CN103492173B - Laminate, method for producing same, and use of same - Google Patents

Laminate, method for producing same, and use of same Download PDF

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Publication number
CN103492173B
CN103492173B CN201280019767.8A CN201280019767A CN103492173B CN 103492173 B CN103492173 B CN 103492173B CN 201280019767 A CN201280019767 A CN 201280019767A CN 103492173 B CN103492173 B CN 103492173B
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CN
China
Prior art keywords
inorganic insulating
insulating membrane
glass substrate
resin bed
gripper shoe
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Expired - Fee Related
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CN201280019767.8A
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Chinese (zh)
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CN103492173A (en
Inventor
江畑研一
松山祥孝
内田大辅
川原健吾
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AGC Inc
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Asahi Glass Co Ltd
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    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • B32B17/10—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 synthetic resin
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • B32B2383/00—Polysiloxanes

Abstract

The present invention relates to a laminate which comprises a layer of a supporting plate, a resin layer, and a layer of a glass substrate with an inorganic insulating film, sequentially in this order, with the inorganic insulating film of the glass substrate with an inorganic insulating film being in contact with the resin layer. The glass substrate with an inorganic insulating film has an inorganic insulating film, which contains an oxide, nitride or oxynitride containing at least one element selected from the group consisting of silicon and aluminum, on one surface of a glass substrate. The total content of alkali metal atoms and alkaline earth metal atoms in a surface of the inorganic insulating film, said surface being in contact with the resin layer, is 0.5 at% or less. The peel strength at the interface between the layer of the supporting plate and the resin layer is higher than the peel strength at the interface between the resin layer and the inorganic insulating film. The present invention also relates to: a display device panel with a supporting plate, which comprises the laminate and a display device member that is provided on the glass substrate surface of the laminate; a display device panel which is obtained by removing the supporting plate with the resin layer from the display device panel with a supporting plate, using the interface between the inorganic insulating film and the resin layer as a releasing surface; and a display device which has the display device panel.

Description

Duplexer, its manufacture method and purposes
Technical field
The present invention relates to duplexer, the manufacture method of duplexer, display unit panel, display unit panel and the display unit with gripper shoe.
Background technology
In recent years, advance the slimming of the devices (electronic equipment) such as solar cell (PV), liquid crystal panel (LCD), organic EL panel (OLED), lightweight, and advance the thin plate of the substrate used in these devices.When the intensity of substrate is not enough due to thin plate, in the manufacturing process of device, the operability of substrate reduces.
Therefore, extensively adopt following method: form device component (such as thin film transistor (TFT)) on the substrate thicker than final thickness after, make substrate thin plate by chemical etching process all the time.But, in the method, such as, by the thickness of a plate base from 0.7mm thin plate to 0.2mm, 0.1mm, eliminating by the major part of etching solution by original baseplate material, is therefore not preferred from the viewpoint such as productivity ratio, raw-material service efficiency.
In addition, utilize in the thin plate method of the substrate of chemical etching above-mentioned, when substrate surface exists fine cut, be that starting point forms fine pit (etching indenture) sometimes with cut due to etch processes, thus form optical defect.
Recently, in order to tackle above-mentioned problem, propose following method: prepare glass sheet substrate and the stacked and duplexer obtained of reinforcement plate, after the glass sheet substrate of duplexer is formed device component, the method (such as, referenced patent document 1) of reinforcement plate is separated from glass sheet substrate.Reinforcement plate has gripper shoe and is fixed to the resin bed in this gripper shoe, and resin bed and glass sheet substrate adhere in the mode that can peel off.The resin bed of duplexer and the interface of glass sheet substrate is stripped, the reinforcement plate separated from glass sheet substrate, can stacked with new glass sheet substrate, recycle with the form of duplexer.
Prior art document
Patent document
Patent document 1:WO No. 2007/018028 pamphlet
Summary of the invention
Invent problem to be solved
But in the duplexer of above-mentioned existing formation, when being separated from glass sheet substrate by reinforcement plate, a part for resin bed can be attached in the release surface as the glass sheet substrate of goods side sometimes.After particularly under the high temperature conditions duplexer being heated, understand the attachment of a part to the release surface of the glass sheet substrate as goods side of frequent generation tree lipid layer, its result, there is the worry causing yield rate to reduce.
In addition, there is the situation glass sheet substrate release surface after to separation being implemented further process, expect clean surface.
But, in the above-mentioned duplexer in the past formed, the part of resin bed composition is attached to the release surface of the glass sheet substrate after separation, even if for by utilizing the purifying process of the washing that uses solvent etc. etc. to remove this attachment, also cannot remove level desired to practicality.
In addition, in the duplexer in the past formed, in the release surface of glass sheet substrate after isolation, during operation when peeling off or after peeling off, producing sometimes break (crackle) etc. of glass, thus sometimes causing the reduction of yield rate.
The present invention makes in view of above-mentioned problem, its object is to the manufacture method that a kind of duplexer and duplexer are provided, even if this duplexer is after enforcement high-temperature heating treatment, also resin bed can be suppressed to the attachment of the release surface of glass substrate when resin bed and glass substrate being peeled off, and can, by implementing purifying process to keep the cleanliness of the release surface of the glass substrate after being separated, can suppress in addition to crack in the release surface of glass substrate.
In addition, the object of the present invention is to provide the display unit panel with gripper shoe comprising this duplexer, the display unit panel using the display unit panel with gripper shoe to be formed and display unit.
Solve the means of problem
The present inventor has carried out research extensively and profoundly to solve above-mentioned problem, and completes the present invention.
Namely, to achieve these goals, the 1st aspect of the present invention is a kind of duplexer, it has the layer of gripper shoe successively, the layer of resin bed and the glass substrate with inorganic insulating membrane, and should contact with this resin bed with the inorganic insulating membrane of the glass substrate of inorganic insulating membrane, wherein, should with in the glass substrate of inorganic insulating membrane, at the one side of glass substrate, there is inorganic insulating membrane, this inorganic insulating membrane contains the oxide of at least one in the group comprising and be selected from and be made up of Silicified breccias, nitride or oxynitride, in the face contacted with this resin bed of this inorganic insulating membrane, the atom of alkali and alkaline earth metal ions adds up to content to be 0.5 below atom %, the peel strength at the interface of the layer of this gripper shoe and this resin bed is higher than the peel strength at the interface of this resin bed and this inorganic insulating membrane.
In first method, this inorganic insulating membrane preferably comprises the film of silica, silicon nitride, silicon oxynitride or aluminium oxide.
In first method, the surface roughness (Ra) in the face contacted with this resin bed of this inorganic insulating membrane is preferably less than 30nm.
In first method, the thickness of this inorganic insulating membrane is preferably 5 ~ 5000nm.
In first method, the thickness of this glass substrate is preferably 0.03 ~ 0.8mm.
In first method, the resin of this resin bed is preferably polyorganosiloxane resin.
In first method, this polyorganosiloxane resin is preferably the reaction solidfied material of olefinic organic based polysiloxane and organic hydrogen polysiloxanes.
In first method, the thickness of this resin bed is preferably 1 ~ 100 μm.
In first method, this gripper shoe is preferably glass plate.
The 2nd aspect of the present invention is a kind of manufacture method of duplexer, for the manufacture of the layer successively with gripper shoe, the duplexer of resin bed and the layer with the glass substrate of inorganic insulating membrane, wherein, prepare the glass substrate with inorganic insulating membrane, inorganic insulating membrane should be had at the one side of glass substrate with the glass substrate of inorganic insulating membrane, this inorganic insulating membrane contains the oxide of at least one in the group comprising and be selected from and be made up of Silicified breccias, nitride or oxynitride, in the face contacted with this resin bed of this inorganic insulating membrane, the atom of alkali and alkaline earth metal ions adds up to content to be 0.5 below atom %, prepare the gripper shoe with resin bed, this resin bed of the one side being fixed to this gripper shoe should be had with the gripper shoe of resin bed, and the surface of exposing of this resin bed has non-tack, using this face with the inorganic insulating membrane of the glass substrate of inorganic insulating membrane, with this resin layer surface with the gripper shoe of resin bed as lamination surface, by stacked with the gripper shoe of resin bed to this glass substrate with inorganic insulating membrane and this.
In second method, olefinic organic based polysiloxane and organic hydrogen polysiloxanes preferably should be had reacts in this gripper shoe with gripper shoe of resin bed and solidify and the gripper shoe of the layer of polyorganosiloxane resin that obtains.
The 3rd aspect of the present invention is a kind of display unit panel with gripper shoe, and it has the duplexer of first method of the present invention and is arranged on the display device component of glass baseplate surface of this duplexer.
The 4th aspect of the present invention is a kind of display unit panel, and the gripper shoe with resin bed to be peeled off using the interface of this inorganic insulating membrane and this resin bed as release surface by the display unit panel with gripper shoe from Third Way of the present invention and removed and formed by it.
The 5th aspect of the present invention is a kind of display unit, has the display unit panel of fourth way of the present invention.
Invention effect
According to the present invention, the manufacture method of a kind of duplexer and duplexer can be provided, even if described duplexer is after being implemented high-temperature heating treatment, also can suppress when resin bed and glass substrate are peeled off release surface from the resin of resin bed to glass substrate side (, the surface of inorganic insulating membrane) attachment, and can by implementing purifying process to keep the cleanliness of release surface of the glass substrate side after being separated, the chemical-resistant of the release surface of glass substrate side can be improved in addition and suppress the generation of crackle.
In addition, according to the present invention, the display unit panel with gripper shoe of this duplexer, the display unit panel using the display unit panel with gripper shoe to be formed and display unit can be contained by providing package.
Accompanying drawing explanation
Fig. 1 is the schematic cross sectional view of an embodiment of duplexer of the present invention.
Fig. 2 is the schematic cross sectional view of an embodiment of the display unit panel with gripper shoe of the present invention.
Detailed description of the invention
Below, be described for implementing mode of the present invention with reference to accompanying drawing, but the present invention is not limited to following embodiment, when not departing from the scope of the present invention, can add various distortion and displacement to following embodiment.
