CN106928707A - Polyimide polymer composition, method for producing same, and polyimide film - Google Patents
Polyimide polymer composition, method for producing same, and polyimide film Download PDFInfo
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- CN106928707A CN106928707A CN201611257137.0A CN201611257137A CN106928707A CN 106928707 A CN106928707 A CN 106928707A CN 201611257137 A CN201611257137 A CN 201611257137A CN 106928707 A CN106928707 A CN 106928707A
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- 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
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to a polyimide polymer composition, a method for producing the same, and a polyimide film using the polyimide polymer composition. The polyimide polymer composition includes dimethylpropionamide and a polyamic acid-polyimide copolymer of chemical formula 1, and thus can provide a polyimide film having improved physical properties such as a Coefficient of Thermal Expansion (CTE) and transmittance compared to a conventional polar solvent. In the following chemical formula 1, R1Is a fluoro group or aromatic anhydride monomer, R is a diamine monomer, n is an integer of 1 to 1000, and m is an integer of 1 to 1000. [ chemical formula 1]。
Description
Technical field
The present invention relates to polyimides polymeric composition and its manufacture method and using the polyimides high score sub-portfolio
The polyimide film of thing.
Background technology
Compared to other macromolecules, the electric, hot, chemical of polyimide resin, engineering properties are excellent, thus diversely apply
In heat-resisting advanced material and field of electronic materials.Especially, in field of display, as the material for manufacturing flexible base board,
The heat-resistant quality of Yin Qigao and get most of the attention.
For synthesis of polyimides, usually using diamine monomer, dianhydride monomer and polar solvent.According to imidizate side
Method, more using hot-imide method, chemical imidization method etc., and for applied chemistry imidizate method, can also make
Chemical imidization reaction is carried out with catalyst and dehydrating agent.
In order to synthesize the polyimide resin of excellent heat resistance, the monomer of aromatic structure should be used, but due to aromatic series
The high density of ring, the color of film is brown or yellow, so as in visible region, its transmitance step-down.This polyimides
Resin is restricted in the field for needing the transparency, in order to replace glass substrate material to use, it is necessary to other compositions and structure
Design.But, the property of another physical property reduction during due to obtaining improving with a kind of physical property, thus make polyamides sub- to manufacture
The transparent flexible substrate that the transparency of amine, thermal property, engineering properties are met, actual conditions are to need to develop polyamic acid
(polyamic acid) composition.
The solvent major part used for synthesis of polyimides is polar solvent, is the material (Japan limited by environment
Registered patent the 5201155th).But, when its is replaced, it is impossible to the physical property needed for obtaining, so as to also be continuing with.
The content of the invention
Problem to be solved
In order to solve above-mentioned the problems of the prior art, the present invention by by dimethylpropionamide (DMPA,
Dimethylpropionamide) it is used as synthetic or dispersion solvent to manufacture polyamic acid-polyimide copolymer, so that
Complete the present invention.
The method for solving problem
It is an aspect of the invention to, there is provided polyimides polymeric composition, it is used as by by dimethylpropionamide
Synthetic or dispersion solvent are manufactured and obtained, and comprising the polyamic acid-polyimide copolymer represented by formula 1 below：
[chemical formula 1]
In above-mentioned chemical formula 1, R1It is fluorine-based or aromatic acid anhydride monomer, R is diamine monomer, and n is 1 to 1000 integer, m
It is 1 to 1000 integer.
Another aspect of the present invention is, there is provided the transparent polyimide film manufacture system of polyimides polymeric composition
Method is made, it includes：The step of anhydride monomers being added in the synthetic comprising diamine monomer to be reacted；Above-mentioned anti-
Answering the step of add catalyst and dehydrating agent in solution and solidified after being reacted；And above-mentioned solidfied material is scattered in diformazan
Step in base propionamide.
