CN103168068A

CN103168068A - Matte finish polyimide films and methods relating thereto

Info

Publication number: CN103168068A
Application number: CN2011800349125A
Authority: CN
Inventors: T·E·卡内; J·M·巴尔托灵; M·L·邓巴; S·J·赫尔曼
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2010-07-23
Filing date: 2011-02-14
Publication date: 2013-06-19
Also published as: WO2012011970A1; JP2013532752A; EP2596052A1

Abstract

The present disclosure is directed to a base film having a thickness from 8 to 152 microns, a 60 degree gloss value from 2 to 35, an optical density greater than or equal to 2 and a dielectric strength greater than 1400 V/mil. The base film comprises a chemically converted (partially or wholly aromatic) polyimide in an amount from 71 to 96 weight percent of the base film. The base film further comprises a pigment and a matting agent. The matting agent is present in an amount from 1.6 to 10 weight percent of the base film, has a median particle size from 1.3 to 10 microns, and has a density from 2 to 4.5 g/cc. The pigment is present in an amount from 2 to 9 weight percent of the base film. The present disclosure is also directed to coverlay films comprising the base film in combination with an adhesive layer.

Description

Mat finish polyimide film and methods involving thereof

Technical field

The disclosure relates generally to mat finish and is used for the basement membrane that dielectric characteristics and optical characteristics were used and had to the table sheath.More particularly, the basement membrane of mat finish of the present disclosure comprises pigment and the matting agent of the relative lower concentration in the polyimide film of the imidization by chemistry (with heat contrast) method for transformation.

Background technology

In a broad aspect, the table sheath is known as barrier film for the protection of electronic material, such as for the protection of the lead frame of flexible printed circuit board, electronic package, integrated antenna package etc.Yet; needs table sheath is more and more thinner and cost is more and more lower; need simultaneously to show sheath and (for example not only have acceptable electrical property; dielectric strength); and have acceptable structural performance and optical characteristics, carry out unwanted visual inspection and interference with the electronic component of taking precautions against being shown the sheath protection.

Summary of the invention

The disclosure relates to basement membrane.This basement membrane comprises the polyimide by the chemical conversion of the weighing scale 71-96 % by weight of basement membrane.The polyimide of this chemical conversion derived from: i. based on the dianhydride total content meter in described polyimide, the aromatic dianhydride of at least 50 % by mole, and ii. is based on the diamines total content meter in polyimide, the aromatic diamine of at least 50 % by mole.This basement membrane also comprises: the low conductivity carbon black, and described carbon black exists with the amount of the 2-9 % by weight of basement membrane; And matting agent, described matting agent:

A. the amount with the 1.6-10 % by weight of basement membrane exists,

B. the median particle that has the 1.3-10 micron, and

C. the density that has 2-4.5g/cc.

In one embodiment, basement membrane has: i.8-152 the micron thickness; The 60 degree gloss values of ii.2-35; Iii. more than or equal to 2 optical density(OD); And iv. is greater than the dielectric strength of 1400 volts/mil.The disclosure also relates to table sheath film, and this table sheath film comprises the basement membrane of being combined with binder layer.

The disclosure also relates to basement membrane, and described basement membrane comprises:

A. press the polyimide of chemical conversion of the weighing scale 40-90 % by weight of basement membrane, the polyimide of described chemical conversion derived from:

A. based on the dianhydride total content meter in described polyimide, the aromatic dianhydride of at least 50 % by mole, and

B. based on the diamines total content meter in described polyimide, the aromatic diamine of at least 50 % by mole;

B. press the filler of the weighing scale 10-60 % by weight of basement membrane, do not comprise carbon black and pigment; And wherein the thickness of basement membrane is the 8-152 micron.

Embodiment

Definition

As used herein, term " comprises ", " comprising ", " having " or their any other modification all are intended to contain comprising of nonexcludability.For example, method, technique, goods or the equipment that comprises the key element list needn't only only limit to those key elements but can comprise other key element of clearly not listing or these class methods, technique, goods or equipment are intrinsic.In addition, unless specify in addition, otherwise "or" refer to inclusive or, rather than refer to exclusiveness or.For example, any one all represent to satisfy condition A or B:A below are that genuine (or existence) and B are that false (or non-existent), A are that false (or non-existent) and B are that genuine (or existence) and A and B are genuine (or existence).

In addition, use " one " or " a kind of " to describe element of the present invention and assembly.Do like this is only for convenient and provide general sense of the present invention.This description is understood to include one (kind) or at least one (kind), unless and refer else significantly, otherwise odd number also comprises plural number.

As used herein, " dianhydride " is intended to comprise its precursor or derivative, and they may not be proper dianhydride, but still can be with diamine reactant to form polyamic acid, and polyamic acid can be converted into polyimide then.

As used herein, " diamines " is intended to comprise its precursor or derivative, and they may not be proper diamines, but still can be with two anhydride reactants to form polyamic acid, and polyamic acid can be converted into polyimide then.

As used herein, " polyamic acid " is intended to comprise derived from being combined of dianhydride and diamine monomer or its function equivalent and can be converted into by chemical conversion process any polyimide precursor material of polyimide.

As used herein, " prepolymer " is intended to the relatively low-molecular-weight polyamic acid solution of expression, and this solution prepares with the excessive diamines of stoichiometry, to give the soltion viscosity of about 50-100 pool.

As used herein, " chemical conversion " or " chemically transforming " expression use catalyzer (promotor) or dewatering agent (or both) polyamic acid is converted into polyimide, and be intended to comprise the polyimide of partly chemical conversion, it at high temperature is dried to solids content subsequently greater than 98%.

As used herein, " conversion chemical " or " imidization chemical " refers to polyamic acid to be changed into the catalyzer (promotor) of polyimide and/or polyamic acid can be changed into the dewatering agent of polyimide.

Dianhydride in " finisher solution " expression polar aprotic solvent of this paper, dianhydride is added in pre-polymer solution to improve molecular weight and viscosity.Dianhydride used is identical with the dianhydride of preparation prepolymer (maybe when use during more than a kind of dianhydride, with wherein a kind of identical) usually.

When content, concentration or other numerical value or parameter with scope, preferred scope or have the preferred upper limit value and the tabular form of preferred lower limit value when providing, should be understood as all scopes that any pairing by any range limit or preferred value and any scope lower limit or preferred value forms that specifically disclose, no matter whether scope is open separately.Except as otherwise noted, allly provide in this article a certain numerical range part, this scope all is intended to comprise its end points, and all integers and the mark that are positioned at this scope.The occurrence that describes in detail when not being intended to limit the scope of the present invention to limited range.

When describing some polymkeric substance, should be appreciated that what use when the applicant mentions polymkeric substance sometimes is the amount of making their monomer or being used for making their monomer.Although this class description may not comprise be used to the concrete name of describing final polymkeric substance or may not comprise the term that limits product with method, but any this type of of monomer and amount mentioned to be interpreted as referring to that polymkeric substance made by those monomers, unless context indicates in addition or hints.

Unless specifically indicate, the material of this paper, method and example are only illustrative, are not to be intended to restriction.Although also can be used for practice of the present invention or test with methods described herein and materials similar or the method that is equal to and material, this paper describes suitable method and material.

Basement membrane

Basement membrane of the present disclosure comprises the polyimide substrate of filling, and wherein said polyimide forms by chemical conversion process.An advantage of chemical conversion process (with respect to single thermal conversion process) is, the amount that reaches the required matting agent of enough low glossiness lacks at least 10%, 20%, 30%, 40% or 50% when using thermal conversion process.The scope of generally accepted 60 degree gloss values is:

＜10 delustrings

10 – 70 dumb lights, satin face, semi-gloss (having used multiple term)

70 Gao Guang.

In some embodiments, basement membrane have between following any two values and randomly comprise these two values 60 the degree gloss values: 2,3,4,5,10,15,20,25,30 and 35.In some embodiments, basement membrane has the 60 degree gloss values of 2-35.In some embodiments, basement membrane has the 60 degree gloss values of 10-35.Measure 60 degree gloss values with the Micro-TRI-Gloss glossmeter.The matting agent (may prepare by chemical conversion) of low loading is favourable, because its: i. reduces overall cost; Ii. simplify matting agent is distributed to step in polyamic acid (or other polyimide precursor material); And iii. provides the have better mechanical characteristics gained basement membrane of (for example, less fragility).Another advantage of chemical conversion process (with respect to thermal conversion process) is that the dielectric strength of the basement membrane of chemical conversion is higher.In some embodiments, the basement membrane dielectric strength is greater than 1400 volts/mil (55 volts/micron).

In some embodiments, by with polyamic acid solution with polyamic acid can be changed into the catalyzer of polyimide or step that dewatering agent mixes and prepare the polyimide of chemical conversion.In another embodiment, by with polyamic acid solution with polyamic acid can be changed into the catalyzer of polyimide and step that dewatering agent mixes and prepare the polyimide of chemical conversion.In chemical conversion process, polyamic acid solution immerses and transforms (imidization) chemical or mix with it.In one embodiment, transforming chemical is tertiary amine catalyst (promotor) and acid anhydrides dehydrating material.In one embodiment, the acid anhydrides dehydrating material is diacetyl oxide, and its mole dosage surpasses the amount of amino acid (amido acid) group in polyamic acid usually, is generally 1.2-2.4 mole of approximately every equivalent polyamic acid.In one embodiment, use the tertiary amine catalyst of a great deal of.

