KR101665186B1 - Base material having surface-treating coat and preparing method of the same - Google Patents

Abstract

The present invention relates to a substrate to which a surface treated film is applied and a method for producing the same, and more particularly to a surface treated film comprising a polysilazane on a substrate having a three-dimensional surface pattern to provide excellent stain resistance, weather resistance, And a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a base material to which a surface treated film is applied, and a method of manufacturing the same. BACKGROUND ART [0002]

The present invention relates to a substrate to which a surface treated film is applied and a method for producing the same, and more particularly to a surface treated film comprising a polysilazane on a substrate having a three-dimensional surface pattern to provide excellent stain resistance, weather resistance, And a method for producing the same.

BACKGROUND OF THE INVENTION [0002] A substrate made of a polymer composite material is mainly used as an exterior material for electronic devices, household products, ships, automobiles, and panel products.

Of these, the exterior materials of electronic appliances and furniture products have various designs, but most of them have a flat shape.

In recent years, many studies have been made to apply such a planar shape to a substrate having a three-dimensional surface pattern.

On the other hand, the application of a glass film such as a glass film coating by vapor deposition, an inorganic coating, and a glass film coating by using polysilazane is increasing to protect the surface of an electronic device exterior and automobile exterior, and to maintain the appearance.

Conventionally, polyurethane coatings have been applied to substrates for the purpose of preventing electrification. However, polyurethane coatings are vulnerable to scratches and have a disadvantage of discoloration.

Accordingly, there is a need for a base material and a method for producing the base material that have excellent stain resistance, weather resistance, and chemical resistance by solving the drawbacks of the polyurethane coating and especially applying it to a substrate having a three-dimensional surface pattern.

It is an object of the present invention to provide a base material that realizes excellent stain resistance, weather resistance, and chemical resistance by applying a surface treated film containing polysilazane to a base material having a three-dimensional surface pattern.

Another object of the present invention is to provide a best manufacturing method for providing the substrate.

In order to achieve the above-described object, a substrate to which a surface treatment film according to an embodiment of the present invention is applied is characterized in that the surface treatment film comprises polysilazane.

According to another aspect of the present invention, there is provided a method for manufacturing a substrate to which a surface treatment film according to another embodiment of the present invention is applied, comprising the steps of: (a) applying NC (numerical control) Preparing a substrate on which a three-dimensional surface pattern having a thickness of 1 mm or more is formed using a metal mold having a three-dimensional pattern having a thickness; (b) applying a polysilazane to the surface of the substrate to form a polysilazane coating film; And (c) heating the substrate having the polysilazane coating film formed thereon to convert the polysilazane coating film into a silica layer.

The substrate to which the surface treated coating according to the present invention is applied has the effect of being excellent in stain resistance, weather resistance and chemical resistance.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Hereinafter, a substrate to which a surface treated film according to an embodiment of the present invention is applied and a method for producing the same will be described in detail.

A substrate to which a surface treatment film is applied

In the substrate to which the surface treatment film according to the embodiment of the present invention is applied, the surface treatment film may include polysilazane.

The polysilazane is a polymer in which Si-N (silicon-nitrogen) bonds are repeated in the molecule, and the kind thereof is not particularly limited as long as it can be easily converted into silica. Generally, two hydrogen atoms are bonded to a Si atom in Si-N (silicon-nitrogen) bond and it is easy to call silica.

The molecular structure of such polysilazane includes linear, branched, linear, branched, cyclic, and bridged structures, or those having both structures in the molecule at the same time. In the present invention, these may be used singly or as a mixture.

Typical examples of these polysilazanes are polymers having a repeating unit of a silazane unit represented by the following formula (1). Here, the polymer also includes an oligomer.

(1)

Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group.

In terms of ease of telephone with silica, R ^1, R ² is one of both is preferred, and the R ^1, R ² in the molecule hydrogen atom containing units is a hydrogen atom, in particular R ^1, R ² And R < ³ > are both hydrogen atoms.

On the other hand, R ¹ and R ² And R ³ are all hydrogen atoms have a repeating unit represented by the following formula (2) and are referred to as perhydropolysilazane.

(2)

The perhydro polysilazane has a chemical structural moiety represented by the following formula (3).

(3)

The perhydro polysilazane may be one in which a part of the hydrogen atoms bonded to the silicon atom is substituted with a hydroxyl group.

