KR101579257B1 - Hybrid thin films using silica-zirconia sol and their manufacturing method - Google Patents

Abstract

The present invention relates to a hybrid thin film using a silica-zirconia fused ceramic sol and a method for producing the hybrid thin film and a method of manufacturing the same. A second step of treating the surface of the silica nanosol by adding a functional silane to the silica nanosol of the first step; A third step of replacing or concentrating the solvent contained in the silica nanosol that has been subjected to the second step with an organic solvent; and forming a silica nanosol by adding a solvent to the zirconium precursor and stirring to form a colloidal zirconia nanosol (4); A fifth step of adding a functional silane to the zirconia nano sol of the fourth step to treat the surface of the zirconia nano sol; A step of replacing or concentrating the solvent contained in the zirconia nanosol that has been subjected to the fifth step with an organic solvent to form a zirconia nano sol; A seventh step of fusing the zirconia nanosol formed through the first step; An eighth step of adding a functional silane, a silicone compound and a functional organic polymer to the silica-zirconia fused ceramic sol fused in the seventh step and stirring the silica-zirconia fused ceramic sol to prepare a silica-zirconia nanosolve hybrid coating solution; And a ninth step of wet-coating the silica-zirconia nano-sol hybrid coating solution of the eighth step on the substrate and drying the silica-zirconia nano-sol hybrid coating solution to form a hybrid silica-zirconia hybrid coating film. The method is a technical point. According to another aspect of the present invention, And a silica-zirconia hybrid thin film coated on the upper surface of the substrate, wherein the silica-zirconia hybrid thin film is produced by preparing a silica nanosol and a zirconia nanosol using a silicon precursor and a zirconium precursor, respectively, And then mixed with the functional silane to form a hybrid coating solution comprising the silica-zirconia fused ceramic sol formed by mixing the functional silane, the silicon compound and the heat or photocurable polymer, A hybrid thin film using a silica-zirconia fused ceramic sol formed by coating on a substrate is also a technical point. Accordingly, functional silane or the like is added to the silica-zirconia fused ceramic nano sol prepared by using the silicon and zirconium precursor, and a hybrid material is prepared by mixing with a functional organic polymer, and then a hybrid coating film is formed therefrom, Energy, and photo-functional films.

Description

TECHNICAL FIELD The present invention relates to a hybrid thin film using silica-zirconia fused ceramic sol,

The present invention relates to a hybrid thin film using a silica-zirconia fused ceramic sol and a method for producing the same. More specifically, the present invention relates to a method for producing a silica nanosol using a silicon precursor and a zirconia nanosol using a zirconium precursor, Functional silica and the like, and then mixing them to prepare a hybrid material including silica-zirconia fused ceramic sol. Then, a silica-zirconia hybrid coating film is formed therefrom to form a silica-zirconia fusion To a hybrid thin film using a ceramic sol and a manufacturing method thereof.

In general, silica nanosol has been widely used in fields such as insulating materials, protective coating materials and packaging materials because of its excellent properties such as high insulating property, high light transmittance, excellent mechanical property, chemical resistance and heat resistance, And active research for broader application in the field of energy.

In the prior art using silica sol, "Organic solvent-type silica sol and its production method" are disclosed in Korean Patent Application Publication No. 10-2009-0053155 (published on May 27, 2009). The prior art processes include a silica sol forming step of forming a colloidal silica sol by adding a solvent to an alkoxysilane collected through purification, and stirring the silica sol; and a step of adding a functional alkoxysilane containing an organic functional group to the silica sol formed in the silica sol forming step A step of replacing the solvent contained in the silica sol with the organic solvent by the surface treatment step, and a step of replacing the organic solvent with the organic solvent, And a concentration step of concentrating the silica sol, and a method for producing the organic solvent-type silica sol, Coated silica sol is applicable to electric and electronic materials such as semiconductor displays.

There has been an attempt to improve the physical properties by hybridizing silica sol with an organic resin. Thus, a solvent-controlled silica-epoxy hybrid packaging material was manufactured in Korean Patent Registration No. 10-1321981 (published on October 28, 2013) Method, and a method of manufacturing a solvent-controlled photocurable silica-acrylic hybrid packaging material is disclosed in Korean Patent Registration No. 10-1321983 (published on Oct. 28, 2013).

