KR20210107963A - Method for producing polysilazane-based film - Google Patents

Abstract

The present invention includes the steps of: preparing a mixed solution comprising a substrate and a polysilazane-based resin composition; applying the mixed solution on the substrate; and curing the resin composition by immersing the substrate coated with the mixed solution in ammonia water in which oxygen is dissolved. A method for preparing a polysilazane-based film of the present invention can shorten a curing time of a curing step.

Description

Method for producing polysilazane-based film {Method for producing polysilazane-based film}

The present invention relates to a method for producing a polysilazane-based film, and more particularly, to a method for producing a polysilazane-based film comprising curing a polysilazane-based resin composition applied to the surface of a substrate using an ammonia water impregnation method. will be.

Silica film is transparent and has excellent insulating properties and wear resistance, so it is widely applied as a functional material for semiconductor insulating film, anti-reflection film, anti-corrosion film, and packaging material. It is mainly formed using vacuum deposition such as physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma chemical vapor deposition (PECVD) and atomic layer deposition (ALD).

However, in the case of a thin film formed by vacuum deposition, pinholes and cracks are high, and the manufacturing cost is high because of high cost and long process time.

Therefore, interest in silane-based materials with excellent chemical and physical properties after thin film formation among organic materials that can be printed in a solution state to replace them is increasing. Among them, polysilazane having a Si-N repeating unit in the polymer main chain has excellent adhesion to the substrate and can be applied to various substrates, and has excellent scratch resistance, corrosion resistance, chemical resistance, heat resistance, durability, etc. Therefore, active research is in progress.

As the curing process of the polysilazane material, various methods of curing the coating film under certain oxygen and humidity conditions by using the fact that the organosilazane has high reactivity with oxygen and moisture and shows a fast curing behavior with an ammonia catalyst This study was conducted, and a study was conducted on the curing method using steam such as ammonia water, hydrogen peroxide solution, and distilled water, and the characteristics of the coating film.

However, the curing process performed in the atmosphere of aqueous ammonia and hydrogen peroxide takes a long time, and the manufacturing process of the polysilazane-based film including the curing process also takes a long time.

Accordingly, there is a need for a manufacturing method capable of producing a polysilazane-based film with improved surface hardness and uniformity as well as shortening of the process time.

Republic of Korea Patent Publication No. 10-2019-0067644

In order to improve the above technical problems, one technical object of the present invention is to provide a method for producing a polysilazane-based film having a shortened curing time.

Another technical object of the present invention is to provide a polysilazane-based film manufactured by using the above manufacturing method.

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

In order to achieve the above technical problem, one aspect of the present invention comprises the steps of preparing a mixed solution comprising a substrate and a polysilazane-based resin composition; applying the mixed solution on the substrate; and curing the resin composition by impregnating the substrate coated with the mixed solution in aqueous ammonia in which oxygen is dissolved.

In an embodiment of the present invention, in the curing step, the dissolved oxygen (DO) of the ammonia water may be 10 ppm to 100 ppm.

In one embodiment of the present invention, in the curing step, the concentration of the ammonia water may be 5% to 35%.

In one embodiment of the present invention, the curing step may be performed at a temperature of 20 ℃ to 40 ℃.

In one embodiment of the present invention, the curing step may be performed for 1 hour to 4 hours.

In an embodiment of the present invention, the applying may be performed through any one of a supporting method, an impregnating method, and a spraying method.

In an embodiment of the present invention, the substrate may include a plastic, metal, or ceramic material.

In an embodiment of the present invention, the polysilazane-based resin composition may include any one or more of polysilazane-based materials represented by the following Chemical Formulas 1, 2, and 3:

[Formula 1]

In the above formula,

R, R' and R'' are each hydrogen, C ₁ to C ₂₀ alkyl or acrylate,

n is an integer from 1 to 10,000.

