CN114341277A - Coating composition - Google Patents
Coating composition Download PDFInfo
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- CN114341277A CN114341277A CN201980100130.3A CN201980100130A CN114341277A CN 114341277 A CN114341277 A CN 114341277A CN 201980100130 A CN201980100130 A CN 201980100130A CN 114341277 A CN114341277 A CN 114341277A
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- coating composition
- polysilazane
- coating
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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Abstract
The invention relates to a coating composition comprising at least one polysilazane, at least one curing catalyst, at least one hydrophobic and oleophobic agent and at least one first organic solvent. The coating composition exhibits excellent pencil hardness, initial performance, durability, cleaning performance, acid resistance, alkali resistance, solvent resistance, and thermal and moisture resistance.
Description
Technical Field
The invention relates to a coating composition comprising at least one polysilazane, at least one curing catalyst, at least one hydrophobic and oleophobic agent, and at least one first organic solvent. Coatings made from the coating compositions of the present invention exhibit excellent pencil hardness, initial performance, durability, cleaning performance, retort resistance, acid resistance, alkali resistance, solvent resistance, adhesive strength, and resistance to heat and humidity (thermal and humidity endpoint).
Background
Tempered glass (tempered glass) has been widely used in kitchen appliances such as kitchen hoods (kitchen ventilators) and cookers. Due to the use of oil during cooking, oil fumes and splashes are inevitably generated in the kitchen area. The surface of the kitchen utensils is easily oiled and greasy. Often, one has to use a cleaning agent comprising an acid or a base to clean the surface of the kitchen appliance. However, the detergent causes environmental pollution and requires a large amount of water to be washed away. Furthermore, the cleaning tool can also leave scratches on the surface of the kitchen utensil during cleaning, which can affect not only the appearance, but also the service life of the kitchen utensil.
Therefore, there is a need to develop a coating composition that produces a coating layer having excellent pencil hardness, initial properties, durability, cleaning properties, retort resistance, acid resistance, alkali resistance, solvent resistance, adhesive strength, and resistance to heat and moisture.
Disclosure of Invention
The present invention relates to a coating composition comprising:
a) at least one polysilazane;
b) at least one curing catalyst;
c) at least one hydrophobic and oleophobic agent; and
d) at least one first organic solvent.
The invention also relates to a coating formed from the coating composition.
The coating of the present invention has excellent pencil hardness, initial properties, durability, cleaning properties, retort resistance, acid resistance, alkali resistance, solvent resistance, adhesive strength, and resistance to heat and moisture.
The invention also relates to articles coated with the coating.
Detailed Description
The present invention is described in more detail in the following paragraphs. Each aspect so described may be combined with one or more of any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In the context of the present invention, the terms used should be interpreted according to the following definitions, unless the context indicates otherwise.
As used herein, the singular forms "a", "an", "the" and "the" include singular and plural referents unless the context clearly dictates otherwise.
As used herein, the terms "comprising," "including," and "consisting of," are synonymous with "including" or "containing," are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps.
The enumeration of logarithmic value endpoints includes: all numbers and fractions within the corresponding ranges are inclusive of the recited endpoints.
All references cited in this specification are incorporated herein by reference in their entirety.
Unless defined otherwise, all terms (including technical and scientific terms) used in disclosing the invention have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to better understand the teachings of the present invention.
In the context of the present disclosure, a number of terms will be used.
The term "substantially all" when used with respect to the inorganic polysilazane or perhydropolysilazane means that the amount of inorganic polysilazane or perhydropolysilazane is greater than 90 wt%, such as greater than 95 wt%, greater than 99 wt%, or even 100 wt% relative to the total amount of polysilazane contained in the coating composition.
< polysilazane >
The present invention comprises at least one polysilazane known in the art. Polysilazanes include organic and inorganic polysilanes, and may contain linear, branched, or crosslinked structural units. Preferably, the at least one polysilazane comprises at least one inorganic polysilazane. More preferably, the at least one polysilazane comprises at least one perhydropolysilazane. The perhydropolysilazane comprises the following repeating units:
specific examples of perhydropolysilazanes are shown below.
In some embodiments of the invention, the at least one polysilazane preferably comprises substantially all of the inorganic polysilazane, and more preferably comprises substantially all of the perhydropolysilazane.
