CN106432724B - A kind of black matt polyimide film and preparation method thereof - Google Patents
A kind of black matt polyimide film and preparation method thereof Download PDFInfo
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- 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
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- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2433/20—Homopolymers or copolymers of acrylonitrile
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Abstract
The invention discloses a kind of polyacrylonitrile blended black matt polyimide films and preparation method thereof, prepare polyacrylonitrile using situ aggregation method and polyamic acid forms the blend solution of Molecule interpenetration network.Preparation method includes：Polyacrylonitrile powder and highly polar aprotic organic solvent are mixed, heating stirring fully dissolves postcooling, aromatic dicarboxylic primary amine is added, after being completely dissolved, aromatic dicarboxylic anhydride is added, under heating stirring, the homogeneous blend solution of polyacrylonitrile and polyamic acid in microphase-separated is obtained；Wherein, by selecting the polyacrylonitrile of different weight average molecular weight, different separation phase domains can be obtained；Black matt polyimide film is made in the blend solution obtained in above-mentioned steps imidization after salivation, drying and heating.The film has higher power frequency electrical strength, excellent mechanical performance, extremely low light transmittance and good black matt effect.
Description
Technical field
The invention belongs to polyimides functionalization film and its preparation fields, more particularly to black matt polyimide film
And preparation method thereof.
Background technology
Black polyamide thin film is on the basis of with traditional Kapton excellent comprehensive performance, with more preferable
Shading performance and apparent color discrimination performance, be widely used in black flex circuit application, black covering film, LED show, black
The sciemtifec and technical spheres such as High temperature-resistanadhesive adhesive tape, black high temp resistance label.
Currently, the external import black polyamide thin film product sale such as domestic existing Dupont, South Korea SKC, but valence
Lattice are expensive.Domestic Ningbo the present mountain, Jiang Subei Noboru, three Wo Deng companies of Shaanxi released black polyamide thin film, but its preparation side
Method all needs after nano carbon black to be carried out to cumbersome surface treatment and dispersion, is added in polyamic acid solution or passes through its in-situ polymerization
Mixed solution is made, then is prepared through solution salivation and hot imidization.Since carbon black has certain conductive capability, so preparing
Film power frequency electrical strength be both less than 50V/ μm, therefore, require high field that cannot use insulating properties, normally only conduct
The application of black high temp resistance adhesive tape, black high temp resistance label, this preparation method complex process, influences environment, gives production system
Also result in larger inconvenience.Meanwhile to the preparation of the black matt polyimide film with soft appearance, also need to be added certain
The micron order flatting silica of amount, causes the decline of film mechanical performance, limits domestic black polyamide thin film in black flexible
The application of the high-end fields such as circuit.
In 15th Chinese copper-clad plate technology international symposium collected works, Yang Zhilan of Jianghan University et al. exists《A kind of black
The preparation of Kapton and performance study》In describe black polyamide thin film in the synthesis of polyimide precursor or
Surface-modified and dispersion nano carbon black is added after synthesis, is then made through imidization.
The yellow training of Jiangsu Nan Fangbei Noboru photoelectric materials Co., Ltd, Lv Liang are disclosed in Chinese patent 201210277962.2
?《A kind of preparation method of black polyamide thin film》, raw material is using diamines, dianhydride, black filler.
The Xiang Zhidu of SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS, the Wang Wei people et al. are disclosed in Chinese patent 200910053045.4
?《A kind of preparation method of black matt polyimide film》, matt agent is from silica, alchlor, zirconium oxide and oxygen
Change and chooses any one kind of them in iron.
The martial virtue of Beijing University of Chemical Technology is precious, Zu Meng Yi et al. discloses in Chinese patent 201610282673.x《It is a kind of
Black polyamide/polyacrylonitrile blended film and preparation method thereof》, by the method for mechanical blending by polyamic acid and poly- third
It is prepared after alkene nitrile solution blending, does not refer to matt effect.
Invention content
Technical problem to be solved by the invention is to provide a kind of black matt polyimide film, which has higher
Insulating properties, i.e., higher power frequency electrical strength and excellent mechanical performance.
