TW201442971A - Glass substrate with low-reflection films on both sides and manufacturing process thereof - Google Patents

Abstract

To provide a method for manufacturing a laminate, the laminate being suitable for use as the cover glass of a display device or the like, and has low-reflection films formed on both sides and free of stains at the outer periphery. A manufacturing method for forming a laminate on a glass substrate with low-reflection films on both sides is characterized by printing on one surface of the glass substrate to form a light-shielding portion, and by means of a dry film-forming method to form a low-reflection film on the entire surface of the afore-mentioned glass substrate already formed with the light-shielding portion, and then by using a dry film-forming method to form a low-reflection film on the entire surface of the afore-mentioned glass substrate not formed with the light-shielding portion.

Description

Glass substrate with double-sided low reflection film and manufacturing method thereof Field of invention

The present invention relates to a method of producing a glass substrate having a double-reflective film formed on both sides. More specifically, it relates to a chemically strengthened glass substrate in which a low reflection film is formed on both sides and a method for producing the same.

Background of the invention

In recent years, mobile devices such as tablet PCs (Personal Computers) and smart phones (hereinafter also referred to as "smart phones"), or display devices such as LCD TVs and touch panels (hereinafter, this specification will The cover glass (protective glass) used to improve the protection and appearance of the display surface of the display is often used.

These cover glasses are glass substrates in which a low reflection film is formed on both sides. Thereby, it is possible to suppress light reflection on the display surface of the display device or the like, and it is possible to further improve the visibility of the display.

Patent Documents 1 and 2 disclose a method of simultaneously forming a low-reflection film on both sides of a glass substrate. Figs. 1 and 2 are views showing the film forming process of the conventional low-reflection film, i.e., the simultaneous film formation on both sides. Fig. 1 shows the state at the time of film formation, and Fig. 2 shows the state after film formation.

In these methods, in order to maintain the film formation, it is impossible to form a low-reflection film on the outer periphery of the glass substrate, so that a glass substrate having a size larger than that of the product is prepared and the substrate is held at a position outside the product size. After the low-reflection film was formed on both sides, it was cut into a predetermined size to obtain a glass substrate as a product. Fig. 3 is a view showing an example of a cutting line of a glass substrate having a double-sided low reflection film produced by simultaneous film formation on both sides.

Further, in the methods described in Patent Documents 1 and 2, a sputtering method is used for the film formation of the low-reflection film. With respect to the wet film formation method such as the coating method, a dry film formation method such as a sputtering method or a vapor deposition method has the advantage that it can be reduced by multilayering a film having a different physical property such as a plurality of layers of a refractive index. The reflection, the hardness of the film are large, and the scratch resistance is more excellent. Moreover, all the dry film forming methods have the advantages of a film thickness controllability and a more stable film forming method.

In order to reduce the difference in the thin design and the load on the movement, the display device and the like are required to be lighter and thinner. Therefore, the cover glass required for the protection of the display surface must also be thinned. At the same time, in order to secure the strength of the cover glass, a cover glass which is reinforced by forming a compressive stress layer on the surface of the glass by chemical strengthening treatment may be used (see Patent Document 3). Further, in Patent Document 3, a compressive stress layer is formed on the surface of the glass by chemical strengthening treatment, and a compressive stress layer is formed on the surface of the glass by physical strengthening treatment.

However, the tempered glass substrate is difficult to cut into a desired size after the formation of the compressive stress layer, so that it is convenient to perform physical strengthening treatment or chemical strengthening treatment after cutting into a desired product size, and then proceeding. Film formation of a low-reflection film. When the entire surface film formation is performed in the film formation of the low-reflection film, the double-sided simultaneous film formation method described in Patent Documents 1 and 2 cannot be applied from the viewpoint of holding the substrate, and the following procedure must be employed. After the low reflection film is formed on one of the surfaces by a dry film formation method, the glass substrate is reversed and the low reflection film is formed on the other surface of the glass substrate.

Fig. 4 is a schematic view showing a procedure when a conventional low-reflection film is formed into a single film on one side, and shows a state in which single-sided film formation is performed. In FIG. 4, the light shielding portion 20 is formed on the outer peripheral portion of one surface (the left side surface in the drawing) of the glass substrate 10 by printing. In a state in which the surface of the light-shielding portion 20 is formed on the non-display surface side of the glass substrate 10 in the holding jig 50, the surface of the display surface when the cover glass is used as a display device or the like, that is, the surface side without the light-shielding portion is formed. Low reflection film. FIG. 5 shows a state in which the low-reflection film 30a has been formed on the display surface side of the glass substrate 10. Next, as shown in FIG. 6, the glass substrate 10 is inverted and the low reflection film is formed on the entire non-display surface side of the glass substrate 10 in which the light shielding portion 20 is formed.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent No. 3768547

Patent Document 2: Japanese Patent No. 3254782

Patent Document 3: Japanese Patent Laid-Open Publication No. 2013-006755

Summary of invention

By the above dry film forming method, each side of the glass substrate is formed In the procedure of the film low-reflection film, the display surface side of the glass substrate, that is, the display surface when the cover glass is used, can be directly viewed. Therefore, the low-reflection film on the display surface side must be mixed with pinholes and foreign matter as much as possible. membrane. For this reason, it is considered that it is effective to eliminate the risk of film formation on the surface of the contaminated substrate inside the film forming apparatus when the film forming step is excluded, and to prepare a clean clean substrate, before forming the film on the display side, and then It is preferred to form the film on the side.

However, it is known that when the low-reflection film is formed on both sides of the substrate in this procedure, color spots are generated on the outer peripheral portion of the low-reflection film on the display surface side.