The perhydro polysilazane can be easily synthesized by reacting dihydrogendichlorosilane with an organic base (for example, pyridine or picoline) to form an adduct and reacting the adduct with ammonia.

The number average molecular weight of such polysilazane, especially perhydro polysilazane, is usually from 100 to 50,000, more preferably from 200 to 2,500 in terms of nonvolatility upon heating and solubility in solvents.

Polysilazanes, particularly perhydropolysilazanes, according to embodiments of the present invention may contain small amounts of silica-catalyzed catalysts.

Examples of the silica-catalyzed catalyst include organic amine compounds, organic acids, inorganic acids, carboxylic acid metal salts, and organic metal complex salts.

Particularly preferred organic amine compounds are 1-methylpiperazine, 1-methylpiperidine, 4,4'-trimethylenedipiperidine, 4,4'-trimethylenebis (1-methylpiperidine) , Diazabicyclo- [2,2,2] octane, cis-2,6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, pyridine, dipyridine, pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3, 4-trimethylenedipyridine, 2- (methylamino) pyridine, Nitrogen containing cyclic organic amines such as pyrroline, imidazole, triazole, tetrazole, 1-methylpyrrolidine and the like; Examples of the amine include methylamine, dimethylamine, trimethylamine, itelamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tri Aliphatic or aromatic amines such as pentylamine, hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine and triphenylamine; DBU (1,8-diazabicyclo [5,4,0] 7-undecene), DBN (1,5-diazabicyclo [4,3,0] Azacyclododecane, and 1,4,7-triazacyclononane.

The content of the silica phthalocyanine catalyst is preferably 0.1 to 10% by weight based on the total weight of the polysilazane, especially the perhydro polysilazane.

In the substrate to which the surface treatment film according to the embodiment of the present invention is applied, the substrate may have a three-dimensional surface pattern.

The substrate can be used as an exterior material for various electronic devices, household products, ships, automobiles, panel products, and the like.

In this case, the base material has a three-dimensional surface pattern. There is no limitation on the formation method of the three-dimensional pattern, but a resin composition which is cured by heat, light or electron beam is formed on a molding surface of a mold having a three- It is preferably formed of a cured cured product.

In this case, the three-dimensional pattern formed on the molding surface of the mold is transferred to the cured product to form a three-dimensional pattern on the surface of the cured product.

The substrate to which the surface treatment film according to the embodiment of the present invention is applied includes that the substrate is an artificial marble comprising an organic substrate.

The organic material may be at least one selected from the group consisting of a polyethylene resin, a polypropylene resin, an acrylic resin, a polyamide resin, a polyester resin, a polycarbonate resin, a polyvinyl alcohol resin, an acrylonitrile butadiene styrene (ABS) resin, a polyimide resin, Synthetic resins such as resins; Synthetic wood; Bamboo, wood, and the like, and the substrate to which the surface treatment film according to the embodiment of the present invention is applied is particularly preferably a synthetic resin.

Herein, artificial marble generally refers to a synthetic composition including components such as acrylic resin, polyester resin, and epoxy resin, and adding natural stone, minerals, pigments, and additives thereto to realize the texture of natural stone. May be an artificial marble comprising the above organic material.

The shape of the organic substrate may include a plate, a sheet, a film, a foil, a filament, a block, a container, a component, and a shape of an article. The substrate may be used in a place where the substrate of the present invention is applied, And is appropriately selected and used. Specifically, the article to which the present invention is applied may be a household appliance.

The substrate to which the surface treatment film according to the embodiment of the present invention is applied includes those formed in a transparent color or white depending on the raw material in which the substrate is used.

In particular, the three-dimensional surface pattern formed on the substrate may be formed to a thickness of 1 mm or more. This can be achieved by forming a three-dimensional pattern having a thickness of 1 mm or more on the mold by using a metal or the like which is easy to form a pattern as the material of the molding mold and applying NC processing or the like to the molding surface of the mold.

In the base material to which the surface treatment film according to the embodiment of the present invention is applied, it is preferable that the thickness of the film is 3 m or less. If the concentration is out of the above range, it is necessary to increase the concentration of the coating or to apply it several times in order to increase the thickness of the coating. If the concentration is increased, it is difficult to uniformly form the coating. It is not preferable because it falls.