Separately from silica sol, zirconia nano sol has excellent physical properties such as high dielectric constant, high refractive index, chemical resistance and heat resistance, and is actively utilized in fields such as optical materials, structural materials and protective coating materials. Zirconia nanosols having physical properties are required to be applied to electric and electronic materials requiring high purity, and active research for application is underway.

Here, by fusing two ceramic sols having excellent physical properties, it is possible to satisfy not only the physical properties but also the controllability of the physical properties, thereby securing the superior optical and electrical properties as well as compensating the mechanical, thermal and chemical properties Electric, electronic, energy, and optical applications.

Further, in order to implement a wider range of applications, it is required to control the physical properties of the two ceramic sols, and it is expected that the application range will be broadened by broadening the controllability of physical properties. However, the properties of the two ceramic sols There is little control study.

(Patent Document 1) Korean Patent Application Publication No. 10-2009-0053155 (Published Date May 27, 2009) (Document 2) Korea Patent Office Registration No. 10-1321981 (Publication date October 28, 2013) (Document 3) Korea Patent Office Registration No. 10-1321983 (Publication date October 28, 2013)

DISCLOSURE Technical Problem Accordingly, the present invention has been made in order to solve the problems of the prior art described above. Accordingly, it is an object of the present invention to provide a process for producing zirconia nanosilox by preparing a silica nanosol using a silicon precursor and zirconia nanosol using a zirconium precursor, Zirconia fused ceramic sol, and then forming a silica-zirconia hybrid coating film thereon to form a hybrid thin film using a silica-zirconia fused ceramic sol capable of applying electric, electronic, and photofunctional films, and a hybrid thin film using the same And a method for producing the same.

According to an aspect of the present invention, there is provided a method of manufacturing a silica nanosilver, comprising the steps of: preparing a colloidal silica nanosol by adding a solvent to a silicon precursor and stirring the mixture; A second step of treating the surface of the silica nanosol by adding a functional silane to the silica nanosol of the first step; A third step of replacing or concentrating the solvent contained in the silica nanosol that has been subjected to the second step with an organic solvent; and forming a silica nanosol by adding a solvent to the zirconium precursor and stirring to form a colloidal zirconia nanosol (4); A fifth step of adding a functional silane to the zirconia nano sol of the fourth step to treat the surface of the zirconia nano sol; A step of replacing or concentrating the solvent contained in the zirconia nanosol that has been subjected to the fifth step with an organic solvent to form a zirconia nano sol; A seventh step of fusing the zirconia nanosol formed through the first step; An eighth step of adding a functional silane, a silicone compound and a functional organic polymer to the silica-zirconia fused ceramic sol fused in the seventh step and stirring the silica-zirconia fused ceramic sol to prepare a silica-zirconia nanosolve hybrid coating solution; And a ninth step of wet-coating the silica-zirconia nano-sol hybrid coating solution of the eighth step on the substrate and drying the silica-zirconia nano-sol hybrid coating solution to form a hybrid silica-zirconia hybrid coating film. The method is a technical point.

According to another aspect of the present invention, And a silica-zirconia hybrid thin film coated on the upper surface of the substrate, wherein the silica-zirconia hybrid thin film is produced by preparing a silica nanosol and a zirconia nanosol using a silicon precursor and a zirconium precursor, respectively, And then mixed with the functional silane to form a hybrid coating solution comprising the silica-zirconia fused ceramic sol formed by mixing the functional silane, the silicon compound and the heat or photocurable polymer, A hybrid thin film using a silica-zirconia fused ceramic sol formed by coating on a substrate is also a technical point.

Preferably, the silicon precursor is one of silicon alkoxide, silicon chloride, and silicon acetate.

The zirconium precursor is preferably one of zirconium alkoxide, zirconium chloride, and zirconium acetate.

The solvent in the first step and the fourth step is preferably any one of nitric acid, hydrochloric acid, acetic acid, ammonia water, water, alcohol and a mixed solution thereof.

The stirring in the first step and the fourth step is preferably performed by any one of a room temperature stirring reaction, a supercritical reaction, and a hydrothermal reaction.

