CN110116527A - Metal-clad and its manufacturing method - Google Patents
Metal-clad and its manufacturing method Download PDFInfo
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- CN110116527A CN110116527A CN201910084789.6A CN201910084789A CN110116527A CN 110116527 A CN110116527 A CN 110116527A CN 201910084789 A CN201910084789 A CN 201910084789A CN 110116527 A CN110116527 A CN 110116527A
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- layer
- metal
- polyimide
- clad
- insulating resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
-
- 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
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/042—Coating on selected surface areas, e.g. using masks using masks
-
- 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
- C23C14/24—Vacuum evaporation
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/22—Nickel or cobalt
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention provides the metal-clad and its manufacturing method of the peel strength of a kind of metal layer improved containing nickel element and polyimide layer.Metal-clad stack includes: the insulating resin layer of the polyimide layer of the metal layer containing nickel element and the single-layer or multi-layer comprising being laminated on the metal layer, and the metal layer is measured by the surface contacted using x-ray photoelectron optical spectroscopy pair with the insulating resin layer, and observe the peak value of nickel oxide, and do not observe the metal layer of the peak value of nickel.The manufacturing method of the metal-clad includes: (a) by the way that the resin solution of polyimide precursor is coated on the metal component containing nickel element and is heat-treated, and being formed has the step of insulating resin layer of polyimide layer of single-layer or multi-layer；(b) by carrying out oxidation processes to the metal component in the environment comprising oxidant, and the step of the surface for forming the insulating resin layer side forms the envelope of nickel oxide.
Description
Technical field
The present invention relates to a kind of metal-clads and its system in the metal layer upper layer laminated polyimide layer containing nickel element
Make method.
Background technique
Standby used flexible print distributing board (flexible printed circuit, FPC), flexible solar cell,
Suspension (suspension), the liquid crystal display of the cathode material of lithium ion battery, hard disk drive (hard disk drive)
Material, organic electroluminescent (electroluminescence, the EL) display of (liquid crystal display, LCD)
Component, auxiliary material etc. in be widely studied, positive expand uses in a variety of applications where.
For example, organic EL display device be used for giant display as television set, mobile phone, personal computer,
In the miniscopes such as smart phone or illumination etc..The organic EL display device be as supporting base material comprising glass or
Resin is formed thin film transistor (TFT) (thin film transistor) (the following are TFT) in vapor deposition body (deposited substrate),
In turn, electrode, luminescent layer, electrode are sequentially formed, finally, be separately hermetically sealed using glass substrate or plural layers etc. and
Production.
In the past, the luminescent layer of organic EL display device, cathode electrode formation in, for by vapor deposition body, in Ying Jinhang
The region of vapor deposition, such as use the deposition mask only comprising arranging metal layer made of multiple fine opening portions.In addition, in recent years
Come in order to promote productivity, and need to cope with the productive promotion generated due to the enlargement by vapor deposition body or organic EL is shown
The enlargement of showing device, therefore for deposition mask, enlarged requirement is also improving.
For example, disclosing the deposition mask for utilizing bonding agent to be bonded with resin mask metal mask in patent document 1.Separately
Outside, the film that will transmit through the resin of visible light is disclosed in patent document 2 and made of metal plate body carries out the deposition mask of face bonding.
Wherein, it is recorded in patent document 1, as the material of resin mask, is preferably able to form fine by laser processing etc.
Opening portion, and heat or ongoing change is small, material of light weight, as such material, illustration has polyimides, polyamide, polyamide
Acid imide, polyester, polyethylene, polyvinyl alcohol, polypropylene, polycarbonate, polystyrene etc..In addition, being disclosed in patent document 2
For heat resistance is high and can precisely form the aspect of opening portion, preferred polyimides.
However, when made of metal plate body forms patterns of openings, being showed if the made of metal plate body high using roughness
The surface profile of made of metal plate body is transferred to the state of the bottom of resin layer.Therefore, it is desirable that low using surface roughness
Made of metal plate body, but the low made of metal plate body of surface roughness is insulated due to anchoring effect (anchoring effect), i.e.
Resin layer is small to the biting amount of the convex-concave on the surface of made of metal plate body, and is improved the low made of metal plate body of surface roughness and tree
The project of the bonding force of rouge layer.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2013-163864 bulletin
[patent document 2] Japanese Patent Laid-Open 2013-83704 bulletin
Summary of the invention
[problem to be solved by the invention]
The purpose of the present invention is to provide the peel strengths of a kind of metal layer improved containing nickel element and polyimide layer
Metal-clad and its manufacturing method.
[technical means to solve problem]
Metal-clad of the invention includes: metal layer containing nickel element and comprising being laminated on the metal layer
The insulating resin layer of the polyimide layer of single-layer or multi-layer, and the metal layer is by utilizing x-ray photoelectron optical spectroscopy pair
The surface contacted with the insulating resin layer is measured, and observes the peak value of nickel oxide, and do not observe the peak value of nickel
Metal layer.
In addition, metal-clad of the invention is preferably the 350 of the polyimide layer contacted with the metal layer
Storage coefficient of elasticity at DEG C is 1 × 108Pa or more.
In addition, metal-clad of the invention be preferably the insulating resin layer thermal expansion coefficient be -5ppm/K~
In the range of 30ppm/K.
