CN110050013A - The manufacturing method of peeling layer - Google Patents
The manufacturing method of peeling layer Download PDFInfo
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- CN110050013A CN110050013A CN201780075575.1A CN201780075575A CN110050013A CN 110050013 A CN110050013 A CN 110050013A CN 201780075575 A CN201780075575 A CN 201780075575A CN 110050013 A CN110050013 A CN 110050013A
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- peeling layer
- amino
- resin substrate
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- manufacturing
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- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- 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
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- 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
Abstract
The manufacturing method of present invention offer peeling layer, wherein, peeling layer formation comprising polyamic acid and organic solvent is coated on matrix with composition, it is burnt at 400 DEG C of maximum temperature or more, the polyamic acid include the tetracarboxylic dianhydride indicated by formula (1) tetracarboxylic dianhydride's ingredient with comprising selected from aromatic diamine of the ortho position of at least one amino at least one hydroxyl, there is the aromatic diamine of at least one sulfydryl at the ortho position of at least one amino, and the diamine component reaction of at least one of aromatic diamine with carboxyl aromatic diamine obtains.(in formula (1), X1Indicate the group of 4 valences in the group for 4 valences being combined between the group of 4 valences made of contracting ring between phenyl ring selected from 4 valences, 2 or more phenyl ring, 2 or more phenyl ring via singly-bound.).
Description
Technical field
The present invention relates to the manufacturing methods of peeling layer.
Background technique
In recent years, for electronic device, other than requiring 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.For technology related with a new generation's display, the phase
To convert into various fields such as flexible display, flexible intelligent phone, mirror displays.
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.
For example, disclosing following method in patent document 1,2 and 3: forming amorphous si film on the glass substrate
Layer, in the film layer formed plastic base after, from glass substrate side irradiate laser and crystallize amorphous silicon, by with this
The hydrogen that crystallization generates together removes plastic base from glass substrate.
In addition, in patent document 4, following method is disclosed: will be by using technology disclosed in Patent Documents 1 to 3
Peeling layer (" being transferred layer " is recorded as in patent document 4) is pasted on plastic foil and 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.
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
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 can be not to the resin of flexible electronic device
The manufacturing method for the peeling layer that substrate 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: in the manufacture of resin substrate, make
With: comprising making tetracarboxylic dianhydride's ingredient containing specific tetracarboxylic dianhydride and the aromatic series containing specific aromatic diamine two
The peeling layer of polyamic acid obtained from amine component reaction and organic solvent, which is formed, uses composition, in 400 DEG C or more of firing temperature
It is formed on matrix under degree and is formed by peeling layer, thus obtained with the excellent adaptation with matrix and flexible with being used as
The peeling layer of the fissility of the adaptation and appropriateness of the appropriateness of the resin substrate of electronic device, completes the present invention.
That is, the present invention provides:
1. the manufacturing method of peeling layer, which is characterized in that include following process: will be comprising polyamic acid and organic solvent
Peeling layer formation is coated on matrix with composition, is burnt at 400 DEG C of maximum temperature or more, the polyamic acid be make include
Tetracarboxylic dianhydride's ingredient of the tetracarboxylic dianhydride indicated by following formula (1) has with comprising being selected from the ortho position of at least one amino
Have at least one hydroxyl aromatic diamine, the ortho position of at least one amino have at least one sulfydryl aromatic diamine and
The diamine component reaction of at least one of aromatic diamine with carboxyl aromatic diamine obtains,
[changing 1]
(in formula (1), X1Indicate phenyl ring selected from 4 valences, between 2 or more phenyl ring 4 valences made of contracting ring group and 2
The group of 4 valences in the group for 4 valences being combined between a above phenyl ring via singly-bound.)
The manufacturing method of 2.1 peeling layer, wherein above-mentioned aromatic diamine be in following formula (B1)~(B4) extremely
Few one kind,
[changing 2]
The manufacturing method of 3.1 or 2 peeling layer, wherein the above-mentioned tetracarboxylic dianhydride indicated by formula (1) includes the formula that is selected from
(C1) at least one of~(C12),
[changing 3]
4. 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 1~3 manufacturing method and formed.
5. the manufacturing method of flexible electronic device, it includes following process: in the manufacturing method using any one of 1~3
And after being coated with resin substrate formation composition on the peeling layer formed, it is burnt into and is formed at 400 DEG C of maximum temperature or more
Resin substrate,
The manufacturing method of 6.4 or 5 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 film with the adaptation of the appropriateness of resin substrate and appropriate fissility.By implementing manufacturer of the invention
Method will not be to the resin substrate formed on matrix and then the electricity being arranged on it in the manufacturing process of flexible electronic device
Road etc. causes to damage, and the resin substrate is separated into possibility from the matrix together with the circuit etc..Therefore, manufacture of the invention
Method can help to the easy of the manufacturing process for the flexible electronic device for having resin substrate, its yield improves etc..