Substitute as the diacetyl oxide of acid anhydrides dehydrating material comprises: other aliphatic anhydrides of i., for example propionic acid acid anhydrides, butyric acid acid anhydrides, pivalic anhydride and their mixture; Ii. one dollar aromatic carboxylic acid's acid anhydrides; III. the mixture of aliphatic anhydrides and aromatic anhydride; Iv. carbodiimide; And v. aliphatic series ketenes (ketenes can be regarded as the carboxylic acid anhydride derived from the strong dehydration of acid).

In one embodiment, tertiary amine catalyst is pyridine and beta-picoline, and its consumption is usually close with the mole dosage of acid anhydrides dehydrating material.Can use lower or higher amount according to required transformation efficiency and used catalyst.Also can use the tertiary amine that has with pyridine and the roughly the same activity of beta-picoline.These tertiary amines comprise α-methylpyridine; 3,4-lutidine; 3,5-lutidine; The 4-picoline; The 4-isopropyl pyridine; N, the N-dimethyl benzylamine; Isoquinoline 99.9; 4-benzyl-pyridine, N, N-dimethyl n-Laurylamine, triethylamine etc.Be used for that multiple other catalyzer of imidization is known in the art, imidazoles for example, and can use according to the disclosure.

Transform chemical generally can be at about room temperature or higher temperature reaction so that polyamic acid is converted into polyimide.In one embodiment, the chemical conversion reaction occurs at the temperature of 15 ℃ to 120 ℃, wherein should react very fast at higher temperature and relatively slow at lower temperature.

In one embodiment, chemically treated polyamic acid solution can be poured into a mould or is expressed in thermal transition surface or substrate.In one embodiment, chemically treated polyamic acid solution can be poured on band or cylinder.Solvent can evaporate from solution, and polyamic acid can partly be chemically converted into polyimide.Then gained solution is the form of polyamic acid-polyimide gel.Alternatively, polyamic acid solution can be expressed in the bath that transforms chemical, and this transforms chemical and is comprised of anhydride component (dewatering agent), tertiary amine component (catalyzer) or both, has or do not have diluting solvent.In either case, all form gel-film, and the conversion percentages that the amic acid group in gel-film is converted into imide group depends on duration of contact and temperature, but be generally the approximately complete per-cent of 10-75%().In order to be solidified into solids content greater than 98%, gel-film usually must be lower dry at high temperature (approximately 200 ℃, at the most approximately 550 ℃), and this will be tending towards making imidization complete.In some embodiments, preferably use dewatering agent and catalyzer, with the transformation efficiency that is conducive to form gel-film and reach expectation.

Although gel-film has high solvent content, it is self-supporting often.Usually, the subsequent drying gel-film to be removing moisture, residual solvent and residual conversion chemical, and polyamic acid is converted into polyimide (namely greater than 98% by imidization) basically fully in this process.Dry can carrying out under the condition that relatively relaxes, this moment, polyamic acid not exclusively was converted into polyimide, maybe can adopt higher temperature to carry out simultaneously drying and conversion.

In dry and step of converting, have the liquid that must remove in a large number due to gel, therefore generally must retrain gel in drying process, to avoid unexpected contraction.In producing continuously, basement membrane can be remained on edge, for example in the tentering machine frame, use the constraint of tentering fixture or pin.

Can use high temperature dry basement membrane and induce further imidization at short notice, in same steps as, gel-film is converted into polyimide base film.In one embodiment, basement membrane is heated to the temperature of 200 ℃ to 550 ℃.In general, film is than thick film needs heat and the time still less.

Dry and (being converted into polyimide from the polyamic acid) process of conversion, can retrain the basement membrane excess shrinkage at this type of, in fact, its extensible original dimension reach 150%.In the manufacturing of film, stretching, extension can be carried out on vertical or horizontal or this both direction.If necessary, go back the capable of regulating constraint degree, to allow the contraction of some limited extents.

Another advantage is, the basement membrane both sides of chemical conversion of the present disclosure are lacklustre, even be poured on smooth surface.If it is lacklustre that the both sides of basement membrane are, any extra play can be applied to the either side of basement membrane.Comparatively speaking, when similar filled polyimide precursor film only for thermal transition and when being poured on smooth surface, the cast side is often glossiness, and air side is often lacklustre.

Compare with the basement membrane of only thermal transition, another advantage is that the basement membrane of chemical conversion has higher dielectric strength.Usually, dielectric strength reduces with the amount increase of matting agent.Therefore, although can reach 60 lower degree gloss values (only air side) by the amount that increases matting agent in single thermal conversion processes, dielectric strength will reduce.

In one embodiment, prepare by the following method polyamic acid: dianhydride and the diamines of about equimolar amount are dissolved in solvent, and stir gained solution under the controlled temperature condition, until complete the polymerization of dianhydride and diamines.Usually, use the one (being generally diamines) of slightly excessive monomer that molecular weight and viscosity are initially controlled, then can increase molecular weight and viscosity by adding a small amount of not enough monomer.The example that is used for the suitable dianhydride of disclosure polyimide comprises aromatic dianhydride, aliphatic dianhydride and their mixture.In one embodiment, aromatic dianhydride is selected from:

Pyromellitic acid anhydride;

3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride;

3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride;

4, the two Tetra hydro Phthalic anhydrides of 4 '-oxygen;

3,3 ', 4,4 '-sulfobenzide tetracarboxylic acid dianhydride;

2,2-two (3,4-dicarboxyl phenyl) HFC-236fa;

The dihydroxyphenyl propane dianhydride; And

Their mixture and derivative.

In another embodiment, aromatic dianhydride is selected from:

2,3,6,7-naphthalenetetracarbacidic acidic dianhydride;

1,2,5,6-naphthalenetetracarbacidic acidic dianhydride;

2,2', 3,3'-bibenzene tetracarboxylic dianhydride;

2,2-two (3,4-dicarboxyl phenyl) propane dianhydride;

Two (3,4-dicarboxyl phenyl) sulfone dianhydride;

3,4,9,10-perylene tetracarboxylic acid dianhydride;

1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride;

1,1-two (3,4-dicarboxyl phenyl) ethane dianhydride;

Two (2,3-dicarboxyl phenyl) methane dianhydride;

Two (3,4-dicarboxyl phenyl) methane dianhydride;

The two Tetra hydro Phthalic anhydrides of oxygen;

Two (3,4-dicarboxyl phenyl) sulfone dianhydride;

Their mixture and derivative.

The example of aliphatic series dianhydride comprises:

The tetramethylene dianhydride;

[1S*, 5R*, 6S*]-3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3-(tetrahydrofuran (THF)-2,5-diketone);

Their mixture.

The example that is used for the suitable diamines of disclosure polyimide comprises aromatic diamine, aliphatic diamine and their mixture.In one embodiment, aromatic diamine is selected from:

3,4 '-diaminodiphenyl oxide;

1,3-two (4-amino-benzene oxygen) benzene;

4,4 '-diaminodiphenyl oxide;

Isosorbide-5-Nitrae-diaminobenzene;

1,3-diaminobenzene;

2,2 '-two (trifluoromethyl) p-diaminodiphenyl;

4,4'-benzidine base;

4,4 '-diamino-diphenyl thioether;

9,9 '-two (4-is amino) fluorine;

Their mixture and derivative.

In another embodiment, aromatic diamine is selected from:

4,4'-benzidine base propane;

4,4'-benzidine methylmethane;

Benzidine;

3,3'-dichlorobenzidine;

3,3'-diamino diphenyl sulfone;

4,4'-diamino diphenyl sulfone;

1,5-diaminonaphthalene;

4,4'-diamino-diphenyl diethylsilane;

4,4'-diamino-diphenyl silane;

4,4'-diamino-diphenyl ethyl phosphine oxide;

4,4'-diamino-diphenyl N-methylamine;

4,4'-diamino-diphenyl N-phenyl amine;

Isosorbide-5-Nitrae-diaminobenzene (P-pHENYLENE dI AMINE);

1,2-diaminobenzene;

Their mixture and derivative.

The example of suitable aliphatic diamine comprises:

1,6-hexanediamine;

The dodecane diamines;

Cyclohexane diamine;

And their mixture.

In one embodiment, the polyimide of chemical conversion is derived from pyromellitic acid anhydride (" PMDA ") and 4,4 '-diaminodiphenyl oxide (" 4,4ODA ").In one embodiment, disclosure polyimide is derived from copolyimide any in above-mentioned diamines and dianhydride.In one embodiment, copolyimide derived from the Ursol D of the pyromellitic acid anhydride of the bibenzene tetracarboxylic dianhydride of 15-85 % by mole, 15-85 % by mole, 30-100 % by mole and randomly comprise 0-70 % by mole 4,4'-diamino-diphenyl ether and/or 4,4'-diamino-diphenyl ether.This type of copolyimide is further described in United States Patent (USP) 4,778,872 and United States Patent (USP) 5,166,308 in.