Second technical problem to be solved of the present invention is to provide a kind of preparation of black matt polyimide film
Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of black matt polyimide film, it is by polyacrylonitrile and aromatic dicarboxylic primary amine, aromatic dicarboxylic anhydride
Reaction is prepared, and wherein polyacrylonitrile content accounts for the 8-22% of total reactant weight；Preferably, polyacrylonitrile content accounts for total anti-
Answer 10-the 15% of object weight.When polyacrylonitrile content accounts for 8% or less total reactant weight, the film translucency of preparation compared with
Height, blackness are poor；When polyacrylonitrile content accounts for 22% or more total reactant weight, cause in polyacrylonitrile molecule preoxidation process
The increase of contraction causes the film prepared easy to crack.
Preferably, the weight average molecular weight of polyacrylonitrile is 4 ten thousand -20 ten thousand；It is furthermore preferred that the weight average molecular weight of polyacrylonitrile
It is 6 ten thousand -12 ten thousand.By selecting the polyacrylonitrile of different weight average molecular weight, the film being prepared can be made to generate the Asia of differentiation
Light effect.Under the conditions of same process, with the reduction of polyacrylonitrile weight average molecular weight, the glossiness of film gradually increases,
That is matt effect reduces.Illustrate that the weight average molecular weight of polyacrylonitrile is bigger, the separation phase domain formed with polyamic acid is got over
Greatly, to make film obtained that there is better matt effect.
Meanwhile the weight average molecular weight of polyacrylonitrile be more than 200,000 when, polyacrylonitrile in preoxidation process molecular contraction compared with
Greatly, it is difficult to complete film be made；When the weight average molecular weight of polyacrylonitrile is less than 40,000, film matt effect obtained is poor.
The weight of the total reactant refer to polyacrylonitrile and aromatic dicarboxylic anhydride and aromatic dicarboxylic primary amine weight it
With.
The preparation method of above-mentioned black matt polyimide film, includes the following steps：
(1) polyacrylonitrile powder and highly polar aprotic organic solvent are mixed, is stirred to fully molten for 70 DEG C in room temperature-
Solution is cooled to 25 DEG C hereinafter, fully after dissolving aromatic dicarboxylic anhydride is added, in 25 DEG C -60 in addition aromatic dicarboxylic primary amine
It is reacted 2-6 hours within the temperature range of DEG C, obtains the homogeneous blend solution of polyacrylonitrile/polyamic acid of microphase-separated；Microfacies
Separation can make the surface of the finally formed black thin film of reaction form uniform roughness and good matt effect is presented；
Preferably, aromatic dicarboxylic anhydride is equal with the molal quantity of aromatic dicarboxylic primary amine, highly polar non-proton organic molten
The weight ratio of agent and total reactant is 3-6 grams：1 gram；The weight of polyacrylonitrile accounts for 8-22 weight % of total reactant weight；
(2) composite solution obtained in step (1) is formed a film with casting method；The film forming can be in non-porous support, institute
It can be glass plate or metallic plate to state non-porous support；
(3) salivation film obtained in step (2) is dried；
(4) salivation film heat temperature raising obtained in step (3) is subjected to the pre-oxidation of polyacrylonitrile and taking off for polyamic acid
Hydro-thermal imidization, until obtaining the matt polyimide film of black.
Preferably, the highly polar aprotic organic solvent is selected from n,N-Dimethylformamide, N, N- dimethylacetamides
It is one or more in amine, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones or dimethyl sulfoxide (DMSO).
Preferably, the aromatic dicarboxylic primary amine is selected from 4,4- diaminodiphenyl ethers, 3,4- diaminodiphenyl ethers, to benzene two
Bis- (4- aminophenyls) thioethers of amine, m-phenylene diamine (MPD), 3,3- diamino benzophenone, 4,4-, 4,4- diaminodiphenylsulfones or isophthalic two
It is one or more in phenol diphenylamines.
Preferably, the aromatic dicarboxylic anhydride is selected from pyromellitic acid dianhydride, diphenyl sulphone (DPS) tetracid dianhydride, benzophenone tetracid two
Acid anhydride, diphenyl ether tetracid dianhydride, biphenyltetracarboxylic dianhydride, 4,4- be bis--(2,2- hexafluoroisopropyli,enes) diphthalic anhydrides or bisphenol-A
It is one or more in type dianhydride.