In some embodiments of the invention, the at least one polysilazane preferably comprises a polysilazane having a number average molecular weight of 1000 to 8000g/mol, more preferably comprises a polysilazane having a number average molecular weight of 2000 to 8000g/mol, and even more preferably comprises a polysilazane having a number average molecular weight of 2000 to 4000g/mol, as measured by Gel Permeation Chromatography (GPC) according to ASTM methods (e.g., D3016-72, D3536-76, D3593-80, or D3016-78).
The polysilazanes of the invention can be prepared by the following steps:
(a) by reacting pyridine with H2SiCl2Mixing in a container under the protection of nitrogen to form H2SiCl2Py complexes;
(b) pouring (flood) excess dry ammonia gas into the container to make the H2SiCl2The complex of Py starts to react with ammonia and is kept under reflux during the reaction;
(c) obtaining a precursor by washing the reaction product from step (b) with pyridine and filtering the reaction product from step (b) under an inert gas atmosphere with a 0.1 to 0.5 μm filter;
(e) obtaining the polysilazane by removing the remaining pyridine in the precursor by distillation; and
(f) optionally diluting the polysilazane with a second organic solvent to 20 wt.%;
wherein the second organic solvent is selected from aromatic, cyclic and aliphatic hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters or any combination thereof.
Examples of commercially available polysilazanes are, for example: HTA 1500SC, HTA 1500RC from AZ Electronic Materials co., ltd.; Iota-OPSZ-9150 from Iota Silicone Oil (Anhui) co., ltd.; NL120A-20 and NP110-20 from Clariant Japan K.K.
In some embodiments of the invention, the amount of polysilazane in the coating composition of the invention is from 0.2 to 5 wt.%, preferably from 1 to 4 wt.%, more preferably from 2 to 4 wt.%, based on the total weight of the coating composition.
< curing catalyst >
The coating composition of the present invention comprises at least one curing catalyst. Suitable curing catalysts may be selected from organic amines, organic acids, metals, metal salts or any combination thereof. Exemplary organic amines are, for example, methylamine, dimethylamine, trimethylamine, N-dimethylpiperazine, 4-trimethylenebis (1-methylpyridine) and 4, 4-methylene-bis (cyclohexylamine). Exemplary organic acids are, for example, acetic acid, propionic acid, butyric acid, valeric acid, and caproic acid. Exemplary metals and metal salts are, for example, palladium acetate, palladium acetylacetonate, palladium propionate, allyl palladium (II) trifluoroacetate dimer (allylpalladium (II) triflate dimer), nickel acetylacetonate, platinum, and platinum acetylacetonate. Preferably, the curing catalyst is 4, 4-trimethylenebis (1-methylpyridine), allylpalladium (II) trifluoroacetate dimer, or a combination thereof. More preferably, the curing catalyst is allyl palladium (II) trifluoroacetate dimer.
Examples of commercially available curing catalysts are 4, 4-trimethylenebis (1-methylpyridine) and the palladium (II) allyltrifluoroacetate dimer, e.g.from sigma-Aldrich.
In some embodiments of the present invention, the amount of curing catalyst in the coating composition of the present invention is from 0.01 to 5 weight percent, preferably from 0.01 to 0.5 weight percent, more preferably from 0.01 to 0.1 weight percent, based on the total weight of the coating composition.
< Water and oil repellant >
The coating composition of the present invention comprises at least one hydrophobic and oleophobic agent that is unreactive with the polysilazane. Suitable hydrophobic and oleophobic agents include, but are not limited to, hydroxyl-containing polydimethylsiloxanes, hydroxyl-containing silicone modified polyacrylates, fluorine-containing zirconia/silica composites having methacrylate functionality, modified silicone oils, or any combination thereof. Preferably, the hydrophobic and oleophobic agent is selected from the group consisting of modified silicone oils in combination with hydroxyl-containing polydimethylsiloxanes, and/or hydroxyl-containing silicone modified polyacrylates, and/or fluorine-containing zirconia/silica composites having methacrylate functionality. It has been surprisingly found that the durability, acid and alkali resistance and cleaning performance of coatings made from the coating composition are greatly improved when the modified silicone oil is used with other hydrophobic and oleophobic agents.
Exemplary modified silicone oils are, for example, amino-modified silicone oils, fatty acid/alcohol-modified silicone oils, polyether-modified silicone oils, epoxy-modified silicone oils, fluorine-modified silicone oils, and alkyl-modified silicone oils. In some embodiments of the present invention, the modified silicone oil is preferably a fluorine-modified silicone oil.
