CN1732230A - Polyimide precursor liquid composition and polyimide coating film - Google Patents
Polyimide precursor liquid composition and polyimide coating film Download PDFInfo
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- CN1732230A CN1732230A CN 200380107473 CN200380107473A CN1732230A CN 1732230 A CN1732230 A CN 1732230A CN 200380107473 CN200380107473 CN 200380107473 CN 200380107473 A CN200380107473 A CN 200380107473A CN 1732230 A CN1732230 A CN 1732230A
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- polyimide
- film
- precursor liquid
- coating film
- polyimide precursor
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 104
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000002243 precursor Substances 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 26
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- 150000004985 diamines Chemical class 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 25
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- 238000009835 boiling Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
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Abstract
A polyimide precursor liquid composition of the present invention includes at least one type of tetracarboxylic dianhydride or derivative thereof, at least one type of diamine or derivative thereof, and a polar polymerization solvent, wherein the polyimide precursor liquid composition further includes a cyclic compound, and wherein the cyclic compound has a boiling point of 200 DEG C. or more and comprises carbon, hydrogen and oxygen atoms. A polyimide coating film of the present invention is obtained by converting the polyimide precursor liquid composition into imide. Thus, the present invention provides a polyimide coating or film that is substantially colorless and transparent, and that is useful as, for example, a heat resistant coating film for liquid crystals, organic electroluminescence, touch panels and solar cells and the like.
Description
Technical field
The present invention relates to colourless and transparent basically polyimide precursor and polyimide coating film (comprising film, sheet material and tubing).More specifically; the present invention relates to colourless basically transparent aspect for example optical fiber, the substrate that is used for liquid-crystal display face, electroluminescence substrate and protection sheet material useful polyimide coating film, and relate to colourless basically transparent polyimide film as refractory coating etc.
Background technology
Polyimide coating and film are widely used in the product applications that many different requirements have thermostability and good electric and mechanical characteristics, and are considered to ideal.In addition, has the film that the polyimide coating of good clear characteristic and film are widely used as for example liquid crystal display, electroluminescence substrate, fiber optic cables coat film, waveguide and are used for the protection mulch film aspect of solar cell.Though this polyimide coating and film have the good transparency, because the hot state of over-drastic that stands in film formation process to be experienced, they can become yellow or brown usually.This variable color exists the variable color of some problems such as liquid crystal film to make the viewing area deepening in application facet, thereby the forfeiture liquid crystal indicator is functional.
At the problems referred to above, people have developed various polyimide coating and the films that show low discoloration degree and high transparent.Use the exploitation of the coating and the film of this prior art, by a series of institute's guiding that concentrate on the variable color factor that relates to the clear polyimides film.According to this class research, the variable color of polyimide depends on the aromatic tetracarboxylic acid dianhydride that selection uses as the polyimide starting raw material and the type of diamino compounds greatly.Especially the aromatic diamine that comprises an amino group on a position, position is effective especially as aminocompound, and according to this class research, this diamine compound and phenylbenzene tetracarboxylic dianhydride's mixture can cause the formation of water white polyimide (following patent documentation 1).Use the coating of this prior art and the exploitation of film, the principle that the variable color degree of resulting polyimide produces harmful effect is guided by known higher generation temperature or polymerization temperature.In fact in these prior aries, use the polymerization under 80 ℃ or following temperature of aromatic tetracarboxylic acid dianhydride and diamino compounds by heat or chemical process polyamic acid to be transformed into imido method afterwards and to make polyimide to produce polyamic acid solution.
But, in patent documentation 1, because therefore polyamic acid polymerization under 80 ℃ or following temperature exists the problem that polymerization velocity is low, production cost is high.In order to address this problem, in the patent documentation 2 below, Deets has proposed a kind of polyimide of low production cost.
Patent documentation 1: United States Patent (USP) the 4th, 876, No. 330,64 row～2 hurdles, 1 hurdle, 6 row, 8 hurdles, 25～39 row.
Patent documentation 2: Japan's special permission discloses 2000-313804A number
Yet in the last few years, in imaging device or for example optical fiber, the optical waveguide of electroluminescence (EL) of using liquid crystal cell, and electronic unit required polyimide to have the higher transparency as being used for the supercoat aspect of solar cell and printed circuit board (PCB).
Summary of the invention
The present invention has improved traditional technology, and provides a kind of and have the more polyimide coating film of high transparent, and the polyimide precursor liquid that wherein is used for polyimide coating film.
Polyimide precursor liquid composition of the present invention comprises at least one class tetracarboxylic dianhydride's or derivatives thereof, at least one class diamines or derivatives thereof, and a kind of polarity polymer solvent, wherein polyimide precursor liquid composition further comprises a kind of ring compound, and wherein this ring compound has 200 ℃ or above boiling point, and it comprises carbon, hydrogen and Sauerstoffatom.
Obtain polyimide coating film of the present invention by polyimide precursor liquid composition being transformed into imide.
Description of drawings
Fig. 1 is the heat analysis data of the BPADA of use in the embodiment of the invention of measuring by differential scanning calorimetry device (DSC) 1～7.
The O1s spectrogram that Fig. 2 obtains for the XPS analysis by the polyimide that obtains in the embodiment of the invention 1.
The O1s spectrogram that Fig. 3 obtains for the XPS analysis by the polyimide that obtains in the comparative example 1.
