CN106062037B - The manufacturing method of display base plate resin combination, display base plate resin film and display base plate resin film - Google Patents
The manufacturing method of display base plate resin combination, display base plate resin film and display base plate resin film Download PDFInfo
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- CN106062037B CN106062037B CN201580010820.1A CN201580010820A CN106062037B CN 106062037 B CN106062037 B CN 106062037B CN 201580010820 A CN201580010820 A CN 201580010820A CN 106062037 B CN106062037 B CN 106062037B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/18—Polybenzimidazoles
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- 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
-
- 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
Abstract
Pass through the present invention, it is possible to provide a kind of display base plate resin combination, the display base plate resin combination can form the display base plate resin film of linear expansion coefficient and high-tensile with high-fire resistance and appropriateness.The present invention solves the above subject by following display base plates with resin combination, the display base plate resin combination contains following polyamic acids and organic solvent, the polyamic acid includes the structural unit that formula (1) represents, and weight average molecular weight is 10, more than 000.Herein, in formula (1), X1The aromatic group of 4 valencys of expression (3), Y1The group that expression (P) represents, also, n represents the number of repetitive unit.
Description
Technical field
The present invention relates to display base plate resin combination, display base plate resin film and display base plate trees
The manufacturing method of membrane of lipoprotein.
Background technology
In recent years, in the field of the display devices such as display of organic electroluminescence, liquid crystal display, except to high-resolution
Outside the requirement of change, the requirement to lightweight, flexibility etc. is increasingly increased.In consideration of it, easy to manufacture and it is known have high-fire resistance
Polyimide resin as instead of glass base plate for displaying material and be concerned.
However, for the materials'use using polyimides as display base plate, its linear expansion coefficient is needed to be and glass
The close value of linear expansion coefficient (about 3~10ppm/K or so), but most of polyimides has 60~80ppm/K's or so
Therefore linear expansion coefficient, is not suitable for the baseplate material of display.
Used in high resolution display active matrix (active matrix) drive panel, in order to formed in addition to
Active matrix layer including further including film active element except rectangular pixel electrode, not only needs 300~500 DEG C of carry out
The high-temperature process of left and right, and need accurately contraposition.However, polyimides in terms of linear expansion coefficient characteristic due to comparing glass
Difference, thus at high temperature can be than glass substrate contraction or expansion to a greater degree.Therefore, polyimides is being used as substrate material
During material, it is commonly in the situation for being difficult to maintain high-dimensional stability in the manufacturing process of display.
Therefore, it in order to play the heat resistance of polyimides and realize suitable linear expansion coefficient characteristic, is closed
Suitable MOLECULE DESIGN.
As the polyimides for showing low linear expansion, it is proposed that the high polyamides formed by acid dianhydride and diamines of rigidity
Imines, but it is there are more problem, for example, the high-temperature area (300~500 DEG C) near the glass transition temperature of polymer
As high linear expansivity；When the rigidity of polymer backbone is excessively high, film strength, flexibility can be damaged；Etc. it is (patent document 1, non-
Patent document 1), the polyimides for fully meeting the requirement of height is not yet known.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-202729 bulletins
Non-patent literature
Non-patent literature 1：Journal of Applied Polymer Science, Vol.62,2303-2310
(1996)
Invention content
Problems to be solved by the invention
Therefore, remaining that manufacture can become and have a high-fire resistance and suitable instead of the base plate for displaying material of glass
The linear expansion coefficient of degree and the display base plate resin film of the polyimides system of high-tensile.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a kind of display base plate resin combinations
Object, the display base plate resin combination can form strong with high-fire resistance and appropriate linear expansion coefficient and high tensile
The display base plate resin film of degree.
Specifically, the purpose of the present invention is to provide a kind of display base plate resin combination, the display bases
Plate resin combination can be formed using the acid dianhydride with versatility and diamines as principal component with tolerable display
The linear expansion coefficient of the heat resistance of manufacturing process, the flexibility of appropriateness and appropriateness be (appropriateness near especially 400~500 DEG C
Linear expansion coefficient) resin film.
It should be noted that so-called appropriate flexibility herein, refer to the high flexibility of following degree：Resin film has
There is a self-supporting, and do not rupture even if be bent 90 degree or close to 90 degree of angle.
Means for solving the problems
Further investigation has this time been repeated in present inventors, as a result, surprisingly, it is found that, by using containing
Have by 3,3 ' -4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), p-phenylenediamine (p-PDA) and 4,4 "-diamino para-terpheny
(DATP) resin combination of specific polyamic acid derived from can obtain having required heat-resisting for display base plate
Property, appropriateness flexibility and appropriateness linear expansion coefficient resin film.Obtained resin film is also (excellent with high bending strength
Different self-supporting), from above-mentioned characteristic it is found that the resin film can become the excellent display with the characteristic that can replace glass
Device baseplate material.In addition, present inventors it has also been found that, by using also using 2- in addition to the above ingredients
The polyamic acid of (3- aminophenyls) -5- aminobenzimidazoles (APAB), can further enhance said effect.The present invention is
It is completed based on above-mentioned discovery.
Therefore, the present invention relates to inventions as described below.
1 ＞ display base plate resin combinations of ＜, containing following polyamic acids and organic solvent, the polyamic acid
Comprising the structural unit that following formulas (1) represents, and weight average molecular weight is 10, more than 000.
