KR20210123879A - Impact resistance layer, method for manufacturing thereof, and a substrate including thereof - Google Patents

Abstract

The present invention relates to an impact resistant layer to increase impact resistance of a substrate, which comprise a primer formed by polymerization of a silicone-based polymer and an organic-inorganic silane compound, wherein the thickness of the impact resistant layer is 300 to 500nm, and a substrate including the same. According to the present invention, a method for applying an impact resistant layer comprises the following steps: (A) treating the substrate of a surface with plasma; (B) depositing an impact resistant layer on the plasma-treated substrate; (C) and treating the deposited impact resistant layer with plasma, wherein the thickness of the deposited impact resistant layer is 300 to 500 nm.

Description

Impact resistance layer, method for introducing same, and substrate including same {Impact resistance layer, method for manufacturing thereof, and a substrate including thereof}

The present invention relates to an impact resistant layer, a method for introducing the same, and a substrate comprising the same.

Many electronic devices such as displays and semiconductor integrated circuits include a configuration for absorbing or mitigating shock in order to prevent damage to electronic devices or components due to external impact. In particular, as displays having a touch sensor function, such as smartphones and tablet PCs, are commercialized, a protective film for protecting the display from external impacts or scratches is widely used.

In addition, as the demand for thinness and weight reduction of the display increases due to the recent development of technology, in order to meet these demands, a shock absorbing functional layer using a sheet or film to directly absorb impact without using a protective plate on the display is provided. A technology is being developed, and a commonly used protective film is a method of mitigating impact through lamination of various structures including PET (Polyethylene Terephthalate). The reason is that PET is relatively easy to process and inexpensive among plastics used for various optical purposes.

However, PET has a disadvantage in that the transmittance is lower than that of glass and the surface hardness is relatively low, about 3H (Pencil Hardness), so that it is easy to be scratched by coins in real life. In order to solve this problem, Patent Registration No. 10-1517681 discloses a base layer formed of an acrylic plate; hard coating layer; PET layer for impact mitigation; UV adhesive layer; Disclosed is a liquid crystal protective film for display protection including an adhesive layer, but the base layer has a thickness of 0.1 mm to 0.3 mm, the hard coat layer has a thickness of 0.01 mm to 0.02 mm, and the PET layer has a thickness of 0.07 mm to 0.08 mm, thereby reducing the size of the display. , there is a problem that it is too thick and does not meet the requirement of thinning.

In order to solve this problem, Patent Publication No. 10-2008-0065484 discloses a shock-resistant shock-absorbing layer in which microbubbles having a size of 1 μm or less are included in an amount of 100 or less per 1 mm 3 of the shock-absorbing layer, but the thickness is 30 In the case of less than ㎛, the impact that has not been absorbed is transmitted to the layer located next to the impact absorption layer because the thickness of the impact absorption layer is insufficient to completely absorb the impact that has reached the impact absorption layer. However, since it discloses that it may cause damage to glass windows and other transparent substrates, there is still a problem that the thickness is 30 μm or more.

Patent Publication No. 10-2008-0065484 Registered Patent No. 10-1517681

In order to solve this problem, the present invention provides an impact-resistant layer comprising a primer formed through a polymerization reaction of a silicone-based and organic-inorganic silane compound as a means for strengthening the impact resistance of the substrate by reducing the stress difference between the coating layer and the substrate. It is an object of the invention to provide a shock-resistant layer for reinforcing impact resistance even with a thin thickness by coating at a thickness of 300 nm to 500 nm, which is thinner than the prior art, a method for introducing the shock-resistant layer into a substrate, and a substrate including the same .

The present invention relates to an impact-resistant layer comprising a primer formed by polymerization of a silicone-based polymer and an organic-inorganic silane compound, wherein the impact-resistant layer has a thickness of 300 nm to 500 nm.

In a first aspect of the present invention, the impact-resistant layer comprises the steps of plasma-treating the substrate surface (A); depositing an impact resistant layer on the plasma-treated substrate (B); and plasma-treating the deposited shock-resistant layer (C).

