CN109851232A - The manufacturing method of two sides band low-reflection film - Google Patents
The manufacturing method of two sides band low-reflection film Download PDFInfo
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- CN109851232A CN109851232A CN201910104255.5A CN201910104255A CN109851232A CN 109851232 A CN109851232 A CN 109851232A CN 201910104255 A CN201910104255 A CN 201910104255A CN 109851232 A CN109851232 A CN 109851232A
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- Prior art keywords
- film
- glass substrate
- low
- reflection film
- manufacturing
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
Abstract
Present invention offer is suitble to form low-reflection film on the two sides of the cover glass of display device etc. and does not have the manufacturing method of the laminated body of color difference in peripheral part.The manufacturing method of laminated body is that the manufacturing method of the laminated body of low-reflection film is formed on the two sides of glass substrate, characterized in that is formed with light shielding part by printing on a face of above-mentioned glass substrate；After forming low-reflection film by dry type membrane formation process whole face on the face that the formation of above-mentioned glass substrate has above-mentioned light shielding part, low-reflection film is formed by dry type membrane formation process whole face on the face for not forming above-mentioned light shielding part of above-mentioned glass substrate, to be formed with low-reflection film on the two sides of glass substrate.
Description
The application be national application number be 201410147780.2 it is entitled " glass substrate of two sides band low-reflection film and
The divisional application of the Chinese patent application of its manufacturing method ".
Technical field
The present invention relates to the manufacturing methods for the glass substrate that low-reflection film is formed on two sides.More specifically, it is related to
Two sides is formed with the chemically reinforced glass substrate and its manufacturing method of low-reflection film.
Background technique
In recent years, for plate PC (PersonalComputer: PC) and smart phone is (hereinafter also referred to
" smart phone etc. ") etc. the display devices such as mobile devices or LCD TV and touch screen (hereinafter, by them in this specification
It is referred to as " display device etc. "), use for improving as the protection of the display surface of display and the (protection of beautiful cover glass
Glass) the case where gradually increase.
These cover glass, which use, is formed with the glass substrate of low-reflection film on two sides.Whereby, it can inhibit display device etc.
Display surface on light reflection, the visibility of display can be further increased.
Patent document 1,2 discloses the method for being formed simultaneously low-reflection film on the two sides of glass substrate.Fig. 1,2 are that these are existing
The film formation step of some low-reflection films is the schematic diagram for indicating two sides while film forming, and Fig. 1 shows the state implemented when forming a film, Fig. 2
State after indicating film forming.
In these methods, due to keeping when film forming, low-reflection film, institute can not be formed in the peripheral part of glass substrate
To prepare the size glass substrate bigger than product, keep substrate in the position more more outward than product size and in two sides shape
After low-reflection film, is cut according to the size of regulation, obtain the glass substrate as product.Fig. 3 is indicated through above-mentioned two sides
The schematic diagram of the example of the cutting line of the glass substrate of two sides band low-reflection film manufactured by forming a film simultaneously.
In addition, the film forming of low-reflection film uses sputtering method in method described in patent document 1,2.Sputtering method, vapour deposition method etc.
Dry type membrane formation process has advantage in terms of following characteristic relative to wet type membrane formations such as rubbing methods: by by objects such as a variety of refractive index
Property different film layer is folded carries out multiple stratification, be able to achieve low reflectionization；Big, excellent scratch resistance of the hardness of film etc..In addition, if adopting
With dry type membrane formation process, that there are also the controllings of film thickness compared with wet type membrane formation is good, can stablize advantage in the preparation methods such as form a film.
In order to reduce burden caused by differential as caused by thin design and movement, it is desirable that above-mentioned display device etc. is light
Amount and slimming.It is therefore desirable to which the cover glass of the protection for display surface is also thin.It is strong in order to ensure cover glass simultaneously
Degree also forms the cover glass through enhancing of compressive stress layers (referring to specially in glass surface using by chemical intensification treatment
Sharp document 3).In addition, being formed with compressive stress layers in glass surface by chemical intensification treatment, but sometimes in patent document 3
It is handled by physical strengthening and forms compressive stress layers in glass surface.
But the glass substrate through enhancing is difficult to be cut into required size after forming compressive stress layers, so first
After being first cut into required product size, implement physical strengthening processing or chemical intensification treatment, then carry out low-reflection film at
Film.It,, can not be using as specially from the viewpoint of keeping substrate in the case where carrying out whole face film forming in the film forming of the low-reflection film
The method that such two sides documented by sharp document 1,2 forms a film simultaneously needs to use through dry type membrane formation process in a surface shape
After low-reflection film, overturn glass substrate, in the step of another surface of glass substrate forms low-reflection film.
Fig. 4 is schematic diagram the step of expression when existing single side one by one forms low-reflection film, indicates to implement single side film forming
When state.In Fig. 4, the peripheral part in a face (in figure, left side) for glass substrate 10 is formed with light shielding part by printing
20.With holding jig 50 keep glass substrate 10 non-display surface side, i.e., be formed with the face of light shielding part 20 in the state of, oneself
Display surface side when cover glass as display device etc. uses, the surface side i.e. without light shielding part form low-reflection film.Fig. 5 is indicated
State after the display surface side of glass substrate 10 forms low-reflection film 30a.Then, as shown in fig. 6, turning over glass substrate 10
Turn, forms low-reflection film in the non-display surface side whole face for the glass substrate 10 for being formed with light shielding part 20.
Existing technical literature
Patent document
Patent document 1: No. 3768547 specifications of Japanese Patent No.
Patent document 2: No. 3254782 specifications of Japanese Patent No.
Patent document 3: Japanese Patent Laid-Open 2013-006755 bulletin
Summary of the invention
The technical problems to be solved by the invention
Pass through above-mentioned dry type membrane formation process, in the step of single side of glass substrate forms low-reflection film one by one, glass base
The display surface side of plate, display surface when using as cover glass are faces that can be directly visible, so display surface side is low
Reflectance coating must be the low-reflection film for not being mixed into stomata or foreign matter etc. as far as possible.Thus, it is believed that in film formation process, exclude
The risk to be formed a film on the substrate surface of the internal contamination of film formation device is effective, it is generally desirable to prepare cleaned cleaning
Substrate forms a film in display surface side first, then forms a film in non-display surface side.
But through the step in the case where substrate two sides forms low-reflection film, it is evident that in the low anti-of display surface side
The peripheral part for penetrating film generates color difference.
