KR20230056437A - Water repellent composition - Google Patents

Abstract

The present invention relates to a water repellent composition which comprises: a compound including at least one element selected from a carbon group excluding carbon (C); a fluoride source; and an organic solvent. According to the present invention, it is possible to perform water-repellent surface treatment with high durability and environmental friendliness while super water-repellent properties are maintained.

Description

Water repellent composition {Water repellent composition}

The present invention relates to a water repellent composition that can be used at high temperatures and has improved durability and stability.

The water-repellent property that reduces contact with water on the surface is a property that is attributed to the chemical property with low surface energy and the surface structure with small contact area, Exterior materials, self-cleaning of windows, etc.) to industrial vehicles/plants (enhanced visibility of automobiles, ships, aircraft, anti-fouling, anti-icing, etc.).

However, most of the existing technologies use a method of coating a fluoroorganic compound (perfluorinated compound (Teflon)) or a silicon organic compound-based material alone or in combination. There are problems with durability and stability for application. In particular, in the case of perfluorinated compounds (Teflon), they decompose at 200°C, causing fatal hazards to the environment and human body. Non-environmental issues have emerged, such as the resolution of technical guidelines for the environmentally sound management of wastes containing perfluorochemicals at the 11th meeting of the Basel Convention in February.

Therefore, it is necessary to develop an eco-friendly water-repellent surface treatment technology from a new perspective that can be used at high temperatures and has durability and stability.

One object of the present invention is to provide a water repellent composition having high durability and environmental friendliness.

Another object of the present invention is to provide a method for preparing a water repellent composition using only inorganic precursors.

Another object of the present invention is to provide an environmentally friendly water-repellent surface treatment method with improved durability and stability.

The technical problem to be achieved by the water repellent composition according to the technical idea of the present invention is not limited to the above-mentioned problem, and another problem not mentioned will be clearly understood by those skilled in the art from the description below.

A detailed description of this is as follows. Meanwhile, each description and embodiment disclosed in this application may also be applied to each other description and embodiment. That is, all combinations of various elements disclosed in this application fall within the scope of this application. In addition, the scope of the present application is not to be construed as being limited by the specific descriptions described below.

In order to achieve the above object, according to an embodiment of the present invention, one or more element-containing compounds selected from group 14 elements except for carbon (C); fluoride source; And it provides a water repellent composition containing an organic solvent.

According to one embodiment, the compound containing one or more elements selected from group 14 elements other than carbon (C) may be a silicon-containing compound or a tin-containing compound.

According to one embodiment, the silicon-containing compound includes a compound represented by the following chemical formula, a water repellent composition:

(R ¹ ) _n Si(OR ² ) _4-n

In the formula, R ¹ is a substituted or unsubstituted alkyl group or aryl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms, R ¹ and R ² may be the same or different, and n is It is an integer from 0 to 2.

According to one embodiment, the silicon-containing compound is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraisopropoxysilane ( tetraisopropoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, ethoxytrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane , ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, tetramethoxymethylsilane, tetramethoxyethylsilane ( tetramethoxyethylsilane) and tetraethoxymethylsilane (tetraethoxymethylsilane).

According to one embodiment, the tin-containing compound is a water repellent composition comprising a compound represented by the following formula:

Sn(OR) ₂ (ORN) ₂

In the formula, R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

According to one embodiment, the tin-containing compound is tin acetate, tin diacetate, dibutyl tin acetate, tin butoxide, or tin acetylacetonate. acetylacetonate), tin hexafluoroacetylacetonate, tin bis(acetylacetonate), and tin chloride.

According to one embodiment, the fluorine source is ammonium fluoride, ammonium bifluoride, hydrogen fluoride, potassium fluoride, sodium fluoride ), tetraalkylammonium difluorides ((R) ₄ NHF ₂ , where R is methyl, ethyl, butyl, phenyl or fluorided Cl _{-C 4} alkyl group), alkyl phosphonium difluorides ( alkyl phosphonium difluorides) ((R) ₄ PHF ₂ , where R is a methyl, ethyl, butyl, phenyl or fluoridated Cl _{-C 4} alkyl group), triethylamine trihydrofluoride and fluoro It may include one or more selected from the group consisting of silicic acid (fluorosilicic acid).

According to one embodiment, the organic solvent is ethanol, 2-butanol, 1,4-butanediol, 1,3-butanediol, Ethylene glycol, propylene glycol, N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), r-butyrolactone , propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monobenzylether, ethyl lactate, ammonium lactate ( ammonium lactate) and dimethyl acetamide (dimethyl acetamide).

