CN110078920A - The preparation method and display device of modified polyimide, alignment films - Google Patents
The preparation method and display device of modified polyimide, alignment films Download PDFInfo
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- CN110078920A CN110078920A CN201910365987.XA CN201910365987A CN110078920A CN 110078920 A CN110078920 A CN 110078920A CN 201910365987 A CN201910365987 A CN 201910365987A CN 110078920 A CN110078920 A CN 110078920A
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- modified polyimide
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 239000004642 Polyimide Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- -1 aliphatic diamine Chemical class 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 44
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000007774 anilox coating Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
Classifications
-
- 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
- C08G73/1075—Partially aromatic polyimides
-
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to display field more particularly to the preparation methods and display device of modified polyimide, alignment films.Modified polyimide of the invention, including polyimides main chain, and graft on the styrene performed polymer on the polyimides main chain or side chain；The styrene performed polymer is connect by bridging agent with the secondary carbon of the polyimides main chain or side chain.Modified polyimide of the invention, the diamine by being grafted with styrene prepolymer introduce polyimides main chain or side chain, can be used to form the alignment films of the biggish high intensity of cohesive energy.Include the diamine for being grafted with styrene prepolymer in the orientation liquid of preparation, increase intermolecular distance, and reduce molecule interchain active force, improve mobility, and is easy to coat the good alignment films of forming properties by ink-jet or roll-type.When the modified polyimide is used to form alignment films, alignment films film surface intensity and liquid crystal pretilt angle are improved, and reduce the production cost.
Description
Technical field
The present invention relates to display field more particularly to the preparation methods and display device of modified polyimide, alignment films.
Background technique
With social progress and development in science and technology, Thin Film Transistor-LCD (TFT-LCD) has become current era
The main product of display field plays the role of vital in industrial production, daily life.
Alignment films of polyimide film (PI) film as liquid crystal molecule, orientation and subsequent display to liquid crystal molecule are played
Vital effect.The quality of liquid crystal orientation film directly affects the arrangement effect of liquid crystal molecule, and the arrangement shadow of liquid crystal molecule
It rings contrast, threshold voltage, the response time etc. of liquid crystal display device, therefore the materialization of polyimide material selected by alignment films
It can be very crucial to liquid crystal display.
Polyimide material used in alignment films requires following characteristics: hydrolysis, high temperature resistant, mechanical property are strong, are orientated
The superperformance of stability is good, film-forming process is simple etc..And the acquisition of these superperformances needs polyimides to have foot
Enough molecular weight.
The preparation method of alignment film of polyimide is general are as follows: diamine and dibasic anhydride are formed into polyamic acid precursor liquid, it will
The forerunner is also coated on substrate, by solidification, obtains alignment films.If wanting to obtain the biggish alignment films of molecular weight, forerunner
The viscosity of liquid can correspondingly increase.The increase of viscosity is unfavorable for soaking and spread, the particularly disadvantageous coating procedure in precursor liquid.
Existing PI film coating equipment is mainly ink-jet application equipment (Inkjet Coater) and print roll coating equipment
(Roller Coater).It for ink-jet coating equipment, is coated with using piezoelectric ceramics using spraying method, before accurate control
It drives drop amount (about 70pL) to spray out of about 50 μm size diameter nozzles, it is solid that the nozzle diameter of 50 microns of sizes limits precursor liquid
Content (wt) range is 3%-5%, and when solid content is bigger than normal, macromolecular is gathered in nozzle and nozzle is caused not spue, does not spue
Cause the displays such as the black and white block of PI film surface exception.Precursor liquid molecular weight is low to be easy to cause PI film surface intensity low, is passing through inscription rubbing
When friction process, it be easy to cause the foreign matters badness such as broken bright spot (Zara, Particle).
For roller type coating apparatus, to be orientated on liquid even spread to anilox roll using high pressure, recycle APR impact transfer printing
Onto glass substrate, anilox roll and APR editions mesh depth, line number, running speed and product edge distance (EM) value etc. are determined
Forerunner's fluid viscosity cannot be low, and it is bad not so to will cause that precursor liquid coating (diffusion) is uneven and EM is excessive etc., but precursor liquid glues
It spends and needs ink tank (Ink Tank) N2 pressure excessive greatly, excessive pressure tank will cause boosting difficulty, flux modification fails,
The amount of dripping is abnormal and changes a series of problems, such as liquid is dangerous.
A kind of polyimides for the high intensity how to obtain high molecular weight using simple preparation method has very high reality
With value and economic benefit.
