CN109880366A - A kind of high insulation resistance black polyamide composite membrane and preparation method thereof - Google Patents
A kind of high insulation resistance black polyamide composite membrane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high insulation resistance black polyamide composite membranes, which is characterized in that is combined by the first black polyamide film layer and the second black polyamide film layer, dielectric strength is 160kv/mm or more.High insulation resistance black polyamide composite membrane of the invention has extremely excellent dielectric strength and shading performance, and splitting phenomenon does not occur, can be widely used for the fields such as smart phone, display, lithium battery pack for inter-layer bonding force height.
Description
Technical field
The present invention relates to polyimide material fields, and in particular to a kind of high insulation resistance black polyamide composite membrane and
Preparation method.
Background technique
Polyimides (PI) film is because it is with excellent high temperature resistant cryogenic property, chemical-resistant stability, mechanically performance
And the performances such as dimensional stability and be widely used in optics, electronics and aerospace field.
Compared to common yellow polyimide film, black polyamide thin film is in addition to the self-characteristic with polyimides
Outside, also have the characteristics that opacity, optical transmittance are low and luminous reflectivity is low, therefore can apply in flexible electric circuit board base
Material, video camera electronic device, LED are shown and the photoelectricity such as illumination backlight source, light screening material optical stationary attenuator and optical terminus device
On sub- product.The competition being especially growing more intense recently as electronic intelligence product wishes one kind occur in electronics market
The leakage of product electronic circuitry design and constructing technology is avoided with the black polyamide thin film for covering performance.
The production of black polyamide thin film at present is the addition black face in the production process of Kapton mostly
Feed additives improve the shading performance of film to reduce the light transmission of Kapton, however it is black in order to increase to change method
Degree needs to be added a large amount of black pigment, but will be greatly reduced the dielectric strength of Kapton in this way.For example, patent
200910053045.4 (CN101579904) disclose a kind of black polyamide thin film, and dielectric strength is only 82KV/mm.
In order to obtain good shading performance, need largely to add black pigment, thus dielectric strength dramatic decrease.In addition, recently
Have in the report of black multilayer polyimide composite membrane, such as patent 201710653735.8 (CN107226921) and discloses one
Kind multilayer black polyamide thin film and preparation method thereof, in one layer of polyimide precursor film layer, (polyimide precursor film presents yellow
Color) on painting black polyamic acid solution, prepare black polyamide thin film, it is one that Kapton, which is made, in this method first
The composite membrane of layer yellow original film and one layer of black film, overall appearance are the yellow combination blackened, and visual effect is poor；Secondly, should
The dielectric strength for the polyimide composite film that method obtains not be improved significantly, and the composite membrane contains because of black polyimide layer
There are the colorants such as black dyes and makes between black polyimide layer and polyimide precursor film layer that there are physical property differences, therefore
And leading to splitting phenomenon easily occur, i.e. thus interlaminar separation affects the application performance of the Kapton.
Summary of the invention
It is an object of the present invention to overcome the above deficiencies, provides a kind of mechanical property and shading performance is excellent, simultaneously
Especially has the black polyamide composite membrane of excellent dielectric strength, and the composite membrane of the invention is less prone to interlaminar separation
Phenomenon.
According to technical solution provided by the invention, can provide a kind of high insulation resistance black polyamide composite membrane and its
Preparation method, high insulation resistance black polyamide composite membrane of the invention is by the first black polyamide film layer and the second black
Polyimide film is combined, and dielectric strength is 160kv/mm or more.
Wherein, the light transmittance of the composite membrane is 1% or less.
In addition, by weight percentage, in the first black polyamide film layer containing 0.1~1% black colorant and 1~
10% inorganic oxide particle, the second black polyamide film layer contain 1~8% black colorant and 1~10% it is inorganic
Oxide fine particle.
In addition, the black colorant is one or more of carbon black, graphite.
In addition, the average grain diameter of the black colorant is 20nm~1000nm.
In addition, the inorganic oxide particle be aluminium oxide, silica, titanium oxide, zirconium oxide, boron nitride, aluminium nitride,
One or more of silicon carbide, calcium oxide.
In addition, the inorganic oxide particle is aluminium oxide, silica.
In addition, the partial size of the inorganic oxide particle is 20~1000nm.
In addition, the first black polyamide thicknesses of layers is 10~200um, the second black polyamide thicknesses of layers is 5
~50um.