According to one embodiment, the volume ratio of the fluorine source: a compound containing one or more elements selected from group 14 elements other than carbon (C): the organic solvent may be 1: 1 to 5: 20 to 50.

According to one embodiment, the water repellent composition is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH), sodium borohydride (NaBH ₄ ), hydrazine (N ₂ H ₄ ) and hydriodine ( HI) may further include one or more reducing agents selected from the group consisting of.

In order to achieve the above object, according to an embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; centrifuging the first precursor and dispersing it in water; And adding a fluorine source to the first precursor, reacting at room temperature, drying, and then calcining to form silicon oxide particles containing elemental fluorine.

In order to achieve the above object, according to an embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; and adding a fluorine source to the first precursor, followed by centrifugation, drying, and calcination to form silicon oxide particles containing elemental fluorine.

In order to achieve the above object, according to an embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; centrifuging the first precursor and dispersing it in water; and adding a fluorine source to the first precursor and reacting hydrothermal to form silicon oxide particles containing elemental fluorine.

In order to achieve the above object, according to an embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; and adding a fluorine source to the first precursor and performing a hydrothermal reaction to form silicon oxide particles containing elemental fluorine.

According to one embodiment, the method for preparing the water repellent composition may further include mixing a dye with the water repellent composition.

According to one embodiment, the particle may have a diameter of 100 nm or less.

According to one embodiment, the diameter of the particles may be characterized in that they are different from each other in the nano size to the micro size.

In order to achieve the above object, according to an embodiment of the present invention, a method of treating the surface of an article using a water repellent composition is provided.

In order to achieve the above object, according to an embodiment of the present invention, an article surface-treated using a water repellent composition is provided.

According to one embodiment, a dye is mixed with the water repellent composition to provide a surface-treated article to have a color.

According to one embodiment, a particle included in the water repellent composition has a size of 100 nm or less in diameter to provide an article surface-treated to be transparent.

According to one embodiment, particles included in the water repellent composition are manufactured to have different diameters and are mixed with each other for surface treatment, thereby providing an article surface-treated to have mechanical durability.

According to one embodiment of the present invention, a super water-repellent surface having a contact angle of 150° or more can be formed.

In addition, according to one embodiment of the present invention, an environmentally friendly water-repellent surface treatment is possible due to an inorganic material-based composition that does not contain carbon.

According to one embodiment of the present invention, it is possible to form a second water-repellent surface having second repellency while being transparent.

According to one embodiment of the present invention, a super-water-repellent surface having color and super-hydrophobicity may be formed.

According to one embodiment of the present invention, a second water-repellent surface having mechanical durability maintaining water repellency for a long time can be formed.

However, the effects that can be achieved by the water repellent composition according to an embodiment of the present invention are not limited to those mentioned above, and other effects not mentioned may be clearly understood by those skilled in the art from the description below. will be.

In order to more fully understand the drawings cited herein, a brief description of each drawing is provided.
Figure 1 (a) is a diagram schematically showing a method (2 step calcination method) for producing a water repellent composition according to an embodiment of the present invention, and Figure 1 (b) is a method for producing a water repellent composition according to an embodiment ( 2 step calcination method) is a diagram showing the reactants prepared.
Figure 2 (a) is a diagram schematically showing a method (1 step calcination method) of a water repellent composition according to an embodiment of the present invention, and Figure 2 (b) is a water repellent composition according to an embodiment It is a diagram showing a reactant prepared according to the method (1 step calcination method).
3 is a view showing reactants according to a method for preparing a water repellent composition according to an embodiment of the present invention (2 step hydrothermal method).
4 is a view showing reactants according to a method for preparing a water repellent composition according to an embodiment of the present invention (1 step hydrothermal method).
5 is an XPS spectrum of silicon oxide particles (F-SiO ₂ NPs) containing fluorine element according to an embodiment of the present invention before and after calcination at 300 ° C and particles of a comparative example, showing a state in which fluorine is combined with silicon oxide is the drawing shown.
6 is a view showing TEM images of silicon oxide particles containing elemental fluorine according to an embodiment of the present invention and particles of a comparative example.
7 is a view showing super-hydrophobic properties by comparing wettability by dropping water droplets on silicon oxide particles containing fluorine element according to an embodiment of the present invention and particles of a comparative example.
8 is a graph of a substrate (glass, SUS, PET, cloth, cotton, paper) of a surface-treated article using silicon oxide particles containing a fluorine element according to an embodiment of the present invention and a substrate of an unsurface-treated article. This is a picture showing the degree of spread when water droplets are placed.
9 is a view showing super-hydrophobic properties by dropping water droplets on a substrate (glass, SUS, PET, cotton, paper) of a surface-treated article using silicon oxide particles containing fluorine according to an embodiment of the present invention. am.
10 is a view showing self-cleaning characteristics of glass surface-treated using silicon oxide particles containing elemental fluorine according to an embodiment of the present invention.
11 is a view showing the results obtained after testing the superhydrophobic properties of glass surface-treated using silicon oxide particles containing fluorine element according to an embodiment of the present invention for 500 hours at 8585.