In one embodiment, polyimide dianhydride component is pyromellitic acid anhydride (" PMDA "), and the polyimide diamine components is the combination of 4,4'-diaminodiphenyl oxide (" 4,4ODA ") and Ursol D (" PPD ").In one embodiment, polyimide dianhydride component is pyromellitic acid anhydride (" PMDA "), the polyimide diamine components is 4, the combination of 4 '-diaminodiphenyl oxide (" 4; 4ODA ") and Ursol D (" PPD "), wherein the ratio of ODA and PPD (ODA:PPD) is following arbitrary molar ratio: i.20-80:80-20; Ii.50-70:50-30; Or iii.55-65:45-35.In one embodiment, polyimide dianhydride component is PMDA, and diamine components to be mol ratio (ODA:PPD) be approximately ODA and the PPD of 60:40.

In one embodiment, polyimide dianhydride component is 3,3', 4,4'-bibenzene tetracarboxylic dianhydride (" BPDA "), and the polyimide diamine components is the combination of 4,4'-diaminodiphenyl oxide (" 4,4ODA ") and Ursol D (" PPD ").In one embodiment, polyimide dianhydride component is BPDA, and the polyimide diamine components is the combination of 4,4ODA and PPD, and wherein the ratio of ODA and PPD (ODA:PPD) is following arbitrary molar ratio: I.20-80:80-20; II.50-70:50-30; Or iii.55-65:45-35.In one embodiment, polyimide dianhydride component is BPDA, and diamine components to be mol ratio (ODA:PPD) be approximately ODA and the PPD of 60:40.

In one embodiment, one or both of the necessary solvent polymerization reactant of polyamic acid solvent, and in one embodiment, will dissolve the polyamic acid polymerisate.This solvent should be basically not with all polymerization reactant and reaction of polyamic acid polymerisate.

In one embodiment, the polyamic acid solvent is liquid N, N-dialkyl group Carboxylamide, for example lower molecular weight Carboxylamide, particularly DMF and N, N-diethyl acetamide.The compound of this kind solvent that other is available is N, N-diethylformamide and N, N-diethyl acetamide.Other available solvent is tetramethylene sulfone, METHYLPYRROLIDONE, tetramethyl-urea, dimethyl sulfone etc.Solvent can be used in combination separately or mutually.The consumption of solvent is preferably in the scope of the weighing scale 75-90 % by weight of pressing polyamic acid.

Polyamic acid solution is preparation in the following manner usually: diamines is dissolved in anhydrous solvent, in inert atmosphere, slowly adds dianhydride under the condition of stirring and temperature control.

Pigment

Almost can use any pigment (or combination of pigment) in enforcement of the present invention.In some embodiments, useful pigment includes but not limited to following pigment: barium lemon yellow, cadmium lemon yellow, cadmium lemon yellow, cadmium are pale yellow, yellow in cadmium, cadmium orange is yellow, scarlet lake, cadmium red, G cadmium scarlet, purplish red, durable purplish red, iron oxide brown, raw unmber is green or burnt umber.in some embodiments, available black pigment comprises: cobalt oxide, iron-manganese-bismuth is black, the iron-manganese oxide spinel is black, (iron, manganese) 2O3 is black, the copper chromite black spinel, dim, bone black, bone ash, boneblack, rhombohedral iron ore, black iron oxide, iron mica, black composite inorganic coloured pigment (CICP), copper chromium 2O4 is black, (nickel, manganese, cobalt) (chromium, iron) 2O4 is black, nigrosine, perylene is black, anthraquinone is black, chrome green-Hei rhombohedral iron ore, the ferrochrome oxide compound, Pigment green 17, Pigment black 26, Pigment black 27, Pigment black 28, pigment brown 29, Pigment black 30, Pigment black 32, Pigment black 33 or their mixture.

In some embodiments, use the low conductivity carbon black.The amount of low conductivity carbon black and the thickness of basement membrane will affect optical density(OD) usually.If the too high levels of low conductivity carbon black is even in the situation that use low conductivity carbon black basement membrane also can conduct electricity.If the content of low conductivity carbon black is too low, basement membrane possibly can't obtain required optical density(OD) and color.For the purposes of the present invention, be used to basement membrane to give black the low conductivity carbon black, and realize required basement membrane optical density(OD), wherein the thickness of basement membrane also randomly comprises this two values between following any two values: 8,10,15,20,25,30,35,40,45,50,60,70,80,90,100,110,120,130,140 and 152 microns.In some embodiments, basement membrane thickness is the 8-152 micron.In some embodiments, basement membrane thickness is the 8-127 micron.In another embodiment, basement membrane thickness is the 10-40 micron.The low conductivity carbon black is intended to represent thermally oxidized black or furnace treated black.In some embodiments, can give black with bone black.In one embodiment, comprise randomly also between following any two values of low conductivity carbon black that the amount of these two values exists: 2,3,4,5,6,7,8 and 9 % by weight of basement membrane.In some embodiments, the optical density(OD) of expectation (opaque) (for example, can't see in flexible circuit wire) is more than or equal to 2.Optical density(OD) is 2 to be intended to represent 1 * 10 ^-2Or 1% light transmission basement membrane.

In some embodiments, the low conductivity carbon black is the carbon black of surface oxidation.The method of a kind of assessment (carbon black) surface oxidation degree is to measure the volatile content of carbon black.Volatile content can lose by calculated weight (calcining is 7 minutes under 950 ℃) and measure.In general, the carbon black of surface elevation oxidation (high volatility) can disperse in polyamic acid solution (polyimide precursor) easily, then can be turned to by imines (finely disseminated) filled-type polyimide of the present invention based polyalcohol.It has been generally acknowledged that, if carbon black pellet (aggregate) does not contact each other, electron tunneling, Spectrametry of Electron Exchange or other electronics flow mechanism generally can be suppressed, thereby cause lower specific conductivity.In some embodiments, the low conductivity carbon black has the volatile content more than or equal to 1%.In some embodiments, the low conductivity carbon black has the volatile content more than or equal to 5,9 or 13%.In some embodiments, can carry out surface treatment to furnace treated black, to increase volatile content.

The Uniform Dispersion of each particle (aggregate) that separates not only can reduce specific conductivity, produces uniform colour strength toward the contact meeting.In some embodiments, the low conductivity carbon black is ground.In some embodiments, the mean particle size of low conductivity carbon black between following any two values (and randomly comprising this two values): 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 and 1.0 micron.Can be according to specifically being used for customizing the thickness of basement membrane.

In some embodiments, can use dyestuff.The example of available dyestuff is black or their mixture of (but being not limited to) nigrosine, monoazo chromium complex.In some embodiments, can use the mixture of dyestuff and pigment.

Matting agent

Polymeric material has intrinsic surface gloss usually.In order to control glossiness (and therefore producing lacklustre surface characteristic), various additive methods all may be realized dim and low-luster surface characteristic.In a broad aspect, additive method is all based on identical fundamental physics, namely generates the modified surface of (micron order) coarse and irregular moulding, thereby allows luminous reflectance still less to return at a distance (for example, greater than 50 centimetres) viewer.When multi beam light directive glossiness when surface, most of light is with similar angle reflection, and therefore can be observed the luminous reflectance factor of higher level.When identical light source directive lacklustre (namely irregular) surface, light is to many different directions scatterings, and quite high component is absorbed.Therefore, on uneven surface, light is often to all directions diffuse scattering, and image quality weakens (object of reflection is no longer bright dazzling, but smudgy) greatly.

Be used for characterizing the glossmeter of specifically surperficial gloss level based on this same principle.Usually, light source reads catoptrical amount by phototube with fixed angle directive surface after reflection.Can read reflection by a plurality of angles.The maximum glossiness performance on extremely vernicose surface often shows 100% reflection, and complete lacklustre surface often demonstrates 0% reflection.

Silicon-dioxide is for grinding and be filtered to the inorganic particle of specified particle size scope.The irregular shape of silica dioxide granule and porosity and low cost make it become matting agent commonly used.Other potential matting agent can comprise: other pottery of i., for example boride, nitride, carbide and other oxide compound (for example, aluminum oxide, titanium dioxide etc.); With the ii. organic granular, precondition is the processing temperature (depend on selected specific polyimide method, processing temperature is approximately 250 ℃ to approximately 550 ℃) that this organic granular can stand the polyimide of chemical conversion.The matting agent that can be used for polyimide application (can stand the synthetic thermal conditions of polyimide) is polyimide particles.

The amount of matting agent, median particle and density must be enough to produce 60 degree gloss values of expectation.In some embodiments, basement membrane 60 degree gloss values are between following any two values and randomly comprise this two values: 2,5,10,15,20,25,30 and 35.In some embodiments, basement membrane 60 degree gloss values are 10-35.