The present invention also provides a kind of preparation methods of composite membrane comprising following step:
(1) diamine and dibasic anhydride be dissolved in highly polar organic solvent to prepare polyamic acid molten under nitrogen protection
Liquid；
(2) the first black polyamide film layer black colorant and inorganic oxide particle, the second black are gathered respectively
Filler mixing is made in highly polar organic solvent in acid imide film layer black colorant and inorganic oxide particle dispersing and dissolving
Liquid；Wherein, the first black polyamide film layer solvent and the second black polyamide film layer solvent can it is identical can also be with
It is different；
(3) filler mixed liquor is added in polyamic acid solution, the first black polyamide film layer film forming is made respectively and uses
Mixed liquor and the second black polyamide film layer film forming use mixed liquor；
(4) compound to prepare black polyamide composite membrane.
Wherein, the compound polyimide composite film for preparing can be following methods:
(1) the first black polyamide film layer film forming mixed liquor and the second black polyamide film layer film forming are used respectively
Mixed liquor respectively sloughs solvent and imidization, the first black polyamide film layer and the second black polyamide film layer is made, so
Hot pressing afterwards；
(2) after coating the first black polyamide film layer film forming mixed liquor on substrate, the second black is coated on it
Polyimide film film forming mixed liquor, sloughs solvent together and imidization prepares black polyamide composite membrane；
(3) the first black polyamide film layer film forming is coated on substrate sloughs solvent imidization obtained first with mixed liquor
After black polyamide film layer, the second black polyamide film layer film forming mixed liquor is coated on it, is synthesized through temperature programming
Black polyamide composite membrane.
In addition, the diamine is p-phenylenediamine, m-phenylene diamine (MPD), benzidine, p dimethylamine, 4,4 '-diamino hexichol
Base ether, 3,4 '-diamino-diphenyl ethers, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino diphenyl sulfones, 3,3 '-diformazans
Base -4,4 '-diaminodiphenyl-methane, 1,5 '-diaminonaphthalenes, 3,3 '-dimethoxy benzidines, 1,4 '-bis- (- 5 ammonia of 3- methyl
Base phenyl) one or more of benzene and the amide formative derivative of above-mentioned diamine；In addition to these diamines, it can also be
2,2'- dimethyl -4,4'- benzidine (tolidine), 3,3 '-benzidines, 2,2 '-two (trifluoromethyl) biphenyl
Amine, 3,3'- bis- (trifluoromethyl) benzidine, 4,4 '-diaminobenzene formailides, 3,4 '-diaminobenzene formailides, N, N'-
Two (4- aminophenyl) terephthalamides, N, N'- is to benzene two (Para Amino Benzamide), 4- amino-benzene oxygen -4- diamino
Benzoic ether, two (4- aminophenyl) terephthalates, biphenyl -4,4 '-dioctyl phthalate two (4- aminophenyl) ester, to benzene two
(P aminobenzoates), two (4- aminophenyls)-[1,1'- xenyl] -4,4'- dicarboxylic acid esters and [1,1'- biphenyl] -4,
(one or more of the 4-aminobenzoic acid ester of 4'- diyl two.
The dibasic anhydride is pyromellitic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,3 ', 3,4 '-biphenyl tetracarboxylics
Acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,3 ', 6,7 '-naphthalenetetracarbacidic acidics, 2,2- bis- (3,4- dicarboxyphenyis)
The derivative that the amide of ether, pyridine -2,3,5,6- tetracarboxylic acid or above-mentioned several dibasic anhydride is formed；Except above-mentioned points, 2 be can also be,
The double O-phthalics of bis- (3,4- dicarboxyphenyi) hexafluoropropane dianhydrides of 2-, bis- (3,4- dicarboxyphenyi) methane dianhydrides, 4,4'- oxygen
Acid dianhydride, bis- (3,4- dicarboxyphenyi) sulfone dianhydrides, triphenyl -3,4,3', 4'- tetracarboxylic dianhydride, to triphenyl -3,4,
3', 4'- tetracarboxylic dianhydride, bis- (3,4- dicarboxyphenyi) thioether dianhydrides, TOPOT 2,2′ p phenylenebis (trimellitic anhydride monoesters), vinyl
Bis- (trimellitic anhydride monoesters), bisphenol-A bis- (trimellitic anhydride monoesters), bis- (the 3,4- dicarboxyphenyis) -1,1,1,3,3 of 2,2-,
Bis- (2,3- the dicarboxyphenyi) -1,1,1,3,3,3- hexafluoropropane dianhydrides of 3- hexafluoropropane dianhydride, 2,2-, 1,2,5,6- naphthalene tetracarboxylic acid
Bis- { 4- [4- (1,2- dicarboxyl) the benzene oxygen of acid dianhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 2,2-
Base] phenyl } propane dianhydride, 2,2- bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } propane dianhydrides, bis- { 4- [4- (1,2- bis-
Carboxyl) phenoxy group] phenyl } ketone dianhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } ketone dianhydrides, the bis- [4- of 4,4'-
(1,2- dicarboxyl) phenoxy group] biphenyl dianhydride, bis- [3- (1,2- dicarboxyl) phenoxy group] biphenyl dianhydrides of 4,4'-, it is bis- 4- [4- (1,
