CN106947080A - Kapton preparation compositions and preparation method thereof and the preparation method using its Kapton - Google Patents

Kapton preparation compositions and preparation method thereof and the preparation method using its Kapton Download PDF

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CN106947080A
CN106947080A CN201611223753.4A CN201611223753A CN106947080A CN 106947080 A CN106947080 A CN 106947080A CN 201611223753 A CN201611223753 A CN 201611223753A CN 106947080 A CN106947080 A CN 106947080A
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preparation
polyimide precursor
double
anhydride
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CN106947080B (en
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车荣哲
朴势周
安民石
李承埈
边滋勋
洪宇成
朴圣然
郑载勋
裴珉英
梁奇锡
李相准
金东敏
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Dongjin Semichem Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • C08K5/18Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Manufacturing & Machinery (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

The preparation method of Kapton the present invention relates to polyimide precursor and preparation method thereof and using the polyimide precursor.

Description

Kapton preparation compositions and preparation method thereof and utilize its polyamides The preparation method of imines film
Technical field
The present invention relates to Kapton preparation compositions comprising polyimide precursor and preparation method thereof with And the preparation method of the Kapton using the polyimide precursor.
Background technology
The heat-resistant quality and chemical resistance of polyimides raw material are outstanding, be it is a kind of can as flexible display substrate use On the way come the high raw material of the possibility being applicable.
Polyimide substrate raw material generally using applicator (applicator) or flat painting machine by polyamic acid (PAA, Polyamic acid) it is coated in after slide (carrier glass), by the hot imide reaction of high temperature, it is prepared into thin Sheet type.However, by the process rather than series-operation of batch-type (batch type), can be carried out in convection constant temperature baking oven The output of curing process (that is, hot-imide process) is limited, and the process grown is needed very much because of more than 400 DEG C of high-temperature process Time.
For the production capacity (CAPA, capacity) depending on the curing process carried out in convection constant temperature baking oven, In order to improve process speed, at a high temperature of more than 120 DEG C that baking oven is not cooled down completely, it is put into coated substrate to carry out heat Imidizate.Now, the homogenizing of film surface (leveling) characteristic is caused to be reduced because solvent rapidly volatilizees.Thus, it is Improve this problem using crosslinking agent and carry out many correlative studys (Korean granted patent the 10-0889910th).
The content of the invention
The present invention uses the polyamides of the crosslinking agent comprising certain content to solve above-mentioned produced problem in the prior art Imines presoma, even if the imidizate performed at high temperature, can also improve the characteristic on Kapton surface, so as to complete The present invention.
One embodiment of the present invention provides the preparation method of polyimide precursor, and it includes:Including diamine monomer Polymer solvent in addition acid anhydride (anhydride) monomer to be reacted the step of;End-capping reagent is added in above-mentioned reaction solution The step for carrying out synthesizing polyamides acid is reacted after (end capping agent);And added in above-mentioned polyamic acid The step of crosslinking agent is to be mixed.
Another embodiment of the present invention provides the preparation method of Kapton, and it includes:Including diamine monomer Polymer solvent in addition anhydride monomer to be reacted the step of;Reacted in above-mentioned reaction solution after addition end-capping reagent Carry out the step of synthesizing polyamides acid;The step of crosslinking agent is to be mixed is added in above-mentioned polyamic acid;It will include and be added with The composition of the polyamic acid of above-mentioned crosslinking agent is coated in the step on carrier;And more than 100 DEG C at a temperature of, to coating The step of polyimide precursor on above-mentioned carrier carries out hot-imide.
The polyimide precursor of the present invention is that the crosslinking agent of certain content is added to formed by polyamic acid, even if It can also improve the surface characteristic of Kapton in the imidizate of high temperature.Especially, the table of Kapton can be improved Homogenizing (levelling) characteristic in face, and transmitance loss can be reduced.
Brief description of the drawings
Fig. 1 is the image of the Kapton of one embodiment of the invention.
Fig. 2 is the image of the Kapton of one embodiment of the invention.
Fig. 3 is the image of the Kapton of one embodiment of the invention.
Fig. 4 is the image of the Kapton of the comparative example of the present invention.
Fig. 5 is the image of the Kapton of the comparative example of the present invention.