In a second aspect of the present invention, further depositing an impact-resistant layer on the plasma-treated impact-resistant layer (D); and plasma-treating the shock-resistant layer deposited by the step (D) (E), wherein the total thickness of the shock-resistant layer may be 300 nm to 500 nm.

In a third aspect of the present invention, the substrate on which the impact-resistant layer is applied may be an ultra-thin tempered glass (UTG).

In the fourth aspect of the present invention, the plasma used in at least one of the steps (A) and (C) is one or more mixed gas plasmas selected from the group consisting of argon, nitrogen, and oxygen. can

In the fifth aspect of the present invention, the plasma used in at least one of the steps (A) and (C) is a power of 700 to 800W of RF power in the device maintained at ^{10 -4} to 10 ^{-7 Torr} It may be a mixed gas plasma formed by applying

In the sixth aspect of the present invention, the step (B) is CVD (Chemical Vapor Deposition), PECVD (Plasma-Enhanced Chemical Vapor Deposition), LPCVD (Low Pressure Chemical Vapor Deposition), PVD (Physical Vapor Deposition), and ALD (Atomic Layer Deposition) may be performed by one or more processes selected from the group consisting of.

In the seventh aspect of the present invention, the silicone-based polymer may include at least one selected from the group consisting of an amino group, an epoxy group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenyl group.

In the eighth aspect of the present invention, the organic-inorganic silane compound may include at least one selected from the group consisting of an amino group, a vinyl group, an epoxy group, an alkoxy group, a halogen group, a mercapto group, and a sulfide group.

In the ninth aspect of the present invention, the organic-inorganic silane compound is aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N-(2-aminoethyl )-3-Aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltridimethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(methoxyethoxy)silane, di-, tri- or tetraalkoxysilane, vinylmethoxysilane, Vinyltrimethoxysilane, vinylepoxysilane, vinyltriepoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- Methacryloxypropyltrimethoxysilane, chlorotrimethylsilane, trichloroethylsilane, trichloromethylsilane, trichlorophenylsilane, trichlorovinylsilane, mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, It may include at least one selected from the group consisting of bis(trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)tetrasulfide, and combinations thereof.

In addition, the present invention, plasma treatment of the surface of the substrate (A); depositing an impact resistant layer on the plasma-treated substrate (B); and plasma-treating the deposited shock-resistant layer (C), wherein the deposited shock-resistant layer has a thickness of 300 nm to 500 nm.

In a tenth aspect of the present invention, further depositing an impact-resistant layer on the plasma-treated impact-resistant layer (D); and plasma-treating the shock-resistant layer deposited by the step (D), wherein the total thickness of the shock-resistant layer is 300 nm to 500 nm.

The present invention also relates to a substrate comprising the impact-resistant layer described above.

In an eleventh aspect of the present invention, the impact-resistant layer may be a substrate including an impact-resistant layer, characterized in that it is formed on at least one or more surfaces of the substrate.

The shock-resistant layer introduced by the method of introducing the shock-resistant layer of the present invention has a thickness of 300 nm to 500 nm compared to the thickness of the shock-resistant layer of the prior art having a thickness of about 10 µm to 500 µm, despite the relatively thin thickness By the effect of reducing the stress difference between the substrate and the coating layer, it is possible to prevent the surface cracking phenomenon due to an external impact.

In addition, in that it can be directly configured on the outer surface of the substrate to the substrate, it provides an effect that can greatly contribute to the improvement of the impact resistance of the substrate to the substrate compared to the prior art located below the substrate to the substrate.

1 is a cross-sectional view of a UTG coated with an impact resistant layer, which is an embodiment of the present invention.

The present invention relates to a method of introducing an impact-resistant layer for preventing surface cracking of ultra-thin tempered glass (UTG), an impact-resistant layer introduced by the introduction method, and a substrate including the same.

