KR101921170B1 - A manufacturing method of substrate formed patterns and patterning substrate using thereof - Google Patents

Abstract

The present invention relates to a method to manufacture a substrate with a pattern and a patterned substrate formed thereby. According to the present invention, the substrate with a pattern does not indicate any mark in ordinary use, such that user′s vision is not interfered even if the substrate with a pattern is used for a product requiring transparency, such as a lens, a mobile phone liquid crystal display (LCD), a mirror, and the like. Moreover, a mark or symbol of a product, or a pattern is indicated only when breath is blown or fogging occurs, such that an effect of providing aesthetic sense is provided as necessary and illegal use is prevented in the case that a trademark is engraved so as to provide an advantage of protecting a customer. Moreover, the pattern is formed by surface deposition using a metal oxide, not a method for forming corrugation or irradiating laser beam on a surface of the substrate, and thus the aesthetic sense is not damaged or a reflective ratio is not affected by exposure of the corrugation. Moreover, the corresponding method is applicable to all objects capable of being deposited, and thus a substrate of various materials, such as glass, metal, and plastic, is able to be used. According to the present invention, the method comprises a substrate preparing step, a primer layer forming step, a pattern layer forming step, a hard coat layer forming step, and a waterproof layer forming step.

Description

TECHNICAL FIELD The present invention relates to a method for producing a patterned substrate and a patterned substrate using the patterned substrate,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a patterned substrate and a substrate on which a pattern is formed using the patterned substrate. More specifically, A pattern is formed on the surface of the substrate, the pattern is not observed, but a pattern is formed by lubrication, moisture, fogging or the like, and a substrate on which a pattern is formed by using the method.

Optical products including plastic lenses for spectacles, transparent plastic, and the like may be used to identify their own products and other products, or to provide product numbers, specifications, instructions of specific locations, And so on. When a mark is given to the lens for spectacles, it is required that the mark is as inconspicuous as possible due to the nature of the product. Therefore, in many cases, so-called hiding marks are given in many cases, which are difficult to recognize with the naked eye in general, and can be recognized, for example, by observation from a specific angle as necessary.

Examples of the method of applying such a mark to the lens include a method of carving the lens with a needle made of a hard material such as diamond, a method of marking with a laser, a method of transferring irregularities formed on a molding die . A laser marking method is to irradiate a plastic lens with a laser beam to give a mark. This method has recently been used because it is easy to operate and easy to automate.

Usually, however, a thin film such as an antireflection film is coated on the surface of a plastic lens for spectacles. Therefore, if the mark is struck by the needle or the laser after forming the antireflection film, the antireflection film may be damaged, and the thin film may peel off from the mark portion. In addition, the portion where the thin film is damaged by the marking is liable to penetrate moisture and the like, which may cause deterioration of the lens.

On the other hand, when concave / convex portions are provided on the lens base material itself at the time of lens molding as in the case of transferring marks by the above-described molding die, marking is performed before the shape of the lens cut is determined. Therefore, marks can be set at predetermined positions in the lens cut shape none.

Therefore, several methods for laser marking without damaging the thin film of the antireflection film or the like on the surface of the lens have been proposed. For example, there are a laser marking method in which laser light is focused inside a spectacle lens to give a mark to the inside of the spectacle lens and a laser marking method in which laser light is focused near the surface of the lens base of the spectacle lens, There has been proposed a marking method for giving a mark inside.

However, this method must also precisely adjust the energy amount of the laser focused on the lens or the focal point, and the output and irradiation time of the laser must be made larger in order to improve the visibility. In addition, the mark may affect the refraction index of the glasses themselves, which may cause a malfunction.

It is also conceivable to form a hard coat film on the lens base material and then deposit an antireflection film thereon. However, since the raw material liquid of the hard coat film enters the concave portion and hardens, the mark becomes unclear There is a case. In addition, when the antireflection film is deposited, it is necessary to heat the lens. Therefore, the surface of the hard coat film may be smoothed due to the influence of this heat, and the mark may not be clear.

As described above, in the conventional lens, it is difficult to distinguish the product from the lens itself and it is difficult to distinguish the product from the lens itself. Even if the laser is used to engrave the mark, the markers interfere with the user's vision. Technology that can be done is not yet available.

Korean Patent Publication No. 10-2008-0009339 (Jan. 28, 2008)

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an antireflection film or the like which does not damage a thin film thereof and ensures visibility, aesthetics and discrimination from other products. Normally, The present invention also provides a method for producing a base material and a base material produced by using the base material, in which a pattern or a mark formed by bending, moisture, fogging, or the like is exposed without interfering with the user's safety.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a patterned substrate and a substrate on which a pattern is formed using the method.

According to an aspect of the present invention,

a) preparing a substrate;

b) a primer layer forming step of depositing a primer composition on the substrate;

c) depositing a mask having a predetermined pattern slot on the surface of the primer layer so as to closely adhere thereto, and then depositing a pattern forming composition;

d) forming a hard coat layer on the surface of the pattern layer and the primer layer; And

e) forming a water repellent coating composition on the surface of the hard coating layer;

Wherein at least one of the primer composition, the pattern forming composition and the hard coating composition is at least one selected from the group consisting of a titanium compound, an aluminum compound, a silicon compound, a zirconium compound, a chromium compound, a molybdenum compound, an iron compound, a cerium compound, a tungsten compound, , A zinc compound, a beryllium compound, and an indium tin compound. The present invention also relates to a method for producing a patterned substrate.

