KR102155047B1 - Base-resistant coating composition and method for preparing thereof - Google Patents

Abstract

A method of preparing a silane coating composition according to an embodiment of the present invention includes preparing a first solution by mixing a fluoroalkyl silane and a solvent; Preparing a second solution by mixing the first solution, a polysilazane solution, and a metal precursor; And removing the solvent from the second solution.

Description

Base-resistant coating composition and method for preparing thereof

The present invention relates to a coating composition having improved basic resistance and a method for preparing the same.

As technologies are advanced and diversified across industries such as electricity/electronics, semiconductors, displays, automobiles, ships, architecture, bio, and energy/environments, the demand for materials with new properties and innovative functions is increasing rapidly.

As a means of responding to these demands, research is being conducted on water-repellent coating materials for highly functional water-repellent thin films or molecular films. There are various types of water-repellent materials such as acrylic resin, polyurethane resin, fluorine resin, silicone acrylic resin, silane-based, siloxane-based, and siliconate-based.

Among them, fluorine-based materials have a structure in which hydrogen elements substituted in the carbon-carbon main skeleton are substituted with fluorine, and have excellent water and antifouling properties, but conventional fluorine-based polysilazane coating compositions and other polysilazane coating compositions have basic resistance. Due to this vulnerability, improvement has been demanded.

Korean Patent Registration No. 10-1596441

The technical object of the present invention is to provide a coating composition manufacturing method with improved basic resistance and a coating composition with improved basic resistance prepared thereby.

The technical problem to be achieved by the present invention is not limited to the technical problems mentioned above, and other technical problems that are not mentioned can be clearly understood by those of ordinary skill in the technical field to which the present invention belongs from the following description. There will be.

In order to achieve the above technical problem, an embodiment of the present invention provides a method of preparing a silane coating composition with improved basic resistance.

One aspect of the present invention comprises the steps of preparing a first solution by mixing a fluoroalkyl silane and a solvent; Preparing a second solution by mixing the first solution, a polysilazane solution, and a metal precursor; And it provides a method for producing a silane coating composition comprising the step of removing the solvent from the second solution.

According to an embodiment of the present invention, the step of preparing the first solution may further include an alkyl silane.

According to an embodiment of the present invention, the fluoroalkyl silane may have the structure of Formula 1:

[Formula 1]

In this case, R is independently hydrogen or a C ₁ to C ₃ alkyl group, and a and b are integers of 1 to 10.

According to an embodiment of the present invention, the step of preparing the first solution may provide the fluoroalkyl silane in an amount of 1% to 30% by weight.

According to an embodiment of the present invention, the solvent may include alcohol or water.

According to an embodiment of the present invention, the alcohol is methanol, ethanol, n-propanol, n-butanol, amyl alcohol, n-hexyl alcohol, n-heptanol, n-octanol, isopropanol, isobutanol, isoamyl alcohol , 3-pentanol, t-butanol, t-amyl alcohol, 2,3-dimethyl-2-butanol, 2-(trifluoromethyl)-2-propanol, 3-methyl-3-pentanol, 3-ethyl- 3-pentanol, 2-methyl-2-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-2-pentanol, 2-methyl-2-hexanol, 2-cyclopropyl- 2-propanol, 2-cyclopropyl-2-butanol, 2-cyclopropyl-3-methyl-2-butanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 3-propylcyclopentanol, 1-methyl Cyclohexanol, 1-ethylcyclohexanol, 1-methylcycloheptanol, and combinations thereof.

According to an embodiment of the present invention, the solvent may further include the alcohol or the co-solvent of the water.

According to an embodiment of the present invention, the polysilazane solution may be provided with a polysilazane binder or an organic polysilazane binder in an amount of 5 to 500 parts by weight based on 100 parts by weight of the fluoroalkyl silane.

According to an embodiment of the present invention, the metal precursor may be any one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof.

According to an embodiment of the present invention, the metal precursor may be provided in an amount of 5 to 500 parts by weight based on 100 parts by weight of the fluoroalkyl silane.

According to an embodiment of the present invention, the step of removing the solvent may be performed through vacuum distillation or rotary evaporation.

According to an embodiment of the present invention, the step of removing the solvent may be performed at a vacuum degree of 0.02 MPa to 0.2 MPa.

According to an embodiment of the present invention, the alkyl silane may have the structure of Formula 2:

[Formula 2]

In this case, R is independently hydrogen or a C ₁ to C ₃ alkyl group, and c is an integer of 1 to 20.

According to an embodiment of the present invention, the alkyl silane may be provided in an amount of 1 to 200 parts by weight based on 100 parts by weight of the fluoroalkyl silane.

According to an embodiment of the present invention, after the step of removing the solvent, a step of mixing a binder and/or a catalyst with the coating composition may be further included.

According to an embodiment of the present invention, the catalyst may include a primary amine-based, secondary amine-based, tertiary amine-based or platinum-based catalyst, and may be provided in an amount of 1 to 30 PHR compared to the polysilazane solution.

According to an embodiment of the present invention, the binder may be provided in an amount of 5 to 500 parts by weight based on 100 parts by weight of the solid content of the second solution.

According to an embodiment of the present invention, the catalyst may include a primary amine-based, secondary amine-based, tertiary amine-based or platinum-based catalyst, and may be provided at 1 PHR to 30 PHR compared to the binder.