The manufacturing method of metal-clad of the invention includes the following steps (a) and step (b):
(a) by the way that the resin solution of polyimide precursor is coated on the metal component containing nickel element and is heat-treated,
And being formed has the step of insulating resin layer of polyimide layer of single-layer or multi-layer；
(b) by carrying out oxidation processes to the metal component in the environment comprising oxidant, and it is described exhausted being formed
The surface of edge resin layer side forms the step of envelope of nickel oxide.
In addition, the manufacturing method of metal-clad of the invention is preferably the process in the heat treatment of the step (a)
The middle oxidation processes for carrying out the step (b).
In addition, it is oxygen, and the oxygen that the manufacturing method of metal-clad of the invention, which is preferably the oxidant,
Concentration be 1 volume of volume %~25 % in the range of.
[The effect of invention]
In metal-clad of the invention, the adhesion of metal layer and insulating resin layer is excellent, and thermal stability and ruler
Very little excellent in stability.In addition, the manufacturing method of metal-clad according to the present invention, manufactures using simple method and touches
The excellent metal-clad of property.
Specific embodiment
< metal layer >
There is no particular restriction as long as containing nickel element for metal layer, can be suitable for using as nickel alloy person.Specifically, can
Illustrate stainless steel, iron-nickel alloy, monel etc..In these, caused by invar alloy (Invar) as iron-nickel alloy is by warm
Deformation it is few, thus can be suitable for using.In addition, magnetite is being arranged by the rear of vapor deposition body when to being deposited by vapor deposition body
Deng and in the case where attracting deposition mask by magnetic force, metal layer is preferably formed by magnetic substance.
Metal foil can be used in metal layer, can also form metal layer for example, by the methods of sputtering (sputtering).Separately
Outside, the thickness of metal layer can also be optionally adjusted by plating etc..There is no particular restriction for the thickness of metal layer, can be set as pressing down
System fracture deforms and considers the thickness that the generation of shade is deposited, preferably 2 μm~100 μm.
Metal layer has the feature that by utilizing x-ray photoelectron optical spectroscopy (X-ray photoelectron
Spectroscopy, XPS) surface contacted with insulating resin layer is measured, and observe the peak value of nickel oxide, and do not see
Measure the peak value of nickel.In addition, will be distinguish respectively and use the term of " nickel oxide " Yu " nickel " in this specification, only claiming
It indicates not including nickel oxide in the case where for " nickel ".
Except NiO and Ni2O3In addition, nickel oxide can be with Ni (OH)2Form exist, be formed as being present in metal layer
The envelope of the nickel oxide on surface.The envelope of such nickel oxide can be present in the envelope on the surface of metal layer for part, preferably time
And the envelope of the entire surface of the metal layer.In addition, the envelope of nickel oxide may include the high nickel oxide of crystallinity, also may include
The nickel oxide of the low amorphous of crystallinity.
About the factor for the peel strength for reducing metal layer and insulating resin layer, not yet find out completely now, deducibility with
Under i) or ii) the phenomenon that.
I) because there are nickel contained in metal layer, and fragile surface layer is formed in the inside of insulating resin layer, as a result, be easy
The local failure of insulating resin layer is generated on the surface layer, sufficient peel strength can not be obtained.
Ii) because there are nickel contained in metal layer, and became the bonding force at the interface of metal layer and insulating resin layer
In secured, as a result, be easy to generate local failure in the inside of insulating resin layer, sufficient peel strength can not be obtained.
Herein, as it is described i) in the case where, because nickel there are due to form surface layer the reasons why, consider it is following any one.
(1) because of the effect of nickel, and local low point in the surface section of the polyimide precursor contacted with metal layer is generated
Son quantization, so that the surface section in the polyimide layer contacted with metal layer forms surface layer.
(2) because of the effect of nickel, and the misorientation of the part in the surface section of the polyimide layer contacted with metal layer is generated,
To form surface layer in the surface section of the polyimide layer contacted with metal layer.
In the metal-clad of present embodiment, on the surface of metal layer, there are the envelopes of nickel oxide, speculate therefrom:
It is described i) in the case where, can inhibit the formation on the surface layer in polyimide layer, in addition, in the ii) in the case where, can be appropriate
Adjust the bonding force at the interface of metal layer and insulating resin layer.As a result, think to can inhibit the office of polyimide layer
The concentration of tear stress can promote the peel strength of metal layer and insulating resin layer.
< insulating resin layer >
It is also multilayer that the polyimide layer for constituting insulating resin layer, which can be single layer, preferably comprises non-thermal plasticity polyimides
Layer.Herein, so-called " non-thermal plasticity polyimides " is usually heated the polyamides Asia that can also soften without showing cementability
Amine, the present invention in, refer to using measurement of dynamic viscoelasticity device (Dynamic Mechanical Analyzer (Dynamic mechanical
Analyzer, DMA)) and determine 300 DEG C at storage coefficient of elasticity be 1.0 × 109Pa or more, the storage bullet at 350 DEG C
Property coefficient is 1.0 × 108The polyimides of Pa or more.