In order to solve the problems of the above-described conventional techniques, an object of the present invention is to provide a method for producing a laminate which is suitable as a cover glass for a display device or the like and which has a low-reflection film formed on both surfaces and which has no unevenness on the outer peripheral portion.

In order to achieve the above object, the present invention provides a method for producing a laminate having a low-reflection film formed on both surfaces of a glass substrate, wherein a light-shielding portion is formed on one of outer peripheral portions of the glass substrate by printing; In the dry film formation method, a low reflection film is formed on the entire surface of the glass substrate on which the light shielding portion is formed, and then a low reflection film is formed on the glass substrate by a dry film formation method, and the light shielding portion is not formed. The entire face of the face.

In the method for producing a laminate according to the present invention, the glass substrate may be subjected to a chemical strengthening treatment in advance.

In the method for producing a laminate according to the present invention, the antifouling film may be formed on the low-reflection film in which the glass substrate is not formed on the surface of the light-shielding portion. on.

In the method for producing a laminated body according to the present invention, the reflective film is preferably a laminated film in which a film composed of a high refractive index material and a film composed of a low refractive index material are alternately laminated.

In the above laminated film, the high refractive index material is preferably cerium oxide or cerium oxide, and the low refractive index material is preferably cerium oxide.

Further, in the laminated film, the high refractive index material is preferably tantalum nitride, and the low refractive index material preferably contains any of the following mixed oxides: mixed oxide of Si and Sn, and mixed oxidation of Si and Zr a mixed oxide of Si, Al and Al.

The laminated film is preferably two or more layers and six or less layers of a film composed of the high refractive index material and the low refractive index material.

In the method for producing a laminate according to the present invention, the reflective film is preferably formed by sputtering.

In the method for producing a laminate according to the present invention, the antifouling film is preferably composed of a fluorine-containing organic ruthenium compound.

The fluorine-containing organic ruthenium compound preferably has one or more selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group.

In the method for producing a laminate according to the present invention, the antifouling film is preferably formed by a vacuum deposition method.

Further, the present invention provides a laminate in which a low-reflection film is formed on both surfaces of a glass substrate, which is obtained by the method of the present invention.

The glass substrate having the double-sided low reflection film obtained by the present invention has good low reflection characteristics, high glass substrate strength, and no color unevenness on the outer periphery of the display surface. Therefore, it is suitable as a cover glass of a display device or the like.

10‧‧‧ glass substrate

20‧‧‧Lighting Department

30, 30a, 30b‧‧‧ low reflection film

40a‧‧‧ particles (back surround particles)

50‧‧‧Keeping fixture

80‧‧‧ stains

Fig. 1 is a schematic view showing a film forming procedure (simultaneous film formation on both sides) of a conventional low-reflection film, showing a state at the time of film formation.

Fig. 2 is a schematic view showing a film forming procedure (simultaneous film formation on both sides) of a conventional low-reflection film, showing a state after film formation.

Fig. 3 is a view showing an example of a cutting line of a glass substrate having a double-sided low-reflection film produced by a conventional method (two-sided simultaneous film formation).

Fig. 4 is a schematic view showing a film forming procedure (single-sided film formation) of a conventional low-reflection film, showing a state in which single-sided film formation is performed.

Fig. 5 is a schematic view showing a film forming procedure (single-sided film formation) of a conventional low-reflection film, showing a state after single-sided film formation.

Fig. 6 is a schematic view showing a film forming procedure of a conventional low-reflection film (film formation on each side), showing a state in which film formation on the back surface is performed.

Fig. 7 is a schematic view showing a glass substrate having a double-sided low reflection film produced by a conventional method (film formation on each side).

Fig. 8 is a schematic view of the glass substrate of the double-sided low-reflection film of Fig. 7 viewed from the side of the low-reflection film 30a.

Fig. 9 is a schematic view showing a film forming procedure of a low-reflection film in the method of the present invention, showing a state in which single-sided film formation is carried out.

Fig. 10 is a schematic view showing a film forming procedure of the low-reflection film in the method of the present invention, showing a state after single-sided film formation.

Fig. 11 is a schematic view showing a film forming procedure of the low-reflection film in the method of the present invention, showing the state at the time of performing film formation on the back surface.

Figure 12 is a schematic view showing a glass substrate having a double-sided low reflection film produced by the method of the present invention.

Fig. 13 is a schematic view of the glass substrate of the double-sided low-reflection film of Fig. 13 viewed from the side of the low-reflection film 30b.

Form for implementing the invention

Hereinafter, the present invention will be described with reference to the drawings.

First of all, the first step of the invention is shown.

The reason why the color unevenness is formed on the outer peripheral portion of the low-reflection film is found by the inventors of the present application as a result of the fact that when the low-reflection film is formed on one of the surfaces by a dry film formation method, the film material is generated on the glass substrate. The phenomenon of the back side ring is covered, and particles of a nanometer size (hereinafter also referred to as a nanometer size) adhere to the outer peripheral portion of the back surface side of the substrate to generate scattered light. Further, the particles whose ring is coated on the back side of the substrate are also referred to as back-surrounding particles.

The display surface side of the glass substrate is an important side that can be directly observed. Therefore, in general, the glass substrate holding mechanism is set to be in a state where the display surface is not in contact with the substrate holding jig, and then the display surface side is first Film the entire surface.

For example, when the non-display surface side of the glass substrate is held (FIG. 5) and the low-reflection film is formed on the display surface side, it is confirmed that the outer peripheral portion of the non-display surface of the glass substrate 10 on which the light-shielding portion 20 is formed has the nano-sized particles 40a. Attached (Figure 6). It is known that the particles 40a are formed on the display surface side of the glass substrate 10 in accordance with the procedure shown in FIG. In the film low-reflection film, a part of the film-forming material is attached to the back surface side of the glass substrate 10, that is, the non-display surface side of the glass substrate 10 on which the light-shielding portion 20 is formed, and adheres to the outer peripheral portion of the non-display surface of the glass substrate 10. .

