CN107030393A - The cutting-off method of glass laminate - Google Patents
The cutting-off method of glass laminate Download PDFInfo
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- CN107030393A CN107030393A CN201611008161.0A CN201611008161A CN107030393A CN 107030393 A CN107030393 A CN 107030393A CN 201611008161 A CN201611008161 A CN 201611008161A CN 107030393 A CN107030393 A CN 107030393A
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- Prior art keywords
- glass
- resin bed
- glass plate
- laser
- formula
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- 0 CC(C(CC1C(S)=O)C2CC1C(C)=*)OC2=O Chemical compound CC(C(CC1C(S)=O)C2CC1C(C)=*)OC2=O 0.000 description 2
- YHIBTPHFIKHKSY-UHFFFAOYSA-N NC1C=CC(N)=CC1 Chemical compound NC1C=CC(N)=CC1 YHIBTPHFIKHKSY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B33/00—Severing cooled glass
- C03B33/07—Cutting armoured, multi-layered, coated or laminated, glass products
- C03B33/076—Laminated glass comprising interlayers
- C03B33/078—Polymeric interlayers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/38—Removing material by boring or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28D—WORKING STONE OR STONE-LIKE MATERIALS
- B28D5/00—Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor
- B28D5/04—Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor by tools other than rotary type, e.g. reciprocating tools
-
- 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
- B32B17/10005—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 laminated safety glass or glazing
- B32B17/10009—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B33/00—Severing cooled glass
- C03B33/08—Severing cooled glass by fusing, i.e. by melting through the glass
- C03B33/082—Severing cooled glass by fusing, i.e. by melting through the glass using a focussed radiation beam, e.g. laser
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B33/00—Severing cooled glass
- C03B33/09—Severing cooled glass by thermal shock
- C03B33/091—Severing cooled glass by thermal shock using at least one focussed radiation beam, e.g. laser beam
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Plasma & Fusion (AREA)
- Laminated Bodies (AREA)
- Laser Beam Processing (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
A kind of cutting-off method of the glass laminate for the cutting residual for reducing resin bed than ever is provided.The cutting-off method of the glass laminate is characterised by, the glass laminate is laminated with the 1st glass plate and 2nd glass plate thinner than the 1st glass plate across resin bed, the cutting-off method has the process that laser is irradiated to the glass laminate, the pulse energy density F [J/mm of the laser2] and Duplication [%] L meet following formula (A) and formula (B)：The formula (A) of F >=3；F ＞ 0.09L+11.8 formulas (B).Here, L=(D0 v/f)/D0 × 100, D0 represents the spotlight diameter (mm) of the pulse of the laser, and v represents cut-off velocity (mm/s), and f represents the frequency of oscillation (Hz) of the laser.
Description
Technical field
The present invention relates to the cutting-off method of glass laminate.
Background technology
All the time, as organic el display/panel substrate, using glass plate, recently, also begin to making and use
The substrate of the resin plates such as polyimides.Resin plate is flexible more excellent compared with glass plate, and the organic EL for easily making bending is shown
Device/panel.Such organic EL panel is used for smart mobile phone, television set of display surface bending etc..
On the other hand, resin plate gas barrier property compared with glass plate is poor, therefore exists through moisture, oxygen from extraneous air,
The problem of making element deterioration.Therefore, in order to solve such the problem of, carried out that resin film will be formed on the very thin plate of glass system
Prepared by complex be used for organic EL panel research.For example, Patent Document 1 discloses a kind of include cage model sesquialter silica
Alkane resin and glass plate, be used as flexibility/display glass substitutes the complex of substrate.
But, because such complex is to be formed on very thin glass plate obtained from resin film, therefore rigidity
It is low, it can be so easily bent because of own wt.When manufacturing organic el display/panel, used by being fitted on complex
In ensure its it is rigid support glass and make glass laminate, use the glass laminate carry out panel manufacture.Support glass
Glass is temporarily used in the manufacture of panel, is stripped after the manufacture of panel.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-107354 publications
Patent document 2：Japanese Unexamined Patent Publication 2015-78106 publications
The content of the invention
Problems to be solved by the invention
But, when using such glass laminate to manufacture the electronic devices such as organic el display/panel, exist sometimes
Problem is produced in the cut-out of glass laminate.
All the time, as the cutting-off method of complex, it is known that the use break bar (cutter as shown in patent document 2
Wheel method).By break bar glass plate surface cut score line after to glass plate imposed load so that with cut
Line is that starting point cuts folding glass plate.
But, when using the high resin bed of Fracture Toughness as polyimides as resin bed, even if glass sometimes
Plate is cut off, and a part for resin bed is also not switched off, and remains as the state of connection.
Therefore, there is provided a kind of cutting compared with the past for reducing resin bed is residual for the problem of present invention is in order to solve such
The cutting-off method for the glass laminate stayed.
The solution used to solve the problem
An embodiment of the invention is the cutting-off method of glass laminate, it is characterised in that the glass laminate
The 1st glass plate and 2nd glass plate thinner than the 1st glass plate are laminated with across resin bed, the cutting-off method has to glass
Layered product irradiates the process of laser, the pulse energy density F [J/mm of the laser2] and Duplication [%] L meet following formula (A) and
Formula (B).
The formula (A) of F >=3
F ＞ -0.09L+11.8 formulas (B)
Here, L=(D0-v/f)/D0 × 100, D0 represents the spotlight diameter (mm) of the pulse of the laser, and v represents cut-out
Speed (mm/s), f represents the frequency of oscillation (Hz) of the laser.
In other embodiments of the present invention, resin bed is the layer comprising polyimides.
In other embodiments of the present invention, laser is by CO2The laser that laser is obtained.
In other embodiments of the present invention, the thickness of the 1st glass plate is more than 0.1mm and below 1.1mm.
In other embodiments of the present invention, the thickness of the 2nd glass plate is more than 0.03mm and below 0.3mm.
In other embodiments of the present invention, the thickness of resin bed is more than 0.1 μm and less than 100 μm.
The effect of invention
The present invention can provide the cutting-off method of the glass laminate of the cutting residual compared with the past for reducing resin bed.
Brief description of the drawings
Fig. 1 is the side view for an embodiment for representing the shearing device of the present invention.
Fig. 2 is the top view for representing to cut off the situation of glass laminate.
Fig. 3 (a) is that sectional view, (b) of an embodiment for representing complex are an implementation for representing complex
Portion fractures sectional view, (c) of mode are the sectional views for an embodiment for representing glass laminate.
Fig. 4 is the flow chart of one for representing the process untill the cut-out for being fabricated onto layered product of polyamic acid solution.
Fig. 5 is the explanation figure for illustrating Duplication.
Fig. 6 is the figure for the relation for representing embodiment, the pulse energy density of comparative example and Duplication.
Description of reference numerals
10：Glass laminate
10a：Complex
11：Glass plate
12：Resin bed
13：Support glass
14：Cut off preset lines
15：Laser-irradiated domain
20：Shearing device
21：XY platforms
22：Nozzle
22a：Pipe
23：Transmit optical system
24：Laser oscillator
FS：Focus
AG：Aid in gas
LB：Laser
Embodiment
Hereinafter, an embodiment of the invention is illustrated.
Fig. 1 represents an embodiment of the shearing device of the present invention.In shearing device 20, main composition, tool are used as
Standby XY platforms 21, nozzle 22, transmission optical system 23 and laser oscillator 24.Nozzle 22 is to possess poly- in metal housing
The nozzle of optical lens, is connected with the side of housing for the pipe 22a by gas AG importing nozzles 22 are aided in.Laser oscillator 24
For CO2Laser, YAG (yttrium-aluminium-garnet, Yttrium Aluminum Garnet) laser, excimer laser, copper evaporation
The laser oscillators such as laser, in the cut-out of glass laminate, preferably use CO2Laser.
