CN110062784A - The manufacturing method of peeling layer - Google Patents

The manufacturing method of peeling layer Download PDF

Info

Publication number
CN110062784A
CN110062784A CN201780075600.6A CN201780075600A CN110062784A CN 110062784 A CN110062784 A CN 110062784A CN 201780075600 A CN201780075600 A CN 201780075600A CN 110062784 A CN110062784 A CN 110062784A
Authority
CN
China
Prior art keywords
peeling layer
group
manufacturing
formula
alkali
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201780075600.6A
Other languages
Chinese (zh)
Other versions
CN110062784B (en
Inventor
江原和也
进藤和也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN110062784A publication Critical patent/CN110062784A/en
Application granted granted Critical
Publication of CN110062784B publication Critical patent/CN110062784B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The manufacturing method of present invention offer peeling layer, it includes the process for being coated on matrix peeling layer formation with composition, being burnt at 450~550 DEG C of maximum temperature, peeling layer formation composition includes by least one of following formula (1A)~(1C) polyamic acid indicated and organic solvent.(in formula, X is independently of one another the aromatic group with 4 valences of 2 carboxylic acid derivates, and Y is independently of one another the aromatic group of divalent, Z1And Z2The independently of one another organic group of 1 valence, in formula (1A), Y, Z1And Z2At least one of there is alkali-soluble group, in formula (1B), Y and 2 Z1At least one of there is alkali-soluble group, in formula (1C), Y and 2 Z2At least one of there is alkali-soluble group, m indicates natural number independently of each other.).