Specifically, in one embodiment of the present invention, the impact-resistant layer comprising a primer formed by a polymerization reaction of a silicone-based polymer and an organic-inorganic silane compound, the thickness of the impact-resistant layer is about the impact-resistant layer of 300nm ~ 500nm.

Specifically, in an embodiment of the present invention, plasma-treating the surface of the substrate (A), depositing a shock-resistant layer on the plasma-treated substrate (B), and plasma-treating the deposited shock-resistant layer (C) ), wherein the deposited shock-resistant layer has a thickness of 300 nm to 500 nm.

Hereinafter, the advantages and features of the present invention, and a method for achieving it will become clear with reference to the embodiments described below in detail in conjunction with the accompanying drawings.

<Shock-resistant layer>

The impact-resistant layer of the present invention includes a primer for absorbing shock, and the primer may be formed by polymerization of a silicone-based polymer and an organic-inorganic silane compound.

In an embodiment of the present invention, the impact-resistant layer is plasma-treated on the surface of the substrate (A); depositing an impact resistant layer on the plasma-treated substrate (B); and plasma-treating the deposited shock-resistant layer (C). As an impact-resistant layer introduced to the substrate by a method comprising a, the thickness of the impact-resistant layer may be 300 nm to 500 nm.

In an embodiment of the present invention, further depositing an impact-resistant layer on the plasma-treated impact-resistant layer (D); And further comprising the step (E) of plasma-treating the shock-resistant layer deposited by the step (D), the total thickness of the shock-resistant layer may be 300nm to 500nm.

Steps (A) to (E) may be the same as those of each step described in <Method for introducing impact-resistant layer> to be described later.

silicone polymer

The silicone polymer of the present invention is not particularly limited as long as it has a function of absorbing impact, and in one or more embodiments, any silicone polymer or oligomer having various molecular weights and a linear or cyclic branched or crosslinked structure It can be obtained by polymerization and/or polycondensation of appropriately functionalized silanes. In one example, silicon atoms consist essentially of major repeating units (siloxane bonds ≡Si-O-Si≡) linked together by oxygen atoms, optionally in which a substituted hydrocarbon radical is a silicon atom described above via a carbon atom. Including, but not limited to, directly connected to.

In the present invention, the silicone-based polymer is, in one or more embodiments, an amino group, an epoxy group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenyl group having at least one functional group selected from a modified silicone polymer or a combination thereof and the like, preferably a polymer of methyltrimethoxysilane.

Organic-Inorganic Silane Compounds

The organic-inorganic silane compound of the present invention is not particularly limited as long as it serves to strengthen hardness and surface scratches, and is a compound containing silane, which is a compound of silicon and hydrogen, for example, methylsilane (SiH ₄ ), ethylsilane. (Si ₂ H ₆ ) and some higher silicon hydrogen compounds.

In the present invention, the organic-inorganic silane compound includes at least one functional group selected from the group consisting of an amino group, a vinyl group, an epoxy group, an alkoxy group, a halogen group, a mercapto group, and a sulfide group, and more specifically, aminopropyltriethoxysilane. , aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ -Aminopropylmethyldimethoxysilane, γ-aminopropyltridimethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldiethoxysilane, vinyltriethoxysilane, vinyl tri Methoxysilane, vinyltri(methoxyethoxy)silane, di-, tri- or tetraalkoxysilane, vinylmethoxysilane, vinyltrimethoxysilane, vinylepoxysilane, vinyltriepoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, chlorotrimethylsilane, trichloroethylsilane, trichloromethyl Silane, trichlorophenylsilane, trichlorovinylsilane, mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bis(trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)tetra It may be at least one selected from the group consisting of sulfides and combinations thereof, and preferably aminopropyltriethoxysilane or a combination containing the same.

additive

In addition, the primer included in the impact-resistant layer of the present invention may further include an additive, specifically, an additional agent such as a crosslinking agent and a catalyst may be further included as an additive.