However, in FIG. 6, the nanosized particle 40a adhered to the outer peripheral portion of the non-display surface of the glass substrate 10 is formed into a low-reflection film on the non-display surface side in the next step, and the film is formed on the particle 40a. The reflective film 30b is therefore not a problem. Fig. 7 is a schematic view showing a glass substrate having a double-sided low reflection film produced by a conventional method (film formation on each side).

Next, when the low-reflection film is formed on the non-display surface side of the glass substrate 10, the film formation material may be circulated to the back surface side of the glass substrate 10. The nano-sized particles 40b of FIG. 7 are partially coated with a film-forming material on the back surface side of the glass substrate 10, that is, on the display surface side of the glass substrate 10, and adhered to the low-reflection on the display surface side of the glass substrate 10. On the outer circumference of the film 30a.

As a result, it is apparent that the nano-sized particles 40b adhering to the film-forming low-reflection film 30a generate scattered light, and as shown in FIG. 8, the color spots 80 are formed on the outer peripheral portion of the display surface of the glass substrate 10. On the other hand, the color spots 80 are generated on the outer peripheral portion of the substrate in the range from the end surface of the glass substrate 10 to about 10 mm.

On the other hand, in the manufacturing method of the laminated body of the present invention, as shown in FIG. 9, in the state in which the holding jig 50 holds the display surface side of the glass substrate 10, the low-reflection film is first formed on the cover glass as a display device or the like. In the non-display surface side at the time of use, the entire surface side of the light-shielding portion 20 is formed, and then the low-reflection film is formed on the entire surface of the display surface side. FIG. 10 shows a state in which the low-reflection film 30a has been formed on the non-display surface side of the glass substrate 10.

At this time, it was confirmed that the nanosized particle 40a was adhered to the back surface side of the glass substrate 10, that is, the outer peripheral portion of the display surface (FIG. 11). When the low-reflection film is formed on the non-display surface side of the glass substrate 10 in accordance with the procedure shown in FIGS. 9 and 10, a part of the film-forming material is displayed on the back surface side of the glass substrate 10, that is, the glass substrate 10. The surface side is covered and attached to the outer peripheral portion of the display surface of the glass substrate 10.

Next, as shown in FIG. 11, the glass substrate 10 is inverted, and the low-reflection film is formed on the entire surface of the display surface side of the glass substrate 10. In other words, the low-reflection film is formed on the display surface side of the glass substrate 10 while the holding jig 50 is held on the non-display surface side of the glass substrate 10 on which the low-reflection film 30a is formed by the previous process.

As a result, when the low-reflection film is formed on the display surface side, the low-reflection film 30b is formed on the particles 40a, and the nano-sized particles 40a which are attached to the outer peripheral portion of the display surface of the glass substrate 10 are coated. It is low in the reflective film, so it is not a problem. Figure 12 is a schematic view showing a glass substrate having a double-sided low reflection film produced by the method of the present invention.

As shown in FIG. 12, when the low-reflection film 30b is formed on the display surface of the glass substrate 10, the film-forming material is also circulated toward the non-display surface side of the glass substrate 10 on the back side of the glass substrate 10, and The nanosized particle 40b adheres to the outer peripheral portion of the non-display surface of the glass substrate 10.

At this time, the nanosized particle 40b is adhered to the low reflection film 30a which is formed into a film, and since it is the non-display surface side of the glass substrate 10, even if the particle 40b causes the scattered light to be generated, it is not possible to display it. The surface is visually observed and does not generate on the outer peripheral portion of the display surface of the glass substrate 10 as shown in FIG. Spot.

When the glass substrate 10 is used as a cover glass of a mobile device or a display device, the surface of the glass substrate 10 on which the light shielding portion 20 is formed is a non-display surface (with respect to the back surface of the display surface). The light-shielding portion 20 is formed on the non-display surface, whereby the wiring portion such as a mobile device or a display device cannot be viewed from the display surface side, and the design having the light-shielding portion can improve the creativity. In the aspect (not shown), the light shielding portion is formed in an outer frame shape on the outer peripheral portion of the glass substrate. However, the light shielding portion may be formed only in one portion of the non-display surface, and the shape of the light shielding portion is not necessarily limited to the outer frame shape. . For example, it may be formed on only a portion of an edge or a portion of a side in accordance with the design of a mobile machine or display device.

Further, the formation of the light shielding portion can be performed by a printing method. For example, screen printing or ink jet printing is preferred from the viewpoint of production cost and printing accuracy.

As the holding means of the glass substrate, various types of jigs can be used as long as they can form a film on the entire surface. For example, the glass substrate holding mechanism described in the above-mentioned JP-A-2012-89837 is suitable as a jig.

Further, as long as it is not disadvantageous for forming the low-reflection film on the entire surface of the display surface side of the glass substrate 10, the glass substrate can be fixed and held by an adhesive such as an electrostatic chuck or a double-sided tape. This point is also the same when the low reflection film is formed on the entire non-display surface side of the glass substrate.

Hereinafter, the method for producing the laminated body of the present invention will be further described.

glass substrate

In the present invention, the production of the laminate is preferably carried out using a chemical that has been previously applied. The treated glass substrate. However, a glass substrate not subjected to chemical strengthening treatment can also be used for the production of a laminate.

In a glass plate substrate subjected to chemical strengthening treatment, alkali metal ions (typically Li ions, Na ions) having a small ionic radius on the surface of the substrate are exchanged by ion exchange into alkali ions having a large ionic radius (typically K ion). Thereby, a compressive stress layer is formed on the surface of the substrate.

