CN107263984A - Polyimide resin layer stack and its manufacture method and the polyimide film with functional layer - Google Patents
Polyimide resin layer stack and its manufacture method and the polyimide film with functional layer Download PDFInfo
- Publication number
- CN107263984A CN107263984A CN201710205150.XA CN201710205150A CN107263984A CN 107263984 A CN107263984 A CN 107263984A CN 201710205150 A CN201710205150 A CN 201710205150A CN 107263984 A CN107263984 A CN 107263984A
- Authority
- CN
- China
- Prior art keywords
- layer
- polyimide resin
- carrier
- substrate
- substrate layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/0046—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
- B32B37/0053—Constructional details of laminating machines comprising rollers; Constructional features of the rollers
-
- 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
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
-
- 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
- B32B7/02—Physical, chemical or physicochemical properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of polyimide resin layer stack and its manufacture method and the polyimide film with functional layer, polyimide resin layer stack is the polyimide resin layer stack with carrier for being used as the substrate instead of glass in display or touch-screen, even if using in the case of can be applicable to the heat-resistant resins of RTR techniques as carrier material, also the operability in manufacturing process can be maintained with the thinness as the support base material in display or touch-screen and suppress warpage (curling) as possible, and easily and easily base material can will be supported to be separated from carrier material.In the polyimide resin layer stack of the present invention, there is the curling inhibition layer comprising polyimide resin in a surface side of the carrier layer comprising polyimide resin, and then with the substrate layer for including polyimide resin for being bonded in curling inhibition layer in a releasable manner, the thermal coefficient of expansion of curling inhibition layer is less than or greater than any one of the thermal coefficient of expansion of support layer and substrate layer.
Description
Technical field
Liquid crystal display device, organic electroluminescent are formed with polyimide substrate the present invention relates to one kind
(Electroluminescence, EL) display, organic EL illuminating, Electronic Paper, touch-screen (touch panel), colorized optical filtering
The polyimide resin layer stack and its manufacture method and the polyamides with functional layer of the functional layers such as piece (color filter)
Imines film.
Background technology
The display device such as liquid crystal display device or organic EL display is widely used in large-scale display as TV
Device to mobile phone, personal computer (personal computer), smart mobile phone (smart phone) etc. miniscope.Example
If organic EL display is to form thin film transistor (TFT) (Thin Film Transistor, TFT), successively shape on the glass substrate
Into electrode, luminescent layer, electrode etc., finally it is hermetically sealed and is made with glass substrate or plural layers etc. in addition.
Here, there is no particular restriction for the species of display device, also comprising with liquid crystal display device, organic EL display,
Electronic Paper is the constituent part of the display devices such as the display device and colored filter of representative.In addition, also described comprising being appended hereto
Display device and the various functions device used, including organic EL illumination device, touch panel device, are laminated with tin indium oxide
The conductive film of (Indium Tin Oxide, ITO) etc., prevent moisture or oxygen etc. infiltration gas barrier film, flexible circuit board
Constituent part etc..That is, so-called flexible member in the present invention, not only comprising liquid crystal display device, organic EL display and coloured silk
The constituent parts such as colo(u)r filter, and comprising organic el illumination device, touch panel device, organic EL display electrode layer
Or the one of luminescent layer, gas barrier film, bonding film, thin film transistor (TFT) (TFT), the wiring layer of liquid crystal display device or transparency conducting layer etc.
Plant or two or more combinations.
By the way that glass substrate is substituted for into resin base material, slimming, lightweight, flexibility can be achieved, so as to further
Expand the purposes of display device.But, compared with glass, resin has dimensional stability, the transparency, heat resistance, moisture-proof, choke
The problems such as property equal difference.
For example, patent document 1 be related to it is a kind of with as flexible display plastic base useful polyimides and its
The relevant invention of predecessor, it has been disclosed that：Use the tetracarboxylic acid acids containing ester ring type structure as cyclohexyl phenyl tetracarboxylic acid etc.
It is transparent excellent with the polyimides of various diamine reactants.In addition, also attempted using flexible resin base material
Realize to propose in lightweight, such as non-patent literature 1 and non-patent literature 2 instead of glass substrate and gather using the transparency is high
Imido organic EL display.
Like this, it is known that the resin film of polyimides etc. is useful as the support base material of flexible display, but display
The manufacturing process of device is carried out using glass substrate, and its production equipment is set premised on using glass substrate
Meter.Therefore, it is desirable that with existing production equipment and display device effectively can be produced.
One of example is studied as it, there are following methods：Complete set to be laminated with the state of resin on the glass substrate
The manufacturing process of display device, then removes glass substrate, thus manufactures the display device for possessing display part on resin base material
(with reference to 2~patent document of patent document 3,3~non-patent literature of non-patent literature 4).In the case of this method, it is important that
The display part formed on resin base material is not caused to damage and separate resin base material with glass.
That is, in patent document 3 or non-patent literature 3, to coating on the glass substrate and the resin base material through set is formed
After set display part, (Electronics on Plastic by Laser are discharged by being referred to as plastic electronic laser
Release, EPLaR) method of technique irradiates laser from glass side, and it will be provided with the resin base material of display part and forced from glass substrate
Separation.In addition, in patent document 2 or non-patent literature 4, being formed on the glass substrate after peel ply, it is coated with bigger than peel ply by one
The polyimide resin of circle and form polyimide layer, be carved into reach peel ply cutting line, the polyimide film that small one is enclosed
Peeled off from peel ply.
On the other hand, in the case where making laminated resin on the glass substrate, warpage turns into big problem.That is, glass substrate
Thermal coefficient of expansion be several ppm/K, in contrast, generally resin has tens more than ppm/K thermal coefficient of expansion, therefore for example
If by resin solution coating on the glass substrate, harden it by heating etc. and form resin bed, and placement is cooled to
Room temperature, then can produce warpage.If this warpage can not be suppressed, formation of subsequent display part etc. can be had undesirable effect.
In the process using polyimides layered product, flexible display TFT substrate process is usually using In-Ga-Zn-O
Semiconductor (indium gallium zinc oxide (Indium Gallium Zinc Oxide, IGZO)) or low temperature polycrystalline silicon (Low
Temperature Poly-silicon, LTPS) engineering method, by more than 350 DEG C heat.Now, the thermal expansion system of glass substrate
Number is several ppm/K, in contrast, generally resin has tens more than ppm/K thermal coefficient of expansion, it is thus possible to which layered product is produced
Warpage, it is impossible to realize the miniaturization of display part.
On in this respect, Patent Document 3 discloses supporting to set thermal coefficient of expansion to exist between substrate and resin film (a)
Such resin bed (b) between substrate and resin film (a) is supported, but the inhibition of warpage is insufficient.
In addition, with volume to volume (Roll to Roll；Hereinafter also referred to " RTR ") mode manufactures display or touch-screen etc.
In the case of, the high-temperature process more than 300 DEG C is can tolerate in process as the film of base material is supported, it is therefore necessary to excellent for heat resistance
Different material.In addition, if in view of preferred film if light transmission rate.But, the operating difficulties of film, manufacture is also difficult, present situation
Lower hyaline membrane is the thickness using more than 50 μm.
In addition, being used as the method for the easiness and thinness for having operation or manufacture concurrently, it is proposed that the hyaline membrane with carrier.Should
Stacked film with carrier is to be laminated carrier film with transparent base film without using adhesive, forms thin over the transparent substrate
After the functional layers such as film transistor, and then fit, then peel off carrier film with front panel, thus can have the behaviour in manufacturing process concurrently
The property made and the thinness as the transparent support base material in display or touch-screen.
However, the former stacked film with carrier easily produce in warpage (curling), manufacturing process it is operational very
Difference.
Patent Document 4 discloses set thermal coefficient of expansion to supports such as glass substrates to suppress the generation of warpage
Compared with its first small polyimide layer, thermal coefficient of expansion is set to be more than the second polyimide layer of support thereon, but not
The open research relevant with the support comprising heat-resistant resin of not glass substrate.