Embodiment
The present invention can provide a kind of ratio to have the more polyimide coating film of high transparent by the polyimide coating film of traditional technology preparation by a kind of polyimide precursor liquid composition of at least one class tetracarboxylic dianhydride's or derivatives thereof, at least one class diamines or derivatives thereof and a kind of polarity polymer solvent that comprises is provided, wherein polyimide precursor liquid composition also further comprises a kind ofly having 200 ℃ or above boiling point, and comprises the ring compound of carbon, hydrogen and Sauerstoffatom.
Can be used in preferred raw material of the present invention forms and comprises: at least one class be selected from following chemical formula A and B (wherein X representative-O-,-S-,-SO-,-SO
2-,-CH
2-,-CF
2-,-C (CH
3)
2-,-C (CF
3)
2-or directly in conjunction with) aromatic tetracarboxylic acid dianhydride's or derivatives thereof; At least one class be selected from following Formula I and II (wherein Y representative-O-,-S-,-SO-,-SO
2-,-CH
2-,-CF
2-,-C (CH
3)
2-,-C (CF
3)
2-,-CO-or directly in conjunction with) the aromatic diamine or derivatives thereof; A kind of polarity polymer solvent; And a kind of ring compound, wherein this ring compound has 200 ℃ or above boiling point, and comprises carbon, hydrogen and Sauerstoffatom.
Usually can be used for the polymerization polyimide precursor is the compound such as the N of the polarity polymer solvent of polyamic acid, dinethylformamide (DMF), N, strong solvation takes place or forms complex compound with attached in the polyamic acid in the presoma polyamic acid of N-N,N-DIMETHYLACETAMIDE (DMAC), N-N-methyl-2-2-pyrrolidone N-(NMP) and methyl-sulphoxide (DMSO) and polyimide, when in the heating of 300 ℃ or above temperature, they can thermolysis.Because they comprise for example nitrogen (N) and sulphur (S) atom, therefore when these solvent thermal were decomposed, they may be factors that causes variable color.
If at large having studied, inventors of the present invention will not comprise heteroatoms such as nitrogen, p and s, and having the compound that is higher than as the polar organic solvent boiling point of polymer solvent joins in the polar organic solvent as polyimide precursor, with polar organic solvent displacement compound, when at high-temperature firing, may prevent the principle of variable color so then with lower boiling polymer solvent.They find not comprise heteroatoms such as nitrogen, p and s when using, and when having high boiling ring compound, are preventing that aspect the variable color be effective.Especially, they find to have bigger moment of dipole and specific inductivity owing to have the compound of the five-membered ring structure that comprises carbonyl (C=O key) than the polar organic solvent that is generally used for polymeric polyamide acid, therefore make these compounds and polyamic acid solvation consumingly owing to be derived from pentacyclic two dimensional structure, when using these compounds, they can replace polar organic solvent, thereby have the effect of the variable color of preventing when high-temperature firing.
The specific inductivity of compound be 30 or more than, be preferably 40 or more than.The moment of dipole of compound be 3 debye (debye) or more than, be preferably 4 debye or more than.
The institute preferably, employed compound is at least a compound that is selected from following group among the present invention: ethylene carbonate, Texacar PC, butylene carbonate and gamma-butyrolactone.
When the solid part of polyimide precursor liquid was 100 mass parts, the polarity polymer solvent was in the scope of 150～900 mass parts, and ring compound is preferred in the scope of 15～750 mass parts.
After the polymerization polyimide precursor, it is preferred adding ring compound again in the polarity polymer solvent.
When polyimide coating film of the present invention for having the film of 50 ± 10 microns (μ m) thickness or filming, and when the time with the rayed of 420 nanometers (nm), polyimide coating film show 50% or above transmitance be preferred, more preferably polyimide coating film shows 60% or above transmitance, particularly preferably is polyimide coating film and shows 70% or above transmitance.
The tetracarboxylic dianhydride's of aromatics example is 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, diphenylsulfone acid's dianhydride, 2, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2-, diphenyl sulfide tetracarboxylic dianhydride, thionyl benzene tetracarboxylic dianhydride, oxydiphthalic acid dianhydride, phenylbenzene tetracarboxylic dianhydride and benzophenonetetracarboxylic dianhydride.In preferred embodiments, X is the aliphatic hydrocarbon group that fluorine replaces.In a more preferred embodiment, aromatic tetracarboxylic acid dianhydride's monomeric compound of the present invention is the BPADA shown in following formula 1.
In another preferred embodiment, X is direct combination, and tetracarboxylic dianhydride's monomer component of aromatics is the phenylbenzene tetracarboxylic dianhydride shown in following formula 2, i.e. BPDA.
The example of tetracarboxylic dianhydride and derivative thereof is tetracarboxylic acid, carboxylicesters and tetracarboxylic dianhydride, but the tetracarboxylic dianhydride is preferred.
Aromatic diamine of the present invention is any represented replacement aromatic diamine among general formula I or the general formula I I.In preferred embodiments, Y is a sulfone, and aromatic diamine is two (aminophenyl of replacement) sulfones (DDS of replacement).In the formula 3 below, can be between position form or para-forms, but be preferably para-forms.The example of the aromatic diamine of para-orientation is to p-diaminodiphenyl, 4,4 '-oxo dianiline, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino thionyl benzene, 4,4 '-methylene-dianiline, 4,4 '-diamino-diphenyl methylene fluoride, 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-and two [4-(4-amino-benzene oxygen) phenyl] sulfone (BAPS).
The example of diamines or derivatives thereof is diamines, vulcabond and diamino disilane, but diamines is preferred.
