CN114479073A - Polyamide acid resin composition, flexible AMOLED polyimide substrate and preparation method thereof - Google Patents
Polyamide acid resin composition, flexible AMOLED polyimide substrate and preparation method thereof Download PDFInfo
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Abstract
The composition comprises polyamide acid resin terminated by anhydride group and aromatic diamine after amino protection, and has high solid content, low viscosity and high molecular weight, and can meet the requirements of a flexible AMOLED substrate polyamide acid resin coating process. The aromatic diamine after amino protection in the polyamic acid composition coating is subjected to amino protecting group removal, and then is subjected to repolymerization molecular chain growth with the polyamic acid resin terminated by anhydride group, so that the molecular weight of the polyamic acid is improved to ensure the high strength, high modulus and high heat resistance of the polyimide substrate obtained through imidization. Through diamine amino protection and removal and molecular chain repolymerization growth in the processes of preparing polyamic acid and preparing a polyimide substrate, the polyamic acid resin composition has high solid content, low viscosity and high molecular weight.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polyamic acid resin composition, a flexible AMOLED polyimide substrate and a preparation method thereof.
Background
In recent years, with the technological progress and rapid development of industries such as OLED lighting, display, organic photovoltaic, flexible printed circuit board and the like, the upstream industry is also active. At present, the flexible AMOLED display screen mainly uses polyimide to replace glass to be used as a substrate, so that the screen can be bent, and the hard screen is a soft screen. With the benefit of the continuous increase of the OLED production, PI substrate materials have a strong market demand and have a large growth space in the future. Because the polyimide substrate belongs to the high-technology barrier industry, the polyimide market for the flexible AMOLED display substrate is basically monopolized by the Happy production of the Japanese ministry of Japan and the Brillouin chemistry at present. The polyimide for the flexible AMOLED display substrate is researched late in China, influenced by a plurality of factors such as enterprise research and development force and application technology and the like, and still stays at the stage of simulating foreign research and development, the mass production of the series of products is not available, and the maturity of the products is low.
As a substrate material for replacing the traditional glass as a flexible AMOLED, the substrate material is used in the form of polyamic acid resin in the application process, a polyimide substrate is prepared by thermal imide after coating on a glass plate by a precise coating technology, and then a series of AMOLED processes such as a barrier layer, a Thin Film Transistor (TFT), a light-emitting layer and the like are carried out on the substrate, and a plurality of complex and harsh processing conditions and use working conditions are involved, so that the polyimide material is required to meet the harsh performances such as high strength and high modulus which can withstand the process temperature of more than 450 ℃ and the material requirement, and low linear expansion coefficient matched with the glass substrate.
Disclosure of Invention
The present invention is to overcome the above-mentioned drawbacks and drawbacks of the background art, and to provide a polyamic acid resin composition and a method for preparing the same, and to provide a flexible AMOLED polyimide substrate made of the polyamic acid resin composition and a method for preparing the same.
In order to solve the above technical problems, the present invention provides the following technical solutions based on a general inventive concept:
in a first aspect, the present invention provides a polyamic acid resin composition comprising an anhydride group-terminated polyamic acid resin and an amino-protected aromatic diamine, the anhydride group-terminated polyamic acid resin having the following general formula:
wherein n is 0 to 1000;
r1 is selected from any one or combination of structures:
wherein R2 is selected from the group consisting of one or more of the following structures:
the general formula of the aromatic diamine after amino protection is as follows:
Y-HN-R2-NH-Y，
wherein Y is selected from one or a combination of more of the following structures:
in the polyamic acid resin composition for a flexible AMOLED, the molar ratio of the anhydride group-terminated polyamic acid resin to the amino group-protected aromatic diamine is preferably 1:0.001 to 0.1, and more preferably 1:0.01 to 0.05.
Preferably, the polyamic acid resin composition has a resin solid content (mass solid content) of 15% to 30%, more preferably 18% to 20%, and a resin viscosity of 1000 to 15000cP, more preferably 5000 to 8000 cP.
