CN108929052A - The manufacturing method and display device of covering member, covering member - Google Patents

The manufacturing method and display device of covering member, covering member Download PDF

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Publication number
CN108929052A
CN108929052A CN201810503188.XA CN201810503188A CN108929052A CN 108929052 A CN108929052 A CN 108929052A CN 201810503188 A CN201810503188 A CN 201810503188A CN 108929052 A CN108929052 A CN 108929052A
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CN
China
Prior art keywords
interarea
covering member
transparent base
layer
glass plate
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Granted
Application number
CN201810503188.XA
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Chinese (zh)
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CN108929052B (en
Inventor
藤井健辅
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AGC Inc
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AGC Inc
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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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • G02F1/133331—Cover glasses
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention relates to the manufacturing methods and display device of covering member, covering member.The present invention relates to a kind of covering members, it is the covering member comprising transparent base, wherein, above-mentioned transparent base has the 2nd interarea of 1st interarea opposite with coating The lid component and the side opposite with above-mentioned 1st interarea, the compound comprising F atom is attached on above-mentioned 1st interarea, the contact angle of above-mentioned 1st interarea is 50 ° or less.

Description

The manufacturing method and display device of covering member, covering member
Technical field
The present invention relates to covering (カ バ ー) component, covering member manufacturing method and display device.
Background technique
All the time, in order to protect the display panel of display device, the covering structure with transparent bases such as glass plates is used Part (for example, see patent document 1).
Sometimes the side for covering wiring etc. is printed with frame-shaped at the edge of the interarea of the display panel side of transparent base Frame portion.
Existing technical literature
Patent document
Patent document 1：International Publication No. 2011/148990
Summary of the invention
Problem to be solved by the invention
In general, the interarea of covering member to be fitted in the display surface of display panel using adhesive layers such as optical bonding films.
At this point, the gases such as air enter between the interarea and adhesive layer of covering member (transparent base) sometimes, to generate Bubble.Especially, in the display that the covering member on the interarea of display panel side with frame portion is fitted in display panel In the case where face, height difference part between frame portion and transparent base is easy to generate gas between covering member and adhesive layer Bubble.
When the bubble generated between covering member and adhesive layer makes to watch the display surface of display panel across covering member The visual of display image be deteriorated.
Therefore, it in the case where a large amount of bubbles are produced between covering member and adhesive layer, needs to carry out using autoclave And make the operations such as bubble collapse, it is many and diverse.
The present invention makes in view of problem above, and its purpose is to provide the systems of a kind of covering member, above-mentioned covering member It makes method and has used the display device of above-mentioned covering member, the covering member is the display surface side for being configured at display panel Covering member be able to suppress covering member when being bonded covering member with the display surface of display panel via adhesive phase Bubble between adhesive layer generates.
The means used to solve the problem
Present inventor has performed further investigations, as a result, it has been found that, above-mentioned purpose is realized by using following compositions, thus complete At the present invention.
That is, the covering member of an embodiment of the invention is covering member as described below, to include transparent base The covering member of body, wherein above-mentioned transparent base have 1st interarea opposite with coating The lid component and with above-mentioned 1st interarea 2nd interarea of opposite side is attached with the compound comprising F atom, the contact of above-mentioned 1st interarea on above-mentioned 1st interarea Angle is 50 ° or less.
The manufacturing method of the covering member of an embodiment of the invention is the manufacturer of covering member as described below Method, the method for the covering member for manufacture comprising transparent base, wherein the manufacturing method comprises the following steps：
Prepare transparent base, the transparent base has 1st interarea opposite with coating The lid component and with the above-mentioned 1st 2nd interarea of the opposite side of interarea,
Preparing transfer matrix, the transfer is attached with fluorochemical with matrix in one side,
Above-mentioned fluorine-containing chemical combination is attached in above-mentioned 1st interarea and above-mentioned transfer matrix by making above-mentioned transparent base The face contact of object, so that above-mentioned fluorochemical is transferred on above-mentioned 1st interarea of above-mentioned transparent base,
By above-mentioned transfer, it is attached to the compound comprising F atom on above-mentioned 1st interarea, and by above-mentioned 1st interarea Contact angle is adjusted to 50 ° or less.
The display device of an embodiment of the invention is display device as described below, to have above-mentioned covering structure The display device of part, adhesive layer and display panel, wherein above-mentioned covering member is with above-mentioned 1st interarea of above-mentioned transparent base Opposite with above-mentioned display panel direction is bonded via above-mentioned adhesive layer with above-mentioned display panel.
Invention effect
According to the present invention it is possible to provide a kind of when being bonded covering member with the display surface of display panel via adhesive layer Be able to suppress covering member, above-mentioned covering member that bubble between covering member and adhesive layer generates manufacturing method and The display device of above-mentioned covering member is used.
Detailed description of the invention
Fig. 1 is the cross-sectional view for showing the display device of present embodiment.
Fig. 2 is the cross-sectional view of amplification display covering member, adhesive layer and display panel.
Fig. 3 is the cross-sectional view for the state that previous covering member is fitted in display panel using adhesive layer by amplification display.
Fig. 4 is the cross-sectional view for showing the covering member of present embodiment.
Appended drawing reference
11：Covering member
12：Transparent base
12a：1st interarea
12b：2nd interarea
14：Adhesive layer
100：Display device
102：Back light unit
104：Display panel (coating The lid component)
104a：Display surface
106：Shell
107：Housing Base
131：Adhesive layer
132：Frame portion
141：Wiring
511：Covering member
512：Transparent base
512a：1st interarea
551：Bubble
561：Height difference part
Specific embodiment
Based on attached drawing, embodiments of the present invention will be described.
The composition of the display device of < present embodiment>
Fig. 1 is the cross-sectional view for showing the display device 100 of present embodiment.
As display device 100, the display device such as smart phone, tablet computer terminal can be enumerated, it is vehicle-mounted to lead Navigate device, for back seat passenger watch image etc. RSE (rear seat entertainment) device etc. display device for mounting on vehicle, be mounted on ice Display device in the shutter door of the household appliances such as case, washing machine, micro-wave oven, etc.；But it is not limited to these.
Display device 100 has display panel 104 and a covering member 11, display panel 104 and covering member 11 via Adhesive layer 14 and be bonded.
Display device 100 has the shell 106 for accommodating each portion, is formed with opening portion on shell 106.In shell 106 It is placed with aforementioned display panel 104 and back light unit 102.As shown in Figure 1, in the Housing Base 107 of the bottom plate as shell 106 On be placed with back light unit 102, display panel 104 is placed on back light unit 102.In the present embodiment, display panel 104 be liquid crystal display panel.Shell 106 inside and in the outside of display panel 104, configured with being connect with display panel 104 Wiring 141.
Back light unit 102 and being constructed without for display panel 104 are particularly limited to, and can use well known composition.About The material etc. of shell 106 (including Housing Base 107), is similarly not particularly limited.
As display device 100, it is not limited to the display device for having liquid crystal display panel as display panel 104, it can also be with It is that there is the display device such as organic EL panel, PDP, electronic ink type panel.For display device 100, according to The type of display panel 104 does not have back light unit 102 sometimes.Display device 100 can have touch panel etc..As touching Panel is controlled, capacitive touch panel, touch panel of resistive film mode etc. can be enumerated.