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 by the stripping comprising polyamic acid and organic solvent
Absciss layer formation is coated on matrix with composition, is burnt at 400 DEG C of maximum temperature or more, the polyamic acid be make comprising by
The tetracarboxylic dianhydride's ingredient for the tetracarboxylic dianhydride that following formula (1) indicates has extremely with comprising being selected from the ortho position of at least one amino
The aromatic diamine of a few hydroxyl has the aromatic diamine and tool of at least one sulfydryl at the ortho position of at least one amino
There is the diamine component reaction of at least one of the aromatic diamine of carboxyl aromatic diamine to obtain.
Peeling layer in the so-called present invention is the layer set right above glass matrix according to the purpose of regulation, as
Its typical case can be enumerated and be constituted in matrix and the resin as polyimides in the manufacturing process of flexible electronic device
In order to which the resin substrate is fixed and be arranged and in the resin in defined technique between the resin substrate of flexible electronic device
The peeling layer being arranged after electronic circuit etc. in order to enable the resin substrate to be easily peeled off from the matrix is formed on substrate.
[changing 4]
In formula (1), X1Indicate phenyl ring selected from 4 valences, between 2 or more phenyl ring 4 valences made of contracting ring group and 2
The group of 4 valences in the group for 4 valences being combined between a above phenyl ring via singly-bound.
As the concrete example of the group of 4 valences made of contracting ring between 2 or more phenyl ring, can enumerate 4 valences naphthalene nucleus, 4
The anthracene nucleus of valence, the phenanthrene ring of 4 valences, aphthacene ring of 4 valences etc..
The concrete example of group as 4 valences being combined between 2 or more phenyl ring via singly-bound, can enumerate 4 valences
Xenyl, the terphenyl of 4 valences etc..
As the concrete example of the above-mentioned aromatic tetracarboxylic dianhydride indicated by formula (1), Pyromellitic Acid two can be enumerated
Acid anhydride, benzene -1,2,3,4- tetracarboxylic 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- tetrabasic carboxylic acid
Dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, biphenyl -2,2', 3,3'- tetracarboxylic dianhydride, biphenyl -2,3,3', 4'- tetrabasic carboxylic acid two
Acid anhydride, 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- tetracarboxylic dianhydride, anthracene -1,2,7,8- tetracarboxylic dianhydride, anthracene -2,3,6,7- tetracarboxylic dianhydride, phenanthrene -1,2,3,4- four
Carboxylic acid 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- tetracarboxylic 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 dianhydrides, phenanthrene -3,4,9,10- tetracarboxylic dianhydrides etc. are not limited to these.
These can a kind be used alone or two or more be applied in combination.
Particularly as the aromatic tetracarboxylic dianhydride indicated by above-mentioned formula (1), from the viewpoint of ensuring heat resistance,
It is preferably selected from least one of the group being made of formula (C1)~(C12), is more preferably selected from and is made of formula (C1) and formula (C9)
At least one of group.
[changing 5]
In the present invention, can with it is above-mentioned by formula (1) indicate aromatic tetracarboxylic dianhydride be used together other than it four
Carboxylic acid dianhydride.
For such tetracarboxylic dianhydride, preferably aliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride and above-mentioned
Aromatic tetracarboxylic dianhydride other than formula (1).
In the present invention, the tetracarboxylic acid other than it is being used together with the above-mentioned aromatic tetracarboxylic dianhydride indicated by formula (1)
In the case where acid dianhydride, for the usage amount of the aromatic tetracarboxylic dianhydride indicated by formula (1), in whole tetracarboxylic dianhydrides
In, preferably 70 moles of % or more, more preferably 80 moles of % or more, further preferably 90 moles of % or more, further
Preferably 95 moles of % or more.By using such usage amount, can reproducibility obtain that there is good fissility well
Film.
The above-mentioned aromatic diamine being selected from the ortho position of amino with hydroxyl has the aromatic series of sulfydryl at the ortho position of amino
The aromatic diamine of at least one of diamines and aromatic diamine with carboxyl (hereinafter also referred to has alkali-soluble base
The aromatic diamine of group) it is the base that at least one of phenolic hydroxyl group, carboxyl, benzenethiol base or more are selected from one or more
The aromatic diamine of group.
It is described below that there is phenolic hydroxyl group, carboxyl, the diamines of benzenethiol base and the aromatic diamine without these groups
Concrete example, but the present invention is not limited to these, in addition, they can a kind be used alone or make two or more combination
With.