Description

The manufacturing method of peeling layer
Technical field
The present invention relates to the manufacturing methods of peeling layer.
Background technique
In recent years, for electronic device, other than needing characteristic as slimming and lighting, it is also necessary to assign energy It is enough to be bent such function.Be thus taken into account, it is desirable that substitute previous weight, fragility, unyielding glass substrate and using lightweight Flexible plastic substrates.
Particularly, for display of new generation, it is desirable that using the flexible plastic substrates of lightweight, (following table is denoted as exploitation Resin substrate) the panchromatic TFT display panel of active array type.
Therefore, begin one's study the manufacturing methods of the various electronic devices using resin film as substrate, and a new generation is shown For device, carry out can convert existing TFT display panel manufacture equipment technique research.In patent document 1,2 With 3 in disclose following method: on the glass substrate formed amorphous si film layer, plastics base is formd in the film layer After plate, laser is irradiated from glass substrate side and crystallizes amorphous silicon, it will using the hydrogen for accompanying with the crystallization and generating Plastic base is removed from glass substrate.
In addition, disclosing following method in patent document 4: will be shelled using technology disclosed in Patent Documents 1 to 3 Absciss layer (" being transferred layer " is recorded as in patent document 4) is pasted on plastic foil, completes liquid crystal display device.
But in method disclosed in Patent Documents 1 to 4, particularly method disclosed in Patent Document 4, exist as Lower problem: in order to make laser light, it is necessary to use the high substrate of translucency；It needs to be enough to make it through substrate and then makes without fixed The irradiation of the laser for the bigger energy that hydrogen contained in shape silicon is released；Due to the irradiation of laser, stripped layer is made sometimes At damage.
Also, in the case where stripped layer is large area, laser treatment needs for a long time, and therefore, it is difficult to improve device system The productivity of work.
As the means for solving such problems, following manufacturing process is used in patent document 5: using existing glass Glass substrate uses polymer as cyclic olefin copolymer as matrix (hereinafter referred to as glass matrix) on the glass matrix Peeling layer is formed, after forming the heat resistant resin films such as polyimide film on the peeling layer, is formed on the film using vacuum technology Ito transparent electrode, TFT etc. and seal after, finally by glass matrix remove remove.
But now, as TFT, fast 2 times of low temperature polycrystalline silicon TFT of mobility ratio amorphous silicon TFT is used.It should be low For warm multi-crystal TFT, after amorphous silicon vapor deposition, need to carry out dehydrogenation annealing at 400 DEG C or more, irradiated with pulse laser makes Silicon crystallization (hereinafter called them TFT process), the temperature of above-mentioned dehydrogenation annealing process are the vitrifying of existing polymer It is more than transition temperature (being denoted as Tg below).
But for existing polymer, it is known that in the case where being heated to the temperature of Tg or more, adaptation is improved (referring for example to patent document 6), after a heating treatment the adaptation of peeling layer and resin substrate improve, sometimes by resin substrate from Matrix stripping becomes difficult.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 10-125929 bulletin
Patent document 2: Japanese Unexamined Patent Publication 10-125931 bulletin
Patent document 3: International Publication No. 2005/050754
Patent document 4: Japanese Unexamined Patent Publication 10-125930 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2010-111853 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2008-188792 bulletin
Summary of the invention
Subject to be solved by the invention
The present invention is completed in view of above-mentioned actual conditions, and it is an object of the present invention to provide being capable of not resin base to flexible electronic device The manufacturing method for the peeling layer that plate is removed with causing damage.
Means for solving the problems
The present inventor conscientiously studies repeatedly in order to solve the above problems, as a result, it has been found that: use comprising having alkali in the molecule The polyamic acid and organic solvent composition of soluble groups, firing temperature when forming peeling layer are defined up to Up to more than temperature, thus, it is possible to formed have excellent adaptation with matrix and with resin base used in flexible electronic device The peeling layer of the fissility of the adaptation and appropriateness of the appropriateness of plate, completes the present invention.
That is, the present invention provides:
1. the manufacturing method of peeling layer, it includes peeling layer formation is coated on matrix with composition, in maximum temperature The process being burnt at 450~550 DEG C, the peeling layer formation include to be indicated by following formula (1A)~(1C) with composition At least one of polyamic acid and organic solvent,
[changing 1]
(in formula, X is independently of one another the aromatic group with 4 valences of 2 carboxylic acid derivates, and Y is independently of one another 2 The aromatic group of valence, Z1And Z2The independently of one another organic group of 1 valence, in formula (1A), Y, Z1And Z2At least one of tool There is an alkali-soluble group, in formula (1B), Y and 2 Z1At least one of there is alkali-soluble group, in formula (1C), Y and 2 Z2 At least one of there is alkali-soluble group, m indicates natural number independently of each other.)
The manufacturing method of 2.1 peeling layer, wherein above-mentioned alkali-soluble group be carboxyl or phenolic hydroxyl group,
The manufacturing method of 3.1 or 2 peeling layer, wherein above-mentioned Y includes the aromatic series base indicated by following formula (2)~(5) Group,
[changing 2]
(in formula, W indicates carboxyl or hydroxyl, R independently of each other1~R3It indicates to be substituted with halogen atoms independently of each other , the alkylidene of carbon atom number 1~20, the alkenylene of carbon atom number 2~20, the alkynylene of carbon atom number 2~20, carbon atom number 6~20 arlydene or inferior heteroaryl, ether, ester group or the acylamino- of carbon atom number 2~20, zero indicates bonding end.)
The manufacturing method of 4.3 peeling layer, wherein above-mentioned Y includes the aromatic group indicated by following formula (6)~(9),
[changing 3]
(in formula, zero indicates bonding end.)
The manufacturing method of any one of 5.1~4 peeling layer, wherein above-mentioned Z1For 1 valence that is indicated by following formula (10) Organic group,
[changing 4]
(in formula, Z3Indicate carboxyl or hydroxyl, zero indicates bonding end.)
The manufacturing method of any one of 6.1~5 peeling layer, wherein above-mentioned Z2For 1 valence that is indicated by following formula (11) Organic group,
[changing 5]
(in formula, Z3Indicate carboxyl or hydroxyl, zero indicates bonding end.)
The manufacturing method of any one of 7.3~6 peeling layer, wherein above-mentioned Y also includes without alkali-soluble group Aromatic group,
The manufacturing method of 8.7 peeling layer, wherein the above-mentioned aromatic group without alkali-soluble group is sub- benzene Base, biphenylene or sub- terphenyl,
9. the manufacturing method for having the flexible electronic device of resin substrate, which is characterized in that use peeling layer, the removing Layer for using any one of 1~8 manufacturing method and formed,
10. the manufacturing method of flexible electronic device, it includes following process: in the manufacturing method using any one of 1~8 It is formed by after being coated with resin substrate formation composition on peeling layer, is burnt into and is formed at 450 DEG C of maximum temperature or more Resin substrate,
The manufacturing method of 11.9 or 10 flexible electronic device, wherein above-mentioned resin substrate is polyimide resin substrate.
The effect of invention
By using the manufacturing method of peeling layer of the invention, can reproducibility obtain having well it is excellent with matrix Adaptation and peeling layer with the adaptation of the appropriateness of resin substrate and appropriate fissility.Therefore, by implementing this hair Bright manufacturing method, in the manufacturing process of flexible electronic device, not to the resin substrate formed on matrix and then on it The circuit etc. of setting causes to damage, and the resin substrate is separated into possibility from the matrix together with the circuit etc..Therefore, this hair Bright manufacturing method can help to the easy of the manufacturing process for the flexible electronic device for having resin substrate, its yield improves Deng.
Specific embodiment
Hereinafter, the present invention is described in more detail.
The manufacturing method of peeling layer of the present invention, which is characterized in that comprising peeling layer formation to be coated with composition In the process being burnt on matrix, at 450~550 DEG C of maximum temperature, peeling layer formation composition includes under State at least one of polyamic acid of formula (1A)~(1C) expression and organic solvent.
Wherein, the peeling layer in the so-called present invention, is the layer being arranged right above glass matrix according to the purpose of regulation, makees For its typical case, it can enumerate and be made in the manufacturing process of flexible electronic device in matrix and the resin as polyimides Flexible electronic device resin substrate between in order to which the resin substrate is fixed and be arranged and in the tree in defined technique It is rear in order to enable the resin substrate can be from the removing that the matrix is easily peeled off and is arranged that electronic circuit etc. is formed on aliphatic radical plate Layer.
[changing 6]
In the above formulas, X is independently of one another the aromatic group with 4 valences of 2 carboxylic acid derivates, and Y is mutually indepedent Ground is the aromatic group of divalent, Z1And Z2The independently of one another organic group of 1 valence, in formula (1A), Y, Z1And Z2In at least One has alkali-soluble group, in formula (1B), Y and 2 Z1At least one of there is alkali-soluble group, in formula (1C), Y And 2 Z2At least one of have alkali-soluble group.
M indicates natural number, preferably 2 or more integer independently of each other.
Above-mentioned X preferably comprises the aromatic rings of 4 valences of 1~5 phenyl ring, the phenyl ring of more preferable 4 valence, the naphthalene nucleus of 4 valences, 4 valences Cyclohexyl biphenyl, the cyclohexyl biphenyl of the phenyl ring of further preferred 4 valence, 4 valences.
The aromatic group of divalent as above-mentioned Y preferably comprises the aromatic group of 1~5 phenyl ring, more preferably under State the group of formula (2 ')~(5 ') expression.
[changing 7]
In above-mentioned formula (2 ')~(5 '), R1~R3Expression independently of each other can be substituted with halogen atoms, carbon atom number 1~ 20 alkylidene, the alkenylene of carbon atom number 2~20, the alkynylene of carbon atom number 2~20, carbon atom number 6~20 arlydene Or inferior heteroaryl, ether, ester group or the acylamino- of carbon atom number 2~20, zero indicates bonding end.
As halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, preferably fluorine atom can be enumerated.