When preparation polyamic acid solution of the present invention, comprise SO if use
2Functional group (for example, 4,4-DDS) and/or aromatics-O-aromatics ehter bond () diamines for example, BAPP or BAPS so for the color of desalinating resulting polyimide and/or improve toughness, preferably uses with second kind of diamine monomer jointly.This second kind of diamine monomer can be aromatic diamine or the alicyclic diamine that a contraposition or a position replace.Between the example of the aromatic diamine that replaces of position be two [4-(3-amino-benzene oxygen) phenyl] sulfones (BAPSM), 1,3-mphenylenediamine (MPDA), 1,3-pair of (3-amino-benzene oxygen) benzene (m-ABP) and 3,4 '-the oxo dianiline (3,4 '-ODA).The example of alicyclic diamine is cyclohexane diamine, different fluorine that ketone diamines and norbornane diamines.
In the present invention, wherein among the chemical formula B X of indication be-(CH
3)
2-compd B PADA preferably have 187 ℃ or above pass through the fusing point endotherm peak temperature that differential scanning calorimetry device (DSC) is measured, and be lower than neither also not heat release of heat absorption basically under the temperature that fusing begins to absorb heat.When using this BPADA, can keep even the higher transparency.
And if the compound shown in the chemical formula A is phenylbenzene tetracarboxylic dianhydride (BPDA, a Chemical formula 1), the mixture ratio of the BPADA shown in the chemical formula B (Chemical formula 2) is preferably at BPDA so: BPADA=9: 1～5: in 5 the scope.If in this scope, can when keeping high transparent, increase toughness so.
When on the aromatic tetracarboxylic acid dianhydride, introducing replacement functional group, has the tendency that increases cost.When especially introducing fluorine, manufacturing cost increases substantially.For this reason, the phenylbenzene tetracarboxylic dianhydride (BPDA) shown in the Chemical formula 2 is preferred.
In preferred embodiments, by in polar organic solvent with above-mentioned aromatic tetracarboxylic acid dianhydride (being also referred to as the difunctionality acid anhydrides) component and aromatic diamine monomer component at inert atmosphere and be lower than under 90 ℃ the temperature reaction or polymerization prepares polyamic acid of the present invention or coating solution.Reaction times is 6 hours or longer.
When preparation polyamic acid or coating solution, as far as possible preferably with etc. mol ratio with difunctionality acid anhydrides component and diamine monomer component reaction with the raising polymerization degree.Therefore, the mol ratio that preferably keeps difunctionality acid anhydrides/diamines is in the scope of 0.9～1.1/1.0, and 1.00～1.04/1.0 is preferred.The molecular weight of the polyamic acid in the polyamic acid solution of the present invention is preferably 5,000～500, and 000, more preferably 15,000～100,000.
The example of available polar organic solvent comprises N among the present invention, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolidone, N-methyl caprolactam, HMPA, 1,2-glycol dimethyl ether, diglyme, triglyme, tetrahydrofuran (THF), 1,4-diox, gamma-butyrolactone, methylcarbonate, diethyl carbonate, ethylene carbonate, Texacar PC, diethoxyethane, methyl-sulphoxide and tetramethylene sulfone.Preferred solvent is N,N-dimethylacetamide (DMAC).These solvents can use separately or as mixture, and perhaps with optional solvent such as toluene and dimethylbenzene, promptly other aromatic hydrocarbon mixes use.
Except difunctionality acid anhydrides component and diamine monomer component, reaction mixture also can comprise does not have the additive of harmful effect such as processing aid or glidant (for example Modaflow (registered trademark) glidant), antioxidant, dyestuff, mineral dye (for example, titanium dioxide TiO to the transparency of polyimide coating film or film and yellowness index characteristic
2) and filler (for example, tetrafluoroethylene and ethylene fluoride/propylene copolymer).
For the processing that makes polyamic acid solution becomes easily, the concentration of polyamic acid is in the scope of 10～30wt% in the solution, and preferably in the scope of 20～25wt%, and the viscosity of solution is preferably 1～5, in the scope of 000 pool.
When the processing polyamic acid solution, can be in useful articles top casting aspect the optics or polyamide coating acid.For purposes of the invention, the example that is considered to available optics aspect useful articles is liquid-crystal display, electroluminescence, fiber optic cables, waveguide, solar cell and the transparent fixedly film that a part of light disclosed in Japanese Patent 2003-5548A number, that allow the toning agent absorbing wavelength of electrophotographic device passes, or disclosed transparent annular support member at the employed photoreceptor of method that is used for recorded electronic camera image among the Japanese Patent S58-153957A, but the present invention is not limited to these.
When casting or film coating procedure when finishing, polar organic solvent is removed from polyamic acid solution, then polyamic acid is carried out chemistry or thermal transition with the preparation polyimide.
In preferred embodiments, with the polyamic acid solution of viscosity in about 5～2500 pool scopes of 20～25wt%, at sheet glass or stainless steel plate or the specified thickness of other similar plate top castings.Order or the removal and the polyamic acid that carry out polar solvent simultaneously become imido conversion then.In a more preferred embodiment, polyamic acid solution cast in wants coated body surface, then under 80～120 ℃ temperature dry 30～120 minutes to form film.Then temperature is risen to 200 ℃, under this temperature, kept 10～180 minutes.Afterwards, temperature is risen to 250～300 ℃, under this temperature, keep 30～120 minutes film is transformed into imide formation polyimide film.
Perhaps, can be by being used for the imido method cyclisation of chemical conversion imide.In preferred embodiments, acetic anhydride and the third amine are used as cyclization catalyst.In a more preferred embodiment, strong acid such as methylsulfonic acid are used as catalyzer, and azeotropic water is removed by cosolvent such as toluene.
