Coating composition, coating, preparation method and application thereof, and coating
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:
methyl polysiloxane resin, polysilazane, modified silicone oil, a fluorine-containing surfactant and a solvent;
the polysilazane has a structure represented by the formula (1),
wherein the content of the first and second substances,
in the formula (1), R1、R2And R3Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy group of (C)1-20alkyl-NH-; n is a positive integer, and n enables the weight average molecular weight of the polysilazane to be 100-1000;
based on the total weight of the coating composition, the content of the methyl polysiloxane resin is 5-50 wt%, the content of the polysilazane is 5-25 wt%, the content of the modified silicone oil is 0.005-0.2 wt%, the content of the fluorine-containing surfactant is 0.005-0.15 wt%, and the content of the solvent is 30-85 wt%.
2. The coating composition according to claim 1, wherein the content of the methyl polysiloxane resin is 10 to 35 wt%, the content of the polysilazane is 10 to 20 wt%, the content of the modified silicone oil is 0.02 to 0.08 wt%, the content of the fluorine-containing surfactant is 0.01 to 0.05%, and the content of the solvent is 50 to 75 wt%, based on the total weight of the coating composition.
3. The coating composition of claim 1, wherein the weight average molecular weight of the methylpolysiloxane resin is 300-5000, preferably 1500-3000.
4. The coating composition according to claim 1, wherein, in formula (1), R1、R2And R3Each independently selected from hydrogen and C1-10Alkyl of (C)2-10Alkenyl of, C6-20Aryl of (C)1-10Alkoxy group of (C)1-10alkyl-NH-; n is a positive integer, and n enables the weight average molecular weight of the polysilazane to be 400-900;
preferably, in formula (1), R1、R2And R3Are the same or different, and R1、R2At least one of which is methyl.
5. The coating composition according to claim 1, wherein the modified silicone oil is at least one selected from the group consisting of methyl silicone oil, vinyl silicone oil, methyl hydrogen silicone oil, methyl fluorosilicone oil, polyether modified silicone oil, amino modified silicone oil, and hexadecyl triethoxysilane;
preferably, the modified silicone oil is selected from at least one of methyl silicone oil, vinyl silicone oil, methyl fluorosilicone oil, methyl hydrogen-containing silicone oil and hexadecyl triethoxy silane.
6. The coating composition according to claim 1, wherein the solvent is selected from at least one of n-hexane, n-octane, n-decane, chloroform, dichloromethane, dichloroethylene, diethyl ether, petroleum ether, toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, butyl acetate, ethyl acetate;
preferably, the solvent is at least one selected from n-hexane, toluene, ethyl acetate, acetone, xylene, butyl acetate, petroleum ether.
7. The coating composition according to claim 1, wherein the fluorosurfactant is selected from at least one of perfluoroalkyl phosphate ester, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl amine oxide compound, fluoroaliphatic amine oxide, fluoroaliphatic sodium sulfosuccinate, fluoroaliphatic stearate, fluoroaliphatic phosphate ester, fluoroaliphatic quaternary ammonium salt, fluoroaliphatic polyethylene oxide;
preferably, the fluorosurfactant is selected from at least one of FC-170C from 3M, FC-129 from 3M, FC-430 from 3M, FC-4430 from 3M, FSO from DuPont, FSO-100 from DuPont, FSN-100 from DuPont, FS-63 from DuPont, FS-3100 from DuPont and FS-300 from DuPont, PF-136A from OMNOVA, PF-151N, OMNOVA, and PF-156A from OMNOVA.
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 step 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 methyl phenyl polysiloxane resin and modified silicone oil to obtain a diluent;
(2) and carrying out a second contact reaction on the diluent, polysilazane and a fluorine-containing surfactant 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 300-1000rpm, the temperature is 5-35 ℃, 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 400-800rpm, the temperature is 15-30 ℃, and the time is 15-35 min.
11. The method of claim 9, wherein in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 500-2000rpm, the temperature is 5-35 ℃, and the time is 5-40 min;
preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1000-1600rpm, the temperature is 15-30 ℃, and the time is 10-30 min.
12. A coating produced by the method of any one of claims 8 to 11.
13. Use of the coating as claimed in claim 12 in household appliances, sanitary ware or automobiles.
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 thickness of the coating is 0.1-100 μ ι η, preferably 1-20 μ ι η.
17. Coating according to claim 15 or 16, wherein the drying conditions are at least such that: the temperature is 20-40 deg.C, and the time is 0.5-5 h.
18. Coating according to claim 15 or 16, wherein the conditions of the curing at least satisfy: the temperature is 90-200 ℃ and the time is 0.5-2 h.
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.
In the process of using the household electrical appliance for a long time, more oil stains and stains can be adhered to the surface of the household electrical appliance, and the cleaning is very troublesome.