Summary of the invention
The technical problem to be solved by the present invention is providing the preparation method and display of a kind of modified polyimide, alignment films
Device；Modified polyimide of the invention, molecular weight with higher can be used to form alignment films of good performance, make simultaneously
During the standby alignment films, the orientation liquid intermolecular force of formation is small, and more liquid, viscosity is lower, is easy to pass through spray
Ink or roll-type coat to form film layer.
The invention discloses a kind of modified polyimides, including polyimides main chain, and graft on the polyimides
Styrene performed polymer on main chain or side chain；
The styrene performed polymer is connect by bridging agent with the secondary carbon of the polyimides main chain or side chain.
Preferably, the structural formula of the polyimides main chain are as follows:
Wherein, R1For any one in group shown in formula (II)~formula (X),
R2And R3It is respectively selected fromWithIn any one, 5≤n≤15；
The styrene performed polymer passes through bridging agent and R2Or R3Secondary carbon connection.
Preferably, the styrene performed polymer is linear molecule chain structure, and the styrene performed polymer number-average molecular weight is
200~1550000, molecular weight distribution index 1.
Preferably, styrene performed polymer mass percent shared in modified polyimide is 0.01~3wt%.
Preferably, the bridging agent is maleic anhydride.
The invention discloses a kind of alignment films, the modified polyimide as described in above-mentioned technical proposal forms film and makes
At.
The invention discloses a kind of preparation methods of alignment films, comprising the following steps::
Styrene performed polymer, maleic anhydride, aliphatic diamine and initiator are uniformly mixed in the first solvent, heating
After reaction, the aliphatic diamine for being grafted with styrene performed polymer is obtained；
The aliphatic diamine, dibasic anhydride and non-grafted diamine of being grafted with styrene performed polymer is molten second
Hybrid reaction in agent obtains orientation liquid；
The orientation liquid is coated on substrate, precuring and main solidification is successively carried out, obtains alignment films.
Preferably, the styrene performed polymer the preparation method comprises the following steps:
Styrene monomer is heated under the conditions of 10~200 DEG C, obtains styrene performed polymer.
Preferably, the orientation liquid is coated on substrate by way of ink-jet application or print roll coating.
The invention discloses a kind of display devices, including alignment films or above-mentioned technical proposal described in above-mentioned technical proposal
The alignment films of the method preparation.
Compared with prior art, modified polyimide of the invention, the diamine by being grafted with styrene prepolymer introduce
Polyimides main chain or side chain can be used to form the alignment films of the biggish high intensity of cohesive energy.In the process of preparation alignment films
In, include the diamine for being grafted with styrene prepolymer in the orientation liquid of formation, increases intermolecular distance, and reduce molecule interchain
Active force improves mobility, and is easy to coat the good alignment films of forming properties by ink-jet or roll-type.Further
Ground when the modified polyimide is used to form alignment films, improves alignment films film surface intensity and liquid crystal pretilt angle, and reduce
Cost of manufacture.
Detailed description of the invention
Fig. 1 is the flow chart that the embodiment of the present invention prepares alignment films.
Specific embodiment
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 limiting the invention.
Embodiment of the invention discloses a kind of modified polyimides, including polyimides main chain, and graft on described
Styrene performed polymer on polyimides main chain or side chain；
The styrene performed polymer is connect by bridging agent with the secondary carbon of the polyimides main chain or side chain.
The polystyrene performed polymer the preparation method comprises the following steps: styrene monomer by heat draw method occur polymerization reaction, i.e.,
It is reacted by 3 molecules, generates Diel-Alder intermediate by two styrene molecules, then generate freely with styrene monomer molecule
Base, rear to cause polymerization, styrene thermal polymerization carries out in pure liquid phase styrene, accelerates as the temperature rises, typical temperature
At 12 DEG C or more.The preparation of styrene performed polymer can also be polymerize by initiator, and single-initiator polymerization rate is fast, it is not easy to
The uniform performed polymer of molecular weight distribution is obtained, so this method uses thermal-initiated polymerization.It is as follows to polymerize principle:
(1) heat causes
(2) chain growth
The double bond that heat causes monomer radical second monomer molecule of opening generated forms new free radical, and new free radical is living
Property it is unattenuated, continue with the chain addition of styrene monomer.Mechanism is as follows:
Preferably, stating styrene performed polymer is linear molecule chain structure, and the styrene performed polymer number-average molecular weight is 200
~1550000, molecular weight distribution index 1.
The styrene performed polymer plays the role of external plasticizer in polyimides macromolecular, in addition styrene performed polymer
It can also play the role of improving liquid crystal pretilt angle.