It is preferable that the organic solvent in the third step and the sixth step is any one of alcohol series, glycol series and cellosol series.

The functional silanes of the second and fifth steps may be selected from the group consisting of acrylic group, methacryl group, allyl group, alkyl group, ketone group, aromatic group, ester group, nitro group, hydroxyl group, cyclobutene group, , A mercapto group, a nitrile group, a vinyl group, an amine group, and an epoxy functional group.

The silicon compound of the eighth step is an organic-inorganic hybrid material, which is based on a siloxane (-Si-O-) and has a linear, branched or cyclic hydrocarbon group in any one of four bonding sites of silicon atoms And the cyclic hydrocarbon group may be an alkyl group, a ketone group, an acryl group, a methacryl group, an allyl group, an alkoxy group, an aromatic group, an amino group, an ether group, an ester group, a nitro group, a hydroxyl group, a cyclobutene group, A vinyl group, a nitrile group, a hydrogen or an epoxy functional group, or a part of the cyclic hydrocarbon group substituted with fluorine is preferable.

The functional organic polymer in the eighth step is a thermosetting polymer having at least one functional group capable of thermally polymerizing at both ends of the chain or side chains of the chain and having an organic functional group capable of thermosetting with an acryl group, an epoxy group, And an organic polymer containing a functional group abnormality.

The functional organic polymer in the eighth step is a photo-curable polymer, which comprises at least one functional group capable of photopolymerizing at both ends of the chain or an allyl group, an acryl group, a methacrylate group and a photo- , And is preferably one selected from the group consisting of an epoxy-based acrylic resin, an ether-based acrylic resin, an ester-based acrylic resin and a urethane-based acrylic resin.

The wet coating in the ninth step is preferably performed by any one of spin, bar, spray, gravure, doctor blade, dip, flow and roll-to-roll processes.

Accordingly, functional silane or the like is added to the silica-zirconia fused ceramic nano sol prepared by using the silicon and zirconium precursor, and a hybrid material is prepared by mixing with a functional organic polymer, and then a hybrid coating film is formed therefrom, Energy, and photo-functional films.

The present invention based on the above-mentioned constitution is characterized in that a silica-zirconia fused ceramic sol prepared by surface-treating a functional silane and a surface-treated silica and a zirconia nano-sol by using a silica and zirconia nanosol prepared using silicon and a zirconium precursor Functional silane and the like can be added and mixed with the functional organic polymer to produce a hybrid material, and then a hybrid coating film can be formed thereon, so that it is possible to apply electric, electron, energy, and photofunctional film.

1 is a process for producing a hybrid thin film using a silica-zirconia fused ceramic sol according to the present invention.

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

1 is a process for producing a hybrid thin film using a silica-zirconia fused ceramic sol according to the present invention.

As shown in the figure, the method for preparing a hybrid thin film using the silica-zirconia fused ceramic sol according to the present invention comprises: a first step of preparing a colloidal silica nanosol; A second step of treating the surface of the silica nanosol; A fourth step of forming a silica nanosol through a third step of replacing or concentrating a solvent contained in the silica nanosol with an organic solvent and preparing a colloidal zirconia nanosol; A fifth step of treating the surface of the zirconia nanosol; A seventh step of forming a zirconia nanosol through a sixth step of replacing or concentrating the solvent contained in the zirconia nanosol with an organic solvent and fusing the silica nanosol and the zirconia nanosol; Silica-zirconia nano sol hybrid coating solution; And a ninth step of wet-coating the hybrid coating solution on the substrate to produce a silica-zirconia hybrid thin film.

First, a silica nanosol and a zirconia nanosol should be formed.

Silica nanosol is formed by using a silicon precursor. To hydrolyze and condense 0.5 mol of purified silicon precursor (tetraososilicate), 1.75 mol of distilled water having a pH of about 10 is added and hydrolysis condensation reaction is performed at 50 ° C. for 20 hours To form a colloidal silica nanosole.

For the surface treatment of the prepared silica nanosol, methyltrimethoxysilane and glycidoxypropyltrimethoxysilane were added in an amount of 2.5 wt% based on the solids content of the silica nanosol, respectively, and the water and reaction product byproducts The organic solvent - dispersed silica nanosol was surface - treated with a high concentration of organosilane through concentration by replacing the solvent with cellosolve.