[in formula,
X1Represent the aromatic group of 4 valencys of following formulas (3),
Y1Represent the group that following formulas (P) represents, also,
N represents the number of repetitive unit,
(in formula,
The alkyl or phenyl of R expressions F, Cl, carbon atom number 1~3,
M represents 0~4 integer, also,
R represents 1~3 integer)].
In above-mentioned 1 ＞ of ＜ of 2 ＞ of ＜, it is preferred that the structural unit that formula (1) represents has the weight by formula of more than two kinds (1)
The random or block copolymer structure that multiple unit is formed.
In above-mentioned 1 ＞ of ＜ of 3 ＞ of ＜, it is preferred that containing following polyamic acids and organic solvent, the polyamic acid includes
The structural unit that following formulas (1-1) and formula (1-2) represent, and weight average molecular weight is 10, more than 000.
[in formula,
X1Represent the aromatic group of 4 valencys of above-mentioned formula (3),
Y2Represent following formula (P1) or the group that (P2) is represented,
Y3Represent the group that following formulas (P3) represents, also,
n1And n2Represent the number of each repetitive unit,
(in formula,
R1、R2、R3、R4、R5And R6Can be the same or different, represent F, Cl, carbon atom number 1~3 alkyl or benzene
Base,
M1, m2, m3, m4, m5 and m6 can be the same or different, and represent 0~4 integer)].
In any one of above-mentioned 1 ＞ of ＜~＜, 3 ＞ of 4 ＞ of ＜, it is preferred that polyamic acid also includes following formulas (2)
The structural unit of expression.
[in formula,
X1Represent the aromatic group of 4 valencys of above-mentioned formula (3),
Y4Represent the group that following formulas (P4) represents, also,
n3Represent the number of repetitive unit,
(in formula,
R7And R8Can be the same or different, represent F, Cl, carbon atom number 1~3 alkyl or phenyl,
The alkyl or phenyl of R ' expressions hydrogen atom, carbon atom number 1~3, and
L and m can be the same or different, and represent 0~4 integer)].
In 5 ＞ of ＜ above-mentioned 3 ＞ of ＜ or 4 ＞ of ＜, it is preferred that n1And n2Meet n1/n2=1.7~20 condition.
In above-mentioned 4 ＞ of ＜ of 6 ＞ of ＜, it is preferred that above-mentioned n1、n2And n3Meet n3/(n1+n2+n3)≤0.2。
7 ＞ of ＜ preferably, the structural unit or at least that the formula (1) that above-mentioned polyamic acid contains at least 60 moles % represents
The structural unit that the formula (1-1) and formula (1-2) of 60 moles of % represents.
8 ＞ display base plate resin films of ＜ are the display bases using any one of above-mentioned 1 ＞ of ＜~＜, 7 ＞
Plate is made with resin combination.
9 ＞ image display devices of ＜, the display base plate resin film with above-mentioned 8 ＞ of ＜.
The manufacturing method of 10 ＞ display base plate resin films of ＜, which is characterized in that use above-mentioned 1 ＞ of ＜~＜, 7 ＞
Any one of display base plate resin combination.In a kind of preferred embodiment, aforementioned display device substrate resin film
Manufacturing method includes the process that aforementioned display device substrate is coated on substrate with resin combination and is heated.
The manufacturing method of 11 ＞ image display devices of ＜, which is characterized in that use the display base plate tree of above-mentioned 8 ＞ of ＜
Membrane of lipoprotein.
The effect of invention
The display base plate resin combination of the present invention can be with the acid dianhydride with versatility and with versatility
Diamines is manufactured for principal component, by using the composition, so as to using wet process (wet process), reappear
Property well with large area obtain with high-fire resistance, appropriateness flexibility and appropriateness linear expansion coefficient (especially 400~
Near 500 DEG C appropriateness linear expansion coefficient) resin film.
Therefore, by using the present invention display base plate resin combination, can not only realize display lightweight,
Compact (compact) changes, and can also be achieved reduced by cost of raw and processed materials, manufacture efficiency improves and the low price of display brought
Change etc..
Specific embodiment
Hereinafter, the present invention is described in detail.
Display base plate resin combination
As described above, the display base plate resin combination of the present invention contains following polyamic acids and organic solvent, institute
It states polyamic acid and includes the structural unit that formula (1) represents, and its weight average molecular weight is 10, more than 000.
In addition, as described above, in formula (1), X1The aromatic group of 4 valencys of expression (3), Y1The base that expression (P) represents
Group.
In addition, in formula (P), R represents F, Cl or the alkyl or phenyl of carbon atom number 1~3, preferably represents F, Cl.Equally
Ground, in above-mentioned formula (P), m represents 0~4 integer, preferably represents 0~2, more preferably represents 0~1, particularly preferably represents 0.Separately
Outside, in above-mentioned formula (P), r represents 1~3 integer.
It should be noted that the alkyl of carbon atom number 1~3 includes methyl, ethyl, n-propyl and isopropyl, preferably carbon is former
The alkyl of subnumber 1~3 is methyl, more preferably methyl.
In formula (1), n represents the number of repetitive unit, is positive integer, equal according to the weight of the polyamic acid used in the present invention
Molecular weight determines.