[prior art literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2008-231327 publications
No. 4834758 publications of [patent document 2] Japan Patent
No. 5408848 publications of [patent document 3] Japan Patent
[patent document 4] Japanese Patent Laid-Open 2015-182393 publications
[non-patent literature]
[non-patent literature 1] S. peaces (S.An) et al.,《The high-effect low-temperature polysilicon film crystal of use on plastic base
2.8 inches of WQVGA flexibilities AMOLED (2.8-inch WQVGA Flexible AMOLED Using High of pipe
Performance Low Temperature Polysilicon TFT on Plastic Substrates)》, presentation of information
Association 2010 makes a summary (SID2010DIGEST), p706 (2010)
[non-patent literature 2] great Shi (Oishi) et al.,《Transparent PI (Transparent PI for flexible display
for flexible display)》, the world shows workshop (International Display Workshops, IDW) ' 11
FLX2/FMC4-1
[non-patent literature 3] E.I. Haas card (E.I.Haskal) et al.,《The flexible OLED manufactured using EPLaR techniques
Display (Flexible OLED Displays Made with the EPLaR Process)》, Europe shows document
(Proc.Eurodisplay) ' 07, pp.36~39 (2007)
[non-patent literature 4] Li Zhengzhong (Cheng-Chung Lee) et al.,《Manufacture the new of flexible active matrix display
Method (A Novel Approach to Make Flexible Active Matrix Displays)》, presentation of information association
10 summaries (SID10 Digest), pp.810~813 (2010)
The content of the invention
[invention problem to be solved]
Therefore, it is an object of the invention to provide a kind of polyimide resin layer stack and its manufacture method, the polyamides
Imide resin layered product is the polyimides tree with carrier for being used as the substrate instead of glass in display or touch-screen
Lipid layer stack, even and if in the case of using the heat-resistant resin that can be applicable in RTR techniques as carrier material, also may be used
The operability in manufacturing process and the thinness as the support base material in display or touch-screen are maintained, and suppresses warpage as far as possible
(curling), and easily and easily base material can will be supported to be separated from carrier material.Another one kind that provides of the invention carries functional layer
Polyimide film.
[technological means for solving problem]
Therefore, the present inventor makes great efforts research in order to solve these problems, as a result it was surprisingly found that by set
A surface side of the substrate layer comprising polyimide resin be laminated the set curling inhibition layer comprising polyimide resin and both
The fixed carrier layer for including polyimide resin, can maintain operability or as the thinness of base material, and improve warpage (curling),
So as to complete the present invention.
That is, the present invention is a kind of polyimide resin layer stack, and it is the curling inhibition layer comprising polyimide resin, bag
The layered product of carrier layer containing polyimide resin and the substrate layer comprising polyimide resin, and in the one side of the substrate layer
Side is bonded with curling inhibition layer and carrier layer, the thermal coefficient of expansion of the layer contacted with the substrate layer in a releasable manner
(Coefficient of thermal expansion, CTE) is less than or greater than any one of the CTE of other layers.
The polyimide resin layer stack of the present invention is preferably in a surface side of the carrier layer comprising polyimide resin
With the curling inhibition layer comprising polyimide resin, and then with the bag for being bonded in the curling inhibition layer in a releasable manner
Substrate layer containing polyimide resin, the thermal coefficient of expansion (CTE) of curling inhibition layer is less than or greater than support layer and substrate layer
Any one of thermal coefficient of expansion (CTE)；Or, have in a surface side of the carrier layer comprising polyimide resin with strippable
The substrate layer for including polyimide resin that mode is bonded, has in the opposite surface side of the carrier layer and includes polyimide resin
Curling inhibition layer, the thermal coefficient of expansion (CTE) of carrier layer is less than or greater than substrate layer and crimps the thermal coefficient of expansion of inhibition layer
(CTE) any one.
Thermal coefficient of expansion (CTE) that the polyimide resin layer stack of the present invention is preferably substrate layer and carrier layer is poor,
Or substrate layer and thermal coefficient of expansion (CTE) difference of curling inhibition layer are ± below 40ppm/K.
The polyimide resin layer stack of the present invention is preferably used as in a surface side of carrier layer across curling inhibition layer
And substrate layer so formed functional layer polyimide resin layer stack or enter in a surface side of carrier layer across substrate layer
And form the polyimide resin layer stack with functional layer of functional layer.
In addition, the polyimide resin layer stack of the present invention be preferably the total light transmittance of substrate layer for 80% with
On, and thickness is less than 50 μm, and it is more than 300 DEG C to preferably form the Tg of the polyimide resin of substrate layer.
The other embodiment of the present invention is a kind of polyimide film with functional layer, and it is functional using the band
The polyimide resin layer stack of layer, enters in curling inhibition layer and the interface of substrate layer or the interface of carrier layer and substrate layer
Row is peeled off, and carrier layer and curling inhibition layer are removed and formed.
In addition, the present invention is a kind of manufacture method of polyimide resin layer stack, it is the manufacture polyimides tree
The method of lipid layer stack, and curling inhibition layer and substrate layer is formed using casting on a carrier layer.
The manufacture method, which is preferably, makes coating curling inhibition layer on a carrier layer and substrate layer integrally harden, and excellent
Choosing is that casting is the coating for utilizing multilayer die head or continuous die head.
[The effect of invention]
According to the present invention, can maintain operability in manufacturing process with as the support base material in display or touch-screen
Thinness, and suppress warpage (curling) as possible, polyimide resin layer stack in display or touch-screen purposes can be met
It is required that characteristic.
Brief description of the drawings
Fig. 1 is that the profile that each layer with functional layer is constituted is shown to the polyimide resin layer stack of the present invention.
Fig. 2 is the schematic diagram for the device to layered product formation functional layer.
Fig. 3 produces the simulation drawing of the state of warpage for expression polyimides layered product.
Fig. 4 is to show what each layer with functional layer was constituted to the polyimide resin layer stack of the present invention.
Symbol description
1：Functional layer
2：Substrate layer
3：Carrier layer
4：Crimp inhibition layer
10：Layered product
11：Sputtering unit
12、13：Deflector roll
14：Roll out roller
15：Takers-in
Embodiment
First, polyimide resin layer stack of the invention possesses the carrier layer comprising polyimide resin.Carrier layer exists
The substrate layer of film is maintained at set shape in RTR techniques, and is to form the functional layers such as ito film across substrate layer
Afterwards, peel off and remove from substrate layer.Therefore, in order to adapt to RTR techniques, it is desirable to flexible and enhancing base materials layer and maintain intensity, but not
It is necessarily transparent.Therefore, the thickness of carrier layer is more than the substrate layer of film, preferably 10 μm~100 μm, more preferably 30 μm~75
μm.Further, since require to can be applied to the heat resistance of RTR high-temperature technology, thus preferably 300 DEG C of glass transition temperature (Tg) with
On, more preferably 300 DEG C~450 DEG C.
The present invention polyimide resin layer stack for the curling inhibition layer comprising polyimide resin (hereinafter also referred to as
" curling inhibition layer "), the carrier layer (hereinafter also referred to as " carrier layer ") comprising polyimide resin and include polyimides tree
The layered product of the substrate layer (hereinafter also referred to as " substrate layer ") of fat, and glued in a releasable manner in a surface side of substrate layer
Close the layered product for having curling inhibition layer and carrier layer.And then, the polyimide resin layer stack is characterised by：With substrate layer
The thermal coefficient of expansion (CTE) of the layer of contact is less than or greater than any one of the CTE of other layers.
Herein, the so-called layer contacted with substrate layer, refer to crimp inhibition layer or carrier layer any one etc. two kinds of aspects.Institute
Call other layers, the layer contacted with substrate layer for curling inhibition layer in the case of, refer to substrate layer and carrier layer, with substrate layer
In the case that the layer of contact is carrier layer, refer to substrate layer and curling inhibition layer.
In addition, the form of the polyimide resin layer stack has two kinds (form one and forms two).Hereinafter, to each form
It is specifically described.