Fig. 6 is the image of the Kapton of the comparative example of the present invention.
Fig. 7 is the image of the Kapton of the comparative example of the present invention.
Embodiment
Hereinafter, the example and embodiment of the present invention are described in detail referring to the drawings, in order to skill belonging to the present invention The those of ordinary skill in art field can easily implement.
But, the present invention can be realized with a variety of different forms, be not limited to example described herein and embodiment.And And, in order to clearly state the present invention, the part unrelated with explanation is eliminated in figure, in the specification, for similar Part, is labelled with similar reference.
One embodiment of the present invention provides the preparation method of polyimide precursor, and it includes:Including diamine monomer Polymer solvent in addition anhydride monomer to be reacted the step of;End-capping reagent (end capping are added in above-mentioned reaction solution Agent the step for carrying out synthesizing polyamides acid is reacted after);And add crosslinking agent in above-mentioned polyamic acid to be mixed The step of conjunction.
In the example of the present invention, above-mentioned diamine monomer can be included and is selected from by p-phenylenediamine (PPDA, p- Phenylenediamine), 4,4- diaminodiphenyl ethers (ODA, 4,4'-Oxydianiline), 4,4- MDAs Tolidine (2,2'- dimethyl -4,4'- benzidine) (4,4'- between (MDA, 4,4'-Methylenedianiline), m- (2,2'-Dimethyl-4,4'-Diaminobiphenyl)), 1,3- double (4'- amino-benzene oxygens) benzene (TPE-R, 1,3-BIS (4'-Aminophenoxyl) benzene), double (trifluoromethyl) benzidine of 2,2'-) (TFMB, 2,2'-Bis (trifluoromethyl) benzidine), double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (HFBAPP, 2,2- of 2,2- BIS [4- (4-Aminophenoxy) Phenyl] Hexafluoropropane), double (3- amino-4-hydroxylphenyls) hexafluoros of 2,2- Propane (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'- diaminodiphenylsulfones (DDS, 3,3'-Diaminodiphenyl Sulfone), 4,4'- diaminodiphenylsulfones (ASD, 4,4'-Diaminodiphenyl Sulfide), double [4- (4- amino-benzene oxygens) phenyl] sulfone (BAPS, Bis [4- (4-aminophenoxy) phenyl] Sulfone), double [4- (3- amino-benzene oxygens) benzene] sulfones of 2,2-) (mBAPS, 2,2-Bis [4- (3-Aminophenoxy) Benzene] Sulfone) and combinations thereof composition group in composition, can preferably be p-phenylenediamine (PPDA).It is above-mentioned P-phenylenediamine (PPDA) is the monomer of aromatic structure, it is possible to provide high heat-resistant quality.
In the example of the present invention, above-mentioned anhydride monomer can be aromatic dianhydride monomer, be selected from for example, can include by 3, 3', 4,4'- benzophenone tetracarboxylic dianhydrides (BTDA, 3,3', 4,4'-benzopheno Netetracarboxylicdianhydride), pyromellitic acid anhydride (PMDA, pyromellit icdianhydride), 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides (BPDA, 3,3', 4,4'-biphenyl Tetracarboxylicaciddianhydride), double (3,4- dicarboxylic acids) hexafluoropropane dianhydride (6FDA, 2,2-bis of 2,2'- (3,4anhydrodicarboxyphenyl)-hexafluoropropanedi anhydride), a- biphenyl tetracarboxylic dianhydrides The double phthalic acids of (a-BPDA, 2,3,3', 4biphenyl tetracar boxylicaciddianhydride), 4,4'- oxygen Acid anhydride (ODPA, 4,4'-oxydi phthalic anhydride), 3,3', 4,4'- diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides (DSDA, 3, 3', 4,4'-diphenylsulfone-tetracarboxylic dianhydride), double [4 (the 3,4- dicarboxyl benzene oxygen of 2,2- Base) phenyl] propane dianhydride) (BPADA, 2,2-bis [4 (3,4-dicarboxyphenoxy) phenyl] propane Dianhydride), the anhydride phthalic acid of quinhydrones two (HQDA, hydro quinone diphthalic anhydride) and their group Composition in the group being combined into.More than one can be used in above-mentioned aromatic dianhydride monomer, for example, at least two monomers can be used.