In some embodiments, matting agent is also to comprise that randomly the amount of these two values exists between following any two values: weighing scale 1.6 % by weight, 2 % by weight, 3 % by weight, 4 % by weight, 5 % by weight, 6 % by weight, 7 % by weight, 8 % by weight, 9 % by weight and 10 % by weight of pressing basement membrane.In some embodiments, matting agent has between following any two values and randomly comprises the median particle of these two values: 1.3,2,3,4,5,6,7,8,9 and 10 microns.Duller particle should have less than (or equaling) approximately 10 microns and greater than (or equaling) the about mean particle size of 1.3 microns.Larger duller particle can negatively affect the mechanical characteristics of final basement membrane.In some embodiments, matting agent has between following any two values and randomly comprises the density of these two values: 2,3,4 and 4.5g/cc.In some embodiments, when the amount of matting agent during lower than 1.6 % by weight of basement membrane, even when matting agent median particle and density all in the scope of expectation, do not reach 60 degree gloss values of expectation yet.In some embodiments, when the intermediate value granularity during lower than 1.3 microns, even when the amount of matting agent and density all in the scope of expectation, do not reach 60 degree gloss values of expectation yet.In some embodiments, matting agent is selected from siallite, barium sulfate and their mixture.

Can prepare basement membrane by any method of the filled polyimide layer for the preparation of chemical conversion well known in the art.In this type of embodiment, preparation comprises the slurries of low conductivity carbon black, and preparation matting agent slurries.Described slurries can use or can not use ball mill grinding, to reach the granularity of expectation.Described slurries can filter or can not filter to remove the macrobead of any remnants.Can prepare polyamic acid solution by method well known in the art.Polyamic acid solution can filter or can not filter.In some embodiments, with high-shear mixer, solution is mixed with low conductivity carbon black slurry and matting agent slurries.When polyamic acid solution prepares with slightly excessive diamines, can add or can not add two additional anhydride solutions, increase to the level of film cast expectation with the viscosity with mixture.Can regulate the amount of polyamic acid solution, low conductivity carbon black slurry and matting agent slurries, to reach required content in the basement membrane that solidifies.In some embodiments, lower than 0 ℃ of cooling this mixture, and with its before the rotation rotating cylinder that is poured into heating or band with transform chemical and mix, in order to prepare the gel-film of part imidization.Gel-film can be peeled from rotating cylinder or band, be placed on the tentering machine frame, then use convection current and radiant heat to be cured in baking oven, with desolventizing and complete imidization, reach the solids content greater than 98%.

Tackiness agent

In some embodiments, basement membrane is the multilayer film that comprises basement membrane and binder layer.The contiguous basement membrane of binder layer also directly contacts basement membrane.Basement membrane of the present disclosure can comprise binder layer, in case after applying, binder layer is basement membrane fixedly.In one embodiment, tackiness agent is comprised of epoxy resin and stiffening agent, and randomly also comprises annexing ingredient, for example elastomerics, curing catalyst (catalyzer), stiffening agent, filler and fire retardant.

In some embodiments, tackiness agent is epoxy resin.In some embodiments, epoxy resin is selected from:

Bisphenol f type epoxy resin,

Bisphenol-s epoxy resin,

The phenol phenol aldehyde type epoxy resin,

Biphenyl type epoxy resin,

The biphenyl aralkyl-type epoxy resin,

Aralkyl-type epoxy resin,

Dicyclopentadiene-type epoxy resin,

Multifunctional type epoxy resin,

Naphthalene type epoxy resin,

Rubber modified epoxy resin, and

Their mixture.

In another embodiment, tackiness agent is to be selected from following epoxy resin: bisphenol A type epoxy resin, cresols phenol aldehyde type epoxy resin, phosphorous epoxy resin and their mixture.In some embodiments, tackiness agent is the mixture of two or more epoxy resin.In some embodiments, tackiness agent is the mixture with identical epoxy resin of different molecular weight.

In some embodiments, epoxy adhesive comprises stiffening agent.In one embodiment, stiffening agent is phenolic compound.In some embodiments, phenolic compound is selected from:

Phenolic novolak,

The aralkyl-type phenolic resin,

Biphenyl aralkyl-type phenolic resin,

Multifunctional type phenolic resin,

Nitrogenous phenolic resin,

The dicyclopentadiene-type phenolic resin,

Phosphorous phenolic resin, and

Contain the triazine phenol novolac epoxy resins.

In another embodiment, stiffening agent is aromatic diamine compound.In some embodiments, aromatic diamine compound is the benzidine based compound.In some embodiments, the benzidine based compound is 4,4'-benzidine or 4,4'-diamino-2, the 2'-dimethyl diphenyl.In some embodiments, aromatic diamine compound is diamino hexichol hydride compounds.In some embodiments, diamino hexichol hydride compounds is 4,4'-diaminodiphenylmethane or 4,4'-diamino diphenylethane.In some embodiments, aromatic diamine compound is the diaminodiphenyl oxide compound.In some embodiments, the diaminodiphenyl oxide compound is 4,4'-diaminodiphenyl oxide or two (4-amino-3-ethylphenyl) ether.In some embodiments, aromatic diamine compound is the diamino-diphenyl sulfide compound.In some embodiments, the diamino-diphenyl sulfide compound is 4,4'-diamino-diphenyl thioether or two (4-amino-3-propyl group phenyl) thioether.In some embodiments, aromatic diamine compound is the diaminodiphenylsulfone(DDS) compound.In some embodiments, the diaminodiphenylsulfone(DDS) compound is 4,4'-diaminodiphenylsulfone(DDS) or two (4-amino-3-isopropyl phenyl) sulfone.In some embodiments, aromatic diamine compound is phenylenediamine.In one embodiment, stiffening agent is aminated compounds.In some embodiments, aminated compounds is guanidine.In some embodiments, guanidine is Dicyanodiamide (DICY).In another embodiment, aminated compounds is aliphatic diamine.In some embodiments, aliphatic diamine is quadrol or diethyl diamines.

In some embodiments, epoxy adhesive comprises catalyzer.In some embodiments, catalyzer is selected from imidazole type, Triazine, 2-ethyl-4-methyl-imidazoles, linearity and contains triazine phenol type and their mixture.

In some embodiments, epoxy adhesive comprises the elastic body toughening agent.In some embodiments, elasticity toughner is selected from the acrylonitrile-butadiene rubber of ethylene-propylene aldehyde radical rubber, acrylonitrile-butadiene rubber, carboxy blocking and their mixture.

In some embodiments, epoxy adhesive comprises fire retardant.In some embodiments, fire retardant is selected from aluminium hydroxide, trimeric cyanamide polyphosphate, concentrated polyphosphate ester, other phosphonium flame retardant and their mixture.

In some embodiments, binder layer is selected from:

Polyimide,

Butyral resol,

Polysiloxane,

Polyimidesiloxane,

Fluorinated ethylene propylene copolymer,

Perfluoroalkyl alkoxy copolymer,

Ethylene vinyl acetate copolymer,

Ethane-acetic acid ethyenyl ester glycidyl acrylate terpolymer,

Ethane-acetic acid ethyenyl ester glycidyl methacrylate terpolymer,

Ethylene alkyl acrylate copolymer with tackifier,

Ethylene methacrylic acid alkyl ester copolymer with tackifier,

The ethylene, propylene acid glycidyl ester,

The ethylene methacrylic acid glycidyl ester,

Ethylene alkyl acrylate glycidyl acrylate terpolymer,

Ethylene methacrylic acid alkyl ester glycidyl acrylate terpolymer,

The ethylene alkyl acrylate maleic anhydride terpolymer,

Ethylene methacrylic acid alkyl ester maleic anhydride terpolymer,

Ethylene alkyl acrylate glycidyl methacrylate terpolymer,

Ethylene methacrylic acid alkyl ester glycidyl methacrylate terpolymer,

Alkyl acrylate vinyl cyanide acrylic terpolymer,

Alkyl acrylate vinyl cyanide methacrylic acid ter-polymer,

Ethylene acrylic acid co polymer (comprising its salt),

Ethylene methacrylic acid copolymer (comprising its salt),

Alkyl acrylate vinyl cyanide glycidyl methacrylate terpolymer,

Alkyl methacrylate vinyl cyanide glycidyl methacrylate terpolymer,

Alkyl acrylate vinyl cyanide glycidyl acrylate terpolymer,

Alkyl methacrylate vinyl cyanide glycidyl acrylate terpolymer,

Polyvinyl butyral acetal,

Ethylene alkyl acrylate methacrylic acid ter-polymer and salt thereof,

Ethylene methacrylic acid alkyl ester methacrylic acid ter-polymer and salt thereof,

Ethylene alkyl acrylate acrylic terpolymer and salt thereof

Ethylene methacrylic acid alkyl ester acrylic terpolymer and salt thereof,

The EMA mono ethyl ester,

The ethylene alkyl acrylate ethyl maleate,

Ethylene methacrylic acid alkyl ester ethyl maleate,

And their mixture.

In some embodiments, multilayer film is table sheath film.

Although can be used for showing sheath, uses basement membrane of the present disclosure, but the polyimide of chemical conversion (wherein the polyimide of chemical conversion prepares by following steps: polyamic acid solution is mixed with catalyzer and/or the dewatering agent that polyamic acid can be changed into polyimide, or polyamic acid is poured into a mould or is expressed in the mixture or solution of catalyzer and/or dewatering agent) will be favourable for the polyimide film of filling with the filler of any type.Authorize the people's such as Kreuz U.S.5,166,308 disclose a kind of aromatics copolyimide film, its Young's modulus is 600-1200Kpsi, thermal expansivity is 5-25ppm/ ℃, the wet swelling coefficient is 2-30ppm/%RH, and the water-intake rate under 100%RH is less than 3.0%, and erosion rate is greater than the identical copolyimide film of using the preparation of same time and temperature condition by thermal conversion process.Yet the people such as Kreuz are not open adds filler in polyimide film.