In a preferred embodiment, polyamic acid solution of the present invention is coated on the optical fiber as coating.Especially, optical fiber is passed coating unit, the polyamic acid solution of the viscosity of such 20～25wt% in about 5～25 pool scopes just is coated on the length of whole fiber.Afterwards, 120 ℃～300 ℃ the temperature province of preferably passing baking oven by the optical fiber that will apply with the speed of 0.3 meter/minute (m/min)～9.3-12.4m/min is carried out the removal of polar catalyst and the imide conversion of polyamic acid.
Resulting imide film or coating are water white basically.In preferred embodiments, when film or the thickness of (μ m) that has 50 ± 10 microns and during of filming with the rayed of 420 nanometers (nm), film or film and show at least 50% transmitance.
In addition, the second-order transition temperature of the preferred polyimide coating film of the present invention (Tg) be 200 ℃ or more than, more preferably 250 ℃ or more than.
The water-intake rate of the preferred polyimide coating film of the present invention be 2.0% or below.
On at least one side of polyimide coating film, can further form layer of transparent film at least.This is the adhesive power for the nesa coating that increases under the prerequisite of not losing the transparency and describe below.The example of transparent film is the carbon of clear films such as aluminum oxide, silicon oxide, silicon nitride, silicon oxynitride, tantalum oxide and similar diamond.Transparent film can use by single or multiple lift.Film thickness is preferred in the scope of 50nm～5 μ m.These transparent films can form by for example vacuum vapor deposition method, reactive sputtering, ion plating or plasma CVD method.
On at least one side of polyimide coating film or transparent film, can form the conducting film of layer of transparent at least.The resistance of nesa coating is preferably 1 * 10
-2Ω cm or following.The example of nesa coating has the alloy of indium-tin-oxide etc., and film thickness is preferred in the scope of 50nm～1 μ m.Conducting film can form by for example vacuum vapor deposition method, reactive sputtering, ion plating or plasma CVD method.By improving the transparency, thermotolerance and the electroconductibility of film being not less than the time of under 170 ℃ the high temperature film heating (annealing) being lacked relatively.Because polyimide coating film of the present invention has high Tg, therefore annealing is feasible.
Embodiment
Measure the various characteristics of the polyimide film of in embodiment and comparative example, making by the measuring method of describing below.
(1) measurement of light transmission rate
The spectrophotometer UV-2550 that uses Shimadzu Corporation to make measures the transmitance of 420nm light.
(2) measurement of water-intake rate
According to ASTM D570, polyimide film was heated to 150 ℃ of dryings 30 minutes, after its weight of weighing (A), it is immersed in the pure water 24 hours, take out, weigh (B) is calculated as follows water-intake rate once more.
Water-intake rate (%)=[(B-A)/A] * 100
(3) x-ray photoelectron power spectrum (XPS)
The X-ray photoelectron spectroscopic analysis instrument XPS-700 that utilizes Rigaku to make carries out XPS analysis to polyimide surface.Suppose that in conjunction with the peak be Gauss (Gaussian) peak, the base spectrum of the 1s track (01s) of the oxygen that will obtain by XPS analysis is carried out waveform and is separated, and estimates and be transformed into imido degree.
(4) second-order transition temperature
The dynamic viscoelastic device DM 6100 that uses Seiko Instruments to make measures second-order transition temperature, in order to measure storage elasticity and loss energy in the process that increases with 2 ℃/min in temperature, it is that 98mN, frequency are the sinusoidal load of 1.0Hz that the polyimide film of high 8mm, wide 30mm is applied amplitude.
(5) thickness of polyimide film
The crystal oscillation film controller CRTM-6000 that uses Nippon Vacuum Technology Co. to make measures the thickness of film.
(6) resistivity
Abide by JIS K 7194 by 4 probe method measured resistivity.
(7) bond test
The Sebastian V-type tester that utilizes Quad Group to make adopts aluminium stud pin and epoxyn and ceramic blanket template and epoxyn test adhesive power.
(8) flexible is measured
With hand that film is folding, and move along folding line with fingernail, make it to become blocky folding line, afterwards film is launched and make it smooth, and then fold and make it to become blocky folding line with fingernail, repeat 10 times.Form crackle or film destroy with (F) expression film in the test, these situations do not take place with (P) expression.
(9) analysis of transparent conductive film
X-ray photoelectron power spectrum (XPS)
The X-ray photoelectron spectroscopic analysis instrument XPS-700 that utilizes Rigaku to make carries out XPS analysis to the surface of formed transparent conductive film on the polyimide surface.
Film X-ray diffraction (XRD)
The film X-ray diffractometer that utilizes Rigaku to make carries out XRD analysis to the surface of formed transparent conductive film on the polyimide surface.
(10) film thickness of transparent conductive film
The crystal oscillation film controller CRTM-6000 that uses Nippon Vacuum Technology Co. to make measures the film thickness of transparent conductive film.
