CN108997753A - A kind of high barrier transparent flexible display material and preparation method thereof - Google Patents
A kind of high barrier transparent flexible display material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of high barrier transparent flexible display base plate materials and preparation method thereof.Preparation method provided by the invention first heats anionic two-dimensional layer material with organic intercalation agent in a solvent reacts, carry out lift-off processing in a solvent again, home position polymerization reaction is mixed and carried out with the polymerized monomer of polyimides later, is finally heat-treated, flexible display substrates material is obtained.The resulting material of preparation method according to the invention has high water oxygen barrier property, excellent thermal stability, low thermal coefficient of expansion and high grade of transparency etc., is the flexible material of excellent combination property.
Description
Technical field
The present invention relates to flexible material technical field, in particular to a kind of high barrier transparent flexible display base plate material and
Preparation method.
Background technique
Currently, Color flat panel display technology not only pursues high image quality, low-power consumption but also gradually to flexible, flexible, frivolous side
To development.Flexible flat display technology is greatly expanded the application scenarios and imagination space of traditional display screen, is more downstreams
The birth of application product provides possibility, such as prepares foldable mobile phone, e-newspaper, rollable TV that people dream of
With wearable display etc., and flexible, flexible, frivolous Flexible Displays, touch-control device etc. has been increasingly becoming electronic field
The indispensable element of high-tech product.
According to the processing and application demand of flexible display device, the baseplate material as flexible display needs to have specific
Performance requirement: the light transmittance of 1. good light transmittance, 500nm above wavelength requires more than 90%；2. good heat resistance (Tg >
250 DEG C), to meet the needs of processing conditions such as magnetron sputtering, higher heat resistance is needed, and heat resistance is higher, it is more advantageous
In the processing of low temperature polycrystalline silicon device；3. lower thermal expansion coefficient (CTE < 20ppm/ DEG C), lower thermal expansion coefficient can
It is preferably matched with functional layer, guarantees the high temperature dimensional stability of flexible display, if baseplate material is not able to maintain excellent ruler
Very little stability, it will quality and reliability to final display generate detrimental effects；4. to oxygen, vapor barrier properties
It is good, in case display medium is exposed to steam and deteriorates with performance in oxygen atmosphere.
Conventional transparent display material is mostly glass substrate material, however, it does not have flexibility, water oxygen barrier property is poor,
It is unable to satisfy the basic demand of Flexible Displays.Transparent polymer substrate material is gradually adopted to replace traditional glass substrate material later
Material, common transparent polymer substrate material include polyethylene terephthalate (i.e. PET), it is poly- how naphthalate
(i.e. PEN), polycarbonate (i.e. PC), polymethyl methacrylate (i.e. PMMA), polyimides (i.e. PI).However, these polymerize
Though object flexible material is able to satisfy the transparency and flexibility requirements, thermal expansion coefficient and water oxygen barrier property are still poor, are not able to satisfy
Practical application request.
In view of the above problems, the prior art is usually taken in polymer flexibility material surface building water oxygen barrier layer as aoxidized
Silicon, alumina layer etc., however, these water oxygen barrier layers are not resistant to bending, flexibility is insufficient, destroys the basic of flexible display material
Flexible demand, and the easy brittle failure of these barrier properties falls off, cannot the long-acting improvement for realizing water oxygen barrier property, and increase barrier layer and also hold
Easily influence the transparency of flexible display material.As it can be seen that the various aspects of performance of flexible material is difficult to balance and reconcile, property in a certain respect
Can promotion be easy to influence the performance of other aspects, therefore, how to obtain and have both high-fire resistance, low thermal coefficient of expansion, high flexible
The flexible substrate material of the excellent combination property of property, preferable water and oxygen barrier property, high transparency etc., which has become, urgently to be solved in the industry
Certainly the problem of.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of high barrier transparent flexible display base plate material and its preparations
Method, preparation method according to the invention can be obviously improved the toughness of material, promote heat resistance, reduce thermal expansion coefficient, with
And excellent water oxygen barrier property and excellent transparency are generated, obtain the flexible substrate material of excellent combination property.
The present invention provides a kind of preparation methods of high barrier transparent flexible display base plate material, comprising the following steps:
A) anionic two-dimensional layer material is heated in a solvent with organic intercalation agent and is reacted, obtain organic intercalation modification
Stratified material；
B) stratified material for modifying the organic intercalation carries out lift-off processing in a solvent, obtains nanometer sheet dispersion liquid；
C) nanometer sheet dispersion liquid is mixed to the polymerized monomer of polyimides and carried out home position polymerization reaction, gathered
Amic acid slurry；
D) the polyamic acid slurry is heat-treated, obtains flexible display substrates material；
The anionic two-dimensional layer material is one of binary metal hydroxide and mixed metal hydroxide
Or it is several；
The organic intercalation agent is selected from the metal salt and organic sulphur of organic carboxyl acid, organic sulfonic acid, the organic carboxyl acid
One or more of the metal salt of acid.
Preferably, the organic carboxyl acid is selected from the binary aliphatic carboxylic of the aliphatic monocarboxylic acid of C1~C22, C1~C26
In acid, the aliphatic tricarboxylic acid of C1~C40, aromatic series monocarboxylic acid, aromatic binary carboxylic acid and aromatic series tricarboxylic acid
It is one or more of；
The organic sulfonic acid is selected from one of aliphatic unitary sulfonic acid and aromatic series unitary sulfonic acid of C1~C22 or several
Kind.
Preferably, the organic carboxyl acid is selected from compound shown in formula (1-1), compound, formula (1-3) institute shown in formula (1-2)
Show one of compound shown in compound shown in compound, formula (1-4), compound and formula (1-6) shown in formula (1-5) or several
Kind；
Wherein, n1For 0~20, n2For 0~10, n3For 0~10, n4For 0~10, n5For 0~10, n6It is 0~10；
R、R1、R2、R3、R4、R5、R6、R7、R8、R1、R2And R3It is each independently selected from hydrogen, alkyl, aryl, fluoroalkyl, hydroxyl
Base, alkoxy, phenoxy group, cyano, nitro, amino, acetylamino, ester group, acyl group, halogen or carboxyl；
The organic sulfonic acid is selected from one or more of compound shown in compound shown in formula (2-1) and formula (2-2)；
Wherein, n is 0~20；
R9And R4Be each independently selected from hydrogen, alkyl, aryl, fluoroalkyl, hydroxyl, alkoxy, phenoxy group, cyano, nitro,
Amino, acetylamino, ester group, acyl group, halogen or carboxyl；
Metal ion in the metal salt of the organic carboxyl acid is selected from monovalence alkali metal ion or divalent alkali metal ion；
Metal ion in the metal salt of the organic sulfonic acid is selected from monovalence alkali metal ion or divalent alkali metal ion.
