CN106133077A - Peel ply formation compositions - Google Patents

Peel ply formation compositions Download PDF

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Publication number
CN106133077A
CN106133077A CN201580017801.1A CN201580017801A CN106133077A CN 106133077 A CN106133077 A CN 106133077A CN 201580017801 A CN201580017801 A CN 201580017801A CN 106133077 A CN106133077 A CN 106133077A
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peel ply
formula
compositions
represent
formation compositions
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CN106133077B (en
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江原和也
小出泰之
进藤和也
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to CN201810542076.5A priority Critical patent/CN108690495B/en
Priority to CN201810541291.3A priority patent/CN108690494B/en
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G73/18—Polybenzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Thin Film Transistor (AREA)

Abstract

Pass through the present invention, a kind of compositions for forming following peel ply can be provided, described peel ply can maintain and arrange the glass substrate of this peel ply adaptation thus not interface between glass substrate be peeling, also can realize will be formed in the layer on peel ply top simultaneously or layer group is peeled off simply from this peel ply.The present invention provides following peel ply formation compositions, described peel ply formation compositions contains polyamic acid and organic solvent, described polyamic acid comprises the monomeric unit shown in formula (1) of 50 moles of more than %, and weight average molecular weight is 10, more than 000.Herein, in formula (1), X1Represent the organic group of tetravalence, Y1Represent the divalent group shown in following formula (P).

Description

Peel ply formation compositions
Technical field
The present invention relates to for being formed at the peel ply that the top (ガ ラ ス substrate is straight) being in close proximity to glass substrate is arranged Compositions.
Background technology
In recent years, for electronic device, giving its flexible function, slimming and light-weighted performance is to make us Desired.Because of this it may be desirable to use the flexible plastic substrates of light weight, replace conventional heavy and fragile and unyielding glass Glass substrate.Additionally, for a new generation's display, it is desirable to use the flexible plastic substrates of light weight to develop active full-color (active full-color) TFT display floater.
Therefore, starting the manufacture method of the electronic device using resin molding as substrate is carried out various research, The technique that existing TFT equipment can be diverted to manufacture a new generation's display is studied.
Patent documentation 1,2 and 3 discloses following method: form amorphous thin Film layers on the glass substrate, at this thin layer After upper formation plastic base, from glass surface side irradiating laser, utilize the hydrogen produced with the crystallization of non-crystalline silicon and by plastics Substrate is peeled off from glass substrate.
Additionally, patent document 4 discloses that and use the technology disclosed in patent documentation 1～3 will be stripped layer (patent documentation 4 Described in for " being transferred layer (by writing) ") be attached at plastic foil thus make the method for liquid crystal indicator.
But, method disclosed in patent documentation 1～4 (especially method disclosed in patent documentation 4) must use light transmission , there is following problems: be enough to make laser pass through substrate and then make the hydrogen contained in non-crystalline silicon release to bestow in high substrate Energy, the irradiation of laser largely is considered as necessary, and it will cause damage to being stripped layer.Additionally, due to laser Process needs the long period, and by have larger area be stripped layer peel off be difficult, therefore there is also and be difficult to improve The problem of the productivity ratio of element manufacturing.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-125929 publication.
Patent documentation 2: Japanese Unexamined Patent Publication 10-125931 publication.
Patent documentation 3:WO2005/050754 pamphlet.
Patent documentation 4: Japanese Unexamined Patent Publication 10-125930 publication.
Summary of the invention
Invent problem to be solved
Therefore, it is an object of the invention to solve above-mentioned problem.
Specifically, it is an object of the invention to provide the compositions for forming following peel ply, described peel ply is used This peel ply is peeled off in the case of the substrate being applicable to flexible electronic device is not caused damage in realization.
It addition, in addition to above-mentioned purpose, or beyond above-mentioned purpose, the present invention also aims to provide for shape Becoming the compositions of following peel ply, described peel ply can maintain and arrange the adaptation of the glass substrate of this peel ply thus not exist And the interface between glass substrate is peeling, also can realize will be formed in the layer on peel ply top or layer group from this stripping simultaneously Absciss layer is peeled off simply.
For solving the means of problem
This time, present inventor is made that following such invention.That is, present inventor sends out unexpectedly Existing, when using the compositions containing following polyamic acid and organic solvent to form peel ply, this layer has can be to being suitable for The ideal characterisitics being stripped in the case of the substrate of flexible electronic device etc. causes damage, described polyamic acid contains 50 and rubs The monomeric unit of the ad hoc structure of your more than %, and weight average molecular weight is more than certain value.Above-mentioned layer not only can maintain and set The interface putting the adaptation of the glass substrate of this peel ply thus be not easy between glass substrate is peeling, Er Qieling On the one hand, for being layer or the layer group that opposition side is formed at peel ply top with glass substrate, can be simple from peel ply by it Ground is peeled off.The present invention is with the above-mentioned invention being found to be basis.
＜ 1 ＞ peel ply formation compositions, it contains polyamic acid and organic solvent, and described polyamic acid comprises 50 and rubs The monomeric unit shown in following formula (1) of you more than %, the weight average molecular weight of described polyamic acid is 10, more than 000.
[in formula (1), X1Represent the organic group of tetravalence, Y1Represent the divalent group shown in following formula (P)；
(in formula (P), R represents F, Cl, the alkyl of carbon number 1～3 or phenyl, and m represents the integer of 0～4, and, r table Show the integer of 1～4)].
In ＜ 2 ＞ above-mentioned ＜ 1 ＞, described Y1It is preferably any one the shown bilvalent radical in following formula (P1)～(P3) Group.
(in formula (P1)～(P3), R1、R2、R3、R4、R5And R6Can be the same or different, represent F, Cl, carbon number 1 ～the alkyl of 3 or phenyl,
M1, m2, m3, m4, m5 and m6 can be the same or different, and represent the integer of 0～4).
In ＜ 3 ＞ above-mentioned ＜ 2 ＞, described Y1Divalent group shown in the most contained (P1).
In any one in ＜ 4 ＞ above-mentioned ＜ 1 ＞～＜ 3 ＞, polyamic acid the most also comprises the list shown in following formula (2) Body unit.
