KR20190060570A - Polysilazane thin film having fingerprint and durability characteristics and manufacturing method thereof - Google Patents

Abstract

An embodiment of the present invention provides a polysilazane-based thin film material composition having anti-fingerprint properties and durability properties. The polysilazane-based thin film material composition may comprise a perhydroxypolysilazane (PHPS)-based compound having a structure of chemical formula 1, and a phase separating organic compound. In chemical formula 1, X^1 or X^2 are each independently hydrogen, fluorine, a C_1-C_12 alkyl group, a C_1-C_12 alkylhalide or a C_1-C_12 acrylic compound, and n is an integer of 1 to 10,000.

Description

TECHNICAL FIELD The present invention relates to a polysilazane-based thin film having fingerprints and durability characteristics and a method for manufacturing the same.

TECHNICAL FIELD The present invention relates to a polysilazane thin film, and more particularly, to a polysilazane thin film having fingerprint resistance and durability.

The anti-reflection, anti-fingerprint and scratch characteristics have been pointed out as a problem to be solved in the optical lens market for decades, and currently, the characteristics required for the optical lens are partially applied to the window of the mobile display, High durability and stain resistance are demanded due to the characteristics of the product which the hands of the user often touch.

Therefore, as the display device such as LDC and OLED is enlarged and advanced, it is possible to prevent the deterioration of image quality due to high hardness and light reflection on the screen. Research on water repellent or fingerprint coating is required.

Double inner fingerprint coating is a technology that can control the wettability of the solid surface and keep the display surface clean by oneself. This is also referred to as the long-leaf effect because it prevents dust or foreign matter from adhering to the surface of the object by mimicking the surface tension that occurs on the leaves.

Currently, the morphology technique that imitates the surface shape of the lotus leaf in order to realize the lotus leaf effect has been studied in various fields, and research for using it for the lotus coating is also required.

Korean Patent No. 10-1752489

SUMMARY OF THE INVENTION The present invention provides a polysilazane based thin film material composition having fingerprint resistance and durability characteristics.

SUMMARY OF THE INVENTION The present invention provides a method for producing a polysilazane thin film having fingerprint resistance and durability characteristics.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

In order to accomplish the above object, an embodiment of the present invention provides a polysilazane thin film material composition having a transparency and durability.

At this time, the polysilazane thin film material composition may include a perhydroxypolysilazane (PHPS) -based compound having a structure represented by the following formula (1) and a phase-separation organic compound.

[Chemical Formula 1]

Here, X ¹ or X ² may each independently represent hydrogen, fluorine, an alkyl group having 1 to 12 carbon atoms, an alkyl halide having 1 to 12 carbon atoms, or an acrylic compound having 1 to 12 carbon atoms.

Herein, n is an integer of 1 to 10,000.

The phase-separation organic compound may include polystyrene (PS), polymethylmethacrylate (PMMA), polyethylene (PE) or polypropylene (PP).

The PHPS compound may be present in an amount of 1 wt% to 10 wt% based on the total weight of the composition.

The phase separation organic compound may be present in an amount of 0.1 wt% to 10 wt% based on the total weight of the composition.

According to an aspect of the present invention, there is provided a method for manufacturing a polysilazane thin film having a textural and durability characteristic.

At this time, the method for manufacturing a polysilazane thin film may include the steps of: coating the base material of the polysilazane thin film composition according to the first aspect of the present invention; curing the composition coated on the base material; curing the base material subjected to the preliminary heat treatment; Ring, developing the cured base material, and drying the base material after the development has been completed.

At this time, the coating step may include blade coating, bar coating, slit coating, gravure coating or spin coating.

When spin coating is performed in the coating step, the spin coating is performed at a speed of 400 rpm to 1200 rpm for 5 seconds to 10 seconds.

At this time, the step of curing the composition may include ammonia water immersion, steam curing, thermal curing, E-beam curing or pulse UV curing.

At this time, the pulse UV curing is characterized by irradiating the pulsed ultraviolet ray 100 to 1000 times.

Here, the thermosetting is performed at a temperature of 80 ° C to 120 ° C for 1 minute to 10 minutes.

At this time, the step of performing the curing is characterized in that the immersion is performed in a 15% to 45% aqueous ammonia solution at a temperature of 20 ° C to 40 ° C for 24 hours to 72 hours.

At this time, the developing step is performed by immersing in a developing solvent for 10 minutes to 60 minutes.

