CN104066768A - Resin composition for display substrates - Google Patents

Resin composition for display substrates Download PDF

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Publication number
CN104066768A
CN104066768A CN201280067828.8A CN201280067828A CN104066768A CN 104066768 A CN104066768 A CN 104066768A CN 201280067828 A CN201280067828 A CN 201280067828A CN 104066768 A CN104066768 A CN 104066768A
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Prior art keywords
formula
represent
carbonatoms
base plate
display base
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CN201280067828.8A
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CN104066768B (en
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江原和也
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Nissan Chemical Corp
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Nissan Chemical Corp
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • 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
    • C08G73/14—Polyamide-imides
    • 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
    • C08G73/16—Polyester-imides
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Abstract

The invention aims to provide a resin composition for display substrates which is capable of forming a useful polyimide film with an appropriate linear expansion coefficient and an appropriate flexibility. The solution is that this resin composition for display substrates contains a polyamic acid which includes a structural unit represented by formula (1) and a structural unit represented by formula (3), or a polyimide which includes a structural unit represented by formula (2) and a structural unit represented by formula (4). [In formulae 1 through 4, X1 represents a tetravalent organic group having an aromatic group and two carbonyl groups, Y1 represents a divalent aromatic group or aliphatic group, Y2 represents a divalent aromatic group having two or more nitrogen atoms, and n and m represent natural numbers.]

Description

Display base plate resin combination
Technical field
The present invention relates to display base plate resin combination, in particular to display base plate resin combination, its can form there is appropriate linear expansivity, the useful polyimide film of flexibility of appropriateness.
Background technology
Polyimide resin, because thermotolerance is high, be flame retardancy and electrical insulating property excellent, so be widely used in electric and electronic Material Field.Particularly, as film, be used to the base material of flexible printing wiring board, thermotolerance adhesive tape, as resin paint, be used to semi-conductive insulating coating, protection epithelium etc.
On the other hand, the display unit such as organic EL (electroluminescent) indicating meter, liquid-crystal display only require high precision always, but by its purposes rapidly to expansions such as information equipments.For example, in order to meet ultrathin light-weighted requirement, use plastic film just to receive publicity as the flexible display of substrate.
In the past, for high precision indicating meter, use the panel of driven with active matrix.Except rectangular pixel electrode, in order to form the active matrix layer that comprises film active element, in its manufacturing process, need to carry out more than 200 ℃ pyroprocessing, and need alignment very accurately.Yet owing to becoming plastic material for flexibility from glass substrate, so thermotolerance, dimensional stability variation, therefore, it is very difficult directly forming active component thereon.
Therefore, for fear of such problem, following method (patent documentation 1 and 2) has been proposed, on glass substrate, form polyimide film, not limit the mode of creating conditions, the high precision of usining is alignd and is formed non-crystalline silicon tft element, colour filter etc. as transfer printing layer, then by this transfer printing layer transfer printing is formed on plastic film, thereby manufactures display element.
In addition, as the characteristic of needed polyimide in aforementioned operation, can enumerate linear expansivity.But in the situation that most of polyimide is, the linear expansivity of film, in the scope of 60～80ppm/K, does not have low linear expansion characteristic.Wherein, although developed the low polyimide film of linear expansivity, owing to using the acid dianhydride that lacks versatility in raw material, so the valuable product (patent documentation 3) obtaining.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-356370 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2010-539293 communique
Patent documentation 3: No. 2008/047591 brochure of international publication
Summary of the invention
The problem that invention will solve
The present invention proposes in view of such circumstances, object is to provide a kind of display base plate resin combination, even if it does not use the acid dianhydride that lacks versatility in raw material, also can form there is appropriate linear expansivity, the flexibility of appropriateness and stable on heating useful cured film fully.In addition, the flexibility of alleged appropriateness refers to here, even if having self-supporting and crooked 90 high flexibilities of spending the degree of also not breaking.
The means of dealing with problems
Present inventor has carried out found that of concentrated research to achieve these goals, by be used in combination the acid anhydrides with biphenyl backbone as acid dianhydride composition and the diamines with benzoglyoxaline skeleton as two amine components, can derived from this acid dianhydride composition and the polyamic acid of this two amine component or the display base plate of polyimide, with resin combination, obtain the useful cured film with appropriate linear expansivity and appropriate flexibility by containing, thereby complete the present invention.
; the present invention; as the 1st aspect; relate to a kind of display base plate resin combination; it contains polyamic acid or polyimide; described polyamic acid contains the represented structural unit of following formula (1) and the represented structural unit of formula (3), and described polyimide contains the represented structural unit of following formula (2) and the represented structural unit of formula (4).
[changing 1]
[in formula (1)～formula (4),
X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls,
Y 1the aromatic group or the aliphatic group that represent divalent,
Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms,
N and m represent natural number.]
As the 2nd aspect, relate to according to the display base plate resin combination described in the 1st aspect, aforementioned Y 2represent to have the aromatic group of heterocycle structure.
As the 3rd aspect, relate to according to the display base plate resin combination described in the 2nd aspect, aforementioned Y 2by following formula (5), represent.
[changing 2]
(in formula,
R 1～R 7represent independently respectively the alkyl of hydrogen atom, carbonatoms 1～10, the alkoxyl group of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1～10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10,
A represents the alkyl of hydrogen atom, carbonatoms 1～10 or the haloalkyl of carbonatoms 1～10.In addition, zero represents associative key.)
As the 4th aspect, relate to according to the display base plate resin combination described in the 3rd aspect, aforementioned R 1～R 7represent hydrogen atom with A.
As the 5th aspect, relate to according to the display base plate resin combination described in any one in the 1st aspect, aspect～4th, aforementioned Y 1by following formula (6), represent.
[changing 3]
(in formula,
R 8～R 11represent independently respectively the alkyl of hydrogen atom, carbonatoms 1～10, the alkoxyl group of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1～10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10,
Q represents 1 or 2.In addition, zero represents associative key.)
As the 6th aspect, relate to according to the display base plate resin combination described in the 5th aspect, the represented divalent aromatic group of aforementioned formula (6) is the group derived from phenylenediamine.
As the 7th aspect, relate to according to the display base plate resin combination described in the 6th aspect, aforementioned R 8～R 11represent hydrogen atom.
As the 8th aspect, relate to according to the display base plate resin combination described in any one in the 1st aspect, aspect～7th, aforementioned X 1by following formula (7), represent.
[changing 4]
(in formula,
R 12～R 21represent independently respectively the alkyl of hydrogen atom, carbonatoms 1～10, the alkoxyl group of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1～10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10,
Z 1and Z 2difference is expression-NH-,-NZ independently 3-or Sauerstoffatom,
Z 3the alkyl that represents carbonatoms 1～10,
P represents 1 or 2.In addition, zero represents associative key.)