As the aromatic diamine with phenolic hydroxyl group, 2,4- diaminophenol, 2,5- diaminophenol, 4 can be enumerated,
6- diamino resorcin, 2,5- diamino quinhydrones, bis- (3- amino-4-hydroxylphenyl) ethers, bis- (4- amino-3-hydroxy bases)
Ether, bis- (4- amino -3,5- dihydroxy phenyl) ethers, bis- (3- amino-4-hydroxylphenyl) methane, bis- (4- amino-3-hydroxies
Base) methane, bis- (4- amino -3,5- dihydroxy phenyl) methane, bis- (3- amino-4-hydroxylphenyl) sulfones, bis- (4- amino -3- hydroxyls
Base phenyl) sulfone, bis- (4- amino -3,5- dihydroxy phenyl) sulfones, 2,2- bis- (3- amino-4-hydroxylphenyl) hexafluoropropane, 2,2-
Bis- (4- amino -3, the 5- dihydroxy phenyl) hexafluoropropane of bis- (4- amino-3-hydroxy base) hexafluoropropane, 2,2-, the bis- (3- of 2,2-
Amino-4-hydroxylphenyl) ketone, bis- (the 4- amino-3-hydroxy base) ketone of 2,2-, 2,2- bis- (4- amino -3,5- dihydroxy phenyls)
Ketone, 3- amino-N- (3- amino-4-hydroxylphenyl) -4- hydroxybenzamide, 4- amino-N- (4- amino-3-hydroxy base) -
3- hydroxybenzamide, 4,4'- diamino -3,3'- dihydroxybiphenyl, 4,4'- diamino -3,3'- dihydroxy -5,5'- diformazan
Base biphenyl, 4,4'- diamino -3,3'- dihydroxy -5,5'- dimethoxy-biphenyl, Isosorbide-5-Nitrae-are bis- (3- amino-4-hydroxy phenoxy group)
Bis- (the 3- amino-4-hydroxy phenoxy group) benzene of benzene, 1,3-, bis- (the 4- amino-3-hydroxy oxygroup) benzene of Isosorbide-5-Nitrae-, bis- (the 4- amino-of 1,3-
3- hydroxyphenoxy) benzene, bis- [4- (3- amino-4-hydroxy phenoxy group) phenyl] sulfones, bis- [4- (3- amino-4-hydroxy phenoxy group)
Phenyl] propane, bis- [4- (the 3- amino-4-hydroxy phenoxy group) phenyl] hexafluoropropane of 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, Isosorbide-5-Nitrae -,
1,3- bis- (4- amino -3- carboxyphenoxy) benzene, 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, the bis- (3- of 2,2-
Amino -4- carboxyl phenyl) ketone, bis- (4- amino -3- carboxyl phenyl) ketone of 2,2-, 2,2- bis- (4- amino -3,5- dicarboxyphenyis)
Ketone, 3- amino-N- (3- amino -4- carboxyl phenyl) -4- carboxybenzoyl amine, 4- amino-N- (4- amino -3- carboxyl phenyl) -
3- carboxybenzoyl amine etc..
As the aromatic diamine with benzenethiol base, 1,3- diamino -4- sulfydryl benzene, 1,3- diamino-can be enumerated
5- sulfydryl benzene, Isosorbide-5-Nitrae-diamino -2- sulfydryl benzene, bis- (4- amino -3- mercaptophenyl) ethers, the bis- (3- amino -4- sulfydryl benzene of 2,2-
Base) hexafluoropropane etc..
In turn, as the aromatic diamine with alkali-soluble group of more than two kinds, bis- (4- amino -4- carboxylics can be enumerated
Base -5- hydroxy phenyl) ether, bis- (4- amino -3- carboxyl -5- hydroxy phenyl) methane, bis- (4- amino -3- carboxyl -5- hydroxy benzenes
Base) sulfone, bis- (4- amino -3- carboxyl -5- hydroxy phenyl) propane of 2,2-, bis- (the 4- amino -3- carboxyl -5- hydroxy phenyls) six of 2,2-
Fluoro-propane etc..
In these aromatic diamines, it is preferably selected from the aromatic diamine that there is hydroxyl at the ortho position of amino, in the neighbour of amino
Position has the aromatic diamine of at least one of aromatic diamine of carboxyl, is more preferably selected from following formula (B1)~(B4)
One kind or two or more aromatic diamine.
[changing 6]
In addition, the solvent-soluble polyimide resin that can be easily manufactured in order to obtain by catalysis imidizate,
It is preferred that the aromatic diamine with carboxyl.
In the present invention, other diamines can be used together with the above-mentioned aromatic diamine containing alkali-soluble group.
Such diamines can be any one of aliphatic diamine, aromatic diamine, from the thin film strength that ensures and heat-resisting
From the viewpoint of property, the preferred aromatic diamine that is all free of of ester bond and ehter bond.
