CN108948354A - Modified polyimide resin and preparation method thereof and application - Google Patents
Modified polyimide resin and preparation method thereof and application Download PDFInfo
- Publication number
- CN108948354A CN108948354A CN201710386970.3A CN201710386970A CN108948354A CN 108948354 A CN108948354 A CN 108948354A CN 201710386970 A CN201710386970 A CN 201710386970A CN 108948354 A CN108948354 A CN 108948354A
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- China
- Prior art keywords
- modified
- polyimide resin
- substrate
- preparation
- flexible display
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
Abstract
The present invention relates to a kind of modified polyimide resin and preparation method thereof and applications.The preparation method of above-mentioned modified polyimide resin obtains prepolymer polyamic acid the following steps are included: by dianhydride and diamines progress pre-polymerization；By the material copolymerization of prepolymer polyamic acid and synthesis bismaleimide-triazine resin, modified prepolymers are obtained；And solidify modified prepolymers, obtain modified polyimide resin.In the preparation method of the substrate of above-mentioned flexible display, on the one hand, the features such as remaining the heat resistance and good mechanical property, dielectric properties, humidity resistance, radiation resistance, machining property of polyimide resin；On the other hand, there is tridimensional network after modification by copolymerization, when being used as the substrate of flexible display, is able to ascend the smooth and stability of substrate, it is not easy to which warpage avoids influencing packages and devices characteristic, is conducive to apply.
Description
Technical field
The present invention relates to flexible display field, more particularly to a kind of modified polyimide resin and preparation method thereof,
And application.
Background technique
In recent years, flexible display becomes the research hotspot of domestic and international each colleges and universities and research institution.Flexible display is by soft
Soft material is made, and has the characteristics that low-power consumption, directly visual flexible panel, is a kind of flexible display device of changeable type.
Compared to traditional monitor, flexible display it is with the obvious advantage, it is not only more frivolous in volume, also below original device in power consumption
Part facilitates the cruising ability of lifting means, while characteristic flexible based on its, that flexibility is good, and robustness is also significantly
Higher than previous screen, the probability of equipment accidental injury can reduce.
Polyimides (PI) resin is due to excellent heat resistance and good mechanical property, dielectric properties, wet-heat resisting
The features such as property, radiation resistance, machining property, therefore it is often used as the substrate of flexible display.However, traditional being used as is flexible aobvious
Show that the polyimide resin substrate of device is easy to warpage, influences packages and devices characteristic.
Summary of the invention
Based on this, it is necessary to be easy asking for warpage for traditional polyimide resin substrate as flexible display
Topic, be not easy when a kind of substrate as flexible display is provided modified polyimide resin of warpage and preparation method thereof, with
And application.
A kind of preparation method of modified polyimide resin, comprising the following steps:
Dianhydride and diamines are subjected to pre-polymerization, obtain prepolymer polyamic acid；
By the material copolymerization of the prepolymer polyamic acid and synthesis bismaleimide-triazine resin, modified pre-polymerization is obtained
Object；
The modified prepolymers are solidified, modified polyimide resin is obtained.
In the preparation method of the substrate of above-mentioned flexible display, on the one hand, remain polyimide resin heat resistance and
The features such as good mechanical property, dielectric properties, humidity resistance, radiation resistance, machining property；On the other hand, modification by copolymerization
There is tridimensional network later, when being used as the substrate of flexible display, be able to ascend the smooth and stability of substrate, do not allow
Easy warpage avoids influencing packages and devices characteristic, is conducive to apply.
The molar ratio of the dianhydride and the diamines is 1:1 in one of the embodiments,.
Temperature when dianhydride and diamines being carried out pre-polymerization in one of the embodiments, is 70 DEG C~120 DEG C.
The raw material of the synthesis bismaleimide-triazine resin includes bismaleimide in one of the embodiments,
Amine, triazine and modified component, the modified component include polyphenylene oxide resin or allyl compound and epoxy resin.
The temperature when modified prepolymers being solidified in one of the embodiments, is 150 DEG C~190 DEG C.
A kind of modified polyimide resin is also provided, is prepared into using the preparation method of above-mentioned modified polyimide resin
It arrives.
In above-mentioned modified polyimide resin, on the one hand, remain polyimide resin heat resistance and good mechanics
The features such as performance, dielectric properties, humidity resistance, radiation resistance, machining property；On the other hand, have three after modification by copolymerization
Reticular structure is tieed up, when being used as the substrate of flexible display, is able to ascend the smooth and stability of substrate, it is not easy to which warpage is kept away
Exempt to influence packages and devices characteristic, is conducive to apply.
A kind of substrate of flexible display is also provided, the material of the substrate of the flexible display is above-mentioned modification polyamides
Imide resin.