[form one]
The polyimide resin layer stack of form one has curling inhibition layer in a surface side of carrier layer, and then with can
The mode of stripping is bonded in the substrate layer of the curling inhibition layer, and the CTE of curling inhibition layer is less than or greater than carrier layer and substrate layer
CTE any one.
In addition, from the viewpoint of warpage is suppressed, the CTE of carrier layer is advisable with the CTE for being similar to substrate layer, both heat
Within poor (also referred to as Δ CTE, " CTE difference ") preferably ± 15ppm/K of the coefficient of expansion, more preferably compared with the CTE of carrier layer
And within the CTE difference+15ppm/K of substrate layer, i.e., CTE difference is 0ppm/K~+15ppm/K.In addition, the CTE of such as carrier layer is excellent
Select 10ppm/K~85ppm/K.Here so-called CTE difference is " within ± 15ppm/K ", to refer to compared with the CTE of carrier layer and base material
CTE difference -15ppm/K~+15ppm/K of layer.
In a surface side of carrier layer across aftermentioned curling inhibition layer with substrate layer.Substrate layer, which turns into, replaces the saturating of glass
Bright base material, and be to be formed on the functional layers such as ito film and complete after RTR techniques, carrier layer is peeled off and supports function after removing
Layer.Therefore, the total light transmittance of substrate layer preferably more than 80%, more preferably more than 90%.From slimming, lightweight, flexibility
From the point of view of the requirement characteristic of change, the thickness of substrate layer with try one's best it is thin be advisable, preferably less than 50 μm, more preferably 5 μm~25 μm.As above
Described such, the CTE of substrate layer is advisable with approximate with the CTE of carrier layer, preferably 10ppm/K~80ppm/K.Further, since will
The heat resistance for the high-temperature technology that can be applied to RTR, therefore preferably more than 300 DEG C of the glass transition temperature (Tg) of substrate layer are asked, more
It is preferred that 300 DEG C~450 DEG C.Due to as replace glass resin base material, therefore substrate layer modulus of elasticity for example with 2GPa~
15GPa is advisable.
In a surface side of carrier layer, between carrier layer and substrate layer there is the curling comprising polyimide resin to suppress
Layer.From adapt to RTR techniques from the viewpoint of, curling inhibition layer be in order to as possible suppress with carrier substrate layer warpage and shape
Into between carrier layer and substrate layer, the functional layers such as ito film are formed simultaneously across substrate layer in carrier layer and curling inhibition layer
Complete after RTR techniques, when carrier layer is peeled off into removing, be removed together with carrier layer.Therefore, in order to most in RTR techniques
Power suppresses warpage (curling) and selects thickness or thermal coefficient of expansion.Therefore, preferably less than 50 μm of the thickness of inhibition layer is crimped, it is more excellent
Select 5 μm~30 μm.Further, since require to can be applied to the heat resistance of RTR high-temperature technology, therefore glass transition temperature (Tg) is excellent
Select more than 300 DEG C, more preferably 300 DEG C~450 DEG C.
The CTE of curling inhibition layer is with selected with the relatively large mode of the CTE difference of carrier layer and substrate layer.Such as carrier
The CTE of layer and substrate layer can be also not necessarily the same, but to crimp CTEs of the CTE relative to both carrier layer and substrate layer of inhibition layer
And select and be advisable with certain poor mode above.
Accordingly, with respect to the CTE of curling inhibition layer, the CTE difference preferably ± 15ppm/ with the CTE difference of carrier layer and with substrate layer
The CTE difference of more than K, more preferably -15ppm/K~-60ppm/K scope.In addition, the CTE of curling inhibition layer preferably -10ppm/K
~20ppm/K.Here, so-called CTE difference is " ± more than 15ppm/K ", is referred to compared with the CTE of carrier layer and the CTE of substrate layer
And the CTE difference for crimping inhibition layer is more than -15ppm/K, or difference is more than+15ppm/K.
For the base material with carrier formed by carrier layer and substrate layer, even if by making curling inhibition layer
Be present between carrier layer and substrate layer, and be especially made equivalent to so-called glass substrate forth generation (680mm × 880mm~
730mm × 920mm) in the case of later relatively large layered product, it also can fully obtain the inhibition of warpage.In addition,
Can be by there is the design freedom for crimping inhibition layer and improving substrate layer.And then, the foreign matter for being attached to carrier layer is difficult to be mixed into
Into substrate layer.In addition, the surface state of carrier layer is difficult to influence substrate layer, therefore optional inexpensive polyimide film etc.,
The design freedom of carrier layer can be improved.
[form two]
The polyimide resin layer stack of form two has the base bonded in a releasable manner in a surface side of carrier layer
Material layer, and then there is in the opposite surface side of the carrier layer curling inhibition layer, the CTE of the carrier layer be less than or greater than the substrate layer and
Any one of the CTE of the curling inhibition layer.
That is, carrier layer is located between substrate layer and curling inhibition layer.If this composition, then from the viewpoint of warpage is suppressed
It is preferred that.In addition, the preferred 10ppm/K~70ppm/K of the CTE of such as carrier layer.
Substrate layer turns into the transparent base for replacing glass, and is to be formed on the functional layers such as ito film and complete RTR techniques
Afterwards, carrier layer is peeled off to the transparent base that functional layer is supported after removing.Therefore, the total light transmittance of substrate layer preferably 80% with
On, more preferably more than 90%.From the point of view of slimming, lightweight, the requirement characteristic of flexibility, the thickness of substrate layer not undermining plus
Bao Yuehao, preferably less than 50 μm, more preferably 5 μm~25 μm are got in the range of work.The preferred 1ppm/K of CTE of substrate layer~
80ppm/K。
Further, since require to can be applied to the heat resistance of RTR high-temperature technology, therefore glass transition temperature (Tg) is preferably
More than 300 DEG C, more preferably 300 DEG C~450 DEG C.Due to as the resin base material for replacing glass, therefore the modulus of elasticity of substrate layer
For example it is advisable with 2GPa~15GPa.
There is the curling inhibition layer comprising polyimide resin in the opposite surface side of carrier layer.From the sight for adapting to RTR techniques
From the point of view of point, curling inhibition layer is to be formed to suppress the warpage of the substrate layer with carrier as possible opposite with substrate layer one
Side, forms the functional layers such as ito film across substrate layer on a carrier layer and completes after RTR techniques, when carrier layer is peeled off into removing,
It is removed together with carrier layer.Therefore, thickness or thermal expansion system are selected in order to suppress warpage (curling) as possible in RTR techniques
Number.Therefore, preferably less than 50 μm, more preferably 6 μm~30 μm of the thickness of inhibition layer is crimped.Further, since requiring to can be applied to RTR
High-temperature technology heat resistance, therefore preferably more than 300 DEG C, more preferably 300 DEG C~450 DEG C of glass transition temperature (Tg).
The CTE of curling inhibition layer is advisable with approximate with the CTE of substrate layer, and to eliminate the CTE difference of carrier layer and substrate layer
Mode selected be advisable.Therefore, it is within ± 40ppm/K, within preferably ± 15ppm/K with the CTE difference of substrate layer.For example crimp
Preferred 1ppm/K~the 90ppm/K of CTE of inhibition layer.
For the base material with carrier formed by carrier layer and substrate layer, even if by making curling inhibition layer
Be present in the side opposite with base material, and be especially made equivalent to so-called glass substrate forth generation (680mm × 880mm~
730mm × 920mm) in the case of later relatively large layered product, it also can fully obtain the inhibition of warpage.In addition,
Can be by there is the design freedom for crimping inhibition layer and improving substrate layer.
Hereinafter, content common in form 1 and form 2 is specifically described.
As long as the polyimide resin as curling inhibition layer meets the characteristic, then there is no particular restriction, for example, can lift
Go out and formed by the polyimides with the construction unit represented by following formulas (1).Preferably to contain 50 moles of %
The polyimides of construction unit represented by following formulas (1) above is advisable.