As above-mentioned other diamines, can enumerate p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 2,4- diaminotoluene,
2,5- diaminotoluene, 2,6- diaminotoluene, 4,6- dimethyl-m-phenylenediamine, 2,5- dimethyl-p-phenylenediamine, 2,6- diformazan
Base p-phenylenediamine, m-xylene diamine, p dimethylamine, 5- trifluoromethylbenzene -1,3- diamines, 5- trifluoromethylbenzene -1,2- diamines,
Bis- (trifluoromethyl) benzene -1,2- diamines of 3,5-, 1,2- naphthylenediamine, 1,3- naphthylenediamine, 1,4- naphthylenediamine, 1,5- naphthylenediamine, 1,6-
Naphthylenediamine, 1,7- naphthylenediamine, 1,8- naphthylenediamine, 2,3- naphthylenediamine, 2,6- naphthylenediamine, 4,4'- benzidine, the bis- (trifluoros of 2,2'-
Methyl) -4,4'- benzidine, 3,3'- dimethyl -4,4'- diaminodiphenyl-methane, 3,3', tetramethyl -4 5,5'-,
4'- diaminodiphenyl-methane, 4,4'- diamino-N-benzanilide, 3,3'- dichloro-benzidine, 3,3'- dimethyl diphenyl
Amine, 2,2'- dimethylbenzidine, 3,3'- diaminodiphenyl-methane, 3,4'- diaminodiphenyl-methane, 4,4'- diamino
Bis- (3- aminophenyl) propane of diphenyl methane, 2,2-, bis- (4- aminophenyl) propane of 2,2-, 2,2- bis- (3- aminophenyls)-
Bis- (4- the aminophenyl) -1,1,1,3,3,3- hexafluoropropane of 1,1,1,3,3,3- hexafluoropropane, 2,2-, 3,3'- diamino hexichol
Bis- (trifluoromethyl) biphenyl -4 of base sulfoxide, 3,4'- diaminodiphenyl sulfoxide, 4,4'- diaminodiphenyl sulfoxide, 3,3'-,
4'- diamines, 3,3', 5,5'- tetrafluoro biphenyl -4,4'- diamines, 4,4'- diamino octafluorobiphenyl, 1,5- diaminoanthraquinone-, 2,6- bis-
Amino anthracene, 9,10- diaminoanthraquinone-, 1,8- diamino are luxuriant and rich with fragrance, 2,7- diamino is luxuriant and rich with fragrance, 3,6- diamino is luxuriant and rich with fragrance, 9,10- diamino phenanthrene, 1,
Bis- (3- aminophenyl) benzene of 3-, bis- (4- aminophenyl) benzene of 1,3-, bis- (3- aminophenyl) benzene of 1,4-, bis- (the 4- aminobenzenes of 1,4-
Base) benzene, bis- (3- aminophenyl-thioether) benzene of 1,3-, bis- (4- aminophenyl-thioether) benzene of 1,3-, bis- (the 4- aminophenyl sulphur of 1,4-
Ether) benzene, bis- (the 3- aminophenyl sulfone) benzene of 1,3-, bis- (the 4- aminophenyl sulfone) benzene of 1,3-, 1,4- bis- (4- aminophenyl sulfone) benzene, 1,
Bis- [2- (4- aminophenyl) isopropyl] benzene of 3-, bis- [2- (3- aminophenyl) isopropyl] benzene of 1,4-, bis- [2- (the 4- amino of 1,4-
Phenyl) isopropyl] benzene, 4,4- methylene-bis- (2,6- ethyl aniline), 4,4'- methylene-bis- (2- isopropyl -6- methylbenzene
Amine), 4,4'- methylene-bis- (2,6-DIPA), 2,4,6- trimethyl -1,3- phenylenediamines, 2,3,5,6- tetramethyls -
Isosorbide-5-Nitrae-phenylenediamine, o- toluidines, m- toluidines, 3,3',5,5'-tetramethylbenzidine, bis- [4- (3- amino-benzene oxygen) benzene
Base] sulfone, bis- [4- (3- amino-benzene oxygen) phenyl] propane of 2,2-, bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-,
4,4'- diamino -3,3'- dimethyidicyclohexyl-methanes, 4,4'- diamino-diphenyl ether, 3,4- diamino-diphenyl ether, 4,
Bis- (4- anilino-) hexafluoropropane of 4'- diaminodiphenyl-methane, 2,2-, bis- (3- anilino-) hexafluoropropane of 2,2-, 2,2- are bis-
(3- amino -4- toluyl groups) hexafluoropropane, bis- (4- amino-benzene oxygen) benzene of Isosorbide-5-Nitrae -, bis- (4- amino-benzene oxygen) benzene of 1,3-,
Bis- [4- (4- amino-benzene oxygen) phenyl] propane of bis- [4- (4- amino-benzene oxygen) phenyl] sulfones, 2,2-, bis- [4- (the 4- amino of 2,2-
Phenoxy group) phenyl] hexafluoropropane etc., they can a kind be used alone or two or more be applied in combination.
In these, from the aspect of the solvent soluble of polyimides, preferably 4,4'- methylene-bis- (2,6- ethylo benzenes
Amine), it is 4,4'- methylene-bis- (2- isopropyl -6- methylaniline), 4,4'- methylene-bis- (2,6-DIPA), double
Bis- [4- (3- amino-benzene oxygen) phenyl] propane of [4- (3- amino-benzene oxygen) phenyl] sulfone, 2,2-, bis- [4- (the 3- aminobenzenes of 2,2-
Oxygroup) phenyl] hexafluoropropane etc..