As the 9th aspect, relate to according to the display base plate resin combination described in the 8th aspect, aforementioned p represents 2.
As the 10th aspect, relate to according to the display base plate resin combination described in the 9th aspect, aforementioned R 12～R 21represent hydrogen atom.
As the 11st aspect, relate to according to the display base plate resin combination described in any one in the 1st aspect, aspect～10th, the pass of the m in the n in aforementioned formula (1) and aforementioned formula (3) is n/m=70/30～99/1.
As the 12nd aspect, relate to according to the display base plate resin combination described in any one in the 1st aspect, aspect～10th, the pass of the m in the n in aforementioned formula (2) and aforementioned formula (4) is n/m=70/30～99/1.
As the 13rd aspect, relate to according to the display base plate resin combination described in any one in the 1st aspect, aspect～12nd, it further contains linking agent.
As the 14th aspect, relate to according to the display base plate resin combination described in the 13rd aspect, aforementioned linking agent is the compound with 2 above epoxy group(ing).
As the 15th aspect, relate to according to the display base plate resin combination described in the 14th aspect, aforementioned linking agent is the compound with aromatic group.
As the 16th aspect, relate to according to the display base plate resin combination described in the 15th aspect, aforementioned linking agent is the compound with 6 following epoxy group(ing), and this compound has the alkyl of the carbonatoms 1～10 that epoxy group(ing) is combined with aromatic group.
As the 17th aspect, relate to according to the display base plate resin combination described in any one in the 13rd aspect, aspect～16th, with respect to the aforementioned polyamic acid of 100 mass parts or polyimide, aforementioned linking agent is below 20 mass parts.
As the 18th aspect, relate to a kind of paint, it is characterized in that, be in the 1st aspect, aspect～17th display base plate described in any one with resin combination, be dissolved at least a kind of solvent and.
As the 19th aspect, relate to a kind of cured film, it is by using the paint described in the 18th aspect to burn till and obtain above at 230 ℃.
As the 20th aspect, relate to a kind of structure, it has the layer of the cured film described in comprising aspect the 19th of one deck at least on substrate.
As the 21st aspect, relate to a kind of polyamic acid, it contains the represented structural unit of following formula (1) and the represented structural unit of formula (3).
[changing 5]
[in formula (1) and formula (3),
X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls,
Y 1the aromatic group or the aliphatic group that represent divalent,
Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms,
N and m represent natural number.]
As the 22nd aspect, relate to a kind of polyimide, it contains the represented structural unit of following formula (2) and the represented structural unit of formula (4).
[changing 6]
[in formula (2) and formula (4),
X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls,
Y 1the aromatic group or the aliphatic group that represent divalent,
Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms,
N and m represent natural number.]
As the 23rd aspect, relate to a kind of base plate for displaying, it comprises the polyimide described in the 22nd aspect.
The effect of invention
Display base plate of the present invention with resin combination, can form there is appropriate linear expansivity, the flexibility of appropriateness and sufficient stable on heating useful cured film.Therefore, this cured film can be for basement membrane etc. for flexible display.
Embodiment
[display base plate resin combination]
The present invention relates to a kind of display base plate resin combination, it contains the polyamic acid that comprises the represented structural unit of following formula (1) and the represented structural unit of formula (3) or comprises the represented structural unit of following formula (2) and the polyimide of the structural unit that formula (4) is represented.
[changing 7]
[in formula (1)～formula (4),
X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls,
Y 1the aromatic group or the aliphatic group that represent divalent,
Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms,
N and m represent natural number.]
Here, the meaning of the polyamic acid that comprises the represented structural unit of the represented structural unit of above-mentioned formula (1) and formula (3) refers to, comprise n structural unit and m the represented structural unit of following formula (b) that following formula (a) is represented, the compound that this (n+m) individual structural unit is combined in any order, the meaning of the polyimide that comprises the represented structural unit of the represented structural unit of above-mentioned formula (2) and formula (4) refers to, comprise n structural unit and m the represented structural unit of following formula (d) that following formula (c) is represented, the compound that this (n+m) individual structural unit is combined in any order.
In addition, the polyamic acid that contains the represented structural unit of the represented structural unit of above-mentioned formula (1) and formula (3) also can have any one or two kinds of in the represented structural unit of following formula (c) and the represented structural unit of formula (d) in molecule, and the polyimide that contains the represented structural unit of the represented structural unit of above-mentioned formula (2) and formula (4) also can have any one or two kinds of in the represented structural unit of following formula (a) and the represented structural unit of formula (b) in molecule.
[changing 8]
[in formula (a)～formula (d), X 1, Y 1and Y 2represent respectively the meaning identical with definition in aforementioned formula (1)～formula (4).]
Display base plate (all contains sometimes at the two with above-mentioned polyamic acid or polyimide in resin combination, polyamic acid and polyimide) content, the content of the solids component based on this resin combination, be 8～99.9 quality %, be preferably 40～99.9 quality %, more preferably 80～99.9 quality %.
Here, solids component refers to, from display base plate, uses whole compositions of resin combination except residual composition after desolventizing.
Display base plate of the present invention contains polyamic acid or polyimide with resin combination.
< polyamic acid >
Display base plate of the present invention can be by obtaining acid anhydrides composition and the polymerization in solvent of two amine components with the contained polyamic acid of resin combination.
Polyamic acid can be by known method, for example, in the inert gas atmospheres such as nitrogen, represented at least a kind of diamines and at least a kind of represented diamines of following formula (10) of at least a kind of acid dianhydride, following formula (9) that following formula (8) is represented is dissolved in solvent, makes its reaction and obtains.
[changing 9]
(in formula, X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls.)
H 2N-Y 1-NH 2(9)
(in formula, Y 1the aromatic group or the aliphatic group that represent divalent.)
H 2N-Y 2-NH 2(10)
(in formula, Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms.)。
Temperature of reaction is now-20～100 ℃, is preferably 20～60 ℃.Reaction times is 1～72 hour.
In the present invention, can directly use the reaction soln of polyamic acid as display base plate resin combination, or can be by the reaction soln dilution of polyamic acid or concentrated or first reclaim polyamic acid from reaction soln by modes such as redeposition and then make it be dissolved or dispersed in again in suitable solvent, thereby use with resin combination as display base plate.For dilution, the solvent that dissolves or disperse again, so long as the solvent that can make obtained polyamic acid dissolve or disperse, be not particularly limited, but can enumerate, for example, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, NVP, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-oxyethyl group-N, N-dimethyl propylene acid amides, 3-propoxy--N, N-dimethyl propylene acid amides, 3-isopropoxy-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides, 3-sec-butoxy-N, N-dimethyl propylene acid amides, 3-tert.-butoxy-N, N-dimethyl propylene acid amides, gamma-butyrolactone etc.These solvents can be used separately, or also can be used in combination two or more.