In this case, the developing solvent is a nonpolar solvent containing dichloroethane, hexane, carbon tetrachloride or benzene.

At this time, the drying step is performed at 100 ° C to 140 ° C.

According to the embodiment of the present invention, it is possible to provide an anti-fingerprint and a durable polysilazane thin film having various types of nanostructures.

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

1 is a flowchart showing a method of manufacturing a polysilazane thin film according to an embodiment of the present invention.
FIG. 2 is a table for analyzing characteristics of the polysilazane thin film PHPST1 (5% + 5%) according to an embodiment of the present invention.
FIG. 3 is a table for analyzing characteristics of the polysilazane thin film PHPST2 (5% + 5%) according to one embodiment of the present invention.
4 is a table for analyzing characteristics of the polysilazane thin film PHPST5 (5% + 3%) according to one embodiment of the present invention.
FIG. 5 is a graph of infrared spectroscopic analysis according to the number of times of pulsed ultraviolet irradiation according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as " comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

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

A polysilazane thin film film material composition having an emulsifying property and a durability characteristic according to an embodiment of the present invention will be described.

When the contact angle of the surface with water is 90 DEG or more, the hydrophobic property is exhibited. When the contact angle is 110 DEG or more, the hydrophobic property is exhibited. The self-cleansing ability, ornamental and pollution resistance of the lotus leaf is caused by the nanostructure of the surface of the lotus leaf. By adopting nanostructure using fine protrusions and fine protrusions on the surface of the lotus leaf, it becomes super hydrophobic with a contact angle of 140 ° or more.

In order to realize such a nanostructure, a composition comprising a polysilazane compound and an organic compound for phase separation may be used as a coating solvent. When the polysilazane-based compound and the phase-separated free compound are mixed and cured on the base material, the polysilazane-based compound and the phase-separated organic compound are separated from each other to form a nano-pattern.

After the composition film having the nanopattern formed thereon is cured and the phase separation organic compound is removed using an organic solvent, a nanostructure capable of performing a similar role to the nanostructure of the lotus leaf can be formed on the coating surface.

At this time, the polysilazane thin film material composition may include a perhydroxypolysilazane (PHPS) -based compound having a structure represented by the following formula (1) and a phase-separation organic compound.

[Chemical Formula 1]

Here, X ¹ or X ² may each independently represent hydrogen, fluorine, an alkyl group having 1 to 12 carbon atoms, an alkyl halide having 1 to 12 carbon atoms, or an acrylic compound having 1 to 12 carbon atoms.

Herein, n is an integer of 1 to 10,000.

The phase-separation organic compound may include polystyrene (PS), polymethylmethacrylate (PMMA), polyethylene (PE) or polypropylene (PP).

The PHPS compound may be present in an amount of 1 wt% to 10 wt% based on the total weight of the composition.

At this time, when the PHPS compound has a content of less than 1% by weight based on the total weight of the composition, the implementation of the nanostructure may be difficult due to the low concentration of the PHPS compound.

At this time, when the PHPS compound has a content of more than 10% by weight based on the total weight of the composition, the effect of phase separation by the phase separation organic compound decreases due to the concentration of the high PHPS compound, and thus it may be difficult to realize the nanostructure.

The phase separation organic compound may be present in an amount of 0.1 wt% to 10 wt% based on the total weight of the composition.

At this time, when the phase-separated organic compound has a content of less than 0.1% by weight based on the total weight of the composition, the phase separation effect is insufficient due to the concentration of the low phase-separating organic compound, so that implementation of the nanostructure may be difficult.

At this time, when the phase-separated organic compound has a content of more than 10% by weight based on the total weight of the composition, the phase separation may be excessively generated due to the concentration of the high phase-separating organic compound, and thus it may be difficult to realize the nanostructure.

When the polysilazane thin film composition according to one embodiment of the present invention is used as a coating solvent, a nanostructure is formed on the surface of the coating, thereby providing a polysilazane thin film having good transparency and durability.

A method for producing a polysilazane thin film having the emulsifying and durability characteristics according to an embodiment of the present invention will be described.

1 is a flowchart showing a method of manufacturing a polysilazane thin film according to an embodiment of the present invention.