In the present invention, the diamines being used together with the aromatic diamine with alkali-soluble group other than it the case where
Under, with regard to alkali-soluble group aromatic diamine usage amount for, in whole diamines, preferably 70 moles of % with
On, more preferably 80 moles of % or more, further preferably 90 moles of % or more are still more preferably 95 moles of % or more.
By using such usage amount, can reproducibility obtain the film with good fissility well.
By reacting tetracarboxylic dianhydride's ingredient described above with diamine component, removing of the present invention can be obtained
Layer forms the polyamic acid contained in composition.
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 7]
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, imidizate in the solution of the polyamic acid obtained in order to prevent, 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.
By method described above, the reaction solution comprising target polyamic acid can be obtained.
The weight average molecular weight of polyamic acid obtain, above-mentioned like this for, usually 5,000~500,000 or so, from
From the viewpoint of the function as peeling layer of the film made improves, preferably 6,000~200,000 or so, more preferably
7,000~150,000 or so.It should be noted that weight average molecular weight is to be measured using gel permeation chromatography (GPC) in the present invention
The polystyrene scaled value arrived.
In the present invention, above-mentioned reaction solution usually can be directly used as peeling layer formation composition of the invention or
Solution obtained from person is diluted or is concentrated is 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 the closely sealed of obtained peeling layer
The impurity of the reason of deterioration of property, fissility etc. is mixed into, and can efficiently obtain peeling layer formation composition.Separately
Outside, solvent can be dissolved in again and peeling layer formation composition is made after solution isolates polyamic acid from the reactions above.Make
For solvent at this time, 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.With regard to for for diluted solvent, can a kind be used alone or make two or more combination
With.Wherein, polyamic acid is dissolved into consideration, preferably n,N-Dimethylformamide, n,N-dimethylacetamide, N- first from well
Base -2-Pyrrolidone, 1,3-Dimethyl-2-imidazolidinone, N- ethyl-2-pyrrolidone, gamma-butyrolacton, more preferable N- methyl -
2-Pyrrolidone.
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 become such concentration, can reproducibility obtain well 0.05~5 μm or so thickness peeling layer.With regard to polyamide
Acid concentration for, can by adjusting the raw material as polyamic acid diamines and tetracarboxylic dianhydride usage amount, will be above-mentioned
Its filtrate is diluted after reaction solution filtering or is concentrated, make the polyamic acid of isolation adjust when dissolving in a solvent its amount etc. come into
Row 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 composition described above is coated on matrix, using included in 400 DEG C of maximum temperature
Polyamic acid is carried out hot-imide by the sintering method for the process being burnt into above, and thus, it is possible to obtain having and matrix
Excellent adaptation and with the adaptation of the appropriateness of resin substrate and appropriate fissility, the stripping that is made of polyimide film
Absciss layer.
In the present invention, if maximum temperature when above-mentioned firing be 400 DEG C or more and the heat resisting temperature of polyimides with
Under range, then be not particularly limited, if it is considered that improving the above-mentioned adaptation with matrix, appropriate close with resin substrate
Conjunction property and fissility, then preferably 450 DEG C or more, more preferable 500 DEG C or more.In addition, its upper limit is usually 550 DEG C or so, preferably
510 DEG C or so.By making heating temperature above range, while the fragilityization of the film prevented, can also fully into
Row imidization reaction uses the cyclisation and decarburization acid for having the benzoxazoles in diamines of the ortho position of amino with phenolic hydroxyl group
Reaction.
It is different because of heating temperature for heating up the time, therefore cannot entirely provide, usually 5 minutes~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
The process be burnt into of temperature.
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 400 DEG C or more.Particularly as the more preferable of heating method
An example, following gimmick can be enumerated: being heated at 50~100 DEG C, be greater than 100 DEG C and less than 400 DEG C heat, at 400 DEG C
The above heating.In turn, as preferred another example of heating method, following gimmick can be enumerated: being heated at 50~150 DEG C
Afterwards, it is being greater than 150 DEG C and 350 DEG C or less heating, is then being greater than 350 DEG C and 400 DEG C or less heating, finally more than 400 DEG C
And 510 DEG C or less 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 400 DEG C at heat 5 minutes~2 hours, heated at 400 DEG C or more 30 points~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, is heated 5 minutes~2 hours being greater than 150 DEG C and 350 DEG C or less, be then greater than 350 DEG C and 400 DEG C or less
Heating 30 minutes~4 hours is finally being greater than 400 DEG C and 510 DEG C or less heating 30 minutes~4 hours.