As the represented acid dianhydride of aforementioned formula (8), preferred X 1for the acid dianhydride of the represented structure of following formula (7), particularly preferably X 1acid dianhydride for the represented structure of following formula (7-1).
[changing 10]
(in formula,
R 12～R 21represent independently respectively the alkyl of hydrogen atom, carbonatoms 1～10, the alkoxyl group of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1～10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10,
Z 1and Z 2difference is expression-NH-,-NZ independently 3-or Sauerstoffatom,
Z 3the alkyl that represents carbonatoms 1～10,
P represents 1 or 2.In addition, zero represents associative key.)
In aforementioned formula (7), aforementioned p is preferably 2.
As the represented acid dianhydride of such formula (8), can enumerate, for example, to phenylene two (trimellitic acid monoesters acid anhydride), 2-methyl isophthalic acid, 4-phenylene two (trimellitic acid monoesters acid anhydride), 2, 5-dimethyl-1, 4-phenylene two (trimellitic acid monoesters acid anhydride), 2, 3, 5, 6-tetramethyl--1, 4-phenylene two (trimellitic acid monoesters acid anhydride), 2-Trifluoromethyl-1, 4-phenylene two (trimellitic acid monoesters acid anhydride), 2, 5-bis-Trifluoromethyl-1s, 4-phenylene two (trimellitic acid monoesters acid anhydride), 2-chloro-1, 4-phenylene two (trimellitic acid monoesters acid anhydride), 2, 5-bis-chloro-1, 4-phenylene two (trimellitic acid monoesters acid anhydride), 2-fluoro-1, 4-phenylene two (trimellitic acid monoesters acid anhydride) and 2, 5-bis-fluoro-1, 4-phenylene two (trimellitic acid monoesters acid anhydride), and N, N '-(1, 4-phenylene) two (1, 3-dioxo-1, 3-Dihydrobenzofuranes-5-methane amide) and N, N '-(1, 4-phenylene) two (N-methyl isophthalic acids, 3-dioxo-1, 3-Dihydrobenzofuranes-5-methane amide) etc.
In aforementioned acid dianhydride, the angle from the cured film that makes to be obtained by resin combination of the present invention with fully low linear expansivity and abundant high intensity is considered, the R in preferred aforementioned formula (7) 12～R 21represent hydrogen atom, Z 1and Z 2represent that Sauerstoffatom and p represent that 2 compounds are 4,4 '-biphenyl two (trimellitic acid monoesters acid anhydrides) (following formula (11)).
[changing 11]
With regard to the represented aromatic series or aliphatie diamine of aforementioned formula (9), the angle from the cured film that makes to be obtained by resin combination of the present invention with fully low linear expansivity considers, preferably uses upright and outspoken and has a diamines of linear molecular structure.Wherein, as the represented diamines of aforementioned formula (9), preferred Y 1the diamines of the represented structure of following formula (6), particularly preferably Y 1it is the diamines of the represented structure of following formula (6-1).
[changing 12]
(in formula,
R 8～R 11represent independently respectively the alkyl of hydrogen atom, carbonatoms 1～10, the alkoxyl group of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1～10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10,
Q represents 1 or 2.In addition, zero represents associative key.)
The represented divalent aromatic group of aforementioned formula (6) is preferably the group derived from phenylenediamine.
In addition, from the cured film that makes to be obtained by resin combination of the present invention, there is fully low linear expansivity and consider with the angle of abundant high intensity, in aforementioned formula (6), preferred aforementioned R 8～R 11for hydrogen atom.
As the represented aromatic diamine of aforementioned formula (9), can enumerate, for example, Ursol D, O-Phenylene Diamine, methyl isophthalic acid, 4-phenylenediamine, 2-Trifluoromethyl-1, 4-phenylenediamine, 2-methoxyl group-1, 4-phenylenediamine, 2, 5-dimethyl-1, 4-phenylenediamine, 2, 5-bis-(trifluoromethyl)-1, 4-phenylenediamine, 4, 4 '-diaminobenzene formylaniline, 4-aminophenyl-4 '-Aminobenzoate, p-diaminodiphenyl, 3, 3 '-dimethoxy benzidine, 3, 3 '-dichlorobenzidine, o-tolidine, between tolidine, 2, 2 '-bis-(trifluoromethyl) p-diaminodiphenyl, 3, 3 '-bis-(trifluoromethyl) p-diaminodiphenyl, octafluoro p-diaminodiphenyl, 3, 3 ', 5, 5 '-tetramethyl benzidine, 2, 2 ', 5, 5 '-tetrachloro benzidine etc., but in the middle of them, the angle from the cured film that makes to be obtained by resin combination of the present invention with fully low linear expansivity and abundant high intensity is considered, particularly preferably Ursol D and mphenylenediamine.
As the represented aliphatie diamine of aforementioned formula (9), can enumerate, for example, 4, 4 '-methylene radical two (hexahydroaniline), 4, 4 '-methylene radical two (3-methyl cyclohexylamine), different fluorine that ketone diamines, anti-form-1, 4-cyclohexanediamine, cis-1, 4-cyclohexanediamine, 1, 4-hexanaphthene two (methylamine), 2, 5-bis-(amino methyl) dicyclo (2.2.1) heptane, 2, 6-bis-(amino methyl) dicyclo (2.2.1) heptane, 3, 8-bis-(amino methyl) three ring (5.2.1.0) decane, 1, 3-diamino diamantane, 2, 2-bis-(4-aminocyclohexyl) propane, 2, 2-bis-(4-aminocyclohexyl) HFC-236fa, 1, 3-propylene diamine, 1, 4-butanediamine, 1, 5-pentamethylene diamine, 1, 6-hexanediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine etc.
In the middle of aforementioned aliphatie diamine, the angle from the cured film that makes to be obtained by resin combination of the present invention with fully low linear expansivity considers, preferably uses upright and outspoken and has the diamines of linear molecular structure, for example, can use suitably anti-form-1,4-cyclohexanediamine.
In addition, the angle from the cured film that makes to be obtained by resin combination of the present invention with fully low linear expansivity considers, the represented diamines of aforementioned formula (10) is also preferably used upright and outspoken and has a diamines of linear molecular structure.