The insulating resin layer of present embodiment has the polyimide layer comprising polyimides, constitutes the poly- of polyimide layer
Acid imide is that tetracarboxylic dianhydride will be made to be subject to imidizate with polyamic acid obtained by diamine reactant and obtained.Therefore, this is constituted
The polyimides of the polyimide layer of embodiment includes the tetrabasic carboxylic acid residue as derived from tetracarboxylic dianhydride and is spread out by diamines
Raw diamines residue.In addition, so-called tetrabasic carboxylic acid residue indicates the tetravalence base as derived from tetracarboxylic dianhydride, so-called in the present invention
Diamines residue indicates the bilvalent radical as derived from diamine compound.In addition, as the polyimides in the present invention, except so-called
It is also sub- comprising polyamidoimide, polybenzimidazoles, polyester-imides, polyetherimide, polysiloxanes acyl other than polyimides
Amine etc. has imide person in the structure.
Hereinafter, being appreciated that the tool of polyimides used in present embodiment and being illustrated to acid anhydrides and diamines
Body example.
For the viewpoint of thermal stability and dimensionally stable, the polyimide layer contacted with metal layer is preferably at 350 DEG C
Storage coefficient of elasticity be 1 × 108Pa or more.In addition, can inhibit by the polyimide layer for forming such storage coefficient of elasticity
It is spread from metal layer to the metal of insulating resin layer.
In addition, in order to reduce change in size, thermal expansion coefficient (the coefficient of thermal of insulating resin layer
Expansion, CTE) preferably in the range of -5ppm/K~30ppm/K.In addition, just passing through the CTE of metal layer and insulating resin layer
For viewpoint of the difference to mitigate internal stress, the CTE difference of metal layer and insulating resin layer is preferably set as ± 5ppm/K or less.
For example, in the case where invar alloy (Fe-Ni alloy/C) is applied to metal layer, the CTE of insulating resin layer can for preferably-
In the range of 5ppm/K~10ppm/K, in the range of more preferable -3ppm/K~5ppm/K.By being set as in such range, can subtract
The dimensional discrepancy of the small polyimide layer exposed after the etching of metal layer.Therefore, it can be ensured that the polyamides between metal layer is sub-
Furthermore the position precision of opening portion in amine layer may also suppress warpage, thus advantageous.
In order to form the insulating resin layer of such CTE, the main polyimides for preferably forming insulating resin layer is that will have
There is the polyimide precursor of structural unit represented by following formula (1) to be subject to imidizate to form, being more preferably will be comprising 60
The polyimide precursor of structural unit represented by the formula (1) of mole % or more and then preferably 80 moles % or more is subject to acyl
Imidization forms.Herein, so-called " main polyimides " refers to that the polyamides is sub- in the case where insulating resin layer is single layer
Amine layer itself refers in the case where insulating resin layer is multilayer for the polyimide layer of the maximum layer of volume fraction.Passing through will
The main polyimides is set as that will there is the polyimide precursor (polyamic acid) of structural unit represented by formula (1) to be subject to acyl
Imidization and winner can get the polyimides of low heat expansion, just make the CTE 10ppm/K side below of polyimide layer
For face preferably.In addition, being made by the polyimide precursor polyimides obtained of the structural unit represented by with formula (1)
Agent of low hygroscopicity is shown for polyimides, therefore the humidity environment in step is changed to the aspect that also can inhibit the variation of size
For it is advantageous.In addition, remaining polyimide precursor different from general formula (1) for forming it has no about main polyimides
Especially limitation, can be used common polyimide precursor.
[changing 1]
In the formula (1), R1Indicate the divalent organic base being selected from group represented by following formula (2), R2Indicate following formula
(3) quadrivalent organic radical in group represented by, R each independently represent hydrogen atom or any monovalent organic radical, and n is to indicate repeat number
Positive integer.
[changing 2]
In the formula (2), R' each independently represents the aromatic series of the alkyl of carbon number 1~6, halogenated alkyl, carbon number 6~18
The hydrogen atom of base or halogen radical, the aromatic series base can be replaced by halogen atom, the alkyl of carbon number 1~6 or halogenated alkyl, Z
For NH or O.
[changing 3]
But the polyimide precursor with structural unit represented by the formula (1) is formed poly- being subject to imidizate
When acid imide, cementability is poor sometimes.Therefore, can make insulating resin layer includes multilayer polyimide layer, and will be contacted with metal layer
Layer be set as the polyimides of low heat expansion.That is, will include polyimide precursor (or by polyimide precursor be subject to acyl Asia
Polyimides obtained by amination) liquid composition be coated on metal layer and heated and formed the tape casting of polyimide layer
In the case where, as long as that will include polyimide precursor (or polyimide precursor is subject to polyimides obtained by imidizate)
The first liquid composition be coated on metal layer after, by coating be formed on comprising have formula (1) represented by knot
The polyimides of the polyimide precursor of structure unit.
In addition, in order to promote with the bonding force of metal layer or adjust the CTE of insulating resin layer, for example, insulating resin can be made
Layer includes multilayer polyimide layer, and it is adjacent with the polyimides to be less than the CTE of the polyimide layer contacted with metal layer
Other polyimide layers CTE.Alternatively, in order to adjust the CTE of insulating resin layer, can also make insulating resin layer include three layers with
On multilayer polyimide layer, and be clipped in the CTE of the two layers of polyimide layer for the most surface to form surface and the back side compared with formation
The CTE of the polyimide layer of middle layer in the polyimide layer of these most surfaces is big, in addition, making to be formed any one of most surface
Polyimide layer contacted with metal layer.
