1. An easy-to-clean coating composition, which is characterized by comprising the following components stored independently or in a mixture of more than two of the components: acrylic acid modified polysiloxane resin, perhydropolysilazane, a solvent, modified silicone oil, a silane coupling agent and nano metal oxide;

the perhydropolysilazane has a structure represented by the formula (1),

wherein the content of the first and second substances,

in the formula (1), n is a positive integer, and n enables the weight average molecular weight of the perhydropolysilazane to be 100-1000;

based on the total weight of the coating composition, the content of the acrylic modified polysiloxane resin is 5-50 wt%, the content of the perhydropolysilazane is 4-20 wt%, the content of the solvent is 25-85 wt%, the content of the modified silicone oil is 0.01-0.1 wt%, the content of the silane coupling agent is 0.01-0.1 wt%, and the content of the nano metal oxide is 0.5-5 wt%.

2. The coating composition according to claim 1, wherein the acrylic modified polysiloxane resin is contained in an amount of 10 to 30 wt%, the perhydropolysilazane is contained in an amount of 5 to 10 wt%, the solvent is contained in an amount of 50 to 85 wt%, the modified silicone oil is contained in an amount of 0.01 to 0.03 wt%, the silane coupling agent is contained in an amount of 0.01 to 0.05 wt%, and the nano metal oxide is contained in an amount of 1 to 3 wt%, based on the total weight of the coating composition.

3. The coating composition according to claim 1 or 2, wherein the weight average molecular weight of the acrylic modified polysiloxane resin is 500-12000, preferably 1000-8000.

4. The coating composition as claimed in claim 1, wherein, in formula (1), n is such that the perhydropolysilazane has a weight average molecular weight of 300-600.

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-containing silicone oil, methyl fluorosilicone oil, polyether modified silicone oil, and amino modified silicone oil;

preferably, the modified silicone oil is at least one selected from vinyl silicone oil, methyl hydrogen-containing silicone oil, methyl silicone oil, polyether modified silicone oil and methyl fluorosilicone oil.

6. The coating composition of claim 1, wherein the silane coupling agent is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, isobutyltriethoxysilane, 3-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane;

preferably, the silane coupling agent is selected from at least one of gamma-mercaptopropyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

7. The coating composition of claim 1, wherein the nano metal oxide is selected from at least one of nano silica, nano zirconia, nano alumina, nano manganese oxide, nano titania, nano zinc oxide;

preferably, the nano metal oxide is at least one selected from nano titanium oxide, nano zirconium oxide, nano aluminum oxide and nano zinc oxide.

8. The coating composition according to claim 1, wherein the nano metal oxide has an average particle size of 15-80nm, preferably 20-60 nm.

9. 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 of toluene, acetone and butyl acetate.

10. A method of preparing an easy-clean coating, the method comprising: mixing the components of the easy-to-clean coating composition of any one of claims 1-9.

11. The method of claim 10, wherein the step of mixing the components of the easy-clean coating composition comprises the steps of:

(1) in the presence of a solvent, carrying out a first contact reaction on acrylic acid modified polysiloxane resin and modified silicone oil to obtain a diluent;

(2) and carrying out a second contact reaction on the diluent, perhydropolysilazane, nano oxide and a silane coupling agent to obtain the easy-to-clean coating.

12. The method of claim 11, wherein in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 300-800rpm, the temperature is 5-60 ℃, and the time is 5-60 min;

preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 500-700rpm, the temperature is 20-30 ℃, and the time is 15-30 min.

13. The process according to claim 11 or 12, wherein in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1000-2000rpm, the temperature is 5-60 ℃, and the time is 5-60 min;

preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1200-1500rpm, the temperature is 20-30 ℃, and the time is 10-20 min.

14. An easy-to-clean coating prepared by the method of any one of claims 10 to 13.

15. Use of the easy-to-clean coating of claim 14 in household appliances, bathroom fixtures, or automobiles.

16. Use of the easy-to-clean coating of claim 14 in a kitchen appliance.

17. An easy-to-clean coating, which is obtained by spraying the easy-to-clean coating as claimed in claim 14 on the surface of a substrate, and then drying and curing the coating in sequence.

18. Easy-to-clean coating according to claim 17, wherein the easy-to-clean coating has a thickness of 0.1-100 μm, preferably 5-40 μm.

19. Easy-to-clean coating according to claim 17 or 18, wherein the drying conditions at least satisfy: the temperature is 20-40 deg.C, and the time is 0.5-5 h.

