CN110077065A - Polyimides laminated body and its manufacturing method - Google Patents
Polyimides laminated body and its manufacturing method Download PDFInfo
- Publication number
- CN110077065A CN110077065A CN201910106754.8A CN201910106754A CN110077065A CN 110077065 A CN110077065 A CN 110077065A CN 201910106754 A CN201910106754 A CN 201910106754A CN 110077065 A CN110077065 A CN 110077065A
- Authority
- CN
- China
- Prior art keywords
- supporting substrate
- polyimides
- laminated body
- polyimide
- 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.)
- Pending
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
- B32B27/06—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
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides the operability with the polyimide film of the transparency, excellent in dimensional stability and polyimides laminated body and its manufacturing method that polyimide film can be easily separated from supporting substrate.A kind of polyimides laminated body, it is to have the polyimides laminated body of supporting substrate in the back side of polyimide layer, polyimide layer is 70% or more in the transmissivity of defined wavelength region, the surface of supporting substrate in their interfaces is formed by the heat resistant poly acid imide that glass transition temperature Tg is 300 DEG C or more, and surface roughness Ra is 100nm or less, the adhesive strength of supporting substrate and polyimide layer is 1N/m~500N/m, can separate polyimide layer from supporting substrate；In addition, a kind of manufacturing method of polyimides laminated body is coated with the resin solution of polyamic acid on one side, makes its imidizate and form defined polyimide layer on one side using the supporting substrate of roll-to-roll technique transmission strip.
Description
The application be September in 2013 23 application No. is the 201310435394.9, applying date, entitled " polyamides
The divisional application of the patent application of imines laminated body and its manufacturing method ".
Technical field
The present invention relates to polyimides laminated body and its manufacturing methods, in particular to the polyamides that will have the transparency
Polyimides laminated body and its manufacturing method made of imine layer is layered on supporting substrate.
Background technique
The display devices such as liquid crystal display device, organic EL display device are mobile for giant display as television set
The various display applications such as the miniscopes such as phone, personal computer, smart phone.Wherein, it is with organic EL display device
Example forms on the basis of thin film transistor (TFT) (hereinafter, TFT) on the glass substrate, stacks gradually electrode, luminescent layer, electrode, finally
It is gas-tight seal with other glass substrate, plural layers etc. and be made.
Herein, by the way that glass substrate is substituted for resin substrate, slim lightness and flexibilityization be can be realized, it can
Further widen the purposes of display device.For example, proposing the polyimides application that the transparency is high in non-patent literature 1 and 2
In the organic EL display device of supporting substrate.However, usually resin and glass phase are than the dimensional stability, transparency, heat resistance, resistance to
Moist, barrier properties for gases equal difference, so there is the exploitation with the resin of the comparable characteristic of simple glass at present.
For example, patent document 1 is related to the invention of polyimides and its precursor as flexible display plastic base, it is public
It has opened using the tetracarboxylic acid acids as cyclohexyl phenyl tetrabasic carboxylic acid etc. containing ester ring type structure and has been formed with various diamine reactants
Polyimides the transparency and excellent heat resistance.
On the other hand, it finds the problem when the advantages of studying resin substrate, i.e. the operability of resin substrate itself, dimensionally stable
Property.That is, it is membranaceous if being as thin as resin substrate, it is difficult to prevent the generation of wrinkle, rupture, it is difficult to stacking be maintained to form TFT, electrode
Etc. functional layers when position precision and formed functional layer after dimensional accuracy.Therefore, it proposes in non-patent literature 3 in glass
Be coated on glass fixed resin substrate formed as defined in after functional layer, utilize referred to as EPLaR (Electronics on Plastic
By Laser Release) method of technique irradiates laser from glass side, it is strong from glass to will be provided with the resin substrate of functional layer
Make isolated method.
It is coated with polyamic acid solution across peeling layer on glass in addition, proposing in non-patent literature 4, to making its solidification
After defined functional layer is arranged in obtained polyimide substrate, the method for polyimide substrate is removed from glass.For the party
For method, polyamic acid solution is coated with area more wide than peeling layer, keeps the peripheral portion of the polyimide substrate after solidifying straight
It connects and is fixed on glass, cut notch in the part for being formed with functional layer in such a way that the peripheral portion remains on glass, it will
The polyimide substrate formed across peeling layer is separated from glass.
The technology recorded in these non-patent literatures 3 and 4 is to use glass as supporting substrate, on being fixed on glass
Resin substrate form functional layer, therefore ensure that operability, the dimensional stability of resin substrate, but due to setting separating from glass
Special method is used in terms of aliphatic radical plate, so there are productivity low the problem of waiting.That is, for using remembering in non-patent literature 3
For the method for the EPLaR technique of load, not only separation resin substrate needs to expend the time from glass, but also may be to resin base
The surface texture of plate can also generate adverse effect.In addition, process number is more for the method recorded in non-patent literature 4, remove
Except this, generates the region for being not used as resin substrate and waste.Therefore, strong expectation, which is developed, plays resin substrate
Advantage and can with to industrial advantageous approach come using technology.
It is related to the invention of the manufacturing method of polyimide film it should be noted that describing in patent document 2 and 3, shows
It is coated with polyamic acid solution on the polyimide layer for having the metal foil of defined polyimide layer respectively, peels off and carries out at heating
It manages and the polyimides of imidizate, thus the method for manufacturing the polyimide film that the bad orders such as wrinkle, rupture are suppressed,
But polyimide film shown herein is opaque, in addition, there is no record to be laminated with the state of polyimides and be used as
Resin substrate.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2008-231327 bulletin
Patent document 2: No. 4260530 bulletins of Japanese Patent No.
Patent document 3: Japanese Unexamined Patent Publication 2011-56825 bulletin
Non-patent literature
Non-patent literature 1:S.An et.al., " 2.8-inch WQVGA Flexible AMOLED Using High
Performance Low Temperature Polysilicon TFT on Plastic Substrates”,SID2010
DIGEST,p706(2010)
Non-patent literature 2:Oishi et.al., " Transparent PI for flexible display ", IDW
‘11FLX2/FMC4-1
Non-patent literature 3:E.I.Haskal et.al. " Flexible OLED Displays Made with the
EPLaR Process”,Proc.Eurodisplay'07,pp.36-39(2007)
Non-patent literature 4:Cheng-Chung Lee et.al. " A Novel Approach to Make Flexible
Active Matrix Displays”,SID10Digest,pp.810-813(2010)
Summary of the invention
Therefore, the inventors of the present invention are to can will ensure that operational (also referred to as treatability), dimensional stability etc. and heat-resisting
Property and the excellent polyimide film of the transparency be used as the method for resin substrate and furtherd investigate repeatedly, as a result, it has been found that one kind exists
The back side of polyimide layer with the transparency has the polyimides laminated body of supporting substrate, by by having regulation character
Polyimides form the surface of supporting substrate and the polyimide film that be made of polyimide layer can be separated from supporting substrate,
So as to all solve the problems, such as conventional art, and then complete the present invention.
Therefore, the purpose of the present invention is to provide can will have the transparency polyimide film be used as resin base material and
Operability, excellent in dimensional stability and can be easily separated from supporting substrate polyimide film polyimides laminated body and
Its manufacturing method.
That is, purport of the invention is as described below.
(1) a kind of polyimides laminated body, which is characterized in that be to have supporting substrate in the back side of polyimide layer
Polyimides laminated body, polyimide layer are 70% or more in the transmissivity of the wavelength region of 440nm~780nm, polyimides
The surface of layer and the supporting substrate in the interface of supporting substrate is the heat resistant poly for being 300 DEG C or more by glass transition temperature Tg
Acid imide formed and surface roughness Ra be 100nm hereinafter, the adhesive strength of supporting substrate and polyimide layer be 1N/m~
500N/m can separate the polyimide film being made of above-mentioned polyimide layer from supporting substrate.