In the present invention, the primer composition is characterized by containing a silicon compound and a zirconium compound. More specifically, the step b)

b1) forming a first silicon dioxide layer on the substrate to deposit silicon dioxide in a thickness of 2,000 to 3,000 Å; And

b) forming a first zirconium dioxide layer on the surface of the first silicon dioxide layer to deposit zirconium dioxide in a thickness of 100 to 500 Å;

And a control unit.

Another aspect of the present invention is

a) preparing a substrate;

b) a primer layer forming step of depositing a primer composition on the substrate;

c) depositing an intermediate layer composition on the surface of the primer layer to form an intermediate layer;

d) forming a hard coat layer on the surface of the intermediate layer to deposit a hard coat composition; And

(e) a pattern water repellent layer forming step of depositing a water repellent coating composition on the surface of the hard coating layer so that a mask having a predetermined pattern slot is closely attached thereto;

Wherein at least one of the primer composition, the intermediate layer composition, and the hard coating composition is a titanium compound, an aluminum compound, a silicon compound, a zirconium compound, a chromium compound, a molybdenum compound, an iron compound, a cerium compound, a tungsten compound, A zinc compound, a beryllium compound, and an indium tin compound. The present invention also relates to a method for producing a patterned substrate.

The hard coating composition of the present invention is characterized in that it comprises a zirconium compound and a chromium compound. More specifically, the step d)

d1) forming a second zirconium dioxide layer on the surface of the pattern layer and the primer layer by depositing zirconium dioxide to a thickness of 500 to 1,000 Å; And

d2) forming a chromium layer on the surface of the second zirconium dioxide layer to deposit chromium at a thickness of 500 to 1,000 angstroms;

And a control unit.

The water-repellent coating composition may further include 0.5 to 1 wt% of halogenated silane, 5 to 12 wt% of halogenated ether, and 87 to 94 wt% of transition metal.

Further, in the present invention, the deposition is characterized by electron beam evaporation under vacuum conditions, and if necessary,

f) finishing any one or more of the post-processing selected from dyeing, antifouling coating and UV-blocking coating on the substrate;

And further comprising:

Another aspect of the present invention relates to a substrate formed with the pattern produced by the above manufacturing method.

Since the substrate on which the pattern according to the present invention is formed is free of signs on the substrate in normal use, even if it is used for a product such as a lens, a mobile phone liquid crystal, or a mirror requiring transparency, it does not disturb the user's sheath at all, Since the mark, pattern, and pattern of the product are displayed only when the product is given or fogged, the product has an effect of providing aesthetics when needed, and also protects the consumer by preventing theft when a trademark or the like is imprinted.

Further, since the pattern is formed by surface deposition using a metal oxide, not by a method of forming irregularities on the surface of the substrate or by irradiating a laser beam, all objects capable of deposition It is possible to use various materials such as glass, metal, and plastic.

FIG. 1 illustrates a sunglass using a patterned substrate manufactured according to an embodiment of the present invention.
2 is a view illustrating a manufacturing process of a patterned substrate according to an embodiment of the present invention.
FIG. 3 illustrates a manufacturing process of a patterned substrate according to another embodiment of the present invention.
Fig. 4 shows a cross-sectional view of a lens manufactured according to the manufacturing process of Fig. 2. Fig.
Figure 5 shows a cross-sectional view of a lens made according to the manufacturing process of Figure 3;
Fig. 6 shows a normal state of the lens manufactured according to the first embodiment of the present invention and a state when the lens is blown.
Fig. 7 shows a normal state of the lens manufactured according to Comparative Example 1 of the present invention and a state when the lens is blown.

Hereinafter, a method for manufacturing a substrate having a pattern according to the present invention and a substrate having a pattern formed using the method will be described in detail with reference to specific embodiments. The following specific embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention.

Therefore, the present invention is not limited to the embodiments shown below, but may be embodied in other forms. The embodiments shown below are only for clarifying the spirit of the present invention, and the present invention is not limited thereto.

Here, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In the following description, the gist of the present invention is unnecessarily blurred And a description of the known function and configuration will be omitted.

In addition, the following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the drawings presented below may be exaggerated in order to clarify the spirit of the present invention. Also, throughout the specification, like reference numerals designate like elements.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

A method of manufacturing a substrate on which a pattern according to the present invention is formed,

a) preparing a substrate;

b) a primer layer forming step of depositing a primer composition on the substrate;

c) depositing a mask having a predetermined pattern slot on the surface of the primer layer so as to closely adhere thereto, and then depositing a pattern forming composition;

d) forming a hard coat layer on the surface of the pattern layer and the primer layer; And

e) forming a water repellent coating composition on the surface of the hard coating layer;

, ≪ / RTI >

a) preparing a substrate;

b) a primer layer forming step of depositing a primer composition on the substrate;

c) depositing an intermediate layer composition on the surface of the primer layer to form an intermediate layer;

d) forming a hard coat layer on the surface of the intermediate layer to deposit a hard coat composition; And

(e) a pattern water repellent layer forming step of depositing a water repellent coating composition on the surface of the hard coating layer so that a mask having a predetermined pattern slot is closely attached thereto;

You can proceed.