In the case where insulating resin layer is set as multilayer, the number of plies is not particularly limited, excellent for productive viewpoint
It selects two layers or three layers.It can be using same coating machine come coating while coating multiple about coating, it can also be different to utilize
The gradually coating that coating machine is successively coated.
In addition, the peel strength that metal-clad of the invention is preferably metal layer and insulating resin layer be 300N/m with
On.More preferably 600N/m or more.If the peel strength of metal layer and insulating resin layer is 300N/m or more, such as when repeatedly
Carry out vapor deposition ingredient when the operation for the Thinfilm pattern for forming certain shapes is deposited on by vapor deposition body or accompanying when cleaning
When, metal layer is not easily stripped with insulating resin layer.In addition, peel strength is to utilize method, the condition recorded in aftermentioned embodiment
And the value determined.
(synthesis of polyimide precursor polyimides)
Polyimides usually can generate polyimide precursor by reacting acid anhydrides ingredient in a solvent with diamine component
After carry out heating closed loop and manufacture.For example, dissolve substantially equimolar acid anhydrides ingredient in organic solvent with diamine component,
It is stirred 30 minutes~24 hours at a temperature in the range of 0 DEG C~100 DEG C and carries out polymerization reaction, obtained therefrom sub- as polyamides
The polyimide precursor of the precursor of amine.It is in organic solvent 5 weight of weight %~30 % with precursor generated in reaction
In the range of, the mode preferably in the range of 10 weight of weight %~20 % dissolves reacted constituent.As in polymerization reaction
The organic solvent used, such as can enumerate: n,N-Dimethylformamide (N, N-dimethyl formamide, DMF), N, N- bis-
Methylacetamide (N, N-dimethyl acetamide, DMAc), N, N- diethyl acetamide, n-methyl-2-pyrrolidone (N-
Methyl-2-pyrrolidone, NMP), 2- butanone, dimethyl sulfoxide (dimethylsulfoxide, DMSO), hexamethyl first
Amide, N- methyl caprolactam, dimethyl suflfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether
(diglyme), triglyme, cresols etc..Can also be two or more using these solvents together, so can also and with two
Aromatic hydrocarbon as toluene, toluene.In addition, there is no particular restriction for the usage amount of these organic solvents, it is preferably regulated as passing through
Polymerization reaction and the concentration of the resin solution of polyimide precursor obtained is use as 5 weight of weight %~30 % or so
Amount is to use.
Synthesized polyimide precursor can usually be advantageously used for reaction dissolvent solution, optionally can be concentrated, is dilute
Release or be replaced into other organic solvents.In addition, typically solvent soluble is excellent for polyimide precursor, thus can advantageously make
With.In the range of the viscosity of the resin solution of polyimide precursor is preferably 500cps~100,000cps.If exceeding the model
It encloses, then when carrying out coating operation using coating machine etc., it is bad that uneven thickness, striped etc. is easy to produce in film.Make polyimides
Precursor imidizate carrys out the method for synthesis of polyimides, and there is no particular restriction, such as can be suitable for using in the solvent, 80
DEG C~400 DEG C in the range of temperature under the conditions of last 1 hour~24 hours the heat treatment heated.
< solvent >
In addition, the resin solution of the polyimide precursor of present embodiment is preferably made with the state of the varnish containing solvent
With.As solvent, organic solvent illustrated above used in the polymerization reaction of polyimide precursor can be enumerated.Solvent can
Using one kind, or can also be together using two or more.
< any ingredient >
The resin solution of the polyimide precursor of present embodiment can be in the range of lossless The effect of invention containing for example
Any ingredients such as fire retardant, filling material.
[manufacturing method of metal-clad]
Secondly, there is the metal-clad of metal layer and the insulating resin layer being laminated on the metal layer to manufacture
Method is illustrated.The manufacturing method of the metal-clad of present embodiment is preferably by by the polyimide precursor
Resin solution be coated on the surface as the metal component of metal layer and form coated film after, polyimide precursor is subject to acyl
Imidization carries out to form the method (the tape casting) of polyimide layer.The peel strength of metal layer and polyimide layer is preferably
300N/m or more, more preferably 600N/m or more, the cementability for being formed by polyimide layer and metal layer by the tape casting is high,
It is not easily stripped, there is no need to the adhesive layers of thermoplastic resin can ensure sufficient cementability.In addition, passing through the tape casting institute shape
At polyimide layer in, longitudinal direction (longitudinal the direction (machine dirction, MD)) with width direction (laterally
The direction (transverse direction, TD)) the orientation of polymer chain be not likely to produce difference, therefore also have in face
The small advantage of dimensional discrepancy.
Hereinafter, enumerate formed in the case where polyimide layer by the tape casting for metal is covered to present embodiment
The manufacturing method of plywood is specifically described.
The manufacturing method of the metal-clad of present embodiment may include following steps (1)~step (3).
Step (1):
Step (1) is the step of obtaining the resin solution of polyimide precursor.In this step, firstly, as described above, passing through
React the diamine component as raw material and synthesis of polyimides precursor in solvent appropriate with acid anhydrides ingredient.Before polyimides
Body can be used as the resin solution of polyimide precursor in the state of wrapping solvent-laden solution.