(2) the polyimides laminated body as described in (1), wherein polyimide layer is made of single layer or multilayer, at least with
The layer that supporting substrate connects is fluorinated polyimide.
(3) the polyimides laminated body as described in (1) or (2), wherein the heat resistant poly acid imide in supporting substrate is tool
There is the polyimides of following structural units.
(4) the polyimides laminated body as described in any one of (1)~(3), wherein the thermal expansion coefficient of polyimide layer
For 15ppm/K or less.
(5) the polyimides laminated body as described in any one of (1)~(4), wherein polyimide layer with a thickness of 3 μm
~50 μm, in addition, supporting substrate with a thickness of 10 μm~100 μm.
(6) the polyimides laminated body as described in any one of (1)~(5), wherein the polyamides after supporting substrate removing
The surface roughness Ra of the release surface of imines film is 100nm or less.
(7) the polyimides laminated body as described in any one of (1)~(6), wherein in the surface side shape of polyimide layer
After defined functional layer, separates the supporting substrate of back side and use.
(8) the polyimides laminated body as described in any one of (1)~(7), wherein supporting substrate back side into one
Step has adhesive layer.
(9) a kind of manufacturing method of polyimides laminated body, which is characterized in that had in the back side of polyimide layer
The manufacturing method of the polyimides laminated body of supporting substrate, will have on one side by glass transition temperature Tg be 300 DEG C or more and
Surface roughness Ra is that the strip supporting substrate in the heat-proof polyimide face that 100nm heat resistant poly acid imide below is formed is used
Roll-to-roll technique transmission, is coated with the resin of fluorine-containing polyamic acid on the heat-proof polyimide face of the supporting substrate of strip on one side
Solution, carrying out heat treatment at 200 DEG C or more together with supporting substrate makes polyamic acid imidizate and is formed on supporting substrate
It is 70% or more polyimide layer in the transmissivity of the wavelength region of 440nm~780nm, and keeps supporting substrate and polyamides sub-
The adhesive strength of amine layer can separate the polyimide film that be made of polyimide layer from supporting substrate for 1N/m~500N/m.
(10) manufacturing method of the polyimides laminated body as described in (9), wherein the heat treatment condition of polyamic acid is
It is within 15 minutes, when the high-temperature heating temperature region refers to than heating heating in the heating time of high-temperature heating temperature region
Low 20 DEG C of the temperature~maximum temperature reached of maximum temperature reached.
(11) manufacturing method of the polyimides laminated body as described in (9) or (10), wherein formed resistance in supporting substrate
The heat resistant poly acid imide in hot polymerization acid imide face is the polyimides with following structural units.
(12) a kind of manufacturing method of polyimide film, which is characterized in that from the side as described in any one of (9)~(11)
The polyimides laminated body that method obtains separates polyimide layer.
Polyimides laminated body according to the present invention, due to the transparency and excellent heat resistance polyimide layer with it is defined
Supporting substrate integration, so can ensure operability, dimensional stability etc., and can be easily separated poly- from supporting substrate
Imide layer and polyimide film is made, so the polyimide film can suitably be used as resin substrate.In addition, for this hair
For bright polyimides laminated body, the heat resistance of laminated body itself is also high, can in heat treatment process at high temperature
Enough applications, and there is flexibility and making thinner, it can be applied to the user being transmitted using roll-to-roll technique
Method, so the manufacture of touch panel, display device etc. can be suitably used for.
Detailed description of the invention
Fig. 1 is the cross-sectional view for indicating a mode of polyimides laminated body of the invention.
Fig. 2 is the section view for indicating another mode (when polyimide layer is multilayer) of polyimides laminated body of the invention
Figure.
Fig. 3 is the section view for indicating another mode (when supporting substrate layer is multilayer) of polyimides laminated body of the invention
Figure.
Fig. 4 is the schematic diagram for indicating the roll-to-roll device for forming polyimide layer on the supporting substrate of strip.
Fig. 5 is the schematic diagram for indicating the supporting substrate of strip web-like.
Symbol description
1 polyimide layer
2 supporting substrates
3 functional layers
4 adhesive layers
10 polyimides laminated bodies
11 coating heat treatment portions
12 delivering mechanisms
13 winding mechanisms
14 send out the Gun Juan mechanism of side
The Gun Juan mechanism of 15 winding sides
Specific embodiment
Hereinafter, the present invention will be described in detail.
Polyimides laminated body of the invention is using polyimide layer and supporting substrate as necessary component parts, such as Fig. 1
The shown back side in polyimide layer 1 has supporting substrate 2.The thickness of polyimide layer 1 in polyimides laminated body 10
Preferably 3 μm~50 μm.If the thickness of polyimide layer 1 when less than 3 μm, being used as insulating layer may insulation performance not
Foot, and it is also poor from the treatability of the polyimide film after the separation of polyimides laminated body 10, on the other hand, then if more than 50 μm
It may be decreased by the flexibility of isolated polyimide film, the transparency.The thickness of supporting substrate 2 is as long as being easily isolated without special
Limitation, preferably 10 μm~100 μm.If supporting substrate 2 thickness less than 10 μm if can not fill as the supporting of supporting substrate 2
Distribution is waved, and transmissibility, treatability may be decreased, then unfavorable to goods cost if more than 100 μm.
Polyimides laminated body 10 of the invention can be easily separated supporting substrate 2 and polyimide layer 1.The present invention
In, in order to show the separation easiness, preferably by either in supporting substrate 2, polyimide layer 1 or both sides use following institute
The specific component shown.
Firstly, being illustrated to supporting substrate 2 used in the present invention.
For the supporting substrate 2 used in the present invention, the supporting substrate 2 as shown in Fig. 1 (A) can be enumerated by resin base material
The case where composition, forms composite base material made of resin layer 2a on metal foil 2b as shown in Figure 3, as long as can be with polyimides
Layer 1 can be easily separated and show that defined characteristic is just not particularly limited.It can be easily separated with polyimide layer 1 and refer to supporting substrate 2
The range that adhesive strength with polyimide layer 1 is 1N/m~500N/m, preferably 5N/m~300N/m, more preferably 10N/m
~200N/m.Peel strength by making supporting substrate 2 and polyimide layer 1 can obtain can provide no folding in the range
Wrinkle, rupture etc. it is bad in appearance, industrially can steady production transparent polyimide film polyimides laminated body 10.
Polyimides laminated body 10 of the invention can be used in the manufacture of touch panel, display device etc., thus need sometimes
Want heat resistance.Therefore, in the case that supporting substrate 2 is made of resin base material, such as preferably polyimide base material can be illustrated, separately
Outside, in the case where being made of composite base material, the laminated body of preferably metal foil and polyimides can be illustrated.
Herein, it is at least formed and is needed with the surface of the supporting substrate 2 at the interface of polyimide layer 1 by glass transition temperature
Tg is that 300 DEG C or more of heat resistant poly acid imide is formed.If the glass transition of the heat-proof polyimide on the supporting substrate surface
Temperature Tg is then reduced as the heat resistance of polyimides laminated body 10 less than 300 DEG C, in addition to this, point with polyimide layer 1
It may deteriorate from property.In addition, the surface roughness Ra in heat-proof polyimide face needs for 100nm or less.If surface roughness Ra
The reason of greater than 100nm, then still deteriorating with the separation property of polyimide layer 1, not only becoming deformation when polyimides separation,
And its transparency is also easily reduced.
Next, being illustrated to the polyimide layer 1 for constituting polyimides laminated body 10 of the invention.