In order to realize precise coating of polyimide, the polyamic acid resin composition needs to have good fluidity, that is, to have a relatively low viscosity, however, in the case of the same solid content, the polyamic acid resin with low viscosity has a low molecular weight, and the flexible AMOLED polyimide substrate obtained after imidization has relatively low mechanical properties and heat resistance, so as to solve the contradiction between the use requirement and the performance requirement, the polyamic acid resin composition needs to have high solid content, low viscosity and high molecular weight. According to the invention, after amino protection is carried out on part of aromatic diamine, the part of aromatic diamine is released under certain conditions to participate in reaction, so that the low viscosity of the polyamide acid resin composition can be realized during early molding, and the protective group is removed after coating so as to increase the molecular weight of the resin.
In a second aspect, the present invention also provides a method for preparing a polyamic acid resin composition, comprising the steps of:
(1) under the inert gas atmosphere, carrying out polycondensation reaction on aromatic dianhydride and aromatic diamine in an aprotic polar solvent to obtain polyamide acid resin with end capped by anhydride groups;
(2) mixing aromatic diamine with the amino protection mixture to obtain amino protected aromatic diamine;
(3) and (2) uniformly mixing the polyamide acid resin with the end capped by the anhydride group obtained in the step (1) and the aromatic diamine with the protected amino group obtained in the step (2) to obtain the polyamide acid resin composition.
In the preparation method of the polyamic acid resin composition for the flexible AMOLED, in the step (1), the molar ratio of the aromatic dianhydride to the aromatic diamine is preferably 1: 0.9-0.999, and more preferably 1: 0.95-0.99; the aprotic polar solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and is more preferably N-methylpyrrolidone (NMP has higher polarity and is more favorable for the reaction of monomers with relatively weaker reactivity); the polycondensation reaction is carried out at the temperature of-20-100 ℃, more preferably at the temperature of 50-80 ℃ for 1-12 h, and more preferably for 6-8 h.
Preferably, in step (2), the amino protecting mixture is selected from one or more of the following mixtures in combination: mixtures of benzyl chloroformate/sodium carbonate/water, di-tert-butyl dicarbonate/sodium hydroxide/water, fluorenylmethoxycarbonylcarbonyl chloride/sodium bicarbonate/water, ArCHO/NaCNBH3A methanol mixture and a benzyl bromide/potassium carbonate/triethylamine mixture, wherein the mixing molar ratio of the components in the mixture is 1:1: 1; the mass ratio of the aromatic diamine to the amino protection mixture is 1: 5-20, and more preferably 1: 10.
Preferably, in the step (3), the molar ratio of the amino-protected aromatic diamine to the aromatic dianhydride added in the step (1) is 0.001-0.1: 1, preferably 0.01-0.05: 1.
In a third aspect, the invention also provides a flexible AMOLED polyimide substrate, which comprises a flexible AMOLED glass substrate and a polyamic acid composition coating, wherein the polyamic acid composition coating is obtained by coating the polyamic acid resin composition, removing an amino protecting group, growing a repolymerizing molecular chain and imidizing.
In a fourth aspect, the invention further provides a preparation method of the flexible AMOLED polyimide substrate, which comprises the following steps:
s1, mixing the polyamic acid resin composition with an amino protecting group remover, and coating the mixture on a flexible AMOLED glass substrate;
s2, heating the glass substrate obtained in the step S1 to 60-80 ℃ in an inert gas atmosphere, keeping for a period of time, removing amino protecting groups in the amino-protected aromatic diamine, and carrying out repolymerization molecular chain growth with the polyamide acid resin with the end capped by anhydride groups;
and S3, continuously heating the glass substrate obtained in the step S2 in an inert gas atmosphere to imidize the glass substrate to obtain the flexible AMOLED polyimide substrate.
