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CN113462286A - Coating composition, coating, preparation method and application thereof, and coating - Google Patents

Coating composition, coating, preparation method and application thereof, and coating Download PDF

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Publication number
CN113462286A
CN113462286A CN202110613480.9A CN202110613480A CN113462286A CN 113462286 A CN113462286 A CN 113462286A CN 202110613480 A CN202110613480 A CN 202110613480A CN 113462286 A CN113462286 A CN 113462286A
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Prior art keywords
coating
mass
coating composition
content
fluorine
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Inventor
孟繁轲
陈三名
张天保
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Foshan Shunde Midea Washing Appliances Manufacturing Co Ltd
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Foshan Shunde Midea Washing Appliances Manufacturing Co Ltd
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Priority to CN202110613480.9A priority Critical patent/CN113462286A/en
Publication of CN113462286A publication Critical patent/CN113462286A/en
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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
    • C09D183/04—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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (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, fluorine modified polysilazane, alkylsilane, inorganic antibacterial agent and solvent; based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the fluorine-modified polysilazane is 5-30 mass%, the content of the alkylsilane is 0.01-0.5 mass%, the content of the inorganic antibacterial agent is 0.1-1 mass%, and the content of the solvolane is 30-85 mass%. According to the invention, a specific amount of fluorosilicone resin, fluorine modified polysilazane, alkylsilane, an inorganic antibacterial agent and a solvent are compounded to obtain the coating composition, and a coating prepared from the coating composition has the advantage of good adhesion.

Description

Coating composition, coating, preparation method and application thereof, and coating
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
Along with the improvement of living standard, people have more and more strong demand on easy cleaning of kitchen appliances such as range hoods, gas stoves and ovens. However, in a long-term use environment, the surfaces of the kitchen appliances are adhered with more oil stains and stains, and the cleaning is troublesome.
At present, in order to solve the problems of oil smoke and oil stain, common metal materials such as an aluminum-plated plate and a stainless steel plate are usually adopted by kitchen appliances such as an oven and an oven to be directly used as a cavity, when the kitchen appliances work, the oil smoke for baking food is directly discharged to the external space through an exhaust hole, and the oil stain staying on the wall of the oven and the wall of the oven cavity is manually scrubbed by a cleaning agent after the cavity is cooled.
In addition, in the prior art, a coating is usually sprayed on the inner wall of an oven or a baking oven, so that oil stains cannot be bonded on the surface, the problem of difficulty in cleaning is effectively solved, and the problem that the exhausted oil smoke pollutes the surrounding environment still exists; in addition, the surface coating materials generally used for kitchen electrical products mainly comprise fluorocarbon coatings, organic silicon coatings and epoxy powder, and the coatings have the defects of poor adhesion and difficult cleaning.
Therefore, in order to solve the problem that the oil stains on the surface of the kitchen household electrical appliance are difficult to clean, a coating which is strong in adhesive force and easy to clean needs to be developed.
Disclosure of Invention
The invention aims to solve the problems of poor adhesion and difficult cleaning of the surface coating of the kitchen electrical appliance products 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, fluorine modified polysilazane, alkylsilane, inorganic antibacterial agent and solvent;
the fluorine-modified polysilazane has a structure represented by the formula (1), the alkylsilane has a structure represented by the formula (2),
Figure BDA0003096988940000021
wherein,
in the formula (1), R1Is selected from C3-30Perfluoroalkyl group of (1), C3-30Perfluoroheteroalkyl group of (A), C3-30Perfluoroalkylene of (A), C3-30At least one of perfluoroheteroalkylene(s), R2And R3Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy and C1-20alkyl-NH-, n is an integer from 1 to 100;
in the formula (2), R4Is selected from C1-20Alkyl of R5、R6And R7Each independently selected from C1-20Alkoxy group of (a);
based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the fluorine-modified polysilazane is 5-30 mass%, the content of the alkylsilane is 0.01-0.5 mass%, the content of the inorganic antibacterial agent is 0.1-1 mass%, and the content of the solvolane 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 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.
The coating composition is obtained by compounding specific amounts of the fluorosilicone resin, the fluorine modified polysilazane, the alkylsilane, the inorganic antibacterial agent and the solvent, the coating prepared by using the coating composition has the advantage of good adhesiveness, and the obtained coating is applied to kitchen electrical products, so that the defect that the surface of the traditional kitchen electrical products is difficult to clean can be effectively overcome, and the hydrophobic and oleophobic effects of kitchen electrical appliances can be given.