According to an embodiment of the present invention, the step of mixing the binder and/or catalyst with the coating composition may be physically stirred to control the composition of the silane coating composition.

According to an embodiment of the present invention, the binder and/or the catalyst may be controlled so that the total solid content of the silane coating composition is 1% to 90% by weight, for example, 1% to 50% by weight. .

Another aspect of the present invention provides a silane coating composition prepared by the above manufacturing method.

Another aspect of the present invention is the step of applying the silane coating composition to a substrate; And curing the silane coating composition applied to the substrate to form a coating layer.

According to an embodiment of the present invention, the step of applying the silane coating composition to a substrate may be selected from the group consisting of a supporting method, an impregnation method, and a spraying method using spinning, slot die, microgravure, gravure or spray. It can be done through one.

According to an embodiment of the present invention, the step of applying the silane coating composition to a substrate may be performed for 1 second to 20 minutes while rotating the substrate at 500 rpm to 4,000 rpm.

According to an embodiment of the present invention, the forming of the coating layer may cure the coating composition by pulse UV irradiation, exposure to ammonia water, exposure to hydrogen peroxide, or heat treatment.

According to one embodiment of the invention, the UV irradiation pulse is 1,000V to 4,000V, 5Hz to 50Hz and at 150nm to 450nm wavelength 0.5J / cm ² to the ultraviolet to 50㎲ of 100J / cm ² ultraviolet irradiation condition 1000㎲ And 10 ms to 5 s UV irradiation may be repeatedly performed.

According to an embodiment of the present invention, the exposure to the ammonia water may be performed for 12 hours to 120 hours using 5% to 35% by weight of ammonia water at 15°C to 35°C.

According to an embodiment of the present invention, the exposure to the hydrogen peroxide solution may be performed for 12 to 120 hours using 5% to 50% by weight of hydrogen peroxide at 15°C to 100°C.

According to an embodiment of the present invention, after the step of forming the coating layer, a step of heat-treating the coating film may be further included.

According to an embodiment of the present invention, the heat treatment step may be heat treated under a temperature condition of 70 ℃ to 120 ℃.

Another embodiment of the present invention provides a coating film manufactured by the method of manufacturing the coating film.

According to an embodiment of the present invention, a silane coating composition having improved basic resistance can be provided.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flow chart showing a method of manufacturing a silane coating composition according to an embodiment of the present invention.
2 is a flow chart showing a method of manufacturing a silane coating composition according to another embodiment of the present invention.
3 is a flow chart showing a method of manufacturing a coating film according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, bonded)" with another part, it is not only "directly connected", but also "indirectly connected" with another member in the middle. "Including the case. In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

The terms used in the present specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or a combination thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

An embodiment of the present invention provides a method of preparing a silane coating composition.

Referring to FIG. 1, the method of preparing the silane coating composition includes preparing a first solution by mixing a fluoroalkyl silane and a solvent (S1110), and mixing the first solution, a polysilazane solution, and a metal precursor. 2 It may include preparing a solution (S1120), and removing the solvent from the second solution (S1130).

In the present specification, “fluoroalkyl silane” is a C ₁ to C ₂₁ alkyl in which one substituent bonded to Si is substituted with one or more hydrogens with fluorine (F), and at least one substituent of the remaining three bonded to Si May be a compound in which is an alkoxy group. For example, the fluoroalkyl silane may have the structure of Formula 1:

[Formula 1]

In this case, R is independently hydrogen or a C ₁ to C ₃ alkyl group, and a and b are integers of 1 to 10.

In the step of preparing the fluoroalkyl silane solution (S1110), the fluoroalkyl silane may be provided in an amount of 1% to 30% by weight and dissolved in the solvent. At this time, when the concentration of the fluoroalkyl silane is less than 1% by weight, the water repellency may decrease due to the decrease in reactivity due to a low concentration, and when the concentration of the fluoroalkyl silane is more than 30% by weight, unreacted fluorine The printing properties of the coating film may be deteriorated by the roalkyl silane.

In the present specification, “solvent” refers to a compound containing a hydroxy group (-OH) in a molecule so that hydrolysis can be performed. The solvent may include alcohol or water. The alcohol is, for example, methanol, ethanol, n-propanol, n-butanol, amyl alcohol, n-hexyl alcohol, n-heptanol and n-octanol as primary alcohols, isopropanol, isobutanol as secondary alcohols. , Isoamyl alcohol and 3-pentanol, and tertiary alcohols t-butanol, t-amyl alcohol, 2,3-dimethyl-2-butanol, 2-(trifluoromethyl)-2-propanol, 3-methyl- 3-pentanol, 3-ethyl-3-pentanol, 2-methyl-2-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-2-pentanol, 2-methyl-2 -Hexanol, 2-cyclopropyl-2-propanol, 2-cyclopropyl-2-butanol, 2-cyclopropyl-3-methyl-2-butanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 3 -Propylcyclopentanol, 1-methylcyclohexanol, 1-ethylcyclohexanol and 1-methylcycloheptanol may be included, preferably t-butanol in primary alcohol, secondary alcohol or tertiary alcohol , t-amyl alcohol, 2,3-dimethyl-2-butanol or 2-(trifluoromethyl)-2-propanol.