In the above preparation method of the flexible AMOLED polyimide substrate, preferably, in step S1, the amino protecting group removing agent is selected from one or more of the following mixtures: a hydrogen bromide/acetic acid mixture, a hydrochloric acid/methanol mixture, a piperidine/DMF mixture, a trifluoroacetic acid/potassium dichloride alkane mixture and formic acid/palladium carbon, wherein the mixing molar ratio of the components in the mixture is 1: 1.
Preferably, in step S1, the mixing is performed at 0 to 50 ℃; in step S2, the temperature for the growth of the repolymerization molecular chain is 60-80 ℃ and the time is 1-2 h; in step S3, the temperature of the temperature raising process is controlled to 100 to 500 ℃, and the specific temperature raising process is as follows: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
The overall technical principle of the invention is as follows:
firstly, regulating the amine-anhydride ratio to prepare low-viscosity and high-solid-content anhydride-terminated polyamide acid resin; and then the aromatic diamine monomer is subjected to amino protection and then combined with the polyamide acid resin terminated by the anhydride group, so that the ratio of the dianhydride to the diamine monomer is close to 1:1, and the composition system still keeps low viscosity to meet the requirement of a flexible AMOLED substrate polyamide acid resin coating process.
When the flexible AMOLED polyimide substrate is prepared, after the polyamic acid resin composition is coated, the amino protecting group of the aromatic diamine is removed after the amino protection in the coating, and the aromatic diamine and the polyamic acid resin terminated by the anhydride group are subjected to secondary polymerization molecular chain growth, so that the molecular weight of the polyamic acid is improved to ensure the high strength, the high modulus and the high heat resistance of the polyimide substrate obtained through imidization. The diamine amino protection and the removal of the protective group and the molecular chain repolymerization growth in the processes of preparing the polyamic acid and preparing the polyimide substrate are ingeniously and innovatively realized, so that the polyamic acid resin composition has high solid content, low viscosity and high molecular weight, and the defects in the background art are overcome.
Compared with the prior art, the invention has the beneficial effects that:
1. the polyamide acid resin composition for the flexible AMOLED has high solid content, low viscosity and high molecular weight, and can meet the requirements of a polyamide acid resin coating process of a flexible AMOLED substrate.
2. The flexible AMOLED polyimide substrate can bear the processing temperature of more than 450 ℃, has certain harsh performances such as high strength, high modulus, low linear expansion coefficient matched with a glass substrate and the like, and is suitable for various complex and harsh processing conditions and use working conditions.
3. The preparation method disclosed by the invention is simple to operate, low in cost, green and environment-friendly, and high in preparation efficiency, realizes that the polyamide acid resin composition has high solid content, low viscosity and high molecular weight, and overcomes the defects in the background art.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of the manufacturing process of the present invention.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In the following examples 1 to 5, the anhydride group-terminated polyamic acid resin obtained in step (1) has the following general formula:
wherein n is 0 to 1000;
R1any one or combination of more of the following structures:
wherein R is2A combination of one or more selected from the following structures:
the general formula of the amino-protected aromatic diamine obtained in the step (2) is as follows: Y-HN-R2-NH — Y, wherein Y is selected from one or a combination of more of the following structures:
example 1:
a polyamide acid resin composition for a flexible AMOLED comprises polyamide acid resin terminated by an anhydride group and aromatic diamine after amino protection, and the preparation method comprises the following steps:
(1) adding 183.3g N-methyl pyrrolidone, 0.1mol of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 0.095mol of p-phenylenediamine into a three-neck flask under an argon atmosphere, and stirring and reacting at 50 ℃ for 8 hours to obtain polyamide acid resin with end capped by anhydride groups;
(2) introducing an amino protecting group into a mixture of p-phenylenediamine and di-tert-butyl dicarbonate/sodium hydroxide/water (the mixing molar ratio of the p-phenylenediamine to the di-tert-butyl dicarbonate/the sodium hydroxide to the water is 1:1:1), wherein the mass ratio of an amino protecting agent mixture to aromatic diamine is 1:10, so as to obtain amino-protected aromatic diamine;
(3) 0.005mol of the amino group-protected aromatic diamine was added to the anhydride group-terminated polyamic acid resin, and mixed uniformly to obtain a polyamic acid resin composition.