Step (2):
Before step (2) is the polyimides obtained in the surface of the metal component as metal layer, application step (1)
The resin solution of body and the step of form coated film.Until this step, can in the metal component as metal layer with it is poly-
The surface of imide layer contact forms the envelope of nickel oxide, and the envelope of nickel oxide can also be formed after this step.About formation
The method of the envelope of nickel oxide, is described below.
The resin solution of the polyimide precursor of solution shape can be by after being directly coated on metal component by coated film
It is dried and is formed.There is no particular restriction for coating method, such as can utilize wheeled unfilled corner, mode, scraper type, die lip formula etc.
Coating machine be coated.
It, can be in the tree of the polyimide precursor comprising differently composed ingredient in the case where polyimide layer is set as multilayer
Successively coating forms other polyimide precursors on rouge layer.In this case, it is preferable to be at least one layer for the formula (1) institute
The resin solution of the polyimide precursor of the structural unit of expression.In the situation that the layer of polyimide precursor includes three layers or more
Under, it can also be by the polyimide precursor of same composition using more than twice.In addition it is possible to the polyamides of single-layer or multi-layer is sub-
The temporary imidizate of the layer of amine precursor and after the polyimide layer of single-layer or multi-layer is made, and then before being formed on polyimides
The resin layer of body.
In addition it is also possible to polyimide layer is divided into more than two regions in the face of metal layer and is laminated
Mode is separately coated with the resin solution of polyimide precursor.By in the face of metal layer by different types of polyimide layer
More than two regions are layered in, the warpage of metal-clad can be effectively inhibited.
Step (3):
Step (3) is the step of be heat-treated to coated film and be subject to imidizate and form polyimide layer.Acyl is sub-
There is no particular restriction for the method for amination, for example, it is preferable under the conditions of using temperature in the range of 80 DEG C~400 DEG C, with 1 minute
The heat treatment that time in the range of~60 minutes is heated.By heat treatment, the polyimide precursor acyl in coated film is sub-
Amination, and form polyimides.
It is excellent in order to aoxidize nickel efficiency well during the coated film to polyimide precursor is heat-treated
It is selected as the oxygen transmission coefficient of polyimide layer (or polyimide film) being 1 × 10-19mol·m/m2SPa or more.Just
For such viewpoint, the thickness of polyimide layer is preferably in the range of 1 μm~25 μm.
In the above-described manner, the metal-clad with polyimide layer (single-layer or multi-layer) and metal layer can be manufactured.And
It, can and in addition to the step of manufacturing method (1)~(3) described in of deposition mask using the metal-clad of present embodiment
Include the steps that following (4) and step (5).
Step (4):
Step (4) is the step of processed to the metal layer of metal-clad and form multiple opening portions.This step
In, multiple patterns of openings in regulation shape are formed in metal layer.For example, using photolithographic techniques, on the surface of metal layer
It is coated with photonasty resist, and by after the exposure of defined position, development, forms opening portion and being etched, can also pass through
Laser irradiation and form opening portion.
Step (5):
Step (5) is that the step of deposition mask is obtained and the polyimide layer formation opening portion in metal-clad
Suddenly.In this step, correspond in the opening range of the opening portion of metal layer formed in step (4), and in polyimide layer
The middle multiple pass through openings patterns of processing.The pass through openings pattern corresponds to the Thinfilm pattern that formation is deposited on vapor deposition body.
There is no particular restriction for the method that through hole is arranged in polyimide layer to form patterns of openings, such as can enumerate:
The surface of polyimide layer is coated with photonasty resist, and by after the exposure of defined position, development, forms perforation by etching
The method in hole；The method for irradiating laser to form through hole；Perforation is formed using mechanical drill (mechanical drill)
The method etc. in hole.For the viewpoints such as precision or productivity, preferred laser irradiation.It is being formed by laser irradiation and film figure
In the case where the corresponding patterns of openings of case, if the transmitance of the polyimide layer under the wavelength of laser is high, it can not obtain good
Patterns of openings shape.Therefore, the light transmittance of the polyimide layer under the wavelength of laser be preferably 50% hereinafter, preferably 10% with
Under, more preferably 0%.Herein, opening figure is formed as being used to that through hole to be arranged in polyimide layer by laser irradiation
The laser of case, such as it is able to use ultraviolet light (ultraviolet, UV)-yttrium-aluminium-garnet (yttrium aluminum
Garnet, YAG) laser (wavelength 355nm), excimer laser (wavelength 308nm) etc., in these, preferred UV-YAG laser (wavelength
355nm)。
In the above-described manner, the deposition mask with polyimide layer (single-layer or multi-layer) and metal layer can be manufactured.
(formation of the envelope of nickel oxide)
The envelope that the surface of the metal component containing nickel forms nickel oxide can oxygen in the environment by the inclusion of oxidant
Change is handled to carry out.There is no particular restriction as long as the envelope for forming nickel oxide on the surface of the metal member for oxidant, can enumerate:
Oxygen, ozone, water, hydrogen peroxide, sodium hypochlorite, potassium permanganate, manganese dioxide, two potassium chromates, potassium iodide, sodium sulfite, bromic acid
These can be used alone or in combination for sodium, potassium bromate, chloramines, nitric acid, sulfuric acid etc..As long as the concentration of the oxidant in environment is examined
Consider easness of oxidation of metal layer etc. and is suitably determined.In addition, the environment comprising oxidant includes atmospheric environment.Separately
Outside, oxidation processes further include the autoxidation under atmospheric environment.