The solvent is an organic solvent such as dibutylether (DBE, dibutylether), toluene, tetrahydrofuran (THF, tetrahydrofuran), n-methylpyrrolidone (NMP, n-) in order to increase the solubility of the binder and/or catalyst. methyl pyrolidone), xylene, propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether acetate (PMA), or cyclohexane. can do.

The solvent may further include the alcohol or a co-solvent of the water to lower the boiling point of the solvent to lower the distillation time and temperature under reduced pressure, and to facilitate removal of the solvent.

The co-solvent may include, for example, chloroform, dichloromethane, acetone, diethyl ether, tetrahydrofuran, or a combination thereof. However, the co-solvent is not limited to the solvents listed above, and any type of solvent capable of dissolving polysilazane and lowering the boiling point may be used as the co-solvent.

In the present specification, the "polysilazane solution" may be prepared by mixing a polysilazane binder or an organic polysilazane binder in an amount of 5 parts by weight to 500 parts by weight based on 100 parts by weight of the fluoroalkyl silane. At this time, if the concentration of the polysilazane is less than 5 parts by weight, the printability and water repellency of the coating film may be reduced by a low concentration, and when the concentration of the polysilazane is more than 500 parts by weight, unreacted polysilazane The glass may change the coating composition and the water repellency properties of the coating film.

The polysilazane binder may further include an organic solvent used to dissolve the polysilazane binder. For example, the organic solvent is dibutylether (DBE, dibutylether), toluene, tetrahydrofuran (THF), n-methylpyrrolidone (NMP, n-methyl pyrolidone), xylene, Propylene glycol methyl ether acetate (PGMEA, propylene glycol methyl ether acetate), propylene glycol monomethyl ether acetate (PMA, propylene glycol monomethyl ether acetate), or cyclohexane may be included. However, the organic solvent is not limited to the solvents listed above, and any type of solvent may be used as the solvent capable of dissolving polysilazane as the organic solvent.

In the present specification, the “metal precursor” may include any one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof. The metal precursor may be, for example, zirconium butoxide or titanium isopropoxide, but is not limited thereto.

The metal precursor may be provided in an amount of 5 to 500 parts by weight based on 100 parts by weight of the fluoroalkyl silane. The step of preparing the second solution (S1120) may be performed at 25°C to 70°C. In addition, the step of preparing the second solution (S1120) may be performed for 0.5 to 240 hours. Meanwhile, after preparing the mixed solution (S1120) and removing the solvent from the second solution (S1130), mixing a binder and/or a catalyst in the second solution (S1140) may be further included. I can.

The binder may contain polysilazane, organic polysilazane, urethane, acrylic, vinyl, amine, imide, amide, silane, silicone, cellulose, epoxy, or fluorine compounds alone or in combination. have. The binder may be prepared by mixing 5 parts by weight to 500 parts by weight based on 100 parts by weight of the solid content of the second solution. When the concentration of the binder is less than 5 parts by weight, the printability and water repellency of the coating film may be reduced by a low concentration and a decrease in the thickness of the thin film. When the concentration of the binder is more than 500 parts by weight, unreacted polysilazane As a result, the coating composition may be changed and the water-repellent property of the coating film may be changed.

The “total weight of the solid content of the second solution” or the “total weight of the solid content of the silane coating solution” refers to the total weight of the fluoroalkyl silane, polysilazane, metal precursor and alkyl silane contained in the second solution or the silane coating solution, respectively. it means.

The binder may be used alone or in combination of polysilazane or organic polysilazane material.

The binder may further include an organic solvent capable of dissolving polysilazane and fluorine-based polysilazane.

For example, the organic solvent is dibutylether (DBE, dibutylether), toluene, tetrahydrofuran (THF), n-methylpyrrolidone (NMP, n-methyl pyrolidone), xylene, Propylene glycol methyl ether acetate (PGMEA, propylene glycol methyl ether acetate), propylene glycol monomethyl ether acetate (PMA, propylene glycol monomethyl ether acetate), or cyclohexane may be included. However, the organic solvent is not limited to the solvents listed above, and any type of solvent may be used as the solvent capable of dissolving polysilazane and an organic binder as the organic solvent.

The catalyst may include a catalyst for accelerating curing of the coating film. The catalyst may include a primary amine-based, secondary amine-based, tertiary amine-based and/or platinum-based catalyst.

For example, the catalyst may be provided in 1 PHR (Part per Hundred parts of Resin) to 30 PHR compared to the polysilazane solution. When the catalyst is less than 1 PHR compared to the polysilazane solution, the effect of the catalyst may be insufficient and the degree of curing may be weak. When the catalyst is more than 30 PHR compared to the polysilazane solution, the amount of added catalyst is increased. The properties of the coating liquid may deteriorate due to hardening and generation of deposits.

For example, the catalyst may be provided at 1 PHR to 30 PHR compared to the binder. When the catalyst is less than 1 PHR compared to the binder, the degree of curing may be weak due to insufficient effect of the catalyst. When the catalyst is more than 30 PHR compared to the binder, due to rapid curing and precipitation due to an increase in the content of the added catalyst. The properties of the coating liquid may deteriorate.

