CN109476951A - Peeling layer, which is formed, uses composition and peeling layer - Google Patents
Peeling layer, which is formed, uses composition and peeling layer Download PDFInfo
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- CN109476951A CN109476951A CN201780046634.2A CN201780046634A CN109476951A CN 109476951 A CN109476951 A CN 109476951A CN 201780046634 A CN201780046634 A CN 201780046634A CN 109476951 A CN109476951 A CN 109476951A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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- 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
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- 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
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Abstract
The peeling layer that the present invention provides polyamic acid and organic solvent comprising being indicated by following formula (1), which is formed, uses composition.In formula, X indicates the aromatic group indicated by following formula (2a) or (2b), Y indicates the aromatic group with the divalent of fluorine atom, Z is in the case where X is formula (2a), the aromatic group indicated by following formula (3a) or (4a) is indicated independently of each other, in the case where X is formula (2b), indicate that the aromatic group indicated by following formula (3b) or (4b), m indicate natural number independently of each other.
Description
Technical field
The present invention relates to peeling layer formation composition and peeling layers.
Background technique
In recent years, for electronic device, other than needing to be thinned with characteristic as lighting, it is also necessary to assign energy
It is enough to be bent such function.Based on this, require to substitute previous weight, fragility, unyielding glass substrate and use lightweight
Flexible plastic substrates.
Particularly, for display of new generation, it is desirable that exploitation has used flexible plastic substrates (the following table note of lightweight
For resin substrate) the panchromatic TFT display panel of active array type.It waits in expectation and turns technology related with a new generation's display
For various fields such as flexible display, flexible intelligent mobile 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.In addition, in touch surface
In board-like display, in research for efficiently manufacturing the transparent electrode for the touch panel being applied in combination in display pannel
The countermeasure of resin substrate etc..Generally, in the same manner as resin substrate used in touch panel and TFT display panel etc.
It used the polyimide resin substrate with the transparency with glass equal extent, acrylic resin substrate, gathered to benzene two
The ilm substrate of formic acid glycol ester (PET) resin substrate, cyclic olefin resins substrate etc..
As the production method of flexible display, main known direct method (non-patent literature 1).As direct method, have by
The resin substrate of pre-production is pasted on the glass substrate via adhesive layer, directly forms the picture comprising TFT on the substrate
The method of plain circuit and organic EL；Resin substrate is made on the glass substrate, directly forms the pixel comprising TFT on the substrate
The method of circuit and organic EL.
Moreover, the tree of pixel circuit etc. will be formd on glass substrate using aftermentioned various methods in the direct method
Rouge strippable substrate, the production of the electronic device for targets such as display pannels.
For example, disclosing following method in patent document 1,2 and 3: forming amorphous si film on the glass substrate
Layer, after foring plastic base in the film layer, from glass substrate side irradiate laser, crystallize amorphous silicon, using with
The hydrogen that the crystallization generates together removes plastic base from glass substrate.
In addition, Patent Document 4 discloses following methods: 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；By 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, in patent document 5, using following manufacturing process: using existing
Glass substrate as matrix (hereinafter referred to as glass matrix), gather on the glass matrix using as cyclic olefin copolymer
It closes object and forms peeling layer, after forming the heat resistant resin films (resin substrate) such as polyimide film on the peeling layer, adopted on the film
With vacuum technology by after the formation such as ito transparent electrode, TFT sealing, finally glass matrix is removed and is removed.
On the other hand, it for display of new generation, for the requirement for coping with big picture, raising yield rate etc., needs
Substrate it is larger in area.When resin combination to be equably coated on to the coated face of large area, it is considered that used slit painting
The slot coated mode of cloth device etc. is advantageous.Slot coated mode is the coating method for having used gap nozzle, is not needed as existing
Rotary coating mode rotate substrate like that, therefore cut down from the usage amount of resin combination and the viewpoint of process safety goes out
Hair, widely uses.But for the slot coated mode, from the perspective of improving productivity, it is desirable to be coated with work
The high speed of sequence.In order to realize the high speed of slot coated mode, the generation for needing striped when inhibiting coating unequal, therefore
Need to reduce the viscosity of the solution as one of most important parameter.
For example, in patent document 6 and 7, it is open as the composition for the photoresist for being suitable for slot coated mode
Use the composition of the so-called low viscosity solvent such as propylene glycol monomethyl ether, propylene glycol monomethyl ether.But peeling layer
The resins (or its precursor) such as polyimide resin used in general in composition are formed in these low viscosity solvents not
Dissolution, therefore, it is difficult to slot coated mode is used in the formation of peeling layer.Therefore, if made in peeling layer formation composition
Used in resin (or its precursor) dissolve and be possibly realized in above-mentioned low viscosity solvent, then not only with existing rotary coating
The coating of mode improves, and can make it also and can be suitble to use in slot coated mode.
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: International Publication No. 2011/030744
Patent document 7: Japanese Unexamined Patent Publication 2008-70480 bulletin
Non-patent literature
Non-patent literature 1:NHK skill grinds R&D/No.145/2014.5
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 peeling layer formation composition, the third two
It is also solvable in the so-called low viscosity solvent such as alcohol monomethyl ether, it is also readily applicable to slot coated mode, gives peeling layer,
The peeling layer can be in the resin substrate for not damaging the flexible electronic device being formed on, particularly using polyimides tree
It is removed in the case where the ilm substrates of formation such as rouge, acrylic resin, cyclic olefin polymerization resin.
Means for solving the problems
The present inventor conscientiously studies repeatedly in order to solve the above problems, as a result knows the polyamic acid with specific structure
It can also easily be dissolved in low viscosity solvent, and it was found that giving comprising the polyamic acid and organic solvent composition has
With the excellent adaptations of the matrixes such as glass substrate and with the resin substrate, particularly wavelength for flexible electronic device
The peeling layer of the fissility of the adaptation and appropriateness of the appropriateness for the resin substrate that the light transmittance of 400nm is 80% or more, completes
The present invention.
Therefore, the present invention provides following peeling layer formation composition and peeling layer.
[1] peeling layer, which is formed, uses composition, which is characterized in that comprising the polyamic acid that is indicated by following formula (1) and organic
Solvent.
[changing 1]
(in formula, X indicates that the aromatic group indicated by following formula (2a) or (2b), Y indicate the virtue with the divalent of fluorine atom
Race's group, Z are indicated independently of each other in the case where X is the aromatic group indicated by formula (2a) by following formula (3a) or (4a)
The aromatic group of expression is indicated independently of each other in the case where X is the aromatic group indicated by formula (2b) by following formula (3b)
Or the aromatic group that (4b) is indicated, m indicate natural number.)
[changing 2]
[changing 3]
[2] peeling layer described in [1], which is formed, uses composition, wherein above-mentioned Y is the aromatic group indicated by following formula (5).
[changing 4]
[3] peeling layer described in [2], which is formed, uses composition, wherein above-mentioned Y is the aromatic group indicated by following formula (6).
[changing 5]
[4] peeling layer described in any one of [1]~[3], which is formed, uses composition, wherein in above-mentioned X, by above-mentioned formula
The aromatic group that (2a) is indicated is the aromatic group indicated by following formula (7a) or (8a), and above-mentioned Z is by following independently of each other
The aromatic group that formula (9a) or formula (10a) indicate.