Although the gel-film with the chemical conversion process preparation has high solvent content, but still is self-supporting.It is believed that any filler all can shift along with removing of large quantity of fluid for having much more so gel-films that need the liquid that removes, or even along with solvent is with membrane.If with the removing and shift of solvent, film will not have curling trend to the filler in the polyimide gel-film so.What expect is Uniform Dispersion.Therefore, it is believed that chemical conversion does not produce and has the homodisperse filled polyimide film that is enough to keep the characteristic on whole film.Therefore, the people such as Kreuz does not imagine the filler that uses any amount.Unexpected is that the polyimide film of chemical conversion is so crisp unlike the polyimide film with identical amount of filler for preparing with thermal transition, and can realize the more Uniform Dispersion of filler with chemical conversion.Fig. 1 is the transmission electron micrograph available from the cross section of three layers of thermal transition polyimide film of the gaseous oxidation aluminium of E.I.du Pont de Nemours and Company (Wilmington, DE) that comprises 20 % by weight.Fig. 2 is that the chemical monolayer with gaseous oxidation aluminium of 13 % by weight transforms PMDA/4, and the transmission electron micrograph of the cross section of 4-ODA, this figure demonstrate than the polyimide film for preparing by thermal transition shown in Figure 1 and disperse more uniformly.

In some embodiments, the filler that can be used for the polyimide film for preparing by chemical conversion except carbon black or pigment is selected from talcum powder, titanium dioxide, needle-like titanium dioxide, zinc oxide, boron nitride, silicon-dioxide, pyrogenic silica, aluminum oxide, gaseous oxidation aluminium, sepiolite, wollastonite and their mixture.The required purposes of polyimide film is depended in the selection of filler.For example, can be by adding boron nitride to improve the thermal conductivity of polyimide film.The boron nitride that adds is more, and the thermal conductivity of polyimide film is just larger.In some embodiments, filler is heat conductive filler.In another embodiment, filler is dielectric filler.In another embodiment, filler is conductive filler material.In some embodiments, filler is any filler that can be used for polyimide.There is physical constraints in amount of filler in the polyimide film that can mix given thickness, and when surpassing this restriction, due to the fragility of film, the polyimide film of filling becomes and is difficult to process.In some embodiments, when filler was selected from talcum powder, titanium dioxide, needle-like titanium dioxide, zinc oxide, boron nitride, silicon-dioxide, pyrogenic silica, aluminum oxide, gaseous oxidation aluminium, sepiolite, wollastonite and their mixture, the filler of 9 % by weight can replace with low conductivity carbon black or pigment at the most.

Polyimide film is thinner, with regard to more being difficult in the situation that film does not become fragile fills.In order to address this problem, usually prepare trilamellar membrane.Fill two skins, interior (core) layer is not filled or is comprised filler less than 5 % by weight.Sandwich layer allows multilayer film to keep acceptable mechanical characteristics.When adopting chemical conversion, can prepare polyimide film that individual layer fills and it still keeps good mechanical characteristics.Another advantage of chemical conversion is the polyimide film that the individual layer for preparing by chemical conversion is filled can be made than thinner with the film of thermal transition preparation.In some embodiments, basement membrane comprises by the polyimide of the chemical conversion of the weighing scale 40-90 % by weight of basement membrane, by the filler (or filler mixture) of the weighing scale 10-60 % by weight of basement membrane, and wherein the thickness of basement membrane is the 8-152 micron.The polyimide of this chemical conversion derived from: based on the dianhydride total content meter in polyimide, the aromatic dianhydride of at least 50 % by mole; And based on the diamines total content meter in polyimide, the aromatic diamine of at least 50 % by mole.In another embodiment, basement membrane comprises by the polyimide of the chemical conversion of the weighing scale 50-90 % by weight of basement membrane, by the filler (or filler mixture) of the weighing scale 10-50 % by weight of basement membrane, and wherein the thickness of basement membrane is the 8-76 micron.

In the following example, except as otherwise noted, otherwise all umbers and per-cent are all by weight.

Embodiment

The present invention will further describe in following examples, and described embodiment is not intended to limit the scope of the invention described in claim.

Measure optical density(OD) with Macbeth TD904 photodensitometer.Record the mean value of 5-10 independent measurement.

Measure 60 degree gloss values with Micro-TRI-Gloss glossmeter (Gardner USA (Columbia, MD)).Record the mean value of 5-10 independent measurement.

Use has the Advantest Model R8340 ultra-high-impedance meter measurement surface resistivity of UR type concentric ring probe, and depresses measurement at 1000 voltaisms.Record the mean value of 3-5 independent measurement.

According to ASTM D149, use Beckman Industrial AC dielectric breakdown tester to measure dielectric strength.Record the mean value of 5-10 independent measurement.

Use Horiba LA-930 particle size analyzer (Horiba, Instruments, Inc. (Irvine CA)) to measure median particle.Use the DMAC(N,N-DIMETHYLACETAMIDE) as carrier fluid.

When using the continuous film casting to prepare sample, use ashing method to determine the amount of matting agent in film.The cineration step of film is as follows: by heating, burn all polymkeric substance and low conductivity carbon black in the smelting furnace of 900 ℃, only stay the matting agent resistates of white.Weight ratio before and after ashing has demonstrated and has comprised the amount of matting agent in the film.

Carry out the polyamic acid viscosity measurement on the Brookeld DV-II+ viscometer able to programme that uses RV/HA/HB#7 spindle or LV#5 spindle.Viscometer speed does not wait from 5-100rpm, so that acceptable moment of torsion percent value to be provided.Reading is to be corrected to the temperature of 25 ℃.

Measure tensile properties according to ASTM D-882-91 method A.Sample size is 25mm * 150mm; Spacing jig is 100mm; Fixture speed is 50mm/min.

100CR is three layers of thermal transition polyimide film that comprise the gaseous oxidation aluminium of 20 % by weight.It is available from E.I.du Pont de Nemours and Company (Wilmington, DE).

Embodiment 1-5 shows, in the situation that use the low levels matting agent, chemical conversion has all realized 60 lower degree gloss values (lacklustre outward appearance) on the basement membrane two sides, has also realized simultaneously high dielectric strength.

Embodiment 1

Preparation is by the carbon black slurry of low conductivity carbon black powder (Special Black4 the derives from Evonik Degussa) composition of the DMAC of 80 % by weight, the polyamic acid prepolymer solution of 10 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and 10 % by weight.Above composition is mixed in rotor stator high speed dispersion shredder fully.Then process slurries in ball mill, in order to make any large agglomerate disperse and reach the granularity of expectation.The median particle of slurries is 0.3 micron.

Prepared silica slurry composed of the following components: the SiO 2 powder of the polyamic acid prepolymer solution of the DMAC of 75.4 % by weight, 9.6 % by weight (the DMAC solution of 20.6 % by weight polyamic acid solids) and 15.0 % by weight (

C803 derives from W.R.Grace Co.).Thoroughly mix each composition in high-shear rotor stator type agitator.Median particle is the 3.3-3.6 micron.

The 16.4kg carbon black slurry is mixed into 158kgPMDA/4 in the groove of 50 gallons (189.3 liters), in 4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pools).Groove is equipped with three independent stirrer shafts of controlling: low speed anchor stirrer, high speed disc decollator and high-shear rotor-stator emulsor.Add DMAC solution and the mixing of the PMDA of about 7kg5.8 % by weight with incremental mode, complete the preparation of mixture, in order to molecular weight is increased and make viscosity reach about 3000 pools.Regulate as required the speed of anchor stirrer, decollator and emulsor, in order in the situation that can not guarantee effectively mix and disperse by the superheated mixture.Cross by making cooling glycol flow the temperature that the tempering tank chuck is further regulated mixture.Filter final solution by 20 micron filters, and remove the air of deentrainment by vacuum outgas.

The silica slurry of metering is added in quantitative final polymkeric substance/carbon black stock liquid stream, and thoroughly mix with high-shear rotor-stator agitator.Mixed flow is cooled to about 6 ℃, adds quantitative conversion chemical diacetyl oxide (0.14cm ³/ cm ³Polymers soln) and 3-picoline (0.15cm ³/ cm ³Polymers soln) also mix, with the hot rotating cylinder top casting film forming of slot die at 90 ℃.The gel-film of gained is peeled and sends into Tenter oven from rotating cylinder, adopt convection current and radiation heating to carry out drying and curing, make solids content greater than 98%.Basement membrane comprises the carbon black of 5 % by weight and the silicon-dioxide of 3.5 % by weight.

The results are shown in table 1.

Tensile strength and elongation at break are shown in Table 3.

Embodiment 2

Preparation is the about aluminum oxide slurries that form of the α-aluminum oxide powder of 2.2 microns by the median particle of the DMAC of 41.7 % by weight, the polyamic acid prepolymer solution of 23.3 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and 35.0 % by weight.Above composition is mixed in rotor stator high speed dispersion shredder fully.

