KR102494283B1 - Polysilazane-based coating material, a method of manufacturing a coating thin film using the same, and a coating thin film manufactured through the same - Google Patents

Abstract

One embodiment of the present invention provides a polysilazane-based coating material. A polysilazane-based coating material according to an embodiment of the present invention includes a polysilazane-based resin composition; and an organic siloxane compound for haze control. According to one embodiment of the present invention, by adding organic siloxane compounds having different surface energies to a polysilazane-based resin composition, optical properties such as haze value of a coating film prepared by adjusting the addition amount can be adjusted. There is an effect that can provide a polysilazane-based coating material.

Description

Polysilazane-based coating material, method for manufacturing a coating film using the same, and coating film manufactured through the same

The present invention relates to a polysilazane-based coating material and a coating film using the same, and more particularly, to a polysilazane-based resin composition capable of adjusting the haze of a coating film prepared by adding an organic siloxane compound for haze control. It relates to a polysilazane-based coating material characterized by

As technologies are advanced and diversified across industries such as electric/electronic, semiconductor, display, automobile, ship, construction, bio, and energy/environment, the demand for materials with new properties and innovative functions is rapidly increasing.

As a way to meet 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 resins, polyurethane resins, fluororesins, silicone acrylic resins, silanes, siloxanes, and siliconates.

However, conventional water-repellent coating materials form a transparent coating film with low haze. Therefore, in order to be applied as an anti-glare (AG) or anti-fingerprint coating material, haze is controlled through the formation of morphology on the surface of the coating film by mixing nanoparticles or introducing an additional process such as spray coating There are process and cost problems to be performed, and improvement thereof is required.

Republic of Korea Patent No. 10-1596441

The technical problem to be achieved by the present invention is that by adding organic siloxane compounds having different surface energies to a polysilazane-based resin composition, optical properties such as haze value can be adjusted by phase separation characteristics between the materials induced in the thin film formation process. To provide a polysilazane-based coating material.

In addition, a technical problem to be achieved by the present invention is a method for manufacturing a polysilazane-based coating film capable of adjusting optical properties such as haze value of a thin film with only a simple coating process without a separate additional process and solving the above-mentioned problems of the prior art, and To provide a coating film prepared through.

The technical problem to be achieved by the present invention is not limited to the above-mentioned technical problem, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.

In order to achieve the above technical problem, one embodiment of the present invention provides a polysilazane-based coating material.

A polysilazane-based coating material according to an embodiment of the present invention includes a polysilazane-based resin composition; and an organic siloxane compound for haze control.

The polysilazane-based resin composition may be characterized in that it is represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a hydroxy group (-OH), a chloro group (-Cl) or a primary amine group (-NH ₂ );

n ₁ is an integer from 1 to 10,000.

In this case, the molecular weight of the polysilazane-based resin composition may be 1,000 to 500,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

At this time, the structure of the polysilazane-based resin composition may include 1 mol% to 70 mol% of the cyclic type.

Alternatively, the polysilazane-based resin composition may be characterized in that it is represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₃ is an amino group, a chloro group or a hydroxy group;

R ₄ is an ether group (-O-) or a secondary amine group (-NH-);

R ₅ is a hydrogen group (-H) or a silazane group (-SiH ₂ NH-);

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

n ₂ is an integer from 1 to 10,000;

n ₃ and n ₄ are each independently an integer of 1 to 2,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

The organic siloxane compound for haze control may be characterized in that it is represented by Formula 3 below.

[Formula 3]

In Formula 3,

n ₅ is an integer from 1 to 50;

R ₆ and R ₇ are each independently (CH ₂ ) _x CH ₃ (x is an integer from 0 to 20).

More preferably, the organic siloxane compound for haze control may be characterized by being represented by Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

n ₆ is an integer from 1 to 50;

In this case, the organic siloxane compound for haze control may have a molecular weight of 500 to 5,000.

In this case, the organic siloxane compound for haze control may be added in an amount of 10 parts per hundred resin (PHR) to 50 PHR per 100 parts by weight of the polysilazane-based resin composition.

The polysilazane-based coating material may further include a solvent, an additive, an inorganic precursor, and a catalyst.

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 PHR to 30 PHR compared to the polysilazane-based resin composition.

The inorganic precursor may be one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof.

The additive may be one selected from the group consisting of antioxidants, UV absorbers, and combinations thereof.

In order to achieve the above technical problem, another embodiment of the present invention provides a method for producing a polysilazane-based coating material.

A method for producing a polysilazane-based coating material according to an embodiment of the present invention includes preparing a polysilazane-based resin composition and an organic siloxane compound for haze control; adjusting haze of a thin film to be made of the coating material by preparing a coating material by adding and mixing an organic siloxane compound with the polysilazane-based resin composition; applying the polysilazane-based coating material to a substrate; and forming a coating layer by curing the polysilazane-based coating material applied to the substrate.