The purpose of the present invention is to solve above-mentioned problem of the prior art, provide a kind of be suitble in display device etc.
The manufacturing method of low-reflection film and the laminated body in peripheral part no color differnece is formed on the two sides of cover glass.
Technical scheme applied to solve the technical problem
In order to achieve the above object, the present invention provides a kind of manufacturing method of laminated body, it is on the two sides of glass substrate
On be formed with low-reflection film laminated body manufacturing method, characterized in that the peripheral part in a face of above-mentioned glass substrate is logical
It crosses printing and is formed with light shielding part；Pass through dry type membrane formation process whole face shape on the face that the formation of above-mentioned glass substrate has above-mentioned light shielding part
After low-reflection film, formed on the face for not forming above-mentioned light shielding part of above-mentioned glass substrate by dry type membrane formation process whole face low
Reflectance coating, to be formed with low-reflection film on glass substrate two sides.
In the manufacturing method of laminated body of the invention, chemical intensification treatment can be implemented in advance to above-mentioned glass substrate.
It, can be in the face for the above-mentioned light shielding part for not forming above-mentioned glass substrate in the manufacturing method of laminated body of the invention
Low-reflection film on form anti-soil film.
In the manufacturing method of laminated body of the invention, above-mentioned reflectance coating is the film that will be made of high-index material and by low
Stacked film obtained by the film that refraction materials are constituted is alternately laminated.
In above-mentioned stacked film, above-mentioned high-index material is preferably niobium oxide or tantalum oxide, above-mentioned low-index material compared with
It is well silica.
In addition, above-mentioned high-index material is preferably silicon nitride in above-mentioned stacked film, above-mentioned low-index material is preferably
Any one of the mixed oxide of mixed oxide, Si and Zr comprising Si and Sn, mixed oxide of Si and Al.
Above-mentioned stacked film is preferably by the film that will be made of above-mentioned high-index material and by above-mentioned low-index material
Alternately laminated 2 layers of the film of composition or more 6 layers or less form.
In the manufacturing method of laminated body of the invention, above-mentioned reflectance coating is preferably by sputtering film-forming.
In the manufacturing method of laminated body of the invention, above-mentioned anti-soil film is preferably made of fluorine-containing organic silicon compound.
Above-mentioned fluorine-containing organic silicon compound is preferably one had selected from multi-fluoro polyether base, polyfluoro alkylidene and Polyfluoroalkyl
A above group.
In the manufacturing method of laminated body of the invention, above-mentioned anti-soil film forms a film preferably by vacuum vapour deposition.
In addition, the present invention provide be formed on a kind of two sides being manufactured by method of the invention, in glass substrate it is low anti-
Penetrate the laminated body of film.
The effect of invention
Low reflection characteristic by the glass substrate of the resulting two sides band low-reflection film of the present invention is good, glass substrate intensity
It is high and in the peripheral part no color differnece of display surface.Therefore, it is suitable as the cover glass of display device etc..
Detailed description of the invention
Fig. 1 is the schematic diagram for indicating the film formation step (two sides while forming a film) of existing low-reflection film, indicates to implement film forming
When state.
Fig. 2 is the schematic diagram for indicating the film formation step (two sides while forming a film) of existing low-reflection film, after indicating film forming
State.
Fig. 3 is to indicate that the glass substrate of two sides band low-reflection film by existing method (two sides while forming a film) manufacture is cut
The schematic diagram of the example of secant.
Fig. 4 is the schematic diagram for indicating the film formation step (single side forms a film one by one) of existing low-reflection film, indicates to implement single side
State when film forming.
Fig. 5 is the schematic diagram for indicating the film formation step (single side forms a film one by one) of existing low-reflection film, indicates single side film forming
State afterwards.
Fig. 6 is the schematic diagram for indicating the film formation step (single side forms a film one by one) of existing low-reflection film, indicates to implement the back side
State when film forming.
Fig. 7 is to indicate that the glass substrate of the two sides band low-reflection film manufactured by existing method (single side forms a film one by one) shows
It is intended to.
Schematic diagram when Fig. 8 is the glass substrate of the two sides band low-reflection film of Fig. 7 from the side low-reflection film 30a.
Fig. 9 be indicate using method of the invention low-reflection film film formation step schematic diagram, indicate implement single side at
State when film.
Figure 10 is the schematic diagram for indicating the film formation step of the low-reflection film using method of the invention, after indicating single side film forming
State.
Figure 11 be indicate using method of the invention low-reflection film film formation step schematic diagram, indicate implement the back side at
State when film.
Figure 12 is the schematic diagram for indicating the glass substrate of the two sides band low-reflection film manufactured by method of the invention.
Schematic diagram when Figure 13 is the glass substrate of the two sides band low-reflection film of Figure 13 from the side low-reflection film 30b.
The explanation of symbol
10: glass substrate
20: light shielding part
30,30a, 30b: low-reflection film
40: around rear particle
50: holding jig
80: color difference
Specific embodiment
The present invention will be described with reference to the accompanying drawings.
It shows first and realizes process of the invention.
As a result present inventor sends out for conscientiously being studied the reasons why the peripheral part of low-reflection film generates color difference
It is existing the reason is that: using dry type membrane formation process when a surface forms low-reflection film, membrane material detour occurs to glass substrate
Back side, the particle of nano-grade size (hereinafter also referred to nanoscale) are attached to the peripheral part of substrate back side, generate scattering light.
In addition, the particle of the back side of such detour to substrate is also referred to as " around rear particle (Japanese: inner ま わ り particle) ".
The display surface side of glass substrate is important face that can be directly visible, thus usually as far as possible so that display surface and
The discontiguous mode of substrate holding jig is designed the holding means of glass substrate, on this basis, is carried out first aobvious
Show the whole face film forming of surface side.
For example, keeping the non-display surface side (Fig. 5) of glass substrate, after display surface side forms low-reflection film, confirm in shape
Nanometer particle 40a (Fig. 6) is attached at the peripheral part in the non-display face for the glass substrate 10 for having light shielding part 20.Know the particle
40a is following particle: in step shown in Fig. 4, when the display surface side of glass substrate 10 forms low-reflection film, filmogen
A part of detour to glass substrate 10 back side, i.e. be formed with light shielding part 20 glass substrate 10 non-display surface side, attachment
In the particle of the peripheral part in the non-display face of glass substrate 10.