Wherein, as the represented diamines of aforementioned formula (10), preferred Y 2be have imidazoles, the diamines of the aromatic group of the heterocycle structure that azoles, thiazole, four azepine pyrenes, imidazoles pyrrolidone (イ ミ ダ ゾ ピ ロ ロ Application), quinoxaline (キ サ ノ リ Application), indoles quinoxaline (イ Application De ロ キ サ ノ リ Application), isoindole quinazoline diones are such, more preferably Y 2the diamines that this heterocycle structure has the aromatic group of the aromatic ring structures such as benzene, naphthalene, anthracene, preferred Y 2the diamines of the represented structure of following formula (5), particularly preferably Y 2it is the diamines of the represented structure of following formula (5-1).
[changing 13]
(in formula,
R 1～R 7represent independently respectively the alkyl of hydrogen atom, carbonatoms 1～10, the alkoxyl group of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1～10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1～10, carbonatoms 1～10,
A represents the alkyl of hydrogen atom, carbonatoms 1～10 or the haloalkyl of carbonatoms 1～10.In addition, zero represents associative key.)
As the represented diamines of aforementioned formula (10), can enumerate the amino benzo of 2-(4-aminophenyl)-5- azoles, the amino benzo of 2-(3-aminophenyl)-5- azoles, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(3-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-5-aminobenzothiazole, the amino benzodiazole of 2-(3-aminophenyl)-5-etc.
In the middle of aforementioned diamines, from it, obtain easiness and consider with the angle that improves the self-supporting of the cured film being obtained by resin combination of the present invention, the R in preferred aforementioned formula (5) 1～R 7represent that with A the compound of hydrogen atom is 2-(3-aminophenyl)-5-aminobenzimidazole.
The solvent using in formation reaction as polyamic acid, be not particularly limited, but can enumerate, for example, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, N, dinethylformamide, N-Methyl pyrrolidone, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-oxyethyl group-N, N-dimethyl propylene acid amides, 3-propoxy--N, N-dimethyl propylene acid amides, 3-isopropoxy-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides, 3-sec-butoxy-N, N-dimethyl propylene acid amides, 3-tert.-butoxy-N, N-dimethyl propylene acid amides, hexamethylphosphoramide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 1, 3-dimethyl-2-imidazolinone, 1, 2-glycol dimethyl ether-bis-(2-methoxy ethyl) ether, tetrahydrofuran (THF), 1, 4-bis- the protic solvents such as the non-protonic solvents such as alkane, picoline, pyridine, acetone, chloroform, toluene, dimethylbenzene and phenol, ortho-cresol, meta-cresol, p-cresol, ortho chloro phenol, m-Chlorophenol, para-chlorophenol etc.These solvents can be used separately, or also can be used in combination two or more.
In above-mentioned reaction, with regard to the ratio of two amine components, the mol ratio of the diamines that the diamines that above-mentioned formula (9) is represented and above-mentioned formula (10) are represented is preferably 70/30～99/1, the angle from the cured film that makes to be obtained by resin combination of the present invention with fully low linear expansivity and fully high intensity considers, more preferably 75/25～95/5.
In addition, in above-mentioned reaction, the ratio of acid dianhydride composition and two amine components is preferably, with molar ratio computing, and acid dianhydride composition/bis-amine component=0.8～1.2.With common polycondensation similarly, this mol ratio more approaches 1, the polymerization degree of the polymkeric substance generating is larger.If the polymerization degree is too small, polyimide curing film strength becomes insufficient, in addition, if the polymerization degree is excessive, has the situation of the operability variation while forming polyimide curing film.
In order to maintain the curing film strength being obtained with resin combination by the display base plate that contains polyamic acid, the weight-average molecular weight of the polyamic acid generating, by polystyrene conversion, is preferably 3000～200000.This be because, in the situation that weight-average molecular weight is less than 3000, the possibility that exists made film to become fragile, on the other hand, if the possibility that weight-average molecular weight over 200000, exists the viscosity of the paint of polyamic acid to become too high, its result, it is difficult that operation becomes.
The relation of the quantity m of the structural unit that the quantity n of the structural unit that the formula in the polyamic acid generating (1) is represented and formula (3) are represented is preferably n/m=70/30～99/1, and more preferably 75/25～95/5.
In addition, the angle from obtained cured film with fully low linear expansivity and abundant high intensity is considered, the ratio of the represented structural unit (the represented structural unit of following formula (3-1)) of the represented structural unit (the represented structural unit of following formula (1-1)) of following formula (1) and following formula (3) particularly, in the repeating unit of generated polyamic acid, with the summation meter of the two, be preferably more than 70 % by mole, more preferably more than 80 % by mole, further be preferably more than 85 % by mole, wherein, X in the represented structural unit of described formula (1) 1r 12～R 21for hydrogen atom and Z 1and Z 2for the formula (7) of Sauerstoffatom represented structure and Y 1r 8～R 11for the represented structure of formula (6) of hydrogen atom, X in the represented structural unit of described formula (3) 1r 12～R 21for hydrogen atom and Z 1and Z 2for the formula (7) of Sauerstoffatom represented structure and Y 2r 1～R 7with the A represented structure of formula (5) that is hydrogen atom.
[changing 14]
[in formula, q and p represent respectively the meaning identical with definition in aforementioned formula (6) and formula (7).]
In the situation that use the polyamic acid obtaining by method described above, make resin combination for display base plate, particularly in the situation that make its be dissolved or dispersed in solvent in paint form make this resin combination, the polyamic acid (be designated as below and form A) that preferably contains the represented structural unit of the represented structural unit of following formula (1) and following formula (3), wherein, X in the represented structural unit of described formula (1) 1represented structure and Y of following formula (7-2) 1the represented structure of following formula (6-2), X in the represented structural unit of described formula (3) 1represented structure and Y of following formula (7-2) 2it is the represented structure of following formula (5-2); More preferably the polyamic acid (be designated as below and form B) that contains the represented structural unit of the represented structural unit of following formula (1) and following formula (3), wherein, X in the represented structural unit of described formula (1) 1represented structure and Y of following formula (7-3) 1the represented structure of following formula (6-3), X in the represented structural unit of described formula (3) 1represented structure and Y of following formula (7-3) 2it is the represented structure of following formula (5-3); The polyamic acid (be designated as below and form C) that further preferably contains the represented structural unit of the represented structural unit of following formula (1) and following formula (3), wherein, X in the represented structural unit of described formula (1) 1that p is 2 represented structure and the Y of following formula (7-3) 1that q is 1 the represented structure of following formula (6-3), X in the represented structural unit of described formula (3) 1that p is 2 represented structure and the Y of following formula (7-3) 2it is the represented structure of following formula (5-3).
[changing 15]
[in formula, q and p represent respectively the meaning identical with definition in aforementioned formula (6) and formula (7).In addition, zero represents associative key.]
And, in addition, at these preferred each, form and (form A, B or C) under, the relation of the quantity m of the structural unit that the quantity n of the structural unit that formula (1) is represented and formula (3) are represented meets n/m=70/30～99/1, preferably meet n/m=75/25～95/5, the ratio of the structural unit that the structural unit that above-mentioned formula (1-1) is represented and above-mentioned formula (3-1) are represented, with the summation meter of the two, in the repeating unit of polyamic acid, be more than 70 % by mole, be preferably more than 80 % by mole, more preferably more than 85 % by mole, and the weight-average molecular weight of polyamic acid is preferably 3000～200000 (polystyrene conversion).
In addition, the polyamic acid that contains the represented structural unit of formula (1) and the represented structural unit of formula (3) of above explanation is also object of the present invention.
< polyimide >
Contained polyimide in resin combination for display base plate of the present invention, can by heating in the above described manner synthetic polyamic acid carry out dehydration closed-loop (hot-imide) and obtain.In addition, now, also can make polyamic acid in solvent, be converted into imide, thereby use as the polyimide of solvent soluble.In addition, also can adopt and use known dehydration closed-loop catalyzer with chemical mode, to carry out the method for closed loop.Method by heating can be carried out under the arbitrary temp in 100～300 ℃, preferably under the arbitrary temp in 120～250 ℃, carries out.With chemical mode, carry out the method for closed loop, for example, can under the existence of pyridine, triethylamine etc. and acetic anhydride etc., carry out, temperature now can be selected the arbitrary temp in-20～200 ℃.
In the present invention, can directly use the reaction soln of polyimide as display base plate resin combination, or can be by the reaction soln dilution of polyimide or concentrated, or first by redeposition etc., from reaction soln, reclaim polyimide and then it is dissolved or dispersed in suitable solvent again, thereby use with resin combination as display base plate.For dilution, the solvent that dissolves or disperse again, so long as the solvent that can make obtained polyimide dissolve or disperse, be not particularly limited, but can enumerate, for example, meta-cresol, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, NVP, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-oxyethyl group-N, N-dimethyl propylene acid amides, 3-propoxy--N, N-dimethyl propylene acid amides, 3-isopropoxy-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides, 3-sec-butoxy-N, N-dimethyl propylene acid amides, 3-tert.-butoxy-N, N-dimethyl propylene acid amides, gamma-butyrolactone etc.These solvents can be used separately, or also can be used in combination two or more.
In order to maintain the curing film strength being obtained with resin combination by the display base plate that contains polyimide, the weight-average molecular weight of the polyimide generating, by polystyrene conversion, is preferably 3000～200000.This be because, in the situation that weight-average molecular weight is less than 3000, the possibility that exists formed film to become fragile, on the other hand, if the possibility that weight-average molecular weight over 200000, exists the viscosity of the paint of polyimide to become too high, its result, it is difficult that operation becomes.
The relation of the quantity m of the structural unit that the quantity n of the structural unit that the formula in the polyimide generating (2) is represented and formula (4) are represented is preferably n/m=70/30～99/1, and more preferably 75/25～95/5.
In addition, the angle from the cured film obtaining with fully low linear expansivity and abundant high intensity is considered, the ratio of the represented structural unit (the represented structural unit of following formula (4-1)) of the represented structural unit (the represented structural unit of following formula (2-1)) of following formula (2) and following formula (4) particularly, with the summation meter of the two, in the repeating unit of generated polyimide, be preferably more than 70 % by mole, more preferably more than 80 % by mole, further be preferably more than 85 % by mole, wherein, X in the represented structural unit of described formula (2) 1r 12～R 21for hydrogen atom and Z 1and Z 2for the formula (7) of Sauerstoffatom represented structure and Y 1r 8～R 11for the represented structure of formula (6) of hydrogen atom, X in the represented structural unit of described formula (4) 1r 12～R 21for hydrogen atom and Z 1and Z 2for the formula (7) of Sauerstoffatom represented structure and Y 2r 1～R 7with the A represented structure of formula (5) that is hydrogen atom.
[changing 16]
[in formula, q and p represent respectively the meaning identical with definition in aforementioned formula (6) and formula (7).]
In the situation that use the polyimide obtaining by method described above, make resin combination for display base plate, particularly in the situation that make its be dissolved or dispersed in solvent in and with paint form make this resin combination, the polyimide (be designated as below and form D) that preferably contains the represented structural unit of the represented structural unit of following formula (2) and following formula (4), wherein, X in the represented structural unit of described formula (2) 1represented structure and Y of above-mentioned formula (7-2) 1the represented structure of above-mentioned formula (6-2), X in the represented structural unit of described formula (4) 1represented structure and Y of above-mentioned formula (7-2) 2it is the represented structure of above-mentioned formula (5-2); More preferably the polyimide (be designated as below and form E) that contains the represented structural unit of the represented structural unit of following formula (2) and following formula (4), wherein, X in the represented structural unit of described formula (2) 1represented structure and Y of above-mentioned formula (7-3) 1the represented structure of above-mentioned formula (6-3), X in the represented structural unit of described formula (4) 1represented structure and Y of above-mentioned formula (7-3) 2it is the represented structure of above-mentioned formula (5-3); The polyimide (be designated as below and form F) that further preferably contains the represented structural unit of the represented structural unit of following formula (2) and following formula (4), wherein, X in the represented structural unit of described formula (2) 1that p is 2 represented structure and the Y of above-mentioned formula (7-3) 1that q is 1 the represented structure of above-mentioned formula (6-3), X in the represented structural unit of described formula (4) 1that p is 2 represented structure and the Y of above-mentioned formula (7-3) 2it is the represented structure of above-mentioned formula (5-3).
And, in addition, at these preferred each, form and (form D, E or F) under, the relation of the quantity m of the structural unit that the quantity n of the structural unit that formula (2) is represented and formula (4) are represented meets n/m=70/30～99/1, preferably meet n/m=75/25～95/5, the ratio of the structural unit that the structural unit that above-mentioned formula (2-1) is represented and above-mentioned formula (4-1) are represented, with the summation meter of the two, in the repeating unit of polyimide, be more than 70 % by mole, be preferably more than 80 % by mole, more preferably more than 85 % by mole, and the weight-average molecular weight of polyimide is preferably 3000～200000 (polystyrene conversion).
In addition, the polyimide that contains the represented structural unit of formula (2) and the represented structural unit of formula (4) of above-mentioned explanation is also object of the present invention.
Display base plate of the present invention with resin combination also can comprise polyamic acid and polyimide the two, described polyamic acid contains the represented structural unit of above-mentioned formula (1) and the represented structural unit of formula (3), and described polyimide contains the represented structural unit of above-mentioned formula (2) and the represented structural unit of formula (4).
Display base plate of the present invention preferably comprises solvent and polyamic acid or polyimide with resin combination and dissolves or disperse equably, and more preferably polyamic acid or polyimide are dissolved in solvent.As such solvent, can enumerate, for example, the solvent of recording in aforementioned paragraphs etc.
In addition, display base plate of the present invention can comprise linking agent with resin combination and (also claim below cross-linked compound.)。
< linking agent >
With regard to cross-linked compound, so long as there is the compound of the group that reacts of organic group that can be contained with at least one party in polyamic acid or polyimide in the operation that filming of obtaining using its positive type photosensitive organic compound change into cured film, be not particularly limited.As such compound, can enumerate, for example, the compounds that contain 2 above epoxy group(ing), have amino hydrogen atom the two group having replaced by methylol, alkoxy methyl or its, melamine derivative, benzo guanamine derivative or glycoluril etc.This melamine derivative and benzo guanamine derivative can be dimer or tripolymer, or can be also optional mixtures from monomer, dimer and tripolymer.These melamine derivatives and benzo guanamine derivative preferably every 1 triazine ring have more than average 3 and are less than 6 methylols or alkoxy methyl.
In addition, the linking agent using in the present invention can be used separately, or also can be used in combination two or more.
Although enumerated below the concrete example of cross-linked compound, be not limited thereto.
As the compound that contains 2 above epoxy group(ing), can enumerate, エ ポ リ ー De GT-401, エ ポ リ ー De GT-403, エ ポ リ ー De GT-301, エ ポ リ ー De GT-302, セ ロ キ サ イ De 2021, セ ロ キ サ イ De 3000 (being produced by ダ イ セ Le chemical industry (strain) above) etc. have the epoxy compounds of cyclohexene, the bisphenol type epoxy compounds such as エ ピ コ ー ト 1001, エ ピ コ ー ト 1002, エ ピ コ ー ト 1003, エ ピ コ ー ト 1004, エ ピ コ ー ト 1007, エ ピ コ ー ト 1009, エ ピ コ ー ト 1010, エ ピ コ ー ト 828 (being produced by ジ ャ パ Application エ Port キ シ レ ジ Application (strain) above), the Bisphenol F type epoxy compoundss such as エ ピ コ ー ト 807 (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) production), the phenol phenolic varnish type epoxy compoundss such as エ ピ コ ー ト 152, エ ピ コ ー ト 154 (being produced by ジ ャ パ Application エ Port キ シ レ ジ Application (strain) above), EPPN201, EPPN202 (being produced by Japanese chemical drug (strain) above), the cresols phenolic varnish type epoxy compoundss such as ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (being produced by Japanese chemical drug (strain) above), エ ピ コ ー ト 180S75 (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) production), the naphthalene type epoxy compoundss such as V8000-C7 (DIC (strain) production), デ ナ コ ー Le EX-252 (Na ガ セ ケ system テ ッ Network ス (strain) production), CY175, CY177, CY179, ARALDITE CY-182, ARALDITE CY-192, ARALDITE CY-184 (being produced by BASF AG above), エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (being produced by DIC (strain) above), エ ピ コ ー ト 871, エ ピ コ ー ト 872 (being produced by ジ ャ パ Application エ Port キ シ レ ジ Application (strain) above), ED-5661, the alicyclic epoxy compounds such as ED-5662 (being produced by セ ラ ニ ー ズ コ ー テ ィ Application グ (strain) above), the aliphatic poly glycidyl ether compounds such as デ Na コ ー Le EX-611, デ Na コ ー Le EX-612, デ Na コ ー Le EX-614, デ Na コ ー Le EX-622, デ Na コ ー Le EX-411, デ Na コ ー Le EX-512, デ Na コ ー Le EX-522, デ Na コ ー Le EX-421, デ Na コ ー Le EX-313, デ Na コ ー Le EX-314, デ Na コ ー Le EX-312 (being produced by Na ガ セ ケ system テ ッ Network ス (strain) above).
As have amino hydrogen atom the two group having replaced by methylol, alkoxy methyl or its, melamine derivative, benzo guanamine derivative or glycoluril, can enumerate the MW-30 (being produced by (strain) three and ケ ミ カ Le above) that the MX-750 that every 1 triazine ring has been replaced by average 3.7 methoxymethyies, every 1 triazine ring have been replaced by average 5.8 methoxymethyies; The methoxymethyl melamines such as サ イ メ Le 300, サ イ メ Le 301, サ イ メ Le 303, サ イ メ Le 350, サ イ メ Le 370, サ イ メ Le 771, サ イ メ Le 325, サ イ メ Le 327, サ イ メ Le 703, サ イ メ Le 712; The methoxymethyl butoxymethyl melamines such as サ イ メ Le 235, サ イ メ Le 236, サ イ メ Le 238, サ イ メ Le 212, サ イ メ Le 253, サ イ メ Le 254; The butoxymethyl melamines such as サ イ メ Le 506, サ イ メ Le 508; The methoxymethyl isobutoxy methylated melamines that contains carboxyl such as サ イ メ Le 1141; Methoxymethyl ethoxyl methyl benzo guanamine such as サ イ メ Le 1123; Methoxymethyl butoxymethyl benzo guanamine such as サ イ メ Le 1123-10; Butoxymethyl benzo guanamine such as サ イ メ Le 1128; The methoxymethyl ethoxyl methyl benzo guanamine that contains carboxyl such as サ イ メ Le 1125-80; Butoxymethyl glycoluril such as サ イ メ Le 1170; Such as the methylolation glycoluril of サ イ メ Le 1172 (being produced by Mitsui サ イ ア Na ミ ッ De (strain) above) etc.
In addition, from improving the angle of the storage stability of resin combination, consider, the content of linking agent in resin combination for display base plate of the present invention, with respect to 100 mass parts polyamic acids or polyimide (when containing the two, polyamic acid and polyimide), be preferably below 20 mass parts, the angle from the cured film that makes to be obtained by resin combination of the present invention with fully low linear expansivity is considered, more preferably below 15 mass parts.
[paint and cured film]
The concrete method of using display base plate of the present invention to form cured film with resin combination is as described below.
First, by the polyamic acid that contains the represented structural unit of the represented structural unit of above-mentioned formula (1) and formula (3) or contain the represented structural unit of above-mentioned formula (2) and the polyimide of the structural unit that formula (4) is represented is dissolved or dispersed in solvent, thereby make resin combination with the form (forming the material of film) of paint.Or, by the polyamic acid of the above-mentioned explanation of direct use or the reaction soln of polyimide, prepare the resin combination of form of paint, or by by its dilution or concentrate to prepare the resin combination of the form of paint.
Then, by curtain coating coating method, spin-coating method, spread coating, dip coating, rolling method, excellent painting method, mouthful mould coating method, ink jet method, print process (relief printing plate, intaglio plate, lithographic plate, screen painting etc.) etc., this paint is coated on substrate and obtains and film.Then by using hot-plate, baking oven etc. that obtained filming burnt till and formed cured film.
The firing temperature that is used to form cured film is generally 100～400 ℃, is preferably 100～350 ℃, by this, burns till processing, solvent evaporation, polyamic acid generation dehydration closed-loop (imidization) thus form polyimide.Now, for making it show higher even film-forming properties, the object of reacting on substrate, also can adopt temperature variation more than 2 stages.
In addition; as used substrate; can enumerate; for example, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefine, epoxy resin, melamine resin, tri acetyl cellulose, ABS, AS, norbornene resin etc.), metal, timber, paper, glass, slate etc.
As the solvent using in the form of aforementioned paint, so long as the solvent that can make polyamic acid or polyimide dissolve or disperse is not particularly limited, still can enumerate, for example, the solvent using in the formation reaction of above-mentioned polyamic acid etc.These solvents can be used separately, or also can be used in combination two or more.
In addition, make polyamic acid or polyimide (when containing the two, polyamic acid and polyimide.Identical below.) dissolve or be dispersed in the concentration in above-mentioned solvent, total mass (total quality) with respect to polyamic acid or polyimide and solvent is generally 5～40 quality %, from improving the angle of the storage stability of resin combination, consider, be preferably 5～20 quality %, from improving the angle of the coating of paint, consider, be preferably 5～15 quality %.
The thickness of the cured film being formed with resin combination by display base plate is not particularly limited, but is generally 1～50 μ m, is preferably 5～40 μ m.
Embodiment
Provide embodiment below, more specifically the present invention will be described, but the present invention is not subject to the restriction of following embodiment.
[dummy suffix notation using in embodiment]
The meaning of the dummy suffix notation using in following examples is as described below.
< acid dianhydride >
BP-TME:4,4 '-biphenyl two (trimellitic acid monoesters acid anhydrides) (Honshu chemical industry (strain) production) (following formula (11))
[changing 17]
TAHQ: to phenylene two (trimellitic acid monoesters acid anhydrides) (マ Na ッ Network (strain) production) (following formula (12))
[changing 18]
< diamines >
PDA: Ursol D (Tokyo changes into (strain) and produces)
APABI:2-(3-aminophenyl)-5-aminobenzimidazole (Changzhou SunlightPharmaceutical Co., Ltd. produces)
BABP:4,4 '-bis-(3-amino-benzene oxygen) benzophenone (Changzhou SunlightPharmaceutical Co., Ltd. produces)
BAPB:4,4 '-bis-(4-amino-benzene oxygen) biphenyl (Tokyo changes into (strain) and produces)
< linking agent >
V8000-C7: naphthalene type epoxy compounds (DIC (strain) production)
< solvent >
NMP:N-methyl-2-pyrrolidone
[mensuration of number-average molecular weight and weight-average molecular weight]
The weight-average molecular weight of polymkeric substance is (hereinafter to be referred as Mw.) and molecular weight distribution, using the GPC device that Japanese light splitting (strain) produces (Shodex[registered trademark] post KF803L and KF805L), is that 1mL/ minute, column temperature are to measure under the condition of 50 ℃ making flow as the dimethyl formamide of eluting solvent.In addition, Mw is polystyrene conversion value.
< synthesis example P1: the synthetic > of polyamic acid (P1)
1.66g PDA (0.015 mole) and 0.862g APABI (0.004 mole) are dissolved in 70gNMP, add 10.1g BP-TME (0.019 mole), and then add 7.4g NMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 134000, and molecular weight distribution is 2.8.
< synthesis example P2: the synthetic > of polyamic acid (P2)
1.82g PDA (0.017 mole) and 0.42g APABI (0.002 mole) are dissolved in 80gNMP, add 9.77g BP-TME (0.018 mole), and then add 8gNMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 138600, and molecular weight distribution is 2.3.
< synthesis example P3: the synthetic > of polyamic acid (P3)
1.42g PDA (0.013 mole), 0.16g APABI (0.001 mole) and 0.6g BABP (0.002 mole) are dissolved in to 70g NMP, add 8.78g BP-TME (0.016 mole), and then interpolation 9.2gNMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 151400, and molecular weight distribution is 2.8.
< synthesis example P4: the synthetic > of polyamic acid (P4)
1.42g PDA (0.013 mole), 0.16g APABI (0.001 mole) and 0.5g BAPB (0.002 mole) are dissolved in to 70g NMP, add 7.36g BP-TME (0.014 mole), and then interpolation 11.0g NMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 138600, and molecular weight distribution is 2.3.
< Comparative Example H P1: the synthetic > of polyamic acid (HP1)
22.7g PDA (0.210 mole) is dissolved in to 700g NMP, adds 94.3g TAHQ (0.205 mole), and then add 83g NMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 142700, and molecular weight distribution is 2.5.
< Comparative Example H P2: the synthetic > of polyamic acid (HP2)
3.78g APABI (0.017 mole) is dissolved in 70g NMP, adds 8.82g BP-TME (0.017 mole), and then add 7.4g NMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 148400, and molecular weight distribution is 2.5.
< Comparative Example H P3: the synthetic > of polyamic acid (HP3)
1.46g PDA (0.014 mole) and 2.30g BABP (0.006 mole) are dissolved in 70g NMP, add 8.79g BP-TME (0.019 mole), and then add 7.4gNMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 102000, and molecular weight distribution is 3.3.
< Comparative Example H P4: the synthetic > of polyamic acid (HP4)
4.46g APABI (0.018 mole) is dissolved in 80g NMP, adds 8.00g TAHQ (0.017 mole), and then add 8g NMP, under nitrogen atmosphere, it is reacted 24 hours at 23 ℃.The Mw of the polymkeric substance obtaining is 142700, and molecular weight distribution is 2.5.
< sample production: paint >
According to the composition shown in table 1, mixed polymer solution, linking agent and as the NMP of solvent, form uniform solution lower stir more than 6 hours of room temperature (approximately 23 ℃), thereby modulated resin combination for display base plate (paint).
[table 1]
The composition of table 1 resin combination (paint) for display base plate
< coated film and linear expansivity are evaluated >
Evaluate by the following method the resin combination for display base plate (paint) of above-mentioned modulation.Evaluation result is as shown in table 2.