In this case, the polysilazane-based resin composition in the step of preparing the polysilazane-based resin composition and the organic siloxane compound for haze control may be characterized in that it is represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a hydroxy group (-OH), a chloro group (-Cl) or a primary amine group (-NH ₂ );

n ₁ is an integer from 1 to 10,000.

In this case, the molecular weight of the polysilazane-based resin composition may be 1,000 to 500,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

At this time, the structure of the polysilazane-based resin composition may include 1 mol% to 70 mol% of the cyclic type.

[Formula 2]

In Formula 2,

R ₃ is an amino group, a chloro group or a hydroxy group;

R ₄ is an ether group (-O-) or a secondary amine group (-NH-);

R ₅ is a hydrogen group (-H) or a silazane group (-SiH ₂ NH-);

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

n ₂ is an integer from 1 to 10,000;

n ₃ and n ₄ are each independently an integer of 1 to 2,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

The organic siloxane compound for adjusting the haze in the step (S2) of adjusting the haze of the thin film to be made of the coating material may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

n ₅ is an integer from 1 to 50;

R ₆ and R ₇ are each independently (CH ₂ ) _x CH ₃ (x is an integer from 0 to 20).

More preferably, the organic siloxane compound for haze control may be characterized by being represented by Chemical Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

n ₆ is an integer from 1 to 50;

At this time, the organic siloxane compound for haze control is added at 10 parts per hundred resin (PHR) to 50 PHR per 100 parts by weight of the polysilazane-based resin composition, and the haze value of the coating film made of the polysilazane-based coating material is adjusted. It can be characterized by doing.

The step of applying the polysilazane-based coating material to the substrate is performed through any one selected from the group consisting of a supporting method, an impregnation method, and a spraying method using spinning, slot die, micro gravure, gravure, and spray can be characterized.

The step of applying the polysilazane-based coating material to the substrate may be characterized by spraying the polysilazane-based coating material for 1 second to 20 minutes while rotating the substrate at 500 rpm to 4,000 rpm.

The forming of the coating layer may be characterized in that the polysilazane-based coating material is cured by pulse UV irradiation, exposure to ammonia water, exposure to hydrogen peroxide water, or heat treatment.

In the curing of the coating layer, the polysilazane-based coating material may be cured by heating using a steam method or an impregnation method under a chemical atmosphere.

The pulsed UV irradiation is 1,000 V to 4,000 V, 5 Hz to 50 Hz, and 0.5 J / cm ² to 100 J / cm 2 at a wavelength of 50 μs to 1000 μs UV irradiation and 10 ms to 100 J / cm ² conditions It may be characterized in that 5 s UV non-irradiation is repeatedly performed.

The ammonia water exposure may be characterized in that it is performed for 12 hours to 120 hours using 5% by weight to 35% by weight of ammonia water at 15 ℃ to 35 ℃.

The hydrogen peroxide solution exposure may be characterized in that it is performed for 12 hours to 120 hours using 5% by weight to 50% by weight hydrogen peroxide at 15 ℃ to 100 ℃.

The method of manufacturing the polysilazane-based coating film may further include heat-treating the coating film after the forming of the coating layer.

The heat treatment step may be characterized by heat treatment under a temperature condition of 70 ℃ to 120 ℃.

In order to achieve the above technical problem, another embodiment of the present invention provides a polysilazane-based coating film.

The polysilazane-based coating film according to one embodiment of the present invention may be characterized in that it is manufactured according to the manufacturing method of the polysilazane-based coating film according to another embodiment of the present invention.

According to one embodiment of the present invention, by adding organic siloxane compounds having different surface energies to a polysilazane-based resin composition, optical properties such as haze value of a coating film prepared by adjusting the addition amount can be adjusted. There is an effect that can provide a polysilazane-based coating material.

In addition, according to an embodiment of the present invention, a method for manufacturing a polysilazane-based coating film capable of solving the above-described problems of the prior art and adjusting optical properties such as haze value of a thin film using a simple coating process without a separate additional process, and thereby There is an effect that can provide a coating film prepared according to.

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 detailed description of the present invention or the configuration of the invention described in the claims.

1 is a flowchart schematically showing a method for manufacturing a polysilazane-based 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 embodied in many different forms and, therefore, 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, combined)" with another part, this is not only "directly connected", but also "indirectly connected" with another member in between. "Including cases where In addition, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

Terms used in this 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 dictates otherwise. In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

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

A polysilazane-based coating material according to an embodiment of the present invention will be described.