2- dicarboxyl) phenoxy group] phenyl } ketone dianhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } ketone dianhydrides, bis- { 4-
[4- (1,2- dicarboxyl) phenoxy group] phenyl } it is sulfone dianhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } sulfone dianhydrides, double
{ 4- [4- (1,2- dicarboxyl) phenoxy group] phenyl } thioether dianhydride and bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } thioethers
One or more of dianhydride.The solvent can be such as water or such as n,N-Dimethylformamide, N, N- dimethyl second
The aprotic solvent such as amide, n-methyl-2-pyrrolidone, 1,3- dimethyl-2-imidazolinone and dimethyl sulfoxide.However, first
Beginning monomer component and the polyimide precursor of formation can be dissolved under conditions of the solvent, be used with can be convenient any molten
Agent, therefore solvent is not limited to above structure.As solvent, water can be preferably used；Or amide solvent, such as N, N- dimethyl
Formamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone；Cyclic ester solvent, such as gamma-butyrolacton, gamma-valerolactone, δ-penta
Lactone, γ-hexalactone, 6-caprolactone and Alpha-Methyl-gamma-butyrolacton；Carbonate solvent, such as ethylene carbonate and propylene carbonate
Ester；Diol solvent, such as triethylene glycol；Phenol solvent, such as metacresol, paracresol, 3- chlorophenol and 4- chlorophenol；Acetophenone,
1,3- dimethyl-2-imidazolinone, sulfolane and dimethyl sulfoxide etc..Further, it is possible to use other common organic solvents, that is, benzene
Phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve,
2- methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxy-ethane, two
Ethoxyethane, dibutyl ethers, diethylene glycol dimethyl ether, methyl iso-butyl ketone (MIBK), diisobutyl ketone, cyclopentanone, cyclohexanone, first
Base ethyl ketone, acetone, butanol, ethyl alcohol, dimethylbenzene, toluene, chlorobenzene, turpentine oil, mineral spirits and petroleum naphtha class solvent etc..
Solvent can be applied in combination with multiple types.
Beneficial effects of the present invention: black polyamide composite membrane of the invention has the dielectric strength promoted, and light hides
Covering property is good, is extremely suitable for use as the masked film of electronic product, and be not easily stripped between two layers of black polyamide composite membrane, complete
Whole property is good.
Specific embodiment
It enumerates embodiment more specifically to illustrate the present invention, but the present invention is not by any limit of these embodiments
System, in the technical concept of the present invention, those skilled in the art can carry out various deformation.
Black polyamide composite membrane of the invention is by the first black polyamide film layer and the second black polyamide
Film layer is combined.Wherein, the host molecule structure of the first black polyamide film layer and the second black polyamide film layer is equal
For polyimides, and passes through and add black colorant in polyimides and realize shading performance, i.e. reduction light transmission rate and raising
Absorbance.In addition, also improving the dielectric strength of film layer by addition inorganic oxide particle.Black polyamide of the invention
Composite membrane can inhibit to cause under dielectric strength because black colorant is excessively added compared with single layer black polyamide thin film
Thus drop can provide a kind of Kapton with high insulation resistance and every excellent in mechanical performance.
In the present invention, the polyimides, which can be, is synthesized with dibasic anhydride by common diamine in the art
Polyimides can enumerate pyromellitic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,3 ', 3,4 '-connection as dibasic anhydride
Pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,3 ', 6,7 '-naphthalenetetracarbacidic acidics, 2,2- bis- (3,4- dicarboxyls
Base phenyl) ether, pyridine -2,3, the derivative of the amide formation of 5,6- tetracarboxylic acids or above-mentioned several dibasic anhydride, the diamine can
It enumerates such as p-phenylenediamine, m-phenylene diamine (MPD), benzidine, p dimethylamine, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino hexichol
Base ether, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino diphenyl sulfones, 3,3 '-dimethyl -4,4 '-diamino-diphenyl
Methane, 1,5 '-diaminonaphthalenes, 3,3 '-dimethoxy benzidines, 1,4 '-bis- (- 5 aminophenyl of 3- methyl) benzene and above-mentioned two
The amide of first amine forms one or more of derivative.During preparing polyimides, mole of diamine and dibasic anhydride
Than can be 1.1~1:1.Diamine can be for example dissolved in highly polar organic solvent by the process for specifically preparing polyimides
In, dibasic anhydride is then added, after dissolution be made polyamic acid solution, after slough solvent imidizate, be made polyimide film.