Embodiment 1
(a) synthesis of polyimides presoma (polyamic acid) liquid
With on it with on the agitator of tetrafluoroethylene paddle wheel and the three-necked flask that the nitrogen tubular stinger is connected in 500ml as aggregation container, and all being reflected under the nitrogen atmosphere carried out.4 of the commodity that 33.565g (0.135mol) Wakayama Seika Kogyo Co.Ltd. is sold " Seika Cure S " by name, 4 '-N that diaminodiphenylsulfone(DDS) (44DDS) is sold as diamine components and 216.0g Mitsubishi Gas Chemical Corporation as polymer solvent, N-N,N-DIMETHYLACETAMIDE (DMAC) joins in the container, and the solid part in the polyimide precursor liquid is 28% like this.After 44DDS is dissolved in DMAC fully, within 5 minutes with the mol ratio of 1.03 times of diamine components add 28.69g (0.0976mol) solid, the phenylbenzene tetracarboxylic dianhydride (BPDA) of the commodity " BPDA " by name sold as the difunctionality acid anhydrides, by Mitsubishi Chemical Corporation and trade(brand)name " BPADA " that 21.747g (0.0418mol) SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS is sold 2, two [4-(di carboxyl phenyloxy) phenyl] the propane dianhydrides (BPADA) of 2-.Reaction after 12 hours, obtained the polyimide precursor liquid with 205 pool viscosity of viscosity 40 ℃ of reactions in 1 hour then under the room temperature.Then, add the Texacar PC of 36.0g, make that like this ring compound accounts for 43 mass parts when the percentage of solids of polyimide precursor liquid is 100 mass parts by Huntsman LLC preparation.As shown in Figure 1, " BPADA " has 189.96 ℃ the fusing point endotherm peak temperature of being measured by differential scanning calorimeter (DSC), and begins neither also not heat release of heat absorption basically under the endothermic temperature (187.26 ℃) being lower than fusing point.This shows that at low-temperature region the transparency to be had the impurity of harmful effect considerably less or do not exist.
(b) make polyimide film
Polyimide precursor liquid is placed in the moisture eliminator, and 1.33 * 10
3The pressure of Pa (10mmHg) keeps 1 hour down to remove gas from solution.Then, on the sheet glass that scribbles the leafing film, the thickness of cast membrane is consistent on width the solution-cast of removing gas by having the presser bar of regulating the gap.Afterwards, with the sheet glass of casting be positioned in the baking oven 80 ℃ following 45 minutes, then 120 ℃ following 30 minutes, afterwards 150 ℃ following 30 minutes, again after 300 ℃ following 30 minutes so that imide conversion reaction and cured film to take place.Afterwards, take out sheet glass from baking oven, cool to room temperature separates film then from sheet glass.Measure the light transmission rate and the water-intake rate of polyimide film subsequently.Find that second-order transition temperature is 304 ℃.
Embodiment 2～6
Except adding with the mass parts shown in the table 1 ring compound shown in the table 3, prepare polyimide precursor liquid and polyimide film with similarly to Example 1 method, measure the light transmission rate and the water-intake rate of polyimide film.The second-order transition temperature of all polyimide films all is 304 ℃.
Comparative example 1～8
Except adding with the mass parts shown in the table 1 ring compound shown in the table 4, prepare polyimide precursor liquid and polyimide film with similarly to Example 1 method, and measure the light transmission rate and the water-intake rate of polyimide film.
Above-mentioned condition and result's summary are listed in table 1 and table 2.Table 3 has been listed the structure of additive in the embodiment of the invention 1～6, and table 4 has been listed the structure of additive in the comparative example 1～8.
Table 1
| Additive | Additive (mass parts) | Boiling point (℃) | Proportion | |
| Embodiment 1 | Texacar PC | 43 | 242 | 1.21 |
| Embodiment 2 | Texacar PC | 214 | 242 | 1.21 |
| Embodiment 3 | Ethylene carbonate | 43 | 238 | 1.32 |
| Embodiment 4 | Ethylene carbonate | 214 | 238 | 1.32 |
| Embodiment 5 | Gamma-butyrolactone | 43 | 204 | 1.13 |
| Embodiment 6 | Gamma-butyrolactone | 214 | 204 | 1.13 |
| Comparative example 1 | DMAC (polymer solvent) | 43 | 164 | 0.94 |
| Comparative example 2 | NMP | 43 | 202 | 1.03 |
| Comparative example 3 | DMSO | 43 | 189 | 1.10 |
| Comparative example 4 | Diglyme | 43 | 162 | 0.95 |
| Comparative example 5 | Ethylene glycol monobutyl ether | 43 | 171 | 0.90 |
| Comparative example 6 | Tetrahydrofuran (THF) | 43 | 66 | 0.89 |
| Comparative example 7 | Cyclopentanone | 43 | 131 | 0.95 |
| Comparative example 8 | Tetramethylene sulfone | 43 | 285 | 1.26 |
Table 2
| Specific inductivity | Moment of dipole (debye) | Thickness (μ m) | Light transmission rate (%) | Water-intake rate (%) | |
| Embodiment 1 | 66.1 | 4.9 | 52 | 76.9 | 1.9 |
| Embodiment 2 | 66.1 | 4.9 | 52 | 76.6 | 1.9 |
| Embodiment 3 | 89.8 | 4.9 | 51 | 73.5 | 1.8 |
| Embodiment 4 | 89.8 | 4.9 | 49 | 74.3 | 1.8 |
| Embodiment 5 | 39.0 | 4.3 | 48 | 72.8 | 1.7 |
| Embodiment 6 | 39.0 | 4.3 | 54 | 75.2 | 1.8 |
| Comparative example 1 | 38.9 | 3.7 | 53 | 67.0 | 2.4 |
| Comparative example 2 | 32.6 | 4.1 | 51 | 58.8 | 2.3 |
| Comparative example 3 | 46.7 | 3.9 | 51 | 48.7 | 2.5 |
| Comparative example 4 | 7.2 | 2.0 | 49 | 67.9 | 2.3 |
| Comparative example 5 | 9.4 | 2.1 | 52 | 62.5 | 2.2 |
| Comparative example 6 | 7.5 | 1.8 | 55 | 66.3 | 2.4 |
| Comparative example 7 | 14.0 | 3.3 | 46 | 55.9 | 2.3 |
| Comparative example 8 | 43.3 | 4.8 | 48 | 57.0 | 1.8 |
Annotate: the value of additive mass parts refers to when polyimide precursor (solid partly) mass parts of additive when being 100 mass parts.