The amine-based catalyst is, for example, methylamine, aniline, 1,3-cyclohexanebis (methylamine), 1,5-diamino-2-methylpentane, 2,4-diaminotoloene, 2 ,2-dimethyl-1,3-propanediamine, 4.4'-methylenebis(cyclohexylamine), p-xylenediamine or a primary amine including tris(2-aminoethyl), dimethylamine, diethylamine, Piperidine, N,N'-diethyl-2-butene-1,4-diamine, N,N'-diisopropylethylenediamine, N,N'-diisopropyl-1,3-propanediamine, N ,N'-difetyl-p-phethylenediamine, 2-isopropyl-2-oxazoline, 1,4,8,12-tetrazacyclopentadecane or 1,4,8,11-tetrazacyclotetradecane -2,7-dione-containing secondary amine or trimethylamine, N,N-dimethylpentylamine, N-ethyl-N-methylbutylamine, N,N-dimethylcyclohexylamine, N-ethyl-N-propyl Aniline, N,N,N',N'-tetramethyl-1,6-diaminohexane, or a tertiary amine including N,N-dimethylbenzanthracene-6-amine.

The platinum-based catalyst is, for example, powdered with fine platinum powder, platinum black, chloroplatinic acid, platinum tetrachloride, alcohol solution of chloroplatinic acid, platinum-olefin complex, platinum-alkenylsiloxane complex, platinum-carbonyl complex. Methyl methacrylate resins, polycarbonate resins, polystyrene resins, silicone resins, or similar thermoplastic organic resins (in which a platinum-based catalyst is dispersed).

However, the amine-based catalyst is not limited to the compounds listed above, and any type of catalyst may be used as the catalyst capable of converting the polysilazane or the binder.

The step of removing the solvent from the second solution (S1130) may be performed at 30°C to 70°C for 1 to 30 minutes. When the step of removing the solvent from the second solution (S1130) is performed at less than 30° C. or less than 1 minute, the composition of the coating composition may change due to a reaction between the binder and the catalyst under the residual solvent. 2 When the step of removing the solvent from the solution (S1130) is performed at more than 70° C. or for more than 30 minutes, it may be difficult to prepare a clean coating film due to the generation of metal oxide particles.

The step of removing the solvent from the second solution (S1130) may be performed at a vacuum degree of 0.02 MPa to 0.2 MPa. If the step of removing the solvent from the second solution (S1130) is performed at a vacuum degree of less than 0.02 MPa, the composition of the coating composition may change due to a reaction between the binder and the catalyst under the residual solvent, and in the second solution, the When the step of removing the solvent (S1130) is performed at a vacuum degree of 0.2 MPa or more, it may be difficult to prepare a clean coating film due to the generation of zirconium oxide particles. The manufacturing method of the silane coating composition according to an exemplary embodiment of the present invention can reduce the manufacturing time of the silane coating composition by reducing the vacuum distillation process time by using a co-solvent.

In the step of mixing the binder and/or the catalyst with the second solution (S1140), stirring may be performed to control the composition of the silane coating composition. At this time, the stirring may be physically stirring to control the composition of the silane coating composition.

For example, the step of mixing a binder and/or a catalyst in the coating composition may be controlled so that the total solid content of the silane coating composition is 1% to 90% by weight, for example, 1% to 50% by weight. I can. If the total solid content is less than 1% by weight, printability and surface hardness may decrease due to a decrease in the thickness of the thin film, and if the total solid content is more than 50% by weight, the thickness of the thin film increases, thereby increasing the curing process time. Can cause.

For example, the step (S1140) of mixing the binder and/or catalyst with the coating composition may be performed at 25°C to 70°C for 1 hour to 24 hours.

In addition, another embodiment of the present invention provides a method of preparing another silane coating composition.

Among the configurations of the present embodiment, the same contents as those in the above embodiment are replaced with the above description, and the differences between the present embodiment and the above embodiment are mainly described.

Referring to FIG. 2, the method of preparing the silane coating composition includes preparing a first solution by mixing a fluoroalkyl silane, an alkyl silane, and a solvent (S1210), the first solution, a polysilazane solution, and a metal precursor. It may include preparing a second solution by mixing (S1220), and removing the solvent from the second solution (S1230).

After the step of preparing the second solution (S1220), a step (S1240) of mixing a binder and/or a catalyst with the second solution may be optionally further included.

The alkyl silane may be a compound in which one substituted or unsubstituted C ₁ to C ₂₀ alkyl bonded to Si, and at least one of the other three substituents bonded to Si is an alkoxy group. For example, the alkyl silane may have the structure of Formula 2:

[Formula 2]

In this case, R is independently hydrogen or a C ₁ to C ₃ alkyl group, and c is an integer of 1 to 20.

The alkyl silane may be provided in an amount of 1 to 200 parts by weight based on 100 parts by weight of the fluoroalkyl silane.

Another embodiment of the present invention provides a silane coating composition.

The silane coating composition may be prepared by a method of preparing a silane coating composition according to an embodiment of the present invention.

The silane coating composition according to an embodiment of the present invention improves the basic resistance of the coating film by introducing a metal precursor and/or an alkyl silane to the fluoroalkyl silane, and accelerates the curing of the coating film by amine-based and platinum-based catalysts. It is possible to reduce the manufacturing time of the coating film.

In addition, another embodiment of the present invention provides a method of manufacturing a coating film.

Referring to Figure 3, the method of manufacturing the coating film is a step of applying a silane coating composition prepared by the method of manufacturing a silane coating composition according to an embodiment of the present invention to a substrate (S2110) and silane applied to the substrate. It may include curing the coating composition to form a coating layer (S2120).