The polyamic acid resin composition obtained in the embodiment is prepared into a flexible AMOLED polyimide substrate, and the method comprises the following steps:
s1, mixing an amino protecting group remover piperidine/DMF mixture (mixing molar ratio is 1:1) with the polyamic acid resin composition at low temperature (40 ℃), wherein the mass ratio of the amino protecting group remover mixture to the polyamic acid resin composition is 1:10, and coating the mixture on a flexible AMOLED glass substrate to obtain a polyamic acid composition coating;
s2, heating to 60 ℃ in an argon atmosphere to remove the amino-protecting group from the aromatic diamine, and carrying out the repolymerization molecular chain growth for 2 hours with the polyamide acid resin terminated by the anhydride group;
s3, carrying out temperature programming on the coating grown by the repolymerization molecular chain under the argon atmosphere to prepare the polyimide substrate, wherein the temperature programming flow is as follows: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
The flow of the preparation process of this example is shown in fig. 1.
Example 2:
a polyamide acid resin composition for a flexible AMOLED comprises polyamide acid resin terminated by an anhydride group and aromatic diamine after amino protection, and the preparation method comprises the following steps:
(1) adding 183.3g N-methyl pyrrolidone, 0.1mol of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 0.09mol of p-phenylenediamine into a three-neck flask under argon atmosphere, and stirring and reacting at 50 ℃ for 8 hours to obtain polyamide acid resin with end capped by anhydride groups;
(2) introducing an amino protecting group into a mixture of p-phenylenediamine and di-tert-butyl dicarbonate/sodium hydroxide/water (the mixing molar ratio is 1:1:1), wherein the mass ratio of an amino protecting agent mixture to aromatic diamine is 1:10, so as to obtain amino-protected aromatic diamine;
(3) 0.01mol of amino-protected aromatic diamine was added to the anhydride group-terminated polyamic acid resin, and uniformly mixed to obtain a polyamic acid resin composition.
The polyamic acid resin composition obtained in the embodiment is prepared into a flexible AMOLED polyimide substrate, and the method comprises the following steps:
s1, mixing an amino protecting group remover piperidine/DMF mixture (mixing molar ratio is 1:1) with the polyamic acid resin composition at low temperature (40 ℃), wherein the mass ratio of the amino protecting group remover mixture to the polyamic acid resin composition is 1:10, and coating the mixture on a flexible AMOLED glass substrate to obtain a polyamic acid composition coating;
s2, heating to 60 ℃ in an argon atmosphere to remove the amino-protecting group from the aromatic diamine, and carrying out the repolymerization molecular chain growth for 2 hours with the polyamide acid resin terminated by the anhydride group;
s3, carrying out temperature programming on the coating grown by the repolymerization molecular chain under the argon atmosphere to prepare the polyimide substrate, wherein the temperature programming flow is as follows: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
The flow of the preparation process of this example is shown in fig. 1.
Example 3:
a polyamide acid resin composition for a flexible AMOLED comprises polyamide acid resin terminated by an anhydride group and aromatic diamine after amino protection, and the preparation method comprises the following steps:
(1) adding 183.3g of N-methyl pyrrolidone, 0.1mol of pyromellitic dianhydride and 0.095mol of diaminodiphenyl ether into a three-neck flask under the argon atmosphere, and stirring at 50 ℃ for reacting for 8 hours to obtain polyamide acid resin terminated by anhydride groups;
(2) introducing amino protecting groups into a mixture (mixing molar ratio is 1:1:1) of diaminodiphenyl ether and di-tert-butyl dicarbonate/sodium hydroxide/water, wherein the mass ratio of the amino protecting agent mixture to the aromatic diamine is 1:10, so as to obtain amino-protected aromatic diamine;
(3) 0.005mol of the amino group-protected aromatic diamine was added to the anhydride group-terminated polyamic acid resin, and mixed uniformly to obtain a polyamic acid resin composition.
The polyamic acid resin composition obtained in the embodiment is prepared into a flexible AMOLED polyimide substrate, and the method comprises the following steps:
s1, mixing an amino protecting group remover piperidine/DMF mixture (mixing molar ratio is 1:1) with the polyamic acid resin composition at low temperature (40 ℃), wherein the mass ratio of the amino protecting group remover mixture to the polyamic acid resin composition is 1:10, and coating the mixture on a flexible AMOLED glass substrate to obtain a polyamic acid composition coating;
s2, heating to 60 ℃ in an argon atmosphere to ensure that the amino-protected aromatic diamine deamination protecting group and the amino-terminated polyamide acid resin undergo repolymerization molecular chain growth for 2 hours;
s3, carrying out temperature programming on the coating grown by the repolymerization molecular chain under the argon atmosphere to prepare the polyimide substrate, wherein the temperature programming flow is as follows: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
The flow of the preparation process of this example is shown in fig. 1.
Example 4:
a polyamide acid resin composition for a flexible AMOLED comprises polyamide acid resin terminated by an anhydride group and aromatic diamine after amino protection, and the preparation method comprises the following steps:
(1) adding 183.3g N-methyl pyrrolidone, 0.1mol of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 0.095mol of p-phenylenediamine into a three-neck flask under an argon atmosphere, and stirring and reacting at 50 ℃ for 8 hours to obtain polyamide acid resin with end capped by anhydride groups;
(2) introducing an amino protecting group into a mixture (the mixing molar ratio is 1:1:1) of p-phenylenediamine and benzyl chloroformate/sodium carbonate/water, wherein the mass ratio of an amino protecting agent mixture to aromatic diamine is 1:10, so as to obtain amino-protected aromatic diamine;
(3) 0.005mol of the amino group-protected aromatic diamine was added to the anhydride group-terminated polyamic acid resin, and mixed uniformly to obtain a polyamic acid resin composition.
The polyamic acid resin composition obtained in the embodiment is prepared into a flexible AMOLED polyimide substrate, and the method comprises the following steps:
s1, mixing an amino protecting group remover trifluoroacetic acid/potassium dichloride alkane mixture (mixing molar ratio is 1:1) with the polyamide acid resin composition at low temperature (40 ℃), wherein the mass ratio of the amino protecting group remover mixture to the polyamide acid resin composition is 1:10, and coating the mixture on a flexible AMOLED glass substrate to obtain a polyamide acid composition coating;
s2, heating to 60 ℃ in an argon atmosphere to remove the amino-protecting group from the aromatic diamine, and carrying out the repolymerization molecular chain growth for 2 hours with the polyamide acid resin terminated by the anhydride group;
s3, carrying out temperature programming on the coating grown by the repolymerization molecular chain under the argon atmosphere to prepare the polyimide substrate, wherein the temperature programming flow is as follows: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
The flow of the preparation process of this example is shown in fig. 1.
Example 5:
a polyamide acid resin composition for a flexible AMOLED comprises polyamide acid resin terminated by an anhydride group and aromatic diamine after amino protection, and the preparation method comprises the following steps:
(1) adding 183.3g N-methyl pyrrolidone, 0.1mol of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, 0.09mol of p-phenylenediamine and 0.05mol of diaminodiphenyl ether into a three-neck flask under the argon atmosphere, and stirring at 50 ℃ for reacting for 8 hours to obtain anhydride-terminated polyamide acid resin;
(2) introducing an amino protecting group into a mixture (the mixing molar ratio is 1:1:1) of p-phenylenediamine and benzyl chloroformate/sodium carbonate/water, wherein the mass ratio of an amino protecting agent mixture to aromatic diamine is 1:10, so as to obtain amino-protected aromatic diamine;
(3) 0.005mol of the amino group-protected aromatic diamine was added to the anhydride group-terminated polyamic acid resin, and mixed uniformly to obtain a polyamic acid resin composition.
The polyamic acid resin composition obtained in the embodiment is prepared into a flexible AMOLED polyimide substrate, and the method comprises the following steps:
s1, mixing an amino protecting group remover trifluoroacetic acid/potassium dichloride alkane mixture (mixing molar ratio is 1:1) with the polyamide acid resin composition at low temperature (40 ℃), wherein the mass ratio of the amino protecting group remover mixture to the polyamide acid resin composition is 1:10, and coating the mixture on a flexible AMOLED glass substrate to obtain a polyamide acid composition coating;
s2, heating to 60 ℃ in an argon atmosphere to remove the amino-protecting group from the aromatic diamine, and carrying out the repolymerization molecular chain growth for 2 hours with the polyamide acid resin terminated by the anhydride group;
s3, carrying out temperature programming on the coating grown by the repolymerization molecular chain under the argon atmosphere to prepare the polyimide substrate, wherein the temperature programming flow is as follows: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
The flow of the preparation process of this example is shown in fig. 1.
Comparative example 1:
a preparation method of a flexible AMOLED polyimide substrate comprises the following steps:
firstly, adding 183.3g N-methyl pyrrolidone, 0.1mol of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 0.095mol of p-phenylenediamine into a three-neck flask under the argon atmosphere, stirring and reacting for 8 hours at 50 ℃ to obtain polyamide acid resin terminated by anhydride groups, coating the polyamide acid resin on a flexible AMOLED glass substrate to obtain a polyamide acid composition coating, and carrying out temperature programming under the argon atmosphere to prepare a polyimide substrate, wherein the temperature raising process comprises the following steps: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
Comparative example 2:
a preparation method of a flexible AMOLED polyimide substrate comprises the following steps:
firstly, adding 183.3g N-methyl pyrrolidone, 0.1mol of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 0.1mol of p-phenylenediamine into a three-neck flask under the argon atmosphere, stirring and reacting for 8 hours at 50 ℃ to obtain polyamide acid resin terminated by anhydride groups, coating the polyamide acid resin on a flexible AMOLED glass substrate to obtain a polyamide acid composition coating, and carrying out temperature programming under the argon atmosphere to prepare a polyimide substrate, wherein the temperature raising process comprises the following steps: the heating rate is 10 ℃/min, the temperature is kept at 100 ℃ for 30min, the temperature is kept at 150 ℃ for 30min, and the temperature is kept at 250 ℃ for 30 min; keeping the temperature at 450 ℃ for 10min, and naturally cooling to room temperature.
The results of the performance test of the polyimide substrates prepared in examples 1 to 5 and comparative examples 1 to 2 are shown in Table 1.
Table 1: performance test results of polyimide substrates prepared in examples 1 to 5 and comparative examples 1 to 2
As can be seen from Table 1, in order to achieve the same resin viscosity in examples 1-5 as in comparative example 1, the comparative example requires a lower amine anhydride ratio and would severely compromise mechanical strength and other balance of properties. Examples 1-5 and comparative example 2 in the case of 1:1 total dianhydride and diamine, examples 1-5 can prepare a resin with lower viscosity, which is more beneficial for resin processing and molding, while comparative example 2 cannot be coated by AMOLE coating process.
Claims (10)
1. A polyamic acid resin composition, comprising a polyamic acid resin terminated with an anhydride group and an amino-protected aromatic diamine, wherein the polyamic acid resin terminated with an anhydride group has the following general formula:
wherein n is 0 to 1000;
R1any one or combination of more of the following structures:
wherein R is2A combination of one or more selected from the following structures:
the general formula of the aromatic diamine after amino protection is as follows:
Y-HN-R2-NH-Y
wherein Y is selected from one or a combination of more of the following structures:
2. the polyamic acid resin composition according to claim 1, wherein the molar ratio of the anhydride group-terminated polyamic acid resin to the amino group-protected aromatic diamine is 1:0.001 to 0.1.
3. The polyamic acid resin composition according to claim 1 or 2, wherein the polyamic acid resin composition has a resin solid content of 15% to 30% and a resin viscosity of 1000 to 15000 cP.
4. A preparation method of a polyamic acid resin composition is characterized by comprising the following steps:
(1) under the inert gas atmosphere, carrying out polycondensation reaction on aromatic dianhydride and aromatic diamine in an aprotic polar solvent to obtain polyamide acid resin with end capped by anhydride groups;
(2) mixing aromatic diamine with the amino protection mixture to obtain amino protected aromatic diamine;
(3) and (2) uniformly mixing the polyamide acid resin with the end capped by the anhydride group obtained in the step (1) and the aromatic diamine with the protected amino group obtained in the step (2) to obtain the polyamide acid resin composition.
5. The method according to claim 4, wherein in the step (1), the molar ratio of the aromatic dianhydride to the aromatic diamine is 1: 0.9-0.999; the aprotic polar solvent is selected from one or more of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the temperature of the polycondensation reaction is-20-100 ℃, and the time is 1-12 h.
6. The method according to claim 4 or 5, wherein in step (2), the amino protecting mixture is selected from one or more of the following mixtures: mixtures of benzyl chloroformate/sodium carbonate/water, di-tert-butyl dicarbonate/sodium hydroxide/water, fluorenylmethoxycarbonylcarbonyl chloride/sodium bicarbonate/water, ArCHO/NaCNBH3Methanol mixture, brominationBenzyl/potassium carbonate/triethylamine mixtures;
in the step (3), the molar ratio of the aromatic diamine after the amino protection to the aromatic dianhydride added in the step (1) is 0.001-0.1: 1.
7. A flexible AMOLED polyimide substrate is characterized by comprising a flexible AMOLED glass substrate and a polyamic acid composition coating, wherein the polyamic acid composition coating is obtained by coating, amino protecting group removal, repolymerization molecular chain growth and imidization of the polyamic acid resin composition prepared according to any one of claims 1-3 or according to any one of claims 4-6.
8. The method of preparing the flexible AMOLED polyimide substrate of claim 7, comprising the steps of:
s1, mixing the polyamic acid resin composition with an amino protecting group remover, and coating the mixture on a flexible AMOLED glass substrate;
s2, heating the glass substrate obtained in the step S1 to 60-80 ℃ in an inert gas atmosphere, and keeping the temperature for a period of time;
and S3, continuously heating the glass substrate obtained in the step S2 in an inert gas atmosphere to imidize the glass substrate to obtain the flexible AMOLED polyimide substrate.
9. The method according to claim 8, wherein the amino-protecting group removing agent is selected from one or more of the following mixtures: hydrogen bromide/acetic acid mixtures, hydrochloric acid/methanol mixtures, piperidine/DMF mixtures, trifluoroacetic acid/potassium dichloride alkane mixtures, formic acid/palladium on carbon.