[in formula (2), X1As defined in above-mentioned ＜ 1 ＞, Y2Represent the group shown in following formula (P4)；
(in formula (P4), R7And R8Can be the same or different, represent F, Cl, the alkyl of carbon number 1～3 or phenyl,
R ' represents hydrogen atom, the alkyl of carbon number 1～3 or phenyl,
L represents the integer of 0～4, and
M is as defined in above-mentioned ＜ 1 ＞)].
In any one in ＜ 5 ＞ above-mentioned ＜ 1 ＞～＜ 4 ＞, X1It is preferably the aromatic group of tetravalence.
In ＜ 6 ＞ above-mentioned ＜ 5 ＞, the aromatic group of described tetravalence preferably has selected from benzene skeleton, naphthalene skeleton and biphenyl At least one in skeleton.
In any one in ＜ 7 ＞ above-mentioned ＜ 1 ＞～＜ 6 ＞, described organic solvent is preferably following formula (A) or (B) institute The solvent shown.
(in formula (A) and (B), RaAnd RbCan be the same or different, represent the alkyl of carbon number 1～4, h represents certainly So number).
In any one in ＜ 8 ＞ above-mentioned ＜ 1 ＞～＜ 7 ＞, the monomer shown in described formula (1) in described polyamic acid The content of unit is preferably 60 moles of more than %.
In any one in ＜ 9 ＞ above-mentioned ＜ 1 ＞～＜ 8 ＞, the peel ply formation of the present invention is preferably by compositions and uses In the compositions being formed at the peel ply being provided above being in close proximity to glass substrate.
＜ 10 ＞ peel ply, it is in the stripping being applicable between the flexible base board of flexible electronic device and basal substrate formation Absciss layer, wherein, described peel ply is that the peel ply formation compositions in using any one of above-mentioned ＜ 1 ＞～＜ 9 ＞ makes 's.
＜ 11 ＞ board structure, it is the board structure being applicable to flexible electronic device, it is characterised in that including:
Basal substrate；
Peel ply, described peel ply in matrix described in the region overlay of 1 or more than 2, and, described peel ply It is that the peel ply formation compositions in utilizing any one of above-mentioned ＜ 1 ＞～＜ 9 ＞ is formed；With
Flexible base board, described flexible base board covers described basal substrate and described peel ply,
Further, closely sealed than described peel ply and described matrix of described flexible base board and the closing force of described peel ply Power is big.
In ＜ 12 ＞ above-mentioned ＜ 11 ＞, basal substrate preferably comprises glass.
The manufacture method of ＜ 13 ＞ peel ply, it is characterised in that the stripping in using any one of above-mentioned ＜ 1 ＞～＜ 9 ＞ Absciss layer formation compositions.In a kind of optimal way, the manufacture method of described peel ply includes forming described peel ply using Resin combination is coated substrate and carries out the operation heated.
＜ 14 ＞ is applicable to the manufacture method of the board structure of flexible electronic device, it is characterised in that include following operation:
Prepare the operation of basal substrate；
Peel ply formation compositions in using any one of above-mentioned ＜ 1 ＞～＜ 9 ＞ makes the operation of peel ply, institute State peel ply in matrix described in the region overlay of 1 or more than 2；With
Described basal substrate and described peel ply are formed the operation of flexible base board,
Further, closely sealed than described peel ply and described matrix of described flexible base board and the closing force of described peel ply Power is big.
The effect of invention
By the invention it is possible to solve above-mentioned problem.
Specifically, by means of the invention it is possible to provide the compositions for forming following peel ply, described peel ply is used for Realize being peeled off by this peel ply in the case of the substrate being applicable to flexible electronic device does not causes damage.
It addition, in addition to the above-described effects, or beyond the effect above, also provide for for being formed following by the present invention The compositions of peel ply, described peel ply can maintain and arrange the glass substrate of this peel ply adaptation thus not with glass Interface between substrate is peeling, and also can realize will be formed in the layer on peel ply top or layer group from this peel ply letter simultaneously Change places stripping.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
Peel ply formation compositions
As it has been described above, the peel ply formation compositions of the present invention contains polyamic acid and organic solvent, described polyamide Acid comprises the monomeric unit shown in formula (1) of 50 moles of more than %, and its weight average molecular weight is 10, more than 000.
It addition, as it has been described above, in formula (1), X1Represent the organic group of tetravalence, Y1Represent the bilvalent radical shown in following formula (P) Group.
It addition, in formula (P), R represents F, Cl or the alkyl of carbon number 1～3 or phenyl, preferably represents F, Cl.Equally Ground, in above-mentioned formula (P), m represents the integer of 0～4, preferably represents 0～2, more preferably represents 0～1, particularly preferably represent 0.Separately Outward, in above-mentioned formula (P), r represents the integer of 1～3.
It should be noted that the alkyl of carbon number 1～3 includes methyl, ethyl, n-pro-pyl and isopropyl, carbon number The alkyl of 1～3 is preferably methyl, more preferably methyl.
The weight average molecular weight of the polyamic acid with the monomeric unit shown in formula (1) used in the present invention is necessary for 10, More than 000, preferably 15, more than 000, more preferably 20, more than 000, the most preferably 30, more than 000.The opposing party Face, about the higher limit of the weight average molecular weight of the polyamic acid used in the present invention, it typically is 2, and less than 000,000, but examine When the excess stickiness considering suppression resin combination raises, repeatability obtains the high resin film etc. of flexibility well, it is preferably Less than 1,000,000, more preferably 200, less than 000.
The polyamic acid used in the present invention contains 50 moles of more than %, preferably 60 moles more than %, more preferably 70 rubs The monomer list shown in formula (1) of you more than %, the most preferably 80 moles more than %, the most preferably 90 moles of more than % Unit.By using monomer unit content polyamic acid as above, it is possible to repeatability obtains well to have and is suitable to stripping film The resin film of characteristic.
According to the optimal way of the present invention, the polyamic acid that the peel ply formation compositions of the present invention contains is only by formula (1) polymer that the monomeric unit shown in is formed, i.e. be to contain the poly-of the monomeric unit shown in formula (1) with the amount of 100 moles of % Compound.Now, for the monomeric unit in such polyamic acid, as long as it is the monomeric unit shown in formula (1), then may be used With the most specific a kind, it is also possible to for two or more.In the latter case, the monomeric unit of the formula (1) that polyamic acid contains Number be preferably 2～4, more preferably 2～3.