But in Fig. 6, the nanometer particle 40a of the peripheral part in the non-display face of glass substrate 10 is attached to as under
One process when non-display surface side forms low-reflection film, low-reflection film 30b is also formed on particle 40a, so will not be at
For problem.Fig. 7 is to indicate that the glass substrate of the two sides band low-reflection film manufactured by existing method (single side forms a film one by one) shows
It is intended to.
Then, also the same that filmogen detour occurs extremely when the non-display surface side of glass substrate 10 forms low-reflection film
The case where back side of above-mentioned glass substrate 10.The nanometer particle 40b of Fig. 7 is following particle: one of filmogen
Divide detour to the back side of glass substrate 10, the i.e. display surface side of glass substrate 10, glass substrate 10 is formed in front of being attached to
Display surface side low-reflection film 30a peripheral part on particle.
As a result, the nanometer particle 40b on the low-reflection film 30a formed before being attached to generates scattering light, such as Fig. 8
It is shown, color difference 80 is obviously produced in the peripheral part of the display surface of glass substrate 10.In addition, color difference 80 is mostly from glass substrate
The substrate peripheral part that the range of 10mm or so is played in 10 end face generates.
In contrast, in the manufacturing method of laminated body of the invention, as shown in figure 9, keeping glass with holding jig 50
In the state of the display surface side of substrate 10, non-display surface side first when the cover glass as display device etc. uses, i.e.
The surface side whole face for being formed with light shielding part 20 forms low-reflection film, then forms low-reflection film in display surface side whole face.Figure 10 is indicated
State after the non-display surface side of glass substrate 10 forms low-reflection film 30a.
At this point, confirmation is attached with nanometer particle 40a (figure in the peripheral part of the back side of glass substrate 10, i.e. display surface
11).Particle 40a is following particle: in Fig. 9, step shown in Fig. 10, being formed in the non-display surface side of glass substrate 10 low anti-
When penetrating film, a part of detour of filmogen is attached to the back side of glass substrate 10, the i.e. display surface side of glass substrate 10
The particle of the peripheral part of the display surface of glass substrate 10.
Then, as shown in figure 11, glass substrate 10 is overturn, forms low reflection in the display surface side whole face of glass substrate 10
Film.I.e., the non-display surface side of the glass substrate 10 of low-reflection film 30a is formed in front of being kept with holding jig 50 the step of
In the state of, low-reflection film is formed in the display surface side of glass substrate 10.
As a result, also forming low-reflection film 30b on particle 40a, before when display surface side forms low-reflection film
The nanometer particle 40a for being attached to the peripheral part of the display surface of glass substrate 10 is caught into low-reflection film, will not be become and be asked
Topic.Figure 12 is the schematic diagram for indicating the glass substrate of the two sides band low-reflection film manufactured by method of the invention.
As shown in figure 12, when the display surface of glass substrate 10 forms low-reflection film 30b, filmogen detour also occurs extremely
The non-display surface side of the back side of glass substrate 10, glass substrate 10, nanometer particle 40b are attached to the non-aobvious of glass substrate 10
Show the peripheral part in face.
In this case, the state on the low-reflection film 30a that nanometer particle 40b is formed before being attached to, but due to
Be in the non-display surface side of glass substrate 10, even if so particle 40b generates light at random, it is also invisible from display surface, such as Figure 13
It is shown, color difference will not be generated in the peripheral part of the display surface of glass substrate 10.
The formation of glass substrate 10 has the face of light shielding part 20 using the glass substrate as mobile device and display device
Cover glass is in use, become non-display face (back side opposite with display surface).It, can by forming light shielding part 20 in non-display face
So that it is invisible when the wiring portion of mobile device and display device etc. is from display surface side, furthermore by using with light shielding part
Design, appearance design can be improved.In addition, in the form of diagram, the frame-shaped (Japanese: outer other than the peripheral part of glass substrate
Frame shape) it is formed with light shielding part, but light shielding part can only be formed in a part in non-display face, and the shape of light shielding part is also not necessarily
It is confined to outer frame-shaped.For example, can only be existed on the side of a part or only according to the design as mobile device and display device
The a part on side forms light shielding part.
Print process can be used in the formation of light shielding part.For example, from the viewpoint of production cost and printing precision, it is preferable to use
Silk-screen printing or ink jet printing.
As the holding means of glass substrate, as long as the holding means of whole face film forming can be coped with, can be used various
Fixture, but it is preferable to use such as glass substrates described in existing literature Japanese Patent Laid-Open 2012-89837 to keep means conduct
Fixture.
As long as in addition, not to glass substrate 10 display surface side whole face formed low-reflection film generate adverse effect, can also
With by other means, such as keeping glass substrate using the fixation of binding electrostatic chuck, double-sided adhesive tape.About this
Aspect, it is also the same when the non-display surface side whole face of glass substrate forms low-reflection film.
Hereinafter, the manufacturing method of laminated body of the invention is further described.
Glass substrate
In the present invention, it is preferable to use implementing the glass substrate of chemical intensification treatment in advance in the manufacture of laminated body.But
It is that the glass substrate for not implementing chemical intensification treatment also can be used in the manufacture of laminated body.
It implements in the glass panel substrate of chemical intensification treatment, by ion exchange, the ionic radius of substrate surface is small
Alkali metal ion (representative is Li ion, Na ion) and the bigger alkali metal ion of ionic radius (it is representative be K from
Son) exchange.Whereby, compressive stress layers are formed in substrate surface.
Thus, glass substrate is made of the glass containing alkali metal component, can enumerate such as soda-lime glass, alumino-silicate glass
Glass, aluminium borosilicate glass, lithium alumina silicate glass etc..Wherein, the reinforcing from price and when implementing chemical intensification treatment is special
From the viewpoint of property, preferably alumina silicate glass or soda-lime glass.
In addition, glass substrate used in the manufacture of laminated body preferably satisfies condition as shown below.
I.e., the surface compression stress (hereinafter also referred to CS) of glass substrate used in the manufacture of laminated body is preferably
400MPa or more and 1200MPa are hereinafter, more preferable 700MPa or more and 900MPa or less.If CS is in 400Pa or more, conduct
Intensity in practical use is enough.In addition, if CS is in 1200MPa hereinafter, then can tolerate the compression stress of itself, without nature
The worry of destruction.Cover glass as display device etc. is in use, CS is particularly preferably 700MPa or more and 850MPa or less.