As the alkylidene of carbon atom number 1~20, preferably carbon atom number 1~10, straight chain, branch, cricoid alkylidene are equal Can, such as methylene, methylmethylene, dimethylmethylene, ethylidene, trimethylene, propylidene, four methylenes can be enumerated Base, pentamethylene, hexa-methylene etc..
As the alkenylene of carbon atom number 2~20, preferably carbon atom number 2~10, straight chain, branch, cricoid alkenylene are equal Can, such as ethenylidene, allylidene, butenylidene, inferior pentenyl, sub- hexenyl, heptene base, sub- octene can be enumerated Base, nonyl alkenyl etc..
As the alkynylene of carbon atom number 2~20, preferably carbon atom number 2~10, straight chain, branch, cricoid alkynylene are equal Can, such as ethynylene, sub- propinyl, butynelene, sub- pentynyl, sub- hexin base, sub- heptynyl, sub- octyne can be enumerated Base, sub- n-heptylacetylene base etc..
In addition, preferably being wrapped in the case where Y is the aromatic group of the divalent at least one alkali-soluble group Organic group containing the phenyl ring replaced by least one alkali-soluble group, particularly, more preferably comprising 2 or more by least The organic group for the phenyl ring that one alkali-soluble group replaces, the aromatic series base further preferably indicated by following formula (2)~(5) Group, particularly, the structure more preferably indicated by following formula (6)~(9), most preferably relative to carrying out adjacent bonding end at ortho position The structure indicated by formula (6), (7) and (9) with phenolic hydroxyl group.
[changing 8]
(in formula, W indicates alkali-soluble group, preferably carboxyl or phenolic hydroxyl group, R1~R3Indicate same as described above with zero Meaning.)
[changing 9]
(in formula, zero indicates bonding end.)
In the polyamic acid being used in the present invention, above-mentioned Y may include: the aromatic series of the divalent with alkali-soluble group Both group and the aromatic group of divalent without alkali-soluble group.
In this case, for the ratio of the aromatic group of the divalent with alkali-soluble group in whole Y, energy Enough it is set as 0.1~99.9 mole of % or so, preferably 1~50 mole of %, more preferable 1~10 mole of %.
In addition, in above-mentioned formula (1A)~(1C), Z1And Z2For the organic group of 1 valence, the organic of 1 valence of phenyl ring is preferably comprised Group preferably comprises the organic group of 1 valence of 1 phenyl ring, the Z being bonded with tetrabasic carboxylic acid end side1It is preferred that by following formula (10A) table The organic group of 1 valence shown, the Z being bonded with diamines end side2It is preferred that by the organic group of following formula (11A) 1 valence indicated.
[changing 10]
(in formula, zero indicates bonding end.)
In addition, in Z1And Z2In the case where aromatic group for the divalent with alkali-soluble group, preferably the alkali is solvable Property group and aromatic rings Direct Bonding, additionally, it is preferred that alkali-soluble group is 1.
More specifically, the Z being bonded with tetrabasic carboxylic acid end side1It is preferred that by the organic group of following formula (10B) 1 valence indicated, More preferable alkali-soluble group is present in the organic group of 1 valence indicated by following formula (10) at ortho position relative to NH, with diamines The Z of end side bonding2It is preferred that more preferable alkali-soluble group is relative to CO by the organic group of following formula (11B) 1 valence indicated It is present in the organic group of 1 valence indicated by following formula (11) at ortho position.
Particularly, there is hydroxyl by polymer ends, is capable of forming flexible base board used in upper layer and skeleton Difference, therefore the raising it is possible to realize obtained film as the function of peeling layer.
[changing 11]
(in formula, Z3Indicate carboxyl or hydroxyl, zero indicates bonding end.)
[changing 12]
(in formula, Z3Indicate carboxyl or hydroxyl, zero indicates bonding end.)
It, can be by making defined virtue with defined ratio for the polyamic acid indicated by above-mentioned formula (1A)~(1C) Fragrant race tetracarboxylic dianhydride ingredient is reacted with aromatic diamine ingredient to be obtained.
Aromatic tetracarboxylic acid used in synthesis below for polyamic acid used in the manufacturing method of the present invention Two anhydride components and aromatic diamine ingredient are illustrated.
As the aromatic tetracarboxylic dianhydride used in the synthesizing of the polyamic acid indicated by above-mentioned formula (1A)~(1C), As long as with 2 dicarboxylic anhydride positions and there is aromatic rings in the molecule, it is not particularly limited, preferably comprises 1~5 benzene nucleus Aromatic tetracarboxylic dianhydride.
As the concrete example of above-mentioned aromatic tetracarboxylic dianhydride, pyromellitic acid anhydride, benzene -1,2 can be enumerated, 3,4- tetra- Carboxylic acid dianhydride, naphthalene -1,2,3,4- tetracarboxylic dianhydride, naphthalene -1,2,5,6- tetracarboxylic dianhydride, naphthalene -1,2,6,7- tetracarboxylic dianhydride, Naphthalene -1,2,7,8- tetracarboxylic dianhydride, naphthalene -2,3,5,6- tetracarboxylic dianhydride, naphthalene -2,3,6,7- tetracarboxylic dianhydride, naphthalene -1,4,5,8- Tetracarboxylic dianhydride, biphenyl -2,2', 3,3'- tetracarboxylic dianhydride, biphenyl -2,3,3', 4'- tetracarboxylic dianhydride, biphenyl -3,3', 4, 4'- tetracarboxylic dianhydride, anthracene -1,2,3,4- tetracarboxylic dianhydride, anthracene -1,2,5,6- tetracarboxylic dianhydride, anthracene -1,2,6,7- tetrabasic carboxylic acid two Acid anhydride, anthracene -1,2,7,8- tetracarboxylic dianhydride, anthracene -2,3,6,7- tetracarboxylic dianhydride, phenanthrene -1,2,3,4- tetracarboxylic dianhydride, phenanthrene -1,2, 5,6- tetracarboxylic dianhydride, phenanthrene -1,2,6,7- tetracarboxylic dianhydride, phenanthrene -1,2,7,8- tetracarboxylic dianhydride, phenanthrene -1,2,9,10- tetrabasic carboxylic acid Dianhydride, phenanthrene -2,3,5,6- tetracarboxylic dianhydride, phenanthrene -2,3,6,7- tetracarboxylic dianhydride, phenanthrene -2,3,9,10- tetracarboxylic dianhydride, phenanthrene -3, 4,5,6- tetracarboxylic dianhydride, phenanthrene -3,4,9,10- tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, 3,3 ', 4,4 '-two Phenyl ether tetrabasic carboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acids, 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic, 2,2- Bis- (3,4- dicarboxyphenyi) hexafluoroisopropyli,enes, 4,4 '-hexafluoroisopropyli,ene, two phthalic acid etc., these can individually make With two or more can also be applied in combination.
On the other hand, diamine component preferably comprises the aromatic diamine of 1~5 benzene nucleus, more preferably can by least one alkali The aromatic diamine that soluble group replaces, the aromatic series two of the aromatic rings further preferably with carboxyl or phenolic hydroxyl group Amine, the aromatic diamine of the aromatic group further preferably replaced with phenolic hydroxyl group.
As the aromatic diamine with phenolic hydroxyl group, such as 3,3 '-diamino -4,4 '-dihydroxybiphenyls can be enumerated (4BP), 3,3 '-diamino -2,2 '-dihydroxybiphenyl (2BP), 2,2 '-bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (BAHF), bis- (4- amino -3,5- dihydroxy phenyl) hexafluoropropane of 2,2-, bis- [4- (the 3- amino-4-hydroxy phenoxy group) benzene of 2,2- Base] hexafluoropropane, bis- (3- amino-4-hydroxylphenyl) methane (BAPF), 3,3 '-diamino -4,4 '-dihydroxy benaophenonel (AHPK), 3,3 '-diamino -4,4 '-dihydroxy-phenylate (AHPE), 3,3 '-diamino -4,4 '-dihydroxy-diphenyl sulfide, 2, 2 '-bis- (3- amino-4-hydroxylphenyl) propane (BAPA), (3- amino-4-hydroxy) phenyl (3- amino-4-hydroxy) aniline (AHPA), bis- (3- amino-4-hydroxylphenyl) sulfones (BSDA), double-N, N '-(p- amino benzoyl)-hexafluoro -2,2 '-are bis- (4- hydroxy phenyl) propane (BABHBPA), [4- (4- amino-benzene oxygen) phenyl] sulfone, 2,4- diaminophenol, 3,5- diamino Phenol, 2,5- diaminophenol, 4,6- diamino resorcin, 2,5- diamino quinhydrones, bis- (3- amino-4-hydroxylphenyl) sulphur Ether, bis- (4- amino -3,5- dihydroxy phenyl) thioethers, bis- (3- amino-4-hydroxylphenyl) ethers, bis- (4- amino -3,5- dihydroxy Phenyl) ether, bis- (3- amino-4-hydroxylphenyl) methane, bis- (4- amino -3,5- dihydroxy phenyl) methane, bis- (3- amino -4- Hydroxy phenyl) sulfone, bis- (4- amino -3,5- dihydroxy phenyl) sulfones, 4,4 '-diamino -3,3 '-dihydroxybiphenyl (3BP), 4, 4 '-diamino -3,3 '-dihydroxy -5,5 '-dimethyl diphenyl, 4,4 '-diamino -3,3 '-dihydroxy -5,5 '-dimethoxy connection Bis- (the 3- amino-4-hydroxy phenoxy group) benzene of benzene, 1,4-, bis- (the 3- amino-4-hydroxy phenoxy group) benzene of 1,3-, bis- (the 4- amino-of 1,4- 3- hydroxyphenoxy) benzene, bis- (the 4- amino-3-hydroxy oxygroup) benzene of 1,3-, bis- [4- (3- amino-4-hydroxy phenoxy group) phenyl] Sulfone, bis- [4- (3- amino-4-hydroxy phenoxy group) phenyl] propane or bis- (4- amino-benzene oxygen) benzene of Isosorbide-5-Nitrae-, but do not limit In this.
In above-mentioned diamine component, 3,3 '-diamino -4,4 '-dihydroxybiphenyls (4BP), 3,3 '-can be preferably enumerated Diamino -2,2 '-dihydroxybiphenyl (2BP), 2,2 '-bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (BAHF), 2,2- are bis- Bis- [4- (the 3- amino-4-hydroxy phenoxy group) phenyl] hexafluoropropane of (4- amino -3,5- dihydroxy phenyl) hexafluoropropane, 2,2-, Bis- (3- amino-4-hydroxylphenyl) methane (BAPF), 3,3 '-diamino -4,4 '-dihydroxy benaophenonel (AHPK), 3,3 '-two Amino -4,4 '-dihydroxy-phenylate (AHPE), 3,3 '-diamino -4,4 '-dihydroxy-diphenyl sulfide, 2,2 '-bis- (3- amino -4- Hydroxy phenyl) propane (BAPA), (3- amino-4-hydroxy) phenyl (3- amino 4- hydroxyl) aniline (AHPA), bis- (3- amino -4- Hydroxy phenyl) sulfone (BSDA), double-N, bis- (4- hydroxy phenyl) propane of N '-(p- amino benzoyl)-hexafluoro -2,2 ' - (BABHBPA), between [4- (4- amino-benzene oxygen) phenyl] sulfone, 2,4- diaminophenol, 2,5- diaminophenol, 4,6- diamino Benzenediol, 2,5- diamino quinhydrones, bis- (3- amino-4-hydroxylphenyl) thioethers, bis- (4- amino -3,5- dihydroxy phenyl) sulphur Ether, bis- (3- amino-4-hydroxylphenyl) ethers, bis- (3- amino-4-hydroxylphenyl) methane, bis- (3- amino-4-hydroxylphenyl) sulfones, 4,4 '-diamino -3,3 '-dihydroxybiphenyl (3BP), 4,4 '-diamino -3,3 '-dihydroxy -5,5 '-dimethyl diphenyl, 4, Bis- (the 3- amino-4-hydroxy phenoxy group) benzene of 4 '-diamino -3,3 '-dihydroxy -5,5 '-dimethoxy-biphenyl, 1,4-, 1,3- are bis- Bis- (the 4- amino-3-hydroxy oxygroup) benzene of (3- amino-4-hydroxy phenoxy group) benzene, 1,4-, bis- (the 4- amino-3-hydroxies of 1,3- Oxygroup) benzene, bis- [4- (3- amino-4-hydroxy phenoxy group) phenyl] sulfones, bis- [4- (3- amino-4-hydroxy phenoxy group) phenyl] third Alkane or bis- (4- amino-benzene oxygen) benzene of 1,4-.
As particularly preferred diamine component, bis- (3- amino-4-hydroxylphenyl) methane (BAPF), 2,2 '-can be enumerated Bis- (3- amino-4-hydroxylphenyl) propane (BAPA), 2,2 '-bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (BAHF), 3, 3 '-diamino -4,4 '-dihydroxy-phenylate (AHPE), 3,3 '-diamino -4,4 '-dihydroxy benaophenonel (AHPK), bis- (3- Amino-4-hydroxylphenyl) thioether (BSDA), (3- amino-4-hydroxy) phenyl (3- amino-4-hydroxy) aniline (AHPA), double-N, Bis- (4- hydroxy phenyl) propane (BABHBPA) of N '-(p- amino benzoyl)-hexafluoro -2,2 '-etc..
As the aromatic diamine with carboxyl, 2,4- diaminobenzoic acid, 2,5- diaminobenzoic acid, 3 can be enumerated, 5- diaminobenzoic acid, 4,6- diaminostilbene, 3- phthalic acid, 2,5- diaminostilbene, 4- phthalic acid, bis- (4- amino -3- carboxylics Base phenyl) ether, bis- (4- amino -3,5- dicarboxyphenyi) ethers, bis- (4- amino -3- carboxyl phenyl) sulfones, bis- (4- amino -3,5- Dicarboxyphenyi) sulfone, 4,4 '-diamino -3,3 '-dicarboxylate biphenyl, 4,4 '-diamino -3,3 '-dicarboxyl -5,5 '-dimethyl Bis- (4- amino -3- carboxyphenoxy) benzene of biphenyl, 4,4 '-diamino -3,3 '-dicarboxyl -5,5 '-dimethoxy-biphenyl, 1,4-, Bis- (4- amino -3- carboxyphenoxy) benzene of 1,3-, bis- [4- (4- amino -3- carboxyphenoxy) phenyl] sulfones, bis- [4- (4- amino - 3- carboxyphenoxy) phenyl] propane, 2,2- bis- [4- (4- amino -3- carboxyphenoxy) phenyl] hexafluoropropane, 3,3 '-dicarboxyls Base -4,4 '-diaminodiphenyl-methane etc..