In the present invention, the group shown in formula (P) preferably comprises any one shown divalent group in formula (P1)～(P3), more Preferably comprise the divalent group shown in formula (P1) or (P3), further preferably comprise the divalent group shown in formula (P3).
In above-mentioned formula (P1), formula (P2) and formula (P3), R1、R2、R3、R4、R5And R6Can be the same or different, expression F, Cl, the alkyl of carbon number 1～3 or phenyl, preferably represent F or Cl.
Similarly, in above-mentioned formula (P1), formula (P2) and formula (P3), m1, m2, m3, m4, m5 and m6 can identical can also Difference, represents the integer of 0～4, preferably represents 0～2, more preferably represents 0～1, particularly preferably represent 0.
The polyamic acid used in the present invention is in addition to containing the monomeric unit shown in formula (1), it is also possible to containing other Monomeric unit.The content of other monomeric units as above have to be lower than 50 moles of %, preferably shorter than 40 moles %, more preferably Less than 30 moles of %, the most preferably shorter than 20 moles %, the most preferably shorter than 10 moles %.
As other monomeric units as above, such as, can enumerate the monomeric unit of formula (2).
In formula (2), X1Represent the organic group of tetravalence, Y2Represent the above-mentioned group shown in formula (P4).
In formula (P4), R7And R8Can be the same or different, represent F, Cl, the alkyl of carbon number 1～3 or phenyl. R7Preferably represent F or Cl.R8Preferably represent F or Cl.
R ' represents hydrogen atom, the alkyl of carbon number 1～3 or phenyl, preferably represents hydrogen atom or carbon number 1～3 Alkyl, more preferably represent hydrogen atom.
Additionally, l and m can be the same or different, represent 0～4 integer, preferably represent 0～2, more preferably represent 0～ 1, particularly preferably represent 0.
As other monomeric units as above, in addition to the monomeric unit of above-mentioned formula (2), it is also possible to enumerate by The structure etc. that following diamidogen and following acid dianhydride derive, described diamidogen is o-phenylenediamine, m-diaminobenzene., p-phenylenediamine, 2- Methyl isophthalic acid, 4-phenylenediamine, 5-methyl isophthalic acid, 3-phenylenediamine, 4-methyl isophthalic acid, 3-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2-(trifluoromethyl)-1,3-phenylenediamine and 4-(trifluoromethyl)-1,3-phenylenediamine, benzidine, 2,2 '-dimethylbenzidine, 3, 3 '-dimethylbenzidine, 2,3 '-dimethylbenzidine, 2,2 '-bis-(trifluoromethyl) benzidine, 3,3 '-bis-(trifluoromethyls) join Aniline, 2,3 '-bis-(trifluoromethyl) benzidine, 4,4 '-diphenyl ether, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-two Aminobenzoic anilide, 5-amino-2-(3-aminophenyl)-1H-benzimidazole, 9, double (4-aminophenyl) fluorenes of 9-etc., described Acid dianhydride be pyromellitic dianhydride (PMDA), 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, the double phthalic anhydride of 4,4 '-epoxide, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid anhydride etc..
In formula (1) and formula (2), as it has been described above, X1Aromatic group for the organic group of tetravalence, preferably tetravalence.
During the polyamic acid used in making the present invention, X1The aromatic group of the tetravalence that can take can be by using Aromatic tetracarboxylic acid's dianhydride as described below and make.
I.e., it is possible to enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone Tetracarboxylic acid dianhydride, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid dianhydride, 1,4,5,8-naphthalene tetramethyl Acid dianhydride, 1,2,5,6-naphthalenetetracarbacidic acidic dianhydride, 4,4 '-epoxide double phthalic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silicon Alkane tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4 '-bis-(3, 4-di carboxyl phenyloxy) diphenyl propane dianhydride, the double phthalic anhydride of 4,4 '-hexafluoroisopropylidenyl, adjacent benzene two double to penylene Formic acid dianhydride, 2,2-be double-(3,4-dicarboxyphenyi)-hexafluoropropane dianhydride, double (3,4-dicarboxyphenyi) the fluorenes dianhydride of 9,9-, 9, 9 '-bis-[4-(3,4-di carboxyl phenyloxy) phenyl] fluorenes dianhydrides, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 2,3,5,6-pyridine Tetracarboxylic acid dianhydride, 3,4,9,10-tetracarboxylic acid dianhydride, 4,4 '-sulfonyl double O-phthalic acid dianhydride, para-terpheny-3,3 ', 4, 4 '-tetracarboxylic acid dianhydride, meta-terphenyl-3,3 ', 4,4 '-tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 1,3-are double (3,4-dicarboxyphenyi)-1,1,3,3-tetramethyl disiloxane dianhydride, 1-(2,3-dicarboxyphenyi)-3-(3,4-dicarboxyl Phenyl)-1,1,3,3-tetramethyl disiloxane dianhydride, 3,3 ', 4,4 '-hydroquinone dibenzoate tetracarboxylic acid dianhydride, 2,2 '- Double (4-hydroxy phenyl) propane dibenzoate-3,3 ', 4,4 '-tetracarboxylic acid etc..
Preferably, preferably aromatic tetracarboxylic acid's dianhydride is selected from following compound group herein.
(in formula, R3It is the divalent organic group at least with an aromatic rings, it is however preferred to have phenyl, xenyl, naphthalene bone The group of frame).
Therefore, according to the optimal way of the present invention, X1The aromatic group of the tetravalence that can take has benzene skeleton, naphthalene bone Any skeleton in frame, biphenyl backbone, terphenyl skeleton, more preferably has any bone in benzene skeleton, naphthalene skeleton, biphenyl backbone Frame, further preferably has any skeleton in benzene skeleton, biphenyl backbone.
According to the optimal way of the present invention, the polyamic acid used in the present invention can pass through to make 3,3 ' as acid dianhydride, 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) (formula (4)) and the p-phenylenediamine (pPDA) (formula (5)) and 4,4 as diamidogen "-diamino Base para-terpheny (DATP) (formula (6)) reacts and obtains, or makes pyromellitic acid anhydride (the PMDA) (formula as acid dianhydride (7)) react with the pPDA (formula (5)) as diamidogen and obtain.