In addition, the depth (hereinafter also referred to DOL) of the stressor layers of glass substrate used in the manufacture of laminated body is preferably
15~50 μm, more preferably 20~40 μm.If DOL is 15 μm or more, even if the fixture sharp keen using gauge glass cutter etc.
Do not have the worry for being easy to damage and destroying.In addition, if DOL at 40 μm hereinafter, then can tolerate substrate itself compression stress,
There is no the worry of corollary failure.Cover glass as display device etc. is in use, DOL is particularly preferably 25 μm or more and 35 μm
Below.
In addition, the size of glass substrate used in the manufacture of laminated body can suitably be selected according to the purposes of laminated body.Make
For mobile device cover glass in use, having a size of 30mm × 50mm~300 × 400mm and with a thickness of 0.1~2.5mm；Make
For display device cover glass in use, having a size of 50mm × 100mm~2000 × 1500mm and with a thickness of 0.5~4mm.
Low-reflection film
The material of low-reflection film is not particularly limited, as long as the material that light can be inhibited to reflect, can be used various
Material.For example, can be used as low-reflection film by the film being made of high-index material and the film being made of low-index material
Structure obtained by stacking.The film mentioned here being made of high-index material be by wavelength 550nm refractive index be 1.9 with
On material constitute film, the film being made of low-index material refer to by wavelength 550nm refractive index be 1.6 materials below
Expect the film constituted.
The film being made of high-index material and the film being made of low-index material refer to that can be each respectively has 1
The form of layer, is also possible to the structure for respectively having 2 layers or more.It the film that is made of high-index material and is made of low-index material
Film respectively have 2 layers or more in the case where, preferably by the film being made of high-index material and the film being made of low-index material
Stacked film obtained by alternately laminated.
Especially for improve antireflection property, low-reflection film preferably it is multilayer laminated obtained by laminated body, such as preferably should
2 layers or more 6 layers of layer below are laminated in laminated body on the whole, more preferably 2 layers of stacking or more, 4 layers of layer below.Here laminated body
Laminated body obtained by preferably as described above folding the film being made of high-index material and the film layer being made of low-index material,
The number of plies obtained by each number of plies of the film, the film being made of low-index material that are made of high-index material is total is preferably above-mentioned
In range.
The material of the film being made of high-index material, the film being made of low-index material is not particularly limited, it can
Degree and productivity of antireflection needed for considering etc. are selected.Composition material as the film being made of high-index material
Material, such as preferably using selected from silicon nitride, indium oxide, tin-oxide, niobium oxide, titanium oxide, Zirconium oxide, cerium oxygen
The metal oxides such as compound, tantalum pentoxide, aluminum oxide, zinc oxide more than one.It is constituted as by low-index material
Film constituent material, preferably using be selected from silica (SiO2), the material of mixed oxide comprising Si and Sn, include
The material of the mixed oxide of Si and Zr, mixed oxide comprising Si and Al material more than one.
As the film being made of high-index material, consider from the degree of productivity and refractive index, preferably by selected from oxidation
Any one of niobium layer or tantalum oxide layers are constituted.In this case, the film being made of low-index material is preferably by silica
It constitutes.
In addition, the film being made of high-index material is preferred from the viewpoint of the hardness and surface roughness of membrane material
Be made of silicon nitride, the film being made of low-index material preferably by the material comprising Si and the mixed oxide of Sn, include Si
With the material of the mixed oxide of Zr, any one of the material of mixed oxide comprising Si and Al constitutes.
In the manufacturing method of laminated body of the invention, as the method for forming low-reflection film, dry type membrane formation process is used.As long as
It is that dry type membrane formation process is just not particularly limited, the various dry type membrane formation process such as sputtering method, vapour deposition method, ion plating can be used.But
It is, it is preferable to use sputtering method from the viewpoint of the stability and productivity of film thickness.As sputtering method, such as pulse can be used
The various sputtering methods such as sputtering method, AC sputtering method, digital sputtering method.
Using the laminated body by method manufacture of the invention as the cover glass of display device etc. in use, it is preferred that in glass
Anti-soil film is formed on the low-reflection film of the display surface side of substrate (on the low-reflection film 30b of laminated body shown in Figure 12).As anti-
Vacuum vapour deposition, Assisted by Ion Beam vapour deposition method, ion plating, sputtering method, plasma CVD can be used in the membrane formation process of dirty film
The dry methods such as method, any one of damp process such as spin-coating method, dip coating, casting coating, slot coated method, spray-on process.But from resistance to
, it is preferable to use dry type membrane formation process from the viewpoint of scratch resistance.
In addition, in the case where forming anti-soil film on the low-reflection film of the display surface side of glass substrate, as shown in figure 11,
The state of the non-display surface side of the glass substrate 10 of low-reflection film 30a is formd in the step of before being maintained at holding jig 50
Under, anti-soil film is formed on the low-reflection film 30b of the display surface side of glass substrate 10.
The constituent material of anti-soil film can from can assign soil resistance, water repellency, oil repellent material in suitably select.Specifically may be used
Enumerate such as fluorine-containing organic silicon compound.As fluorine-containing organic silicon compound, as long as being to confer to soil resistance, water repellency and oil repellent
Fluorine-containing organic silicon compound can use unlimitedly.
As such fluorine-containing organic silicon compound, such as it is preferable to use have to be selected from multi-fluoro polyether base, polyfluoro alkylidene
And the fluorine-containing organic silicon compound of the more than one group of Polyfluoroalkyl.In addition, multi-fluoro polyether base is with polyfluoro alkylidene
The divalent group of structure made of being alternately bonded with etheric oxygen atom.
Have as with 1 or more the fluorine-containing of group selected from the multi-fluoro polyether base, polyfluoro alkylidene and Polyfluoroalkyl
The concrete example of organic silicon compound can enumerate the compound etc. indicated with the following general formula (I)~(V).
[changing 1]
In formula, Rf is the Polyfluoroalkyl of the straight-chain of carbon number 1~16 (as alkyl, such as methyl, ethyl, n-propyl, different
Propyl, normal-butyl etc.), X is low alkyl group (such as methyl, ethyl, n-propyl, isopropyl, the positive fourth of hydrogen atom or carbon number 1~5
Base etc.), R1 is the group (such as amino, alkoxy etc.) or halogen atom (such as fluorine, chlorine, bromine, iodine etc.) that can be hydrolyzed, m is 1~
50, preferably 1~30 integer, n are the integers of 0~2, preferably 1~2, and p is the integer of 1~10, preferably 1~8.