The substrate may include a plastic, metal material, or ceramic material. For example, the plastic may include PET, PI, PMMA, PP, PE, PEN, EVOH, PVA, TAC, PC, or bioplastic. Alternatively, for example, the substrate may include clay, fiberglass, a composite including silica, and a glass or silicon wafer. For example, the metal material may include aluminum, stainless steel (SUS), or iron. The step of applying the silane coating composition to a substrate (S2110) includes a supporting method, an impregnation method, and applying the coating composition to the surface of the substrate. Spinning, slot die, microgravure, gravure, or spraying using a spray method can be performed.

For example, the step of applying the silane coating composition to a substrate (S2110) is characterized in that it is performed for 1 second to 20 minutes while rotating the substrate at 500 rpm to 4,000 rpm.

In this case, the step of applying the silane coating composition to a substrate (S2110) is a process performed to ensure that the state of the silane coating composition is uniformly present and at the same time, the number of rotations or the time is within a general range. The condition is not limited to the number of revolutions and time within the above range, and the silane coating composition may be coated by varying the conditions.

A pretreatment step may be optionally further included between the step of applying the silane coating composition (S2110) and the step of forming the coating layer (S2120).

The pretreatment step may be performed by heat treatment under a temperature condition of 70°C to 120°C.

In the step of forming the coating layer (S2120), the coating composition may be cured by pulsed UV irradiation, ammonia water exposure, and hydrogen peroxide exposure.

In this case, when the coating composition is cured by chemical treatment, it is not limited to exposure to aqueous ammonia and hydrogen peroxide, and can be cured by heating by steam and impregnation under a chemical atmosphere.

The pulsed UV irradiation is a total exposure amount (energy) of 0.5J/cm ² to 100J/cm ² at a wavelength of 1,000 V to 4,000 V, 5 Hz to 50 Hz, and 150 nm to 450 nm. It can be carried out by repeating 5s ultraviolet irradiation.

For example, the pulsed UV irradiation may be performed 1,000 to 5,000 times.

The exposure to the ammonia water may be performed for 12 hours to 120 hours using 5% to 35% by weight of ammonia water at 15°C to 35°C.

The exposure to hydrogen peroxide may be performed for 12 hours to 120 hours using 5% to 35% by weight of ammonia water at 15°C to 100°C.

After the forming of the coating layer (S2120), a step of heat-treating the coating film (not shown) may be optionally further included.

The step of heat-treating the coating film may be performed so that the fluoroalkyl groups present in the coating film are arranged toward the surface of the coating film. When the fluoroalkyl groups are arranged toward the surface of the coating film, the water repellency of the coating film may be improved.

For example, the step of heat-treating the coating film may be performed under a temperature condition of 70°C to 120°C. However, it is not necessarily limited to the above temperature, and if the fluorine alkyl functional group is in a range in which the arrangement is induced toward the coating surface, it may be suitable as a heat treatment temperature.

However, if it exceeds 120°C, heat damage may occur when using plastic as a substrate, so it is more preferable to perform it at a temperature of less than 120°C.

The method of manufacturing a coating film according to an embodiment of the present invention may improve the basic resistance and water/oil repellency of the coating film by using a silane coating composition in which fluorine particles are easily dispersed during manufacture.

The method of manufacturing a coating film according to an exemplary embodiment of the present invention may improve basic resistance and water/oil repellency of the coating film by introducing a metal precursor and/or an alkyl silane to the fluoroalkyl silane during manufacture.

In the method of manufacturing a coating film according to an embodiment of the present invention, it is possible to uniformly apply the silane coating composition during manufacture, thereby improving optical properties such as transmittance of the coating film.

The coating film according to an embodiment of the present invention can be applied to various applications for forming a coating. For example, the application field may include, but is not limited to, surface treatment of displays, sunlight, interior and exterior materials for buildings, heat exchange pipes, wire surfaces, piers, water purifier pipes, automobiles, transportation devices, or optical devices. . At this time, by applying the coating film according to an embodiment of the present invention, it is possible to improve the basic resistance and/or water/oil repellency properties of the application field.

Hereinafter, it will be described in detail through examples.

Example

Example 1.

First, 0.001 mol of perfluorooctyltriethoxysilane (1H,1H,2H,2H-Perfluorooctyltriethoxysilane) and 0.003 mol of trimethoxy(octyl)silane and ethanol were mixed and stirred. To this, a 0.03M hydrochloric acid solution was added, followed by stirring at 40°C for 17 hours. After the reaction, ethanol was removed by distillation at 80° C. under reduced pressure with a vacuum degree of 0.09 MPa for 10 minutes, and dried.

1.2% by weight of the dried compound and 10% by weight of a polysilazane solution, dibutyl ether, and an amine-based catalyst were mixed and stirred at room temperature for 1 day to obtain a final coating composition of 11.2% by weight.

Example 2.

First, 0.001 mol of perfluorooctyltriethoxysilane (1H,1H,2H,2H-Perfluorooctyltriethoxysilane) and 0.003 mol of trimethoxy(octyl)silane and ethanol were mixed and stirred. To this, a 0.03M hydrochloric acid solution was added, followed by stirring at 40°C for 17 hours. After the reaction, ethanol was removed by distillation at 80° C. under reduced pressure with a vacuum degree of 0.09 MPa for 10 minutes, and dried.