10. The production method according to claim 8 or 9, wherein in step S1, the mixing is performed at 0 to 50 ℃; in step S2, the time for keeping the temperature after the temperature is raised to 60-80 ℃ is 1-2 h; in step S3, the temperature of the temperature raising process is controlled to be 100 ℃ to 500 ℃ and the temperature raising rate is 10 ℃/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117806123A (en) * | 2024-02-29 | 2024-04-02 | 明士(北京)新材料开发有限公司 | Chemical amplification type negative photosensitive polyimide composition and application thereof |
| CN117866199A (en) * | 2024-03-11 | 2024-04-12 | 烟台三月科技有限责任公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632554A (en) * | 1967-05-29 | 1972-01-04 | Toray Industries | Process for preparing heat resisting polyimides |
| US4956450A (en) * | 1989-05-26 | 1990-09-11 | Ethyl Corporation | Process for forming end-capped polyamic acids polyimides |
| JP2009109589A (en) * | 2007-10-26 | 2009-05-21 | Asahi Kasei Corp | Photosensitive resin composition, photosensitive resin composition film and coverlay using them |
| CN103068795A (en) * | 2010-08-17 | 2013-04-24 | 日产化学工业株式会社 | Method for preparing diamine precursor compound |
| CN109721749A (en) * | 2018-12-14 | 2019-05-07 | 上海市合成树脂研究所有限公司 | A kind of thermostable type Kapton and preparation method containing heteroaromatic |
| CN111072964A (en) * | 2019-12-31 | 2020-04-28 | 阜阳欣奕华材料科技有限公司 | Polyimide precursor composition and preparation method and application thereof |
| CN111440590A (en) * | 2020-04-09 | 2020-07-24 | 株洲时代新材料科技股份有限公司 | Polyamide acid adhesive composition for chip packaging, and preparation method and application thereof |
| US20200407593A1 (en) * | 2017-12-28 | 2020-12-31 | Ube Industries, Ltd. | Polyimide precursor resin composition for forming flexible device substrate |
| CN112876680A (en) * | 2021-02-04 | 2021-06-01 | 武汉柔显科技股份有限公司 | Polyamide acid slurry, preparation method thereof and polyimide film |
-
2021
- 2021-12-20 CN CN202111563522.9A patent/CN114479073B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632554A (en) * | 1967-05-29 | 1972-01-04 | Toray Industries | Process for preparing heat resisting polyimides |
| US4956450A (en) * | 1989-05-26 | 1990-09-11 | Ethyl Corporation | Process for forming end-capped polyamic acids polyimides |
| JP2009109589A (en) * | 2007-10-26 | 2009-05-21 | Asahi Kasei Corp | Photosensitive resin composition, photosensitive resin composition film and coverlay using them |
| CN103068795A (en) * | 2010-08-17 | 2013-04-24 | 日产化学工业株式会社 | Method for preparing diamine precursor compound |
| US20200407593A1 (en) * | 2017-12-28 | 2020-12-31 | Ube Industries, Ltd. | Polyimide precursor resin composition for forming flexible device substrate |
| CN109721749A (en) * | 2018-12-14 | 2019-05-07 | 上海市合成树脂研究所有限公司 | A kind of thermostable type Kapton and preparation method containing heteroaromatic |
| CN111072964A (en) * | 2019-12-31 | 2020-04-28 | 阜阳欣奕华材料科技有限公司 | Polyimide precursor composition and preparation method and application thereof |
| CN111440590A (en) * | 2020-04-09 | 2020-07-24 | 株洲时代新材料科技股份有限公司 | Polyamide acid adhesive composition for chip packaging, and preparation method and application thereof |
| CN112876680A (en) * | 2021-02-04 | 2021-06-01 | 武汉柔显科技股份有限公司 | Polyamide acid slurry, preparation method thereof and polyimide film |
Non-Patent Citations (1)
| Title |
|---|
| 郝彩霞等: ""热塑性聚酰亚胺及其改性材料的制备与性能"", 《高分子通报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117806123A (en) * | 2024-02-29 | 2024-04-02 | 明士(北京)新材料开发有限公司 | Chemical amplification type negative photosensitive polyimide composition and application thereof |
| CN117806123B (en) * | 2024-02-29 | 2024-05-31 | 明士(北京)新材料开发有限公司 | Chemical amplification type negative photosensitive polyimide composition and application thereof |
| CN117866199A (en) * | 2024-03-11 | 2024-04-12 | 烟台三月科技有限责任公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element thereof |
| CN117866199B (en) * | 2024-03-11 | 2024-05-28 | 烟台三月科技有限责任公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element thereof |
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