The preferable production process of the metal-clad of envelope with nickel oxide may include following step (a) and step
(b)。
(a) by the way that the resin solution of polyimide precursor is coated on the metal component containing nickel element and is heat-treated,
And being formed has the step of insulating resin layer of polyimide layer of single-layer or multi-layer
(b) by carrying out oxidation processes to metal component in the environment comprising oxidant, and insulating resin layer is being formed
The surface of side forms the step of envelope of nickel oxide.
Herein, step (a) and the sequence of step (b) do not limit, and can be step (a) preceding, and step (b), can also rear
It is step (b) preceding, step (a) is rear, it will be able to which for the viewpoint for simplifying technique, the oxidation processes in step (b) are most preferably
To be carried out in the heat treatment process of step (a).That is, the most preferably implementation of the manufacturing method in metal-clad of the invention
In mode, by the way that the resin solution of polyimide precursor is coated on the metal component containing nickel element, and with concentration for 1 body
Containing being heat-treated under aerobic environment in the range of the product volume of %~25 %, and form the polyimide layer of single-layer or multi-layer.
About the environment in heat treatment, keep oxygen concentration within the said range, in addition to this, such as may include nitrogen, helium, argon etc..
[embodiment]
Embodiment described below to carry out more specific description to feature of the invention.But the scope of the present invention is not
It is defined in embodiment.In addition, in following embodiment, as long as no special instructions, then various measurements, evaluation be by following manner come
It carries out.
[measurement of viscosity]
In the measurement of viscosity, using E type viscosimeter, (Bo Lefei (Brookfield) company is manufactured, trade name: DV-II+
Pro), the viscosity at 25 DEG C is measured.Revolution is set in such a way that torque is 10%~90%, is starting to have measured by two minutes
Afterwards, value when viscosity stabilization is read.
[measurement of the storage coefficient of elasticity at 350 DEG C]
Storing coefficient of elasticity is to use measurement of dynamic viscoelasticity device to the polyimide film having a size of 5mm × 20mm
(manufacture of DMA:UBM company, trade name: E4000F), is warming up to 400 DEG C with 4 DEG C/min from 30 DEG C of heating rate, with frequency
11Hz is measured.At this point, the storage coefficient of elasticity at 350 DEG C of confirmation.
[measurement of thermal expansion coefficient (CTE)]
To the polyimide film having a size of 3mm × 20mm, thermomechanical analyzer (Brooker (Bruker) corporation is used
Make, trade name: 4000SA), certain heating rate of withing while applying the load of 5.0g from 30 DEG C is warming up to 250 DEG C, into
And keep after ten minutes, being cooled down with 5 DEG C/min of speed at said temperatures, it finds out from 250 DEG C to 100 DEG C and is averaged
Thermal expansion coefficient (thermal expansion coefficient).In addition, being to implement measurement to longitudinal direction (direction MD) and width direction (direction TD).
[measurement of peel strength]
After the metal-foil circuits of metal-clad (metal/polyimide layer) are processed as width 1.0mm, it is cut to width
8cm × length 4cm is spent, as measurement sample.Peel strength is using edrophonium chloride tester (Tensilon tester) (Japan
Manufactured by smart mechanism is made, trade name: this spy Roger pressgang (Strograph) VE-1D), the tree of sample will be measured using double-sided adhesive
Aluminium sheet is fixed in rouge layer side, finds out to 180 ° of directions with 50mm/ minutes speed, when copper foil is removed 10mm from resin layer in
Entreat intensity.
[measurement (narrow scan (narrow scan)) of XPS]
Using photoelectron device the JPS9010 of manufacture (Japan Electronics), in MgK α 12kV, 20mA, without in and rifle
Under the conditions of, carry out the narrow scan of the peak value of Ni (2p3/2).Later, by using Gaussian function and Lorentz (Lorentz) letter
Several mixed functions carries out automatic Fitting, and carries out being calculated as Ni:852.7eV, NiO:854.0eV, Ni (OH) with literature value2:
855.7eV、Ni2O3: the waveform separation of the peak value of 856.6eV, and respective peak area ratio is calculated, and it is opposite to calculate metallic nickel
In the peak area ratio comprising whole nickel peak areas including nickel oxide.The situation that calculating value at this time is 15% or less is regarded
Not observe peak value.In addition, being considered as and peak value being not detected in the case where calculating value is 5% situation below.
[measurement of imide concentration]
Refer in the polyimides obtained and being heated to polyimide precursor and being subject to imidizate
Acid imide base portion (- (CO)2- N-) the value that is obtained divided by the molecular weight of the structure entirety of polyimides of molecular weight.
[oxygen permeability measurement]
For polyimide film, differential gas vapor transmission detecting device (GTR-30XAD2, G6800T- are used
F) [GTR science and technology (stock) manufacture, Ya Nake engineering department skill (Yanaco Technical Science) (stock) manufacture], 23 DEG C,
Implement the measurement of oxygen permeability under conditions of 65%RH, test pressure difference 1atm.At this point, [the heat conductivity detection of using gas chromatograph
Device (Thermal Conductivity Detector, TCD)] carry out the detection of penetrated oxygen.
Abbreviation used in Examples and Comparative Examples indicates following compound.