20. The easy-clean coating according to any one of claims 17-19, wherein the curing conditions at least satisfy: the temperature is 90-200 ℃ and the time is 0.5-5 h.

Background

Along with the increasing requirements of people on living quality, the requirements of people on household appliances are also increasing, and especially for kitchen appliances which are contacted with various oil stains, seasonings and acid and alkali at high frequency for a long time, the requirements of people are that the products have the characteristics of no oil smoke exudation and easy cleaning of oil stains on the surfaces of the products in the working process besides the conventional product performance.

The surface energy is an important factor influencing the antifouling effect of the paint, and the low-surface-energy coating is a coating with the critical surface tension of 25-30 mN/m when contacting with a substrate. At present, antifouling coatings gradually evolve from single materials to low-surface-energy modified composite coatings, such as epoxy-modified organic silicon resin coatings, organic silicon-modified acrylic resin coatings, organic silicon-modified polyurethane coatings, organic silicon-modified fluorocarbon resin coatings and the like. However, the coating obtained by the coating still has the defects of low hardness, poor adhesion, poor temperature resistance, difficult cleaning, potential food contact safety hazard and the like.

Therefore, the development of a coating which has high hardness, high temperature resistance, easy cleaning and hydrophobic and oleophobic properties is of great significance in the application of kitchen appliances.

Disclosure of Invention

The invention aims to solve the problems that in the prior art, oil stains are easy to adhere to the surfaces of kitchen electrical products and the kitchen electrical products are difficult to clean.

In order to achieve the above object, a first aspect of the present invention provides an easy-to-clean coating composition comprising the following components stored independently of each other or in a mixture of two or more of them: acrylic acid modified polysiloxane resin, perhydropolysilazane, a solvent, modified silicone oil, a silane coupling agent and nano metal oxide;

the perhydropolysilazane has a structure represented by the formula (1),

wherein the content of the first and second substances,

in the formula (1), n is a positive integer, and n enables the weight average molecular weight of the perhydropolysilazane to be 100-1000;

based on the total weight of the coating composition, the content of the acrylic modified polysiloxane resin is 5-50 wt%, the content of the perhydropolysilazane is 4-20 wt%, the content of the solvent is 25-85 wt%, the content of the modified silicone oil is 0.01-0.1 wt%, the content of the silane coupling agent is 0.01-0.1 wt%, and the content of the nano metal oxide is 0.5-5 wt%.

A second aspect of the present invention provides a method of preparing an easy-clean coating, the method comprising: mixing the components of the easy-to-clean coating composition of the first aspect.

In a third aspect of the invention, there is provided an easy-to-clean coating obtained by the method of the second aspect.

A fourth aspect of the invention provides the use of the easy-to-clean coating of the third aspect in household appliances, bathroom fixtures or automobiles.

According to a fifth aspect of the invention, there is provided use of the high temperature resistant coating of the third aspect in a kitchen appliance.

The sixth aspect of the invention provides an easy-to-clean coating, which is obtained by spraying the easy-to-clean coating of the third aspect on a substrate, and then drying and curing the coating in sequence.

According to the invention, the coating composition is obtained by compounding the acrylic acid modified polysiloxane resin, the perhydropolysilazane, the solvent, the modified silicone oil, the silane coupling agent and the nano metal oxide with specific contents, and the coating prepared by using the coating composition has the advantages of high hardness and easiness in cleaning.

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.

As described above, the first aspect of the present invention provides an easy-to-clean coating composition containing the following components stored independently of each other or in a mixture of two or more of them: acrylic acid modified polysiloxane resin, perhydropolysilazane, a solvent, modified silicone oil, a silane coupling agent and nano metal oxide;

the perhydropolysilazane has a structure represented by the formula (1),

wherein the content of the first and second substances,

in the formula (1), n is a positive integer, and n enables the weight average molecular weight of the perhydropolysilazane to be 100-1000;

based on the total weight of the coating composition, the content of the acrylic modified polysiloxane resin is 5-50 wt%, the content of the perhydropolysilazane is 4-20 wt%, the content of the solvent is 25-85 wt%, the content of the modified silicone oil is 0.01-0.1 wt%, the content of the silane coupling agent is 0.01-0.1 wt%, and the content of the nano metal oxide is 0.5-5 wt%.

Preferably, the content of the acrylic modified polysiloxane resin is 10-30 wt%, the content of the perhydropolysilazane is 5-10 wt%, the content of the solvent is 50-85 wt%, the content of the modified silicone oil is 0.01-0.03 wt%, the content of the silane coupling agent is 0.01-0.05 wt%, and the content of the nano metal oxide is 1-3 wt%, based on the total weight of the coating composition. The inventors have found that with this preferred embodiment, a coating with higher hardness and better ease of cleaning can be obtained.