Preferably, in step (3), the temperature of the drying is 80 DEG C -100 DEG C, and drying time is 30-60 minutes.
Preferably, in step (4), the heating rate of the reaction is 4-5 DEG C/min, and final temperature is 300-400 DEG C,
Reaction time is 20-50 minutes；It is furthermore preferred that final temperature is 340-380 DEG C.
When final heating temperature is too low, film obtained is in sepia, illustrates that the preoxidation degree of polyacrylonitrile is inadequate
Fully.When final heating temperature is excessively high, film obtained has cracking phenomena, illustrates that the preoxidation degree of polyacrylonitrile excessively fills
Point, destroy the heat-resisting trapezoidal molecular structure of its formation.
Advantageous effect
(1) preparation method of the invention, it is technically simple, it is easy to operate, it is at low cost, since polyacrylonitrile and polyamic acid can
Form intermolecular mixing, be not related in prepared by usual black polyamide thin film being the reunion for preventing black filler, need by
Nano carbon black etc. carries out the complicated technology of surface modification and decentralized processing.
(2) in preparation process, polyacrylonitrile can just become black after needing high temperature pre-oxidation fully, so, very to environment
Close friend, according to related open source literature introduction, the polyacrylonitrile after pre-oxidation forms trapezoidal molecular structure, and aromatization index is relatively low,
It is carbonized far away, so relatively low compared to materials, electric conductivity such as carbon black, graphite.
(3) since polyacrylonitrile and polyamic acid compatibility are poor, microphase-separated is formd, and will not change after the heating
Become, so without adding the flatting silicas such as silica, alundum (Al2O3), the film of preparation can be made to generate good matt effect
And shading performance.
(4) preparation process of the invention complies fully with the complete set of equipments of existing production Kapton to realize this hair
Bright, industrialization level is high.
(5) Kapton prepared by the present invention has excellent mechanical performance, light-proofness, matt degree, relatively high
Power frequency electrical strength.Its 60 ° of specular gloss degree are less than 50%, and black is opaque, and power frequency electrical strength is more than 100V/ μm.
Specific implementation mode
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
Embodiment 1：
At room temperature, by 7.2 grams of polyacrylonitrile (Mw:100000, the place of production：Zhejiang Jie Ma companies) and 223 grams of N, N- dimethyl
Acetamide is put into polymerization bottle, and under stirring, after fully being dissolved in 70 DEG C of room temperature-, cold bath is cooled to 25 DEG C hereinafter, being added
After 4, the 4- diaminodiphenyl ethers of 20.0 grams (0.1 moles) are completely dissolved, the equal benzoic acid dianhydride of 21.8 grams (0.1 mole) is added
Be stirred to react within the temperature range of 25 DEG C -60 DEG C 2 hours, obtain microphase-separated polyacrylonitrile and polyamic acid it is uniform
Mixed solution.
The total reactant content in mixed solution is diluted with 136 grams of n,N-dimethylacetamide to 12 weight %, it is static de-
After bubble, in salivating film forming on glass plate, sets 80 DEG C of baking ovens and be warming up to 100 DEG C and maintain 40 minutes, cooling is taken out, by salivation film from glass
It is fixed, is set in 80 DEG C of baking ovens with metal frame after being removed in glass plate, be heated to 360 DEG C with 4 DEG C/min of heating rate, maintain 30
Minute, 80 DEG C of taking-ups are cooled to, are cooled to room temperature.
Digital display optical thickness gauge is used to measure film thickness as 14.2 μm -15.6 μm；Using photoelectricity glossometer, light enters
It is 42% that 60 ° of firing angle, which measures film surface glossiness,；Tensile strength is measured using electronic tension tester and is more than 125MPa, extension at break
Rate is more than 38%；752N ultraviolet visible light spectrophotometers are used to measure visible light transmittance as 0%；It is tested using proof voltage
Instrument, it is Φ 6mm to use electrode in air, and the power frequency electrical strength for measuring film is more than 105V/ μm.