The weight average molecular weight of the polyamic acid of repetitive unit that there is formula (1) to represent used in the present invention is necessary for 10,
More than 000, preferably 15, more than 000, more preferably 20, more than 000, it is still more preferably 30, more than 000.The opposing party
Face, the upper limit value of the weight average molecular weight about the polyamic acid used in the present invention, it typically is 2,000,000 hereinafter, but examining
Whens the excess stickiness raising of worry inhibition resin combination (varnish), reproducibility obtain high resin film of flexibility etc. well,
Preferably 1,000,000 hereinafter, more preferably 200, and less than 000.
The polyamic acid used in the present invention contains at least % of 50 moles of %, preferably at least 60 moles, more preferably at least 70
The repetitive unit that represents of formula (1) of mole %, still more preferably at least 80 moles of %, further preferably at least 90 moles %.
During using such amount, using polyamic acid can reproducibility well obtain with suitable for display base plate characteristic resin
Film.
Preferred embodiment according to the present invention, polyamic acid are the copolymers that the repetitive unit only represented by formula (1) is formed,
That is, it is the polymer that these repetitive units are contained with the amount of 100 moles of %.At this time, it is preferred that the formula in the polyamic acid
(1) structural unit represented has the random or block copolymer structure formed by the repetitive unit of formula of more than two kinds (1), and
Specific a kind in the repetitive unit not only represented by formula (1) forms.The type of the repetitive unit of workable formula (1) is more
Preferably 2~4, further preferably 2~3.
Preferred embodiment according to the present invention, as described above, the present invention display base plate resin combination contain it is following
Polyamic acid and organic solvent, the polyamic acid includes the structural unit that formula (1-1) and formula (1-2) represent, and its is heavy
Molecular weight is more than 10,000.
In addition, as described above, in formula (1-1) and formula (1-2), X1Represent the aromatic series base of 4 valencys of above-mentioned formula (3)
Group, Y2Represent above-mentioned formula (P1) or the group that (P2) is represented, the group that preferably expression (P1) represents, Y3Represent above-mentioned formula
(P3) group represented.
In addition, in formula (P1), formula (P2) and formula (P3), R1、R2、R3、R4、R5And R6It can be the same or different, represent
F, Cl, carbon atom number 1~3 alkyl or phenyl, preferably represent F or Cl.
Similarly, in above-mentioned formula (P), m1, m2, m3, m4, m5 and m6 can be the same or different, and represent 0~4
Integer preferably represents 0~2, more preferably represents 0~1, particularly preferably represents 0.
In formula (1-1) and formula (1-2), n1、n2It represents the number of each repetitive unit, meets n1/n2=1.7~20 item
Part.Herein, above-mentioned n1/n2The lower limiting value of numberical range be preferably 2.1, further preferably 2.2, still more preferably for
2.3.On the other hand, n1/n2The upper limit value of numberical range be preferably 19, more preferably 18.
Consider that reproducibility is obtained well with appropriate linear expansion coefficient, heat resistance, (especially tension is strong for flexibility
Degree) resin film when, n1/n2Preferably satisfy 2.1~7.5, more preferably meet 2.1~6.8, still more preferably meet 3.2~
6.0, further preferably meet 3.2~5.1.
The polyamic acid used in the present invention contains at least % of 50 moles of %, preferably at least 60 moles, more preferably at least 70
Mole %, further preferably still more preferably at least 80 moles of %, the formula (1-1) of at least 90 moles % and formula (1-2) table
The repetitive unit shown.During using such amount, using polyamic acid can reproducibility well obtain be suitable for display base
The resin film of the characteristic of plate.
Particularly preferred mode according to the present invention, polyamic acid are the repetitions only represented by formula (1-1) and formula (1-2)
The copolymer that unit is formed, that is, be the polymer that these repetitive units are contained with the amount of 100 moles of %.
The weight average molecular weight of the polyamic acid used in the present invention is necessary for 10, more than 000, preferably 15, and more than 000,
More preferably 20, more than 000, it is still more preferably 30, more than 000.On the other hand, about the polyamide used in the present invention
Acid weight average molecular weight upper limit value, it typically is 2,000,000 hereinafter, but consider inhibit resin combination (varnish) viscosity
Whens excessively raising, reproducibility obtain high resin film of flexibility etc. well, preferably 1,000,000 hereinafter, more preferably
Less than 200,000.
Preferred mode according to the present invention, the polyamic acid used in of the invention can also include the knot of formula (2) expression
Structure unit.
As described above, in formula (2), X1Represent the aromatic group of 4 valencys of above-mentioned formula (3), Y4Represent above-mentioned formula (P4)
The group of expression, in addition, n3Represent the number of each repetitive unit.
In addition, in formula (P4), R7And R8Can be the same or different, represent F, Cl, carbon atom number 1~3 alkyl or
Phenyl.R7It is preferred that represent F or Cl.R8It is preferred that represent F or Cl.
The alkyl or phenyl of R ' expressions hydrogen atom, carbon atom number 1~3, preferably represent hydrogen atom or carbon atom number 1~3
Alkyl, more preferably represent hydrogen atom.
In addition, l and m can be the same or different, the integer of expression 0~4, preferably expression 0~2, more preferably expression 0~
1, particularly preferably represent 0.