The surface coating material generally used for kitchen electrical products mainly comprises fluorocarbon coating, organosilicon coating and epoxy powder.
However, the coating has the disadvantages of low hardness, poor adhesion, poor temperature resistance, difficult cleaning, potential food contact safety hazards and the like.
Therefore, the development of a coating which is high temperature resistant, easy to clean, hydrophobic and oleophobic is of great significance in the application of kitchen appliances.
Disclosure of Invention
The invention aims to solve the problems that the surfaces of electric appliances, especially kitchen electric appliances, in the prior art are easy to be adhered with oil stains and difficult to clean, and the coating hardness is low.
In order to achieve the above object, one 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:
methyl polysiloxane resin, polysilazane, modified silicone oil, a fluorine-containing surfactant and a solvent;
the polysilazane has a structure represented by the formula (1),
wherein the content of the first and second substances,
in the formula (1), R1、R2And R3Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy group of (C)1-20alkyl-NH-; n is a positive integer, and n enables the weight average molecular weight of the polysilazane to be 100-1000;
based on the total weight of the coating composition, the content of the methyl polysiloxane resin is 5-50 wt%, the content of the polysilazane is 5-25 wt%, the content of the modified silicone oil is 0.005-0.2 wt%, the content of the fluorine-containing surfactant is 0.005-0.15 wt%, and the content of the solvent is 30-85 wt%.
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.
A third aspect of the invention provides a coating produced by the method of the second aspect.
A fourth aspect of the invention provides the use of a coating according to the third aspect in a domestic appliance, a bathroom fitting or an automobile.
According to a fifth aspect of the invention, there is provided the use of a coating according to the third aspect in a kitchen appliance.
According to a sixth aspect of the present invention, there is provided a coating layer obtained by spraying the coating material according to the third aspect onto a surface of a substrate and then curing the coating material.
According to the invention, the coating composition is obtained by compounding methyl polysiloxane resin, polysilazane, modified silicone oil, fluorine surfactant and solvent with specific contents, and the coating prepared from the coating composition has the advantages of high hardness and easiness in cleaning. Moreover, the coating formed by the composition system has obviously lower surface energy, and can improve the hydrophobic and oleophobic effects of the coating.
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.
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 same applies to alkyl groups "and the like, differing only in the total number of carbon atoms.
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 same applies to the "alkenyl group" and the like, differing only in the total number of carbon atoms.
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 same applies to aryl "and the like, differing only 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 "etc. has a similar explanation as 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"can be substitutedChanged to be selected from C1-20Any group of alkyl groups. "C1-10alkyl-NH- "and the like have similar explanations, differing only 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:
methyl polysiloxane resin, polysilazane, modified silicone oil, a fluorine-containing surfactant and a solvent;
the polysilazane has a structure represented by the formula (1),
wherein the content of the first and second substances,
in the formula (1), R1、R2And R3Each independently selected from hydrogen and C1-20Alkyl of (C)2-20Alkenyl of, C6-20Aryl of (C)1-20Alkoxy group of (C)1-20alkyl-NH-; n is a positive integer, and n enables the weight average molecular weight of the polysilazane to be 100-1000;
based on the total weight of the coating composition, the content of the methyl polysiloxane resin is 5-50 wt%, the content of the polysilazane is 5-25 wt%, the content of the modified silicone oil is 0.005-0.2 wt%, the content of the fluorine-containing surfactant is 0.005-0.15 wt%, and the content of the solvent is 30-85 wt%.
Preferably, the content of the methyl polysiloxane resin is 10-35 wt%, the content of the polysilazane is 10-20 wt%, the content of the modified silicone oil is 0.02-0.08 wt%, the content of the fluorine-containing surfactant is 0.01-0.05 wt%, and the content of the solvent is 50-75 wt%, based on the total weight of the coating composition. The inventors have found that with this preferred coating composition a harder, easier to clean coating is obtained.
Preferably, the weight average molecular weight of the methylpolysiloxane resin is 300-5000, preferably 1500-3000.
Particularly preferably, the methyl polysiloxane resin is selected from the methyl polysiloxane resin with the trademark SH-9601 of Shenzhen Shenpeng silicon fluoride materials Limited or the methyl polysiloxane resin with the trademark SH-9602 of Shenzhen Shenpeng silicon fluoride materials Limited. The inventors have found that with this preferred coating composition a harder, easier to clean coating is obtained.
Preferably, in formula (1), R1、R2And R3Each independently selected from hydrogen and C1-10Alkyl of (C)2-10Alkenyl of, C6-20Aryl of (C)1-10Alkoxy group of (C)1-10alkyl-NH-, n is a positive integer, and n is such that the weight average molecular weight of the polysilazane is 400-900.