In above-mentioned reaction, for 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) and by p-phenylenediamine (pPDA) and 4, 4 " diamidogen that-diaminourea para-terpheny (DATP) forms, or the charging of pyromellitic acid anhydride (PMDA) and pPDA than (mole Than) for, it is contemplated that the molecular weight of desired polyamic acid, the ratio etc. of monomeric unit and suitably set, make with amine component If being 1, generally can make anhydride composition is 0.7～about 1.3, preferably 0.8～about 1.2.
On the other hand, for the charging ratio of pPDA with DATP as diamidogen, by the amount (m of the material of DATP2) During as 1, generally can make the amount (m of the material of pPDA1) be 1.7～about 20, preferably 2.1～20, more preferably 2.2～ 20, the most preferably 2.3～19, much further preferably from 2.3～18.That is, for m1And m2For, generally, m1/m2= 1.7～20, preferably 2.1～20, more preferably 2.2～20, the most preferably 2.3～19, much further preferably from 2.3 ～18.
Above-mentioned reaction is carried out in organic solvent.That is, the peel ply formation compositions of the present invention contains described having Machine solvent.For the most spendable organic solvent, as long as bringing harmful effect to above-mentioned reaction, can use various molten Agent.
As concrete example, metacresol, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrroles can be enumerated Alkanone, NVP, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, 3-methoxyl group-N, N-diformazan Base propionic acid amide., 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-tertiary fourth oxygen The protonic solvents etc. such as base-N, N-dimethylpropionamide, gamma-butyrolacton.They can be used alone, or can also combine 2 Use more than kind.
According to the optimal way of the present invention, organic solvent is the solvent shown in formula (A) or (B).
In formula (A) and formula (B), RaAnd RbCan be the same or different, represent the alkyl of carbon number 1～4, preferably carbon Atomic number is 1～3.It addition, herein, h represents natural number, preferably 1～3.
For reaction temperature, suitably set to boiling point, generally at the fusing point from the solvent used It is about 0～100 DEG C, in order to prevent the imidizate of the polyamic acid obtained, and maintains the high-load of polyamic acid unit, instead Temperature is answered to be preferably about 0～70 DEG C, more preferably about 0～60 DEG C, the most preferably about 0～50 DEG C.
Response time depends on the reactivity of reaction temperature, raw material, thus cannot without exception depending on, but it typically is 1 ～about 100 hours.
Utilize method described above, the reaction solution containing target polyamic acid can be obtained.
In the present invention, generally, after above-mentioned reaction solution is filtered, its filtrate is formed directly as peel ply and uses Compositions uses, or uses as peel ply formation compositions after being diluted or concentrating.Operate as described above, Can not only reduce may result in the thermostability of the resin film obtained, impurity that flexibility or linear expansion coefficient characteristic are deteriorated mixed Enter, and compositions can be efficiently obtained by.
Solvent for being diluted or concentrating is not particularly limited, and such as, can enumerate and the reaction dissolvent of above-mentioned reaction The same solvent of concrete example, they can be used alone, or also two or more be can be combined and use.
In above-mentioned solvent, it is considered to when repeatability obtains the resin film of high flatness (flatness) well, as making Solvent, preferably DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, 1,3-dimethyl- 2-imidazolone (imidazolidinone), N-ethyl-2-pyrrolidone, gamma-butyrolacton.
For polyamic acid for peel ply formation is by the concentration of compositions gross mass, it is considered to the thin film of making The thickness of (peel ply), composition viscosity etc. and suitably set, usually about 0.5～30 mass %, preferably 5～25 matter Amount about %.
It addition, for the viscosity of peel ply formation compositions, it is also considered that the thickness of the thin film of making etc. and suitable Set, but for the purpose of the resin film of the thickness obtained well by repeatability about especially 0.05～5 μm in the case of, The viscosity of peel ply formation compositions is generally 10～10 when 25 DEG C, 000mPa about s, preferably 20～ 1000mPa about s, more preferably 20～200mPa about s.
Herein, for the viscosity of peel ply formation compositions, can use and be commercially for measuring liquid viscosity Viscometer, referring for example to the step described in JIS K7117-2, in the condition that temperature is 25 DEG C of peel ply formation compositions Under be measured.Preferably, mensuration can be carried out as follows: use cone-plate type (cone plate type) rotating cylinder viscometer as viscous Degree meter, preferably use when using the viscometer of the type 1 ° of 34 ' × R24 as standard cone rotor (cone rotor), Peel ply formation compositions temperature is measured under conditions of being 25 DEG C.As such rotating cylinder viscometer, such as, can enumerate Toki Sangyo Co., Ltd. TVE-25H.
It should be noted that the compositions of the present invention is in addition to containing polyamic acid and organic solvent, it is also possible to containing each Plant composition.For example, it is possible to enumerate cross-linking agent (hereinafter also referred to as cross-linked compound.), but it is not limited to this.
As above-mentioned cross-linked compound, such as, can enumerate the compound containing more than 2 epoxy radicals, there is amino Hydrogen atom by methylol, alkoxy methyl or both replace obtained by the melamine derivative of group, benzoguanamine derivant Or glycoluril etc., but it is not limited to this.
Hereinafter enumerate the concrete example of cross-linked compound, but be not limited to this.