Embodiment 2：
With the method for embodiment 1, the difference is that the weight average molecular weight of polyacrylonitrile is 80,000, same thickness film is made
Glossiness is 45%, it is seen that light transmission rate 0%.
Embodiment 3：
With the method for embodiment 1, the difference is that the weight average molecular weight of polyacrylonitrile is 60,000, same thickness film is made
Glossiness is 48%, it is seen that light transmission rate 0%.
Embodiment 4：
With the method for embodiment 1, the difference is that the weight average molecular weight of polyacrylonitrile is 40,000.Same thickness film is made
Glossiness is 53%, it is seen that light transmission rate 0%.
Embodiment 5：
At room temperature, by 3.9 grams of polyacrylonitrile (Mw：Ten thousand) 8 are put into 272 grams of n-methyl-2-pyrrolidone in polymerization bottle,
Under stirring after 70 DEG C of abundant dissolvings of room temperature-, cold bath is cooled to 25 DEG C hereinafter, 4, the 4- bis- of 20.0 grams (0.1 mole) is added
Amino-diphenylethers, be added after being completely dissolved 8.8 grams (0.03 mole) biphenyltetracarboxylic dianhydride and 15.3 grams (0.07 mole) it is equal
Acid dianhydride is stirred to react 2 hours within the temperature range of 25-60 DEG C, obtains the polyacrylonitrile and polyamide of microphase-separated
The homogeneous mixture solotion of acid.
The total reactant content in mixed solution is diluted with 80 grams of n-methyl-2-pyrrolidone to 12 weight %, it is static de-
It in salivating film forming on glass plate after bubble, sets 80 DEG C of baking ovens and is warming up to 100 DEG C and maintain 1 hour, cooling is taken out, by salivation film from glass
It removes on plate, is fixed with metal frame, set in 80 DEG C of baking ovens and be heated to 370 DEG C with 5 DEG C/min of heating rate, maintain 20 minutes,
80 DEG C of taking-ups are cooled to, are cooled to room temperature.
Character：The film thickness of preparation is 14.5 μm -15.8 μm, and film surface glossiness is less than 48%；Tensile strength is more than
140MPa；Elongation at break is more than 35%；Visible light transmittance is less than 2.5%；Power frequency electrical strength is more than 150V/ μm.
Embodiment 6：
At room temperature, by 4.5 grams of polyacrylonitrile (Mw：Ten thousand) 8 are added with 265 grams of n,N dimethylformamide in polymerization bottle, stir
It mixes down after 70 DEG C of abundant dissolvings of room temperature-, cold bath is cooled to 25 DEG C hereinafter, by 4, the 4- diaminos of 15.9 grams (0.075 mole)
Base benzophenone, 2.7 grams (0.025 mole) p-phenylenediamine be added polymerization bottle in stir, after being completely dissolved be added 21.8 gram (0.1
Mole) pyromellitic acid dianhydride be stirred to react 4 hours within the temperature range of 60 DEG C of room temperature-, obtain poly- the third of microphase-separated
The homogeneous mixture solotion of alkene nitrile and polyamic acid.
Total reactant content is diluted in above-mentioned mixed solutions with 64 grams of n-methyl-2-pyrrolidone to 12 weight %, it is static
In salivating film forming on glass plate after deaeration, set 80 DEG C of baking ovens and be warming up to 100 DEG C and maintain 50 minutes, take out it is cooling after, by salivation film
It removes from glass plate, is fixed with metal frame, set in 80 DEG C of baking ovens, be heated to 380 DEG C with 4 DEG C/min of heating rate, maintain
25 minutes, 80 DEG C of taking-ups are cooled to, are cooled to room temperature.
Character：The film thickness of preparation is 14.4 μm -15.8 μm, and film surface glossiness is 45%, and tensile strength is more than
135MPa, elongation at break are more than 32%；Visible light transmittance is 0%；Power frequency electrical strength is more than 140V/ μm.