When also using the structural unit that formula (2) represents other than the structural unit in addition to using formula (1) expression, n, n3It is preferred that
Meet n3/(n+n3)≤0.2, more preferably meets n3/(n+n3)≤0.1, still more preferably meets n3/(n+n3)≤0.05.For
During above range, reproducibility well obtain with appropriateness linear expansion coefficient, heat resistance, (especially tension is strong for flexibility
Degree) resin film in terms of be advantageous.
In the knot that formula (2) is also used to represent other than using and including the structural unit that formula (1-1) and formula (1-2) represent
During structure unit, n1、n2、n3It represents the number of each repetitive unit, preferably satisfies n3/(n1+n2+n3)≤0.2, more preferably meets n3/
(n1+n2+n3)≤0.1, still more preferably meets n3/(n1+n2+n3)≤0.05.During for above range, in reproducibility well
Obtain with appropriateness linear expansion coefficient, heat resistance, flexibility (especially tensile strength) resin film in terms of be advantageous
's.
The polyamic acid used in the present invention can be in addition to the structural unit or formula (1-1) and formula that are represented comprising formula (1)
Other than the structural unit that (1-2) is represented, also comprising other structures unit (repetitive unit).The content of above-mentioned other structures unit
50 moles of %, preferably shorter than 40 moles of %, more preferably less than 30 moles of % are had to be lower than, are still more preferably rubbed less than 20
You are %, still further preferably less than 10 moles %.
As above-mentioned other structures unit, can enumerate by o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2- methyl-1s,
4- phenylenediamines, 5- methyl-1s, 3- phenylenediamines, 4- methyl-1s, 3- phenylenediamines, 2- (trifluoromethyl) -1,4- benzene two
Amine, 2- (trifluoromethyl) -1,3- phenylenediamines and 4- (trifluoromethyl) -1,3- phenylenediamines, benzidine, 2,2 '-dimethyl
Benzidine, 3,3 '-dimethylbenzidine, 2,3 '-dimethylbenzidine, 2,2 '-bis- (trifluoromethyl) benzidine, 3,3 '-
Bis- (trifluoromethyl) benzidine, 2,3 '-bis- (trifluoromethyl) benzidine, 4,4 '-diphenyl ether, 4,4 '-bis- (4- aminobenzenes
Oxygroup) biphenyl, 4,4 '-diaminobenzene formailide, 5- amino -2- (3- aminophenyls) -1H- benzimidazoles, 9,
Bis- (4- aminophenyls) diamines as fluorenes of 9- and pyromellitic dianhydride (PMDA), 2,3,6,7- naphthalenetetracarbacidic acidics dianhydride, 4,
4 '-oxygroup double phthalic anhydride, 3,3 ', structure etc. derived from acid dianhydride as 4,4 '-benzophenone tetracarboxylic acid anhydride.
Preferred embodiment according to the present invention, in the present invention polyamic acid that uses can by making to be used as the 3,3 ' of acid dianhydride,
4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) (formula (4)), with as the p-phenylenediamine (pPDA) (formula (5)) of diamines and 4,4 "-two
Amino para-terpheny (DATP) (formula (6)) reaction obtains.
In above-mentioned reaction, for 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), with by p-phenylenediamine (pPDA) and 4,
For the charging of the diamines of 4 "-diamino para-terpheny (DATP) composition is than (molar ratio), it is contemplated that desired polyamic acid
Molecular weight, structural unit ratio etc. and suitably set, using amine component as if 1, can usually make as acid anhydrides ingredient
BPDA is 0.7~1.3 or so, preferably 0.8~1.2 or so.
On the other hand, for the charging ratio as the pPDA and DATP of diamines, by the amount (m of the substance of DATP2)
During as 1, it can usually make the amount (m of the substance of pPDA1) for 1.7~20 or so, preferably 2.1~20, more preferably 2.2~
20, it is still more preferably 2.3~19, much further preferably from 2.3~18.That is, for m1And m2For, in general, m1/m2=
1.7~20, preferably 2.1~20, more preferably 2.2~20 are still more preferably 2.3~19, much further preferably from 2.3
~18.
Preferred mode according to the present invention, can be by making to be used as the 3 of acid dianhydride, 3 ', 4,4 '-bibenzene tetracarboxylic two
Acid anhydride (BPDA), with the p-phenylenediamine (pPDA) and 4,4 "-diamino para-terpheny (DATP) and 2- (3- ammonia as diamines
Base phenyl) -5- aminobenzimidazoles (APAB) (formula (7)) reaction obtain.
In above-mentioned reaction, for 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), with by p-phenylenediamine (pPDA), 4,
The diamines of 4 "-diamino para-terpheny (DATP) and 2- (3- aminophenyls) -5- aminobenzimidazoles (APAB) composition
Charging than (molar ratio) for, it is contemplated that the molecular weight of desired polyamic acid, ratio of structural unit etc. and suitably set,
Using amine component as if 1, can usually making the BPDA as acid anhydrides ingredient left for 0.7~1.3 or so, preferably 0.8~1.2
It is right.
On the other hand, for the charging ratio as the pPDA and DATP of diamines and APAB, by the substance of pPDA
Measure (m1) amount (m with the substance of DATP2) amount (m with the substance of APAB3) it is total as 1 when, the amount (m of the substance of APAB3)
Preferably 0.2 hereinafter, more preferably 0.1 hereinafter, still more preferably be less than 0.05.That is, for m1And m2And m3For, it is excellent
Be full sufficient m3/(m1+m2+m3)≤0.2, more preferably meets m3/(m1+m2+m3)≤0.1, still more preferably meets m3/(m1+m2+
m3)≤0.05。
Above-mentioned reaction preferably carries out in a solvent, when using solvent, for its type, as long as not giving reaction zone
Carry out harmful effect, various solvents can be used.
As concrete example, metacresol, 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- ethyls -2- can be enumerated
Pyrrolidones, n-vinyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, 3- methoxies
Base-N, N- dimethylpropionamide, 3- ethyoxyls-N, N- dimethylpropionamide, 3- propoxyl group-N, N- dimethyl propionyl
Amine, 3- isopropoxies-N, N- dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide, 3- sec-butoxies-
Protonic solvents such as N, N- dimethylpropionamide, 3- tert-butoxies-N, N- dimethylpropionamide, gamma-butyrolacton etc..It
Can be used alone or can also combine two or more and use.
For reaction temperature, suitably set in the range of the fusing point to boiling point from the solvent used, usually
For 0~100 DEG C or so, the imidizate of the polyamic acid obtained in order to prevent maintains the high-content of polyamic acid unit, reacts
Temperature is preferably 0~70 DEG C or so, more preferably 0~60 DEG C or so, is still more preferably 0~50 DEG C or so.
Reaction time depends on reaction temperature, the reactivity of raw material, thus can not without exception depending on, but it typically is 1
~100 hours or so.
Using method described above, the reaction solution containing target polyamic acid can be obtained.
In the present invention, in general, after being filtered to above-mentioned reaction solution, its filtrate is used directly as display base plate
Resin combination (varnish) makes after using or being diluted or concentrate as display base plate resin combination (varnish)
With.By operating as described above, heat resistance, flexibility or the line expansion for the resin film that can cause can not only be reduced
The impurity that coefficient feature is deteriorated is mixed into, and can be efficiently obtained composition.
Solvent for being diluted or concentrating is not particularly limited, for example, can enumerate and the above-mentioned reaction dissolvent reacted
The same solvent of concrete example, they can be used alone or can also combine two or more and use.
In above-mentioned solvent, reproducibility is considered when obtaining the resin film of high flatness (flatness) well, as making
Solvent, preferably n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone, 1,3- bis-
Methyl -2- imidazolones (imidazolidinone), N- ethyl-2-pyrrolidones, gamma-butyrolacton.
In addition, in the present invention, can make the varnish obtained by the following method as display base plate resin combination
With the method is：Above-mentioned reaction solution is post-processed using conventional method, isolates polyamic acid, then, will be detached
The polyamic acid gone out is dissolved or dispersed in solvent.In this case, when considering that reproducibility obtains the film of high flatness well,
It is preferred that polyamic acid is dissolved in solvent.Solvent for being dissolved or being disperseed is not particularly limited, for example, can enumerate with it is upper
The same solvent of concrete example of the reaction dissolvent of reaction is stated, they can be used alone or can also combine two or more and use.
For polyamic acid for the concentration of varnish gross mass, thickness, the varnish viscosity of the film made are considered
Deng and suitably set, usually 0.5~30 mass % or so, preferably 5~25 mass % or so.
In addition, for the viscosity of varnish, it is also considered that thickness of the film of making etc. and suitably set, but with reappear
In the case of for the purpose of the resin film of thickness that property obtains especially 5~50 μm or so well, the viscosity of varnish usually exists
It is 500~50,000mPas or so, preferably 1,000~20,000mPas or so at 25 DEG C.
Herein, for the viscosity of varnish, the viscosimeter for being commercially for measuring liquid viscosity can be used, referring for example to
The step of described in JIS K7117-2, is measured under conditions of being 25 DEG C in varnish temperature.Preferably, it can be surveyed as follows
It is fixed：Using cone-plate type (cone plate types), rotational viscometer is as viscosimeter, preferably in the viscosimeter for using the type
When use 1 ° of 34 ' × R24 as standard cone rotor (cone rotor), surveyed under conditions of being 25 DEG C in varnish temperature
It is fixed.As such rotational viscometer, for example, Toki Sangyo Co., Ltd. TVE-25H can be enumerated.
It, can by the way that the display base plate of present invention mentioned above is coated on matrix with resin combination and is heated
Obtain the resin film formed by polyimides with the linear expansion coefficient of high-fire resistance, the flexibility of appropriateness and appropriateness.
As matrix (base material), for example, can enumerate plastics (makrolon, polymethacrylates, polystyrene, polyester,
Polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin etc.), metal (silicon wafer etc.), wood
Material, paper, glass, slabstone etc..
The method being coated is not particularly limited, for example, casting coating (cast coat method) method, spin coating can be enumerated
Method, scraper for coating method, dip coating, rolling method, stick coating method, die coating method, gunite, print process (relief printing plate, intaglio plate, lithographic plate, screen printing
Brush etc.) etc..
In addition, as the side of polyamic acid imidizate contained in the display base plate resin combination for making the present invention
Method can enumerate the hot-imide that is directly heated to the resin combination having been coated with onto substrate and in resin combination
Middle addition catalyst and the catalyst imidizate heated.