In the example of the present invention, above-mentioned polymer solvent, as long as the solvent used in the art, it is possible to it is unrestricted Use to system, be selected from for example, can include by acid amides series solvent, ketone series solvent, ether series solvent, ester series solvent, symmetrical ethylene glycol two Composition in the group of ether solvent, ether solvent and combinations thereof composition.Above-mentioned acid amides series solvent can include dimethyl formyl Amine (DMF), dimethylacetylamide (DMAC), n- methyl pyrrolidones (NMP) etc., above-mentioned ketone series solvent can include acetone, methyl Ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), cyclopentanone, cyclohexanone etc..Above-mentioned ether series solvent can include tetrahydrofuran (THF), DOX and Isosorbide-5-Nitrae-dioxane etc., above-mentioned ester series solvent can include methyl acetate, ethyl acetate, acetic acid fourth Ester, gamma-butyrolacton, α-acetic acid lactone, beta-propiolactone, δ-valerolactone etc..The above-mentioned ether solvent of symmetrical ethylene glycol two can include first Ethyl glycol monomethyl ether (1,2- dimethoxy-ethanes), methyl diglycol dimethyl ether (double (2- methoxy ethyls) ethers), methyl three Glyme (double (2- methoxy ethoxies) ethane of 1,2-), methyl tetraethylene glycol dimethyl ether (double [2- (2- methoxy ethoxies Ethyl)] ether), ethohexadiol monomethyl ether (1,2- dimethoxy-ethanes), ethyl diglyme (double (2- ethyoxyl second Base) ether), butyldiglycol 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, DPG n- propyl ether, propane diols n- butyl ether, DPG n- Butyl ether, tripropylene glycol n- propyl ether, propane diols phenyl ether, dimethyl ether, 1,3- dioxolanes, ethylene glycol monobutyl ether, two Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether etc..Above-mentioned polymer solvent is preferably used more than one molten Agent, for example, can be used n- methyl pyrrolidones (NMP).
In the example of the present invention, above-mentioned end-capping reagent uses for telo merization, and acid anhydride form can be used Monomer.The monomer of above-mentioned acid anhydride form, for example, may be selected from by phthalic anhydride (PA, phthallic anhydride), myristyl butanedioic acid Acid anhydride (TSA, tetradecyl succinic anhydride), cetyl succinyl oxide (HAS, hexadecyl succinic Anhydride), octadecylsuccinic acid acid anhydride (OSA, octadecyl succinic anhydride) and combinations thereof composition Group in, it is preferable that can be phthalic anhydride (PA).Above-mentioned end-capping reagent adjusts the molecular weight of polymer with list-acid anhydride form, reduces not anti- The content of thing is answered, and improves keeping stability.
In the example of the present invention, it may also include the steps of:Synthesize after above-mentioned polyamic acid, addition conforms to prepare Product benchmark solid and the step of solvent in order to adjust viscosity.Above-mentioned solvent can be used and above-mentioned synthetic identical Solvent, in order to improve physical property, it is also possible to use other kinds of solvent.
In the example of the present invention, above-mentioned crosslinking agent can include 4,4 '-di-2-ethylhexylphosphine oxide (the ring propoxyl group aniline of N, N- bis-).On It is preferably 4,4 '-di-2-ethylhexylphosphine oxide (N, N- diglycidylaniline) with below formula to state crosslinking agent:
In the example of the present invention, relative to monomer, the above-mentioned crosslinking agent of about 2000 to about 4000ppm amount can be added. When above-mentioned crosslinking agent with less than 2000ppm content add when, the surface of Kapton can be bad, when with more than During 4000ppm content addition, the transmitance of Kapton can be reduced.
Another embodiment of the present invention provides the preparation method comprising the polyimide precursor by the application and prepared Obtained by polyimide precursor Kapton preparation compositions.
In the example of the present invention, above-mentioned polyimide precursor can include polyamic acid polymer morphology.
In the example of the present invention, above-mentioned polyimide precursor is that the crosslinking agent of certain content is added into polyamic acid Formed by, the imidizate even in high temperature can also improve the surface characteristic of Kapton.Especially, polyamides can be improved Homogenizing (leve lling) characteristic on the surface of imines film, and transmitance loss can be reduced.