The polyimide layer 1 of polyimides laminated body 10 of the invention shows the wavelength region in 440nm~780nm
Transmissivity is 70% or more (in this specification, when meeting the transmission characteristics, showing as the display transparency).Polyimides
Layer 1 is set up directly on supporting substrate 2, and polyimide layer 1 can be only made of single layer, in addition, for example as shown in Figure 2 can also be with
It is made of multilayer (1a, 1b, 1c).When polyimide layer 1 is made up of multiple layers, above-mentioned transmissivity is integrally indicated with multilayer.
Polyimide layer 1 and formation and the polyamides in polyimides laminated body 10 of the invention, on supporting substrate
The surface of the supporting substrate 2 at the interface of imine layer 1 is made of defined polyimides respectively.
Polyimides be usually as raw material acid anhydrides and diamines polymerization obtained from, by the following general formula (1) indicate.
In formula, Ar1Indicate the organic group of 4 valences, Ar2For the organic group of divalent, from the viewpoint of heat resistance, Ar1、
Ar2In at least one party be preferably aromatic residue.
Herein, as the acid anhydrides for becoming polyimides raw material, when illustrating representative acid anhydrides, Pyromellitic Acid two can be enumerated
Acid anhydride, 3,3',4,4' benzophenone tetracarboxylic dianhydride, 2,2', 3,3'- benzophenone tetracarboxylic dianhydride, 2,3,3', 4'- hexichol first
Ketone tetracarboxylic dianhydride, naphthalene -2,3,6,7- tetracarboxylic dianhydride, naphthalene -1,2,5,6- tetracarboxylic dianhydride, naphthalene -1,2,4,5- tetrabasic carboxylic acid two
Acid anhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, naphthalene -1,2,6,7- tetracarboxylic dianhydride, 4,8- dimethyl -1,2,3,5,6,7- hexahydro naphthalene -
1,2,5,6- tetracarboxylic dianhydride, 4,8- dimethyl -1,2,3,5,6,7- hexahydro naphthalene -2,3,6,7- tetracarboxylic dianhydride, 2,6- dichloro
Naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7- dichloronaphtalene -1,4,5,8- tetracarboxylic dianhydride, 2,3,6,7- Tetrachloronaphthalene -1,4,5,8- four
Carboxylic acid dianhydride, 1,4,5,8- Tetrachloronaphthalene -2,3,6,7- tetracarboxylic dianhydride, 3,3', 4,4'- biphenyltetracarboxylic dianhydride, 2,2', 3,
3'- biphenyltetracarboxylic dianhydride, 2,3,3', 4'- biphenyltetracarboxylic dianhydride, 3,3 ", 4,4 "-para-terpheny tetracarboxylic dianhydrides, 2,2 ",
3,3 "-para-terpheny tetracarboxylic dianhydrides, 2,3,3 ", 4 "-para-terpheny tetracarboxylic dianhydrides, 2,2- bis- (2,3- dicarboxyphenyis)-
Bis- (3,4- the dicarboxyphenyi)-propane dianhydrides of propane dianhydride, 2,2-, bis- (2,3- dicarboxyphenyi) ether dianhydrides, bis- (2,3- dicarboxyls
Base phenyl) methane dianhydride, bis- (3.4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- dicarboxyphenyi) sulfone dianhydrides, bis- (3,4- bis-
Carboxyl phenyl) sulfone dianhydride, bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,1-, bis- (3,4- dicarboxyphenyi) ethane two of 1,1-
Acid anhydride, -2,3,8,9- tetracarboxylic dianhydride, -3,4,9,10- tetracarboxylic dianhydride, -4,5,10,11- tetracarboxylic dianhydride, -5,
6,11,12- tetracarboxylic dianhydride, phenanthrene -1,2,7,8- tetracarboxylic dianhydride, phenanthrene -1,2,6,7- tetracarboxylic dianhydride, phenanthrene -1,2,9,10- four
Carboxylic acid dianhydride, pentamethylene -1,2,3,4- tetracarboxylic dianhydride, pyrazine -2,3,5,6- tetracarboxylic dianhydride, pyrrolidines -2,3,4,5- four
Carboxylic acid dianhydride, thiophene -2,3,4,5- tetracarboxylic dianhydrides, the double O-phthalic acid dianhydrides of 4,4'- oxygen etc., they can independent or mixing
Two or more is used.
In addition, when illustrating representative diamines, 4,6- dimethyl-can be enumerated as the diamines for becoming polyimides raw material
M-phenylene diamine (MPD), 2,5- dimethyl-p-phenylenediamine, 2,4- diamino mesitylene, two ortho-aminotoluene of 4,4'- methylene, 4,4'- are sub-
Two -2,6- dimethylaniline of methyl, 4,4'- methylene -2,6- diethylaniline, 2,4- toluenediamine, m-phenylene diamine (MPD), to benzene two
Amine, 4,4'- diamino-diphenyl propane, 3,3'- diamino-diphenyl propane, 4,4'- diamino-diphenyl ethane, 3,3'- bis-
Bis- [4- (the 4- aminobenzenes of aminodiphenyl base ethane, 4,4'- diaminodiphenyl-methane, 3,3'- diaminodiphenyl-methane, 2,2-
Oxygroup) phenyl] propane, 4,4'- diamino-diphenyl sulfide, 3,3'- diamino-diphenyl sulfide, 4,4'- diamino two
Phenylsulfone, 3,3'- diamino diphenyl sulfone, 3,3'- diamino-diphenyl ether, 4,4'- diamino-diphenyl ether, 3,4'- diamino
Bis- (3- amino-benzene oxygen) benzene of base diphenyl ether, 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,3-, 1,4- bis- (4- amino-benzene oxygens)
Benzene, benzidine, 3,3'- benzidine, 3,3'- dimethyl -4,4'- benzidine, 3,3'- dimethoxy benzidine, 4,
It is 4'- diamino-para-terpheny, 3,3'- diamino-para-terpheny, bis(p-aminocyclohexyl)methane, bis- (to the tertiary fourth of beta-amino-
Base phenyl) ether, bis- (to Beta-methyl-δ-Aminopentyl) benzene, to bis- (2- methyl -4- Aminopentyl) benzene, to bis- (1,1- diformazans
Base -5- Aminopentyl) benzene, 1,5- diaminonaphthalene, 2,6- diaminonaphthalene, bis- (beta-amino-tert-butyl) toluene of 2,4-, 2,4- diamino
Base toluene, meta-xylene -2,5- diamines, paraxylene -2,5- diamines, sub- dimethylphenylene diamine, to sub- dimethylphenylene diamine, 2,6-
Diamino-pyridine, 2,5- diamino-pyridine, 2,5- diaminostilbene, 3,4-Diazole, piperazine etc., they can independent or mixing 2
Kind is used above.
Wherein, the heat resistant poly for forming with the interface of polyimide layer 1, composition supporting substrate 2 surface is imido
Glass transition temperature Tg is necessary for 300 DEG C or more, preferably following knots to be formed by biphenyltetracarboxylic dianhydride and phenylenediamine
Structure unit is the polyimides of principal component,
Particularly preferably using structural unit shown in following as the polyimides of principal component.
It should be noted that so-called principal component refers to 50 moles of % for accounting for and constituting the imido structural unit of heat resistant poly herein
More than, preferably 80 moles of % or more.
On the other hand, for the polyimide layer 1 on the supporting substrate 2 in polyimides laminated body 10 of the invention and
Speech, in the case that supporting substrate 2 uses above-mentioned preferred polyimides, as long as can be easily separated and provide transparent polyimide layer
It can use without particular limitation, in the case of supporting substrate surface does not use above-mentioned preferred polyimides, to separate more
In easy situation, the layer preferably to connect with supporting substrate 2 uses fluorinated polyimide.This refers to polyimide layer 1 by single layer
When composition, polyimides is fluorinated polyimide, in the case that polyimide layer as shown in Figure 2 is made up of multiple layers, with bearing
The layer 1a that the heat-proof polyimide of substrate surface connects is fluorinated polyimide.