The aluminum oxide slurries of metering together with in the final polymkeric substance that transforms chemical and add the metering of cooling (7 ℃) embodiment 1/carbon black stock liquid stream, are cast and the cure polyimide film with method substantially the same manner as Example 1.The basement membrane of gained comprises the carbon black of 5 % by weight and the aluminum oxide of 7 % by weight.

The results are shown in table 1.

Embodiment 3

Prepare as described in Example 1 carbon black and silica slurry.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pools) mixes, and its consumption should make the film of curing produce the carbon black of 5 % by weight and the silicon-dioxide of 2 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of about 2250 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.Use stainless steel cast rod, polymeric blends manually is poured into is connected with sheet glass The polyethylene terephthalate sheet material.To comprise wetting casting films

In the bath of polyethylene terephthalate sheet material immersion by 50/50 compositions of mixtures of 3-picoline and diacetyl oxide.This is bathed slowly stirred 3-4 minute in order to produce imidization and the pectisation of film.From

Peel off gel-film on the polyethylene terephthalate sheet material, and be placed on pin frame, to retrain film and to prevent from shrinking.After making the residual solvent venting in film, the pin frame that will comprise film is put into the stove of 120 ℃.Make furnace temperature rise to gradually 320 ℃ in 60-75 minute, kept under 320 ℃ 10 minutes, then transfer in the stove of 400 ℃, kept 5 minutes, then take out also cooling from stove.

The results are shown in table 1.

Embodiment 4

Prepare as described in Example 3 basement membrane, the film that wherein solidifies comprises the silicon-dioxide of 3 % by weight.

The results are shown in table 1.

Embodiment 5

Prepare as described in Example 1 carbon black slurry.Synthetic barium sulfate (the Blanc Fixe F of preparation, derive from Sachtleben Chemie GmbH) slurries, the pre-polymer solution of its DMAC by 51.7 % by weight, 24.1 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and the barium sulfate powder of 24.1 % by weight form.Thoroughly mix each composition in high-shear rotor stator type agitator.Median particle is 1.3 microns.

With slurries and PMDA/4,4 ' ODA polyamic acid solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and comprise the carbon black of 7 % by weight and the barium sulfate of 10 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 2400 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.As described in Example 3, polymeric blends is cast to

On the polyethylene terephthalate thin plate and carry out chemical imidization and curing.

The results are shown in table 1.

Comparing embodiment 1

Comparing embodiment 1 shows, the thermal transition meeting of using the matting agent with embodiment 5 equivalent to carry out produces higher (worthless) 60 and spends gloss value and low dielectric strengths on two faces of basement membrane.

Prepare as described in Example 1 carbon black slurry.Synthetic barium sulfate (the Blanc Fixe F of preparation, derive from Sachtleben Chemie GmbH) slurries, the polyamic acid prepolymer solution of its DMAC by 51.7 % by weight, 24.1 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and the barium sulfate powder of 24.1 % by weight form.Thoroughly mix each composition in high-shear rotor stator type agitator.Median particle is 1.3 microns.

With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 7 % by weight and the barium sulfate of 10 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 1500 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.With the stainless steel casting rod with the film hand teeming to sheet glass.The sheet glass that will comprise wet casting films is placed on the hot plate of 80-100 ℃ 30-45 minute, and forming section is dry, " base substrate " film of part imidization.Peel off the base substrate film and be placed on pin frame from glass.The pin frame that will comprise the base substrate film is put into the stove of 120 ℃.Furnace temperature was risen to 320 ℃ gradually in 60-75 minute, kept under 320 ℃ 10 minutes, then transfer in the stove of 400 ℃, kept 5 minutes, then take out also cooling from stove.

The results are shown in table 1.

Comparing embodiment 2

Comparing embodiment 2 shows, the thermal transition meeting of carrying out with the matting agent of 4 % by weight produces higher (worthless) 60 and spends gloss values on two faces of basement membrane, and has low dielectric strength.

Prepare as described in Example 1 carbon black and silica slurry.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pools) mixes, and its consumption should make the film of curing produce the carbon black of 5 % by weight and the silicon-dioxide of 4 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 2250 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.With the stainless steel casting rod with the film hand teeming to sheet glass.The sheet glass that will comprise wet casting films is placed on the hot plate of 80-100 ℃ 30-45 minute, " base substrate " film of, part imidization dry with forming section.Peel off the base substrate film and be placed on pin frame from glass.The pin frame that will comprise the base substrate film is put into the stove of 120 ℃.Furnace temperature was risen to 320 ℃ gradually in 60-75 minute, kept under 320 ℃ 10 minutes, then transfer in the stove of 400 ℃, kept 5 minutes, then take out also cooling from stove.

The results are shown in table 1.

Comparing embodiment 3

Comparing embodiment 3 demonstrations, thermal transition need to use the matting agent of high level could produce 60 lower degree gloss values (lacklustre outward appearance) on air side, but opposite side (non-air side) still has worthless 60 degree gloss values.

Prepare as described in Example 1 carbon black slurry.Preparation aluminum oxide slurries, the median particle of the polyamic acid prepolymer solution of its DMAC by 51.72 % by weight, 24.14 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and 24.14 % by weight are that the α-aluminum oxide powder of 2.3 microns forms.Thoroughly mix each composition in rotor stator high speed dispersion shredder.Slurries are ground destroy afterwards large agglomerate in ball mill.Filter carbon black and aluminum oxide slurries, with macrobead or the agglomerate of removing any remnants.

Complete PMDA/4 by mixing with the DMAC solution of the PMDA of 5.8 % by weight in high-shear mixer, the preparation of 4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pools) is to increase molecular weight and to make viscosity reach about 1500 pools.Final solution is filtered and mixes with low conductivity carbon black and aluminum oxide slurries in high-shear mixer, and extra PMDA final solution and a small amount of band stripper (green film of casting can be separated from watering the Cast Strip easily).Adjust the amount of PMDA final solution to obtain the viscosity of 1200 pools.Relative content by telomerized polymer, slurries and final solution obtains the desired pressure that the carbon black of expectation and aluminum oxide load level and casting die place.Final polymkeric substance/slurry mixture is pumped to slot die by strainer, here in the outer field mode that forms three-layer co-extruded membrane, the liquid flow point is opened.

Complete the 2nd PMDA/4 in high-shear mixer, the preparation of 4 ' ODA prepolymer polymers soln liquid stream makes viscosity reach 1500 pools, then is pumped to casting die by strainer, with the unfilled polyimide sandwich layer in the centre that forms three-layer co-extruded membrane.Regulate the flow of outer and unfilled polyimide sandwich layer solution, to reach the bed thickness of expectation.

Cast to prepare three-layer co-extruded membrane by assembly described above by the slot die on mobile Stainless Steel Band.Make band pass through convection furnace, with evaporating solvent and make the polymer moieties imidization, thereby produce " base substrate " film.The solids content of base substrate film (by the weight loss tolerance that is heated to after 300 ℃) is 72.6%.The base substrate film is peeled off and rolled from the casting band.Then make the base substrate film by Tenter oven, the polyimide film that obtains solidifying.In the tentering process, can shrink to control by film being limited in the edge.The solids content of cured film (by the weight loss tolerance that is heated to after 300 ℃) is 98.8%.

Middle not packing layer accounts for 33% or 1/3 of multilayer film total thickness, and skin comprises aluminum oxide and the low conductivity carbon black that thickness equates.Skin comprises the low conductivity carbon black of 7 % by weight and the aluminum oxide of 30 % by weight.The total thickness of film is 0.49 mil.

The results are shown in table 1.

Tensile strength and elongation at break are shown in Table 3.

Comparing embodiment 4 and 5 shows, needs a certain amount of matting agent to obtain 60 lower degree gloss values (lacklustre outward appearance) on two faces of basement membrane, also shows, granularity can obtain glossiness basement membrane lower than the matting agent of 1.3 microns.

Comparing embodiment 4

Prepare as described in Example 1 median particle and be the carbon black slurry of 0.3 micron.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pools), its consumption should make the film of curing produce the carbon black of 7 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 1900 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.As described in Example 3, polymeric blends is cast to

The results are shown in table 1.

Comparing embodiment 5

Add quantitative extra carbon black slurry in the polyamic acid/carbon black stock liquid stream of the final embodiment 1 of metering, in order to make the content of carbon black in cured film increase to 7 % by weight, then thoroughly mix two kinds of liquid streams with high-shear rotor stator agitator.The basement membrane for preparing as described in Example 1 chemical imidization.

The results are shown in table 1.

Comparing embodiment 6

Comparing embodiment 6 shows, with the BaSO with 10 % by weight ₄The chemical conversion of embodiment 5 compare, with the BaSO of 30 % by weight ₄The dielectric strength that the chemical conversion of carrying out does not demonstrate expectation reduces.But it is shocking, with the BaSO with 10 % by weight ₄The thermal transition of comparing embodiment 1 compare, with the BaSO of 30 % by weight ₄The chemical conversion of carrying out has higher dielectric strength.