In addition, as described above, diamine component used in synthesis as above-mentioned polyamic acid, is also able to use and does not have There is the aromatic diamine of alkali-soluble group.
As do not have alkali-soluble group aromatic diamine concrete example, can enumerate p-phenylenediamine, m-phenylene diamine (MPD), 2,4,6- trimethyl -1,3- phenylenediamine, 2,3,5,6- tetramethyl -1,4- phenylenediamine, 4,4 '-diamino-diphenyl ethers (ODA), 3, 4 '-diamino-diphenyl ethers, 3,3 '-diamino-diphenyl ethers, 4,4 '-diamino diphenyl sulfides, 4,4 '-diamino-diphenyls Methane, 3,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 4,4- methylene-bis- (2-aminotoluene), 4, 4 '-methylene-bis- (2,6- dimethylaniline), 4,4- methylene-bis- (2,6- diethylaniline), 4,4 '-methylene-bis- (2- Isopropyl -6- methylaniline), 4,4 '-methylene-bis- (2,6- diisopropyl aniline), 4,4 '-diamino diphenyl sulfones, 3,3 ' - Diamino diphenyl sulfone, benzidine, ortho-aminotoluene, meta-aminotoluene, 3,3 ', bis- (the 4- amino of 5,5 '-tetramethyl benzidines, 1,4- Phenoxy group) benzene, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- [4- (4- amino-benzene oxygen) benzene Base] sulfone, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, the bis- [4- of 2,2- (3- amino-benzene oxygen) phenyl] propane.
For the charge ratio of diamine component and tetracarboxylic dianhydride's ingredient, target molecular weight, molecular weight distribution, diamines are considered Type, the type of tetracarboxylic dianhydride etc. and suitably determine, therefore cannot entirely provide, can be with 1:1 (molar ratio) Benchmark is set as the ratio being consistent with desired molecule chain end, be set as two end of strand from tetrabasic carboxylic acid the case where Under (formula (1B)), relative to 1 mole of diamine component, preferably 1.05~3.0 moles of tetracarboxylic dianhydride's ingredient, more preferable 1.07~ 2.5 moles, further preferred 1.1~2.0 moles, in the case where being set as two end of strand from diamines (formula (1C)), Relative to 1 mole of tetracarboxylic dianhydride's ingredient, preferably 1.00~2.5 moles of diamine component, more preferable 1.01~1.5 moles, into one Preferably 1.02~1.3 moles of step.
For the organic solvent used in such reaction, as long as not generating adverse effect to reaction, spy is had no It does not limit, as its concrete example, metacresol, 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- ethyl -2- pyrroles can be enumerated Alkanone, n-vinyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, 3- methoxyl group-N, N- diformazan Base propionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- propoxyl group-N, N- dimethylpropionamide, 3- isopropoxy-N, N- Dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide, 3- sec- butoxy-N, N- dimethylpropionamide, 3- tert- fourth oxygen Base-N, N- dimethylpropionamide, gamma-butyrolacton etc..Be explained, organic solvent can a kind be used alone or by two or more It is applied in combination.
Particularly, for the organic solvent for reaction, from fully dissolution diamines and tetracarboxylic dianhydride and polyamides Amino acid considers, is preferably selected from amides, the amide by (S2) amides indicated and being indicated by formula (S3) indicated by formula (S1) At least one of class.
[changing 13]
In formula, R1And R2The alkyl of carbon atom number 1~10 is indicated independently of each other.R3Indicate hydrogen atom or carbon atom number 1~ 10 alkyl.H indicates natural number, preferably 1~3, more preferably 1 or 2.
As the alkyl of carbon atom number 1~10, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl can be enumerated Base, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc..In these, preferably carbon is former The alkyl of subnumber 1~3, the alkyl of more preferable carbon atom number 1 or 2.
For reaction temperature, can suitably it be set in range of the fusing point to boiling point of the solvent used, usually 0~ 100 DEG C or so, the polyamic acid obtained in order to prevent imidizate in the solution and the high-content for maintaining polyamic acid unit, Preferably 0~70 DEG C or so, more preferably 0~60 DEG C or so, further preferably 0~50 DEG C or so.
For the reaction time, due to depending on reaction temperature, the reactivity of raw material, cannot entirely it advise It is fixed, but usually 1~100 hour or so.
Further make to give Z1And/or Z2, end-caps with alkali-soluble group or do not have alkali-soluble base Group end-caps with make tetracarboxylic dianhydride's ingredient discussed above reacted with diamine component obtained from polyamic acid it is anti- It answers, the polyamic acid that thus, it is possible to obtain being indicated by formula (1A)~(1C).
More specifically, as the Z being bonded with tetrabasic carboxylic acid end side is given1End-caps, virtue can be preferably used Fragrant race's monoamine.
Aromatic series monoamine preferably has the aromatic series monoamine of the aromatic rings of carbon atom number 6~30, preferably has carbon atom number 6 The aromatic series monoamine of~15 aromatic rings, more preferably the aromatic series monoamine of the aromatic rings with carbon atom number 6~10, institute as above It states, preferably comprises 1 phenyl ring.
As the concrete example for the aromatic series monoamine for not having alkali-soluble group, aniline, naphthalidine, 2- naphthalene can be enumerated Amine, 1- amino anthracene, 2- amino anthracene, 9- amino anthracene, 9- aminophenanthrene, 2- aminobphenyl, 3- aminobphenyl, 4- aminobphenyl etc..
As the concrete example of the aromatic series monoamine with alkali-soluble group, Ortho-Aminophenol, 3- aminobenzene can be enumerated Phenol, 4-aminophenol etc. have the aromatic series monoamine of phenolic hydroxyl group；2- aminobenzoic acid, 3- aminobenzoic acid, 4- aminobenzoic Acid etc. have the aromatic series monoamine etc. of carboxyl.
In these, as giving Z1End-caps, preferably with alkali-soluble group aromatic series monoamine, more preferably Aromatic series monoamine with phenolic hydroxyl group, further preferred Ortho-Aminophenol.
On the other hand, as giving the Z being bonded with diamines end side2End-caps, can it is preferable to use aromatic series Carboxylic acid.
Aromatic carboxylic acid preferably has the aromatic carboxylic acid of the aromatic rings of carbon atom number 6~30, preferably has carbon atom number 6 The aromatic carboxylic acid of~15 aromatic rings, the more preferably aromatic carboxylic acid of the aromatic rings with carbon atom number 6~10, institute as above It states, preferably comprises the aromatic carboxylic acid of 1 phenyl ring.
As the concrete example for the aromatic carboxylic acid for not having alkali-soluble group after sealing end, benzoic acid, 1- naphthalene can be enumerated Formic acid, 2- naphthoic acid, 1- anthroic acid, 2- anthroic acid, 9- anthroic acid, 2- Phenylbenzoic acid, 3- Phenylbenzoic acid, 4- phenyl benzene first The aromatic monocarboxylates such as acid.
As after sealing end with alkali-soluble group aromatic carboxylic acid concrete example, can enumerate phthalic acid, The aromatic dicarboxylic acids such as phthalic acid, terephthalic acid (TPA)；Salicylic acid, 3- hydroxybenzoic acid, 4-HBA etc. have phenol The aromatic monocarboxylate etc. of hydroxyl.
It is explained, above-mentioned carboxylic acid can be the form of etheride, acid anhydrides.
In these, as giving Z2End-caps, preferably block after with alkali-soluble group aromatic carboxylic acid, Optimization aromatic dicarboxylic acids, more preferable phthalic acid.
The polyamic acid indicated by formula (1A)~(1C) of the invention only use the diamines without alkali-soluble group at In the case where being allocated as diamine component (that is, in the case where not having alkali-soluble group in whole Y), Z1And/or Z2It needs With alkali-soluble group, in this case, any one of molecule chain end of polyamic acid of synthesis or both can be used The above-mentioned monoamine with alkali-soluble group, carboxylic acid closing.
It can be 1 mole or more relative to 1 mole of above-mentioned polyamic acid for the inlet amount of end-caps, preferably 2 Mole or more, more preferable 2~4 moles, further preferred 2~3 moles.It is explained, using aromatic series monoamine, For its additive amount, 1 mole of tetracarboxylic dianhydride used in the synthesis relative to above-mentioned polyamic acid preferably can be with 0.1 mole the above are targets, more preferably can be with 0.2~4 mole for target, further preferably can be with 0.2~3 mole For target.In addition, for the additive amount of aromatic carboxylic acid, diamines used in the synthesis relative to above-mentioned polyamic acid at Point 1 mole, preferably can the above are targets with 0.1 mole, more preferably can be further excellent with 0.2~4 mole for target Selection of land can be with 0.2~3 mole for target.
For organic solvent used in the closing in the molecule chain end of polyamic acid, as long as not generated to reaction Adverse effect is then not particularly limited, and is able to use the same solvent of solvent illustrated in synthesizing with above-mentioned polyamic acid.
For reaction temperature when being closed the molecule chain end of polyamic acid, when synthesis with polyamic acid is same Sample can suitably be set, usually 0~100 DEG C or so in range of the fusing point to boiling point of the solvent used, from reliably From the viewpoint of the molecule chain end closing of the polyamic acid of synthesis, it can be preferably set to 0~70 DEG C or so, more preferably set It is 0~60 DEG C or so, is further preferably set as 0~50 DEG C or so.For the reaction time, due to dependent on reaction temperature, The reactivity of raw material, therefore cannot entirely provide, but usually 1~100 hour or so.
The weight average molecular weight of either or both polyamic acid being closed obtain like this, molecule chain end and Speech, usually 5,000~500,000 or so, from the viewpoint of improving from the function as peeling layer of the film made, preferably It is 6,000~200,000 or so, more preferably 7,000~150,000 or so.It should be noted that in the present invention, weight average molecular weight To measure obtained polystyrene scaled value using gel permeation chromatography (GPC).
In the present invention, the reaction solution after endcapped usually can be directly used as to peeling layer of the invention and form use Composition or solution obtained from being diluted or being concentrated are used as peeling layer formation composition of the invention.It is explained, For above-mentioned reaction solution, can be filtered as needed.By being filtered, can not only reduce can become obtained removing The impurity of the reason of deterioration of adaptation, the fissility of layer etc. is mixed into, and can be efficiently obtained peeling layer and be formed use Composition.In addition, solvent can be dissolved in again and peeling layer is made is formed and use after solution isolates polyamic acid from the reactions above Composition.As the solvent at this point, organic solvent used in above-mentioned reaction etc. can be enumerated.
It is not particularly limited to for diluted solvent, as its concrete example, can enumerate molten with the above-mentioned reaction reacted The identical solvent of the concrete example of agent.For diluted solvent can a kind be used alone or two or more be applied in combination.Wherein, Consider from fully polyamic acid is dissolved, preferably n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- pyrrole Pyrrolidone, 1,3-Dimethyl-2-imidazolidinone, N- ethyl-2-pyrrolidone, gamma-butyrolacton, more preferable N- methyl -2- pyrroles Alkanone.