Fluorinated polyimide refer in polyimide structures have fluorine atom, as polyimides raw material acid anhydrides and
At least one party in diamines has fluoro-containing group.As such fluorinated polyimide, Ar in above-mentioned general formula (1) can be illustrated in2
It is indicated by the following general formula (2) or general formula (3).
(herein, the R in general formula (2) or general formula (3)1~R8Independently of one another hydrogen atom, fluorine atom, carbon atom number 1~5
Alkyl or alkoxy or fluorine substituted hydrocarbon radical, when being general formula (2), R1~R4In at least one for fluorine atom or fluorine replace hydrocarbon
Base, in addition, when being general formula (3), R1~R8In at least one be fluorine atom or fluorine substituted hydrocarbon radical.〕
As R1~R8Preferred concrete example can enumerate-H ,-CH3、-OCH3、-F、-CF3Deng, in formula (2) or formula (3),
At least one substituent group is-F or-CF3Either one or two of.
In addition, as the Ar in the general formula (1) when forming fluorinated polyimide1Concrete example, such as below 4 can be enumerated
The anhydride residue of valence.
In addition, when forming fluorinated polyimide, as the Ar provided in general formula (1)2Specific diamines residue, such as can
Enumerate substance below.
The preferred heat resistance of polyimide layer 1 is high, and thermal expansion coefficient is 15ppm/K hereinafter, foregoing illustrative polyimides tree
In rouge, preferably there is the structural unit indicated by following formula (4) or (5) with the ratio of 80 moles of % or more.
Above explained various polyimides can be obtained and making polyamic acid imidizate, herein, polyamic acid
Resin solution can diamines and acid dianhydride by substantial equimolar used as raw material, react obtain in organic solvent.
More specifically, after by making diamines be dissolved in the organic polar solvents such as n,N-dimethylacetamide under nitrogen flowing, four are added
Carboxylic acid dianhydride, room temperature reaction 5 hours or so and obtain.From the machine of uniform film thicknessization when coating and obtained polyimide film
From the perspective of tool intensity, the weight average molecular weight of obtained polyamic acid is preferably 10,000~300,000.It should be noted that polyimides
The preferred molecular weight ranges of layer are also molecular weight ranges identical with polyamic acid.
It, can for the maximum except the polyimides when making the polyimides of the structure of polyimides general formula (4) or (5)
To be not particularly limited with other polyimides of the ratio addition less than 20 moles of %, can be used general acid anhydrides and
Diamines.As it is preferable to use acid anhydrides, pyromellitic acid anhydride, 3,3', 4,4'- biphenyltetracarboxylic dianhydrides, Isosorbide-5-Nitrae-ring can be enumerated
Hexane dicarboxylic acid, 1, bis- (3,4- dicarboxyphenyi) hexafluoropropane dianhydrides of 2,3,4- cyclobutane tetracarboxylic dianhydrides, 2,2'- etc., separately
Outside, 4,4'- diamino diphenyl sulfone, anti-form-1,4- diaminocyclohexane, 4,4'- diamino butylcyclohexyl can be enumerated as diamines
Bis- (4- the aminocyclohexyl)-hexafluoropropane of methane, 2,2'-, bis- (the trifluoromethyl) -4,4'- diamino bicyclohexane of 2,2'- etc..
The polyimide layer 1 obtained in this way can as described above be single layer, can also be made up of multiple layers, be made up of multiple layers
When can also suitably select raw material, it will thus provide transparent polyamic acid forms multilayer, thus it enables that polyimide layer is integrally saturating
It is bright.
In the present invention, polyimide film by supporting substrate 2 formed polyimide layer 1, with removing the methods of by its
It is isolated, the preferred surface roughness Ra of release surface from the polyimide film after the removing of supporting substrate 2 is 100nm or less.
In order to reduce the surface roughness of the release surface, preferably makes the smooth surface of 2 side of supporting substrate, metal is used with supporting substrate 2
For the composite substrate of foil and resin, the resin solution of polyamic acid is formed using rubbing method on metal foil, by being used
In dry and/or cured heat treatment, the surface roughness Ra 100nm or less in heat-proof polyimide face can be made.
In the present invention, other than the polyimides laminated body 10 made of 2 upper layer laminated polyimide layer 1 of supporting substrate,
As shown in Fig. 1 (B), the surface side that can be formed in the polyimide layer 1 of the polyimides laminated body 10 forms defined function
The polyimides laminated body of ergosphere 3.Such polyimides laminated body provides after the supporting substrate of separation back side with function
The polyimide film of ergosphere.It is used as functional layer herein, the display devices such as organic EL, liquid crystal display, touch panel etc. can be illustrated
Input unit, the barrier layer for being not through gas, moisture, transparent conductive film etc..It should be noted that functional layer as defined in being formed
As long as the separation of the supporting substrate 2 after 3 can be arbitrary process after functional layer is formed.
In addition, polyimides laminated body 10 of the invention can supporting substrate 2 back side, i.e. with polyimide layer 1
The surface of the supporting substrate 2 of the side opposite with the interface that supporting substrate 2 is formed is further equipped with by epoxy resin, acrylic acid tree
The adhesive layer 4 of the formation such as rouge.After polyimides laminated body 10 is attached at other components as a result, can only it be separated poly-
The operation of the polyimide film of acid imide film or separation with functional layer.
Next, being explained in detail to the manufacturing method further progress of polyimides laminated body of the invention.
The preferred manufacturing method of polyimides laminated body 10 of the invention, which is characterized in that will have by vitrifying on one side
Transition temperature Tg is 300 DEG C or more and surface roughness Ra is the heat-resisting polyamides that 100nm heat resistant poly acid imide below is formed
The strip supporting substrate 2 in imines face is transmitted with roll-to-roll technique, on one side in the heat-proof polyimide of the supporting substrate of strip 2
The resin solution of fluorine-containing polyamic acid is coated on face, carrying out heat treatment at 200 DEG C or more together with supporting substrate 2 makes polyamic acid
Imidizate and polyamides that the transmissivity that the wavelength region of 440nm~780nm is formed on supporting substrate 2 is 70% or more is sub-
Amine layer 1, and make adhesive strength 1N/m~500N/m of supporting substrate 2 and polyimide layer 1 and can divide from supporting substrate 2
From the polyimide film being made of polyimide layer 1.
That is, the preferred manufacturing method of polyimides laminated body 10 in the present invention is due to that can utilize roll-to-roll technique, institute
Having with the supporting substrate 2 that uses is 300 DEG C or more by strip, glass transition temperature Tg and surface roughness Ra is
The heat-proof polyimide face that 100nm heat resistant poly acid imide below is formed.In roll-to-roll technique, supporting substrate 2 is to be wound into
The state of web-like prepares, and extraction part of it is spare as supporting substrate 2.It should be noted that providing the poly- of heat-proof polyimide face
Acid imide is preferably using the identical polyimides recorded in the invention of above-mentioned polyimides laminated body.In addition, if bearing base
Material is conductive, or has conductive layer at the back side of the side opposite with polyimide layer, then has the advantage that
It prevents from extracting film out repeatedly in a manner of roll-to-roll and electrification caused by the electrostatic that generates when being wound.
On the heat-proof polyimide face of the supporting substrate 2 of the strip provided in this way, coating is used as polyimide precursor
Polyamic acid resin solution.As polyamic acid, it is preferable to use above-mentioned fluorine-containing polyamic acid.
After being coated with the resin solution of polyamic acid, carried out at heating together with the supporting substrate 2 of strip at 150~160 DEG C
It manages and removes the solvent contained in resin solution, and polyamic acid imidizate is further made with the heat treatment of high temperature.Acyl is sub-
After the heat treatment carried out when amination can be removing solvent to a certain degree, from 160 DEG C or so of temperature to 350 DEG C or so of temperature
It heats up with spending the continuous or stage.