Since the invention disclosed in this specification can have various changes and various embodiments, specific embodiments are illustrated in the drawings and will be described in detail through detailed description. However, this is not intended to limit the technology disclosed in this specification to specific embodiments, and it should be understood that the technology disclosed in this specification includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In describing the invention disclosed herein, if it is determined that a detailed description of related known technologies may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, numbers (eg, first, second, etc.) used in the description process of this specification are only identifiers for distinguishing one component from another component.

In the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise specified.

As used herein, the terms "about," "substantially," and the like are used at or approximating that number when manufacturing and material tolerances inherent in the stated meaning are given, and are intended to assist in the understanding of this disclosure. Accurate or absolute figures are used to prevent undue exploitation by unscrupulous infringers of the stated disclosure.

As used herein, the term "step of (doing)" or "step of" does not mean "step for".

In this specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited to a position where a hydrogen atom is substituted, that is, a position where the substituent is substituted, and two or more When substituted, two or more substituents may be the same as or different from each other.

In this specification, the term “substituted or unsubstituted” refers to deuterium (-D); halogen group; nitrile group; nitro group; hydroxy group; silyl group; boron group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, or is substituted with a substituent in which two or more substituents from among the above exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

As used herein, “halo” or “halogen” refers to bromo (Br), chloro (Cl), fluoro (F) or iodo (I), and preferred halogen as a substituent is fluoro or chloro can be

In the present specification, the term "alkyl group" refers to a saturated aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., which represents a substituent You may or may not have it. The additional substituent in the case of being substituted is not particularly limited, and examples thereof include an alkyl group, a halogen group, an aryl group, and a heteroaryl group, and this point is also common to the description below. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 4 or less, from the viewpoint of availability and cost.

In this specification, the term "aryl group" refers to an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, anthracenyl group, a pyrenyl group, a fluoranthenyl group, etc., which is a substituent group. You do not have to have it even if you have it. The number of carbon atoms in the aryl group is not particularly limited, but is preferably in the range of 6 or more and 40 or less, and more preferably in the range of 6 or more and 24 or less. As a specific example of an aryl group, Preferably they are a phenyl group, 1-naphthyl group, and 2-naphthyl group.

In this specification, "alkoxy group" represents a functional group to which an aliphatic hydrocarbon group is bonded via an ether bond, such as methoxy group, ethoxy group, propoxy group, etc., and this aliphatic hydrocarbon group may or may not have a substituent. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 4 or less.

In this specification, when a part such as a film, layer, region, component, etc. is said to be "on" or "on" another part, it is not only directly on top of another part, but also another film, layer, region, A case where a component or the like is interposed is also included.

In this specification, a “nano” object refers to an object having at least one dimension in the nm range. Nano-sized objects can have any of a wide variety of shapes and can be formed from a wide variety of materials, including, for example, nanowires, nanotubes, nanoplatelets, nanoparticles, and other nanostructures. .

In this specification, a “micro” object refers to an object having at least one dimension in the μm range. Typically, the angular dimension of micro-sized objects is in the μm range or exceeds the μm range. Micro-sized objects can have any of a wide variety of shapes and can be formed from a wide variety of materials, including, for example, microwires, microtubes, microparticles, and other microstructures.

In this specification, the term "combination of these" included in the expression of the Markush form means a mixture or combination of one or more selected from the group consisting of the components described in the expression of the Markush form, It means including one or more selected from the group consisting of.

In addition, each of the components to be described below may additionally perform some or all of the functions of other components in addition to its own main function, and some of the main functions of each component may be different from other components. Of course, it may be performed exclusively by a component.

Expressions such as “first”, “second”, “first”, or “second” used in various embodiments in this specification may modify various components regardless of order and/or importance, and corresponding components are not limited. Illustratively, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, the second component may also be renamed to the first component.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used in a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless explicitly specifically defined.

Hereinafter, a water repellent composition according to a preferred embodiment will be described in detail.