Preferably, in the organic carboxyl acid, n1For 1~10, n2For 0~6, n3For 0~6, n4For 0~6, n5For 0~6, n6
It is 0~6；
R、R1、R2、R3、R4、R5、R6、R7、R8、R1、R2And R3Be each independently selected from hydrogen, hydroxyl, alkoxy, phenoxy group or
Fluoroalkyl；
In the organic sulfonic acid, n is 0~16；R9And R4It is each independently selected from hydrogen, hydroxyl, alkoxy, phenoxy group or fluorine
Alkyl；
Metal ion in the metal salt of the organic carboxyl acid is selected from Na+、K+Or Mg2+；
Metal ion in the metal salt of the organic sulfonic acid is selected from Na+、K+Or Mg2+。
Preferably, the organic carboxyl acid is selected from hydroxyacetic acid, hydroxybutyric acid, citric acid, tartaric acid, trifluoroacetic acid, benzene first
Acid, phthalic acid, M-phthalic acid, trifluoromethylbenzoic acid, hydroxybenzoic acid, dihydroxy-benzoic acid, methoxy benzoic acid,
Dimethoxybenzoic acid, phenoxy benzoic acid, two phenoxy benzoic acids, two (trifluoromethyl) benzoic acid, hydroxyl phthalic,
Trifluoromethyl phthalic acid, methoxyl group phthalic acid, methoxyl group M-phthalic acid, phenoxy group phthalic acid, phenoxy group
One or more of M-phthalic acid, Hydroxy M Phthalic Acid and trifluoromethyl M-phthalic acid；
The organic sulfonic acid is selected from dodecyl sodium sulfonate, perfluoro octyl sulfonic acid, perfluoro butyl sulfonic acid, benzene sulfonic acid, dodecane
One or more of base benzene sulfonic acid and hydroxy benzene sulfonic acid.
Preferably, in the anionic two-dimensional layer material, at least one metal is divalent metal, and at least one golden
Belonging to is trivalent metal；
The divalent metal is selected from Mg2+、Zn2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Ca2+Or Cd2+；
The trivalent metal is selected from Al3+、Co3+、Fe3+、Mn3+、Cr3+Or Ga3+；
The anion of interlayer is selected from NO3-、Cl-、SO4 2-Or CO3 2-。
Preferably, the anionic two-dimensional layer material is magnalium hydrotalcite, and the anion of interlayer is CO3 2-。
Preferably, in the step a), the molar ratio of organic intercalation agent and anionic two-dimensional layer material be (0.5~
4.0):1；
Polyamides in flexible display substrates material obtained by nanometer sheet and step c) in step c) in nanometer sheet dispersion liquid is sub-
The mass ratio of amine is (0.1~20): 100.
Preferably, in the step b), the lift-off processing includes stir process or ultrasonic treatment；
The revolving speed of the stir process is 200~2000 revs/min, and the time is 10~30h, and temperature is 50~120 DEG C；
The power of the ultrasonic treatment is 50~500W, and the time is 0.5~3h；
In the step c), the temperature of home position polymerization reaction is 0~50 DEG C, and the time is 1~72 hour；
The polymerized monomer of the polyimides includes dianhydride and diamines.
The present invention also provides flexible display substrates materials made from preparation method described in a kind of above-mentioned technical proposal.
The present invention provides a kind of preparation methods of high barrier transparent flexible display base plate material, comprising the following steps:
A) anionic two-dimensional layer material is heated in a solvent with organic intercalation agent and is reacted, obtain the stratiform material of organic intercalation modification
Material；B) stratified material for modifying the organic intercalation carries out lift-off processing in a solvent, obtains nanometer sheet dispersion liquid；C) by institute
It states nanometer sheet dispersion liquid and home position polymerization reaction is mixed and carried out with the polymerized monomer of polyimides, obtain polyamic acid slurry；d)
The polyamic acid slurry is heat-treated, flexible display substrates material is obtained；The anionic two-dimensional layer material is
One or more of binary metal hydroxide and mixed metal hydroxide；The organic intercalation agent be selected from organic carboxyl acid,
One or more of organic sulfonic acid, the metal salt of the organic carboxyl acid and metal salt of the organic sulfonic acid.
In above-mentioned preparation method provided by the invention, first organic intercalation agent is reacted with anionic two-dimensional layer material,
Increase the spacing of stratified material using organic intercalation agent, while carrying out ion exchange between stratified material, forms organic intercalation
The stratified material of modification improves and subsequent polymerized monomer and final polymer matrix that it changes the surface characteristic of stratified material
The compatibility of body；Lift-off processing is carried out to the stratified material of organic intercalation modification again, the stratified material of organic intercalation modification is shelled
Home position polymerization reaction and heat treatment, two-dimensional nano piece and polymer phase interaction are carried out from two-dimensional nano piece, then with polymerized monomer
With being dispersed in polyimide matrix, obtained the composite material comprising two-dimensional nano piece and polyimides.Using removing
Two-dimensional nano piece afterwards only needs less dosage that can make composite material water oxygen barrier property with higher, excellent thermal stability
And low thermal coefficient of expansion, and the transparency of composite material is not influenced, obtain the flexible display substrates material of excellent combination property.
Test result shows that the glass transition temperature of flexible substrate material made from preparation method according to the invention is super
250 DEG C are crossed, thermal expansion coefficient is lower than 20ppm/ DEG C, can preferably meet the high-fire resistance demand of flexible display substrates；Meanwhile
The tensile strength of resulting materials is more than 90MPa, and stretch modulus is more than 1.5GPa, shows excellent toughness；The water of resulting materials
Vapour transmitance is in 0.30g.cm-2.day-1Hereinafter, OTR oxygen transmission rate is in 0.20cm3.cm-2.day-1Hereinafter, showing excellent water
Oxygen barrier performance；The light transmittance of resulting materials is more than 90%, has preferable transparency, and resulting materials have in preferable face respectively
To the same sex, it is easy to laser lift-off, no residue glue with support plate.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the x-ray diffraction pattern of the hydrotalcite of hydroxybutyric acid intercalation modification in embodiment 1；
Fig. 2 is the x-ray diffraction pattern of the hydrotalcite of 4-HBA intercalation modification in embodiment 2；
Fig. 3 is the x-ray diffraction pattern of the hydrotalcite of 4- hydroxyl phthalic intercalation modification in embodiment 3；
Fig. 4 is the x-ray diffraction pattern of the hydrotalcite of citric acid intercalation modification in embodiment 4；
Fig. 5 is the x-ray diffraction pattern of the hydrotalcite of perfluoro octyl sulfonic acid potassium intercalation modification in embodiment 5；
Fig. 6 is the x-ray diffraction pattern of the hydrotalcite of 4- trifluoromethylbenzoic acid intercalation modification in embodiment 6；
Fig. 7 is the x-ray diffraction pattern of the hydrotalcite of trifluoroacetic acid intercalation modification in embodiment 7.