The zirconia nano-sol is formed by using a zirconium precursor. For the hydrolysis and condensation of 0.5 mol of the purified zirconium precursor (zirconium propoxide), 200 ml of distilled water having a pH of 0.9 is added, and hydrolysis condensation reaction is performed at 80 ° C for 24 hours To form a colloidal high-crystalline zirconia nanosol.

Methyltrimethoxysilane and glycidoxypropyltrimethoxysilane were added in an amount of 2.5 wt% based on the solids content of the zirconia nano sol for the surface treatment of the prepared zirconia nano sol, and the water and the polar solvent as a reaction byproduct were dissolved in ethyl The organic solvent - dispersed zirconia nanoparticles were surface - treated with a high concentration of organosilane through concentration by changing the solvent with cellosolve.

Generally, a sol having a tin oxide crystal is prepared by adding an excess amount of water in an acidic atmosphere of about 0.9 with a tin precursor at 80 ° C. However, since the prepared sol is unstable and has a very low content, However, the organic solvent-dispersed zirconia nanosol surface-treated with the organosilane prepared according to the present invention can produce a thin film having a high and high refractive index, which is excellent in mechanical properties and chemical resistance because the phase is stable and the crystal content is high There are advantages.

A silica-zirconia fused ceramic sol was prepared by mixing the above-prepared silica nanosol and zirconia nanosol at a ratio of 7: 3, 5: 5, 3: 7 by weight at room temperature for 30 minutes.

The amount of glycidoxypropyltrimethoxysilane, which is a thermosetting silane that can be coated on the silica-zirconia fused ceramic sol prepared above, was added in various amounts as shown in Table 1 below, and the amount of 3 After the addition of the molar, the mixture was stirred at 25 ° C for 9 hours, and then a silane-treated silica-zirconia fused ceramic sol capable of coating with the silicone compound formed by the reaction of glycidoxypropyltrimethoxysilane was hybridized A functional hybrid coating material was prepared.

Silica-zirconia fusion ratio Silica-Zirconia Fusion Sol: Silane Refractive index
(632.6 nm) Light transmittance (%)
(400 to 800 nm) Adhesive force (B) Silica: zirconia = 7: 3
(15 wt% solids content) 1: 2 1.561 91 5 1: 1.5 1.555 91 5 1: 1.0 1.542 91 4 Silica: zirconia = 5: 5
(15 wt% solids content) 1: 2 1.595 91 5 1: 1.5 1.605 90 4 1: 1.0 1.621 90 4 Silica: zirconia = 3: 7
(15 wt% solids content) 1: 2 1.612 90 5 1: 1.5 1.623 90 4 1: 1.0 1.645 90 4

Then, the high-refraction hybrid coating material was coated on the silicon wafer and the glass substrate through spin coating, and then the silica-zirconia hybrid thin film was prepared by low-temperature firing at 150 ° C for 90 minutes.

Table 1 shows the refractive index data measured using a prism coupler and the UV-Visible spectroscopy data of the hybrid thin films prepared by varying the content of silica-zirconia nano sol and the added silane content in the silica-zirconia hybrid thin film prepared according to the present invention The transmittance measured in a visible light range of 400 to 800 nm and the adhesive force measured through a tape test.

As shown in Table 1, the refractive index of the silica-zirconia hybrid thin film prepared using the silica-zirconia fused ceramic sol was as high as 1.5 or more, and it was found that the ratio of silica-zirconia sol ratio to silane It is confirmed that the refractive index can be controlled through the control.

Also, as shown in Table 1, it was confirmed that the transmittance of the silica-zirconia hybrid thin film prepared using the silica-zirconia fused ceramic sol exhibited a high transmittance of 90% or more regardless of the content of the fused sol and the silane, As shown in Table 1, it was confirmed that the adhesion of the silica-zirconia hybrid thin film prepared using the silica-zirconia fused ceramic sol exhibits a high adhesion property of 4B or more regardless of the ratio of the fused sol and the silane content.