[changing 1]
Here, the X in the formula (1) is aromatic series base or ester ring type base, and for more than one aromatic rings or
The quadrivalent organic radical of alicyclic ring, R is the substituent of carbon number 1~6.Wherein, the suitable concrete example as the raw material for forming group X
It can such as enumerate：Pyromellitic acid anhydride (Pyromellitic dianhydride, PMDA), naphthalene -2,3,6,7- tetracarboxylic acids two
Acid anhydride (Naphthalene tetracarboxylic dianhydride, NTCDA), 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride
(Biphenyl tetracarboxylic dianhydride, BPDA) etc..In addition, R suitable concrete example can for example enumerate-
CH3、-CF3Deng.
Wherein, if R is-CF3, then the fissility with the interface of substrate layer can be improved, easily can be separated these layers.
In addition, on that can contain in addition to the construction unit represented by the formula (1) and suitably maximum can contain
There is the construction unit less than 50 moles of %, the construction unit using common acid anhydrides and diamines can be enumerated.Wherein, can suitably it make
Acid anhydrides is pyromellitic acid anhydride (PMDA), naphthalene -2,3,6,7- tetracarboxylic acid dianhydrides (NTCDA), 3,3 ', 4,4 '-biphenyl four
Formic acid dianhydride (BPDA), cyclohexanetetracarboxylic acid dianhydride, phenylene double (trimellitic acid monoesters acid anhydride), 4, the double O-phthalics of 4 '-oxygen
Acid dianhydride, BP-3,4,3 ', 4 '-tetracarboxylic acid dianhydride, diphenyl sulfone -3,4,3 ', 4 '-tetracarboxylic acid dianhydride, 2,3,6,7- naphthalenes
Tetracarboxylic acid dianhydride, 4,4 '-(2,2 '-hexafluoroisopropylidenyl) double O-phthalic acid dianhydrides etc..On the other hand, diamines has isophthalic two
Amine, p-phenylenediamine, 2,4- diaminotoluenes, 4,4 '-diamino-diphenyl ether, 1,3- double (4- amino-benzene oxygens) benzene, 4,4 '-two
Aminodiphenyl base sulfone, 2,2- double (4- amino benzyloxy-phenyl) propane, double [4- (4- amino-benzene oxygens) phenyl] sulfones, 4,4 '-two
Double (4- aminophenyls) fluorenes of aminobenzoic anilide, 9,9- etc..
The transparency reduction generally if the thermal coefficient of expansion of polyimides diminishes, and the delay of thickness direction
(retardation) (phase difference caused by the difference of birefringence) is uprised.Therefore it is unsuitable for situations below：Complete RTR techniques
Afterwards, the substrate layer separated from carrier layer is used as to the resin base material of such as display device, or for gas barrier film, touch screen base plate.
In contrast, in the present invention, by there is the curling inhibition layer of opposite side, and allowing to use the thermal expansion with more than carrier layer
The substrate layer of coefficient.
Forming the polyimides of substrate layer can suitably select according to the purposes of polyimide resin layer stack.Wherein, exist
Can for having in the display devices such as liquid crystal display device, organic EL display, Electronic Paper, colored filter, touch-screen
In the case of flexible resin base material, the polyimides with the construction unit represented by following formulas (2) can be enumerated, is preferably contained
There is the polyimides of the construction unit represented by 50 moles of more than % formula (2).In addition, on except formula (2) institute
The construction unit (suitably maximum to contain the construction unit for being less than 50 moles of %) that can contain beyond the construction unit of expression,
As long as not undermining the transparency, then the construction unit identical construction unit with explanation in formula (1) can be enumerated.Can suitably it use
Acid anhydrides be pyromellitic acid anhydride (PMDA), naphthalene -2,3,6,7- tetracarboxylic acid dianhydrides (NTCDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic
Acid dianhydride (BPDA), cyclohexanetetracarboxylic acid dianhydride, phenylene double (trimellitic acid monoesters acid anhydride), 4, the double phthalic acids of 4 '-oxygen
Dianhydride, BP-3,4,3 ', 4 '-tetracarboxylic acid dianhydride, diphenyl sulfone -3,4,3 ', 4 '-tetracarboxylic acid dianhydride, 2,3,6,7- naphthalenes four
Formic acid dianhydride, 4,4 '-(2,2 '-hexafluoroisopropylidenyl) double O-phthalic acid dianhydrides etc..On the other hand, diamines be m-phenylene diamine (MPD),
P-phenylenediamine, 2,4- diaminotoluenes, 4,4 '-diamino-diphenyl ether, 1,3- double (4- amino-benzene oxygens) benzene, 4,4 '-diamino
Base diphenyl sulfone, 2,2- double (4- amino benzyloxy-phenyl) propane, double [4- (4- amino-benzene oxygens) phenyl] sulfones, 4,4 '-diamino
Double (4- aminophenyls) fluorenes of base benzanilide, 9,9- etc..
[changing 2]
In the formula (2), Y is the quadrivalent organic radical of aromatic series or ester ring type, preferably any represented by following formula (3)
Group.
[changing 3]
Wherein, it is more than 80% from the transmitance under the 500nm in the wave-length coverage for obtaining 440nm~780nm, and thickness
The delay in direction for below 200nm polyimide resin as substrate layer from the viewpoint of, more preferably any one following.
[changing 4]
Most suitable is the polyimide resin represented by following formula (4).
[changing 5]
As long as the polyimide resin as carrier layer meets characteristic described above, then there is no particular restriction, for example, make
For usual retrievable polyimide resin, kapton (Kapton) (Dong Li Du Ponts (Toray-Dupont) company system can be used
Make), excellent Simon Rex (Upilex) (manufacture of Yu Buxingchan companies), A Bika (Apical) (manufacture of clock (Kaneka) company)
Or the commercially available polyimides with the structure similar with these polyimide resins, also can be as following will be described by diamines
Synthesize and obtain with acid dianhydride.
Various polyimides described above are that polyimides predecessor (hereinafter also referred to " polyamic acid ") is subject into acyl
Imidization and obtain, the resin solution of polyamic acid can be by using being essentially the equimolar diamines as raw material and acid two
Acid anhydride reacts and obtained in organic solvent.Specifically, it can for example obtain in the following manner：Make two amine solvents under nitrogen flowing
After in the organic polar solvents such as DMA, tetracarboxylic acid dianhydride is added, is reacted 5 hours or so at room temperature.This
In, from the viewpoint of the uniform film thickness or the mechanical strength of the polyimides of gained during coating, the weight of polyamic acid is put down
Average molecular weight (Mw) preferably 10,000~300,000 or so.The suitable molecular weight ranges of polyimide resin are identical with polyamic acid
Molecular weight ranges.
The substrate layer and curling inhibition layer of the present invention is described preferably to be advisable respectively by so-called casting
Casting is the resin solution of coating polyimides or polyimides predecessor and is subject to drying, is heated.That is, obtain
The present invention polyimide resin layer stack when, be suitably respectively coated in a surface side of carrier layer or two sides polyimides or
The resin solution of polyimides predecessor is simultaneously subject to drying, is heated, and thus can form substrate layer and curling inhibition layer.
The pre-add carried out such as preferably in order to be dried and at 90 DEG C~130 DEG C 5 minutes~30 minutes or so is heat-treated
Afterwards, and then in order to carry out imidizate at the high-temperature heating that 10 minutes~240 minutes or so are carried out at 130 DEG C~360 DEG C
Reason.
The polyimide resin layer stack obtained like this can substrate layer with and the layer (carrier layer that contacts of the substrate layer
Or curling inhibition layer) interface separation, but for the separation of the interface that easily carries out these layers, preferably with base material
Layer is advisable by having the fluorinated polyimide of fluorine atom to be formed in polyimide structures.By using this fluorine-containing polyamides
Imines, can make substrate layer with and the peel strength of layer that contacts of the substrate layer turn into suitably 1N/m~200N/m, it is more suitable
Be 1N/m~100N/m, therefore the separation property for the degree being for example easily peeled off with available human hand.In addition, point of substrate layer
The surface roughness (usual surface roughness Ra=1nm~80nm or so) as obtained by casting is directly maintained from face, therefore
Also visuality of display device etc. will not be had undesirable effect.