CqF2q+1CH2CH2Si(NH2)3 (II)
Here, q is the integer of 1 or more, preferably 2~20.
As to lead to the compound that formula (II) indicates, such as n- trifluoro (1,1,2,2- tetrahydro) propyl silazane can be illustrated
(n-CF3CH2CH2Si(NH2)3), seven fluorine of n- (1,1,2,2- tetrahydro) amyl silazane (n-C3F7CH2CH2Si(NH2)3) etc..
Cq'F2q'+1CH2CH2Si(OCH3)3 (III)
Here, q ' is the integer of 1 or more, preferably 1~20.
As to lead to the compound that formula (III) indicates, 2- (perfluoro capryl) ethyl trimethoxy silane (n- can be illustrated
C8F17CH2CH2Si(OCH3)3) etc..
[changing 2]
In formula (IV), Rf2It is with-(OC3F6)s-(OC2F4)t-(OCF2)u(s, t, u be separately 0~200 it is whole
Number) indicate divalent straight-chain multi-fluoro polyether base；R2、R3It is separately the monovalent hydrocarbon of carbon atom number 1~8 (such as first
Base, ethyl, n-propyl, isopropyl, normal-butyl etc.).X2、X3It independently is group (such as amino, alkoxy, the acyl-oxygen that can be hydrolyzed
Base, alkenyloxy, isocyanate group etc.) or halogen atom (such as fluorine atom, chlorine atom, bromine atom, iodine atom etc.)；D, e is independent
The integer that ground is 1~2；C, f independently is the integer of 1~5 (preferably 1~2)；A and b independently is 2 or 3.
R possessed by compound (IV)f2In, s+t+u is preferably 20~300, and more preferable 25~100.In addition, as R2、
R3, more preferable methyl, ethyl, butyl.As with X2、X3The hydrolization group of expression, the alkoxy of more preferable carbon number 1~6 are special
Not preferred methoxyl group, ethyoxyl.In addition, a and b are respectively preferably 3.
[changing 3]
F-(CF2)v-(OC3F6)w-(OC2F4)y-(OCF2)z(CH2)hO(CH2)i-Si(x4)3-k(R4)k (V)
In formula (V), v is 1~3 integer；W, y, z are separately 0~200 integer；H is 1 or 2；I is 2~20
Integer；X4It is hydrolization group；R4It is the straight chain of carbon number 1~22 or the alkyl of branch；K is 0~2 integer.W+y+z is preferred
It is 20~300, more preferable 25~100.In addition, i is more preferably 2~10.X4The preferably alkoxy of carbon number 1~6, more preferably
Methoxyl group, ethyoxyl.As R4, the more preferably alkyl of carbon number 1~10.
In addition, there is 1 or more the group selected from multi-fluoro polyether base, polyfluoro alkylidene and perfluoroalkyl as commercially available
Fluorine-containing organic silicon compound, it is preferable to use KP-801 (trade name, Shin-Etsu Chemial Co., Ltd's (SHIN-ETSU HANTOTAI's chemical industry strain
Formula commercial firm) system), KY178 (trade name, Shin-Etsu Chemial Co., Ltd's system), KY-130 (trade name, SHIN-ETSU HANTOTAI's chemical industry strain
Formula commercial firm system), KY185 (trade name, Shin-Etsu Chemial Co., Ltd's system), OPTOOL (オ プ Star-Le, registered trademark) DSX
And OPTOOL (registered trademark) AES (being trade name, Daikin Ind Ltd (ダ イ キ Application Industrial Co., Ltd) system) etc..
In addition, in order to inhibit deterioration etc., usual fluorine-containing organic silicon compound because caused by with the reaction of moisture in air
It mixes and saves with fluorine solvent equal solvent, but if directly with the state comprising these solvents for film formation process, sometimes
Durability to resulting film etc. generates adverse effect.
So according to subsequent steps, in the case where forming anti-soil film by vacuum vapour deposition, it is preferable to use with adding
Heat container has carried out the fluorine-containing organic silicon compound that solvent removes processing in advance before being heated.Furthermore it is preferred that using not using
Solvent dilutes the fluorine-containing organic silicon compound of (being not added with solvent).For example, as contained in fluorine-containing organic silicon compound solution
The concentration of solvent, preferably 1 mole of % solvent strength below, more preferable 0.2 mole of % or less.Particularly preferably using without solvent
Fluorine-containing organic silicon compound.
In addition, such as more fluoride hexane, hexafluoro can be enumerated as the solvent used when saving above-mentioned fluorine-containing organic silicon compound
For meta-xylene (C6H4(CF3)2), hydrogen perfluoroalkyl polyether, HFE7200/7100 (trade name, Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ
System society) system, HFE7200 expression C4F9C2H5, HFE7100 expression C4F9OCH3) etc..
The processing for removing solvent from the fluorine-containing organic silicon compound solution comprising fluorine solvent can be for example, by equipped with containing
The container vacuum-pumping of fluorine organo-silicon compound solution carries out.
For the time vacuumized, become due to amount of exhaust capacity, solution with exhaust line, vacuum pump etc. etc.
Change, thus it is unlimited to it, it can implement for example, by vacuumizing about 10 hours or more.
As described above, as the membrane formation process of anti-soil film, vacuum evaporation can be used in the manufacturing method of laminated body of the invention
The dry methods such as method, Assisted by Ion Beam vapour deposition method, ion plating, sputtering method, plasma CVD method, spin-coating method, dip coating, casting
Any one of damp process such as coating, slot coated method, spray-on process.But, it is preferable to use dry from the viewpoint of marresistance
Formula membrane formation process.With foregoing illustrative fluorine-containing organic silicon compound formed anti-soil film in the case where, it is preferable to use vacuum vapour deposition.
In the case where using vacuum vapour deposition, the removing processing of above-mentioned solvent can also be by filling to the film forming for forming anti-soil film
It is next to being vacuumized inside heating container in room temperature before heating after importing fluorine-containing organic silicon compound solution in the heating container set
Implement.In addition it is also possible to implement solvent removing with evaporator etc. in advance before importing heating container.