By above-mentioned heat treatment, the polyamides that can obtain being formed polyimide layer 1 on the supporting substrate 2 of strip is sub-
Amine layer stack 10.Herein, the polyimide layer 1 on supporting substrate 2 is to be in the transmissivity of the wavelength region of 440nm~780nm
70% or more clear polyimides layer 1, the present invention in, particularly preferably make in above-mentioned heat treatment from than heating when highest
Low 20 DEG C of the temperature of heating temperature (maximum temperature reached) to maximum temperature reached high-temperature heating temperature region heating time
(hereinafter referred to as high temperature hold time) is within 15 minutes.If the high temperature hold time is greater than 15 minutes, have due tos coloring etc.
The trend that the transparency of polyimide layer reduces.In order to maintain the transparency, preferably high temperature hold time is short, but when the time is too short,
There is a possibility that effect for being unable to fully be heat-treated.Optimal high temperature hold time is according to heating method, supporting substrate 2
Thermal capacitance, the thickness etc. of polyimide layer 1 and it is different, more preferably 0.5 minute~5 minutes.
The adhesive strength of the supporting substrate 2 of polyimides laminated body 10 of the invention and polyimide layer 1 1N/m~
The range of 500N/m becomes the shape that the polyimide film being made of polyimide layer 1 can be easily separated from supporting substrate 2
State, isolated form are not particularly limited.For example, the polyimides laminated body being made of supporting substrate 2 and polyimide layer 1
10 can be directly with the state of its original sample be wound in roller and forms the laminated body of web-like, alternatively, it is also possible to as roll-to-roll work
After the imidizate process of the intermediate process of skill, supporting substrate 2 and polyimide layer 1 are removed before rolling step and makes it
Separation.Or the polyimides laminated body 10 for the sheet that every is cut into predetermined size can be prepared, it is poly- from the removing of supporting substrate 2 respectively
Imide layer 1 and make its separation.In any case, it if forming functional layer 3 on the surface of polyimide layer 1, separates
Polyimide film can be used as resin substrate, especially if forming function before separating polyimide layer 1 from supporting substrate 2
Layer 3, then can substantially ensure operability, dimensional stability of the polyimide film etc..
Polyimides laminated body 10 of the invention, which is characterized in that the adhesive strength of supporting substrate 2 and polyimide layer 1
It is low, easily they can be separated, it, can be in supporting substrate 2 during obtaining such polyimides laminated body 10
High (the being greater than 500N/m) position of adhesive strength is temporarily set with some at the interface of polyimide layer 1, cuts off the portion thereafter
Divide to wait and obtains polyimides laminated body 10 of the invention.That is, for example, from form stable when improving long-term keeping, conveying
Property the purpose of set out, using specially the methods of polyamic acid solution shape will be coated with after a part roughening on the surface of supporting substrate 2
At polyimide layer 1, keep the adhesive strength of a part at interface higher (being greater than 500N/m) than other most surfaces,
Afterwards, by removing the high part of adhesive strength using the methods of cutting, polyimides laminated body 10 of the invention can be made.
Hereinafter, based on embodiment etc., the content of the present invention will be explained in more detail, and the present invention is not by the model of these embodiments
Enclose restriction.
Embodiment
Firstly, the survey of the abbreviation of starting monomer, solvent when by synthesis of polyimides and the various physical property in embodiment
Method and its condition are determined described below.
[abbreviation]
DMAc:N, N- dimethyl acetamide
PDA:1,4- phenylenediamine
Bis- (the trifluoromethyl) -4,4'- benzidines of TFMB:2,2'-
DADMB:4,4'- diamino -2,2'- dimethyl diphenyl
Bis- (4- amino-benzene oxygen) benzene of 1,3-BAB:1,3-
BPDA:3,3', 4,4'- biphenyltetracarboxylic dianhydride
Bis- (3,4- dicarboxyphenyi) hexafluoropropane dianhydrides of 6FDA:2,2'-
PMDA: pyromellitic acid anhydride
(surface roughness (Ra))
Surface sight is carried out with tapping-mode using the atomic force microscope (AFM) " Multi Mode8 " of Bruker corporation
It examines.The visual field observation for carrying out 4 10 μm of square, acquires their average value.Surface roughness (Ra) indicates arithmetic mean roughness
It spends (JIS B0601-1991).
(fissility)
Will by 50mm square size cut polyimides laminated body made of material as evaluation sample, from one angle into
The removing of row polyimide layer and supporting substrate.In the sample that can be removed, damage will not be brought to polyimide layer
The sample that ground is easily peeled off is evaluated as zero, it will be observed that and the sample of elongation, the rupture of film is evaluated as ×.Polyamides is sub- when will remove
The sample that the bonding force of amine layer and supporting substrate is strong and can not remove is evaluated as not peelable.
(peel strength)
Using Toyo Seiki manufacturing company Strograph R-1, width is cut by polyimides laminated body
The sample of the short strip shape of 10mm is evaluated by measuring peel strength using T word disbonded test method.
(transmissivity (%))
The light transmittance of 440nm~780nm is found out to polyimide film (50mm × 50mm) using U4000 type spectrophotometer
Average value.
(glass transition temperature Tg)
Glass transition temperature uses determination of viscoelasticity instrument (Rheometric Scientific Co. Ltd. system RSA-
II), using the sample of 10mm wide, when by being warming up to 400 DEG C from room temperature in the vibration for giving 1Hz with 10 DEG C/min of speed
The maximum of loss angle tangent (Tan δ) acquire.
(thermal expansion coefficient (CTE))
5.0g load one is applied on one side using thermo-mechanical analysis (TMA) device to the polyimide film of 3mm × 15mm size
While the temperature range with constant heating rate (20 DEG C/min) at 30 DEG C~260 DEG C carries out tension test, by polyimide film
Amount of tension relative to temperature measures thermal expansion coefficient (× 10-6/K)。
Synthesis example 1 (polyimides A)
Under nitrogen stream, PDA8.00g is set to be dissolved in solvent DMAc while stirring in the detachable flask of 300ml.
Then, solution B PDA22.00g is added.Thereafter, solution is persistently stirred into 5 hours progress polymerization reactions in room temperature, is kept for a daytime
Night.Confirmation obtains sticky polyamic acid solution, generates the polyamic acid A of high polymerization degree.
Synthesis example 2 (polyimides B)
Under nitrogen stream, make the 1 of DADMB19.11g and 2.92g while stirring in the detachable flask of 300ml,
3-BAB is dissolved in solvent DMAc.Then, the PMDA of the BPDA and 17.17g of 5.79g are added in the solution.Thereafter, by solution
5 hours progress polymerization reactions are persistently stirred in room temperature, keep diel.Confirmation obtains sticky polyamic acid solution, generates high
The polyamic acid B of the degree of polymerization.
Synthesis example 3 (polyimides C)
Under nitrogen stream, TFMB12.08g is set to be dissolved in solvent while stirring in the detachable flask of 300ml
DMAc.Then, PMDA6.20g and 6FDA4.21g is added in the solution.Thereafter, solution is persistently stirred 5 hours in room temperature and is carried out
Polymerization reaction keeps diel.Confirmation obtains sticky polyamic acid solution, generates the polyamic acid C of high polymerization degree.
Synthesis example 4 (polyimides D)
Under nitrogen stream, TFMB13.30g is set to be dissolved in solvent while stirring in the detachable flask of 300ml
DMAc.Then, PMDA9.20g is added in the solution.Thereafter, solution is persistently stirred into 5 hours progress polymerization reactions in room temperature,
Keep diel.Confirmation obtains sticky polyamic acid solution, generates the polyamic acid D of high polymerization degree.