[changing 6]
[changing 7]
[5] peeling layer described in any one of [1]~[3], which is formed, uses composition, wherein in above-mentioned X, by above-mentioned formula
The aromatic group that (2b) is indicated is the aromatic group indicated by following formula (7b) or (8b), and above-mentioned Z is by following independently of each other
The aromatic group that formula (9b) or formula (10b) indicate.
[changing 8]
[changing 9]
[6] peeling layer described in any one of [1]~[5], which is formed, uses composition, wherein above-mentioned organic solvent is selected from tool
Have at least one kind of in the organic solvent by following formula (S1)~(S7) structure indicated.
[changing 10]
(in formula, R1~R8The alkyl of hydrogen atom or carbon atom number 1~10, R are indicated independently of each other9And R10Independently of each other
Indicate that hydrogen atom, the alkyl of carbon atom number 1~10 or the acyl group of carbon atom number 1~10, b and n indicate natural number)
[7] peeling layer described in [6], which is formed, uses composition, wherein above-mentioned organic solvent is propylene glycol monomethyl ether or third
Glycol monomethyl ether acetic acid esters.
[8] peeling layer for using peeling layer formation described in any one of [1]~[7] to be formed with composition.
[9] manufacturing method of resin substrate uses peeling layer described in [8].
[10] manufacturing method described in [9], wherein above-mentioned resin substrate is polyimide resin substrate or wavelength 400nm
Light transmittance be 80% or more resin substrate.
The effect of invention
By using peeling layer formation composition of the invention, had well so as to reproducibility and matrix
Excellent adaptation and peeling layer with the adaptation of the appropriateness of resin substrate and appropriate fissility.Particularly, of the invention
Used in dissolubility of the polyamic acid in low viscosity solvent it is excellent, can be easily therefore by using low viscosity solvent
Preparation can also apply to the composition of slot coated mode, is equably coated with and becomes easy in the coated face of large area.In turn,
It, will not be to the resin substrate formd on matrix and then the electricity being arranged on it in the manufacturing process of flexible electronic device
Road etc. causes to damage, and can separate the resin substrate and the circuit etc. from the matrix together.Therefore, peeling layer of the invention is formed
It can help to the high speed of the manufacturing process for the flexible electronic device for having resin substrate, the raising of its yield rate with composition
Deng.
Specific embodiment
The present invention is described in more detail below.
Peeling layer formation of the invention composition includes the polyamic acid and organic solvent indicated by following formula (1).
In the present invention, peeling layer is the layer being arranged right above the matrix (glass matrix etc.) of resin substrate to be formed.Make
For its typical case, can enumerate in the manufacturing process of flexible electronic device in order to above-mentioned matrix with by polyimide resin,
It is between the resin substrate of the flexible electronic device of the formation such as acrylic resin that the resin substrate is fixed in defined technique
And be arranged and formd on the resin substrate electronic circuit etc. it is rear in order to enable the resin substrate can from the matrix be easy
The peeling layer of ground removing and setting.
[changing 11]
In formula (1), X indicates that the aromatic group indicated by following formula (2a) or (2b), Y indicate the divalent with fluorine atom
Aromatic group, Z indicate the aromatic group indicated by following formula (3a) or (4a) in the case where X is formula (2a) independently of each other,
In the case where X is formula (2b), indicate that the aromatic group indicated by following formula (3b) or (4b), m indicate nature independently of each other
Number.
[changing 12]
[changing 13]
In above-mentioned X, the aromatic group indicated by above-mentioned formula (2a) is preferably by following formula (7a) or the aromatic group of (8a) expression
Group, the aromatic group that the aromatic group indicated by above-mentioned formula (2b) is preferably indicated by following formula (7b) or (8b).
[changing 14]
[changing 15]
In addition, in above-mentioned Z, the aromatic group indicated by above-mentioned formula (3a) or (4a) preferably by following formula (9a) or
The aromatic group that (10a) is indicated, the aromatic group indicated by above-mentioned formula (3b) or (4b) is preferably by following formula (9b) or (10b) table
The aromatic group shown.
[changing 16]
[changing 17]
Above-mentioned Y preferably has fluorine atom and includes the aromatic group of 1~5 phenyl ring, is more preferably selected from following formula (5)
Aromatic group, further preferably be selected from following formula (6) aromatic group.
[changing 18]
[changing 19]
As long as above-mentioned m is natural number, preferably 100 natural numbers below, more preferable 2~100 natural number.
The polyamic acid indicated by above-mentioned formula (1) is by obtaining defined tetracarboxylic dianhydride's ingredient and reaction with diamine component
It arrives.
As above-mentioned tetracarboxylic dianhydride's ingredient, pyromellitic dianhydride or bibenzene tetracarboxylic dianhydride are used.As above-mentioned diamines
Ingredient, if having fluorine atom, fat chain, alicyclic ring, aromatics, fragrance it is alicyclic, in the present invention, especially from improve for
The dissolubility of low viscosity solvent, and from the perspective of improving the obtained function as peeling layer of film, preferably make above-mentioned benzene four
Polyamic acid obtained from formic acid dianhydride or bibenzene tetracarboxylic dianhydride are reacted with the diamine component comprising above-mentioned aromatic diamine, it is more excellent
The acid of Wholly aromatic polyamide obtained from choosing reacts above-mentioned tetracarboxylic dianhydride with aromatic diamine.
Below for having the benzene tetracarboxylic acid being able to use in the synthesizing of the polyamic acid of structure indicated by above-mentioned formula (1)
Two anhydride components, bibenzene tetracarboxylic dianhydride and diamine component are described in detail.
As pyromellitic dianhydride, as long as with 2 dicarboxylic anhydride positions and there is phenyl ring in the molecule, have no
It is particularly limited to.As its concrete example, pyromellitic acid anhydride, benzene -1,2,3,4- tetracarboxylic acid dianhydrides etc. can be enumerated, the present invention
In, preferred pyromellitic acid anhydride.1 kind to can be used alone in these, two or more can also be applied in combination.
As bibenzene tetracarboxylic dianhydride, as long as with 2 dicarboxylic anhydride positions and there is xenyl in the molecule,
It is not particularly limited.As its concrete example, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 2,3,3 ', 4 '-biphenyl tetracarboxylics can be enumerated
Acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides etc., the present invention in, preferably 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides.It can be single
Solely using a kind in these, two or more can also be applied in combination.
On the other hand, it as aromatic diamine, is bound directly as long as having with fluorine atom and in the molecule with aromatic rings
2 amino, then be not particularly limited, preferably comprise 1~5, particularly 1~2, and then 2 phenyl ring aromatic diamine.Separately
Outside, more preferably there is fluoroalkyl or perfluoroalkyl, further preferred perfluoroalkyl.As above-mentioned perfluoroalkyl, such as can enumerate
Trifluoromethyl, pentafluoroethyl group, n- heptafluoropropyl and iso- heptafluoropropyl etc. out.
As the concrete example of above-mentioned aromatic diamine, 5- trifluoromethylbenzene -1,3- diamines, 5- trifluoromethyl can be enumerated
Benzene -1,2- diamines, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines and 3,3 '-bis- (trifluoromethyl) biphenyl -4,4 '-two
Amine etc., but it is not limited to these.In the present invention, 2,2 '-bis- (trifluoromethyl) -4 can be particularly preferably used in these,
4 '-benzidines.1 kind to can be used alone in these, two or more can also be applied in combination.