As the compound containing more than 2 epoxy radicals, can enumerate Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celloxide 2021, Celloxide 3000 (are Co., Ltd. above Daicel system) etc. there is the epoxide of cyclohexene；Epikote1001、Epikote 1002、Epikote 1003、 Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (are Japan above Epoxy Resin Co., Ltd. system (existing: Mitsubishi chemical Co., Ltd's system, jER (registered trade mark) series)) etc. bisphenol type epoxy Compound；The bisphenol F type epoxy compounds such as Epikote 807 (Japan Epoxy Resin Co., Ltd. system)；Epikote 152, Epikote 154 (be that Japan Epoxy Resin Co., Ltd. system (shows: Mitsubishi chemical Co., Ltd's system, jER above (registered trade mark) series)), the phenol Novolacs type such as EPPN 201, EPPN 202 (being Nippon Kayaku K. K's system above) Epoxide；ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (are above Nippon Kayaku K. K's system), (Japan Epoxy Resin Co., Ltd. is (existing: Mitsubishi Chemical's strain formula for Epikote 180S75 Commercial firm's system, jER (registered trade mark) series) system) and etc. cresol Novolacs type epoxide；V8000-C7 (Dainippon Ink Chemicals System) etc. naphthalene type epoxide；Denacol EX-252 (Nagase ChemteX Co., Ltd. system), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (being BASF AG's system above), Epiclon 200, Epiclon 400 (above for Dainippon Ink Chemicals's system), Epikote 871, Epikote 872 (are above Japan Epoxy Resin Co., Ltd.'s system (existing: Mitsubishi chemical Co., Ltd's system, jER (registered trade mark) series)), ED- 5661, the cycloaliphatic epoxy such as ED-5662 (be above Celanese Coating Co., Ltd. system)；Denacol EX- 611、Denacol EX-612、Denacol EX-614、Denacol EX-622、Denacol EX-411、Denacol EX- 512、Denacol EX-522、Denacol EX-421、Denacol EX-313、Denacol EX-314、Denacol EX- The aliphatic polyglycidyl ether compounds such as 312 (are above Nagase ChemteX Co., Ltd. system).
As have the hydrogen atom of amino by methylol, alkoxy methyl or both replace obtained by the melamine of group Amine derivative, benzoguanamine derivant or glycoluril, can enumerate every 1 triazine ring and be averaged 3.7 substituted MX-of methoxy 750, every 1 triazine ring is averaged 5.8 substituted MW-30 of methoxy (above for Sanwa Co., Ltd.'s chemistry system)； Cymel 300、Cymel 301、Cymel 303、Cymel 350、Cymel 370、Cymel 771、Cymel 325、Cymel 327, the methoxymethylated tripolycyanamide such as Cymel 703, Cymel 712；Cymel 235、Cymel 236、Cymel 238、 The methoxymethylated butoxymethyl tripolycyanamide such as Cymel 212, Cymel 253, Cymel 254；Cymel 506、 The butoxymethyl tripolycyanamide such as Cymel 508；The such methoxymethylated isobutyl oxygen containing carboxyl of Cymel 1141 Ylmethyl tripolycyanamide；The such methoxymethylated ethoxyl methyl benzoguanamine of Cymel 1123；Cymel 1123-10 Such methoxymethylated butoxymethyl benzoguanamine；Cymel 1128 such butoxymethyl benzoguanamine；Cymel The such methoxymethylated ethoxyl methyl benzoguanamine containing carboxyl of 1125-80；The such butoxy of Cymel 1170 Methylate glycoluril；Cymel 1172 such methylolation glycoluril (be above Mitsui Cyanamid Co., Ltd. system (show: Nihon Cytec Industries Co., Ltd.) etc..
By the peel ply formation compositions of present invention mentioned above is coated matrix and heated, available There is the thin film (peel ply) formed by polyimides of the linear expansion coefficient of high-fire resistance, the flexibility of appropriateness and appropriateness.
As matrix (base material), for example, it is possible to it is (Merlon, polymethacrylates, poly-to enumerate glass, plastics Styrene, polyester, polyolefin, epoxy, tripolycyanamide, triacetyl cellulose, ABS, AS, norbornene resin etc.), metal (silicon wafer etc.), timber, paper, slabstone (slate) etc..
The method being coated is not particularly limited, and such as, can enumerate casting coating (cast coat method), spin coating Method, scraper for coating method, dip coating, rolling method, stick coating method, die coating method, spurt method, print process (relief printing plate, intaglio plate, lithographic plate, screen printing Brush etc.) etc..
It addition, as making the method for polyamic acid imidizate that contains in the peel ply formation compositions of the present invention, The hot-imide directly compositions having been coated with on substrate heated can be enumerated and add catalyst in the composition And carry out the catalyst imidizate heated.
For the catalyst imidizate of polyamic acid, by adding in the peel ply formation compositions of the present invention Adding catalyst and be stirred, preparation is added with the compositions of catalyst, then, to base plate coating and heat, thus may be used Obtain resin film (peel ply).The amount of catalyst is 0.1～30 mole times of amic acid group, preferably 1～20 mole times. Additionally, it is possible in the compositions be added with catalyst, add the acetic anhydride etc. as dehydrant, in an amount of from the 1 of amic acid group ～50 moles times, preferably 3～30 moles times.
As imidization catalyst, tertiary amine is preferably used.As tertiary amine, preferably pyridine, substituted-pyridines, imidazoles, take For imidazoles, picoline, quinoline, isoquinolin etc..
Heating-up temperature when hot-imide and catalyst imidizate is preferably less than 450 DEG C.During higher than 450 DEG C, deposit Become fragile at the resin film obtained, cannot obtain being suitable to the situation of the resin film of intended applications.
Additionally, it is contemplated that when the thermostability of the resin film obtained and linear expansion coefficient characteristic, it is preferred that in 50 DEG C～ After 100 DEG C of compositionss by coating heat 5 minutes～2 hours, the most stepwise raise heating-up temperature, finally higher than 375 DEG C and be at a temperature of less than 450 DEG C heat 30 minutes～4 hours.
For the compositions of coating, it is therefore particularly preferred that after 50 DEG C～100 DEG C heating 5 minutes～2 hours, Higher than 100 DEG C and be at a temperature of less than 200 DEG C heat 5 minutes～2 hours, it follows that higher than 200 DEG C and be 375 DEG C with At a temperature of Xia heat 5 minutes～2 hours, finally, higher than 375 DEG C and be at a temperature of less than 450 DEG C heating 30 minutes～4 Hour.
About the utensil for heating, such as, heating plate, baking oven etc. can be enumerated.For heating atmosphere, can be Under air, it is also possible to be under non-active gas, furthermore it is possible to be at ambient pressure, it is also possible to be under reduced pressure.
About the thickness of resin film, especially when using as peel ply, usually about 0.01～10 μm, preferably It is about 0.05～5 μm, adjusts the thickness of the film before heating thus form the resin film of desired thickness.
The substrate being applicable to flexible electronic device is not being caused damage most suitable as realization by thin film described above The peel ply carrying out in the case of wound peeling off uses.