Even in addition, individually not by the solvent of polyamic acid dissolution in situation, as long as what polyamic acid was not precipitated Range can also be mixed in peeling layer formation of the invention in composition.Particularly, can moderately make ethyl cellosolve, Butyl cellosolve, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanol, 1- second Oxygroup -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, third Glycol -1- monomethyl ether -2- acetic acid esters, propylene glycol -1- list ethylether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygen Base) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc. be with low surface tension Solvent mixes.It is known thus to base plate coating when film homogeneity improve, in peeling layer formation composition of the invention It is preferable to use.
For the concentration of the polyamic acid in peeling layer formation composition of the invention, the peeling layer of production is considered Thickness, viscosity of composition etc. are suitably set, usually 1~30 mass % or so, preferably 1~20 mass % or so.It is logical Cross and be formed as such concentration, can reproducibility obtain well 0.05~5 μm or so thickness peeling layer.With regard to polyamic acid Concentration for, can by adjusting the raw material as polyamic acid diamines and tetracarboxylic dianhydride usage amount, will be above-mentioned anti- Its filtrate is diluted after answering solution to filter or is concentrated, the polyamic acid of isolation is made to adjust its amount etc. when dissolving in a solvent to carry out Adjustment.
In addition, considering that the thickness etc. of the peeling layer of production is suitably set for the viscosity of peeling layer formation composition Calmly, in the case where for the purpose of especially obtaining the film of 0.05~5 μm or so of thickness well by reproducibility, in general, at 25 DEG C For 10~10,000mPas or so, preferably 20~5,000mPas or so.
Wherein, for viscosity, it is able to use the viscosimetric analysis viscosimeter of commercially available liquid, referring for example to JIS The step of recording in K7117-2 is measured under conditions of 25 DEG C of temperature of composition.Preferably as viscosimeter, use Cone-plate type (cone-plate type) rotational viscometer, it is preferable that use 1 ° of 34 ' × R24 as standard cone in the viscosimeter of homotype Shape rotor can be measured under conditions of 25 DEG C of temperature of composition.As such rotational viscometer, such as can enumerate East machine industry (strain) TVE-25L processed out.
It is explained, for peeling layer of the present invention is formed with composition, in addition to polyamic acid and organic solvent It in addition, may include the ingredients such as crosslinking agent such as in order to improve film-strength.
After peeling layer formation described above is coated on matrix with composition, using be included in maximum temperature 450~ The sintering method of 550 DEG C or more the processes being burnt into carries out hot-imide to polyamic acid, and thus, it is possible to be had and base The excellent adaptation of body and with the adaptation of the appropriateness of resin substrate and appropriate fissility, be made of polyimide film Peeling layer.
In the present invention, if maximum temperature when above-mentioned firing be 450~550 DEG C and the heat resisting temperature of polyimides with Under range, then be not particularly limited, if it is considered that making the above-mentioned adaptation with matrix, closely sealed with the appropriateness of resin substrate Property and fissility improve, then preferably 500 DEG C or more.In addition, its upper limit is usually 550 DEG C or so, preferably 510 DEG C or so.Pass through Make heating temperature above range, while the fragilityization of the film prevented, imidization reaction can also be sufficiently carried out.
It is different because of heating temperature for heating up the time, therefore cannot entirely provide, usually 1 minute~5 hours. In addition, acid imide rate can be 50~100% range.
In addition, as long as maximum temperature becomes above range, may include below it for temperature when above-mentioned firing At a temperature of the process be burnt into.
As preferred an example of the heating method in the present invention, following gimmick can be enumerated: being heated at 50~150 DEG C Afterwards, directly periodically increase heating temperature, finally heated at 450~550 DEG C.Particularly as the more excellent of heating method An example of choosing can enumerate following gimmick: heating at 50~100 DEG C, be greater than 100 DEG C and heating less than 450 DEG C, 450 DEG C or more heat.In turn, as preferred another example of heating method, following gimmick can be enumerated: being added at 50~150 DEG C After heat, it is being greater than 150 DEG C and 350 DEG C or less heating, is then being greater than 350 DEG C and is being heated less than 450 DEG C, finally 450~550 DEG C heating.
In addition, preferred an example as heating method when considering firing time, can enumerate following gimmick: After being heated 1 minute~2 hours at 50~150 DEG C, directly periodically increase heating temperature, finally heated at 400 DEG C or more 30 minutes~4 hours.Particularly as preferred an example of heating method, it can enumerate and heat 1 point at 50~100 DEG C Clock~2 hour, be greater than 100 DEG C and less than 450 DEG C at heat 5 minutes~2 hours, heated at 450 DEG C or more 30 minutes~4 small When.In turn, as preferred another example of heating method, following gimmick can be enumerated: heating 1 point at 50~150 DEG C Behind clock~2 hour, heated 5 minutes~2 hours being greater than 150 DEG C and 350 DEG C or less, next greater than 350 DEG C and less than 450 DEG C heating 30 minutes~4 hours, finally heated 30 minutes~4 hours at 450~510 DEG C.
It is explained, in the case where forming peeling layer of the invention on matrix, peeling layer can be formed in the part of matrix Surface can also be formed in all surfaces.The form that peeling layer is formed as the part of the surface in matrix has only in matrix surface Defined range form the form of peeling layer, formed with pattern-likes such as dot pattern, line and space patterns in entire matrix surface The form etc. of peeling layer.It is explained, in the present invention, so-called matrix, it is meant that peeling layer shape of the invention is coated on its surface At with composition, for flexible electronic device etc. manufacture component.
As matrix (substrate), such as glass, metal (silicon wafer etc.), slabstone can be enumerated etc., particularly, from by the present invention The peeling layer formation being related to has with the peeling layer that composition obtains considers its sufficient adaptation, preferably glass.It gives With explanation, matrix surface can be made of single material, can also be made of material of more than two kinds.As by material of more than two kinds Material constitutes the form of matrix surface, there is that certain range in matrix surface is made of certain material, remaining surface is by other materials The form of composition；Certain material is present in other materials with pattern-likes such as dot pattern, line and space patterns in matrix surface entirety In form etc..As the form for constituting matrix surface with material of more than two kinds, there is in matrix surface certain range by certain material It constitutes, the form that remaining surface is constituted with other materials；In entire matrix surface material with dot pattern, line and space pattern Equal pattern-likes form present in other materials etc..
The method of coating is not particularly limited, such as cast coating method, spin-coating method, scraper for coating method, leaching can be enumerated Coating, rolling method, stick coating method, mouth die coating method, ink-jet method, print process (relief printing plate, intaglio plate, lithographic plate, silk-screen printing etc.) etc..
As utensil for heating, such as hot plate, baking oven can be enumerated etc..Heating atmosphere can be under air, can also Think under non-active gas, furthermore it is possible under normal pressure, or under decompression.
For the thickness of peeling layer, usually 0.01~50 μm or so, from the viewpoint of productivity, preferably 0.05 ~20 μm or so, more preferably 0.05~5 μm or so adjust the thickness of the film before heating to realize desired thickness.
Peeling layer described above has the excellent adaptation and and resin substrate with the matrix of matrix, particularly glass Appropriateness adaptation and appropriateness fissility.Therefore, peeling layer of the invention can be suitable for: in flexible electronic device Not to the resin substrate of the device with bringing damage by the resin substrate and the electricity formed on the resin substrate in manufacturing process Road etc. is together from matrix stripping.
Hereinafter, being illustrated to an example of the manufacturing method for the flexible electronic device for using peeling layer of the invention.
Using peeling layer formation composition of the invention, peeling layer is formed on glass matrix by above-mentioned method. Coating is used to form the resin substrate formation solution of resin substrate, is burnt into the film on the peeling layer, be consequently formed through The resin substrate of glass matrix is fixed on by peeling layer of the invention.
For the firing temperature of above-mentioned film, suitably set according to type of resin etc., in the present invention, it is preferred to make The maximum temperature when firing is 450~550 DEG C or more, more preferably 480 DEG C or more, further preferably 490 DEG C or more, more Further preferably 500 DEG C or more.Maximum temperature range when firing when by making resin substrate, can be into one Step makes to mention as the peeling layer of substrate and adaptation, the adaptation of the appropriateness of peeling layer and resin substrate and the fissility of matrix It is high.
In this case, as long as and maximum temperature become above range, may include being burnt at its temperature below At process.
Preferred an example of heating method when as resin substrate production, can enumerate following gimmick: at 50~150 DEG C After lower heating, directly periodically increase heating temperature, is finally heated at 450~550 DEG C.Particularly as heating method Preferred an example, following gimmick can be enumerated: being heated at 50~100 DEG C, be greater than 100 DEG C and less than 450 DEG C heat, It is heated at 450 DEG C or more.In turn, as preferred another example of heating method, following gimmick can be enumerated: 50~100 After heating at DEG C, it is being greater than 100 DEG C and 200 DEG C or less heating, is then being greater than 200 DEG C and is being heated less than 300 DEG C, at 300 DEG C It heats above and less than 400 DEG C, heats at 400 DEG C or more and less than 450 DEG C, finally heated at 450~550 DEG C.
In addition, preferred an example as heating method when considering firing time, can enumerate following gimmick: After heating 5 minutes~2 hours at 50~150 DEG C, directly periodically increase heating temperature, is finally heated at 450~550 DEG C 30 minutes~4 hours.Particularly as preferred an example of heating method, it can enumerate and heat 5 points at 50~100 DEG C Clock~2 hour, be greater than 100 DEG C and less than 450 DEG C at heat 5 minutes~2 hours, heated at 450 DEG C or more 30 minutes~4 small When.In turn, as preferred another example of heating method, following gimmick can be enumerated: heating 5 points at 50~100 DEG C Behind clock~2 hour, heated 5 minutes~2 hours being greater than 100 DEG C and 200 DEG C or less, next greater than 200 DEG C and less than 300 DEG C heating 30 minutes~4 hours, at 300 DEG C or more and less than 400 DEG C heating 30 minutes~4 hours, at 400 DEG C or more and less than 450 DEG C are heated 30 minutes~4 hours, are finally heated 30 minutes~4 hours at 450~550 DEG C.