The polymer matrix of the polysilazane coating according to an embodiment of the present invention can be processed to nanoparticle level, and the raw material is processed by providing a different profile according to the application.

The polysilazane is highly reactive and can be bonded to almost all materials due to its high reactivity, and it forms an extremely thin layer and maintains a very stable bonding state after bonding (bonding) with the target substrate.

In the present invention, the coating film bonded to the target substrate is transparent and has an extremely thin and dense structure.

METHOD FOR PRODUCING SUBSTRATE USING SURFACE TREATED COAT

A method of manufacturing a substrate to which a surface treated film according to another embodiment of the present invention is applied includes the steps of forming a polysilazane coating film by applying polysilazane to the surface of a substrate and heating the substrate having the polysilazane coating film formed thereon, And converting the residual coating to a silica layer.

Specifically, (a) a metal mold having a three-dimensional pattern having a thickness of 1 mm or more is formed on the molding surface by applying NC (numerical control) processing to the molding surface, Preparing a substrate having a dimensional surface pattern formed thereon; (b) applying a polysilazane to the surface of the substrate to form a polysilazane coating film; And (c) heating the substrate having the polysilazane coating film formed thereon to convert the polysilazane coating film into a silica layer.

Here, in step (a), in applying or coating the polysilazane, particularly the perhydro polysilazane, on the surface of the substrate, it is preferable to dissolve the polysilazane, especially the perhydro polysilazane, in a solvent to prepare a solution Do.

The solvent for this purpose is not particularly limited so long as it dissolves polysilazane, in particular, a perhydro polysilazane to impart fluidity to the solution and does not modify or decompose the polysilazane, especially the perhydro polysilazane.

As such a solvent, aromatic hydrocarbons such as toluene, xylene and hexylene; Ethers such as ethyl butyl ether, dibutyl ether, dioxane, and tetrahydrofuran; And aliphatic hydrocarbons such as hexane, heptane, and cyclohexane.

These organic solvents may be used alone or in combination of two or more. The solid content concentration of the polysilazane, particularly the polysilazane in the hydrogenated polysilazane solution, particularly the hydrogenated polysilazane is preferably 0.1 to 35% by weight, more preferably 0.2 to 10% by weight.

In the step (a), in order to form a polysilazane, in particular a perhydro polysilazane film, by coating and coating a polysilazane, in particular a perhydro polysilazane, on the surface of the substrate, the usual application method, coating method, , Roll coating, blade coating, brushing, spraying, blow coating, spin coating, and the like.

When the substrate is polished, degreased, and subjected to various blast surface treatment before coating, adhesion of the polysilazane, especially the perhydro polysilazane, is improved.

When the polysilazane, in particular, the hydrogenated polysilazane solution is applied and coated, it is preferable to perform air drying or hot air drying after coating and coating.

On the other hand, after the step (a) is completed, (b) the substrate on which the polysilazane coating film is formed is heated to convert the polysilazane coating film into a silica layer.

The heating temperature at this time is preferably within the range of 100 to 400 占 폚, and more preferably within the range of 100 to 300 占 폚. When the polysilazane, particularly the perhydropolysilazane, contains a silica-catalyzed catalyst, the heating temperature may be lower than the above-mentioned temperature range, and preferably about 50 to 200 ° C.

In the case where the substrate is organic, it is preferable to select conditions under which each substrate is not thermally decomposed or deteriorated. In particular, the heating temperature and the heating time are desirably appropriately selected depending on the type of the specific substrate.

Since heating includes oxygen gas and water vapor, heating in air is preferred. Instead of air, an oxygen gas containing nitrogen gas, a water vapor containing nitrogen gas, an oxygen gas and a water vapor containing nitrogen gas may be used.

At this time, the conversion rate from polysilazane, especially hydrogen polysilazane to silica is preferably 80% or more, more preferably 90% or more, and most preferably 98 to 100%.

Appliances containing substrates with surface treated coatings

The present invention provides a household electric appliance including a substrate to which the surface treatment film of the present invention is applied.

The type of the household appliance is not particularly limited, and all kinds of household appliances to which artificial marble can be applied can be provided.

Example  And Comparative Example

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

In Examples and Comparative Examples, surface characteristics were measured, evaluated, and observed in the following manner.