That is, the method of manufacturing a substrate having a pattern according to the present invention is different depending on the position of a coating layer having a pattern in a plurality of coating layers. In the present specification, a method of forming a pattern layer in the middle of a plurality of coating layers will be described.

As a first step, prepare a substrate description of the pattern.

In the present invention, the substrate is not limited to the type as long as it has a material capable of depositing a metal oxide to be described later, and its shape, thickness and size are not limited.

Examples of the material of the substrate include metals, ceramics, organic polymers, glass, and the like, and may include living bodies of animals and plants. Of these, it is preferable to use ceramics, organic polymers, glass, or the like because the patterns and patterns are clearly expressed when necessary while maintaining transparency.

In particular, it is preferable that the base material is an organic polymer or a glass material having high transparency. The base material can be applied to a lens of sunglasses or eyeglasses as shown in Fig. 1. In general, when the base material is used, If not, the pattern is developed by blowing on the lens so that the brand or information of the lens can be confirmed or aesthetics can be given.

More preferably, the material of the substrate is a copolymer of methyl methacrylate homopolymer, methyl methacrylate and at least one other monomer, diethylene glycol bisallylcarbonate homopolymer, diethylene glycol bisallyl carbonate, and at least one There may be mentioned copolymers with other monomers, sulfur-containing copolymers, halogen copolymers, polycarbonates, polystyrenes, polyvinyl chlorides, unsaturated polyesters, polyethylene terephthalates, polyurethanes, polythiourethanes and compounds having epithio groups , It is preferable to use a sulfur-containing polymer, particularly an epithio group-containing compound, because of its excellent adhesion property with a primer layer to be described later.

Examples of the compound having an epithio group include bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3- (Β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4- (Β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β (Epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6- 1- (β-epithiopropylthio) -2 - [(2 -? - epithiopropylthioethyl) thio] ethane and 1- (β-epithiopropylthio) -2 - [[2- (2-β-epithiopropylthioethyl) thioethyl] thio] And the like, and the like.

Further, it is also possible to use tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,5- bis (? - epithiopropylthiomethyl) -3-thiapentane, 1- (5-epithiopropylthio) (β-epithiopropylthio) -4- (β-epithiopropylthio) -2,2-bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6- Epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (? - epithiopropylthio) -4- Bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) Bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8- -3,6-dithiaoctane, 1,8- Bis (β-epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) (3-epithiopropylthio) -5 - [(2 -? - epithiopropylthioethyl) thiomethyl] -3,7-dithianone, 1,10- , 6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -Epithiopropylthiomethyl) -3,6,9-trithiandecane, 1,11-bis (? -Epithiopropylthio) -5,7-bis (? (6-epithiopropylthio) -5,7 - [(2 -? - epithiopropylthioethyl) thiomethyl] -3,6,9-tri Branched organic compounds such as thiodecane, 1,11-bis (β-epithiopropylthio-4,7-bis (β-epithiopropylthiomethyl) -3,6,9- A small amount of hydrogen of the episulfide group in the compound 1 dog may be mentioned a compound substituted with a methyl group.

(? - epithiopropylthio) cyclohexane, 1,3- and 1,4-bis (? -Epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- , 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) Aliphatic organic compounds and compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group, and 1,3- and 1,4-bis (? - epithiopropylthio) benzene, 1,3- and 1, Bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) Bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropyl (Phenyl) sulfone, 4,4'-bis (? - epithiopropylthio) biphenyl, and compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group It is possible.

Since it is necessary to deposit an inorganic compound on the surface of the substrate, it is desirable to reliably remove foreign matter on the surface through a plurality of cleaning processes. In this case, the washing process is not limited to the present invention, and it is preferable to wash the surface of the washing solution by hot air or natural drying after washing with the washing solution several times. If necessary, the surface of the substrate may further be subjected to an alkali treatment, an acid treatment, a surfactant treatment, a peeling / polishing treatment with an inorganic or organic fine particle, a plasma treatment, and the like.

Next, a primer layer may be formed on the substrate surface as described above.

The primer layer is formed on the surface of the base material. The primer layer is disposed between both interfaces of the base material and a pattern layer to be described later, and has adhesion to both the lens base material and the pattern layer. The primer layer includes a platemaking layer, Thereby improving the durability of the whole. In addition, it also has a property as an absorbent layer for absorbing impact from the outside, thereby enhancing the impact resistance of the entire coating layer, and can have a hue as a color and can act as a pigment.

The primer layer may include one or a plurality of inorganic compounds. Examples of the primer layer include titanium compounds, aluminum compounds, silicon compounds, zirconium compounds, chromium compounds, molybdenum compounds, iron compounds, cerium compounds, tungsten compounds, antimony compounds, A zinc compound, a beryllium compound, and an indium tin compound.

The inorganic compound may be contained in the composition for forming the primer layer in the form of fine particles. Preferable examples thereof include silicon dioxide (SiO ₂ ), zirconium dioxide (ZrO ₂ ), cerium dioxide (CeO ₂ ), titanium dioxide (TiO ₂ ) and the like. At this time, the inorganic fine particles are not limited in size, but may preferably have a diameter of 1 to 200 nm. They may also be added in the form of a colloidal dispersion in water or an organic solvent.

The inorganic compound is prepared by mixing the metal or oxides thereof as a starting material, mixing the mixture in a predetermined ratio, granulating the obtained mixture powder into a compact having a diameter of 1 to 10 mm, In an inert gas such as nitrogen at a temperature of 800 to 2,000 占 폚.