Another embodiment of the invention provides the preparation method of Kapton, and it includes:Including diamine monomer Polymer solvent in addition anhydride monomer to be reacted the step of;Reacted in above-mentioned reaction solution after addition end-capping reagent Carry out the step of synthesizing polyamides acid;The step of crosslinking agent is to be mixed is added in above-mentioned polyamic acid;It will include and be added with The composition of the polyamic acid of above-mentioned crosslinking agent is coated in the step on carrier;And more than 100 DEG C at a temperature of, to coating The step of polyimide precursor on above-mentioned carrier carries out hot-imide.
In the example of the application, above-mentioned hot-imide for example can be in about 100 DEG C to about 500 DEG C, about 100 DEG C to about 400 DEG C, about 100 DEG C to about 300 DEG C, about 100 DEG C to about 200 DEG C, about 200 DEG C to about 500 DEG C, about 300 DEG C to about 500 DEG C, about Performed at 400 DEG C to about 500 DEG C, it is likely that being not limited to this.
Hereinafter, further illustrated by embodiments of the invention, the scope of the present invention is not limited to the present embodiment.
[embodiment]
Embodiment 1
In the 529.2g n- methyl pyrrolidones (NMP) of normal temperature are maintained, 21.62g (0.2mol) pair is completely dissolved After phenylenediamine (PPDA), successively put into 52.96g (0.18mol) 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides (BPDA) and 4.36g (0.02mol) pyromellitic acid anhydride (PMDA).Etc. be completely dissolved and by after 1 hour, putting into 0.43g The phthalic anhydride (PA) of (0.0029mol), reaction polymerize for 16 hours to terminate polyamic acid (PAA).Then, be up to monomer (PPDA, BPDA and PMDA) 2000ppm 4,4 '-di-2-ethylhexylphosphine oxide (the ring propoxyl group aniline of N, N- bis-) (0.15874g) of content is dissolved in phase After reaction dissolvent n- methyl pyrrolidones (NMP), it is added to above-mentioned polyamic acid (PAA) to be mixed.
Embodiment 2
Maintain normal temperature 529.2g n- methyl pyrrolidones (NMP) in, addition 21.62g (0.2mol) to benzene two Amine (PPDA) puts into 52.96g (0.18mol) 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides come after being completely dissolved successively (BPDA) and 4.36g (0.02mol) pyromellitic acid anhydride (PMDA).Etc. be completely dissolved and by after 1 hour, input 0.43g (0.0029mol) phthalic anhydride (PA).After reaction 16 hours, monomer (PPDA, BPDA and PMDA) content is up to (the ring propoxyl group aniline of N, N- bis-) (0.23811g) is dissolved in same reaction solvent n- methyl for the 4,4 ' of 3000ppm-di-2-ethylhexylphosphine oxide After pyrrolidones (NMP), it is put into above-mentioned polyamic acid (PAA) to add mixing.
Embodiment 3
In the 529.2g n- methyl pyrrolidones (NMP) of normal temperature are maintained, 21.62g (0.2mol) pair is completely dissolved After phenylenediamine (PPDA), successively put into 52.96g (0.18mol) 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides (BPDA) and 4.36g (0.02mol) pyromellitic acid anhydride (PMDA).Etc. be completely dissolved and by after 1 hour, putting into 0.43g The phthalic anhydride (PA) of (0.0029mol).After reaction 16 hours, the 4000ppm of monomer (PPDA, BPDA and PMDA) content is up to 4,4 '-di-2-ethylhexylphosphine oxide (the ring propoxyl group aniline of N, N- bis-) (0.31748g) is dissolved in after solvent, be put into reaction terminate Polyamic acid (PAA) adds mixing.
Comparative example 1
In the 529.2g n- methyl pyrrolidones (NMP) of normal temperature are maintained, 21.62g (0.2mol) pair is completely dissolved After phenylenediamine (PPDA), successively put into 52.96g (0.18mol) 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides (BPDA) and 4.36g (0.02mol) pyromellitic acid anhydride (PMDA).Etc. be completely dissolved and by after 1 hour, putting into 0.43g The phthalic anhydride (PA) of (0.0029mol), reaction polymerize for 16 hours to terminate polyamic acid (PAA).Then will be same as Example 1 The solvent n- methyl pyrrolidones (NMP) of amount are put into the above-mentioned polyamic acid (PAA) of reaction end to add mixing.
