formula VIII, p R24, p R27、R25And R26It is identical or different, it is each independently C1-C22Alkyl, C6-C12Virtue
Base, hydrogen atom orR30、R31And R32It is identical or different, it is each independently C1-C22Alkyl, C6-C12
Aryl or hydrogen atom,
R28And R29It is identical or different, it is each independently selected from C1-C22Alkyl, C6-C12Aryl or hydrogen atom,
P is in the range of 1-500, preferably in the range of 2-100, more preferably in the range of 2-50, further preferably in 2-
In the range of 20, still more preferably in the range of 2-10；
In Formula IX, R33、R34、R35And R36It is identical or different, it is each independently C1-C22Alkyl, C6-C12Aryl, hydrogen atom
OrAnd R33、R34、R35And R36At least one of beR37、R38And R39It is identical or not
Together, it is each independently C1-C22Alkyl, C6-C12Aryl or hydrogen atom；
In Formula X, q R40With q R41It is identical or different, it is each independently C1-C22Alkyl, C6-C12Aryl or hydrogen it is former
Son,
Q is in the range of 2-500, preferably in the range of 2-100, more preferably in the range of 2-50, further preferably in 2-
In the range of 20, still more preferably in the range of 2-10.
5. coating composition according to claim 1, wherein the fluorochemical is 1H, 1H, 2H, 2H- perfluor 17
Alkane dimethylsilane, perfluor -2,3,5,6- tetramethyl-ring hexane, perfluorotetracosane, perfluorooctylethyl group trisiloxanes and five
Methyl -3,6, one or more of 9,12,15,18- six oxa- heneicosanes, the siloxanes are 1,1,1,3,5,5,
5,-seven methyl -3- octyl trisiloxanes, ten hexamethyls, seven siloxanes, 20 prestox ring tetradecane siloxanes, 1,3- diethoxy
One or more of base -1,1,3,3- tetramethyl disiloxane and octadecyl heptamethyltrisiloxane.
6. coating composition according to claim 1, wherein the inorganic particle is silica dioxide granule, zinc oxide
One or more of grain, alumina particle and diboron trioxide particle；
Preferably, the average particle size particle size of the inorganic particle is 2-50nm, more preferably 5-30nm, further preferably 10-
20nm。
7. coating composition according to claim 1, wherein the catalyst is that amines catalyst and/or metal class are urged
One or both of agent, preferably aliphatic amine, cycloaliphatic amines, hydramine, aromatic amine, organotin catalysts and palladium catalyst
More than, preferably diethylamine, triethylamine, triethylene tetramine, triethylenediamine, piperazine, piperidines, morpholine, N, N- dimethyl second
Hydramine, diisopropanolamine (DIPA), N, N- diethyl ethylene diamine, aniline, o-phenylenediamine, benzidine, N, accelerine, dibutyl tin
In dilaurate, stannous octoate, stannous methide, triphenyltin, palladium charcoal, palladium chloride, palladium propionate, acid chloride and triphenyl phosphorus palladium
One or more；
The silane coupling agent is triethoxy -3- thiocyanogen propyl silane, tetraethoxysilane, [(3- trimethoxy silicon substrate)
Propyl] diethyl ethylenediamine, triethoxy octyl silane, (trimethoxy silane base) ethylene, N- phenylaminomethyl triethoxy
Silane, bis- [3- (triethoxy silicon substrate) propyl] disulphide, trimethoxymethylsila,e, 3- glycidylpropyl trimethoxy
Silane, 3- (trimethoxysilyl) propyl -2- methyl -2- acrylate, 6- ethyl -6- (2- methoxy ethoxy) -2,
One or more of tetra- oxa- -6- sila hendecane of 5,7,10- and 3- r-chloropropyl trimethoxyl monosilane.
8. coating composition described in any one of -5 according to claim 1, wherein relative to the 100 poly- silicon of parts by weight perhydro
Azane, the content of the fluorochemical are 0.1-70 parts by weight, preferably 0.5-40 parts by weight；The content of the siloxanes is
0.01-150 parts by weight, preferably 0.1-80 parts by weight, more preferably 2-60 parts by weight；The content of the inorganic particle is 0.1-
50 parts by weight, preferably 1-40 parts by weight；The content of the catalyst is 0-8 parts by weight, preferably 1-6 parts by weight；The silicon
The content of alkane coupling agent is 0-40 parts by weight, preferably 1-20 parts by weight.
9. a kind of coating, which contains coating composition described in any one of liquid dispersant and claim 1-8,
Each component in the coating composition is dispersed in the liquid dispersant.
10. coating according to claim 9, wherein the liquid dispersant is C3-C10Alkane, C1-C5Alkyl halide
Hydrocarbon, C4-C10Ether, C3-C10Ketone, C7-C12Aromatic hydrocarbons, C6-C12Halogenated aryl hydrocarbon and C4-C20One or both of ester
More than.