Another aspect of the invention is, there is provided the manufacture method of polyimides polymeric composition, it includes：In bag
The step of anhydride monomers being added in dimethylpropionamide solution containing diamine monomer and are reacted；Add in above-mentioned reaction solution
Plus reacted after end-capping reagent and the step of synthesizing polyamides acid；And add crosslinking agent in above-mentioned polyamic acid and mixed
The step of.
Another aspect of the invention is, there is provided transparent or coloured polyimide film, it is by above-mentioned side of the invention
The polyimides polymeric composition in face is formed.
Invention effect
The present invention is used to synthesize or disperses come instead of being made in synthesis of polyimides in the past by by dimethylpropionamide
Polar solvent such that it is able to instead of the polar solvent that object is limited as environment.By the present invention in that with DMPA, Neng Gouti
For compared with conventional polar solvent is used, the polyimide film that is improved of the physical property such as thermal coefficient of expansion (CTE), transmitance.
Specific embodiment
One aspect of the present invention is, there is provided polyimides polymeric composition, it is used by by dimethylpropionamide
Make synthetic or dispersion solvent manufacture and obtain, and comprising the polyamic acid represented by formula 1 below-polyimides copolymerization
Thing：
[chemical formula 1]
In above-mentioned chemical formula 1, R1It is fluorine-based or aromatic acid anhydride monomer, R is diamine monomer, and n is 1 to 1000 integer, m
It is 1 to 1000 integer.
In an embodiment of the invention, above-mentioned polyimides polymeric composition can be used to manufacture transparent or coloured
Polyimide film.
In an embodiment of the invention, above-mentioned diamine monomer can be comprising selected from by p-phenylenediamine (PPD A, p-
Phenylenediamine), 4,4- diaminodiphenyl ethers (ODA, 4,4'-Oxydianiline), 4,4- MDAs
(MDA, 4,4'-Methylenedianiline), a tolidine (2,2'-Dimethyl-4,4'-Diaminobiphenyl),
1,3- double (4'- amino-benzene oxygens) benzene (TPE-R, 1,3-BIS (4'-Aminophenoxyl) benzene), the double (trifluoros of 2,2'-
Methyl) benzidine (TFMB, 2,2'-Bis (trifluoromethyl) benzidine), the double [4- (4- amino-benzene oxygens) of 2,2-
Phenyl] HFC-236fa (HFBAPP, 2,2-BIS [4- (4-Aminophenoxy) Phenyl] Hexafluoropropane), 2,2-
Double (3- amino-4-hydroxylphenyls) HFC-236fa (BIS-AP-AF, 2,2-Bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane), 1,3- diaminourea -2,4,5,6- phenyl tetrafluorides (DRFB, 1,3-Diamino-2,4,5,6-
Tetrafluorobenzene), 3,3'- DADPSs (DDS, 3,3'-Diaminodiphenyl Sulfone), 4,4'-
Diaminodiphenyl sulfide (ASD, 4,4'-Diaminodiphenyl Sulfide), double [4- (4- amino-benzene oxygens) phenyl] sulfones
Double [4- (3- amino-benzene oxygens) benzene] sulfones of (BAPS, Bis [4- (4-aminophenoxy) phenyl] sulfone), 2,2-
Thing in the group of (mBAPS, 2,2-Bis [4- (3-Aminophenoxy) Benzene] Sulfone) and combinations thereof composition
Matter.Physical property appropriate diamine monomer can be selected to use according to needed for the application field of polyimides.In order to manufacture with height
Heat-resistant quality and the polyimide film of low thermal coefficient of expansion is presented, the diamine monomer of aromatic structure may be selected to use,
When coloured polyimides of the synthesis without the transparency, it is adapted to use PPDA monomers.Additionally, sub- in order to synthesize transparent polyamides
Amine, can be used fluorine system monomer, for example, TFMB monomers can be used.