Particularly preferably, in the formula (1), R1、R2And R3Are the same or different, and R1、R2At least one of which is methyl.
Particularly preferably, the polysilazane is at least one selected from methylpolysilazanes under the designations 440191, 379212, 52619 of merck reagent. The inventors have found that with this preferred coating composition a harder, easier to clean coating is obtained.
Preferably, the modified silicone oil is at least one of methyl silicone oil, vinyl silicone oil, methyl hydrogen-containing silicone oil, methyl fluorosilicone oil, polyether modified silicone oil, amino modified silicone oil and hexadecyl triethoxy silane.
More preferably, the modified silicone oil is at least one selected from the group consisting of methyl silicone oil, vinyl silicone oil, methyl fluorosilicone oil, methyl hydrogen-containing silicone oil, and hexadecyl triethoxy silane. The inventors have found that with this preferred coating composition a harder, easier to clean coating is obtained.
Preferably, the solvent is at least one selected from the group consisting of n-hexane, n-octane, n-decane, chloroform, dichloromethane, dichloroethylene, diethyl ether, petroleum ether, toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, butyl acetate, and ethyl acetate.
More preferably, the solvent is at least one selected from the group consisting of n-hexane, toluene, ethyl acetate, acetone, xylene, butyl acetate, petroleum ether.
Preferably, the fluorinated surfactant is at least one selected from the group consisting of perfluoroalkyl phosphate esters, perfluoroalkyl betaines, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl amine oxide compounds, fluoroaliphatic amine oxides, fluoroaliphatic sodium sulfosuccinates, fluoroaliphatic stearates, fluoroaliphatic phosphate esters, fluoroaliphatic quaternary ammonium salts, and fluoroaliphatic polyethylene oxides.
More preferably, the fluorosurfactant is selected from at least one of FC-170C from 3M, FC-129 from 3M, FC-430 from 3M, FC-4430 from 3M, FSO from DuPont, FSO-100 from DuPont, FSN-100 from DuPont, FS-63 from DuPont, FS-3100 from DuPont and FS-300 from DuPont, PF-136A from OMNOVA N, OMNOVA and PF-156A from OMNOVA.
Particularly preferably, the fluorosurfactant is selected from at least one of FC-430 of 3M, FC-4430 of 3M, FS-3100 of dupont, and PF-156A of OMNOVA, and the inventors have found that the coating composition obtained in this preferred case produces a coating that is easier to clean and has better hydrophobic and oleophobic properties.
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.
Preferably, 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 methyl phenyl polysiloxane resin and modified silicone oil to obtain a diluent;
(2) and carrying out a second contact reaction on the diluent, polysilazane and a fluorine-containing surfactant to obtain the coating.
Preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 300-1000rpm, the temperature is 5-35 ℃, and the time is 10-60 min.
More preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 400-800rpm, the temperature is 15-30 ℃, and the time is 15-35 min.
Preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 500-2000rpm, the temperature is 5-35 ℃, and the time is 5-40 min.
More preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1000-1600rpm, the temperature is 15-30 ℃, and the time is 10-30 min.
As previously mentioned, a third aspect of the invention provides a coating produced by the method of the second aspect.
As mentioned above, a fourth aspect of the invention provides the use of a coating according to the third aspect in a domestic appliance, a sanitary fitting or a vehicle.
As mentioned above, a fifth aspect of the invention provides the use of a coating according to 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 glass substrate.
In particular, the inventors have found that coatings prepared using the compositions of the present invention have significantly better easy-to-clean properties when applied to glass substrates.
Preferably, the thickness of the coating is 0.1 μm to 100 μm, preferably 1 μm to 20 μm.
Preferably, the drying conditions at least satisfy: the temperature is 20-40 deg.C, and the time is 0.5-5 h.
More preferably, the drying conditions at least satisfy: the temperature is 20-25 ℃ and the time is 1-3 h.
Preferably, the curing conditions at least satisfy: the temperature is 90-200 ℃ and the time is 0.5-5 h.
More preferably, the curing conditions at least satisfy: the temperature is 120 ℃ 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, various raw materials used unless otherwise specified are commercially available.
In the following examples, the room temperature or room temperature according to the present invention is 25. + -. 2 ℃ unless otherwise specified.
Methylpolysiloxane resin I: the weight-average molecular weight is 1800, the mark SH-9601, and the weight-average molecular weight is purchased from Shenzhen Shenpeng silicon fluoride materials GmbH;
methylpolysiloxane resin II: the weight-average molecular weight is 2400, the trademark SH-9602, and the weight-average molecular weight is purchased from Shenzhen Jipeng silicon fluoride materials GmbH;
methylpolysiloxane resin III: the weight-average molecular weight is 3000, the mark SH-9602, purchased from Shenzhen Jipeng silicon fluoride materials GmbH;
methyl phenyl polysiloxane resin: the weight average molecular weight was 2800, designation SH-021, available from Jinan Yisheng resins, Inc.