Examples of commercially available hydrophobic and oleophobic agents are for example: tego 5000N from Evonik; BYK-SILCLEAN 3700 from BYK; silixan A250 from Silixan GmbH; and ShinEstu X22-176F from ShinEstu Silicone.
In some embodiments of the present invention, the amount of hydrophobic and oleophobic agent in the coating composition of the present invention is from 1 to 10 weight percent, preferably from 1 to 5 weight percent, more preferably from 1 to 2.5 weight percent, based on the total weight of the coating composition.
< first organic solvent >
The coating compositions of the invention comprise at least one first organic solvent, which makes it possible to prepare solutions containing polysilazane, a curing catalyst and a hydrophobic and oleophobic agent with long storage times. Suitable first organic solvents include, but are not limited to, aromatic hydrocarbons, cyclic and aliphatic hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters, and any combination thereof. Preferably, the first organic solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof. More preferably, the first organic solvent is a combination of an aliphatic hydrocarbon and an aromatic hydrocarbon. Exemplary aliphatic hydrocarbons are, for example, propane and 1-butene. Exemplary aromatic hydrocarbons are, for example, toluene, xylene. The first organic solvent may be the same as or different from the second organic solvent of the present invention.
In some embodiments of the invention, a combination of aliphatic and aromatic hydrocarbons is used as the first organic solvent. The weight ratio of aliphatic hydrocarbon to aromatic hydrocarbon is preferably 10:1 to 30:1, more preferably 15:1 to 25:1, even more preferably 18:1 to 19: 1.
Examples of commercially available first organic solvents are, for example, Pegasol AN45 and Pegasol 3040 from Mobil Sekiyu Corp.
In some embodiments of the present invention, the amount of the first organic solvent in the coating composition of the present invention is from 50 to 99 weight percent, preferably from 70 to 99 weight percent, more preferably from 80 to 97 weight percent, based on the total weight of the coating composition.
Optionally present additives
The coating composition may also comprise optional additives. The selection of suitable additives for use in the coating compositions of the present invention depends on the particular intended use of the coating composition and can be determined in individual cases by the person skilled in the art. Examples of optionally present additives are, for example, fillers, biocides (biochides), dyes, pigments and mixtures thereof.
In a preferred embodiment, the coating composition comprises:
(a)0.2 to 5% by weight of at least one polysilazane;
(b)0.01 to 5 wt% of at least one curing catalyst;
(c)1 to 10 wt% of at least one hydrophobic and oleophobic agent; and
(d)50 to 99% by weight of at least one first organic solvent,
the weight percentages of all components add up to 100 wt%.
The coating composition of the present invention can be prepared by the following steps:
(a) dissolving polysilazane in a first organic solvent to obtain a solution;
(b) adding a curing catalyst and a hydrophobic and oleophobic agent to the solution of step (a) with stirring to obtain a homogeneous mixture; and
(c) the coating composition is obtained by shaking the homogeneous mixture with ultrasonic waves.
The coating composition of the present invention may be sprayed onto a substrate and baked at a temperature of 150 to 350 ℃ for curing. Preferably, the coating composition is baked at 170 to 290 ℃ for 25 to 35 minutes.
The coating layer formed from the coating composition of the present invention preferably has a pencil hardness of 9H. The pencil hardness of the coating can be assessed according to GB/T6739-2006.
The coatings formed from the coating compositions of the invention have good initial properties, such as good scratch resistance, small rolling angle, large water contact angle and oil contact angle. Preferably, the coating has a sliding angle of less than or equal to 30 degrees, a water contact angle of greater than or equal to 110 degrees, and an oil contact angle of greater than or equal to 65 degrees.
Coatings formed from the coating compositions of the present invention have good durability, such as good scratch resistance, small rolling angle, large water contact angle, and oil contact angle, after thousands of washes. Preferably, the coating has a sliding angle of less than or equal to 60 degrees, a water contact angle of greater than or equal to 105 degrees, and an oil contact angle of greater than or equal to 55 degrees.
The coatings formed from the coating compositions of the present invention also preferably have good resistance to heat and moisture, retort, acid, base, solvent, and adhesive strength.
Example (b):
the present invention is further described in detail and illustrated with reference to the following examples. The examples are intended to assist those skilled in the art in better understanding and practicing the invention, but are not intended to limit the scope of the invention. All numbers in the examples are based on weight unless otherwise indicated.
Examples 1 to 12
The following materials were used in the examples.