As can be seen from the above physical properties, it can be said that it can be used as an optical material and a protective coating material which require a high transmittance, and it is very applicable to electric, electronic, energy and optical applications.

Claims (20)

Adding a solvent to the silicon precursor and stirring to produce a colloidal silica nanosol; A second step of treating the surface of the silica nanosol by adding a functional silane to the silica nanosol of the first step; And a third step of replacing or concentrating the solvent contained in the silica nanosol that has undergone the second step with an organic solvent to form a silica nanosol,
A fourth step of adding a solvent to the zirconium precursor and stirring the zirconium precursor to prepare a colloidal zirconia nanosol; A fifth step of adding a functional silane to the zirconia nano sol of the fourth step to treat the surface of the zirconia nano sol; And a sixth step of replacing or concentrating the solvent contained in the zirconia nanosol after the fifth step with an organic solvent to form a zirconia nano sol,
A seventh step of fusing the silica nanosol formed through the third step with the zirconia nanosol formed through the six steps;
An eighth step of adding a functional silane, a silicone compound and a functional organic polymer to the silica-zirconia fused ceramic sol fused in the seventh step and stirring the silica-zirconia fused ceramic sol to prepare a silica-zirconia nanosolve hybrid coating solution;
And a ninth step of wet-coating the silica-zirconia nano-sol hybrid coating solution of the eighth step on the substrate and drying the silica-zirconia nano-sol hybrid coating solution to form a silica-zirconia hybrid thin film,
In the seventh step, the silica nanosol and zirconia nanosol are mixed in a weight ratio of 3: 7,
Wherein the silica-zirconia fused ceramic sol is formed by mixing the functional silane, the silicon compound, and the functional organic polymer at a weight ratio of 1: 1 to 2: 1. A method for manufacturing a hybrid thin film. The method of claim 1, wherein the silicon precursor is one of silicon alkoxide, silicon chloride, and silicon acetate. The method of claim 1, wherein the zirconium precursor is one of zirconium alkoxide, zirconium chloride, and zirconium acetate. The method of claim 1, wherein the solvent in the first step and the fourth step is any one of nitric acid, hydrochloric acid, acetic acid, ammonia water, water, alcohol, and a mixed solution thereof. A method for producing a hybrid thin film. The method according to claim 1, wherein the stirring of the first step and the fourth step is performed by any one of a room temperature stirring reaction, a supercritical reaction, and a hydrothermal reaction, and the hybrid thin film preparation method using the silica-zirconia fused ceramic sol . The hybrid thin film manufacturing method according to claim 1, wherein the organic solvent in the third step and the sixth step is any one of alcohol series, glycol series, and cellosolve series. The method of claim 1, wherein the functional silanes of the second and fifth steps are selected from the group consisting of an acryl group, a methacryl group, an allyl group, an alkyl group, a ketone group, an aromatic group, an ester group, a nitro group, , A silane having at least one of an alkoxide group, an urethane group, a mercapto group, a nitrile group, a vinyl group, an amine group and an epoxy functional group. The method according to claim 1, wherein the silicon compound in the eighth step is an organic-inorganic hybrid material, and the siloxane (-Si-O-) is used as a base, and any one of four bonding sites of the silicon atom may be linear, Wherein the cyclic hydrocarbon group is an alkyl group, a ketone group, an acryl group, a methacryl group, an allyl group, an alkoxy group, an aromatic group, an amino group, an ether group, an ester group, a nitro group, A cyclohexyl group, a cyclobutene group, a carboxyl group, an alkyd group, a urethane group, a vinyl group, a nitrile group, a hydrogen or an epoxy functional group, or a part of the hydrogen atoms of the cyclic hydrocarbon group is substituted with fluorine (Manufacturing Method of Hybrid Thin Film Using Silica - Zirconia Fused Ceramic Sol). The functional organic polymer according to claim 1, wherein the functional organic polymer in the eighth step is a thermosetting polymer. The functional organic polymer is selected from the group consisting of a vinyl group, an acryl group, an epoxy group, an amino group, an imide group, and a thermosetting group capable of thermopolymerizing at both ends of the chain Wherein the organic thin film is one selected from the group consisting of organic polymers