Methylpolysilazane I: weight average molecular weight 600, designation 440191, available from merck reagent;
methylpolysilazane II: weight average molecular weight 800, designation 379212, available from merck reagent;
methylpolysilazane III: weight average molecular weight 450, designation 52619, available from merck reagent;
1,1,3, 3-tetramethyldisilazane: weight average molecular weight 133.34, designation 741869, available from merck reagent;
methyl silicone oil: purchased from Shenzhen Jipeng silicon fluoride materials GmbH;
methyl fluorosilicone oil: purchased from Shenzhen Jipeng silicon fluoride materials GmbH;
methyl hydrogen silicone oil: purchased from Shenzhen Jipeng silicon fluoride materials GmbH;
vinyl silicone oil: purchased from Shenzhen Jipeng silicon fluoride materials GmbH;
hexadecyl triethoxysilane: purchased from Shenzhen Jipeng silicon fluoride materials GmbH;
fluorosurfactant PF-156A, available from OMNOVA corporation;
fluorosurfactant PF-136, available from OMNOVA corporation;
fluorosurfactant FC-4430 available from 3M company;
fluorosurfactant FS-3100, available from dupont;
fluorosurfactants FS-63, available from DuPont;
fluorosurfactants FS-300, available from DuPont;
fluorosurfactant FSO-100, available from dupont;
fluorosurfactant FC-170C available from 3M company;
glass substrate: available from Asaho glass Co., Ltd, Dongguan.
Spraying equipment: model W-71, available from Nippon rock Co., Ltd., spraying distance 200(mm), nozzle diameter 0.8mm, and air pressure 0.3 MPa.
The amounts of the components in the following examples are all expressed in "wt%" based on the total mass of the coating composition, and the total mass of the coating composition is 1000 g.
Example 1
This example illustrates the formulation and processing parameters of the coating composition of the present invention according to Table 1, and the preparation of the coating according to the method described below.
The method for preparing the coating comprises the following steps:
(1) under the conditions of stirring speed of 600rpm and room temperature, carrying out first contact reaction on toluene, methyl polysiloxane resin and methyl silicone oil, and reacting for 20min to obtain a diluent;
(2) carrying out a second contact reaction on the diluent obtained in the step (1), methyl polysilazane and a fluorine-containing surfactant PF-156A at the stirring speed of 1000rpm and at room temperature, and reacting for 20min to obtain the coating;
(3) and (3) spraying the coating obtained in the step (2) on the surface of a glass substrate to form a coating layer, drying the glass substrate with the coating layer at room temperature for 1h, putting the glass substrate with the coating layer into an oven, and curing at the temperature of 150 ℃ 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 modified silicone oil was not included in the formulation, see in particular table 1.
Comparative example 2
This comparative example was carried out using a procedure similar to that of example 1, except that: the formulations contained no fluorinated surfactant, as shown in table 1.
Comparative example 3
This comparative example was carried out using a procedure similar to that of example 1, except that: the formula adopts equal weight of methyl phenyl polysiloxane resin to replace methyl polysiloxane resin.
Comparative example 4
This comparative example was carried out using a procedure similar to that of example 1, except that: in the formula, 1,3, 3-tetramethyl disilazane with equal weight is used to replace polysilazane.
TABLE 1
Table 1 (continuation 1)
Table 1 (continuation 1)
Test example 1
The example and comparative products were subjected to water contact angle, hardness and adhesion tests, and the results are shown in table 2 below.
Wherein, the water contact angle is tested by adopting a full-automatic water contact angle tester;
testing the hardness of the coating according to the national standard GB/T6739-2009;
the adhesion performance of the coating was tested according to the national standard GB/T9286-1998.
TABLE 2
Water contact angle/° c
hardness/H
Adhesion force
Example 1
104.1
6H
0
Example 2
105.6
6H
0
Example 3
103.8
5H
0
Example 4
102.6
5H
0
Example 5
105.8
6H
0
Example 6
106.3
5H
0
Example 7
105.9
6H
0
Example 8
103.8
5H
0
Example 9
106.2
6H
0
Comparative example 1
94.3
3H
0
Comparative example 2
95.1
3H
0
Comparative example 3
96.2
4H
0
Comparative example 4
97.4
4H
0
As can be seen from the results in Table 2, the coating prepared by using the coating composition with the specific ratio has the advantages of easy cleaning and high hardness; meanwhile, the coating is applied to kitchen appliances and also has hydrophobic and oleophobic effects.
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.