By the compositions of the application, it is possible to formed and may be provided at flexible base board and the substrate being applicable to flexible electronic device Peel ply between substrate.As basal substrate, preferably comprise the basal substrate of glass or silicon wafer, more preferably comprise glass Glass.
For example, it is possible to utilize the most known method the compositions of the application to be coated on glass substrate, and with regulation Temperature the coated film obtained is heated, be consequently formed peel ply.
Can be formed on peel ply additionally, be stripped body layer.Being stripped body layer can be monolayer, it is also possible to for multilamellar. For the making of various devices, it reality is multilamellar.
For be stripped in body layer be located close in the layer of the top of peel ply for, although depend on use stripping Layer, but with the fissility of this peel ply good layer, in other words, the adaptation of the peel ply that be preferably used and use are preferably used The highest layer.
Other aspects as the application, it is provided that be stripped the manufacture method of body.
The method is by having following operation a)～c), such that it is able to obtain being stripped body.
A), after the compositions of the application being coated on glass substrate, the operation of peel ply is formed；
B) on this peel ply, formation is stripped the operation of body；And
C) operation that body is peeled off will be stripped in peel ply and the interface being stripped body；
In b) operation, " being stripped body " can be monolayer, it is also possible to for multilamellar.It should be noted that for " being stripped Body " in be located close to for the layer of the top of peel ply, although depend on the peel ply used, but be preferably used and this stripping The layer that the fissility of absciss layer is good, in other words, the layer that the adaptation of the peel ply being preferably used and using is the highest.
Another optimal way according to the present invention, it is possible to provide a kind of board structure, it is to be applicable to flexible electronic device Board structure, it is characterised in that including:
Basal substrate；
Peel ply, described peel ply in matrix described in the region overlay of 1 or more than 2, and, described peel ply It is that the peel ply formation compositions utilizing the present invention is formed；With
Flexible base board, described flexible base board covers described basal substrate and described peel ply,
Further, closely sealed than described peel ply and described matrix of described flexible base board and the closing force of described peel ply Power is big.The size of the most so-called closing force can be carried out by the such as cross-cut test shown in embodiments herein Confirm.
Hereinafter, according to embodiment, the present invention will be described, but the present invention is not limited to such an embodiment.
Embodiment
For the abbreviation used in the present embodiment, below carry out enumerating explanation.
＜ solvent ＞
NMP:N-methyl pyrrolidone.
＜ amine ＞
P-PDA: p-phenylenediamine.
APAB:2-(3-aminophenyl)-5-aminobenzimidazole.
DATP:4,4 '-diaminourea para-terpheny.
Double (3-amino-4-hydroxylphenyl) HFC-236fa of 6FAP:2,2-.
＜ acid dianhydride ＞
BPDA:3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride.
BA-TME:4,4-biphenylene is double (trimellitic acid monoester anhydride).
PMDA: pyromellitic acid anhydride.
＜ aldehyde ＞
IPHA: m-terephthal aldehyde.
[number-average molecular weight and the mensuration of weight average molecular weight]
For the weight average molecular weight (hereinafter referred to as " Mw ") and molecular weight distribution of polymer, use Japan's light splitting strain Formula commercial firm GPC device (Shodex (trade mark) post KF803L and KF805L), makes the dimethylformamide as eluting solvent Flow be 1ml/ minute, column temperature is measured under conditions of being 50 DEG C.It should be noted that Mw is polystyrene conversion value.
＜ synthesis example ＞
The synthesis ＞ of ＜ synthesis example 1 polyimide precursor P1
BPDA(98)//p-PDA(90)/DATP(10)
By molten for 17.8g (0.164 mole) p-PDA, 2.38g (0.009 mole) DATP and 2.05g (0.009 mole) APAB Solution, in the NMP of 425g, is added 52.8g (0.179 mole) BPDA simultaneously, then, is again added the NMP of 7.4g, at nitrogen gas Under atmosphere, carry out reaction in 24 hours in 23 DEG C.The Mw of the polyimide precursor P1 obtained is 63000, and molecular weight distribution is 9.9.
The synthesis ＞ of ＜ synthesis example 2 polyimide precursor P2
BPDA(98)/DATP(100)
The DATP of 30.8g (0.118 mole) is dissolved in the NMP of 425g, adds 34.1g (0.116 mole) simultaneously BPDA, then, again adds the NMP of 10g, in a nitrogen atmosphere, carries out reaction in 24 hours in 23 DEG C.Before the polyimides obtained The Mw of body P2 is 70700, and molecular weight distribution is 9.7.
The synthesis ＞ of ＜ synthesis example 3 polyimide precursor P3
PMDA(98)/p-PDA(80)/DATP(20)
20.261g (0.1875 mole) p-PDA and 12.206g (0.0469 mole) TPDA is dissolved in the NMP of 617.4g In, after cooling down in 15 DEG C, add 50.112g (0.2298 mole) PMDA, in a nitrogen atmosphere, carry out 48 hours instead in 50 DEG C Should.The Mw of the polyimide precursor P3 obtained is 82,100, and molecular weight distribution is 2.7.
The synthesis ＞ of ＜ synthesis example 4 polyimide precursor P4
BP-TME(98)//p-PDA(95)/APAB(5)
9.66g (0.089 mole) p-PDA and 1.05g (0.005 mole) APAB is dissolved in the NMP of 440g, adds 49.2g (0.092 mole) BP-TME, in a nitrogen atmosphere, carries out reaction in 24 hours in room temperature.The polyimide precursor P4 obtained Mw be 57000, molecular weight distribution is 9.3.
The synthesis ＞ of ＜ synthesis example 5 polyimide precursor P5
BPDA(98)//p-PDA(100)
3.176g (0.02937 mole) p-PDA is dissolved in the NMP of 88.2g, adds 8.624g (0.02931 mole) After BPDA, in a nitrogen atmosphere, reaction in 24 hours is carried out in 23 DEG C.The Mw of the polyimide precursor P5 obtained is 107,300, point Son amount is distributed as 4.6.
The synthesis ＞ of ＜ synthesis example 6 polybenzoxazole precursor (P6)
IHPA(98)//6FAP(100)
3.18g (0.059 mole) 6FAP is dissolved in the NMP of 70g, after adding 7.92g (0.060 mole) IPHA, Under nitrogen atmosphere, carry out reaction in 24 hours in 23 DEG C.The Mw of the polymer obtained is 107,300, and molecular weight distribution is 4.6.