According to one embodiment of the present invention, a compound containing one or more elements selected from group 14 elements other than carbon (C); fluoride source; And it provides a water repellent composition comprising an organic solvent.

The water repellent composition may have a contact angle of 150° or more and a sliding angle of 10° or less, water repellent or super water repellent properties. Here, the contact angle refers to the angle formed between the liquid surface and the solid surface where the surface of the still liquid is in contact with the solid wall. In addition, the sliding angle means an inclination angle at which the liquid starts to flow with respect to the horizontal floor surface.

Since the water repellent composition uses a solution containing a fluorine source, which is a precursor composed only of inorganic materials, a compound containing one or more elements selected from group 14 elements except for carbon (C), and an organic solvent, it is possible to use eco-friendly coating and resist scratches and shocks. It has high abrasion resistance that can be endured. In addition, the water repellent composition not only provides long-term storage stability, but also has excellent water repellency and excellent lubricity in the case of surface-treated articles.

According to one embodiment, the fluorine source is ammonium fluoride, ammonium bifluoride, hydrogen fluoride, potassium fluoride, sodium fluoride ), tetraalkylammonium difluorides ((R) ₄ NHF ₂ , where R is methyl, ethyl, butyl, phenyl or fluorided Cl _{-C 4} alkyl group), alkyl phosphonium difluorides ( alkyl phosphonium difluorides) ((R) ₄ PHF ₂ , where R is a methyl, ethyl, butyl, phenyl or fluoridated Cl _{-C 4} alkyl group), triethylamine trihydrofluoride and fluoro including, but not limited to, fluorosilicic acid.

By including a fluorine source, the water repellent composition can improve surface lubricity, permeability, film formation, and texture while maintaining water repellency, while lowering surface energy.

According to one embodiment, the compound containing one or more elements selected from group 14 elements other than carbon (C) is a compound containing an element other than carbon (C) among chemical elements belonging to the 14th group of the periodic table, for example , silicon (Si), germanium (Ge), tin (Sn), or a compound containing a combination thereof. According to a preferred embodiment, the compound containing one or more elements selected from Group 14 elements other than carbon (C) may be a silicon-containing compound or a tin-containing compound.

According to one embodiment, the silicon "containing" compound may include a "compound represented by the following chemical formula:

(R ¹ ) _n Si(OR ² ) _4-n

In the formula, R ¹ is a substituted or unsubstituted alkyl group or aryl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms, R ¹ and R ² may be the same or different, and n is It is an integer from 0 to 2.

According to one embodiment, the silicon-containing compound is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraisopropoxysilane ( tetraisopropoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, ethoxytrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane , ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, tetramethoxymethylsilane, tetramethoxyethylsilane ( tetramethoxyethylsilane) and tetraethoxymethylsilane, but are not limited thereto.

According to one embodiment, the tin-containing compound may include a compound represented by the following formula:

Sn(OR) ₂ (ORN) ₂

In the formula, R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

According to one embodiment, the tin-containing compound is tin acetate, tin diacetate, dibutyl tin acetate, tin butoxide, or tin acetylacetonate. acetylacetonate), tin hexafluoroacetylacetonate, tin bis(acetylacetonate), tin chloride (SnCl ₄ 5H ₂ O or SnCl ₂ 2H ₂ O ), but is not limited thereto.

According to one embodiment, the organic solvent may be used without limitation as long as it is capable of diluting and dissolving one or more element-containing compounds selected from group 14 elements other than fluorine-source and carbon (C), which are precursors. Illustratively, the organic solvent is ethanol, 2-butanol, 1,4-butanediol, 1,3-butanediol, ethylene glycol (ethylene glycol), propylene glycol, N-methyl-2-pyrrolidone, DMSO, r-butyrolactone, propylene glycol monomethyl ether ( propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate, diethylene glycol monobenzylether, ethyl lactate, ammonium lactate, dimethyl acetamide (dimethyl acetamide) and mixtures thereof, but are not limited thereto.

According to one embodiment, the water repellent composition may optionally further include a reducing agent. The reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH), sodium borohydride (NaBH ₄ ), hydrazine (N ₂ H ₄ ), hydriodine (HI) and mixtures thereof Including, but not limited to.