It should be noted that, in the present invention, for the peel strength at the layer of gripper shoe and the interface of resin bed higher than the peel strength at the interface of resin bed and inorganic insulating membrane, be referred to as resin bed hereinafter and inorganic insulating membrane adheres in the mode that can peel off, gripper shoe and resin bed are fixed.
In the present invention, atom % refers to the ratio of each atom relative to total atom number.
Fig. 1 is the schematic cross sectional view of an example of duplexer of the present invention.
As shown in Figure 1, duplexer 10 be the layer of glass substrate 24 with inorganic insulating membrane, the layer of gripper shoe 31 and be present in the duplexer of the resin bed 32 between them.
The inorganic insulating membrane 22 that glass substrate 24 with inorganic insulating membrane has glass substrate 20 and arranges in its surface.With the layer of the glass substrate 24 of inorganic insulating membrane, the mode contacted with resin bed 32 with its inorganic insulating membrane 22 is configured on resin bed 32, and its inorganic insulating membrane 22 adheres in the mode that can peel off with the interface of resin bed 32.It should be noted that, being denoted as surface 221 by becoming the inorganic insulating membrane surface of inorganic insulating membrane 22 with the interface of resin bed 32, resin layer surface being denoted as surface 321.
In addition, about resin bed 32, one face is fixed to the layer of gripper shoe 31, and its another face (surface 321) contacts with the inorganic insulating membrane 22 of the glass substrate 24 with inorganic insulating membrane, and resin bed 32 adheres in the mode that can peel off with the interface of inorganic insulating membrane 22.Comprise the layer of gripper shoe 31 and two layer segments of resin bed 32, in the operation manufacturing the devices (electronic equipment) such as liquid crystal panel, reinforcing band has the glass substrate 24 of inorganic insulating membrane.It should be noted that, comprise the layer of gripper shoe 31 in duplexer 10 and two layer segments of resin bed 32 are called the gripper shoe (hereinafter also referred to reinforcement plate) with resin bed from the object that duplexer 10 is independent, this two layer segment in duplexer 10 is called the layer of reinforcement plate 30.In reinforcement plate 30, resin bed 32 is fixed to gripper shoe 31.
Use this duplexer 10, until the midway of the manufacturing process of device.That is, this duplexer 10 is used, until at device components such as its glass baseplate surface (that is, with second interarea 202 that there is not inorganic insulating membrane 22 of the glass substrate 24 of inorganic insulating membrane) upper formation thin film transistor (TFT)s.Then, the layer of reinforcement plate 30 is stripped in the interface of the layer with the glass substrate 24 with inorganic insulating membrane, thus the layer of the reinforcement plate 30 of duplexer 10 does not become the part forming device.The reinforcement plate 30 separated from the glass substrate 24 with inorganic insulating membrane, namely with the gripper shoe of resin bed, can be stacked with the new glass substrate 24 with inorganic insulating membrane, thus recycle with the form of duplexer 10.
Find in the present invention, by the duplexer 10 of formation contacted with resin bed 32 for inorganic insulating membrane 22, the effect expected can be obtained.
Below, each formation (glass substrate, resin bed, gripper shoe with inorganic insulating membrane) is described in detail.
< is with the glass substrate > of inorganic insulating membrane
First, the glass substrate 24 with inorganic insulating membrane is described.
The inorganic insulating membrane 22 that glass substrate 24 with inorganic insulating membrane has glass substrate 20 and arranges in its surface.Inorganic insulating membrane 22 is configured in the most surface in the glass substrate 24 of inorganic insulating membrane, makes to adhere in the mode that can peel off with resin bed 32 described later.
Below, the manufacture method of glass substrate 20, inorganic insulating membrane 22 and inorganic insulating membrane 22 is described in detail in detail.
(glass substrate)
Glass substrate 20 has inorganic insulating membrane 22 on the first interarea 201 of resin bed 32 side, with the second interarea 202 of opposition side, resin bed 32 side on form device component thus form device.At this, device component refers to component at least partially as the member of formation of display unit panel described later, that form device.As concrete example, can enumerate: thin film transistor (TFT) (TFT), colour filter (CF).As device, can illustrate: solar cell (PV), liquid crystal panel (LCD), organic EL panel (OLED) etc.
The kind of glass substrate 20 can be general glass substrate, can enumerate the glass substrate etc. of the display unit such as such as LCD, OLED.The chemical-resistant of glass substrate 20, resistance to excellent moisture permeability, and percent thermal shrinkage is low.As the index of percent thermal shrinkage, use the linear expansion coefficient that JIS R 3102 (nineteen ninety-five revision) specifies.
When the linear expansion coefficient of glass substrate 20 is large, due to manufacturing process's many heat tracings process of device, therefore easily produce various problem.Such as, when glass substrate 20 forms TFT, when being cooled by the glass substrate 20 being formed with TFT under heating, due to the thermal contraction of glass substrate 20, the position of TFT is departed from and is likely become excessive.
Glass substrate 20 is by being configured as frit melting tabular by melten glass and obtaining.This manufacturing process can be general method, such as, draws method, vertical drawing process (Off Le コ ー Le method), machinery winding-up cylinder method (ラ バ ー ス method) etc. under using float glass process, fusion method, discharge orifice.In addition, the thin especially glass substrate 20 of thickness can by being first configured as the glass heats of tabular to the temperature that can be shaped, and the means such as recycling extension carry out stretching, the method (again daraf(reciprocal of farad) (リ ド ロ ー method)) of thinning obtains.
The glass of glass substrate 20 is not particularly limited, and preferred alkali-free pyrex, pyrex, soda-lime glass, high silicon dioxide glass, other take silica as the oxide based glass of main component.As oxide based glass, the content being preferably based on the silica that oxide converts is the glass of 40 ~ 90 quality %.
As the glass of glass substrate 20, adopt kind, the matched glass of its manufacturing process with device.Such as, because the stripping of alkali metal component easily impacts liquid crystal, therefore the glass substrate of liquid crystal panel is by not forming (but, usually contain alkaline earth metal component) containing the glass (alkali-free glass) of alkali metal component in fact.So, the glass of glass substrate is suitably selected based on the kind of applied device and manufacturing process thereof.
The thickness of glass substrate 20 is not particularly limited, and from slimming and/or the light-weighted viewpoint of glass substrate 20, is generally below 0.8mm, is preferably below 0.3mm, more preferably below 0.15mm.More than 0.8mm when, the slimming of glass substrate 20 and/or light-weighted requirement cannot be met.When below 0.3mm, the flexibility that glass substrate 20 is good can be given.When below 0.15mm, glass substrate 20 can be batched as drum.In addition, from being easy to manufacture glass substrate 20, being easy to the reasons such as operation glass substrate 20, the thickness of glass substrate 20 is preferably more than 0.03mm.
It should be noted that, glass substrate 20 can comprise two-layer more than, in this case, the material forming each layer can for same material, also can be foreign material.In addition, in this case, " thickness of glass substrate 20 " represents the aggregate thickness of whole layer.
(inorganic insulating membrane)
The oxide of inorganic insulating membrane 22 containing at least one comprised in the group that is selected from and is made up of Silicified breccias, nitride or oxynitride, also can mixture containing these compounds.The oxide of preferred inorganic insulating membrane 22 containing silicon or aluminium, nitride or oxynitride also can be the mixture of these compounds.Inorganic insulating membrane 22 preferably comprise in the oxide of silicon or aluminium, nitride or oxynitride any one.According to circumstances, inorganic insulating membrane 22 also can containing the metallic atom beyond silicon atom and aluminium atom as metallic atom.Such as titanium atom, tungsten atom, tantalum atom, molybdenum atom etc. can be contained.But, as described later, preferably in fact not containing alkali metal atom and alkaline earth metal atom.
Specifically, silica (SiO can be enumerated 2), aluminium oxide (Al 2o 3), silicon nitride (Si 3n 4), aluminium nitride (AlN), silicon oxynitride (SiO xn 2-x, x is 0.1 ~ 1.9), aluminium oxynitride (Al 2o yn 3-y, y is 0.1 ~ 2.9), oxynitriding sial (Al 2-xsi xo zn 4-x, x is 0.1 ~ 1.9, z is 0.1 ~ 3.9) etc.Or, can be their mixture.
Wherein, from excellent heat resistance, resistance to well anti-thread breakage, silica (SiO is preferably enumerated 2), silicon nitride (Si 3n 4), with SiO xn 2-xshown wherein x is in silicon oxynitride, aluminium oxide (Al in 0.6 ~ 1.4 scope 2o 3).Particularly preferably crystallinity silica.
Inorganic insulating membrane 22 preferably contains above-mentioned oxide, nitride or oxynitride as main component, specifically, the content of above-mentioned oxide, nitride and oxynitride is preferably more than 98 quality % relative to inorganic insulating membrane total amount, be more preferably more than 99 quality %, be particularly preferably more than 99.999 quality %.
Inorganic insulating membrane 22 demonstrates excellent heat resistance.Therefore, even if under duplexer 10 is exposed to hot conditions, also not easily cause the chemical change of film itself, not easily between resin bed 32, produce chemical bonding, not easily produce the attachment of resin to the glass substrate 24 with inorganic insulating membrane of the resin bed 32 caused by re-separation.In addition, inorganic insulating membrane 22 itself has excellent mechanical strength, can give resistance to anti-thread breakage to glass substrate 20 surface.
Above-mentioned re-separation refers to, the peel strength at the interface of inorganic insulating membrane 22 and resin bed 32, all larger with any one in the peel strength at interface of resin bed 32 and the intensity (bulk strength) of the material of resin bed 32 itself than gripper shoe 31.When inorganic insulating membrane 22 produces re-separation with the interface of resin bed 32, the resin on the surface 321 of resin bed 32 is easily attached to the inorganic insulating membrane surface 221 of exposing, its surface easily become be difficult to purifying.Resin, to the attachment on inorganic insulating membrane surface 221, refers to that resin bed 32 entirety is attached to inorganic insulating membrane surface 221, and resin bed 32 surface 321 produce damage and a part for the resin on the surface 321 of resin bed 32 is attached to inorganic insulating membrane surface 221 etc.