For the charge ratio of diamine component and tetracarboxylic dianhydride's ingredient, molecular weight, the molecular weight distribution, two of target are considered
Amine and the type of tetracarboxylic dianhydride etc. suitably determine, therefore cannot entirely provide, in order to obtain the polyamide of above-mentioned formula (1)
Acid preferably makes the molal quantity of tetracarboxylic dianhydride's ingredient slightly more relative to the molal quantity of diamine component.As specific molar ratio,
Relative to 1 mole of diamine component, preferred 1.05~2.5 moles of tetracarboxylic dianhydride's ingredient, more preferable 1.07~1.5 moles, into one
Preferably 1.1~1.3 moles of step.
By reacting tetracarboxylic dianhydride's ingredient described above with diamine component, so as to obtain removing of the invention
Layer forms the polyamic acid contained in composition.
As long as organic solvent used in the synthesis of polyamic acid does not generate adverse effect to reaction, special limit is had no
It is fixed, as its concrete example, metacresol, 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- ethyl -2- pyrrolidines can be enumerated
Ketone, n-vinyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, 3- methoxyl group-N, N- dimethyl
Propionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- propoxyl group-N, N- dimethylpropionamide, 3- isopropoxy-N, N- bis-
Methyl propanamide, 3- butoxy-N, N- dimethylpropionamide, 3- sec-butoxy-N, N- dimethylpropionamide, 3- tert-butoxy-
N, N- dimethylpropionamide, gamma-butyrolacton, propylene glycol monomethyl ether and propylene glycol monomethyl ether etc..It should be noted that having
Solvent can a kind be used alone or two or more be applied in combination.
The reaction temperature when synthesis of polyamic acid can suitably be set in range of the fusing point to boiling point of the solvent used
It is fixed, usually 0~100 DEG C or so, from imidizate, the maintenance polyamic acid unit of the polyamic acid prevented in the solution
High-content from the perspective of, preferably 0~70 DEG C or so, more preferably 0~60 DEG C or so, further preferably 0~50 DEG C
Left and right.Reaction time due to depending on reaction temperature, the reactivity of raw material, cannot entirely provide, but usually 1
~100 hours or so.
The weight average molecular weight of the polyamic acid obtained in this way is usually 5,000~500,000 or so, the film obtained from raising
The function as peeling layer from the perspective of, preferably 10,000~200,000 or so, more preferably 10,000~150,
000 or so.It should be noted that weight average molecular weight is to measure obtained polystyrene using gel permeation chromatography (GPC) in the present invention
Scaled value.
As in the present invention can it is preferable to use polyamic acid concrete example, can enumerate by following formula indicate polyamides
Amino acid, but not limited to this.
[changing 20]
(in formula, m1 and m2 indicate the number of repetitive unit, and m1 and m2's is total identical as above-mentioned m.)
[changing 21]
(in formula, m1 and m2 indicate the number of repetitive unit, and m1 and m2's is total identical as above-mentioned m.)
Peeling layer formation of the invention composition includes organic solvent.As the organic solvent, can be used and above-mentioned anti-
The same organic solvent of the concrete example for the reaction dissolvent answered, dissolves well from by polyamic acid of the invention, and it is equal to be easy preparation
The high composition of even property sets out, the organic solvent being preferably selected from amides, alcohols, esters, ethers and ketone, particularly preferably wraps
Containing with by at least one kind of of following formula (S1)~(S7) structure indicated.
[changing 22]
In above-mentioned formula, R1~R8The alkyl of hydrogen atom or carbon atom number 1~10, preferably 1~5 is indicated independently of each other.R9
And R10The alkyl or carbon atom number 1~10, preferably 1 of hydrogen atom, carbon atom number 1~10, preferably 1~5 are indicated independently of each other
~5 acyl group.B indicates natural number, preferably 1~5 natural number, more preferable 1~3 natural number.N expression natural number, preferably 1~
5 natural number, more preferable 1~3 natural number.
The concrete example of alkyl as carbon atom number 1~10, straight-chain, branch-like, cricoid alkyl, can enumerate
Methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, the positive fourth of 1- methyl
Base, 2- methyl normal-butyl, 3- methyl normal-butyl, 1,1- dimethyl n propyl, 1,2- dimethyl n propyl, 2,2- dimethyl n third
Base, 1- ethyl n-propyl, cyclopenta, n-hexyl, 1- methyl n-amyl, 2- methyl n-amyl, 3- methyl n-amyl, 4- methyl are just
Amyl, 1,1- dimethyl n butyl, 1,2- dimethyl n butyl, 1,3- dimethyl n butyl, 2,2- dimethyl n butyl, 2,3-
Dimethyl n butyl, 3,3- dimethyl n butyl, 1- ethyl normal-butyl, 2- ethyl normal-butyl, 1,1,2- trimethyl n-propyl, 1,
It is 2,2- trimethyl n-propyl, 1- ethyl -1- methyl n-propyl, 1- Ethyl-2-Methyl n-propyl, cyclohexyl, n-heptyl, just pungent
Base, n-nonyl and positive decyl etc..
The concrete example of acyl group as carbon atom number 1~10, can enumerate formoxyl, acetyl group, propiono, bytyry,
Isobutyryl, valeryl, isovaleryl, caproyl, isocaproyl, heptanoyl group, different heptanoyl group, caprylyl, different caprylyl, nonanoyl
Base, different nonyl acyl, capryl, isodecyl acyl and benzoyl etc..
As the concrete example of the organic solvent indicated by above-mentioned formula (S1)~(S7), organic solvent below can be enumerated.
Formula (S1): 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- propoxyl group-
N, N- dimethylpropionamide, 3- isopropoxy-N, N- dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide, 3- Zhong Ding
Oxygroup-N, N- dimethylpropionamide, 3- tert-butoxy-N, N- dimethylpropionamide
Formula (S2): 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone
Formula (S3): N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- dimethylpropionamide, N, N- dimethyl
Butyramide
Formula (S4): gamma-butyrolacton
Formula (S5): cyclopentanone, cyclohexanone, cycloheptanone
Formula (S6): methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, 2- hydroxy-isobutyric
Sour methyl esters, 2- ethyl butyrate of hydroxyl iso, 2- hydroxy-isobutyric propyl propionate, 2- hydroxy-isobutyric acid butyl ester
Formula (S7): ethyl cellosolve, butyl cellosolve, ethylene glycol, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol,
1- butoxy -2- propyl alcohol, propylene glycol monomethyl ether, propylene glycol -1- monomethyl ether -2- acetic acid esters, propylene glycol -1- list ethylether -
2- acetic acid esters
In the present invention, in these, preferably n-methyl-2-pyrrolidone, butyl cellosolve, propylene glycol monomethyl ether and third
Glycol monomethyl ether acetic acid esters, more preferable propylene glycol monomethyl ether and propylene glycol monomethyl ether, further preferred the third two
Alcohol monomethyl ether.These organic solvents can a kind be used alone or two or more be applied in combination.
Especially using so-called low viscosity as propylene glycol monomethyl ether and propylene glycol monomethyl ether molten
In the case that agent is as above-mentioned organic solvent, the peeling layer shape that can be also suitably applied the low viscosity of slit coating can be obtained
At with composition.Further more, in the case where peeling layer formation of the invention is used for slit coating with composition, in solvent entirety
In shared above-mentioned low viscosity solvent ratio preferably 60 mass % or more, more preferable 70 mass % or more, most preferably 80 matter
Measure % or more.