In the present invention, the impact-resistant layer may be formed to a thickness of 300 to 600 nm, more preferably formed in a thickness of 300 nm to 500 nm. When the impact-resistant layer of the present invention is formed to a thickness of 300 nm or less, it does not provide an effect of protecting the impact of the substrate, In the case of being formed to a thickness of 600 nm or more, the effect of protecting the impact is rather reduced, whereas the effect of protecting the impact is generally increased as the thickness is increased, so it is not preferable.

<Method of introducing impact-resistant layer>

The method for introducing a shock-resistant layer of the present invention comprises the steps of plasma-treating a substrate surface (A); depositing an impact resistant layer on the plasma-treated substrate (B); and plasma-treating the deposited shock-resistant layer (C), wherein the deposited shock-resistant layer may have a thickness of 300 nm to 500 nm.

In addition, the number of times of deposition of the shock-resistant layer of the present invention may be singular or plural, and in one or a plurality of embodiments, further depositing a shock-resistant layer on the plasma-treated shock-resistant layer (D); And further comprising the step (E) of plasma-treating the shock-resistant layer deposited by the step (D), the total thickness of the shock-resistant layer may be 300nm to 500nm.

The step (A) of the present invention may be performed for the purpose of surface modification and cleaning of the substrate to which the impact resistant layer is to be applied in a later step, and in one or a plurality of embodiments, treatment for 100 seconds to 500 seconds it may be

In the step (B) of the present invention, the thickness of the shock-resistant layer to be deposited may be 300 nm to 500 nm, and when the shock-resistant layer is deposited by a plurality of depositions, specifically, the shock-resistant layer of step (D) is further deposited In this case, the total thickness of the impact-resistant layer may be 300 nm to 500 nm, wherein the thickness of each of the impact-resistant layers may be appropriately selected, and preferably may be selected from 50 nm to 250 nm.

The step (C) of the present invention may be performed for the purpose of improving roughness, haze improvement, and surface cleaning, but in the case of additionally depositing the impact resistance layer of step (D), impact resistance It may be performed for the purpose of strengthening the adhesion between the layers.

The step (E) of the present invention may be performed for the purpose of improving roughness, improving haze, and cleaning the surface.

The steps (C) and (E) may be performed for 10 seconds to 50 seconds, preferably 10 seconds to 30 seconds, respectively.

Plasma used in at least one plasma treatment step of step (A), step (C), and step (E) of the present invention is at least one mixed gas plasma selected from the group consisting of argon, nitrogen, and oxygen can be

In the apparatus maintained at ^{10 -4} to 10 ^-7 Torr at room temperature, the plasma used in the plasma processing step of at least one of the steps (A), (C), and (E) of the present invention, the RF It may be a mixed gas plasma formed by applying a power of 700 to 800W.

The step (B) of the present invention and the step of depositing at least one impact resistant layer of step (D) include CVD (Chemical Vapor Deposition), PECVD (Plasma-Enhanced Chemical Vapor Deposition), LPCVD (Low Pressure Chemical Vapor Deposition) ), PVD (Physical Vapor Deposition), and ALD (Atomic Layer Deposition) may be performed by one or more processes selected from the group consisting of.

<Substrate Containing Impact-Resistant Layer>

The substrate including the impact-resistant layer of the present invention includes a substrate including the above-described impact-resistant layer on at least one surface of the substrate, more specifically, on the upper and/or lower portion of the substrate. All of the descriptions for the impact-resistant layer described above are equally applied. The substrate, by including the above-described impact-resistant layer, the surface cracking phenomenon due to external impact can be prevented, and in particular, the effect of reducing the stress difference between the substrate and the coating layer despite the relatively thin thickness of the impact-resistant layer can protect the substrate from external impact.

Materials that can be used as the base material of the impact resistant layer of the present invention are not particularly limited, but are preferably used for protection of ultra-thin tempered glass (UTG).

Hereinafter, examples of the present invention will be specifically described. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout.