When above-mentioned modified polyimide resin is used as the substrate of flexible display, on the one hand, remain polyimides tree
The features such as heat resistance of rouge and good mechanical property, dielectric properties, humidity resistance, radiation resistance, machining property；Another party
Face has tridimensional network after modification by copolymerization, when being used as the substrate of flexible display, be able to ascend the smooth of substrate and
Stability, it is not easy to which warpage avoids influencing packages and devices characteristic, is conducive to apply.
In addition, also providing a kind of preparation method of the substrate of flexible display, comprising the following steps:
Dianhydride and diamines are subjected to pre-polymerization, obtain soluble prepolymer polyamic acid；
By the material copolymerization of the prepolymer polyamic acid and synthesis bismaleimide-triazine resin, modified pre-polymerization is obtained
Object；
Substrate is provided；
The modified prepolymers are formed a film on the substrate, are solidified on the substrate later, flexible display is obtained
Substrate.
In the preparation method of the substrate of above-mentioned flexible display, on the one hand, remain polyimide resin heat resistance and
The features such as good mechanical property, dielectric properties, humidity resistance, radiation resistance, machining property；On the other hand, modification by copolymerization
There is tridimensional network later, when being used as the substrate of flexible display, be able to ascend the smooth and stability of substrate, do not allow
Easy warpage avoids influencing packages and devices characteristic, is conducive to apply.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with specific embodiment,
The present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are only used to explain this hair
It is bright, it is not intended to limit the present invention.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more
Any and all combinations of relevant listed item.
Traditional polyimides (PI) resin base as flexible display is easy to warpage, influences packages and devices spy
Property, it is a very stubborn problem that this is in the field of business.The present inventor has found after study: this is because the change of PI resin
Learning in structure does not have tridimensional network, and the chemical structure of PI resin is as follows:
Usually there is certain shrinking percentage after curing molding, and after subsequent PI resin and glass substrate removing, glass substrate
Also there is different shrinking percentages with PI resin.This causes PI resin base that apparent warpage can occur, and influences packages and devices
Characteristic.
For this purpose, the present invention provides a kind of preparation method of modified polyimide resin, traditional it is used as flexibility to solve
The polyimide resin substrate of display is easy the problem of warpage.
The preparation method of the modified polyimide resin of one embodiment, comprising the following steps:
S10, dianhydride and diamines are subjected to pre-polymerization, obtain prepolymer polyamic acid.
Dianhydride and diamines are subjected to low temperature pre-polymerization in polar solvent (such as DMF).Preferably, dianhydride and diamines are carried out pre-
Temperature when poly- is 70 DEG C~120 DEG C.
Preferably, the molar ratio of dianhydride and diamines is 1:1.
S20, by the material copolymerization of prepolymer polyamic acid and synthesis bismaleimide-triazine resin, obtain modified pre-polymerization
Object.
Preferably, the raw material for synthesizing bismaleimide-triazine resin includes bismaleimide, triazine and modified component,
Modified component includes polyphenylene oxide resin or allyl compound and epoxy resin.
Obtained modified prepolymers have certain viscosity and molecular weight larger.
S30, modified prepolymers are solidified, obtains modified polyimide resin.
Modified-reaction equation is as follows:
In resin curing process, since solidification temperature will affect the internal stress and shrinking percentage of resin, so establishing with lower section
Method: it using the method for Michelson interferometer measurement residual stress, can be accurately calculated using the interference fringe collected
Micro-structure from the deformation of face direction, and then obtain residual stress, by the method, the modified resin for acquiring different material ratio exists
The residual stress of PI Modified Membrane after forming under different solidification temperatures obtains most preferably modified proportion and solidification temperature, obtains remnants
Stress is minimum, the smallest scheme of warpage degree.
Preferably, temperature when modified prepolymers being solidified is 150 DEG C~190 DEG C.Further, since small molecule chain extender
(small molecule polyols of 2 or more degrees of functionality of connection polyamic acid carboxyl end group (R-COOH) and terminal isocyanate groups (NCO))
In the presence of removing solvent cures at 150 DEG C~190 DEG C, thermal expansion coefficient (CTE, Coefficient Of can be obtained
Thermal Expansion) and the lower modified PI substrate of angularity.Wherein, CTE can be down to 3ppm/ DEG C~7ppm/ DEG C.
Using the method for above-mentioned Michelson interferometer measurement residual stress, obtained best curing temperature is 150 DEG C.
Due in the preparation method of above-mentioned modified polyimide resin, on the one hand, remain the heat-resisting of polyimide resin
The features such as property and good mechanical property, dielectric properties, humidity resistance, radiation resistance, machining property；On the other hand, it is copolymerized
There is tridimensional network after modified, when being used as the substrate of flexible display, be able to ascend the smooth and stability of substrate,
It is not easy warpage, avoids influencing packages and devices characteristic, be conducive to apply.