The amount of the inorganic fine particles to be added is preferably 40 to 70% by weight based on 100% by weight of the entire primer layer composition. If it is added in an amount of less than 40% by weight, the adhesion property between the pattern layer and the substrate is not properly developed, and when it is added in an amount exceeding 70% by weight, it may be vulnerable to cracking.

The inorganic compound for forming the primer layer is not limited to the above-described materials and the order of lamination. For example, silicon dioxide and zirconium dioxide may alternatively be deposited by vapor deposition. In a state where silicon dioxide and zirconium dioxide are mixed It may be directly laminated.

More specifically, the composition of the primer layer may include a silicon compound and a zirconium compound. In step b), more specifically,

b1) forming a first silicon dioxide layer on the substrate to deposit silicon dioxide in a thickness of 2,000 to 3,000 Å; And

b2) forming a first zirconium dioxide layer on the surface of the first silicon dioxide layer by depositing zirconium dioxide to a thickness of 100 to 500 Å;

. ≪ / RTI >

Various deposition methods may be applied to proceed to steps b1) and b2). Specifically, the coating composition may be coated by a dipping method, a spin coating method, a spray coating method, a roll coating method, or a flow coating method, or the deposition by electron beam may be conducted in a vacuum environment in which particles are dispersed.

The deposition method for proceeding to steps b1) and b2) is more preferably performed by electron beam evaporation under a vacuum condition.

In general, various methods such as electron beam deposition, sputtering, and chemical vapor deposition have been studied as a method for producing a thin film of a metal compound. However, physical vapor deposition methods such as electron beam deposition, deposition is known to be the most efficient.

In the electron beam evaporation method, an adherend is accommodated in a chamber, and then a laser beam is irradiated in a state in which oxygen in the chamber is maintained at a constant atmospheric pressure or less to increase the crystal growth direction and crystallization direction of the thin film and oxygen around the substrate, Is a method for producing a thin film having a minute thickness by in-situ growth in a state in which a treatment process is not required.

The electron beam deposition method can improve the uniform deposition rate and thin film thickness by compensating the disadvantage of the chemical vapor deposition method by controlling the electron beam energy continuously, and the uniformity of the thin film is increased.

In the electron beam evaporation method of the present invention, a chamber having one or more pulses is maintained in a high vacuum state of 10 ^-4 torr or less, and then a gas necessary for deposition is injected into the chamber to increase the pressure inside the chamber to about 400 mtorr . The gas required for the deposition is an inert gas for reacting with the inorganic compound to make the inorganic compound into an atomic or molecular state, and a reactive sputter gas for forming a thin film on the substrate. The inert gas may be nitrogen or argon, and the reactive sputter gas may utilize oxygen.

At this time, it is preferable to inject the gas injected into the chamber while controlling the volume of the inert gas and the sputter gas. For example, when the total gas to be injected is 10, it is preferable to control the inert gas to 9 to 9.5 volume ratio and the reactive sputter gas to 0.5 to 1 volume ratio.

Next, a metal oxide or an inorganic compound to be deposited may be charged into the pulse, and the voltage may be accelerated by the electron beam while rotating the adherend. In this case, although the rotation speed of the adherend is not limited, a speed of 1 to 50 rpm is preferable, and an acceleration voltage of the electron beam may be 1 to 10 KV, but the present invention is not limited thereto. If necessary, the plasma may be formed by accelerating the voltage, and then pre-sputtering may be performed for about 20 minutes to remove impurities on the surface of the inorganic compound.

In the step b1) of the present invention, the silicon dioxide may be deposited to a thickness of 2,000 to 3,000 Å through deposition by electron beam as described above. In this case, when the silicon dioxide is deposited to a thickness of less than 2,000 ANGSTROM, the adhesion property and impact resistance of the primer layer may be greatly deteriorated. When the deposition exceeds 3,000 ANGSTROM, the refractive index changes when used as an optical product, can do.

In addition, since the thickness of the inorganic compound deposited in the step b1) is determined according to the deposition time, the deposition time is not limited, but may be 10 to 400 seconds. When the substrate is a polymer, deformation due to heat may occur during the operation. Deg.] C to 80 [deg.] C.

If the first silicon dioxide layer is formed by depositing silicon dioxide as in step b1), then the zirconium dioxide layer may be formed by depositing zirconium dioxide on the surface of the first silicon dioxide layer in step b2).

The zirconium dioxide is provided to improve adhesion with a pattern layer to be described later. When the pattern layer is formed in the form of a thin film, the catalytic reaction proceeds with the inorganic compound contained in the pattern layer, .

The zirconium dioxide layer may be deposited in the same manner as the first silicon dioxide layer in step b1). More specifically, after the deposition of silicon dioxide is completed, the voltage is accelerated to form a plasma. After the plasma is formed, pre-sputtering is performed for about 20 minutes to remove impurities on the surface of the inorganic compound, To 400 seconds.

The zirconium dioxide layer is preferably deposited to a thickness of 100 to 500 Å. When the thickness is less than 100 ANGSTROM, the adhesion and the mechanical properties of the pattern layer may be lowered. When the thickness of the layer is more than 500 ANGSTROM, the color of the metal may be remarkable.

After forming the primer layer as described above, a mask having a pattern slot formed on the surface of the primer layer may be bonded to the surface of the primer layer as in step c), and then the inorganic compound may be deposited to form a pattern layer.