Specific embodiment
A kind of preparation method of high barrier transparent flexible display base plate material, comprising the following steps:
A) anionic two-dimensional layer material is heated in a solvent with organic intercalation agent and is reacted, obtain organic intercalation modification
Stratified material；
B) stratified material for modifying the organic intercalation carries out lift-off processing in a solvent, obtains nanometer sheet dispersion liquid；
C) nanometer sheet dispersion liquid is mixed to the polymerized monomer of polyimides and carried out home position polymerization reaction, gathered
Amic acid slurry；
D) the polyamic acid slurry is heat-treated, obtains flexible display substrates material；
The anionic two-dimensional layer material is one of binary metal hydroxide and mixed metal hydroxide
Or it is several；
The organic intercalation agent is selected from the metal salt and organic sulphur of organic carboxyl acid, organic sulfonic acid, the organic carboxyl acid
One or more of the metal salt of acid.
In preparation method provided by the invention, first organic intercalation agent is reacted with anionic two-dimensional layer material, is utilized
Organic intercalation agent increases the spacing of stratified material, while ion exchange is carried out between stratified material, forms organic intercalation modification
Stratified material improved and subsequent polymerized monomer and final polymeric matrix that it changes the surface characteristic of stratified material
Compatibility；Again to organic intercalation modification stratified material carry out lift-off processing, by organic intercalation modification stratified material removing at
Two-dimensional nano piece, then home position polymerization reaction and heat treatment, two-dimensional nano piece and interpolymer interaction are carried out with polymerized monomer,
It is even to be scattered in polyimide matrix, obtain the composite material comprising two-dimensional nano piece and polyimides.After removing
Two-dimensional nano piece only needs a less dosage that can make composite material water oxygen barrier property with higher, excellent thermal stability and low
Thermal expansion coefficient, and the transparency of composite material is not influenced, obtain the flexible display substrates material of excellent combination property.
According to the present invention, first anionic two-dimensional layer material is heated in a solvent with organic intercalation agent and reacted, obtained
The stratified material of organic intercalation modification.
In the present invention, the anionic two-dimensional layer material is also known as anion type laminated compound, i.e. laminate is positively charged
Lotus, interlayer are the stratified material of balance anion.In the present invention, the anionic two-dimensional layer material is binary metal hydrogen-oxygen
One or more of compound and mixed metal hydroxide；I.e. in stratified material, laminate is by binary metal hydroxide or three
First metal hydroxides is constituted.
Preferably, in the anionic two-dimensional layer material, at least one metal is divalent metal, and at least one golden
Belonging to is trivalent metal.Wherein, the divalent metal is preferably Mg2+、Zn2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Ca2+Or Cd2+；
The trivalent metal is preferably Al3+、Co3+、Fe3+、Mn3+、Cr3+Or Ga3+；The anion of interlayer is preferably NO3-、Cl-、SO4 2-Or
CO3 2-.The present invention is not particularly limited the source of the anionic two-dimensional layer material, is general commercially available product.
In some embodiments, the anionic two-dimensional layer material is magnalium hydrotalcite, and the anion of interlayer is
CO3 2-。
According to the present invention, the organic intercalation agent be selected from organic carboxyl acid, organic sulfonic acid, the organic carboxyl acid metal salt and
One or more of the metal salt of the organic sulfonic acid.
In the present invention, preferably, the organic carboxyl acid is selected from the rouge of the aliphatic monocarboxylic acid of C1~C22, C1~C26
Fat race dicarboxylic acids, the aliphatic tricarboxylic acid of C1~C40, aromatic series monocarboxylic acid, aromatic binary carboxylic acid and aromatic series three
One or more of first carboxylic acid.
It is highly preferred that the organic carboxyl acid is selected from compound shown in (1-1), compound, formula (1-3) institute shown in formula (1-2)
Show one of compound shown in compound shown in compound, formula (1-4), compound and formula (1-6) shown in formula (1-5) or several
Kind；
In formula (1-1)~formula (1-6), n1It is 0~20, preferably 1~10.n2It is 0~10, preferably 0~6.n3For 0~
10, preferably 0~6.n4It is 0~10, preferably 0~6.n5It is 0~10, preferably 0~6.n6It is 0~10, preferably 0~6.
In formula (1-1)~formula (1-6), R, R1、R2、R3、R4、R5、R6、R7、R8、R1、R2And R3Preferably be selected from each independently hydrogen,
Alkyl, aryl, fluoroalkyl, hydroxyl, alkoxy, phenoxy group, cyano, nitro, amino, acetylamino, ester group, acyl group, halogen or
Carboxyl；More preferably hydrogen, hydroxyl, alkoxy, phenoxy group or fluoroalkyl select hydrogen, hydroxyl, alcoxyl compared to other substituent groups
Base, phenoxy group or fluoroalkyl are not only easy to remove in a solvent as high concentration two-dimensional nano piece, can further be obviously improved most
The properties of gained polyimide-based composite material eventually, moreover, removing gained two-dimensional nano piece does not influence final polyimides
The transparency of based composites.Wherein, R1、R2And R3The position of substitution is not limited, can be ortho position, contraposition or the meta position of carboxyl；And
Substituent R1、R2And R3Substitution quantity is not limited, i.e., the substituent group in above-mentioned general formula can be 1, be also possible in different location
Two or more substituent groups, the substituent group of different location can be identical or different.
It is furthermore preferred that the organic carboxyl acid is selected from hydroxyacetic acid, hydroxybutyric acid, citric acid, tartaric acid, trifluoroacetic acid, benzene
Formic acid, phthalic acid, M-phthalic acid, trifluoromethylbenzoic acid, hydroxybenzoic acid, dihydroxy-benzoic acid, methoxybenzene first
Acid, dimethoxybenzoic acid, phenoxy benzoic acid, two phenoxy benzoic acids, two (trifluoromethyl) benzoic acid, hydroxyl O-phthalic
Acid, trifluoromethyl phthalic acid, methoxyl group phthalic acid, methoxyl group M-phthalic acid, phenoxy group phthalic acid, benzene oxygen
One or more of base M-phthalic acid, Hydroxy M Phthalic Acid and trifluoromethyl M-phthalic acid.Further preferably hydroxyl
Base butyric acid, citric acid, benzoic acid, hydroxybenzoic acid, dihydroxy-benzoic acid, hydroxyl phthalic, dimethoxybenzoic acid, three
It is one or more of in methyl fluoride benzoic acid and two (trifluoromethyl) benzoic acid.