Referring to FIG. 1, the method for manufacturing a polysilazane thin film includes the steps of coating a base material of the polysilazane thin film composition of the first embodiment (S100), curing the composition coated on the base material (S200) , Performing a curing process on the preliminary heat treated preform (S300), developing the preformed preform (S400), and drying the preformed preform (S500) .

When the contact angle of the surface with water is 90 DEG or more, the hydrophobic property is exhibited. When the contact angle is 110 DEG or more, the hydrophobic property is exhibited. The self-cleansing ability, ornamental and pollution resistance of the lotus leaf is caused by the nanostructure of the surface of the lotus leaf. By adopting nanostructure using fine protrusions and fine protrusions on the surface of the lotus leaf, it becomes super hydrophobic with a contact angle of 140 ° or more.

In order to realize such a nanostructure, a composition comprising a polysilazane compound and an organic compound for phase separation may be used as a coating solvent. When the polysilazane-based compound and the phase-separated free compound are mixed and cured on the base material, the polysilazane-based compound and the phase-separated organic compound are separated from each other to form a nano-pattern.

After the composition film having the nanopattern formed thereon is cured and the phase separation organic compound is removed using an organic solvent, a nanostructure capable of performing a similar role to the nanostructure of the lotus leaf can be formed on the coating surface.

At this time, the coating (S100) may include blade coating, bar coating, slit coating, gravure coating or spin coating.

At this time, when spin coating is performed in the coating step (S100), the spin coating is performed at a speed of 400 rpm to 1200 rpm for 5 seconds to 10 seconds.

If the rotation speed of the spin coating is less than 400 rpm, it may be difficult to form a uniform coating due to a low rotation speed.

If the rotation speed of the spin coating exceeds 1200 rpm, the thickness of the coating may become thinner than necessary due to a high rotation speed, resulting in a decrease in durability.

At this time, the step of curing the composition (S200) may include ammonia water immersion, steam curing, thermal curing, E-beam curing or pulse UV curing.

At this time, the pulse UV curing is characterized by irradiating the pulsed ultraviolet ray 100 to 1000 times.

Here, the thermosetting is performed at a temperature of 80 ° C to 120 ° C for 1 minute to 10 minutes.

At this time, the step of performing the curing (S300) may be performed in order to increase the stability of the cured coating film in the step of curing the composition (S200).

At this time, the step of performing the curing (S300) is characterized in that the immersion is performed in a 15% to 45% aqueous ammonia solution at a temperature of 20 ° C to 40 ° C for 24 hours to 72 hours.

At this time, the developing step (S400) may be performed to separate the phase-separated organic compound from the coating surface by dissolving it in a developing solvent.

At this time, the developing step (S400) is performed by immersing in a developing solvent for 10 minutes to 60 minutes.

In this case, the developing solvent is a nonpolar solvent containing dichloroethane, hexane, carbon tetrachloride or benzene.

At this time, the drying step (S500) may be performed to remove the developing solvent used in the developing step (S400) remaining on the coating surface.

At this time, the drying step (S500) is performed at 100 ° C to 140 ° C.

Manufacturing example

A polysilazane based thin film was prepared according to one embodiment of the present invention.

≪ Example 1 >

First, 5 wt% PHPS and 5 wt% PS were dissolved in xylene and mixed to prepare a thin film composition.

At this time, the molecular weight of the PS is 800.

Next, the composition was coated on the base material at a speed of 500 rpm for 5 seconds.

Then, thermosetting was performed at 100 ° C for 5 minutes.

Then, curing was performed by immersing in 30% ammonia water at 30 ° C for 72 hours.

Then, the cured base material was immersed in dichloroethane for 30 minutes.

Then, the base material was dried in an oven at 120 ° C to prepare a polysilazane thin film PHPST1 (5% + 5%).

≪ Example 2 >

5 wt% PHPS and 5 wt% PS were dissolved in Xylene and mixed to prepare a thin film composition.

At this time, the molecular weight of the PS is 35000.

Next, the composition was coated on the base material at a speed of 500 rpm for 5 seconds.

Then, thermosetting was performed at 100 ° C for 5 minutes.

Then, curing was performed by immersing in 30% ammonia water at 30 ° C for 72 hours.

Then, the cured base material was immersed in dichloroethane for 30 minutes.

Then, the base material was dried in an oven at 120 ° C to prepare a polysilazane thin film PHPST2 (5% + 5%).

≪ Example 3 >

5 wt% PHPS and 3 wt% PS were dissolved in Xylene and mixed to prepare a thin film composition.