The styrene performed polymer molecule is attached with polyimides macromolecular chain by following two mode:
(1) the styrene performed polymer living free radical graft is in the secondary carbon to polyimides main chain, so that styrene
Performed polymer is connected to the side of polyimides macromolecular chain in the form of branch；
(2) the styrene performed polymer living radical is integrated in the secondary carbon of polyimides side chain, so that styrene is pre-
Aggressiveness is connected to polyimides macromolecular chain side as branch.
The structural formula of the polyimides main chain is preferred are as follows:
Wherein, R1For any one in group shown in formula (II)~formula (X),
R2And R3It is respectively selected fromWithIn any one, 5≤n≤15；
The styrene performed polymer passes through bridging agent and R2Or R3Secondary carbon connection.
Wherein, m is the natural number greater than 0.
The bridging agent is preferably maleic anhydride, with the reacted rear formation of styrene performed polymer and diamine
Preferably, styrene performed polymer mass percent shared in modified polyimide is 0.01~3wt%.
Embodiment of the invention discloses a kind of alignment films, the modified polyimide as described in above-mentioned technical proposal forms thin
Film and be made.
Embodiment of the invention discloses a kind of preparation methods of alignment films, include the following steps, as shown in Figure 1:
Styrene performed polymer, maleic anhydride, aliphatic diamine and initiator are uniformly mixed in the first solvent, heating
After reaction, the aliphatic diamine for being grafted with styrene performed polymer is obtained；
The aliphatic diamine, dibasic anhydride and non-grafted diamine of being grafted with styrene performed polymer is molten second
Hybrid reaction in agent obtains poly- orientation liquid；
The orientation liquid is coated on substrate, precuring and main solidification is successively carried out, obtains alignment films.
The preparation method of alignment films is described in detail according to specific steps below:
S1: styrene performed polymer, maleic anhydride, aliphatic diamine and initiator are uniformly mixed in the first solvent,
After heating reaction, the aliphatic diamine for being grafted with styrene performed polymer is obtained.
Wherein, the preparation method of the styrene performed polymer is preferred are as follows:
Styrene monomer is heated under the conditions of 10~200 DEG C, obtains styrene performed polymer.
It is highly preferred that, according to heating time difference, obtaining number by styrene monomer in 100 DEG C of silicone oil oil bath and dividing equally
Son amount is 200~1550000, the polystyrene performed polymer that molecular weight distribution index is 1.
The aliphatic diamine is preferably straight chain or branched aliphatic diamine containing 5~15 carbon atoms.
The initiator is preferably cumyl peroxide (DCP), hydroquinone (HQ) and dibenzoyl peroxide (BPO)
In any one or more.
In this step, styrene performed polymer, maleic anhydride, aliphatic diamine occur anti-under the action of initiator
It answers, obtains the aliphatic diamine for being grafted with styrene performed polymer.
The styrene performed polymer, maleic anhydride, aliphatic diamine and initiator molar ratio be preferably (1~30): (1
~10): 100:(0.1~0.5), more preferably 2:1:100:0.2.
First organic solvent be preferably one of N-Methyl pyrrolidone, ethylene glycol monobutyl ether, butyrolactone or
Several combinations.
S2: the aliphatic diamine, dibasic anhydride and non-grafted diamine of styrene performed polymer will be grafted with second
Hybrid reaction in solvent obtains orientation liquid.
The non-grafted diamine can be aliphatic diamine, or aromatic diamine.Such as:
5≤n≤15。
Second organic solvent be preferably one of N-Methyl pyrrolidone, ethylene glycol monobutyl ether, butyrolactone or
Several combinations.
Mole of the aliphatic diamine for being grafted with styrene performed polymer, dibasic anhydride and non-grafted diamine
Than preferably (1~50): 100:(1~50).The aliphatic diamine for being grafted with styrene performed polymer and non-grafted two
The sum of molal quantity of first amine is equal with the molal quantity of dibasic anhydride.
S3: the orientation liquid is coated on substrate, is successively carried out precuring and main solidification, is obtained alignment films.
Preferably, the orientation liquid is coated on substrate by way of ink-jet application or print roll coating.
The orientation liquid successively by solidifying twice, obtains alignment film of polyimide.By precuring, polyamide is formed
Acid.The temperature of the precuring is preferably 80~160 DEG C, and the time of precuring is preferably 60~600 seconds.
By main solidification, polyimides is formed.The cured temperature of master is preferably 150~300 DEG C, and the master is cured
Time is preferably 10~60 minutes.
The embodiment of the present invention also discloses a kind of display device, including alignment films described in above-mentioned technical proposal or on
State the alignment films of technical solution the method preparation.