[embodiment 1]
On 18 μm of thickness of electrolytic copper foil, after being coated with the resin solution of polyamic acid A obtained in synthesis example 1,130
It DEG C is thermally dried, removes solvent.Next, by being carried out with about 15 DEG C/min of heating rate from 160 DEG C to 360 DEG C
Heat treatment and imidizate, obtain foring on copper foil 25 μm of thickness polyimide layer (surface roughness Ra=1.3nm,
Tg=355 DEG C) supporting substrate.
On the polyimide layer of obtained supporting substrate, with polyamide obtained in uniform thickness coating synthesis example 3
It after the resin solution of sour C, is thermally dried at 130 DEG C, removes the solvent in resin solution.Next, by from 160 DEG C to
360 DEG C are heat-treated with about 20 DEG C/min of heating rate and make polyamic acid imidizate, and polyimide layer is formed in
Back side has the polyimides laminated body of supporting substrate.It is cooled to room temperature immediately in this state, it is poly- from supporting substrate removing
The part of imide layer and obtain 25 μm of thickness of transparent polyimide film.Supporting substrate and transparent polyimide film when removing
Fissility it is good.It should be noted that when the imidizate of polyamic acid C, from 20 DEG C of temperature lower than maximum temperature reached to most
Height reaches the heating time (high temperature hold time) of the high-temperature heating temperature region of temperature, the high temperature dwell i.e. from 340 DEG C to 360 DEG C
Holding the time is 1 minute.
Include the case where the embodiment 1, is formed by the characteristic of supporting substrate used in each embodiment, on supporting substrate
Polyimide layer or the characteristic of polyimide film and the evaluation result etc. of polyimides laminated body it is shown in table 1.
Table 1
[embodiment 2]
Use 25 μm of thickness of polyimide films (Kapton H, DU PONT-TORAY Co. Ltd. system: surface roughness
Ra=70nm, Tg=428 DEG C) it is used as supporting substrate, it is coated with the resin solution of polyamic acid C obtained in synthesis example 3 on it,
Thereafter, it is thermally dried at 130 DEG C and removes the solvent in resin solution.Next, from 160 DEG C to 360 DEG C with about 20 DEG C/
Minute heating rate carry out heat treatment and make (1 point of high temperature hold time from 340 DEG C to 360 DEG C of polyamic acid imidizate
Clock), the back side for being formed in polyimide layer has the polyimides laminated body of supporting substrate.It is cooled to immediately in this state
Room temperature obtains 25 μm of thickness of transparent polyimide film from the part of supporting substrate removing polyimide layer.Bearing when removing
Substrate and the fissility of transparent polyimide film are good.
[embodiment 3]
Using 25 μm of thickness of polyimide films (Upilex S, Ube Industries, Ltd's system: surface roughness Ra=
15nm, Tg=359 DEG C) it is used as supporting substrate, it is coated with the resin solution of polyamic acid D obtained in synthesis example 4 on it,
Afterwards, it is thermally dried at 130 DEG C and removes the solvent in resin solution.Next, DEG C with about 20 DEG C/minute from 160 DEG C to 360
The heating rate of clock, which carries out heat treatment, makes (1 point of high temperature hold time from 340 DEG C to 360 DEG C of polyamic acid imidizate
Clock), the back side for being formed in polyimide layer has the polyimides laminated body of supporting substrate.It is cooled to immediately in this state
Room temperature obtains 25 μm of thickness of transparent polyimide film from the part of supporting substrate removing polyimide layer.Bearing when removing
Substrate and the fissility of transparent polyimide film are good.
[embodiment 4]
Using 25 μm of thickness of polyimide films (Upilex S, Ube Industries, Ltd's system: surface roughness Ra=
15nm, Tg=359 DEG C) it is used as supporting substrate, it is coated with the resin solution of polyamic acid D obtained in synthesis example 4 on it,
Afterwards, it is thermally dried at 130 DEG C and removes the solvent in resin solution.Next, in 150 DEG C, 200 DEG C, 250 DEG C of heating 30
After minute, heating 1 hour at 350 DEG C makes polyamic acid imidizate, obtains having bearing base in the back side of polyimide layer
The polyimides laminated body of material.It is cooled to room temperature, is obtained from the part of supporting substrate removing polyimide layer immediately in this state
To 25 μm of transparent polyimide film of thickness.The fissility of supporting substrate and transparent polyimide film when removing is good.
[comparative example 1]
Use copper foil as supporting substrate, in addition to this, is coated similarly to Example 1, heat drying and use
In the heat treatment of imidizate, polyimides laminated body is obtained.Although wanting to remove polyimide layer from polyimides laminated body,
The bonding force at the interface of polyimide layer and supporting substrate is strong, can not remove polyimides from supporting substrate.
[comparative example 2]
The copper foil of supporting substrate used in embodiment 1 is etched, the bearing base being made of polyimide film is obtained
Material.The surface roughness Ra of the copper foil etching face of the supporting substrate is 180nm, and Tg is 355 DEG C.In the polyamides as supporting substrate
The resin solution of polyimide acid C obtained in synthesis example 3 is coated on the surface of imines film, it is in addition to this, same with embodiment 1
It carries out to sample obtaining polyimides laminated body.Although wanting to remove polyimide layer, polyimides from polyimides laminated body
It is strong with the bonding force at the interface of supporting substrate, polyimides can not be removed from supporting substrate.
[comparative example 3]
Using thickness 10mm polyimide substrate (UPIMOL, Ube Industries, Ltd's system: surface roughness Ra=
160nm, Tg=401 DEG C) it is used as supporting substrate in addition to this to obtain polyimides laminated body similarly to Example 1, thereafter
After being cooled to room temperature, polyimide layer is removed from supporting substrate and obtains 25 μm of thickness of transparent polyimide film.In bearing base
When the removing of material and transparent polyimide film, the elongation for being also easy to produce transparent polyimide film even ruptures, and fissility is bad.
[comparative example 4]
Use the resin solution of polyamic acid B obtained in synthesis example 2 as polyamic acid, in addition to this, with embodiment 3
Polyimides laminated body is got similarly, after being cooled to room temperature thereafter, polyimide layer is removed from supporting substrate and obtains thickness
25 μm of transparent polyimide film.In the removing of supporting substrate and transparent polyimide film, it is also easy to produce transparent polyimide film
Elongation even rupture, fissility is bad.
[comparative example 5]
Use polyimide film (Kapton H DU PONT-TORAY Co. Ltd. system) as supporting substrate, except this it
Outside, polyimides laminated body is got similarly with comparative example 4.Although wanting to remove polyimide layer from polyimides laminated body,
The bonding force at the interface of polyimides and supporting substrate is strong, can not remove polyimides from supporting substrate.
Claims (11)
1. a kind of polyimides laminated body, which is characterized in that be to have the polyamides of supporting substrate in the back side of polyimide layer
Imines laminated body, polyimide layer the wavelength region of 440nm~780nm transmissivity be 70% or more, polyimide layer with
The surface of supporting substrate in the interface of supporting substrate is the heat resistance polyamides Asia for being 300 DEG C or more by glass transition temperature Tg
Amine formed and surface roughness Ra is 100nm hereinafter, the adhesive strength of supporting substrate and polyimide layer is 1N/m~500N/
M can separate the polyimide film being made of the polyimide layer from supporting substrate,
Polyimide layer is made of single-layer or multi-layer, and the layer at least to connect with supporting substrate is fluorinated polyimide,
The fluorinated polyimide by the following general formula (1) indicate,
In formula, Ar1Indicate the organic group of 4 valences, Ar2It is indicated by the following general formula (2) or general formula (3),
R in formula, in general formula (2) or general formula (3)1~R8Independently of one another hydrogen atom, fluorine atom, carbon atom number 1~5 alkane
Base or alkoxy or fluorine substituted hydrocarbon radical, when being general formula (2), R1~R4In at least one be fluorine atom or fluorine substituted hydrocarbon radical,
In addition, when being general formula (3), R1~R8In at least one be fluorine atom or fluorine substituted hydrocarbon radical.