[Formula 2]

In the above formula,

R is an amino group, a chloro group or a hydroxy group,

R' is an ether group (-O-) or a secondary amine group (-NH-),

a and b are each an integer from 1 to 20,

x is an integer from 1 to 10,000,

y is an integer from 1 to 2,000.

[Formula 3]

In the above formula,

R is an amino group, a chloro group or a hydroxy group,

R' is an ether group (-O-) or a secondary amine group (-NH-),

a, b and c are each an integer from 1 to 20;

x is an integer from 1 to 10,000,

y and z are each an integer from 1 to 2,000.

In one embodiment of the present invention, the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

In one embodiment of the present invention, the molecular weight of the polysilazane-based resin composition may be 1,000 to 400,000.

In an embodiment of the present invention, the polysilazane-based resin composition may be included in an amount of 1 wt% to 20 wt% based on 100 wt% of the polysilazane-based film.

In one embodiment of the present invention, the mixed solution may contain a solvent.

In one embodiment of the present invention, the mixed solution may include an additive.

In one embodiment of the present invention, the mixed solution may contain a catalyst.

In an embodiment of the present invention, the method may further include heat-treating the formed film after the applying.

In an embodiment of the present invention, the heat treatment may be performed at a temperature of 70 °C to 150 °C.

In one embodiment of the present invention, the heat treatment may be performed for 10 minutes to 120 minutes.

In an embodiment of the present invention, the method may further include heat-treating the formed film after the curing step.

In an embodiment of the present invention, the heat treatment may be performed at a temperature of 70 °C to 150 °C.

In one embodiment of the present invention, the heat treatment may be performed for 10 minutes to 120 minutes.

One aspect of the present invention provides a polysilazane-based film prepared by the above manufacturing method.

The method for producing a polysilazane-based film of the present invention performs a curing process in a simple method of impregnating a polysilazane-based resin composition coated on a substrate in ammonia water in which oxygen is dissolved, thereby shortening the curing process time and at the same time reducing surface hardness and uniformity. It is possible to prepare an improved polysilazane-based film.

It should be understood that the effects of the present invention are not limited to the above-described effects, and 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 flowchart of a method for manufacturing a polysilazane-based film of the present invention.
2 and 3 are FT-IR analysis graphs of an embodiment and a comparative example of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is said to be “connected (connected, contacted, coupled)” with another part, it is not only “directly connected” but also “indirectly connected” with another member interposed therebetween. "Including cases where In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprises" or "have" are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

In the present specification, polysilazane (polysilazane) refers to a functional inorganic polymer having a Si-N repeating unit in the polymer main chain, silicon dioxide (SiO ₂ ), silicon nitride (Si ₃ N ₄ ), and silicon nitride carbide (Si _x N _y C _z ) It is a material mainly used as a ceramic precursor for forming the layer. The polysilazane can be formed into a thin film relatively easily through a solution process, and has excellent adhesion to the substrate, so it can be applied to substrates of various materials, and has excellent scratch resistance, corrosion resistance, chemical resistance, heat resistance, and durability. have characteristics.

One aspect of the present invention provides a method for producing a polysilazane-based film of the present invention.

Referring to FIG. 1 , the method for manufacturing a polysilazane-based film of the present invention includes the steps of preparing a mixed solution including a substrate and a polysilazane-based resin composition (S100); applying the mixed solution on the substrate (S200); curing the resin composition by impregnating the substrate coated with the mixed solution in ammonia water in which oxygen is dissolved (S300); and heat-treating the cured resin composition (S400).

First, the method for producing a polysilazane-based film of the present invention includes a step (S100) of preparing a mixed solution including a substrate and a polysilazane-based resin composition.

In an embodiment of the present invention, the substrate may include a plastic, metal, or ceramic material. In the case of the conventional method of forming a silica film, since a heat treatment process at a high temperature is required in the curing process, there is a problem that is limited to a heat-resistant metal or ceramic substrate. It is made at room temperature, and since polysilazane has excellent adhesion to most materials, the material of the substrate is not limited to a material having heat resistance.

For example, the plastic may include PET, PI, PMMA, PP, PE, PEN, EVOH, PVA, TAC, PC or raw plastic.

For example, the metal material may include aluminum, stainless steel (SUS), or iron.

For example, the ceramic material may include glass or a silicon wafer.

In an embodiment of the present invention, the polysilazane-based resin composition may refer to a polymer composition formed including the polysilazane, and any one of the polysilazane-based materials represented by the following Chemical Formulas 1, 2 and 3 These may include, but are not limited to:

[Formula 1]

In the above formula,

R, R' and R'' are each hydrogen, C ₁ to C ₂₀ alkyl or acrylate,

n is an integer from 1 to 10,000.

[Formula 2]

In the above formula,

R is an amino group, a chloro group or a hydroxy group,

R' is an ether group (-O-) or a secondary amine group (-NH-),

a and b are each an integer from 1 to 20,

x is an integer from 1 to 10,000,

y is an integer from 1 to 2,000.

[Formula 3]

In the above formula,

R is an amino group, a chloro group or a hydroxy group,

R' is an ether group (-O-) or a secondary amine group (-NH-),

a, b and c are each an integer from 1 to 20;

x is an integer from 1 to 10,000,

y and z are each an integer from 1 to 2,000.

The polysilazane-based material represented by Formula 1 may not contain carbon, for example, an inorganic polysilazane having a molecular structure consisting only of Si-N, Si-H, and NH, for example, perhydropoly It may be a silazane (perhydropolysilazane).

The polysilazane-based material represented by Formula 2 may be a fluoro-based polysilazane including fluoro, and a silane including a fluoroalkyl group represented by Formula 4 below and a polysilazane-based material represented by Formula 1 It can be prepared by mixing:

[Formula 4]

In the above formula,

R, R' and R'' are independently hydrogen or a C ₁ to C ₃ alkyl group,

a and b are integers from 1 to 20;

_{The alkyl group including the fluoroalkyl group is rich in CF 3} or CF ₂ , a component that imparts low surface energy, and has a structurally linear structure. can provide

The polysilazane-based material represented by Formula 3 may be a fluoro-based polysilazane including fluoro, a silane including an alkyl group represented by Formula 5 below, a polysilazane-based material represented by Formula 4, and the It can be prepared by mixing the polysilazane-based material represented by Formula 1:

[Formula 5]

In the above formula,

R, R' and R" are independently hydrogen or a C ₁ to C ₃ alkyl group,

c is an integer from 1 to 20;

In an embodiment of the present invention, the polysilazane-based material represented by Chemical Formulas 1, 2, and 3 may be linear, branched, cyclic, or a mixture thereof, respectively. Accordingly, the polysilazane-based resin composition of the present invention may be linear, branched, cyclic, or a mixture thereof.

In one embodiment of the present invention, the molecular weight of the polysilazane-based resin composition may be 1,000 to 400,000, and may be included in an amount of 1 wt% to 20 wt% based on 100 wt% of the polysilazane-based film to be prepared.

In one embodiment of the present invention, the mixed solution includes the polysilazane-based resin composition described above, and may also include a solvent.

The solvent is not limited as long as it is a material capable of dissolving and dispersing the polysilazane-based resin composition. For example, the solvent is dibutyl ether (DBE, dibutylether), toluene, tetrahydrofuran (THF, tetrahydrofuran), n-methylpyrrolidone (NMP, n-methyl pyrolidone), xylene (Xylene), propylene It may include glycol methyl ether acetate (PGMEA, propylene glycol methyl ether acetate), propylene glycol monomethyl ether acetate (PMA, propylene glycol monomethyl ether acetate), or cyclohexane.

In an embodiment of the present invention, the mixed solution may include an additive and/or a catalyst.

The additive is not limited as long as it is a material capable of maintaining the stability of the mixed solution, and for example, an antioxidant, a UV absorber, etc. may be included in the additive.

In addition, the catalyst is a material capable of accelerating the curing of the polysilazane-based resin composition, and is not limited as long as it is a material capable of converting the polysilazane-based resin composition or the binder, for example, a primary amine-based catalyst , may be a secondary amine-based catalyst or a tertiary amine-based catalyst, for example, methylamine, aniline, 1,3-cyclohexanebis(methylamine), 1,5-diamino-2-methylpentane, 2 ,4-Diaminotoluene, 2,2-dimethyl-1,3-propanediamine, 4.4'-methylenebis(cyclohexylamine), dimethylamine, diethylamine, piperidine, N,N'- Diethyl-2-butene-1,4-diamine, N,N'-diisopropylethylenediamine, N,N'-diisopropyl-1,3-propanediamine, N,N'-diethyl -p-Petylenediamine, 2-isopropyl-2-oxazoline, 1,4,8,12-tetrazacyclopentadecane, 1,4,8,11-tetrazacycloterenadecane-2.7-da Ion, trimethylamine, triethylamine, N,N-dimethylpentylamine, N-ethyl-N-methylbutylamine, N-ethyl-N-propylaniline, N,N,N',N'-tetramethyl -1,6-diaminohexane or N,N-dimethylbenzanthracen-6-amine.

Next, the method of manufacturing the polysilazane-based film of the present invention includes the step of applying the mixed solution on the substrate (S200).

In one embodiment of the present invention, the step (S200) of applying on the substrate may be any one of a supporting method, an impregnating method, and a spraying method. The spraying method may be performed, for example, by spraying the resin composition onto the surface of the substrate using spinning, slot die, micro gravure, gravure, or spraying. For example, when the step (S200) of applying on the substrate is performed through a method of spraying using spinning, the substrate is rotated at 500 rpm to 4,000 rpm and the resin composition is applied to the substrate for 1 second to 20 This can be done by spraying for minutes. The coating on the substrate (S200) is a process performed so that the state of the polysilazane-based resin composition is uniformly present and uniformly applied at the same time, and the coating method is not limited thereto.

In an embodiment of the present invention, a pretreatment step may be optionally further included between the step of applying the polysilazane-based resin composition (S200) and the step of curing (S300). For example, the pretreatment step may be performed by heat-treating the substrate coated with the polysilazane-based resin composition under a temperature condition of 70°C to 150°C. Preferably, the pretreatment step is selectively included in consideration of the material of the substrate.

Next, the method for producing a polysilazane-based film of the present invention includes a step (S300) of curing the resin composition by immersing the substrate coated with the resin composition in ammonia water in which oxygen is dissolved.

In the present invention, the curing step (S300) may be performed through a method of impregnating the substrate coated with the resin composition in ammonia water and supplying oxygen at the same time, for example, impregnating in ammonia water in which oxygen is dissolved. .

When the polysilazane-based resin composition is exposed to the ammonia water, the Si-H bond contained in the polysilazane-based resin composition is changed to a Si-O bond by the ammonia catalyst and moisture, and a silica film may be formed, and the surface of the substrate A polysilazane-based film having a silica film formed thereon can be obtained.

In the curing process, the concentration of oxygen contained in the ammonia water _{may be an important factor for converting the polysilazane-based resin composition into a silica film (SiO 2} ), for example, dissolved oxygen (DO) in the ammonia water. ) may be 10 ppm to 100 ppm, for example, 30 ppm to 40 ppm.

The curing process includes a process of supplying oxygen, and by making the dissolved oxygen of the ammonia water 30 ppm or more, the hardness and uniformity of the surface of the film produced compared to the process of curing by simply immersing in ammonia water without supplying oxygen It has the advantage of improving performance.

In one embodiment of the present invention, the concentration of the aqueous ammonia may be 5% to 35%, for example, 30%.

If the concentration of the ammonia water is less than 5%, the film may be peeled off because fast curing is not made, and if the concentration of the ammonia water is 35% or more, the uniformity of the film may be deteriorated.

In an embodiment of the present invention, the curing step (S300) may be performed at a temperature of 20 °C to 40 °C, for example, 30 °C. Since the curing step ( S300 ) may be performed at room temperature of about 25° C. to 30° C., the polysilazane-based film can be manufactured using the substrate to be used without being limited by the material of the substrate.

In addition, the curing step (S300) may be performed for 1 hour to 4 hours, for example, 3 hours, compared to the execution time (about 3 days) of the conventional curing process by exposure to ammonia vapor. There is an advantage that the process time can be greatly shortened.

In one embodiment of the present invention, after the step of curing the resin composition (S300), the step of heat-treating the cured resin composition (S400) may be further included.

For example, the heat treatment ( S400 ) may be performed so that fluoroalkyl groups present in the film are aligned toward the film surface. When the fluoroalkyl groups are aligned toward the film surface, the film of water-repellent properties may be improved.

Heating the film may be performed, for example, at a temperature of 70 °C to 150 °C. However, it is not necessarily limited to the above temperature, and if the temperature condition is within a range in which the fluoroalkyl group is induced toward the coating surface, it may be suitable as the temperature for performing the heat treatment. Heating the film may be performed for 10 minutes to 120 minutes, for example, 20 minutes to 60 minutes.

Preferably, the heat treatment is selectively included in consideration of the material of the substrate.

Another aspect of the present invention comprises the steps of preparing a substrate and a polysilazane-based resin composition (S100); applying the resin composition on the substrate (S200); and impregnating the substrate coated with the resin composition in ammonia water in which oxygen is dissolved to cure the resin composition (S300); It provides a polysilazane-based film prepared using a manufacturing method comprising a.

In an embodiment of the present invention, curing the resin composition (S300) may be performed by immersing the substrate coated with the resin composition in ammonia water and supplying oxygen at the same time.

The description of the manufacturing method is replaced with that described in the above embodiment.

In one embodiment of the present invention, the polysilazane-based film prepared by the above method may have a degree of curing of about 95% or more.

In addition, the pencil hardness of the polysilazane-based film may be 9 H or more, and the uniformity of the surface hardness may be good.

In another embodiment of the present invention, the polysilazane-based film prepared by the manufacturing method may have a water repellency property with a contact angle with water droplets of about 100° or more.

The polysilazane-based film according to an embodiment of the present invention can be applied to various applications of forming a coating. For example, the application field may include, but is not limited to, the surface treatment of displays, sunlight, building interior and exterior materials, heat exchange pipes, electric wire surfaces, piers, water purifier pipes, automobiles, transportation devices, or optical devices. . In this case, by applying the polysilazane-based film according to an embodiment of the present invention, it is possible to improve the water-repellent properties of the application field.

Hereinafter, a polysilazane-based film according to an embodiment of the present invention will be described in detail with reference to Examples and Comparative Examples. In addition, the examples shown below are examples for helping understanding of the present invention, and the scope of the present invention is not limited thereto.

Example 1. Preparation of polysilazane-based film

1-1. Preparation of polysilazane-based film (Impregnation for 1 hour)

The glass for coating the polysilazane-based resin 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 each using an ultrasonic cleaner, and then dried in an oven at 120° C.

A polysilazane-based resin composition containing perhydropolysilazane, which is a polysilazane-based material represented by the following Chemical Formula 1, was dripped onto the washed glass and applied at 1,000 rpm for 10 seconds, and freed for 1 minute at 120° C. on a hot plate. - The bake process was performed.

The glass coated with the resin composition was impregnated in ammonia water having a dissolved oxygen (DO) of 38.5 ppm and a concentration of 30% for 1 hour at 30 ° C. Prepared:

[Formula 1]

In the above formula,

R, R' and R'' are each hydrogen, C ₁ to C ₂₀ alkyl or acrylate,

n is an integer from 1 to 10,000.

1-2. Preparation of polysilazane-based film

In Example 1-1, except that fluoro-based polysilazane, which is a polysilazane-based material represented by the following Chemical Formula 2, was used instead of the polysilazane-based material represented by Formula 1, The same method was performed to prepare a polysilazane-based film:

[Formula 2]

In the above formula,

R is an amino group, a chloro group or a hydroxy group,

R' is an ether group (-O-) or a secondary amine group (-NH-),

a and b are each an integer from 1 to 20,

x is an integer from 1 to 10,000,

y is an integer from 1 to 2,000.

1-3. Preparation of polysilazane-based film

Example 1-1, except that in Example 1-1, fluoroalkyl-based polysilazane, which is a polysilazane-based material represented by the following Chemical Formula 3, was used instead of the polysilazane-based material represented by Chemical Formula 1 A polysilazane-based film was prepared by the same method as:

[Formula 3]

In the above formula,

R is an amino group, a chloro group or a hydroxy group,

R' is an ether group (-O-) or a secondary amine group (-NH-),

a, b and c are each an integer from 1 to 20;

x is an integer from 1 to 10,000,

y and z are each an integer from 1 to 2,000.

Example 2. Preparation of polysilazane-based film (impregnated for 3 hours)

2-1. Preparation of polysilazane-based film

The glass for coating the polysilazane-based resin 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 each using an ultrasonic cleaner, and then dried in an oven at 120° C.

The polysilazane-based resin composition including the polysilazane-based material represented by Chemical Formula 1 was dripped onto the washed glass and applied at 1,000 rpm for 10 seconds, and a pre-bake process was performed on a hot plate at 120° C. for 1 minute.

The glass coated with the resin composition was impregnated in ammonia water having a dissolved oxygen (DO) of 38.5 ppm and a concentration of 30% at 30° C. for 3 hours to cure, and dried at a temperature of 120° C. for 1 hour to obtain a polysilazane-based film. prepared.

2-2. Preparation of polysilazane-based film

In Example 2-1, the same method as in Example 2-1 was performed, except that the polysilazane-based material represented by Formula 2 was used instead of the polysilazane-based material represented by Formula 1, and the polysilazane-based material was used. A film was prepared.

2-3. Preparation of polysilazane-based film

In Example 2-1, the same method as in Example 2-1 was performed, except that the polysilazane-based material represented by Formula 3 was used instead of the polysilazane-based material represented by Formula 1, and the polysilazane-based material was used. A film was prepared.

Comparative Example 1. Preparation of uncured polysilazane-based film

1-1. Preparation of uncured polysilazane-based film

The glass for coating the polysilazane-based resin 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 each using an ultrasonic cleaner, and then dried in an oven at 120° C.

The polysilazane-based resin composition including the polysilazane-based material represented by Chemical Formula 1 was dripped onto the washed glass and applied at 1,000 rpm for 10 seconds, and a pre-bake process was performed on a hot plate at 120° C. for 1 minute.

A polysilazane-based film was prepared without curing the glass coated with the resin composition.

1-2. Preparation of uncured polysilazane-based film

In Comparative Example 1-1, the same method as in Comparative Example 1-1 was performed except that the polysilazane-based material represented by Formula 2 was used instead of the polysilazane-based material represented by Formula 1, and the polysilazane-based material was used. A film was prepared.

1-3. Preparation of uncured polysilazane-based film

In Comparative Example 1-1, the same method as in Comparative Example 1-1 was performed except that the polysilazane-based material represented by Formula 3 was used instead of the polysilazane-based material represented by Formula 1, and the polysilazane-based material was used. A film was prepared.

Comparative Example 2. Preparation of polysilazane-based film

2-1. Preparation of polysilazane-based film

The glass for coating the polysilazane-based resin 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 each using an ultrasonic cleaner, and then dried in an oven at 120° C.

The polysilazane-based resin composition including the polysilazane-based material represented by Chemical Formula 1 was dripped onto the washed glass and applied at 1,000 rpm for 10 seconds, and a pre-bake process was performed on a hot plate at 120° C. for 1 minute.

A polysilazane-based film was prepared by curing the glass coated with the resin composition by exposing it to steam of 30% ammonia water at 30° C. for 3 days.

2-2. Preparation of polysilazane-based film

In Comparative Example 2-1, the same method as in Comparative Example 2-1 was performed except that the polysilazane-based material represented by Chemical Formula 2 was used instead of the polysilazane-based material represented by Chemical Formula 1, and a polysilazane-based material was used. A film was prepared.

2-3. Preparation of polysilazane-based film

In Comparative Example 2-1, the same method as in Comparative Example 2-1 was performed, except that the polysilazane-based material represented by Chemical Formula 3 was used instead of the polysilazane-based material represented by Chemical Formula 1, and the polysilazane-based material was used. A film was prepared.

Comparative Example 3. Preparation of polysilazane-based film

3-1. Preparation of polysilazane-based film

The glass for coating the polysilazane-based resin 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 each using an ultrasonic cleaner, and then dried in an oven at 120° C.

The polysilazane-based resin composition including the polysilazane-based material represented by Chemical Formula 1 was dripped onto the washed glass and applied at 1000 rpm for 10 seconds, and a pre-bake process was performed on a hot plate at 120° C. for 1 minute.

The glass coated with the resin composition was cured by being impregnated with ammonia water having a concentration of 30% and not dissolved in oxygen at 30° C. for 3 hours, and dried at 120° C. for 1 hour to prepare a polysilazane-based film.

3-2. Preparation of polysilazane-based film

In Comparative Example 3-1, the same method as in Comparative Example 3-1 was performed, except that the polysilazane-based material represented by Formula 2 was used instead of the polysilazane-based material represented by Formula 1, and the polysilazane-based material was used. A film was prepared.

3-3. Preparation of polysilazane-based film

In Comparative Example 3-1, the same method as in Comparative Example 3-1 was performed except that the polysilazane-based material represented by Formula 3 was used instead of the polysilazane-based material represented by Formula 1, and the polysilazane-based material was used. A film was prepared.

Experimental Example 1. Evaluation of properties of polysilazane-based films

In order to evaluate the properties of the films obtained in Examples 1 to 2 and Comparative Examples 1 to 3, FT-IR analysis of the polysilazane-based film was performed, and the result graph is shown in FIGS. 2 to 3, and the polysilazane-based film The water contact angle (WCA), curing degree, pencil hardness, and surface condition of the surface of the silazane-based film and water droplets were evaluated, and the results are shown in Table 1 below:

W.C.A (°) Hardening (%) Pencil Hardness (1Kg) surface condition Example 1-1 15 98.65 9H Good Example 1-2 102 98.48 9H Good Examples 1-3 107 98.07 9H Good Example 2-1 17 99.40 9H Good Example 2-2 104 99.51 9H Good Example 2-3 109 99.61 9H Good Comparative Example 2-1 54 99.60 9H Good Comparative Example 2-2 111 99.30 9H Good Comparative Example 2-3 111 99.40 9H Good Comparative Example 3-1 13 98.20 7H Bad Comparative Example 3-2 100 98.30 8H Good Comparative Example 3-3 105 98.20 8H Good

Referring to FIGS. 2 to 3 , it was confirmed that Si-H, Si-N, and N-H peaks were converted to Si-O peaks as curing proceeded in Examples 1 and 2 .

Referring to Table 1, in the case of Examples 1 and 2, although the process time was shortened, it was confirmed that the average degree of curing was 95% or more, and the uniformity of the surface hardness was increased.

The description of the present invention described above is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified 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 restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention.