The covering member 11 for constituting a part of display device 100 has transparent base 12.Transparent base 12 utilizes bonding Layer 14 fits in display panel 104.In this way, transparent base 12 is functioned as the covering member of covering display panel 104.
In the present embodiment, the end of transparent base 12 utilizes adhesive layer 131 and 106 gluing of shell.
Fig. 2 is the cross-sectional view of amplification display covering member 11, adhesive layer 14 and display panel 104.
The transparent base 12 for constituting covering member 11 has interarea.That is, transparent base 12 has：With as coating The lid component Opposite the 1st interarea 12a of display panel 104；And the side opposite with the 1st interarea 12a, not with 104 phase of display panel Pair the 2nd interarea 12b.In the present embodiment, display panel 104 is enumerated to be illustrated as coating The lid component, but it is coating The lid component is not limited to display panel.
For transparent base 12, as described later, the compound comprising F atom is attached on the 1st interarea 12a, and And the 1st interarea 12a contact angle be 50 ° or less.
In the present embodiment, frame portion 132 is formed with frame-shaped at the edge of the 1st interarea 12a of transparent base 12, institute The masking wiring 141 of frame portion 132 is stated so that can not observe wiring 141 (referring to Fig.1) from the 2nd side interarea 12b.
The 1st interarea 12a of the transparent base 12 for being formed with frame portion 132 is fitted in into display panel using adhesive layer 14 104 display surface 104a.
It is preferred that adhesive layer 14 and transparent base 12 are equally transparent, and the refractive index of transparent base 12 and adhesive layer 14 Difference is small.
As adhesive layer 14, such as can enumerate comprising saturating as obtained from solidifying liquid curable resin composition In addition to this layer of ming tree rouge is also possible to optical bonding film or optical bonding band.
The thickness of adhesive layer 14 is, for example, 5 μm~1000 μm, preferably 50 μm~500 μm.
< previous covering member>
Fig. 3 is the state that previous covering member 511 is fitted in display panel 104 using adhesive layer 14 by amplification display Cross-sectional view.Identical symbol is used for part identical with the present embodiment illustrated based on Fig. 1 and Fig. 2, and is omitted the description.
The transparent base 512 for constituting previous covering member 511 is fitted in into the aobvious of display panel 104 using adhesive layer 14 Show face 104a.
At this point, as shown in figure 3, the gases such as air enter between transparent base 512 and adhesive layer 14 sometimes, to generate gas Bubble 551.Especially, the feelings of frame portion 132 are printed on the 1st interarea 512a of 104 side of display panel of transparent base 512 Under condition, it is easy to generate bubble 551 in the height difference part 561 formed by frame portion 132.
When watching display panel 104 across transparent base 512, bubble 551 keeps the image shown in display surface 104a (aobvious Diagram picture) visual be deteriorated.
Therefore, it in the case where producing a large amount of bubble 551, needs to carry out that bubble 551 is made to disappear using autoclave Operation etc., it is very many and diverse.
The composition of the covering member of < present embodiment>
Fig. 4 is the cross-sectional view for showing the covering member 11 of present embodiment.
Covering member 11 has transparent base 12, and the transparent base 12 has the 1st interarea 12a and the 2nd interarea 12b.It is right For covering member 11, as needed, there is frame portion 132 on the 1st interarea 12a of transparent base 12, in the 1st interarea There is functional layer (not shown) on 12a or the 2nd interarea 12b.
Hereinafter, each section for constituting covering member 11 is described in more detail.
《Transparent base》
For transparent base 12, the compound comprising F atom, and the 1st interarea are attached on the 1st interarea 12a The contact angle of 12a is 50 ° or less.
As a result, in the display surface that the 1st interarea 12a of transparent base 12 is fitted in display panel 104 using adhesive layer 14 When 104a, it can inhibit to generate bubble between transparent base 12 and adhesive layer 14.It should be noted that for including F atom Compound for, preferred organic compound, this is because can be to control the contact angle of the 1st interarea 12a on a small quantity.
The reasons why obtaining said effect is still not clear, but is presumed as follows.
By the way that the contact angle of the 1st interarea 12a of transparent base 12 is adjusted to 50 ° hereinafter, the 1st interarea 12a and adhesive layer 14 become easy wetting, and adhesiveness can be improved.
In addition, being attached on the 1st interarea 12a of transparent base 12 (for example, glass plate comprising Si) comprising F atom Compound.Small water repellent portion is formed on the 1st interarea 12a as a result,.Furthermore, it is believed that the table in the path that water repellent portion is formed each other Face can reduce, and the gas for becoming bubble is discharged between transparent base 12 and adhesive layer 14 by these water repellent portions.Speculate by This inhibits the generation of bubble.
For the reason that the generation for further suppressing bubble is such, the contact angle of the 1st interarea 12a of transparent base 12 is preferred It is 25 °~45 °, more preferably 28 °~40 °, more preferably 30 °~38 °.
The contact angle of 1st interarea 12a of transparent base 12 is found out in the following manner.
Firstly, the 1st interarea 12a of transparent base 12 (in the case where being printed with frame portion 132 with frame-shaped, is not printed The region of frame portion 132) carry out 4 × 4 equal parts.It measures (total in line (3+3) the mutual intersection point for carrying out that timesharing is waited to draw 9 points) at water contact angle.Specifically, using contact angle meter (consonance interface science company at 23 DEG C of measuring temperature Manufacture, PCA-11) contact angle being added dropwise after 5 μ L pure water after 5 seconds is measured.By the contact angle of total 9 points determined Average value as transparent base 12 the 1st interarea 12a contact angle.It, can be with it should be noted that the measurement about contact angle It is measured using the method for θ/2 (half horn cupping (A half angle method)).
For the such reason of generation for further suppressing bubble, transparent base 12 (for example, glass plate comprising Si) In 1st interarea 12a, F atom quantity relative to Si atom ratio of number (F/Si) (hereinafter also referred to as " atomic ratio (F/ It Si) ") is preferably 0.005~0.13, more preferably 0.015~0.1, further preferably 0.02~0.08.It needs to illustrate It is that, in the case where atomic ratio (F/Si) is big, in the 1st interarea 12a of transparent base 12, the region that surface can be lower becomes larger, with The region that the adhesiveness of adhesive layer 14 reduces becomes more.Therefore, be more than atomic ratio (F/Si) upper limit value when, be easy in the 1st interarea Site residues bubble 1a low with the adhesiveness of adhesive layer 14.
If the atomic ratio (F/Si) of the 1st interarea 12a of transparent base 12 is greater than 0, it is considered as in 12 (example of transparent base Such as, comprising the glass plate of Si) the 1st interarea 12a on be attached with the compound comprising F atom.
The atomic ratio (F/Si) of 1st interarea 12a of transparent base 12 is found out in the following manner.