Even further more, not making the solvent of polyamic acid dissolution in situation individually, as long as what polyamic acid was not precipitated
Range also can be used in the preparation of composition.Particularly, it can moderately make ethyl carbitol, butyl carbitol, ethyl card must
Alcohol acetic ester, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, dipropylene glycol, 2- (2- ethoxy-c
Oxygroup) propyl alcohol etc. mixes with the solvent of low surface tension.It is known that thus in the coating on substrate, painting film uniformity is mentioned
Height can also be suitble to use in the present invention.
Peeling layer formation composition of the invention can be prepared using usual way.As the preferred of preparation method
An example can filter the reaction solution of the polyamic acid comprising target obtained using above explained method, using above-mentioned
The concentration for the filtrate that organic solvent makes becomes defined concentration.By using such method, to can not only reduce
The impurity for the reason of deterioration by adaptation, the fissility of peeling layer of obtained composition manufacture etc. can be become is mixed into, and
And peeling layer formation composition can be efficiently obtained.
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
It crosses and becomes such concentration, obtain the peeling layer of 0.05~5 μm or so of thickness well so as to reproducibility.It is just poly-
It, can be by adjusting the diamine component and tetracarboxylic dianhydride's ingredient and virtue of the raw material as polyamic acid for the concentration of amic acid
The usage amount of race's monoamine makes the polyamic acid of isolation adjust its amount etc. when dissolving in a solvent to be adjusted.
In addition, considering the thickness etc. of the peeling layer of production for peeling layer of the invention forms the viscosity with composition
Suitably set, for the purpose of especially obtaining the film of 0.05~5 μm or so of thickness well by reproducibility in the case where, lead to
It often, is 10~10,000mPas or so, preferably 20~5,000mPas or so at 25 DEG C.In addition, by stripping of the invention
Absciss layer formation composition is used in the slit coating mode, viscosity can be 2~100mPas or so, from life
From the perspective of yield, preferably 2~25mPas or so.
Wherein, viscosity is able to use the viscosimetric analysis viscosimeter of commercially available liquid, referring for example to remembering in JIS K7117-2
The step of load, is measured under conditions of 25 DEG C of temperature of composition.Preferably as viscosimeter, cone-plate type is used
(cone-plate type) rotational viscometer, it is preferable that 1 ° of 34 ' × R24 can be used as standard cone rotor in the viscosimeter of homotype,
It is measured under conditions of 25 DEG C of temperature of composition.As such rotational viscometer, such as eastern machine industry can be enumerated
Co. Ltd. system TVE-25L.
Further more, peeling layer formation composition of the invention is other than polyamic acid and organic solvent, such as in order to mention
High film-strength may include crosslinking agent etc..
It is coated on matrix by the way that the peeling layer of present invention mentioned above is formed composition, obtained film is heated,
Make polyamic acid hot-imide, so as to obtain with matrix excellent adaptation and with resin substrate appropriateness
The peeling layer made of polyimide film of the fissility of adaptation and appropriateness.
In the case where forming such peeling layer of the invention on matrix, peeling layer can be formed in one of matrix surface
Point, all surfaces can also be formed in.The form that peeling layer is formed as a part in matrix surface 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 should be noted that matrix means to be coated with peeling layer formation group of the invention on its surface in the present invention
Close object, for flexible electronic device etc. manufacture component.
As matrix (substrate), such as glass, plastics (polycarbonate, polymethacrylates, polyphenyl second can be enumerated
Alkene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin etc.), metal (silicon wafer etc.),
Timber, paper, slabstone etc..In the present invention, particularly, there is sufficient adaptation from peeling layer, it can it is preferable to use glass
Matrix.Further more, matrix surface can be made of single material, can also be made of material of more than two kinds.As by two or more
Material constitute the form of matrix surface, have that certain range in matrix surface is made of a kind of material, remaining range is by other
The form that material is constituted；Certain material is present in other with pattern-likes such as dot pattern, line and space patterns in entire matrix surface
Form etc. in material.
It is not particularly limited, such as can be enumerated with the method that composition is coated on matrix to by peeling layer formation of the invention
Cast coating method, spin-coating method, slot coated method, scraper for coating method, dip coating, rolling method, stick coating method, molding rubbing method, spray out
The method of the use of ink and water, print process (relief printing plate, intaglio plate, lithographic plate, silk-screen printing etc.) etc..
Heating temperature for carrying out imidizate usually suitably determines in the range of 50~550 DEG C, preferably super
Cross 150 DEG C and 510 DEG C or less.By make heating temperature become such temperature, the fragilityization for the film that can be prevented, simultaneously
It is sufficiently carried out imidization reaction.Heating time is different because of heating temperature, therefore cannot entirely provide, and usually 5 points
Clock~5 hour.As long as in addition, the range that acid imide rate is 50~100%.
As preferred an example of the heating method in the present invention, following gimmick can be enumerated: being heated at 50~150 DEG C
After 5 minutes~2 hours, periodically increase heating temperature like this, is finally heating being greater than 150 DEG C and 510 DEG C or less
30 minutes~4 hours.It is particularly preferred: after heated 5 minutes~2 hours at 50~150 DEG C, be greater than 150 DEG C and 350 DEG C with
Lower heating 5 minutes~2 hours is finally being greater than 350 DEG C and 450 DEG C or less heating 30 minutes~4 hours.
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.
The thickness of peeling layer is usually 0.01~50 μm or so, from the viewpoint of productivity, preferably 0.05~20 μm
Left and right.Further more, realizing desired thickness by adjusting the thickness of the film before heating.
Peeling layer described above have excellent adaptation with matrix, particularly glass matrix and with resin substrate
The adaptation of appropriateness and the fissility of appropriateness.Therefore, peeling layer of the invention can be suitable for: in the system of flexible electronic device
It makes the resin substrate and the electricity formed on the resin substrate with will not bringing damage in technique to the resin substrate of the device
Road etc. is together from matrix stripping.
An example of the manufacturing method for the flexible electronic device for having used peeling layer of the invention is illustrated below.
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 solution of resin substrate by being coated on the peeling layer, which is heated, thus via of the invention
Peeling layer forms the resin substrate for being fixed on glass matrix.At this point, in a manner of all covering peeling layer, than peeling layer
The big area of area forms substrate.As resin substrate, can enumerate representative as the resin substrate of flexible electronic device
The substrate made of polyimide resin, acrylic resin, cyclic olefin polymerization resin, it is molten as the resin for being used to form it
Liquid can enumerate polyimide solution, polyamic acid solution, acrylic polymer solution and cyclic olefin polymer solution etc..
The forming method of the resin substrate can be conventionally.In addition, the resin substrate high as the transparency, may be exemplified and use propylene
The resin substrate that acid system resin, cyclic olefin polymerization resin are formed, the light transmittance of particularly preferred wavelength 400nm are 80% or more
Resin substrate.
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.