At this time, the molecular weight of the PS is 35000.

Next, the composition was coated on the base material at a speed of 500 rpm for 5 seconds.

Then, thermosetting was performed at 100 ° C for 5 minutes.

Then, curing was performed by immersing in 30% ammonia water at 30 ° C for 72 hours.

Then, the cured base material was immersed in dichloroethane for 30 minutes.

Then, the base material was dried in an oven at 120 ° C to prepare a polysilazane thin film PHPST5 (5% + 3%).

FIG. 2 is a table for analyzing characteristics of the polysilazane thin film PHPST1 (5% + 5%) according to an embodiment of the present invention.

FIG. 3 is a table for analyzing characteristics of the polysilazane thin film PHPST2 (5% + 5%) according to one embodiment of the present invention.

4 is a table for analyzing characteristics of the polysilazane thin film PHPST5 (5% + 3%) according to one embodiment of the present invention.

Referring to FIGS. 2 to 4, the shape of the nanostructures formed on the coated surface are different from each other because the phase-separation tendency is different depending on the molecular weight or content of the phase-separated organic compound.

FIG. 5 is a graph of infrared spectroscopic analysis according to the number of times of pulsed ultraviolet irradiation according to an embodiment of the present invention.

Referring to FIG. 5, it can be seen that the Si-H peak decreases and the Si-O peak increases as the number of irradiation of the pulsed ultraviolet ray increases. This means that a Si-H bond of the polysilazane compound turns into a Si-O bond and a thin film is formed.

When a polysilazane based thin film is produced according to an embodiment of the present invention, a fingerprint and a durable polysilazane thin film having various types of nanostructures are formed depending on the molecular weight or content of the polysilazane compound and the phase- Can be provided.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (14)

A perhydroxypolysilazane (PHPS) -based compound having a structure represented by the following formula (1); And
A polysilazane thin film film composition comprising a phase-separating organic compound and having transparency and durability:
[Chemical Formula 1]

X ¹ and X ² each independently represent hydrogen, fluorine, an alkyl group having 1 to 12 carbon atoms, an alkyl halide having 1 to 12 carbon atoms, or an acrylic compound having 1 to 12 carbon atoms, and n is an integer of 1 to 10000 . The method according to claim 1,
Wherein the phase separation organic compound comprises a polystyrene (PS) -based polymer, a polymethylmethacrylate (PMMA) -based polymer, a polyethylene (PE) -based polymer or a polypropylene The composition of the remaining thin film film material. The method according to claim 1,
Wherein the PHPS compound is present in an amount of 1 wt% to 10 wt% based on the total weight of the composition. The method according to claim 1,
Wherein the phase separation organic compound has a content of 0.1% by weight to 10% by weight based on the total weight of the composition. Coating the base material of the polysilazane based thin film material composition of claim 1 on the base material;
Curing the composition coated on the base material;
Performing curing on the preliminary heat-treated base material;
Developing the cured parent material; And
And drying the base material after the development is completed. The method for producing a polysilazane thin film according to claim 1, 6. The method of claim 5,
Wherein the coating step comprises a blade coating, a bar coating, a slit coating, a gravure coating, or a spin coating. The method according to claim 6,
Wherein the spin coating is performed at a speed of 400 rpm to 1200 rpm for 5 seconds to 10 seconds. 6. The method of claim 5,
Wherein the step of curing the composition comprises curing the composition including ammonia water immersion, steam curing, thermal curing, E-beam curing or pulse UV curing. . 9. The method of claim 8,
Wherein the pulsed ultraviolet curing is performed by irradiating the pulsed ultraviolet ray 100 to 1000 times. 9. The method of claim 8,
Wherein the thermosetting is performed at a temperature of 80 ° C to 120 ° C for 1 minute to 10 minutes. 6. The method of claim 5,
Wherein the curing is performed by immersing the film in a 15% to 45% aqueous ammonia solution at a temperature of 20 ° C to 40 ° C for 24 hours to 72 hours. 6. The method of claim 5,
Wherein the developing step is carried out by immersing in a developing solvent for 10 minutes to 60 minutes. 13. The method of claim 12,
Wherein the developing solvent is a nonpolar solvent containing dichloroethane, hexane, carbon tetrachloride or benzene. 6. The method of claim 5,
Wherein the step of drying is performed at 100 ° C to 140 ° C.

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