containing at least one functional group and at least one organic functional group capable of forming a hybrid thin film using the silica-zirconia fused ceramic sol. The functional organic polymer according to claim 1, wherein the functional organic polymer in the eighth step is a photo-curable polymer, which is capable of photopolymerizing at both ends of the chain or side chains thereof, an allyl group, an acryl group, a methacrylate group, Wherein the organic functional group is at least one selected from the group consisting of organic polymers containing at least one functional group and is any one of epoxy-based acrylic resin, ether-based acrylic resin, ester-based acrylic resin and urethane- A method for producing a hybrid thin film using a fused ceramic sol. The method according to claim 1, wherein the wet coating in the ninth step is performed by any one of spin, bar, spray, gravure, doctor blade, dip, flow and roll- Preparation method of hybrid thin film using sol. Claims [1]
And a silica-zirconia hybrid thin film coated on the upper surface of the substrate,
The above-mentioned silica-zirconia hybrid thin film,
A silica nanosol and a zirconia nanosol are prepared using a silicon precursor and a zirconium precursor, respectively, and these are concentrated or replaced with an organic solvent, surface-treated with a functional silane, mixed and mixed with a functional silane, A hybrid coating solution containing a silica-zirconia fused ceramic sol formed by mixing a curable polymer is formed on a substrate,
The silica nanosol and the zirconia nanosol are mixed in a weight ratio of 3: 7,
Wherein the functional silane, the silicon compound, and the heat or photo-curable polymer are mixed at a weight ratio of 1 to 2, based on the weight ratio of the silica-zirconia fused ceramic sol 1, to the weight ratio of the silica-zirconia fused ceramic sol to the silica-zirconia fused ceramic sol. 13. The hybrid thin film according to claim 12, wherein the silicon precursor is one of silicon alkoxide, silicon chloride, and silicon acetate. 13. The hybrid thin film according to claim 12, wherein the zirconium precursor is one of zirconium alkoxide, zirconium chloride, and zirconium acetate. 13. The hybrid thin film according to claim 12, wherein the organic solvent is one selected from the group consisting of alcohol series, glycol series, and cellosolve series. The functional silane according to claim 12, wherein the functional silane is at least one selected from the group consisting of an acryl group, a methacryl group, an allyl group, an alkyl group, a ketone group, an aromatic group, an ester group, a nitro group, a hydroxyl group, a cyclobutene group, Wherein the silicon-zirconia fused ceramic sol is a silane having at least one of nitrogen, phosphorus, nitrogen, nitrile, vinyl, amine and epoxy functional groups. 13. The method of claim 12, wherein the silicon compound is an organic-inorganic hybrid material. The silicon compound is based on siloxane (-Si-O-), and has a linear, branched or cyclic hydrocarbon group Wherein the cyclic hydrocarbon group is an alkyl group, a ketone group, an acryl group, a methacryl group, an allyl group, an alkoxy group, an aromatic group, an amino group, an ether group, an ester group, a nitro group, Wherein at least one of the carboxyl group, the alkyd group, the urethane group, the vinyl group, the nitrile group, the hydrogen or the epoxy functional group has at least one or two or more kinds of hydrogen atoms in the cyclic hydrocarbon group is substituted with fluorine, Hybrid Thin Film Using Ceramic Sol. The thermosetting polymer according to claim 12, wherein the thermosetting polymer has at least one functional group capable of thermopolymerizing at both ends of the chain or in the side chain of the chain with at least one functional group capable of thermopolymerizing the vinyl group, acrylic group, epoxy group, amino group, Wherein the hybrid thin film comprises a silica-zirconia fused ceramic sol. The photocurable polymer according to claim 12, wherein the photocurable polymer comprises at least one functional group capable of photopolymerizing at both ends of the chain or in a side chain of the chain, the vinyl group, the allyl group, the acryl group, the methacrylate group and the photocurable organic functional group Wherein the hybrid thin film is one selected from the group consisting of an epoxy-based acrylic resin, an ether-based acrylic resin, an ester-based acrylic resin, and a urethane-based acrylic resin. 13. The hybrid thin film according to claim 12, wherein the coating is performed by any one of spin, bar, spray, gravure, doctor blade, dip, flow and roll-to-roll processes. .

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