11. coating according to claim 9 or 10, wherein relative to 100 parts by weight Perhydropolysilazanes, the liquid
The content of dispersing agent is 50-10000 parts by weight, preferably 60-5000 parts by weight, more preferably 70-3000 parts by weight.
12. a kind of coating, coating coating as described in any one of claim 9-11 is formed.
13. a kind of silica coating, which contains fluorochemical, in the silica coating, fluorine element and silicon member
The molar ratio of element is 0.01-1:1, and preferably 0.02-0.6:1, the hardness of the silica coating is 6H-9H, preferably 8H-9H；
Heatproof is 300-450 DEG C, preferably 400-450 DEG C；Water contact angle is 90 ° -120 °, preferably 105 ° -115 °.
14. silica coating according to claim 13, wherein in the silica coating, nitrogen and element silicon rub
You are than being 0.01-10:100, preferably 0.1-5:100, more preferably 0.1-1:100, further preferably 0.1-0.5:100.
15. a kind of cated product of tool, the product contain substrate and are attached to the painting on at least partly surface of the substrate
Layer, which is characterized in that the coating is described in any one of coating or claim 13-14 described in claim 12
Silica coating.
16. product according to claim 15, wherein the substrate is metallic substrates, substrate of glass, ceramic bases, wards off
Two or more composite substrates in porcelain substrate, polymeric substrates or above-mentioned substrate.
17. product according to claim 15 or 16, wherein the product is household electrical appliance, preferably micro-wave oven, roasting
Case, kitchen ventilator, kitchen range, dust catcher, dish-washing machine, air-conditioning, refrigerator, water heater or washing machine.
18. a kind of method for forming coating in substrate surface, this method includes will be described in any one of claim 9-11
Coating applies at least partly surface for overlaying on substrate, forms dope layer；By the depositing in water and oxygen of the substrate with the dope layer
Solidified under.
19. according to the method for claim 18, wherein described to be solidificated in the air atmosphere that relative humidity is 45-90%
It carries out.
20. method described in 8 or 19 according to claim 1, wherein the cured condition makes in finally formed coating,
Nitrogen and the molar ratio of element silicon are 0.01-10:100, preferably 0.1-5:100, more preferably 0.1-1:100, further
Preferably 0.1-0.5:100；
Preferably, it is described be solidificated in 25-350 DEG C at a temperature of carry out, preferably 50-320 DEG C at a temperature of carry out, more preferably exist
Carried out at a temperature of 100-300 DEG C, further preferably 200-280 DEG C at a temperature of carry out；The cured duration is excellent
It is selected as 0.5-10 hours, more preferably 1-8 hours, further preferably 2-4 hours.
21. according to the method for claim 20, wherein the substrate is metallic substrates, substrate of glass, ceramic bases, wards off
Two or more composite substrates in porcelain substrate, polymeric substrates or above-mentioned substrate.
22. method described in 8 or 21 according to claim 1, wherein the substrate is arranged in household electrical appliance, the household electric
Device is preferably micro-wave oven, oven, kitchen ventilator, kitchen range, dust catcher, dish-washing machine, air-conditioning, refrigerator, water heater or washing machine.
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| CN113174200A (en) * | 2021-05-21 | 2021-07-27 | 佛山市顺德区美的洗涤电器制造有限公司 | Coating composition, coating, preparation method and application thereof, and coating |
| CN113292925A (en) * | 2021-05-21 | 2021-08-24 | 佛山市顺德区美的洗涤电器制造有限公司 | Coating composition, coating, preparation method and application thereof, and coating |
| CN113402974A (en) * | 2021-06-02 | 2021-09-17 | 佛山市顺德区美的洗涤电器制造有限公司 | Coating composition, coating, preparation method and application thereof, and coating |
| CN113402973A (en) * | 2021-06-02 | 2021-09-17 | 佛山市顺德区美的洗涤电器制造有限公司 | Easy-to-clean coating composition, easy-to-clean coating, preparation method and application of easy-to-clean coating |
| CN113444446A (en) * | 2021-06-02 | 2021-09-28 | 佛山市顺德区美的洗涤电器制造有限公司 | Corrosion-resistant coating composition, corrosion-resistant coating, preparation method and application of corrosion-resistant coating, and corrosion-resistant coating |
| CN113462286A (en) * | 2021-06-02 | 2021-10-01 | 佛山市顺德区美的洗涤电器制造有限公司 | Coating composition, coating, preparation method and application thereof, and coating |
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| CN115449291A (en) * | 2021-06-09 | 2022-12-09 | 荣耀终端有限公司 | Waterproof insulating coating and application thereof |
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