According to one embodiment, the organic solvent may be included in an amount sufficient to dilute the compound containing one or more elements selected from Group 14 elements other than the fluorine-source and the carbon (C). Illustratively, the volume ratio of the fluorine source: a compound containing one or more elements selected from group 14 elements other than carbon (C): the organic solvent may be 1: 1 to 10: 20 to 100, preferably, 1 : 1 to 5: may be 20 to 50. The organic solvent may be used by mixing two or more organic solvents. Illustratively, a composition in which 2-butanol is slightly added may be used as the organic solvent, and solubility of the composition may be improved. As another example, the organic solvent may be a mixture of ethanol and 2-butanol, and the volume ratio of 2-butanol: ethanol may be 1: 3 to 5, preferably may be 1:4.

According to one embodiment, the water repellent composition may include oxide particles of one or more elements selected from group 14 elements except for carbon (C). Illustratively, the particles may be silicon oxide particles. The diameter of the particle may be 100 nm or less. The diameters of the particles may be different from each other.

According to one embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; centrifuging the first precursor and dispersing it in water; And adding a fluorine source to the first precursor, reacting at room temperature, drying at 80 ° C., and then calcining to form silicon oxide particles containing elemental fluorine. It provides a method for producing a water repellent composition.

Figure 1 (a) is a diagram schematically showing a method (2 step calcination method) for producing a water repellent composition according to an embodiment of the present invention, and Figure 1 (b) is a method for producing a water repellent composition according to an embodiment ( 2 step calcination method) is a diagram showing the reactants prepared. Referring to Figure 1 (a), after dissolving tetraethoxysilane (TEOS) and ammonium hydroxide (NH ₄ OH) in an organic solvent that is a mixture of ethanol and 2-butanol, at room temperature A first precursor is prepared by stirring for about 12 hours. Then, the first precursor is centrifuged and dispersed in water (H ₂ O). Then, fluorosilicic acid (H ₂ SiF ₆ ) was added to the first precursor, reacted at room temperature, dried at about 80 ° C, and then calcined at about 300 ° C to form silicon oxide particles containing fluorine. steps may be included. Referring to FIG. 1(b), it can be confirmed by an electron micrograph that silicon oxide particles having a diameter of 100 nm containing elemental fluorine are formed.

According to one embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; and adding a fluorine source to the first precursor, followed by centrifugation, drying, and calcination to form silicon oxide particles containing elemental fluorine.

Figure 2 (a) is a diagram schematically showing a method (1 step calcination method) of a water repellent composition according to an embodiment of the present invention, and Figure 2 (b) is a method of manufacturing a water repellent composition according to an embodiment ( 1 step calcination method) is a diagram showing the reactants prepared. all. Referring to Figure 2, after dissolving tetraethoxysilane (TEOS) and ammonium hydroxide (NH ₄ OH) in an organic solvent that is a mixture of ethanol and 2-butanol, about 12 hours at room temperature While stirring to prepare a first precursor. Then, after adding fluorosilicic acid (H ₂ SiF ₆ ) to the first precursor, centrifuging, drying, and calcination at about 300° C. may include forming silicon oxide particles containing elemental fluorine. Referring to FIG. 1(b), it can be confirmed by an electron micrograph that silicon oxide particles having a diameter of 100 nm containing elemental fluorine are formed.

According to one embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; centrifuging the first precursor and dispersing it in water; and adding a fluorine source to the first precursor and reacting hydrothermal to form silicon oxide particles containing elemental fluorine.

3 is a view showing a reactant according to a method for producing a water repellent composition according to an embodiment of the present invention (2 step hydrothermal method), and it can be confirmed by electron micrographs that silicon oxide particles having a diameter of 100 nm containing elemental fluorine are formed. . Referring to Figure 3, after dissolving tetraethoxysilane (TEOS) and ammonium hydroxide (NH ₄ OH) in an organic solvent that is a mixture of ethanol and 2-butanol, about 12 hours at room temperature While stirring to prepare a first precursor. Then, the first precursor is centrifuged and dispersed in water (H ₂ O), and then fluorosilicic acid (H ₂ SiF ₆ ) is added to the first precursor and hydrothermal for about 1 hour at about 120 ° C. ) to form silicon oxide particles containing elemental fluorine.

According to one embodiment of the present invention, preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; and adding a fluorine source to the first precursor and performing a hydrothermal reaction to form silicon oxide particles containing elemental fluorine.

4 is a view showing a reactant according to a method for producing a water repellent composition (1 step hydrothermal method) according to an embodiment of the present invention, and it can be confirmed by electron micrographs that silicon oxide particles having a diameter of 100 nm containing elemental fluorine are formed. . Referring to Figure 4, after dissolving tetraethoxysilane (TEOS) and ammonium hydroxide (NH ₄ OH) in an organic solvent that is a mixture of ethanol and 2-butanol, about 12 hours at room temperature While stirring to prepare a first precursor. Then, a step of adding fluorosilicic acid (H ₂ SiF ₆ ) to the first precursor and hydrothermally reacting at about 120°C for about 1 hour to form silicon oxide particles containing elemental fluorine may be included.