The mask is a kind of photoresist, which serves to guide an electron beam when depositing an inorganic compound after a pattern is formed, and any kind of conventionally known photoresist may be used. Specific examples of the photoresist include AZ5206, AZ5214, PR2035, PR9260, DNR, GXR, and SU-8. These photoresists may be used singly or in combination.

The mask is applied to the surface of the primer layer, and then heated to a predetermined temperature to increase adhesion with the primer layer. Thereafter, the mask is removed by exposure to remove the mask existing at the portion where the pattern layer is to be laminated. Lt; / RTI > However, when the thickness of the mask is too thick, it may be formed as thin as possible, since a shaded portion in which the inorganic compound as the material of the pattern layer is not deposited may be formed. When the electron beam deposition is performed to form the pattern layer, It is preferable to form the deposition region as wide as possible by rotating the substrate or the deposition equipment by rotating the deposition material.

Also, it is preferable to adjust the inclination angle formed by the side of the mask pattern formed with the primer layer to be as small as possible. When the inclination angle is small, the shaded portion formed by the mask is reduced, and the deposition region of the pattern layer is widened naturally. When the inclination angle is increased, the shaded portion formed by the mask is increased to narrow the deposition region.

When a mask is formed, a pattern forming composition may be deposited on the mask surface to form a pattern layer. Since the pattern layer is deposited only in the pattern slot portion of the mask, the primer layer is deposited in a form of coating only a part of the primer layer, not the entire coating layer. That is, when the pattern layer is formed, the primer layer and the hard coat layer are divided into a predetermined pattern and a non-patterned region on the primer layer, wherein the primer layer, more specifically, the first zirconium dioxide layer and the hard coat layer, Since the coating layer may be a homogeneous coating, the thickness of the entire coating layer is thicker than that of the region where the pattern layer is present. Therefore, the pattern can not be easily distinguished by the naked eye, and the light scattering can be prevented by the pinhole effect without revealing the normal pattern.

In the present invention, the pattern layer is formed so as not to generate fogging at the portion where the pattern layer is formed when fading occurs in the finished substrate, and the pattern is naturally expressed. The inorganic compound forming the pattern layer is the primer It is preferable that the inorganic compound is a hydrophilic inorganic compound having a refractive index lower than that of the inorganic compound forming the surface of the layer and the hard coat layer laminated on the surface of the pattern layer.

Generally, there are many reasons why fogging does not occur on a substrate, but a hydrophilic layer is often formed on the surface in many cases. For example, the initial glass surface forms a hydrophilic layer such as Si-OH or Si-O-Si. However, when exposed to the atmosphere, organic molecules having bipolar polarity are adsorbed in the atmosphere and the properties of the surface are changed by hydrophobicity. Therefore, it is important to prevent the adsorption of such organic molecules, thereby forming a thin water film layer on the surface to obtain a superhydrophilic surface.

The superhydrophilic surface can be provided in various forms. For example, a hydrophilic group and an attached hydrophobic molecule formed on the surface may be removed through a photocatalytic process to form a molecular-level water film, or oxygen and hydroxyl groups may be exchanged to generate a two-dimensional capillary phenomenon. At this time, the photocatalytic process of the hydrophilic group or the capillary phenomenon can be promoted by making the pattern layer contain an inorganic compound having high hydrophilicity.

The inorganic compound forming the pattern layer has an effect of adjusting the refractive index to improve the visibility of the pattern. Specifically, it is preferable to use an inorganic compound having a lower refractive index than an inorganic compound forming a primer layer or a hard coat layer. That is, since the substrate having the pattern according to the present invention is provided with the pattern layer having a low refractive index between the primer layer and the hard coat layer of high refractive index, the reflection of external light is suppressed at the portion where the pattern layer is formed, The primer layer and the hard coat layer are directly contacted with each other at the portions where the pattern layer is not formed, so that when the fogging occurs, the reflection of the external light becomes prominent as compared with the portion where the pattern layer is formed, .

The inorganic compound forming the pattern layer is more preferably silicon dioxide. The silicon dioxide may be at least one selected from the group consisting of zirconium oxide (2.2), chromium (2.5), titanium (2.4), iron (2.23), zinc (2.03), nickel (2.3). Therefore, when the fogging occurs, the portion where the pattern layer is formed has a reduced light reflection compared to the portion where the fogging occurs, so that the visibility of the pattern can be increased.

In the present invention, the pattern layer may be formed by depositing silicon dioxide to a thickness of 50 to 150 Å on the surface of a primer layer having a mask having a pattern slot formed through electron beam evaporation similar to the primer layer. At this time, when the pattern layer is deposited to a thickness of less than 50 angstroms, the hydrophilic property is not properly developed on the surface of the hard coat layer, which will be described later, so that it is difficult to confirm the pattern even after fogging. When the pattern layer is deposited to a thickness exceeding 150 angstroms, And may cause the mechanical strength to decrease.

After the pattern layer is formed as described above, the mask is removed from the substrate, and a hard coating layer may be formed on the surface of the pattern layer and the primer layer as in step d).

The hard coating layer is for protecting the primer layer and the pattern layer from external impact, and may have a structure in which the inorganic compound is deposited as a single layer or a multilayer of two or more layers.