, can be logical according to following idea for the polyimide resin layer stack for being laminated different materials in the present invention
Cross calculating and obtain buckling deformation (amount of warpage), realize the optimization of polyimide resin layer stack.That is, with based on citation
Based on the easy mechanics of materials of 4 idea is calculated, after the influence that deadweight is calculated by three-dimensional material Mechanics Calculation, add
Buckling deformation (amount of warpage) and obtain final amount of warpage.Using Finite Element (finite element method) as
Computational methods, i.e. for thermal deformation and the final buckling deformation of deadweight state in a balanced way, use stacking shell unit (shell
Element discretization) is carried out, computer-implemented computing (reference picture 3) is utilized in numerical computations mode.
As described above, polyimide resin layer stack of the invention can be suitably used for obtaining and have on substrate layer
The display device of standby building blocks of function.That is, as long as being formed on substrate layer after set functional layer, in curling inhibition layer and substrate layer
Interface or substrate layer separated with the interface of carrier layer.Here, carrier layer plays and forms aobvious in substrate layer side
The effect of base when showing portion, ensures treatability or dimensional stability of substrate layer etc. in the manufacturing process of display part, but most
It is removed eventually and does not constitute display device.Similarly, curling inhibition layer is also together to be separated with carrier layer, similarly finally
It is removed and does not constitute display device, even if even transparency difference.By using this polyimide resin layer stack, energy
Set functional layer is reliably formed with good precision and on substrate layer, and can obtain and realize slim, light weight, flexibility
The display device of change.
On forming the functional layer on substrate layer, there is no particular restriction.For example in the case of organic EL display, tool
Representational is equivalent to display part comprising TFT, electrode, organic EL element of luminescent layer etc..In addition, the feelings of liquid crystal display device
Under condition, the functional layer is TFT, drive circuit, is optionally colored filter etc..In addition to these, including Electronic Paper or
Various display devices as MEMS (Micro-Electro-Mechanical System, MEMS) display etc., make
For be previously formed various functions layers on the glass substrate and projection go out set image (animation or image) necessary to part
Equivalent to display part.Wherein, 400 DEG C or so of annealing operation is for example usually required when forming TFT, but the polyamides of the present invention is sub-
Amine resin layer stack has the heat resistance that also can tolerate this annealing operation.
[embodiment]
Hereinafter, the present invention is specifically described according to embodiment and comparative example.In addition, the present invention is not by these contents
Limit.
1. various physical property measurements and method for testing performance
[peel strength]
On the peel strength of substrate layer-(curling inhibition layer)-carrier interlayer, by layered product be processed into width for 1mm~
10mm, length are 10mm~25mm short strip shape, the cupping machine manufactured using Toyo Seiki limited company (this Toro
Ge Lafu (Strograph)-M1) carrier layer is peeled off towards 180 ° of directions, determine peel strength.In addition, peel strength is firm
And the situation for being difficult to peel off is considered as " can not peel off ".
[transmitance]
The substrate layer of 20 μ m-thicks is cut out with 5cm square, the haze meter (HAZE of Japanese electric color industry manufacture is used for
METER) NDH-5000 carries out the measure of 380nm~780nm transmitance.
[Ra]
Substrate layer, carrier layer and curling inhibition layer are individually cut out with 3cm square, Brooker element point is used for
The AFM (AFM) for analysing (Bruker AXS) manufacture carries out Ra measure.
[CTE]
On substrate layer, carrier layer and the CTE for crimping inhibition layer, each layer is cut out with 3mm × 15mm square, is used for
Thermo-mechanical analysis (Thermomechanical analysis, the TMA) dress of Seiko instrument (Seiko Instruments) manufacture
Put, when applying 5.0g heavy burden with certain programming rate (10 DEG C/min) within the temperature range of 30 DEG C~260 DEG C
Carry out tension test, determined according to the elongation relative to the polyimide film of temperature at 100 DEG C~250 DEG C CTE (×
10-6/K)。
[warpage]
Cut out using cutter (cutterknife) from stacked film while for 100mm square sample, with 23 DEG C,
50% condition damping is positioned on price fixing after 24 hours, utilizes slide measure (vernier caliper) to determine sticking up for corner
Height is played, value is averaged as warpage (curling).
The synthesis of polyamic acid 2. (polyimides predecessor) solution
Raw material used in following synthesis example or embodiment etc. is shown in following.
[aromatic series diamino compounds]
4,4 '-diaminourea -2,2 '-bis- (trifluoromethyl) biphenyl (TFMB)
2,2 '-dimethyl -4,4 '-benzidine (m-TB)
1,3- double (4- amino-benzene oxygens) benzene (TPE-R)
2,2- double [4- (4- amino-benzene oxygens) phenyl] propane (BAPP)
Isosorbide-5-Nitrae-phenylenediamine (PPD)
[acid anhydrides of aromatic tetracarboxylic]
Pyromellitic dianhydride (PMDA)
2,2- double (3,4- dehydration dicarboxyphenyi) HFC-236fas (6FDA)
2,3,2 ', 3 '-bibenzene tetracarboxylic dianhydride (BPDA)
[solvent]
DMA (DMAc)
Synthesis example 1
Under nitrogen flowing, TFMB (9.4g, 0.03mol) is added when stirring in 300ml detachable flask
It is added in 127.5g solvent DMAc and is heated, is dissolved at 50 DEG C.Then 6FDA (13.09g, 0.03mol) is added.Make
The mol ratio of diamines and acid anhydrides essentially becomes 1: 1.Then, at room temperature solution is continued to stir 3 hours and polymerize instead
Should, obtain 200g flaxen sticky polyamide acid varnish A.In addition, making the polyamic acid clear under aftermentioned heating condition
A hardening is painted, polyimide resin A is derived from.
Synthesis example 2
Under nitrogen flowing, in 300ml detachable flask when stirring by 10.2g m-TB's and 1.6g
TPE-R is added in 170g solvent DMAc and heated with 90: 10 mol ratio, is dissolved at 50 DEG C.Then with 90: 10
Mol ratio addition 9.2g PMDA and 3.1g BPDA.The mol ratio of diamines and acid anhydrides is set to essentially become 1: 1.Then, will
Solution continues stirring 3 hours and carries out polymerisation at room temperature, obtains the sticky polyamide acid varnish of 200g pale
B.In addition, polyamide acid varnish B is hardened under aftermentioned heating condition, polyimide resin B is derived from.
Synthesis example 3
Under nitrogen flowing, TFMB (12.6g, 0.04mol) is added when stirring in 300ml detachable flask
It is added in 127.5g solvent DMAc and is heated, is dissolved at 50 DEG C.Then 6FDA is added with 12.5: 87.5 mol ratio
(2.2g, 0.005mol) and PMDA (7.7g, 0.035mol).The mol ratio of diamines and acid anhydrides is set to essentially become 1: 1.Then,
Solution is continued into stirring 3 hours at room temperature and polymerisation is carried out, the sticky polyamic acid for obtaining 150g pale is clear
Paint C.In addition, polyamide acid varnish C is hardened under aftermentioned heating condition, polyimide resin C is derived from.
Synthesis example 4
Under nitrogen flowing, m-TB (14.4g, 0.07mol) is added when stirring in 300ml detachable flask
It is added in 170g solvent DMAc and is heated, is dissolved at 50 DEG C.Then with 90：10 mol ratio addition PMDA
(13.6g, 0.06mol) and BPDA (2g, 0.007mol).The mol ratio of diamines and acid anhydrides is set to essentially become 1: 1.Then, will
Solution continues the 3 small times of stirring and carries out polymerisation at room temperature, and the sticky polyamic acid for obtaining 200g pale is clear
Paint D.In addition, polyamide acid varnish D is hardened under aftermentioned heating condition, polyimide resin D is derived from.
Synthesis example 5
Under nitrogen flowing, the TPE-R of diamines will be used as when stirring in 300ml detachable flask
(14.8g, 0.05mol) is added in 170g solvent DMAc and heated, and is dissolved at 50 DEG C.Then add as acid anhydrides
BPDA (15.2g, 0.05mol).The mol ratio of diamines and acid anhydrides is set to essentially become 1: 1.Then, by solution at room temperature after
Continue stirring 3 hours and carry out polymerisation, obtain the sticky polyamide acid varnish E of 200g pale.In addition, by the polyamides
Amino acid varnish E is hardened in aftermentioned heating condition, is derived from polyimide resin E.