Since the present invention can prepare a water repellent composition solution using a precursor composed only of inorganic materials, it is possible to suppress the emission of factors harmful to the human body and the environment that may occur from organic water repellent agents, and to form a water repellent surface with improved durability. In addition, it is possible to prepare a water repellent composition stably and economically, and has excellent adhesion to the surface of an article and excellent water repellency.

According to one embodiment of the present invention, a method of treating the surface of an article using the water repellent composition is provided. Methods for coating the water repellent composition on the surface of the article include spin coating, dip coating, bar coating, spray coating, doctor blade, inkjet It may be processed by a printing method, but is not limited thereto.

According to one embodiment, the surface of the article may be treated by mixing the water repellent composition and a dye. In this case, dyes can be selected and used according to the color to be implemented on the surface of the article, so that various colors of the surface-treated article can be expressed.

According to one embodiment, when the size (diameter) of the silicon oxide particles included in the water repellent composition is prepared to be 100 nm or less and treated on the surface of an article, it is possible to have super water repellency while being transparent.

In addition, it is possible to make the size (diameter) of the silicon oxide particles included in the water repellent composition different from the nano size to the micro size and mix them together when treating the surface of the article. By making the sizes of the silicon oxide particles different from each other, it is possible to increase mechanical durability by minimizing spaces between the particles (voids between particles).

According to one embodiment, examples of articles that can be surface-treated using the water repellent composition include solar cells (cover glass), smart phones, touch panels, displays such as TVs (removal of foreign substances on the surface, blocking of water and preventing fingerprints). ), automobiles (rearview mirror, instrument panel, etc.), secondary batteries (corrosion prevention), electronic products (waterproof treatment), pipes (water repellent treatment), buildings (walls, exterior materials), etc. can be used

In addition, the substrate that can be coated with the water repellent composition is not particularly limited, and may be illustratively glass, ceramic, plastic, cotton, paper or metal.

According to one embodiment of the present invention, an article surface-treated using the water repellent composition is provided. The article may be a solar cell, a smart phone, a touch panel, a secondary battery, a display, a car, a pipe, or a building.

The present invention will be described in more detail through the following examples, but the scope of the present invention is not limited thereto.

(Example)

Preparation of water repellent composition

Dissolve 3 mL of tetraethoxysilane (TEOS; manufacturer: Sigma Aldrich) and 12 mL of ammonium hydroxide (25% NH ₄ OH; manufacturer: Sigma Aldrich) in a mixed solvent of 80 mL of ethanol and 20 mL of 2-butanol. After that, the mixture was stirred at room temperature for about 12 hours to prepare a first precursor. Then, the first precursor was centrifuged and dispersed in water (H ₂ O), and fluorosilicic acid (H ₂ SiF ₆ ) was added to the first precursor, reacted at room temperature, and then dried at about 80 ° C. Calcination was performed at about 300° C. to prepare a water repellent composition comprising silicon oxide particles containing elemental fluorine.

(Comparative example)

Silicon oxide particles (SiO ₂ NPs) containing no fluorine element were prepared as comparative examples. Dissolve 3 mL of tetraethoxysilane (TEOS; manufacturer: Sigma Aldrich) and 12 mL of ammonium hydroxide (25% NH ₄ OH; manufacturer: Sigma Aldrich) in a mixed solvent of 80 mL of ethanol and 20 mL of 2-butanol. After that, the mixture was stirred at room temperature for about 12 hours to prepare a first precursor. Then, the first precursor is centrifuged, washed by dispersing in water (H ₂ O), dried at about 80 ° C and calcined at about 300 ° C to include silicon oxide particles that do not contain fluorine elements. A water repellent composition was prepared.

(experimental example)

Chemical analysis of water repellent composition

(1) FIG. 5 is an XPS spectrum showing elemental components and bonding states of the silicon oxide particles prepared according to Examples. Chemical reactions before (RT) and after (300°C) calcination of silicon oxide particles (SiO ₂ ) prepared as a comparative example and silicon oxide particles (F-SiO ₂ NPs) containing elemental fluorine prepared according to Example 1. As the analysis result, FIG. 5 (a) provides information on the elements constituting the composition of the particles through the overall analysis, and _FIG . Provides information about the binding state of From FIG. 5 (a), the presence of the fluorine element can be confirmed from the fact that the fluorine element peak, which does not appear in the silicon oxide particles prepared in the comparative example, is detected in the silicon oxide particles containing the fluorine element prepared in the example. In addition, it can be confirmed from FIG. 5(b) that the silicon oxide particles containing fluorine element prepared in the example have various bonding states and are stabilized by Si-F bonding after 300 °C pixel.