Embodiment 7：
At room temperature, by 10.8 grams of polyacrylonitrile (Mw：Ten thousand) 6 are added with 247 grams of N, N dimethyl acetamide in polymerization bottle,
Under stirring after 70 DEG C of abundant dissolvings of room temperature-, cold bath is cooled to 25 DEG C hereinafter, by 4, the 4- diamino of 20 grams (0.1 mole)
Diphenyl ether be added polymerization bottle in stir, after being completely dissolved be added 17.4 grams (0.08 mole) pyromellitic acid dianhydride, 5.9 grams
The biphenyltetracarboxylic dianhydride of (0.02 mole) is stirred to react 3 hours within the temperature range of 25 DEG C -60 DEG C, obtains microphase-separated
The homogeneous mixture solotion of polyacrylonitrile and polyamic acid.
Total reactant content is diluted in above-mentioned mixed solutions with 150 grams of n-methyl-2-pyrrolidone to 12 weight %, it is static
In salivating film forming on glass plate after deaeration, set 80 DEG C of baking ovens and be warming up to 100 DEG C and maintain 0.5 hour, take out it is cooling after, by salivation film
It removes from glass plate, is fixed with metal frame, set in 80 DEG C of baking ovens, be heated to 350 DEG C with 4 DEG C/min of heating rate, maintain
0.5 hour, 80 DEG C of taking-ups are cooled to, are cooled to room temperature.
Character：The film thickness of preparation is 14.4 μm -15.8 μm, and film surface glossiness is 50%, and tensile strength is more than
135MPa, elongation at break are more than 32%；Visible light transmittance is 0%；Power frequency electrical strength is more than 100V/ μm.
Comparative example 1：
With the method for embodiment 5, the difference is that salivation film is fixed in 80 DEG C of baking ovens of postposition with metal frame with 5 DEG C/min
Heating rate is heated to 290 DEG C, maintains 0.5 hour, is cooled to 80 DEG C of taking-ups and is cooled to room temperature.
As a result：The film blackness of preparation is inadequate, is in sepia.
Comparative example 2：
With the method for embodiment 5, the difference is that salivation film is fixed in 80 DEG C of baking ovens of postposition with metal frame with 5 DEG C/min
Heating rate is heated to 410 DEG C, maintains 0.5 hour, is cooled to 80 DEG C of taking-ups and is cooled to room temperature.
As a result：Film has cracked on metal frame.
Comparative example 3：
With the method for embodiment 1, the difference is that the weight average molecular weight of polyacrylonitrile is 200,000, as a result film obtained is in gold
Belonging on frame has Local Cracking phenomenon.
Comparative example 4：
With the method for embodiment 1, the difference is that the content of polyacrylonitrile accounts for 5 weight % of overall reaction material, it is made identical
The light transmittance of film thickness film is 19.8%, and film is in yellowish-brown.
Comparative example 5：
With the method for embodiment 1, unlike the content of polyacrylonitrile account for 25 weight % of overall reaction material, it is obtained thin
Film has cracking phenomena in metal frame.
Claims (6)
1. a kind of preparation method of black matt polyimide film, it is characterized in that：Include the following steps：
(1) polyacrylonitrile powder and highly polar aprotic organic solvent are mixed, it is cold in 70 DEG C of stirrings of room temperature-to abundant dissolving
But to 25 DEG C hereinafter, fully after dissolving aromatic dicarboxylic anhydride is added, in 25 DEG C -60 DEG C in addition aromatic dicarboxylic primary amine
Reaction 2-6 hours, obtain the polyacrylonitrile of microphase-separated and the homogeneous blend solution of polyamic acid in temperature range；
(2) blend solution obtained in step (1) is formed a film with the tape casting；
(3) casting films obtained in step (2) are dried；
(4) casting films heat temperature raising obtained in step (3) is carried out to the dehydration fever of the pre-oxidation and polyamic acid of polyacrylonitrile
Imidization, until obtaining the matt polyimide film of black；
The content of the polyacrylonitrile accounts for the 10-15% of total reactant weight；The weight average molecular weight of the polyacrylonitrile is 60,000-
120000；
In step (4), the heating rate of the reaction is 4-5 DEG C/min, and final temperature is 340-380 DEG C, in final temperature
It is 20-50 minutes to be kept for the reaction time.