Wherein, the viscosity of polyamic acid solution is preferably 50000Cps (25 DEG C) or more, preferably 200000Cps (25 DEG C) or more.As
Highly polar organic solvent can be common pyrrolidones series solvent, phenol system solvent or hexamethyl phosphoramide, r- without specifically limited
One or more of butyrolactone aprotic polar solvent, specifically such as n,N-dimethylacetamide, N, N- dimethyl formyl
Amine, N-Methyl pyrrolidone, dimethyl acetamide, dimethyl sulfoxide etc..
In the present invention, it in order to which the first black polyamide film layer or the second black polyamide film layer is made, can incite somebody to action
Black colorant and inorganic oxide particle are first dissolved in advance in highly polar organic solvent, further by the mixed liquor of acquisition press than
Example is added in polyamic acid solution, sloughs solvent and imidizate film forming after mixing, so that it is sub- to obtain the first black polyamides
Amine film layer and the second black polyamide film layer.However two layers of film layer is subjected to compound mode without specifically limited, such as can
To be respectively to slough solvent respectively to prepare the first black polyamide film layer and hot pressing after the second black polyamide film layer；Or
Person coats the second black polyamide after coating the first black polyamide film layer film forming mixed liquor on substrate on it
Film layer film forming mixed liquor, sloughs solvent and prepares black polyamide composite membrane；Alternatively, on substrate that the first black polyamides is sub-
After amine film layer film forming, coating the second black polyamide film layer film forming mixed liquor, sloughing solvent, to prepare black polyamide multiple
Close film.The coating method is not particularly limited, can be cast coat commonly used in the art, slot coated, rod axis coating,
The conventional coatings modes such as blade coating, spraying.
In the present invention, the black colorant does not have electric conductivity, preferably furnace black, channel black, graphite powder etc.,
Preferred channel black is considered from dielectric strength is improved.The commercially available product such as desai 4# carbon black admittedly also can be used voluntarily in the present invention
It is ground to required average grain diameter.
Wherein, in the first black polyamide film layer, the additional amount of black colorant can be polyimides dry film weight
The 0.1~1% of amount, in the second black polyamide film layer, the additional amount of black colorant is the 1 of polyimides dry film weight
~8%, the weight of so-called dry film refers to the weight of polyamic acid removing solvent, the i.e. total weight of diamine and dibasic anhydride.It is comprehensive
The light-proofness and dielectric strength for considering black polyamide composite membrane of the invention are black in the first black polyamide film layer
The additional amount of chromatic colorant agent is preferably the 0.4~0.6% of polyimides dry film weight, in the second black polyamide film layer,
The additional amount of black colorant can be the 3~6% of polyimides dry film weight.Nothing is added in first black polyamide film layer
The additional amount of machine oxide fine particle is 1~10%, and the addition of inorganic oxide particle is added in the second black polyamide film layer
Amount is 1~10%, from the aspect of the comprehensive performances such as film dynamic performance and dielectric strength, is added in the first black polyamide film layer
Enter in the additional amount and the second black polyamide film layer of inorganic oxide particle and the additional amount of inorganic oxide particle is added more
It is preferably 3~6%.In addition, the partial size of black colorant is 20nm~1000nm, from being easier to evenly dispersed better imparting film layer
Coloring effect angle considers that preferably 100~200nm, the partial size of inorganic oxide particle is 20~1000nm, uniform from being easier
From the aspect of dispersion is to assign the better dielectric strength of film layer, preferably 20~500nm；Black colorant and inorganic oxide are micro-
The partial size of grain is too small, and grinding difficulty big experiment room is not readily available, and partial size is excessive, is not easy to disperse, is easy to happen reunion, finally
It influences the uniformity of film layer and leads dielectric strength, ideal shaded effect and dielectric strength can not be obtained.The inorganic oxide
Particle is one of aluminium oxide, silica, titanium oxide, zirconium oxide, boron nitride, aluminium nitride, silicon carbide, calcium oxide or several
Kind, wherein particularly preferred aluminium oxide, silica, specifically for example can be commercially available inorganic oxide particle through laboratory grinding point
It is dissipated to required partial size, the commercially available product for example can be the production of Japanese Admatechs corporation company, trade name
The ball-aluminium oxide particle of AO802, Tekna Corpatation company production, trade name Z060 ball-aluminium oxide particle,
Japanese Denka Electronic materials company production, trade name AFSP-20, UFP-20, UFP-30, UFP-40
Ball-aluminium oxide particle, the production of company, Japanese Micron Co., Ltd. and trade name SO-C1, SO-C2, SO-E1, SO-E2's
Preparing spherical SiO 2 particles etc..