Further more, in Japanese Unexamined Patent Publication 2013-147599 bulletin, it was recently reported that will be so far in high-brightness LED, three-dimensional half
The laser lift-off (LLO method) used in the manufacture of conductor packaging part etc. is applied to the manufacture of flexible display.Above-mentioned LLO method
It is characterized in that, the opposing face from the face for foring circuit etc., from the light of glass matrix side irradiation specific wavelength, such as wavelength
The light of 308nm.The light irradiated penetrates glass matrix, and the polymer (polyimide resin) only near glass matrix is inhaled
It receives the light and evaporates (distillation).Its result is will not be to the performance for determining display, the circuit that is arranged on resin substrate
The property of can choose resin substrate is removed from glass matrix in the case where etc. having an impact.
Peeling layer formation composition of the invention is due to having the application for fully absorbing above-mentioned LLO method to become possible spy
The feature of the light of standing wave long (such as 308nm), therefore can be used as the sacrificial layer of LLO method.Therefore, via using the present invention
The peeling layer that is formed of composition be fixed on the resin substrate of glass matrix and form desired circuit, then, if implemented
LLO method irradiates the light of 308nm, then only has the peeling layer to absorb the light and evaporate (distillation).Above-mentioned peeling layer is sacrificial as a result,
Domestic animal (functions) as sacrificial layer, optionally removes resin substrate from glass matrix.
Embodiment
It is exemplified below embodiment the present invention is described in more detail, but the present invention is not limited to these embodiments.
[1] abbreviation of compound
P-PDA: p-phenylenediamine
TPDA:4,4 "-diamino-p- terphenyl
Bis- (trifluoromethyl) benzidine of TFMB:2,2 '-
BPDA:3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides
PMDA: pyromellitic acid anhydride
DMCBDA:1,3- dimethylcyclobutane tetracarboxylic acid dianhydride
CBDA: cyclobutanetetracarboxylic dianhydride
MMA: methyl methacrylate
MAA: methacrylic acid
HEMA: 2-hydroxyethyl methacrylate
AIBN: azodiisobutyronitrile
CHMI: N-cyclohexylmaleimide
EPOLEAD GT-401: the ester modified 6-caprolactone of ethylene-dimalonic acid four (3,4- epoxycyclohexyl-methyl), (strain) are big
Match fine jade manufacture
3 ', 4 '-epoxycyclohexanecarboxylate of CELLOXIDE 2021P:3,4- 7-oxa-bicyclo[4.1.0 formic acid, the manufacture of (strain) Daicel
The manufacture of 1530: エ ボ ニ ッ Network ジ ャ パ Application (strain) of VESTAGON B
NMP:N- N-methyl-2-2-pyrrolidone N
BCS: butyl cellosolve
PGME: propylene glycol monomethyl ether
PGMEA: propylene glycol monomethyl ether
[2] measuring method of weight average molecular weight and molecular weight distribution
The measurement of the weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of polymer is made using Japan's light splitting (strain)
GPC device (column: Shodex KD801 and KD805；Eluent: dimethylformamide/LiBrH2O(29.6mM)/H3PO4
(29.6mM)/THF (0.1 mass %)；Flow: 1.0mL/ minutes；Column temperature: 40 DEG C；Mw: standard polystyren scaled value) into
Row.
[3] synthesis of polymer
Various polymer used in embodiment and comparative example have been synthesized using the following method.
It should be noted that as described later, passing through not by polymer segregation from the obtained reaction solution containing polymer
Reaction solution is diluted, to prepare resin substrate formation composition or peeling layer formation composition.
The synthesis > of < synthesis example S1 polyamic acid (S1)
P-PDA 3.218g (30mmol) is set to be dissolved in NMP 88.2g.BPDA 8.581g is added in obtained solution
(29mmol) has reacted it 24 hours.The Mw of obtained polymer is 107,300, molecular weight point
Cloth is 4.6.
The synthesis > of < synthesis example S2 polyamic acid (S2)
P-PDA 20.261g (0.1875mol) and TPDA 12.206g (0.0469mol) is set to be dissolved in NMP 617.4g,
After being cooled to 15 DEG C, adds PMDA 50.112g (0.2298mol), reacted it 48 hours.?
The Mw of the polymer arrived is 82,100, molecular weight distribution 2.7.
The synthesis > of < synthesis example S3 acrylic acid series polymeric compounds (S3)
Make MMA 7.20g (0.0719mol), HEMA 7.20g (0.0553mol), CHMI 10.8g (0.0603mol),
MAA 4.32g (0.0502mol), AIBN 2.46g (0.0150mol) are dissolved in PGMEA 46.9g, make it at 60~100 DEG C
Reaction 20 hours, to obtain acrylic polymer solution (40 mass % of solid component concentration).Obtained acrylic acid series
The Mn of polymer is 3,800, Mw 7,300.
The synthesis > of < synthesis example L1 polyamic acid (L1)
TFMB 2.73g (8.53mmol) is set to be dissolved in NMP 38.5g.PMDA 2.06g is added in obtained solution
(9.47mmol) reacts it 24 hours.The Mw of obtained polymer is 17,100, molecular weight point
Cloth is 1.7.Obtained polymer solution 1g is added in PGME 10g, is as a result especially precipitated without discovery.
The synthesis > of < synthesis example L2 polyamic acid (L2)
It is dissolved in TFMB 2.73g (8.53mmol) in PGME 40g.PMDA 2.06g is added in obtained solution
(9.47mmol) reacts it 24 hours.The Mw of obtained polymer is 20,100, molecular weight point
Cloth is 1.8.
The synthesis > of < synthesis example L3 polyamic acid (L3)
It is dissolved in TFMB 23.7g (74.2mmol) in NMP 352g.BPDA 24.2g is added in obtained solution
(82.5mmol) reacts it 24 hours.The Mw of obtained polymer is 16,500, molecular weight point
Cloth is 1.7.Obtained polymer solution 1g is added in PGME 10g, is as a result especially precipitated without discovery.
The synthesis > of < synthesis example L4 polyamic acid (L4)
It is dissolved in TFMB 9.89g (30.9mmol) in PGME380g.BPDA 10.0g is added in obtained solution
(34.3mmol) reacts it 72 hours.The Mw of obtained polymer is 14,700, molecular weight point
Cloth is 1.7.
< compares the synthesis > of synthesis example HL1 polyamic acid (HL1)
P-PDA 3.90g (3.60mmol) is set to be dissolved in NMP 35.2g.DMCBDA 9.27g is added in obtained solution
(4.00mmol) reacts it 24 hours.The Mw of obtained polymer is 45,000, molecular weight point
Cloth is 3.9.Obtained polymer solution 1g is added in PGME 10g, as a result polyamic acid is precipitated.
< compares the synthesis > of synthesis example HL2 polyamic acid (HL2)
TFMB 2.86g (8.91mmol) is set to be dissolved in NMP 35.2g.CBDA 1.94g is added in obtained solution
(9.91mmol) reacts it 24 hours.The Mw of obtained polymer is 69,200, molecular weight point
Cloth is 2.2.Obtained polymer solution 1g is added in PGME 10g, is as a result especially precipitated without discovery.
[4] resin substrate forms the preparation for using composition
Resin substrate formation composition is prepared using the following method.
1 resin substrate of < preparation example, which is formed, uses composition F1 >
Reaction solution obtained in synthesis example S1 is directly used as resin substrate formation composition F1.
2 resin substrate of < preparation example, which is formed, uses composition F2 >
Reaction solution obtained in synthesis example S2 is directly used as resin substrate formation composition F2.