Preferably, the weight average molecular weight of the acrylic-modified polysiloxane resin is 500-12000, preferably 1000-8000.

Particularly preferably, the acrylic modified polysiloxane resin is an acrylic modified polysiloxane resin available from new four seas, Hubei. The inventors have found that with this preferred coating composition a harder, easier to clean coating is obtained.

Preferably, in formula (1), n is such that the perhydropolysilazane has a weight average molecular weight of 300-600.

Particularly preferably, the polysilazane is selected from the group consisting of the polysilazane sold by the company IOTA-PHPS, ibie, or the polysilazane sold by the company DURAZANE1800, 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 selected from the group consisting of methyl silicone oil, vinyl silicone oil, methyl hydrogen-containing silicone oil, methyl fluorosilicone oil, polyether modified silicone oil and amino modified silicone oil.

More preferably, the modified silicone oil is at least one selected from vinyl silicone oil, methyl hydrogen-containing silicone oil, methyl silicone oil, polyether modified silicone oil and methyl fluorosilicone oil. The inventors have found that the coating compositions obtained in this preferred case have the advantage that the coatings produced are easier to clean.

Preferably, the silane coupling agent is at least one selected from the group consisting of gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, isobutyltriethoxysilane, 3-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and 3-aminopropyltriethoxysilane.

More preferably, the silane coupling agent is at least one selected from the group consisting of gamma-mercaptopropyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-methacryloxypropyltrimethoxysilane.

Preferably, the nano metal oxide is at least one selected from nano silicon oxide, nano zirconium oxide, nano aluminum oxide, nano manganese oxide, nano titanium oxide and nano zinc oxide.

More preferably, the nano metal oxide is at least one selected from nano titanium oxide, nano zirconium oxide, nano aluminum oxide and nano zinc oxide. The inventors have found that the coating compositions obtained in this preferred case have the advantage of producing coatings with a higher hardness and easier cleanability.

Particularly preferably, the average particle size of the nano metal oxide is 15 to 80nm, preferably 20 to 60 nm.

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.

Particularly preferably, the solvent is at least one of toluene, acetone and butyl acetate.

As previously mentioned, a second aspect of the present invention provides a method of preparing an easy-clean coating, the method comprising: mixing the components of the easy-to-clean coating composition of the first aspect.

According to a particularly preferred embodiment, the mixing of the components of the easy-clean coating composition comprises the steps of:

(1) in the presence of a solvent, carrying out a first contact reaction on acrylic acid modified polysiloxane resin and modified silicone oil to obtain a diluent;

(2) and carrying out a second contact reaction on the diluent, perhydropolysilazane, nano oxide and a silane coupling agent to obtain the easy-to-clean coating.

Preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 300-800rpm, the temperature is 5-60 ℃, and the time is 5-60 min.

Particularly preferably, in step (1), the conditions of the first contact reaction at least satisfy: the stirring speed is 500-700rpm, the temperature is 20-30 ℃, 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 5-60 ℃, and the time is 5-60 min.

Particularly preferably, in step (2), the conditions of the second contact reaction at least satisfy: the stirring speed is 1200-1500rpm, the temperature is 20-30 ℃, and the time is 10-20 min.

As previously mentioned, a third aspect of the invention provides an easy-to-clean coating produced by the method of the second aspect.

As previously mentioned, a fourth aspect of the invention provides the use of the easy-to-clean coating of the third aspect in household appliances, bathroom fixtures or automobiles.

As previously mentioned, a fifth aspect of the invention provides the use of the easy-clean coating of the third aspect in a kitchen appliance.

As described above, the sixth aspect of the present invention provides an easy-to-clean coating obtained by spraying the coating material of the third aspect on the surface of a substrate and then drying and curing the coating material in this order.

Preferably, the substrate is a glass substrate. In particular, the inventors have found that coatings prepared using the compositions of the present invention provide significantly better ease of cleaning when applied to glass substrates.

Preferably, the easy-clean coating has a thickness of 0.1 μm to 100 μm, preferably 5 μm to 40 μm.

Preferably, the drying conditions at least satisfy: the temperature is 20-40 deg.C, and the time is 0.5-5 h.

Preferably, the curing conditions at least satisfy: the temperature is 90-200 ℃ and the time is 0.5-5 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 present invention, the room temperature or the normal temperature is 25. + -. 2 ℃ unless otherwise specified.