In an embodiment of the invention, above-mentioned anhydride monomers can be aromatic dianhydride monomer, for example, can include
Selected from by 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides (BTDA, 3,3', 4,4'-benzophenonetetra
Carboxylicdianhydride), pyromellitic acid anhydride (PMDA, pyromelliticdianhydride), 3,3', 4,
4'- bibenzene tetracarboxylic dianhydrides (BPDA, 3,3', 4,4'-biphenyl tetracarboxylicaciddianhydrid e), 4,
4'- (hexafluoroisopropyli,ene) double phthalic anhydrides (6FDA, 2,2-bis (3,4anhydrodicarboxyp henyl)-
Hexafluoropropanedianhydride), 2,3,3', 4- bibenzene tetracarboxylic dianhydrides (a-BPDA, 2,3,3', 4biphenyl
Tetracarboxylicaciddianhydride), double phthalic anhydride (ODPA, 4,4'-oxydiphthalic of 4,4'- oxygen
Anhydride), 3,3', 4,4'- diphenyl sulfone tetracarboxylic acid dianhydrides (DSDA, 3,3', 4,4'-dip henylsulfone-
Tetracarboxylic dianhydride), double [4 (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 2,2-) (BPADA,
2,2-bis [4 (3,4-dicarboxyphenoxy) phenyl] propane dianhydride), quinhydrones diphthalic anhydrides
Material in the group of (HQDA, hydroquinone diphthalic anhydride) and combinations thereof composition.Above-mentioned fragrance
Race's dianhydride monomer can be used more than one, for example, at least two monomers can be used.Can be according to institute in the application field of polyimides
Physical property is needed to select appropriate anhydride monomers to use.Heat-resistant quality high is presented and without the coloured polyamides Asia of the transparency when synthesis
During amine film, BP DA and PMDA monomers can be used.Additionally, in order to synthesize transparent polyimides, being adapted to use 6FDA monomers, it is
Raising heat-resistant quality and mechanical properties, are adapted to use BPDA monomers.
Another aspect of the present invention is, there is provided the manufacture method of polyimides polymeric composition, it includes：Comprising
The step of anhydride monomers being added in the synthetic of diamine monomer and are reacted；In above-mentioned reaction solution add catalyst and
Dehydrating agent and the step of solidified after being reacted；And above-mentioned solidfied material is scattered in the step in dimethylpropionamide.
Another aspect of the invention is, there is provided the manufacture method of polyimides polymeric composition, it includes：In bag
The step of anhydride monomers being added in dimethylpropionamide solution containing diamine monomer and are reacted；Add in above-mentioned reaction solution
Plus end-capping reagent and reacted and synthesizing polyamides acid step；And add crosslinking agent in above-mentioned polyamic acid and mixed
The step of.
In an embodiment of the invention, above-mentioned polyimides polymeric composition can be used to manufacture transparent or coloured
Polyimide film.
In an embodiment of the invention, above-mentioned diamine monomer can be comprising selected from by p-phenylenediamine, 4,4- diaminourea
Double (4'- amino-benzene oxygens) benzene of diphenyl ether, 4,4- MDAs, a tolidine, 1,3-, the double (fluoroforms of 2,2'-
Base) benzidine, double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2-, double (3- amino-4-hydroxylphenyls) hexafluoros of 2,2-
Propane, 1,3- diaminourea -2,4,5,6- phenyl tetrafluorides, 3,3'- DADPSs, 4,4'- diaminodiphenyl sulfides, double [4- (4-
Amino-benzene oxygen) phenyl] sulfone, double [4- (3- amino-benzene oxygens) benzene] sulfones of 2,2- and combinations thereof composition group in material.
Physical property appropriate diamine monomer can be selected to use according to needed for the application field of polyimides.In order to manufacture with high resistance to
The polyimide film of thermal characteristics and the low thermal coefficient of expansion of presentation, may be selected the diamine monomer of aromatic structure to use, and work as conjunction
During into without transparent coloured polyimides, it is adapted to use PPDA monomers.Additionally, in order to synthesize transparent polyimides, can
Using fluorine system monomer, for example, TFMB monomers can be used.