Therefore, the glass substrate is made of a glass containing an alkali component, and examples thereof include soda lime glass, aluminosilicate glass, aluminoborosilicate glass, and lithium aluminosilicate glass. Among these, aluminosilicate glass or soda lime glass is preferred from the viewpoint of the price and the reinforcing property at the time of chemical strengthening treatment.

Moreover, it is preferable that the glass substrate used for manufacture of a laminated body satisfies the conditions shown below.

In other words, the surface compressive stress (hereinafter also referred to as CS) of the glass substrate used for producing the laminated body is preferably 400 MPa or more and 1200 MPa or less, and more preferably 700 MPa or more and 900 MPa or less. As long as the CS is at least 400 Pa, it is sufficient in terms of practical strength. Further, as long as the CS is 1200 MPa or less, the CS can withstand its own compressive stress without any concern of natural damage. When used as a cover glass such as a display device, CS is preferably 700 MPa or more and 850 MPa or less.

Further, the depth of the stress layer (hereinafter also referred to as DOL) of the glass substrate used for producing the laminated body is preferably 15 to 50 μm, more preferably 20 to 40 μm. As long as the DOL is 15 μm or more, even if a sharp jig such as a glass cutter is used, there is no doubt that it is easily scratched and broken. Moreover, as long as the DOL is 40 μm or less, the compressive stress of the substrate itself can be withstood without fear of natural damage. As explicit When the cover glass of the display device or the like is used, the DOL is preferably 25 μm or more and 35 μm or less.

Moreover, the size of the glass substrate used for manufacturing a laminated body can be suitably selected according to the use of a laminated body. When used as a cover glass for a mobile machine, it is 30 mm × 50 mm to 300 × 400 mm and has a thickness of 0.1 to 2.5 mm. When used as a cover glass for a display device, it is 50 mm × 100 mm to 2000 × 1500 mm and has a thickness of 0.5 to 4 mm.

Low reflection film

The material of the low-reflection film is not particularly limited, and any material can be used as long as it can suppress light reflection. For example, the low reflection film may be formed by laminating a film made of a high refractive index material and a film made of a low refractive index material. Here, the film composed of the high refractive index material is a film composed of a material having a refractive index of 1.9 or more at a wavelength of 550 nm, and the film composed of the low refractive index material is a refractive index at a wavelength of 550 nm. A film composed of a material of 1.6 or less.

The film composed of the high refractive index material and the low refractive index material may be one layer each, or may be composed of two or more layers. When a film composed of a film composed of a high refractive index material and a film composed of a low refractive index material is contained, a laminated film formed by laminating a film made of a high refractive index material and a film composed of a low refractive index material is good.

In particular, in order to improve the antireflection performance, it is preferable that the low-reflection film is a laminate in which a plurality of layers are laminated. For example, the laminate has two or more layers and six or less layers as a whole, and two or more layers are laminated. Layers below 4 layers are preferred. The laminate body here is preferably a film composed of a high refractive index material as described above. In the laminate of the film composed of the low refractive index material, the total number of layers of the film composed of the high refractive index material and the film composed of the low refractive index material is preferably in the above range.

The material of the film composed of the high refractive index material and the film composed of the low refractive index material is not particularly limited, and can be selected in consideration of the required degree of antireflection and productivity. The material constituting the film composed of the high refractive index material can be suitably selected, for example, from tantalum nitride, indium oxide, tin oxide, cerium oxide, titanium oxide, zirconium oxide, cerium oxide, lanthanum. One or more kinds of metal oxides such as an oxide, an aluminum oxide, and a zinc oxide. The material constituting the film made of the low refractive index material may be one or more selected from the group consisting of cerium oxide (SiO ₂ ), a material containing a mixed oxide of Si and Sn, and Si and Zr. A material of a mixed oxide or a material containing a mixed oxide of Si and Al.

The film composed of the high refractive index material is preferably composed of any one selected from the group consisting of a cerium oxide layer or a cerium oxide layer in terms of productivity and refractive index. At this time, the film composed of the low refractive index material is preferably composed of ruthenium oxide.

Further, from the viewpoint of the hardness of the film material and the surface roughness, the film composed of the high refractive index material is preferably composed of tantalum nitride, and the film composed of the low refractive index material is preferably composed of a material containing the following mixed oxide. Any of the structures: a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, and a material containing a mixed oxide of Si and Al.

In the method for producing a laminate according to the present invention, a dry film formation method is used as a method of forming a low reflection film. The dry film forming method is not particularly limited, and various dry forms such as a sputtering method, a vapor deposition method, and an ion plating method can be used. Membrane method. However, from the viewpoint of film thickness stability and productivity, sputtering is preferred. As the sputtering method, various sputtering methods such as a pulse sputtering method, an AC sputtering method, and a digital sputtering method can be used.

When the laminate produced by the method of the present invention is used as a cover glass for a display device or the like, the antifouling film is preferably formed on the low-reflection film on the display surface side of the glass substrate (the low-reflection film of the laminate shown in FIG. 12). 30b)). As a film forming method of the antifouling film, a dry method such as a vacuum deposition method, an ion beam assisted vapor deposition method, an ion plating method, a sputtering method, or a plasma CVD method, a spin coating method, a dip coating method, or a water coating method can be used. Any of wet methods such as a method, a slit coating method, and a spray coating method. However, from the viewpoint of scratch resistance, a dry film formation method is preferably used.

On the other hand, when the antifouling film is formed on the low reflection film on the display surface side of the glass substrate, as shown in FIG. 11, the glass substrate 10 having the low reflection film 30a formed by the previous process is held by the holding jig 50. In the state of the display surface side, the antifouling film is formed on the low reflection film 30b on the display surface side of the glass substrate 10.