For resin substrate, in a manner of all covering peeling layer, formed with the area that the area than peeling layer is big Resin substrate.As resin substrate, can enumerate representative by polyimides system as the resin substrate of flexible electronic device At resin substrate can enumerate polyimide solution, polyamic acid solution as its resin solution is used to form.The tree The forming method of aliphatic radical plate can be conventionally.
Next, desired circuit is formed on the resin substrate for being fixed on matrix via peeling layer of the invention, Then, such as along peeling layer by resin substrate cut, remove resin substrate from peeling layer together with the circuit, by resin base Plate is separated with matrix.At this point, a part of matrix can be cut together with peeling layer.
It is explained, have will be so far in high-brightness LED, three-dimensional for report in Japanese Unexamined Patent Publication 2013-147599 bulletin Laser lift-off used in the manufacture of semiconductor package part etc. (LLO method) is applied to the manufacture of flexible display.Above-mentioned LLO method It is characterized in that, the opposing face from the face for forming circuit etc. irradiates the light such as wavelength of specific wavelength from glass matrix side The light of 308nm.The light irradiated penetrates glass matrix, and the polymer (polyimides) only near glass matrix absorbs should Light and evaporate (distillation).As a result, can not be produced to the performance for determining display, the circuit being arranged on resin substrate etc. Selectively resin substrate is removed from glass matrix on the raw ground that influences.
For peeling layer of the invention, due to have fully absorb can using above-mentioned LLO method specific wavelength (such as The feature of light 308nm), therefore can be used as the sacrificial layer of LLO method.Therefore, in the present invention via using composition It is formed by peeling layer and is fixed on the resin substrate of glass matrix and forms desired circuit, then, implement LLO method to shine The light of 308nm is penetrated, then only has the peeling layer to absorb the light and evaporate (distillation).Above-mentioned peeling layer sacrifice is (as sacrificial as a result, Domestic animal layer functions), selectively resin substrate can be removed from glass matrix.
Embodiment
The present invention is described in more detail hereinafter, enumerating embodiment, but the present invention is not limited to these embodiments.
[1] abbreviation of compound
NMP:N- methyl pyrrolidone
BCS: butyl cellosolve
P-PDA: p-phenylenediamine
Bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 6FAP:2,2-
2AP:2- amino-phenol
BPDA:3,3-4,4- bibenzene tetracarboxylic dianhydride
Bis- (trifluoromethyl) benzidine of TFMB:2,2 '-
PMDA: pyromellitic acid anhydride
PA: phthalic anhydride
CBDA:1,2,3,4- cyclobutane tetrabasic carboxylic acid -1,2:3,4- dianhydride
[2] measurement of weight average molecular weight and molecular weight distribution
For the weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of polymer, it is divided by using Japan (strain) GPC device processed (Shodex (registered trademark) column KF803L and KF805L) makes the dimethylformamide as dissolution solvent Flow be 1ml/ minutes, measured under conditions of 50 DEG C of column temperature.It should be noted that Mw is set as polystyrene scaled value.
[3] synthesis of polymer
Pass through the following method synthesizing polyamides acid.
It should be noted that not by polymer segregation from the obtained reaction solution containing polymer, as described later, pass through by Reaction solution dilutes to prepare resin substrate formation composition or peeling layer formation composition.
< synthesis example S1 polyamic acid (synthesis of S1) >
P-PDA3.176g (0.02937 mole) is dissolved in NMP88.2g, is added BPDA8.624g (0.02931 mole) Afterwards, it is reacted 24 hours.The Mw of obtained polymer is 107300, molecular weight distribution 4.6.
The synthesis > of < synthesis example L1 polyamic acid (L1)
P-PDA1.507g (0.0139 mole) is dissolved in NMP43.2g, is added PMDA3.166g (0.01452 mole) Afterwards, it is reacted 2 hours.Then, 2AP0.127g (0.0012 mole) further is added, in nitrogen React it 24 hours.The Mw of obtained polymer is 48500, molecular weight distribution 2.08.
The synthesis > of < synthesis example L2 polyamic acid (L2)
P-PDA1.119g (0.01103 mole) is dissolved in NMP35.2g, is added PMDA3.006g (0.01378 mole) Afterwards, it is reacted 2 hours.Then, 2AP0.602g (0.00551 mole) further is added, in nitrogen React it 24 hours.The Mw of obtained polymer is 11700, molecular weight distribution 1.76.
The synthesis > of < synthesis example L3 polyamic acid (L3)
P-PDA0.681g (0.00629 mole) is dissolved in NMP35.2g, is added PMDA2.746g (0.01259 mole) Afterwards, it is reacted 2 hours.Then, 2AP1.373g (0.012588 mole) further is added, in nitrogen React it 24 hours.The Mw of obtained polymer is 8000, molecular weight distribution 1.57.
The synthesis > of < synthesis example L4 polyamic acid (L4)
P-PDA1.5206g (0.01406 mole) and 6FAP0.105g (0.00287 mole) are dissolved in NMP35.2g, added After adding PMDA3.004g (0.01377 mole), react it 22 hours.Then, further addition After PA0.170g (0.00115 mole), react it 22 hours.The Mw of obtained polymer is 22100, molecular weight distribution 1.93.
< compares the synthesis > of synthesis example B1 polyamic acid (B1)
P-PDA1.29g (0.00107 mole) is dissolved in NMP43.2g, is added BPDA3.509g (0.00119 mole) Afterwards, it is reacted 24 hours.The Mw of obtained polymer is 34000, molecular weight distribution 2.03.
< compares the synthesis > of synthesis example B2 polyamic acid (B2)
TFMB2.86g (0.0089 mole) is dissolved in NMP35.2g, is added CBDA1.944g (0.00991 mole), React it 24 hours.The Mw of obtained polymer is 69200, molecular weight distribution 2.2.It obtains Solution is solvable in PGME.
[4] resin substrate forms the preparation for using composition
Reaction solution obtained in synthesis example S1 is directly used as resin substrate formation composition respectively.
[5] peeling layer forms the preparation for using composition
[embodiment 1-1]
BCS and NMP is added in the reaction solution obtained in synthesis example L1, is diluted so that polymer concentration becomes 5wt%, BCS become 20 mass %, obtain peeling layer formation composition.
[embodiment 1-2~1-4]
In addition to replace reaction solution obtained in synthesis example L1 and respectively using reaction solution obtained in synthesis example L2~L4 with Outside, peeling layer formation composition is obtained using method same as embodiment 1-1.
[comparative example 1-1~1-2]
In addition to replacing reaction solution obtained in synthesis example L1 respectively using comparing reaction obtained in synthesis example B1 and B2 Other than liquid, peeling layer formation composition is obtained using method same as embodiment 1-1.
[6] production of peeling layer and resin substrate
[embodiment 2-1]
Using spinner (condition: revolution 3000rpm, about 30 seconds) by peeling layer formation group obtained in embodiment 1-1 Object L1 is closed to be coated on 100mm × 100mm glass substrate (similarly hereinafter) as glass matrix.
Then, obtained film is heated 2 minutes at 100 DEG C using hot plate, then, using baking oven, is added at 300 DEG C Heat 30 minutes heats 30 minutes at 400 DEG C by heating temperature heating (10 DEG C/min) to 400 DEG C, and then heat up (10 DEG C/ Minute) to 500 DEG C, it is heated at 500 DEG C 10 minutes, forms thick about 0.1 μm of peeling layer on the glass substrate, obtain with stripping The glass substrate of absciss layer.Be explained, during heating, not by with film substrate from taken out in baking oven but in baking oven Heating.
It is coated on the peeling layer (resin film) on glass substrate obtained above using rod coaters (gap: 250 μm) Resin substrate, which is formed, uses composition S2.Then, obtained film is heated 30 minutes at 80 DEG C using hot plate, then, is used Baking oven after becoming nitrogen atmosphere, heats 30 minutes at 140 DEG C, by heating temperature heating (2 DEG C/min, similarly hereinafter) to 210 DEG C, It is heated 30 minutes at 210 DEG C, heating temperature is warming up to 300 DEG C, heated 30 minutes at 300 DEG C, heating temperature is warming up to It 400 DEG C, is heated 30 minutes at 400 DEG C, heating temperature is warming up to 500 DEG C, heated 60 minutes at 500 DEG C, in peeling layer It is upper to form thick about 20 μm of polyimide substrate, obtain the glass substrate with resin substrate peeling layer.During heating, do not have Have and heats the substrate with film in baking oven from taking out in baking oven.
[embodiment 2-2~2-4]
In addition to replacing peeling layer formation obtained in embodiment 1-1 to use embodiment 1-2~1-4 respectively with composition L1 Obtained in peeling layer formed with other than composition L2~L4, peeling layer and poly- is formed using method same as embodiment 2-1 Acid imide substrate obtains the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[comparative example 2-1~2-2]
In addition to replacing peeling layer formation obtained in embodiment 1-1 to use comparative example 1-1~1-2 respectively with composition L1 Obtained in peeling layer formed with other than composition B1 and B2, peeling layer and poly- is formed using method same as embodiment 2-1 Acid imide substrate obtains the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[7] evaluation of fissility
For having the glass substrate of peeling layer obtained in above-described embodiment 2-1~2-4 and comparative example 2-1~2-2, adopt With the fissility of following gimmicks confirmation peeling layer and glass substrate.It should be noted that following tests is carried out with same glass substrate.
The cross-cut test fissility of < resin film evaluates >
By the removing on the glass substrate for having peeling layer obtained in embodiment 2-1~2-4 and comparative example 2-1~2-2 Layer cross-cut (in length and breadth the interval 1mm, similarly hereinafter), has carried out the cutting of 100 grids (マ ス カ ッ ト).That is, being cut by the intersection It cuts, forms the mesh of 100 1mm square.
Then, in 100 mesh segmentation bonding partially adhesive tapes, which is removed, is evaluated based on the following benchmarks Fissility.It shows the result in table 1.
< determinating reference >
5B:0% removes (no removing)
4B: the removing less than 5%
The removing of 3B:5~less than 15%
The removing of 2B:15~less than 35%
The removing of 1B:35~less than 65%
The removing of 0B:65%~less than 80%
The removing of B:80%~less than 95%
The removing of A:95%~less than 100%
AA:100% removing (all removings)
The evaluation > of the fissility of < resin substrate
Resin substrate will be had obtained in embodiment 2-1~2-4 and comparative example 2-1~2-2 using cutting tool to shell The resin substrate of the glass substrate of absciss layer is cut into the strip of 25mm wide.Then, it is pasted in the front end of the resin substrate of cutting Cellophane tape, as test film.Use (strain) ア ト ニ ッ Network system push-and-pull tester by peel angle become 90 ° in a manner of pair The test film carries out disbonded test, based on following benchmark evaluation fissilities.Show the result in table 1.
< determinating reference >
5B:0% removes (no removing)
4B: the removing less than 5%
The removing of 3B:5~less than 15%
The removing of 2B:15~less than 35%
The removing of 1B:35~less than 65%
The removing of 0B:65%~less than 80%
The removing of B:80%~less than 95%
The removing of A:95%~less than 100%
AA:100% removing (all removings)
[table 1]
Confirmed by the result of table 1:, can not be by peeling layer from glass substrate for the peeling layer of embodiment 2-1~2-4 Resin substrate is only removed in removing ground, but cannot remove resin substrate in comparative example 2-1 and 2-2.