Glass laminate 10 be on the complex that the interarea of glass plate 11 makes the film forming of resin bed 12 with peelable
From state laminating support glass (carrier glass) 13 obtained from.Wherein, cut-out object of the invention also includes complex.
When cutting off glass laminate 10, glass laminate 10 is loaded on XY platforms 21, nozzle 22 is configured above it.Glass
Glass layered product 10 can make support glass (carrier glass) 13 be located at downside, and glass plate 11 can also be made to configure with being located at downside
On XY platforms 21.Collector lens is pre-set in nozzle 22, the collector lens makes laser LB focus FS converge in glassy layer
The desired depth of stack 10.Then, laser LB is irradiated when moving XY platforms 21, thereby, it is possible to which glass laminate 10 is cut off.
When irradiating laser LB, by blowing auxiliary gas AG to place of incision simultaneously, so as to which the resin melted, glass are blown
Fly, cutting portion can be prevented to be bonded again because of melten glass etc..It should be noted that auxiliary gas AG species is not limited especially
It is fixed, non-flammable gases are preferably used, nitrogen, argon gas etc. can be used.
Fig. 2 is the top view of situation for representing to cut off glass laminate.Glass laminate 10 and XY platforms 21 together edge
Arrow A directions are conveyed.The part (laser-irradiated domain 15) for the laser LB contacts irradiated from Fig. 1 nozzle 22 is along glass laminate
Cut-out preset lines 14 (dotted line) on 10 are mobile, carry out the cut-out of glass laminate 10.Here, by conveying glass laminate 10
Move the position of laser-irradiated domain 15, but it is also possible to using the composition fixed glass laminate 10 and move nozzle 22
To replace aforesaid way.In addition, cut-out preset lines 14 are not limited to straight line, it would however also be possible to employ curve, circular arc, dashed line etc. are any
Line.In addition, the shape of glass laminate 10 is not limited to rectangle.
Fig. 3 (a), (b) represents an embodiment of the glass laminate of the present invention.Complex 10a has in glass
The resin bed 12 formed by polyimide resin of regulation structure etc. of film forming on plate 11.The surface 12b and glass of resin bed 12
The 1st interarea 11a contacts of plate 11, the surface 12a of its opposite side does not contact other materials.(c) that complex 10a passes through such as Fig. 3
The shown surface 12a by resin bed 12 is laminated in the way of directly being contacted with support glass 13, so as to in glass plate 11
The component formation process of the electronic device components such as upper manufacture organic el display/panel, liquid crystal display/panel.
Glass laminate 10 forms TFT (thin in component formation process described later on the 2nd interarea 11b of glass plate 11
Film transistor, Thin Film Transistor) etc. electronic device component.Thereafter, it is formed with the glass of electronic device component
Glass layered product 10 is separated into support glass 13 and complex 10a.Stripped support glass 13 can be answered by the way that stacking is new
It is fit and recycled, other purposes (being used for manufacture of large-scale liquid crystal TV set etc.) can also be reused in.
It should be noted that resin bed 12 is fixed on glass plate 11, complex 10a is with resin bed 12 and support glass
13 modes directly contacted are strippingly layered on support glass 13, and both are closely sealed.In the present invention, " fixation " with it is peelable
From " closely sealed " had differences in peel strength (peel off required stress), " fixation " means peel strength ratio " closely sealed "
It is bigger.That is, resin bed 12 and the stripping of the peel strength than resin bed 12 and the interface of support glass 13 at the interface of glass plate 11
Intensity is big.
More specifically, the interface of glass plate 11 and resin bed 12 has peel strength (x), to glass plate 11 and resin bed
When 12 interface applies the stress more than the peeling direction of peel strength (x), the interface of glass plate 11 and resin bed 12 is shelled
From.The interface of resin bed 12 and support glass 13 has peel strength (y), and the interface of resin bed 12 and support glass 13 is applied
More than the peeling direction of peel strength (y) stress when, resin bed 12 and support glass 13 interface it is peeling-off.
In glass laminate 10 (layered product for also referring to having electronic device component described later), above-mentioned peel strength (x) ratio
Above-mentioned peel strength (y) is high.Therefore, apply direction that glass 13 and glass plate 11 will be supported to peel off to glass laminate 10 should
During power, glass laminate 10, with supporting the interface of glass 13 peeling-off, is separated into complex 10a and support glass in resin bed 12
Glass 13.
In order to improve adhesive force of the resin bed 12 to glass plate 11, for example, it may be implemented in formation resin bed 12 on glass plate 11
Method (preferably make can by heat cure turn into comprising formula (1) represent repeat unit polyimide resin curability
Resin solidifies on glass plate 11, the method for forming defined resin bed 12).Using bonding force when solidifying, can be formed with
The resin bed 12 that high-bond is combined.
On the other hand, the adhesions of 12 pairs of the resin bed after solidification support glass 13 in above-mentioned solidification generally than producing
Adhesion is low.Therefore, by forming resin bed 12 on glass plate 11, support glass 13 is then made to overlap the table of resin bed 12
On face, the glass laminate 10 that peel strength (x), (y) meet desired relation can be manufactured.
Hereinafter, (glass 13, glass plate 11, resin bed are supported to each layer for constituting complex 10a and glass laminate 10
12) it is described in detail.
[support glass]
The composition of support glass 13 is not particularly limited, for example, can use glass (the sodium calcium containing alkali metal oxide
Glass etc.) or the various compositions such as alkali-free glass glass.Wherein, from the small aspect of percent thermal shrinkage, preferably alkali-free glass.
More specifically, the composition on support glass 13, from the aspect that the effect of the present invention is more excellent, is used as glass matrix group
Into being represented with the quality percentage of oxide benchmark, preferably following scope.
SiO2：50~73%
Al2O3：10.5~24%
B2O3：0~5%
MgO：0~10%
CaO：0~14.5%
SrO：0~24%
BaO：0~13.5%
MgO+CaO+SrO+BaO：8~29.5%
And then, from the more excellent aspect of effect of the present invention, more preferably following scope.
SiO2：53~70%
Al2O3：15~22%
B2O3：0.1~3%
MgO：1~7%
CaO：3~10%
SrO：0~12%
BaO：0~12%
MgO+CaO+SrO+BaO：10~25%
The thickness of support glass 13 is not particularly limited, and is preferably capable the manufacturing line with existing electronic device panel
The thickness handled glass laminate 10.For example, the thickness master of the glass plate used in present liquid crystal display/panel
Will 0.4~1.2mm scope, especially mostly 0.7mm or 0.5mm.Used in the thickness and existing process of glass laminate 10
Glass plate be same degree thickness when, can easily in existing manufacturing line flow, so it is preferred that.
For example, existing manufacturing line is in complex 10a thickness to be designed in the way of handling thickness 0.5mm substrate
During 0.1mm, the thickness for supporting glass 13 is set to 0.4mm or so.In addition, if existing manufacturing line is to handle thickness
The mode of 0.7mm glass plate is designed, when complex 10a thickness is 0.2mm, and the thickness for supporting glass 13 is set into 0.5mm
Left and right.
The complex 10a of present invention purposes is not limited to organic el display/panel, liquid crystal display/panel, also may be used
For solar power generation panel etc..Therefore, the thickness of support glass 13 is not limited, preferably 0.1~1.1mm thickness.
And then, in order to ensure complex 10a rigidity, support the thickness of glass 13 preferably thicker than complex 10a.In addition, support glass
13 thickness is preferably more than 0.3mm, and its thickness is more preferably 0.3~0.8mm, more preferably 0.4~0.7mm.
The surface for supporting glass 13 can be the abradant surface for having carried out mechanical lapping or the processing of chemical grinding, or also may be used
Think the non-etched face (black skin) for not being ground processing.From productivity ratio and cost aspect, preferably non-etched face
(black skin).