2. a kind of preparation method of black matt polyimide film as described in claim 1, it is characterized in that：Described is highly polar
Aprotic organic solvent is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyls-
It is one or more in 2-Pyrrolidone or dimethyl sulfoxide (DMSO).
3. a kind of preparation method of black matt polyimide film as described in claim 1, it is characterized in that：The aromatic series two
First primary amine is selected from 4,4- diaminodiphenyl ethers, 3,4- diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), 3,3- diamino hexichol
It is one or more in bis- (4- aminophenyls) thioethers of ketone, 4,4-, 4,4- diaminodiphenylsulfones or resorcinol diphenylamines.
4. a kind of preparation method of black matt polyimide film as described in claim 1, it is characterized in that：The aromatic series two
First acid anhydrides is selected from pyromellitic acid dianhydride, diphenyl sulphone (DPS) tetracid dianhydride, benzophenone tetracid dianhydride, diphenyl ether tetracid dianhydride, biphenyl tetracarboxylic acid
Acid dianhydride, 4,4- be bis--(2,2- hexafluoroisopropyli,enes) diphthalic anhydrides or bisphenol A-type dianhydride in it is one or more.
5. a kind of preparation method of black matt polyimide film as described in claim 1, it is characterized in that：In step (3), institute
The temperature for stating drying is 80 DEG C -100 DEG C, and drying time is 30-60 minutes.
6. the black matt polyimide film that any one of Claims 1 to 5 is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610888836.9A CN106432724B (en) | 2016-10-11 | 2016-10-11 | A kind of black matt polyimide film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610888836.9A CN106432724B (en) | 2016-10-11 | 2016-10-11 | A kind of black matt polyimide film and preparation method thereof |
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| CN107987529A (en) * | 2017-12-15 | 2018-05-04 | 桂林电器科学研究院有限公司 | A kind of sub- black Kapton preparation method |
| CN108047717A (en) * | 2017-12-15 | 2018-05-18 | 桂林电器科学研究院有限公司 | A kind of black low gloss Kapton preparation method |
| CN107987528A (en) * | 2017-12-15 | 2018-05-04 | 桂林电器科学研究院有限公司 | A kind of black polyamide thin film preparation method of matt surface |
| CN108017910A (en) * | 2017-12-15 | 2018-05-11 | 桂林电器科学研究院有限公司 | A kind of matt black polyamide thin film preparation method |
| CN111057260B (en) * | 2019-12-13 | 2022-12-13 | 株洲时代华鑫新材料技术有限公司 | Preparation method of black matte polyimide film |
| CN113265142A (en) * | 2020-02-14 | 2021-08-17 | 北京化工大学 | Black composite film and preparation method and application thereof |
| CN113045782B (en) * | 2021-03-04 | 2023-08-04 | 南京精工新材料有限公司 | Polyimide composite film with ultrahigh light-shielding property and preparation method thereof |
| CN113292787B (en) * | 2021-05-08 | 2022-04-08 | 华南理工大学 | Beta crystal form nucleating agent and preparation method and application thereof |
| CN113353926B (en) * | 2021-05-25 | 2024-04-12 | 安徽国风新材料股份有限公司 | Polyimide film for preparing graphite film, high-heat-conductivity graphite film prepared from polyimide film and preparation method of high-heat-conductivity graphite film |
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| TWI481649B (en) * | 2013-09-09 | 2015-04-21 | Taimide Technology Inc | Black polyimide film and its processing method |
| CN103665865B (en) * | 2013-10-31 | 2016-01-20 | 西安航天三沃化学有限公司 | A kind of Black extinction-type polyimide film and preparation method thereof |
| CN105733001B (en) * | 2014-12-10 | 2019-01-01 | 天津市嘉诺缘电子科技有限公司 | A kind of preparation method of the full matt polyimide film of high-performance black |
| CN105385159A (en) * | 2015-12-25 | 2016-03-09 | 桂林电器科学研究院有限公司 | Black matte polyimide thin film and preparation method thereof |
| CN105860112B (en) * | 2016-05-02 | 2019-01-04 | 北京化工大学 | A kind of black polyamide/polyacrylonitrile blended film and preparation method thereof |
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