IOTA-PHPS (a 20% solution of perhydropolysilazane from Anhui IOTA Silicone Oil in dibutyl ether; the number average molecular weight of the perhydropolysilazane is about 1450 g/mol);
NL120A-20 (20% strength solution of perhydropolysilazane in dibutyl ether, containing palladium propionate as catalyst, from Clariant Japan K.K.; the perhydropolysilazane has a number-average molecular weight of about 2000 g/mol);
NP110-20 (20% strength solution of perhydropolysilazane in xylene, containing 4, 4' -trimethylene-bis (1-methylpiperidine) as catalyst, from Clariant Japan K.K.; the perhydropolysilazane has a number average molecular weight of about 2000 g/mol);
DMPP (4, 4-trimethylenebis (1-methylpyridine) from Sigma-Aldrich);
allyl palladium (II) trifluoroacetate dimer (from Sigma-Aldrich);
tego 5000N (hydroxyl-containing polydimethylsiloxane from Evonik);
BYK-SILCLEAN 3700 (hydroxyl containing silicone modified polyacrylate from BYK);
SiliXan a250 (a fluorine-containing zirconia/silica composite with methacrylate functionality from SiliXan GmbH);
ShinEstu X22-176F (a fluorine-modified Silicone oil derived from ShinEstu Silicone);
pegasol AN45 (mineral terpene from Mobil Sekiyu corp.);
xylene (from Sigma-Aldrich).
< example 1>
Polysilazane FT20 was first prepared by the following steps:
(a) by mixing 500ml of freshly distilled pyridine with 50.5g H2SiCl2Mixing in a four-neck flask with reflux condenser, gas inlet pipe, gas outlet pipe and mixer under nitrogen protection to form H2SiCl2Py complexes;
(b) excess dry ammonia gas was poured into the four-necked flask to make the H2SiCl2The Py complex was started with ammonia and refluxed for 2 hours;
(c) obtaining 900ml of precursor by washing the reaction product from step (b) with pyridine and filtering the reaction product from step (b) with a 0.2 μm filter under inert gas;
(e) 1.76g of polysilazane (70.4% yield) was obtained by removing the remaining pyridine from 100ml of the precursor by vacuum distillation; and
(f) diluting the polysilazane from step (e) to 20 wt% with dibutyl ether to give polysilazane FT 20.
The polysilazane thus prepared had a number average molecular weight of about 2000g/mol as measured by Gel Permeation Chromatography (GPC).
2g of polysilazane FT20 and 0.015g of DMPP were dissolved in a mixed solution containing 86g of Pegasol AN45 and 4.5g of xylene with stirring. 1.2g Tego 5000N was further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 25 minutes to form a coating of about 200nm thickness on the tempered glass.
< example 2>
Polysilazane FT20 was prepared in the same manner as in example 1.
3g of polysilazane FT20 and 0.015g of DMPP were dissolved in a mixed solution containing 95g of Pegasol AN45 and 5g of xylene with stirring. 1.2g Tego 5000N was further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 170 ℃ for 35 minutes to form a coating of about 200nm thickness on the tempered glass.
< example 3>
Polysilazane FT20 was prepared in the same manner as in example 1.
2.5g of polysilazane FT20 and 0.02g of DMPP were dissolved in a mixed solution containing 90.98g of Pegasol AN45 and 5g of xylene with stirring. 1.5g Tego 5000N was further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 4>
Polysilazane FT20 was prepared in the same manner as in example 1.
2.5g of polysilazane FT20 and 0.018g of allyl palladium (II) trifluoroacetate dimer were dissolved with stirring in a mixed solution containing 90.982g of Pegasol AN45 and 5g of xylene. 1.5g Tego 5000N was further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 5>
Polysilazane FT20 was prepared in the same manner as in example 1.
2.5g of polysilazane FT20 and 0.018g of allyl palladium (II) trifluoroacetate dimer were dissolved with stirring in a mixed solution containing 90.982g of Pegasol AN45 and 5g of xylene. 1.5g BYK-SILCLEAN 3700 was further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 6>
Polysilazane FT20 was prepared in the same manner as in example 1.
2.5g of polysilazane FT20 and 0.018g of allyl palladium (II) trifluoroacetate dimer were dissolved with stirring in a mixed solution containing 90.982g of Pegasol AN45 and 5g of xylene. 1.5g of Silixan A250 was further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 7>
Polysilazane FT20 was prepared in the same manner as in example 1.