The constituent material of the antifouling film can be appropriately selected from materials which can impart antifouling properties, water repellency and oil repellency. Specifically, a fluorine-containing organic ruthenium compound can be mentioned. The fluorine-containing organic cerium compound is not particularly limited as long as it can impart antifouling properties, water repellency, and oil repellency.

As the fluorine-containing organic ruthenium compound, for example, a fluorine-containing organic ruthenium compound having at least one selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group can be used. base. Further, the polyfluoropolyether group has a divalent group having a structure in which a polyfluoroalkylene group and an etheric oxygen atom are alternately bonded.

The one having the selected from the group consisting of polyfluoropolyether groups, polyfluoroalkylene groups, and Specific examples of the fluorine-containing organic ruthenium compound having one or more kinds of the groups of the polyfluoroalkyl group include compounds represented by the following general formulae (I) to (V).

Wherein Rf is a linear polyfluoroalkyl group having 1 to 16 carbon atoms (as an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.); X-based hydrogen atom or carbon a lower alkyl group of 1 to 5 (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.); R1 is a hydrolyzable group (e.g., an amine group, an alkoxy group, etc.) or a halogen atom ( For example, fluorine, chlorine, bromine, iodine, etc.; m is an integer from 1 to 50 and ideally from 1 to 30; n is an integer from 0 to 2 and ideally from 1 to 2, p is from 1 to 10 and ideally from 1 to 8 The integer.

C _q F _2q+1 CH ₂ CH ₂ Si(NH ₂ ) ₃ (II)

Here, q is an integer of 1 or more and preferably 2 to 20.

The compound represented by the formula (II) may, for example, be n-trifluoro(1,1,2,2-tetrahydro)propyloxazane (n-CF ₃ CH ₂ CH ₂ Si(NH ₂ ) ₃ ), N- Heptafluoro(1,1,2,2-tetrahydro)pentylindole (nC ₃ F ₇ CH ₂ CH ₂ Si(NH ₂ ) ₃ ) or the like.

C _q' F _2q'+1 CH ₂ CH ₂ Si(OCH ₃ ) ₃ (III)

Here, q' is 1 or more and is preferably an integer of 1 to 20.

The compound represented by the formula (III) may, for example, be 2-(perfluorooctyl)ethyltrimethoxydecane (nC ₈ F ₁₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ) or the like.

In the formula (IV), R ^f2 is represented by -(OC ₃ F ₆ ) _s -(OC ₂ F ₄ ) _t -(OCF ₂ ) _u - (s, t, u are each independently an integer of 0 to 200) a divalent linear polyfluoropolyether group, and each of R ² and R ³ is independently a hydrocarbon having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.) ). X ² and X ³ are independently a hydrolyzable group (for example, an amine group, an alkoxy group, a decyloxy group, an alkenyloxy group, an isocyanate group or the like) or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) ), d and e are independent integers from 1 to 2, c and f are independent integers from 1 to 5 (ideally 1 to 2), and a and b are independently 2 or 3.

In the R ^f2 of the compound (IV), s+t+u is preferably from 20 to 300, and preferably from 25 to 100. Further, as R ² and R ³ , a methyl group, an ethyl group or a butyl group is preferred. The hydrolyzable group represented by X ² or X ³ is preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably a methoxy group or an ethoxy group. Also, a and b should each be 3.

F-(CF ₂ ) _v -(OC ₃ F ₆ ) _w -(OC ₂ F ₄ ) _y -(OCF ₂ ) _z (CH ₂ ) _h O(CH ₂ ) _l -Si(X ⁴ ) _3-k (R ⁴ ) _k (V)

In the formula (V), v is an integer of 1 to 3, and w, y, and z are each independently an integer of 0 to 200, h is 1 or 2, i is an integer of 2 to 20, and X ⁴ is a hydrolyzable group. R ⁴ is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and k is an integer of 0 to 2. w+y+z is preferably 20~300, and 25~100 is better. Also, i is preferably 2 to 10. X ⁴ is preferably an alkoxy group having 1 to 6 carbon atoms, and a methoxy group or an ethoxy group is preferred. As R ⁴ , an alkyl group having 1 to 10 carbon atoms is preferred.

In addition, KP-801 can be suitably used as a commercially available fluorine-containing organic ruthenium compound having one or more groups selected from the group consisting of polyfluoropolyether groups, polyfluoroalkylene groups, and polyfluoroalkyl groups. (product name, Shin-Etsu Chemical Co., Ltd.), KY178 (trade name, Shin-Etsu Chemical Co., Ltd.), KY-130 (trade name, Shin-Etsu Chemical Co., Ltd.), KY185 (trade name, Shin-Etsu Chemical Co., Ltd.) Industrial Co., Ltd.), Optool (registered trademark) DSX, and Optool (registered trademark) AES (all of which are trade names, manufactured by Daikin Industries Co., Ltd.).

In addition, the fluorine-containing organic ruthenium compound is generally mixed with a solvent such as a fluorine-based solvent in order to suppress deterioration by reaction with moisture in the atmosphere, and may be directly supplied to the film formation step in the case where the solvent is contained. The durability of the obtained film and the like adversely affect.

Therefore, when the antifouling film is formed by a vacuum deposition method in accordance with a procedure to be described later, it is preferred to use a fluorine-containing organic antimony compound which has been subjected to a solvent removal treatment before heating in a heating vessel. Further, it is preferred to use a fluorine-containing organic cerium compound which is not diluted with a solvent (no solvent added). For example, the concentration of the solvent contained in the fluorine-containing organic cerium compound solution is preferably 1 mol% or less, and preferably 0.2 mol% or less. It is especially preferred to use a fluorine-containing organic ruthenium compound which does not contain a solvent.