In an embodiment of the invention, above-mentioned anhydride monomers can be aromatic dianhydride monomer, for example, can include
Selected from by 3,3', 4,4'- benzophenone tetracarboxylics dianhydride, pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,
4'- (hexafluoroisopropyli,ene) double phthalic anhydrides, 2,3,3', the double phthalic acids of 4- bibenzene tetracarboxylic dianhydrides, 4,4'- oxygen
Acid anhydride, 3,3', 4,4'- diphenyl sulfones tetracarboxylic acid dianhydride, 2,2- double [4 (3,4- di carboxyl phenyloxies) phenyl] propane dianhydride, quinhydrones
Material in the group of diphthalic anhydrides and combinations thereof composition.Above-mentioned aromatic dianhydride monomer can be used more than one,
For example, at least two monomers can be used.Physical property appropriate anhydride monomers can be selected according to needed for the application field of polyimides
To use.When synthesis is presented heat-resistant quality high and the coloured polyimide film without the transparency, BPDA and PMDA can be used
Monomer.Additionally, in order to synthesize transparent polyimides, be adapted to use 6FDA monomers, in order to improve heat-resistant quality and mechanical properties,
It is adapted to use BPDA monomers.
In an embodiment of the invention, as long as the solvent that uses in the art of above-mentioned synthetic, so that it may
To use without restriction, for example, can be comprising being selected from by acid amides series solvent, ketone series solvent, ether series solvent, ester series solvent, symmetrical
Material in the group of diol bisether class solvent, ether solvent and combinations thereof composition.Above-mentioned acid amides series solvent can include diformazan
Base formamide (DMF), dimethylacetylamide (DMAC), n- methyl pyrrolidones (NMP) etc., above-mentioned ketone series solvent can include third
Ketone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), cyclopentanone, cyclohexanone etc..Above-mentioned ether series solvent can include tetrahydrochysene
Furans (THF), 1,3- dioxolanes and 1,4- bis-Alkane etc., above-mentioned ester series solvent can include methyl acetate, ethyl acetate, second
Acid butyl ester, gamma-butyrolacton, α-acetic acid lactone, beta-propiolactone, δ-valerolactone etc..Above-mentioned symmetrical diol bisether class solvent can be included
Methyl monoethylene glycol dimethyl ether (1,2- dimethoxy-ethanes), methyl diethylene glycol dimethyl ether (double (2- methoxy ethyls) ethers),
Methyl TRIGLYME (double (2- methoxy ethoxies) ethane of 1,2-), methyl tetraethyleneglycol dimethyl ether (double [2- (2- first
Epoxide ethoxyethyl group)] ether), ethyl monoethylene glycol dimethyl ether (1,2- diethoxyethane), ethyl diethylene glycol dimethyl ether
(double (2- ethoxyethyl groups) ethers), butyl diglycol dimethyl ether (double (2- butoxyethyl groups) ethers) etc., above-mentioned ether solvent can
Comprising the ethers of ethylene glycol two, dipropylene glycol methyl ether, tripropylene glycol methyl ether, Propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propane diols
N-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol positive propyl ether, propane diols phenylate, dimethyl ether, 1,3- dioxolanes,
Ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether etc..
In an embodiment of the invention, above-mentioned synthetic can be dimethylpropionamide.
In an embodiment of the invention, above-mentioned end-capping reagent may be selected from by phthalic anhydride (PA, pht hallic
Anhydride), myristyl succinyl oxide (TSA, tetradecyl succinic anhydride), cetyl butanedioic acid
Acid anhydride (HAS, hexadecyl succinic anhydride), octadecylsuccinic acid acid anhydride (OS A, octadecyl succinic
Anhydride) and in the group of combinations thereof composition, it is preferable that can be P A.Above-mentioned end-capping reagent is used for telo merization,
High molecular molecular weight can be adjusted with monoester anhydride form, reduce the content of unreacted reactant, and improve keeping stability.
In an embodiment of the invention, anhydride monomers are added in the synthetic comprising diamine monomer and is carried out
After the step of reaction, the step of adding end-capping reagent can be further included.