For a further understanding of the present invention, below with reference to embodiment to modified polyimide provided by the invention, alignment films
Preparation method and display device be described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Styrene monomer is added in clean three-necked flask, is put into temperature in 100 DEG C of silicone oil oil bath, turned conducive to magnetic
Sub- high-speed stirred, it is different according to heating duration, obtain number-average molecular weight 200-1550000, the pre-polymerization that molecular weight distribution is about 1
Body.
The molecular weight of styrene performed polymer prepared by table one and its distribution
Styrene performed polymer, maleic anhydride, pentanediamine, the ratio that initiator is 2:1:100:0.2 according to molar ratio, suitable
It measures in high-temperature solvent, the pentanediamine for being grafted styrene performed polymer branch is prepared；
Reaction equation are as follows:
Be grafted the pentanediamine of styrene performed polymer branch, dibasic anhydride andAccording to molar ratio 50:
100:50 is mixed in the second solvent, obtains orientation liquid.
The orientation liquid is coated on substrate, the precuring 130 seconds under the conditions of 130 DEG C, it is then main under the conditions of 230 DEG C
Solidification 20 minutes occurs cyclization, obtains alignment film of polyimide.
Reaction equation are as follows:
The orientation fluid solid content range is 6~8%, is easy to coat to form film layer by ink-jet or roll-type, obtain
Alignment film of polyimide film surface intensity is high.
Embodiment 2
Styrene monomer is added in clean three-necked flask, is put into temperature in 100 DEG C of silicone oil oil bath, turned conducive to magnetic
Sub- high-speed stirred, it is different according to heating duration, obtain number-average molecular weight 200-1550000, the pre-polymerization that molecular weight distribution is about 1
Body.
Styrene performed polymer, maleic anhydride,The ratio that initiator is 2:1:100:0.2 according to molar ratio
Example, in appropriate high-temperature solvent, is prepared
The above-mentioned diamine being prepared, dibasic anhydride and pentanediamine are according to molar ratio 50:100:50 in the second solvent
Mixing obtains orientation liquid.
The orientation liquid is coated on substrate, the precuring 130 seconds under the conditions of 130 DEG C, it is then main under the conditions of 230 DEG C
Solidification 20 minutes occurs cyclization, obtains alignment film of polyimide.
The orientation fluid solid content range is 6~8%, is easy to coat to form film layer by ink-jet or roll-type, obtain
Alignment film of polyimide film surface intensity is high.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of modified polyimide, which is characterized in that including polyimides main chain, and graft on the polyimides main chain
Or the styrene performed polymer on side chain；
The styrene performed polymer is connect by bridging agent with the secondary carbon of the polyimides main chain or side chain.
2. modified polyimide according to claim 1, which is characterized in that the structural formula of the polyimides main chain are as follows:
Wherein, R1For any one in group shown in formula (II)~formula (X),
R2And R3It is respectively selected fromIn any one, 5≤n≤15；
The styrene performed polymer passes through bridging agent and R2Or R3Secondary carbon connection.
3. modified polyimide according to claim 1, which is characterized in that the styrene performed polymer is linear molecule chain
Structure, the styrene performed polymer number-average molecular weight are 200~1550000, molecular weight distribution index 1.
4. modified polyimide according to claim 1, which is characterized in that the styrene performed polymer is sub- in modified polyamides
Shared mass percent is 0.01~3wt% in amine.
5. modified polyimide according to claim 1, which is characterized in that the bridging agent is maleic anhydride.
6. a kind of alignment films, which is characterized in that the modified polyimide as described in Claims 1 to 5 any one forms film
And it is made.
7. a kind of preparation method of alignment films, comprising the following steps:
Styrene performed polymer, maleic anhydride, aliphatic diamine and initiator are uniformly mixed in the first solvent, heating reaction
Afterwards, the aliphatic diamine for being grafted with styrene performed polymer is obtained；
The aliphatic diamine, dibasic anhydride and non-grafted diamine of styrene performed polymer will be grafted in the second solvent
Hybrid reaction obtains orientation liquid；
The orientation liquid is coated on substrate, precuring and main solidification is successively carried out, obtains alignment films.
8. preparation method according to claim 7, which is characterized in that the styrene performed polymer the preparation method comprises the following steps:
Styrene monomer is heated under the conditions of 10~200 DEG C, obtains styrene performed polymer.
9. preparation method according to claim 7, which is characterized in that the orientation liquid passes through ink-jet application or print roll coating
Mode be coated on substrate on.
10. a kind of display device, which is characterized in that any including alignment films as claimed in claim 6 or claim 7~9
The alignment films of one the method preparation.
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