With slurries and PMDA/4,4 ' ODA polyamic acid solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 7 % by weight and the barium sulfate of 30 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 2400 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.As described in Example 3, polymeric blends is cast to

The results are shown in table 1.

Embodiment 6-7 shows, by chemical conversion, even use the matting agent of low amount still can obtain 60 lower degree gloss values (lacklustre outward appearance) on two faces of basement membrane, and obtains higher dielectric strength.

Embodiment 6

The black polyamide basement membrane for preparing as described in Example 1 chemical imidization, different is reduces by 37% with the metering ratio of silica slurry.Assign to analyze according to ash, basement membrane comprises the silicon-dioxide of 2.2 % by weight.

The results are shown in table 1.

Tensile strength and elongation at break are shown in Table 3.

Embodiment 7

Prepare as described in Example 1 carbon black and silica slurry.Complete PMDA/4 by mixing with the DMAC solution of the PMDA of 5.8 % by weight in high-shear mixer, the preparation of 4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pools) is in order to increase molecular weight and make viscosity reach about 2500 pools.The liquid stream of final polyamic acid solution of metering is cooled to approximately-10 ℃.With high-shear mixer with similar cooling conversion chemical diacetyl oxide (0.18cm ³/ cm ³Polymers soln) and 3-picoline (0.17cm ³/ cm ³Polymers soln) metering liquid stream and carbon black (0.095cm ³/ cm ³Polymers soln) and silica slurry (0.029cm ³/ cm ³Polymers soln) metering liquid stream is mixed in polyamic acid solution.Filter cooling mixture, and use immediately slot die the hot rotating cylinder top casting film forming of 105 ℃.The gel-film of gained is peeled and sends into Tenter oven from rotating cylinder, adopt convection current and radiation heating to carry out drying and curing, make solids content greater than 98%.Basement membrane comprises the carbon black of about 5.5 % by weight.Assign to analyze according to ash, film comprises the silicon-dioxide of 1.8 % by weight.

The results are shown in table 1.

Tensile strength and elongation at break are shown in Table 3.

Embodiment 8

Prepare as described in Example 1 carbon black slurry.As preparation aluminum oxide slurries as described in comparing embodiment 3.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 5 % by weight and the aluminum oxide of 10 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 1900 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.As described in Example 3, polymeric blends is cast to

The results are shown in table 1.

Comparing embodiment 7

Comparing embodiment 7 demonstrations, the thermal transition meeting that the matting agent of use and embodiment 8 equivalent carries out produce higher (worthless) 60 degree gloss values on two faces of basement membrane, and have low dielectric strength.

Prepare as described in Example 1 carbon black slurry.As preparation aluminum oxide slurries as described in comparing embodiment 3.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 5 % by weight and the aluminum oxide of 10 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 1900 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.As cast membrane as described in comparing embodiment 2 and carry out hot imidization.

The results are shown in table 1.

Comparing embodiment 8 and 9 demonstrations, the content of matting agent must could obtain 60 lower degree gloss values (lacklustre outward appearance) higher than 1.5 % by weight on two faces of basement membrane.

Comparing embodiment 8

Prepare as described in Example 3 basement membrane, comprise the silicon-dioxide of 1 % by weight in the film that wherein solidifies.

The results are shown in table 1.

Comparing embodiment 9

Prepare as described in Example 3 basement membrane, comprise the silicon-dioxide of 1.5 % by weight in the film that wherein solidifies.

The results are shown in table 1.

Comparing embodiment 10 and 11 demonstrations, in order to obtain 60 lower degree gloss values, the median particle of matting agent has lower limit.

Comparing embodiment 10

Prepare as described in Example 1 carbon black slurry.Preparation aluminum oxide slurries, the PMDA/BPDA/ of its DMAC by 81.4 % by weight, 8.3 % by weight/4, the dispersion agent of 4 '-ODA/PPD pre-polymer solution (having the polyamic acid solid of 14.5 % by weight in DMAC), 0.1 % by weight and the gaseous oxidation aluminium powder of 10.2 % by weight form.Above composition is mixed in rotor stator high speed dispersion shredder fully.Then grinding milk in medium grinder decomposing large agglomerate, and reaches the approximately median particle of 0.35 μ m.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 5 % by weight and the aluminum oxide of 2 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 2150 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.As described in Example 3, polymeric blends is cast to

The results are shown in table 1.

Comparing embodiment 11

Preparation calcium phosphate dibasic anhydrous (CaHPO4) slurries, the polyamic acid prepolymer solution of its secondary calcium phosphate by 11.5 % by weight, 64.7 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and the DMAC of 23.8 % by weight form.Thoroughly mix each composition in high-shear rotor stator type agitator.Median particle is 1.25 microns.

The secondary calcium phosphate slurries of metering together with in the metering liquid stream of final polymkeric substance/carbon black stock that transforms chemical and add cooling (8 ℃) embodiment 1 and mix with it, are then cast and the cure polyimide film with method substantially the same manner as Example 1.The basement membrane of gained comprises the carbon black of 5 % by weight and the secondary calcium phosphate of 2.8 % by weight.

The results are shown in table 1.

Comparing embodiment 12

Comparing embodiment 12 demonstrations, high-density matting agent will produce higher (worthless) 60 degree gloss values on two faces of basement membrane.

Prepare as described in Example 1 carbon black slurry.Preparation barium titanate (Sakai, BT-05) slurries, the polyamic acid prepolymer solution of its DMAC by 75 % by weight, 10 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and the barium titanate powder of 15 % by weight form.Thoroughly mix each composition in high-shear rotor stator type agitator, then carry out supersound process, reach the median particle of 1.5 microns.

With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 5 % by weight and the barium titanate of 2 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 1500 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.As described in Example 3, polymeric blends is cast to

The results are shown in table 1.

Embodiment 9,10 and 11

Prepare as described in Example 3 basement membrane, the amount that different is regulates silica slurry makes the silicon-dioxide that comprises respectively 5 % by weight, 7.5 % by weight and 10 % by weight in the film of curing.

The results are shown in table 1.

Embodiment 12 and 13

Prepare as described in Example 1 film.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 5 % by weight and the silicon-dioxide of 2.2 % by weight.Complete as described in Example 1 mixture preparation, casting film, carry out chemical imidization and curing.Condition is adjusted into the basement membrane that obtains 2 mils and 5 mil thick.

The results are shown in table 1.

Embodiment 14 and 15

Process in air classifier SiO 2 powder (

C803), in order to remove the maximum particle of a part.Use as described in Example 1 the silicon-dioxide prepared slarry of air classifying.Median particle is 2.1 microns.Prepare as described in Example 1 carbon black slurry.With carbon black and silica slurry and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 5 % by weight and the silicon-dioxide of 2 % by weight and 4 % by weight.Complete as described in Example 3 the preparation of mixture, and the preparation basement membrane.

The results are shown in table 1.

Embodiment 16

Embodiment 16 demonstrations, the chemical conversion of carrying out with different low conductivity carbon blacks still can obtain 60 lower degree gloss values (lacklustre outward appearance) on two faces of basement membrane, and can obtain high dielectric strength.

The preparation carbon black slurry, the thermally oxidized black with 6% volatile content (Printex U derives from Evonik Degussa) of the pre-polymer solution of its DMAC by 80 % by weight, 10 % by weight (having the polyamic acid solid of 20.6 % by weight in DMAC) and 10 % by weight forms.Thoroughly mix each composition in the rotor stator decollator.Then use ultrasonic processor (Sonics﹠amp; Materials, Inc., VCX-500 type) process slurries, in order to make the carbon black depolymerization.Prepare as described in Example 1 silica slurry.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are about 50 pools) mixes, and its consumption should make the film of curing produce the carbon black of 5 % by weight and the silicon-dioxide of 2 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete the preparation of mixture to obtain the final viscosity of 2250 pools with incremental mode.

The basement membrane for preparing chemical imidization with the operation described in embodiment 3.

The results are shown in table 1.

Comparing embodiment 13

Comparing embodiment 13 shows, the thermal transition meeting of using the matting agent with embodiment 16 equivalent to carry out produces higher (worthless) 60 and spends gloss values on two faces of basement membrane, and low dielectric strength.

As prepared slarry as described in embodiment 16.With the stainless steel casting rod with final polymeric blends hand teeming to sheet glass.The sheet glass that will comprise wet casting films is placed on the hot plate of 80-100 ℃ 30-45 minute, " base substrate " film of, part imidization dry with forming section.Peel off the base substrate film and be placed on pin frame from glass.The pin frame that will comprise the base substrate film is put into the stove of 120 ℃.Made furnace temperature rise to gradually 320 ℃ in 60-75 minute, kept under 320 ℃ 10 minutes, then transfer in the stove of 400 ℃ and kept 5 minutes, then take out from stove and cooling.

The results are shown in table 1.

Embodiment 17

Embodiment 17 demonstrations, the chemical conversion of carrying out with different low conductivity carbon blacks still can obtain 60 lower degree gloss values (lacklustre outward appearance) on two faces of basement membrane, and can obtain high dielectric strength.

As preparation basement membrane as described in embodiment 16, different is that carbon black slurry is prepared by the furnace treated black with 3.5% volatile content (Special Black550 derives from Evonik Degussa).