A polysilazane-based coating material according to an embodiment of the present invention includes a polysilazane-based resin composition; and an organic siloxane compound for haze control.

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

In one embodiment of the present invention, the polysilazane-based resin composition may be characterized by being represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a hydroxy group (-OH), a chloro group (-Cl) or a primary amine group (-NH ₂ );

n ₁ is an integer from 1 to 10,000.

In this case, the molecular weight of the polysilazane-based resin composition may be 1,000 to 500,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

At this time, the structure of the polysilazane-based resin composition may include 1 mol% to 70 mol% of the cyclic type.

Alternatively, in one embodiment of the present invention, the polysilazane-based resin composition may be characterized by including a fluoroalkyl group in a molecule.

The fluoroalkyl group is rich in CF ₃ or CF ₂ , which is a component imparting low surface energy, and has a structurally linear structure, increasing the density of the water repellent group to provide water repellency to the polysilazane-based resin composition. It may be characterized by what can be done.

Specifically, the polysilazane-based resin composition may be characterized in that it is represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₃ is an amino group, a chloro group or a hydroxy group;

R ₄ is an ether group (-O-) or a secondary amine group (-NH-);

R ₅ is a hydrogen group (-H) or a silazane group (-SiH ₂ NH-);

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

n ₂ is an integer from 1 to 10,000;

n ₃ and n ₄ are each independently an integer of 1 to 2,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

The organic siloxane compound for haze control is added to adjust the haze value of the coating film prepared from the polysilazane-based coating material, and more specifically, the polysilazane-based resin composition and the organic siloxane compound are different from each other on the surface It is characterized in that optical characteristics such as haze value of the thin film are adjusted by using the characteristic that phase separation is induced in the process of forming a thin film by having energy.

Specifically, the organic siloxane compound for haze control may be characterized by being represented by Formula 3 below.

[Formula 3]

In Formula 3,

n ₅ is an integer from 1 to 50;

R ₆ and R ₇ are each independently (CH ₂ ) _x CH ₃ (x is an integer from 0 to 20).

More preferably, the organic siloxane compound for haze control may be characterized by being represented by Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

n ₆ is an integer from 1 to 50;

In this case, the organic siloxane compound for haze control may have a molecular weight of 500 to 5,000.

In this case, the organic siloxane compound for haze control may be added in an amount of 10 parts per hundred resin (PHR) to 50 PHR per 100 parts by weight of the polysilazane-based resin composition.

As described above, by adjusting the addition amount of the organic siloxane compound, the haze value of the coating film made of the polysilazane-based coating material can be adjusted to a desired value.

When the added amount of the organic siloxane compound for haze control is less than 10 PHR, the haze value of the coating film made of the polysilazane-based coating material of the present invention is too low and transparent, so that the anti-glare effect or anti-fingerprint effect cannot be sufficiently secured, which is not preferable. not.

When the addition amount of the organic siloxane compound for haze control exceeds 50 PHR, the opacity of the coating film made of the polysilazane-based coating material of the present invention is too high and surface hardness and printability may deteriorate, which is not preferable.

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

In this case, the polysilazane-based coating material may further include additives, inorganic precursors, catalysts, and combinations thereof.

The additive is not limited as long as it is a material capable of maintaining the stability of the coating material, and for example, an antioxidant, a UV absorber, and the like may be included in the additive. The inorganic precursor is not limited thereto as long as it is capable of dissolving and dispersing the coating material and forming a bond therewith. The inorganic precursor may include any one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof. The inorganic precursor may be, for example, zirconium butoxide or titanium isopropoxide, but is not limited thereto.

The inorganic precursor may be any one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof, but is not limited thereto.

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 , secondary amine-based catalysts or tertiary amine-based catalysts, platinum-based catalysts, for example, methylamine, aniline, 1,3-cyclohexanbis(methylamine), 1,5-diamino-2- Methylpentane, 2,4-diaminotoluene, 2,2-dimethyl-1,3-propanediamine, 4.4'-methyleneweiss (cyclohexylamine), dimethylamine, diethylamine, piperidine, N ,N'-diethyl-2-butene-1,4-diamine, N,N'-diisopropylethylenediamine, N,N'-diisopropyl-1,3-propanediamine, N,N '-Diphenyl-p-phenylenediamine, 2-isopropyl-2-oxazoline, 1,4,8,12-tetrazacyclopentadecane, 1,4,8,11-tetrazacyclotenanedecane -2.7-dione, trimethylamine, triethylamine, N,N-dimethylpentylamine, N-ethyl-N-methylbutylamine, N-ethyl-N-propylaniline, N,N,N',N '-tetramethyl-1,6-diaminohexane or N,N-dimethylbenzanthracene-6-amine.