For the catalyst imidizate of polyamic acid, by adding catalyst in the resin combination of the present invention
And be stirred, the resin combination added with catalyst is prepared, then, to base plate coating and is heated, this makes it possible to obtain
Resin film.The amount of catalyst is 0.1~30 mole times of amide acidic group, and preferably 1~20 mole again.It in addition, also can be to adding
The acetic anhydride of addition as dehydrating agent etc. in resin combination added with catalyst, in an amount of from 1~50 mole times of amide acidic group,
Preferably 3~30 moles times.
As imidization catalyst, it is preferable to use tertiary amine.As tertiary amine, preferably pyridine, substituted-pyridines, imidazoles, take
For imidazoles, picoline, quinoline, isoquinolin etc..
Heating temperature when hot-imide and catalyst imidizate is preferably less than 450 DEG C.During higher than 450 DEG C, deposit
Become fragile in obtained resin film, the situation of resin film suitable for display base plate purposes can not be obtained.
Additionally, it is contemplated that when the heat resistance of obtained resin film and linear expansion coefficient characteristic, it is preferred that in 50 DEG C~
After 100 DEG C are heated the resin combination of coating 5 minutes~2 hours, directly stepwise increase heating temperature, finally higher than
375 DEG C and to be heated 30 minutes~4 hours at less than 450 DEG C of temperature.
For the resin combination of coating, it is therefore particularly preferred that heated 5 minutes~2 hours in 50 DEG C~100 DEG C
Afterwards, heat 5 minutes~2 hours at higher than 100 DEG C and for less than 200 DEG C of temperature, next, higher than 200 DEG C and be 375
It is heated at temperature below DEG C 5 minutes~2 hours, finally, 30 minutes~4 is being heated higher than 375 DEG C and at a temperature of being 450 DEG C
Hour.
About utensil for heating, for example, heating plate, baking oven etc. can be enumerated.For heating atmosphere, can be
Under air or under non-active gas, furthermore it is possible to be under normal pressure or under reduced pressure.
About the thickness of resin film, especially in the substrate as flexible display in use, usually 1~60 μm
Left and right, preferably 5~50 μm or so, the thickness of the film before adjustment heating is so as to form the resin film of desired thickness.
Resin film described above meets the required each condition of basilar memebrane as flexible display substrate, therefore,
It is used most suitable as the basilar memebrane of flexible display substrate.
Embodiment
Hereinafter, enumerating embodiment further specifically describes the present invention, but the present invention is not limited by following embodiments.
[1] abbreviation used in embodiment
The abbreviation used in the present embodiment is as described below.
＜ solvents ＞
NMP：N-methyl-2-pyrrolidone
＜ amines ＞
P-PDA：P-phenylenediamine
APAB：2- (3- aminophenyls) -5- aminobenzimidazoles
DATP：4,4 "-diamino para-terpheny
BABP：Bis- (4- amino-benzene oxygens) benzophenone
DABA：N- (4- aminophenyls) -4- aminobenzamides
＜ acid dianhydrides ＞
BPDA：3,3 ' -4,4 '-bibenzene tetracarboxylic dianhydride
TAHQ：TOPOT 2,2′ p phenylenebis (trimellitic acid monoester anhydride)
PMDA：Pyromellitic acid dianhydride
NTCDA：Naphthalene -1,4,5,8- tetracarboxylic acid dianhydrides
[2] measure of number-average molecular weight and weight average molecular weight
For the weight average molecular weight (hereinafter referred to as Mw) of polymer and molecular weight distribution (Mw/Mn), Japan is used
Co. Ltd. system GPC devices (Shodex (trade mark) column KF803L and KF805L) are divided, make the dimethyl as eluting solvent
The flow of formamide is 1ml/ minutes, column temperature is measured under conditions of being 50 DEG C.It should be noted that Mw is changed for polystyrene
Calculation value.It should be noted that herein, Mn is the abbreviation of number-average molecular weight.
[3] preparation (synthesis of polyamic acid) of display base plate resin combination
＜ embodiments 1：The synthesis ＞ of polyamic acid (P1)
BPDA (98) //p-PDA (90)/DATP (5)/APAB (5)
By 17.8g (0.165 mole) p-PDA and 2.38g (0.009 mole) DATP and 2.05g (0.009 mole)
APABI is dissolved in the NMP of 420g, while adds 52.8g (0.179 mole) BPDA, then, the NMP of 5g is added again, in nitrogen
Under gas atmosphere, carry out reacting for 24 hours in 23 DEG C.
The weight average molecular weight (Mw) of obtained polymer is 63800, and molecular weight distribution (Mw/Mn) is 11.3.By the solution
As display base plate resin combination.
＜ embodiments 2：The synthesis ＞ of polyamic acid (P2)
BPDA (98) //p-PDA (70)/DATP (25)/APAB (5)
By 12.9g (0.119 mole) p-PDA and 11.1g (0.043 mole) DATP and 1.90g (0.009 mole)
APABI is dissolved in the NMP of 420g, while adds 49.1g (0.167 mole) BPDA, then, the NMP of 5g is added again, in nitrogen
Under gas atmosphere, carry out reacting for 24 hours in 23 DEG C.
The Mw of obtained polymer is 65500, and molecular weight distribution (Mw/Mn) is 12.8.Using the solution as display base
Plate resin combination.
＜ embodiments 3：The synthesis ＞ of polyamic acid (P3)
BPDA (98) //p-PDA (70)/DATP (30)
12.8g (0.119 mole) p-PDA and 13.2g (0.051 mole) DATP is dissolved in the NMP of 420g, simultaneously
48.9g (0.167 mole) BPDA is added, then, adds the NMP of 5g again, in a nitrogen atmosphere, 24 hours are carried out in 23 DEG C instead
It should.