Support glass 13 that there is the 1st interarea and the 2nd interarea, and its shape is not limited, it is preferably rectangular.Rectangle refers to
The rectangle of essence, can have corner cut.Support glass 13 size do not limit, for example preferably 100~2000mm × 100~
2000mm, more preferably 500~1000mm × 500~1000mm.
[glass plate]
1st interarea 11a of glass plate 11 is contacted with resin bed 12, and electronics is made on the 2nd interarea 11b in opposite side
Device component.That is, glass plate 11 is the substrate used to form electronic device described later.
The species of glass plate 11 can be general glass plate, for example, can include LCD, OLED etc display device
Glass plate etc..The chemical proofing of glass plate 11, resistance to excellent moisture permeability, and percent thermal shrinkage is low.It is used as percent thermal shrinkage
Index, use linear expansion coefficient specified in JIS R 3102 (nineteen ninety-five revision).
When the linear expansion coefficient of glass plate 11 is big, due to many heat tracing processing in component formation process, therefore easily
Produce various unfavorable conditions.For example, in the case of forming TFT on glass plate 11, TFT glass plate will be formd under heating
During 11 cooling, there are problems that the worry that TFT position skew turns into because of the thermal contraction of glass plate 11.
Glass plate 11 is frit is melted and is moltened glass into obtained from tabular.It is used as its shaping side
Method, is general method, such as using float glass process, fusion method, slot draw method, vertical drawing process, Lubbers methods.Separately
Outside, the extremely thin glass plate 11 of thickness can be by the temperature that is heated to shaping by the glass for being temporarily configured to tabular, and utilizes
The means such as stretching are stretched and its thinning method (horizontal sheet process) is formed and is obtained.
The species of the glass of glass plate 11 is not particularly limited, preferably alkali-free pyrex, pyrex, sodium calcium glass
Glass, vagcor, other oxide system glass using silica as main component.It is used as oxide system glass, preferably base
The content of the silica converted in oxide is 40~90 mass % glass.The composition of glass plate 11 can be with support glass 13
It is identical.
Glass plate 11 is using species, the glass of its manufacturing process for being suitable for electronic device component.For example, for liquid crystal
The glass plate of panel, because the dissolution of alkali metal component is easily impacted to liquid crystal, therefore, the glass plate of liquid crystal panel
Constituted by the glass (alkali-free glass) for not including alkali metal component substantially and (wherein, generally comprised alkaline earth metal component).As above
Described, the glass of glass plate 11 is suitably selected according to the species and its manufacturing process of be applicable device.
From the viewpoint of the slimming and/or lightweight of glass plate 11, the thickness of glass plate 11 be preferably 0.3mm with
Under, more preferably below 0.15mm, more preferably below 0.10mm.During for below 0.3mm, glass plate 11 can be assigned
Good flexibility.During for below 0.15mm, glass plate 11 can be coiled into web-like.Wherein, the manufacture for glass plate 11 is held
Easily, the operation of glass plate 11 easily etc. reason, the thickness of glass plate 11 is preferably more than 0.03mm.
It should be noted that glass plate 11 can be constituted more than 2 layers, at this moment, the material for forming each layer can be
Same material, or not same material.For example, nesa coatings such as ITO etc. can be formed on the surface of glass plate 11.Separately
Outside, now, " thickness of glass plate 11 " refers to all layers of gross thickness.
[resin bed]
Resin bed 12, which has, makes glass plate 11 mutually closely sealed untill their lock out operation is carried out with support glass 13
Effect.The surface 12a contacted with support glass 13 of resin bed 12 is strippingly laminated (closely sealed) the 1st of support glass 13
On interarea.Resin bed 12 is with weak adhesion with supporting the 1st interarea of glass 13 to be combined, and the peel strength (y) at its interface is than tree
The peel strength (x) at the interface between lipid layer 12 and glass plate 11 is low.
That is, when glass plate 11 is separated with support glass 13, the 1st interarea and the interface of resin bed 12 in support glass 13
Peeling-off, the interface of glass plate 11 and resin bed 12 is difficult to peel off.In the present invention, it is possible to easily prop up from resin bed 12
The property that support glass 13 is peeled off is referred to as " fissility ".On the other hand, the 1st interarea and resin bed 12 of glass plate 11 are with relative difficult
The adhesion of stripping is combined.It should be noted that resin bed 12 and support glass 13 interface adhesion be it is glass laminated
It can be changed (i.e., before and after forming electronic device component on the face (the 2nd interarea 12b) of the glass plate 11 of body 10
Peel strength (x), peel strength (y) can change).But, after electronic device component is formed, peel strength
(y) it is also lower than peel strength (x).
Think that the adhesion that resin bed 12 and support glass 13 are produced with weak bonding force, by Van der Waals force is combined.In shape
After resin layer 12 in the case of its surface stacking support glass 13, it is believed that the polyimide resin in resin bed 12 is not with
Combined when showing the abundant imidizate of degree of bonding force with the adhesion produced by Van der Waals force.
But, the polyimide resin in resin bed 12 has a case that a certain degree of weak bonding force is many.Think i.e.
In the case of making cementability extremely low, after the manufacture of glass laminate 10, when being formed on electronic device component, by adding
Heat operation etc., the polyimides in resin bed 12 is be bonded with support glass 13, between resin bed 12 and the layer for supporting glass 13
Adhesion is raised.According to circumstances, can also be to the 1st master of the support glass 13 before the surface of the resin bed 12 before stacking, stacking
Face is laminated after carrying out the processing of the adhesion for decrease between the two.By carrying out non-adhesive processing etc. to the face to be laminated,
And be laminated after, resin bed 12 and the adhesion at the interface of support glass 13 can be weakened, weaken peel strength (y).
In addition, resin bed 12 is incorporated into the surface of glass plate 11 with the strong adhesion such as bonding force, bonding force.For example, such as
It is upper described, (preferably make to turn into the repetition represented comprising formula (1) by heat cure by forming resin bed 12 on glass plate 11
The curable resin of the polyimide resin of unit is in the surface cure of glass plate 11) so that by the polyimides being heating and curing
The layer of resin is adhered to the surface of glass plate 11, can obtain high-bond.Furthermore it is possible to implement to make the surface of glass plate 11 and resin
The processing (such as using the processing of coupling agent) of strong adhesion is produced between layer 12 to improve the surface of glass plate 11 and resin bed
Adhesion between 12.
The thickness of resin bed 12 is not particularly limited, preferably 0.1~100 μm, more preferably 0.5~50 μm, further
Preferably 1~30 μm.When the thickness of resin bed 12 is such scope, even if being mingled between resin bed 12 and support glass 13
Bubble, foreign matter, can also suppress glass plate 11 and be deformed defect.In addition, when the thickness of resin bed 12 is blocked up, when formation needs
Between and material, it is thus uneconomical, and there is a situation where heat resistance reduction.In addition, when the thickness of resin bed 12 is excessively thin, there is tree
Lipid layer 12 and the situation of the adaptation reduction of support glass 13.It should be noted that resin bed 12 can include more than 2 layers.This
When, " thickness of resin bed 12 " refers to all layers of gross thickness.
Surface roughness Ra preferably 0~2.0nm, more preferably 0~1.0nm of support glass 13 side surface of resin bed 12,
Further preferred 0.05~0.5nm.Surface roughness Ra within the above range when, complex 10a to support glass 13 it is closely sealed
Property it is excellent, be not susceptible to complex 10a position skew.Generally, the method for polyimide resin being configured into stratiform has：In system
The method for making extrusion molding after thermoplastic polyimide resin, will included by heat cure as polyimide resin
Curable resin solution be coated on base material after solidify it in substrate surface method.Later approach is due to easy
Resin bed 12 of the surface roughness Ra in above range is obtained, so it is preferred that.