But as described above, solvent content is few or not solvent-laden fluorine-containing organic silicon compound with contain the fluorine-containing of solvent
Organo-silicon compound are compared, and are easier to deteriorate due to contacting with atmosphere.
Therefore, the storage container of the fluorine-containing organic silicon compound of solvent content few (or being free of) is, it is preferable to use by container
With the inert gas replacements such as nitrogen, closed storage container, exposure when operation in an atmosphere, time of contact is made to shorten.
Specifically, it is preferable that importing fluorine-containing organic silicon compound to form anti-soil film immediately after storage container breaks a seal
The heating container of film formation device.Then, after importing, preferably to heating container inside vacuumize or with nitrogen, rare gas etc. it is lazy
Property gas displacement, remove atmosphere (air) contained in heating container.More preferably in the case where not contacted with atmosphere from keeping
Mode, such as storage container and the heating container that container (storage container) imports the heating container of this manufacturing device pass through with pump
Pipeline connection.
Then, it after fluorine-containing organic silicon compound preferably being imported heating container, will be set in container with vacuum or inert gas
It changes, starts the heating for film forming immediately after.
It is not special to the film thickness of the anti-soil film formed on the low-reflection film of the display surface side of glass substrate in the present invention
It limits, but preferably 2~20nm, more preferable 2~15nm, further preferred 2~10nm.If film thickness is formed anti-in 2nm or more
Dirty film is equably covered on the state on low-reflection film face, from the viewpoint of abrasion resistance, becomes durable article.In addition,
If film thickness in 20nm hereinafter, if can avoid the reaction site of substrate surface and unreacted antifouling membrane molecule is attached on substrate
State, the optical characteristics such as mist degree as laminated body are good.
(laminated body)
The laminated body manufactured by means of the present invention is formed with low-reflection film on the two sides of glass substrate, so can press down
Make the light reflection on the display surface when the cover glass as display device etc. uses.
So according to the visual reflectivity (Japanese: visual sense reflectivity) of the measurement of step described in aftermentioned embodiment 3%
Hereinafter, it is preferred that 2% hereinafter, more preferable 1% or less.
So according to step described in aftermentioned embodiment measurement visual transmissivity 93% or more, preferably 95% with
On, more preferable 96% or more.
In addition, also meeting above-mentioned visual reflection when forming anti-soil film on the low-reflection film of the display surface side of glass substrate
Rate and visual transmissivity.
Embodiment
Hereinafter, with example, the present invention will be described in more detail.But the invention is not limited to these examples.Example 1
~example 4 is embodiment, and 5~example of example 6 is comparative example.
(example 1)
According to following step, the low reflection of two sides band that the whole face on the two sides of glass substrate is formed with low-reflection film is manufactured
The substrate of film.
As glass substrate, using implement chemical intensification treatment glass substrate (Asahi Glass Co., Ltd's system,
Dragontrail (registered trademark)).
The size of the reinforcing substrate is 600mm × 400mm, with a thickness of 2mm, and the degree of chemical strengthening is that CS is
730MPa, DOL are 30 μm.
Peripheral part in a face of glass substrate passes through frame-shaped other than silk-screen printing and forms light shielding part, will be formed with the screening
Non-display face of the face of the side in light portion as glass substrate.Specifically, the periphery on four sides in a face of glass substrate
Portion implements to print according to following step with 2cm width with black surround shape, forms light shielding part.Firstly, using ink (empire's ink
Manufacture Co., Ltd. (empire イ Application キ manufactures Co., Ltd.) system, GLSHF (ProductName)), using screen process press with 5 μm of thickness
Degree is coated.Then, it is kept for 10 minutes, is made it dry in 150 DEG C with drying machine.Then, using ink, (empire's ink is manufactured
Co. Ltd. system, GLSHF (ProductName)), applied with 5 μm of thickness using on screen process press first layer after the drying
Cloth.Then, it is made it dry with drying machine in 150 DEG C of 40 minutes of holding.It is outer on a face of glass substrate as a result,
Circumference forms light shielding part.
Then, as shown in figure 9, being formed in the state of keeping the display surface side of glass substrate 10 with holding jig 50
Have and low-reflection film is formed by following step whole face on the non-display face of the glass substrate 10 of light shielding part 20.
Firstly, importing the mixed gas for being mixed with the oxygen of 10 volume % in argon gas on one side, niobium oxide target is used on one side
(AGC ceramics Co., Ltd. (AGC セ ラ ミ ッ Network ス Co., Ltd.) system, trade name NBO target (NBO タ ー ゲ ッ ト)), in pressure
0.3Pa, frequency 20kHz, power density 3.8W/cm2, carry out pulsed sputter under conditions of 5 μ sec of rp pulse width, at one
On face, as the film being made of high-index material, whole face formed thickness 14nm by niobium oxide (Nb2O5, hereinafter also referred to oxygen
Change niobium (niobia)) constitute film.
Then, the mixed gas for being mixed with the oxygen of 40 volume % in argon gas is imported on one side, silicon target is used on one side, in pressure
0.3Pa, frequency 20kHz, power density 3.8W/cm2, under conditions of 5 μ sec of rp pulse width with the item of 5 μ sec of pulse width
Part carries out pulsed sputter, and on niobium oxide (niobia) film, as the film being made of low-index material, whole face forms thickness
30nm by silica (SiO2, hereinafter also referred to silica (silica)) and the film that constitutes.
Then, the mixed gas for being mixed with the oxygen of 10 volume % in argon gas is imported on one side, uses niobium oxide target on one side
(AGC ceramics Co. Ltd. system, trade name NBO target), in pressure 0.3Pa, frequency 20kHz, power density 3.8W/cm2, reverse phase arteries and veins
Rush under conditions of 5 μ sec of width and carry out pulsed sputter, at silica (silica)) on film, as by high-index material structure
At film, whole face formed thickness 110nm the film being made of niobium oxide (niobia).
Then, the mixed gas for being mixed with the oxygen of 40 volume % in argon gas is imported on one side, silicon target is used on one side, in pressure
0.3Pa, frequency 20kHz, power density 3.8W/cm2, under conditions of 5 μ sec of rp pulse width with the item of 5 μ sec of pulse width
Part carries out pulsed sputter, and on niobium oxide (niobia) film, as the film being made of low-index material, whole face forms thickness
The film of 80nm being made of silica (silica).