More specifically, the hard coat layer is characterized by containing a zirconium compound and a chromium compound, and the step d)

d1) forming a second zirconium dioxide layer on the surface of the pattern layer and the primer layer by depositing zirconium dioxide to a thickness of 500 to 1,000 Å; And

d2) forming a chromium layer on the surface of the second zirconium dioxide layer to deposit chromium at a thickness of 500 to 1,000 angstroms;

. ≪ / RTI >

The step d1) is provided to improve the adhesion between the pattern layer or the primer layer, more specifically, the first zirconium dioxide layer and the chromium layer, which will be described later, similarly to the step b1). The first zirconium dioxide Lt; RTI ID = 0.0 > and / or < / RTI >

In the step d1), it is preferable that the zirconium dioxide is deposited by electron beam evaporation to a thickness of 500 to 1,000 Å to form a second zirconium dioxide layer. When the zirconium dioxide is deposited to a thickness of less than 500 Å, the mechanical properties of the entire coating layer may be deteriorated due to a decrease in the adhesive strength. If the zirconium dioxide is deposited in a thickness of more than 1,000 Å, In addition, although the deposition time and temperature are not limited, d1) may be performed at 50 to 80 DEG C for 10 to 400 seconds.

Next, the step d2) deposits a chromium layer on the surface of the second zirconium dioxide layer. The chromium layer is resistant to impact, abrasion, and corrosion, thereby protecting the entire coating layer including the second zirconium dioxide layer , The reflectance of the light itself is high so that the substrate has a mirror-like appearance. In addition, the substrate on which the light transmittance is lowered can be used for optical products such as sunglasses.

Preferably, the chromium layer is deposited by electron beam evaporation to a thickness of 500 to 1,000 angstroms. When the chromium layer is deposited to a thickness of less than 500 ANGSTROM, the mechanical properties of the entire coating layer may be significantly reduced. When the chromium layer is deposited to a thickness of more than 1,000 ANGSTROM, the transmittance of light may be excessively low, . Also, like step d1), the step d2) does not limit the deposition time and the temperature, but may proceed at 50 to 80 ° C for 10 to 400 seconds.

When the hard coating layer is formed as described above, the water repellent layer composition may be deposited on the hard coating layer, more specifically, on one side of the chromium layer.

The water-repellent layer is for preventing contaminants, dust, moisture and other substances from adhering to the surface of the substrate, and may include a fluorine compound containing at least one halogenated silane compound and at least one halogenated ether, and a transition metal carrying them.

The fluorine compound has low friction coefficient, high heat resistance, non-tackiness, and inelastic properties but is not suitable for use on the surface of a substrate because of low resistance to organic solvents and insufficient weather resistance. However, since it is possible to form a composite material with another compound having a polar functional group, this can be achieved by introducing a halogen group into the side chain of the silane compound and mixing at least one halogenated ether thereto to secure mechanical properties.

The halogen group to be introduced into the silane compound is not limited to any kind of halogen element which is generally used, and it is preferable to introduce fluorine (F).

Examples of the halogenated silane include fluorosilane, chlorosilane, bromosilane and iodosilane. When the alkyl group or the alkoxy group is substituted for the main chain of the silane in place of the halogen It is acceptable.

The halogenated ether increases the mechanical properties of the water-repellent layer by mixing with the halogenated silane and the transition metal, and has a water-repellent property by itself having a halogen group. Preferably, the fluorinated ether compound represented by the following formula .

[Chemical Formula 1]

C _n H _{2n + 1} OC _m F _{2m + 1}

(Wherein n is an integer of 1 to 4 and m is an integer of 3 to 6.)

More specific examples of the fluorinated ether compound include methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, propyl nonafluorobutyl ether, methyl heptafluoropropyl ether, ethyl heptafluoropropyl Ether, etc. These may be used singly or in combination of two or more.

The transition metal has the role of supporting the halogenated ether and the halogenated silane and determining the physical lifetime of the water repellent layer. In addition, the reflectance can be increased over the entire wavelength of the visible light due to the light reflecting property peculiar to the metal component. Also, the surface can be deposited by a physical vapor deposition method which is similar to the primer layer and the hard coat layer, so that a more uniform thickness can be deposited.

Examples of the transition metal include iron (Fe), chromium (Cr), nickel (Ni), copper (Cu), manganese (Mn), and molybdenum (Mo). These transition metals may be used singly or as a mixture of two or more It may be used.

The water-repellent coating composition may comprise 0.5 to 1 wt% of a halogenated silane, 5 to 12 wt% of a halogenated ether, and 87 to 94 wt% of a transition metal. If the content of the halogenated silane or the halogenated ether is less than the above range, water repellency is not exhibited at all, and if it exceeds the above range, the mechanical properties of the water repellent layer may be deteriorated. If the content of the transition metal is less than the above range, the mechanical properties may deteriorate and the reflectance of the visible light may be lowered. If the content exceeds the above range, the water repellency and the light transmittance are lowered, .

The water-repellent layer may be formed by electron-beam evaporation of the water-repellent coating composition similarly to the primer layer, the pattern layer, the intermediate layer, or the hard coating layer. In this case, the deposition conditions are not limited, but may be formed to have a thickness of 50 to 300 angstroms at a temperature of 50 to 80 DEG C for 10 to 400 seconds similarly to other coating layers. Particularly, when the thickness of the water-repellent layer exceeds 300 ANGSTROM, the light transmittance is lowered as described above, which is unsuitable for use as an optical substrate.