Further, examples of the solvent used for storing the fluorine-containing organic cerium compound include polyfluorohexane, m-xylene hexafluoride (C ₆ H ₄ (CF ₃ ) ₂ ), hydrofluoropolyether, and HFE 7200. /7100 (trade name, manufactured by Sumitomo 3M Co., Ltd., HFE7200 is represented by C ₄ F ₉ C ₂ H ₅ , HFE 7100 is represented by C ₄ F ₉ OCH ₃ ), and the like.

The treatment for removing the solvent (solvent) from the fluorine-containing organic cerium compound solution containing a fluorine-based solvent can be carried out, for example, by evacuating a vessel containing the fluorine-containing organic cerium compound solution.

The time for performing vacuum evacuation is not limited as long as the exhaust capacity, the amount of the solution, and the like of the exhaust line, the vacuum pump, and the like are changed. For example, vacuum evacuation can be performed for about 10 hours or more.

As described above, in the method for producing a laminate according to the present invention, as a film formation method of the antifouling film, a vacuum deposition method, an ion beam assisted vapor deposition method, an ion plating method, a sputtering method, or a plasma CVD method can be used. Wet method such as dry method and spin coating method, dip coating method, pouring coating method, slit coating method, spray coating method, or the like. However, from the viewpoint of scratch resistance, a dry film formation method is preferably used. When the antifouling film is formed by the fluorine-containing organic cerium compound exemplified above, a vacuum deposition method is preferably used.

When the vacuum evaporation method is used, the solvent removal treatment may be carried out by introducing a fluorine-containing organic cerium compound solution into a heating vessel of a film forming apparatus for forming an antifouling film, and then heating the inside of the heating vessel at room temperature before the temperature rise. Exhausted and implemented. Further, the solvent may be removed by an evaporator or the like before being introduced into the heating container.

However, as described above, the fluorine-containing organic ruthenium compound having a small solvent content or no solvent is likely to be deteriorated by contact with the atmosphere as compared with a solvent-containing one.

Therefore, it is preferable to use a container containing a fluorine-containing organic ruthenium compound having a small amount of a solvent (or a solvent) instead of being sealed and sealed with an inert gas such as nitrogen. It is preferable to shorten the time of exposure to and exposure to the atmosphere during the treatment.

Specifically, after the storage container is opened, it is preferred to introduce the fluorine-containing organic cerium compound into the heating container of the film forming apparatus forming the antifouling film. Further, after the introduction, the inside of the heating container is preferably evacuated or replaced with an inert gas such as nitrogen or a rare gas, thereby removing the atmosphere (air) contained in the heating container. In order to introduce the storage container into the heating container of the manufacturing apparatus from the storage container (storage container) without contact with the atmosphere, it is preferable to connect the storage container to the heating container, for example, with a valve attached to the valve.

Further, after the fluorine-containing organic cerium compound is introduced into the heating container, it is preferred to start the heating in the film formation immediately after the vacuum is formed in the container or the inert gas is substituted.

In the present invention, the film thickness of the antifouling film formed on the low reflection film on the display surface side of the glass substrate is not particularly limited, and is preferably 2 to 20 nm, more preferably 2 to 15 nm, and still more preferably 2 to 10 nm. When the film thickness is 2 nm or more, the surface of the low-reflection film can be uniformly covered with the anti-fouling film, and it is practical from the viewpoint of friction resistance. In addition, when the film thickness is 20 nm or less, the reaction between the reaction site on the substrate surface and the unreacted antifouling film molecules can be prevented from adhering to the substrate, and the optical properties such as haze of the laminate are excellent.

(layered body)

Since the laminated body produced by the method of the present invention has a low-reflection film formed on both surfaces of a glass substrate, it is possible to suppress reflection of light on the display surface when used as a cover glass such as a display device.

Therefore, the visual reflectance measured by the procedure described in the examples below is 3% or less, preferably 2% or less, or preferably 1% or less.

Therefore, the visual transmittance measured by the procedure described in the examples below is 93% or more, preferably 95% or more, and more preferably 96% or more.

On the other hand, when the antifouling film is formed on the low-reflection film on the display surface side of the glass substrate, the above-described visual reflectance and visual transmittance are also satisfied.

Example

Hereinafter, the present invention will be described in detail using examples. However, the invention is not limited thereto. Examples 1 to 4 are examples, and examples 5 to 6 are comparative examples.

(example 1)

A substrate having a double-sided low-reflection film having a low-reflection film formed on both sides of a glass substrate was produced by the following procedure.

A glass substrate (Dragontrail (registered trademark) manufactured by Asahi Glass Co., Ltd.) which has been subjected to chemical strengthening treatment is used as the glass substrate.

The reinforced substrate has a size of 600 mm × 400 mm and a thickness of 2 mm, and the degree of chemical strengthening is CS: 730 MPa and DOL: 30 μm.

The outer peripheral portion of one surface of the glass substrate on which the light shielding portion is formed by screen printing has an outer frame shape, and the side on which the light shielding portion is formed serves as a non-display surface of the glass substrate. Specifically, the four outer peripheral portions of one of the glass substrates were printed at a width of 2 cm by the following procedure to form a black frame-shaped light shielding portion. First, a printing ink (manufactured by Imperial Ink Co., Ltd., GLSHF (product name)) was used, and a thickness of 5 μm was applied by a screen printing machine. Thereafter, it was dried by a dryer at 150 ° C for 10 minutes. Then, using a printing ink (manufactured by Imperial Ink Co., Ltd., GLSHF (product name)), a screen printing machine was applied to the dried first layer to a thickness of 5 μm. Thereafter, it was dried in a dryer at 150 ° C for 40 minutes. So, in the glass A light shielding portion is formed on one of the outer peripheral portions of the substrate.