As a result, whole face form total 4 layers of niobium oxide (niobia) film and silica (silica) film it is alternately laminated and
The low-reflection film obtained.
Then, as shown in figure 11, overturn glass substrate 10, in the display surface for keeping glass substrate 10 with holding jig 50
In the state of side, on the non-display face for the glass substrate 10 for being formed with outline border 20, pass through step same as described above, whole face shape
At total 4 layers of niobium oxide (niobia) film and silica (silica) film it is alternately laminated obtained by low-reflection film.
It obtains being formed with the laminated body of low-reflection film in the two sides whole face of glass substrate as a result,.
(example 2)
In this example, other than 85nm is made in the thickness of the 4th layer silica (silica) film, by same with example 1
The step of sample, whole face forms niobium oxide (niobia) film and dioxy on the two sides (display surface, non-display face) of glass substrate
Total 4 layers of SiClx (silica) film it is alternately laminated obtained by low-reflection film.
Then, anti-soil film is formed on the low-reflection film of the display surface side of glass substrate by following step.
Firstly, the fluorine-containing organic silicon compound as evaporation material, Xiang Jiare container is interior to import KY185 (trade name, SHIN-ETSU HANTOTAI
Chemical industry Co. Ltd. system).Then, the solvent in solution is carried out to deaerating 10 hours or more in heating container with vacuum pump
It removes, the composition of fluorine-containing organic silicon compound envelope formation is made.
Then, the heating container of the composition equipped with above-mentioned fluorine-containing organic silicon compound film formation is heated to 270 DEG C.
After reaching 270 DEG C, the state is kept 10 minutes until temperature is stablized.
Then, for being arranged in, vacuum is indoor, is formed with the laminated body of low-reflection film in the two sides whole face of glass substrate
Display surface side low-reflection film, connect from the heating container of the composition equipped with the formation of fluorine-containing organic silicon compound film
Nozzle supplies the composition of fluorine-containing organic silicon compound film formation, forms a film.
When film forming, film thickness is measured in the indoor quartz-crystal resonator of vacuum using setting on one side, carries out forming a film on one side straight
Film thickness to the fluorine-containing organic silicon compound film formed on the low-reflection film of display surface side reaches 7nm.
Stop then taking out from vacuum chamber from nozzle base feed at the time of fluorine-containing organic silicon compound film reaches 7nm
Laminated body obtained.
For the laminated body taken out, film surface is arranged on hot plate in a manner of upward, in an atmosphere in 100 DEG C of heat
Processing 60 minutes.
The stacking that stain-proofing layer in the two sides of glass substrate formation low-reflection film, has also been made in display surface side is obtained as a result,
Body.
(example 3)
In this example, in addition to the thickness of niobium oxide (niobia) film of first layer is made as 13nm, by the titanium dioxide of the second layer
The thickness of silicon (silica) film is made as 35nm, the thickness of niobium oxide (niobia) film of third layer is made as 120nm, by the 4th layer
The thickness of silica (silica) film be made as other than 80nm, by the step same as example 1, on the two sides of glass substrate
Whole face forms niobium oxide (niobia) film on (display surface, non-display face) and silica (silica) film amounts to 4 layers of alternating layer
Low-reflection film obtained by folded.
Then, as the fluorine-containing organic silicon compound of evaporation material, in addition to using OPTOOL (registered trademark) DSX (great Jin
Industrial Co., Ltd's system) it replaces other than KY185 (trade name, Shin-Etsu Chemial Co., Ltd's system), by similarly being walked with example 2
Suddenly, anti-soil film is formed on the low-reflection film of display surface side.
(example 4)
In this example, in addition to the thickness of niobium oxide (niobia) film of first layer is made as 13nm, by the titanium dioxide of the second layer
The thickness of silicon (silica) film is made as 35nm, the thickness of niobium oxide (niobia) film of third layer is made as 120nm, by the 4th layer
The thickness of silica (silica) film be made as other than 80nm, by the step same as example 1, on the two sides of glass substrate
Whole face forms niobium oxide (niobia) film on (display surface, non-display face) and silica (silica) film amounts to 4 layers of alternating layer
Low-reflection film obtained by folded.
Then, as the fluorine-containing organic silicon compound of evaporation material, in addition to using KY178 (trade name, SHIN-ETSU HANTOTAI's chemical industry
Co. Ltd. system) it replaces other than KY185 (trade name, Shin-Etsu Chemial Co., Ltd's system), by the step same as example 2,
Anti-soil film is formed on the low-reflection film of display surface side.
(example 5)
As shown in figure 4, the shape in the non-display surface side for having outline border 20 with the formation of the holding glass substrate 10 of holding jig 50
Under state, after the display surface side of glass substrate forms low-reflection film, as shown in fig. 6, overturning glass substrate 10, with retaining clip
In the state that tool 50 keeps the display surface side of glass substrate 10, in the non-display surface side shape for the glass substrate 10 for being formed with outline border 20
It is in addition to this, whole on the two sides (display surface, non-display face) of glass substrate by the step same as example 1 at low-reflection film
Face formed total 4 layers of niobium oxide (niobia) film and silica (silica) film it is alternately laminated obtained by low-reflection film.
(example 6)
In this example, in addition to the thickness of niobium oxide (niobia) film of first layer is made as 13nm, by the titanium dioxide of the second layer
The thickness of silicon (silica) film is made as 35nm, the thickness of niobium oxide (niobia) film of third layer is made as 120nm, by the 4th layer
The thickness of silica (silica) film be made as other than 80nm, by the step same as example 5, on the two sides of glass substrate
Whole face forms niobium oxide (niobia) film on (display surface, non-display face) and silica (silica) film amounts to 4 layers of alternating layer
Low-reflection film obtained by folded.
Then, OPTOOL (note is used as the fluorine-containing organic silicon compound of evaporation material by the step same as example 3
Volume trade mark) DSX (Daikin Ind Ltd's system), anti-soil film is formed on the low-reflection film of display surface side.
For the laminated body obtained through the above steps, implement evaluation below.
(visual transmissivity)
Using spectrophotometer, (Shimadzu Corporation (Shimadzu Seisakusho Ltd.) is made, device name: SolidSpec-
3700) spectral transmission for, measuring laminated body calculates the values Y of defined in JIS Z8701 according to the spectral transmission.
Then, using values Y as visual transmissivity.