The inventors have found that coatings prepared using the compositions of the present invention exhibit significantly better adhesion and hydrophobicity when applied to metal 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 is3-30The perfluoroalkyl group of (A) is an alkyl group having 3 to 30 carbon atoms in total and all hydrogen atoms in the alkyl group being substituted with fluorine atoms, and includes straight-chain perfluoroalkyl groups and branched-chain perfluoroalkyl groups, and "C" is a group3-20The perfluoroalkyl group of (1) has a similar explanation as this, only differing in the total number of carbon atoms.
Said C is3-30The perfluoroalkyl group of (A) is an alkyl group having 3 to 30 carbon atoms in total and all hydrogen atoms in the alkyl group being substituted with fluorine atoms, and includes straight-chain perfluoroalkyl groups and branched-chain perfluoroalkyl groups, and "C" is a group3-20The perfluoroalkyl group of (1) has a similar explanation as this, only differing in the total number of carbon atoms.
Said C is3-30The perfluoroheteroalkyl group of (a) means a group having 3 to 30 carbon atoms in total and containing at least one heteroatom, which may be, for example, at least one of N, O or S, and any of the alkyl groups may haveSubstituted by fluorine atoms in the substituted positions, including straight-chain perfluoroheteroalkyl and branched perfluoroheteroalkyl,' C3-20The perfluoroheteroalkyl group "has a similar interpretation, only differing in the total number of carbon atoms.
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- "and" C8-18alkyl-NH- "has a similar interpretation, only differing in the total number of carbon atoms.
As described above, 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, fluorine modified polysilazane, alkylsilane, inorganic antibacterial agent and solvent;
the fluorine-modified polysilazane has a structure represented by the formula (1), the alkylsilane has a structure represented by the formula (2),
Figure BDA0003096988940000051
wherein,
in the formula (1), R1Is selected from C3-30Perfluoroalkyl group of (1), C3-30Perfluoroheteroalkyl group of (A), C3-30Perfluoroalkylene of (A), C3-30At least one of perfluoroheteroalkylene(s), R2And R3Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy and C1-20alkyl-NH-, n is an integer from 1 to 100;
in the formula (2), R4Is selected from C1-20Alkyl of R5、R6And R7Each independently selected from C1-20Alkoxy group of (a);
based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the fluorine-modified polysilazane is 5-30 mass%, the content of the alkylsilane is 0.01-0.5 mass%, the content of the inorganic antibacterial agent is 0.1-1 mass%, and the content of the solvolane 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 fluorine-modified polysilazane is 5 to 15 mass%, the content of the alkylsilane is 0.01 to 0.1 mass%, the content of the inorganic antibacterial agent is 0.1 to 0.5 mass%, and the content of the solvolane is 60 to 85 mass%, based on the total mass of the coating composition. The inventors have found that with the preferred embodiment a better adhesion of the coating is obtained.
Preferably, the weight average molecular weight of the fluorosilicone resin is 100-10000, preferably 300-3000, and the relative density (25 ℃) of the fluorosilicone resin is 0.91-1.33g/cm3。
According to a particularly preferred embodiment, the fluorosilicone resin is a fluorosilicone resin available from denham resins ltd. In this preferable case, a coating composition having high hardness and excellent adhesion can be obtained.
Preferably, in formula (1), R1Is selected from C3-20Perfluoroalkyl group of (1), C3-20Perfluoroheteroalkyl group of (A), C3-20Perfluoroalkylene of (A), C3-20At least one of perfluoroheteroalkylene(s), R2And R3Each independently selected from hydrogen and C1-10Alkyl of (C)2-10Alkenyl of, C6-12Aryl of (C)1-10Alkoxy and C1-10alkyl-NH-, n is an integer from 1 to 20.
Preferably, the weight average molecular weight of the fluorine-modified polysilazane is 100-10000, preferably 500-5000.
More preferably, the fluorine-modified polysilazane is a fluorine-modified polysilazane available from silicone oil, Inc., about tower, Anhui. The inventors have found that in this preferred case, the coating obtained from the coating composition is easier to clean.
Preferably, in formula (2), R4Is selected from C8-18Alkyl of R5、R6And R7Each independently selected from C1-10Alkoxy group of (2).
Preferably, the alkylsilane is selected from at least one of octyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylmethyldimethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane.
According to a particularly preferred embodiment, the alkylsilane is at least one of hexadecyltrimethoxysilane, dodecyltrimethoxysilane and octadecyltrimethoxysilane. In this preferred case, the hydrophobic and oleophobic effect of the coating composition can be significantly enhanced.
Preferably, the solvent is selected from at least one of n-hexane, n-octane, n-decane, chloroform, dichloromethane, dichloroethylene, n-butyl ether, diethyl ether, petroleum ether, toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, and butyl acetate.