Table 3
The structural formula of the additive of embodiment 1～6
Table 4
The structural formula of the additive of comparative example 1～8
Can clearly be seen that from above result, for embodiments of the invention 1～6, it is not the second-order transition temperature height, and light transmission rate and the transparency are also higher, and the result learns by XPS analysis, compare with comparative example 1～8 (conventional art), it is bigger that it changes the imido degree of carrying out into, can make polyimide coating film have low water-intake rate like this.
Embodiment 7
(1) aromatic diamine
The commodity that Wakayama Seika Kogyo Co.Ltd. is sold " Seika cureS " by name, have above-mentioned Chemical formula 1 para-forms 4,4-DDS:4,4 '-diaminodiphenylsulfone(DDS) is as aromatic diamine.
(2) alicyclic diamine
The NBDA of the commodity that Mitsui Chemicals Inc. is sold " NBDA " by name: the norbornane diamines is as alicyclic diamine.
(3) two sense acid anhydrides
The BPDA with above-mentioned chemical formula A of the commodity that Mitsubishi Chemical Corporation is sold " BPDA " by name: the commodity that sell phenylbenzene tetracarboxylic dianhydride monomer and SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS " BPADA " by name have 2 of an above-mentioned chemical formula B, two [4-(di carboxyl phenyloxy) phenyl] the propane dianhydrides (BPADA) of 2-are as two sense acid anhydrides.
(4) polar organic solvent
With the DMAC:N that Mitsubishi Gas Chemical Corporation is sold, the N-N,N-DIMETHYLACETAMIDE is as polar organic solvent.
(5) lactone compound
The gamma-butyrolactone that Mitsubishi Chemical Corporation is produced is used as lactone compound.
(6) optionally be used to the diluting solvent that dilutes
Use the tetrahydrofuran (THF) of Wako Pure Chemical Industries Ltd. production and the isophorone of ethylene glycol monobutyl ether and Daicel Chemical Industries Ltd. production.
(7) method of Computer-Assisted Design, Manufacture And Test sample
(a) polyamic acid (polyimide precursor) solution is synthetic
The diamine monomer and the DMAC solvent of fixed amount are joined in the reaction vessel, under nitrogen atmosphere, stir and be dissolved in the DMAC solvent backflow under 40 ℃ then up to diamine monomer fully.Afterwards, the difunctionality acid anhydrides with fixed amount joins in the reaction vessel to generate polyamic acid solution.Two kinds are used to make the difunctionality acid anhydrides component of polyamic acid solution and the mol ratio of diamine monomer component is 1.03/1.0.The ratio of mixture of setting solvent and polyamic acid solid part is so that solid part is 28 quality %.After polyreaction is finished, add the gamma-butyrolactone of predetermined amount.Solid part at polyimide precursor liquid is in the container of 100 mass parts, adds the polarity polymer solvent up to 257 mass parts, and adds additive such as gamma-butyrolactone shown in table 5 and table 6.
(b) make polyimide film
Polyamic acid solution is placed in the moisture eliminator, and under the pressure of 10mmHg, keeps 1 hour from solution, to remove gas.Then, on the sheet glass that scribbles the leafing film, the thickness of cast membrane is consistent on width the solution-cast of removing gas by having the presser bar of regulating the gap.Afterwards, with the sheet glass of casting be positioned in the baking oven 80 ℃ following 45 minutes, then 120 ℃ following 30 minutes, afterwards 150 ℃ following 30 minutes, again after 300 ℃ following 30 minutes so that imide conversion reaction and cured film to take place.Afterwards, from baking oven, take out sheet glass, be cooled to room temperature, and film is separated from sheet glass.Measure the light transmission rate and the water-intake rate of polyimide film subsequently.These the results are shown in table 5 and the table 6.
Embodiment 8～15
Except the mol ratio that changes diamines as table 5 and table 6 as shown in or difunctionality acid anhydrides, prepare polyimide precursor liquid and polyimide film, light transmission rate, toughness and the second-order transition temperature of measurement polyimide film with similarly to Example 7 method.It the results are shown in table 5 and table 6.
Embodiment 16
Except changing diamines and 4 with the mol ratio shown in table 5 and the table 6, the ratio of 4-DDA/NBDA and only changing outside the ratio of difunctionality acid anhydrides and BPDA, prepare polyimide precursor liquid and polyimide film with similarly to Example 7 method, and measuring light transmitance, toughness and second-order transition temperature.These the results are shown in table 5 and table 6.
Embodiment 17
(a) polyimide precursor (polyamic acid) liquid is synthetic
With on it with on the agitator of tetrafluoroethylene paddle wheel and the three-necked flask that the nitrogen tubular stinger is connected in 500ml as aggregation container, and all reactions are all carried out under nitrogen atmosphere.Add the NBDA of 28.317g (0.184mol) as diamine components, and add the DMAC of 216.0g as polymer solvent, the solids component of polyimide precursor liquid is 28 quality % like this.After stirring fully, within 5 minutes, add the BPDA as the difunctionality acid anhydrides of 55.683g (0.189mol) solid form with 1.03 times mol ratio with respect to diamines.After 15 minutes, reaction soln has become the viscosity of yogourt type.Then temperature of reaction is climbed to about 60 ℃, at this moment solution becomes the liquid of viscosity from the viscosity of yogourt type.By further obtaining precursor liquid in 12 hours 40 ℃ of reactions.Then, add the 36.0g gamma-butyrolactone and make that ring compound is 43 mass parts when the solid part of setting polyimide precursor liquid is 100 mass parts.Prepare polyimide film with similarly to Example 7 method, and measure light transmission rate, toughness and the second-order transition temperature of polyimide film.The results are shown in table 5 and table 6.