In addition, the terminology used herein is for the purpose of describing the embodiments, and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, “comprises” and/or “comprising” refers to the presence or addition of one or more other components, steps, operations and/or components other than the stated components, steps, operations and/or components. It is used in the sense of not being excluded.

Hereinafter, preferred embodiments of the present invention will be described in detail.

<Production Example>

First, after setting the deposition processor setting value for ultra-thin tempered glass (UTG) 6 to 10 times, prepare ultra-thin tempered glass (UTG) with a size of 10 mm * 70 mm, and plasma-treat it under ^{10 -5 Torr at room temperature.} It was used for cleaning and surface modification of organic contaminants.

For plasma treatment, argon (Ar) gas and oxygen (O ₂ ^{) gas were used as a mixed gas of 25 sccm and 30 sccm, respectively, under 10 -5} Torr, and plasma formation was induced with an applied power of 700 to 800 W of RF Power, 15 mm Reciprocating processing was performed for 300 seconds at a speed of /sec.

Then, in order to deposit the impact-resistant layer, CVD (Chemical Vapor Deposition) was used, and _{O 2} was used as a medium for the chemical reaction ^{at a temperature of 25 ~ 80 °C, under a pressure of 10 -5} Torr, and the flow rate was It was set as 100-1000 sccm.

After depositing the shock-resistant layer, under the same conditions as the plasma treatment, plasma treatment was performed for 10 to 30 seconds to strengthen the adhesion between the shock-resistant layers, and then an additional shock-resistant layer was deposited in the same manner as the shock-resistant layer, and In the same manner, plasma treatment was performed for 10 to 30 seconds to prepare a substrate including an impact resistant layer.

<Examples and Comparative Examples>

A substrate including an impact-resistant layer was prepared according to the above preparation example, and to the thickness of the impact-resistant layer described in Table 1 below, Examples and Comparative Examples were prepared.

The thickness of the impact-resistant layer shown in Table 1 below means the sum of the total thickness of the impact-resistant layer.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 impact-resistant layer
thickness 300nm 400nm 500nm unprocessed 100nm 200nm 600nm 700nm 800nm

< Experimental example>

The fracture radius of the substrate according to the thickness of the impact-resistant layer of Table 1, Pendrop was evaluated by the following method, and is shown in Table 2 below.

(1) breaking radius

A substrate including a shock-resistant layer corresponding to the above examples and comparative examples is prepared in a size of 10mm * 70mm, the reference speed is set to 20mm/min, and the breaking radius is set to 1mm to 30mm (1R or less). At this time, the radius at the location where the UTG Glass breaks was measured, and is shown in Table 2 below.

(2) Pendrop

A pendrop test was performed on the description of Examples and Comparative Examples as shown in Table 1 above. The pendrop test was performed by free-falling a Big Pen Round Stic Medium pen having a pen tip diameter of 1.0 mm and a weight of 3.6 g onto a substrate by varying the drop height.

Table 2 is shown in Table 2 below by measuring the limit height at which the substrate is damaged by pendrop when pendrop is performed. The larger the threshold height, the better the substrate can withstand external impact.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 breaking radius
(R, mm) 0.7 0.72 0.74 1.08 0.69 0.70 0.82 0.87 0.90 Pendrop
(cm) 20.9 20.8 21.0 14.8 15.0 18.1 20.4 20.1 19.7

Referring to Table 2 showing the evaluation by the method, Examples 1 to 3 including the impact resistance layer introduced at 300 nm to 500 nm by the method for introducing the impact resistance layer of the present invention, and Comparative Examples 1 to 6 outside the range By comparison, it can be seen through the results of the Pendrop experiment that Examples 1 to 3 exhibit increased impact resistance than Comparative Examples 1 to 6, and in particular, Comparative Example 1 which does not include an impact resistance layer and an impact resistance layer having less than an appropriate thickness. It can be seen that the impact resistance is significantly improved compared to Comparative Examples 2 to 3 including

In addition, even in the case of Comparative Examples 4 to 6, in which the thickness of the impact resistance layer exceeds the appropriate thickness of the present invention, it can be confirmed that the impact resistance is lowered, and it can be confirmed that the impact resistance is the most improved in the numerical range, and also , Comparative Examples 4 to 6 contain an excessively thick impact-resistant layer, and it can be seen that, in terms of the fracture radius, they exhibit poor effects compared to Examples 1 to 3.