2.5g of polysilazane FT20 and 0.018g of allyl palladium (II) trifluoroacetate dimer were dissolved with stirring in a mixed solution containing 90.982g of Pegasol AN45 and 5g of xylene. 1.5g Tego 5000N and 0.25g ShinEtsu X22-176F were further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 8>
Polysilazane FT20 was prepared in the same manner as in example 1.
2.5g of polysilazane FT20 and 0.018g of allyl palladium (II) trifluoroacetate dimer were dissolved with stirring in a mixed solution containing 90.982g of Pegasol AN45 and 5g of xylene. 1.5g of Silixan A250 and 0.25g of ShinEtsu X22-176F were further added to the mixed solution. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 9>
2.5g of IOTA-PHPS and 0.02g of DMPP were dissolved with stirring in a mixed solution containing 90.98g of Pegasol AN45 and 5g of xylene. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 10>
Polysilazane FT20 was prepared in the same manner as in example 1.
2.5g of polysilazane FT20 and 0.018g of allyl palladium (II) trifluoroacetate dimer were dissolved with stirring in a mixed solution containing 90.982g of Pegasol AN45 and 5g of xylene. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 11>
2.5g of NP120A-20 was dissolved in a mixed solution containing 92.5g of Pegasol AN45 and 5g of xylene with stirring. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
< example 12>
2.5g of NP110-20 was dissolved in a mixed solution containing 92.5g of Pegasol AN45 and 5g of xylene with stirring. The mixed solution was stirred at 1500r/min for 30 minutes, and then sonicated for 30 minutes to obtain a clear coating composition. The coating composition was sprayed onto the surface of tempered glass and baked at 180 ℃ for 30 minutes to form a coating layer of about 200nm thickness on the tempered glass.
The coated tempered glass from examples 1 to 12 was stored at 25 ℃ for 7 days and subjected to the following various tests.
Test method
< Pencil hardness test >
The pencil hardness of the coating was determined according to GB/T6739-.
< initial Properties >
The initial properties of the coating layer refer to the properties of the coating layer (regarded as the initial coating layer at the time of initial property evaluation) without treatment such as washing and scratching. The coating was considered as the initial coating during the initial performance test. The initial coating was tested for smoothness, scratch resistance, roll angle, water contact angle and oil contact angle.
Smoothness:
the smoothness of the initial coating is rated according to the roll angle of the initial coating. The roll angle is measured by the following steps:
a) providing a movable platform which is horizontally placed, wherein one end of the movable platform is provided with a fixed baffle;
b) placing the coated tempered glass on the movable platform in such a manner that the coated tempered glass is horizontally placed; facing the initial coating of the coated tempered glass upwards; and one side of the coated tempered glass is leaned against the fixed baffle.
c) Slowly dripping a drop of water on the initial coating of the coated toughened glass by using a syringe;
d) slowly tilting the movable platform in a manner that deflects the coated tempered glass against the fixed stop;
e) stopping the tilting of the movable platform when the water droplet starts to roll on the initial coating; and
f) and recording the inclination angle of the movable platform as the rolling angle of the initial coating.
If the roll angle is less than or equal to 30 degrees, the smoothness of the initial coating is rated "excellent";
if the roll angle is greater than 30 degrees and less than or equal to 60 degrees, the smoothness of the initial coating is rated "O";
if the roll angle is greater than 60 degrees and less than or equal to 90 degrees, the smoothness of the initial coating is rated as "Δ"; and
if the roll angle is greater than 90 degrees, the smoothness of the initial coating is rated as "X".
Scratch resistance:
the initially coated surface was scratched 100 times with a towel (towel) at a force of 9.8 newtons.
Scratch resistance was rated "very good" if the surface of the initial coating had no visually detectable scratches;
if the surface of the initial coating had some visually perceptible light scratches, the scratch resistance was rated "O";
scratch resistance was rated "Δ" if the surface of the initial coating had some visually perceptible scratches; and
scratch resistance is rated as "X" if the surface of the initial coating has many visually perceptible scratches.
Water contact angle:
the water contact angle was measured by using the attention Theta from Biolin Scientific. A drop of water was dosed onto the surface of the initial coating and the contact angle was tested after the drop of water no longer changed in shape. The above experiment was repeated 4 times in random areas of the initial coating to obtain 4 water contact angle values, which were then averaged.