Table 5
| Monomer | Additive (mass parts) | ||
| Anhydride component (mol ratio) | Diamine components (mol ratio) | ||
| Embodiment 7 | 4，4-DDS(100) | BPDA/BPADA(90/10) | Gamma-butyrolactone (214) |
| Embodiment 8 | 4，4-DDS(100) | BPDA/BPADA(80/20) | Gamma-butyrolactone (214) |
| Embodiment 9 | 4，4-DDS(100) | BPDA/BPADA(70/30) | Gamma-butyrolactone (214) |
| Embodiment 10 | 4，4-DDS(100) | BPDA/BPADA(60/40) | Gamma-butyrolactone (214) |
| Embodiment 11 | 4，4-DDS(100) | BPDA/BPADA(50/50) | Gamma-butyrolactone (214) |
| Embodiment 12 | 4，4-DDS(100) | BPDA/BPADA(70/30) | Gamma-butyrolactone (43) |
| Embodiment 13 | 4，4-DDS(100) | BPDA/BPADA(70/30) | Gamma-butyrolactone (143) |
| Embodiment 14 | 4，4-DDS(100) | BPDA/BPADA(70/30) | Gamma-butyrolactone (214) |
| Embodiment 15 | 3，3-DDS(100) | BPDA/BPADA(75/25) | Gamma-butyrolactone (42) |
| Embodiment 16 | 4，4-DDS/NBDA(70/30) | BPDA(100) | Gamma-butyrolactone (43) |
| Embodiment 17 | NBDA(100) | BPDA(100) | Gamma-butyrolactone (43) |
| Comparative example 9 | 4，4-DDS(100) | BPDA/BPADA(90/10) | - |
| Comparative example 10 | 4，4-DDS(100) | BPDA/BPADA(80/20) | - |
| Comparative example 11 | 4，4-DDS(100) | BPDA/BPADA(70/30) | - |
| Comparative example 12 | 4，4-DDS(100) | BPDA/BPADA(60/40) | - |
| Comparative example 13 | 4，4-DDS(100) | BPDA/BPADA(50/50) | - |
| Comparative example 14 | 4，4-DDS(100) | BPDA/BPADA(70/30) | Tetrahydrofuran (THF) (214) |
| Comparative example 15 | 4，4-DDS(100) | BPDA/BPADA(70/30) | Ethylene glycol monobutyl ether (214) |
| Comparative example 16 | 4，4-DDS(100) | BPDA/BPADA(70/30) | Isophorone (214) |
| Comparative example 17 | 3，3-DDS(100) | BPDA/BPADA(75/25) | - |
| Comparative example 18 | 4，4-DDS/NBDA(70/30) | BPDA(100) | - |
| Comparative example 19 | NBDA(100) | BPDA(100) | - |
Annotate: the value in the additive hurdle brace refers to when polyimide precursor (solid partly) number of additive mass parts when being 100 mass parts.
Table 6
| Thickness (μ m) | Light transmission rate (%) | Toughness | Second-order transition temperature (℃) | |
| Embodiment 7 | 52 | 73.2 | P | 338 |
| Embodiment 8 | 49 | 72.4 | P | 316 |
| Embodiment 9 | 53 | 76.3 | P | 304 |
| Embodiment 10 | 51 | 74.7 | P | 287 |
| Embodiment 11 | 48 | 73.5 | P | 270 |
| Embodiment 12 | 48 | 72.8 | P | 304 |
| Embodiment 13 | 54 | 75.2 | P | 304 |
| Embodiment 14 | 56 | 71.9 | P | 304 |
| Embodiment 15 | 49 | 76.7 | P | 250 |
| Embodiment 16 | 51 | 68.7 | P | 315 |
| Embodiment 17 | 52 | 66.4 | P | 239 |
| Comparative example 9 | 52 | 67.8 | P | 338 |
| Comparative example 10 | 49 | 68.7 | P | 316 |
| Comparative example 11 | 53 | 67.0 | P | 304 |
| Comparative example 12 | 51 | 66.1 | P | 287 |
| Comparative example 13 | 48 | 69.8 | P | 270 |
| Comparative example 14 | 57 | 65.8 | P | 304 |
| Comparative example 15 | 53 | 62.7 | P | 304 |
| Comparative example 16 | 57 | 0.2 | F | - |
| Comparative example 17 | 50 | 72.5 | P | 250 |
| Comparative example 18 | 48 | 67.7 | P | 315 |
| Comparative example 19 | 52 | 65.8 | P | 239 |
In table 5 and table 6, the result of embodiment 1～8 within the scope of the invention, therefore the transparency and toughness height.By comparison, owing to do not add lactone compound in the comparative example 9～19, so their transparency is lower than the transparency of embodiment product.