3 resin substrate of < preparation example, which is formed, uses composition F3 >
EPOLEAD GT-401 0.60g and PGMEA 11.8g is added in the reaction solution 10g obtained in synthesis example S3,
It is stirred 24 hours at 23 DEG C, prepares resin substrate formation composition F3.
4 resin substrate of < preparation example, which is formed, uses composition F4 >
CELLOXIDE 2021P 0.80g and PGMEA 11.8g is added in the reaction solution 10g obtained in synthesis example S3,
It is stirred 24 hours at 23 DEG C, prepares resin substrate formation composition F4.
5 resin substrate of < preparation example, which is formed, uses composition F5 >
1530 0.60g and PGMEA 11.8g of VESTAGON B is added in the reaction solution 10g obtained in synthesis example S3,
It is stirred 24 hours at 23 DEG C, prepares resin substrate formation composition F5.
6 resin substrate of < preparation example, which is formed, uses composition F6 >
ZEONOR (registered trademark) 1020R (auspicious father-in-law's (strain) of Japan is added in the eggplant type flask equipped with carbon tetrachloride 100g
Manufacture, cyclic olefin polymerization resin) 10g and GT-401 3g.The solution is stirred 24 hours under nitrogen atmosphere and is dissolved, is prepared
Resin substrate, which is formed, uses composition F6.
7 resin substrate of < preparation example, which is formed, uses composition F7 >
ZEONOR (registered trademark) 1060R (auspicious father-in-law's (strain) of Japan is added in the eggplant type flask equipped with carbon tetrachloride 100g
Manufacture, cyclic olefin polymerization resin) 10g.The solution is stirred 24 hours under nitrogen atmosphere and is dissolved, resin substrate is prepared and is formed
With composition F7.
[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 5 matter
% is measured, BCS becomes 20 mass %, obtained peeling layer formation composition.
[embodiment 1-2]
By reaction solution obtained in synthesis example L2 directly as peeling layer formation composition.
[embodiment 1-3]
BCS and NMP is added in the reaction solution obtained in synthesis example L3, is diluted so that polymer concentration becomes 5 matter
% is measured, BCS becomes 20 mass %, obtained peeling layer formation composition.
[embodiment 1-4]
By reaction solution obtained in synthesis example L4 directly as peeling layer formation composition.
[comparative example 1-1]
In the reaction solution obtained in relatively synthesis example HL1 be added BCS and NMP, be diluted so that polymer concentration at
It is 5 mass %, BCS as 20 mass %, has obtained peeling layer formation composition.
[comparative example 1-2]
In the reaction solution obtained in relatively synthesis example HL2 be added BCS and NMP, be diluted so that polymer concentration at
It is 5 mass %, BCS as 20 mass %, has obtained peeling layer formation composition.
[6] production of peeling layer and resin substrate
[embodiment 2-1]
Peeling layer obtained in embodiment 1-1 is formed using spinner (condition: about 30 seconds under revolving speed 3,000rpm) and is used
Composition L1 is 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 should be noted that will not during heating
Substrate with film heats in baking oven from taking out in baking oven.
Using bar coater (gap: 250 μm), it is coated on the peeling layer (resin film) on glass substrate obtained above
Resin substrate, which is formed, uses composition F1.Then, obtained film is heated 30 minutes at 80 DEG C using hot plate, then, is made
It with baking oven, heats 30 minutes at 140 DEG C, by heating temperature heating (2 DEG C/min, similarly hereinafter) to 210 DEG C, is heated at 210 DEG C
30 minutes, heating temperature is warming up to 300 DEG C, is heated 30 minutes at 300 DEG C, heating temperature is warming up to 400 DEG C, 400
It is heated 60 minutes at DEG C, forms thick about 20 μm of resin substrate on peeling layer, obtained with resin substrate peeling layer
Glass substrate.During heating, the substrate with film is not heated in baking oven from taking out in baking oven.
[embodiment 2-2]
It has used resin substrate to be formed in addition to replacing resin substrate formation composition F1 used in embodiment 2-1 and has used
Other than composition F2, peeling layer and resin substrate are made using method same as embodiment 2-1, obtained with peeling layer
Glass substrate and glass substrate with resin substrate peeling layer.
[embodiment 2-3]
It has used in embodiment 1-2 and has obtained in addition to replacing peeling layer formation composition L1 obtained in embodiment 1-1
Peeling layer formed with other than composition L2, peeling layer and resin substrate are made using method same as embodiment 2-1, obtained
Glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-4]
Peeling layer formation composition L2 obtained in embodiment 1-2 is used as peeling layer formation composition, as
Resin substrate formation uses resin substrate formation composition F2, use and embodiment used in embodiment 2-2 with composition
The same method production peeling layer of 2-1 and resin substrate, have obtained the glass substrate with peeling layer and have had resin substrate
The glass substrate of peeling layer.
[embodiment 2-5]
Peeling layer formation composition L1 obtained in embodiment 1-1 is used as peeling layer formation composition, as
Resin substrate formation uses resin substrate formation composition F4 with composition, is made of method same as embodiment 2-1
Peeling layer and resin substrate have obtained the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-6]
Peeling layer formation composition L1 obtained in embodiment 1-1 is used as peeling layer formation composition, as
Resin substrate formation uses resin substrate formation composition F5 with composition, is made of method same as embodiment 2-1
Peeling layer and resin substrate have obtained the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-7]
Peeling layer formation composition L2 obtained in embodiment 1-2 is used as peeling layer formation composition, as
Resin substrate formation uses resin substrate formation composition F5 with composition, is made of method same as embodiment 2-1
Peeling layer and resin substrate have obtained the glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-8]
Using peeling layer formation composition L1 obtained in embodiment 1-1, using method shape same as embodiment 2-1
At peeling layer, the glass substrate with peeling layer has been obtained.
Then, spin coater (condition: about 15 seconds under revolving speed 200rpm) is used immediately, the peeling layer on above-mentioned glass substrate
Resin substrate formation composition F6 is coated on (resin film).Obtained film is heated 2 points at 80 DEG C using hot plate
Then clock using hot plate, heats 30 minutes at 230 DEG C, form thick about 3 μm of resin substrate on peeling layer, obtained band
There is the glass substrate of resin substrate peeling layer.Then, using ultraviolet-uisible spectrophotometer ((strain) Shimadzu Seisakusho Ltd. UV-
2600) light transmittance is determined, as a result resin substrate shows 80% or more transmissivity at 400nm.
[embodiment 2-9]
It has used in embodiment 1-2 and has obtained in addition to replacing peeling layer formation composition L1 obtained in embodiment 1-1
Peeling layer formed with other than composition L2, peeling layer and resin substrate are made using method same as embodiment 2-8, obtained
Glass substrate with peeling layer and the glass substrate with resin substrate peeling layer.
[embodiment 2-10]
Using peeling layer formation composition L1 obtained in embodiment 1-1, using method shape same as embodiment 2-1
At peeling layer, the glass substrate with peeling layer has been obtained.