In addition, from the angle of the compatibility between the adhesion or inorganic particulate and polyimides for improving two membranes interlayer
Degree considers, can add silane coupling agent to improve adsorptivity.The silane coupling agent such as KH540, KH550, KH560,
One or more of KH570, KH590, KH792, A-151, A-171, A-172, Si-563 etc..The additional amount of silane coupling agent
It can be the 0.1~2% of dry film weight.In addition, in order to which black colorant and the better of inorganic oxide particle are dispersed in
In polyamic acid solution, dispersing agent, such as esters of acrylic acid, copolymerization alkylammonium can further be added in polyamic acid solution
Salt, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, BYK-112, BYK-180,
BYK-162 etc..The additional amount of specific such as dispersing agent can be the 0.1~2% of polyimides dry film weight.The addition of dispersing agent
It measures very few, it is possible to it will lead to the reunion of filler, filler dispersion is uneven in film layer obtained, and the additional amount of dispersing agent is excessive,
Then influence the mechanical property of film.
Embodiment 1
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 0.2g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 11.0g N, N- bis- is added in 2.0g silica (partial size 20nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In methylacetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 1.0g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 10.0g N, N- bis- is added in 1.0g silica (partial size 50nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In methylacetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 1000g is taken, above-mentioned the first film forming of whole filler mixed liquor is added, it is black to be denoted as first
Color polyimide film film forming mixed liquor takes 500g polyamic acid solution that above-mentioned the second film forming of whole is added and is mixed with filler
Liquid is denoted as the second black polyamide film layer film forming mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 50um, the dry 20min at 180 DEG C, are gradually heated to 380 DEG C, dry 30min later in 30min, cooling to be made the
One black polyamide film layer is coated with the second black polyamide film layer in the first black polyamide film layer and forms a film with mixed
Liquid, wet-film thickness 25um are closed, the dry 20min at 180 DEG C is gradually heated to 380 DEG C, dry 30min, shape later in 30min
It is answered at the black polyamide being combined by 10um the first black polyamide film layer with 5um the second black polyamide film layer
Close film.
Embodiment 2
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 4.0g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 220.0g N, N- is added in 40.0g silica (partial size 20nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In dimethyl acetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 8.0g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 90.0g N, N- bis- is added in 10.0g silica (partial size 50nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In methylacetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 2000g is taken, above-mentioned the first film forming of whole filler mixed liquor is added, it is black to be denoted as first
Color polyimide film film forming mixed liquor takes 500g polyamic acid solution that above-mentioned the second film forming of whole is added and is mixed with filler
Liquid is denoted as the second black polyamide film layer film forming mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 1000um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C later in 30min, dry 30min, cooling is made
First black polyamide film layer is coated with the second black polyamide film layer film forming in the first black polyamide film layer and uses
Mixed liquor, wet-film thickness 250um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C, dry 30min later in 30min,
It is sub- to form the black polyamides being combined by 200um the first black polyamide film layer and the second black polyamide of 50um film layer
Amine composite membrane.
Embodiment 3
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 0.36g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 15.3g N, N- bis- is added in 2.7g silica (partial size 20nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In methylacetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 1.8g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 27.0g N, N- bis- is added in 3.6g silica (partial size 50nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In methylacetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 450g is taken, above-mentioned the first film forming of whole filler mixed liquor is added, it is black to be denoted as first
Color polyimide film film forming mixed liquor takes 300g polyamic acid solution that above-mentioned the second film forming of whole is added and is mixed with filler
Liquid is denoted as the second black polyamide film layer film forming mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 150um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C later in 30min, dry 30min, cooling is made
First black polyamide film layer is coated with the second black polyamide film layer film forming in the first black polyamide film layer and uses
Mixed liquor, wet-film thickness 100um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C, dry 30min later in 30min,
It is sub- to form the black polyamides being combined by 30um the first black polyamide film layer and the second black polyamide of 20um film layer
Amine composite membrane.
Embodiment 4
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 0.46g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 14.3g N is added in 2.4g aluminium oxide (laboratory partial size 20nm, AFSP-20 grinding distribution, the measurement of Horiba partial size tester),
In N- dimethyl acetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 1.2g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 12.0g N, N- is added in 1.2g aluminium oxide (laboratory partial size 50nm, AO802 grinding distribution, the measurement of Horiba partial size tester)
In dimethyl acetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 400g is taken, above-mentioned the first film forming of whole filler mixed liquor is added, it is black to be denoted as first
Color polyimide film film forming mixed liquor takes 100g polyamic acid solution that above-mentioned the second film forming of whole is added and is mixed with filler
Liquid is denoted as the second black polyamide film layer film forming mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 100um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C later in 30min, dry 30min, cooling is made
First black polyamide film layer is coated with the second black polyamide film layer film forming in the first black polyamide film layer and uses
Mixed liquor, wet-film thickness 25um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C, dry 30min later in 30min,
Form the black polyamide being combined by 20um the first black polyamide film layer and the second black polyamide of 5um film layer
Composite membrane.