(2) Figure 6 is a view showing TEM pictures of the particles of Examples and Comparative Examples. It can be seen that the silicon oxide particles prepared in Comparative Example have a spherical shape, whereas the silicon oxide particles containing fluorine element prepared in Examples have a slightly deformed spherical shape and include nanopores.

(3) Figure 7 is a view showing the superhydrophobic properties of silicon oxide particles containing fluorine prepared in Example by treating the particles of Example and Comparative Example on a substrate of an article. Figure 7 (a) is a photograph showing that water permeates between the particles when a water droplet colored with methylene blue is dropped on a white sample made of silicon oxide particles prepared in Comparative Example, and Figure 7 (b) is a photograph produced in Example When water droplets colored with methylene blue are dropped on a white sample made of silicon oxide particles containing fluorine and fluorine, the superhydrophobicity of the particles is strong and the water does not spread and exists as droplets. Therefore, it can be confirmed that the silicon oxide particles containing elemental fluorine according to Example 1 have very excellent superhydrophobic properties.

Article treated with water repellent composition

Glass (slide glass), stainless steel (SUS304 2B product), PET (film), cloth, cotton (cotton), and paper (printer paper), which are usually easily available in the surroundings, were used as the substrate of the article. The silicon oxide particles containing elemental fluorine prepared in Example 1 were coated on the substrate surface of the article by a dip coating method. 8 shows a group (Bare) on glass, SUS, PET, cloth, cotton, and paper without surface treatment and a group (SH surfaces) treated using silicon oxide particles containing fluorine element prepared in Example 1 This is a picture showing the degree of spreading by dropping water droplets treated with methylene blue on In the surface-treated group, water droplets do not spread and the spherical shape is well maintained, so it can be confirmed that the super-water repellent property is maintained.

9 shows the superhydrophobicity of the substrate (glass, SUS, PET, cotton, paper) of the article surface-treated using the silicon oxide particles containing elemental fluorine prepared in Example 1. The surface coated with the water repellent shows well the splashing behavior of water droplets shown by the surface having excellent super water repellency, and it can be confirmed that the water droplets bounce off quickly when they fall.

Self-cleaning properties

10 is a diagram showing self-cleaning characteristics of glass surface-treated using silicon oxide particles containing elemental fluorine prepared in Example 1; It can be confirmed that the surface of the coated glass has self-cleaning characteristics due to the low surface energy of the silicon oxide particles containing elemental fluorine according to Example 1.

durability evaluation

The chemical durability of the silicon oxide particles containing elemental fluorine prepared in Example 1 can be confirmed through the 585 test. The 8585 test is to check the change rate of physical properties under the conditions of a temperature of 85 ° C and a humidity of 85%. can

Referring to FIG. 11, it can be seen that the glass coated with the silicon oxide particles containing fluorine produced in Example 1 maintains super water repellency of 150 degrees or more even after 500 hours of the 8585 test.

In the above, the technology disclosed in this specification has been described in detail as a preferred embodiment, but the technical spirit of the present invention is not limited to the above embodiments, and those skilled in the art within the scope of the technical spirit of the present invention Various modifications and changes are possible by the person.

Claims (20)