The synthesis ＞ of ＜ synthesis example 7 polyimide precursor P7
PMDA(98)//p-PDA(100)
10.078g (93mmol) p-PDA is dissolved in the NMP of 220.0g.19.922g is added in the solution obtained (91mmol) PMDA, in a nitrogen atmosphere, carries out reaction in 24 hours in 23 DEG C.The Mw of the polymer obtained is 55,900, molecule Amount is distributed as 3.1.
The making ＞ of ＜ peel ply substrate
P1～the P7 NMP obtained in above-mentioned synthesis example 1～7 is diluted to 4wt%, uses spin coater to be coated with After on 100mm × 100mm glass substrate (OA-10G alkali-free glass) or silicon wafer, according to condition of cure A～C, utilize baking oven Carry out burning till thus make peel ply.
Condition of cure A: 120 DEG C maintain 30 minutes → → 300 DEG C of maintenances 60 minutes → intensification → 400 DEG C that heats up to maintain 60 points Clock.It should be noted that programming rate is 10 DEG C/min.
Condition of cure B: 120 DEG C maintain 30 minutes → → 180 DEG C of maintenances 20 minutes → intensification → 240 DEG C that heats up to maintain 20 points Clock → intensification → 300 DEG C maintain 20 minutes → → 400 DEG C of maintenances 20 minutes → intensification → 450 DEG C that heats up to maintain 60 minutes.Need Illustrating, programming rate is 10 DEG C/min.
Condition of cure C: 80 DEG C maintain 10 minutes → → 300 DEG C of maintenances 30 minutes → intensification → 400 DEG C that heats up to maintain 30 points Clock.It should be noted that programming rate is 10 DEG C/min.
Use contact elcometer (Co., Ltd. ULVAC Dektak 3ST), the coated film obtained by mensuration Thickness.
The thickness of the peel ply of the precursor of P1～P7 of use, coated substrates, condition of cure and making is shown in table 1.
Table 1
Precursor Substrate Condition of cure Thickness (μm)
Embodiment 1 P1 Glass A 0.165
Embodiment 2 P2 Glass B 0.857
Embodiment 3 P3 Glass B 0.162
Embodiment 4 P4 Glass A 0.172
Embodiment 5 P7 Glass C 0.125
Comparative example 1 P5 Silicon wafer A 0.167
Comparative example 2 P6 Glass A 0.181
Comparative example 3 P6 Silicon wafer A 0.166
＜ cross-cut test I ＞
For the embodiment 1 shown in table 1～5 and the substrate possessing peel ply of comparative example 1～3, tried by cross-cut Test I and confirm the closing force of substrate (glass or silicon wafer)/peel ply.
Cross-cut test I is carried out as described below.
(1) on film, 100 squares square for 1mm are made.
(2) then, attach above-mentioned square with Continuous pressing device for stereo-pattern (Cellotape (registered trade mark)) and carry out peeling off work Sequence.
(3) counting residues in the above-mentioned foursquare number on substrate after stripping process.
Index ＞ of the result of ＜ cross-cut test I
As the result of cross-cut test, the degree peeled off with following index expression.
5B: unstripped.
The stripping of below 4B:5%.
The stripping of 3B:5～15%.
The stripping of 2B:15～35%.
The stripping of 1B:35～65%.
The stripping of 0B:65%～80%.
The stripping of B:80%～95%.
A:95% is to the stripping less than 100%.
The stripping of AA:100%.
Intersecting cutting test I dividually, for the embodiment 1 shown in table 1～5 and comparative example 1～3 possess stripping The substrate of absciss layer, determines 1% during the weight when characteristic of the composition constituting this peel ply, i.e. (1) demonstrate heating changes The temperature that weight reduces, the refractive index at (2) wavelength 1000nm, the birefringence at (3) wavelength 1000nm, and (4) surface energy. It should be noted that the condition determinations of each characteristic etc. are as follows.
Temperature ＞ that 1% weight in weight change when ＜ (1) demonstrates heating reduces
Use Bruker Co., Ltd. TD-DTA2000ST, carry out thermogravimetric (TG) in a nitrogen atmosphere and measure, obtain weight Amount reduces by the temperature of 1%.
Refractive index at ＜ (2) wavelength 1000nm and (3) birefringence ＞
Use high-speed light spectral pattern ellipsometer test M-2000 (J.A.Woolam Japan Co., Ltd. system), measure refractive index And birefringence.It should be noted that refractive index is refractive index in the face in the numerical value at 1000nm, birefringence is face infolding Penetrate rate and specific refractivity outside face.
＜ (4) surface can ＞
Full-automatic contact angle meter DM-701 (republicanism interface science Co., Ltd. system) is used to measure the surface energy of each parts.Need It is noted that in mensuration that the solvent used is water and diiodomethane, calculates surface energy from the contact angle of these solvents.
＜ is stripped formation and disbonded test (the cross-cut test II) ＞ thereof of body
In embodiment 1～5 and the possessing to be formed on the substrate of peel ply and be stripped body of comparative example 1～3, pass through cross-cut Test II confirms its degree peeled off.
＜ ＜ is stripped the making ＞ ＞ of body layer
On this peel ply of substrate possessing peel ply, formed as the polyimide layer being stripped body.
Specifically, use bar coater, precursor P5 or P1 that will obtain in above-mentioned synthesis example 5 or synthesis example 1, coat table Embodiment shown in 1 1～5 and comparative example 1～3 the substrate possessing peel ply peel ply on.Then, utilize baking oven according under The condition of stating solidifies, make the thickness that formed by polyimides be 15 μm be stripped body layer, described condition is: 120 DEG C of dimensions Hold 30 minutes → → 180 DEG C of maintenances 20 minutes that heat up → → 240 DEG C of maintenances 20 minutes → intensification → 300 DEG C that heats up to maintain 20 minutes → heat up → 400 DEG C maintain 20 minutes → heat up → 450 DEG C maintain 60 minutes (in arbitrarily heating up, programming rate be 10 DEG C/ Minute).