In the manufacturing method of the present invention, in the case where forming peeling layer on matrix, peeling layer can be formed in matrix
Part of the 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 table
Defined range in face forms the form of peeling layer, in entire matrix surface with pattern-likes such as dot pattern, line and space patterns
Form the form etc. of peeling layer.It is explained, in the present invention, so-called matrix, it is meant that be coated on its surface of the present invention
Peeling layer formation 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 using this hair
Peeling layer obtained from the bright peeling layer formation composition being related to, which has, considers its sufficient adaptation, preferably glass
Glass.It is explained, matrix surface can be made of single material, can also be made of material of more than two kinds.As by 2 kinds with
On material constitute the form of matrix surface, have that certain range in matrix surface is made of certain material, remaining surface is by it
The form that his material is constituted；Certain material is present in it with pattern-likes such as dot pattern, line and space patterns in matrix surface entirety
Form etc. in his material.
The method being coated is not particularly limited, such as cast coating method, spin-coating method, blade coating can be enumerated
Method, dip 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.)
Deng.
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, for the peeling layer made in the present invention, can be suitable for:
Damage will not be brought in the manufacturing process of flexible electronic device to the resin substrate of the device by the resin substrate and in the tree
Circuit formed on aliphatic radical plate etc. is together from matrix stripping.
Hereinafter, being illustrated to an example for the method for using the manufacturing method of the present invention manufacture flexible electronic device.
Using peeling layer formation composition of the invention, adopts and form peeling layer on glass matrix with the aforedescribed process.
It is used to form the resin substrate formation solution of resin substrate by being coated on the peeling layer, is burnt into the film, thus shape
At the resin substrate for being fixed on glass matrix via 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 400 DEG C or more, is more preferably set as 450 DEG C or more, is further preferably set as 480 DEG C or more, more
Further preferably it is set as 500 DEG C or more.Maximum temperature range when firing when by making resin substrate, Neng Goujin
One step improves adaptation, the adaptation and removing of the appropriateness of peeling layer and resin substrate of peeling layer and matrix as substrate
Property.
In this case, as long as and maximum temperature become above range, may include being burnt at its temperature below
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 400 DEG C or more.Particularly as heating method
Preferred an example can enumerate following gimmick: it is heated at 50~100 DEG C, is being greater than 100 DEG C and is being heated less than 400 DEG C,
400 DEG C or more are heated.In turn, as preferred another example of heating method, following gimmick can be enumerated: at 50~100 DEG C
After lower heating, be greater than 100 DEG C and 200 DEG C or less heating, then be greater than 200 DEG C and less than 300 DEG C heating, 300 DEG C with
Upper and less than 400 DEG C heating, heat at 400 DEG C or more and less than 450 DEG C, finally heat at 450~510 DEG C.
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 400 DEG C at heat 5 minutes~2 hours, heated at 400 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 50~100 DEG C
Behind clock~2 hour, heated 5 minutes~2 hours being greater than 100 DEG C and 200 DEG C or less, then 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 450~510 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
Substrate.As resin substrate, can enumerate representative made of polyimides as the resin substrate of flexible electronic device
Resin substrate can enumerate polyimide solution, polyamic acid solution as its resin solution is used to form.The resin base
The forming method of plate can be conventionally.
Then, on the resin substrate for being fixed on matrix via peeling layer of the present invention, desired electricity is formed
Then road, such as along peeling layer cuts resin substrate, remove resin substrate from peeling layer together with the circuit, will set
Aliphatic radical plate is separated with matrix.At this point, a part of matrix can be cut together with peeling layer.
It is explained, reporting in Japanese Unexamined Patent Publication 2013-147599 bulletin will be so far in high-brightness LED, three-dimensional
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 is characterized in that the opposing face from the face for being formed with circuit etc. irradiates the light of specific wavelength for example from glass matrix side
The light of wavelength 308nm.The light irradiated penetrates glass matrix, and the polymer (polyimides) only near glass matrix is inhaled
It receives the light and evaporates (distillation).As a result, can not be to the performance for determining display, the circuit that is arranged on resin substrate
Etc. having an impact selectively resin substrate is removed from glass matrix.
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, form desired circuit, then, implement LLO method and come
The light of 308nm is irradiated, then only has the peeling layer to absorb the light and evaporate (distillation).As a result, above-mentioned peeling layer sacrifice (as
Sacrificial 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
TPDA:4,4 "-diamino-p- terphenyl
DBA:3,5- diaminobenzoic acid
HAB:3,3 '-dihydroxybiphenyl amine
Bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 6FAP:2,2-
TFMB:2,2 '-bis- (trifluoromethyl) benzidine
BPDA:3,3-4,4- bibenzene tetracarboxylic dianhydride
PMDA: pyromellitic acid anhydride
PA: phthalic anhydride
CBDA:1,2,3,4- cyclobutane tetrabasic carboxylic acids -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.
The synthesis > of < synthesis example S1 film polyamic acid (S1)
P-PDA20.261g (0.1875 mole) and TPDA12.206g (0.0469 mole) are dissolved in NMP617.4g,
It after being cooled to 15 DEG C, adds PMDA50.112g (0.2298 mole), reacts it 48 hours.It obtains
Polymer Mw be 82100, molecular weight distribution 2.7.