The platinum-based catalyst may be, for example, fine platinum powder, platinum black, chloroplatinic acid,

Platinum tetrachloride, alcohol solution of chloroplatinic acid, platinum-olefin complex, platinum-alkenylsiloxane

complexes, platinum-carbonyl complexes, as well as powdered methyl methacrylate resins, polycarbonate resins, polystyrene resins, silicone resins, or similar thermoplastic organic resins in which a "platinum-based" catalyst is dispersed.

Due to the characteristics of the configuration as described above, according to an embodiment of the present invention, by adding organic siloxane compounds having different surface energies to the polysilazane-based resin composition, the haze value of the coating film prepared by adjusting the addition amount, etc. There is an effect that can provide a polysilazane-based coating material characterized in that the properties can be adjusted.

A method for manufacturing a polysilazane-based coating material according to another embodiment of the present invention will be described.

1 is a flowchart schematically showing a method for manufacturing a polysilazane-based coating material according to another embodiment of the present invention.

Referring to FIG. 1 , a method for manufacturing a polysilazane-based coating material according to an embodiment of the present invention includes preparing the polysilazane-based resin composition of claim 1 and an organic siloxane compound for haze control (S1); Controlling haze of a thin film to be made of the coating material by adding and mixing an organic siloxane compound for haze control with the polysilazane-based resin composition to prepare a coating material (S2); Applying the polysilazane-based coating material to a substrate (S3); and forming a coating layer by curing the polysilazane-based coating material applied to the substrate (S4).

In this case, the polysilazane-based resin composition in the step (S1) of preparing the polysilazane-based resin composition and the organic siloxane compound for haze control may be characterized in that it is represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a hydroxy group (-OH), a chloro group (-Cl) or a primary amine group (-NH ₂ );

n ₁ is an integer from 1 to 10,000.

In this case, the molecular weight of the polysilazane-based resin composition may be 1,000 to 500,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

At this time, the structure of the polysilazane-based resin composition may include 1 mol% to 70 mol% of the cyclic type.

Alternatively, the polysilazane-based resin composition may be characterized in that it is represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₃ is an amino group, a chloro group or a hydroxy group;

R ₄ is an ether group (-O-) or a secondary amine group (-NH-);

R ₅ is a hydrogen group (-H) or a silazane group (-SiH ₂ NH-);

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

n ₂ is an integer from 1 to 10,000;

n ₃ and n ₄ are each independently an integer of 1 to 2,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

The organic siloxane compound for adjusting the haze in the step (S2) of adjusting the haze of the thin film to be made of the coating material may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

n ₅ is an integer from 1 to 50;

R ₆ and R ₇ are each independently (CH ₂ ) _x CH ₃ (x is an integer from 0 to 20).

More preferably, the organic siloxane compound for haze control may be characterized by being represented by Chemical Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

n ₆ is an integer from 1 to 50;

Specifically, in the step of adjusting the haze of the thin film to be made of the coating material (S2), a mixed solution is prepared by mixing a polysilazane-based resin composition and an organic siloxane compound, and the mixed solution is heated to a temperature of 20 ° C to 60 ° C. It can be carried out by stirring for 5 minutes to 24 hours.

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

In this case, the mixed solution may further include additives, inorganic precursors, catalysts, and combinations thereof.

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

The inorganic precursor is not limited thereto as long as it is capable of dissolving and dispersing the coating material and forming a bond therewith. The inorganic precursor may include any one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof. The inorganic precursor may be, for example, zirconium butoxide or titanium isopropoxide, but is not limited thereto.

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 , secondary amine-based catalysts or tertiary amine-based catalysts, platinum-based catalysts, for example, methylamine, aniline, 1,3-cyclohexanbis(methylamine), 1,5-diamino-2- Methylpentane, 2,4-diaminotoluene, 2,2-dimethyl-1,3-propanediamine, 4.4'-methyleneweiss (cyclohexylamine), dimethylamine, diethylamine, piperidine, N ,N'-diethyl-2-butene-1,4-diamine, N,N'-diisopropylethylenediamine, N,N'-diisopropyl-1,3-propanediamine, N,N '-Diphenyl-p-phenylenediamine, 2-isopropyl-2-oxazoline, 1,4,8,12-tetrazacyclopentadecane, 1,4,8,11-tetrazacyclotenanedecane -2.7-dione, trimethylamine, triethylamine, N,N-dimethylpentylamine, N-ethyl-N-methylbutylamine, N-ethyl-N-propylaniline, N,N,N',N '-tetramethyl-1,6-diaminohexane or N,N-dimethylbenzanthracene-6-amine.

