CN107683308A - Polyimides system varnish, manufacture method and polyimides mesentery using its polyimides mesentery - Google Patents
Polyimides system varnish, manufacture method and polyimides mesentery using its polyimides mesentery Download PDFInfo
- Publication number
- CN107683308A CN107683308A CN201680034893.9A CN201680034893A CN107683308A CN 107683308 A CN107683308 A CN 107683308A CN 201680034893 A CN201680034893 A CN 201680034893A CN 107683308 A CN107683308 A CN 107683308A
- Authority
- CN
- China
- Prior art keywords
- polyimides
- varnish
- polyimides system
- mesentery
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
The present invention is for the purpose of providing and can form the polyimides system varnish of the film with good outward appearance and good bendability, provide following polyimides systems varnish, it includes polyimides system macromolecule, solvent and water, polyimides system macromolecule is when forming the film that thickness is 50 μm by the polyimides system macromolecule, the total light transmittance of film is more than 85%, and yellowing is less than 5 clear polyimides system macromolecule, solvent is that can dissolve the high molecular solvent of polyimides system, on the basis of the gross mass of polyimides system varnish, the content of water is 0.60~4.5 mass %.
Description
Technical field
The present invention relates to polyimides system varnish, the manufacture method using its polyimides mesentery and polyimides system
Film.
Background technology
All the time, it is transparent as the base material of the various display units such as solar cell, display and front panel etc. in the past
The material of part, has used glass.However, there is the shortcomings that being easy to be broken, weight in glass.In addition, it is directed to display in recent years
Slimming and lightweight, the flexibility of device, there has been no suitable material.Therefore, as the transparent of the flexible apparatus for substituting glass
Part, just at Study on Polyimide mesentery (for example, with reference to patent document 1).
Prior art literature
Patent document
Patent document 1：No. 8207256 specifications of U.S. Patent No.
The content of the invention
The invention problem to be solved
However, when the display unit or front panel as flexible apparatus, the bendability of conventional polyimides mesentery
(flexibility) it is not necessarily abundant.In addition, for the film for display unit or front panel, it is also desirable to have good outer
See, the defects of no shrinkage cavity (fisheye), aggegation block, striped.
The present invention be in view of situation as described above and make, its object is to, there is provided can be formed with well outside
The polyimides system varnish of the film of sight and good bendability, manufacture method and polyimides using its polyimides mesentery
Mesentery.
Means for solving the problems
To achieve the above object, the present invention provides a kind of polyimides system varnish, and it includes polyimides system macromolecule, molten
Agent and water, wherein, polyimides system macromolecule be when forming the film that thickness is 50 μm by the polyimides system macromolecule, film
The clear polyimides system macromolecule that total light transmittance is more than 85% and yellowing (yellowness) is less than 5, solvent
For that can dissolve the high molecular solvent of polyimides system, on the basis of the gross mass of polyimides system varnish, the content of water is
0.60~4.5 mass %.
According to above-mentioned polyimides system varnish, by containing water with above-mentioned specific ratio, enable to use the polyamides
Imines system varnish and the outward appearance of polyimides mesentery and bendability that are formed become good.Although not yet clearly due to the presence of water
And the outward appearance of polyimides mesentery and bendability can be made to become the reason for good, but it is thought that due to by forming film
When drying when water moderately be present, the high molecular aggegation of polyimides system can be suppressed, the fine and close and uniform film of composition can be formed.
It is believed that thus, it is possible to suppress the problem of following：The defects of by shrinkage cavity, aggegation block, striped caused bad order, it is and curved
Fracture when bent.
In addition, in above-mentioned polyimides system varnish, polyimides system macromolecule is following polyimides system macromolecule,
That is, when forming the film that thickness is 50 μm by the polyimides system macromolecule, the total light transmittance of film is more than 85%, and
Yellowing is less than 5 clear polyimides system macromolecule.The total light transmittance of above-mentioned film is more preferably more than 90%.By making
With clear polyimides system macromolecule, the high polyimides mesentery of the transparency can be obtained.
In above-mentioned polyimides system varnish, polyimides system macromolecule preferably includes halogen atom, halogen atom in intramolecular
More preferably fluorine atom.When halogen atom, particularly fluorine atom are imported into polyimides system macromolecule, helping, which reduces gained, gathers
The yellowing of acid imide mesentery.Here, the reduction of yellowing contributes to the transparency, the improvement of outward appearance.Further, since contain fluorine atom
The high molecular hygroscopicity of polyimides system is low, therefore, water can be fully removed after film is formed, it is good can more easily to obtain outward appearance
Good film.
Above-mentioned polyimides system varnish can further include silicon dioxide granule.In this case, it is poly- that gained can be improved
Imide series film strength, and the good transparency of film can be obtained.
Polyimides system varnish comprising above-mentioned silicon dioxide granule can further include the alkoxyl silicone with amino
Alkane.In this case, there is the trend for further improving following effect, the effect is：Made by what silicon dioxide granule was brought
The effect that polyimides system film strength improves, and obtain the effect of the good transparency of film.
The present invention also provides the polyimides mesentery formed by the polyimides system varnish of the invention described above.The polyamides is sub-
The outward appearance and bendability of amine system film are excellent.
The yellowing of above-mentioned polyimides mesentery is preferably less than 5.In addition, the total light transmittance of above-mentioned polyimides mesentery
Preferably more than 85%.The total light transmittance of polyimides mesentery is more preferably more than 90%.
The present invention, which also provides, to be included the polyimides system varnish of the present invention being coated on base material so as to form the work of film
Sequence and the manufacture method by the polyimides mesentery of the process of dried coating film.As manufacture method, may further include
The process that dry film is peeled off from base material.It is clear using the polyimides system of the water comprising specified quantitative according to the manufacture method
Paint, the coated, each operation of stripping drying and carry out as needed form polyimides mesentery, therefore, as described above, special
It is not in the drying of film, moisture forms behavior to the high molecular structure of polyimides system and produces desirable influence, can obtain
Outward appearance and the excellent polyimides mesentery of bendability.
The present invention further provides polyimides mesentery prepared by the manufacture method using above-mentioned polyimides mesentery.Should
The outward appearance and bendability of polyimides mesentery are excellent.
Invention effect
According to the present invention, it is possible to provide the polyimides system that can form the film with good outward appearance and good bendability is clear
Paint, using the manufacture method of its polyimides mesentery, and the polyimides with good outward appearance and good bendability
Mesentery.
Embodiment
Hereinafter, the present invention is described in detail based on the preferred embodiment of the present invention.
[polyimides system varnish]
Polyimides system of the present embodiment varnish includes polyimides system macromolecule, can dissolve the polyimides system
High molecular solvent, He Shui, on the basis of the gross mass of polyimides system varnish, the content of water is the matter of 0.60 mass %~4.5
Measure %.
In polyimides system varnish, on the basis of the solid state component total amount in varnish, polyimides system is high molecular to be contained
Amount can be set to more than 20 mass %, be preferably set to more than 40 mass %.
In this specification, polyimides system macromolecule refers to the weight represented comprising formula (PI), formula (a), formula (a ') or formula (b)
At least one kind of polymer in complex structure unit.In them, from the viewpoint of film strength and the transparency, it is preferred that formula
(PI) constitutional repeating unit represented is the high molecular main construction unit of polyimides system.With polyimides, system is high molecular
On the basis of whole constitutional repeating units, the constitutional repeating unit that formula (PI) represents is preferably 40 moles of more than %, and more preferably 50
Mole more than %, more preferably 70 moles of more than %, particularly preferably 90 moles of more than %, especially more preferably 98
Mole more than %.
[chemical formula 1]
G in formula (PI) represents the organic group of 4 valencys, and A represents the organic group of divalent.G in formula (a)2Represent trivalent
Organic group, A2Represent the organic group of divalent.G in formula (a ')3Represent the organic group of 4 valencys, A3Represent the organic group of divalent
Group.G in formula (b)4And A4Each represent the organic group of divalent.
In formula (PI), the organic group (below, sometimes referred to as G organic group) of the organic group for 4 valencys that G is represented can be lifted
The group gone out in the group being made up of non-ring type aliphatic group, ring type aliphatic group and aromatic group.It is sub- from polyamides
From the viewpoint of the transparency and bendability of amine system film, G is preferably the ring type aliphatic group of 4 valencys and the aromatic group of 4 valencys.
As aromatic group, monocyclic aromatic group, fused polycyclic aromatic group and the direct phase of aromatic group can be enumerated
Connect or be connected with each other non-condensed polycycle aromatic group formed etc. through binding groups.From the transparent of polyimides mesentery
Property and from the viewpoint of suppressing coloring, G organic group can also be ring type aliphatic group, the ring type with fluorine system substituent
Aliphatic group, the monocyclic aromatic group with fluorine system substituent, the fused polycyclic aromatic series with fluorine system substituent
Group or the non-condensed polycycle aromatic group with fluorine system substituent.In this specification, fluorine system substituent refers to include fluorine
The group of atom.Fluorine system substituent preferably fluorine-based (fluorine atom ,-F) and perfluoroalkyl, more preferably fluorine-based and fluoroform
Base.
More specifically, G organic group is selected from such as saturation or unsaturation ring alkyl, saturation or unsaturated heterocycle alkane
Base, aryl, heteroaryl, aryl alkyl, alkylaryl, miscellaneous alkyl aryl and (can phase with any 2 groups in them
Together) and they are directly connected to each other or are connected with each other the group formed through binding groups.As binding groups ,-O-, carbon can be enumerated
The alkylidene ,-SO of atomicity 1~102-, (R represents the alkane of the carbon numbers 1~3 such as methyl, ethyl, propyl group by-CO- or-CO-NR-
Base or hydrogen atom).
The carbon number of the organic group for 4 valencys that G is represented is usually 2~32, preferably 4~15, more preferably 5~10,
More preferably 6~8.When G organic group is ring type aliphatic group and aromatic group, the carbon of above-mentioned group is formed
At least one in atom can be substituted by hetero atom.As hetero atom, O, N or S can be enumerated.
As G concrete example, can enumerate following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25) or
The group that formula (26) represents.* in formula represents connecting key.Z in formula (26) represents singly-bound ,-O- ,-CH2-、-C(CH3)2-、-
Ar-O-Ar-、-Ar-CH2-Ar-、-Ar-C(CH3)2- Ar- or-Ar-SO2-Ar-.Ar represents the aryl of carbon number 6~20, can
Enumerate such as phenylene.At least one of hydrogen atom of above-mentioned group can be substituted by fluorine system substituent.
[chemical formula 2]
In formula (PI), the organic group (below, sometimes referred to as A organic group) of the organic group for the divalent that A is represented can be lifted
The organic group of the divalent gone out in the group being made up of non-ring type aliphatic group, ring type aliphatic group and aromatic group.
The organic group for the divalent that A is represented is preferably the ring type aliphatic group of divalent and the aromatic group of divalent.As aromatic series base
Group, can enumerate monocyclic aromatic group, fused polycyclic aromatic group and with more than 2 aromatic ring and they
It is directly connected to each other or is connected with each other the non-condensed polycycle aromatic group formed through binding groups.From polyimides mesentery
From the viewpoint of the transparency and suppression coloring, it is preferred that fluorine system substituent is imported with A organic group.
More specifically, A organic group is selected from such as saturation or unsaturation ring alkyl, saturation or unsaturated heterocycle alkane
Base, aryl, heteroaryl, aryl alkyl, alkylaryl, miscellaneous alkyl aryl and (can phase with any 2 groups in them
Together) and they are directly connected to each other or are connected with each other the group formed through binding groups.As hetero atom, O, N or S can be enumerated,
As binding groups ,-O-, the alkylidene of carbon number 1~10 ,-SO can be enumerated2-, (R represents methyl, second by-CO- or-CO-NR-
The alkyl or hydrogen atom of the carbon numbers such as base, propyl group 1~3).
The carbon number of the organic group for the divalent that A is represented is usually 2~40, preferably 5~32, more preferably 12~28,
More preferably 24~27.
As A concrete example, the base that following formula (30), formula (31), formula (32), formula (33) or formula (34) represent can be enumerated
Group.* in formula represents connecting key.Z1~Z3Separately represent singly-bound ,-O- ,-CH2-、-C(CH3)2-、-SO2-、-CO-
Or-CO-NR- (R represents the alkyl or hydrogen atom of the carbon numbers 1~3 such as methyl, ethyl, propyl group).In following radicals, Z1With
Z2And Z2With Z3Respectively preferably with respect to each ring positioned at the position of meta or para position.In addition, Z1Singly-bound, Z with end2With end
The singly-bound and Z at end3The position of meta or para position is preferably placed at respectively with the singly-bound of end.As A 1 example, Z1And Z3For-
O-, also, Z2For-CH2-、-C(CH3)2- or-SO2-.1 or more than 2 in the hydrogen atom of above-mentioned group can be taken by fluorine system
Substitute for base.
[chemical formula 3]
For at least one of A and G, form at least one hydrogen atom in their hydrogen atom can by selected from
At least one kind of functional group in the group be made up of the alkyl etc. of fluorine system substituent, hydroxyl, sulfo group, carbon number 1~10 substitutes.Separately
Outside, when A organic group and G organic group are respectively ring type aliphatic group or aromatic group, it is preferred that A and G
In at least one party there is fluorine system substituent, it is further preferred that this both sides of A and G have fluorine system substituent.
G in formula (a)2For the organic group of trivalent.In addition to for trivalent, the organic group may be selected from formula (PI) in
G organic group identical group.As G2Example, formula (the 20)~formula (26) enumerated as G concrete example can be enumerated
Any one in 4 connecting keys of shown group is replaced by group obtained from hydrogen atom.A in formula (a)2May be selected from
A identical groups in formula (PI).
G in formula (a ')3It may be selected from and the G identical groups in formula (PI).A in formula (a ')3May be selected from formula (PI) in
A identical groups.
G in formula (b)4For the organic group of divalent.In addition to being the group of divalent, the organic group may be selected from and formula
(PI) the organic group identical group of the G in.As G4Example, the formula (20) enumerated as G concrete example can be enumerated
Any 2 in 4 connecting keys of group shown in~formula (26) are replaced by group obtained from hydrogen atom.A in formula (b)4
It may be selected from and the A identical groups in formula (PI).
The polyimides system macromolecule contained in polyimides mesentery can be by by Diamines and tetracarboxylic compound
(including the tetracarboxylic compound such as chloride compounds and tetracarboxylic dianhydride analog) or tricarboxylic acid compound (including chloride compounds
And the tricarboxylic acids compound such as tricarboxylic acid anhydride analog) at least one kind of polycondensation obtained from condensed type macromolecule.In addition, also may be used
With by dicarboxylic acid compound (analog including chloride compounds etc.) polycondensation.The repetitive structure list that formula (PI) or formula (a ') represent
Member is typically derived from Diamines and tetracarboxylic compound.The constitutional repeating unit that formula (a) represents is typically derived from Diamines and three
Carboxylic acid compound.The constitutional repeating unit that formula (b) represents is typically derived from Diamines and dicarboxylic acid compound.
As tetracarboxylic compound, aromatic tetracarboxylic acid's compound, ester ring type tetracarboxylic compound and non-ring type can be enumerated
Aliphatic tetracarboxylic compound.Two or more kinds may be used for tetracarboxylic compound.Tetracarboxylic compound is preferably tetracarboxylic dianhydride.
As tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride, ester ring type tetracarboxylic dianhydride and non-ring type aliphatic tetrabasic carboxylic acid two can be enumerated
Acid anhydride.
From polyimides system macromolecule dissolubility in a solvent, form polyimides mesentery when the transparency and bendability
From the viewpoint of, tetracarboxylic compound is preferably ester ring type tetracarboxylic compound and aromatic tetracarboxylic acid's compound.It is sub- from polyamides
From the viewpoint of the transparency of amine system film and suppression coloring, tetracarboxylic compound is preferably the ester ring type four with fluorine system substituent
Carboxylic acid compound and aromatic tetracarboxylic acid's compound with fluorine system substituent, more preferably ester ring type tetrabasic carboxylic acid chemical combination
Thing.
As tricarboxylic acid compound, aromatic tricarboxylic acids, ester ring type tricarboxylic acids can be enumerated, non-ring type aliphatic tricarboxylic acids and
Chloride compounds, acid anhydrides similar to them etc..Tricarboxylic acid compound is preferably aromatic tricarboxylic acids, ester ring type tricarboxylic acids, non-
Ring type aliphatic tricarboxylic acids and the chloride compounds similar to them.Two or more kinds may be used for tricarboxylic acid compound.
From polyimides system macromolecule dissolubility in a solvent, form polyimides mesentery when the transparency and bendability
From the viewpoint of, tricarboxylic acid compound is preferably ester ring type tricarboxylic acid compound or aromatic tricarboxylic acids compound.It is sub- from polyamides
From the viewpoint of the transparency of amine system film and suppression coloring, tricarboxylic acid compound is preferably the ester ring type three with fluorine system substituent
Carboxylic acid compound and the aromatic tricarboxylic acids compound with fluorine system substituent.
As dicarboxylic acid compound, can enumerate aromatic dicarboxylic acid, ester ring type dicarboxylic acids, non-ring type aliphatic dicarboxylic acid and
Chloride compounds, acid anhydrides similar to them etc..Dicarboxylic acid compound is preferably aromatic dicarboxylic acid, ester ring type dicarboxylic acids, non-
Ring type aliphatic dicarboxylic acid and the chloride compounds similar to them.Two or more kinds may be used for dicarboxylic acid compound.
From polyimides system macromolecule dissolubility in a solvent, form polyimides mesentery when the transparency and bendability
From the viewpoint of, dicarboxylic acid compound is preferably ester ring type dicarboxylic acid compound and aromatic dicarboxylic acid compound.It is sub- from polyamides
From the viewpoint of the transparency of amine system film and suppression coloring, dicarboxylic acid compound is preferably the ester ring type two with fluorine system substituent
Carboxylic acid compound and the aromatic dicarboxylic acid compound with fluorine system substituent.
As Diamines, aromatic diamine, ester ring type diamines and aliphatic diamine can be enumerated.Diamines can be used together 2 kinds
More than.From polyimides system macromolecule dissolubility in a solvent, form polyimides mesentery when the transparency and bendability
Viewpoint considers that Diamines are preferably ester ring type diamines and the aromatic diamine with fluorine system substituent.
It is readily available that there is especially excellent bendability, high printing opacity during using polyimides system macromolecule as described above
Rate (for example, being more than 85%, preferably more than 88% relative to 550nm light) and low yellowing (YI values, such as less than 5, it is excellent
Elect less than 3 as), the polyimides mesentery of low haze (such as less than 1.5%, preferably less than 1.0%).
Polyimides system macromolecule can be the copolymer for including different types of multiple above-mentioned repeat units.Polyimides
It is that high molecular weight average molecular weight is usually 10,000~500,000.The high molecular weight average molecular weight of polyimides system is preferably
50,000~500,000, more preferably 70,000~400,000.Weight average molecular weight is the standard polyphenyl measured by GPC
Ethene conversion molecular weight.Although exist polyimides system high molecular weight average molecular weight it is big when readily available high bendability become
Gesture, if but the high molecular weight average molecular weight of polyimides system it is excessive, the rise of the viscosity of varnish, have what processability reduced to become
Gesture.
Polyimides system macromolecule can also have can be by above-mentioned fluorine system substituent etc. and halogen such as the fluorine atoms of importing
Atom.Halogen atom is included by polyimides system macromolecule, it is possible to increase the modulus of elasticity and drop of polyimides mesentery
Low yellowing.Thereby, it is possible to suppress to produce the situation of cut and fold etc. in polyimides mesentery, further, it is possible to improve polyamides Asia
The transparency of amine system film.As halogen atom, preferably fluorine atom.On the basis of the high molecular gross mass of polyimides system, polyamides
The content of halogen atom in imines system macromolecule is preferably 1~40 mass %, more preferably 1~30 mass %.
Polyimides system macromolecule is preferably following clear polyimides system macromolecule, i.e. sub- by the polyamides when being formed
During film (layer) for 50 μm of the thickness that amine system macromolecule is formed, the total light transmittance of the polyimides system polymeric membrane for 85% with
On, and the yellowing (YI values) of the polyimides system polymeric membrane is less than 10.Above-mentioned total light transmittance be preferably 90% with
On.Above-mentioned yellowing is preferably less than 5.By using clear polyimides system macromolecule, the high polyamides of the transparency can obtain
Imines mesentery.In addition, the total light transmittance of above-mentioned polyimides system polymeric membrane is more preferably more than 91%, further preferably
For more than 92%.Yellowing is more preferably less than 3, particularly preferably less than 2.5.Here, polyimides system polymeric membrane can pass through
Coating by polyimides system macromolecule dissolution in solvent obtained from material and be dried and formed.Polyimides system high score
The total light transmittance of sub- film can be according to JIS K 7105：1981 obtain.The yellowing YI of polyimides system polymeric membrane can be according to
JIS K 7373：2006 obtain.
In polyimides system varnish, as long as solvent is the high molecular solvent of dissolving polyimides system, without especially limit
It is fixed, can enumerate for example DMA (DMAc), DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO),
Gamma-butyrolacton (GBL), 1-METHYLPYRROLIDONE (NMP), ethyl acetate, methyl ethyl ketone (MEK), tetrahydrofuran, 1,4- bis- Evil
Alkane, acetone, cyclopentanone, dimethyl sulfoxide (DMSO), dimethylbenzene and combinations thereof.
In addition to above-mentioned solvent, polyimides system varnish also contains water.In polyimides system varnish, with polyimides system
On the basis of the gross mass of varnish, the content (amount of moisture) of water is 0.60~4.5 mass %, preferably 0.7~4.0 mass %, more
Preferably 1.0~4.0 mass %.The lower limit of the content of water is more preferably 1.5 mass %, particularly preferably 2.0 matter
% is measured, especially more preferably 2.5 mass %.In addition, the higher limit of the content of water is more preferably 3.5 mass %.
When polyimides system varnish includes silicon dioxide granule, on the basis of the gross mass of polyimides system varnish, gather
Amount of moisture in imide series varnish is preferably 1.5~3.5 mass %, more preferably 2.5~3.5 mass %, especially excellent
Elect 2.5~3.0 mass % as.If making film using polyimides system as described above varnish, with readily available bending
The trend of the excellent polyimides mesentery of property.
If the amount of moisture in polyimides system varnish is within the above range, the presence of water is high molecular to polyimides system
Structure forms behavior and produces desirable influence, and the outward appearance of formed film and bendability can be made to become good.Polyimides system is clear
Amount of moisture in paint can utilize karl fischer method to determine.The measure of karl fischer method is according to JIS K 0068：2001
Carry out.Titration uses the reagent that side reaction does not occur with solvent with reagent.As the ketone suitable for DMAC N,N' dimethyl acetamide etc
The combination of the anolyte, catholyte of series solvent, Sigma Aldrich Coulomat AK, Sigma Aldrich systems can be enumerated
Coulomat CG-K combination.As measure device, Metronome Company 831KF Coulomb meters etc. can be used.
From the viewpoint of polyimides system film strength obtained by improving, polyimides system varnish can further contain
Inorganic particulate.As inorganic particulate, the particle comprising silicon atom can be enumerated, as the particle comprising silicon atom, dioxy can be enumerated
SiClx particle.The other examples of inorganic particulate can enumerate TiO 2 particles, aluminium oxide particles, Zirconia particles etc..
The average primary particle diameter of inorganic particulate is usually below 100nm.If the average primary particle diameter of inorganic particulate is 100nm
Hereinafter, then the trend that the transparency with film improves.The primary particle size of inorganic particulate can be set to by transmission electron microscope
(TEM) the orientation diameter obtained.Using tem observation and primary particle size at 10 is determined, obtains their average value as average
Primary particle size.
In polyimides system varnish, by quality ratio, the match ratio of polyimides system macromolecule and inorganic particulate is usual
For 1：9~10：0, preferably 3：7~10：0, more preferably 3：7~8：2, more preferably 3：7~7：3.If polyimides
Be macromolecule and inorganic particulate match ratio in above-mentioned scope, then the transparency and mechanical strength of polyimides mesentery be present
The trend of raising.
When polyimides system varnish contains inorganic particulate, in obtained polyimides mesentery, inorganic particulate each other may be used
Combined by the molecule with siloxanes key (- SiOSi-).
When polyimides system varnish contains inorganic particulate, in order to improve stability of solution, varnish can contain alkoxy
The metal alkoxide of silane etc..Preferably there is the alkoxy silane of amino.Especially, when polyimides system, varnish contains two
When silicon oxide particle is as inorganic particulate, by further containing the alkoxy silane with amino, so as to have following effects
The trend further improved：The effect that the dispersiveness of silicon dioxide granule improves, improves polyimides system film strength, and
To the effect of the good transparency of film.
Relative to the inorganic particulate of 100 mass parts, the addition of metal alkoxide can be set to 0.1~10 mass parts, excellent
Choosing is set to 0.5~5 mass parts.
In the range of the transparency and bendability for the polyimides mesentery for not damaging to obtain, polyimides system varnish can be with
Further contain other compositions.As other compositions, waited for example, antioxidant, releasing agent, stabilizer, blueing agent can be enumerated
Toner, fire retardant, lubricant, thickener, levelling agent etc..On the basis of the gross mass of polyimides mesentery, obtained polyamides is sub-
The content of above-mentioned other compositions in amine system film is preferably greater than 0 mass % and is below 20 mass %, more preferably greater than 0 mass %
And it is below 10 mass %.
Polyimides system varnish can also include tetraalkoxysilanes such as tetraethyl orthosilicate (TEOS) etc., silsesquioxane spreads out
The organo-silicon compound such as biology.
From the viewpoint of storage stability and coating, the solid component concentration of polyimides system varnish is preferably 5~
30 mass %, more preferably 10~25 mass %.
(polyimides mesentery)
The polyimides mesentery of present embodiment is the film formed using above-mentioned polyimides system varnish.
The thickness of polyimides mesentery can suitably be adjusted according to purposes, usually 10~500 μm, preferably 15~200 μ
M, more preferably 20~100 μm.
For the polyimides mesentery, according to JIS K 7105：1981 total light transmittances measured are preferably
More than 85%, more preferably more than 90%.In addition, for the polyimides mesentery, according to JIS K 7105：1981 measure
Mist degree be preferably less than 1, more preferably less than 0.9.In addition, for the polyimides mesentery, according to JIS K 7373：
The 2006 yellowing YI measured are preferably less than 5, and more preferably less than 3.Polyimides mesentery with the optics physical property can close
Be used as suitablely towards require the smart mobile phone of high observability, tablet PC optical film.
(manufacture method)
Next, the manufacture method of polyimides system varnish and the polyimides system of present embodiment to present embodiment
One of the manufacture method of film illustrates.
It is sub- that polyamides obtaining, dissolving in solvent will be polymerize using the known high molecular synthetic method of polyimides system
Amine system macromolecule dissolution further adds water and the as needed above-mentioned inorganic particulate of addition, metal alcoxyl in solvent
Compound and other compositions simultaneously mix, so as to prepare polyimides system varnish.When adding inorganic grain into polyimides system varnish
The period of the day from 11 p.m. to 1 a.m, it is stirred, mixes using known stirring means, thus inorganic particulate can be homogeneously dispersed in polyimides system
Varnish.The example of solvent is as described above.As polyimides system macromolecule, as long as being soluble in the polyimides system high score of solvent
Son, as described above, making aromatic tetracarboxylic acid's dianhydride, ester ring type tetracarboxylic dianhydride, non-ring type aliphatic tetrabasic carboxylic acid
One kind or two or more and aromatic diamines, ester ring type Diamines, non-ring type aliphatic diamine in the tetracarboxylic dianhydrides such as dianhydride
Polyimides system macromolecule obtained from one kind or two or more polycondensation in the Diamines such as class.Tetracarboxylic dianhydride and Diamines are preferred
To be imported with the tetracarboxylic dianhydride of fluorine system substituent and Diamines.
Water is not necessarily added in the preparation of polyimides system varnish.That is, when the polyimides system macromolecule to be coordinated,
When solvent, inorganic particulate, metal alkoxide or other compositions occur moisture absorption etc. and contain moisture, if being made by the moisture
Amount of moisture in polyimides system varnish as defined in present embodiment in scope, then when preparing polyimides system varnish
Water can not further be added.For example, when the preparation that polyimides system varnish is carried out in the environment of with humidity to a certain degree
When, even if not adding water sometimes, moisture also can moderately be ingested into polyimides system varnish.
When polyimides system varnish includes inorganic particulate, water is contained by varnish, so as to solidifying also with varnish
The repressed advantage of gel.Therefore, when polyimides system varnish includes inorganic particulate, varnish appropriateness can particularly marked degree be produced
Effect containing water, the bad order caused by the gelation of varnish is not susceptible in the polyimides mesentery formed,
Also, it can obtain the high film of bendability.
Next, roll-to-roll (roll-to-roll), batch processing mode known to utilizing, by prepared polyimides system
Varnish is coated on PET base material, SUS bands or glass baseplate, so as to form film.The film turns into polyimides through drying
Mesentery.
In 50~350 DEG C of temperature, suitably by solvent and water evaporation under conditions of inert atmosphere or decompression, thus
Carry out the drying of film.The drying of film can also change temperature conditionss and be carried out with the multistage.In this case, can also get over
Carry out more improving temperature to back segment.By carrying out the drying of film with the multistage by this way, solvent and water can be controlled to steam
The speed of hair, the high molecular even structure of polyimides system can be made, and can further suppress polyimides system high score
The aggegation of son, it can further improve the outward appearance and bendability of gained film.
Alternatively, it is also possible to further carry out the drying of film after being peeled off from base material.That is, can be in base for film
After it is dried and (is dried as the 1st) on material, it is peeled off from base material, it is dried and (is dried as the 2nd).2nd is dry
It is dry to be carried out by following manner：Metal frame is installed on the film peeled off from base material；Or stenter known to use
(tenter) equipment；Etc..2nd dries and can be carried out in drying high temperature than the 1st, for example, the 1st can be carried out in 50~190 DEG C
Dry, and carry out the 2nd in 190~350 DEG C and dry.In addition, the 1st dry and the 2nd drying can also change temperature conditionss respectively and
Carried out with the multistage.
(purposes)
Polyimides mesentery as described above is because outward appearance and flexibility are excellent, therefore the composition that can be used as flexible display will
Element.For example, it can be used as the front panel (window film (window film)) of the surface protection of flexible display.
In addition it is possible to additional ultraviolet absorbed layer, hard conating, adhesive layer, form and aspect regulation on the polyimides mesentery
The various functions layers such as layer, adjustable refractive index layer and form layered product.
Embodiment
Hereinafter, the present invention is further elaborated with using embodiment and comparative example, but the invention is not restricted to following examples.
[embodiment 1]
(synthesis of polyimides)
Into the polymerization tank after nitrogen displacement, compound, formula (3) that compound, the formula (2) that formula (1) represents represent are added
The compound of expression, solvent (gamma-butyrolacton and dimethyl acetamide), catalyst.Feeding quantity is set to the compound of formula (1) expression
75.0g, the compound 36.5g of formula (2) expression, the compound 76.4g of formula (3) expression, gamma-butyrolacton 438.4g, dimethyl second
Acid amides 313.1g, catalyst 1.5g.The mol ratio for the compound that the compound that formula (2) represents represents with formula (3) is 3：7, formula (2)
The mol ratio for the compound that the total and formula (1) for the compound that the compound of expression represents with formula (3) represents is 1.00：1.02.
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
In the mixture stirred in polymerization tank and make dissolution of raw material after solvent, be warming up to while mixture is stirred
100 DEG C, then, to be warming up to 200 DEG C without agitating mode, 4 hours are incubated in 200 DEG C, polymerization obtains polyimides.Need
Illustrate, in above-mentioned heating, eliminate the water in liquid.Then, it is purified and dry and obtain polyimides.
(preparation of polyimides system varnish)
Next, by the gamma-butyrolacton solution of the adjusted polyimides for being 20 mass % of concentration, in gamma-butyrolacton
It is dispersed with the two of the dispersion liquid for the silicon dioxide granule that solid component concentration is 30 mass % and the alkoxy silane with amino
Methyl vinyl amine aqueous solution mixes, and stirs 30 minutes, thus prepares polyimides system varnish.
Here, the mass ratio of silica and polyimides is set to 60：40, relative to silica and polyimides
Total 100 mass parts, 1.67 mass parts are set to by the amount of the alkoxy silane with amino.Above-mentioned silica, polyimides,
And with amino alkoxy silane amount be remove solvent after solid state component amount (similarly hereinafter).Utilize karr Fischer
Method determines the amount of moisture of obtained polyimides system varnish, is as a result 0.80 mass %.With Metronome Company's
The amount of moisture of 831KF Coulomb meters measure polyimides system varnish.Measure is according to JIS K 0068：2001 are carried out, and anolyte uses
Sigma Aldrich CoulomatAK, catholyte use Sigma Aldrich CoulomatCG-K.
(making of polyimides mesentery)
Polyimides system varnish is coated on PET substrate's (pet substrate), 30 are heated in 50 DEG C
Minute, next in 140 DEG C heating 10 minutes after, is peeled off from pet substrate and is installed on metal frame, further in 210 DEG C heating 1
Hour, obtain the polyimides mesentery that thickness is 50 μm.
[embodiment 2]
When preparing polyimides system varnish, relative to total 100 mass parts of silica and polyimides, addition 10
The water of mass parts so that the amount of moisture of polyimides system varnish is 2.69 mass %, in addition, according to embodiment 1
Same operation, carry out the preparation of polyimides system varnish and the making using its polyimides mesentery.
[embodiment 3]
When preparing polyimides system varnish, in dimethyl acetamide and the gamma-butyrolacton of silicon dioxide granule dispersion liquid
It is middle using dehydrated solvent (dehydration dimethyl acetamide and dehydration gamma-butyrolacton), in addition, according to similarly to Example 2
Operation, carry out the preparation of polyimides system varnish and the making using its polyimides mesentery.Utilize karl fischer method
The amount of moisture of polyimides system varnish made from measure, it is as a result 2.45 mass %.
[embodiment 4]
The polyimides " KPI-MX300F (100) " of industry companies of Jiang He villages is dissolved in dimethyl acetamide, so as to make
The solution (polyimides system varnish) that standby concentration is 16 mass %.And then a small amount of water is added, amount of moisture is then evaluated, is as a result gathered
The amount of moisture of imide series varnish is 1.22 mass %.In addition to using the polyimides system varnish, according to same with embodiment 1
The operation of sample, carry out the making of polyimides mesentery.
[embodiment 5]
" Neopulim C6A20 " (it is the polyimide varnish of gas chemical company of Mitsubishi) 20 mass % γ-
In butyrolactone solution, point that the silicon dioxide granule that solid component concentration is 30 mass % is dispersed with gamma-butyrolacton is blended in
Dispersion liquid, have amino alkoxy silane dimethylacetamide solution and water, carry out 30 minutes stir, so as to prepare polyamides
Imines system varnish.Relative to total 100 mass parts of silica and polyimides, the addition of water is set to 10 mass parts.
Here, the mass ratio of silica and polyimides is set to 55：45, relative to silica and polyimides
Total 100 mass parts, 1.67 mass parts are set to by the amount of the alkoxy silane with amino.The amount of moisture of polyimides system varnish
For 2.56 mass %.In addition to using the polyimides system varnish, according to operation similarly to Example 1, it is sub- to carry out polyamides
The making of amine system film.
[comparative example 1]
When preparing polyimides system varnish, in dimethyl acetamide and the gamma-butyrolacton of silicon dioxide granule dispersion liquid
It is middle using dehydrated solvent (dehydration dimethyl acetamide and dehydration gamma-butyrolacton), in addition, according to similarly to Example 1
Operation, carry out the preparation of polyimides system varnish and the making using its polyimides mesentery.Utilize karl fischer method
The amount of moisture of polyimides system varnish made from measure, it is as a result 0.55 mass %.In addition, obtained polyimides mesentery is solidifying
Glomeration is more, compared with the film of embodiment 1, poor appearance.
[comparative example 2]
When preparing polyimides system varnish, adjust the blending ratio of water using so that polyimides system varnish amount of moisture as
4.59 mass %, in addition, according to operation similarly to Example 2, carry out the preparation of polyimides system varnish and use it
Polyimides mesentery making.Obtained polyimides mesentery is the film that the transparency is low, fuzzy.In addition, after observation is placed 1 day
Polyimides system varnish, liquid is separated into 2 phases.
[comparative example 3]
When preparing polyimides system varnish, adjust the blending ratio of water using so that polyimides system varnish amount of moisture as
6.48 mass %, in addition, attempt to carry out the preparation and use of polyimides system varnish according to operation similarly to Example 1
The making of its polyimides mesentery, but a large amount of solid state components are separated out when preparing varnish, it is difficult to make uniform film.
[comparative example 4]
The polyimides " KPI-MX300F (100) " of industry companies of Jiang He villages is dissolved in dimethyl acetamide so as to prepare
Concentration is 16 mass % solution, further adds water, so as to prepare the polyimides system varnish that amount of moisture is 10 mass %.Remove
Using beyond the polyimides system varnish, attempting to make polyimides mesentery according to operation similarly to Example 1, but
Solid state component is separated out when preparing polyimides system varnish, it is difficult to makes uniform film.
[comparative example 5]
When preparing polyimides system varnish, water is further added, to cause amount of moisture as 10 mass %, in addition,
According to operation similarly to Example 5, polyimides system varnish is prepared.In addition to using the polyimides system varnish, attempt
Make polyimides mesentery according to operation similarly to Example 1, but separate out when preparing polyimides system varnish solid-state into
Point, it is difficult to make uniform film.
[evaluation of film outward appearance]
The respective outward appearance of polyimides mesentery obtained in embodiment and comparative example is observed by visual observation, will not observe contracting
The polyimides mesentery of the defects of hole, aggegation block, striped is evaluated as " A ", it will be observed that the defects of shrinkage cavity, aggegation block, striped
Polyimides mesentery is evaluated as " B ", it is impossible to though form uniform film or can to form film uneven and exist fuzzy poly-
Acid imide mesentery is evaluated as " C ".Show the result in table 1.For outward appearance be evaluated as the film of " C " for, do not carry out yellowing and complete
The measure of light penetration.
[measure of yellowing (YI values)]
Obtained with the UV, visible light near infrared spectrometer V-670 measure embodiments and comparative example of Japan's light splitting company system
The respective yellowing of polyimides mesentery (the Yellow Index arrived：YI values).Background measure is carried out in the state of no sample
Afterwards, polyimides mesentery is arranged at sample retainer, carries out the transmitance measure relative to 300~800nm light, obtain 3
Values (X, Y, Z).YI values are calculated based on following formula.Show the result in table 1.
YI=100 × (1.2769X-1.0592Z)/Y
[measure of total light transmittance]
According to JIS K 7105：1981, utilize the full-automatic direct-reading of Suga Test Instruments Co., Ltd.s
Formula haze computer HGM-2DP determines the respective total light transmittance of polyimides mesentery obtained in embodiment and comparative example.