If the average water contact angle is greater than or equal to 110 degrees, the water contact angle of the initial coating is rated "excellent";
the water contact angle of the initial coating is rated "O" if the average water contact angle is less than 110 degrees and greater than or equal to 100 degrees;
the water contact angle of the initial coating is rated "Δ" if the average water contact angle is less than 100 degrees and greater than or equal to 95 degrees; and
if the average water contact angle is less than 95 degrees, the water contact angle of the initial coating is rated as "X". Oil contact angle:
the oil contact angle was measured by using the attention Theta from Biolin Scientific. Oil droplets were dosed onto the surface of the initial coating and the contact angle was tested after the shape of the oil droplets no longer changed. The above experiment was repeated 4 times in random areas of the initial coating to obtain 4 oil contact angle values, which were then averaged.
If the average oil contact angle is greater than or equal to 65 degrees, the oil contact angle of the initial coating is rated "excellent";
if the average oil contact angle is less than 65 degrees and greater than or equal to 55 degrees, the oil contact angle of the initial coating is rated "O";
if the average oil contact angle is less than 55 degrees and greater than or equal to 45 degrees, the oil contact angle of the initial coating is rated a "; and
if the average oil contact angle is less than 45 degrees, the oil contact angle of the initial coating is rated as "X".
< durability >
Durability of the coating refers to the performance of a coating that is washed 5000 times with a neutral detergent under 9.8 newtonian forces by using the sponge side of a rag (dish brand, available from Top Group). The coating was considered as an aged coating during durability evaluation. The aged coatings were tested for smoothness, scratch resistance, roll angle, water contact angle, and oil contact angle.
Smoothness:
the smoothness of the aged coating was rated according to the roll angle of the aged coating. The roll angle is measured by the following steps:
a) providing a movable platform which is horizontally placed, wherein one end of the movable platform is provided with a fixed baffle;
b) placing the coated tempered glass on the movable platform in such a manner that the coated tempered glass is horizontally placed; the aged coating side of the coated tempered glass was faced up; and one side of the coated tempered glass is leaned against the fixed baffle.
c) Slowly dripping a drop of water on the aged coating of the coated tempered glass by using a syringe;
d) slowly tilting the movable platform in a manner that deflects the coated tempered glass against the fixed stop;
e) stopping the tilting of the movable platform when the water droplet starts to roll on the aged coating; and
f) recording the tilt angle of the movable platform as the roll angle of the aged coating.
The smoothness of the aged coating is rated "excellent" if the roll angle is less than or equal to 60 degrees;
the smoothness of the aged coating is rated "O" if the roll angle is greater than 60 degrees and less than or equal to 90 degrees;
the smoothness of the aged coating is rated as "Δ" if the roll angle is greater than 90 degrees; and
the smoothness of the aged coating was rated "X" if water remained on the surface of the aged coating.
Scratch resistance:
the surface of the aged coating was scratched 100 times with a towel at a force of 9.8 newtons.
Scratch resistance was rated "excellent" if the surface of the aged coating had no visually detectable scratches;
scratch resistance is rated "O" if the surface of the aged coating has some visually perceptible light scratches (small scratches);
scratch resistance was rated "Δ" if the surface of the aged coating had some visually perceptible visible scratches; and
the scratch resistance is rated "X" if the surface of the aged coating has many visually perceptible scratches.
Water contact angle:
the water contact angle was measured by using the attention Theta from Biolin Scientific. A drop of water was dosed onto the surface of the aged coating and the contact angle was tested after the drop of water no longer changed in shape. The above experiment was repeated 4 times in random areas of the aged coating to obtain 4 water contact angle values, which were then averaged.
The water contact angle of the aged coating is rated "excellent" if the average water contact angle is greater than or equal to 105 degrees;
the water contact angle of the aged coating is rated "O" if the average water contact angle is less than 105 degrees and greater than or equal to 95 degrees;
the water contact angle of the aged coating is rated "Δ" if the average water contact angle is less than 95 degrees and greater than or equal to 85 degrees; and
the water contact angle of the aged coating is rated "X" if the average water contact angle is less than 85 degrees.
Oil contact angle:
the oil contact angle was measured by using the attention Theta from Biolin Scientific. Oil droplets were dosed onto the surface of the aged coating and the contact angle was tested after the oil droplets no longer changed in shape. The above experiment was repeated 4 times in random areas of the aged coating to obtain 4 oil contact angle values, which were then averaged.