The water repellent layer may directly form a pattern on the water repellent layer when a pattern is not formed on the intermediate layer formed between the primer layer and the hard coating layer. In detail, the hard coating layer, more specifically, a mask having a pattern slot formed on the surface of the chromium layer is bonded to the surface of the chromium layer, and then the water repellent coating composition is subjected to electron beam evaporation So that a pattern layer can be formed.

Similar to the pattern layer, the mask having the pattern slots is heated at a predetermined temperature to increase adhesion with the hard coating layer, and then exposed to remove the mask existing in a portion where the pattern layer is to be laminated Pattern. When the mask in which the slots are formed is laminated, the water-repellent coating composition may be formed by electron beam evaporation similarly to the pattern-forming composition. At this time, the deposition conditions are not limited, but the deposition may be performed at a temperature of 50 to 80 캜 for 10 to 400 seconds to have a thickness of 50 to 300 Å.

The substrate having the pattern according to the present invention may be subjected to one or more post-processes in addition to the coating layer. The post-processing is to express other characteristics of the base material in addition to the water repellency effect, and may include one or more selected from dyeing, antifouling coating and ultraviolet barrier coating.

The dyeing process is not limited as long as it is a commonly used method in the art. For example, in the case of a substrate made of an organic polymer, there are a dyeing coloring method, a vacuum vapor deposition coloring method, an impregnation coloring method, a fusion coloring method and a melt coloring method. In the case of a substrate made of glass, , A metal oxide such as zinc oxide, titanium oxide, cobalt, nickel, chromium, copper, silver, neodymium and cerium may be added to the molten glass component in an appropriate amount.

The antifouling coating process is to prevent adhesion of contaminants such as fingerprints, sebum, sweat, and cosmetics, and is applied to a coating liquid containing a perfluoropolyether-modified compound having at least one trifluoromethyl group or fluorine group in its main chain as a main component .

In the present invention, the ultraviolet barrier coating process is preferably carried out by applying a coating solution containing an ultraviolet absorber. Examples of the ultraviolet absorber include oxanilides, benzophenones, dihydroxybenzophenones ), Benzotriazoles, benzoates, phenylbenzoates, benzimidazoles, hydroxyphenyl triazines, sterically hindered amines (HALS), and the like. One or two or more selected.

The substrate having the pattern produced by the manufacturing method according to the present invention is not a method of forming irregularities on the surface of the substrate or irradiating a laser but a pattern is formed by surface deposition using a metal oxide, Or refractive index, and the method can be applied to all objects capable of being deposited, so that substrates of various materials such as glass, metal, and plastic can be used.

In addition, since no indication appears on the substrate during normal use, even if it is used in a product requiring transparency such as a lens, a mobile phone liquid crystal, or a mirror, it does not interfere with the user's sheath at all. Since the mark, pattern, and pattern are displayed, it has the effect of providing aesthetics when needed, and also has the advantage of protecting the consumer by preventing theft even when the trademark is imprinted. The lens for sunglasses, the liquid crystal and protective film for mobile phone, , Mirrors, and other optical products.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The physical properties of the specimens prepared through Examples and Comparative Examples were measured as follows.

(Whether or not the pattern is formed)

The prepared specimens were measured for L *, a * and b * values in a transmission mode and a reflection mode at a wavelength of 550 nm using a UV spectrometer (UV spectrometer, CM-3500d, Minolta) ² = ΔL * ² + Δa * ² + Δb *) were obtained and classified into the following categories to evaluate the non-visibility of the pattern. The specimens prepared in Examples and Comparative Examples were cooled to 10 ° C, and the specimens were placed in a chamber controlled at 25 ° C. and 80% relative humidity. The test specimens were given fogging.

a. Normal state

? E *? 0.5: good (no pattern is seen)

0.5 < DELTA E * &lt; = 1: Normal (pattern is seen to some extent)

1 <ΔE *: Bad (pattern is very visible)

b. Fogging state

3 <ΔE *: Good (pattern is visible)

2 <? E *? 3: Normal (pattern shows some degree)

ΔE * ≤ 2: Bad (pattern not visible)

(Example 1)

0.3 wt% of fluorosilane, 4 wt% of ethyl nonafluorobutyl ether, 3.7 wt% of ethyl nonafluoroisobutyl ether, and iron (Fe) were added as the evaporation material, and a mixture of silicon dioxide (SiO ₂ ), zirconium dioxide (ZrO ₂ ), chromium (Cr) charged with 92% by weight) within the liner Haas vacuum evaporator, and after setting the polymethyl methacrylate samples (5㎝ × 5㎝ × 0.5㎝) having a weight average molecular weight of 50,000, a device within 1.0 × 10 ^-3 Pa Deg.] C, and oxygen was introduced again until the total pressure reached 10 10 ^-2 Pa. Then, the melted evaporation material was irradiated with an electron beam to be vaporized and then formed into a specimen controlled at 65 ° C to form a multilayer coating layer. In this case, the order of deposition of the evaporation material is in the order of silicon dioxide-zirconium dioxide-silicon dioxide-zirconium dioxide-chromium-super water repellent, and the irradiation time and thickness of each coating material are shown in Table 1 below. Were patterned by working after masking. The properties of the prepared specimens were measured and are shown in Table 1 below.