Claims (11)

1. a kind of manufacturing method of peeling layer, it includes peeling layer formation is coated on matrix with composition, in maximum temperature The process being burnt at 450~550 DEG C, the peeling layer formation include to be indicated by following formula (1A)~(1C) with composition At least one of polyamic acid and organic solvent,
In formula, X is independently of one another the aromatic group with 4 valences of 2 carboxylic acid derivates, and Y is independently of one another the virtue of divalent Fragrant race's group, Z1And Z2The independently of one another organic group of 1 valence, in formula (1A), Y, Z1And Z2At least one of have alkali can Soluble group, in formula (1B), Y and 2 Z1At least one of there is alkali-soluble group, in formula (1C), Y and 2 Z2In extremely Few one has alkali-soluble group, and m indicates natural number independently of each other.
2. the manufacturing method of peeling layer according to claim 1, wherein the alkali-soluble group is carboxyl or phenol hydroxyl Base.
3. the manufacturing method of peeling layer according to claim 1 or 2, wherein the Y includes by following formula (2)~(5) table The aromatic group shown,
In formula, W indicates carboxyl or hydroxyl, R independently of each other1~R3Expression independently of each other can be substituted with halogen atoms, carbon original The alkylidene of subnumber 1~20, the alkenylene of carbon atom number 2~20, the alkynylene of carbon atom number 2~20, carbon atom number 6~20 Arlydene or the inferior heteroaryl of carbon atom number 2~20, ether, ester group or acylamino-, zero indicates bonding end.
4. the manufacturing method of peeling layer according to claim 3, wherein the Y includes to be indicated by following formula (6)~(9) Aromatic group,
In formula, zero indicates bonding end.
5. the manufacturing method of peeling layer according to any one of claims 1 to 4, wherein the Z1For by following formula (10) The organic group of 1 valence indicated,
In formula, Z3Indicate carboxyl or hydroxyl, zero indicates bonding end.
6. the manufacturing method of peeling layer according to any one of claims 1 to 5, wherein the Z2For by following formula (11) The organic group of 1 valence indicated,
In formula, Z3Indicate carboxyl or hydroxyl, zero indicates bonding end.
7. the manufacturing method of the peeling layer according to any one of claim 3~6, wherein the Y also includes without alkali The aromatic group of soluble groups.
8. the manufacturing method of peeling layer according to claim 7, wherein the aromatic series without alkali-soluble group Group is phenylene, biphenylene or sub- terphenyl.
9. a kind of manufacturing method for the flexible electronic device for having resin substrate, which is characterized in that use peeling layer, the removing Layer is to be formed using manufacturing method described in any one of claim 1~8.
10. a kind of manufacturing method of flexible electronic device, it includes following process: using any one of claim 1~8 institute The manufacturing method stated is formed by peeling layer after coating resin substrate formation composition, at 450 DEG C of maximum temperature with enterprising Row is burnt into and forms resin substrate.
11. the manufacturing method of flexible electronic device according to claim 9 or 10, wherein the resin substrate is polyamides Imide resin substrate.
CN201780075600.6A 2016-12-08 2017-12-07 Method for producing release layer Active CN110062784B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016238635 2016-12-08
JP2016-238635 2016-12-08
PCT/JP2017/043912 WO2018105676A1 (en) 2016-12-08 2017-12-07 Release layer production method