Embodiment 5
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 0.6g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 78.0g N, N- is added in 15.0g aluminium oxide (laboratory partial size 20nm, Z060 grinding distribution, the measurement of Horiba partial size tester)
In dimethyl acetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 3.0g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 52.5g N is added in 7.5g aluminium oxide (laboratory partial size 50nm, AFSP-20 grinding distribution, the measurement of Horiba partial size tester),
In N- dimethyl acetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 1500g is taken, above-mentioned the first film forming of whole filler mixed liquor is added, it is black to be denoted as first
Color polyimide film film forming mixed liquor takes 750g polyamic acid solution that above-mentioned the second film forming of whole is added and is mixed with filler
Liquid is denoted as the second black polyamide film layer film forming mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 250um, dry 20min, is gradually heated to 380 DEG C later at 180 DEG C in 30min,
Dry 30min, cooling obtained first black polyamide film layer, is coated in the first black polyamide film layer
Second black polyamide film layer film forming mixed liquor, wet-film thickness 125um, the dry 20min at 180 DEG C, later in 30min
380 DEG C, dry 30min are gradually heated to, is formed sub- by 50um the first black polyamide film layer and the second black of 25um polyamides
The black polyamide composite membrane that amine film layer is combined.
Embodiment 6
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 2.4g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 42.0g N, N- bis- is added in 6.0g silica (partial size 20nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In methylacetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 7.0g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 75.0g N, N- bis- is added in 8.0g silica (partial size 50nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In methylacetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 1500g is taken, above-mentioned the first film forming of whole filler mixed liquor is added, it is black to be denoted as first
Color polyimide film film forming mixed liquor takes 500g polyamic acid solution that above-mentioned the second film forming of whole is added and is mixed with filler
Liquid is denoted as the second black polyamide film layer film forming mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 750um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C later in 30min, dry 30min, cooling is made
First black polyamide film layer is coated with the second black polyamide film layer film forming in the first black polyamide film layer and uses
Mixed liquor, wet-film thickness 250um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C, dry 30min later in 30min,
It is sub- to form the black polyamides being combined by 150um the first black polyamide film layer and the second black polyamide of 50um film layer
Amine composite membrane.
Embodiment 7
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 1.2g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 51.0g N, N- diformazan is added in 9.0g aluminium nitride (partial size 20nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In yl acetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 3.0g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 45.0g N, N- diformazan is added in 6.0g aluminium nitride (partial size 50nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In yl acetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 1500g is taken, above-mentioned the first film forming of whole filler mixed liquor is added, it is black to be denoted as first
Color polyimide film film forming mixed liquor takes 500g polyamic acid solution that above-mentioned the second film forming of whole is added and is mixed with filler
Liquid is denoted as the second black polyamide film layer film forming mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 375um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C later in 30min, dry 30min, cooling is made
First black polyamide film layer is coated with the second black polyamide film layer film forming in the first black polyamide film layer and uses
Mixed liquor, wet-film thickness 125um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C, dry 30min later in 30min,
It is sub- to form the black polyamides being combined by 75um the first black polyamide film layer and the second black polyamide of 25um film layer
Amine composite membrane.
Embodiment 8
Under nitrogen protection, 120.14g (0.6mol) 4,4'- diamino-diphenyl ether (ODA), 43.26g (0.4mol) are right
Phenylenediamine is added in the reaction kettle of 10L, adds 2174g n,N-dimethylacetamide, opens stirring, after clarification to be dissolved,
205.95g (0.7mol) 3,3'4,4'- bibenzene tetracarboxylic dianhydride (BPDA), the equal benzene four of 65.44g (0.3mol) 1,2,4,5- is added
Formic acid dianhydride (PMDA) controls reaction temperature at 30 DEG C, reacts 2h.Polyamic acid solution is made, admittedly contain 20.0%, viscosity
80000cps(30℃)。
By 1.2g carbon black (partial size 20nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 56.0g N, N- dimethyl is added in 10g titanium oxide (partial size 20nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In acetamide, dissolution is uniformly dispersed, and the first film forming filler mixed liquor is made.
By 6.0g carbon black (partial size 50nm, Gu desai 4# carbon black laboratory grinding distribution, Horiba partial size tester measure)
And 55.0g N, N- diformazan is added in 5.0g boron nitride (partial size 50nm, laboratory grinding distribution, the measurement of Horiba partial size tester)
In yl acetamide, dissolution is uniformly dispersed, and the second film forming filler mixed liquor is made.