The thickness of inorganic insulating membrane 22 is not particularly limited, the viewpoint of scratch resistance is maintained, preferably 5 ~ 5000nm, more preferably 10 ~ 500nm from the resin bed 32 suppressing further to be caused by re-separation to the attachment of the glass substrate 24 with inorganic insulating membrane.
Consider the glass substrate 24 with inorganic insulating membrane to be used for device application in time, inorganic insulating membrane 22 is preferably transparent.Specifically, the transmissivity under wavelength 380 ~ 780nm, be namely preferably more than 70% with the transmission of visible light of the glass substrate 24 of inorganic insulating membrane, be more preferably more than 80%.
Inorganic insulating membrane 22 is recited as individual layer in FIG, but also can be two-layer above stacked.Such as, when inorganic insulating membrane 22 is two-layer, the first inorganic insulating membrane contacted with glass substrate 20 and the second inorganic insulating membrane be arranged on the first inorganic insulating membrane can be set.When inorganic insulating membrane 22 is two-layer, the first inorganic insulating membrane can be different from the composition of the second inorganic insulating membrane.In addition, inorganic conductive film can be provided with between the first inorganic insulating membrane and the second inorganic insulating membrane or between glass substrate 20 and the first inorganic insulating membrane.
In addition, such as, the surface roughness (Ra) in the face contacted with resin bed 32 of inorganic insulating membrane 22 is in the scope being less than 30nm, and inorganic conductive film can be set to island, strip.
In addition, between glass substrate 20 and inorganic insulating membrane 22, can setting example as the alkali barrier layer preventing basic ion from spreading from glass substrate 20 to inorganic insulating membrane 22, the planarization layer making the surface planarisation of inorganic insulating membrane 22.
In the scope not damaging effect of the present invention, inorganic insulating membrane 22 can be arranged in the part on glass substrate 20 surface.Such as, inorganic insulating membrane 22 can be set to island, strip on the surface at glass substrate 20.
More specifically, the coverage rate of inorganic insulating membrane 22 on glass substrate 20 surface, from the resin bed 32 suppressing further to be caused by re-separation to the viewpoint of the attachment of the glass substrate 24 with inorganic insulating membrane, be preferably 50 ~ 100%, be more preferably 75 ~ 100%.
In duplexer 10, in the face (that is, inorganic insulating membrane surface 221) contacted with resin bed 32 of inorganic insulating membrane 22, the atom of alkali and alkaline earth metal ions adds up to content to be 0.5 below atom %, is more preferably 0.1 below atom %.Before stacked with the glass substrate 24 of inorganic insulating membrane in or after separating from duplexer 10 with in the glass substrate 24 of inorganic insulating membrane, in the surface of the side contrary with the side with glass substrate 20 of inorganic insulating membrane 22, the atom of alkali and alkaline earth metal ions adds up to content to be 0.5 below atom % too, is more preferably 0.1 below atom %.By being set to above-mentioned scope, becoming and not easily producing re-separation etc., the attachment of the resin of the resin bed after high-temperature process 32 can be suppressed further, and the surface that the removability that can obtain the resin adhered to is also more excellent.Below, unless otherwise specified, then inorganic insulating membrane surface 221 is all called by the inorganic insulating membrane surface 221 in duplexer 10 with any one party on the inorganic insulating membrane surface of the glass substrate 24 of inorganic insulating membrane itself.
In the present invention, the atom of alkali and alkaline earth metal ions adds up to content, refers to measure inorganic insulating membrane surperficial and the alkali metal atom on surface that obtains and the content of alkaline earth metal atom with XPS (x-ray photoelectron spectroscopy).In addition, known XPS determinator can be used for XPS to measure.It should be noted that, hereinafter, being added up to by the atom of alkali and alkaline earth metal ions content to be that 0.5 atom % is hereinafter also referred to not containing alkali metal atom and alkaline earth metal atom in fact.
In addition, in duplexer 10, the surface roughness (Ra) in the face (that is, inorganic insulating membrane surface 221) contacted with resin bed 32 of inorganic insulating membrane 22 is preferably less than 30nm.Similarly, with in the glass substrate 24 of inorganic insulating membrane, the surface roughness (Ra) on inorganic insulating membrane surface is also preferably less than 30nm.By being set to above-mentioned scope, becoming and not easily producing re-separation etc., the attachment of the resin of the resin bed 32 after high-temperature process can be suppressed further, and the surface that the removability that can obtain the resin adhered to is also more excellent.Wherein, from making the viewpoint that effect of the present invention is more excellent, surface roughness (Ra) is below 10nm, more preferably below 1nm preferably.It should be noted that, lower limit is not particularly limited, and is preferably 0nm.
Ra measures according to JIS B 0601 (calendar year 2001 revision).
In addition, be more preferably all met with above-mentioned two surfaces characteristic relevant with inorganic insulating membrane side surface of the glass substrate 24 of inorganic insulating membrane.That is, with the inorganic insulating membrane side surface of the glass substrate 24 of inorganic insulating membrane, more preferably in fact not containing alkali metal atom and alkaline earth metal atom, and its surface roughness (Ra) is less than 30nm.
, there is alkali metal atom, alkaline earth metal atom in its surface thus in alkali metal, alkaline earth metal component containing ormal weight in common glass substrate.Such as, although in fact not containing alkali metal component in the glass substrate be made up of alkali-free pyrex, there is alkaline earth metal atom in the alkaline earth metal component containing ormal weight thus in its surface.In addition, by the alkali metal component containing ormal weight in the glass substrate that soda-lime glass is formed and alkaline earth metal component, there is alkali metal atom and alkaline earth metal atom in its surface thus.Therefore, when making glass substrate and resin bed directly contact and be exposed to hot conditions, alkali metal atom, alkaline earth metal atom occur to depart from and also carry out chemical reaction with the composition of resin bed, its result, glass baseplate surface and and the resin bed of its surface contact between adhesion increase.Therefore, glass substrate 20 easily becomes difficulty with being separated of resin bed 32, and also easily causes re-separation.It should be noted that, alkali metal refers to lithium, sodium and potassium, and alkaline-earth metal refers to magnesium, calcium, barium and strontium.
It is believed that, with in the glass substrate 24 of inorganic insulating membrane, alkali metal atom in glass substrate 20, alkaline earth metal atom are stopped due to inorganic insulating membrane 22, and further inorganic insulating membrane surface 221 is set in fact not containing alkali metal atom, alkaline earth metal atom, thus in duplexer 10, alkali metal atom, alkaline earth metal atom can not be carried out depart from and the chemical reaction of generation from inorganic insulating membrane surface 221 to resin bed 32 side, not easily produce re-separation etc.Thus, at duplexer 10 by the stripping after high-temperature process, resin can be suppressed in the attachment on inorganic insulating membrane surface 221, and the surface that the removability that can obtain the resin adhered to is also more excellent.The atom of the alkali metal utilizing XPS to measure in inorganic insulating membrane surface 221, alkaline-earth metal adds up to content to be 0.5 below atom %, is more preferably 0.1 below atom %.
By the material of use in fact containing alkali metal atom, alkaline earth metal atom as the material for the formation of inorganic insulating membrane 22, the surface in fact not containing alkali metal atom, alkaline earth metal atom can be obtained.Such as, when utilizing sputtering method to form inorganic insulating membrane 22, by using material that alkali metal atom, alkaline earth metal atom are few as the material of the inorganic insulation membrane material, sputtering atmosphere gas etc. of sputtering target etc., the inorganic insulating membrane 22 on the surface had in fact containing alkali metal atom, alkaline earth metal atom can be formed.Usually, only otherwise in for the formation of the material described above of inorganic insulating membrane 22, add alkali metal atom, alkaline earth metal atom wittingly, then comprise alkali metal atom within this material with Impure forms, alkaline earth metal atom is few.Therefore, utilize normally used material and the inorganic insulating membrane 22 that obtains, become the inorganic insulating membrane in fact not containing alkali metal atom, alkaline earth metal atom.
In addition, so long as not the inorganic insulating membrane 22 that thickness is thin especially, then the alkali metal atom of glass substrate 20, alkaline earth metal atom can not permeate inorganic insulating membrane 22 and arrive the surface do not contacted with glass substrate.As mentioned above, as long as the thickness of inorganic insulating membrane 22 is about more than 5nm, then alkali metal atom, the alkaline earth metal atom of glass substrate 20 can fully be stopped.
The surface of normally used glass substrate 20 is level and smooth, and the surface of the inorganic insulating membrane 22 formed thereon also becomes level and smooth.That is, the surface roughness (Ra) of normally used glass substrate 20 is less than 30nm, and the surface roughness on the surface (inorganic insulating membrane surface 221) do not contacted with glass substrate 20 of the inorganic insulating membrane 22 formed thereon is less than 30nm.But, according to circumstances, sometimes utilize etching to wait glass substrate 20 surface roughening.Such as, according to the kind of inorganic insulating membrane 22, in order to improve the bond strength with glass substrate 20 surface, sometimes by glass substrate 20 surface roughening.In addition, also sometimes by glass substrate 20 surface roughening, as by from glass substrate 20 surface reverberation diffusion thus reduce the dazzling process (free from glare process) that causes of reverberation.By glass substrate 20 surface roughening when, when the surface roughness (Ra) on the surface after roughening becomes more than 30nm, the surface roughness on the surface (inorganic insulating membrane surface 221) do not contacted with glass substrate 20 of the inorganic insulating membrane 22 likely formed thereon also becomes more than 30nm.It should be noted that, by forming inorganic insulating membrane 22, the surface roughness on glass substrate 20 surface not necessarily directly becomes the surface roughness on inorganic insulating membrane surface 221, also the surface roughness of inorganic insulating membrane 22 is relaxed sometimes, therefore, the surface roughness on inorganic insulating membrane surface 221 is also not only specified by the surface roughness on glass substrate 20 surface.