The synthesis > of < synthesis example S2 film polyamic acid (S2)
P-PDA3.176g (0.0294 mole) is dissolved in NMP88.2g, after addition BPDA8.624g (0.0293 mole),
Under nitrogen atmosphere, 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-PDA1.413g (0.0131 mole) and DBA0.221g (0.0015 mole) are dissolved in NMP35.2g, added
After PMDA3.166g (0.0145 mole), react it 24 hours.The Mw of obtained polymer is
64400, molecular weight distribution 2.9.
The synthesis > of < synthesis example L2 polyamic acid (L2)
P-PDA1.070g (0.0099 mole) and DBA0.645g (0.0042 mole) are dissolved in NMP35.2g, added
After PMDA3.084g (0.0141 mole), react it 24 hours.The Mw of obtained polymer is
57700, molecular weight distribution 2.9.
The synthesis > of < synthesis example L3 polyamic acid (L3)
P-PDA1.404g (0.0124 mole) and HAB0.312g (0.0014 mole) are dissolved in NMP35.2g, added
After PMDA3.084g (0.0141 mole), react it 24 hours.The Mw of obtained polymer is
32900, molecular weight distribution 2.5.
The synthesis > of < synthesis example L4 polyamic acid (L4)
P-PDA1.025g (0.0095 mole) and HAB0.879g (0.0041 mole) are dissolved in NMP35.2g, added
After PMDA2.896g (0.0133 mole), react it 24 hours.The Mw of obtained polymer is
22000, molecular weight distribution 2.0.
The synthesis > of < synthesis example L5 polyamic acid (L5)
P-PDA1.5206g (0.0141 mole) and 6FAP0.105g (0.0029 mole) are dissolved in NMP35.2g, added
After PMDA3.004g (0.0138 mole), react it 22 hours.Then, further addition
After PA0.170g (0.0012 mole), react it 22 hours.The Mw of obtained polymer is
22100, molecular weight distribution 1.9.
< compares the synthesis > of synthesis example B1 polyamic acid (B1)
P-PDA1.29g (0.0011 mole) is dissolved in NMP43.2g, in addition BPDA3.509g (0.0012 mole)
Afterwards, it is reacted 24 hours.The Mw of obtained polymer is 34000, molecular weight distribution 2.0.
< compares the synthesis > of synthesis example B2 polyamic acid (B2)
TFMB2.86g (0.0089 mole) is dissolved in NMP35.2g, is added CBDA1.944g (0.0099 mole), in nitrogen
React it 24 hours.The Mw of obtained polymer is 69200, molecular weight distribution 2.2.What is obtained is molten
Liquid is solvable in PGME.
[4] resin substrate forms the preparation for using composition
Reaction solution obtained in synthesis example S1 and S2 is directly used as resin substrate formation composition respectively.
[5] peeling layer forms the preparation for using composition
[embodiment 1-1]
In the reaction solution obtained in synthesis example L1, BCS and NMP is added, is diluted so that polymer concentration becomes
5wt%, BCS become 20 mass %, obtain peeling layer formation composition.
[embodiment 1-2~1-5]
In addition to replace reaction solution obtained in synthesis example L1 and respectively using reaction solution obtained in synthesis example L2~L5 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 is closed to be coated on 100mm × 100mm glass substrate (similarly hereinafter) as glass matrix.
Then, obtained film is heated 10 minutes at 80 DEG C using hot plate, then, using baking oven, is added at 300 DEG C
Heat 30 minutes heats heating temperature heating (10 DEG C/min) 30 minutes to 400 DEG C, and then at 400 DEG C, in glass substrate
It is upper to form thick about 0.1 μm of peeling layer, obtain the glass substrate with peeling layer.It is explained, during heating, not by band
There is the substrate of film to heat in baking oven from taking out in baking oven.
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 S1.Then, obtained film is heated 30 minutes at 80 DEG C using hot plate, then, is used
Baking oven after being formed as 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 heated up
It to 400 DEG C, is heated 60 minutes at 400 DEG C, forms thick about 20 μm of polyimide resin substrate on peeling layer, had
The glass substrate of resin substrate peeling layer.During heating, the substrate with film is not taken out from baking oven but is being dried
Heating in case.
[embodiment 2-2]
In addition to replace resin substrate formation with composition S1 and use resin substrate formation composition S2 other than, using with
The same method of embodiment 2-1 forms peeling layer and polyimide resin substrate, obtains the glass substrate and band with peeling layer
There is the glass substrate of resin substrate peeling layer.