Acrylic modified silicone resin I: weight average molecular weight is 3000, and the mark is SH-024, purchased from New four sea company in Hubei;

methylpolysiloxane resin: the designation SH-9502, available from New four Hai, Hubei;

perhydropolysilazane I: weight average molecular weight 500, mark IOTA-PHPS, available from Aiyota, Anhui, Inc.;

perhydropolysilazane II: weight average molecular weight 300, trade designation DURAZANE1800, available from merck reagent;

perhydropolysilazane III: weight average molecular weight 700, trade designation DURAZANE, available from merck reagent;

organic polysilazanes: weight average molecular weight 900, designation IOTA-OPSZ-9150, purchased from ai yota, inc;

polyether modified silicone 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;

methyl silicone oil: purchased from Shenzhen Jipeng silicon fluoride materials GmbH;

methyl fluorosilicone oil: purchased from Shenzhen Jipeng silicon fluoride materials GmbH;

nano titanium oxide: the average particle size is 20nm, and the product is of a mark HG-A and is purchased from Shanghai Huizi sub-nanometer new material Co., Ltd;

nano zinc oxide: the average particle size is 30nm, and the product is available from Shanghai Huizi Zi-nanometer New Material Co., Ltd;

nano zirconia: the average particle size is 50nm, and the Nantong Runfeng petrochemical company is purchased;

nano alumina: the average particle size is 60nm, the mark is HG-30, and the product is purchased from Shanghai Huizi sub-nanometer new material Co., Ltd;

gamma-glycidoxypropyltrimethoxysilane: purchased from Nanjing Quanxi chemical Co., Ltd;

3-isocyanatopropyltrimethoxysilane: purchased from Nanjing Quanxi chemical Co., Ltd;

gamma-mercaptopropyl trimethoxysilane: purchased from Nanjing Quanxi chemical Co., Ltd;

3-aminopropyltriethoxysilane: purchased from Nanjing Quanxi chemical Co., Ltd;

γ - (2, 3-epoxypropoxy) propyltrimethoxysilane: purchased from Nanjing Quanxi chemical Co., Ltd;

gamma-methacryloxypropyltrimethoxysilane: purchased from Nanjing Quanxi chemical Co., Ltd;

acetone, purchased from chemical ltd, created by jonan;

toluene: purchased from chemical Limited, Chun-Min-Chun-Shi;

glass substrate: available from Asaho glass Co., Ltd, Dongguan;

spraying equipment: model W-71, available from JEOL Ltd, spraying distance was 200(mm), nozzle diameter was 0.8mm, and air pressure was 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) mixing and stirring acrylic acid modified polysiloxane resin, vinyl silicone oil and toluene at the stirring speed of 600rpm for 20 minutes at room temperature to obtain a diluent;

(2) mixing the diluent with perhydropolysilazane, gamma-mercaptopropyltrimethoxysilane and nano titanium oxide at the stirring speed of 1200rpm and room temperature, and stirring for 20 minutes to obtain the coating;

(3) and spraying the coating on the surface of the glass substrate to form a coating layer, drying the glass substrate with the coating layer at room temperature for 0.5h, and curing the glass substrate with the coating layer in an oven at 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 formulation does not contain nano-metal oxides, see table 1 for details.

Comparative example 2

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 3

This comparative example was carried out using a procedure similar to that of example 1, except that: the formula does not contain a silane coupling agent.

Comparative example 4

This comparative example was carried out using a procedure similar to that of example 1, except that: the formula adopts equal weight of methyl polysiloxane resin to replace acrylic acid modified polysiloxane resin.

Comparative example 5

This comparative example was carried out using a procedure similar to that of example 1, except that: the organic polysilazane with equal weight is adopted to replace perhydropolysilazane in the formula.

TABLE 1

Table 1 (continuation 1)

Table 1 (continuation 2)

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	107.4	5h	0
Example 2	106.1	6h	0
				Example 3	103.6	6h	0
Example 4	102.9	5h	0
				Example 5	104.5	6h	0
Example 6	108.2	5h	0
				Example 7	101.8	5h	0
Example 8	102.6	6h	0
				Example 9	103.5	6h	0
Comparative example 1	97.2	3H	0
				Comparative example 2	95.6	3H	0
Comparative example 3	95.9	3H	0
				Comparative example 4	91.4	4H	0
Comparative example 5	90.6	4H	0

As can be seen from the results in Table 2, the coating prepared by using the coating composition of the present invention with a specific ratio has the advantages of high hardness and easy cleaning; meanwhile, the coating is applied to kitchen appliances, and the surfaces of the kitchen appliance products can obtain 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.