(manufacture method of inorganic insulating membrane)
The manufacture method of inorganic insulating membrane 22 is not particularly limited, and can adopt known method.Such as can enumerate: utilize vapour deposition method or sputtering method that the method for the oxide of regulation, nitride, oxynitride is set on glass substrate 20.Such as, can utilize the methods such as Plasma Nitridation that the silicon dioxide film by CVD film forming is carried out nitrogen treatment and form silicon oxynitride film, also can utilize the methods such as plasma oxidation method that the silicon nitride film by CVD film forming is carried out oxidation processes and form silicon oxynitride film.
About manufacturing condition, suitably select optimum condition according to the oxide of used metal, nitride, oxynitride.
< gripper shoe >
Gripper shoe 31 is worked in coordination with resin bed 32, and supporting also reinforcing band has the glass substrate 24 of inorganic insulating membrane, and in the manufacturing process of device, prevent distortion, generation cut, the breakage etc. of the glass substrate 24 with inorganic insulating membrane.In addition, use Thickness Ratio in the past thinner with inorganic insulating membrane glass substrate 24 when, by forming the thickness duplexer 10 identical with glass substrate in the past, in the manufacturing process of device, can use and the matched manufacturing technology of the glass substrate of thickness in the past, manufacturing equipment, this is also one of object using gripper shoe 31.
As gripper shoe 31, use the metallic plates such as such as glass plate, resin plate, SUS plate, etc.In the manufacturing process of device with under heat treated situation, gripper shoe 31 is preferably formed by the material that the difference of the linear expansion coefficient with glass substrate 20 is little, and more preferably formed by the material identical with glass substrate 20, gripper shoe 31 is preferably glass plate.Especially, gripper shoe 31 preferably comprises the glass plate of the glass material identical with the glass substrate of glass substrate 20.
The thickness of gripper shoe 31 can be thicker than the thickness of glass substrate 20, also can be thinner than the thickness of glass substrate 20.Be preferably based on the thickness of the thickness of the glass substrate 24 with inorganic insulating membrane, the thickness of resin bed 32 and duplexer 10 to select the thickness of gripper shoe 31.Such as, the manufacturing process of existing device is that the mode processing the substrate that thickness is 0.5mm carries out designing, when the thickness of the glass substrate 24 with inorganic insulating membrane and the thickness sum of resin bed 32 are 0.1mm, if the thickness of gripper shoe 31 is 0.4mm.In a general case, the thickness of gripper shoe 31 is preferably 0.2 ~ 5.0mm.
When gripper shoe 31 is glass plate, for being easy to operation, not easily producing reasons such as breaking, the thickness of glass plate is preferably more than 0.08mm.In addition, for expect when peeling off after device component is formed do not produce break when appropriateness flexure the reason of rigidity, the thickness of glass plate is preferably below 1.0mm.
Glass substrate 20 and the difference of the average coefficient of linear expansion (being only called below " average coefficient of linear expansion ") at 25 ~ 300 DEG C of gripper shoe 31, be preferably 500 × 10 -7/ DEG C below, be more preferably 300 × 10 -7/ DEG C below, more preferably 200 × 10 -7/ DEG C below.When this difference is excessive, when the heating in the manufacturing process of device cools, the violent warpage of duplexer 10, thus likely peel off with reinforcement plate 30 with the glass substrate 24 of inorganic insulating membrane.When the material of glass substrate 20 is identical with the material of gripper shoe 31, the generation of this problem can be suppressed.
< resin bed >
Resin bed 32 is fixed in gripper shoe 31, in addition, adheres to the glass substrate 24 with inorganic insulating membrane in the mode that can peel off.Resin bed 32 prevents the position of the glass substrate 24 with inorganic insulating membrane from departing from, until carry out the operation be separated with gripper shoe 31 by the glass substrate 24 with inorganic insulating membrane, and be easy to peel off from the glass substrate 24 with inorganic insulating membrane by lock out operation, prevent glass substrate 24 grade with inorganic insulating membrane damaged due to lock out operation.In addition, resin bed 32 is fixed to gripper shoe 31, there is not the worry that resin bed 32 is peeled off with gripper shoe 31, thus obtain the gripper shoe (reinforcement plate 30) with resin bed by lock out operation in lock out operation.It should be noted that, when starting lock out operation, preferably arranging at resin bed 32 and the interface of inorganic insulating membrane 22 and peeling off starting point and peel off, peeling off easily through lock out operation to make its interface.
The surface 321 contacted with inorganic insulating membrane 22 of resin bed 32, adheres to the surface 221 of inorganic insulating membrane 22 in the mode that can peel off.In the present invention, the character that can easily peel off of this resin layer surface 321 is called fissility.
In the present invention, above-mentioned fixing sticking in peel strength (that is, the stress required for stripping) with (can peel off) there are differences, and fixedly means that peel strength specific adhesion is larger.In addition, the adhesion that can peel off refers to, while can peeling off, peels off when can be peeling in the face not making to be fixed.Specifically, refer in duplexer 10 of the present invention, when carrying out the operation be separated with gripper shoe 31 by the glass substrate 24 with inorganic insulating membrane, being peeled off by the face adhered to, not peeling off in the face be fixed.Therefore, when carrying out duplexer 10 to be separated into the operation with the glass substrate 24 of inorganic insulating membrane and gripper shoe 31, duplexer 10 be separated into the glass substrate 24 with inorganic insulating membrane and the gripper shoe with resin bed (reinforcement plate 30) both.
Resin bed 32 is preferably fixed to gripper shoe 31 surface with the strong adhesion such as adhesive tension, bonding force.Such as, by making reaction curable resin carry out reaction solidification on gripper shoe 31 surface, the resin glue after solidification sticks to gripper shoe 31 surface.In addition, also by implementing the process (such as, using the process of coupling agent) making to produce strong adhesion between gripper shoe 31 surface and resin bed 32, the adhesion between gripper shoe 31 surface and resin bed 32 can be improved.
On the other hand, resin bed 32 and inorganic insulating membrane surface 221 combine with weak binding power, and such as the preferred adhesion caused with the Van der Waals force between molecular solids combines.Resin layer surface 321 before contacting with inorganic insulating membrane 22 is preferably the surface of non-tack, by making the resin layer surface 321 of this non-tack contact with inorganic insulating membrane surface 221, two surfaces can be made to combine with weak binding power.That is, when resin layer surface 321 is non-tack, become better with the fissility of the interface on inorganic insulating membrane surface 221.Two surfaces seamlessly contact, and in the present invention, this state are called adhesion.
It should be noted that, by giving the surface treatment of non-tack to the surface not for the resin bed of non-tack under common meaning, resin layer surface also can be made to become non-tack.In addition, even under common meaning be not the resin bed of non-tack, as long as relative to above-mentioned fixing in adhesion for can carry out adhering to fully low adhesion resin (and, as long as can peel off under the situation such as breakage not producing the stripping of inorganic insulating membrane from glass substrate, the glass substrate with inorganic insulating membrane or gripper shoe), then can not implement surface treatment and as the materials'use of resin bed.
Especially, when the resin layer surface contacted with inorganic insulating membrane is non-tack, when peeling off, to remain in the situation on inorganic insulating membrane surface due to the breakage of resin layer surface few for a part for resin layer surface, in addition, a part for the material of inorganic insulating membrane remains in the situation of resin layer surface also less due to the breakage of inorganic insulating membrane.
As mentioned above, resin bed 32, relative to the adhesion on the surface of gripper shoe 31, is relatively higher than the adhesion of resin bed 32 relative to inorganic insulating membrane surface 221.Therefore, the peel strength between resin bed 32 and gripper shoe 31, higher than resin bed 32 and with inorganic insulating membrane glass substrate 24 between peel strength.Preferably to bond or gluingly to combine between resin bed 32 and gripper shoe 31.But be not limited thereto, as long as be relatively higher than the adhesion of resin bed 32 relative to the glass substrate 24 with inorganic insulating membrane, the power that also can be caused by other adhesions between resin bed 32 and gripper shoe 31 combines.
The size of resin bed 32 is not particularly limited.The size of resin bed 32 can be greater than the size of glass substrate 20, gripper shoe 31, also can be less than the size of glass substrate 20, gripper shoe 31.
The thickness of resin bed 32 is not particularly limited, and is preferably 1 ~ 100 μm, is more preferably 5 ~ 30 μm, more preferably 7 ~ 20 μm.This is because when the thickness of resin bed 32 is this scope, resin bed 32 becomes abundant with the adhesion with the glass substrate 24 of inorganic insulating membrane.Its reason is in addition, even if there is bubble, foreign matter between resin bed 32 and the glass substrate 24 with inorganic insulating membrane, still inhibition zone can have the generation of the strain defect of the glass substrate 24 of inorganic insulating membrane.In addition, when the thickness of resin bed 32 is blocked up, need for the formation of time and materials, therefore uneconomical.
It should be noted that, resin bed 32 can comprise two-layer more than." thickness of resin bed 32 " refers to the aggregate thickness of whole layers in this case.
In addition, resin bed 32 comprise two-layer more than when, the kind forming the resin of each layer can be different.
Resin bed 32 preferably comprises glass transition temperature lower than room temperature (about 25 DEG C) or the material without glass transition temperature.This is because, more easily can peel off with the glass substrate 24 with inorganic insulating membrane, also become abundant with the adhesion of the glass substrate 24 with inorganic insulating membrane simultaneously.
In addition, resin bed 32 mostly experiences heating in the manufacturing process of device, therefore preferably has heat resistance.
In addition, when the elastic modelling quantity of resin bed 32 is too high, there is the tendency with the adhesiveness step-down of the glass substrate 24 with inorganic insulating membrane.On the other hand, when the elastic modelling quantity of resin bed 32 is too low, fissility step-down.
The kind forming the resin of resin bed 32 is not particularly limited.Such as acrylic resin, vistanex, polyurethane resin or polyorganosiloxane resin can be enumerated.Also several mixed with resin can be used.Wherein, preferred polyorganosiloxane resin.This is because heat resistance, the fissility of polyorganosiloxane resin are excellent.In addition also because when gripper shoe 31 is glass plate, by the condensation reaction of the silanol base with glass pane surface, be easy to be fixed to glass plate.From be loaded into gripper shoe 31 and with inorganic insulating membrane glass substrate 24 between state, even if process about 1 hour such as in an atmosphere, at about 200 DEG C, the viewpoint that fissility is substantially not deteriorated yet, polyorganosiloxane resin layer is also preferred.