Claims (21)

preparing a mixed solution comprising a substrate and a polysilazane-based resin composition;
applying the mixed solution on the substrate; and
curing the resin composition by immersing the substrate coated with the mixed solution in ammonia water in which oxygen is dissolved;
A method for producing a polysilazane-based film comprising a. The method of claim 1,
In the curing step, the dissolved oxygen (DO) of the ammonia water is a method of manufacturing a polysilazane-based film, characterized in that 10 ppm to 100 ppm. The method of claim 1,
In the curing step, the concentration of the ammonia water is a method of producing a polysilazane-based film, characterized in that 5% to 35%. The method of claim 1,
The curing step is a method for producing a polysilazane-based film, characterized in that performed at a temperature of 20 ℃ to 40 ℃. The method of claim 1,
The curing step is a method for producing a polysilazane-based film, characterized in that it is performed for 1 hour to 4 hours. The method of claim 1,
The applying step is a method for producing a polysilazane-based film, characterized in that it is performed through any one of a supporting method, an impregnation method and a spraying method. The method of claim 1,
The substrate is a method of manufacturing a polysilazane-based film, characterized in that it comprises a plastic, metal, or ceramic material. The method of claim 1,
The polysilazane-based resin composition is a method for producing a polysilazane-based film, characterized in that it comprises any one or more of the polysilazane-based material represented by the following Chemical Formulas 1, 2, and 3:
[Formula 1]

In the above formula,
R, R' and R'' are each hydrogen, C ₁ to C ₂₀ alkyl or acrylate,
n is an integer from 1 to 10,000.
[Formula 2]

In the above formula,
R is an amino group, a chloro group or a hydroxy group,
R' is an ether group (-O-) or a secondary amine group (-NH-),
a and b are each an integer from 1 to 20,
x is an integer from 1 to 10,000,
y is an integer from 1 to 2,000.
[Formula 3]

In the above formula,
R is an amino group, a chloro group or a hydroxy group,
R' is an ether group (-O-) or a secondary amine group (-NH-),
a, b and c are each an integer from 1 to 20;
x is an integer from 1 to 10,000,
y and z are each an integer from 1 to 2,000. The method of claim 1,
The polysilazane-based resin composition is a method for producing a polysilazane-based film, characterized in that linear, branched, cyclic, and a mixture thereof. The method of claim 1,
The method for producing a polysilazane-based film, characterized in that the molecular weight of the polysilazane-based resin composition is 1,000 to 400,000. The method of claim 1,
The polysilazane-based resin composition is a method for producing a polysilazane-based film, characterized in that it is included in an amount of 1 wt% to 20 wt% based on 100 wt% of the polysilazane-based film. The method of claim 1,
The method for producing a polysilazane-based film, characterized in that the mixed solution contains a solvent. The method of claim 1,
The method for producing a polysilazane-based film, characterized in that the mixed solution includes an additive. The method of claim 1,
The method for producing a polysilazane-based film, characterized in that the mixed solution contains a catalyst. The method of claim 1,
Method for producing a polysilazane-based film, characterized in that it further comprises the step of heat-treating the formed film after the applying step. 16. The method of claim 15,
The heat treatment step is a method for producing a polysilazane-based film, characterized in that performed at a temperature of 70 ℃ to 150 ℃. 16. The method of claim 15,
The method of manufacturing a polysilazane-based film, characterized in that the heat treatment is performed for 10 to 120 minutes. The method of claim 1,
Method for producing a polysilazane-based film, characterized in that it further comprises the step of heat-treating the formed film after the curing step. 19. The method of claim 18,
The heat treatment step is a method for producing a polysilazane-based film, characterized in that performed at a temperature of 70 ℃ to 150 ℃. 19. The method of claim 18,
The method of manufacturing a polysilazane-based film, characterized in that the heat treatment is performed for 10 to 120 minutes. A polysilazane-based film produced by the method of claim 1 .

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