Then, spin coater (condition: about 15 seconds under revolving speed 200rpm) is used immediately, the peeling layer on above-mentioned glass substrate
Resin substrate formation composition F7 is coated on (resin film).Obtained film is heated 2 points at 80 DEG C using hot plate
Then clock using hot plate, heats 30 minutes at 230 DEG C, form thick about 3 μm of resin substrate on peeling layer, obtained band
There is the glass substrate of resin substrate peeling layer.Then, using ultraviolet-uisible spectrophotometer ((strain) Shimadzu Seisakusho Ltd. UV-
2600) light transmittance is determined, as a result resin substrate shows 80% or more transmissivity at 400nm.
[embodiment 2-11]
It has used in embodiment 1-2 and has obtained in addition to replacing peeling layer formation composition L1 obtained in embodiment 1-1
Peeling layer formed with other than composition L2, peeling layer and resin substrate are made using method same as embodiment 2-10, obtained
The glass substrate with peeling layer and the glass substrate with resin substrate peeling layer are arrived.
[comparative example 2-1~2-4]
It has used in comparative example 1-1~1-2 and has obtained in addition to replacing peeling layer formation composition obtained in embodiment 1-1
Other than the peeling layer formation composition arrived, peeling layer and resin substrate are made using method same as above-described embodiment, obtained
The glass substrate with peeling layer and the glass substrate with resin substrate peeling layer are arrived.The group of peeling layer and resin substrate
It closes such as shown in table 1.
[embodiment 2-12]
Peeling layer obtained in embodiment 1-3 is formed using spinner (condition: about 30 seconds under revolving speed 3,000rpm) and is used
Composition L3 is 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 should be noted that will not during heating
Substrate with film heats in baking oven from taking out in baking oven.
Peeling layer (tree using spinner (condition: about 10 seconds under revolving speed 800rpm), on glass substrate obtained above
Membrane of lipoprotein) on be coated with resin substrate formation composition F3.Then, obtained film is heated 30 at 80 DEG C using hot plate
Minute, it then, using baking oven, is heated 30 minutes at 230 DEG C, forms thick about 3 μm of acrylic substrate on peeling layer.It is rising
During temperature, the substrate with film is not heated in baking oven from taking out in baking oven.
[embodiment 2-13]
Resin substrate has been used to be formed in addition to replacing resin substrate formation composition F3 used in embodiment 2-12
Other than composition F4, peeling layer and resin substrate are made using method same as embodiment 2-12, obtained with removing
The glass substrate and glass substrate with resin substrate peeling layer of layer.
[embodiment 2-14]
Resin substrate has been used to be formed in addition to replacing resin substrate formation composition F3 used in embodiment 2-12
Other than composition F5, peeling layer and resin substrate are made using method same as embodiment 2-12, obtained with removing
The glass substrate and glass substrate with resin substrate peeling layer of layer.
[embodiment 2-15]
It has used in embodiment 1-4 and has obtained in addition to replacing peeling layer formation composition L3 obtained in embodiment 1-3
Peeling layer formed with other than composition L4, peeling layer and resin substrate are made using method same as embodiment 2-12, obtained
The glass substrate with peeling layer and the glass substrate with resin substrate peeling layer are arrived.
[embodiment 2-16]
Peeling layer formation composition L4 obtained in embodiment 1-4 is used as peeling layer formation composition, as
Resin substrate formation uses resin substrate formation composition F5, use and embodiment used in embodiment 2-14 with composition
The same method production peeling layer of 2-12 and resin substrate, have obtained the glass substrate with peeling layer and have had resin substrate
The glass substrate of peeling layer.
[embodiment 2-17]
Using peeling layer formation composition L3 obtained in embodiment 1-3, using method same as embodiment 2-12
Peeling layer is formed, the glass substrate with peeling layer has been obtained.
Then, spin coater (condition: about 15 seconds under revolving speed 200rpm) is used immediately, the peeling layer on above-mentioned glass substrate
Resin substrate formation composition F6 is coated on (resin film).Obtained film is heated 2 points at 80 DEG C using hot plate
Then clock using hot plate, heats 30 minutes at 230 DEG C, form thick about 3 μm of resin substrate on peeling layer, obtained band
There is the glass substrate of resin substrate peeling layer.Then, using ultraviolet-uisible spectrophotometer ((strain) Shimadzu Seisakusho Ltd. UV-
2600) light transmittance is determined, as a result resin substrate shows 80% or more transmissivity at 400nm.
[embodiment 2-18]
It has used in embodiment 1-4 and has obtained in addition to replacing peeling layer formation composition L3 obtained in embodiment 1-3
Peeling layer formed with other than composition L4, peeling layer and resin substrate are made using method same as embodiment 2-17, obtained
The glass substrate with peeling layer and the glass substrate with resin substrate peeling layer are arrived.
[embodiment 2-19]
Using peeling layer formation composition L3 obtained in embodiment 1-3, using method same as embodiment 2-12
Peeling layer is formed, the glass substrate with peeling layer has been obtained.
Then, spin coater (condition: about 15 seconds under revolving speed 200rpm) is used immediately, the peeling layer on above-mentioned glass substrate
Resin substrate formation composition F7 is coated on (resin film).Obtained film is heated 2 points at 80 DEG C using hot plate
Then clock using hot plate, heats 30 minutes at 230 DEG C, form thick about 3 μm of resin substrate on peeling layer, obtained band
There is the glass substrate of resin substrate peeling layer.Then, using ultraviolet-uisible spectrophotometer ((strain) Shimadzu Seisakusho Ltd. UV-
2600) light transmittance is determined, as a result resin substrate shows 80% or more transmissivity at 400nm.
[embodiment 2-20]
It has used in embodiment 1-4 and has obtained in addition to replacing peeling layer formation composition L3 obtained in embodiment 1-3
Peeling layer formed with other than composition L4, peeling layer and resin substrate are made using method same as embodiment 2-19, obtained
The glass substrate with peeling layer and the glass substrate with resin substrate peeling layer are arrived.
[comparative example 2-5]
It has used in comparative example 1-1 and has obtained in addition to replacing peeling layer formation composition L3 obtained in embodiment 1-3
Peeling layer formed with other than composition HL1, peeling layer and resin substrate are made using method same as embodiment 2-12, obtained
The glass substrate with peeling layer and the glass substrate with resin substrate peeling layer are arrived.The group of peeling layer and resin substrate
It closes such as shown in table 2.
[comparative example 2-6]
Peeling layer formation composition HL2 obtained in comparative example 1-2 is used as peeling layer formation composition, as
Resin substrate formation uses resin substrate formation composition F4, use and embodiment used in embodiment 2-13 with composition
The same method production peeling layer of 2-12 and resin substrate, have obtained the glass substrate with peeling layer and have had resin substrate
The glass substrate of peeling layer.
[7] evaluation of the solvent resistance of peeling layer
The glass substrate with peeling layer made in obtained embodiment 2-1~2-20, comparative example 2-1~2-6
On peeling layer, dripped the NMP and PGME of 0.1ml using pipette.After 1 minute, after cleaning the peeling layer with pure water, by visual observation
The state for observing the peeling layer of the part for the solvent that drips, evaluates the solvent resistance of peeling layer.The following institute of criterion
It states.It shows the result in Tables 1 and 2.
< criterion >
Zero: also not seeing the trace of drop especially, do not find to dissolve.
△: see the trace of drop, it is seen that residual film.
×: dissolution.
Peeling layer does not dissolve in the solvent to drip to be meaned when foring resin substrate on peeling layer in resin substrate
It is formed in the organic solvent contained in composition and is not dissolved, it is meant that can be with not damaging resin substrate from glass substrate
Removing.