In the present invention, preferably, the organic sulfonic acid is selected from the aliphatic unitary sulfonic acid and aromatic series unitary of C1~C22
One or more of sulfonic acid.
It is highly preferred that the organic sulfonic acid is selected from one of compound shown in compound shown in formula (2-1) and formula (2-2)
Or it is several；
In formula (2-1)~formula (2-2), n is 0~20, preferably 0~16.R9And R4Preferably be selected from each independently hydrogen, alkyl,
Aryl, fluoroalkyl, hydroxyl, alkoxy, phenoxy group, cyano, nitro, amino, acetylamino, ester group, acyl group, halogen or carboxyl；
More preferably hydrogen, hydroxyl, alkoxy, phenoxy group or fluoroalkyl select hydrogen, hydroxyl, alkoxy, benzene compared to other substituent groups
Oxygroup or fluoroalkyl are not only easy to remove in a solvent as high concentration two-dimensional nano piece, can further be obviously improved final gained
The properties of polyimide-based composite material, moreover, removing gained two-dimensional nano piece do not influence it is final polyimide-based compound
The transparency of material.Wherein, R4The position of substitution is not limited, it can be with the ortho position of sulfo group, contraposition or meta position；And substituent R4It does not limit
Replacing quantity, i.e., the substituent group in above-mentioned general formula can be 1, be also possible to two or more substituent groups in different location,
The substituent group of different location can be identical or different.
It is furthermore preferred that the organic sulfonic acid is selected from dodecyl sodium sulfonate, perfluoro octyl sulfonic acid, perfluoro butyl sulfonic acid, benzene sulphur
One or more of acid, dodecyl benzene sulfonic acid and hydroxy benzene sulfonic acid；Further preferably dodecyl sodium sulfonate, perfluoro capryl
One or more of sulfonic acid, benzene sulfonic acid and hydroxy benzene sulfonic acid.
In the present invention, corresponding organic carboxyl acid is as described in the above technical scheme in the metal salt of the organic carboxyl acid
Organic carboxyl acid, details are not described herein.Preferably, the metal ion in the metal salt of the organic carboxyl acid is selected from monovalence alkali metal
Ion or divalent alkali metal ion；More preferably Na+、K+Or Mg2+.It is furthermore preferred that the organic carboxylate includes trifluoroacetic acid
One or more of sodium and sodium citrate.
In the present invention, corresponding organic sulfonic acid is as described in the above technical scheme in the metal salt of the organic sulfonic acid
Organic sulfonic acid, details are not described herein.Preferably, the metal ion in the metal salt of the organic sulfonic acid is selected from monovalence alkali metal
Ion or divalent alkali metal ion；More preferably Na+、K+Or Mg2+.It is furthermore preferred that the organic sulfonate includes hydroxy benzenes sulphur
One or more of sour potassium and perfluoro octyl sulfonic acid potassium.
In one embodiment, organic intercalation agent is hydroxybutyric acid.In another embodiment, organic intercalation agent is 4- hydroxyl
Yl benzoic acid.In another embodiment, organic intercalation agent is 4- hydroxyl phthalic.In another embodiment, organic
Intercalator is citric acid.In another embodiment, organic intercalation agent is perfluoro octyl sulfonic acid potassium.In another embodiment,
Organic intercalation agent is 4- trifluoromethylbenzoic acid.In another embodiment, organic intercalation agent is sodium trifluoroacetate.
The present invention reacts anionic two-dimensional layer material with specific organic intercalation agent, stratified material interlayer balance from
Son exchanges organic intercalation agent with inorganic ions and enters interlayer, form the stratiform material of organic intercalation modification by ion-exchange
Material, through applicants have found that, the interaction between stratified material laminate can be significantly reduced in organic intercalation agent of the invention
Power greatly increases interlamellar spacing, while stratified material is become lipophilic from hydrophily, reduces the surface energy of stratified material, mentions
The high compatibility with polymerized monomer and polymeric matrix, and the stratified material after the modification of these organic intercalations is easy in polyamides Asia
Removing is separated into two-dimensional nano piece in the polymer solvent of amine, and the nanometer sheet after this removing is evenly dispersed in polyimides, assigns
The excellent comprehensive performance of composite material is given, that is, obtains and has both high barrier, low thermal coefficient of expansion and high-fire resistance and the high grade of transparency
Etc. performances.
In the present invention, the molar ratio of organic intercalation agent and anionic two-dimensional layer material is preferably (0.5~4.0): 1.
When organic intercalation agent is monoacid or unitary hydrochlorate, the molar ratio of organic intercalation agent and anionic two-dimensional layer material is preferred
For (1.0~4.0): 1, more preferably (2.0~2.4): 1.When organic intercalation agent is binary acid, polyacid, dicarboxylate or more
When first hydrochlorate, the molar ratio of organic intercalation agent and anionic two-dimensional layer material is preferably (0.5~2.0): 1, more preferably
(1.0~1.5): 1.
According to the present invention, anionic two-dimensional layer material is reacted with organic intercalation agent in a solvent.The present invention
In, the solvent be preferably one of water, methanol, ethyl alcohol, propyl alcohol, butanol, the tert-butyl alcohol, ethylene glycol, glycerine and benzylalcohol or
It is several.The present invention is not particularly limited the dosage of the solvent, can be uniformly mixed raw material.
According to the present invention, above-mentioned reaction is heating reaction.In the present invention, the temperature of the heating reaction is preferably 80~
200 DEG C, more preferably 100~180 DEG C.The time of the heating reaction is preferably 1~48h.In reaction process, organic intercalation agent
Increase the spacing of two-dimensional layer material, and carry out ion exchange with two-dimensional layer material, to form the layer of organic intercalation modification
Shape material.
In the present invention, after the reaction, preferably also it is separated by solid-liquid separation.The present invention does not have the mode of the separation of solid and liquid
Have it is specifically limited, be separation means well known to those skilled in the art, such as filter.In the present invention, after being separated by solid-liquid separation,
It is also preferable to include separating obtained solid matter is dried.The temperature of the drying is preferably 40~120 DEG C, the dry time
Preferably 4~for 24 hours.Solid matter after drying is the stratified material of organic intercalation modification.
According to the present invention, after the stratified material for obtaining organic intercalation modification, stratiform material that the organic intercalation is modified
Material carries out lift-off processing in a solvent, obtains nanometer sheet dispersion liquid.
In the present invention, the solvent is the polymer solvent of polyimides, preferably n,N-Dimethylformamide, N, N- diformazan
One or more of yl acetamide and N-Methyl pyrrolidone.In the present invention, the stratified material of organic intercalation modification with
The mass ratio of solvent is preferably (0.1~10): 100, more preferably (0.4~4): 100.