Here, surface roughness Ra using AFM (Pacific Nanotefchnology companies manufacture,
Nano Scope IIIa；Scan Rate 1.0Hz, Sample Lines256, Off-line Modify Flatten
Order-2, Planefit order-2) it is measured.(it is based on " utilizing the surface of the Fine Ceramic Thim Films of AFM
Roughness assay method, JIS R 1683：2007”)
The polyimide resin of resin bed 12 includes the residue (X) and diamines with tetracarboxylic acid acids that following formula (1) is represented
The repeat unit of the residue (A) of class.It should be noted that polyimide resin contains the repeat unit of formula (1) expression as master
Composition (being 95 moles of more than % preferably with respect to whole repeat units), but it is also possible to contain other repeat units in addition
(for example, repeat unit that formula described later (2-1) or (2-2) are represented).It should be noted that the residue (X) of tetracarboxylic acid acids refers to
From tetrabasic carboxylic acid residue obtained from tetracarboxylic acid acids removal carboxyl, the residue (A) of Diamines refers to remove amino from Diamines and obtain
The diamines residue arrived.
In formula (1), X represent from tetracarboxylic acid acids remove carboxyl obtained from tetrabasic carboxylic acid residue, X total 50 mole % with
It is upper to include at least one of the group constituted selected from the group by following formula (X1)~(X4) expressions group.Wherein, from compound
Body 10a with supporting the fissility of glass 13 or the more excellent aspect of heat resistance of resin bed 12 to set out, preferably X total 80~
100 moles of % are included selected from least one of the group being made up of following formula (X1)~(X4) groups represented group, more excellent
Select X total substantial whole (100 moles of %) to include and be selected from what is be made up of following formula (X1)~(X4) groups represented
At least one of group group.It should be noted that X total less than 50 moles % include be selected from by following formula (X1)~
(X4) during at least one of the group of group composition represented group, complex 10a and support glass 13 fissility and resin
At least one of the heat resistance of layer 12 is poor.
In addition, " A " is represented from diamines residue, total 50 mole more than the % of " A " obtained from Diamines removal amino
Represent selected from least one of the group being made up of (A1)~(A7) groups represented group.Wherein, from complex 10a and support
The fissility of glass 13 or the more excellent aspect of the heat resistance of resin bed 12 are set out, preferably total 80~100 mole % of " A "
Comprising at least one of the group constituted selected from the group by following formula (A1)~(A7) expressions group, more preferably " A's " is total
Several substantial wholes (100 moles of %) is included in the group for being selected from and being made up of following formula (A1)~(A7) groups represented extremely
A kind of few group.It should be noted that A less than 50 moles total % are included to be selected from and represented by following formula (A1)~(A7)
Group composition at least one of group group when, the fissility of complex 10a and support glass 13 and resin bed 12 it is resistance to
At least one hot is poor.
It is excellent from complex 10a and the fissility of support glass 13 or the more excellent aspect of the heat resistance of resin bed 12
Choosing be：X total 80~100 mole % is included in the group for being selected from and being made up of following formula (X1)~(X4) groups represented
At least one group, and total 80~100 mole % of " A " includes the base for being selected from and being represented by following formula (A1)~(A7)
At least one of the group of group's composition group, more preferably：X total substantial whole (100 moles of %) is included and is selected from
At least one of the group being made up of following formula (X1)~(X4) groups represented group, and A total substantial whole
(100 moles of %) is included selected from least one of the group being made up of following formula (A1)~(A7) groups represented group.
Wherein, from complex 10a with support glass 13 fissility or resin bed 12 heat resistance it is more excellent in terms of go out
Hair, the group represented as " X ", preferred formula (X1) group represented and formula (X2), the group that more preferably formula (X1) is represented.
In addition, from complex 10a with support glass 13 fissility or resin bed 12 heat resistance it is more excellent in terms of go out
Hair, as " A ", is preferably selected from the group in the group that is made up of the group that formula (A1)~(A4) is represented, is more preferably selected from by formula
(A1) group in the group of the group composition~(A3) represented.
It is used as the suitable combination comprising formula (X1)~(X4) groups represented and formula (A1)~(A7) group represented
Polyimide resin, can be included：" X " is the group of the group composition for group and formula (X2) expression for selecting free style (X1) to represent
In group, " A " be select free style (A1)~(A5) represent group composition group in group polyimide resin, its
In, preferably include：The polyimide resin 1 that X is the group of formula (X1) expression, " A " is the group that formula (A1) is represented, and " X "
The group, the A that are represented for formula (X2) are the polyimide resin 2 for the group that formula (A5) is represented.Polyimide resin 1 and polyimides
In the case of resin 2, the long-term heat resistance aspect in the environment of 450 DEG C is preferred, is polyimide resin 1
When, the long-term heat resistance aspect in the environment of 500 DEG C is preferred.
In addition, be X be formula (X4) represent group, the combination that A is the group that formula (A6) and formula (A7) are represented when, from transparent
Property aspect to set out be preferred.
The repeat number (n) for the repeat unit that above-mentioned formula (1) represents is not particularly limited in polyimide resin, and preferably 2
More than integer, from the heat resistance and the film forming aspect of film of resin bed 12, more preferably 10~10000, further
Preferably 15~1000.The molecular weight of polyimide resin is from coating, heat resistance aspect preferably 500~100000.
For above-mentioned polyimide resin, in the range of it will not damage heat resistance, the sum of the residue (X) of tetracarboxylic acid acids
The 50 moles of % of being less than can be more than a kind in the group being made up of the group of following illustrations.Furthermore it is possible to include 2 kinds
The group of the following illustrations of the above.
In addition, for above-mentioned polyimide resin, in the range of it will not damage heat resistance, the residue (A) of Diamines
The 50 moles of % that are less than of sum can be more than a kind in the group being made up of the group of following illustrations.Furthermore it is possible to comprising
The group of two or more following illustration.
In addition, above-mentioned polyimide resin can have alkoxysilyl in molecular end.
As the method for importing alkoxysilyl in molecular end, have：The carboxyl with polyamic acid described later
Or the method for amino and the alkoxy silane containing epoxy radicals or part thereof condensation product reaction.Alkoxy silane containing epoxy radicals is for example
Can make in the molecule epoxide and alkoxy silane with hydroxyl or part thereof condensation product react and obtain.With hydroxyl
The preferred carbon number of epoxide of base is below 15, such as can enumerate glycidol.As alkoxy silane, it can enumerate
Go out：The three of the alkyl that tetraalkoxysilane that carbon number is less than 4 or the alkoxy for being less than 4 with carbon number are less than 8 with carbon number
Alkoxy silane.It can specifically include：The tetraalkoxy silicon such as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane
Trialkoxy silanes such as alkanes, MTMS etc..Epoxide and alkoxy first silicon in molecule with hydroxyl
The reaction of alkyl is preferably in the scope of hydroxyl equivalent/alkoxysilyl equivalent=0.001/1~0.5/1 of epoxide
Interior reaction.
And then, can also be formed the alkoxysilyl of the molecular end for making above-mentioned polyimide resin by heating at
Reason hydrolyzes and carries out sol gel reaction, the silicon dioxide structure of dealcoholization condensation reaction.During above-mentioned reaction, Ke Yijia
Enter alkoxy silane.As alkoxy silane, aforesaid compound can be used.
By making molecular end be silicon dioxide structure, the raising of heat resistance can be realized.In addition, it is sub- to reduce polyamides
The linear expansion coefficient of polyimide resin, even if the thinner thickness of supporting base material, can also reduce the warpage of the supporting base material of tape tree lipid layer.
The content of polyimide resin in resin bed 12 is not particularly limited, from complex 10a and support glass 13
The aspect that the heat resistance of fissility or resin bed 12 is more excellent is set out, relative to resin bed gross mass, preferably 50~100 matter
Measure %, more preferably 75~100 mass %, more preferably 90~100 mass %.
In resin bed 12, as needed, (can for example will not comprising other compositions in addition to above-mentioned polyimide resin
Hinder filler of heat resistance etc.).
As the filler of heat resistance will not be hindered, can include threadiness or tabular, flakey, granular, random shape,
The filler of the Non-fibrous such as broken product, specifically for example,：It is PAN systems, the carbon fiber of asphalt series, glass fibre, stainless
The metallic fibers such as steel fibre, aluminum fiber, brass fiber, gypsum fiber, ceramic fibre, asbestos fibre, Zirconium oxide fibre, aluminum oxide
Fiber, silicon dioxide fibre, titanium dioxide fiber, silicon carbide fibre, rock wool, potassium titanate crystal whisker, barium titanate whisker, aluminum borate crystal whisker
Palpus, silicon nitride crystal whisker, mica, talcum, kaolin, silica, calcium carbonate, glass microballoon, sheet glass, glass microsphere, clay,
Molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, metal powder, sheet metal, metal tape, metal oxide,
Carbon dust, graphite, carbon plate, flakey carbon, CNT etc..As metal powder, sheet metal, the metal species of metal tape it is specific
Example, can illustrate silver, nickel, copper, zinc, aluminium, stainless steel, iron, brass, chromium, tin etc..
Resin bed 12 is the layer of the polyimide resin formed on glass plate 11, the layer of the polyimide resin be as
Lower formation：To turning into the residue (X) with tetracarboxylic acid acids represented comprising above-mentioned formula (1) and Diamines by heat cure
The layer of the curable resin of the polyimide resin of the repeat unit of residue (A) or coating include above-mentioned polyimide resin
And layer obtained from the composition of solvent implement successively 60 DEG C less than 250 DEG C at heat the 1st heat and
The 2nd of more than 250 DEG C and less than 500 DEG C heating is heated, and is consequently formed.
On the manufacture method of resin bed 12, it will be described in detail in the manufacture method of the glass laminate of back segment.
[manufacture method of glass laminate]
As the 1st mode of the manufacture method of the glass laminate 10 of the present invention, using curable resin described later in glass
Resin bed 12 is formed in glass plate 11, then, stacking support glass 13, manufactures glass laminate 10 on resin bed 12.
Think to make curable resin in the surface cure of glass plate 11, by during curing reaction with the surface of glass plate 11
Interaction and be bonded, resin bed 12 and the peel strength on the surface of glass plate 11 are uprised.Therefore, even if glass plate 11 and support
Glass 13 is made up of phase same material, also resin bed 12 can be made to be had differences with peel strength between the two.
(resin bed formation process)
Resin bed 12 is the layer of the polyimide resin formed on a glass, the following shape of layer of the polyimide resin
Into：To turning into the residue (X) and the residue of Diamines with tetracarboxylic acid acids represented comprising above-mentioned formula (1) by heat cure
(A) layer of the curable resin of the polyimide resin of repeat unit implement successively 60 DEG C less than 250 DEG C at plus
Heat the 1st heat and more than 250 DEG C and less than 500 DEG C heat the 2nd heating, be consequently formed.Need explanation
Being that the total 50 mole % of the residue (X) of tetracarboxylic acid acids is contained above is selected from the group represented by above-mentioned formula (X1)~(X4)
At least one of group of composition group, the total 50 mole % of the residue (A) of Diamines is contained above to be selected from by above-mentioned formula
(A1) at least one of the group of group composition~(A7) represented group.
Resin bed formation process is following process：Have to being turned into by heat cure comprising above-mentioned formula (1) expression
The layer of the curable resin of the polyimide resin of the repeat unit of the residue (X) of tetracarboxylic acid acids and the residue (A) of Diamines according to
It is secondary implement 60 DEG C less than 250 DEG C at heat the 1st heat and more than 250 DEG C and less than 500 DEG C heat
2nd heats, and is derived from resin bed.As shown in Fig. 3 (a), in the process, at least one surface of glass plate 11
Form resin bed 12.
Hereinafter, it is divided into 3 following processes to illustrate resin bed formation process.
Process (1)：The polyimide resin of the repeat unit represented with above-mentioned formula (1) will be turned into by heat cure
Curable resin be coated on glass plate 11, so as to obtain the process of film
Process (2)：By film 60 DEG C less than 250 DEG C at the process that heats
Process (3)：By film further more than 250 DEG C and less than 500 DEG C heating, so as to form the process of resin bed
(film formation process)
In this process, the polyimide resin of the repeat unit represented with above-mentioned formula (1) will be turned into by heat cure
Curable resin be coated on glass plate 11, obtain film.It should be noted that curable resin, which is preferably comprised, makes tetrabasic carboxylic acid
Dianhydride and polyamic acid obtained from Diamines reaction, preferably at least a portion of tetracarboxylic dianhydride, which is included, is selected from by following formula
(Y1) compound group~(Y4) represented at least one of group tetracarboxylic dianhydride, at least a portion of Diamines includes choosing
The compound group that free following formula (B1)~(B7) is represented at least one of group Diamines.
It should be noted that repetition list of the polyamic acid generally to be represented comprising following formula (2-1) and/or formula (2-2)
The structural formula of member is represented.It should be noted that in formula (2-1), formula (2-2), X, A are as defined above.
The reaction condition of tetracarboxylic dianhydride and Diamines is not particularly limited, from can effectively synthesizing polyamides acid side
Face is set out, and is reacted preferably under -30~70 DEG C (preferably -20~40 DEG C).The blending ratio of tetracarboxylic dianhydride and Diamines does not have
It is particularly limited to, can includes：Relative to 1 mole of Diamines, make preferably 0.66~1.5 mole, more preferably 0.9~1.1
Mole, more preferably 0.97~1.03 mole tetracarboxylic dianhydride reaction.
In the reaction of tetracarboxylic dianhydride and Diamines, as needed, organic solvent can be used.It is used organic molten
The species of agent is not particularly limited, for example, can use：METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, N, N- diethyls
Yl acetamide, N,N-dimethylformamide, N, N- diethylformamides, N- methyl caprolactams, hexamethyl phosphoramide, four methylenes
Base sulfone, dimethyl sulfoxide (DMSO), metacresol, phenol, parachlorophenol, 2- chloro-4-hydroxyls toluene, diethylene glycol dimethyl ether, triethylene glycol
Dimethyl ether, tetraethyleneglycol dimethyl ether, dioxanes, gamma-butyrolacton, dioxolanes, cyclohexanone, cyclopentanone etc., can be applied in combination 2
More than kind.
During above-mentioned reaction, as needed, it can be applied in combination except selected from the compound represented by above-mentioned formula (Y1)~(Y4)
Other tetracarboxylic dianhydrides beyond tetracarboxylic dianhydride in the group of composition.
In addition, during above-mentioned reaction, as needed, can be applied in combination except selected from the change represented by above-mentioned formula (B1)~(B7)
Other Diamines beyond Diamines in the group of compound composition.
Obtained in addition, the curable resin used in this process can also be used except making tetracarboxylic dianhydride be reacted with Diamines
To polyamic acid beyond also added can with polyamic acid react tetracarboxylic dianhydride or Diamines obtained from mixture.Remove
When also adding tetracarboxylic dianhydride or Diamines beyond polyamic acid, it can make by tetracarboxylic dianhydride or Diamines with formula (2-
1) or formula (2-2) represent repeat unit the polyamic acid molecule of more than 2 combination.
When there is amino in the end of polyamic acid, tetracarboxylic dianhydride can be added, is made with 1 mole relative to polyamic acid
Carboxyl adds for 0.9~1.1 mole of mode.When there is carboxyl in the end of polyamic acid, Diamines can be added, with
Added relative to 1 mole of mode for making amino be 0.9~1.1 mole of polyamic acid.It should be noted that in polyamic acid
End when there is carboxyl, sour end can use addition water or arbitrary alcohol and obtained from making the anhydride group open loop of end
Group.
The tetracarboxylic dianhydride added afterwards is more preferably the compound of formula (Y1)~(Y4) expressions.The Diamines added afterwards
Preferably there are the Diamines of aromatic rings, the compound that more preferably formula (B1)~(B7) is represented.
Addition tetracarboxylic dianhydride's class or during Diamines afterwards, the repeat unit represented with formula (2-1) or formula (2-2) it is poly-
The degree of polymerization (n) of amic acid is preferably 1~20.When the degree of polymerization (n) is the scope, even if the polyamide in curable resin solution
Acid concentration is more than 30 mass %, and it is low viscosity that can also make curable resin solution.
In this process, the composition beyond curable resin can be used.
It is, for example, possible to use solvent.More specifically, curable resin can be made to be dissolved in solvent and with curable resin
The form of solution (curable resin solution) use.It is excellent as solvent, especially the dissolubility aspect from polyamic acid
Select organic solvent.As used organic solvent, the organic solvent used during above-mentioned reaction can be included.
It should be noted that one of suitable way as above-mentioned solvent, preferably uses boiling point (under 1 atmospheric pressure) and is less than
250 DEG C of solvent.During for the solvent, solvent is readily volatilized in the 1st heating treatment step, as a result, the outward appearance of film is more excellent.Need
It is noted that the lower limit of above-mentioned boiling point is not particularly limited, from treatability aspect, preferably more than 60 DEG C.
It should be noted that in curable resin solution include organic solvent when, as long as can adjust film thickness,
Coating can be made to become good amount, the content of organic solvent is just not particularly limited, generally, relative to curable resin solution
Gross mass, preferably 10~99 mass %, more preferably 20~90 mass %.
In addition, as needed, can be applied in combination for promoting the dehydrating agent of the dehydration closed-loop of polyamic acid or dehydration to close
Ring catalyst.For example, as dehydrating agent, the acid anhydrides such as can use acetic anhydride, propionic andydride, trifluoro-acetic anhydride.In addition, conduct
Dehydration closed-loop catalyst, the tertiary amine such as can use pyridine, trimethylpyridine, lutidines, triethylamine.
The method that curable resin (or curable resin solution) is coated with the surface of glass plate 11 is not particularly limited,
Known method can be used.It can such as include：Spraying process, die coating method, spin-coating method, Dipcoat method, rolling method, rod are applied
Method, silk screen print method, gravure coating process etc..
It is not particularly limited by the thickness of film obtained from above-mentioned processing, to obtain the resin bed of above-mentioned expectation thickness
12 mode is suitably adjusted.
(process (2)：1st heating treatment step)
Process (2) be by film 60 DEG C less than 250 DEG C at the process that heats., can by implementing this process
Removed it while solvent bumping is prevented, be difficult to form foaming, the film defect of orange peel shape.
The method of heating is not particularly limited, can be suitably using known method (for example, by the glass with film
The method that plate stands and heated in heated oven).
Heating-up temperature be 60 DEG C less than 250 DEG C, from further suppress resin bed foaming aspect, preferably
For 60~150 DEG C, more preferably 60~120 DEG C.In the range of heating-up temperature, particularly preferably in the temperature less than solvent boiling point
Lower heating.
Heat time is not particularly limited, and Best Times are suitably selected according to the structure of used curable resin,
From can further prevent the depolymerization aspect of polyamic acid, preferably 5~60 minutes, more preferably 10~30 minutes.
The atmosphere of heating is not particularly limited, for example, can implement in an atmosphere, under vacuum or in non-active gas.In vacuum
During lower implementation, heated under low temperature, also volatile ingredient can be removed with the shorter time, and can further control
The depolymerization of polyamic acid, so it is preferred that.
In addition, the 1st heating treatment step can also change heating-up temperature and heat time and stage by stage (2 is more than stage) reality
Apply.
(process (3)：2nd heating treatment step)
Process (3) be will be implemented in process (2) film of heating more than 250 DEG C and less than 500 DEG C heating
So as to the process for forming resin bed.Ring-closure reaction, shape are carried out by implementing polyamic acid contained in this process, curable resin
Into desired resin bed.
The method of heating is not particularly limited, can be suitably using known method (for example, by the glass with film
The method that plate stands and heated in heated oven).
Heating-up temperature is more than 250 DEG C and less than 500 DEG C, from residual solvent rate step-down and acid imide rate is further
Rise, complex 10a and the fissility of support glass 13 or the more excellent aspect of the heat resistance of resin bed 12 set out, and preferably 350
~500 DEG C.
Heat time is not particularly limited, and Best Times are suitably selected according to structure of used curable resin etc.,
Further raised from residual solvent rate step-down and acid imide rate, complex 10a and support glass 13 fissility or resin
The aspect that the heat resistance of layer 12 is more excellent is set out, preferably 15~120 minutes, more preferably 30~60 minutes.
The atmosphere of heating is not particularly limited, for example, can implement in an atmosphere, under vacuum or in non-active gas.
By forming the resin bed for including polyimide resin via above-mentioned operation (3).
The acid imide rate of polyimide resin is not particularly limited, from complex 10a and support glass 13 fissility
Or the more excellent aspect of heat resistance of resin bed 12 is set out, preferably more than 99.0%, more preferably more than 99.5%.
On the assay method of acid imide rate, 2 hours that curable resin is carried out to 350 DEG C under nitrogen atmosphere are heated
Situation as 100% acid imide rate, in the IR spectrograms of curable resin, pass through the peak from acid imide carbonyl：About
1780cm-1Peak intensity with heat the 2nd before and after constant peak intensity (for example originating from the peak of phenyl ring：About 1500cm-1)
Strength ratio is obtained.
(lamination process)
Lamination process is following process：On the face upper strata of the resin bed 12 obtained by above-mentioned resin bed formation process
Folded support glass 13, is possessed the glass laminate 10 of support glass 13, resin bed 12 and glass plate 11 successively.
The method for supporting glass 13 to be layered on resin bed 12 is not particularly limited, can be using known method.Example
It can such as enumerate：Under atmospheric pressure environment on the surface of resin bed 12 it is overlapping support glass 13 method.It should be noted that root
According to needs, on the surface of resin bed 12 after overlapping support glass 13, roller, press can be used to crimp support glass 13
In resin bed 12.Crimped by using roller or press, can relatively easily remove and be mixed into resin bed 12 and support glass 13
Layer between bubble, so it is preferred that.
When being crimped using vacuum layer platen press, vacuum pressing, can suppress bubble be mixed into, ensure it is good closely sealed,
So more preferably.By being crimped under vacuo, even if the small bubble of residual, bubble will not also grow up because of heating, also
There is the deformation defect for not being easily caused support glass 13.In addition, by being crimped under heating in vacuum, being less susceptible to residual
Stay bubble.In stacking support glass 13, it is preferred that the surface of pair support glass 13 contacted with resin bed 12 carries out abundant
Cleaning, is laminated under the high environment of cleannes.Cleannes are higher, support the flatness of glass 13 better, so it is preferred that.
It should be noted that after stacking support glass 13, as needed, pre-anneal treatment can be carried out (at heating
Reason).By carrying out the pre-anneal treatment, the support glass 13 of stacking is improved to the adaptation of resin bed 12, resulted in suitable
Peel strength (y), be not susceptible in component formation process described later electronic device component position skew etc., electronics device
The productivity ratio of part is improved.
The condition of pre-anneal treatment species of resin bed 12 used in suitably selects optimum condition, from making support
The more appropriate aspect of peel strength (y) between glass 13 and resin bed 12 is set out, preferably more than 200 DEG C (preferably 200~
400 DEG C) carry out more than 5 minutes (preferably 5~30 minutes) heating.
(glass laminate)
The glass laminate 10 of the present invention can be used for various uses, can for example enumerate manufacture display device panel,
Solar cell, the primary cell of film 2, the purposes for being formed with surface the electronic units such as semiconductor crystal wafer, the liquid crystal lens of circuit
Deng.It should be noted that in the purposes, glass laminate 10 is exposed under hot conditions (such as more than 400 DEG C) (for example mostly
More than 1 hour).
Here, display device is shown with panel including LCD, OLED, Electronic Paper, plasm display panel, field emission
Show that panel, quantum dot LED panel, MEMS (microelectromechanical systems, Micro Electro Mechanical Systems) are fast
Door face board etc..
It should be noted that the mode of the supporting base material to being manufactured tape tree lipid layer using curable resin has been carried out in detail above
Describe in detail bright, but it is also possible to compound to manufacture using layer obtained from composition of the coating comprising above-mentioned polyimide resin and solvent
Body.More specifically, composition of the coating comprising above-mentioned polyimide resin and solvent can also be formed on a glass and is obtained
The layer (film) arrived, and carry out successively 60 DEG C less than 250 DEG C at heat the 1st heat and more than 250 DEG C
And the 2nd of less than 500 DEG C heating is heated, and thus manufactures complex.
The species of used polyimide resin is as described above.In addition, the species of used solvent is not limited especially
It is fixed, it can for example enumerate solvent contained in above-mentioned curable resin solution.
(cutting-off method of glass laminate)
Configuration example to the cutting-off method of glass laminate described above is illustrated.
Here, make support glass 13 be the 1st glass plate, make glass plate 11 be the 2nd glass plate.I.e., it is possible to will be across resin
The layered product of the 1st glass plate and 2nd glass plate thinner than the 1st glass plate is laminated with layer by layer as the glassy layer illustrated since so far
Stack.
Also, the cutting-off method of the glass laminate of present embodiment can have as illustrated in fig. 1 to glass laminate
Irradiate the process of laser.
Also, the pulse energy density F [J/mm of the laser2] and Duplication [%] L preferably meet following formula (A) and formula
(B)。
The formula (A) of F >=3
F ＞ -0.09L+11.8 formulas (B)
Here, L=(D0-v/f)/D0 × 100, D0 represents the spotlight diameter (mm) of the pulse of aforementioned laser, and v represents cut-out
Speed (mm/s), f represents the frequency of oscillation (Hz) of aforementioned laser.
It is compared with the past according to the cutting-off method of the glass laminate, the cutting residual of resin bed can be reduced.
Embodiment
Fig. 4 is the stream of one for representing the series of processes untill the cut-out for being fabricated onto layered product of polyamic acid solution
Cheng Tu.
The manufacture ＞ of ＜ polyamic acid solutions
P-phenylenediamine (10.8g, 0.1mol) is dissolved in DMA (198.6g), be stirred at room temperature.
BPDA (29.4g, 0.1mmol) was added wherein with 1 minute, is stirred at room temperature 2 hours, and obtaining including has above-mentioned formula (2-
1) and/or formula (2-2) represent repeat unit polyamic acid the mass % of solid component concentration 20 polyamic acid solution
(P1) (step S1).
The viscosity of the solution is determined, is as a result 5000 centipoises at 20 DEG C.It should be noted that viscosity is to use TOKYO
KEIKI INC. manufactures, DVL-BII types Digital viscometer (Brookfield viscometer) are determined obtained from the rotary viscosity at 20 DEG C.It is poly-
Group, the A that X in the repeat unit that contained formula (2-1) and/or formula (2-2) are represented in amic acid represents for (X1) are formula
(A1) group represented.
The manufacture ＞ of ＜ glass laminates
First, thickness of slab 0.1mm glass plate is cleaned with pure water, then, then UV cleanings is carried out, carries out purifying (step
S2)。
Then, spin coater (rotating speed is utilized：2000rpm, 15 seconds) polyamic acid solution (P1) is coated on the 1st of glass plate
On interarea (step S3), the film comprising polyamic acid is set into (coated weight 2g/m on a glass2).It should be noted that
Above-mentioned polyamic acid is resin obtained from the compound reaction that the compound for representing formula (Y1) is represented with formula (B1).
Then, in an atmosphere, film is heated at 60 DEG C 15 minutes, then 120 DEG C heat 15 minutes, and then, will
Film is heated 15 minutes at 350 DEG C, forms resin bed (step S4).Being included in the resin bed of formation has following formula (3)
(X in formula (1) is made up of the polyimide resin of the repeat unit of expression (X1) group represented, the base that A is represented by formula (A1)
Group is constituted).
It should be noted that acid imide rate is 99.7%.In addition, the surface roughness Ra of the resin layer surface formed is
0.2nm.The assay method of acid imide rate and the assay method of surface roughness Ra are implemented according to above-mentioned method.
Thereafter, suppressed at room temperature by vacuum and the resin bed 12 for supporting glass 13 and complex 10a is fitted, obtain glass
Glass layered product 10 (step S5).
In obtained glass laminate 10, support glass 13 and glass plate 11 closely sealed without producing bubble with resin bed 12,
Also shape defect is not become, flatness is also good.It should be noted that in glass laminate 10, glass plate 11 and resin bed 12
Interface peel strength (x) it is higher than resin bed 12 and the peel strength (y) at the interface of support glass 13.
Then, above-mentioned glass laminate 10 heat within 60 minutes at 450 DEG C under air, be cooled to room temperature
(step S6), as a result, do not confirm separation, resin beds 12 of the complex 10a in glass laminate 10 with supporting glass 13
The apparent change such as foaming, albefaction.
Thereafter, the glass laminate after above-mentioned heating is cut off into (step S7) using carbon dioxide laser.
(embodiment 1)
Here, embodiment, comparative example obtained from change cut-out condition are illustrated.
From support glass 13 side, from surface to the vertically incident laser LB of glass laminate 10.Now, pulse energy is close
Degree is set to 14.1J/mm2, Duplication be set to 25%.Here, pulse energy density refer to laser LB average pulse energy divided by
It is worth obtained from pulse area.Duplication L following formula 4 represents that schematic diagram is as shown in Figure 5.
D0 represents that spotlight diameter (mm), the v of laser LB pulse represent that cut-off velocity (mm/s), f represent shaking for laser LB
Swing frequency (Hz).After the hot spot SP1 for forming pulse, next hot spot SP2 is travelling displacement v/f's [mm] away from SP1
Position is formed.
The formula (4) of L=(D0-v/f)/D0 × 100
Table 1,2 represents embodiment, and table 3,4 represents comparative example.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Shadow surface | Support glass 13 | Support glass 13 | Support glass 13 | Support glass 13 |
| Duplication % | 25 | 50 | 70 | 50 |
| Pulse energy density J/mm2 | 14.1 | 9.4 | 7.1 | 11.8 |
| Cut-out judges | ◎ | ◎ | ○ | ○ |
[table 2]
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Shadow surface | Support glass 13 | Support glass 13 | Support glass 13 | Support glass 13 |
| Duplication % | 25 | 0 | 0 | 0 |
| Pulse energy density J/mm2 | 23.5 | 31.3 | 20.9 | 15.7 |
| Cut-out judges | ◎ | ○ | ○ | ○ |
[table 3]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Shadow surface | Support glass 13 | Support glass 13 | Support glass 13 | Support glass 13 |
| Duplication % | 83 | 80 | 70 | 67 |
| Pulse energy density J/mm2 | 4.4 | 2.6 | 3.5 | 4.4 |
| Cut-out judges | × | × | × | × |
[table 4]
| Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Shadow surface | Support glass 13 | Support glass 13 | Support glass 13 | Support glass 13 |
| Duplication % | 50 | 25 | 25 | 0 |
| Pulse energy density J/mm2 | 7.8 | 9.4 | 7 | 11.8 |
| Cut-out judges | × | × | × | × |
The meaning of symbol in each table is as follows.
◎：Easily, end face is coarse small for opening operation
○：Opening operation is needed, but can be disconnected
×：It can not cut off
(remarks) here, " opening operation " refers to, the glass laminate imposed load after being irradiated manually to laser, with laser
Irradiation portion is the operation that border separates glass laminate.
As glass plate 11, glass plate (vertical 200mm, horizontal 200mm, the thickness of slab formed by alkali-free pyrex is used
0.1mm, linear expansion coefficient 38 × 10-7/ DEG C, Asahi Glass Co., Ltd manufacture：Trade name " AN100 ").In addition, being used as support glass
Glass 13, using the glass plate with the same composition of glass plate 11, but uses the size glass plate different with thickness of slab (vertical 240mm, horizontal stroke
240mm, thickness of slab 0.5mm).
Other conditions are as follows.Glass laminate 10 after cut-out diametrically 160mm's is round-shaped.Constitute the glass after cut-out
The thickness of the support glass 13 of glass layered product 10 is that 0.5mm, the thickness of glass plate 11 are 0.1mm.Auxiliary gas AG species is
N2.The flow for aiding in gas AG is 50l/min.Laser LB spotlight diameter D0 is 0.3mm.The thickness of resin bed 12 is 23 μm.
Result above, has sufficient energy density under conditions of embodiment 1, by the Duplication that selection is suitable,
So as to occur the welding as caused by glass for melting etc. in laser irradiating part, it is not necessary to which opening operation is cut-off glassy layer
Stack.
(embodiment 2~4)
Pulse energy density and Duplication in embodiment 1 is changed to the value shown in table, other by embodiment 2~4
Part is same as Example 1.
(comparative example 1~8)
Pulse energy density and Duplication in embodiment 1 is changed to the value shown in table, other by comparative example 1~8
Part is same as Example 1.Its energy density is not enough, and laser is substantially all non-through glass laminate, it is impossible to cut off glassy layer
Stack.
As indicated above, it is known that can the Duplication of laser and the selection of value of pulse energy density be cut off to glass laminate
Have a great impact.
Fig. 6 represents the embodiment of table 1,2, the pulse energy density of the comparative example of table 3,4 and the relation of Duplication.Such as figure
It is shown, zero, ◎ result concentrate on upper area substantially, × concentrate on lower area.Thus, it is possible to straight line will × point
The region of cloth and ◎ and the region disconnecting of zero distribution.It is as follows during by the straight line formula, it is known that in cutting for glass laminate
In disconnected, the preferably pulse energy density F [J/mm of laser2] and Duplication [%] L meet following formula 5-1 and formula 5-2.
The formula (5-1) of F >=3
F ＞ -0.09L+11.8 formulas (5-2)
Embodiments of the present invention and embodiment are illustrated above, but the present invention is not limited to the above,
Various modifications and replacement can be carried out to above-mentioned embodiment and embodiment by not departing from the scope of the present invention.
Industrial applicability
As described above, the present invention can be easily by the glass comprising glass plate and resin bed for being difficult to cut off in the past
Layered product is cut off.Therefore, the present invention can be applied to the manufacture of various display device panels.
Claims (6)
1. a kind of cutting-off method of glass laminate, it is characterised in that the glass laminate is laminated with the 1st glass across resin bed
Glass plate and 2nd glass plate thinner than the 1st glass plate,
The cutting-off method has the process that laser is irradiated to the glass laminate,
Pulse energy density F [the J/mm of the laser2] and Duplication [%] L meet following formula (A) and formula (B),
The formula (A) of F >=3
F ＞ -0.09L+11.8 formulas (B)
Here, L=(D0-v/f)/D0 × 100, D0 represents the spotlight diameter (mm) of the pulse of the laser, and v represents cut-off velocity
(mm/s), f represents the frequency of oscillation (Hz) of the laser.
2. the cutting-off method of glass laminate according to claim 1, wherein, the resin bed is to include polyimides
Layer.
3. the cutting-off method of glass laminate according to claim 1 or 2, wherein, the laser is by CO2Laser is obtained
The laser arrived.
4. according to the cutting-off method of glass laminate according to any one of claims 1 to 3, wherein, the 1st glass plate
Thickness is more than 0.1mm and below 1.1mm.
5. according to the cutting-off method of glass laminate according to any one of claims 1 to 4, wherein, the 2nd glass plate
Thickness is more than 0.03mm and below 0.3mm.
6. according to the cutting-off method of glass laminate according to any one of claims 1 to 5, wherein, the thickness of the resin bed
Spend for more than 0.1 μm and less than 100 μm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015227608A JP2017095295A (en) | 2015-11-20 | 2015-11-20 | Method for cutting glass laminate |
| JP2015-227608 | 2015-11-20 |
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| Publication Number | Publication Date |
|---|---|
| CN107030393A true CN107030393A (en) | 2017-08-11 |
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|---|---|---|---|
| CN201611008161.0A Withdrawn CN107030393A (en) | 2015-11-20 | 2016-11-16 | The cutting-off method of glass laminate |
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|---|---|
| JP (1) | JP2017095295A (en) |
| KR (1) | KR20170059395A (en) |
| CN (1) | CN107030393A (en) |
| TW (1) | TW201720769A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110899981A (en) * | 2019-12-04 | 2020-03-24 | 哈尔滨工业大学 | Laser-modified ultra-precision cutting laser-assisted hard and brittle material processing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6777023B2 (en) * | 2017-06-20 | 2020-10-28 | トヨタ自動車株式会社 | Welding method of laminated metal foil |
| TW201946882A (en) * | 2018-05-07 | 2019-12-16 | 美商康寧公司 | Laser-induced separation of transparent oxide glass |
| JP2020071966A (en) * | 2018-10-30 | 2020-05-07 | 三星ダイヤモンド工業株式会社 | Flexible organic el display manufacturing method |
| JP2020071967A (en) * | 2018-10-30 | 2020-05-07 | 三星ダイヤモンド工業株式会社 | Flexible organic el display manufacturing method |
| JP2020071969A (en) * | 2018-10-30 | 2020-05-07 | 三星ダイヤモンド工業株式会社 | Flexible organic el display manufacturing method |
| JP2020071970A (en) * | 2018-10-30 | 2020-05-07 | 三星ダイヤモンド工業株式会社 | Flexible organic el display manufacturing method |
| KR102522773B1 (en) * | 2021-08-09 | 2023-04-18 | 주식회사 도우인시스 | Glass cutting and post-processing method using laser |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI409122B (en) * | 2007-07-13 | 2013-09-21 | Mitsuboshi Diamond Ind Co Ltd | A method for processing a brittle material substrate and a crack forming apparatus for the method |
| JP2010110818A (en) * | 2008-10-09 | 2010-05-20 | Seiko Epson Corp | Workpiece splitting method and object producing method |
| JP5318545B2 (en) * | 2008-12-01 | 2013-10-16 | 株式会社ディスコ | Wafer processing method |
| JP2010219171A (en) * | 2009-03-13 | 2010-09-30 | Omron Corp | Scribe processing method and device |
| JP5888158B2 (en) * | 2012-04-05 | 2016-03-16 | 日本電気硝子株式会社 | Cleaving method of glass film |
| WO2014079478A1 (en) * | 2012-11-20 | 2014-05-30 | Light In Light Srl | High speed laser processing of transparent materials |
| JP6222439B2 (en) * | 2013-10-04 | 2017-11-01 | 日本電気硝子株式会社 | Method for cleaving glass film and method for producing film-like glass |
-
2015
- 2015-11-20 JP JP2015227608A patent/JP2017095295A/en active Pending
-
2016
- 2016-11-10 KR KR1020160149532A patent/KR20170059395A/en unknown
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110899981A (en) * | 2019-12-04 | 2020-03-24 | 哈尔滨工业大学 | Laser-modified ultra-precision cutting laser-assisted hard and brittle material processing method |
| CN110899981B (en) * | 2019-12-04 | 2021-07-02 | 哈尔滨工业大学 | Laser-modified ultra-precision cutting laser-assisted hard and brittle material processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201720769A (en) | 2017-06-16 |
| KR20170059395A (en) | 2017-05-30 |
| JP2017095295A (en) | 2017-06-01 |
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