Resin bed 32 preferably comprises the polyorganosiloxane resin (solidfied material) for peeling paper purposes in polyorganosiloxane resin.The polyorganosiloxane resin of the peel ply of peeling paper, is formed by being cured by the layer of the curability polysiloxane resin composition being applied to peeling paper.Comprise and use this curability polysiloxane resin composition and the resin bed of the solidification polyorganosiloxane resin this curability polysiloxane resin composition being cured on the surface of gripper shoe 31 and being formed, while gluing with gripper shoe 31 surface, its Free Surface has excellent non-tack, therefore preferably.In addition, because flexibility is high, even if be therefore mixed into the foreign matter such as bubble, dust between resin bed 32 and the glass substrate 24 with inorganic insulating membrane, also inhibition zone the generation of the strain defect of the glass substrate 24 of inorganic insulating membrane can be had.
This peel ply in order to form peeling paper etc. and the curability polysiloxane resin composition used, according to its curing mechanism, be categorized as condensation reaction type polysiloxane resin composition, addition reaction-type polysiloxane resin composition, ultraviolet hardening polysiloxane resin composition and electron ray curing type polysiloxane resin composition, can be used wherein any one.In these materials, preferred addition reaction-type polysiloxane resin composition.This is because be easy to be cured reaction, the degree of the non-tack of the resin layer surface 321 after solidification is good, and heat resistance is also high.
Addition reaction-type polysiloxane resin composition is containing host and crosslinking agent and the solidification compound be cured under the existence of the catalyst such as platinum group catalyst.The solidification of addition reaction-type polysiloxane resin composition promotes by heating.Host in addition reaction-type polysiloxane resin composition, preferably has and the organopolysiloxane of the thiazolinyl of silicon atom bonding (vinyl etc.) (that is, olefinic organic based polysiloxane.It should be noted that, be preferably straight-chain), thiazolinyls etc. become crosslinking points.Crosslinking agent in addition reaction-type polysiloxane resin composition, preferably has organopolysiloxane (that is, the organic hydrogen polysiloxanes with the hydrogen atom of silicon atom bonding (hydrogen silicyl).It should be noted that, be preferably straight-chain), hydrogen silicyl etc. becomes crosslinking points.
Addition reaction-type polysiloxane resin composition is carried out addition reaction by the crosslinking points of host and crosslinking agent and is solidified.
In addition, in order to form the peel ply of peeling paper etc. and the curability polysiloxane resin composition used, morphologically there are solvent-borne type, emulsion-type and no-solvent type, any one type can be used.In these, preferred no-solvent type.This is because, productivity ratio, security, environmental characteristics aspect excellence.In addition also because, when carrying out solidification when forming resin bed 32, be namely heating and curing, ultraviolet curing or electron ray curing time, not containing the solvent that can produce foaming, thus be difficult to residual bubble in resin bed 32.
In addition, the curability polysiloxane resin composition used as the peel ply in order to form peeling paper etc., specifically as commercially available trade name or model, can there are: KNS-320A, KS-847 (being polysiloxanes Inc. of SHIN-ETSU HANTOTAI), TPR6700 (Mai Tu new high-tech material Japanese firm (モ メ Application テ ィ Block パ Off ォ ー マ Application ス マ テ リ ア Le ズ ジ ャ パ Application contract commercial firm) system), the combination of vinyl polysiloxane " 8500 " (Huang Chuan chemical industrial company system) and methylhydrogenpolysi,oxane " 12031 " (Huang Chuan chemical industrial company system), the combination of vinyl polysiloxane " 11364 " (Huang Chuan chemical industrial company system) and methylhydrogenpolysi,oxane " 12031 " (Huang Chuan chemical industrial company system), the combination etc. of vinyl polysiloxane " 11365 " (Huang Chuan chemical industrial company system) and methylhydrogenpolysi,oxane " 12031 " (Huang Chuan chemical industrial company system).
It should be noted that, KNS-320A, KS-847 and TPR6700, for containing the curability polysiloxane resin composition of host and crosslinking agent in advance.
In addition, form the polyorganosiloxane resin (solidfied material of above-mentioned curability polysiloxane resin composition) of resin bed 32, preferably there is the compositions such as the low molecular weight polysiloxane in polyorganosiloxane resin layer not easily to character, i.e. oligosiloxane metastatic that the glass substrate 24 with inorganic insulating membrane shifts.
(manufacture method of resin bed)
The method that resin bed 32 is fixed in gripper shoe 31 is not particularly limited, preference is as following method: the layer forming the hardening resin composition for becoming resin bed 32 in gripper shoe 31 on the surface, then, by this hardening resin composition being solidified to form the method for resin bed 32, form the resin bed 32 be fixed in gripper shoe 31.
In addition, also resin bed 32 can be formed by the method on the surface such as membranaceous resin being fixed to gripper shoe 31.Specifically, method can be listed below: in order to give the high bed knife (high-peeling strength) for film surface to the surface of gripper shoe 31, surface modification treatment (primary coat process) is carried out to the surface of gripper shoe 31, makes it be fixed in gripper shoe 31.Can illustrate such as: the mechanical processing method etc. that physical method, blasting treatment and so on that chemical method (silane coupling agent process), flame treatment and so on that silane coupler and so on chemically makes bed knife improve make surface active groups increase make resistance increase by making the roughness increase on surface.
The layer of the hardening resin composition for becoming resin bed 32 is formed on the surface in gripper shoe 31, then this hardening resin composition is made to solidify to form in the method for resin bed 32, as the method for layer forming hardening resin composition in gripper shoe 31 on the surface, the method being such as coated with hardening resin composition in gripper shoe 31 can be enumerated.As the method for being coated with, spraying process can be enumerated, mould is coated with method, spin-coating method, Dipcoat method, rolling method, scraper rubbing method, silk screen print method, gravure coating process etc.In these methods, suitably can select according to the kind of resin combination.
In addition, when gripper shoe 31 is coated with the hardening resin composition for becoming resin bed 32, its coating weight is preferably 1 ~ 100g/m 2, be more preferably 5 ~ 20g/m 2.
Such as, when forming resin bed 32 by addition reaction-type polysiloxane resin composition, utilize the known methods such as above-mentioned spraying process, the hardening resin composition of the mixture comprising organic thiazolinyl polysiloxanes, organic hydrogen polysiloxanes and catalyst is applied in gripper shoe 31, then makes it be heating and curing.The condition that is heating and curing is different according to the use level of catalyst, such as, relative to total amount 100 mass parts of olefinic organic based polysiloxane and organic hydrogen polysiloxanes, when the platinum group catalyst of cooperation 2 mass parts, in an atmosphere, 50 DEG C ~ 250 DEG C, preferably 100 DEG C ~ 200 DEG C at react.In addition, the reaction time under this situation is set as 5 ~ 60 minutes, preferably 10 ~ 30 minutes.
By making hardening resin composition be heating and curing, when curing reaction, polyorganosiloxane resin and gripper shoe 31 chemical bond, additionally by anchoring effect, polyorganosiloxane resin layer is combined with gripper shoe 31, gluing.By these effects, polyorganosiloxane resin layer is fixedly secured to gripper shoe 31.It should be noted that, when being formed the resin bed of the resin comprised beyond polyorganosiloxane resin by hardening resin composition, also by method same as described above, the resin bed 32 being fixed to gripper shoe 31 can be formed.
The manufacture method > of < duplexer and duplexer
As mentioned above, duplexer 10 of the present invention is for having with the glass substrate 24 of inorganic insulating membrane, gripper shoe 31 and the duplexer being present in the resin bed 32 between them.
The manufacture method of duplexer of the present invention is not particularly limited, usually the method be preferably as follows: prepare with the glass substrate 24 of inorganic insulating membrane and the gripper shoe with resin bed (reinforcement plate 30) that made by said method, using the resin layer surface of the face of the inorganic insulating membrane of the glass substrate 24 with inorganic insulating membrane and the above-mentioned gripper shoe with resin bed (reinforcement plate 30) as lamination surface, will both be stacked.When the lamination surface of resin bed 32 has non-tack, utilize common coincidence and pressurization, can easily adhere in the mode that can peel off.
Specifically, the method that can be listed below, under atmospheric pressure environment after the non-tack surface overlap zone of resin bed 32 has the glass substrate 24 of inorganic insulating membrane, makes resin bed 32 crimp with the glass substrate 24 with inorganic insulating membrane by use roller, press.Crimped by use roller, press, resin bed 32 adheres to further with the glass substrate 24 with inorganic insulating membrane, therefore preferably.In addition, by the crimping using roller, press carries out, the bubble be mixed between resin bed 32 and the glass substrate 24 with inorganic insulating membrane can be removed with comparalive ease, therefore preferably.
If utilize vacuum layer platen press, Vacuum Pressure method for making crimps, then can suppress being mixed into of bubble well, guarantee good adhesion, therefore more preferably.By crimping under vacuo, also there is following advantage: even if when remaining small bubble, bubble also can not be grown up due to heating, not easily causing the strain defect of the glass substrate 24 with inorganic insulating membrane.
When will resin bed 32 be made to adhere on the glass substrate 24 with inorganic insulating membrane in the mode that can peel off, preferably fully wash by resin bed 32 with the contact with each other face of side of the glass substrate 24 of inorganic insulating membrane, carry out stacked under the environment that cleannes are high.Even if although be mixed into foreign matter between resin bed 32 and the glass substrate 24 with inorganic insulating membrane, because resin bed 32 deforms, therefore can not impact the flatness on the surface of the glass substrate 24 with inorganic insulating membrane, but cleannes are higher, its flatness is better, therefore preferably.
Duplexer 10 of the present invention can use in a variety of applications where, can enumerate such as: the purposes etc. manufacturing the electronic units such as display unit panel described later, PV, thin-film secondary battery, the semiconductor wafer being formed with circuit on surface.It should be noted that, in this purposes, duplexer 10 is exposed in hot conditions (such as, more than 320 DEG C) (such as, more than 1 hour) in many situations.