A mixed solution of 0.05M of the dried compound, 0.004M aqueous ammonia (NH ₄ OH) and butanol was prepared, and 0.3M zirconium butoxide was mixed thereto, followed by stirring at 40° C. for 4 days. Thereafter, distillation was performed at 80° C. under reduced pressure with a vacuum degree of 0.09 MPa for 10 minutes to obtain zirconium perfluoro alkyl silane and alkyl silane compound.

A final silane coating composition of 32% by weight was obtained by mixing 22% by weight of zirconium perfluoroalkyl silane and an alkyl silane compound, 10% by weight of a polysilazane solution, dibutyl ether, and an amine-based catalyst.

Example 3.

It was carried out in the same manner as in Example 2, except that 0.3M titanium isopropoxide was used instead of 0.3M zirconium butoxide. (In this case, 22% by weight of titanium perfluoroalkyl silane and alkyl silane compound were obtained instead of 22% by weight of zirconium perfluoroalkyl silane and alkyl silane compound.

Comparative Example 1.

First, 0.004 mol of perfluorooctyltriethoxysilane (1H,1H,2H,2H-Perfluorooctyltriethoxysilane) was mixed with ethanol and stirred at 40°C. To this, a 0.03M hydrochloric acid solution was added, followed by stirring at 40°C for 17 hours. After the reaction, ethanol was removed by distillation at 80° C. under reduced pressure with a vacuum degree of 0.09 MPa for 10 minutes, and dried.

1.2% by weight of the dried compound and 10% by weight of a polysilazane solution were mixed and stirred at room temperature for 1 day to obtain a final coating composition of 11.2% by weight.

Example 4.

A coating film was prepared using the silane coating composition prepared according to Example 1 according to an embodiment of the present invention.

First, the glass for applying the coating composition was immersed in an alkaline cleaning solution at 40° C. for 30 minutes, and then subjected to ultrasonic treatment in distilled water, acetone, and isopropyl alcohol for 5 minutes using an ultrasonic cleaner, and then dried in an oven at 120° C.

Next, a silane coating composition was dropped onto the washed glass, applied at 1,000 rpm for 10 seconds, and a prebaking process was performed on a hot plate at 120° C. for 1 minute.

Next, in order to cure the applied coating film, a cured coating film was formed by exposure to 30° C. and 30% ammonia water for 3 days, washed with distilled water, and dried in an oven at 120° C. for 1 hour.

Example 5.

A coating film was prepared using the silane coating composition prepared according to Example 1 according to an embodiment of the present invention.

In order to cure the applied coating film, a cured coating film was formed by exposing it to 30°C and 30% hydrogen peroxide solution for 3 days, and washing with distilled water and drying in an oven at 120°C for 1 hour was carried out in the same manner as in Example 4.

Example 6.

A coating film was prepared using the silane coating composition prepared according to Example 1 according to an embodiment of the present invention.

The applied coating film was carried out in the same manner as in Example 4, except that UV irradiation under conditions of 3,000V, 50Hz and 8J/cm ² was performed 4,000 times using pulsed UV.

Example 7.

A coating film was prepared using the silane coating composition prepared according to Example 2 according to an embodiment of the present invention.

First, the glass for applying the silane coating composition was immersed in an alkaline cleaning solution at 40° C. for 30 minutes, and then subjected to ultrasonic treatment in distilled water, acetone, and isopropyl alcohol for 5 minutes using an ultrasonic cleaner, and then dried in an oven at 120° C.

Next, the coating composition was dripped on the washed glass and applied at 1000 rpm for 10 seconds, and a prebaking process was performed on a hot plate at 120° C. for 1 minute.

Next, in order to cure the applied coating film, a cured coating film was formed by exposure to 30° C. and 30% ammonia water for 3 days, washed with distilled water, and dried in an oven at 120° C. for 1 hour.

Example 8.

A coating film was prepared using the silane coating composition prepared according to Example 2 according to an embodiment of the present invention.

In order to cure the applied coating film, a cured coating film was formed by exposure to 30° C. and 30% hydrogen peroxide solution for 3 days, and it was carried out in the same manner as in Example 7, except that it was washed with distilled water and dried in an oven at 120° C. for 1 hour.

Example 9.

A coating film was prepared using the silane coating composition prepared according to Example 2 according to an embodiment of the present invention.

The applied coating film was carried out in the same manner as in Example 7, except that ultraviolet rays under conditions of 3000V, 50Hz and 8J/cm ² were performed 4,000 times using pulse UV irradiation with 100 μs ultraviolet rays and 20 ms ultraviolet rays.

Example 10.

A coating film was prepared using the silane coating composition prepared according to Example 3 according to an embodiment of the present invention.

First, the glass for applying the silane coating composition was immersed in an alkaline cleaning solution at 40° C. for 30 minutes, and then subjected to ultrasonic treatment in distilled water, acetone, and isopropyl alcohol for 5 minutes using an ultrasonic cleaner, and then dried in an oven at 120° C.

Next, the silane coating composition was dripped on the washed glass and applied at 1000 rpm for 10 seconds, and a prebaking process was performed on a hot plate at 120° C. for 1 minute.

Next, in order to cure the applied coating film, a cured coating film was formed by exposure to 30° C. and 30% ammonia water for 3 days, washed with distilled water, and dried in an oven at 120° C. for 1 hour.

Example 11.