[the thickness stripping means before solidifying]
Use rod coater (section differs from 250 μ m) that the resin combination for display base plate (paint) in table 1 is coated on respectively on the glass substrate of 100mm * 100mm, in baking oven, at the temperature of 110 degree, burn till 10 minutes, at the temperature of 250 degree, burn till 30 minutes, at the temperature of 300 degree, burn till 30 minutes.Use contact determining film thickness device (Dektak3ST that (strain) ULVAC produces) to measure the thickness of the coated film obtaining.Then, standing in 70 degree pure water together with glass substrate in 1L beaker, thus carry out peeling off of film.
[linear expansivity]
The film of above-mentioned acquisition is made to the rectangular of 20mm * 5mm shape, use TMA-4000SA (Block ル カ ー エ イ エ ッ Network ス エ ス (strain) production) from 50 degree, to be warming up to 400 degree with the conditions of 5 degrees/min, again measure from the linear expansivity of 50 degree to 400 degree after cooling.In addition, linear expansivity is represented by the coefficient of low temperature (50 ℃～300 ℃) side and high temperature (300 ℃～400 ℃) side.
[table 2]
The evaluation result of table 2 thickness, self-supporting and linear expansivity
Zero ... there is self-supporting.Even if crooked 90 degree do not break yet
△ ... there is self-supporting, still, because impact is broken
* ... do not there is self-supporting
As shown in table 2, known, by display base plate of the present invention, with the film that resin combination obtains, there is flexibility and the sufficient thermotolerance of appropriate linear expansivity, appropriateness.

Claims (23)

1. a display base plate resin combination, it contains polyamic acid or polyimide, described polyamic acid contains the represented structural unit of following formula (1) and the represented structural unit of formula (3), described polyimide contains the represented structural unit of following formula (2) and the represented structural unit of formula (4)
Formula (1) to formula (4),
X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls,
Y 1the aromatic group or the aliphatic group that represent divalent,
Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms,
N and m represent natural number.
2. display base plate resin combination according to claim 1, wherein, described Y 2represent to have the aromatic group of heterocycle structure.
3. display base plate resin combination according to claim 2, wherein, described Y 2by following formula (5), represent,
In formula,
R 1to R 7represent independently respectively the alkyl of hydrogen atom, carbonatoms 1 to 10, the alkoxyl group of the haloalkyl of carbonatoms 1 to 10, carbonatoms 1 to 10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1 to 10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1 to 10, carbonatoms 1 to 10,
A represents the alkyl of hydrogen atom, carbonatoms 1 to 10 or the haloalkyl of carbonatoms 1 to 10, and in addition, zero represents associative key.
4. display base plate resin combination according to claim 3, wherein, described R 1to R 7and A represents hydrogen atom.
5. according to the display base plate resin combination described in any one in claim 1 to 4, wherein, described Y 1by following formula (6), represent,
In formula,
R 8to R 11represent independently respectively the alkyl of hydrogen atom, carbonatoms 1 to 10, the alkoxyl group of the haloalkyl of carbonatoms 1 to 10, carbonatoms 1 to 10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1 to 10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1 to 10, carbonatoms 1 to 10,
Q represents 1 or 2, and in addition, zero represents associative key.
6. display base plate resin combination according to claim 5, wherein, the represented divalent aromatic group of described formula (6) is the group derived from phenylenediamine.
7. display base plate resin combination according to claim 6, wherein, described R 8to R 11represent hydrogen atom.
8. according to the display base plate resin combination described in any one in claim 1 to 7, wherein, described X 1by following formula (7), represent,
In formula,
R 12to R 21represent independently respectively the alkyl of hydrogen atom, carbonatoms 1 to 10, the alkoxyl group of the haloalkyl of carbonatoms 1 to 10, carbonatoms 1 to 10, hydroxyl, halogen atom, nitro, formyl radical, cyano group, carboxyl, can be by W 1the phenyl replacing, can be by W 1the naphthyl replacing, can be by W 1the thienyl replacing or can be by W 1the furyl replacing,
W 1represent the alkyl of carbonatoms 1 to 10, alkoxyl group, hydroxyl, halogen atom, nitro, formyl radical, cyano group or the carboxyl of the haloalkyl of carbonatoms 1 to 10, carbonatoms 1 to 10,
Z 1and Z 2difference is expression-NH-,-NZ independently 3-or Sauerstoffatom,
Z 3the alkyl that represents carbonatoms 1 to 10,
P represents 1 or 2, and in addition, zero represents associative key.
9. display base plate resin combination according to claim 8, wherein, described p represents 2.
10. display base plate resin combination according to claim 9, wherein, described R 12to R 21represent hydrogen atom.
11. according to the display base plate resin combination described in any one in claim 1 to 10, and wherein, the pass of the m in the n in described formula (1) and described formula (3) is n/m=70/30 to 99/1.
12. according to the display base plate resin combination described in any one in claim 1 to 10, and wherein, the pass of the m in the n in described formula (2) and described formula (4) is n/m=70/30 to 99/1.
13. according to the display base plate resin combination described in any one in claim 1 to 12, and it further contains linking agent.
14. display base plate resin combinations according to claim 13, wherein, described linking agent is the compound with 2 above epoxy group(ing).
15. display base plate resin combinations according to claim 14, wherein, described linking agent is the compound with aromatic group.
16. display base plate resin combinations according to claim 15, wherein, described linking agent is the compound with 6 following epoxy group(ing), and this compound has the alkyl of the carbonatoms 1 to 10 that epoxy group(ing) is combined with aromatic group.
17. according to claim 13 to the display base plate resin combination described in any one in 16, and wherein, with respect to described polyamic acid or the polyimide of 100 mass parts, described linking agent is below 20 mass parts.
18. 1 kinds of paints, is characterized in that, be in claim 1 to 17 display base plate described in any one with resin combination, be dissolved at least a kind of solvent and.
19. 1 kinds of cured film, it requires the paint described in 18 to burn till and obtain above at 230 ℃ by right to use.
20. 1 kinds of structures, it has the layer that one deck at least comprises the cured film described in claim 19 on substrate.
21. 1 kinds of polyamic acids, it contains the represented structural unit of following formula (1) and the represented structural unit of formula (3),
In formula (1) and formula (3),
X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls,
Y 1the aromatic group or the aliphatic group that represent divalent,
Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms,
N and m represent natural number.
22. 1 kinds of polyimide, it contains the represented structural unit of following formula (2) and the represented structural unit of formula (4),
In formula (2) and formula (4),
X 1represent to have 4 valency organic groups of aromatic group and 2 carbonyls,
Y 1the aromatic group or the aliphatic group that represent divalent,
Y 2represent to have the divalent aromatic group of 2 above nitrogen-atoms,
N and m represent natural number.
23. 1 kinds of base plate for displaying, it comprises the polyimide described in claim 22.
CN201280067828.8A 2011-11-25 2012-11-21 Display base plate resin combination Active CN104066768B (en)

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