Show the result in table 1.
[evaluation of bendability]
According to the bendability of the polyimides mesentery obtained in following benchmark evaluation embodiment and comparative example.When with hand by film
Bending and when forming folding line, only will produce folding line and the polyimides mesentery of no exceptions is evaluated as " A " around folding line,
The periphery of folding line is bleached etc., the polyimides mesentery that the outward appearance on folding line periphery changes is evaluated as " B ", creased portion is sent out
The polyimides mesentery of raw fracture is evaluated as " C ".
[table 1]
Claims (11)
1. polyimides system varnish, it includes polyimides system macromolecule, solvent and water,
Polyimides system macromolecule is following clear polyimides systems macromolecule：When forming thickness by polyimides system macromolecule
When spending the film for 50 μm, the total light transmittance of film is more than 85%, and yellowing is less than 5,
Solvent is that can dissolve the high molecular solvent of polyimides system,
On the basis of the gross mass of polyimides system varnish, the content of water is 0.60~4.5 mass %.
2. polyimides system as claimed in claim 1 varnish, wherein, polyimides system macromolecule includes halogen original in intramolecular
Son.
3. polyimides system as claimed in claim 2 varnish, wherein, halogen atom is fluorine atom.
4. such as polyimides system according to any one of claims 1 to 3 varnish, polyimides system varnish further includes
Silicon dioxide granule.
5. polyimides system as claimed in claim 4 varnish, polyimides system varnish is further included with amino
Alkoxy silane.
6. polyimides mesentery, it is formed by polyimides system according to any one of claims 1 to 5 varnish.
7. polyimides mesentery as claimed in claim 6, its yellowing is less than 5.
8. polyimides mesentery as claimed in claims 6 or 7, its total light transmittance is more than 85%.
9. the manufacture method of polyimides mesentery, it includes following processes：
Polyimides system according to any one of claims 1 to 5 varnish is coated on base material, so as to form the work of film
Sequence；With
By the process of the dried coating film.
10. the manufacture method of polyimides mesentery as claimed in claim 9, methods described further comprises dry painting
The process that film is peeled off from base material.
11. polyimides mesentery, it is using made from the manufacture method of the polyimides mesentery described in claim 9 or 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-145210 | 2015-07-22 | ||
| JP2015145210 | 2015-07-22 | ||
| PCT/JP2016/071453 WO2017014286A1 (en) | 2015-07-22 | 2016-07-21 | Polyimide varnish, method for producing polyimide film in which same is used, and polyimide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107683308A true CN107683308A (en) | 2018-02-09 |
Family
ID=57834370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680034893.9A Pending CN107683308A (en) | 2015-07-22 | 2016-07-21 | Polyimides system varnish, manufacture method and polyimides mesentery using its polyimides mesentery |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP6904903B2 (en) |
| KR (1) | KR102560059B1 (en) |
| CN (1) | CN107683308A (en) |
| TW (1) | TWI814695B (en) |
| WO (1) | WO2017014286A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317353A (en) * | 2018-03-28 | 2019-10-11 | 住友化学株式会社 | Include the high molecular optical film of clear polyimides system |
| JP2019203117A (en) * | 2018-05-16 | 2019-11-28 | 東レ株式会社 | Polyimide precursor resin composition, polyimide resin composition and film-like product thereof, laminate comprising the same, and flexible device |
| CN111936581A (en) * | 2018-03-28 | 2020-11-13 | 住友化学株式会社 | Varnish containing transparent polyimide-based polymer and solvent |
| CN113811562A (en) * | 2019-05-10 | 2021-12-17 | 住友化学株式会社 | Varnish, optical film, and method for producing optical film |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110475810B (en) * | 2017-04-05 | 2022-12-20 | 住友化学株式会社 | Polyimide film and display device |
| JP6987633B2 (en) * | 2017-12-20 | 2022-01-05 | 住友化学株式会社 | Transparent film base material for touch sensor panel and touch sensor panel using it |
| JP6530125B1 (en) * | 2018-04-27 | 2019-06-12 | 住友化学株式会社 | Optical film |
| JP2019195997A (en) * | 2018-05-08 | 2019-11-14 | 住友化学株式会社 | Laminate and method for producing the same |
| KR20210123308A (en) | 2019-02-04 | 2021-10-13 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | colorless and transparent polyimide film |
| JP7131728B1 (en) | 2022-03-30 | 2022-09-06 | 日産化学株式会社 | Evaporation mask |
| KR20240003042A (en) * | 2022-06-29 | 2024-01-08 | 피아이첨단소재 주식회사 | Self-lubricating polyimide varnish and Polyimide coating material prepared thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0046074A2 (en) * | 1980-08-07 | 1982-02-17 | Ube Industries, Ltd. | Process for preparing polyimide solution |
| JP2007138142A (en) * | 2005-10-19 | 2007-06-07 | Hitachi Chem Co Ltd | Resin composition, method for producing the same, and film-forming material containing the same |
| JP2009215412A (en) * | 2008-03-10 | 2009-09-24 | New Japan Chem Co Ltd | Polyimide resin composition and molded body thereof |
| JP2010180262A (en) * | 2009-02-03 | 2010-08-19 | Toray Ind Inc | Method of producing resin composition |
| CN102030989A (en) * | 2009-09-29 | 2011-04-27 | 可隆工业株式会社 | Transparent polyimide film with improved solvent resistance |
| JP2012233083A (en) * | 2011-04-28 | 2012-11-29 | Mitsubishi Chemicals Corp | Device manufacturing method |
| CN102918088A (en) * | 2010-03-30 | 2013-02-06 | 可隆工业株式会社 | Polyimide film |
| CN103282414A (en) * | 2010-12-31 | 2013-09-04 | 可隆工业株式会社 | Transparent polyimide film and preparation method thereof |
| CN104411744A (en) * | 2012-06-29 | 2015-03-11 | 可隆工业株式会社 | Polyimide and polyimide film comprising the same |
| WO2016010003A1 (en) * | 2014-07-17 | 2016-01-21 | 旭化成イーマテリアルズ株式会社 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5666076B2 (en) * | 2006-09-19 | 2015-02-12 | 和光純薬工業株式会社 | Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, its production method, said bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic Polyimide obtained from acid dianhydride and use thereof |
| US9115250B2 (en) * | 2006-11-13 | 2015-08-25 | Ube Industries, Ltd. | Process for producing polyamic acid solution and polyamic acid solution |
| TWI434883B (en) | 2009-11-27 | 2014-04-21 | Ind Tech Res Inst | Organic/inorganic hybrid material and fabrication method thereof |
| JP2011221390A (en) * | 2010-04-13 | 2011-11-04 | Toyobo Co Ltd | Positive photosensitive polyimide resin composition |
| JP5789844B2 (en) * | 2011-11-30 | 2015-10-07 | 国立大学法人 千葉大学 | Polycarbazole derivative-containing composition and transparent conductor comprising the composition |
| JPWO2013105556A1 (en) * | 2012-01-10 | 2015-05-11 | 三菱化学株式会社 | Coating composition, porous film, light scattering film, and organic electroluminescent device |
| JP5478701B2 (en) * | 2012-11-30 | 2014-04-23 | 新日鉄住金化学株式会社 | Polyimide film |
| JP2014118463A (en) * | 2012-12-14 | 2014-06-30 | Mitsubishi Chemicals Corp | Polyimide resin molded body and film |
-
2016
- 2016-07-21 KR KR1020187003829A patent/KR102560059B1/en active IP Right Grant
- 2016-07-21 WO PCT/JP2016/071453 patent/WO2017014286A1/en active Application Filing
- 2016-07-21 JP JP2017529939A patent/JP6904903B2/en active Active
- 2016-07-21 CN CN201680034893.9A patent/CN107683308A/en active Pending
- 2016-07-22 TW TW105123206A patent/TWI814695B/en active
-
2021
- 2021-03-04 JP JP2021034756A patent/JP6920568B2/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0046074A2 (en) * | 1980-08-07 | 1982-02-17 | Ube Industries, Ltd. | Process for preparing polyimide solution |
| JP2007138142A (en) * | 2005-10-19 | 2007-06-07 | Hitachi Chem Co Ltd | Resin composition, method for producing the same, and film-forming material containing the same |
| JP2009215412A (en) * | 2008-03-10 | 2009-09-24 | New Japan Chem Co Ltd | Polyimide resin composition and molded body thereof |
| JP2010180262A (en) * | 2009-02-03 | 2010-08-19 | Toray Ind Inc | Method of producing resin composition |
| CN102030989A (en) * | 2009-09-29 | 2011-04-27 | 可隆工业株式会社 | Transparent polyimide film with improved solvent resistance |
| CN102918088A (en) * | 2010-03-30 | 2013-02-06 | 可隆工业株式会社 | Polyimide film |
| CN103282414A (en) * | 2010-12-31 | 2013-09-04 | 可隆工业株式会社 | Transparent polyimide film and preparation method thereof |
| JP2012233083A (en) * | 2011-04-28 | 2012-11-29 | Mitsubishi Chemicals Corp | Device manufacturing method |
| CN104411744A (en) * | 2012-06-29 | 2015-03-11 | 可隆工业株式会社 | Polyimide and polyimide film comprising the same |
| WO2016010003A1 (en) * | 2014-07-17 | 2016-01-21 | 旭化成イーマテリアルズ株式会社 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
Non-Patent Citations (2)
| Title |
|---|
| 张玉龙 等: "《纳米技术与纳米塑料》", 30 April 2002, 中国轻工业出版社 * |
| 朵英贤 等: "《纳米塑料技术》", 31 December 2006, 浙江科学技术出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317353A (en) * | 2018-03-28 | 2019-10-11 | 住友化学株式会社 | Include the high molecular optical film of clear polyimides system |
| CN111936581A (en) * | 2018-03-28 | 2020-11-13 | 住友化学株式会社 | Varnish containing transparent polyimide-based polymer and solvent |
| JP2019203117A (en) * | 2018-05-16 | 2019-11-28 | 東レ株式会社 | Polyimide precursor resin composition, polyimide resin composition and film-like product thereof, laminate comprising the same, and flexible device |
| JP7375318B2 (en) | 2018-05-16 | 2023-11-08 | 東レ株式会社 | Polyimide precursor resin compositions, polyimide resin compositions and films thereof, laminates containing the same, and flexible devices |
| CN113811562A (en) * | 2019-05-10 | 2021-12-17 | 住友化学株式会社 | Varnish, optical film, and method for producing optical film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180033208A (en) | 2018-04-02 |
| JPWO2017014286A1 (en) | 2018-05-17 |
| WO2017014286A1 (en) | 2017-01-26 |
| TW201708395A (en) | 2017-03-01 |
| JP6904903B2 (en) | 2021-07-21 |
| KR102560059B1 (en) | 2023-07-27 |
| JP6920568B2 (en) | 2021-08-18 |
| JP2021103308A (en) | 2021-07-15 |
| TWI814695B (en) | 2023-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107683308A (en) | Polyimides system varnish, manufacture method and polyimides mesentery using its polyimides mesentery | |
| JP5845911B2 (en) | Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition | |
| KR101787862B1 (en) | Transparent polyimide and precursor thereof | |
| CN107760027A (en) | Polyamic acid resin and polyamidoimide film | |
| CN106164132A (en) | Novel polyimide compositions | |
| CN106164178A (en) | The manufacture method of resin film and resin film formation composition | |
| CN107614483B (en) | Diamine and use thereof | |
| CN107001662A (en) | Polyimide film, polyimide precursor and polyimides | |
| CN107614577B (en) | Polyimide film | |
| JPWO2013121917A1 (en) | Diamine, polyimide, and polyimide film and use thereof | |
| JP4367622B2 (en) | Method for producing polyimide / inorganic composite material | |
| CN105315665A (en) | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article | |
| JP5873529B2 (en) | Siloxane dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| TW201615753A (en) | Polyimide polymer, polyimide film including the same and polyimide laminate plate including the same | |
| CN110256671A (en) | The manufacturing method and display base plate resin film formation composition of display base plate resin film | |
| JP7039158B2 (en) | Polyimide precursor solution and a polyimide film using it and a method for manufacturing a polyimide film | |
| CN106916322B (en) | Dispersion liquid, process for producing the same, and organic/inorganic hybrid material | |
| JP6336194B2 (en) | Method for producing polyimide laminate and use thereof | |
| CN109563280A (en) | The manufacturing method of polyimide resin film and polyimide resin film | |
| JP5833698B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element thereof | |
| TWI780171B (en) | Composition for forming flexible device substrate | |
| WO2018186209A1 (en) | Polyimide-based film and display device | |
| TWI515230B (en) | Polyimide polymer and polyimide film including the same | |
| TW202231726A (en) | Polyamic acid, varnish including same, method for producing polyamic acid, polyimide, film including same, and display panel substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230519 Address after: Tokyo, Japan Applicant after: SUMITOMO CHEMICAL Co.,Ltd. Applicant after: Industrial Technology Research Institute Applicant after: MITSUBISHI GAS CHEMICAL Co.,Inc. Address before: Tokyo, Japan Applicant before: SUMITOMO CHEMICAL Co.,Ltd. Applicant before: Industrial Technology Research Institute |