The results are shown in table 1.

Comparing embodiment 14

Comparing embodiment 14 shows, the thermal transition meeting of using the matting agent with embodiment 17 equivalent to carry out produces higher (worthless) 60 and spends gloss values on two faces of basement membrane, and low dielectric strength.

As preparation basement membrane as described in comparing embodiment 13, different is that carbon black slurry is prepared by the furnace treated black with 3.5% volatile content (Special Black550 derives from Evonik Degussa).

The results are shown in table 1.

Embodiment 18

Embodiment 18 demonstrations, the chemical conversion of carrying out with different low conductivity carbon blacks still can obtain 60 lower degree gloss values (lacklustre outward appearance) on two faces of basement membrane, and can obtain high dielectric strength.

As preparation basement membrane as described in embodiment 16, different is that carbon black slurry is prepared by the furnace treated black with 1.2% volatile content (Printex55 derives from Evonik Degussa).

The results are shown in table 1.

Comparing embodiment 15

Comparing embodiment 15 shows, the thermal transition meeting of using the matting agent with embodiment 18 equivalent to carry out produces higher (worthless) 60 and spends gloss values on two faces of basement membrane, and low dielectric strength.

As preparation basement membrane as described in comparing embodiment 13, different is that carbon black slurry is prepared by the furnace treated black with 1.2% volatile content (Printex55 derives from Evonik Degussa).

The results are shown in table 1.

Comparing embodiment 16

Comparing embodiment 16 shows, the matting agent of use high-content (30 % by weight) carries out thermal transition can obtain 60 desired degree gloss values on the air side of basement membrane, but the opposite side of basement membrane has higher (worthless) 60 degree gloss values, and dielectric strength is lower.

Prepare as described in Example 1 carbon black and silica slurry.With slurries and PMDA/4,4 ' ODA pre-polymer solution (20.6% polyamic acid solid, viscosity are approximately 4500 pool) mixes, and its consumption should make in the film of curing and produce the carbon black of 5 % by weight and the silicon-dioxide of 30 % by weight.When mixing, add the DMAC solution of the PMDA of 6 % by weight that the viscosity of mixture is transferred to 300 pools with incremental mode.Final polymeric blends is carried out vacuum outgas.With the stainless steel casting rod with the film hand teeming to sheet glass.The sheet glass that will comprise wet casting films is placed on the hot plate of 80-100 ℃ 30-45 minute, and forming section is dry, " base substrate " film of part imidization.Peel off the base substrate film and be placed on pin frame from glass.The pin frame that will comprise the base substrate film is put into the stove of 120 ℃.Made furnace temperature rise to gradually 320 ℃ in 60-75 minute, kept under 320 ℃ 10 minutes, then transfer in the stove of 400 ℃ and kept 5 minutes, then take out from stove and cooling.

The results are shown in table 1.

Embodiment 19

Embodiment 19 has showed that the chemical conversion of using ultramarine blue pigment all reaches 60 lower degree gloss values (lacklustre outward appearance) on the both sides of basement membrane, and optical density(OD) enlarges markedly.

Prepare silica slurry composed of the following components: the PMDA/4 of the DMAC of 75.4 % by weight, 9.6 % by weight, the SiO 2 powder of 4 ' ODA polyamic acid prepolymer solution (the DMAC solution of 20.6 % by weight polyamic acid solids) and 15.0 % by weight ( C803 derives from W.R.Grace Co.).Thoroughly mix each composition in high-shear rotor stator type agitator.Median particle is the 3.3-3.6 micron.

Prepare in the following way the blue pigments slurries: at first the ultramarine blue pigment (Nubicoat HWR derives from Nubiola) with 7.5 grams is distributed in the DMAC of 38.9 grams, with ultrasonic processor (Sonics﹠amp; Materials, Inc., model VCX-500) process 10 minutes so that depolymerization pigment.Then with the PMDA/4 of dispersion and 3.6 grams, 4 ' ODA polyamic acid prepolymer solution (the DMAC solution of 20.6 % by weight polyamic acid solids) mixes.

When mixing, add the DMAC solution of the PMDA of 6 % by weight to complete PMDA/4 by increment ground, the preparation of 4 ' ODA pre-polymer solution (the DMAC solution of 20.6 % by weight polyamic acid solids) is to reach approximately 3000 final viscosities of mooring.Add 6.1 gram silica slurries and 36.6 gram blue pigments slurries in the polyamic acid solution for preparing to 157.3 grams, and thoroughly mix.The polymeric blends for preparing is degassed.Use stainless steel cast rod, polymeric blends manually is poured into is connected with sheet glass

The polyethylene terephthalate sheet material.To comprise wetting casting films

Peel off gel-film on the polyethylene terephthalate sheet material, and be placed on pin frame, to retrain film and to prevent from shrinking.After making residual solvent discharge film, the pin frame that will comprise film is placed in 120 ℃ of baking ovens.Oven temperature rises to 320 ℃ within the time period of 60-75 minute, kept 10 minutes at 320 ℃, then transfers to 400 ℃ of baking ovens and keeps 5 minutes, then takes out from baking oven and makes it cooling.According to the composition of the polymeric blends for preparing, basement membrane comprises the silicon-dioxide of 2.5 % by weight and the pigment of 15 % by weight.

The results are shown in Table 2.

Comparing embodiment 17

Comparing embodiment 17 has been showed the thermal conversion of using the matting agent with embodiment 19 equivalent to carry out, produces higher (worthless) 60 degree gloss values on basement membrane both sides.

Use stainless steel cast rod, will manually be poured on sheet glass from the degassed polymeric blends for preparing of embodiment 19.The sheet glass that will comprise wetting casting films is placed on the hot plate of 80-100 ℃ 30-45 minute, " base substrate " film of, part imidization dry with forming section.Peel off the base substrate film and be placed on pin frame from glass.The pin frame that will comprise the base substrate film is placed in 120 ℃ of baking ovens.Oven temperature rises to 320 ℃ within the time period of 60-75 minute, kept 10 minutes at 320 ℃, then transfers to 400 ℃ of baking ovens and keeps 5 minutes, then takes out from baking oven and makes it cooling.

The results are shown in Table 2.

Table 3

Be noted that not to be to need that above the part of concrete behavior may not need in all behaviors described in general description or embodiment, and also can be performed except described those other behavior.In addition, the order of the every kind of listed behavior order that needn't must be performed for them wherein.After reading this specification sheets, those of ordinary skills can determine its specific needs or demand behavior used.

In aforementioned specification, the present invention is described with reference to specific embodiment.Yet those of ordinary skill in the art recognizes in the situation that do not break away from the scope of the invention shown in following claim can make multiple modification and change.In this specification sheets, disclosed all parts all can substitutions of elements that is identical by producing, equal or similar action replace.

Therefore, specification sheets and accompanying drawing are considered to illustrative and nonrestrictive, and all these type of modifications are intended to comprise within the scope of the invention.

Claims

1. basement membrane comprises:

A. by the polyimide of the chemical conversion of the weighing scale 40-90 % by weight of described basement membrane, the polyimide of described chemical conversion derived from:

I. based on the dianhydride total content meter in described polyimide, the aromatic dianhydride of at least 50 % by mole, and

Ii. based on the diamines total content meter in described polyimide, the aromatic diamine of at least 50 % by mole;

B. press the filler of the weighing scale 10-60 % by weight of described basement membrane, do not comprise low conductivity carbon black and pigment; And

Wherein, the thickness of described basement membrane is the 8-152 micron.

2. basement membrane according to claim 1, wherein, the polyimide of described chemical conversion be by with polyamic acid solution with polyamic acid can be changed into the catalyzer of polyimide or step preparation that dewatering agent mixes.

3. basement membrane according to claim 1, wherein:

A. described aromatic dianhydride is selected from:

Pyromellitic acid anhydride,

3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride,

3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride,

4, the two Tetra hydro Phthalic anhydrides of 4 '-oxygen,

3,3 ', 4,4 '-diphenyl sulfone tetraformic acid dianhydride,

2,2-two (3,4-dicarboxyl phenyl) HFC-236fa,

The dihydroxyphenyl propane dianhydride, and

Their mixture; And

B. described aromatic diamine is selected from:

3,4 '-diaminodiphenyl oxide,

1,3-two-(4-amino-benzene oxygen) benzene,

4,4 '-diaminodiphenyl oxide,

Isosorbide-5-Nitrae-diaminobenzene,

1,3-diaminobenzene,

2,2 '-two (trifluoromethyl) p-diaminodiphenyl,

4,4'-benzidine base,

4,4 '-diamino-diphenyl thioether,

9,9 '-two (4-is amino) fluorine, and

Their mixture.

4. basement membrane according to claim 1, wherein, the polyimide of described chemical conversion is derived from pyromellitic acid anhydride and 4,4 '-diaminodiphenyl oxide.

5. basement membrane according to claim 1, wherein, described filler is selected from talcum powder, titanium dioxide, needle-like titanium dioxide, zinc oxide, boron nitride, silicon-dioxide, pyrogenic silica, aluminum oxide, gaseous oxidation aluminium, sepiolite, wollastonite and their mixture.