Synthesis example 6
Under nitrogen flowing, in 300ml detachable flask when stirring with m-TB：TPE-R is according to the molar ratio
It is added in 170g solvent DMAc and is heated as 90: 10 mode, is dissolved at 50 DEG C.Then with PMDA: BPDA
Mol ratio turn into 80: 20 mode add.The mol ratio of diamines and acid anhydrides is set to essentially become 1: 1.Then, by solution in room
Temperature is lower to be continued to stir 3 hours and carry out polymerisation, obtains the sticky polyamic acid F varnish of 200g pale.In addition, will
Polyamic acid F varnish is hardened under aftermentioned heating condition, is derived from polyimide resin F.
Synthesis example 7
Under nitrogen flowing, TFMB (16.93g) is added to when stirring in 300ml detachable flask molten
In agent DMAc (170g) and dissolve.Then PMDA (10.12g) and 6FDA (2.95g) is added.Then, by solution at room temperature after
Continue stirring 6 hours and carry out polymerisation, obtain 200g flaxen sticky polyamic acid H varnish.In addition, by the polyamides
Amino acid H varnish is hardened under aftermentioned heating condition, is derived from polyimide resin H.
Synthesis example 8
Under nitrogen flowing, BAPP (19.45g) is added to when stirring in 300ml detachable flask molten
In agent DMAc (170g) and dissolve.Then PMDA (9.85g) and BPDA (0.70g) is added.Then, solution is continued at room temperature
Stir 6 hours and carry out polymerisation, obtain 200g flaxen sticky polyamic acid I varnish.In addition, by the polyamide
Sour I varnish is hardened under aftermentioned heating condition, is derived from polyimide resin I.
Synthesis example 9
Under nitrogen flowing, 4,4 '-DAPE (8.97g) are added when stirring in 300ml detachable flask
Into solvent DMAc (170g) and dissolve.Then PMDA (8.95g) and BPDA (12.08g) is added.Then, by solution in room temperature
It is lower to continue to stir 6 hours and carry out polymerisation, obtain the sticky polyamic acid J varnish of 200g brown.In addition, this is gathered
Amic acid J varnish is hardened under aftermentioned heating condition, is derived from polyimide resin J.
Synthesis example 10
Under nitrogen flowing, in 300ml detachable flask when stirring by 4,4 '-DAPE (8.14g) and PPD
(4.40g) is added in solvent DMAc (170g) and dissolved.Then PMDA (17.45g) is added.Then, by solution at room temperature
Continue to stir 6 hours and carry out polymerisation, obtain the sticky polyamic acid K varnish of 200g brown.In addition, by the polyamides
Amino acid K varnish is hardened under aftermentioned heating condition, is derived from polyimide resin K.
3. the formation of polyimides (PI) layer using coating
Using polyimide film, (the modern mountain of ningbo of china is manufactured, thickness=0.75mm, CTE=45ppm/K, hereinafter also referred to
" carrier film ") it is used as carrier layer.
As carrier layer, 2 kinds of polyimide films are used.
1) polyimide film 1：Ningbo of china the present mountain manufacture, thickness=0.75mm, CTE=45ppm/K, Ra=3nm is (following
Also referred to as carrier film 1)
2) polyimide film 2：Chinese Rui Huatai (Rayitek) manufacture, thickness=0.75mm, CTE=45ppm/K, Ra=
10nm (hereinafter also referred to carrier film 2)
Embodiment 1
Simultaneously using possessing the portion of rolling out, lip type coating machine (lip coater), continuous stove, continuous oven and reeling end
The coating of RTR modes for example shown in Fig. 2 dries hardening equipment by the (the width 520mm × length 500m × μ of thickness 75 of carrier film 1
M) rolled out with 2m/min speed, be simultaneously coated with polyamide in the way of thickness turns into 45 μm using Mono pump (mono pump)
Sour varnish B.The film is passed through in the continuous stove being made up of multiple stoves, dried 2 minutes at 90 DEG C, at 130 DEG C
Dry 1 minute, so be made up of multiple stoves and heater stage of the temperature from the stove of sample inlets side to outlet side increase
Continuous oven in pass through, 400 DEG C are periodically periodically heated to from 130 DEG C within 25 minutes with total, are produced on carrier film
On be formed with as curling inhibition layer polyimide resin B roller.Then, the volume is arranged on identical and applies drying device
Roll out in portion, 100 μm of polyimide acid varnish A is coated with polyimide resin C, by multiple stoves constituted it is continuous
Pass through in drying oven, dried 2 minutes at 90 DEG C, dried 1 minute at 130 DEG C, and then be made up of and temperature multiple stoves
Pass through in the continuous oven increased from the stove of sample inlets side to the heater stage of outlet side, with total 20 minutes periodically from
130 DEG C are periodically heated to 400 DEG C, form the polyimide resin A of 10 μm of the thickness as substrate layer, obtain the poly- of web-like
Imide resin layered product (layered product 1).
On the thickness of each layer of layered product 1, carrier layer is 75 μm, and curling inhibition layer is 4.5 μm, and substrate layer is 10 μm.
The Rotating fields of layered product 1 are illustrated schematically in Fig. 1.
Then, for the polyimide resin layer stack of the web-like, simultaneously using possessing the portion of rolling out, carrying roller, technique
The device of the RTR modes of processing unit and reeling end, is rolled up in the longitudinal direction with 2m/min speed by substrate layer in the way of upward
Go out, simultaneously imported into via carrying roller in the PROCESS FOR TREATMENT portion being arranged in vacuum chamber, using sputtering method by continuously locating
Manage the thickness 50nm ITO film forming as functional layer on substrate layer, with the shape of the polyimide substrate film with functional layer
Formula is batched.
And then, the polyimide substrate film with functional layer is cut into 370mm × 450mm sheet, to through film
ITO carries out transparent circuitry processing on the XY directions of a direction (X-direction) and other direction (Y-direction).Now, Y circuits and X
The intersection point of circuit does not form circuit.
Then, outer paint (over coating) is coated with the intersection point of XY circuits, is heat-treated and made outer at 250 DEG C
Coating is hardened, and carries out bridge joint processing across external coating using silver paste and XY circuits are made, and then in the entire surface of ITO film forming side
The outer paint of coating, is made annealing treatment at 270 DEG C, carries out the hardening of outer paint and ITO crystallization.
Finally, optical clear adhesive tape is attached on the ITO surfaces for being film-made side to cover-plate glass (cover glass)
(Optically Clear Adhesive, OCA) (transparent pressure-sensitive adhesive sheet), then by carrier film and curling inhibition layer mechanical stripping,
It is formed in the touch screen base plate that functional layer is formed with substrate layer.
Comparative example 1
Curling inhibition layer is not formed, and forms the polyimides as substrate layer on a carrier film similarly to Example 1
Resin A (10 μm of thickness), obtains polyimide resin layer stack (layered product C1).
Layered product C1 warpage (curling) greatly, in the manufacturing process of touch-screen by ITO film cut into sheet when
It can not be aligned because of warpage with shade, it is impossible to the transparent circuitry processing in XY directions is carried out, so that touch-screen can not be made.