At this, display unit panel comprises: LCD, OLED, Electronic Paper, plasm display panel, field emission panels, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems: MEMS) shutter face plate etc.
The manufacture method > of the display unit panel of < with gripper shoe and the display unit panel with gripper shoe
In the present invention, by using above-mentioned duplexer to manufacture the display unit panel with gripper shoe.
Fig. 2 is the schematic cross sectional view of an example of the display unit panel with gripper shoe of the present invention.
With the display unit panel 40 of gripper shoe, be made up of the member of formation 50 of above-mentioned duplexer 10, display unit panel.
(member of formation of display unit panel)
The member of formation 50 of display unit panel refers to, such as, in the display unit such as LCD, OLED using glass substrate, forms component on the glass substrate or its part.Such as; in the display unit such as LCD, OLED; the component of tft array (hreinafter referred to as " array "), protective layer, colour filter, liquid crystal, the transparency electrode etc. comprising ITO, various circuit patterns etc. is formed on the surface of substrate, or the component that their combinations are obtained.The semi-conducting material used in above-mentioned array is not particularly limited, and can enumerate such as: the silicon of amorphous, crystallite, polycrystalline etc.; The metal oxides such as ZnO, IGZO; The organic matter such as thiophene derivant, pentacene derivative etc.In addition, such as, in the display unit comprising OLED, transparency electrode, hole injection layer, hole transporting layer, luminescent layer, electron supplying layer etc. that substrate is formed can be set forth in.
The manufacture method of the above-mentioned display unit panel 40 with gripper shoe is not particularly limited, can according to the kind of the member of formation of display unit panel, utilize known method, form the member of formation 50 of display unit panel at the glass substrate 24 with inorganic insulating membrane of duplexer 10 on the surface.
Such as, to manufacture the situation of OLED, in order to form organic EL structure at duplexer 10 with that the surface of the opposition side, resin bed 32 side of the glass substrate 24 with inorganic insulating membrane (is equivalent to the second interarea 202 of glass substrate 20) is upper, carry out formation transparency electrode, and then on the face being formed with transparency electrode evaporation hole injection layer, hole transporting layer, luminescent layer, electron supplying layer etc., form backplate, use sealing plate to carry out the various layer such as sealing and formed or process.Formed or process as these layers, specifically, the gluing process etc. of such as film forming process, vapor deposition treatment, sealing plate can be enumerated.The formation of these member of formation, also can a part in the formation of whole member of formation required for display unit panel.In this case, after the glass substrate 24 with inorganic insulating membrane this being formed with a part of member of formation is separated from reinforcement plate 30, form remaining member of formation with on the glass substrate 24 of inorganic insulating membrane, thus manufacture display unit panel.
The manufacture method > of < display unit panel and display unit panel
As shown in Figure 2, display unit panel 60 of the present invention, is formed by with the glass substrate 24 of inorganic insulating membrane and the member of formation 50 of display unit panel.
Can by from the display unit panel 40 with gripper shoe by inorganic insulating membrane 22 interface peel with resin bed 32, be separated into the glass substrate 24 with inorganic insulating membrane and reinforcement plate 30, thus obtain display unit panel 60.
It should be noted that, when the part of the formation with the whole member of formation of the member of formation on the glass substrate 24 of inorganic insulating membrane required for display unit panel after isolation, afterwards, by manufacturing display unit panel 60 with the glass substrate 24 of inorganic insulating membrane forms remaining member of formation.
The method of inorganic insulating membrane 22 with the fissility sur-face peeling of resin bed 32 is not particularly limited.But, preferably first inorganic insulating membrane 22 and the interface of resin bed 32 formed peel off starting point after peel off.Specifically, such as, preferably in the interface of inorganic insulating membrane 22 with resin bed 32, insert sharp keen cutter shape thing, give the starting point peeled off, after this peeled off by winding-up water and compressed-air actuated fluid-mixing.
It should be noted that, after display unit panel 60 is separated from the display unit panel 40 with gripper shoe, as required, on the inorganic insulating membrane 22 of display unit with the glass substrate 24 with inorganic insulating membrane in panel 60, the member of formation of display unit panel can be set in addition.
In addition, the reinforcement plate 30 after separation stackedly with the new glass substrate with inorganic insulating membrane can manufacture duplexer 10 of the present invention.As the manufacture method of this new duplexer 10, preferred aforesaid manufacture method of the present invention.
< display unit >
In addition, display unit can be obtained by this display unit panel 60.As display unit, LCD, OLED can be enumerated.As LCD, TN type, STN type, FE type, TFT type, mim type can be enumerated.
The operation obtaining display unit at this is not particularly limited, and such as, known method can be utilized to manufacture display unit.
Embodiment
Below, illustrate the present invention by embodiment etc., but the present invention and can't help these examples limit.
In following embodiment 1 ~ 5, comparative example 1,4, as glass substrate, use the glass plate (vertical 720mm, horizontal 600mm, thickness of slab 0.3mm, the linear expansion coefficient 38 × 10 that comprise alkali-free pyrex -7/ DEG C, Asahi Glass Inc. trade name " AN100 ").In addition, as gripper shoe, similarly use the glass plate (vertical 720mm, horizontal 600mm, thickness of slab 0.4mm, the linear expansion coefficient 38 × 10 that comprise alkali-free pyrex -7/ DEG C, Asahi Glass Inc. trade name " AN100 ").
In addition, in embodiment 6 and comparative example 2, as glass substrate and gripper shoe, use the glass plate (linear expansion coefficient 85 × 10 comprising soda-lime glass -7/ DEG C, Asahi Glass Inc. trade name " AS ").In embodiment 7 and comparative example 3, the glass plate this being comprised soda-lime glass floods 1 hour in the potassium nitrate fused salt of 450 DEG C, carries out chemical intensification treatment thus, and is used as glass substrate and gripper shoe by obtained strengthening glass sheets.The size of these glass substrates is identical with the glass substrate used in embodiment 1 ~ 5 with thickness, and the size of these gripper shoes is also identical with the gripper shoe used in embodiment 1 ~ 5 with thickness.
It should be noted that, in embodiment described later and comparative example, surface roughness (Ra) measures by using atomic force microscope (Seiko Instruments company (セ イ コ ー イ Application ス ツルメン Star society) makes, SPA300/SPI3800).
(fissility evaluation)
About the fissility of the glass substrate with inorganic insulating membrane after the heating of aftermentioned duplexer, after heating under aftermentioned rated condition, peel off with the glass substrate of inorganic insulating membrane and resin bed, and visually observe the face contacted with resin bed of the glass substrate with inorganic insulating membrane, evaluate thus.Residue without resin bed is then evaluated as well, has the residue of resin bed to be then evaluated as bad.
(cleanliness evaluation)
After heating under aftermentioned defined terms, the glass substrate with inorganic insulating membrane peeled off from duplexer is carried out ultrasonic process (5 minutes) in hexane, then on the face contacted with resin bed, (on inorganic insulation face) pastes adhesive tape (trade name Sellotape (セ ロ テ ー プ) (registration mark), Nichiban (ニ チ バ Application) makes), carry out 90 ° of strippings, and measure its peel strength.Peel strength is less, and represent the residue that there is resin bed on inorganic insulation face, from the viewpoint of practical, preferred peel strength is more than 0.5N/25mm.
< embodiment 1>
After first the gripper shoe of thickness of slab 0.4mm being carried out pure water, then carry out UV washing, thus purifying.
Then, on the first interarea of gripper shoe, utilize screen process press, with the size of vertical 705mm, horizontal 595mm, by solvent-free addition reaction-type peeling paper polysiloxanes (polysiloxanes Inc. of SHIN-ETSU HANTOTAI, KNS-320A, viscosity: 0.40Pas, solubility parameter (SP value): 7.3) mixed liquor of 100 mass parts and platinum group catalyst (polysiloxanes Inc. of SHIN-ETSU HANTOTAI, CAT-PL-56) 2 mass parts is coated with as rectangle (coating weight 30g/m 2).
Then, at 180 DEG C, in an atmosphere, be heated solidification 30 minutes, the first interarea of gripper shoe is formed the polyorganosiloxane resin layer of thickness 20 μm.
It should be noted that, above-mentioned solvent-free addition reaction-type peeling paper polysiloxanes comprises: have and the straight-chain olefinic organic based polysiloxane (host) of the vinyl of silicon atom bonding and methyl and the straight-chain organic hydrogen polysiloxanes (crosslinking agent) that has with the hydrogen atom of silicon atom bonding and methyl.
Then, the glass substrate of thickness of slab 0.3mm carried out pure water with the face (the first interarea) of polyorganosiloxane resin contact side, then carry out UV washing, thus purifying.In addition, (heating-up temperature 300 DEG C becomes film pressure 4m holder, power density 3W/cm to utilize magnetron sputtering method 2), the face after purifying is formed the SiO of thickness 30nm 2film, obtains the glass substrate with inorganic insulating membrane.Inorganic insulating membrane surface (inorganic insulating membrane with the surface of opposition side, glass substrate side.Below represent identical meanings) surface roughness (Ra) be 0.8nm.In addition, (the Quantera SXM that use ULVAC-PHI company (ア Le バ ッ Network Off ァ イ society) is made is being measured by XPS.Identical below) atom of alkali and alkaline earth metal ions in the inorganic insulating membrane surface that obtains adds up to content to be below detectability (0.1 below atom %).
Then, at room temperature, by the SiO of vacuum pressing by glass substrate 2the polyorganosiloxane resin aspect of film forming face and gripper shoe is pasted, and obtains duplexer A.
In obtained duplexer A, gripper shoe and glass substrate adhere to polyorganosiloxane resin layer when not producing bubble, thus do not strain shape defect, and flatness is also good.
(the fissility evaluation after heating)
For duplexer A, be implement in the blanket of nitrogen of less than 0.1%, at 350 DEG C to heat for 1 hour at aerial oxygen.