A coating film was prepared using the silane coating composition prepared according to Example 1 according to an embodiment of the present invention.

In order to cure the applied coating film, a cured coating film was formed by exposure to 30° C. and 30% hydrogen peroxide solution for 3 days, and it was carried out in the same manner as in Example 10 except that it was washed with distilled water and dried in an oven at 120° C. for 1 hour.

Example 12.

A coating film was prepared using the silane coating composition prepared according to Example 3 according to an embodiment of the present invention.

The applied coating film was carried out in the same manner as in Example 10, except that UV irradiation under conditions of 3000V, 50Hz and 8J/cm ² was performed 4,000 times using pulsed UV light.

Comparative Example 2.

A coating film was prepared using the silane coating composition prepared in Comparative Example 1.

First, the glass for applying the coating composition was immersed in an alkaline cleaning solution at 40° C. for 30 minutes, followed by ultrasonic treatment in distilled water, acetone, and isopropyl alcohol for 5 minutes using an ultrasonic cleaner, and then dried in an oven at 120° C.

Next, the coating composition was dropped onto the washed glass, applied at 1000 rpm for 10 seconds, and a prebaking process was performed on a hot plate at 120° C. for 1 minute.

Next, in order to cure the applied coating film, a cured coating film was formed by exposure to 30° C. and 30% ammonia water for 3 days, washed with distilled water, and dried in an oven at 120° C. for 1 hour.

Comparative Example 3.

A coating film was prepared using the silane coating composition prepared according to Comparative Example 1 in order to compare with an example of the present invention.

The applied coating film was carried out in the same manner as in Comparative Example 2, except that UV irradiation under conditions of 3000V, 50Hz and 8J/cm ² was performed 4,000 times using pulsed UV light.

Experimental Example 1. Evaluation of properties of coating film

In order to analyze the coating films prepared in Examples 4 to 12 and Comparative Examples 2 and 3, the contact angle evaluation, the transmittance evaluation, and the pencil hardness evaluation were performed, and the results are shown in Table 1 below.

Experimental Example 2. Evaluation of properties of base-treated coating film

2.1. Base treatment of coating film

In order to evaluate the basic resistance of the coating films prepared in Examples 4 to 12 and Comparative Examples 2 and 3, the coating film was immersed in 5% KOH solution for 5 hours, and then washed several times with distilled water, and 24 in an oven at 120°C. After drying for time, it was referred to as Examples 4-1 to 12-1, and Comparative Examples 2-1 and 3-1, respectively.

2.2 Evaluation of properties of base-treated coating film

In order to analyze the base-treated coating films of Examples 4-1 to 12-1 and Comparative Examples 2-1 and 3-1, the contact angle evaluation, transmittance evaluation, and pencil hardness evaluation were performed, and the results are shown in the following table. It is shown in 2.

The specific method of the experiment conducted above is as follows:

Experimental Example 3. Evaluation of contact angle of coating film

According to KS L 2110:2006, water (distilled water) or hexadecane was dripped on the surface of each coating film, and the contact angle of the droplets was evaluated.

Experimental Example 4. Evaluation of transmittance of coating film

According to KS M ISO13468-1:2007, the transmittance of each coating film was evaluated based on the C light source.

Experimental Example 5. Evaluation of pencil hardness of coating film

According to KS M ISO15184:2013, each coating film was scratched at a rate of 10 mm/min using a pencil lead having a hardness of 6B to 9H of 500 g, and the pencil hardness of the maximum hardness that did not cause scratches was confirmed.

division Comparative Examples 2 and 3 Examples 4, 5, 6 Experimental substance water Hexadecane water Hexadecane Contact angle 111° 65° 111° 62° Transmittance
(Haze) 92.46%
(0.5) 92.40%
(0.27) Pencil hardness 9H 9H division Examples 7, 8, 9 Examples 10, 11, 12 Experimental substance water Hexadecane water Hexadecane Contact angle 109° 61° 110 62° Transmittance
(Haze) 92.00%
(0.31) 92.27
(0.06) Pencil hardness 9H 9H

division Comparative Examples 2-1, 3-1 Example 4-1, 5-1, 6-1 Experimental substance water water Contact angle 56° 90° division Example 7-1, 8-1, 9-1 Examples 10-1, 11-1, 12-1 Experimental substance water water Contact angle 94° 97°

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains can understand that it is possible to easily transform it into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (32)

Preparing a first solution by mixing a fluoroalkyl silane and a solvent;
Preparing a second solution by mixing the first solution, a polysilazane solution, and a metal precursor; And
Comprising removing the solvent from the second solution,
The method for producing a silane coating composition, wherein the fluoroalkyl silane has a structure represented by the following formula (1).
[Formula 1]