Preferably, the inorganic antimicrobial agent is selected from at least one of titanium dioxide, zinc oxide, zinc sulfide, cadmium sulfide, silver oxide, silver-loaded calcium phosphate, silver-loaded zeolite, and silver-loaded titanium dioxide.
Preferably, the average particle size of the nano zinc oxide is 50-10000 nm.
More preferably, the nano titanium dioxide has an average particle size of 50 to 10000 nm.
According to a particularly preferred embodiment, the inorganic antimicrobial agent is silver-loaded zeolite available from inorganic materials of mansion xindakang, inc.
As previously mentioned, a second aspect of 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 and alkyl silane to obtain a diluent;
(2) and carrying out a second contact reaction on the diluent, the fluorine modified polysilazane and the inorganic antibacterial agent 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.
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.
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.
As previously mentioned, a third aspect of the invention provides a coating produced by the method of the second aspect.
As previously mentioned, a fourth aspect of the invention provides the use of a coating as described by the third aspect in an appliance.
As previously mentioned, a fifth aspect of the invention provides the use of the coating of the third aspect in a kitchen appliance.
As described above, the sixth aspect of the present invention provides a coating layer obtained by applying the coating material according to the third aspect to the surface of a substrate by spraying, followed by drying and curing.
Preferably, the substrate is a metal substrate.
Preferably, the metal in the metal matrix is selected from at least one of titanium, aluminum, iron and alloys.
More preferably, the metal substrate is a stainless steel substrate or an aluminum plate 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.
The present invention will be described in detail below by way of examples.
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: a designation YS1046, available from Jenan Yi resin Limited;
fluorosilicone resin-2: a designation YS1056, available from Jenan Yi resin Limited;
fluorine-silicon resin-3: a designation YS1036 from Jenan resin Productance Limited;
silicone resin: no. H201 Shenzhen Jipeng silicon fluorine Material Co Ltd
Fluorine-modified polysilazane-1: number average molecular weight 900, number IOTA-9150, available from ai xiao ta silicone oil ltd, Anhui;
fluorine-modified polysilazane-2: number average molecular weight 1500, mark IOTA-9118, available from Anhui Aiyuta Silicone oil Co., Ltd;
fluorine-modified polysilazane-3: number average molecular weight is 1800, number IOTA-9118, available from ai xiao ta silicone oil ltd, Anhui;
organic polyborosilazane: number average molecular weight of 700, number IOTA-9120, available from ai xiao ta silicone oil ltd, Anhui;
alkyl silane: hexadecyl trimethoxysilane, available from caruncle morning light chemical;
alkyl silane: dodecyl triethoxysilane, available from caruncle morning light chemical co;
alkyl silane: octadecyltriethoxysilane, available from caruncle morning light chemical;
alkyl silane: hexadecyl triethoxysilane, available from caruncle morning light chemical ltd;
alkyl silane: octadecyltrimethoxysilane, available from caruncle chenopodium chemical;
inorganic antibacterial agents: the nano zinc oxide has the average particle size of 100nm and is purchased from Xuancheng crystal new material Co., Ltd;
inorganic antibacterial agents: the nano titanium dioxide has the average particle size of 100nm and is purchased from Hangzhou Wanjing new material Co., Ltd;
inorganic antibacterial agents: silver-loaded zeolite, available from mansion, xindakang, inorganic materials, ltd;
inorganic antibacterial agents: silver-loaded calcium phosphate, available from xiamengxidakang inorganic materials ltd;
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: n-hexane, available from jonan yuno chemical co;
solvent: ethyl acetate, available from dennay chemical ltd;
an aluminum plate substrate: 3003, available from Yi Xin metals, Inc. of Dongguan;
cold-rolled steel sheet base: a designation dc03, available from Bao Steel company;
galvanized steel sheet substrate: the designation dc03DX51D, available from Bao Steel company;
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) sequentially adding fluorosilicone resin, hexadecyl trimethoxy silane and n-butyl ether into a reaction kettle at room temperature, and stirring at 500rpm for 20min to obtain a diluent;
(2) and (3) adding the fluorine modified polysilazane and the nano zinc oxide 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 substrate by using a spraying instrument to form a coating layer, then drying the substrate with the coating layer at room temperature for 1h, and then putting the substrate with the coating layer into an oven with the temperature of 130 ℃ 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 fluorine modified polysilazane.
Comparative example 3
This comparative example was carried out using a procedure similar to that of example 1, except that: the formula does not contain inorganic antibacterial agents.
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 for replacing fluorine modified polysilazane.