2. polyimides laminated body according to claim 1, wherein heat resistant poly acid imide in supporting substrate be with
The polyimides of following structural units,
3. polyimides laminated body according to claim 1 or 2, wherein the thermal expansion coefficient of polyimide layer is
15ppm/K or less.
4. polyimides laminated body described in any one of claim 1 to 3, wherein polyimide layer with a thickness of 3 μm
~50 μm, in addition, supporting substrate with a thickness of 10 μm~100 μm.
5. polyimides laminated body according to any one of claims 1 to 4, wherein from gathering after supporting substrate removing
The surface roughness Ra of the release surface of acid imide film is 100nm or less.
6. polyimides laminated body according to any one of claims 1 to 5, wherein in the surface side of polyimide layer
After functional layer as defined in being formed, separates the supporting substrate of back side and use.
7. polyimides laminated body described according to claim 1~any one of 6, wherein supporting substrate back side into
One step has adhesive layer.
8. a kind of manufacturing method of polyimides laminated body, which is characterized in that be to have bearing in the back side of polyimide layer
The manufacturing method of the polyimides laminated body of substrate, on one side by the supporting substrate roller of the strip with heat-proof polyimide face
Roller technique is transmitted, the resin for being coated with fluorine-containing polyamic acid on the heat-proof polyimide face of the supporting substrate of strip on one side is molten
Liquid, carrying out heat treatment at 200 DEG C or more together with supporting substrate makes polyamic acid imidizate and is formed on supporting substrate
The transmissivity of the wavelength region of 440nm~780nm is 70% or more polyimide layer, and makes supporting substrate and polyimides
The adhesive strength of layer can separate the polyimide film that be made of polyimide layer, institute for 1N/m~500N/m from supporting substrate
It is 300 DEG C or more that state heat-proof polyimide face, which be by glass transition temperature Tg, and surface roughness Ra is 100nm below resistance to
What hot polyimides was formed,
The layer at least to connect with supporting substrate in the polyimide layer indicates by the following general formula (1),
In formula, Ar1Indicate the organic group of 4 valences, Ar2It is indicated by the following general formula (2) or general formula (3),
R in formula, in general formula (2) or general formula (3)1~R8Independently of one another hydrogen atom, fluorine atom, carbon atom number 1~5 alkane
Base or alkoxy or fluorine substituted hydrocarbon radical, when being general formula (2), R1~R4In at least one be fluorine atom or fluorine substituted hydrocarbon radical,
In addition, when being general formula (3), R1~R8In at least one be fluorine atom or fluorine substituted hydrocarbon radical.
9. the manufacturing method of polyimides laminated body according to claim 8, wherein the heat treatment condition of polyamic acid
Be high-temperature heating temperature region heating time be 15 minutes within, the high-temperature heating temperature region refer to than heating heating
When low 20 DEG C of the temperature~maximum temperature reached of maximum temperature reached.
10. the manufacturing method of polyimides laminated body according to claim 8 or claim 9, wherein formed resistance in supporting substrate
The heat resistant poly acid imide in hot polymerization acid imide face is the polyimides with following structural units,
11. a kind of manufacturing method of polyimide film, which is characterized in that from the side as described in any one of claim 8~10
The polyimides laminated body that method obtains separates polyimide layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-209667 | 2012-09-24 | ||
| JP2012209667A JP5931672B2 (en) | 2012-09-24 | 2012-09-24 | Polyimide laminate and method for producing the same |
| CN201310435394.9A CN103660458A (en) | 2012-09-24 | 2013-09-23 | Polyimide laminating body and manufacturing method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310435394.9A Division CN103660458A (en) | 2012-09-24 | 2013-09-23 | Polyimide laminating body and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110077065A true CN110077065A (en) | 2019-08-02 |
Family
ID=50299815
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910106754.8A Pending CN110077065A (en) | 2012-09-24 | 2013-09-23 | Polyimides laminated body and its manufacturing method |
| CN201710367693.1A Pending CN107253376A (en) | 2012-09-24 | 2013-09-23 | Polyimides layered product and its manufacture method |
| CN201310435394.9A Pending CN103660458A (en) | 2012-09-24 | 2013-09-23 | Polyimide laminating body and manufacturing method thereof |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710367693.1A Pending CN107253376A (en) | 2012-09-24 | 2013-09-23 | Polyimides layered product and its manufacture method |
| CN201310435394.9A Pending CN103660458A (en) | 2012-09-24 | 2013-09-23 | Polyimide laminating body and manufacturing method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5931672B2 (en) |
| KR (2) | KR20140040048A (en) |
| CN (3) | CN110077065A (en) |
| TW (2) | TWI656026B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115175816A (en) * | 2020-03-23 | 2022-10-11 | 东洋纺株式会社 | Laminated body |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5154714B2 (en) | 2011-06-01 | 2013-02-27 | 株式会社Ｊ−オイルミルズ | Oil processed starch and method for producing the same |
| KR102212979B1 (en) * | 2013-07-26 | 2021-02-04 | 닛산 가가쿠 가부시키가이샤 | Resin composition for display substrate, thin resin film for display substrate, and process for producing thin resin film for display substrate |
| KR102467105B1 (en) * | 2014-03-31 | 2022-11-14 | 닛산 가가쿠 가부시키가이샤 | Composition for forming releasing layer |
| JP6610534B2 (en) * | 2014-03-31 | 2019-11-27 | 日産化学株式会社 | Release layer forming composition |
| TW201605646A (en) * | 2014-08-04 | 2016-02-16 | 友達光電股份有限公司 | Method of fabricating flexible display panel |
| CN104211963B (en) * | 2014-09-18 | 2016-09-28 | 吉林奥来德光电材料股份有限公司 | The manufacture method of polyimide resin and utilize its manufactured Kapton |
| JP6561474B2 (en) * | 2015-01-20 | 2019-08-21 | 大日本印刷株式会社 | Method for manufacturing flexible display device |
| JP6808401B2 (en) | 2015-08-31 | 2021-01-06 | 日鉄ケミカル＆マテリアル株式会社 | Manufacturing method of polyimide substrate film with functional layer |
| JP6656861B2 (en) * | 2015-09-25 | 2020-03-04 | 日鉄ケミカル＆マテリアル株式会社 | Laminated body for flexible device and method for manufacturing flexible device |
| KR20170038175A (en) * | 2015-09-29 | 2017-04-06 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method for producing polyimide film |
| JP6706475B2 (en) * | 2015-09-30 | 2020-06-10 | 日鉄ケミカル＆マテリアル株式会社 | Long polyimide laminate film and method for producing the same, and method for producing polyimide film with functional layer |
| JP6937557B2 (en) * | 2015-09-30 | 2021-09-22 | 日鉄ケミカル＆マテリアル株式会社 | Method of manufacturing polyimide film |
| CN108136755B (en) * | 2015-10-15 | 2021-06-29 | 日铁化学材料株式会社 | Polyimide laminate and method for producing same |