The Mw of obtained polymer is 66300, and molecular weight distribution (Mw/Mn) is 12.9.Using the solution as display base
Plate resin combination.
＜ comparative examples 1：The synthesis ＞ of polyamic acid (HP1)
TAHQ//p-PDA
2.33g (0.022 mole) p-PDA is dissolved in the NMP of 700g, adds 9.67g (0.021 mole) TAHQ, so
Afterwards, the NMP of 88g is added again, in a nitrogen atmosphere, carries out reacting for 24 hours in 23 DEG C.
The Mw of obtained polymer is 75200, and molecular weight distribution (Mw/Mn) is 2.6.Using the solution as display base plate
Use resin combination.
＜ comparative examples 2：The synthesis ＞ of polyamic acid (HP2)
BPDA//DATP
7.11g (0.027 mole) DATP and 7.88g (0.027 mole) p-PDA is dissolved in the NMP of 85g, is added
Then 7.88g (0.027 mole) BPDA, in a nitrogen atmosphere, carries out reacting for 24 hours in 23 DEG C.
The Mw of obtained polymer is 70700, and molecular weight distribution (Mw/Mn) is 9.7.Using the solution as display base plate
Use resin combination.
＜ comparative examples 3：The synthesis ＞ of polyamic acid (HP3)
BPDA//p-PDA
4.09g (0.004 mole) p-PDA is dissolved in the NMP of 85g, adds 10.9g (0.037 mole) BPDA, so
Afterwards, in a nitrogen atmosphere, it carries out reacting for 24 hours in 23 DEG C.
The Mw of obtained polymer is 65000, and molecular weight distribution (Mw/Mn) is 2.3.Using the solution as display base plate
Use resin combination.
＜ comparative examples 4：The synthesis ＞ of polyamic acid (HP4)
PMDA//p-PDA
8.23g (0.031 mole) p-PDA is dissolved in the NMP of 85g, adds 6.76g (0.031 mole) PMDA, so
Afterwards, in a nitrogen atmosphere, it carries out reacting for 24 hours in 23 DEG C.
The Mw of obtained polymer is 45000, and molecular weight distribution (Mw/Mn) is 10.6.Using the solution as display base
Plate resin combination.
＜ comparative examples 5：The synthesis ＞ of polyamic acid (HP5)
BPDA/NTCDA//p-PDA/DBAB/BABP
By 3.07g (0.029 mole) p-PDA, 0.27g (0.001 mole) DABA and 0.12g (0.0003 mole) BABP
It is dissolved in the NMP of 88g, 7.73g (0.026 mole) BPDA and 0.80g (0.003 mole) NTCDA is added, then, in nitrogen
Under atmosphere, carry out reacting for 24 hours in 23 DEG C.
The Mw of obtained polymer is 57000, and molecular weight distribution (Mw/Mn) is 9.3.Using the solution as display base plate
Use resin combination.
[3] making of display base plate resin film and evaluation (making and evaluation of polyimide film)
Film thickness ＞ before ＜ curings (cure)
Using bar coater, the polyamic acid made respectively is coated on 100mm × 100mm glass substrates, with 10 degree mins
The heating rate of clock heats up, 120 degree 10 minutes, 300 degree 60 minutes, under 450 degree of temperature conditions of 60 minutes, utilize baking
Case is burnt into, and obtains film.
Using contact elcometer (Co., Ltd. ULVAC Dektak 3ST), obtained coated film is measured
Film thickness.
Obtained result is recorded in table 1.
Then, in 70 degree of pure water being statically placed in 1L beakers together with glass substrate, the stripping of film is carried out.
＜ linear expansion coefficients ＞
The film obtained from the above makes the strip of 20mm × 5mm sizes, uses TMA-4000SA (AXS plants of Bruker
Formula commercial firm system), the linear expansion coefficient measured from 50 degree to 500 degree.
Obtained result is recorded in table 1.
＜ weight reduces ＞
The film obtained from the above makes the strip of 20mm × 3mm sizes, uses TGA-DTA-2000SR (Bruker
AXS Co. Ltd. systems), the weight measured from 50 degree to 600 degree is reduced, and the weight reduction for 5% is confirmed.
Obtained result is recorded in table 1.
It should be noted that it is " 600 degree of ＞ " in the case of not reducing by 5% weight at 600 degree, described in table.
By result it is found that the resin film of the present invention has excellent heat resistance.
＜ self-supportings ＞
By 90 degree of film bending above obtained or more, according to following evaluation criteria, self-supporting is evaluated.
Obtained result is recorded in table 1.
By result it is found that the resin film of the present invention has good flexibility, even and if being to be bent 90 degree or close
The high flexibility for the degree that 90 degree of angle does not also rupture.