TABLE 1
Figure BDA0003096988940000111
Figure BDA0003096988940000121
Table 1 (continuation 1)
Figure BDA0003096988940000122
Figure BDA0003096988940000131
Test example 1
The water contact angle, hardness, adhesion, antibacterial rate and other performances of the example and comparative products are tested, and the results are shown in the following table 2.
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;
performing adhesion performance test on the coating according to the national standard GB/T9286-1998;
the coating was tested for antibacterial efficiency according to national standard QB/T2591-.
TABLE 2
Water contact angle/° c Hardness of Adhesion force Antibacterial ratio/%)
Example 1 103.6 5H 0 99.9
Example 2 104.5 6H 0 99.7
Example 3 102.4 5H 0 99.9
Example 4 101.7 6H 0 99.9
Example 5 102.6 6H 0 99.9
Example 6 103.8 5H 0 99.6
Comparative example 1 100.2 4H 0 99.5
Comparative example 2 99.8 3H 0 99.3
Comparative example 3 101.3 3H 0 60.1
Comparative example 4 95.3 4H 0 56.5
Comparative example 5 96.1 5H 0 62.8
The results in table 2 show that the coating composition obtained by compounding the fluorosilicone resin, the fluorine-modified polysilazane, the alkylsilane, the inorganic antibacterial agent and the solvent according to the specific ratio is used for preparing a coating under specific process conditions, so that the coating with good adhesion, easy cleaning, good antibacterial property and good hydrophobic and oleophobic effects is obtained.
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, fluorine modified polysilazane, alkylsilane, inorganic antibacterial agent and solvent;
the fluorine-modified polysilazane has a structure represented by the formula (1), the alkylsilane has a structure represented by the formula (2),
Figure FDA0003096988930000011
wherein,
in the formula (1), R1Is selected from C3-30Perfluoroalkyl group of (1), C3-30Perfluoroheteroalkyl group of (A), C3-30Perfluoroalkylene of (A), C3-30At least one of perfluoroheteroalkylene(s), R2And R3Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy and C1-20alkyl-NH-, n is an integer from 1 to 100;
in the formula (2), R4Is selected from C1-20Alkyl of R5、R6And R7Each independently selected from C1-20Alkoxy group of (a);
based on the total mass of the coating composition, the content of the fluorosilicone resin is 5-40 mass%, the content of the fluorine-modified polysilazane is 5-30 mass%, the content of the alkylsilane is 0.01-0.5 mass%, the content of the inorganic antibacterial agent is 0.1-1 mass%, and the content of the solvolane 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 fluorine-modified polysilazane is 5 to 15 mass%, the content of the alkylsilane is 0.01 to 0.1 mass%, the content of the inorganic antibacterial agent is 0.1 to 0.5 mass%, and the content of the solvan 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 (25 ℃) of the fluorosilicone resin is 0.91-1.33g/cm3；
Preferably, the fluorosilicone resin is a fluorosilicone resin available from cornan easy resin ltd.
4. The coating composition according to any one of claims 1 to 3, wherein R in formula (1)1Is selected from C3-20Perfluoroalkyl group of (1), C3-20Perfluoroheteroalkyl group of (A), C3-20Perfluoroalkylene of (A), C3-20At least one of perfluoroheteroalkylene(s), R2And R3Each independently selected from hydrogen and C1-10Alkyl of (C)2-10Alkenyl of, C6-12Aryl of (C)1-10Alkoxy and C1-10alkyl-NH-, n is an integer from 1 to 20;
preferably, the weight average molecular weight of the fluorine-modified polysilazane is 100-10000, preferably 500-5000.
5. The coating composition according to any one of claims 1 to 4, wherein R in formula (2)4Is selected from C8-18Alkyl of R5、R6And R7Each independently selected from C1-10Alkoxy group of (a);
preferably, the alkylsilane is selected from at least one of octyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylmethyldimethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane.
6. The coating composition according to any one of claims 1 to 5, wherein the solvent is at least one selected from the group consisting of n-hexane, n-octane, n-decane, chloroform, dichloromethane, dichloroethylene, n-butyl ether, diethyl ether, petroleum ether, toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone and butyl acetate.
7. The coating composition of any one of claims 1-6, wherein the inorganic antimicrobial agent is selected from at least one of titanium dioxide, zinc oxide, zinc sulfide, cadmium sulfide, silver oxide, silver-loaded calcium phosphate, silver-loaded zeolite, and silver-loaded titanium dioxide.
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 and alkyl silane to obtain a diluent;
(2) and carrying out a second contact reaction on the diluent, the fluorine modified polysilazane and the inorganic antibacterial agent 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 produced 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 metal substrate;
preferably, the metal in the metal matrix is selected from at least one of titanium, aluminum, iron and alloys.
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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