The oil contact angle of the aged coating is rated "excellent" if the average oil contact angle is greater than or equal to 55 degrees;
the oil contact angle of the aged coating is rated "O" if the average oil contact angle is less than 55 degrees and greater than or equal to 45 degrees;
the oil contact angle of the aged coating is rated "Δ" if the average oil contact angle is less than 45 degrees and greater than or equal to 35 degrees; and
if the average oil contact angle is less than 35 degrees, the oil contact angle of the aged coating is rated as "X".
< cleaning Performance >
The coated tempered glass was marked with a ZEBRA oil pen with a "#" symbol on the surface of the coating. The "#" symbol in each row is not shorter than 3cm, and the "#" symbol is allowed to stand for 2 minutes. A paper towel was used to rub off the "#" symbol with a force of 9.8 newtons.
If the "#" symbol is easily wiped off completely, the cleaning performance of the coating is rated "excellent";
if the "#" symbol is completely wiped off after several wipes, the cleaning performance of the coating is rated "O";
if most of the "#" symbol is wiped off, the cleaning performance of the coating is rated a "Δ"; and
if a large portion of the "#" symbol cannot be wiped away, the cleaning performance of the coating is rated as "X".
< adhesive Strength >
The adhesion strength of the coating is determined according to GB/T9286. 11 parallel lines were made on the sample plate, with a spacing of about 1mm between adjacent lines. The tape was pressed onto the coating and peeled off at a 45 degree angle. The coating was observed and recorded for flaking.
< boiling resistance >
The coated tempered glass was soaked in water at 100 ℃ for 30 minutes, and the water was kept boiling all the time during the soaking. The coated tempered glass was taken out and dried. The appearance was checked with the naked eye. The coatings were tested for adhesive strength as described above.
< acid resistance >
The acid resistance of the coating is determined according to GB/T9274. The coated tempered glass was placed horizontally. A reservoir (reservoir) with dimensions 50mm X5 mm (length X width X height) was made on the surface of the coating with plasticine (plasticine). HCl solution with a concentration of 1mol/L was added to the reservoir to reach a depth of 3 mm. The HCl solution was removed from the reservoir after 1 hour. The surface of the coating was rinsed with water and dried. The surface of the coating was then inspected.
< alkali resistance >
The alkali resistance of the coating is determined according to GB/T9274. The coated tempered glass was placed horizontally. A reservoir having dimensions of 50mm X5 mm (length X width X height) was made on the surface of the coating with plasticine. NaOH solution with a concentration of 1mol/L was added to the reservoir to reach a depth of 3 mm. The NaOH solution was removed from the reservoir after 1 hour. The surface of the coating was rinsed with water and dried. The surface of the coating was then inspected.
< solvent resistance >
Solvent resistance was determined according to GB/T23989-2009. Cotton cloth was wrapped around the fingers and soaked in MEK solution. The finger was held at a 45 degree angle to the coating and a force of 9.8 newtons was applied to the surface of the coating. The finger is moved back and forth on the surface of the coating to wipe the coating, and the moving distance of the finger is 80 to 100 mm. One finger wipe involves one complete finger back and forth motion, completed in 0.5 seconds. After 25 finger wipes, the coating was turned 180 degrees. The cotton cloth was re-soaked in MEK solution. And repeating the finger wiping until the toughened glass is exposed. The number of finger wipes was recorded.
< Heat resistance and moisture resistance >
The coated tempered glass was exposed to an environment of 85 ℃ and 85RH for 96 hours. The cleaning performance of the coating was determined according to the above method and the appearance of the coating was also checked by naked eye.
Test results
The test results for the coatings prepared in examples 1 to 12 are reported in tables 1A and 1B. The coatings in examples 1 to 8 had good pencil hardness, initial properties, durability, cleaning properties, retort resistance, acid resistance, alkali resistance, solvent resistance, adhesive strength, and resistance to thermal and moisture. In addition, the coatings in examples 4 to 8 had better retort resistance, initial performance, durability and solvent resistance than the coatings in examples 1 to 3. In addition, the coatings in examples 6 to 8 have even better initial properties, durability and solvent resistance than the coatings in examples 1 to 5.
Table 1A: properties of the coating composition
Table 1B: properties of the coating composition
Claims (13)
1. A coating composition comprising:
a) at least one polysilazane;
b) at least one curing catalyst;
c) at least one hydrophobic and oleophobic agent; and
d) at least one first organic solvent.