Embodiment 18
The Indium sesquioxide of the 5 quality % tin that mix is assemblied on the sputtering electrode of high frequency (RF) magnetron sputter equipment, and the polyimide film by the polyimide precursor liquid preparation of embodiment 1 that will have 75 μ m thickness is fixed on substrate one side on the position of target electrode 100mm.Use oil-tightening rotary vacuum pump to reduce pressure roughly, further use oil diffusion pump then vacuum drop to 2.0 * 10
-4Holder.Feed argon gas with the flow velocity of 97sccm, and with the flow velocity aerating oxygen of 3sccm to keep 1.0 * 10
-2The vacuum of holder.Then, forming the thickness of being made by indium tin oxide (ITO) in about 30 minutes by sputter under the RF reflection wave of the capable 0W of involving of the RF of 250W is the transparent conductive film of 300nm, obtains transparent conducting film by annealing in 200 ℃ of following air then.
The light transmission rate that passes this transparent conductive film of 380nm～780nm be 80% or more than.And, in the bond test of transparent conductive film, do not observe the delamination of film.The resistance of nesa coating is 1.7 * 10
-4Ω cm.
Embodiment 19
Silicon target is assemblied on the sputtering electrode of high frequency (RF) magnetron sputter equipment, and the polyimide film by the preparation of the polyimide precursor liquid of embodiment 1 that will have 50 μ m thickness is fixed on substrate one side on the position of target electrode 100mm.Use oil-tightening rotary vacuum pump to reduce pressure roughly, use oil diffusion pump then further with vacuum drop to 2.0 * 10
-4Holder.Flow velocity with 40sccm feeds nitrogen, and feeds argon gas to keep 1.0 * 10 with the flow velocity of 60sccm
-2The vacuum of holder.Then, on polyimide film, formed in about 30 minutes by sputter under the capable RF reflection wave that involves 0W of the RF of 400W by silicon-oxygen nitride (SiO
0.90N
0.58) thickness made is the transparent film of 110nm.Confirm as SiO by XPS and XRD analysis
0.90N
0.58Even form the transparent film of silicon-oxygen nitride, its transmitance is 76.9%, and comparing with embodiment 1 does not have too big difference yet.
Then, on transparent silicon-oxygen nitride film, form the conductive film of layer of transparent with method similarly to Example 18.
The light transmission rate that passes this transparent conductive film of 380nm～780nm be 80% or more than.And, in the bond test of transparent conductive film, do not observe the delamination of film.The resistance of nesa coating is 1.7 * 10
-4Ω cm.
Claims (16)
1. polyimide precursor liquid composition, it comprises:
At least one class tetracarboxylic dianhydride's or derivatives thereof;
At least one class diamines or derivatives thereof; And
The polarity polymer solvent;
Wherein this polyimide precursor liquid composition further comprises ring compound; And
This ring compound has 200 ℃ or above boiling point and comprises carbon, hydrogen and Sauerstoffatom.
2. according to the polyimide precursor liquid of claim 1,
Wherein tetracarboxylic dianhydride's or derivatives thereof be at least one class be selected from following chemical formula A and B (wherein X representative-O-,-S-,-SO-,-SO
2-,-CH
2-,-CF
2-,-C (CH
3)
2-,-C (CF
3)
2-or directly in conjunction with) compound.
3. according to the polyimide precursor liquid composition of claim 1, wherein the diamines or derivatives thereof be a class be selected from following Formula I and II (wherein Y representative-O-,-S-,-SO-,-SO
2-,-CH
2-,-CF
2-,-C (CH
3)
2-,-C (CF
3)
2-,-CO-or directly in conjunction with) compound.
4. according to the polyimide precursor liquid composition of claim 1, wherein the specific inductivity of ring compound is not less than 30.
5. according to the polyimide precursor liquid composition of claim 1, wherein the moment of dipole of ring compound is not less than 3 debye.
6. according to the polyimide precursor liquid composition of claim 1, wherein when the solid part of polyimide precursor liquid is 100 mass parts, the polarity polymer solvent is in the scope of 150～900 mass parts, and ring compound is in the scope of 15～750 mass parts.
7. according to the polyimide precursor liquid composition of claim 1, wherein polymerization polyimide precursor in the polarity polymer solvent adds ring compound afterwards.
8. one kind is transformed into imido polyimide precursor liquid composition from polyimide precursor liquid composition, and this polyimide precursor liquid composition comprises:
At least one class tetracarboxylic dianhydride's or derivatives thereof;
At least one class diamines or derivatives thereof; And
The polarity polymer solvent;
Wherein this polyimide precursor liquid composition further comprises ring compound; And
This ring compound has 200 ℃ or above boiling point and comprises carbon, hydrogen and Sauerstoffatom.
9. according to the polyimide coating film of claim 8, wherein when polyimide coating film for having the film of 50 ± 10 microns (μ m) thickness or film, and during with the rayed of 420 nanometers (nm), this polyimide coating film shows 50% or above transmitance.
10. according to the polyimide coating film of claim 8, wherein the second-order transition temperature of this polyimide coating film (Tg) be 200 ℃ or more than.
11. according to the polyimide coating film of claim 8, wherein the water-intake rate of polyimide coating film be 2.0% or below.
12., wherein at least one side of polyimide coating film, further form the nesa coating of individual layer at least according to the polyimide coating film of claim 8.
13. according to the polyimide coating film of claim 12, the resistance of wherein said nesa coating is 1 * 10
-2Ω cm or following.
14., wherein at least one side of polyimide coating film, further form the transparent film of individual layer at least according to the polyimide coating film of claim 8.
15., wherein at least one side of transparent film, further form the nesa coating of individual layer at least according to the polyimide coating film of claim 14.
16. according to the polyimide coating film of claim 15, the resistance of wherein said nesa coating is 1 * 10
-2Ω cm or following.
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| CN107268109B (en) * | 2016-03-31 | 2019-10-15 | 株式会社I.S.T | The manufacturing method of polyimide fiber and polyimide fiber |
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