Publications (2)

Publication Number Publication Date
CN110062784A true CN110062784A (en) 2019-07-26
CN110062784B CN110062784B (en) 2023-01-10

Family

ID=62491224

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780075600.6A Active CN110062784B (en) 2016-12-08 2017-12-07 Method for producing release layer

Country Status (5)

Country Link
JP (1) JP6954308B2 (en)
KR (1) KR102481072B1 (en)
CN (1) CN110062784B (en)
TW (1) TWI755459B (en)
WO (1) WO2018105676A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7230398B2 (en) * 2018-09-26 2023-03-01 東レ株式会社 SACRIFIC LAYER RESIN COMPOSITION AND METHOD FOR MANUFACTURING SEMICONDUCTOR ELECTRONIC PARTS

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102186904A (en) * 2008-10-20 2011-09-14 日本化药株式会社 Polyamide resin and composition thereof
CN102199290A (en) * 2011-04-12 2011-09-28 中国科学院化学研究所 Thermoplastic polyimide adhesive film as well as preparation method and application thereof
CN104918983A (en) * 2013-01-16 2015-09-16 日产化学工业株式会社 Method for producing resin thin film for display substrates and composition for forming resin thin film for display substrates
KR20160004468A (en) * 2014-07-02 2016-01-13 주식회사 이녹스 Polyamic acid having ester group, method for manufacturing thereof, and polyimide film comprising cured polyimide comprising polyamic acid
WO2016014648A2 (en) * 2014-07-22 2016-01-28 Brewer Science Inc. Polyimides as laser release materials for 3-d ic applications
CN105612600A (en) * 2013-10-07 2016-05-25 东丽株式会社 Element-processing layered structure, method for manufacturing element-processing layered structure, and method for manufacturing thin element using same
CN105820338A (en) * 2016-04-25 2016-08-03 全球能源互联网研究院 Polyimide and preparation method thereof
WO2016129546A1 (en) * 2015-02-10 2016-08-18 日産化学工業株式会社 Composition for forming release layer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3809681B2 (en) 1996-08-27 2006-08-16 セイコーエプソン株式会社 Peeling method
JP4619462B2 (en) 1996-08-27 2011-01-26 セイコーエプソン株式会社 Thin film element transfer method
JP4619461B2 (en) 1996-08-27 2011-01-26 セイコーエプソン株式会社 Thin film device transfer method and device manufacturing method
GB0327093D0 (en) 2003-11-21 2003-12-24 Koninkl Philips Electronics Nv Active matrix displays and other electronic devices having plastic substrates
JP5119401B2 (en) 2007-02-01 2013-01-16 倉敷紡績株式会社 Flexible laminate having thermoplastic polyimide layer and method for producing the same
TWI354854B (en) 2008-09-15 2011-12-21 Ind Tech Res Inst Substrate structures applied in flexible electrica

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102186904A (en) * 2008-10-20 2011-09-14 日本化药株式会社 Polyamide resin and composition thereof
CN102199290A (en) * 2011-04-12 2011-09-28 中国科学院化学研究所 Thermoplastic polyimide adhesive film as well as preparation method and application thereof
CN104918983A (en) * 2013-01-16 2015-09-16 日产化学工业株式会社 Method for producing resin thin film for display substrates and composition for forming resin thin film for display substrates
CN105612600A (en) * 2013-10-07 2016-05-25 东丽株式会社 Element-processing layered structure, method for manufacturing element-processing layered structure, and method for manufacturing thin element using same
KR20160004468A (en) * 2014-07-02 2016-01-13 주식회사 이녹스 Polyamic acid having ester group, method for manufacturing thereof, and polyimide film comprising cured polyimide comprising polyamic acid
WO2016014648A2 (en) * 2014-07-22 2016-01-28 Brewer Science Inc. Polyimides as laser release materials for 3-d ic applications
WO2016129546A1 (en) * 2015-02-10 2016-08-18 日産化学工業株式会社 Composition for forming release layer
CN105820338A (en) * 2016-04-25 2016-08-03 全球能源互联网研究院 Polyimide and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
哈尔滨电工学院 等: "《绝缘材料工艺原理》", 31 May 1990, 机械工业出版社 *

Also Published As

Publication number Publication date
TWI755459B (en) 2022-02-21
TW201842019A (en) 2018-12-01
JPWO2018105676A1 (en) 2019-10-24
KR102481072B1 (en) 2022-12-27
JP6954308B2 (en) 2021-10-27
CN110062784B (en) 2023-01-10
WO2018105676A1 (en) 2018-06-14
KR20190089208A (en) 2019-07-30

Similar Documents

Publication Publication Date Title
TWI695855B (en) Polyimide precursor, resin composition and resin film manufacturing method
TWI768234B (en) Laminate
JP7038630B2 (en) Polyimide precursor, resin composition, resin film and its manufacturing method
TWI615420B (en) Polyimide-polybenzoxazole precursor solution, polyimide-polybenzoxazole films and process for producing thereof
EP2803702B1 (en) Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition
WO2014046180A1 (en) Polyimide and molded body thereof
CN107810222A (en) Polyamidoimide precursor, polyamidoimide film and the display device for including the polyamidoimide film
TWI788288B (en) Polyimide resin
TW201708394A (en) Composition for forming release layer, and release layer
TWI659064B (en) Resin composition for display substrate, resin film for display substrate, and method for manufacturing resin film for display substrate
JPWO2018025954A1 (en) Composition for forming peeling layer for transparent resin substrate
CN110062784A (en) The manufacturing method of peeling layer
WO2018025955A1 (en) Composition for forming releasing layer
CN110050013A (en) The manufacturing method of peeling layer
TWI785179B (en) Method of preparing polyamic acid and polyamic acid, polyimide resin, polyimide film and image display element thereby
JP6897690B2 (en) Method of manufacturing the release layer

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
GR01 Patent grant
GR01 Patent grant