[evaluation criteria]
○：There is self-supporting.Even if be bent 90 degree do not rupture
△：It is ruptured when having self-supporting, but being bent
×：Without self-supporting
××：It is decomposed on substrate
[table 1]
Table 1
Claims (10)
1. display base plate resin combination, containing following polyamic acids and organic solvent, the polyamic acid includes down
The structural unit that the formula (1-1) and formula (1-2) stated represent, and weight average molecular weight is 10, more than 000,
In formula,
X1Represent the aromatic group of 4 valencys of following formulas (3),
Y2Represent following formula (P1) or the group that (P2) is represented,
Y3Represent the group that following formulas (P3) represents, also,
n1And n2Represent the number of each repetitive unit,
In formula,
R1、R2、R3、R4、R5And R6Can be the same or different, represent F, Cl, carbon atom number 1~3 alkyl or phenyl,
M1, m2, m3, m4, m5 and m6 can be the same or different, and represent 0~4 integer.
2. display base plate resin combination as described in claim 1, wherein, the polyamic acid has by formula (1-1)
And the random or block copolymer structure of structural unit formation that formula (1-2) represents.
3. display base plate resin combination as claimed in claim 1 or 2, wherein, polyamic acid also includes following formulas
(2) structural unit represented,
In formula,
X1Represent the aromatic group of 4 valencys of the formula (3),
Y4Represent the group that following formulas (P4) represents, also,
n3Represent the number of repetitive unit,
In formula,
R7And R8Can be the same or different, represent F, Cl, carbon atom number 1~3 alkyl or phenyl,
The alkyl or phenyl of R ' expressions hydrogen atom, carbon atom number 1~3, and
L and m can be the same or different, and represent 0~4 integer.
4. display base plate resin combination as claimed in claim 1 or 2, wherein, n1And n2Meet n1/n2=1.7~20
Condition.
5. display base plate resin combination as claimed in claim 3, wherein, the n1、n2And n3Meet n3/(n1+n2+
n3)≤0.2。
6. display base plate resin combination as claimed in claim 1 or 2, wherein, the polyamic acid contain add up to
The structural unit that the formula (1-1) and formula (1-2) of few 60 moles of % represents.
7. display base plate resin film is using the display base plate resin described in any one of claim 1~6
What composition was made.
8. image display device, with the display base plate resin film described in claim 7.
9. the manufacturing method of display base plate resin film, which is characterized in that using described in any one of claim 1~6
Display base plate resin combination.
10. the manufacturing method of image display device, which is characterized in that use the display base plate resin described in claim 7
Film.
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| JP2014038167 | 2014-02-28 | ||
| JP2014-038167 | 2014-02-28 | ||
| PCT/JP2015/055513 WO2015129780A1 (en) | 2014-02-28 | 2015-02-26 | Resin composition for display substrate, resin thin film for display substrate, and method for producing resin thin film for display substrate |
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| JP6733142B2 (en) * | 2015-09-18 | 2020-07-29 | 日産化学株式会社 | Resin composition for thin film formation |
| KR102442540B1 (en) * | 2016-10-31 | 2022-09-13 | 유비이 가부시키가이샤 | Polyimide film for metal lamination and polyimide metal laminate using same |
| KR102608548B1 (en) * | 2017-09-27 | 2023-12-04 | 닛산 가가쿠 가부시키가이샤 | Composition for forming a temporary adhesive layer and temporary adhesive layer |
| KR102345722B1 (en) * | 2019-11-07 | 2022-01-03 | 피아이첨단소재 주식회사 | High Heat Resistant and Low Dielectric Polyimide Film and Manufacturing Method Thereof |
| KR102347633B1 (en) * | 2019-11-07 | 2022-01-10 | 피아이첨단소재 주식회사 | Polyimide film with improved dielectric properties and manufacturing method thereof |
| KR102347588B1 (en) | 2019-11-07 | 2022-01-10 | 피아이첨단소재 주식회사 | High Heat Resistant and Low Dielectric Polyimide Film and Manufacturing Method Thereof |
| WO2023100951A1 (en) * | 2021-11-30 | 2023-06-08 | Ｕｂｅ株式会社 | Polyimide film, high-frequency circuit substate, and flexible electronic device substrate |
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| JP2012035583A (en) * | 2010-08-11 | 2012-02-23 | Kaneka Corp | Method of manufacturing laminate, and flexible device |
| JP2012207147A (en) * | 2011-03-30 | 2012-10-25 | Ube Industries Ltd | Method for producing polyimide film, polyimide film, and polyimide metal laminate using the same |
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| JPS61212096A (en) * | 1985-03-18 | 1986-09-20 | 株式会社日立製作所 | Multilayer interconnection board |
| JPH01214840A (en) * | 1988-02-24 | 1989-08-29 | Hitachi Ltd | Formation of polyimide pattern |
| JPH06212096A (en) * | 1992-09-30 | 1994-08-02 | Sugai Kagaku Kogyo Kk | Antistatic agent |
| JP2002338710A (en) * | 2001-03-16 | 2002-11-27 | Sumitomo Bakelite Co Ltd | Plastic base plate for indication element |
| JP2010202729A (en) * | 2009-03-02 | 2010-09-16 | Hitachi Chemical Dupont Microsystems Ltd | Polyimide precursor resin composition for flexible device substrates and method for producing flexible device using the same, and flexible device |
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- 2015-02-26 KR KR1020167025061A patent/KR102312132B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012035583A (en) * | 2010-08-11 | 2012-02-23 | Kaneka Corp | Method of manufacturing laminate, and flexible device |
| JP2012207147A (en) * | 2011-03-30 | 2012-10-25 | Ube Industries Ltd | Method for producing polyimide film, polyimide film, and polyimide metal laminate using the same |
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