Then, disbonded test is carried out.Specifically, first, the second interarea of the glass substrate in duplexer A is fixed on fixed station.On the other hand, with the second interarea of absorption layer adsorbent support plate.Then, the angle place in four bights that duplexer A has, in the glass substrate of inorganic insulating membrane and the interface of resin bed, the cutter of inserting thickness 0.4mm, makes the interface of inorganic insulating membrane and resin bed slightly peel off, thus gives the starting point peeled off.Then, absorption layer is moved to the direction left from fixed station, the interface entirety of inorganic insulating membrane and resin bed is peeled off, isolates the glass substrate with inorganic insulating membrane and the gripper shoe with resin bed.
In the release surface of the glass substrate with inorganic insulating membrane after isolation (on inorganic insulating membrane), there is no the residue of resin.
In addition, carry out above-mentioned cleanliness evaluation to the glass substrate with inorganic insulating membrane after being separated, peel strength is 0.7N/25mm, and known have excellent face cleanliness.
Then, at 50 DEG C, the anticorrosive additive stripping liquid controlling ((パ ー カ ー コ ー ポ レ ー シ ョ Application society of Parker Corporation company) that glass substrate is being diluted to 20 % by weight with inorganic insulating membrane after separation is made, potassium hydroxide containing 20 quality % is as main component) in dipping 10 minutes, after carrying out utilizing the scrubbing and wash of water, be flood 20 hours in the aqueous hydrochloric acid solution of 0.1 mol/L in concentration at 90 DEG C, and carry out utilizing scrubbing of water to wash and air blast.By the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
(embodiment 1b)
By thermal cvd, (reacting gas is tetraethoxysilane and ozone/oxygen gas, and carrier gas is nitrogen for heating-up temperature 400 DEG C, reaction pressure 1Pa; 2000sccm, ozone/oxygen gas compares: 3%) replace magnetron sputtering method, forms the SiO of thickness 100nm 2film, in addition, according to the order identical with embodiment 1, obtains duplexer A '.It should be noted that, the surface roughness (Ra) with the inorganic insulating membrane surface of the glass substrate of inorganic insulating membrane is 2nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the inorganic insulating membrane surface obtained by XPS adds up to content to be 0.5 atom %.
Then, in the same manner as example 1 fissility evaluation is carried out to duplexer A '.The release surface of the glass substrate with inorganic insulating membrane after isolation there is no the residue of resin.
In addition, carry out cleanliness evaluation to the glass substrate with inorganic insulating membrane after being separated, peel strength is 0.8N/25mm, and known have excellent face cleanliness.
Then, according to the order identical with embodiment 1, carry out alkali, acid and scrub washing to the glass substrate with inorganic insulating membrane after being separated, and by the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
It should be noted that, it is believed that, the impurity that the atom of the alkali and alkaline earth metal ions in inorganic insulating membrane surface results from tetraethoxysilane.
< embodiment 2>
By ICP-CVD method (inductively coupled plasma CVD), (heating-up temperature 400 DEG C becomes film pressure 1Pa, RF power 400W, DC power 230V/0.5A/80W, gas flow (100%SiH 4: 10sccm, N 2: 140sccm)) form the Si of thickness 100nm 3n 4film replaces forming SiO 2film, in addition, according to the order identical with embodiment 1, obtains duplexer B.It should be noted that, the surface roughness (Ra) with the inorganic insulating membrane surface of the glass substrate of inorganic insulating membrane is 2nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the inorganic insulating membrane surface obtained by XPS adds up to content to be below detectability (0.1 below atom %).
Then, in the same manner as example 1 fissility evaluation is carried out to duplexer B.The release surface of the glass substrate with inorganic insulating membrane after isolation there is no the residue of resin.
In addition, carry out cleanliness evaluation to the glass substrate with inorganic insulating membrane after being separated, peel strength is 0.6N/25mm, and known have excellent face cleanliness.
Then, according to the order identical with embodiment 1, carry out alkali, acid and scrub washing to the glass substrate with inorganic insulating membrane after being separated, and by the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
< embodiment 3>
By magnetron sputtering method, (heating-up temperature 300 DEG C becomes film pressure 4m holder, power density 3W/cm 2) form the SiO of thickness 100nm 2film, then carries out plasma nitridation process (heating-up temperature 300 DEG C, cavity indoor pressure 100Pa, gas flow (N 2: 100sccm, Ar:1000sccm, H 2: 10sccm)), form the SiO of thickness 100nm an b(a=1, b=1) film replaces forming SiO 2film, in addition, according to the order identical with embodiment 1, obtains duplexer C.It should be noted that, the surface roughness (Ra) with the inorganic insulating membrane surface of the glass substrate of inorganic insulating membrane is 1nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the inorganic insulating membrane surface obtained by XPS adds up to content to be below detectability (0.1 below atom %).
Then, in the same manner as example 1 fissility evaluation is carried out to duplexer C.The release surface of the glass substrate with inorganic insulating membrane after isolation there is no the residue of resin.
In addition, carry out cleanliness evaluation to the glass substrate with inorganic insulating membrane after separation in the same manner as example 1, peel strength is 0.6N/25mm, and known have excellent face cleanliness.
Then, according to the order identical with embodiment 1, carry out alkali, acid and scrub washing to the glass substrate with inorganic insulating membrane after being separated, and by the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
< embodiment 4>
By (about 20 seconds) buffered hydrofluoric acid (hydrofluoric acid 6 % by weight: ammonium fluoride 30 % by weight of spraying to the glass baseplate surface used in embodiment 1, all the other are water, identical below) carry out roughening, on surface after the roughening of glass substrate, utilize the magnetron sputtering method implemented in embodiment 1 on glass substrate, make the SiO of thickness 30nm 2film, uses this glass substrate with inorganic insulating membrane to replace the glass substrate with inorganic insulating membrane used in embodiment 1, according to the order identical with embodiment 1, obtains duplexer D.It should be noted that, the surface roughness (Ra) with the inorganic insulating membrane surface of the glass substrate of inorganic insulating membrane is 25nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the inorganic insulating membrane surface obtained by XPS adds up to content to be below detectability (0.1 below atom %).
Then, in the same manner as example 1 fissility evaluation is carried out to duplexer D.The release surface of the glass substrate with inorganic insulating membrane after isolation there is no the residue of resin.
In addition, carry out cleanliness evaluation to the glass substrate with inorganic insulating membrane after peeling off, peel strength is 0.6N/25mm, and known have excellent face cleanliness.
Then, according to the order identical with embodiment 1, carry out alkali, acid and scrub washing to the glass substrate with inorganic insulating membrane after being separated, and by the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
< embodiment 5>
By reactive sputtering method, (aluminium target, without heating, becomes film pressure 0.1Pa, gas flow (O 2: 25sccm, Ar:25sccm)) form the Al of thickness 50nm 2o 3film replaces forming SiO 2film, in addition, according to the order identical with embodiment 1, obtains duplexer E.It should be noted that, in the present embodiment, the surface roughness (Ra) with the inorganic insulating membrane surface of the glass substrate of inorganic insulating membrane is 0.8nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the inorganic insulating membrane surface obtained by XPS adds up to content to be below detectability (0.1 below atom %).
Then, in the same manner as example 1 fissility evaluation is carried out to duplexer E.The release surface of the glass substrate with inorganic insulating membrane after isolation there is no the residue of resin.
In addition, carry out cleanliness evaluation to the glass substrate with inorganic insulating membrane after being separated, peel strength is 0.6N/25mm, and known have excellent face cleanliness.
Then, according to the order identical with embodiment 1, carry out alkali, acid and scrub washing to the glass substrate with inorganic insulating membrane after being separated, and by the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
< embodiment 6>
Use the glass plate comprising soda-lime glass as gripper shoe and glass substrate, in addition, by the method identical with embodiment 1, obtain duplexer F.It should be noted that, in the present embodiment, the surface roughness (Ra) with the inorganic insulating membrane surface of the glass substrate of inorganic insulating membrane is 0.8nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the inorganic insulating membrane surface obtained by XPS adds up to content to be below detectability (0.1 below atom %).
Then, in the same manner as example 1 fissility evaluation is carried out to duplexer F.The release surface of the glass substrate with inorganic insulating membrane after isolation there is no the residue of resin.
In addition, carry out cleanliness evaluation to the glass substrate with inorganic insulating membrane after being separated, peel strength is 0.6N/25mm, and known have excellent face cleanliness.
Then, according to the order identical with embodiment 1, carry out alkali, acid and scrub washing to the glass substrate with inorganic insulating membrane after being separated, and by the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
< embodiment 7>
Use chemical enhanced after glass plate as gripper shoe and glass substrate, in addition, by the method identical with embodiment 2, obtain duplexer G.It should be noted that, the surface roughness (Ra) with the inorganic insulating membrane surface of the glass substrate of inorganic insulating membrane is 0.8nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the inorganic insulating membrane surface obtained by XPS adds up to content to be below detectability (0.1 below atom %).
Then, in the same manner as example 1 fissility evaluation is carried out to duplexer G.The release surface of the glass substrate with inorganic insulating membrane after stripping there is no the residue of resin.
In addition, carry out cleanliness evaluation to the glass substrate with inorganic insulating membrane after being separated, peel strength is 0.6N/25mm, and known have excellent face cleanliness.
Then, according to the order identical with embodiment 1, carry out alkali, acid and scrub washing to the glass substrate with inorganic insulating membrane after being separated, and by the release surface of observation by light microscope with the glass substrate of inorganic insulating membrane, result has no crackle.
It should be noted that, about the duplexer A ~ G used in above-described embodiment 1 ~ 7, in above-mentioned disbonded test, between polyorganosiloxane resin layer and inorganic insulating membrane, create stripping, instead of between polyorganosiloxane resin layer and gripper shoe.Confirm from this point, adhesion between polyorganosiloxane resin layer and gripper shoe is greater than the adhesion between polyorganosiloxane resin layer and inorganic insulating membrane, in other words, the peel strength between polyorganosiloxane resin layer and gripper shoe is higher than the peel strength between polyorganosiloxane resin layer and inorganic insulating membrane.