In an embodiment of the invention, when the synthesis of polyimides high score subgroup in polyamic acid Polymer Solution
During compound, imidization reaction can be parallel by hot imide reaction and chemical imidization reaction.By two kinds of imidizates
In the case that reaction is parallel, have the following advantages that：When hot imide reaction is carried out, reaction temperature can be reduced, and can lead to
Cross precipitation operation and remove the unreacted phase remained during synthesis in advance.
In an embodiment of the invention, above-mentioned dehydrating agent and catalyst can be used for chemical imidization reaction, on
Stating dehydrating agent can include the tertiary amines such as pyridine, isoquinolin, β-picoline comprising the acid anhydrides such as acetic anhydride, above-mentioned catalyst.
In an embodiment of the invention, above-mentioned crosslinking agent can include 4,4 '-di-2-ethylhexylphosphine oxide (N, N- 2-glycidyl
Base aniline).Above-mentioned 4,4 '-di-2-ethylhexylphosphine oxide (N, N- diglycidylaniline) can have following structure：
In an embodiment of the invention, can further include to be added in above-mentioned polyimides polymeric composition
The step of crosslinking agent.
Another aspect of the invention is, there is provided by formed transparent of polyimides polymeric composition of the invention or
Coloured polyimide film.
In an embodiment of the invention, above-mentioned polyimide film can be manufactured by the following steps and obtain：Will be above-mentioned
Polyimides polymeric composition is coated on the step on substrate；And carried out to being coated with the high molecular substrate of above-mentioned polyimides
The step of heat drying.
In an embodiment of the invention, can be used according to when manufacturing above-mentioned polyimides polymeric composition
The species of diamine monomer and anhydride monomers manufactures transparent or coloured polyimide film.
Hereinafter, carried out by embodiments of the invention more specifically bright, the scope of the present invention is not limited to this implementation
Example.
Embodiment
Embodiment 1：Manufacture for manufacturing the polyimides Polymer Solution of transparent polyimide film
While make nitrogen by being connected with the stirred reactor of the temperature-adjustable of nitrogen injection device and dropping funel, while
Filled under normal temperature after the DMAC of 704.2g, dissolved the TFMB as fluorine system diamine monomer of 32.02g (0.1mol).
The fluorine system of aromatic monomer BPDA and 31.1g (0.07mol) as the 8.83g (0.03mol) of anhydride monomers is put into wherein
Monomer 6FDA and reacted.Be completely dissolved and by 1 hour afterwards, put into as catalyst and the pyridine and acetic acid of dehydrating agent
Acid anhydride, is warming up to 70 DEG C afterwards, carries out the reaction of 1 hour, and be cooled to normal temperature.
Afterwards, MeOH and distilled water (3 are deposited in：1) solidified in mixed solution.It is fully cleaned in MeOH
Afterwards, the abundant drying of 6 hours is carried out in 80 DEG C of vacuum drying oven, so as to obtain polyimides polymeric solid.
The polyimide solids of acquisition is scattered in DMPA solution, and be stirred well to after the solid not remained,
Filtered to remove foreign matter and unreacted phase, so as to obtain polyimides Polymer Solution.
Comparative example 1
While make nitrogen by being connected with the stirred reactor of the temperature-adjustable of nitrogen injection device and dropping funel, while
Filled under normal temperature after the DMAC of 704.2g, make to be completely dissolved as the TFMB of the 32.02g (0.1mol) of fluorine system diamine monomer.
The fluorine system of aromatic monomer BPDA and 31.1g (0.07mol) as the 8.83g (0.03mol) of anhydride monomers is added wherein
Monomer 6FDA and reacted.Be completely dissolved and by 1 hour afterwards, put into as catalyst and the pyridine and acetic acid of dehydrating agent
Acid anhydride, is warming up to 70 DEG C afterwards, carries out the reaction of 1 hour, and be cooled to normal temperature.
Afterwards, it is deposited in MeOH and distillation water mixed solution to be solidified.After abundant cleaning in MeOH, 80
DEG C vacuum drying oven in carry out the abundant drying of 6 hours, so as to obtain polyimide solids.