Next, as shown in FIG. 9, the low-reflection film is formed on the non-display surface of the glass substrate 10 on which the light-shielding part 20 has formed by the following procedure in the state which hold|maintains the display surface side of the glass substrate 10 with the holding clamp 50. The whole face.

First, a mixed gas of 10% by volume of oxygen mixed with argon gas was introduced, and a cerium oxide target (manufactured by AGC CERAMICS Co., Ltd., trade name NBO target) was used, and the pressure was 0.3 Pa, the frequency was 20 kHz, and the power density was 3.8. Pulse sputtering was performed under conditions of W/cm ² and reverse pulse width of 5 μsec, and a film having a thickness of 14 nm and composed of yttrium oxide (Nb ₂ O ₅ , hereinafter also referred to as niobia) was formed therein. The entire surface of one side is a film composed of a high refractive index material.

Next, a mixed gas containing 40% by volume of oxygen mixed in argon gas was introduced while using a ruthenium target at a pressure of 0.3 Pa, a frequency of 20 kHz, a power density of 3.8 W/cm ² , a reverse pulse width of 5 μsec, and a pulse width. Pulse sputtering was performed under conditions of 5 μsec, and a film made of yttrium oxide (SiO ₂ , hereinafter also referred to as silica) having a thickness of 30 nm was formed on the entire surface of the niobium film as A film composed of a low refractive index material.

Next, a mixed gas of 10% by volume of oxygen mixed with argon gas was introduced, and a cerium oxide target (manufactured by AGC CERAMICS Co., Ltd., trade name NBO target) was used, and the pressure was 0.3 Pa, the frequency was 20 kHz, and the power density was 3.8. Pulse sputtering was performed under conditions of W/cm ² and reverse pulse width of 5 μsec, and a film having a thickness of 110 nm and composed of niobium was formed on the entire surface of the cerium oxide film as high. A film composed of a refractive index material.

Further, while introducing a mixed gas of 40% by volume of oxygen mixed with argon gas and using a ruthenium target at a pressure of 0.3 Pa, a frequency of 20 kHz, a power density of 3.8 W/cm ² , a reverse pulse width of 5 μsec, and a pulse width. Pulse sputtering was carried out under conditions of 5 μsec, and a film made of lanthanum oxide having a thickness of 80 nm was formed on the entire surface of a niobium film to form a film composed of a low refractive index material.

In this way, a low-reflection film in which a total of four layers of a niobium film and a silica film are interlaced and laminated is formed on the entire surface.

Then, as shown in FIG. 11, the glass substrate 10 is reversed and the niobia film and the yttrium oxide are laminated in the same manner as described above while the holding jig 50 holds the display surface side of the glass substrate 10. A thin film of a total of four layers of a thin film is formed on the entire surface of the non-display surface of the glass substrate 10 on which the outer frame 20 is formed.

In this way, a laminate having a low-reflection film formed on both sides of the glass substrate is obtained.

(Example 2)

In the same manner as in Example 1, except that the thickness of the silica film of the fourth layer was 85 nm, a niobium film and a silica film were laminated in the same manner as in Example 1. The four-layer low-reflection film is formed on the entire surface of both sides (display surface, non-display surface) of the glass substrate.

Next, the antifouling film was formed on the low reflection film on the display surface side of the glass substrate by the following procedure.

First, KY185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a fluorine-containing organic ruthenium compound as a vapor deposition material, is introduced into the heating. Inside the container. Thereafter, the inside of the heating vessel was deaerated by a vacuum pump for 10 hours or more, and the solvent in the solution was removed to prepare a composition for forming a fluorine-containing organic cerium compound coating film.

Next, the heating vessel containing the composition for forming a fluorine-containing organic cerium compound film described above was heated to 270 °C. After reaching 270 ° C, this state was maintained for 10 minutes until the temperature stabilized.

Then, the low-reflection film on the display surface side of the laminate provided with the low-reflection film formed on the entire surface of the glass substrate in the vacuum chamber is formed from a heating vessel containing the composition for forming a fluorine-containing organic germanium compound film. The nozzle to be connected is supplied with a composition for forming a fluorine-containing organic germanium compound film to form a film.

At the time of film formation, the film thickness is measured by a crystal oscillation monitor provided in a vacuum chamber, and film formation is performed until the film thickness of the fluorine-containing organic germanium compound film formed on the low reflection film on the display surface side reaches 7 nm. .

The supply of the raw material from the nozzle was stopped at the time when the fluorine-containing organic cerium compound film reached 7 nm, and thereafter the produced laminated body was taken out from the vacuum chamber.

The taken-up laminate was placed on the hot plate with the film facing upward, and heat-treated at 100 ° C for 60 minutes in the atmosphere.

In this way, a laminate having a low-reflection film formed on both surfaces of the glass substrate and having an anti-fouling layer on the display surface side can be obtained.

(Example 3)

In this example, the thickness of the first layer of niobium film is set to 13 nm, the thickness of the second layer of the silica film is set to 35 nm, and the thickness of the third layer of niobium film is set. The cross-sectional product was the same procedure as in Example 1 except that the thickness of the silica film of 120 nm and the fourth layer was set to 80 nm. A low-reflection film having a total of four layers of a niobium film and a silica film is formed on the entire surface of both sides (display surface, non-display surface) of the glass substrate.

Next, in place of KY185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Opto (registered trademark) DSX (manufactured by Daikin Industries Co., Ltd.) is used as the fluorine-containing organic ruthenium compound as a vapor deposition material, and The antifouling film was formed on the low reflection film on the display surface side in the same procedure as in Example 2.