Embodiment 2
Simultaneously using possessing for example shown in Fig. 2 of the portion of rolling out, lip type coating machine, continuous stove, continuous oven and reeling end
RTR modes coating dry hardening equipment by carrier film (width 520mm × length 500m × 75 μm of thickness) with 2m/min's
Speed is rolled out, and is simultaneously coated with polyamide acid varnish E in the way of thickness turns into 100 μm using Mono pump.Make the film by multiple
Pass through in the continuous stove that stove is constituted, dried 2 minutes at 90 DEG C, dried 1 minute at 130 DEG C, be produced on carrier film
On be formed with as curling inhibition layer polyimide resin E roller.Then, the volume is arranged on identical and applies drying device
Roll out in portion, 100 μm of polyamide acid varnish A is coated with polyimide resin E opposite side, what is be made up of multiple stoves
Pass through in continuous stove, dried 2 minutes at 90 DEG C, dried 1 minute at 130 DEG C, so being made up of multiple stoves and
Pass through in the continuous oven that temperature increases from the stove of sample inlets side to the heater stage of outlet side, to add up to 20 minutes stages
Ground is periodically heated to 400 DEG C from 130 DEG C, forms the polyimide resin A of 10 μm of the thickness as substrate layer, is rolled up
The polyimide resin layer stack (layered product 2) of shape.
On the thickness of each layer of layered product 2, carrier film is 75 μm, and curling inhibition layer is 13 μm, and substrate layer is 10 μm.Will
The Rotating fields of layered product 2 are illustrated schematically in Fig. 4.
Then, for layered product 2, it is formed in using method same as Example 1 on substrate layer and is formed with functional layer
Touch screen base plate.
Embodiment 3
Replaced using polyamide acid varnish C instead of polyamide acid varnish A as substrate layer, and using polyamide acid varnish D
Polyamide acid varnish E in addition, polyimide resin is obtained using method same as Example 2 as curling inhibition layer
Layered product (layered product 3).
On the thickness of each layer of layered product 3, carrier layer is 75 μm, and substrate layer is 12 μm, and curling inhibition layer is 13 μm.
On the layered product 3, ITO and XY circuits are film-made using method same as Example 1, touch-screen is obtained.
Embodiment 4
Using polyimide film 2 as carrier layer, curling is used as instead of polyamide acid varnish C using polyamide acid varnish F
Inhibition layer, in addition, polyimide resin layer stack (layered product 4) is obtained using method same as Example 1.
On the thickness of each layer of layered product 4, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 4 μm.
Embodiment 5
Replaced using polyamide acid varnish H instead of polyamide acid varnish A as substrate layer, and using polyamide acid varnish E
Polyamide acid varnish B in addition, polyimide resin is obtained using method same as Example 1 as curling inhibition layer
Layered product (layered product 5).
On the thickness of each layer of layered product 5, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 50 μm.
Embodiment 6
In addition to substrate layer and the thickness of curling inhibition layer, method same as Example 2 is utilized to obtain polyimides
Laminated resin body (layered product 6).
On the thickness of each layer of layered product 6, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 13 μm.
Embodiment 7
Replaced using polyamide acid varnish H instead of polyamide acid varnish A as substrate layer, and using polyamide acid varnish B
Polyamide acid varnish E in addition, polyimide resin is obtained using method same as Example 2 as curling inhibition layer
Layered product (layered product 7).
On the thickness of each layer of layered product 7, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 15 μm.
Comparative example 2
Except use polyamide acid varnish I replace polyamide acid varnish B as curling inhibition layer in addition to, using with embodiment
1 identical method obtains polyimide resin layer stack (layered product C2).
On the thickness of layered product C2 each layer, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 4 μm.
Comparative example 3
Except use polyamide acid varnish J replace polyamide acid varnish E as curling inhibition layer in addition to, using with embodiment
2 identical methods obtain polyimide resin layer stack (layered product C3).
On the thickness of layered product C3 each layer, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 15 μm.
Comparative example 4
Except use polyamide acid varnish I replace polyamide acid varnish B as curling inhibition layer in addition to, using with embodiment
1 identical method obtains polyimide resin layer stack (layered product C4).
On the thickness of layered product C4 each layer, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 13 μm.
Comparative example 5
The polyamic acid A of embodiment 4 is replaced using polyamic acid H, and polyamic acid E is replaced using polyamic acid K, except this
In addition, operated similarly to Example 1.
Replaced using polyamide acid varnish H instead of polyamide acid varnish A as substrate layer, and using polyamide acid varnish K
Polyamide acid varnish B in addition, polyimide resin is obtained using method same as Example 1 as curling inhibition layer
Layered product (layered product C5).
On the thickness of layered product C5 each layer, carrier layer is 75 μm, and substrate layer is 10 μm, and curling inhibition layer is 13 μm.
The physical property of the polyimide resin layer stack of gained is shown in Table 1 in embodiment and comparative example by more than.
Claims (14)
1. a kind of polyimide resin layer stack, it is the curling inhibition layer comprising polyimide resin, includes polyimides tree
The layered product of the carrier layer of fat and substrate layer comprising polyimide resin, and be characterized in that：The one of the substrate layer
Surface side is bonded with the curling inhibition layer and carrier layer in a releasable manner, the layer contacted with the substrate layer it is hot swollen
Swollen coefficient is less than or greater than any one of the thermal coefficient of expansion of other layers.
2. polyimide resin layer stack according to claim 1, wherein having in a surface side of the carrier layer described
Inhibition layer is crimped, and then with the substrate layer for being bonded in the curling inhibition layer in a releasable manner, the curling suppression
The thermal coefficient of expansion of preparative layer is less than or greater than any one of the thermal coefficient of expansion of the carrier layer and the substrate layer.
3. polyimide resin layer stack according to claim 2, wherein the substrate layer and the carrier layer is hot swollen
Swollen coefficient difference is ± below 40ppm/K.
4. polyimide resin layer stack according to claim 2, wherein in a surface side of the carrier layer across described
Crimp inhibition layer and the substrate layer and be formed further with functional layer.
5. polyimide resin layer stack according to claim 1, wherein having in a surface side of the carrier layer with can
The substrate layer that the mode of stripping is bonded, has the curling inhibition layer, the carrier in the opposite surface side of the carrier layer
The thermal coefficient of expansion of layer is less than or greater than any one of the substrate layer and the thermal coefficient of expansion of the curling inhibition layer.
6. polyimide resin layer stack according to claim 5, wherein the substrate layer and the curling inhibition layer
Coefficient of thermal expansion differences is ± below 40ppm/K.
7. polyimide resin layer stack according to claim 5, wherein in a surface side of the carrier layer across described
Substrate layer and be formed further with functional layer.
8. the polyimide resin layer stack according to claim 2 or 5, wherein the total light transmittance of the substrate layer is
More than 80%, and thickness is less than 50 μm.
9. the polyimide resin layer stack according to claim 2 or 5, wherein forming the polyimides tree of the substrate layer
The glass transition temperature of fat is more than 300 DEG C.
10. a kind of polyimide film with functional layer, it is characterised in that：It is to use polyamides according to claim 4
Imide resin layered product, is peeled off in the curling inhibition layer and the interface of the substrate layer, by the carrier layer and institute
Curling inhibition layer removing is stated to form.
11. a kind of polyimide film with functional layer, it is characterised in that：It is to use polyamides according to claim 7
Imide resin layered product, is peeled off in the carrier layer and the interface of the substrate layer, by the carrier layer and the volume
Bent inhibition layer is removed and formed.
12. a kind of manufacture method of polyimide resin layer stack, it is manufacture polyimides tree according to claim 1
The method of lipid layer stack, and be characterized in that：The curling inhibition layer and institute are applied in the carrier layer using casting
State substrate layer.
13. the manufacture method of polyimide resin layer stack according to claim 12, it makes to be coated in the carrier layer
On the curling inhibition layer and the substrate layer integrally harden.