The polyimide solids of acquisition is scattered in after DMAC solution, be stirred well to the solid not remained, in order to
Remove foreign matter and unreacted phase and filtered, so as to obtain polyimides Polymer Solution.
Comparative example 2
While make nitrogen by being connected with the stirred reactor of the temperature-adjustable of nitrogen injection device and dropping funel, while
Filled under normal temperature after the DMPA of 704.2g, make to be completely dissolved as the TFMB of the 32.02g (0.1mol) of fluorine system diamine monomer.
The fluorine system of aromatic monomer BPDA and 31.1g (0.07mol) as the 8.83g (0.03mol) of anhydride monomers is added wherein
Monomer 6FDA and reacted.Be completely dissolved and by 1 hour afterwards, put into as catalyst and the pyridine and acetic acid of dehydrating agent
Acid anhydride, is warming up to 70 DEG C afterwards, carries out the reaction of 1 hour, and be cooled to normal temperature.
Afterwards, it is deposited in MeOH and distillation water mixed solution to be solidified.After abundant cleaning in MeOH, 80
DEG C vacuum drying oven in carry out the abundant drying of 6 hours, so as to obtain polyimide solids.
The polyimide solids of acquisition is scattered in after DMPA solution, be stirred well to the solid not remained, in order to
Remove foreign matter and unreacted phase and filtered, so as to obtain polyimides Polymer Solution.
Embodiment 2：The manufacture of transparent polyimide film
Using applicator (applicator), with 400 μm of wet-film thickness, will be in above-described embodiment 1, comparative example 1 and ratio
It is coated on glass substrate compared with the polyimides Polymer Solution obtained in example 2, then in convection oven (convection
Oven heat drying is to 280 DEG C in), so as to manufacture the polyimide film that thickness is 30 μm.
Embodiment 3：Manufacture for manufacturing the polyimides Polymer Solution of coloured polyimide film
While make nitrogen by being connected with the stirred reactor of the temperature-adjustable of nitrogen injection device and dropping funel, while
Filled under normal temperature after the DMPA of 242.45g, be completely dissolved the PPDA of 10.91g, the BPDA of 26.48g has then been put into successively
With the PMDA of 2.18g.After being completely dissolved and by 1 hour afterwards, the PA of 0.2g is put into, and carries out the reaction of 16 hours, from
And synthesized polyacrylamide (PA A, Polyacrylamide).Afterwards, monomer (DMPA, BPDA and PMDA) content is made
4, the 4'- di-2-ethylhexylphosphine oxides (N, N- diglycidylaniline) of 4000pp m be dissolved in in reaction dissolvent identical solvent, and
Be added to reaction terminate PAA in mixed.
Comparative example 3
While make nitrogen by being connected with the stirred reactor of the temperature-adjustable of nitrogen injection device and dropping funel, while
Filled under normal temperature after the NMP of 242.45g, be completely dissolved the PPDA of 10.91g, the BPDA of 26.48g has then been put into successively
With the PMDA of 2.18g.Be completely dissolved and by 1 hour afterwards, put into the PA of 0.2g, and the reaction of 16 hours is carried out, so as to close
Into PAA.Afterwards, (N, N- bis- shrinks to make 4, the 4'- di-2-ethylhexylphosphine oxides of the 4000ppm of monomer (PP DA, BPDA and PMDA) content
Glyceryl aniline) be dissolved in solvent, and be added to reaction terminate PAA in mixed.
Embodiment 4：The manufacture of coloured polyimide film
Using applicator, with 350 μm of wet-film thickness, the polyimides that will be obtained in above-described embodiment 3 and comparative example 3
Polymer Solution is coated on glass substrate, then in convection oven heat drying to 450 DEG C, so as to manufacture thickness for 20 μm
Polyimide film.
Experimental example 1
The physical property of the polyimide film synthesized in above-described embodiment 2 and embodiment 4 is have rated by the following method, and will
Its result is shown in following table 1 to table 3.