The platinum-based catalyst may be, for example, fine platinum powder, platinum black, chloroplatinic acid,

Platinum tetrachloride, alcohol solution of chloroplatinic acid, platinum-olefin complex, platinum-alkenylsiloxane

complexes, platinum-carbonyl complexes, as well as powdered methyl methacrylate resins, polycarbonate resins, polystyrene resins, silicone resins, or similar thermoplastic organic resins in which a "platinum-based" catalyst is dispersed.

At this time, the organic siloxane compound for haze control is added at 10 parts per hundred resin (PHR) to 50 PHR per 100 parts by weight of the polysilazane-based resin composition, and the haze value of the coating film made of the polysilazane-based coating material is adjusted. It can be characterized by doing.

When the added amount of the organic siloxane compound for haze control is less than 10 PHR, the haze value of the coating film made of the polysilazane-based coating material of the present invention is too low and transparent, so that the anti-glare effect or anti-fingerprint effect cannot be sufficiently secured, which is not preferable. not.

When the addition amount of the organic siloxane compound for haze control exceeds 50 PHR, the opacity of the coating film made of the polysilazane-based coating material of the present invention is too high and surface hardness and printability may deteriorate, which is not preferable.

The step of applying the polysilazane-based coating material to the substrate (S3) may include applying the coating material on the substrate.

The substrate may include plastic, metal or ceramic materials. For example, the plastic may include PET, PI, PMMA, PP, PE, PEN, EVOH, PVA, TAC, PC or raw plastic. Alternatively, for example, the substrate may include clay, glass fiber, a composite containing silica, glass, or a silicon wafer. For example, the metal material may include aluminum, stainless (SUS), or iron.

In one embodiment of the present invention, the step (S3) of applying the polysilazane-based coating material to the substrate may be any one of a supporting method, an impregnation method, and a spraying method. The spraying method may be performed, for example, through a method of spraying the resin composition on the surface of the substrate using spinning, slot die, micro gravure, gravure, or spray. For example, when the step (S3) of applying the polysilazane-based coating material to the substrate is performed by spraying using spinning, the substrate is rotated at 500 rpm to 4,000 rpm and the resin composition is applied to the substrate. It may be performed by spraying for 1 second to 20 minutes.

Forming a coating layer by curing the polysilazane-based coating material applied to the substrate (S4) is a process performed to ensure that the coating material for the water-repellent film is uniformly present and uniformly applied, and the application method , number of rotations, and the time are not limited thereto.

In one embodiment of the present invention, after the step (S3) of applying the polysilazane-based coating material to the substrate, a step (not shown) of pre-treating the substrate to which the coating material is applied may be included.

The pretreatment step (not shown) may be performed by heat-treating the substrate coated with the coating material for the water-repellent film 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, in one embodiment of the present invention, a step (S4) of forming a coating layer by curing the polysilazane-based coating material applied to the substrate after the pretreatment may be included.

In one embodiment of the present invention, the step (S4) of forming a coating layer by curing the polysilazane-based coating material applied to the substrate is not limited as long as it is an obvious method in the art of the present invention. For example, the curing may be performed through pulsed UV irradiation, ammonia water vapor exposure, and hydrogen peroxide water exposure.

At this time, when the coating composition is cured by chemical treatment, it is not limited to exposure to ammonia water and hydrogen peroxide water, and it can be cured by heating by steam and impregnation in a chemical atmosphere.

The pulse UV irradiation is 50 μs to 1000 μs ultraviolet rays irradiation and 10 ms to 1000 μs ultraviolet rays under conditions of a total exposure (energy) of 0.5 J/cm ² to 100 J/cm ² at wavelengths of 1,000 V to 4,000 V, 5 Hz to 50 Hz, and 150 nm to 450 nm. It can be performed by repeating 5 s UV non-irradiation.

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

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

When the coating material is exposed to the vapor of the ammonia water, the Si-H bonds included in the coating material are changed to Si-O bonds by the ammonia catalyst and moisture, and a silica film can be formed, and a silica film is formed on the surface of the substrate. A water-repellent film coating film can be obtained.

After curing the polysilazane-based coating material applied to the substrate to form a coating layer (S4), a step (not shown) of heat-treating the coating film may optionally be further included.

The heat treatment of the coating film may be performed to align fluoroalkyl groups present in the coating film toward the surface of the coating film. When the fluoroalkyl group is arranged toward the surface of the coating film, water repellency of the coating film may be improved.

For example, the heat treatment of 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 a temperature condition in a range in which the fluoroalkyl functional group is induced to align toward the coating surface may be suitable as the heat treatment temperature.

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

Due to the structural features as described above, according to an embodiment of the present invention, a polysilazane system capable of solving the above-described problems of the prior art and adjusting optical properties such as haze value of a thin film with a simple coating process without a separate additional process. There is an effect that can provide a method for producing a coating film.

A polysilazane-based coating film according to another embodiment of the present invention will be described.

A polysilazane-based coating film according to another embodiment of the present invention may be characterized in that it is manufactured through a manufacturing method of a polysilazane-based coating film according to another embodiment of the present invention, and the polysilazane-based resin composition And the description of the organic siloxane compound is replaced with that described in the above embodiment.

Due to the structural features described above, according to one embodiment of the present invention, there is an effect of providing a polysilazane-based coating film capable of adjusting optical properties such as haze value of a thin film with only a simple coating process.

Hereinafter, the present invention will be described in more detail through Preparation Examples, Comparative Examples and Experimental Examples. However, the present invention is not limited to the following Preparation Examples and Experimental Examples.

<Production Example 1>

To prepare a polysilazane-based coating film according to an embodiment of the present invention, a polysilazane-based coating material was prepared.

The polysilazane-based coating material is obtained by adding 20 PHR of a polysilazane-based resin composition including a compound represented by Formula 1 below and an organic siloxane compound represented by Formula 3-1 below, and dibutyl ether solvent at 25° C. for 24 hours. Prepared by stirring.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a hydroxy group (-OH), a chloro group (-Cl) or a primary amine group (-NH ₂ );

n ₁ is an integer from 1 to 10,000.

In this case, the molecular weight of the polysilazane-based resin composition may be 1,000 to 500,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

At this time, the structure of the polysilazane-based resin composition may include 1 mol% to 70 mol% of the cyclic type.

[Formula 3-1]

In Formula 3-1,

n ₆ is an integer from 1 to 50;

<Production Example 2>

In Preparation Example 1, Preparation Example 2 was prepared under the same process conditions as Preparation Example 1, except that 30 PHR of the organic siloxane compound was added.

<Production Example 3>

In Preparation Example 1, Preparation Example 3 was prepared under the same process conditions as Preparation Example 1, except that 40 PHR of the organic siloxane compound was added.

<Production Example 4>

In Preparation Example 1, Preparation Example 4 was prepared under the same process conditions as Preparation Example 1, except that a polysilazane-based resin composition containing a compound represented by Formula 2 was used as the polysilazane-based resin composition.

[Formula 2]

In Formula 2,

R ₃ is an amino group, a chloro group or a hydroxy group;

R ₄ is an ether group (-O-) or a secondary amine group (-NH-);

R ₅ is a hydrogen group (-H) or a silazane group (-SiH ₂ NH-);

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

n ₂ is an integer from 1 to 10,000;

n ₃ and n ₄ are each independently an integer of 1 to 2,000.

At this time, the structure of the polysilazane-based resin composition may be linear, branched, cyclic, or a mixture thereof.

<Production Example 5>

In Preparation Example 4, Preparation Example 5 was prepared under the same process conditions as Preparation Example 4, except that 30 PHR of the organic siloxane compound was added.

<Production Example 6>

In Preparation Example 4, Preparation Example 6 was prepared under the same process conditions as Preparation Example 4, except that 40 PHR of the organic siloxane compound was added.

<Production Example 7>

A coating film was prepared using the coating material prepared in Preparation Example 1 according to one preparation example of the present invention.

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

Next, the coating material was dropped on 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.

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.

<Production Example 8>

A coating film was prepared using the coating material prepared in Preparation Example 2 according to one preparation example of the present invention.

The same method as in Preparation Example 7 was performed to cure the applied coating film.

<Production Example 9>

A coating film was prepared using the coating material prepared in Preparation Example 3 according to one preparation example of the present invention.

The same method as in Preparation Example 7 was performed to cure the applied coating film.

<Production Example 10>

A coating film was prepared using the coating material prepared in Preparation Example 4 according to one preparation example of the present invention.

The same method as in Preparation Example 7 was performed to cure the applied coating film.

<Production Example 11>

A coating film was prepared using the coating material prepared in Preparation Example 5 according to one preparation example of the present invention.

The same method as in Preparation Example 7 was performed to cure the applied coating film.

<Production Example 12>

A coating film was prepared using the coating material prepared in Preparation Example 6 according to one preparation example of the present invention.

The same method as in Preparation Example 7 was performed to cure the applied coating film.

<Comparative Example 1>

In Preparation Example 1, instead of the organic siloxane compound, an amine-based siloxane compound represented by Formula 4 used in a conventional coating material was used, and 10 PHR of it was added to Comparative Example in the same manner as in Preparation Example 1. 1 was prepared.

[Formula 4]

In Formula 4,

n is an integer from 1 to 30;

<Comparative Example 2>

In Comparative Example 1, Comparative Example 2 was prepared in the same manner as in Comparative Example 1, except that 20 PHR of the amine-based siloxane compound was added.

<Comparative Example 3>

In Comparative Example 1, Comparative Example 3 was prepared in the same manner as in Comparative Example 1, except that 30 PHR of the amine-based siloxane compound was added.

<Comparative Example 4>

In Preparation Example 4, instead of the organic siloxane compound, an amine-based siloxane compound represented by Formula 4 used in conventional coating materials was used, and 20 PHR was added, except that Comparative Example was prepared in the same manner as in Preparation Example 4. 4 was prepared.

[Formula 4]

In Formula 4,

n is an integer from 1 to 30;

<Comparative Example 5>

In Comparative Example 4, Comparative Example 5 was prepared in the same manner as in Comparative Example 4, except that 30 PHR of the amine-based siloxane compound was added.

<Comparative Example 6>

In Comparative Example 4, Comparative Example 6 was prepared in the same manner as in Comparative Example 4, except that 40 PHR of the amine-based siloxane compound was added.

<Comparative Example 7>

A coating film was prepared using the coating material prepared in Comparative Example 1 according to one comparative example of the present invention.

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

Next, the coating material was dropped on 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.

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 8>

A coating film was prepared using the coating material prepared in Comparative Example 2 according to Comparative Example 1 of the present invention.

In order to cure the applied coating film, the same method as in Comparative Example 7 was performed.

<Comparative Example 9>

A coating film was prepared using the coating material prepared in Comparative Example 3 according to one comparative example of the present invention.

The same method as in Preparation Example 7 was performed to cure the applied coating film.

<Comparative Example 10>

A coating film was prepared using the coating material prepared in Comparative Example 4 according to one comparative example of the present invention.

In order to cure the applied coating film, the same method as in Comparative Example 7 was performed.

<Comparative Example 11>

A coating film was prepared using the coating material prepared in Comparative Example 5 according to one comparative example of the present invention.

In order to cure the applied coating film, the same method as in Comparative Example 7 was performed.

<Comparative Example 12>

A coating film was prepared using the coating material prepared in Preparation Example 6 according to one preparation example of the present invention.

In order to cure the applied coating film, the same method as in Comparative Example 7 was performed.

<Experimental example. Characteristic evaluation of coating film>

In order to analyze the coating films prepared according to Preparation Examples 7 to 12 and Comparative Examples 7 to 12, contact angle evaluation, total light transmittance (haze) evaluation, and pencil hardness evaluation were performed, and the following Tables 1 to 4 showed up

<Experimental Example 1. Contact angle evaluation of coating film>

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

<Experimental Example 2. Evaluation of the transmittance of the coating film

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

<Experimental Example 3. Pencil Hardness Evaluation of Coating Film>

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

[Table 1]

[Table 2]

[Table 3]

[Table 4]

Referring to Tables 1 to 4, it can be seen that the haze value of the coating material according to an embodiment of the present invention has a higher value than that of the comparative example, and the haze value is adjusted according to the amount of the organic siloxane material added. can confirm that it is. In addition, it can be confirmed that the coating material according to an embodiment of the present invention has good contact angle and hardness values.

The above description of the present invention is for illustrative purposes, and those skilled in the art 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, the embodiments described above should be understood as 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 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 equivalent concepts thereof should be construed as being included in the scope of the present invention.

Claims (26)

In the polysilazane-based coating material,
polysilazane-based resin compositions; and
Including; organic siloxane compound for haze control;
The polysilazane-based resin composition is a polysilazane-based coating material, characterized in that represented by the following formula (2):

[Formula 2]

In Formula 2,
R ₃ is an amino group, a chloro group or a hydroxy group;
R ₄ is an ether group (-O-) or a secondary amine group (-NH-);
R ₅ is a hydrogen group (-H) or a silazane group (-SiH ₂ NH-);
a, b and c are each independently an integer from 1 to 20;
n ₂ is an integer from 1 to 10,000;
n ₃ and n ₄ are each independently an integer of 1 to 2,000.
According to claim 1,
The polysilazane-based resin composition is a polysilazane-based coating material, characterized in that the molecular weight of 1,000 to 500,000.
According to claim 1,
The polysilazane-based coating material, characterized in that the structure of the polysilazane-based resin composition is linear, branched, cyclic or a mixture thereof.
According to claim 3,
The polysilazane-based coating material, characterized in that the structure of the polysilazane-based resin composition comprises 1 mol% to 70 mol% of the cyclic type.
According to claim 1,
The organic siloxane compound for haze control is a polysilazane-based coating material, characterized in that represented by the following formula (3):
[Formula 3]