The above-mentioned polyamic acid solution of 1000g is taken, above-mentioned whole the first film forming filler mixed liquor and 0.45g is added
BYK-180,2g KH570 are denoted as the first black polyamide film layer film forming mixed liquor, and 500g polyamic acid solution is taken to be added
All the second film forming filler mixed liquor and 0.60g BYK-114,2.0g KH560 are stated, the second black polyamide film layer is denoted as
Film forming uses mixed liquor.
Suitable first black polyamide film layer film forming is taken to be coated on glass (40*20cm) substrate with mixed liquor, it is wet
Film thickness 500um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C later in 30min, dry 30min, cooling is made
First black polyamide film layer is coated with the second black polyamide film layer film forming in the first black polyamide film layer and uses
Mixed liquor, wet-film thickness 250um, the dry 20min at 180 DEG C are gradually heated to 380 DEG C, dry 30min later in 30min,
It is sub- to form the black polyamides being combined by 100um the first black polyamide film layer and the second black polyamide of 50um film layer
Amine composite membrane.
Comparative example 1
1.66g carbon black and 3.6g silica are disposably all added in polyamic acid and slough solvent imidizate, is made
One layer of black polyamide thin film is obtained, it is in addition to this same as Example 4.
Comparative example 2
It is same as Example 4 in addition to being added without charcoal infrablack in second layer black polyamide film layer.
Test example
Following measuring mechanical properties are carried out to black polyamide composite membrane obtained above, test result is shown in Table 1.
(1) appearance: sampling range estimation
(2) light transmittance: with the measurement of BYK Gardner haze meter 4725；
(3) thermal expansion coefficient: Mei Tele company static heat mechanical tester TMA/SDTA2+ is used, in measuring temperature range
It is 50-200 DEG C, heating rate measures under conditions of being 10 DEG C/min
(4) tensile modulus of elasticity: using Testometric universal testing machine, at 25 DEG C of room temperature, according to standard ASTM
D882 measurement
(5) it initial modulus: is tested using the dynamic thermomechanical analysis apparatus DMA1 that Mei Tele company produces
(6) surface tension: dyne pen test
(7) shrinking percentage: the Ai Sida Quadratic Finite Element micro-tester of Guangzhou decent job group production
(8) dielectric strength: the black polyamide thin film (circle of diameter 25.4cm is measured with film proof voltage breakdown tester
Disk sample) breakdown voltage.Test temperature and humidity: 20 DEG C, RH 50%；Electrode: circular shape electrode, air dielectric；Medium
Thickness: 25um.According to voltage of film when breakdown, calculating breakdown voltage is sought, dielectric strength is the ratio of breakdown voltage and film thickness
Value.
Table 1
Splitting test
Hydrothermal aging (DH) 2000h is carried out to composite membrane made from embodiment 1-8 and comparative example 2, wet jelly (HF) 20 is followed
Ring, accelerated hydrothermal aging (105 DEG C, 100%RH, 192h) and UV60kWh aging process.Composite membrane through aging process is carried out
Splitting is tested, and in Examples 1 to 8, in 10N/cm or more, and in comparative example 2, splitting power is splitting power
3N/cm。
By above, black polyamide thin film produced by the present invention while having good mechanical performance, has extremely excellent
Different dielectric strength and shading performance, and inter-layer bonding force height not stripping layering.
Claims (12)
1. a kind of high insulation resistance black polyamide composite membrane, which is characterized in that by the first black polyamide film layer and the
Two black polyamide film layers are combined, and dielectric strength is 160kv/mm or more.
2. composite membrane according to claim 1, which is characterized in that the light transmittance of the composite membrane is 1% or less.
3. composite membrane according to claim 1 or 2, which is characterized in that by weight percentage, the first black polyamide
In film layer containing 0.1~1% black colorant and 1~10% inorganic oxide particle, the second black polyamide film layer contains
There is the inorganic oxide particle of 1~8% black colorant and 1~10%.
4. composite membrane according to claim 3, which is characterized in that the black colorant is one of carbon black, graphite
Or it is several.
5. composite membrane according to claim 4, which is characterized in that the average grain diameter of the black colorant be 20nm~
1000nm。
6. composite membrane according to claim 3, which is characterized in that the inorganic oxide particle is aluminium oxide, titanium dioxide
One or more of silicon, titanium oxide, zirconium oxide, boron nitride, aluminium nitride, silicon carbide, calcium oxide.
7. composite membrane according to claim 6, which is characterized in that the inorganic oxide particle is aluminium oxide, titanium dioxide
Silicon.