< comparative example 1>
Use the glass substrate without inorganic insulating membrane to replace the glass substrate with inorganic insulating membrane used in embodiment 1, in addition, according to the order identical with embodiment 1, obtain duplexer H.Inorganic insulating membrane is not comprised in duplexer H.It should be noted that, to glass substrate and the face of resin layer surface contact side carry out pure water, then carry out UV washing, thus purifying.In addition, the surface roughness (Ra) of the glass substrate after purifying is 0.5nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the glass baseplate surface obtained by XPS adds up to content to be 1.0 atom %.
Then, according to the order identical with embodiment 1, after heating, carry out fissility evaluation, the glass substrate in duplexer H is separated with the gripper shoe with resin bed.
On the face contacted with resin bed of glass substrate after isolation, be attached with a part for the resin of resin bed, the appropriate section of resin layer surface on the supporting plate confirms breakage.
In addition, carry out cleanliness evaluation to the glass substrate after being separated, peel strength is 0.1N/25mm, knownly the resin be attached on surface fully cannot be removed.
After cutter removing resin, observe by the release surface of light microscope to glass substrate, in a part for release surface, see crackle produce.
< comparative example 2>
Use the glass plate that comprise soda-lime glass identical with embodiment 6 as gripper shoe and glass substrate, in addition, by the method identical with comparative example 1, obtain duplexer J.Inorganic insulating membrane is not comprised in duplexer J.It should be noted that, the surface roughness (Ra) of the glass substrate after purifying is 0.5nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the glass baseplate surface obtained by XPS adds up to content to be 1.5 atom %.
Then, according to the order identical with embodiment 1, after heating, carry out fissility evaluation, the glass substrate in duplexer J is separated with the gripper shoe with resin bed.
On the face contacted with resin bed of glass substrate after isolation, be attached with a part for the resin of resin bed, the appropriate section of resin layer surface on the supporting plate confirms breakage.
In addition, carry out cleanliness evaluation to the glass substrate after being separated, peel strength is 0.1N/25mm, knownly the resin be attached on surface fully cannot be removed.
< comparative example 3>
Use identical with embodiment 7 chemical enhanced after glass plate as gripper shoe and glass substrate, in addition, by the method identical with comparative example 1, obtain duplexer K.Inorganic insulating membrane is not comprised in duplexer K.It should be noted that, the surface roughness (Ra) of the glass substrate after purifying is 0.5nm.In addition, the atom being measured the alkali and alkaline earth metal ions in the glass baseplate surface obtained by XPS adds up to content to be 1.5 atom %.
Then, according to the order identical with embodiment 1, after heating, carry out fissility evaluation, the glass substrate in duplexer K is separated with the gripper shoe with resin bed.
On the face contacted with resin bed of glass substrate after isolation, be attached with a part for the resin of resin bed, the appropriate section of resin layer surface on the supporting plate confirms breakage.
In addition, carry out cleanliness evaluation to the glass substrate after being separated, peel strength is 0.1N/25mm, knownly the resin be attached on surface fully cannot be removed.
< comparative example 4>
By carrying out roughening to glass baseplate surface spraying (the about 60 seconds) buffered hydrofluoric acid used in comparative example 1, this roughening glass substrate is used to replace the glass substrate with inorganic insulating membrane used in embodiment 1, according to the order identical with embodiment 1, obtain duplexer L.Inorganic insulating membrane is not comprised in duplexer L.It should be noted that, roughening glass substrate carry out pure water with the face of resin bed contact side, then carry out UV washing, thus purifying.
The roughening glass substrate obtained purifying after the surface roughness (Ra) on surface (face after roughening) be 100nm.In addition, measured by XPS the roughening glass substrate that obtains purifying after surface in the atom of alkali and alkaline earth metal ions add up to content to be 1.1 atom %.
Then, according to the order identical with embodiment 1, after heating, carry out fissility evaluation, the glass substrate in duplexer L is separated with the gripper shoe with resin bed.
On the face contacted with resin bed of glass substrate after isolation, be attached with a part for the resin of resin bed, the appropriate section of resin layer surface on the supporting plate confirms breakage.
< embodiment 8>
In this example, the duplexer C obtained in embodiment 3 is used to manufacture OLED.
Be supplied to the operation forming transparency electrode, form the operation of auxiliary electrode, the operation of evaporation hole injection layer, hole transporting layer, luminescent layer, electron supplying layer etc., by the operation that gains seal, thus forms organic EL structure on the glass substrate of duplexer C.There is the duplexer C (hereinafter referred to as panel C) of organic EL structure on the glass substrate, for of the present invention with the display unit panel of supporter.
Then, by the sealing side vacuum suction of panel C on platen, then in the glass substrate in the bight of panel C and the interface of resin bed, the stainless steel cutter of inserting thickness 0.1mm, gives the inorganic insulation layer of glass substrate and the interface of resin bed and peels off starting point.Then, with the gripper shoe surface of 24 vacuum suction pad absorption panel C, from the absorption layer in the bight close to panel C, it is sequentially made to raise afterwards.Its result, platen only remains the glass substrate being formed with organic EL structure, the gripper shoe with resin bed can be peeled off.
Then, use laser cutting method or line sliver method (ス Network ラ イ ブ ー Block レ イ Network method), glass substrate after being separated is cut, after being cut into 288 unit of vertical 41mm × horizontal 30mm, assembling is formed with glass substrate and the counter substrate of organic EL structure, implement module generation operation, thus make OLED.The OLED obtained so characteristically can not have problems.
Describe the present invention with reference to detailed and specific embodiment, but it is obvious to the skilled person that when not departing from the scope of the present invention with spirit, various amendment, change can be carried out to the present invention.
The Japanese patent application 2011-095632 that the application submitted to based on April 22nd, 2011, is incorporated in the present invention as a reference in this its content.
Symbol description
10 duplexers
20 glass substrates
22 inorganic insulating membranes
24 with the glass substrate of inorganic insulating membrane
First interarea of 201 glass substrates
Second interarea of 202 glass substrates
221 inorganic insulating membrane surfaces
30 reinforcement plates (gripper shoe with resin bed)
31 gripper shoes
32 resin beds
321 resin layer surfaces
40 with the display unit panel of gripper shoe
The member of formation of 50 display unit panels
60 display unit panels

Claims (14)

1. a duplexer, it has the layer of the layer of gripper shoe, resin bed and the glass substrate with inorganic insulating membrane successively, and the inorganic insulating membrane of the described glass substrate with inorganic insulating membrane contacts with described resin bed, wherein,
It is described with in the glass substrate of inorganic insulating membrane,
Have inorganic insulating membrane at the one side of glass substrate, described inorganic insulating membrane contains the oxide of at least one in the group comprising and be selected from and be made up of Silicified breccias, nitride or oxynitride,
In the face contacted with described resin bed of described inorganic insulating membrane, the atom of alkali and alkaline earth metal ions adds up to content to be 0.5 below atom %,
The peel strength at the layer of described gripper shoe and the interface of described resin bed is higher than the peel strength at the interface of described resin bed and described inorganic insulating membrane.
2. duplexer as claimed in claim 1, wherein, described inorganic insulating membrane is the film comprising silica, silicon nitride, silicon oxynitride or aluminium oxide.
3. duplexer as claimed in claim 1 or 2, wherein, the surface roughness (Ra) in the face contacted with described resin bed of described inorganic insulating membrane is less than 30nm.
4. duplexer as claimed in claim 1 or 2, wherein, the thickness of described inorganic insulating membrane is 5 ~ 5000nm.
5. duplexer as claimed in claim 1 or 2, wherein, the thickness of described glass substrate is 0.03 ~ 0.8mm.
6. duplexer as claimed in claim 1, wherein, the resin of described resin bed is polyorganosiloxane resin.
7. duplexer as claimed in claim 6, wherein, described polyorganosiloxane resin is the reaction solidfied material of olefinic organic based polysiloxane and organic hydrogen polysiloxanes.
8. duplexer as claimed in claims 6 or 7, wherein, the thickness of described resin bed is 1 ~ 100 μm.
9. duplexer as claimed in claims 6 or 7, wherein, described gripper shoe is glass plate.
10. a manufacture method for duplexer, for the manufacture of the duplexer successively with the layer of gripper shoe, resin bed and the layer with the glass substrate of inorganic insulating membrane, wherein,
Prepare the glass substrate with inorganic insulating membrane, the described glass substrate with inorganic insulating membrane has inorganic insulating membrane at the one side of glass substrate, described inorganic insulating membrane contains the oxide of at least one in the group comprising and be selected from and be made up of Silicified breccias, nitride or oxynitride, and in the face contacted with described resin bed of described inorganic insulating membrane, the atom of alkali and alkaline earth metal ions adds up to content to be 0.5 below atom %;
Prepare the gripper shoe with resin bed, the described gripper shoe with resin bed has the described resin bed of the one side being fixed to described gripper shoe, and the surface of exposing of this resin bed has non-tack;
Using the face of the inorganic insulating membrane of the described glass substrate with inorganic insulating membrane, with the resin layer surface of the described gripper shoe with resin bed as lamination surface, by the described glass substrate with inorganic insulating membrane and the described gripper shoe with resin bed stacked.
The manufacture method of 11. duplexers as claimed in claim 10, wherein, the described gripper shoe with resin bed is have the gripper shoe of olefinic organic based polysiloxane and organic hydrogen polysiloxanes being reacted in this gripper shoe the layer solidifying the polyorganosiloxane resin obtained.
12. 1 kinds of display unit panels with gripper shoe, have the duplexer according to any one of claim 1 ~ 9 and are arranged on the display device component of glass baseplate surface of described duplexer.
13. 1 kinds of display unit panels, it removes by the gripper shoe with resin bed being peeled off from the display unit panel with gripper shoe according to claim 12 using the interface of described inorganic insulating membrane and described resin bed as release surface and is formed.
14. 1 kinds of display unit, have display unit panel according to claim 13.
CN201280019767.8A 2011-04-22 2012-04-17 Laminate, method for producing same, and use of same Expired - Fee Related CN103492173B (en)

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