Comparative example 2
Maintain normal temperature 529.2g n- methyl pyrrolidones (NMP) in, addition 21.62g (0.2mol) to benzene two Amine (PPDA) puts into 52.96g (0.18mol) 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides come after being completely dissolved successively (BPDA) and 4.36g (0.02mol) pyromellitic acid anhydride (PMDA).Etc. be completely dissolved and by after 1 hour, input 0.43g (0.0029mol) phthalic anhydride (PA), reaction polymerize for 16 hours to terminate polyamic acid (PAA).Then it is up to monomer The 1000ppm of (PPDA, BPDA and PMDA) content 4,4 '-di-2-ethylhexylphosphine oxide (the ring propoxyl group aniline of N, N- bis-) (0.07937g) is molten Solution is put into above-mentioned polyamic acid (PAA) to be mixed after same reaction solvent n- methyl pyrrolidones (NMP).
Comparative example 3
Maintain normal temperature 529.2g n- methyl pyrrolidones (NMP) in, addition 21.62g (0.2mol) to benzene two Amine (PPDA) puts into 52.96g (0.18mol) 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides come after being completely dissolved successively (BPDA) and 4.36g (0.02mol) pyromellitic acid anhydride (PMDA).Etc. be completely dissolved and by after 1 hour, input 0.43g (0.0029mol) phthalic anhydride (PA), reaction polymerize for 16 hours to terminate polyamic acid (PAA).Then it is up to monomer The 1500ppm of (PPDA, BPDA and PMDA) content 4,4 '-di-2-ethylhexylphosphine oxide (the ring propoxyl group aniline of N, N- bis-) (0.119055g) It is dissolved in after same reaction solvent n- methyl pyrrolidones (NMP), is put into above-mentioned polyamic acid (PAA) to be mixed.
Comparative example 4
Maintain normal temperature 529.2g n- methyl pyrrolidones (NMP) in, addition 21.62g (0.2mol) to benzene two Amine (PPDA) puts into 52.96g (0.18mol) 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides come after being completely dissolved successively (BPDA) and 4.36g (0.02mol) pyromellitic acid anhydride (PMDA).Etc. be completely dissolved and by after 1 hour, input 0.43g (0.0029mol) phthalic anhydride (PA).After reaction 16 hours, monomer (PPDA, BPDA and PMDA) content is up to (the ring propoxyl group aniline of N, N- bis-) (0.39685g) is dissolved in same reaction solvent n- methyl for the 4,4 ' of 5000ppm-di-2-ethylhexylphosphine oxide After pyrrolidones (NMP), it is put into the polyamic acid (PAA) of reaction end to add mixing.
Experimental example 1
Using applicator (Baker applicator), with 400 μm of wet films (wet) thickness, by embodiment 1 to embodiment 3 and the polyimide precursor of comparative example 1 to comparative example 4 be coated in LCD Glass SM TECH, new glass (200*200* 0.63) after, it is put into the convection constant temperature baking oven of 120 DEG C of heating to carry out hot imide reaction.Then, heating 3 per minute DEG C, Slow cooling after being maintained 1 hour under maximum 450 DEG C.Reclaimed after cooling, analysed film formalness and optics are special Property etc., and the results are shown in Fig. 1 to Fig. 4 and table 1 and table 2.
Table 1
Table 2
As shown in Figures 1 to 7, confirm as addition 2000ppm to the 4 of 4000ppm contents, 4 '-di-2-ethylhexylphosphine oxide (N, N- Two ring propoxyl group aniline) when (Fig. 1 to Fig. 3), the homogenizing of film surface is in good condition, but is not added with 4,4 '-di-2-ethylhexylphosphine oxide (N, The ring propoxyl group aniline of N- bis-) when (Fig. 4) and when being added with 1000ppm or 5000ppm content (Fig. 5 to Fig. 7), film surface Homogenizing state is bad.
Also, as shown in table 1 and table 2, confirm when addition is less than 2000ppm or more than 5000ppm, transmitance Rapid reduction.