8. composite membrane according to claim 6 or 7, which is characterized in that the partial size of the inorganic oxide particle is 20-
1000nm。
9. composite membrane according to claim 1 or 2, which is characterized in that the first black polyamide thicknesses of layers be 10~
200um, the second black polyamide thicknesses of layers are 5~50um.
10. the preparation method of composite membrane described in -9 according to claim 1, which is characterized in that include the following steps:
(1) diamine and dibasic anhydride are dissolved in highly polar organic solvent under nitrogen protection and prepare polyamic acid solution；
(2) respectively that the first black polyamide film layer black colorant and inorganic oxide particle, the second black polyamides is sub-
Filler mixed liquor is made in highly polar organic solvent in amine film layer black colorant and inorganic oxide particle dispersing and dissolving；
Wherein, the first black polyamide film layer solvent and the second black polyamide film layer solvent can be identical or not
Together；
(3) filler mixed liquor is added in polyamic acid solution, the film forming mixing of the first black polyamide film layer is made respectively
Liquid and the second black polyamide film layer film forming use mixed liquor；
(4) compound to prepare black polyamide composite membrane.
11. preparation method according to claim 10, which is characterized in that the compound polyimide composite film for preparing can be with
It is following methods:
(1) respectively by the first black polyamide film layer film forming mixed liquor and the film forming mixing of the second black polyamide film layer
Liquid respectively sloughs solvent and imidization, and the first black polyamide film layer and the second black polyamide film layer is made, then hot
Pressing；
(2) after coating the first black polyamide film layer film forming mixed liquor on substrate, the second black polyamides is coated on it
Imines film layer film forming mixed liquor, sloughs solvent together and imidization prepares black polyamide composite membrane；
(3) the first black polyamide film layer film forming is coated on substrate sloughs obtained first black of solvent imidization with mixed liquor
After polyimide film, the second black polyamide film layer film forming mixed liquor is coated on it, through temperature programming synthesizing black
Polyimide composite film.
12. preparation method according to claim 10, which is characterized in that the diamine be p-phenylenediamine, m-phenylene diamine (MPD),
Benzidine, p dimethylamine, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 4,4 '-diamino-diphenyl first
Alkane, 4,4 '-diamino diphenyl sulfones, 3,3 '-dimethyl -4,4 '-diaminodiphenyl-methane, 1,5 '-diaminonaphthalenes, 3,3 ' -
In the amide formative derivative of dimethoxy benzidine, 1,4 '-bis- (- 5 aminophenyl of 3- methyl) benzene and above-mentioned diamine
One or more；The dibasic anhydride is pyromellitic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,3 ', 3,4 '-biphenyl
Tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,3 ', 6,7 '-naphthalenetetracarbacidic acidics, 2,2- bis- (3,4- dicarboxyls
Phenyl) ether, pyridine -2,3,5,6- tetracarboxylic acid or above-mentioned several dibasic anhydride amide formed derivative；The solvent is pyrroles
One or more of alkanone series solvent, phenol system solvent or hexamethyl phosphoramide, r- butyrolactone aprotic polar solvent；It is described
Intensive polar solvent is pyrrolidinone compounds solvent, phenol solvent or hexamethyl phosphoramide, in r- butyrolactone aprotic polar solvent
One or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437614A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of formable polyimide film |
| CN112812559A (en) * | 2021-01-28 | 2021-05-18 | 苏州泰仑电子材料有限公司 | Insulating PI film and preparation method thereof |
| CN112920600A (en) * | 2019-12-06 | 2021-06-08 | 无锡顺铉新材料有限公司 | Black polyimide composite film with two different gloss degrees and preparation method thereof |
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| CN103561953A (en) * | 2011-03-30 | 2014-02-05 | 宇部兴产株式会社 | Polyimide film |
| CN105916684A (en) * | 2013-12-17 | 2016-08-31 | E.I.内穆尔杜邦公司 | A multilayer film |
| CN109021566A (en) * | 2018-06-27 | 2018-12-18 | 桂林电器科学研究院有限公司 | A kind of high insulation black matt polyimide film and multilayer film |
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| JPS6268746A (en) * | 1985-09-20 | 1987-03-28 | 三菱化学株式会社 | Laminated polyimide film and manufacture thereof |
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| CN105916684A (en) * | 2013-12-17 | 2016-08-31 | E.I.内穆尔杜邦公司 | A multilayer film |
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| CN110437614A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of formable polyimide film |
| CN112920600A (en) * | 2019-12-06 | 2021-06-08 | 无锡顺铉新材料有限公司 | Black polyimide composite film with two different gloss degrees and preparation method thereof |
| CN112812559A (en) * | 2021-01-28 | 2021-05-18 | 苏州泰仑电子材料有限公司 | Insulating PI film and preparation method thereof |
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