It (in the case where being printed with frame portion 132 with frame-shaped, is not printed firstly, for the 1st interarea 12a of transparent base 12 The region of brush frame portion 132), F is found out using x-ray photoelectron spectroscopy device (Japan Electronics Corporation manufactures, JPS-9000MC) Atomic concentration (unit：Atom %) and Si atomic concentration (unit：Atom %).Calculated F atom concentration and Si atom is dense Atomic ratio (F/Si) of the ratio between the degree as the 1st interarea 12a of transparent base 12.
More specifically, it is surveyed under conditions of the radiographic source of X-ray is MgK alpha ray, acceleration voltage 12kV, 25mA It is fixed.It is that 6mm φ is measured with spot diameter.There is no the inclination of sample.It is 50eV, measures step in logical energy (pass energy) A length of 0.5eV, residence time (Dwell Time) are 100 milliseconds, scanning times are measured under conditions of being 30 times.For surveying Fixed result, bonded energy peak i.e. obtained, using Shirley method background correction, then according to F1s peak intensity and Si2p3/2 Peak intensity calculate the atomic concentration ratio of F/Si.
As long as transparent base of the transparent base 12 comprising transparent material, there is no particular limitation, it is preferable to use for example wrap The transparent base etc. of combination (composite material, stacking material etc.) containing glass or glass and resin.For transparent base 12 Shape is also not particularly limited, such as can enumerate the plate with rigidity.In addition, transparent base 12 does not need as tabular, It can be shape, a part of shape for having bending section of integrally bending.
As the glass plate for being used as transparent base 12, can enumerate as main component general comprising being made with silica The glass of the glass such as glass, such as soda lime glass, alumina silicate glass, pyrex, alkali-free glass, quartz glass Plate.
In the case where using glass plate as transparent base 12, about the composition of glass, it is preferably able to forming, utilizes change The composition that intensive treatment is strengthened is learned, sodium is preferably comprised.
The composition of glass is not particularly limited, and can use the glass with various compositions.It can enumerate for example, with oxidation Mole % of object benchmark indicates there is the alumina silicate glass of composition below.
(i) include 50%~80% SiO2, 2%~25% Al2O3, 0%~10% Li2O, 0%~18% Na2O, 0%~10% K2O, the ZrO of 0%~15% MgO, 0%~5% CaO and 0%~5%2Glass.
(ii) containing 50%~74% SiO2, 1%~10% Al2O3, 6%~14% Na2O, 3%~11% K2O, the ZrO of 2%~15% MgO, 0%~6% CaO and 0%~5%2, and SiO2And Al2O3Content add up to 75% hereinafter, Na2O and K2The glass for adding up to 7%~15% of the content for adding up to 12%~25%, MgO and CaO of the content of O Glass.
(iii) containing 68%~80% SiO2, 4%~10% Al2O3, 5%~15% Na2O, 0%~1% K2O, the ZrO of 4%~15% MgO and 0%~1%2Glass.
(iv) containing 67%~75% SiO2, 0%~4% Al2O3, 7%~15% Na2O, 1%~9% K2O、 The ZrO of 6%~14% MgO and 0%~1.5%2, and SiO2And Al2O3Content add up to 71%~75%, Na2O and K2The content of O adds up to 12%~20%, glass of its content less than 1% containing CaO.
(v) include 60%~75% SiO2, 0.5%~8% Al2O3, 10%~18% Na2O, 0%~5% K2O, 6%~15% MgO, 0%~8% CaO glass.
(vi) containing 63%~75% SiO2, 3%~12% Al2O3, 3%~10% MgO, 0.5%~10% CaO, 0%~3% SrO, 0%~3% BaO, 10%~18% Na2O, 0%~8% K2O, 0%~3% ZrO2、 0.005%~0.25% Fe2O3, and R2O/Al2O3(in formula, R2O is Na2O+K2It O) is 2.0 or more and 4.6 glass below Glass.
(vii) containing 66%~75% SiO2, 0%~3% Al2O3, 1%~9% MgO, 1%~12% CaO, 10%~16% Na2O, 0%~5% K2The glass of O.
As transparent base 12, preferably glass plate.
The manufacturing method of glass plate is not particularly limited.It can manufacture by the following method：By desired glass raw material It puts into melting furnace, in 1500 DEG C~1600 DEG C progress heating meltings and carries out limpid, be then supplied in forming device and will melt Melting forming of glass is plate, and carries out Slow cooling.
The manufacturing process of glass plate is not particularly limited, and can use such as glass tube down-drawing (for example, overflow downdraw, discharge orifice Under draw method, again traction method (リ ド ロ ー method) etc.), float glass process, roll-in method, pressing etc..
In the case where using glass plate as transparent base 12, in order to improve intensity, chemistry preferably is implemented to glass plate Intensive treatment or physical strengthening processing.
Method of chemical strengthening treatment is not particularly limited, and ion exchange is carried out to the interarea of glass plate, to form residual The superficial layer of compression.Specifically, at glass transition temperature temperature below, by the glass near the interarea of glass plate Contained in the small alkali metal ion (for example, Li ion, Na ion) of ionic radius be replaced into the biggish alkali metal of ionic radius Ion (being K ion for Na ion for example, being Na ion or K ion for Li ion).As a result, in glass plate Interarea remain compression, the intensity of glass plate improves.
Glass plate as transparent base 12 preferably satisfies condition as shown below.By carrying out at above-mentioned chemical strengthening Reason, can satisfy such condition.
The compression (hereinafter referred to as " CS ") of glass plate is preferably 400MPa or more and 1200MPa hereinafter, more preferably 700MPa or more and 900MPa or less.It is enough as intensity in practical use if CS is 400Pa or more.On the other hand, If CS be 1200MPa hereinafter, if be resistant to itself compression, be not concerned about and destroy naturally.
The stress layer depth (hereinafter referred to as " DOL ") of glass plate is preferably 15 μm~50 μm, more preferably 20 μm~40 μ m.If DOL be 15 μm or more, even if using the sharp keen fixture of glass cutting machine etc., be also not concerned about be easy to produce damage and It is destroyed.On the other hand, if DOL be 40 μm hereinafter, if be resistant to itself compression, be not concerned about and destroy naturally.
The thickness of transparent base 12 can be selected suitably depending on the application.For example, in the case where glass plate, thickness is preferably 0.1mm~5mm, more preferably 0.2mm~2mm.
Glass plate is being used as transparent base 12 and in the case where carrying out above-mentioned chemical intensification treatment, for making Intensive treatment is more effective, and the thickness of glass plate is preferably generally 5mm hereinafter, more preferably 3mm or less.
The size of transparent base 12 can be selected suitably depending on the application.
《Frame portion》
Frame portion 132 is formed and colored ink (coloring イ Application Network) is printed on transparent base 12.Frame portion 132 It is preferably formed in the peripheral part of the 1st interarea 12a of transparent base 12.
As print process, such as there are scraper rubbing method, reverse rubbing method, gravure coating process, mouth die coating method, roller coating Method, silk screen print method, ink-jet method etc., but for can easily print, various transparent base frame portions, energy can be printed as It is enough to carry out the reason, preferably silk screen print method such as printing according to the size of transparent base frame portion.