The modified polyimide resin of one embodiment is prepared using the preparation method of above-mentioned modified polyimide resin
It obtains.
In above-mentioned modified polyimide resin, on the one hand, remain polyimide resin heat resistance and good mechanics
The features such as performance, dielectric properties, humidity resistance, radiation resistance, machining property；On the other hand, have three after modification by copolymerization
Reticular structure is tieed up, when being used as the substrate of flexible display, is able to ascend the smooth and stability of substrate, it is not easy to which warpage is kept away
Exempt to influence packages and devices characteristic, is conducive to apply.
The substrate of the flexible display of one embodiment.The material of the substrate of above-mentioned flexible display is poly- for above-mentioned modification
Imide resin.
Preferably, flexible display OLED.More preferably, flexible display AMOLED.
When above-mentioned modified polyimide resin is used as the substrate of flexible display, on the one hand, remain polyimide resin
Heat resistance and good mechanical property, dielectric properties, humidity resistance, radiation resistance, machining property the features such as；Another party
Face has tridimensional network after modification by copolymerization, when being used as the substrate of flexible display, be able to ascend the smooth of substrate and
Stability, it is not easy to which warpage avoids influencing packages and devices characteristic, is conducive to apply.
The preparation method of the substrate of the flexible display of one embodiment, comprising the following steps:
S100, dianhydride and diamines are subjected to pre-polymerization, obtain prepolymer polyamic acid.
Dianhydride and diamines are subjected to low temperature pre-polymerization in polar solvent such as DMF.Preferably, dianhydride and diamines are subjected to pre-polymerization
When temperature be 70 DEG C~120 DEG C.
S200, by the material copolymerization of prepolymer polyamic acid and synthesis bismaleimide-triazine resin, obtain modified pre-
Polymers.
S300, substrate is provided.
S400, modified prepolymers are formed a film on substrate, is solidified on substrate later, obtain the substrate of flexible display.
Preferably, temperature when modified prepolymers being solidified is 150 DEG C~190 DEG C.Due to the presence of small molecule chain extender,
In 150 DEG C~190 DEG C removing solvent cures, the modification PI substrate of low CTE and low warpage can be obtained.
In the preparation method of the substrate of above-mentioned flexible display, on the one hand, remain polyimide resin heat resistance and
The features such as good mechanical property, dielectric properties, humidity resistance, radiation resistance, machining property；On the other hand, modification by copolymerization
There is tridimensional network later, when being used as the substrate of flexible display, be able to ascend the smooth and stability of substrate, do not allow
Easy warpage avoids influencing packages and devices characteristic, is conducive to apply.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (8)
1. a kind of preparation method of modified polyimide resin, which comprises the following steps:
Dianhydride and diamines are subjected to pre-polymerization, obtain prepolymer polyamic acid；
By the material copolymerization of the prepolymer polyamic acid and synthesis bismaleimide-triazine resin, modified prepolymers are obtained；
The modified prepolymers are solidified, modified polyimide resin is obtained.
2. the preparation method of modified polyimide resin according to claim 1, which is characterized in that the dianhydride with it is described
The molar ratio of diamines is 1:1.
3. the preparation method of modified polyimide resin according to claim 1, which is characterized in that by dianhydride and diamines into
Temperature when row pre-polymerization is 70 DEG C~120 DEG C.
4. the preparation method of modified polyimide resin according to claim 1, which is characterized in that the synthesis span comes
The raw material of acid imide cyanate resin includes bismaleimide, triazine and modified component, and the modified component includes polyphenylene oxide tree
Rouge or allyl compound and epoxy resin.
5. the preparation method of modified polyimide resin according to claim 1, which is characterized in that by the modified pre-polymerization
Temperature when object solidifies is 150 DEG C~190 DEG C.
6. a kind of modified polyimide resin, which is characterized in that gathered using such as modification according to any one of claims 1 to 5
The preparation method of imide resin is prepared.
7. a kind of substrate of flexible display, which is characterized in that the material of the substrate of the flexible display is such as claim 6
The modified polyimide resin.
8. a kind of preparation method of the substrate of flexible display, which comprises the following steps:
Dianhydride and diamines are subjected to pre-polymerization, obtain prepolymer polyamic acid；
By the material copolymerization of the prepolymer polyamic acid and synthesis bismaleimide-triazine resin, modified prepolymers are obtained；
Substrate is provided；
The modified prepolymers are formed a film on the substrate, are solidified on the substrate later, the base of flexible display is obtained
Bottom.
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| CN201710386970.3A CN108948354A (en) | 2017-05-26 | 2017-05-26 | Modified polyimide resin and preparation method thereof and application |
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| CN201710386970.3A CN108948354A (en) | 2017-05-26 | 2017-05-26 | Modified polyimide resin and preparation method thereof and application |
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Application publication date: 20181207 |