(Example 4)

In this example, the thickness of the first layer of niobium film is set to 13 nm, the thickness of the second layer of the silica film is set to 35 nm, and the thickness of the third layer of niobium film is set. A niobium film and a silica film were laminated in a total of four layers in the same manner as in Example 1 except that the thickness of the silica film of the 120 nm layer and the fourth layer was 80 nm. The low-reflection film is formed on the entire surface of both sides (display surface, non-display surface) of the glass substrate.

Next, KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of KY185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a fluorine-containing organic ruthenium compound as a vapor deposition material, and other examples were used. 2 The same procedure was used to form an antifouling film on the low reflection film on the display surface side.

(Example 5)

As shown in FIG. 4, the low-reflection film is formed on the display surface side of the glass substrate with the holding jig 50 holding the non-display surface side of the outer frame 20 on which the glass substrate 10 is formed, as shown in FIG. The glass substrate 10 is reversed, and low reflection is performed in a state where the holding surface of the glass substrate 10 is held by the holding jig 50 The film was formed on the non-display surface side of the glass substrate 10 on which the outer frame 20 was formed, and a niobium film and a silica film were laminated in a total of four layers in the same manner as in Example 1. The low-reflection film is formed on the entire surface of both sides (display surface, non-display surface) of the glass substrate.

(Example 6)

In this example, the thickness of the first layer of niobium film is set to 13 nm, the thickness of the second layer of the silica film is set to 35 nm, and the thickness of the third layer of niobium film is set. A niobium film and a silica film were laminated in a total of four layers in the same manner as in Example 5 except that the thickness of the silica film of the 120 nm layer and the fourth layer was 80 nm. The low-reflection film is formed on the entire surface of both sides (display surface, non-display surface) of the glass substrate.

Then, in the same procedure as in Example 3, a fluorine-containing organic ruthenium compound as a vapor deposition material was used as a vapor-deposited fluorine-containing organic ruthenium compound in the same procedure as in Example 3, and the antifouling film was formed on the display surface side with low reflection. On the membrane.

The following evaluations were carried out for the laminates produced by the above procedure.

(visual transmittance)

The spectral transmittance of the laminated body was measured using a spectrophotometer (manufactured by Shimadzu Corporation, device name: SolidSpec-3700), and the stimulation value Y prescribed in JIS Z8701 was calculated from the spectral transmittance. Further, the stimulation value Y is made to be a visual transmittance.

(visual reflectance)

The reflectance of the laminate was measured by a spectrophotometer (formed by Shimadzu Corporation, Form: SolidSpec-3700), and the reflectance of the reflectance was obtained from the reflectance (stimulus Y of the reflection specified in JIS Z8701:1999). .

(reflective stain)

When the laminate was observed from the display surface side under a fluorescent lamp (1500 Lx), it was evaluated that the end of the substrate was discolored as ×, and if not observed, it was evaluated as ○.

(water contact angle)

The measurement was carried out by a contact angle meter (Concord Interface Science; PCA-1). Specifically, pure water was dropped onto the film-formed substrate by a 1 μL dropper, and the contact angle was obtained from the image of the droplet by a three-point method.

The results are shown in the table below.

As can be seen from Table 1, each of the examples was a result of good visual reflectance and visual transmittance. However, in Examples 5 and 6 in which a low-reflection film was formed from the display surface side, color spots were confirmed at the end portions of the display surface of the laminate.

Further, in Examples 2 to 4 and Example 6 in which the antifouling film was formed on the low-reflection film on the display surface side, the water contact angle was high, and the effect of water repellency was confirmed.

Claims (12)

A method for producing a laminate having a low-reflection film formed on both surfaces of a glass substrate, wherein a peripheral portion of one of the glass substrates is formed by printing to form a light-shielding portion; and a low-reflection film is formed by a dry film formation method. After the film is formed on the entire surface of the glass substrate on which the light-shielding portion is formed, a low-reflection film is formed on the entire surface of the glass substrate on which the light-shielding portion is not formed by a dry film formation method. The method for producing a laminate according to claim 1, wherein the glass substrate has been subjected to a chemical strengthening treatment in advance. The method for producing a laminate according to claim 1 or 2, wherein the antifouling film is formed on the low reflection film on the surface of the glass substrate where the light shielding portion is not formed. The method for producing a laminated body according to any one of claims 1 to 3, wherein the reflective film is a laminated film obtained by laminating a film composed of a high refractive index material and a film composed of a low refractive index material. The method for producing a laminate according to claim 4, wherein the high refractive index material is cerium oxide or cerium oxide, and the low refractive index material is cerium oxide. The method for producing a laminate according to claim 4, wherein the high refractive index material is tantalum nitride, and the low refractive index material contains any of the following mixed oxides: a mixed oxide of Si and Sn, A mixed oxide of Si and Zr, and a mixed oxide of Si and Al. The method for producing a laminate according to any one of claims 4 to 6, wherein the laminated film is formed by laminating a film composed of the high refractive index material and a film composed of the low refractive index material of two or more layers and 6 Below the layer. The method for producing a laminate according to any one of claims 1 to 7, wherein the reflective film is formed by sputtering. The method for producing a laminate according to any one of claims 3 to 8, wherein the antifouling film is composed of a fluorine-containing organic cerium compound. The method for producing a laminate according to claim 9, wherein the fluorine-containing organic phosphonium compound has one or more selected from the group consisting of polyfluoropolyether groups, polyfluoroalkylene groups, and polyfluoroalkyl groups. . The method for producing a laminate according to any one of claims 3 to 10, wherein the antifouling film is formed by a vacuum evaporation method. A laminate in which a low-reflection film is formed on both surfaces of a glass substrate, which is obtained by the method of any one of claims 1 to 11.