[Pencil hardness on the surface of the test piece (pencil scratch value)]

The surface of the test piece was scratched with a pencil lead having a hardness of 6B to 9H according to 8.4.2 of JIS K5400 to show the hardness of the pencil having the maximum hardness at which no scratches occurred.

[Stain resistance on the surface of the test specimen]

In order to measure the contamination resistance to life pollution such as oil paint (manicure), soy sauce, and kochujang, the manicure, soy sauce, and kochujang were put on the surface of the test piece,

[Chemical resistance of surface of test specimen]

Acetone, alcohol, and MEK were applied to the surface of the test specimens, and the specimens were removed after 24 hours.

        [Ultraviolet ray performance of the surface of the test piece]

The sample was placed at a distance of 20cm below two 15W UV (ultraviolet) A and B, and left for 96 hours. The ΔE (color difference) value of the product was measured and compared.

Example  One

A 2 wt% xylene solution of perhydro-polysilazane (trade name: N-P110, containing an amine-based catalyst) having - (SiH ₂ -NH) - as a repeating unit was applied on the surface of a methyl methacrylate resin test piece having a three- Respectively. At this time, the coating amount was an amount that formed a 2-μm thick perhydro polysilazane coating. The specimen was allowed to stand and air-dried. After xylene had been removed, the test plate was placed in an electric furnace and heated in air at 60 DEG C for 10 minutes. Then, it was allowed to stand in the air at room temperature for 24 hours and air-dried.

Example  2

(Me ₂ SiNH) - instead of perhydro-polysilazane was used instead of the organopolysiloxane.

Comparative Example

An acrylic resin sample having a three-dimensional pattern formed on its surface was coated with polyurethane instead of perhydro polysilazane to form a film

Test result

Example  One Example  2 Comparative Example burglar
(Pencil hardness) 4H 3H 2H Stain resistance Good weakness Good general pollution
Vulnerable to meteors Chemical resistance Good Good Good My ultraviolet
(? E) 1.4 1.6 3.2

As shown in Table 1, it was found that the substrate to which the surface treatment film according to the embodiment of the present invention was applied had excellent strength, stain resistance, chemical resistance, and ultraviolet ray resistance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. . Accordingly, the true scope of the present invention should be determined by the following claims.

Claims (10)

(a) applying a NC (numerical control) process to a molding surface to form a three-dimensional surface pattern having a thickness of at least 1 mm using a metal mold having a three-dimensional pattern having a thickness of at least 1 mm formed on the molding surface, Preparing;
(b) applying a polysilazane to the surface of the substrate to form a polysilazane coating film; And
(c) heating the substrate having the polysilazane coating film to heat the polysilazane coating film to a silica layer;
Wherein the surface treatment film is applied to the base material.
The method according to claim 1,
Wherein the polysilazane has a repeating unit represented by the following formula
Method for producing substrate for household appliances applying surface treated coating:
[Chemical Formula 1]

In the above formula, R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The method according to claim 1,
The polysilazane is a perhydro polysilazane
A method for manufacturing a base material for a household appliance to which a surface treated film is applied.
The method according to claim 1,
Wherein the polysilazane is selected from the group consisting of
A method for manufacturing a base material for a household appliance to which a surface treated film is applied.
5. The method of claim 4,
Wherein the silica-catalyzed catalyst is an amine-based catalyst
A method for manufacturing a base material for a household appliance to which a surface treated film is applied.
The method according to claim 1,
The substrate may be formed of a material selected from the group consisting of polyethylene resin, polypropylene resin, acrylic resin, polyamide resin, polyester resin, polycarbonate resin, polyvinyl alcohol resin, ABS resin, polyimide resin, epoxy resin and polyurethane resin Artificial marble containing organic substrate containing more than species
A method for manufacturing a base material for a household appliance to which a surface treated film is applied.
The method according to claim 1,
The substrate is an artificial marble comprising an acrylic resin
A method for manufacturing a base material for a household appliance to which a surface treated film is applied.
The method according to claim 1,
The thickness of the coating is 3 mu m or less
A method for manufacturing a base material for a household appliance to which a surface treated film is applied.
The method according to claim 1,
The heating temperature is preferably 100 to 400 DEG C
A method for manufacturing a base material for a household appliance to which a surface treated film is applied.
A household appliance comprising a substrate for a home appliance to which a surface treatment film produced by the manufacturing method according to any one of claims 1 to 9 is applied.