In Formula 3,
n ₅ is an integer from 1 to 50;
R ₆ and R ₇ are each independently (CH ₂ ) _x CH ₃ (x is an integer from 0 to 20).
According to claim 1,
The organic siloxane compound for haze control is a polysilazane-based coating material, characterized in that represented by the following formula 3-1:
[Formula 3-1]

In Formula 3-1,
n ₆ is an integer from 1 to 50;
According to claim 1,
The organic siloxane compound for haze control is a polysilazane-based coating material, characterized in that the molecular weight of 500 to 5000.
According to claim 1,
The organic siloxane compound for haze control is a polysilazane-based coating material, characterized in that added in 10 parts per hundred resin (PHR) to 50 PHR per 100 parts by weight of the polysilazane-based resin composition.
According to claim 1,
A polysilazane-based coating material further comprising a solvent, an additive, an inorganic precursor, and a catalyst.
According to claim 9,
The catalyst includes 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-based resin composition. Polysilazane-based coating material, characterized in that .
According to claim 9,
The inorganic precursor is a polysilazane-based coating material, characterized in that any one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, zeolite, and combinations thereof.
According to claim 9,
The additive is a polysilazane-based coating material, characterized in that any one selected from the group consisting of antioxidants, UV absorbers and combinations thereof.
Preparing the polysilazane-based resin composition of claim 1 and an organic siloxane compound for haze control (S1);
Adjusting the haze of a thin film to be made of the coating material by adding and mixing an organic siloxane compound to the polysilazane-based resin composition to prepare a coating material (S2);
Applying the polysilazane-based coating material to a substrate (S3); and
Forming a coating layer by curing the polysilazane-based coating material applied to the substrate (S4);
Method for producing a coating film comprising a.
According to claim 13,
The organic siloxane compound for haze control is a method for producing a polysilazane-based coating film, characterized in that represented by the following formula (3):
[Formula 3]

In Formula 3,
n ₅ is an integer from 1 to 50;
R ₆ and R ₇ are each independently (CH ₂ ) _x CH ₃ (x is an integer from 0 to 20).
According to claim 13,
The organic siloxane compound for haze control is a method for producing a polysilazane-based coating film, characterized in that represented by the following formula 3-1:
[Formula 3-1]

In Formula 3-1,
n ₆ is an integer from 1 to 50;
According to claim 13,
The method for producing a polysilazane-based coating film, characterized in that the organic siloxane compound for haze control is added at 10 parts per hundred resin (PHR) to 50 PHR per 100 parts by weight of the polysilazane-based resin composition.
According to claim 13,
The step of applying the polysilazane-based coating material to the substrate is performed through any one selected from the group consisting of a supporting method, an impregnation method, and a spraying method using spinning, slot die, micro gravure, gravure, and spray Method for producing a polysilazane-based coating film, characterized in that.
According to claim 13,
In the step of applying the polysilazane-based coating material to the substrate, the substrate is rotated at 500 rpm to 4,000 rpm and the polysilazane-based coating material is sprayed for 1 second to 20 minutes. .
According to claim 13,
Forming the coating layer is a method for producing a polysilazane-based coating film, characterized in that for curing the polysilazane-based coating material by pulse UV irradiation, exposure to ammonia water, exposure to hydrogen peroxide water, or heat treatment.
According to claim 13,
The curing of the coating layer is a method for producing a polysilazane-based coating film, characterized in that for curing the polysilazane-based coating material by heating by a steam method or an impregnation method in a chemical atmosphere.
According to claim 19,
The pulsed UV irradiation is 1,000 V to 4,000 V, 5 Hz to 50 Hz, and 0.5 J / cm ² to 100 J / cm 2 at a wavelength of 50 μs to 1000 μs UV irradiation and 10 ms to 100 J / cm ² conditions Method for producing a coating film, characterized in that by repeatedly performing 5 s UV non-irradiation.
According to claim 19,
The ammonia water exposure is a method for producing a polysilazane-based coating film, characterized in that carried out for 12 hours to 120 hours using 5% by weight to 35% by weight of ammonia water at 15 ℃ to 35 ℃.
According to claim 19,
The method for producing a polysilazane-based coating film, characterized in that the exposure to hydrogen peroxide is carried out for 12 hours to 120 hours using 5% by weight to 50% by weight of hydrogen peroxide at 15 ° C to 100 ° C.
According to claim 16,
Method for producing a polysilazane-based coating film, characterized in that it further comprises the step of heat-treating the coating film after the step of forming the coating layer.
According to claim 24,
The heat treatment step is a method for producing a polysilazane-based coating film, characterized in that the heat treatment under a temperature condition of 70 ℃ to 120 ℃.
A polysilazane-based coating film produced according to claim 13.

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