The measure of thermal coefficient of expansion
Using static thermomechanical analyzer (TMA) (TA instrument companies), Q400), line style heat is determined according to TMA- methods
The coefficient of expansion.Programming rate is determined by 5 DEG C per minute, and cooling velocity is determined by 20 DEG C per minute, due to having in film
Stress may be remained, thus under Tg temperature below, is measured in 30 DEG C to 300 DEG C temperature ranges.Thermal coefficient of expansion
Value is determined in cooling from slope.
The measure of transmitance
Using measurement optical device (electricity color (Nippon Denshoku) company, COH-400 of Japan), in visible region
Middle measure 5 times determines average value afterwards.
The measure of yellow chromaticity
Yellow chromaticity is determined using measurement optical device (Japanese electricity Se companies, COH-400).
The above results that will be determined are shown in table 1 to table 3.
[table 1]
The manufacture (30 μm of film thicknesses) of clear polyimides
[table 2]
The manufacture (20 μm of film thicknesses) of coloured polyimides
[table 3]
The comparing of synthetic physical property：DMPA、DMAC、NMP
Such as from above-mentioned table 1 to table 3 can confirm that to, with the past manufacture polyimide film when used as polar solvent
DMAC (DMA) or NMP (pyrrolidones of n- methyl 2) compare, when using DMPA (dimethylpropionamide)
When, the physical property such as thermal coefficient of expansion, transmitance is more excellent.Additionally, monomer is easier dissolving in DMPA, it is high molten so as to present
Xie Du.
Above-mentioned explanation of the invention is used to illustrate, and general technical staff of the technical field of the invention is appreciated that
In the case of not changing technological thought of the invention or essential feature, can be easily deformed as other specific forms.Therefore,
It is in all respects exemplary to be interpreted as the embodiment of above description, and is infinite.For example, with configuration
Each inscape for illustrating also can dispersedly be implemented, and equally, the inscape of dispersion explanation also can be with the form of combination
Implement.
The scope of the present invention by institute's appended claims Range Representation, rather than above-mentioned detailed description, claim
The implication and scope of scope and the form for having altered or deforming derived from its equivalents should be interpreted as including at this
The scope of invention.
Claims (14)
1. a kind of polyimides polymeric composition, its polyamic acid-polyimides for including dimethylpropionamide and chemical formula 1
Copolymer：
[chemical formula 1]
In the chemical formula 1,
R1It is fluorine-based or aromatic acid anhydride monomer,
R is diamine monomer,
N is 1 to 1000 integer,
M is 1 to 1000 integer.
2. polyimides polymeric composition according to claim 1, the diamine monomer is selected from by p-phenylenediamine, 4,4-
Double (4'- amino-benzene oxygens) benzene of diaminodiphenyl ether, 4,4- MDAs, a tolidine, 1,3-, 2,2'- double (three
Methyl fluoride) benzidine, double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2-, 2,2- be double (3- amino-4-hydroxylphenyls)
It is HFC-236fa, 1,3- diaminourea -2,4,5,6- phenyl tetrafluorides, 3,3'- DADPSs, 4,4'- diaminodiphenyl sulfides, double
In the group of double [4- (3- amino-benzene oxygens) benzene] sulfones of [4- (4- amino-benzene oxygens) phenyl] sulfone, 2,2- and combinations thereof composition.
3. polyimides polymeric composition according to claim 1, the anhydride monomers comprising being selected from by 3,3', 4,
4'- benzophenone tetracarboxylics dianhydride, pyromellitic acid anhydride, 3,3', (hexafluoro Asia is different for 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'-
Propyl group) double phthalic anhydrides, 2,3,3', 4- bibenzene tetracarboxylic dianhydrides, 4,4'- oxygen double phthalic anhydride, 3,3', 4,4'-
Diphenyl sulfone tetracarboxylic acid dianhydride, 2,2- double [4 (3,4- di carboxyl phenyloxies) phenyl] propane dianhydride, quinhydrones diphthalic anhydrides
And the material in the group of combinations thereof composition.