a compound containing at least one element selected from Group 14 elements other than carbon (C);
a fluoride source; and
A water repellent composition comprising an organic solvent. According to claim 1,
The compound containing one or more elements selected from group 14 elements other than carbon (C) is a silicon-containing compound or a tin-containing compound, a water repellent composition. According to claim 2,
The silicon-containing compound comprises a compound represented by the following formula, a water repellent composition:
(R ¹ ) _n Si(OR ² ) _4-n
(Wherein, R ¹ is a substituted or unsubstituted alkyl group or aryl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms, R ¹ and R ² may be the same or different, and n is an integer from 0 to 2). According to claim 2,
The silicon-containing compound is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraisopropoxysilane, methoxytri methoxytriethoxysilane, dimethoxydiethoxysilane, ethoxytrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane (ethyltriethoxysilane), dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, tetramethoxymethylsilane, tetramethoxyethylsilane and tetraethoxy A water repellent composition comprising at least one selected from the group consisting of methylsilane (tetraethoxymethylsilane). According to claim 2,
The tin-containing compound comprises a compound represented by the following formula, a water repellent composition:
Sn(OR) ₂ (ORN) ₂
(Wherein R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms). According to claim 2,
The tin-containing compound is tin acetate, tin diacetate, dibutyl tin acetate, tin butoxide, tin acetylacetonate, tin hexafluoro Roacetylacetonate (tin hexafluoroacetylacetonate), tin bis (acetylacetonate) (tin bis (acetylacetonate) (tin bis (acetylacetonate)), containing at least one selected from the group consisting of tin chloride (tin chloride), a water repellent composition. According to claim 1,
The fluorine source is ammonium fluoride, ammonium bifluoride, hydrogen fluoride, potassium fluoride, sodium fluoride, tetraalkylammonium di tetraalkylammonium difluorides ((R) ₄ NHF ₂ , where R is methyl, ethyl, butyl, phenyl or fluorided Cl _{-C 4} alkyl group), alkyl phosphonium difluorides (( R) ₄ PHF ₂ , where R is a methyl, ethyl, butyl, phenyl or fluorided C _l -C ₄ alkyl group), triethylamine trihydrofluoride and fluorosilicic acid; A water repellent composition comprising at least one selected from the group consisting of. According to claim 1,
The organic solvent is ethanol, 2-butanol, 1,4-butanediol, 1,3-butanediol, ethylene glycol , propylene glycol, N-methyl-2-pyrrolidone, DMSO (dimethyl sulfoxide), r-butyrolactone, propylene glycol monomethyl ether (propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate, diethylene glycol monobenzylether, ethyl lactate, ammonium lactate and dimethyl acetate A water repellent composition comprising at least one selected from the group consisting of amide (dimethyl acetamide). According to claim 1,
The fluorine source: a compound containing one or more elements selected from group 14 elements other than carbon (C): the volume ratio of the organic solvent is 1: 1 to 5: 20 to 50, the water repellent composition. According to claim 1,
At least one reducing agent selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH), sodium borohydride (NaBH ₄ ), hydrazine (N ₂ H ₄ ) and hydriodine (HI) Further comprising a water repellent composition. Preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature;
centrifuging the first precursor and dispersing it in water; and
Adding a fluorine source to the first precursor, reacting at room temperature, drying and calcination to form silicon oxide particles containing fluorine element,
The volume ratio of the fluorine source: the silicon-containing compound: the organic solvent is 1: 1 to 5: 20 to 50,
The organic solvent is a mixture of ethanol and 2-butanol,
Method for preparing a water repellent composition. Preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; and
Adding a fluorine source to the first precursor, centrifuging, drying, and calcining to form silicon oxide particles containing elemental fluorine,
The volume ratio of the fluorine source: the silicon-containing compound: the organic solvent is 1: 1 to 5: 20 to 50,
The organic solvent is a mixture of ethanol and 2-butanol,
Method for preparing a water repellent composition. Preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature;
centrifuging the first precursor and dispersing it in water; and
Adding a fluorine source to the first precursor and hydrothermal reaction to form silicon oxide particles containing elemental fluorine,
The volume ratio of the fluorine source: the silicon-containing compound: the organic solvent is 1: 1 to 5: 20 to 50,
The organic solvent is a mixture of ethanol and 2-butanol,
Method for preparing a water repellent composition. Preparing a first precursor by dissolving a silicon-containing compound and a reducing agent in an organic solvent and stirring at room temperature; and
Adding a fluorine source to the first precursor and performing a hydrothermal reaction to form silicon oxide particles containing elemental fluorine,
The volume ratio of the fluorine source: the silicon-containing compound: the organic solvent is 1: 1 to 5: 20 to 50,
The organic solvent is a mixture of ethanol and 2-butanol,
Method for preparing a water repellent composition. According to any one of claims 11 to 14,
A method for producing a water repellent composition, further comprising mixing a dye with the water repellent composition. According to any one of claims 11 to 14,
Characterized in that the particle diameter is 100 nm or less, water repellent composition manufacturing method. According to any one of claims 11 to 14,
The method for producing a water repellent composition, characterized in that the diameter of the particles is different from the nano size to the micro size. A water repellent composition prepared by the method according to any one of claims 11 to 14. A method of treating the surface of an article using the water repellent composition according to any one of claims 1 to 10. An article surface-treated using the water repellent composition according to any one of claims 1 to 10.

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