[embodiment 2-3]
It uses and is shelled obtained in embodiment 1-2 in addition to replacing peeling layer formation composition obtained in embodiment 1-1
Absciss layer is formed with other than composition L2, forms peeling layer and polyimide resin substrate using method same as embodiment 2-2,
Obtain the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-4]
It uses and is shelled obtained in embodiment 1-3 in addition to replacing peeling layer formation composition obtained in embodiment 1-1
Absciss layer is formed with other than composition L3, forms peeling layer and polyimide resin substrate using method same as embodiment 2-1,
Obtain the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-5]
It uses and is shelled obtained in embodiment 1-3 in addition to replacing peeling layer formation composition obtained in embodiment 1-1
Absciss layer is formed with other than composition L3, forms peeling layer and polyimide resin substrate using method same as embodiment 2-2,
Obtain the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-6]
It uses and is shelled obtained in embodiment 1-4 in addition to replacing peeling layer formation composition obtained in embodiment 1-1
Absciss layer is formed with other than composition L4, forms peeling layer and polyimide resin substrate using method same as embodiment 2-1,
Obtain the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-7]
It uses and is shelled obtained in embodiment 1-4 in addition to replacing peeling layer formation composition obtained in embodiment 1-1
Absciss layer is formed with other than composition L4, forms peeling layer and polyimide resin substrate using method same as embodiment 2-2,
Obtain the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-8]
Using spinner (condition: revolution 3000rpm, about 30 seconds) by peeling layer formation group obtained in embodiment 1-5
Object L5 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 being formed as 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 heated up
It to 400 DEG C, is heated 30 minutes at 400 DEG C, heating temperature is warming up to 500 DEG C, heated 60 minutes, removing at 500 DEG C
Thick about 20 μm of polyimide resin substrate is formed on layer, obtains the glass substrate with resin substrate peeling layer.It is heating up
Period does not heat the substrate with film from taking out in baking oven in baking oven.
[comparative example 2-1~2-2]
In addition to replacing peeling layer formation composition obtained in embodiment 1-1 respectively using in comparative example 1-1~1-2
Other than obtained peeling layer formation composition, peeling layer is formed using method same as embodiment 2-2.
[7] evaluation of fissility
For having the glass substrate of peeling layer obtained in above-described embodiment 2-1~2-8 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 2-1~2-8 and comparative example 2-1~2-2
Layer cross-cut (in length and breadth the interval 1mm, similarly hereinafter), carries out the cutting of 100 grids (マ ス カ ッ ト).That is, by the cross-cut,
Form the mesh of 100 1mm square.
Then, in 100 mesh segmentation bonding partially adhesive tapes, which is removed, based on the following benchmarks (5B~
0B, B, A, AA) evaluate 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 2-1~2-8 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, evaluates fissility based on following standards.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 2-1~2-8
Resin substrate is only removed in removing ground, but fails to remove in comparative example 2-1 and 2-2.
Claims (6)
1. a kind of manufacturing method of peeling layer, which is characterized in that include following process: will be comprising polyamic acid and organic solvent
Peeling layer formation is coated on matrix with composition, is burnt at 400 DEG C of maximum temperature or more, the polyamic acid be make include
Tetracarboxylic dianhydride's ingredient of the tetracarboxylic dianhydride indicated by following formula (1) has with comprising being selected from the ortho position of at least one amino
The aromatic diamine of at least one hydroxyl, the ortho position of at least one amino have at least one sulfydryl aromatic diamine and
The diamine component of at least one of aromatic diamine with carboxyl aromatic diamine reacts,
In formula (1), X1Indicate phenyl ring selected from 4 valences, the group of 4 valences made of contracting ring between 2 or more phenyl ring, 2 or more
The group of 4 valences in the group for 4 valences being combined between phenyl ring via singly-bound.
2. the manufacturing method of peeling layer according to claim 1, wherein the aromatic diamine is selected from by following formula
(B1)~(B4) at least one of the group formed,
3. the manufacturing method of peeling layer according to claim 1 or 2, wherein the tetracarboxylic dianhydride indicated by formula (1)
At least one of group comprising selecting free style (C1)~(C12) composition,
4. 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 claims 1 to 33.
5. a kind of manufacturing method of flexible electronic device, it includes following process: using any one of claims 1 to 33 institute
The manufacturing method stated and after being coated with resin substrate formation composition on the peeling layer that is formed, at 400 DEG C of maximum temperature with enterprising
Row is burnt into and forms resin substrate.
6. the manufacturing method of flexible electronic device according to claim 4 or 5, wherein the resin substrate is that polyamides is sub-
Polyimide resin substrate.
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| JP2016-238642 | 2016-12-08 | ||
| JP2016238642 | 2016-12-08 | ||
| PCT/JP2017/043911 WO2018105675A1 (en) | 2016-12-08 | 2017-12-07 | Release layer production method |
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| CN110050013B CN110050013B (en) | 2022-11-29 |
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| JP (1) | JP7088023B2 (en) |
| KR (1) | KR102439479B1 (en) |
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| 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 |
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| KR102439479B1 (en) | 2022-09-05 |
| JP7088023B2 (en) | 2022-06-21 |
| TW201831621A (en) | 2018-09-01 |
| JPWO2018105675A1 (en) | 2019-10-24 |
| WO2018105675A1 (en) | 2018-06-14 |
| TWI823840B (en) | 2023-12-01 |
| CN110050013B (en) | 2022-11-29 |
| KR20190094198A (en) | 2019-08-12 |
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