2. The coating composition according to claim 1, wherein the at least one polysilazane preferably comprises at least one inorganic polysilazane, more preferably comprises at least one perhydropolysilazane.
3. The coating composition according to claim 1 or 2, wherein the at least one polysilazane preferably comprises substantially all inorganic polysilazane, even more preferably comprises substantially all perhydropolysilazane.
4. The coating composition according to any one of the preceding claims, wherein the at least one polysilazane comprises preferably a polysilazane having a number average molecular weight of 1000 to 8000g/mol, more preferably a polysilazane having a number average molecular weight of 2000 to 8000g/mol, even more preferably a polysilazane having a number average molecular weight of 2000 to 4000g/mol, wherein the number average molecular weight is determined by gel permeation chromatography.
5. The coating composition according to any of the preceding claims, wherein the curing catalyst is preferably selected from 4, 4-trimethylenebis (1-methylpyridine), allylpalladium (II) trifluoroacetate dimer, or a combination thereof, more preferably allylpalladium (II) trifluoroacetate dimer.
6. Coating composition according to any one of the preceding claims, in which the hydrophobic and oleophobic agent is preferably a hydroxyl-containing polydimethylsiloxane, a hydroxyl-containing silicone-modified polyacrylate, a fluorine-containing zirconia/silica complex with methacrylate functionality, a modified silicone oil or any combination thereof, more preferably a combination of a modified silicone oil with a further hydrophobic and oleophobic agent selected from a hydroxyl-containing polydimethylsiloxane, a hydroxyl-containing silicone-modified polyacrylate, a fluorine-containing zirconia/silica complex with methacrylate functionality or any combination thereof.
7. The coating composition according to any one of the preceding claims, wherein the modified silicone oil is preferably a fluoro-modified silicone oil.
8. The coating composition according to any one of the preceding claims, wherein the first organic solvent is preferably selected from aliphatic hydrocarbons, aromatic hydrocarbons and combinations thereof, more preferably combinations of aliphatic hydrocarbons and aromatic hydrocarbons.
9. The coating composition of any one of the preceding claims, comprising:
(a)0.2 to 5% by weight of at least one polysilazane;
(b)0.01 to 5 wt% of at least one curing catalyst;
(c)1 to 10 wt% of at least one hydrophobic and oleophobic agent; and
(d)50 to 99% by weight of at least one first organic solvent,
wherein the weight percentages of all components add up to 100 weight%.
10. The coating composition according to any one of the preceding claims, wherein the polysilazane is prepared by the steps of:
(a) by reacting pyridine with H2SiCl2Mixing in a container under the protection of nitrogen to form H2SiCl2Py complexes;
(b) pouring excess dry ammonia gas into the vessel to make the H2SiCl2The complex of Py starts to react with ammonia and is kept under reflux during the reaction;
(c) obtaining a precursor by washing the reaction product from step (b) with pyridine and filtering the reaction product from step (b) under an inert gas atmosphere with a 0.1 to 0.5 μm filter;
(d) obtaining the polysilazane by removing the remaining pyridine in the precursor by distillation; and
(e) optionally diluting the polysilazane with a second organic solvent to 20 wt.%;
wherein the second organic solvent is selected from aromatic, cyclic and aliphatic hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters or any combination thereof.
11. An article coated with the coating composition of any one of the preceding claims.
12. A method of preparing a coating composition according to any preceding claim, comprising the steps of:
(a) dissolving polysilazane in a first organic solvent to obtain a solution;
(b) adding a curing catalyst and a hydrophobic and oleophobic agent to the solution of step (a) with stirring to obtain a homogeneous mixture; and
(c) the coating composition is obtained by shaking the homogeneous mixture with ultrasonic waves.
13. Use of a coating composition according to any one of the preceding claims.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2019/105045 WO2021046701A1 (en) | 2019-09-10 | 2019-09-10 | Coating composition |
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| CN114341277A true CN114341277A (en) | 2022-04-12 |
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| WO (1) | WO2021046701A1 (en) |
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| CN116376436A (en) * | 2023-05-07 | 2023-07-04 | 广州希森美克新材料科技股份有限公司 | High-wear-resistance easy-cleaning hydrophobic oleophobic nano-coating and preparation method and use method thereof |
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| CN112980032B (en) * | 2021-04-23 | 2022-07-01 | 浙江华帅特新材料科技有限公司 | Transparent, robust self-cleaning organic glass and manufacturing method thereof |
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