(visual reflectivity)
Using spectrophotometer (Shimadzu Corporation's system, model: SolidSpec-3700), laminated body is measured
Reflectivity calculates visual reflectivity (the values Y of reflection specified in JIS Z8701:1999) according to the reflectivity.
(color difference of reflection)
(1500Lx) when laminated body, will have observed that commenting for the end discoloration of substrate from display surface side under fluorescent light
Valence be ×, not it is observed that end discoloration be evaluated as zero.
(water contact angle)
Utilize contact angle instrument (consonance interface science Co., Ltd. (consonance interface science) system；PCA-1 it) is measured.
Specifically, 1 μ L pure water is added dropwise on the substrate after film forming with syringe, connect according to the image of drop using 3 method calculatings
Feeler.
As a result it is shown in following table.
[table 1]
As known from Table 1, in all examples, the result of visual reflectivity and visual transmissivity is all good.But certainly
Display surface side is formed in the example 5,6 of low-reflection film, has confirmed color difference in the end of the display surface of laminated body.
In addition, being formed with the example 2~4 of anti-soil film on the low-reflection film of display surface side, in example 6, water contact angle is high, confirmation
The effect of water repellency.
Claims (11)
1. a kind of manufacturing method of the glass substrate of two sides band low-reflection film, it be formed on the two sides of glass substrate it is low anti-
Penetrate the manufacturing method of the glass substrate of the two sides band low-reflection film of film, which is characterized in that
Peripheral part in a face of the glass substrate is formed with light shielding part by printing；
After forming low-reflection film by dry type membrane formation process whole face on the face that the formation of the glass substrate has the light shielding part,
Low-reflection film is formed by dry type membrane formation process whole face on the face for not forming the light shielding part of the glass substrate, thus in glass
Glass substrate two sides is formed with low-reflection film.
2. the manufacturing method of the glass substrate of two sides band low-reflection film as described in claim 1, which is characterized in that the glass
Glass substrate implements chemical intensification treatment in advance.
3. the manufacturing method of the glass substrate of two sides band low-reflection film as claimed in claim 1 or 2, which is characterized in that in institute
It states and forms anti-soil film on the low-reflection film in the face for not forming the light shielding part of glass substrate.
4. the manufacturing method of the glass substrate of two sides band low-reflection film as described in claim 1, which is characterized in that described low anti-
Penetrate film be by the film being made of high-index material and the film being made of low-index material it is alternately laminated obtained by stacked film.
5. the manufacturing method of the glass substrate of two sides band low-reflection film as claimed in claim 4, which is characterized in that the stacking
In film, the high-index material is niobium oxide or tantalum oxide, and the low-index material is silica.
6. the manufacturing method of the glass substrate of two sides band low-reflection film as claimed in claim 4, which is characterized in that the stacking
In film, the high-index material is silicon nitride, and the low-index material includes the mixed oxide, Si and Zr of Si and Sn
Any one of mixed oxide, mixed oxide of Si and Al.
7. the manufacturing method of the glass substrate of two sides band low-reflection film as claimed in claim 4, which is characterized in that the stacking
Film is by by the film being made of the high-index material and alternately laminated 2 layers of the film being made of the low-index material or more
6 layers or less form.
8. the manufacturing method of the glass substrate of two sides band low-reflection film as described in claim 1, which is characterized in that described low anti-
It penetrates film and passes through sputtering film-forming.
9. the manufacturing method of the glass substrate of two sides band low-reflection film as claimed in claim 3, which is characterized in that described antifouling
Film is made of fluorine-containing organic silicon compound.
10. the manufacturing method of the glass substrate of two sides band low-reflection film as claimed in claim 9, which is characterized in that described to contain
Fluorine organo-silicon compound have the more than one group selected from multi-fluoro polyether base, polyfluoro alkylidene and Polyfluoroalkyl.
11. the manufacturing method of the glass substrate of two sides band low-reflection film as claimed in claim 3, which is characterized in that described anti-
Dirty film is formed a film by vacuum vapour deposition.
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| CN114578461A (en) | 2015-05-12 | 2022-06-03 | Ａｇｃ株式会社 | Substrate with low reflection film |
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| JP6780619B2 (en) * | 2016-11-11 | 2020-11-04 | Ａｇｃ株式会社 | Substrate with low reflective film and its manufacturing method |
| WO2018105602A1 (en) * | 2016-12-08 | 2018-06-14 | 旭硝子株式会社 | Transparent substrate having light blocking region and display device |
| JP2018197183A (en) * | 2017-05-23 | 2018-12-13 | Ａｇｃ株式会社 | Glass article, and display unit |
| JP7100225B2 (en) * | 2017-08-02 | 2022-07-13 | 日東電工株式会社 | Anti-reflective film |
| JP7025892B2 (en) * | 2017-11-07 | 2022-02-25 | デクセリアルズ株式会社 | Laminates, anti-reflection structures and camera module mounting devices |
| JP6863343B2 (en) * | 2018-07-12 | 2021-04-21 | Ａｇｃ株式会社 | Manufacturing method of glass laminate, front plate for display, display device and glass laminate |
| CN110863185B (en) * | 2019-12-06 | 2023-09-22 | 天津美泰真空技术有限公司 | Low-reflection high-transmission film and preparation method thereof |
| CN114551607B (en) * | 2022-02-25 | 2023-12-12 | 陕西迪泰克新材料有限公司 | Shading layer, composite film layer and preparation method of shading layer |
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- 2014-03-05 TW TW103107491A patent/TW201442971A/en unknown
- 2014-04-04 KR KR20140040581A patent/KR20140126663A/en not_active Application Discontinuation
- 2014-04-14 CN CN201410147780.2A patent/CN104118994A/en active Pending
- 2014-04-14 CN CN201910104255.5A patent/CN109851232B/en active Active
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| JP2001242480A (en) * | 1999-12-21 | 2001-09-07 | Seiko Epson Corp | Liquid crystal display device its manufacturing method and electronic apparatus |
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| CN113493313B (en) * | 2020-04-08 | 2023-11-21 | Ａｇｃ株式会社 | Glass with heat ray reflecting film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104118994A (en) | 2014-10-29 |
| JP2014224979A (en) | 2014-12-04 |
| JP6361162B2 (en) | 2018-07-25 |
| TW201442971A (en) | 2014-11-16 |
| KR20140126663A (en) | 2014-10-31 |
| CN109851232B (en) | 2022-11-04 |
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