(In this case, R is independently hydrogen or a C ₁ to C ₃ alkyl group, and a and b are integers of 1 to 10.) The method of claim 1,
Preparing the first solution is a method of manufacturing a silane coating composition, characterized in that it further comprises an alkyl silane. delete The method of claim 1,
The step of preparing the first solution is a method for producing a silane coating composition, characterized in that the fluoroalkyl silane is provided in an amount of 1% to 30% by weight. The method of claim 1,
The method for producing a silane coating composition, characterized in that the solvent contains alcohol or water. The method of claim 5,
The solvent is methanol, ethanol, n-propanol, n-butanol, amyl alcohol, n-hexyl alcohol, n-heptanol, n-octanol, isopropanol, isobutanol, isoamyl alcohol, 3-pentanol, t-butanol , t-amyl alcohol, 2,3-dimethyl-2-butanol, 2-(trifluoromethyl)-2-propanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2-methyl- 2-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-2-pentanol, 2-methyl-2-hexanol, 2-cyclopropyl-2-propanol, 2-cyclopropyl- 2-butanol, 2-cyclopropyl-3-methyl-2-butanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 3-propylcyclopentanol, 1-methylcyclohexanol, 1-ethylcyclohexane A method for producing a silane coating composition, comprising one from ol, 1-methylcycloheptanol, and combinations thereof. The method of claim 5,
The solvent is a method for producing a silane coating composition, characterized in that it further comprises a co-solvent of the alcohol or the water. The method of claim 1,
The polysilazane solution is a method for producing a silane coating composition, characterized in that a polysilazane binder or an organic polysilazane binder is provided in an amount of 5 to 500 parts by weight based on 100 parts by weight of the fluoroalkyl silane. The method of claim 1,
The metal precursor is a method for producing a silane coating composition, characterized in that any one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof. The method of claim 1,
The metal precursor is a method for producing a silane coating composition, characterized in that provided in 5 parts by weight to 500 parts by weight based on 100 parts by weight of the fluoroalkyl silane. The method of claim 1,
The step of removing the solvent is a method for producing a silane coating composition, characterized in that performed through vacuum distillation or rotary evaporation. The method of claim 1,
The step of removing the solvent is a method for producing a silane coating composition, characterized in that performed at a vacuum degree of 0.02 MPa to 0.2 MPa. The method of claim 2,
The alkyl silane is a method for producing a silane coating composition, characterized in that it has the structure of the following formula (2):
[Formula 2]

In this case, R is independently hydrogen or a C ₁ to C ₃ alkyl group, and c is an integer of 1 to 20. The method of claim 2,
The alkyl silane is a method for producing a silane coating composition, characterized in that provided in an amount of 1 to 200 parts by weight based on 100 parts by weight of the fluoroalkyl silane. The method of claim 1,
After the step of preparing the second solution, the method of manufacturing a silane coating composition, further comprising mixing a binder or a catalyst with the coating composition. The method of claim 15,
The catalyst comprises a primary amine-based, secondary amine-based, tertiary amine-based or platinum-based catalyst, and is provided in 1 PHR to 30 PHR compared to the polysilazane solution. The method of claim 15,
The method for producing a silane coating composition, wherein the binder is provided in an amount of 5 to 500 parts by weight based on 100 parts by weight of the solid content of the second solution. The method of claim 15,
The catalyst comprises a primary amine-based, secondary amine-based, tertiary amine-based, or platinum-based catalyst, and is provided at 1 PHR to 30 PHR relative to the binder. The method of claim 15,
The step of mixing the binder or the catalyst with the coating composition is a method for producing a silane coating composition, characterized in that physically agitating the silane coating composition to be uniform in order to control the composition of the silane coating composition. The method of claim 15,
The binder or catalyst is a method for producing a silane coating composition, characterized in that controlling the total solid content of the silane coating composition to be 1% by weight to 90% by weight. A silane coating composition prepared by the manufacturing method of claim 1. Applying the silane coating composition of claim 21 to a substrate; And
Curing the silane coating composition applied to the substrate to form a coating layer. The method of claim 22,
The step of applying the silane coating composition to the substrate is carried out through any one selected from the group consisting of a support method, an impregnation method, and a spray method using spinning, slot die, micro gravure, gravure or spray. Method for producing a coating film. The method of claim 22,
In the step of applying the silane coating composition to a substrate, the substrate is rotated at 500 rpm to 4,000 rpm and the silane coating composition is sprayed for 1 second to 20 minutes. The method of claim 22,
The step of forming the coating layer is a method of producing a coating film, characterized in that curing the coating composition by pulse UV irradiation, exposure to ammonia water, exposure to hydrogen peroxide, or heat treatment. The method of claim 25,
The step of curing the coating layer is a method for producing a coating film, characterized in that the coating composition is cured by heating by a steam method and an impregnation method under a chemical atmosphere. The method of claim 25,
The pulsed UV irradiation repeats UV irradiation under conditions of 0.5J/cm ² to 100J/cm ² at 1,000V to 4,000V, 5Hz to 50Hz, and 150nm to 450nm wavelengths from 50µs to 1000µs ultraviolet irradiation and 10ms to 5s ultraviolet irradiation Method for producing a coating film, characterized in that carried out by. The method of claim 25,
The method of manufacturing a coating film, characterized in that the exposure to the ammonia water is performed for 12 to 120 hours using 5% to 35% by weight of ammonia water at 15°C to 35°C. The method of claim 25,
The method of manufacturing a coating film, characterized in that the exposure to the hydrogen peroxide solution is performed for 12 to 120 hours using 5% to 50% by weight of hydrogen peroxide at 15°C to 100°C. The method of claim 22,
After the step of forming the coating layer, the method of manufacturing a coating film, further comprising heat-treating the coating film. The method of claim 30,
The heat treatment step is a method of manufacturing a coating film, characterized in that the heat treatment under a temperature condition of 70 ℃ to 120 ℃. A coating film manufactured by the method of manufacturing the coating film of claim 22.

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