M-TB:2,2'- dimethyl -4,4'- benzidine
4,4'-DAPE:4,4'- diamino-diphenyl ether
Bis- [4- (4- amino-benzene oxygen) phenyl] propane of BAPP:2,2-
PMDA: pyromellitic acid anhydride
BPDA:3,3', 4,4'- biphenyltetracarboxylic dianhydride
DMAc:N, N- dimethyl acetamide
(synthesis example 1)
Under stream of nitrogen gas, in the detachable flask of 300ml, in such a way that solid component concentration becomes 15 weight %
4,4'-DAPE (0.0043 mole), the m-TB (0.0817 mole) of 17.381g and the DMAc of 212.5g for putting into 0.862g,
It is stirred and makes it dissolve at room temperature.Secondly, the PMDA of the BPDA (0.0126 mole) and 15.554g of addition 3.703g
After (0.0712 mole), continues stirring at room temperature 3 hours to carry out polymerization reaction, prepare polyamic acid solution a, and viscosity is
28600cP。
(synthesis example 2)
Under stream of nitrogen gas, in the detachable flask of 300ml, in such a way that solid component concentration becomes 15 weight %
The DMAc for putting into the BAPP (0.0578 mole) and 212.5g of 23.734g, is stirred at room temperature and makes it dissolve.Secondly,
After the PMDA (0.0472 mole) for adding the BPDA (0.0118 mole) and 10.292g of 3.471g, it is small to continue stirring 3 at room temperature
When carry out polymerization reaction, prepare polyamic acid solution b, and viscosity is 11200cP.
[embodiment 1]
On the invar alloy (30 μm of thickness, 100mm × 300mm) of sheet, with the thickness of the polyimide layer after heat treatment
Degree becomes 10 μm of mode, and polyimide solution a is coated with using applicator, under air environment, is heated 5 minutes with 100 DEG C
Afterwards, stage is warming up to 360 DEG C to be heated, and prepares metal-clad 1.The peel strength of metal-clad 1
The peak value of nickel oxide is observed, but do not observe Ni peak value in the narrow scan using XPS for 1.2kN/m.In addition, covering gold
The CTE for belonging to the direction MD of polyimide layer in plywood 1 is 2.4ppm/K, and the CTE in the direction TD is 2.1ppm/K, at 350 DEG C
Storing coefficient of elasticity is 1 × 108Pa or more.
[embodiment 2]
The invar alloy of sheet (30 μm of thickness, 100mm × 300mm) add within 1 minute under 360 DEG C of air environment
After heat treatment, on the invor alloy foil, in such a way that the thickness of the polyimide layer after being heat-treated becomes 10 μm, painting is used
Applicator is coated with polyimide solution a, in a nitrogen environment (oxygen concentration is less than 0.1%), after five minutes with 100 DEG C of heating, the stage
Property is warming up to 360 DEG C to be heated, and prepares metal-clad 2.The peel strength of metal-clad 2 is 0.3kN/
M observes the peak value of nickel oxide, but do not observe Ni peak value in the narrow scan using XPS.In addition, metal-clad
The CTE in the direction MD of polyimide layer is 1.9ppm/K in 2, and the CTE in the direction TD is 2.3ppm/K, the storage elasticity at 350 DEG C
Coefficient is 1 × 108Pa or more.
[embodiment 3]
On the invar alloy (30 μm of thickness, 100mm × 300mm) of sheet, with the thickness of the polyimide layer after heat treatment
Degree becomes 10 μm of mode, and polyimide solution b is coated with using applicator, under air environment, is heated 5 minutes with 100 DEG C
Afterwards, stage is warming up to 360 DEG C to be heated, and prepares metal-clad 3.The peel strength of metal-clad 3
The peak value of nickel oxide is observed, but do not observe Ni peak value in the narrow scan using XPS for 0.8kN/m.In addition, covering gold
The CTE for belonging to the direction MD of polyimide layer in plywood 3 is 58.1ppm/K, and the CTE in the direction TD is 56.4ppm/K, at 350 DEG C
Storage coefficient of elasticity less than 1 × 108Pa。
Comparative example 1
On the invar alloy (30 μm of thickness, 100mm × 300mm) of sheet, with the thickness of the polyimide layer after heat treatment
Degree becomes 10 μm of mode, polyimide solution a is coated with using applicator, in a nitrogen environment (oxygen concentration is less than 0.1%),
After five minutes with 100 DEG C of heating, stage is warming up to 360 DEG C to be heated, and prepares metal-clad 4.Metal-clad
The peel strength of lamination 4 is less than 0.1kN/m, to the thin of the polyimides for being close contact in invar alloy surface securely in release surface
Film is confirmed, observes the destruction of the inside of polyimide layer, and Ni peak value is observed in the narrow scan using XPS.Separately
Outside, the CTE in the direction MD of polyimide layer is 2.1ppm/K in metal-clad 4, and the CTE in the direction TD is 1.5ppm/K, 350
Storage coefficient of elasticity at DEG C is 1 × 108Pa or more.
More than, embodiments of the present invention are described in detail for the purpose of illustrating, but the present invention is not limited to
The embodiment.