In the present invention, the mode of the lift-off processing is not particularly limited, the stratified material that can modify organic intercalation
Removing is two-dimensional nano piece, preferably includes stir process or ultrasonic treatment.In the present invention, the revolving speed of the stir process is excellent
It is selected as 200~2000 revs/min；The time of the stir process is preferably 10~30h；The temperature of the stir process is preferably
50~120 DEG C.In the present invention, the power of the ultrasonic treatment is preferably 50~500W；The time of the ultrasonic treatment is preferably
0.5~3h；The temperature of the ultrasonic treatment is not particularly limited, room temperature.It is release-treated in a solvent, by organic intercalation
At single layer or the two-dimensional nano piece dispersion liquid of several lamellar spacings, which is transparent colloid for the stratified material removing of modification
Dispersion liquid has typical Tyndall phenomenon.If the stratified material directly by organic intercalation modification carries out without lift-off processing
Subsequent polymerisation reaction then needs the stratified material of high level, and will necessarily reduce the transparent of gained flexible base board display material
Property, and after the present invention is release-treated, using the nanometer sheet after removing, it is only necessary to which it is suitable that less content can be such that composite material has
High water oxygen barrier property, excellent thermal stability, low thermal coefficient of expansion, and will not influence the transparency of composite material.
According to the present invention, after obtaining nanometer sheet dispersion liquid, the nanometer sheet dispersion liquid and polyimides are polymerize list
Body mixes and carries out home position polymerization reaction, obtains polyamic acid slurry.
The present invention is not particularly limited the polymerized monomer type of polyimides, using use well known to those skilled in the art
The monomer of polyimides is generated in polymerization.In the present invention, the polymerized monomer preferably includes dianhydride and diamines.The present invention couple
The type of the dianhydride and diamines is not particularly limited, and is the dianhydride well known to those skilled in the art for synthesis of polyimides
Monomer and diamine monomer.
Wherein, preferably, the dianhydride is preferably one or more of compound shown in formula (7)；
In formula (7), R7It is preferably selected from formula (7-1), formula (7-2), formula (7-3), formula (7-4), formula (7-5), formula (7-6), formula
Structure shown in (7-7), formula (7-8) or formula (7-9), above-mentioned formula (7-1)~formula (7-9) structure is referring to table 1:
1 formula of table (7-1)~formula (7-9)
Wherein, preferably, the diamines is selected from one or more of compound shown in formula (8)；
N2N-R8-NH2Formula (8).
In formula (8), R8It is preferably selected from formula (8-1), formula (8-2), formula (8-3), formula (8-4), formula (8-5), formula (8-6), formula
Structure shown in (8-7), formula (8-8), formula (8-9) or formula (8-10), above-mentioned formula (8-1)~formula (8-10) structure is referring to table 2:
2 formula of table (8-1)~formula (8-10)
In the present invention, in the polymerized monomer of the polyimides, the molar ratio of all dianhydride monomers and diamine monomer is preferred
It is 100: (95~105), more preferably 100: 100.
In the present invention, when raw material is mixed progress home position polymerization reaction, the solid content in reaction system is preferably 5wt%
~50wt%, more preferably 10wt%~30wt%.
In the present invention, when carrying out above-mentioned home position polymerization reaction, the temperature of reaction is preferably 0~50 DEG C, more preferably 0~
30℃；Home position polymerization reaction can be made sufficiently to carry out within the said temperature range, and keep two-dimensional nano piece in the course of the polymerization process
It is evenly dispersed.In the present invention, the time of the polymerization reaction is preferably 1~72 hour, and more preferably 5~48 hours.Described
After polymerization reaction, polyamic acid slurry is obtained, includes two-dimensional nano piece and polyamic acid (the i.e. forerunner of polyimides in the slurry
Body).In the present invention, preferably, bulk viscosity >=1.0dL/g of the polyamic acid slurry, rotary viscosity >=15 ×
105cP。
According to the present invention, after obtaining polyamic acid slurry, the polyamic acid slurry is heat-treated, flexibility is obtained
Display base plate material.
In the present invention, the temperature of the heat treatment is preferably 50~400 DEG C, and more preferably 200~300 DEG C.In the present invention,
The time of the heat treatment is preferably 5~300 minutes, and more preferably 10~120 minutes.Polyamides through Overheating Treatment, in slurry
Amino acid forms polyimides, meanwhile, nanoscale twins are dispersed in polyimide matrix, to be formed polyimide-based compound
Material.In the present invention, the polyamides formed in the additive amount of nanometer sheet and gained flexible display substrates material in nano dispersion fluid is sub-
The mass ratio of amine is preferably (0.1~20): 100, more preferably (0.2~10): 100, further preferably (0.5~5): 100.
Wherein, shown in the forming process of polyimides such as reaction equation (9):
In the present invention, before being heat-treated to polyamic acid slurry, preferably first slurry is coated on substrate, then again
It is heat-treated, after heat treatment, obtained composite material is in film-form, i.e. polyimides based coextruded film.Gained film tool
There are high water oxygen barrier property, high-fire resistance, low thermal coefficient of expansion and high transparency, can be applied to the base of Flexible Displays and flexible touch-control
Plate material.
The present invention also provides flexible display substrates materials made from preparation method described in a kind of above-mentioned technical proposal.Institute
Obtaining flexible display substrates material has high water oxygen barrier property, high-fire resistance, low thermal coefficient of expansion and high transparency etc., can be preferable
Be applied to Flexible Displays and flexible touch-control field.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.In following embodiment, all raw materials are commercially available, wherein magnalium hydrotalcite is provided by Aldrich, interlamellar spacing
For 0.76nm.In following embodiment and comparative example, gained Polyimide based films material with a thickness of 25 microns.
In following embodiment and comparative example, the test equipment and condition be tested for the property to sample is as follows:
1. Wide angle X-ray diffraction is tested: Bruker D8Advance, CuK α line, 40kV, 200mA, wavelength 0.154nm.
2. bulk viscosity: Ubbelohde viscometer, concentration 0.5g/dl, solvent DMAC, 30 DEG C of temperature.
3. rotary viscosity: Digital Viscometer, room temperature.
4. thermal expansion coefficient (CTE): being carried out using Thermo plas TMA thermomechanical analyzer (TMA, TA company Q400)
Test；Test condition: 10 DEG C/min, 100~300 DEG C of sections.
5. extension test: NSTRON-1121 type electronic universal tester, rate of extension 5mm/min.
6. water vapor transmittance: Perme W3/030 water vapor permeation rate tester.
7. OTR oxygen transmission rate: Labthink, VAC-V2 gas permeation test instrument.
8. optical transmittance: Shimadzu Uv-2550 uv-vis spectra tester.
9. glass transition temperature (Tg): dynamic thermal mechanical properties analyzer, Rheometric Scientific Inc,
The rate of heat addition 2 DEG C/min, frequency 1Hz.
Embodiment 1
Be added in the ethylene glycol (100mL) hydroxybutyric acid (2.29g, 0.022mol) and magnalium hydrotalcite (6.04g,
0.01mol), 130 DEG C are heated to, 12h is reacted.Later, solid matter, drying are filtered out, hydroxybutyric acid intercalation modification water is obtained
Talcum, yield 98%.Wide angle X-ray diffraction test is carried out to gained sample, as a result as shown in FIG. 1, FIG. 1 is in embodiment 1
The x-ray diffraction pattern of the hydrotalcite of hydroxybutyric acid intercalation modification.As can be seen that have obvious characteristic peak at 2 θ=6.0 °, in conjunction with
Bragg equation calculation goes out its interlamellar spacing and is extended to 1.47nm.
Gained hydroxybutyric acid intercalation modification hydrotalcite (0.11g) is added in n,N-dimethylacetamide (20.0g), room
Warm ultrasound 3h, obtains the hydrotalcite nano piece dispersion liquid of removing dispersion.2,2 '-two (trifluoromethyls)-are added into this dispersion liquid
4,4 '-benzidines (3.20g, 10.0mmol) and hexafluorodianhydride (6FDA) (4.44g, 10.0mmol), are stirred at room temperature 24 hours, obtain
Polymeric solution.After tested, the bulk viscosity of the solution is 1.0dL/g, and rotary viscosity is 16 × 105cP.The solution is coated on
Glass surface is placed in baking oven and heats, and is heated to 300 DEG C, is heat-treated 120 minutes, obtains the transparent polyamides of high barrier
Imines based film material.
Embodiment 2
Be added in the ethylene glycol (100mL) 4-HBA (3.18g, 0.023mol) and magnalium hydrotalcite (6.04g,
0.01mol), 160 DEG C are heated to, 12h is reacted.Later, solid matter, drying are filtered out, 4-HBA intercalation is obtained and repairs
Adorn hydrotalcite, yield 97%.Wide angle X-ray diffraction test is carried out to gained sample, as a result as shown in Fig. 2, Fig. 2 is embodiment
The x-ray diffraction pattern for the hydrotalcite that 4-HBA intercalation is modified in 2.As can be seen that having obvious characteristic at 2 θ=9.6 °
Peak goes out its interlamellar spacing in conjunction with Bragg equation calculation and is extended to 0.89nm.
Gained 4-HBA intercalation modification hydrotalcite (0.08g) is added to N,N-dimethylformamide (19.0g)
In, room temperature ultrasound 2h obtains the hydrotalcite nano piece dispersion liquid of removing dispersion.1,4- diamino hexamethylene is added into this dispersion liquid
Alkane (1.14g, 10.0mmol) and hexafluorodianhydride (6FDA) (4.44g, 10.0mmol), are stirred at room temperature 24 hours, obtain polymeric solution.Through surveying
Examination, the bulk viscosity of the solution are 1.1dL/g, and rotary viscosity is 18 × 105cP.The solution is coated on glass surface, is placed
Heat in baking oven, be heated to 300 DEG C, is heat-treated 120 minutes, obtains high barrier clear polyimides base film material
Material.
Embodiment 3
4- hydroxyl phthalic (2.73g, 0.015mol) and magnalium hydrotalcite are added in benzylalcohol (100mL)
(6.04g, 0.01mol) is heated to 140 DEG C, reacts 12h.Later, solid matter, drying are filtered out, 4- hydroxyl neighbour benzene two is obtained
The hydrotalcite of formic acid intercalation modification, yield 95%.Wide angle X-ray diffraction test is carried out to gained sample, as a result such as Fig. 3 institute
Show, Fig. 3 is the x-ray diffraction pattern of the hydrotalcite of 4- hydroxyl phthalic intercalation modification in embodiment 3.As can be seen that in 2 θ
There is obvious characteristic peak at=10.4 °, goes out its interlamellar spacing in conjunction with Bragg equation calculation and be extended to 0.85nm.
Gained 4- hydroxyl phthalic intercalation modification hydrotalcite (0.12g) is added to DMAC N,N' dimethyl acetamide
In (16g), room temperature ultrasound 1h obtains the nanometer sheet dispersion liquid of removing dispersion.4,4 '-diamino union IIs are added into this dispersion liquid
Hexamethylene (1.96g, 10.0mmol) and cyclohexanetetracarboxylic acid dianhydride (2.24g, 10.0mmol), are stirred at room temperature 24 hours, obtain
Mixed solution.After tested, the bulk viscosity of the mixed solution is 1.2dL/g, and rotary viscosity is 15 × 105cP.The mixing is molten
Liquid is coated on glass surface, is placed in baking oven and heats, and is heated to 400 DEG C, is heat-treated 120 minutes, obtains high barrier
Clear polyimides based film material.
Embodiment 4
Be added in the ethylene glycol (100mL) citric acid (2.30g, 0.012mol) and magnalium hydrotalcite (6.04g,
0.01mol), 130 DEG C are heated to, 12h is reacted.Later, solid matter, drying are filtered out, the water of citric acid intercalation modification is obtained
Talcum, yield 94%.Wide angle X-ray diffraction test is carried out to gained sample, as a result as shown in figure 4, Fig. 4 is in embodiment 4
The x-ray diffraction pattern of the hydrotalcite of citric acid intercalation modification.As can be seen that have obvious characteristic peak at 2 θ=7.2 °, in conjunction with
Bragg equation calculation goes out its interlamellar spacing and is extended to 1.23nm.
Gained citric acid intercalation modification hydrotalcite (0.16g) is added in n,N-dimethylacetamide (20g), room temperature is super
Sound 1h obtains the nanometer sheet dispersion liquid of removing dispersion.Two (4- amino -2- tri fluoromethy I-phenoxies) are added into this dispersion liquid
Diphenyl sulphone (DPS) (5.68g, 10.0mmol) and cyclobutane tetracarboxylic dianhydride (1.96g, 10.0mmol), are stirred at room temperature 24 hours, obtain
Mixed solution.After tested, the bulk viscosity of the mixed solution is 1.2dL/g, and rotary viscosity is 18 × 105cP.The mixing is molten
Liquid is coated on glass surface, is placed in baking oven and heats, and is heated to 300 DEG C, is heat-treated 120 minutes, obtains high barrier
Clear polyimides based film material.
Embodiment 5
Be added in the water (100mL) perfluoro octyl sulfonic acid potassium (12.9g, 0.024mol) and magnalium hydrotalcite (6.04g,
0.01mol), 100 DEG C are heated to, 12h is reacted.Later, solid matter, drying are filtered out, perfluoro octyl sulfonic acid potassium intercalation is obtained
The hydrotalcite of modification, yield 96%.Wide angle X-ray diffraction test is carried out to gained sample, as a result as shown in figure 5, Fig. 5 is real
Apply the x-ray diffraction pattern for the hydrotalcite that perfluoro octyl sulfonic acid potassium intercalation is modified in example 5.As can be seen that having at 2 θ=3.5 ° bright
Aobvious characteristic peak, goes out its interlamellar spacing in conjunction with Bragg equation calculation and is extended to 2.59nm.
Gained citric acid intercalation modification hydrotalcite (0.15g) is added in N-Methyl pyrrolidone (18g), room temperature ultrasound
1h obtains the nanometer sheet dispersion liquid of removing dispersion.(the 4- aminophenyl hexafluoropropane of 2,2- bis- is added into this dispersion liquid
(3.34g, 10.0mmol) and connection cyclopentanetetracarboxylic's dianhydride (3.06g, 10.0mmol), is stirred at room temperature 24 hours, is mixed
Solution.After tested, the bulk viscosity of the mixed solution is 1.3dL/g, and rotary viscosity is 18 × 105cP.The mixed solution is applied
It is overlying on glass surface, is placed in baking oven and heats, is heated to 400 DEG C, is heat-treated 120 minutes, it is transparent to obtain high barrier
Polyimide based films material.
Embodiment 6
4- trifluoromethylbenzoic acid is added in the mixed solvent (ethylene glycol 80mL, water 20mL) of ethylene glycol and water
(4.18g, 0.022mol) and magnalium hydrotalcite (6.04g, 0.01mol) is heated to 140 DEG C, reacts 12h.Later, it filters out solid
Body substance, drying, obtain the hydrotalcite of 4- trifluoromethylbenzoic acid intercalation modification, yield 92%.Gained sample is carried out wide
Angle X-ray diffraction test, as a result as shown in fig. 6, Fig. 6 is the hydrotalcite of 4- trifluoromethylbenzoic acid intercalation modification in embodiment 6
X-ray diffraction pattern.As can be seen that there is obvious characteristic peak at 2 θ=10.8 °, go out its interlamellar spacing in conjunction with Bragg equation calculation
It is extended to 0.82nm.
Gained 4- trifluoromethylbenzoic acid intercalation modification hydrotalcite (0.13g) is added to N-Methyl pyrrolidone (17g)
In, room temperature ultrasound 1h obtains the nanometer sheet dispersion liquid of removing dispersion.Two (4- amino -2- fluoroforms are added into this dispersion liquid
Base-phenoxy group) benzene (4.28g, 10.0mmol) and bicyclic (2,2,1) heptane -2,3,4,6- tetracarboxylic dianhydrides (2.36g,
10.0mmol), it is stirred at room temperature 24 hours, obtains mixed solution.After tested, the bulk viscosity of the mixed solution is 1.3dL/g, rotation
Turning viscosity is 18 × 105cP.The mixed solution is coated on glass surface, is placed in baking oven and heats, be heated to 400
DEG C, it is heat-treated 120 minutes, obtains high barrier clear polyimides based film material.
Embodiment 7
Be added in the water (100mL) sodium trifluoroacetate (3.3g, 0.022mol) and magnalium hydrotalcite (6.04g,
0.01mol), 100 DEG C are heated to, 12h is reacted.Later, solid matter, drying are filtered out, the modification of trifluoroacetic acid intercalation is obtained
Hydrotalcite, yield 95%.Wide angle X-ray diffraction test is carried out to gained sample, as a result as shown in fig. 7, Fig. 7 is embodiment 7
The x-ray diffraction pattern of the hydrotalcite of middle trifluoroacetic acid intercalation modification.As can be seen that there is obvious characteristic peak at 2 θ=4.6 °, tie
Conjunction Bragg equation calculation goes out its interlamellar spacing and is extended to 1.92nm.
Gained trifluoroacetic acid intercalation modification hydrotalcite (0.20g) is added in N-Methyl pyrrolidone (19g), room temperature is super
Sound 1h obtains the nanometer sheet dispersion liquid of removing dispersion.2,2- bis- (4- (4- amino-benzene oxygen) phenyl) is added into this dispersion liquid
Hexafluoropropane (5.18g, 10.0mmol) and bicyclic (2,2,2) octane -2,3,4,6- tetracarboxylic dianhydrides (2.50g, 10.0mmol),
It is stirred at room temperature 24 hours, obtains mixed solution.After tested, the bulk viscosity of the mixed solution is 1.5dL/g, rotary viscosity 17
×105cP.The mixed solution is coated on glass surface, is placed in baking oven and heats, is heated to 400 DEG C, heat treatment 120
Minute, obtain high barrier clear polyimides based film material.
Embodiment 8
Thermal expansion coefficient CTE, optical transmittance, the water of 1~7 gained Polyimide based films material of testing example respectively
Oxygen barrier performance, toughness and glass transition temperature Tg, test result is referring to table 3.
The performance test results of 3 Examples 1 to 7 of table
As 3 test result of table it is found that polyimide-based composite material made from preparation method according to the invention have compared with
Low thermal expansion coefficient (being below 20ppm/ DEG C), shows material dimensional stability with higher, can satisfy Flexible Displays
Primary demand.And resulting materials have high optical transmittance, it was demonstrated that material has the high grade of transparency.Meanwhile material have compared with
Low water oxygen transmitance, it was demonstrated that material water oxygen barrier property with higher.Material tensile strength also with higher and stretching die
Amount, it was demonstrated that material flexibility with higher can satisfy the demand of flexible display material.In addition, the glass transition of material
Temperature is higher than 250 DEG C, it was demonstrated that material has high-fire resistance.It follows that material made from preparation method according to the invention is simultaneous
Have the excellent properties such as low-expansion coefficient, the high grade of transparency, high water oxygen barrier property, high tenacity and high-fire resistance.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments
A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article
It encloses.
Claims (10)
1. a kind of preparation method of high barrier transparent flexible display base plate material, which comprises the following steps:
A) anionic two-dimensional layer material is heated in a solvent with organic intercalation agent and is reacted, obtain the layer of organic intercalation modification
Shape material；
B) stratified material for modifying the organic intercalation carries out lift-off processing in a solvent, obtains nanometer sheet dispersion liquid；
C) nanometer sheet dispersion liquid is mixed to the polymerized monomer of polyimides and carried out home position polymerization reaction, obtain polyamide
Wintercherry material；
D) the polyamic acid slurry is heat-treated, obtains flexible display substrates material；
The anionic two-dimensional layer material is one of binary metal hydroxide and mixed metal hydroxide or several
Kind；
The organic intercalation agent is selected from organic carboxyl acid, organic sulfonic acid, the metal salt of the organic carboxyl acid and the organic sulfonic acid
One or more of metal salt.
2. preparation method according to claim 1, which is characterized in that the organic carboxyl acid is selected from the aliphatic of C1~C22
Monocarboxylic acid, the aliphatic dicarboxylic acid of C1~C26, the aliphatic tricarboxylic acid of C1~C40, aromatic series monocarboxylic acid, fragrance
One or more of race's dicarboxylic acids and aromatic series tricarboxylic acid；
The organic sulfonic acid is selected from one or more of aliphatic unitary sulfonic acid and aromatic series unitary sulfonic acid of C1~C22.
3. preparation method according to claim 1 or 2, which is characterized in that the organic carboxyl acid is selected from formula (1-1) shownization
Close compound shown in compound shown in object, formula (1-2), compound, formula (1-4) shown in formula (1-3), compound shown in formula (1-5)
One or more of with compound shown in formula (1-6)；
Wherein, n1For 0~20, n2For 0~10, n3For 0~10, n4For 0~10, n5For 0~10, n6It is 0~10；
R、R1、R2、R3、R4、R5、R6、R7、R8、R1、R2And R3It is each independently selected from hydrogen, alkyl, aryl, fluoroalkyl, hydroxyl, alkane
Oxygroup, phenoxy group, cyano, nitro, amino, acetylamino, ester group, acyl group, halogen or carboxyl；
The organic sulfonic acid is selected from one or more of compound shown in compound shown in formula (2-1) and formula (2-2)；
Wherein, n is 0~20；
R9And R4Be each independently selected from hydrogen, alkyl, aryl, fluoroalkyl, hydroxyl, alkoxy, phenoxy group, cyano, nitro, amino,
Acetylamino, ester group, acyl group, halogen or carboxyl；
Metal ion in the metal salt of the organic carboxyl acid is selected from monovalence alkali metal ion or divalent alkali metal ion；
Metal ion in the metal salt of the organic sulfonic acid is selected from monovalence alkali metal ion or divalent alkali metal ion.
4. preparation method according to claim 3, which is characterized in that in the organic carboxyl acid, n1For 1~10, n2For 0~
6, n3For 0~6, n4For 0~6, n5For 0~6, n6It is 0~6；
R、R1、R2、R3、R4、R5、R6、R7、R8、R1、R2And R3It is each independently selected from hydrogen, hydroxyl, alkoxy, phenoxy group or fluothane
Base；
In the organic sulfonic acid, n is 0~16；R9And R4It is each independently selected from hydrogen, hydroxyl, alkoxy, phenoxy group or fluoroalkyl；
Metal ion in the metal salt of the organic carboxyl acid is selected from Na+、K+Or Mg2+；
Metal ion in the metal salt of the organic sulfonic acid is selected from Na+、K+Or Mg2+。
5. preparation method according to claim 1 or 4, which is characterized in that the organic carboxyl acid is selected from hydroxyacetic acid, hydroxyl
Butyric acid, citric acid, tartaric acid, trifluoroacetic acid, benzoic acid, phthalic acid, M-phthalic acid, trifluoromethylbenzoic acid, hydroxyl
Benzoic acid, dihydroxy-benzoic acid, methoxy benzoic acid, dimethoxybenzoic acid, phenoxy benzoic acid, two phenoxy benzoic acids,
Two (trifluoromethyl) benzoic acid, hydroxyl phthalic, trifluoromethyl phthalic acid, methoxyl group phthalic acid, methoxyl group
M-phthalic acid, phenoxy group phthalic acid, phenoxy group M-phthalic acid, Hydroxy M Phthalic Acid and trifluoromethyl isophthalic diformazan
One or more of acid；
The organic sulfonic acid is selected from dodecyl sodium sulfonate, perfluoro octyl sulfonic acid, perfluoro butyl sulfonic acid, benzene sulfonic acid, detergent alkylate
One or more of sulfonic acid and hydroxy benzene sulfonic acid.
6. preparation method according to claim 1, which is characterized in that in the anionic two-dimensional layer material, at least
A kind of metal is divalent metal, and at least one metal is trivalent metal；
The divalent metal is selected from Mg2+、Zn2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Ca2+Or Cd2+；
The trivalent metal is selected from Al3+、Co3+、Fe3+、Mn3+、Cr3+Or Ga3+；
The anion of interlayer is selected from NO3-、Cl-、SO4 2-Or CO3 2-。
7. preparation method according to claim 1 or 6, which is characterized in that the anionic two-dimensional layer material is magnesium
Aluminum hydrotalcite, the anion of interlayer are CO3 2-。
8. preparation method according to claim 1, which is characterized in that in the step a), organic intercalation agent and anion
The molar ratio of type two-dimensional layer material is (0.5~4.0): 1；
Nanometer sheet in step c) in nanometer sheet dispersion liquid and the polyimides in flexible display substrates material obtained by step c)
Mass ratio is (0.1~20): 100.
9. preparation method according to claim 1, which is characterized in that in the step b), the lift-off processing includes stirring
Mix processing or ultrasonic treatment；
The revolving speed of the stir process is 200~2000 revs/min, and the time is 10~30h, and temperature is 50~120 DEG C；
The power of the ultrasonic treatment is 50~500W, and the time is 0.5~3h；
In the step c), the temperature of home position polymerization reaction is 0~50 DEG C, and the time is 1~72 hour；
The polymerized monomer of the polyimides includes dianhydride and diamines.
10. flexible display substrates material made from a kind of preparation method according to any one of claims 1 to 9.
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|---|---|---|---|---|
| CN110581059A (en) * | 2019-08-13 | 2019-12-17 | 福建华佳彩有限公司 | preparation method of flexible composite substrate film |
| CN111925643A (en) * | 2020-08-18 | 2020-11-13 | 上海蒂姆新材料科技有限公司 | High-water-oxygen-barrier waterborne polyurethane, preparation method thereof and bi-component polyurethane adhesive |
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| CN106519229A (en) * | 2016-11-16 | 2017-03-22 | 陕西品达石化有限公司 | Preparation method of polyimide nano composite material |
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| CN106519229A (en) * | 2016-11-16 | 2017-03-22 | 陕西品达石化有限公司 | Preparation method of polyimide nano composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110581059A (en) * | 2019-08-13 | 2019-12-17 | 福建华佳彩有限公司 | preparation method of flexible composite substrate film |
| CN111925643A (en) * | 2020-08-18 | 2020-11-13 | 上海蒂姆新材料科技有限公司 | High-water-oxygen-barrier waterborne polyurethane, preparation method thereof and bi-component polyurethane adhesive |
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| CN108997753B (en) | 2020-11-13 |
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