＜ ＜ cross-cut test II ＞ ＞
It is stripped the substrate of body layer and peel ply for possessing of above-mentioned gained, confirms to be shelled by cross-cut test II Closing force between in vitro layer/peel ply.
Cross-cut test II is carried out in the same manner as cross-cut test I.
Temperature (in table 2, marking with " (1) ") that 1% weight in weight change when (1) demonstrate heating reduces, (2) refractive index of (2) and the difference (table 2 of birefringence are somebody's turn to do in refractive index (in table 2, marking with " (2) "), (3) at wavelength 1000nm In, with " (3) " mark), (4) surface can (in table 2, with " (4) " mark.Wherein, unit is dyne/cm), be stripped in body layer The result of the polyimide precursor used and cross-cut test I and II is shown in table 2.
Table 2
(1) (2) (3) (4) Polyimides Test I Test II
Embodiment 1 530℃ 1.80 0.21 52.1 P5 5B AA
Embodiment 2 550℃ 1.79 0.20 50.6 P5 5B AA
Embodiment 3 570℃ 1.78 0.23 52.5 P5 5B AA
Embodiment 4 500℃ 1.76 0.19 50.9 P5 5B AA
Embodiment 5 530℃ 1.75 0.22 53.8 P5 5B AA
Comparative example 1 560℃ 1.81 0.21 48.8 P5 AA **
Comparative example 2 440℃ 1.59 * 36.2 P5 5B 5B
Comparative example 3 560℃ 1.81 0.21 48.8 P1 AA **
*: the birefringence of comparative example 2 cannot measure.
The cross-cut test II of *: comparative example 1 and comparative example 3 is low with the adaptation of substrate due to peel ply, so Cannot measure.
Following conclusion can be learnt by table 2.For the peel ply of embodiment 1～5, it is 5B according to the result of test I, can Know that peel ply does not peels off from substrate, and on the other hand, be AA according to the result of test II, it is known that be only stripped body layer from peel ply Peel off.Generally speaking, it is known that the peel ply formed by the peel ply compositions of the present invention can bring desired peel results.
On the other hand, for comparative example 1 and comparative example 3, owing to the result of test I is AA, so understanding peel ply Peel off from substrate.Generally speaking, it is known that comparative example 1 and comparative example 3 can not obtain desired peel results.It addition, for For comparative example 2, be 5B according to test I and test II, it is known that the interface of peel ply and substrate and peel ply with shelled The interface of in vitro layer is the most peeling-off, it is impossible to obtain desired peel results.

Claims (14)

1. peel ply formation compositions, it contains polyamic acid and organic solvent, described polyamic acid comprise 50 moles of % with On the monomeric unit shown in following formula (1), the weight average molecular weight of described polyamic acid is 10, more than 000,
In formula (1), X1Represent the organic group of tetravalence, Y1Represent the divalent group shown in following formula (P)；
In formula (P), R represents F, Cl, the alkyl of carbon number 1～3 or phenyl, and m represents the integer of 0～4, and, r represent 1～ The integer of 4.
2. peel ply formation compositions as claimed in claim 1, wherein, described Y1For appointing in following formula (P1)～(P3) Divalent group shown in one,
In formula (P1)～(P3), R1、R2、R3、R4、R5And R6Can be the same or different, represent F, Cl, carbon number 1～3 Alkyl or phenyl,
M1, m2, m3, m4, m5 and m6 can be the same or different, and represent the integer of 0～4.
3. peel ply formation compositions as claimed in claim 2, wherein, described Y1Including at least the bivalence shown in formula (P1) Group.
4. the peel ply formation compositions as according to any one of claims 1 to 3, wherein, described polyamic acid also comprises Monomeric unit shown in following formula (2),
In formula (2), X1As defined in claim 1, Y2Represent the group shown in following formula (P4),
In formula (P4), R7And R8Can be the same or different, represent F, Cl, the alkyl of carbon number 1～3 or phenyl,
R ' represents hydrogen atom, the alkyl of carbon number 1～3 or phenyl,
L represents the integer of 0～4, and,
M is as defined in claim 1.
5. the peel ply formation compositions as according to any one of Claims 1 to 4, wherein, described X1Aromatic series for tetravalence Group.
6. compositions as claimed in claim 5, wherein, the aromatic group of described tetravalence has selected from benzene skeleton, naphthalene skeleton And at least one in biphenyl backbone.
7. the compositions as according to any one of claim 1～6, wherein, described organic solvent is following formula (A) or (B) institute The solvent shown,
In formula (A) and (B), RaAnd RbCan be the same or different, represent the alkyl of carbon number 1～4, h represents natural number.
8. the peel ply formation compositions as according to any one of claim 1～7, wherein, the institute in described polyamic acid The content stating the monomeric unit shown in formula (1) is 60 moles of more than %.
9. the peel ply formation compositions as according to any one of claim 1～8, it is used for being formed at and is in close proximity to glass base The peel ply being provided above of plate.
10. peel ply, it is at the peel ply being applicable between the flexible base board of flexible electronic device and basal substrate formation, its In, described peel ply is to use the peel ply formation compositions according to any one of claim 1～9 to make.
11. board structures, it is the board structure being applicable to flexible electronic device, it is characterised in that including:
Basal substrate；
Peel ply, described peel ply in matrix described in the region overlay of 1 or more than 2, and, described peel ply be profit Formed by peel ply formation compositions according to any one of claim 1～9；With
Flexible base board, described flexible base board covers described basal substrate and described peel ply,
Further, the closing force of described flexible base board and described peel ply is than the closing force of described peel ply Yu described matrix Greatly.
12. board structures as claimed in claim 11, wherein, basal substrate comprises glass.
The manufacture method of 13. peel plies, it is characterised in that use the peel ply according to any one of claim 1～9 to be formed and use Compositions.
The manufacture method of 14. board structures being applicable to flexible electronic device, it is characterised in that include following operation:
Prepare the operation of basal substrate；
The peel ply formation compositions according to any one of claim 1～9 is used to make the operation of peel ply, described stripping Layer is in matrix described in the region overlay of 1 or more than 2；With
Described basal substrate and described peel ply are formed the operation of flexible base board,
Further, the closing force of described flexible base board and described peel ply is than the closing force of described peel ply Yu described matrix Greatly.
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