[8] evaluation of fissility
For having resin substrate peeling layer obtained in above-described embodiment 2-1~2-20 and comparative example 2-1~2-6
Glass substrate confirmed the fissility of peeling layer and glass substrate using following gimmicks.It should be noted that following tests is using same
One glass substrate carries out.
The fissility of < peeling layer and glass substrate evaluates >
By the removing on the glass substrate for having peeling layer obtained in embodiment 2-1~2-20 and comparative example 2-1~2-6
Layer cross-cut (interval 1mm in length and breadth, similarly hereinafter), has carried out the cutting of 100 grids.That is, being formd by the cross-cut
The grid in 100 four directions 1mm.
Then, in 100 mesh segmentation bonding partially adhesive tapes, which is removed, based on standard below (5B~
0B, B, A, AA) degree of removing is evaluated.
In turn, it in the substrate all removed, is removed using what is made in embodiment 2-5~2-20 with resin substrate
The glass substrate of layer, implements peeling force evaluation test.Test method is the glass base for having resin substrate peeling layer
The resin substrate of plate forms cut mark with 25mm × 50mm wide rectangle, using paper knife so as to penetrate into the back of resin substrate
Face makes strip.In turn, after pasting adhesive tape (NICHIBAN CT-24) in the strip of production, AUTOGRAPH is used
AG-500N (manufacture of (strain) Shimadzu Seisakusho Ltd.), relative to the face of substrate, with 90 degree, vertically remove, measurement removing
Power, by 100% removing (all removing) and situation of the peeling force less than 0.1N/25mm is denoted as AAA.
It the above results are shown in Tables 1 and 2.
< criterion >
5B:0% removes (no removing)
4B: the removing less than 5%
3B:5% or more and removing less than 15%
2B:15% or more and removing less than 35%
1B:35% or more and removing less than 65%
0B:65% or more and removing less than 80%
B:80% or more and removing less than 95%
A:95% or more and removing less than 100%
AA:100% removing (all removings)
AAA:100% is removed and peeling force is less than 0.1N/25mm
The fissility of < peeling layer and resin substrate evaluates >
For having the glass of resin substrate peeling layer obtained in embodiment 2-1~2-20 and comparative example 2-1~2-6
Substrate evaluates its fissility using same step is evaluated with above-mentioned fissility.Show the result in Tables 1 and 2
In.
[table 1]
[table 2]
As Table 1 and Table 2 below like that, it is thus identified that the peeling layer of embodiment 2-1~2-20 and the adaptation of glass substrate
It is excellent, it is easily peeled off with resin film.In addition, also confirmed also by the result of dissolubility test not in resin substrate formation group
It closes and is dissolved in organic solvent contained in object.
On the other hand, it is thus identified that the peeling layer of comparative example 2-1~2-6 and the excellent adhesion of glass substrate, but and resin
The fissility of substrate is poor.
Claims (10)
1. peeling layer, which is formed, uses composition, which is characterized in that it include the polyamic acid and organic solvent indicated by following formula (1),
[changing 1]
In formula, X indicates that the aromatic group indicated by following formula (2a) or (2b), Y indicate the aromatic group with the divalent of fluorine atom
Group, Z indicate to be indicated by following formula (3a) or (4a) independently of each other in the case where X is the aromatic group indicated by formula (2a)
Aromatic group, in the case where X is the aromatic group indicated by formula (2b), indicate independently of each other by following formula (3b) or
The aromatic group that (4b) is indicated, m indicate natural number,
[changing 2]
[changing 3]
2. peeling layer according to claim 1, which is formed, uses composition, wherein the Y is the aromatics indicated by following formula (5)
Group,
[changing 4]
3. peeling layer according to claim 2, which is formed, uses composition, wherein the Y is the aromatics indicated by following formula (6)
Group,
[changing 5]
4. peeling layer described in any one of claim 1 to 3, which is formed, uses composition, wherein in the X, by described
The aromatic group that formula (2a) indicates is the aromatic group indicated by following formula (7a) or (8a), and the Z is under independently of each other
The aromatic group that formula (9a) or formula (10a) indicate is stated,
[changing 6]
[changing 7]
5. peeling layer described in any one of claim 1 to 3, which is formed, uses composition, wherein in the X, by described
The aromatic group that formula (2b) indicates is the aromatic group indicated by following formula (7b) or (8b), and the Z is under independently of each other
The aromatic group that formula (9b) or formula (10b) indicate is stated,
[changing 8]
[changing 9]
6. peeling layer according to any one of claims 1 to 5, which is formed, uses composition, wherein the organic solvent is choosing
It is at least one kind of in organic solvent by following formula (S1)~(S7) structure indicated from having,
[changing 10]
In formula, R1~R8The alkyl of hydrogen atom or carbon atom number 1~10, R are indicated independently of each other9And R10It indicates independently of each other
The acyl group of hydrogen atom, the alkyl of carbon atom number 1~10 or carbon atom number 1~10, b and n indicate natural number.
7. peeling layer according to claim 6, which is formed, uses composition, wherein the organic solvent is propylene glycol monomethyl ether
Or propylene glycol monomethyl ether.
8. the peeling layer formed using peeling layer formation described in any one of claim 1~7 with composition.
9. the manufacturing method of resin substrate uses peeling layer according to any one of claims 8.
10. manufacturing method according to claim 9, wherein the resin substrate is polyimide resin substrate or wavelength
The resin substrate that the light transmittance of 400nm is 80% or more.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2016152507 | 2016-08-03 | ||
| JP2016-152549 | 2016-08-03 | ||
| JP2016152549 | 2016-08-03 | ||
| JP2016-152507 | 2016-08-03 | ||
| PCT/JP2017/028204 WO2018025953A1 (en) | 2016-08-03 | 2017-08-03 | Composition for forming release layer, and release layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109476951A true CN109476951A (en) | 2019-03-15 |
| CN109476951B CN109476951B (en) | 2022-07-29 |
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| CN201780046634.2A Active CN109476951B (en) | 2016-08-03 | 2017-08-03 | Composition for forming release layer and release layer |
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| JP (1) | JP7063266B2 (en) |
| KR (2) | KR20230020011A (en) |
| CN (1) | CN109476951B (en) |
| TW (1) | TWI737781B (en) |
| WO (1) | WO2018025953A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| CN115003505A (en) * | 2020-01-21 | 2022-09-02 | 日产化学株式会社 | Composition for forming peeling layer for alkali glass and peeling layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20220120621A (en) * | 2019-12-25 | 2022-08-30 | 닛산 가가쿠 가부시키가이샤 | A composition for forming a release layer and a release layer |
| CN116917399A (en) * | 2021-03-03 | 2023-10-20 | 日产化学株式会社 | Compositions and release layers for forming release layers |
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| Publication number | Publication date |
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| TWI737781B (en) | 2021-09-01 |
| JP7063266B2 (en) | 2022-05-09 |
| TW201817775A (en) | 2018-05-16 |
| CN109476951B (en) | 2022-07-29 |
| KR20230020011A (en) | 2023-02-09 |
| WO2018025953A1 (en) | 2018-02-08 |
| KR20190037265A (en) | 2019-04-05 |
| JPWO2018025953A1 (en) | 2019-06-06 |
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