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 the technological thought or essential feature that do not change the present invention, it can be easily deformed with different specific forms.Therefore, The multiple embodiments for being interpreted as above description are exemplary, and non-limiting in all respects.For example, illustrated with single type Each structural element can also dispersedly be implemented, equally, and the multiple structural elements for disperseing explanation also can be real with the form of combination Apply.
Range Representation, rather than above-mentioned detailed description is claimed by appended invention in the scope of the present invention, and invention will The form for asking the implication and scope of protection domain and having altered or deform derived from its equivalents should be interpreted bag Include in the scope of the present invention.

Claims (10)

1. a kind of polyimide precursor composition, it is characterised in that include:
Polyamic acid;And
Crosslinking agent, the content relative to polyamic acid is 2000 to 4000ppm.
2. the preparation method of polyimide precursor according to claim 1, it is characterised in that above-mentioned diamine monomer is selected from By double (the 4'- aminobenzenes of tolidine, 1,3- between p-phenylenediamine, 4,4- diaminodiphenyl ethers, 4,4- MDAs, m- Epoxide) benzene, double (trifluoromethyl) benzidine of 2,2'-), double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2-), 2,2- it is double (3- amino-4-hydroxylphenyls) HFC-236fa, 1,3- diaminourea 2,4,5,6- phenyl tetrafluorides, 3,3'- diaminodiphenylsulfones, 4,4'- Double [4- (3- amino-benzene oxygens) benzene] sulfones of diaminodiphenylsulfone, double [4- (4- amino-benzene oxygens) phenyl] sulfones, 2,2-) and they In the group for combining composition.
3. the preparation method of polyimide precursor according to claim 1, it is characterised in that above-mentioned anhydride monomer is fragrance Race's dianhydride monomer.
4. the preparation method of polyimide precursor according to claim 3, it is characterised in that above-mentioned aromatic dianhydride list Body, which is included, to be selected from by 3,3', 4,4'- benzophenones tetracarboxylic dianhydride, pyromellitic acid anhydride, 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides, Double (3,4- dicarboxylic acids) hexafluoropropane dianhydrides of 2,2'-, a- biphenyl tetracarboxylic dianhydrides, 4,4'- oxygen double phthalic anhydride, 3,3', Double [4 (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides of 4,4'- diphenyl sulfone tetrabasic carboxylic acids dicarboxylic anhydride, 2,2-), the phthalandione of quinhydrones two Composition in the group of acid anhydride and combinations thereof composition.
5. the preparation method of polyimide precursor according to claim 1, it is characterised in that addition at least two acid anhydride list Body.
6. the preparation method of polyimide precursor according to claim 1, it is characterised in that above-mentioned polymer solvent is included Selected from by acid amides series solvent, ketone series solvent, ether series solvent, ester series solvent, the ether solvent of symmetrical ethylene glycol two, ether solvent and it Combination composition group in composition.
7. the preparation method of polyimide precursor according to claim 1, it is characterised in that above-mentioned end-capping reagent be selected from by The group that phthalic anhydride, myristyl succinyl oxide, cetyl succinyl oxide, octadecylsuccinic acid acid anhydride and combinations thereof are constituted In.
8. the preparation method of polyimide precursor according to claim 1, it is characterised in that above-mentioned crosslinking agent includes 4, 4 '-di-2-ethylhexylphosphine oxide (the ring propoxyl group aniline of N, N- bis-).
9. the preparation method of polyimide precursor according to claim 1, it is characterised in that whole relative to used Body monomer, the above-mentioned crosslinking agent of the amount of addition 2000 to 4000ppm.
10. a kind of preparation method of Kapton, it is characterised in that including:
The step of anhydride monomer is to be reacted is added in the polymer solvent comprising diamine monomer;
The step for carrying out synthesizing polyamides acid is reacted after end-capping reagent is added in answering solution;
The step of crosslinking agent is to be mixed is added in above-mentioned polyamic acid;
Composition comprising the polyamic acid added with above-mentioned crosslinking agent is coated in the step on carrier;And
At a temperature of more than 100 DEG C, the step of hot-imide is carried out to the polyimide precursor being coated on above-mentioned carrier Suddenly.
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