Claims (14)

An impact-resistant layer comprising a primer formed by polymerization of a silicone-based polymer and an organic-inorganic silane compound, wherein the impact-resistant layer has a thickness of 300 nm to 500 nm.
The method according to claim 1,
The impact-resistant layer is plasma-treated on the surface of the substrate (A);
depositing an impact resistant layer on the plasma-treated substrate (B); and
Plasma treatment of the deposited shock-resistant layer (C); characterized in that introduced into the substrate by a method comprising, the shock-resistant layer.
3. The method according to claim 2,
depositing an additional shock-resistant layer on the plasma-treated shock-resistant layer (D); and
Plasma treatment of the impact resistant layer deposited by the step (D) further comprises (E),
The total thickness of the impact-resistant layer is characterized in that 300nm to 500nm, impact-resistant layer.
3. The method according to claim 2,
The substrate is an ultra-thin tempered glass (UTG), characterized in that the impact-resistant layer.
3. The method according to claim 2,
The plasma used in at least one of the steps (A) and (C) is one or more mixed gas plasmas selected from the group consisting of argon, nitrogen, and oxygen, the impact resistant layer.
3. The method according to claim 2,
The plasma used in at least one of the steps (A) and (C) is a mixed gas plasma formed by applying an RF power of 700 to 800 W in an apparatus maintained at ^{10 -4} to 10 ^{-7 Torr.} Characterized in that, the impact-resistant layer.
3. The method according to claim 2,
The step (B) is from the group consisting of Chemical Vapor Deposition (CVD), Plasma-Enhanced Chemical Vapor Deposition (PECVD), Low Pressure Chemical Vapor Deposition (LPCVD), Physical Vapor Deposition (PVD), and Atomic Layer Deposition (ALD). Impact-resistant layer, characterized in that carried out in one or more processes selected.
The method according to claim 1,
The silicone-based polymer includes at least one selected from the group consisting of an amino group, an epoxy group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group and a phenyl group, the impact resistant layer.
The method according to claim 1,
The organic-inorganic silane compound comprises at least one selected from the group consisting of an amino group, a vinyl group, an epoxy group, an alkoxy group, a halogen group, a mercapto group, and a sulfide group.
The method according to claim 1,
The organic-inorganic silane compound is aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Silane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltridimethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyl diethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(methoxyethoxy)silane, di-, tri- or tetraalkoxysilane, vinylmethoxysilane, vinyltrimethoxysilane, vinylepoxysilane , vinyltriepoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, Chlorotrimethylsilane, trichloroethylsilane, trichloromethylsilane, trichlorophenylsilane, trichlorovinylsilane, mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bis(trimethoxysilylpropyl)amine , Bis (3-triethoxysilyl propyl) tetrasulfide, characterized in that it comprises one or more selected from the group consisting of combinations thereof, impact resistant layer.
Plasma treatment of the substrate surface (A);
depositing an impact resistant layer on the plasma-treated substrate (B); and
Plasma treatment (C) of the deposited shock-resistant layer, wherein the deposited shock-resistant layer has a thickness of 300 nm to 500 nm, the shock-resistant layer introduction method.
12. The method of claim 11,
depositing an additional shock-resistant layer on the plasma-treated shock-resistant layer (D); and
Plasma treatment of the impact resistant layer deposited by the step (D) further comprises (E),
The total thickness of the impact-resistant layer is 300nm to 500nm, characterized in that the impact-resistant layer introduction method.
A substrate comprising the impact-resistant layer of any one of claims 1 to 10.
14. The method of claim 13,
The impact-resistant layer is a substrate comprising an impact-resistant layer, characterized in that formed on at least one surface of the substrate

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