4. a kind of manufacture method of polyimides polymeric composition, it includes：
The step of anhydride monomers being added in the synthetic comprising diamine monomer and are reacted；
The step of being solidified after addition catalyst in reaction solution and dehydrating agent are reacted；And
Step in making solidfied material be scattered in dimethylpropionamide.
5. a kind of manufacture method of polyimides polymeric composition, it includes：
The step of anhydride monomers being added in the dimethylpropionamide solution comprising diamine monomer and are reacted；
Reacted after adding end-capping reagent in reaction solution and the step of synthesizing polyamides acid；And
The step of crosslinking agent being added in the polyamic acid and is mixed.
6. the manufacture method of the polyimides polymeric composition according to claim 4 or 5, the diamine monomer be selected from by
P-phenylenediamine, 4,4- diaminodiphenyl ethers, 4,4- MDAs, a tolidine, 1,3- are double (4'- amino-benzene oxygens)
Double (trifluoromethyl) benzidine of benzene, 2,2'-, double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2-, double (the 3- ammonia of 2,2-
Base -4- hydroxy phenyls) HFC-236fa, 1,3- diaminourea -2,4,5,6- phenyl tetrafluorides, 3,3'- DADPSs, 4,4'- diaminos
Double [4- (3- amino-benzene oxygens) benzene] sulfones of base diphenyl sulfide, double [4- (4- amino-benzene oxygens) phenyl] sulfones, 2,2- and their group
In the group being combined into.
7. the manufacture method of the polyimides polymeric composition according to claim 4 or 5, the anhydride monomers are fragrance
Race's dianhydride monomer.
8. the manufacture method of polyimides polymeric composition according to claim 7, the aromatic dianhydride monomer bag
Containing selected from by 3,3', 4,4'- benzophenone tetracarboxylics dianhydride, pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides,
4,4'- (hexafluoroisopropyli,ene) double phthalic anhydrides, 2,3,3', the double phthalic acids of 4- bibenzene tetracarboxylic dianhydrides, 4,4'- oxygen
Acid anhydride, 3,3', 4,4'- diphenyl sulfones tetracarboxylic acid dianhydride, 2,2- double [4 (3,4- di carboxyl phenyloxies) phenyl] propane dianhydride, quinhydrones
Material in the group of diphthalic anhydrides and combinations thereof composition.
9. the manufacture method of the polyimides polymeric composition according to claim 4 or 5, adds more than one acid anhydrides
Monomer.
10. the manufacture method of polyimides polymeric composition according to claim 4, the synthetic is comprising being selected from
By acid amides series solvent, ketone series solvent, ether series solvent, ester series solvent, symmetrical diol bisether class solvent, ether solvent and their group
Material in the group being combined into.
The manufacture method of 11. polyimides polymeric compositions according to claim 4, the dehydrating agent includes acid anhydrides,
The catalyst includes tertiary amines.
The manufacture method of 12. polyimides polymeric compositions according to claim 5, the end-capping reagent is selected from by adjacent benzene
Dicarboxylic acid anhydride, myristyl succinyl oxide, cetyl succinyl oxide, octadecylsuccinic acid acid anhydride and combinations thereof composition
In group.
The manufacture method of 13. polyimides polymeric compositions according to claim 5, the crosslinking agent comprising 4,4 '-
Di-2-ethylhexylphosphine oxide (N, N- diglycidylaniline).
14. a kind of transparent or coloured polyimide films, it is as the polyimides polymeric composition shape described in claim 1
Into.
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201736442A (en) | 2017-10-16 |
| JP7384546B2 (en) | 2023-11-21 |
| TWI814701B (en) | 2023-09-11 |
| CN106928707B (en) | 2021-07-20 |
| JP2017119868A (en) | 2017-07-06 |
| KR102580455B1 (en) | 2023-09-20 |
| KR20170079896A (en) | 2017-07-10 |
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