(Example 2)

A pattern was formed in the super-water-repellent layer, not the second silicon dioxide layer, by patterning in Example 1, and the pattern was formed in the same manner as in Example 1. The properties of the prepared specimens were measured and are shown in Table 1 below.

(Comparative Example 1)

Except that a pattern was not formed on the second silicon oxide layer in Example 1. The properties of the prepared specimens were measured and are shown in Table 1 below.

(Comparative Examples 2 to 5)

The specimens were prepared in the same manner as in Example 1 except that the irradiation time and the thickness of the coating film were changed as shown in Table 1 for each evaporation material. The properties of the prepared specimens were measured and are shown in Table 1 below.

[Table 1]

As shown in Table 1 and FIG. 6, the pattern formed on the substrate according to the present invention does not show a pattern in a normal state, but it can be seen that a pattern is naturally exposed when fogging or the like is applied. In contrast, in Comparative Example 2 in which the thickness of the pattern layer was smaller than that in Comparative Example 1 in which the pattern was not formed, the pattern was not revealed even in the fogged state as shown in FIG. 7, 3 shows that the pattern is exposed even when no fogging is given due to an excessive change in the refractive index of the entire coating layer. In addition, even in the case of Comparative Examples 4 and 5 in which the thickness of the hard coating layer was excessively applied, the pattern was not revealed in the normal state, but the pattern was not formed in the fogging state.

Although the present invention has been described with reference to the preferred embodiments and the comparative examples, those skilled in the art will appreciate that various modifications, substitutions, and alterations can be made hereto without departing from the spirit and scope of the present invention as defined by the following claims It will be understood that the invention may be modified and varied without departing from the scope of the invention.

100: substrate
200: primer layer
210: a first silicon dioxide layer
220: a first zirconium dioxide layer
300: second silicon dioxide layer
310: pattern layer
320: middle layer
400: hard coat layer
410: second zirconium dioxide layer
420: chrome layer
500: water repellent layer

Claims (10)

a) preparing a substrate;
b) a primer layer forming step of depositing a primer composition on the substrate;
c) depositing a mask having a predetermined pattern slot on the surface of the primer layer so as to closely adhere thereto, and then depositing a pattern forming composition;
d) forming a hard coat layer on the surface of the pattern layer and the primer layer; And
e) forming a water repellent coating composition on the surface of the hard coating layer;
Wherein the step b) comprises:
b1) forming a first silicon dioxide layer on the substrate to deposit silicon dioxide in a thickness of 2,000 to 3,000 Å; And
b2) forming a first zirconium dioxide layer on the surface of the first silicon dioxide layer by depositing zirconium dioxide to a thickness of 100 to 500 Å;
Wherein the step d)
d1) forming a second zirconium dioxide layer on the surface of the pattern layer and the primer layer to deposit zirconium dioxide in a thickness of 500 to 1,000 Å; And
d2) forming a chromium layer on the surface of the second zirconium dioxide layer to deposit chromium at a thickness of 500 to 1,000 angstroms;
Wherein the pattern forming composition is any one selected from the group consisting of titanium compounds, aluminum compounds, silicon compounds, zirconium compounds, chromium compounds, molybdenum compounds, iron compounds, cerium compounds, tungsten compounds, antimony compounds, zinc compounds, beryllium compounds, A method for producing a patterned substrate, which comprises a plurality of inorganic compounds.
a) preparing a substrate;
b) a primer layer forming step of depositing a primer composition on the substrate;
c) depositing an intermediate layer composition on the surface of the primer layer to form an intermediate layer;
d) forming a hard coat layer on the surface of the intermediate layer to deposit a hard coat composition; And
(e) a pattern water repellent layer forming step of depositing a water repellent coating composition on the surface of the hard coating layer so that a mask having a predetermined pattern slot is closely attached thereto;
Wherein the step b) comprises:
b1) forming a first silicon dioxide layer on the substrate to deposit silicon dioxide in a thickness of 2,000 to 3,000 Å; And
b2) forming a first zirconium dioxide layer on the surface of the first silicon dioxide layer by depositing zirconium dioxide to a thickness of 100 to 500 Å;
Wherein the step d)
d1) forming a second zirconium dioxide layer on the surface of the intermediate layer to deposit zirconium dioxide in a thickness of 500 to 1,000 angstroms; And
d2) forming a chromium layer on the surface of the second zirconium dioxide layer to deposit chromium at a thickness of 500 to 1,000 angstroms;
Wherein the intermediate layer composition is selected from titanium compounds, aluminum compounds, silicon compounds, zirconium compounds, chromium compounds, molybdenum compounds, iron compounds, cerium compounds, tungsten compounds, antimony compounds, zinc compounds, beryllium compounds and indium tin compounds A method of producing a patterned substrate, which comprises one or a plurality of inorganic compounds.
delete delete delete delete 3. The method according to claim 1 or 2,
Wherein the water-repellent coating composition comprises 0.5 to 1 wt% of a halogenated silane, 5 to 12 wt% of a halogenated ether, and 87 to 94 wt% of a transition metal.
3. The method according to claim 1 or 2,
Wherein said deposition is by electron beam evaporation under vacuum conditions.
3. The method according to claim 1 or 2,
The method may further comprise, after step e)
f) finishing any one or more of the post-processing selected from dyeing, antifouling coating and UV-blocking coating on the substrate;
And forming a pattern on the substrate.
A patterned substrate produced by the manufacturing method according to claim 1 or 2.

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