| JP6611325B2 (en) * | 2015-12-03 | 2019-11-27 | 東京応化工業株式会社 | Laminate manufacturing method and use thereof |
| CN107263984B (en) * | 2016-03-31 | 2021-01-12 | 日铁化学材料株式会社 | Polyimide resin laminate, method for producing same, and polyimide film with functional layer |
| JP6891564B2 (en) * | 2017-03-16 | 2021-06-18 | コニカミノルタ株式会社 | Transparent heat-resistant laminated film, transparent flexible printed circuit board, transparent electrode substrate, lighting device and organic electroluminescence display device |
| KR102018455B1 (en) * | 2017-05-24 | 2019-09-04 | 주식회사 엘지화학 | A roll of polyimide film laminate and a method for producing same |
| JP7248394B2 (en) * | 2017-09-29 | 2023-03-29 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide film and metal-clad laminate |
| WO2019073628A1 (en) * | 2017-10-11 | 2019-04-18 | 株式会社カネカ | Polyimide resin and production method therefor, polyimide solution, and polyimide film and production method therefor |
| JP7204658B2 (en) * | 2017-10-19 | 2023-01-16 | デンカ株式会社 | Single-layer film and heat-resistant adhesive tape using the same |
| WO2019142790A1 (en) * | 2018-01-18 | 2019-07-25 | Ａｇｃ株式会社 | Long laminate, method for producing same, and printed wiring board |
| JP7195530B2 (en) * | 2019-01-11 | 2022-12-26 | エルジー・ケム・リミテッド | Film, metal-clad laminate, flexible substrate, method for producing film, method for producing metal-clad laminate, and method for producing flexible substrate |
| KR102306950B1 (en) | 2021-02-05 | 2021-09-29 | 최유경 | Polyimide film, method of manufacturing the same, and flexible printed circuit board |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04328524A (en) * | 1991-04-26 | 1992-11-17 | Nippon Telegr & Teleph Corp <Ntt> | Liquid crystal curved surface display element |
| TW200712098A (en) * | 2005-08-03 | 2007-04-01 | Du Pont | Low color polyimide compositions useful in optical type applications and methods and compositions relating thereto |
| CN101160202A (en) * | 2005-04-14 | 2008-04-09 | 三菱瓦斯化学株式会社 | Process for producing polyimide film |
| JP2009091470A (en) * | 2007-10-09 | 2009-04-30 | Ube Ind Ltd | Polyimide film producing method, and aromatic polyimide |
| JP2011056825A (en) * | 2009-09-11 | 2011-03-24 | Nippon Steel Chem Co Ltd | Method for manufacturing polyimide film |
| JP2012062344A (en) * | 2010-09-14 | 2012-03-29 | Kaneka Corp | Polyimide precursor, polyimide resin, and use thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100590615B1 (en) * | 2001-05-29 | 2006-06-15 | 히다치 가세고교 가부시끼가이샤 | Electrode structure |
| JP4816850B2 (en) | 2001-07-06 | 2011-11-16 | 凸版印刷株式会社 | Method for producing polymer optical film |
| JP4260530B2 (en) | 2003-04-24 | 2009-04-30 | 新日鐵化学株式会社 | Method for producing polyimide film |
| JP2005064107A (en) * | 2003-08-08 | 2005-03-10 | Teijin Ltd | Method of manufacturing laminate and method of collecting the same |
| JP2008231327A (en) | 2007-03-22 | 2008-10-02 | Ihara Chem Ind Co Ltd | Polyimide having high transparency and its manufacturing method |
| JP5252986B2 (en) * | 2008-05-07 | 2013-07-31 | 国立大学法人東京工業大学 | Silicon-containing polyimide and method for producing the same |
| JP5126555B2 (en) * | 2008-12-19 | 2013-01-23 | 東洋紡株式会社 | LAMINATE, ITS MANUFACTURING METHOD, AND LAMINATE CIRCUIT BOARD |
-
2012
- 2012-09-24 JP JP2012209667A patent/JP5931672B2/en active Active
-
2013
- 2013-09-16 TW TW106115607A patent/TWI656026B/en active
- 2013-09-16 TW TW102133456A patent/TWI656025B/en active
- 2013-09-23 CN CN201910106754.8A patent/CN110077065A/en active Pending
- 2013-09-23 CN CN201710367693.1A patent/CN107253376A/en active Pending
- 2013-09-23 CN CN201310435394.9A patent/CN103660458A/en active Pending
- 2013-09-24 KR KR1020130113308A patent/KR20140040048A/en not_active Application Discontinuation
-
2020
- 2020-06-29 KR KR1020200079105A patent/KR102246488B1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04328524A (en) * | 1991-04-26 | 1992-11-17 | Nippon Telegr & Teleph Corp <Ntt> | Liquid crystal curved surface display element |
| CN101160202A (en) * | 2005-04-14 | 2008-04-09 | 三菱瓦斯化学株式会社 | Process for producing polyimide film |
| TW200712098A (en) * | 2005-08-03 | 2007-04-01 | Du Pont | Low color polyimide compositions useful in optical type applications and methods and compositions relating thereto |
| JP2009091470A (en) * | 2007-10-09 | 2009-04-30 | Ube Ind Ltd | Polyimide film producing method, and aromatic polyimide |
| JP2011056825A (en) * | 2009-09-11 | 2011-03-24 | Nippon Steel Chem Co Ltd | Method for manufacturing polyimide film |
| JP2012062344A (en) * | 2010-09-14 | 2012-03-29 | Kaneka Corp | Polyimide precursor, polyimide resin, and use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115175816A (en) * | 2020-03-23 | 2022-10-11 | 东洋纺株式会社 | Laminated body |
| CN115175816B (en) * | 2020-03-23 | 2024-03-08 | 东洋纺株式会社 | Laminate body |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201730011A (en) | 2017-09-01 |
| TW201420342A (en) | 2014-06-01 |
| KR20140040048A (en) | 2014-04-02 |
| JP2014061685A (en) | 2014-04-10 |
| JP5931672B2 (en) | 2016-06-08 |
| CN103660458A (en) | 2014-03-26 |
| CN107253376A (en) | 2017-10-17 |
| KR102246488B1 (en) | 2021-04-30 |
| TWI656026B (en) | 2019-04-11 |
| KR20200083410A (en) | 2020-07-08 |
| TWI656025B (en) | 2019-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110077065A (en) | Polyimides laminated body and its manufacturing method | |
| KR102066280B1 (en) | Transparent flexible laminate and laminate roll | |
| US10414869B2 (en) | Laminite, and element comprising substrate manufactured using same | |
| CN104015466B (en) | The manufacturing method of laminated member | |
| JP5910236B2 (en) | Method for producing polyamideimide film | |
| WO2008072495A1 (en) | Polyamide-imide resin, colorless transparent flexible metal laminate made of the same, and wiring board | |
| JP5946348B2 (en) | Transparent conductive film and polyimide film for production thereof | |
| JP2016120630A (en) | Method for producing peeling layer and polyimide laminate | |
| JP6409540B2 (en) | Film, film manufacturing method and laminate | |
| JP2017083669A (en) | Polarizing plate and manufacturing method therefor | |
| JP2010155360A (en) | Laminate for wiring board, having transparent insulating resin layer | |
| KR102313706B1 (en) | Polyimide resin laminate and method for producing same | |
| JP2011012255A (en) | Film having negative thermal expansion coefficient, manufacturing method therefor and laminate | |
| JP2018172562A (en) | Polyimide precursor and polyimide | |
| TW201922866A (en) | Manufacturing method of resin film and resin film with minimal scratches | |
| JP2017179150A (en) | Polyimide film | |
| JP2019065266A (en) | Polyimide film, metal-clad laminate, and circuit board | |
| JP7248394B2 (en) | Polyimide film and metal-clad laminate | |
| JP2017179148A (en) | Polyimide film | |
| JP2017179149A (en) | Polyimide film | |
| JP2019143043A (en) | Polyimide film for forming display device, polyimide laminate, and display device and method for manufacturing the same | |
| TW201927872A (en) | Manufacturing method of resin film | |
| TWI780244B (en) | Manufacturing method of resin film | |
| KR20220097473A (en) | Method of making dry film rolls |
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 |