It as colored ink, is not particularly limited, can be used such as comprising inorganic ink ceramic sintering body, include The organic inks of the colorants such as dyestuff or pigment and organic resin, etc..The colored ink for being used to form frame portion 132 is black mostly Or white, but its color is not particularly limited.Furthermore it is possible to be the wave-length coverage for only making infrared ray light penetrate have color ink Water.
As the ceramics contained in inorganic ink, such as there are the oxides such as chromium oxide, iron oxide, chromium carbide, tungsten carbide etc. Carbide, carbon black, mica, etc..
Organic inks are the compositions comprising dyestuff or pigment and organic resin.Dyestuff or pigment can be not particularly limited Ground uses.
As organic resin, can enumerate for example epoxy resin, acrylic resin, polyethylene terephthalate, Polyether sulfone, polycarbonate, Transparent ABS Resin, phenol resin, acrylonitrile-butadiene-styrene resin, polyurethane, gathers polyarylate Methyl methacrylate, polyvinyl formal, polyvinyl butyral, polyether-ether-ketone, polyethylene, polyester, polypropylene, polyamides The homopolymers such as amine, polyimides, the monomer of these resins and the copolymer of copolymerisable monomer, etc..
In inorganic ink and organic inks, from fired temperature it is low from the aspect of, it is preferable to use organic inks, from chemically-resistant It more preferably include the organic inks of pigment from the viewpoint of moral character.
《Functional layer》
Covering member 11 has function (not shown) preferably on the 1st interarea 12a of transparent base 12 or the 2nd interarea 12b Layer, in particular, having functional layer more preferably on the 2nd interarea 12b of transparent base 12.
Functional layer is the layer for showing characteristic not available for transparent base 12.As functional layer, can enumerate for example anti- Dizzy layer, antireflection layer, stain-proofing layer etc..
(antiglare layer)
Covering member 11 has antiglare layer preferably on the 1st interarea 12a of transparent base 12 or the 2nd interarea 12b.By setting Set antiglare layer, it is possible to reduce the mapping (Ying り Write body of the light of surrounding), so as to prevent the visual of display image from reducing.It is special It is not that antiglare layer more preferably is set on the 2nd interarea 12b of transparent base 12.
Antiglare layer can be by carrying out that concaveconvex shape is arranged on the 1st interarea 12a of transparent base 12 or the 2nd interarea 12b Processing, i.e. so-called non-glare treated and formed.
As non-glare treated, well known method can be applied, for example, using the case where glass plate is as transparent base 12 Under, it can use following method：Chemical surface treatment or physical surface treatment are implemented to the interarea of glass plate, to form institute's phase Method or wet coating of the concaveconvex shape of the surface roughness of prestige etc..
As the method for carrying out chemical non-glare treated, implement frosted processing (Off ロ ス ト processing) specifically, can enumerate Method.Frosted is handled for example by the way that the glass plate for being used as treated object to be impregnated in the mixed solution of hydrogen fluoride and ammonium fluoride And implement.
As the method for carrying out physics non-glare treated, for example following method can use：Using compressed air to glass plate Interarea blowing ground silica, carborundum powder etc., so-called blasting treatment；Knot is attached with using after being soaked with water The method etc. that the brush of brilliant silicon dioxide powder, carborundum powder etc. is rubbed and (wipes Ru).
Among these methods, frosted processing is not susceptible to machinery due to being not easy to generate micro-crack on treated object surface The reduction of intensity, thus preferably as the method for carrying out non-glare treated to glass plate.
For implementing the interarea of glass plate of chemical non-glare treated or physics non-glare treated in this way, it is Adjustment surface shape, is preferably etched.As etching process, such as can use by the way that glass plate is impregnated in work For the aqueous solution of hydrogen fluoride etching solution and the method that carries out chemical etching.About etching solution, in addition to containing hydrogen fluoride with Outside, the acid such as hydrochloric acid, nitric acid, citric acid can also be contained.By can not only inhibit by containing in glass plate containing these acid The part generation of the cation such as Na ion, K ion and precipitate caused by the reacting of hydrogen fluoride, and can make to be etched in place It is equably carried out in reason face.
In the case where being etched, by the concentration, the leaching of glass plate in the etch solution that adjust etching solution Stain time etc. and adjust etch quantity, it is possible thereby to which the haze value in the non-glare treated face of glass plate is adjusted to desired value.? In the case where the physical surface treatments such as sandblasting are carried out as non-glare treated, crack sometimes, but can be by etching at It manages and removes such crackle.Using etching process, the effect for inhibiting flash of light (ギ ラ Star キ) is also obtained.Herein, flash of light refers to Phenomenon as described below：In the case where transparent base 12 to be used for the display device covering member of picture element matrix type, covering Observe a large amount of light beads (light bead) with the period greater than picture element matrix in The lid component surface.
The surface roughness (r.m.s. roughness, RMS) of the interarea of glass plate after non-glare treated and etching process is preferred It is 0.01 μm~0.5 μm.Surface roughness (RMS) is more preferably 0.01 μm~0.3 μm, more preferably 0.01 μm~0.2 μm. By adjusting surface roughness (RMS) into above range, the haze value of the glass plate after non-glare treated can be adjusted to 1%~30%.Haze value is JIS K 7136：(2000) it is worth specified in.
Surface roughness (RMS) can be according to JIS B 0601：(2001) method specified in is measured.It is specific and Speech, utilizes laser microscope (trade name：VK-9700, the manufacture of Keyemce company), for the glass after the non-glare treated as sample The aspect of measure of glass plate, sets the field range of 200 μm of 300 μ m, and measures the elevation information of glass plate.Measured value is carried out Cutoff correction (correction of カ ッ ト オ Off), and the root mean square of obtained height is found out, it is possible thereby to calculate surface roughness (RMS).As cutoff value (カ ッ ト オ Off value), it is preferable to use 0.08mm.
The surface of glass plate after implementing non-glare treated and etching process has concaveconvex shape, from the upper of glass pane surface When it is observed by side, it appears that be circular hole.The size (diameter) in the circular hole observed in this way be preferably 1 μm with It is upper and 10 μm or less.Flash of light and anti-glare are prevented by that in the range, can take into account.
(antireflection layer)
When antireflection layer is arranged as functional layer on the interarea of transparent base 12, it is possible to reduce the mapping of exterior light, from And it can prevent the visual of display image from reducing.In the case where being provided with antiglare layer on the interarea of transparent base 12, preferably Antireflection layer is set in antiglare layer.
As the composition of antireflection layer, as long as can be as long as the composition in the reflection suppression to prescribed limit by light without spy It does not limit, for example, it may be composition obtained from high refractive index layer and low-index layer are laminated.Herein, high refractive index Layer for example refers to that the refractive index of the light of wavelength 550nm is 1.9 or more layer, and low-index layer refers to the folding of the light of wavelength 550nm Penetrating rate is 1.6 layers below.
About the number of plies of high refractive index layer and low-index layer in antireflection layer, can be comprising 1 layer of high refractive index layer With the mode of 1 layer of low-index layer, it is also possible to the composition comprising 2 layers or more high refractive index layers and 2 layers or more low-index layer. Comprising the composition of 1 layer of high refractive index layer and 1 layer of low-index layer, preferably on the interarea of transparent base 12 successively Antireflection layer obtained from high refractive index layer, low-index layer is laminated.Low comprising 2 layers or more high refractive index layers and 2 layers or more In the case where the composition of index layer, preferably according to the side that is laminated of sequence alternate ground of high refractive index layer, low-index layer Formula.
In order to improve reflection preventing ability, laminated body obtained from preferably multiple layers are laminated for antireflection layer.The layer Stack such as 2 layers or more and 8 layers of laminated body below, more preferably 2 layers or more and 6 layers of stacking below preferably in terms of whole Body, further preferably 2 layers or more and 4 layers of laminated body below.As described above, laminated body herein is preferably by high refractive index Laminated body obtained from layer is alternately laminated with low-index layer.The number of plies of high refractive index layer and low-index layer it is total preferably Within the above range.Can also in the range of not damaging optical characteristics adding layers.For example, in order to prevent from glass matrix Na diffusion, can be inserted into SiO between glass and the 1st layer2Layer.
The thickness of high refractive index layer and the thickness of low-index layer can be adjusted suitably.
Constitute high refractive index layer, the material of low-index layer is not particularly limited, it may be considered that required antireflective Can degree, productivity etc. and select.
As the material for constituting high refractive index layer, such as niobium oxide (Nb can be enumerated2O5), titanium oxide (TiO2), zirconium oxide (ZrO2), tantalum oxide (Ta2O5), aluminium oxide (Al2O3), silicon nitride (Si3N4) etc..It can it is preferable to use in these materials 1 kind or more.
As the material for constituting low-index layer, silica can be enumerated (in particular, silica SiO2), comprising Si with The material of the mixed oxide of Sn, the material of mixed oxide comprising Si and Zr, mixed oxide comprising Si and Al material Material etc..It can it is preferable to use one or more of selected from these materials.
From the viewpoint of productivity, refractive index, preferably following composition：High refractive index layer be comprising selected from niobium oxide, The layer of a kind of material in tantalum oxide, silicon nitride, low-index layer are the layer comprising silica.
It forms the method for constituting each layer of antireflection layer to be not particularly limited, various methods can be used.For example, can make With vacuum vapour deposition, Assisted by Ion Beam vapour deposition method, ion plating method, sputtering method, plasma CVD method etc..Among those methods, By using sputtering method, fine and close and high durability layer can be formed, thus preferably.Particularly preferred pulsed sputter method, AC sputtering The sputtering methods such as method, digital sputtering method.
For example, in the case where pulsed sputter method, in the mixed gas gas of non-active gas (not active ガ ス) and oxygen In the chamber of atmosphere, the transparent bases 12 such as configuration glass plate, and target is selected in the way of forming desired composition.At this point, chamber The gaseous species of indoor non-active gas are not particularly limited, and the various non-active gas such as argon gas, helium can be used.
It is not particularly limited by the indoor pressure of chamber that the mixed gas of non-active gas and oxygen generates, but by setting It is set to 0.5Pa range below, is easy to adjust the surface roughness for being formed by layer into preferred range.
The lower limit value of the indoor pressure of chamber generated by the mixed gas of non-active gas and oxygen is not particularly limited, example It is such as preferably 0.1Pa or more.
In the case where forming high refractive index layer and low-index layer by pulsed sputter method, the adjusting of the thickness of each layer can To be carried out for example, by the adjusting of discharge power, the adjusting of time for forming each layer etc..
(stain-proofing layer)
It is preferred that stain-proofing layer is arranged on the interarea of transparent base 12 as functional layer.When stain-proofing layer is arranged, it is easy to remove attached In the spot (fingerprint etc. of people) of transparent base 12.For stain-proofing layer, in order to give full play to its function, preferably constitute The layer of the outmost surface of functional layer.
As the forming method of stain-proofing layer, vacuum vapour deposition can be used, Assisted by Ion Beam vapour deposition method, ion plating method, splash The dry methods such as method, plasma CVD method are penetrated, in the damp process such as spin-coating method, dip coating, the tape casting, slit coating method, spray-on process Any method.From the viewpoint of marresistance, preferred dry method.
About the constituent material of stain-proofing layer, can from can assign soil resistance, water repellency, oil repellent material in suitably select It selects.Specifically, fluorine-containing organic silicon compound can be enumerated.For fluorine-containing organic silicon compound, as long as can assign anti- Dirt, water repellency and oil repellent, so that it may be not particularly limited using.
As fluorine-containing organic silicon compound, such as can it is preferable to use have selected from by multi-fluoro polyether base, polyfluoro alkylidene The organo-silicon compound of one or more of the group constituted with Polyfluoroalkyl group.Multi-fluoro polyether base refers to polyfluoro alkylidene The bivalent group of structure obtained from being alternately bonded with etheric oxygen atom.
As with selected from one or more of the group being made of multi-fluoro polyether base, polyfluoro alkylidene and perfluoroalkyl group Fluorine-containing organic silicon compound commercially available product, such as (can be quotient it is preferable to use KP-801, KY-178, KY-130, KY-185 The name of an article, the manufacture of chemical company of SHIN-ETSU HANTOTAI), OPTOOL DSX and OPTOOL AES (being trade name, big King Company's manufacture), S550 (trade name, the manufacture of Asahi Glass company) etc..
For fluorine-containing organic silicon compound, in order to inhibit by with deteriorated caused by the reacting of the moisture in atmosphere Deng, it usually mixes and saves with fluoride solvent equal solvent, but in use, sometimes to institute in the state of comprising these solvents The durability etc. of obtained stain-proofing layer causes adverse effect.
Therefore, in the case where forming stain-proofing layer using vacuum vapour deposition according to subsequent steps, it is preferable to use heating The fluorine-containing organic silicon compound that solvent removes processing has been carried out before being heated in container in advance.
Herein, it as the solvent used when saving above-mentioned fluorine-containing organic silicon compound, can enumerate for example：Polyfluoro oneself Alkane, dual-trifluoromethyl benzene (C6H4(CF3)2), hydrogen perfluoroalkyl polyether, HFE7200/7100 (trade name, Sumitomo 3M company manufacture, HFE7200 is by formula C4F9OC2H5It indicates, HFE7100 is by formula C4F9OCH3Indicate) etc..For example, the solution of fluorine-containing organic silicon compound Contained in the concentration of solvent be preferably 1 mole of % hereinafter, more preferably 0.2 mole of % or less.Particularly preferred use does not include The fluorine-containing organic silicon compound of solvent.
About the processing for removing solvent from the solution of the fluorine-containing organic silicon compound comprising above-mentioned fluoride solvent, for example, It can implement and the container to the solution equipped with fluorine-containing organic silicon compound vacuumizes.About the time vacuumized, Amount according to the exhaust capacity of exhaust line, vacuum pump etc., solution etc. and change, because such as 10 can be carried out without limiting Hour or more vacuumize.
In the case where forming the stain-proofing layer comprising above-mentioned fluorine-containing organic silicon compound, it is preferable to use vacuum vapour deposition.? In the case where using vacuum vapour deposition, the removing processing of above-mentioned solvent can carry out in the following manner：It is antifouling to being used to form The solution of fluorine-containing organic silicon compound is imported in the heating container of the film formation device of layer, then before being heated up at room temperature It is vacuumized to heating in container.The progress solvent such as evaporator can also be advanced with before importing in heating container to remove It goes.
Compared with wrapping solvent-laden fluorine-containing organic silicon compound, poor or the containing not comprising solvent of above-mentioned solvent Fluorine organo-silicon compound are easy to deteriorate due to contacting with atmosphere.It is therefore preferable that solvent content it is few (or do not include it is molten Agent) the preservation container of fluorine-containing organic silicon compound using using the non-active gas such as nitrogen to replaced in container, it is closed Container afterwards, and the exposure duration of shortening in an atmosphere when being operated.
Specifically, it is preferable that fluorine-containing organic silicon compound is imported adding for film formation device immediately after it will save container Kaifeng In heat container.It moreover, after importing fluorine-containing organic silicon compound, will preferably be vacuumized in heating container, or utilize nitrogen, dilute There are the non-active gas such as gas to be replaced, to remove atmosphere (air) contained in heating container.More preferably for example save Container, by connecting with valvular pipeline, enables to hold in the case where not contacting with atmosphere from preservation with heating container Device (storage container) imports in the heating container of film formation device.
Moreover, preferably being vacuumized in by container or sharp after importing fluorine-containing organic silicon compound in heating container The heating for film forming is immediately begun to after being replaced with non-active gas.
The thickness of stain-proofing layer is preferably generally 2nm~20nm, more preferably 2nm~15nm, and further preferably 2nm~ 10nm。
The manufacturing method of < covering member>
The manufacturing method of covering member 11 is not particularly limited, and can enumerate the method for example comprised the following steps：Prepare Transparent base 12 with the 1st interarea 12a and the 2nd interarea 12b；Preparation is attached with fluorochemical (not shown) in one side Matrix (not shown) is used in transfer；Make the fluorochemical that is attached in the 1st interarea 12a and transfer matrix of transparent base 12 Face (hereinafter also referred to as " transfer surface ") contact is led to so that fluorochemical is transferred on the 1st interarea 12a of transparent base 12 The transfer is crossed, is attached to the compound comprising F atom on the 1st interarea 12a, and the contact angle of the 1st interarea 12a is adjusted to 50 ° or less.
As the manufacturing method of covering member 11, the method etc. that can also be listed below：Make the 1st interarea of transparent base 12 The surface of 12a and the fluorochemical layer on transfer matrix face in the state of separating predetermined distance (for example, 1mm~10mm) Opposite, and stand 1 hour~48 hours.
From the value of the easy contact angle for adjusting the 1st interarea 12a and the viewpoint for the adhesion amount for being easy to control fluorochemical Consider, the preferably above-mentioned method using transfer of the manufacturing method of covering member 11.
In at least one side of the 1st interarea 12a or the 2nd interarea 12b of transparent base 12, above-mentioned side is formed as needed Frame portion 132 or functional layer.
In the case where transparent base 12 is glass plate, transfer is preferably also glass plate with matrix.The transfer thickness of matrix Degree is not particularly limited, but the size of transfer matrix is preferably identical as transparent base 12 or is greater than transparent base 12.
The fluorochemical being attached on the transfer surface of transfer matrix is preferably the stratiform with a degree of thickness.
The fluorochemical (hereinafter also referred to as " transfer use fluorochemical layer ") of stratiform preferably with monomolecular thickness Degree is formed in the state on transfer matrix compared to enough amounts.
Transfer is formed with fluorochemical layer according to the step same as the stain-proofing layer of covering member 11.But transfer is used The thickness of fluorochemical layer is preferably than the antifouling thickness of covering member 11, specifically, for example, 50nm~180nm, preferably For 60nm~170nm.
Transfer can not be the continuous pantostrat on the interarea direction of transfer matrix with fluorochemical layer, can be Discontinuity layer (interrupted layer (Inter owes Layer)).
It constitutes in the fluorochemical (such as fluorine-containing organic silicon compound) of transfer fluorochemical layer, pass through reaction The fluorochemical that the transparent bases 12 such as (such as silane coupled reaction) and glass plate are chemically bonded securely be normally only with The molecule that the transparent bases such as glass plate 12 contact.Therefore, (fluorine-containing in molecule present on the molecule contacted with transparent base 12 Chain) only physically assemble, it is easy to dissociate, so as to be transferred on other components.
The transfer surface of the 1st interarea 12a (could be formed with frame portion 132) and transfer matrix that make transparent base 12 connect Touching, after the stipulated time, the two is removed.It will be attached to the fluorochemical on transfer matrix in this way (transfer fluorochemical layer) is transferred on the 1st interarea 12a of transparent base 12.
At this point, the time of contact (also referred to as " transfer time ") of transparent base 12 and transfer matrix is preferably 0.5 minute More than and less than 60 minutes, more preferably 0.5 minute or more and 30 minutes hereinafter, further preferably 0.5 minute or more and 15 Minute or less.
Embodiment
Hereinafter, specifically describing embodiments of the present invention using embodiment etc..But the present invention is not limited to below Example.Example 1~6 is embodiment, and example 7~8 is comparative example.
< example 1>
The covering member of example 1 is produced according to mode described below.
《Prepare transparent base (glass plate)》
In each case, use glass plate as the transparent base for being used to form covering member.
More specifically, firstly, preparing Dragontrail (trade name, the Asahi Glass public affairs as chemical strengthening glass plate Department's manufacture, thickness 1.3mm).
It is cut into the size of 100mm × 100mm, then carries out chemical intensification treatment.That is, by chemical strengthening glass For plate dipping 2 hours in the potassium nitrate (fuse salt) for being heated to 450 DEG C and melting, the then pull-up from fuse salt is slow with 1 hour Slow cool down is to room temperature.Obtained in this way bearing stress (CS) be 730MPa, stress layer depth (DOL) be 30 μm Implement the glass plate of chemical intensification treatment.
《The formation of frame portion》
In the outer periphery portion of the 1st interarea of the glass plate for being used to form covering member, formd by silk-screen printing The frame portion of outer frame-shaped.
Specifically, according to following step, on four sides in the outer periphery portion of the 1st interarea of glass plate, with 10mm wide Black surround shape implement printing, so as to form frame portion.
Firstly, using screen process press, the thickness for being 5 μm by black ink coating, then kept for 10 minutes at 150 DEG C and It makes it dry, so as to form the 1st printing layer.Then, in the 1st printing layer, according to step same as described above, by black ink Then the thickness that water coating is 5 μm is kept for 40 minutes at 150 DEG C and is made it dry, so as to form the 2nd printing layer.With in this way Mode form the 1st printing layer and the 2nd printing layer are laminated obtained from frame portion.
As black ink, use HFGV3RX01 (trade name, the manufacture of Seiko company).
《The formation of stain-proofing layer》
According to following step, stain-proofing layer is formd on the 2nd interarea of the glass plate for being used to form covering member.
Firstly, the solution as the fluorine-containing organic silicon compound of the material of stain-proofing layer is imported in heating container.Then, sharp It will be heated in container with vacuum pump and deaerate 10 hours or more to remove the solvent in solution, be made into stain-proofing layer formation group Close object.
In example 1, as the material of stain-proofing layer, use KY185 (trade name, the manufacture of chemical company of SHIN-ETSU HANTOTAI).
Then, the heating container equipped with stain-proofing layer formation composition is heated to 270 DEG C, after reaching 270 DEG C, kept The state 10 minutes until temperature stabilization.Then, glass plate is set in vacuum chamber, is then formed from equipped with stain-proofing layer Stain-proofing layer formation composition is supplied to the 2nd interarea of glass plate with the nozzle of the heating container connection of composition, to be formed Stain-proofing layer.
While using the thickness for being set to the indoor quartz oscillator monitor measurement stain-proofing layer of vacuum chamber, shape At stain-proofing layer until the thickness of stain-proofing layer reaches 4nm.
Then, it will be set on hot plate in a manner of upward from the glass plate taken out in vacuum chamber by stain-proofing layer, in atmosphere In carried out at 150 DEG C heat treatment 60 minutes.
Stain-proofing layer is formd in the entire surface on the 2nd interarea of glass plate in this way.
《Transfer》
Using transfer matrix, transfer is transferred to the of the glass plate for being used to form covering member with fluorochemical layer On 1 interarea (interarea for being formed with the side of frame portion).
Specifically, firstly, preparing another 1 and the glass that is used to form covering member with identical size (100mm × 100mm) The identical glass plate of glass plate, as transfer matrix.On an interarea (transfer surface) of transfer matrix, according to it is upper The identical step of the step of stating record in " formation of stain-proofing layer ", forms transfer fluorochemical layer.Transfer is with containing fluorination Close nitride layer with a thickness of 70nm.
Then, be used in the 1st interarea (interarea for being formed with the side of frame portion) of the glass plate to form covering member with The surface (face with the face opposite side of transfer matrix side) for being formed in the transfer fluorochemical layer of the transfer on matrix connects Touching.The time (transfer time) of the contact is set as 10 minutes.After transfer, the two is removed.
< example 2>
Antireflection layer is formed on the 2nd interarea of the glass plate for being used to form covering member, is formed on the antireflection layer Stain-proofing layer, and the thickness of transfer fluorochemical layer is changed to 150nm from 70nm, in addition to this, according to same as example 1 The step of, make the covering member of example 2.
《The formation of antireflection layer》
It is formed in the entire surface of the 2nd interarea of glass plate and high refractive index layer and low-index layer is alternately laminated and obtained The antireflection layer of the structure arrived.
More specifically, in example 2, the high refractive index layer comprising niobium oxide and the low folding comprising silica are sequentially formed Rate layer is penetrated, the antireflection layer for being 2 layers so as to form stacking number.About the thickness of each layer, the 1st layer of high refractive index layer is 13nm, the 2nd layer of low-index layer are 120nm.
Hereinafter, recording the forming method of high refractive index layer and low-index layer respectively.
(formation of high refractive index layer)
In vacuum chamber, the gaseous mixture for being mixed with oxygen in such a way that oxygen reaches 10 volume % in argon gas is being imported While body, in pressure 0.3Pa, frequency 20kHz, power density 3.8W/cm2, under conditions of 5 microsecond of reverse impulse width, make With niobium oxide target (trade name：NBO target, the manufacture of AGC ceramics Co., Ltd.) pulsed sputter is carried out, thus to be formed in glass plate The high refractive index layer comprising niobium oxide is formd in the entire surface in the face of high refractive index layer.
(formation of low-index layer)
In vacuum chamber, the gaseous mixture for being mixed with oxygen in such a way that oxygen reaches 40 volume % in argon gas is being imported While body, in pressure 0.3Pa, frequency number 20kHz, power density 3.8W/cm2, under conditions of 5 microsecond of reverse impulse width, Pulsed sputter is carried out using silicon target, to form in the entire surface in the face of low-index layer to be formed comprising the low of silica Index layer.
< example 3>
Antireflection layer is formed on the 2nd interarea of the glass plate for being used to form covering member, is formed on the antireflection layer Stain-proofing layer and the material of transfer fluorochemical layer are changed to OPTOOL DSX (trade name, great Jin from KY185 by stain-proofing layer Company's manufacture), and transfer time was changed to 1 minute from 10 minutes, in addition to this, according to the step same as example 1, production The covering member of example 3.Antireflection layer is formd according to the step same as example 2.
< example 4>
Antireflection layer is formed on the 2nd interarea of the glass plate for being used to form covering member, is formed on the antireflection layer Stain-proofing layer and the material of transfer fluorochemical layer are changed to S550 (trade name, Asahi Glass company from KY185 by stain-proofing layer Manufacture), and transfer time was changed to 1 minute from 10 minutes, in addition to this, according to the step same as example 1, make example 4 covering member.Antireflection layer is formd according to the step same as example 2.
< example 5>
Contact transfer fluorochemical layer and the 1st interarea of the glass plate for being used to form covering member, except this with Outside, according to the step same as example 1, the covering member of example 5 has been made.
Specifically, in example 5, firstly, foring transfer on transfer surface of the transfer with matrix in the same manner as example 1 and using Fluorochemical layer (thickness：70nm).Then, the 1st interarea for being used in the glass plate to form covering member (is formed with frame portion Side interarea) with the surface of transfer fluorochemical layer that is formed on transfer matrix (with transfer matrix side The face of face opposite side) it is face-to-face in the state of separating 5mm, and stand 24 hours.
< example 6>
Antireflection layer is formed on the 2nd interarea of the glass plate for being used to form covering member, is formed on the antireflection layer Stain-proofing layer, and transfer time was changed to 60 minutes from 10 minutes, in addition to this, according to the step same as example 1, production The covering member of example 6.Antireflection layer is formd according to the step same as example 2.
< example 7>
The thickness of transfer fluorochemical layer is changed to 200nm from 70nm, and transfer time was become from 10 minutes More 60 minutes, in addition to this, according to the step same as example 1, the covering member of example 7 is made.
< example 8>
Transfer is not transferred to fluorochemical layer on the 1st interarea for being used to form the glass plate of covering member.As Substitution pastes the polyamides Asia for being coated with polysiloxane-based adhesive on the 1st interarea of the glass plate for being used to form covering member Amine adhesive tape (manufactured by Kapton tape 650S, the production of temple ridge), is removed immediately after.In addition to this, according to same as example 1 Step has made the covering member of example 8.
< contact angle>
The contact angle of 1st interarea of glass plate is found out in the following manner.
Firstly, the region of the frame portion for not printing frame-shaped on the 1st interarea of glass plate is carried out 4 × 4 equal parts.Measurement exists Carry out connecing for the water at line (3+3) mutual intersection point (adding up to 9 points) that equal timesharing are drawn on the 2nd interarea of glass plate Feeler.Specifically, at 23 DEG C of measuring temperature, using contact angle meter (consonance interface science company manufactures, PCA-11) to drop The contact angle after 5 μ L pure water after 5 seconds is added to be measured.Using the average value of the contact angle of total 9 points determined as glass The contact angle of 1st interarea of plate.
< atomic ratio (F/Si)>
The atomic ratio (F/Si) of 1st interarea of glass plate is found out in the following manner.
Firstly, for the region of the frame portion for not printing frame-shaped on the 1st interarea of glass plate, x-ray photoelectron is used Spectroscopy device (Japan Electronics Corporation's manufacture, JPS-9000MC), finds out F atom concentration (unit：Atom %) and Si atom it is dense Spend (unit：Atom %).The ratio between calculated F atom concentration and Si atomic concentration is former as the F in the 1st interarea of glass plate Ratio of number (F/Si) of the quantity of son relative to Si atom.
More specifically, it is surveyed under conditions of the radiographic source of X-ray is MgK alpha ray, acceleration voltage 12kV, 25mA It is fixed.It is that 6mm φ is measured with spot diameter.It is set as the inclination of not sample.It is logical can be 50eV, measure step-length and be 0.5eV, residence time are 100 milliseconds, scanning times are measured under conditions of being 30 times.For measurement result, obtained Then the bonded energy peak obtained is calculated using Shirley method background correction according to the peak intensity of F1s peak intensity and Si2p3/2 The atomic concentration ratio of F/Si.
< evaluation>
For the covering member of each example, evaluated in the following manner.
《The production of test body》
Prepare soda-lime glass (plate thickness：0.7mm, size：100mm × 100mm), as display panel substitute.
It is main by the 1st of the glass plate of the covering member in each example the using adhesive layer (Ba Chuan Zhi Zhisuo company manufactures, MK64) Face (including frame portion) fits in an interarea of display panel substitute.Test body has been made in this way.It is being bonded When, use laminating apparatus (manufacture of Climb Products company).
For each example, 300 test body have been made.
《Bubble frothing percentage》
For each test body, it is thus identified that whether produce the gas of 30 μm or more of size between glass plate and adhesive layer Bubble.
For each example, find out produce 30 μm or more bubble test body number of the number relative to total Test body The ratio (%) of (300).
The ratio is smaller, then can be evaluated as the bubble being more able to suppress between glass plate and adhesive layer generation, the ratio Preferably 6% or less.
Above result is summarized in following table 1." material of stain-proofing layer " in following table 1, which also refers to, " to be transferred with fluorine-containing The material of compound layer ".
Table 1
※ 1 replaces transfer, faces the surface of the 1st interarea and transfer fluorochemical layer in the state of separating 5mm Face, and stand 24 hours.
※ 2 replaces transfer, contacts polysiloxane-based adhesive with the 1st interarea.
As shown in Table 1 above, the compound (atomic ratio (F/Si) comprising F atom is attached on the 1st interarea of glass plate Greater than 0) and the contact angle of the 1st interarea be 50 ° of examples 1~6 below, compared with the example 7~8 for being unsatisfactory for these conditions, inhibit Bubble between glass plate and adhesive layer generates.
Example 1~4 of the atomic ratio (F/Si) in the range of 0.005~0.13, outside this range with atomic ratio (F/Si) Example 5~6 compare, it is suppressed that bubble between glass plate and adhesive layer generates.
It, should compared with the atomic ratio (F/Si) of the 1st interarea of glass plate is 0.012 example 3 when example 1~4 is compared The example 1,2 and 4 that atomic ratio (F/Si) is 0.023~0.075 further suppresses bubble generation.It should be noted that in example 7 In, it is believed that greatly due to atomic ratio (F/Si), the region that surface can be low is more, thus the generation rate height of bubble instead.
The application is used as based on Japanese patent application 2017-102481 filed on May 24th, 2017, content with reference to simultaneously Enter in the application.

Claims (19)

1. a kind of covering member is the covering member comprising transparent base, wherein
The transparent base has the with the 1st opposite interarea of coating The lid component and the side opposite with the 1st interarea 2 interareas,
It is attached with the compound comprising F atom on the 1st interarea,
The contact angle of 1st interarea is 50 ° or less.
2. covering member as described in claim 1, wherein
In 1st interarea, F atom quantity is 0.005~0.13 relative to the ratio of number (F/Si) of Si atom.
3. covering member as claimed in claim 2, wherein
It is described than (F/Si) be 0.015~0.1.
4. covering member according to any one of claims 1 to 3, wherein
The contact angle is 25 °~45 °.
5. covering member as claimed in claim 4, wherein
The contact angle is 28 °~40 °.
6. such as covering member according to any one of claims 1 to 5, wherein
The transparent base with a thickness of 0.1mm or more and 5mm or less.
7. such as covering member according to any one of claims 1 to 6, wherein
The compound comprising F atom is organic compound.
8. such as covering member according to any one of claims 1 to 7, wherein
The transparent base is glass plate.
9. covering member as claimed in claim 8, wherein
The glass plate is chemically reinforced glass plate.
10. covering member as claimed in claim 8 or claim 9, wherein
The compression (CS) of any one interarea of the glass plate is 400MPa or more and 1200MPa or less.
11. the covering member as described in any one of claim 8~10, wherein
The stress layer depth (DOL) of any one interarea of the glass plate is 15 μm or more and 50 μm or less.
12. the covering member as described in any one of claim 1~11, wherein
There is frame portion on the 1st interarea.
13. the covering member as described in any one of claim 1~12, wherein
The covering member is also equipped with functional layer, and the functional layer configuration is on the 2nd interarea of the transparent base.
14. covering member as claimed in claim 13, wherein
The functional layer includes stain-proofing layer.
15. covering member as claimed in claim 14, wherein
The stain-proofing layer with a thickness of 2nm or more and 20nm or less.
16. the covering member as described in any one of claim 13~15, wherein
The functional layer includes antireflection layer.
17. a kind of manufacturing method of covering member, the method for the covering member for manufacture comprising transparent base, wherein described Manufacturing method comprises the following steps：
Prepare transparent base, the transparent base have 1st interarea opposite with coating The lid component and with the 1st interarea 2nd interarea of opposite side,
Preparing transfer matrix, the transfer is attached with fluorochemical with matrix in one side,
Connect the 1st interarea of the transparent base with the face for being attached with the fluorochemical in the transfer matrix Touching, so that the fluorochemical is transferred on the 1st interarea of the transparent base,
By the transfer, it is attached to the compound comprising F atom on the 1st interarea, and by the contact of the 1st interarea Angle is adjusted to 50 ° or less.
18. the manufacturing method of covering member as claimed in claim 17, wherein
By the transfer, the contact angle of the 1st interarea is adjusted to 25 °~45 °, and by the 1st interarea, F The quantity of atom is adjusted to 0.005~0.13 relative to the ratio of number (F/Si) of Si atom.
19. a kind of display device is to have covering member described in any one of claim 1~16, adhesive layer and show Show the display device of panel, wherein
The covering member with the 1st interarea of the transparent base it is opposite with the display panel direction, via described Adhesive layer is bonded with the display panel.
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TWI757490B (en) 2022-03-11
KR20180128859A (en) 2018-12-04

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