Claims (6)
1. a kind of metal-clad comprising: metal layer, the metal layer contain nickel element；And insulating resin layer, it is described
Insulating resin layer includes the polyimide layer for the single-layer or multi-layer being laminated on the metal layer, the spy of the metal-clad
Sign is:
The metal layer is surveyed by the surface contacted using x-ray photoelectron optical spectroscopy pair with the insulating resin layer
It is fixed, and observe the peak value of nickel oxide, and do not observe the metal layer of the peak value of nickel.
2. metal-clad according to claim 1, which is characterized in that the polyamides contacted with the metal layer is sub-
Storage coefficient of elasticity at 350 DEG C of amine layer is 1 × 108Pa or more.
3. metal-clad according to claim 1 or 2, which is characterized in that the thermal expansion system of the insulating resin layer
In the range of number is -5ppm/K~30ppm/K.
4. a kind of manufacturing method of metal-clad, which is characterized in that include the following steps (a) and step (b):
(a) by the way that the resin solution of polyimide precursor is coated on the metal component containing nickel element and is heat-treated, and shape
At the polyimide layer with single-layer or multi-layer insulating resin layer the step of；
(b) by carrying out oxidation processes to the metal component in the environment comprising oxidant, and the insulation tree is being formed
The surface of rouge layer side forms the step of envelope of nickel oxide.
5. the manufacturing method of metal-clad according to claim 4, which is characterized in that in the heat of the step (a)
The oxidation processes of the step (b) are carried out during processing.
6. the manufacturing method of metal-clad according to claim 4 or 5, which is characterized in that the oxidant is oxygen
Gas, and the concentration of the oxygen is in the range of 1 volume of volume %~25 %.
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| CN112571901A (en) * | 2019-09-28 | 2021-03-30 | 日铁化学材料株式会社 | Polyimide film, metal-clad laminate, and circuit board |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291808A (en) * | 2005-08-19 | 2008-10-22 | 旭化成株式会社 | Laminate and process for producing the same |
| JP2008258559A (en) * | 2006-08-10 | 2008-10-23 | Nippon Steel Chem Co Ltd | Laminated body for wiring board |
| JP2009298065A (en) * | 2008-06-16 | 2009-12-24 | Sumitomo Metal Mining Co Ltd | Metal-clad polyimide substrate and its production method |
| CN102458848A (en) * | 2009-04-14 | 2012-05-16 | 宇部兴产株式会社 | Polyimide film for metallizing, method for producing same, and metal-laminated polyimide film |
| CN102576735A (en) * | 2009-09-30 | 2012-07-11 | 大日本印刷株式会社 | Substrate for flexible device, thin film transistor substrate for flexible device, flexible device, substrate for thin film element, thin film element, thin film transistor, method for manufacturing substrate for thin film element, method for manufac |
| CN103548135A (en) * | 2011-03-23 | 2014-01-29 | 大日本印刷株式会社 | Heat dissipating substrate, and element equipped with same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4230488B2 (en) * | 2002-07-29 | 2009-02-25 | 三井化学株式会社 | Metal laminate and etching method thereof |
| JP2005293645A (en) * | 2004-03-31 | 2005-10-20 | Nippon Steel Chem Co Ltd | Stacked body for hdd suspension and its manufacturing method |
| WO2006059692A1 (en) * | 2004-12-03 | 2006-06-08 | Mitsui Chemicals, Inc. | Polyimide metal laminate and suspension for hard disk using same |
| CN101232995B (en) * | 2005-08-04 | 2012-09-05 | 株式会社钟化 | Metal-coated polyimide film |
| JP2010120239A (en) * | 2008-11-19 | 2010-06-03 | Nippon Steel Chem Co Ltd | Metal-clad laminate and its production method |
| JP5515025B2 (en) | 2011-10-06 | 2014-06-11 | 株式会社ブイ・テクノロジー | Mask, mask member used therein, mask manufacturing method, and organic EL display substrate manufacturing method |
| TWI687315B (en) | 2012-01-12 | 2020-03-11 | 日商大日本印刷股份有限公司 | Vapor deposition mask, pattern manufacturing method, organic semiconductor element manufacturing method |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291808A (en) * | 2005-08-19 | 2008-10-22 | 旭化成株式会社 | Laminate and process for producing the same |
| JP2008258559A (en) * | 2006-08-10 | 2008-10-23 | Nippon Steel Chem Co Ltd | Laminated body for wiring board |
| JP2009298065A (en) * | 2008-06-16 | 2009-12-24 | Sumitomo Metal Mining Co Ltd | Metal-clad polyimide substrate and its production method |
| CN102458848A (en) * | 2009-04-14 | 2012-05-16 | 宇部兴产株式会社 | Polyimide film for metallizing, method for producing same, and metal-laminated polyimide film |
| CN102576735A (en) * | 2009-09-30 | 2012-07-11 | 大日本印刷株式会社 | Substrate for flexible device, thin film transistor substrate for flexible device, flexible device, substrate for thin film element, thin film element, thin film transistor, method for manufacturing substrate for thin film element, method for manufac |
| CN103548135A (en) * | 2011-03-23 | 2014-01-29 | 大日本印刷株式会社 | Heat dissipating substrate, and element equipped with same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112571901A (en) * | 2019-09-28 | 2021-03-30 | 日铁化学材料株式会社 | Polyimide film, metal-clad laminate, and circuit board |
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| KR20190094291A (en) | 2019-08-13 |
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| KR102619451B1 (en) | 2024-01-02 |
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