14. the manufacture method of polyimide resin layer stack according to claim 13, wherein the casting is utilization
The coating of multilayer die head or continuous die head.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016071526 | 2016-03-31 | ||
| JP2016-071525 | 2016-03-31 | ||
| JP2016071525 | 2016-03-31 | ||
| JP2016-071526 | 2016-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107263984A true CN107263984A (en) | 2017-10-20 |
| CN107263984B CN107263984B (en) | 2021-01-12 |
Family
ID=60046052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710205150.XA Active CN107263984B (en) | 2016-03-31 | 2017-03-30 | Polyimide resin laminate, method for producing same, and polyimide film with functional layer |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7030418B2 (en) |
| KR (1) | KR102313706B1 (en) |
| CN (1) | CN107263984B (en) |
| TW (1) | TWI719184B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111070832A (en) * | 2018-10-18 | 2020-04-28 | 达迈科技股份有限公司 | Strippable polyimide composite film |
| CN111433020A (en) * | 2018-09-11 | 2020-07-17 | 株式会社Lg化学 | Laminate for manufacturing flexible display and method for manufacturing flexible display using the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7506391B2 (en) | 2020-03-11 | 2024-06-26 | 河村産業株式会社 | Metal-polyimide laminate |
| CN114506101A (en) | 2020-11-17 | 2022-05-17 | 臻鼎科技股份有限公司 | Polyimide thick film and preparation method thereof |
| TWI758954B (en) * | 2020-11-17 | 2022-03-21 | 臻鼎科技股份有限公司 | Polyimide thick film and method for manufacturing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101345218A (en) * | 2007-07-11 | 2009-01-14 | 株式会社日立显示器 | Method for manufacturing thin film transistors |
| JP2011011493A (en) * | 2009-07-03 | 2011-01-20 | Nippon Steel Chem Co Ltd | Method for producing laminated body of transparent conductive film |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS548848B1 (en) | 1968-06-28 | 1979-04-19 | ||
| JPS4834758B1 (en) | 1968-11-06 | 1973-10-23 | ||
| JP4699261B2 (en) * | 2005-03-31 | 2011-06-08 | 新日鐵化学株式会社 | Multilayer laminate and flexible copper-clad laminate |
| JP2007001173A (en) * | 2005-06-24 | 2007-01-11 | Toyobo Co Ltd | Multilayered polyimide film |
| US20070298260A1 (en) * | 2006-06-22 | 2007-12-27 | Kuppusamy Kanakarajan | Multi-layer laminate substrates useful in electronic type applications |
| JP2008231327A (en) | 2007-03-22 | 2008-10-02 | Ihara Chem Ind Co Ltd | Polyimide having high transparency and its manufacturing method |
| JP2009083201A (en) * | 2007-09-28 | 2009-04-23 | Toyobo Co Ltd | Multi-layer polyimide film and structure, multi-layer circuit substrate |
| JP2010221523A (en) * | 2009-03-24 | 2010-10-07 | Toray Ind Inc | Method for manufacturing metallic layer laminated film |
| JP5487066B2 (en) * | 2010-10-04 | 2014-05-07 | ルネサスエレクトロニクス株式会社 | Inspection method of semiconductor device |
| JP2012146905A (en) * | 2011-01-14 | 2012-08-02 | Kaneka Corp | Utilization of soluble polyimide resin film |
| KR102038135B1 (en) * | 2011-12-28 | 2019-10-30 | 주식회사 넥스플렉스 | Flexible metal-clad laminate manufacturing method thereof |
| JP5931672B2 (en) * | 2012-09-24 | 2016-06-08 | 新日鉄住金化学株式会社 | Polyimide laminate and method for producing the same |
| JP5478701B2 (en) * | 2012-11-30 | 2014-04-23 | 新日鉄住金化学株式会社 | Polyimide film |
| JP6067419B2 (en) * | 2013-02-28 | 2017-01-25 | 新日鉄住金化学株式会社 | Method for manufacturing laminated member |
| KR101802558B1 (en) * | 2013-04-09 | 2017-11-29 | 주식회사 엘지화학 | Method for manufacturing display device and display device manufactured by using same |
| JP6411047B6 (en) * | 2014-03-25 | 2018-12-05 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide laminated structure and manufacturing method thereof |
| CN106541652B (en) * | 2015-09-23 | 2021-03-30 | 日铁化学材料株式会社 | Polyimide laminate structure, method for producing same, display device, and touch panel |
-
2017
- 2017-03-30 CN CN201710205150.XA patent/CN107263984B/en active Active
- 2017-03-30 JP JP2017068868A patent/JP7030418B2/en active Active
- 2017-03-31 KR KR1020170041552A patent/KR102313706B1/en active IP Right Grant
- 2017-03-31 TW TW106110944A patent/TWI719184B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101345218A (en) * | 2007-07-11 | 2009-01-14 | 株式会社日立显示器 | Method for manufacturing thin film transistors |
| JP2011011493A (en) * | 2009-07-03 | 2011-01-20 | Nippon Steel Chem Co Ltd | Method for producing laminated body of transparent conductive film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111433020A (en) * | 2018-09-11 | 2020-07-17 | 株式会社Lg化学 | Laminate for manufacturing flexible display and method for manufacturing flexible display using the same |
| CN111433020B (en) * | 2018-09-11 | 2022-11-15 | 株式会社Lg化学 | Laminate for manufacturing flexible display and method for manufacturing flexible display using the same |
| US11597193B2 (en) | 2018-09-11 | 2023-03-07 | Lg Chem, Ltd. | Laminate for manufacturing flexible display, and flexible display manufacturing method using same |
| CN111070832A (en) * | 2018-10-18 | 2020-04-28 | 达迈科技股份有限公司 | Strippable polyimide composite film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107263984B (en) | 2021-01-12 |
| TW201736139A (en) | 2017-10-16 |
| KR102313706B1 (en) | 2021-10-18 |
| JP2017185806A (en) | 2017-10-12 |
| KR20170113434A (en) | 2017-10-12 |
| TWI719184B (en) | 2021-02-21 |
| JP7030418B2 (en) | 2022-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107263984A (en) | Polyimide resin layer stack and its manufacture method and the polyimide film with functional layer | |
| JP6457168B2 (en) | POLYIMIDE FILM FOR DISPLAY DEVICE SUPPORTING SUBSTRATE, ITS LAMINATE, AND METHOD FOR PRODUCING THE SAME | |
| JP6963504B2 (en) | Polyimide laminate and its manufacturing method | |
| KR101773651B1 (en) | Laminate structure for manufacturing substrate and device comprising substrate manufactured by using same | |
| EP2984544B1 (en) | Polyimide cover substrate | |
| CN104015466B (en) | The manufacturing method of laminated member | |
| TWI654251B (en) | Display device and method for producing the same, and polyimide film for display device | |
| JP6956501B2 (en) | Flexible substrate manufacturing method | |
| JP6601693B2 (en) | Laminated body with metal wiring layer formed and method for manufacturing the same | |
| CN107253376A (en) | Polyimides layered product and its manufacture method | |
| CN104380366A (en) | Display device, method for manufacturing same, polyimide film for display device supporting bases, and method for producing polyimide film for display device supporting bases | |
| KR20170038718A (en) | Method for producing laminate with polyimide layer and method for producing polyimide film | |
| JP2012102155A (en) | Polyimide film, laminate, and flexible device | |
| TW201707922A (en) | Polyimide substrate film with functional layer, manufacturing method thereof and long polyimide laminate capable of preventing the polyimide substrate film from being mixed with foreign matter and providing a good peeling capability | |
| JP2017069200A (en) | Manufacturing method of functional layer-attached polyimide film | |
| TW202108664A (en) | Resin film, metal-clad laminate and method for producing same | |
| CN107686962A (en) | Deposition mask and its manufacture method and deposition mask layered product and its manufacture method | |
| JP2016186936A (en) | Method for producing transparent conductive film | |
| KR20180018373A (en) | Polyimide precursor and polyimide made therefrom | |
| JP7102191B2 (en) | Method of manufacturing polyimide film | |
| TWI555637B (en) | Release layer, substrate structure, and method for manufacturing flexible electronic device | |
| JP6029499B2 (en) | Manufacturing method of input device | |
| JP6078319B2 (en) | Manufacturing method of input device, substrate with conductive film used therefor, and laminated member | |
| CN106541652A (en) | Polyimides laminate structure and its manufacture method and display device and touch screen | |
| TWI698347B (en) | Polyimide laminated structure, manufacturing method thereof, display device and touch panel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190125 Address after: Japan Tokyo Chiyoda international Kanda four chome 14 No. 1 Applicant after: Nippon Iron Chemical Materials Co., Ltd. Address before: Japan Tokyo Chiyoda international Kanda four chome 14 No. 1 Applicant before: Nippon Steel Chemical Co. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |