CN101506283A - Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof - Google Patents
Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof Download PDFInfo
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- CN101506283A CN101506283A CNA2007800309174A CN200780030917A CN101506283A CN 101506283 A CN101506283 A CN 101506283A CN A2007800309174 A CNA2007800309174 A CN A2007800309174A CN 200780030917 A CN200780030917 A CN 200780030917A CN 101506283 A CN101506283 A CN 101506283A
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Abstract
A solvent cast film comprises a polyimide comprising structural units derived from polymerization of a dianhydride component comprising a dianhydride selected from the group consisting of 3,4'-oxydiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, and combinations thereof, with a diamine component wherein the polyimide has a glass transition temperature of at least 190 DEG C.; wherein the film has a coefficient of thermal expansion of less than 60 ppm/ DEG C., a thickness from 0.1 to 250 micrometers, and less than 5% residual solvent by weight; wherein the polyimide has less than 15 molar % of structural units derived from a member selected from the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and a combination thereof.
Description
The cross reference of related application
The application requires the right of priority of the common unsettled U.S. Provisional Application 60/805,821 of submission on June 26th, 2006, incorporates its full content into the application by reference.
Invention field
The method that the present invention relates to comprise the solvent cast film of polyimide and prepare this film.Described film forms by the polyreaction of dianhydride component and diamine components, and Tg is 180 ℃ to 450 ℃, especially 190 ℃ or bigger, and wherein said film has: a) less than 70ppm/ ℃, especially less than 60ppm/ ℃ CTE; B) 0.1 micron to 250 microns, 5 to 250 microns thickness especially; With, c) contain residual solvent less than 5wt%.
Background technology
Thermoplastic sheets and film have wide in range application.For example, thermoplastic film and sheet material can be applied to automobile application, electronic application, Military Application, apparatus, industrial equipments and furniture.
Thermoplastic sheets and film can be enhanced or non-enhanced, porous or non-porous, and can comprise single thermoplastics or multiple thermoplastics of planting.When thermoplastic sheets or film comprised multiple thermoplastics, it can be blend, a plurality of layer or the two.
A kind of important purposes of film is to use (flex circuit application) at flexible circuitry to go up as substrate or coating.In order to be used for this purposes, new film should satisfy two requirements for flexible circuitry substrate key: i.e. low thermal coefficient of expansion (CTE) and high temperature tolerance (especially when using the high temperature manufacturing step).
Need low CTE to be complementary with the CTE (CTE=17ppm/ ℃) of copper as much as possible.This prevents that film from curling because of temperature variation as the substrate of copper layer or copper circuit trace the time.Low CTE prevents also between copper and the stratum basale that dimensional change does not match when thermal cycling, the stress and the tired life-span that increases final flexible circuitry of its copper tracing wire by reducing patterning.In other words, when the film substrate of flexible circuit board is expanded with identical ratio with the conductive metal layer that applies and shunk, be favourable to the character of flexible circuit board.When these layers do not expand with identical ratio and shrink, meeting and being bound to occur with bond and layer the relevant problem of orientation.Though,, even low warpage is arranged more specifically will allow thermal cycling the time less than 30ppm/ ℃ CTE particularly less than 60ppm/ ℃ less than 70ppm/ ℃, be common target, when the CTE of this film become with the CTE of copper more near the time will obtain better result.
TMA or thermo-mechanical analysis test CTE.The dimensional change of membrane sample is determined as the function of temperature, and calculates CTE from the slope meter of this variation.Usually, must on the temperature range that this film will experience, measure CTE in the flexible circuitry course of processing.20 to 250 ℃ temperature range is the rational temperature scope for measuring CTE.
High temperature tolerance also can be the critical nature of the welding process in the basilar membrane tolerance flexible circuitry manufacturing processed.For new pb-free solder method, this film should demonstrate short-term high temperature 260 ℃ tolerance for example.Standard test for temperature tolerance is solder flux float test (solder float test), and wherein the film with small pieces is fixed on the cork, and is immersed in the melt flux 10 seconds.Remove this film then, wipe solder flux, and detect this film.If have any visible warpage or bubbling, this film just can not pass through this test.Though this test does not have the thickness of standard, can write down the minimum thickness of this film by the solder flux float test.The temperature of 260 ℃ and 288 ℃ is the floating temperature of standard solder flux that is respectively applied for the solder flux and the unleaded solder of plumbous congruent melting.
Low CTE and thermo-tolerance to the flexible circuitry substrate require by using polyimide film to solve.Many commercially available polyimide (PI) film has high glass-transition temperature (greater than 350 ℃), and can be partial cross-linked, has excellent temperature tolerance.Polymer molecule in these films is subjected to slight stress when producing them, cause the alignment of polymer molecule and give low CTE for the PI film.Because this film never lives through the temperature of the second-order transition temperature (Tg) that is higher than material, so stress can not relax, and this film is a dimensional stabilizing when flexible manufacturing temperature (flex fabrication temperature).
Because thermoplastic sheets and film use in more and more wide in range application, more and more need thermoplastic sheets and film can withstand one section of the temperature of rising suitable during, and remarkable deterioration.More and more need film to have: a) be lower than 70ppm/ ℃, be lower than 30ppm/ ℃ CTE particularly, and the technical CTE that approaches copper as much as possible; And b) high thermotolerance.
Summary of the invention
The disclosure relates to thermoplastic sheets and the film with wide in range application.For example, thermoplastic film and sheet material can be applied to automobile application, electronic application, Military Application, apparatus, industrial equipments and furniture.
In one embodiment, solvent cast film comprises polyimide, it comprises the structural unit of the polyreaction that is derived from dianhydride component and diamine components, described dianhydride component comprises and is selected from 3,4 '-oxygen di-O-phthalic acid dianhydride, 3,3 '-oxygen di-O-phthalic acid dianhydride, 4,4 '-dianhydride of oxygen di-O-phthalic acid dianhydride and combination thereof; The second-order transition temperature of wherein said polyimide is at least 190 ℃; Wherein said film has the thermal expansivity less than 60ppm/ ℃, 0.1 to 250 micron thickness and less than the residual solvent of 5wt%; Wherein said polyimide has the structural unit that is selected from the material of the ester of dianhydride, biphenyltetracarboxyacid acid of biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid and combination thereof less than being derived from of 15mol%.
The method for preparing the solvent cast polyimide film comprises the polyamic acid composition curtain coating is formed film to substrate; Heat this casting films, heat-up time and Heating temperature make can remove effectively that to desolvate and form thermal expansivity be 0.1 to 125 micron solvent cast polyimide film less than 60ppm/ ℃ and thickness; Thereby with this solvent cast polyimide film of processing the thermal expansivity of this film is reduced to and is lower than 35ppm/ ℃.
In another embodiment, solvent cast film comprises the polyimide that contains the structural unit that is derived from dianhydride component and diamine components, wherein said dianhydride component comprises 3,4 '-oxygen di-O-phthalic acid dianhydride, 3,3 '-oxygen di-O-phthalic acid dianhydride, 4,4 '-oxygen di-O-phthalic acid dianhydride, or its combination, described diamine components comprises 4,4 '-diaminodiphenylsulfone(DDS), mphenylenediamine, Ursol D, 4,4 '-oxygen connection dianiline, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (3-amino-benzene oxygen) benzene of 3-, or its combination; Wherein said film has the thermal expansivity less than 60ppm/ ℃, 0.1 to 250 micron thickness and less than the residual solvent of 5wt%; And wherein said polyimide has the structural unit less than the ester of the dianhydride that is derived from biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid of 15mol% or biphenyltetracarboxyacid acid.
In another embodiment, solvent cast film comprises: contain be derived from 4,4 '-polyimide of the structural unit of oxygen di-O-phthalic acid dianhydride and 4,4; Wherein said polyimide has 190 ℃ to 400 ℃ second-order transition temperature; And wherein said film has the thermal expansivity less than 60ppm/ ℃, 0.1 to 250 micron thickness and less than the residual solvent of 5wt%; And wherein said polyimide has the structural unit less than the ester of the dianhydride that is derived from biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid of 15mol% or biphenyltetracarboxyacid acid.
Preparation circulation polyimide film method for compositions comprises this solvent cast polyimide film of fusion; With fused solvent cast polyimide film and polymer composition are merged, form circulation polyimide film composition.
Another preparation circulation polyimide film method for compositions comprises making this solvent cast polyimide film dissolving; With dissolved film and polymer composition are merged, form circulation polyimide film composition.
The goods that comprise by the described circulation polyimide film composition of method for preparing have also been described.
In another embodiment, solvent cast film comprises: the polyimide that contains the structural unit that is derived from dianhydride and diamines, wherein said dianhydride is selected from 3,4 '-oxygen di-O-phthalic acid dianhydride, 3,3 '-oxygen di-O-phthalic acid dianhydride, 4,4 '-oxygen di-O-phthalic acid dianhydride, and combination, described diamines is selected from 4,4, mphenylenediamine, Ursol D, and combination; The second-order transition temperature of wherein said polyimide is 190 ℃ to 400 ℃; Wherein said film has the dianhydride that is selected from biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid less than 15mol%, the ester of biphenyltetracarboxyacid acid, and the structural unit of combination; And in addition, wherein said film have thermal expansivity less than 60ppm/ ℃ (thermal expansivity of wherein said film copper, silicon, aluminium, gold and silver, nickel, glass, pottery or The thermal expansion of polymer coefficient ± 20ppm/ ℃ in), 0.1 to 250 microns thickness with less than the residual solvent of 5wt%; And wherein said solvent is selected from N, the N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide, tetramethylene sulfone, tetrahydrofuran (THF), benzophenone, pimelinketone, phenol, ortho-cresol, p-cresol, meta-cresol, phenol, ethylphenol, isopropyl-phenol, tert.-butyl phenol, xylenol, pseudocuminol, chlorophenol, chlorophenesic acid, phenylphenol, in alkyl, has 1 ethylene glycol monoalkyl ether to about 4 carbon atoms, in alkyl, has 1 diglycol monotertiary alkyl oxide to about 4 carbon atoms, the glycol monomethyl aryl ethers, propylene glycol list aryl ethers, tetramethyl-urea, Phenoxyethanol, propylene glycol phenyl ether, methyl-phenoxide, veratrole, orthodichlorobenzene, chlorobenzene, trichloroethane, methylene dichloride, chloroform, pyridine, N-cyclohexyl pyrrolidone, ethyl lactate, ionic liquid, and combination.
Description of drawings
Fig. 1 is the figure of time/temperature that is used to prepare the imidization process (profile) of polyetherimide.
Embodiment
When in this specification sheets and claims, using thermoplastic sheets and film, will be with reference to many terms, these terms should be defined as has following implication.Unless context is pointed out clearly in addition, otherwise ＂ of singulative ＂, ＂ ＂ and ＂ should comprise plural indicator by (described) ＂.Unless otherwise defined, otherwise technology that the application is used and scientific terminology have the common identical meanings of understanding of those skilled in the art.Compound uses standardized denomination to describe.
Except operation embodiment, perhaps unless otherwise noted, otherwise used all numerals or statement about composition, reaction conditions equivalent in this specification sheets and claim all are construed as and modified by term " about ".Its combination of term ＂ ＂ is meant and has one or more listed components and one or more optional similar components of not enumerating.Various numerical ranges have been disclosed in the present patent application.Because these scopes are successive, so they comprise each value between minimum value and the maximum value.Unless point out in addition clearly, otherwise the various numerical ranges of pointing out in this application are approximations.All scopes that relate to same composition or character all comprise end points, and end points can make up independently mutually.
For purpose of the present invention, ＂ film ＂ is the planar slice (flatsection) of thermoplastic resin or other material, compares with width with its length, and it is extremely thin.
Term ＂ curtain coating ＂ is meant molding or the forming method that uses mobile or fused material preparation printing (impression), comprises pouring in the mould or pouring on the sheet material, and described material is hardened in described mould or on the described sheet material or solidifies.
＂ solvent cast film ＂ carries out curtain coating by convection cell on molded surface, and the solvent of removing in the curtain coating liquid forms sheet material or breadth (web), thus the film that forms.
Unless otherwise noted, otherwise all ASTM test and data all come from 1991 editions Annual Book of ASTM Standards.
＂ thermal expansivity ＂ is the raise increase of volume 1 ℃ time of the polymkeric substance of unit volume temperature under constant pressure.For the present invention, the CTE measurement is that the thermo-mechanical analysis (TMA) of the heat-up rate (thermal ramp rate) by 5 ℃/minute is carried out.It is wide that test sample is of a size of 23mm length * 5mm.Test sample stands 0 ℃ to 250 ℃ the heating first time of 5 ℃/min rate of heating, and the CTE pH-value determination pH is at the slope of length variations under 0.05 newton's the power (length change) in 30 ℃ to 200 ℃ temperature range.
＂ chemical resistance ＂ is the ability of the infringement of solid material opposing chemical reaction or solvent action, can test D543-06 according to ASTM and measure.
＂ specific inductivity ＂ (specific inductivity constant (permittivity constant)): all strong between any two electrified body (attracting or repulsion), this power changes with following factor: the intensity of electric charge (q1 and q2), distance between the electrified body (r), with the character (ε is called specific inductivity) of the medium (dielectric medium) of this two electrified body at interval.This power is by following Equation for Calculating: F=q1q2/ (ε r
2).
＂ modulus in flexure ＂ (modulus in flexure) is in 3 static deflections (static flexure), in elastic limit (elastic limit) scope to the stress that outermost fibers applied of test sample, with the strained ratio of the outermost fibers of calculating, can test D790 or D790M mensuration according to ASTM.
＂ flexural strength ＂ (modulus in flexure of break (rupture)) stands the maximum stress that the outermost fibers of the strip of three point loads is calculated when splitting or rupture.ASTM test D 790 and D 790M are widely used for measuring this character.For most of plastics, flexural strength usually is significantly higher than direct tensile strength (straight tensile strength).
＂ glass transition ＂ is that reversible changes, it betide in the amorphous polymer or the amorphous domain of partially crystalline polymer in (when with it when low-down temperature is heated to a certain scope), this variation is that each polymkeric substance is peculiar, it is characterized in that quite suddenly becoming flexibility or elastic stage from hard, glassy or brittle state.Meanwhile, physical properties such as thermal expansivity, specific heat and density etc. usually change to the derivative of temperature.In this transforming process, usually coil at low temperatures, winding and immobilized molecular chain become and can freely rotate each other and slip over.
The chances are that the mid point of the temperature range of glass transition takes place for ＂ second-order transition temperature ＂ (Tg).Tg is unconspicuous (being similar to fusing point), it by secondary character along with the variation of the rising of temperature (as than perhaps electrical property or mechanical properties with variation of temperature speed) record.In addition, observed Tg can the noticeable change along with the specific nature of selecting to be used for observing and experimental detail such as heating rate or electric frequency.Therefore should to be considered as be estimated value to the Tg of record.The most reliable estimated value derives from the loss peak (loss peak) or the expansion data (dilatometric data) of dynamic test usually.For purpose of the present invention, second-order transition temperature (Tg) is determined by the maximum point of mechanical loss angle tangent cutve (tan delta curve).Tg also can pass through the flex point of DSC (difference formula scanning calorimetric) trace (ASTM tests D3148) and measure.
＂ melt temperature ＂ (hereinafter is designated as its symbol ＂ T
m＂) be following temperature: in this temperature, the heat energy of solid material is enough to overcome intermolecular magnetism in the lattice, thereby lattice is destroyed, and material becomes liquid, i.e. its fusion.According to the present invention, T
mAccording to ASTM test D3148 standard test.
＂ melt viscosity ＂ is a molten resin to the patience of shearing, and is quantified as any some place shear-stress in the mobile material divided by the merchant of shearing rate.The definition of elongation viscosity is that similarly it works when the stretching extrudate.In polymkeric substance, viscosity not only depends on temperature, also more weakly, depends on pressure, also depends on the level (perhaps shearing rate) of shear-stress.For purpose of the present invention, melt viscosity is learned mensuration at 380 ℃ by capillary rheology according to ASTM D3835 standard.
The steam that absorbs during ＂ moisture absorption (Moisture Absorption) ＂ to be material expose in the atmosphere of specifying humidity and temperature regular hour section.There is not the ASTM test in character hereto.Measure moisture absorption in 50% relative humidity by being immersed in the water increase by weight.
＂ tensile modulus ＂ or ＂ Young's modulus ＂ are the nominal tensile stresses and the ratio of corresponding elongation, and it is lower than the proportionality limit of material.Suitable ASTM test is D638.
＂ tensile strength ＂ is at specified temperature and the specified rate of extension maximum nominal stress that it bears during from two ends tension test sample.When the nominal stress of maximum comes across yield-point, should be designated as surrender tensile strength.When it produces fracture, should be designated as fracture tensile strength.The ASTM test of plastics is D638 ((metric) of metric system, D638M) standards.The SI unit of tensile strength is pascal (N/m
2).
Channel pitch (Gallery spacing) or d-spacing (d-spacing) are the distances that forms between each microplate (microplate) of nano silicate (and nanoclay synonym).As if the variation of channel pitch depend on the nano silicate of modification and the composition of solvent.
＂ inserts (Intercalate) ＂ and is meant by adding properties-correcting agent, solvent or polymkeric substance to the method that the d-spacing is increased.The d-spacing of the nanoclay of modification is greater than the d-spacing of identical unmodified nanoclay.
＂ peels off (Exfoliate) ＂ and is meant that the sheet that forms this caly structure separates fully.Sometimes, exist not exclusively peel off to become to have a plurality of than minor structure, be called viscoloid (tactoids).
＂ polyamic acid solution ＂ (be also referred to as poly--acid amides-acid, poly-(amido acid) (poly (amic acid)), amido acid (amic acid), polyamic acid (polyamicacid), poly-(amido acid) (poly (amic acid)), poly-(amido acid) (poly (amide acid)), poly-(acid amides) acid (poly (amic) acid), poly-(acid amides-acid) (poly (amide-acid)), or polymeric amide-acid) be to contain the unitary solution of amido acid that can form imide group with organic group reaction on every side.
The used ＂ polyimide ＂ of the application is meant and contains multiple imide functionality and the other functional group of choosing wantonly such as the polymkeric substance of acid amides and/or ether.Therefore, ＂ polyimide ＂ is also included within polyamidoimide and polyetherimide in its scope.
Term ＂ inertia ＂ is meant that the atmosphere in the container replaces with rare gas element such as nitrogen.
＂ circulation ＂ is meant that all or part polymkeric substance according to the present invention can be used further to the initial purposes that this polymkeric substance is used for.For example, if polymkeric substance at first as the solvent cast film of flexible circuit board, is then using or do not using under the situation of other monomer or polymkeric substance, all or partial polymer can circulate and be dissolved in the solvent.Circulation is meant that also this polymkeric substance can partially or completely be reused in another purposes such as the moulding by another renovation process.
When thinking that the structural unit of chemical part is derived from precursor portions among the application in form, the actual chemical reaction that is used to produce this chemical part there is not implicit restriction.For example, when thinking that chemical part such as polyetherimide have the structural unit that in form is derived from dianhydride and diamines, so any known method all can be used for preparing this polyetherimide, comprise the reaction of dianhydride and diamines, or phenates thing class (phenoxide species) and have substitution reaction between the imide that can replace group, or other known method, essential only is that this chemical part comprises the structural unit that can be present in the described precursor portions.
The disclosure relates to the solvent cast film that comprises dianhydride component and diamine components, and its Tg is 180 ℃ to 450 ℃, especially 190 ℃ or bigger, and wherein said film has: a) less than 70ppm/ ℃, especially less than 60ppm/ ℃ CTE; B) 5 microns to 250 microns, 0.1 to 250 micron thickness especially; With, c) contain residual solvent less than 5wt%.
According to solvent cast film of the present invention can be that 180 ℃ to 450 ℃ polyimide is made by at least a Tg.In another embodiment, the Tg of this polyimide is 190 ℃ or bigger, 190 ℃ to 500 ℃ particularly, and more specifically 190 ℃ to 400 ℃.Those skilled in the art should understand that, the Tg of any specific polyimide can vary widely, depend on following factor, comprise: quantity, the processing conditions in the film production process of the selection of dianhydride monomer, the quantity of different dianhydride monomer (structure relative), the selection of diamine monomer, different diamine monomer (structure relative), be used to make the type of the imidization method of polymer cure with the unit with the unit, etc.It will be understood to those of skill in the art that to produce ability, depend on used monomer, end capped use etc. with polymkeric substance of any desired Tg in the aforementioned Tg scope.
The type of making the polyimide of this film can change similarly.The present invention comprises particularly, exists with all combinations, can prepare described one or more dianhydrides of polyimide of the present invention and the random and block polymer and the multipolymer of described one or more diamines.Can there be polyimide, for example combination of polyamidoimide and polyetherimide, the perhaps combination of two kinds of dissimilar polyetherimides more than one type.Equally, the present invention relates to comprise the solvent cast film of one or more polyimide films that contain other polymkeric substance, described other polymkeric substance is selected from unbodied thermoplastic polymer, comprise PPSU (Polyphenylene Sulfone), PSU (polysulfones), PC (polycarbonate), PPO (polyphenylene oxide), PMMA (polymethylmethacrylate), ABS (acrylonitrile-butadiene-styrene terpolymer), PS (polystyrene), PVC (polyvinyl chloride), the crystalline thermoplastic resin, comprise PFA (PFA), MFA (multipolymer of TFE (tetrafluoroethylene) and PFVE (perfluorinated vinyl ethers)), FEP (fluorinated ethylene-propylene polymer), PPS (polyphenylene sulfide), PEK (polyetherketone), PEEK (polyethers-ether ketone), ECTFE (ethylene-chlorotrifluoro-ethylene copolymer), PVDF (poly(vinylidene fluoride)), PTFE (tetrafluoroethylene), PET (polyethylene terephthalate), POM (polyacetal), PA (polymeric amide), UHMW-PE (ultrahigh molecular weight polyethylene(UHMWPE)), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene(HDPE)), LDPE (new LDPE (film grade)), with advanced person's engineering resin (engineering resin) as PBI (polybenzimidazole), poly-(ether sulfone), poly-(aryl sulfone), polyphenylene oxide, polybenzoxazole, and polybenzothiozole, and blend and multipolymer.
The CTE of the film of measuring can be the inherent nature of material, depends on the chemical constitution of material.Perhaps, this CTE can be by using additive and/or significantly being lower than the intrinsic CTE of this mould material by carrying out other procedure of processing.The CTE of this solvent cast film can be and is lower than 70ppm/ ℃, is lower than any CTE of 60ppm/ ℃ particularly, and makes this film can be used as its desired use.For example, for flexible circuit board, this CTE can make this film to be used as desired use as the lid of layer in dielectric substrate, the laminating material and/or flexible circuit board enough near the CTE of adjacent metal conductive layer.In the embodiment that separates, this CTE is less than 70ppm/ ℃, less than 50ppm/ ℃, and less than 40ppm/ ℃, less than 35ppm/ ℃, less than 30ppm/ ℃, or less than 20ppm/ ℃.According to other embodiment, the CTE of this film is 5ppm/ ℃ at least.The CTE of this film also can be 5 to 60ppm/ ℃, and more specifically this thermal expansivity is 10ppm/ ℃ to 30ppm/ ℃, even more specifically 10ppm/ ℃ to 20ppm/ ℃.
Perhaps, the CTE of film is adjusted to its on place this film base material be complementary.In one embodiment, the CTE of this film the CTE of copper, silicon, aluminium, gold and silver, nickel, glass, pottery or polymkeric substance ± 20ppm/ ℃ in, particularly the CTE of copper, silicon, aluminium, gold and silver or nickel ± 20ppm/ ℃ in.In another embodiment, the CTE of this film is at copper, silicon, aluminium, gold and silver or nickel, particularly the thermal expansivity of copper ± 15ppm/ ℃ in.
In favourable one side, the CTE that has been found that this film is very stable.For example, before the CTE of this film is lamination after 250 to 450 ℃ temperature is laminated to substrate the CTE of this film ± 10ppm/ ℃ in.
The thickness of this film can vary widely according to following factor: the final application prepares the method for this film, solid content of curtain coating solution or the like.Thickness can be 0.1 micron to 10,000 microns at the most, perhaps more specifically 5 microns to 1,000 micron at the most, still, expectation be that in order to be used for flexible circuit board, most probable thickness can be 0.1 micron to 250 microns.
Final solvent cast film can contain residual solvent, still can bring into play its desired use.The residual solvent of minimum is the maximum residual solvent levels that this film still can be brought into play its desired use.On the other hand, this solvent cast film also can contain the low residue solvent that reaches as far as possible.For example, solvent is expensive and may has environmental hazard.Can reach the saving cost simultaneously and improve envrionment conditions by minimizing the amount that is included in the solvent in the finished product.Residual solvent levels can be less than 5% of this film gross weight.In another embodiment, the amount of residual solvent will be for less than 1% of this film gross weight.
The solvent that can be used in this method comprises any solvent that can be used to prepare solvent cast film.This solvent can be the good solvent of polyimide, for example, has high relatively boiling point, is convenient to form solution film or directly carries out devolatilization by extruding.Be used to form solvent phase that the solvent of film can prepare polyamic acid solution with being used to hereinafter described with.The example of suitable solvent includes but not limited to N-Methyl pyrrolidone (N-methyl pyrrolidinone NMP), trichloroethane, N, N-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), methyl-sulphoxide (DMSO), tetramethylene sulfone, tetrahydrofuran (THF) (THF), benzophenone, pimelinketone, phenol, adjacent-, right-and-mixture of cresols, the mixture of cresols and phenol, ethylphenol, isopropyl-phenol, tert.-butyl phenol, xylenol, pseudocuminol, chlorophenol, chlorophenesic acid, as orthodichlorobenzene (o-DCB), phenylphenol, in alkyl, has 1 ethylene glycol monoalkyl ether to about 4 carbon atoms, in alkyl, has 1 diglycol monotertiary alkyl oxide to about 4 carbon atoms, the glycol monomethyl aryl ethers, propylene glycol list aryl ethers, N, dinethylformamide, tetramethyl-urea, Phenoxyethanol, propylene glycol phenyl ether, methyl-phenoxide, veratrole, orthodichlorobenzene, chlorobenzene, trichloroethane, methylene dichloride, chloroform, pyridine, N-cyclohexyl pyrrolidone, ethyl lactate, ionic liquid, and the mixture that contains one or more these solvents.Ionic liquid generally includes the salt of fusing point low relatively (being lower than 100 ℃).Ion liquid example include but not limited to based on ammonium, imidazoles-, Phosphonium-, pyridine-, tetramethyleneimine-and the salt of sulfonium.Counter ion in these liquid can include but not limited to following: bromide anion, chlorion, tetrafluoroborate, acetate moiety, phosphate radical, carbonate, sulfate radical, methane sulfate radical, nitrate radical, thiocyanate ion, and combination.
It should be appreciated by those skilled in the art that used concrete solvent depends on many factors, comprise for example polyimide and the solubleness of precursor monomer in solvent and the volatility of solvent.
Can be according to solvent cast film of the present invention by any method preparation known in the art.Transfer GE following Patent publish the general method of preparation solvent cast film and curtain coating solution: 4,115,34l; 4,157,996; 4,307,226; 4,360,633; 4,374,972; With, 3,847,867.A kind of preparation method can may further comprise the steps: form polyamic acid solution, described polyamic acid solution contains the polyamic acid product that is partly dissolved in the monomer component that comprises one or more dianhydrides and one or more organic diamines in the solvent system at least; To substrate, make this polyamic acid solution have the form of length, width and the degree of depth on the substrate surface this polyamic acid solution curtain coating; Remove and to desolvate, and solidify this polyamic acid solution, form film, this film has less than 70ppm/ ℃, particularly less than 60ppm/ ℃ CTE and 0.5 micron to 250 microns, and 0.1 to 250 micron thickness particularly.
Perhaps, this method can comprise the preparation solvent cast film, comprising: preparation comprises the curtain coating solution of polyamic acid solution, and described polyamic acid solution is by monomer component that forms polyamic acid and solvent composition preparation; The film of curtain coating curtain coating solution on support base; Remove the one section preset time that desolvates from this casting films, form the solvent cast polyimide film, this film has less than 70ppm/ ℃, particularly less than 60ppm/ ℃ CTE and 5 microns to 250 microns, and 0.1 to 250 micron thickness particularly; Open this solvent cast film is carried out other procedure of processing, be lower than 35ppm/ ℃, be lower than 30ppm/ ℃ particularly thereby the CTE of this film is reduced to.
Described polyamic acid solution can be prepared as follows: mix one or more dianhydrides, water and solvent by stirring, up to described one or more dianhydride components dissolved.Can add one or more monomer diamines then, with this solution stirring up to amine solvent.The component that constitutes described dianhydride component and described diamine components can comprise l, 2,3,4,5 or more kinds of different dianhydride and diamines.Scope of the present invention is intended to comprise all arrangements and the combination of described many and various dianhydride and diamine monomer particularly.For example, in one embodiment, described polyamic acid solution will be made up of with two kinds of different diamines two kinds of different dianhydrides.In another embodiment, a kind of of described one or more dianhydrides is ODPA.
Usually, described organic amine components contents can be every mole of dianhydride component 0.5mol to 2.0mol, perhaps more specifically 1 to 1.3mol.When in the component that is included in solution of the present invention more than a kind of compound, the umber of described this component, mole number or other amount are considered as being included in umber, mole number or this other amount sum of every kind of compound in this component respectively.Therefore, for example, total amine content obtains by the equivalents addition calculation to every kind of diamines in the amine component, for example, and 2 (mole number of first kind of diamines)+2 (mole number of second kind of diamines)=total amine equivalents.
Calculate total acid anhydride content in a similar fashion.Excessive a little amine can be used for giving film extra flexible or possible crosslinked.Have been found that polyimide enamel (enamel) can have 5 to 500, preferred 10 to 200 multiple dianhydrides-diamine reactant product unit.Also can there be end capped amino and phthalic acid or Tetra hydro Phthalic anhydride or various suitable end group.
Experience shows, should utilize enough solvents that solid content is provided, thereby the solution that has for stirring and handle feasible viscosity is provided.In one embodiment, this solid content is 1-65wt%.In other embodiments, this solid content is 1-40%, 1-30%, 1-25%, 1-15%, or 1-12.5wt%.
In the manufacturing of solvent cast film, the solution that the ratio of monomer reactant and organic solvent component is high advantageously makes the amount of the organic solvent that discharges in the formation of ensuing polyetherimide resin and solidification process minimize.This solution with high-load monomer reactant can have and is used for the high viscosity of the required viscosity of some solvent cast films.Usually, comprise water and reduced soltion viscosity.Given viscosity reduces can use additional water to produce, and the amount of described additional water produces the low effect of identical viscosity drop with respect to needs and the amount of the organic solvent component of adding is less.
Water can be or can not be the part of polyamic acid solution.The amount that water can exist can be any amount to this solution at the most and is substantially free of sedimentary maximum.Though water can be miscible with all basically ratios with this organic solvent component, in monomer solution of the present invention, comprise too many water and can cause forming precipitation or other a plurality of phases.The amount of the water that can exist depends on concrete dianhydride and diamine components, concrete organic solvent component, and the weight ratio of monomer reactant and organic solvent.
Advantageously, polyamic acid solution of the present invention can comprise monomer reactant, and its total amount is 40 or bigger wt%, for example 40 to 75wt% or bigger, and based on the weight of solution.In general, the solution of this high monomer content comprises the water that may need, the temperature range that is generally used for preparing solvent cast film for example 15 ℃ to 200 ℃ have suitable viscosity.
Wrapping aqueous solution can be more easily by preparing in the solution that under agitation the monomer reactant component is added to water and organic solvent component.Usually can quicken the preparation of solution in the temperature that raises.
Additive can be added in the polyamic acid solution, be lower than this material and do not having the CTE that has under the situation of additive thereby CTE is reduced to.These additives comprise the CTE that can auxiliary reduce solvent cast film those and can in film of the present invention, assist those of another desirable properties of generation.Can use these compositions with any amount of giving desirable properties, ratio can be 0.001 to 60 part of additive of per 100 weight part polyimide.Perhaps, the addition of these additives can be the additive of 0.01 to 30 part of per 100 weight part polyimide, more specifically 0.1 to 10 part additive.
The type of additive that can be used for reducing the CTE of solvent cast polyimide film comprises nano-complex silicate (nanoclay) and the soluble nanoparticle precursor such as the praseodynium aluminium of modification.
Nanoclay after forming, polyamic acid composition directly can be added in the said composition.Find that also polyimide can easily be dissolved in the nano-complex solution that peels off, and peel off can by devolatilization or in non-solvent precipitation remove desolvate after maintenance.Can or melt extrude the polyimide-nano complexes material that to obtain by solution casting and be shaped to film.The film that obtains has high Tg and low CTE.
In addition, have been found that the polyreaction of diamines and dianhydride causes the Nano filling of modification to have good dispersiveness in the presence of organically-modified nano silicate.Can be by melt extruding or solution casting is shaped to film with described nano-filled polyimide compositions, thus low CTE, high Tg, polyimide film obtained.
The most normally used is the nanoclay that peels off.For example peel off and in solvent system, carry out by supersound process.For example, peel off in the composition of the solvent system that contains 10 to 90wt% nanoclay and 10 to 90wt% and carry out.Can be before adding polyamic acid solution to, after adding polyamic acid solution to, or described dianhydride component and organic diamine component are peeled off before reacting in solvent system.Perhaps, in the nano silicate solution that peels off, add the high Tg nano-complex that high molecular weight polymers obtains peeling off.Can be film with these forming materials by solution casting, obtain low CTE polyimide film.In one embodiment, make the nano silicate of modification in selected solvent, after the homogenize, then carry out supersound process.Can intermittently or successive technology in carry out supersound process.In described batch technology, the silicate/solvent mixture of the modification of homogenize is contacted placement with described sound source (sonicsource).This mixture is fully stirred to guarantee that whole mixture is carried out uniform supersound process.In successive technology, the nano silicate/solvent mixture of modification is crossed ultrasonic zone with given velocity flow.Nano silicate/the solvent mixture of this modification is fully stirred, to guarantee the homodisperse of nano silicate.In intermittence or continuous processing, peeling off required ultrasound condition (is flow velocity, ultrasonic power, ultrasonic time) depend on the type, solvent, the size (batch size) of batch of material, the configuration and the size of sound source of used properties-correcting agent, and the temperature of carrying out supersound process.The insertion of nano silicate particle and peel off and to observe by gained solution being carried out X-ray diffraction (XRD).Peel off and can more directly observe by following steps: the nano silicate solution and the polyimide solution of supersound process are merged, remove by evaporation or precipitation and desolvate, curtain coating or compacting (pressing) film, and carry out tem analysis.
Nano silicate can be peeled off, thus the d-spacing that had originally when making the d-spacing of this material not peel off step greater than this material.According to the present invention, this d-spacing can be any value greater than the d-spacing of the unmodified nano silicate of the CTE that will reduce polyimide film.According to alternative embodiment, the nano silicate of modification will have the d-spacing greater than 15,20,25,30,40,50 and 75 dusts.
Have been found that the use nanoclay, the nanoclay that especially peels off provides unexpected advantage.The film that comprises nanoclay can have the CTE lower than the film of the same composition that does not contain nanoclay.Alternatively, perhaps in addition, comprise that the film of nanoclay can have the Tg identical with the film of the same composition that does not contain nanoclay.The film that comprises nanoclay is also transparent.The amount of the nanoclay that uses in this film can change according to the film character of expectation.For example, this film can comprise 0.1 to 10wt% nanoclay, and 1 to 10wt% nanoclay particularly is based on the gross weight of this film.
Nano silicate can have the organic modifiers that has the functionalized cationic degree, and can be heat-staple in the processing temperature of film moulding.
According to the common method for preparing solvent cast film of this method be included in selection solvent (for example, DMAc) in by ultrasonic or high shear mixing clay dispersion with modification.Described clay dispersion is mixed with the solid that contains 1-15wt%, perhaps more specifically, the solid of 1-5wt%.With described monomer, at least a dianhydride monomer and at least a diamine monomer add in this clay dispersion, form the polyamic acid solution of modification.Equally, not that polyamic acid is added in this clay dispersion, but the solvable polyimide of complete imidization can be dissolved among solvent such as DMAc and the NMP, form the solid of 5-25wt% (for example 10wt%).In another embodiment, the limiting viscosity of the 10wt% solution of exsiccant film in N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone is greater than 0.05dl/g.Can and carry out curtain coating as mentioned above with described polyimide solution and clay dispersion merging then.
Another additive that can be used for reducing the CTE of solvent cast polyimide film is the metal oxide nanoparticles that can be formed by Organometallic precursor.Metal oxide nanoparticles can original position form by making organometallic precursors decompose.An example of this material is praseodynium aluminium (Al (acac)
3).(Al (acac)
3) pyrolysis produce aluminum oxide.When in dilute solution (small molecules solvent or polymer melt), carrying out, form Al
2O
3Nanoparticle.In order to reach the Al that has the 1wt% carrying capacity in the final polymkeric substance
2O
3, can before the polyreaction of dianhydride and diamine monomer (oxygen di-Tetra hydro Phthalic anhydride and diaminodiphenylsulfone(DDS) particularly), add precursor.Compare with unfilled control sample, what obtain is filled with Al
2O
3The CTE that the polymkeric substance of nanoparticle demonstrates has reduced above 15%.
Except organometallic precursor is added to the polyreaction, also this precursor and polyamic acid solution or final solvable polyimide can be carried out solvent blend (solvent blended), perhaps with final polymkeric substance blend and extrude the system that obtains filling.Can be film and curing with this material curtain coating of solution form, the film that obtains filling.Other suitable Organometallic precursor comprises acetylacetonate metal-salt (metal (acac)) mixture and ceramic precursor such as moly-sulfide.
The additive that can be used for giving other type of desirable properties (except the CTE that reduces polyimide film or be different from the CTE that reduces polyimide film) comprises filler and toughener for example glass fibre, milled glass, granulated glass sphere, sheet glass etc.Can add mineral such as talcum, wollastonite, mica, kaolin or montmorillonitic clay, silicon-dioxide, pyrogenic silica, perlite, quartz and barite.Also for example carbon fiber and carbon nanotube, glass fibre, steel fiber, metal-powder, conductive carbon and other additive (comprising the nano level toughener) carry out modification to said composition in the mineral filler of available significant quantity.
In some cases, metal oxide can be added in the polymkeric substance of the present invention.In some cases, metal oxide also can improve fire-retardant (FR) performance by reducing the time that heat discharges and the increase peak heat discharges.Titanium dioxide is important.Other metal oxide comprises zinc oxide, boron oxide, weisspiessglanz, ferric oxide and transition metal oxide.Bai Se metal oxide may be expected in some cases.Metal oxide can use separately or use with other oxide-metal combinations.Can be with any significant quantity, be that 0.01 to 20wt% amount of polymkeric substance is used metal oxide in some cases.
Other useful additive comprises smoke suppressant (smoke suppressant) for example metal borate such as zinc borate, the borate of basic metal or alkaline-earth metal or other borate.In addition, can use other boron-containing compound, as boric acid, boric acid ester, boron oxide (boron oxide), or other oxygenatedchemicals of boron.In addition, can use other flame retardant additives such as aryl phosphate ester and bromination of aromatic compound, comprise the polymkeric substance that contains the linking group that constitutes by the bromination aryl compound.The example of halogenated aromatic substance is bromination phenoxy resin, halogenated polystyrene, halogenation imide, brominated polycarbonate, brominated epoxy resin and composition thereof.
In some cases, can expect to have and be substantially free of the especially flame retardant composition of bromine and chlorine of halogen atom.Being substantially free of halogen atom is meant in some embodiments, said composition has 3% halogen less than composition weight, chlorine and/or bromine particularly, and in other embodiments, contain halogen atom, particularly chlorine and/or bromine less than the 1wt% of composition.The amount of halogen atom can be determined by common chemical analysis.
Said composition also can randomly comprise 0.01 to 5.0wt% the fluoropolymer of its amount for composition weight.Described fluoropolymer can use with any effective amount that antidrip character is provided to resin combination.The method of some examples of suitable fluoropolymer and this fluoropolymer of preparation for example is described in the United States Patent (USP) 3,671,487,3,723,373 and 3,383,092.Suitable fluoropolymer comprises homopolymer and the multipolymer that contains the structural unit that is derived from one or more fluorizated alpha olefin monomers.Term ＂ fluorizated alpha olefin monomers ＂ is meant and comprises the substituent alpha olefin monomers of at least one fluorine atom.The alpha olefin monomers of fluoridizing that some are suitable comprises for example vinyl fluoride such as CF
2=CF
2, CHF=CF
2, CH
2=CF
2And CH
2=CHF and fluorine propylene such as CF
3CF=CF
2, CF
3CF=CHF, CF
3CH=CF
2, CF
3CH=CH
2, CF
3CF=CHF, CHF
2CH=CHF and CF
3CF=CH
2
Some are suitable fluoridize alpha-olefin copolymer comprise contain be derived from two or more structural units of fluoridizing 'alpha '-olefin monomers multipolymer as poly-(hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)), and contain be derived from one or more fluorinated monomers and can with the multipolymer of the structural unit of one or more nonfluorinated list ethylenically unsaturated monomers of described fluorinated monomer copolymerization as poly-(tetrafluoroethylene-ethylene-propylene) multipolymer.Suitable do not fluoridize single ethylenically unsaturated monomers and for example comprise 'alpha '-olefin monomers such as ethene, propylene, butylene, acrylate monomer such as methyl methacrylate, butyl acrylate etc., wherein preferably poly-(tetrafluoroethylene) homopolymer (PTFE).
Other additive that can add this solvent cast film to comprises for example phosphorous acid ester of antioxidant, phosphinate, and hindered phenol.Phosphorus-containing stabilizers comprises triarylphosphite and phosphonic acids aryl ester, is important useful additive.Also can use the P contained compound of bifunctional.Preferred molecular weight is more than or equal to about 300 daltonian stablizers.In other cases, can use molecular weight more than or equal to 500 daltonian phosphorus-containing stabilizers.Phosphorus-containing stabilizers is present in the composition with 0.05～0.5% amount of formulation weight usually.Also can use tinting material and photostabilizer and UV absorption agent.Also can consider to use flow aids and releasing agent.The example of releasing agent is the alkyl carboxylic acid ester, for example, and pentaerythritol tetrastearate, Tristearoylglycerol and diglycol stearate.The amount that releasing agent exists in composition is generally 0.05～0.5% of formulation weight.Preferred releasing agent has big molecular weight, typically is greater than 300 dalton, to prevent that releasing agent loses in the melt process from the melt polymers mixture.
The composition that is used to form article according to the invention also can comprise for example nucleator, finings, stiffening agent and/or crystallization rate agent of various additives (crystallization rate agent).These reagent amount with routine in the material of routine is used.
Can make in all sorts of ways described component and aforementioned composition blend, described method comprises mixes the even matter of any other additive required in this material and the preparation.Preferred step comprises solution blending, but also can carry out melt blending after carrying out solvent cast film.The illustrative examples of used equipment comprises in this melt processing method: the extrusion equipment of rotation and reverse rotation forcing machine, single screw extrusion machine, common kneader (co-kneader), disk groups processing machine (disc-pack processor) and various other types in the same way.
Can use above-mentioned polyimide compositions and film-forming soln to form the liquid coating solution.Described liquid coating solution has the purposes of many variations.Can use any suitable coating method, for example dip-coating, brushing, spraying, trowelling (wiping) etc. are applied to various substrates with this coating solution, heat then so that solvent system evaporates, and form solidified polyetherimide resin coating.Preferably temperature is raise gradually, thereby produce slick resin coating.Polyreaction and solidifying advantageously 125 ℃ to 300 ℃ or higher temperature is carried out.
Also can be with polyamic acid solution as coating solution, this coating solution can be used or store the back immediately and use after preparation.Usually, Zui Da storage life can obtain by store this solution under covering at nitrogen under no optical condition.
The polymkeric substance that is used to prepare described solvent cast film and coating is a polyimide, and under some concrete situations, polyetherimide.Polyimide according to the present invention has general formula (1):
Wherein a is generally 10 to 1,000 or bigger greater than 1, perhaps more specifically is 10 to 500; And wherein V is hard-core tetravalence linking group, as long as this linking group does not hinder the synthetic of polyimide and uses.Suitable linking group includes but not limited to: (a) have 5 to 50 carbon atoms, that replace or unsubstituted, saturated, undersaturated or aromatic monocyclic and many cyclic groups, (b) have 1 to 30 carbon atom replacement or unsubstituted, straight chain or branching, saturated or unsaturated alkyl; Or comprise the combination of at least a aforementioned substances.Suitable substituents and/or linking group include but not limited to ether, epoxide, acid amides, ester and comprise the combination of at least a aforementioned group.At least a portion linking group V contains the part that is derived from bis-phenol.The ideal linking group includes but not limited to the tetravalence aromatic group of structure (2):
Wherein W is a divalent group, comprise-O-,-S-,-C (O)-,-SO
2-,-SO-,-C
yH
2y-(y is 1 to 5 integer), and halogenated derivative comprise perfluorinated alkylidene, or the group of formula-O-Z-O-, wherein said-O-or-two valence links of O-Z-O-group 3,3 ', 3,4 ', 4,3 ' or 4,4 ' position on, and wherein Z includes but not limited to the divalent group of formula 3:
Wherein Q includes but not limited to divalent moiety, comprise-O-,-S-,-C (O)-,-SO
2-,-SO-,-C
yH
2y-(y is 1 to 5 integer), and halogenated derivative comprise perfluorinated alkylidene.
R in the formula (1) include but not limited to divalent organic group that replace or unsubstituted as: (a) have the aromatic hydrocarbon group and the halogenated derivative thereof of about 6～about 20 carbon atoms; (b) has the chain alkylidene group of the straight or branched of about 2～about 20 carbon atoms; (c) have the cycloalkylidene group of about 3～about 20 carbon atoms, perhaps the divalent group of (d) general formula (4):
Wherein Q includes but not limited to divalent group, it comprises-O-,-S-,-C (O)-, SO
2-,-SO-,-C
yH
2y-(y is 1～5 integer) and halogenated derivative (comprising perfluorinated alkylidene) thereof.
Exemplary polyimide comprises polyamidoimide and polyetherimide, those polyetherimides of melt-processable especially, and for example preparation and property description be in United States Patent (USP) 3,803, those in 085 and 3,905,942.
Exemplary polyetherimide resin comprises greater than 1, is generally about 10～about 1000, perhaps more particularly is the structural unit of about 10～about 500 formulas (5):
Wherein T is-group of O-or formula-O-Z-O-, wherein said-O-or-two valence links of O-Z-O-group 3,3 ', 3,4 ', 4,3 ' or 4,4 ' position on, and wherein Z includes but not limited to the divalent group of formula 10 as defined above.
In one embodiment, described polyetherimide can be except containing above-mentioned ether imide unit, also contains the unitary multipolymer of polyimide structures of formula (6):
Wherein R in the front formula (6) definition, M includes but not limited to the group of following formula:
Polyetherimide can pass through prepared in various methods, and described method includes but not limited to the reaction of aromatics two (ether acid anhydride) with the organic diamine of formula (8) of formula (7),
H
2N-R-NH
2 (8)
Wherein R and T are suc as formula defining in (1) and (5).
The example of concrete aromatics two (ether acid anhydrides) and organic diamine for example is disclosed in the United States Patent (USP) 3972902 and 4455410.The illustrative example of dianhydride molecule comprises:
2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-;
4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
2, two [4-(2, the 3-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-;
4,4 '-two (2, the 3-di carboxyl phenyloxy) phenyl ether dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) benzophenone dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenylbenzene-2,2-propane dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) benzophenone dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
1, two (2, the 3-di carboxyl phenyloxy) benzene dianhydrides of 3-;
1, two (2, the 3-di carboxyl phenyloxy) benzene dianhydrides of 4-;
1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 3-;
1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 4-;
3,3 ', 4,4 '-the phenylbenzene tetracarboxylic dianhydride;
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride;
The naphthalene dicarboxylic anhydride, as 2,3,6,7-naphthalene dicarboxylic anhydride, etc.;
3,3 ', 4,4 '-phenylbenzene sulfonic acid tetracarboxylic dianhydride (3,3 ', 4,4 '-biphenylsulphonictetracarboxylic dianhydride);
3,3 ', 4,4 '-the diphenyl ether tetracarboxylic dianhydride;
3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride;
3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
Two (phthalic acid) phenyl hydroxide sulphur dianhydride (bis (phthalic) phenylsulphineoxidedianhydride);
To phenylene-two (triphenyl phthalic acid) dianhydride;
Metaphenylene-two (triphenyl phthalic acid) dianhydride;
Two (triphenyl phthalic acids)-4,4 '-the phenyl ether dianhydride;
Two (triphenyl phthalic acids)-4,4 '-the ditan dianhydride;
2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride;
4,4 '-oxygen di-O-phthalic acid dianhydride;
Pyromellitic acid dianhydride;
3,3 ', 4,4 '-diphenylsulfone acid dianhydride;
4 ', 4 '-the dihydroxyphenyl propane dianhydride;
Quinhydrones two O-phthalic acid dianhydrides;
6,6 '-two (3, the 4-di carboxyl phenyloxy)-2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-two [1H-indenes] dianhydrides of spiral shell;
7,7 '-two (3, the 4-di carboxyl phenyloxy)-3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl--2,2 '-two [2H-1-chromene] dianhydrides of spiral shell;
1,1 '-two [1-(3, the 4-di carboxyl phenyloxy)-2-methyl-4-phenyl] hexanaphthene dianhydride;
3,3 ', 4,4 '-diphenylsulfone acid dianhydride;
3,3 ', 4,4 '-diphenyl sulfide tetracarboxylic dianhydride;
3,3 ', 4,4 '-thionyl benzene tetracarboxylic dianhydride;
4,4 '-oxygen di-O-phthalic acid dianhydride;
3,4 '-oxygen di-O-phthalic acid dianhydride;
3,3 '-oxygen di-O-phthalic acid dianhydride;
3,3 '-benzophenone tetracarboxylic dianhydride;
4,4 '-carbonyl diurethane O-phthalic acid dianhydride;
3,3 ', 4,4 '-ditan tetracarboxylic dianhydride;
2, two (4-(3,3-dicarboxyl phenyl) the propane dianhydrides of 2-;
2, two (4-(3, the 3-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-;
(3,3 ', 4,4 '-phenylbenzene) Phenylphosphine tetracarboxylic dianhydride;
(3,3 ', 4,4 '-phenylbenzene) phenylphosphine oxide tetracarboxylic dianhydride;
2,2 '-two chloro-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-dimethyl-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-dicyano-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two bromo-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two iodo-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (trifluoromethyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-methyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-2-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-3-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-phenyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
4,4 '-the dihydroxyphenyl propane dianhydride;
3,3 ', 4,4 '-thionyl benzene tetracarboxylic dianhydride;
4,4 '-carbonyl diurethane O-phthalic acid dianhydride;
3,3 ', 4,4 '-ditan tetracarboxylic dianhydride;
2,2 '-two (1,3-trifluoromethyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, and all isomer, and the combination of aforementioned substances.
Two (ether acid anhydrides) can prepare by the following method: (for example, the reaction product of metal-salt BPA) in the presence of the bipolarity aprotic solvent is hydrolyzed the phenyl dintrile that nitro is replaced, and follows and dewaters with bisphenol cpd.An exemplary class aromatics two (ether acid anhydride) included with following formula (7) includes but not limited to that wherein T is the compound of formula (9):
And the ether linking group, for example, 3,3 ', 3,4 ', 4,3 ' or 4,4 ' position on, and the mixture that comprises at least a aforementioned substances, wherein Q as defined above.
Can use any diamino compounds.The example of suitable compound is:
Mphenylenediamine;
Ursol D;
2,4 di amino toluene;
2, the 6-diaminotoluene;
M-xylene diamine;
The p dimethylamine;
P-diaminodiphenyl;
3,3 '-tolidine;
3,3 '-dimethoxy benzidine;
1, the 5-diaminonaphthalene;
Two (4-aminophenyl) methane;
Two (4-aminophenyl) propane;
Two (4-aminophenyl) thioether;
Two (4-aminophenyl) sulfone;
Two (4-aminophenyl) ether;
4,4 '-diamino-diphenyl propane;
4,4 '-diaminodiphenyl-methane (4,4 '-methylenedianiline);
4,4 '-diaminodiphenyl sulfide;
4,4;
4 (4,4 '-oxygen connection dianiline);
1, the 5-diaminonaphthalene;
3,3 ' tolidine;
3-methyl heptamethylene diamines;
4,4-dimethyl heptamethylene diamines; 2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-two [the 1H-indenes]-6,6 of spiral shell '-diamines;
3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl--2,2 '-two [the 2H-1-chromenes]-7,7 of spiral shell '-diamines;
1,1 '-two [1-amino-2-methyl-4-phenyl] hexanaphthene, and isomer, and the mixture and the blend that comprise at least a aforementioned substances.
It is desirable to, described diamino compounds is an aromatic diamine, especially between-and Ursol D, and the mixture that comprises at least a aforementioned substances.
In one embodiment, described polyetherimide resin comprises the structural unit according to formula 12, and wherein each R is independently for to phenylene or metaphenylene or comprise the mixture of at least a aforementioned group, and T is the divalent group of formula (10):
Many methods that prepare polyimide, particularly polyetherimide are disclosed in United States Patent (USP) 3847867,3850885,3852242,3855178,3983093 and 4443591.
For the reaction between the diamines of the acid anhydrides of realization formula (7) and formula (8), can utilize solvent such as orthodichlorobenzene, m-cresol/toluene etc. under about 100 ℃～about 250 ℃ temperature, to react.In this reaction, also can use chain terminator and branching agent.
When use contains ether and do not contain the polyimide copolymer of subunit of ether, be used in combination dicarboxylic anhydride such as pyromellitic acid acid anhydride and two (ether acid anhydride).Polyimide can be randomly by the prepared in reaction of aromatics two (ether acid anhydride) with organic diamine, wherein diamines excessive in reaction mixture is less than or equal to about 0.2 mole.Under this condition, when with weight percent being its chloroformic solution of solution titration in glacial acetic acid of the Hydrogen bromide of 33wt%, polyetherimide resin can have and is less than or equal to the titrating group of the every gram of about 15 microequivalents (μ eq/g) theobromine, perhaps more specifically, have and be less than or equal to the titrating group of about 10 μ eq/g theobromines.In polyetherimide resin, the titrating group of theobromine in fact owing to amine end groups.
One of approach of synthesis of polyimides starts from two (the 4-halophthalimide) with following structure (11):
Wherein R as mentioned above, X is a halogen.Wherein R is 1, and two (4-halophthalimide) (12) of 3-phenyl group are useful especially.
Usually, two (halophthalimide) (11) and (12) be by amine as 1, condensation forms as 4-halophthalic acid acid anhydride (13) for 3-diaminobenzene and acid anhydrides:
Polyetherimide can be by two (halophthalimide) and bis-phenol being combined in to react under the situation that has or do not exist phase-transfer catalyst and synthesizing of an alkali metal salt of an alkali metal salt of dihydroxyphenyl propane or an alkali metal salt of bis-phenol and the aromatic hydrocarbons that another kind of dihydroxyl replaces for example.Suitable phase-transfer catalyst is disclosed in the United States Patent (USP) 5229482.The aromatic hydrocarbons that suitable dihydroxyl replaces comprises have formula those of (14):
HO-A
2-OH (14)
A wherein
2It is the bivalent aromatic hydrocarbon group.Proper A
2Group comprise metaphenylene, to phenylene, 4,4 '-biphenylene and similar group.
As mentioned above, fresh (virgin) polyimide can be used for forming the solvent cast polyimide film.But in concrete embodiment, polyimide film comprises 50wt% at the most, particularly the circulation polyimide of 30wt% at the most.The second-order transition temperature of this circulation polyimide before circulation can be 210 ℃ to 450 ℃.In one embodiment, fresh polyimide and circulation polyimide have for example been formed the polyimide melt blending of above-mentioned film.In another embodiment, the polyimide that fresh polyimide and circulation polyimide has for example been formed above-mentioned film carries out solvent.The polyimide compositions that comprises the circulation polyimide can be shaped to the curtain coating composition then, and for example carry out curtain coating as mentioned above from containing 1 to 30wt% solid composition.In aforementioned embodiments, comprise that the CTE of the film of circulation polyimide can be in CTE ± 10ppm/ ℃ of the film with the same composition that does not contain the circulation polyimide.
Above-mentioned solvent cast polyimide film can be used for making the circulation film composition that is used for various uses.Described circulation film composition can or pass through solvent by melt blending (when the circulation film can carry out melt blending) and form.In one embodiment, the method for manufacturing circulation polyimide compositions comprises the described solvent cast polyimide film of fusion the application; The solvent cast polyimide film and the polymer composition of fused claim 1 are merged, form the circulation polyimide compositions.In another embodiment, the method for making the circulation polyimide compositions comprises and makes the dissolving of solvent cast polyimide film; Merge with film and polymer composition, form the circulation polyimide compositions dissolved claim 1.In in aforementioned embodiments any, this polymer composition can comprise fresh polyimide.Then, the circulation composition can be used for making composition known in the art and goods.For example, can extrude or curtain coating the circulation polyimide compositions as mentioned above.The goods that comprise described circulation polyimide compositions within the scope of the invention.
As produce CTE less than 70ppm/ ℃ (in another embodiment less than 60ppm/ ℃, perhaps in another embodiment, less than 35ppm/ ℃) the alternative plan of solvent cast film, can add other procedure of processing, CTE is higher than 70ppm/ ℃ (is higher than 60ppm/ ℃ in another embodiment, perhaps in another embodiment, be higher than 35ppm/ ℃) the CTE of solvent cast film be reduced to the CTE that is lower than 60ppm/ ℃ (be lower than 35ppm/ ℃ in another embodiment, be lower than 30ppm/ ℃ particularly).
The CTE of solvent cast film can be lowered by biaxial stretch-formed, as United States Patent (USP) 5,460, described in 890.Similarly, the CTE of the solvent cast film of film that melt extrudes or complete imidization can be lowered by heat is biaxial stretch-formed, as United States Patent (USP) 5,260, described in 407.Those skilled in the art will understand that other currently known methods of the CTE that reduces polyimide film.
For example, can be obtained having the film of CTE in the low degree by polyimide resin composition, this is because described resin demonstrates partially crystalline after annealing, described crystallization phases can be after extruding by biaxial stretch-formed and on two dimension, align.This film is limited in the framework (frame) simultaneously in thermofixation, makes the pars amorpha of this film turn back to random non-oriented configuration, keep the alignment (also inducing the crystal region that produces more alignment) of crystallization phases simultaneously.The alignment of crystallization phases causes film to have low CTE.Because the pars amorpha of material has been got back to its disorganized form, this film just can not demonstrate contraction, or even when also being like this when being higher than the Tg of material.This can cause the film of dimensional stabilizing when flexible manufacturing temperature (flexfabrication temperature), and this is because crystal region all is stable for the temperature that is higher than 400 ℃.Because the high Tg and the partially crystalline of material, this film has high temperature tolerance.The Tg of described material is higher than the temperature of solder flux float test, and this makes this material also can stand this test.This polymer crystals surpasses 400 ℃ of just fusions up to temperature, and 400 ℃ temperature is far above the temperature that experiences in the flexible manufacturing process.Crystal produces effectively crosslinked when being lower than Tm, keeps this material together, thereby has high temperature tolerance.Below the kinetics of crystallization of the said composition of Que Dinging is slow, allows that material was melted to extrude before remarkable crystallization takes place.When being higher than Tg, make this film thermofixation then, induced crystallization.
Contain monomer 4,4 '-oxygen di-Tetra hydro Phthalic anhydride (ODPA), dihydroxyphenyl propane dianhydride (BPADA) ,-the wide in range polyether imide copolymer of the combination of phenylenediamine (mPD) and p-phenylenediamine (pPD) demonstrates partially crystalline, and makes this film demonstrate desirable properties required high heat-resisting (high heat).Available for example aniline carries out end-blocking to this polymkeric substance.Scope of the present invention is intended to contain described monomer particularly and has partially crystalline and keep the required end-blocking of workability.Concrete example can be 80-100% ODPA as dianhydride and 30-100% pPD as diamines, use 3.5-5% aniline as end-capping reagent.
Change these compositions and can change kinetics of crystallization, obtain the processibility of expectation and the balance of the obtained processibility that reduces CTE.In one embodiment, according to processibility, ductility, slow kinetics of crystallization and maximum obtained crystallinity, the optimal set compound is the dianhydride component that contains 95% ODPA and 5%BPADA in equivalent, with the diamine components that contains 70% mPD and 30% pPD in equivalent, and 5% aniline, based on the total yield of dianhydride component and diamine components.
When using specific dianhydride combination, especially when specific dianhydride and specific diamines are used in combination, can obtain very good film character.In one embodiment, described dianhydride comprises 3,4 '-oxygen di-Tetra hydro Phthalic anhydride, 3,3 '-oxygen di-Tetra hydro Phthalic anhydride, 4,4 '-oxygen di-Tetra hydro Phthalic anhydride, and combination.The character that can exist other additional dianhydride to regulate film.But in one embodiment, polyimide has less than being derived from of 15mol% and is selected from the dianhydride of biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid, the ester of biphenyltetracarboxyacid acid and the structural unit of combination thereof.
Perhaps, polyimide by mainly by 3,4 '-oxygen di-Tetra hydro Phthalic anhydride, 3,3 '-oxygen di-Tetra hydro Phthalic anhydride, 4,4 '-oxygen di-Tetra hydro Phthalic anhydride, and the dianhydride component that combination is formed forms.In another embodiment, polyimide is formed by the dianhydride component, described dianhydride component by 3,4 '-oxygen di-Tetra hydro Phthalic anhydride, 3,3 '-oxygen di-Tetra hydro Phthalic anhydride, 4,4 '-oxygen di-Tetra hydro Phthalic anhydride and combination thereof form.
Have been found that also working as diamine components comprises 4,4, mphenylenediamine, Ursol D, 4,4 '-oxygen connection dianiline, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-when two (3-amino-benzene oxygen) benzene of 3-and combination thereof, obtain having the film of advantageous property.In one embodiment, described diamine components mainly by 4,4, mphenylenediamine, Ursol D, 4,4 '-oxygen connection dianiline, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (3-amino-benzene oxygen) benzene of 3-and combination thereof are formed.In another embodiment, diamine components is by 4,4, mphenylenediamine, Ursol D, 4,4 '-oxygen connection dianiline, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (3-amino-benzene oxygen) benzene of 3-and combination thereof are formed, and do not have other diamines.
Polyimide is also advantageously formed by such structural unit, and diamine components comprises the 4,4 more than or equal to 10mol% of diamine components total mole number in described structural unit.In one embodiment, diamine components comprises 10 to 100mol% 4,4.
This film can have many favorable properties, except low CTE, also has useful Tg and low solvent conservation rate.In one embodiment, this film is stable, and also, loss is less than 5% of its initial weight 25 ℃ are stored 24 hours in water after, and particularly, loss is less than 2% of its initial weight 25 ℃ are stored 24 hours in water after.
Unexpectedly, the contriver finds, polyimide especially can be comprised the unitary polyetherimide that is derived from specific diamines, is mixed with and demonstrates relative constant CTE, obtains 220 to 375 ℃ Tg simultaneously.This result is unexpected, and this is that CTE is along with Tg changes linearly because usually for the unbodied film of thermoplasticity.Therefore, the optional Tg that hopes that selects a time keeps specific CTE simultaneously.
Liquid coating solution of the present invention, film curtain coating solution, coating and solvent cast film have the purposes of many variations.Can use any suitable coating method, for example dip-coating, brushing, spraying, trowelling (wiping) etc. are applied to various substrates with this coating solution, heat then so that solvent system evaporates, and form solidified polyimide resin coating and/or solvent cast film.Preferably temperature is raise gradually, thereby produce slick resin coating.The reaction that forms polyimide is advantageously carried out 125 ℃ to 450 ℃ or higher temperature.Can use various substrates, for example copper, silicon, aluminium, gold and silver, nickel, glass, pottery and polymkeric substance comprise polymkeric substance releasing layer (release layer).
Coating of the present invention and curtain coating solution comprise the composition that contains the circulation polyimide film, can be used for making various goods.In one embodiment, described coating and curtain coating solution are used to make the film that is used for wiring board, comprise flexible circuit board.In this embodiment, the solvent cast polyetherimde films adhesively places conductive substrates for example on the surface of metal level such as copper.Can be with second substrate, for example, another layer electro-conductive material is the layer of metal such as copper, places on the side of the film relative with first substrate.Can use other concrete goods of solvent cast polyimide film manufacturing to comprise electric capacity, the simplest embodiment comprises and places for example solvent cast polyimide film between two copper layers of two conductive layers.In another embodiment, this solution can be used as the line glaze (wireenamel) that forms insulating resin coating layer on copper and aluminum steel.In this embodiment, polyimide film forms the coating on the conductive electric wire.This solution also can be used as varnish, and it is used for applying or floods for example volume (for example coil of motor and generator) of former insulating electric wire (previouslyinsulated wire) of various substrates, and fabric or nonwoven fabric, etc.Solvent cast film of the present invention also can be used for flexible print circuit board (FPC), mantle structure dress (chip-on-flex, COF) and tape automated bonding (tape automated bonding TAB) uses.Term ＂ goods ＂ also can comprise diffuser (speaker cone), band and label, solderless wrapped connection line (wire wrap), etc.
Embodiment
Think to need not further detailed description, those skilled in the art just can use the application's description, and preparation is also used the present invention.Describing following examples to provide extra guidance to implementing those skilled in the art of the present invention.These embodiment are provided,, and help instruction of the present invention as the representative of work.Therefore, these embodiment are not intended to limit the scope of the invention from any aspect.Unless hereinafter point out in addition, otherwise all umbers are based on weight, all temperature all are degree centigrade.
Material
ODPA is a dianhydride monomer, be also referred to as 4,4 '-oxygen di-Tetra hydro Phthalic anhydride, it can be as US6, and 028,203, US 4,870,194 or US 5,021, preparation described in 168.
BPDA is a dianhydride monomer, be also referred to as 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, it is commercially available to be in Leawood, the Chriskev Company of Kansas from handling affairs.
PMDA is a dianhydride monomer, is also referred to as pyromellitic acid dianhydride, and its commercially available working certainly is in Milwaukee, the Aldrich Chemical Company of Wisconsin.
BPADA is a dianhydride monomer, is also referred to as 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-, and its commercially available working certainly is in Milwaukee, the Aldrich ChemicalCompany of Wisconsin.
BTDA is a dianhydride monomer, be also referred to as 3,3 '-benzophenone tetracarboxylic dianhydride, it is commercially available to be in Portland, the TCI America of Oregon from handling affairs.
BPhDA is a dianhydride monomer, be also referred to as 4,4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride, it can be as Journal ofPolymer Science, Polymer Chemistry Edition, 1985, the described preparation of Vol.23 (6) 1759-1769 pages or leaves.
DDS is a diamine monomer, is also referred to as 4,4, and its commercially available working certainly is in Leawood, the Chriskev Company of Kansas.
MPD is a diamine monomer, between being also referred to as-phenylenediamine, its commercially available working certainly is in Milwaukee, the Aldrich Chemical Company of Wisconsin.
PPD is a diamine monomer, is also referred to as Ursol D, and its commercially available working certainly is in Milwaukee, the Aldrich Chemical Company of Wisconsin.
ODA is a diamine monomer, be also referred to as 4,4 '-oxygen connection dianiline, it is commercially available to be in Leawood, the Chriskev Company of Kansas from handling affairs.
1,3,4-APB is a diamine monomer, is also referred to as 1, two (4-amino-benzene oxygen) benzene of 3-, and its commercially available working certainly is in Leawood, the Chriskev Company of Kansas.
1,3,3-APB is a diamine monomer, is also referred to as 1, two (3-amino-benzene oxygen) benzene of 3-, and its commercially available working certainly is in Leawood, the Chriskev Company of Kansas.
TPPBr is a phosphonium salt, is also referred to as the bromine tetraphenylphosphoniphenolate, and its commercially available working certainly is in OldGlossop, the Fluorochem Ltd. of United Kingdom.
Sodium montmorillonite (Sodium montmorillonite) is inorganic stratified silicate, and its commercially available working certainly is in Dusseldorf, the Sud-Chemie of Germany.
Embodiment 1-72
Film casting method and the experiment of embodiment 1-72:
The composition preparation of listing in the preparation 1-72 use table 1 of the present invention.For every kind of acid anhydride, every kind of monomeric amount uses the stoichiometry of 1 amine of each acid anhydride to calculate, corrected purity not, (purity is proofreaied and correct final molecular weight that can impact polymer and can be influenced the final performance of goods).Set up MicrosoftExcel spreadsheet counter, calculate every kind of monomeric gram number based on the total polymer gram number of expectation and the monomer feed of dianhydride and amine.It will be understood to those of skill in the art that and exist many different modes to confirm to be used to prepare correct weight according to every kind of composition of film of the present invention.Those skilled in the art have the ability to calculate the weight of each composition and calculate final percentage of solids according to the reaction mechanism that the application enumerates based on total stoichiometry.
Casting method: on analytical balance, take by weighing the dianhydride and the diamines of correct mol ratio as shown in table 1, be accurate to the 4th (four decimal place accuracy) behind the radix point.
Table 1
The CH=pimelinketone
Then with monomer transfer to scintillation vial, and with the used pan paper of solvent wash (weigh paper).The solvent of residual volume is transferred in this pipe, and makes this pipe inerting with nitrogen.Then the inertia pipe that seals is placed on the shaking table and spend the night, gathered (amido acid) solution.The strainer drip (drop cast) that then described poly-(amido acid) solution is passed through 0.45 micron is to cleaning on the clean slide glass for preparing with hexane in advance.
Then the slide glass that applies is placed on the hot plate, this hot plate is equipped with: thermopair; The controller (ramp and soak temperature controller) that temperature rises and descends; Purging with nitrogen gas (nitrogenpurge); And lid.Add heat distribution with this film imidization according to listed among table 2 and Fig. 1 then.
Table 2.
Temperature (℃) time (min)
25 0
40 45
40 60
120 90
120 120
160 150
160 165
200 180
200 195
300 210
When imidization is finished, remove the film of preparation like this from slide glass, be used for the embodiment of back, perhaps be used to make a service test.
Table 3
*At 30-150 ℃ of CTE that records
*At 30-175 ℃ of CTE that records
* *Tg with DMA mensuration
ND-DSC does not record Tg
* * *A+ shows solidified film dissolving when the 10wt% solid.
A-shows that this film not exclusively dissolves when the 10wt% solid.
Weight % (wt%) is defined as: [weight of component/(weight of the weight of component+all other components)] x100.Because initial solidification process is not optimum for each preparation/solvent combination, some films are not suitable for the test described in the table 3, are not representational therefore.One skilled in the art would recognize that the appropriate combination that to develop solvent and hot procedure (solvent and thermal processing profile), this film can be tested.
Embodiment 73
Detailed film curtain coating embodiment:
On analytical balance, weigh up the 4,4 of 4,4 of 0.5937g (0.001914mol) '-oxygen di-Tetra hydro Phthalic anhydride and 0.4752g (0.001914mol), be accurate to desired wt ± 0.0005g in.Described monomer transfer in the 20mL scintillation vial, with 2.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, is guaranteed that monomer shifts fully.Pipette remaining solvent (5.47mL N,N-DIMETHYLACETAMIDE) with volume transfer pipet (volumetric pipette), obtain 12.5wt% solid solution.Make this pipe inerting by making nitrogen gas stream cover this pipe in 1 minute then rapidly through this pipe.Then sample is placed on the shaking table and spend the night, thereby form poly-(amido acid) solution.
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer (syringe tip filter), arrive on the slide glass.The slide glass that solution is applied places on the hot plate that is equipped with lower device then: the controller that temperature rises and descends, lid and 85 liters (3 cubic feet)/hour controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet).Use the temperature distribution described in above embodiment 1-8 and table 3 and Fig. 1 (thermal profile outline) to make this sample imidization then.After the imidization, by being immersed in 25 ℃ the water and this film is discharged (free standing) polyimide film that obtains supporting oneself from slide glass.Then this film is used for the embodiment of back or tests and analyze.
Embodiment 74
Detailed film curtain coating embodiment:
On analytical balance, weigh up the mphenylenediamine of 4,4 of 0.8113g '-oxygen di-Tetra hydro Phthalic anhydride and 0.0566g and the Ursol D of 0.2263g, be accurate to desired wt ± 0.0005g in.Described monomer transfer in the 20mL scintillation vial, with 1.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, is shifted to guarantee monomer fully.Pipette remaining solvent (5.47mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain 12.5wt% solid solution.Make this pipe inerting by making nitrogen gas stream cover this pipe in 1 minute then rapidly through this pipe.Then sample is placed on the shaking table and spend the night, thereby form poly-(amido acid) solution.
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer, arrive on the slide glass.After solution is filled on the slide glass, use 635 microns scrapers (25mil gap) to produce wet film.(final film thickness is the function in the gap on concentration and the scraper).
The slide glass that solution is applied places on the hot plate that is equipped with lower device then: the controller that temperature rises and descends, lid and 85 liters (3 cubic feet)/hour controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet).Use the temperature distribution described in above embodiment 1-72 and table 2 and Fig. 1 to make this sample imidization then.After the imidization, by being immersed in 25 ℃ the water and this film is discharged the polyimide film that obtains supporting oneself from slide glass.Then this film is used for the embodiment of back or tests and analyze.
Embodiment 75
Carry out additional embodiments, define following term:
DSC: on Perkin Elmer DSC 7, differ from formula scanning calorimetric, measure second-order transition temperature in the heat-processed in the second time with the rate of heating of 20 ℃/min.This method is based on the ASTMD3418 standard.
DMA: the membrane sample that will accurately cut into known length, width and thickness is being analyzed in stretch mode 40-350 ℃ temperature range with the rate of heating of the frequency of 1Hz and 5 ℃/min on the dynamic mechanical analysis instrument.Dynamic mechanical analysis (DMA) carries out according to ASTM test D5026, and different is only to test a sample.Second-order transition temperature (Tg) is determined by the maximum point of mechanical loss angle tangent cutve.
TMA: the CTE value of casting films goes up at thermodynamic analyzer (thermo-mechanical analyzer) uses the rate of heating of 5 ℃/min to record on 0-250 ℃.The CTE value is calculated by the slope on the 30-200 ℃ of scope.
The equilibrium water: equilibrium water content is defined as and makes the moisture content that keeps the film of 72h (about 25 ℃ and 70%RH) in envrionment conditions in the laboratory.Moisture content by before drying and the membrane sample of the 1.27 centimetres of x of 10.2 centimetres of x 63.5 microns (0.0025 inch of 0.5 inch x of about 4 inches x) that accurately weigh afterwards record.Film is weighed (being accurate to 0.00005g), and dry 4h in 150 ℃ stove weighs to determine moisture loss then immediately.Mass loss when equilibrium water content is heating accounts for the percentage ratio of dry film quality.
Moisture absorption: the dry film sample of known quality (in 150 ℃ of baking ovens 4 hours) was immersed in the water of envrionment temperature (25 ℃) 72h hour.After 72 hours time, this film is removed from water, by removing redundant moisture with the Kimwipe drying.Moisture absorption is the percentage ratio that the quality increase when being immersed in the water accounts for the dry film quality.
Solubleness: positive findings shows in 10% solid concentration, is dissolved in N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone (in the test pointed solvent) and can be passed through 0.45 micron filter by the film of the complete imidization of poly-(amido acid) solution casting.
Embodiment 76, the A part
The modification of nanoclay.
The method for preparing organically-modified clay:
Organically-modified clay by in water or the ion-exchange in the combination of water and alcohol (or water and acetonitrile) prepare.With Na
+MMT (clay with sodium counter ion) is dispersed in water or the water/solvent combination with 1-5wt%, and is heated to 80 ℃.With organic cation, the Xiuization tetraphenylphosphoniphenolate, be dissolved in or be dispersed in the combination of water or aforesaid solvent, its ratio makes that existence equals or exceeds the organic cation of the cation exchange capacity (CEC) of dispersed clay when this organic cations solution or dispersion liquid add in the clay dispersion.Mixture heating up is refluxed 1-2 hour then.Then be cooled to room temperature, by centrifugal collection modified clay.Outwell supernatant liquor, in deionized water or deionized water solvent combination and by centrifugal, collect once more, come the clay of this solid modification is washed by making clay dispersion.Outwell washing soln, the repeated washing process is 2 times again.After at last centrifugal, solid clay drying in stove is ground to form fine powder then.
Embodiment 76, the B part
Specific embodiment: with 2.0g Na
+(cation exchange capacity (CEC) is the 0.000926molNa+/g clay to the MMT clay; 0.001852mol positively charged ion altogether) is distributed in 200mL50/50 deionized water and the alcoholic acid mixture, and is heated to backflow.(1.4167g 0.002216mol), and stirred 2 hours dispersion under refluxing to add the Xiuization tetraphenylphosphoniphenolate.Mixture is cooled to room temperature and is transferred in 4 50mL centrifuge tubes.These pipes are placed whizzer and rotate 5min with 3000rpm.Outwell supernatant liquor, and wash remaining solid, by the centrifugal solid of collecting once more by clay is dispersed in 50/50 deionized water and the alcoholic acid fresh mixture again.The repeated washing process is 2 times again.After the last centrifugal and decant,, grind to form fine powder then with remaining solid in 120 ℃ of stoves dry 2 hours.Table 4 shows the character of organically-modified montmorillonite.
Table 4
Embodiment 77
Use Al (AcAc)
3Reduce the detailed experimental technique of the CTE of film
Soluble nanoparticle precursor: praseodynium aluminium is added to as mentioned above in poly-(amido acid) solution that embodiment 1-72 prepares in each, or add in the solution of soluble polyimide in DMAc, obtain having 5-30wt% polyimide precursor or polyimide and 0.5%-31.8%Al (acac)
3Solution.Then this solution is filled on the slide glass.Then the substrate that applies is placed hot plate and stands the temperature distribution described in the embodiment 1-72 as mentioned above, thereby finish imidization.The film that will so form is removed from slide glass then, and is used for the embodiment of back or analyzes.
Embodiment 78
The adherent detailed experimental analysis of film on copper
Metal adhesion: the membrane sample of 2.54 square centimeters (1 square inches) is clipped between two Copper Foils.A slice paper tinsel is to have the granular surface that increases adherent hair side, and another copper surface is that polishing is slick.On hydraulic ram, use three tons pressure then, this sandwich was pressed 1 minute between the hot pressed parallel plate of 421 ℃ (7900F).Service rating 1-5 carries out classification with the adhesion of film on copper then.Two surfaces of 1 expression do not adhere to.2 expression appropriateness adhere to the copper of hair side.3 expression good adhesion are to the copper surface of hair side, and 4 expression good adhesion to the surface and the appropriateness of hair side adheres to smooth surface.5 expression good adhesion to two kind of copper surfaces equate with the benchmark film or better.Reference material is the film that the film extruded of GE resin XH6050 and CRS5001 extrude.
Embodiment 79
Be used to reduce the specific embodiment of the solvent cast film of CTE with Nano filling
Under ultransonic help, TPP-MMT (montmorillonitic clay that tetraphenylphosphoniphenolate is handled) is distributed in the nmp solvent.Oxygen is joined dianiline (ODA) add in the solution that obtains, and mechanical stirring is dissolved in room temperature fully up to diamines.Then oxygen di-O-phthalic acid dianhydride (ODPA) is added in this solution, and under mechanical stirring, disperse, have poly-(amido acid) solution of 20wt% solid heavy-gravity thereby form.Make this solution in room temperature room temperature reaction 12 hours.70 ℃ with this solution casting on substrate of glass, and by 70 ℃ of continuously heating 2 hours, 150 ℃ of heating 4 hours continuously, 200 ℃ of heating 1 hour and 300 ℃ heating 1 hour and make its imidization continuously continuously.The polyimide film of the Nano filling that obtains peeled off from substrate of glass be used for test.
Table 5
| Sample # | Polymkeric substance | Nanoclay | Silicate weight % | CTE (ppm/ ℃) is scanning (0-200) for the second time | %CTE reduces (scanning for the second time) | Standardized %CTE reduces (scanning for the second time) | |
| 49-42A1 | 44ODPA- | None | 0 | 44.0 | 0％ | ||
| 49- 074A1 | 44ODPA-44ODA | TPPBr | 3.8 | 39.4 | 11％ | 2.8％ | |
| 49- 074A2 | 44ODPA-44ODA | TPPBr | 7.5 | 37.2 | 15％ | 2.1％ | |
| 49- 074A3 | 44ODPA-44ODA | TPPBr | 15.0 | 30.9 | 30％ | 2.0％ |
Embodiment 80
Film circulation embodiment:
(40ODPA/10BPDA//40DDS/10pPD) is dissolved among 120 ℃ the DMAc to the 5wt% solid with the film fragment of embodiment 11.This solution is filtered by 0.45 micron filter.With solution casting slowly heating on substrate of glass and on hot plate, described hot plate is equipped with controller, lid and the controlled purging with nitrogen gas that temperature rises and descends then.Last 4 hours temperature slowly is increased to 200 ℃, the DMAc steam of three hours retaining part atmosphere in front, thereby control evaporation rate of solvent.By being immersed in the water, and allow water make this film floating, and the polyimide film that obtains is discharged from substrate of glass from substrate.
Embodiment 81
Film circulation embodiment:
Perhaps, polyimide solution and the monomer that derives from embodiment 80 merged, thereby obtain polyimide and the solution that gathers (amido acid).With similar among the embodiment 80,1.0g derived from 11 film and be dissolved among the 7gDMAc, obtain 12.5wt% solid solution.Poly-(amido acid) solution of preparation embodiment 11 merges described two kinds of solution, obtains 12.5wt% solid final solution.Deriving from again, the composition of the 1-20% of dissolved fragment film is suitable for present method.Then with this solution casting on substrate of glass, and carry out imidization, and discharge from substrate with the heat distribution that adds among the embodiment 1.
Embodiment 82
Film circulation embodiment:
Perhaps, use the polyimide film fragment grind into powder of mill with embodiment 11, then with itself and for example GE resin XH6050 or other high-performance polymer (for example polyetherketone or polysulfones) blend of polyetherimide resin, this is undertaken by at first described two kinds of powder being mixed in mixing tank (shaker), uses the film fragment of the grinding of 30wt% at the most.Then powder/powder blend is extruded on list or twin screw extruder and granulation.Be moulded component end item with blend or by injection mould then, perhaps film extrusion.
Embodiment 83
Solubility test embodiment: can be applicable to any film:
Prescription is by weight added in the pipe that contains the 10mL N,N-DIMETHYLACETAMIDE for a slice film of 40ODPA/10BPDA//40DDS/10pPD (quality is 0.6420g).Make this container inerting with nitrogen then and add a cover.Content was heated 24 hours at 120 ℃ under mild stirring.Solution was yellow after 24 hours, had slight mist degree, and did not remain film in blocks.Make solution easily by 0.45 micron filter then, wherein〉90% solids content has been passed through strainer, obtains yellow transparent solution.
Embodiment 84
Solubility test embodiment: applicable to any film that derives from embodiment 1-172:
Prescription is added in the pipe that contains 1.080mL JV-methyl-2-pyrrolidone for a slice film of 50ODPA//50DDS (quality is 0.05834g).Make this container inerting with nitrogen then and add a cover.Content was heated 12 hours at 120 ℃.Solution for amber deeply, did not remain film in blocks after 12 hours.Make solution easily by 0.45 micron filter then, wherein〉90% solids content has been passed through strainer, obtains yellow transparent solution.
Embodiment 85
Solubility test embodiment: applicable to any film that derives from embodiment 1-72:
A slice film (quality is 0.3100g) that to fill a prescription to 50ODPA//10DDS/40pPD (embodiment 51) adds in the pipe that contains the 5.741mL N,N-DIMETHYLACETAMIDE.Make this container inerting with nitrogen then and add a cover.Content was heated 12 hours at 120 ℃.Solution was light yellow after 12 hours, and the film of all amounts all remains intact basically.
Embodiment 86
Utilize reactive different preparation segmented copolymer: ester-sour method:
On analytical balance, take by weighing 0.7825g (1.5033mmol) 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, be accurate to expected value ± 0.0005g in, and take by weighing 0.16256g (1.5033mmol) mphenylenediamine, be accurate to expected value ± 0.0005g in.With described monomer transfer in the 20mL scintillation vial.With 1.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer transfers in the pipe fully.Pipette more multi-solvent (4.97mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain the monomeric solution of the first couple of multipolymer.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed on the shaking table and spend the night, thereby form poly-(amido acid).
On analytical balance, take by weighing the diacid diethyl alcohol ester of 0.1166g (0.3758mmol) pyromellitic acid dianhydride, be accurate to expected value ± 0.0005g in; And take by weighing 0.04064g (0.3758mmol) mphenylenediamine, be accurate to expected value ± 0.0005g in.With described monomer transfer in the 20mL scintillation vial of the amido acid mixture that contains as above preparation.With 1.49mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer transfers in the pipe fully.This obtains the solution of about 12.5% solid polyimide.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Sample was placed shaking table 1 hour then, guarantee to mix.
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer, arrive on the slide glass.The slide glass that solution is applied places on the hot plate then, and this hot plate is equipped with: the controller that temperature rises and descends, lid and 85 liters (3 cubic feet)/hour controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet).The heat distribution that adds in the use table 6 is carried out imidization to sample then.
Table 6
Temperature (℃) time (min)
25 0
40 45
40 60
120 90
120 120
160 150
160 165
200 180
200 195
300 210
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer, arrive on the slide glass.The slide glass that solution is applied places on the hot plate then, and this hot plate is equipped with: the controller that temperature rises and descends, lid and 85 liters (3 cubic feet)/hour controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet).The heat distribution that adds in the use table 6 is carried out imidization to sample then.
After imidization, by being immersed in 25 ℃ the water and this film is discharged the polyimide film that obtains supporting oneself from slide glass.Then this film is tested and analyzed.
Embodiment 87
Utilize reactive difference to prepare the polymkeric substance of block
On analytical balance, take by weighing 0.2657g (0.903mmol) 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), be accurate to expected value ± 0.0005g in, and take by weighing 0.0977g (0.9032mmol) Ursol D (pPD), be accurate to expected value ± 0.0005g in.With described monomer transfer in the 20mL scintillation vial.With 1.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer transfers in the pipe fully.Pipette more multi-solvent (2.74mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain the monomeric solution of the first couple of multipolymer.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed shaking table last 3 hour, thereby form poly-(amido acid).
On analytical balance, take by weighing 0.4701g (0.9032mmol) 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides (BPADA) of 2-, be accurate to expected value ± 0.0005g in; And take by weighing 0.2243g (0.9032mmol) 4,4 (DDS), be accurate to expected value ± 0.0005g in.With described monomer transfer in the 20mL scintillation vial of poly-(amido acid) mixture that contains as above preparation.With 1.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer shifts fully, add the other N,N-DIMETHYLACETAMIDE of 2.74mL then, obtain final reaction mixture.This obtains the solution of about 12.5% solid polyimide.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Sample was placed shaking table 12 hours then, guarantee to mix.
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer, arrive on the slide glass.The slide glass that solution is applied places on the hot plate then, and this hot plate is equipped with: the controller that temperature rises and descends, lid and 85 liters (3 cubic feet)/hour controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet).The heat distribution that adds in the use table 7 is carried out imidization to sample then:
Table 7
Temperature (℃) time (min)
25 0
40 45
40 60
120 90
120 120
160 150
160 165
200 180
200 195
300 210
After imidization, by being immersed in 25 ℃ the water and this film is discharged the polyimide film that obtains supporting oneself from slide glass.Then this film is tested and analyzed.
Embodiment 88
Working power and machined parameters prepare segmented copolymer.
2 vessel process.
On analytical balance, take by weighing 0.0892g (0.3033mmol) 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), be accurate to expected value ± 0.0005g in, and take by weighing 0.0328g (0.3033mmol) mphenylenediamine (MPD), be accurate to expected value ± 0.0005g in.With described monomer transfer in 20mL scintillation vial (No. 1 pipe).With 2.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer transfers in No. 1 pipe fully.Pipette more multi-solvent (1.0mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain the monomeric solution of the first couple of multipolymer.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed shaking table last 24 hour, thereby form poly-(amido acid).
On analytical balance, take by weighing 0.6314g (1.2130mmol) 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides (BPADA) of 2-, be accurate to expected value ± 0.0005g in; And take by weighing 0.3012g (1.2130mmol) 4,4 (DDS), be accurate to expected value ± 0.0005g in.In described monomer transfer to the second a 20mL scintillation vial (No. 2 pipes).With 1.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer shifts fully.Pipette more multi-solvent (3.47mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain the monomeric solution of the second couple of multipolymer.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed shaking table last 24 hour, thereby form poly-(amido acid).
After the mixing, the content of No. 2 pipes is added in the content of No. 1 pipe, and with the flushing of 2mL N,N-DIMETHYLACETAMIDE, shift fully guaranteeing.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then pipe is placed shaking table last 30 minute.This obtains the solution of about 12.5% solid polyimide copolymer.
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer, arrive on the slide glass.The slide glass that solution is applied places on the hot plate then, and this hot plate is equipped with: the controller that temperature rises and descends, lid and 85 liters (3 cubic feet)/hour controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet).The heat distribution that adds in the use table 8 is carried out imidization to sample then:
Table 8
Temperature (℃) time (min)
25 0
40 45
40 60
120 90
120 120
160 150
160 165
200 180
200 195
300 210
Embodiment 89
Use preformed imide polymer and method to prepare segmented copolymer.2 vessel process.
On analytical balance, take by weighing 0.6894g (0.9408mmol)
6050 (homopolymer of BPADA and DDS), be accurate to expected value ± 0.0005g in, this polymkeric substance is transferred to 20mL scintillation vial (No. 1 pipe).With 2.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer transfers in the pipe fully.Pipette more multi-solvent (2.74mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain the solution of polymkeric substance.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed shaking table last 12 hour.
On analytical balance, take by weighing 0.2782g (0.8967mmol) 4,4 '-oxygen di-O-phthalic acid dianhydride (ODPA), be accurate to expected value ± 0.0005g in; And take by weighing the Ursol D (PPD) of 0.0970g (0.8967mmol), be accurate to expected value ± 0.0005g in.In described monomer transfer to the second a 20mL scintillation vial (No. 2 pipes).With 2.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer shifts fully.Pipette more multi-solvent (1.74mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain the monomeric solution of the second couple of multipolymer.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed shaking table last 12 hour, thereby form poly-(amido acid).
After the mixing, the content of No. 2 pipes is added in the content of No. 1 pipe, and with the flushing of 1mL N,N-DIMETHYLACETAMIDE, shift fully guaranteeing.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then pipe is placed shaking table last 6 hour.This obtains the solution of about 12.5% solid polyimide copolymer.
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer, arrive on the slide glass.The slide glass that solution is applied places on the hot plate then, and this hot plate is equipped with: the controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet) of the controller that temperature rises and descends, lid and 3 cubic feet/hour.The heat distribution that adds in the use table 9 is carried out imidization to sample then:
Table 9.
Temperature (℃) time (min)
25 0
40 45
40 60
120 90
120 120
160 150
160 165
200 180
200 195
300 210
After imidization, by being immersed in 25 ℃ the water and this film is discharged the polyimide film that obtains supporting oneself from slide glass.Then this film is tested and analyzed.
Embodiment 90
Use preformed prepolymer or polymkeric substance and method to prepare random copolymers, the envrionment temperature method:
On analytical balance, take by weighing 0.9255g (1.2630mmol)
6050 (homopolymer of BPADA and DDS), be accurate to expected value ± 0.0005g in; And take by weighing 0.0326g (0.3018mmol) mphenylenediamine (MPD), be accurate to expected value ± 0.0005g in.This polymkeric substance and diamines are transferred in the 20mL scintillation vial (No. 1 pipe).With 2.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer shifts fully.Pipette water (0.01mL) and multi-solvent (4.98mL N,N-DIMETHYLACETAMIDE) more with the volume transfer pipet, obtain the solution of polymkeric substance and diamines and water.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed shaking table last 24 hour.(can randomly be heated to this mixture about 50 ℃ this moment, shakes simultaneously to help randomized response (randomization reaction)).
After 24 hours, take by weighing 0.0936g (0.3018mmol) 4,4 '-oxygen di-O-phthalic acid dianhydride (ODPA), be accurate to expected value ± 0.0005g in.This dianhydride is transferred in the 20mL scintillation vial (No. 1 pipe).With 1.49mL N,N-DIMETHYLACETAMIDE flushing pan paper, guarantee that monomer shifts fully.By making nitrogen gas stream make this pipe inerting with nitrogen, and rapidly pipe is added a cover through this pipe 1 minute.Then sample is placed shaking table last 12 hour, thereby form random poly-(amido acid).This obtains the solution of about 12.5% solid polyimide copolymer.
Clean slide glass (the prewashed slide of Fisherbrand) with hexane.Solution (2.0mL) is filtered pass through 0.45 micron syringe nozzle strainer, arrive on the slide glass.The slide glass that solution is applied places on the hot plate then, and this hot plate is equipped with: the controller that temperature rises and descends, lid and 85 liters (3 cubic feet)/hour controlled purging with nitrogen gas (equipment volume is 0.1 cubic feet).Use the following heat distribution that adds that sample is carried out imidization then:
Table 10.
The temperature ℃ time (min)
25 0
40 45
40 60
120 90
120 120
160 150
160 165
200 180
200 195
300 210
After imidization, by being immersed in 25 ℃ the water and this film is discharged the polyimide film that obtains supporting oneself from slide glass.Then this film is tested and analyzed.
Embodiment 91-204
The embodiment 91-204 that lists in the table 11 prepares according to the described method of embodiment 1-72.
Casting method: on analytical balance, take by weighing the dianhydride and the diamines of correct mol ratio as shown in table 11, be accurate to behind the radix point the 4th.
Table 11
Then monomer transfer is arrived scintillation vial, and use the solvent washing pan paper.The solvent of residual volume is transferred in this pipe, and made this pipe inerting with nitrogen.Then the inertia pipe that seals is placed on the shaking table and spend the night, gathered (amido acid) solution.The strainer drip that then described poly-(amido acid) solution is passed through 0.45 micron is to cleaning on the clean slide glass for preparing with hexane in advance.
Then the slide glass that applies is placed on the hot plate, this hot plate is equipped with: thermopair; The controller that temperature rises and descends; Purging with nitrogen gas; And lid.Add heat distribution with this film imidization according to listed among Fig. 1 and the table 2 then.
When imidization is finished, remove the film of preparation like this from slide glass, be used for the embodiment of back, perhaps be used to make a service test.The physical property measurement value of embodiment 91-204 is listed in the table 12.
Table 12
ND=does not detect Tg
Embodiment 205
FPC embodiment
On analytical balance, weigh up 4,4 of 11.3387g '-oxygen di-Tetra hydro Phthalic anhydride, 1.8151g diaminodiphenylsulfone(DDS) and 3.1620g Ursol D, be accurate to desired wt ± 0.0005g in.This monomer transfer in the 100mL pipe, with 2.0mL N,N-DIMETHYLACETAMIDE flushing pan paper, is guaranteed that monomer shifts fully.Pipette remaining solvent (55.63mL N,N-DIMETHYLACETAMIDE) with the volume transfer pipet, obtain 12.5wt% solid solution.By making nitrogen gas stream make this pipe inerting in 1 minute, cover this pipe then rapidly through this pipe.Then sample is placed on the shaking table and spend the night, thereby form poly-(amido acid) solution.
Then, use syringe and 0.45 micron filter, 5mL solution is transferred to the prewashed a slice of Virahol slick metal copper foil (20.4 centimetres of 10.2 centimetres of x, 50.8 micron thickness, promptly, 8 inches of 4 inches x and 2mil are thick) on, and form thin uniform coating with 381 microns (15mil) wet film spreaders.Use the heat distribution of describing in detail among above embodiment 1-72 described and table 2 and Fig. 1 that adds that this sample is carried out imidization then, obtain polyimide/copper laminate.
Then this laminate is covered the pattern of the copper cash of the various width (from 1mm to 5mm) that obtain exposing with scotch tape.Then with concentrated nitric acid with the copper etching that exposes 1 minute, then use deionized water wash, obtain having the patterning lamination thing of discrete copper conductor.
Embodiment 206
Solderless wrapped connection embodiment (Wire wrap example) #1
By 45% 4,4 of above preparation '-oxygen di-Tetra hydro Phthalic anhydride, 5% 3,3 ', 4,4 '-the preparation of compositions film of biphenyl tetracarboxylic dianhydride and 50% diaminodiphenylsulfone(DDS).This film is cut into the bar that 1mm is wide and 5cm is long.With the bar of this film with a band with respect to No. 16 stainless steel wires with on No. 6 stainless steel wires of miter angle stuck-at-.Then this bar is twined tightly, overlapping 0.1mm on the limit, thus high heat, flexible, insulating coating are provided around this line.
Embodiment 207
Solderless wrapped connection embodiment #2
By 50% 4,4 of above preparation '-the preparation of compositions film of oxygen di-Tetra hydro Phthalic anhydride, 10% mphenylenediamine and 40% Ursol D.This film is cut into the bar that 1mm is wide and 5cm is long.With the bar of this film with a band with respect to No. 18 copper cash with on No. 8 copper cash of miter angle stuck-at-.Then this bar is twined tightly, overlapping 0.1mm on the limit, thus high heat, flexible, insulating coating are provided around this line.
Embodiment 208
Electric capacity
As mentioned above, use 381 microns (15mil) scrapers by 50% 4,4 '-oxygen di-Tetra hydro Phthalic anhydride, with a slice film of 7.62 centimetres of x 7.62 centimetres (3 ＂ x, 3 ＂) of the preparation of compositions of 10% mphenylenediamine and 40% Ursol D, place between 5.08 centimetres of two 5.08 centimetres of x (2 inches x 2 inches) Copper Foil.On hydraulic ram, use three tons pressure then, this sandwich was pressed 1 minute between the hot pressed parallel plate of 404 ℃ (7600F).Passing through of the obtaining adhesion grade that afore-mentioned test records is 4 goods, is two electric capacity that parallel conductor constitutes that separated by thin polyimide insulator.
The full content of all patents, patent application and other publication that the application is disclosed is just all put down in writing the same in this application by with reference to incorporating the application into to them.
Though with reference to preferred embodiment having described the present invention, it should be appreciated by those skilled in the art that and to make various variations, and Equivalent can replace its composition, and not depart from scope of the present invention.In addition, can make many versions,, and not depart from scope of the present invention so that concrete situation or material are adapted to instruction of the present invention.Therefore, expectation the invention is not restricted to conduct and carries out the disclosed embodiment of best mode of the present invention, and the present invention will comprise all embodiments in the scope that falls into claims.
Claims (47)
1. solvent cast film comprises:
Polyimide, it comprises the structural unit of the polyreaction that is derived from dianhydride component and diamine components, described dianhydride component comprise be selected from 3,4 '-oxygen di-O-phthalic acid dianhydride, 3,3 '-oxygen di-O-phthalic acid dianhydride, 4,4 '-dianhydride of oxygen di-O-phthalic acid dianhydride and combination thereof;
The second-order transition temperature of wherein said polyimide is at least 190 ℃;
Wherein said film has
Less than 60ppm/ ℃ thermal expansivity,
0.1 to 250 microns thickness and
Residual solvent less than 5wt%;
Wherein said polyimide has less than being derived from of 15mol% and is selected from the dianhydride of biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid, the ester of biphenyltetracarboxyacid acid and the structural unit of combination thereof.
2. the film of claim 1, the second-order transition temperature of wherein said polyimide is 190 ℃ to 500 ℃.
3. the film of claim 1, wherein said dianhydride component also comprise and are selected from following dianhydride:
2,2 '-two (1,3-trifluoromethyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-methyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-phenyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-2-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-3-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride;
2, two ((4-(3, the 3-di carboxyl phenyloxy) phenyl) hexafluoropropane dianhydrides of 2-;
2, two ((4-(3, the 3-di carboxyl phenyloxy) phenyl) the propane dianhydrides of 2-;
2, two [4-(2, the 3-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-;
2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-;
2,2 '-two bromo-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,3,6,7-naphthalene dicarboxylic anhydride;
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride;
3,3 ', 4,4 '-the diphenyl ether tetracarboxylic dianhydride;
3,3 ', 4,4 '-phenylbenzene sulfonic acid tetracarboxylic dianhydride;
3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride;
3,3 ', 4,4 '-the ditan tetracarboxylic dianhydride;
3,3 ', 4,4 '-the diphenyl sulfide tetracarboxylic dianhydride;
3,3 ', 4,4 '-diphenylsulfone acid's dianhydride;
3,3 ', 4,4 '-the thionyl benzene tetracarboxylic dianhydride;
3,3 '-benzophenone tetracarboxylic dianhydride;
3,3 '-oxygen di-O-phthalic acid dianhydride;
3,4 '-oxygen di-O-phthalic acid dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) benzophenone dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenylbenzene-2,2-propane dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) benzophenone dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) phenyl ether dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4,4 '-the dihydroxyphenyl propane dianhydride;
4,4 '-carbonyl diurethane O-phthalic acid dianhydride;
4,4 '-oxygen di-O-phthalic acid dianhydride;
6,6 '-two (3, the 4-di carboxyl phenyloxy)-2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-two [1H-indenes] dianhydrides of spiral shell;
7,7 '-two (3, the 4-di carboxyl phenyloxy)-3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl--2,2 '-two [2H-1-chromene] dianhydrides of spiral shell;
Two (phthalic acid) phenyl hydroxide sulphur dianhydride;
Two (triphenyl phthalic acids)-4,4 '-the phenyl ether dianhydride;
Two (triphenyl phthalic acids)-4,4 '-the ditan dianhydride;
Quinhydrones two O-phthalic acid dianhydrides;
Metaphenylene-two (triphenyl phthalic acid) dianhydride;
To phenylene-two (triphenyl phthalic acid) dianhydride;
Pyromellitic acid dianhydride;
(3,3 ', 4,4 '-phenylbenzene) the Phenylphosphine tetracarboxylic dianhydride;
(3,3 ', 4,4 '-phenylbenzene) phenylphosphine oxide tetracarboxylic dianhydride;
1, two (2, the 3-di carboxyl phenyloxy) benzene dianhydrides of 3-;
1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 3-;
1, two (2, the 3-di carboxyl phenyloxy) benzene dianhydrides of 4-;
1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 4-; And combination.
4. the film of claim 1, wherein said diamine components also comprise the diamines that is selected from down group:
1, the 5-diaminonaphthalene;
2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-two [the 1H-indenes]-6,6 of spiral shell '-diamines;
2,4 di amino toluene;
2, the 6-diaminotoluene;
3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl--2,2 '-two [the 2H-1-chromenes]-7,7 of spiral shell '-diamines;
3,3 '-dimethoxy benzidine;
3,3 '-tolidine;
4 (4,4 '-oxygen connection dianiline);
4,4 '-diaminodiphenyl sulfide;
4,4;
4,4 '-diaminodiphenyl-methane (4,4 '-methylenedianiline);
4,4 '-diamino-diphenyl propane;
P-diaminodiphenyl;
Two (4-aminophenyl) ether;
Two (4-aminophenyl) thioether;
Two (4-aminophenyl) sulfone;
Two (4-aminophenyl) methane;
Two (4-aminophenyl) propane;
Mphenylenediamine;
M-xylene diamine;
Ursol D;
The p dimethylamine; And combination.
5. the film of claim 1, wherein said diamine components comprises the 4,4 more than or equal to 10mol%, based on the total mole number of diamines.
6. the film of claim 1, wherein said diamine components comprise the diamines that is selected from down group: 4,4, mphenylenediamine, Ursol D, 4,4 '-oxygen connection dianiline, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (3-amino-benzene oxygen) benzene of 3-, and combination.
7. the film of claim 6, wherein said film comprise the combination of the diamines that is enough to give the CTE that this film remains unchanged, and the Tg of 220 ℃ to 375 ℃ of this films is also given in the combination of this diamines simultaneously.
8. the film of claim 1, wherein said solvent is selected from: N, the N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide, tetramethylene sulfone, tetrahydrofuran (THF), benzophenone, pimelinketone, phenol, ortho-cresol, p-cresol, meta-cresol, ethylphenol, isopropyl-phenol, tert.-butyl phenol, xylenol, pseudocuminol, chlorophenol, chlorophenesic acid, phenylphenol, in alkyl, has 1 ethylene glycol monoalkyl ether to about 4 carbon atoms, in alkyl, has 1 diglycol monotertiary alkyl oxide to about 4 carbon atoms, the glycol monomethyl aryl ethers, propylene glycol list aryl ethers, tetramethyl-urea, Phenoxyethanol, propylene glycol phenyl ether, methyl-phenoxide, veratrole, orthodichlorobenzene, chlorobenzene, trichloroethane, methylene dichloride, chloroform, pyridine, N-cyclohexyl pyrrolidone, ethyl lactate, ionic liquid, and combination.
9. the film of claim 1, wherein said film also comprises nanoclay.
10. the film of claim 9, the CTE of wherein said film is lower than the film of the same composition that does not contain nanoclay.
11. the film of claim 10, the Tg of wherein said film is identical with the film of the same composition that does not contain nanoclay.
12. the film of claim 9, wherein said film is transparent.
13. the film of claim 1, the thermal expansivity of wherein said film is 5ppm/ ℃ at least.
14. the film of claim 7, the thermal expansivity of wherein said film are 5 to 60ppm/ ℃.
15. the film of claim 1, the thermal expansivity of wherein said film are 10 to 30ppm/ ℃.
16. the film of claim 1, the thermal expansivity of wherein said film are 10 to 20ppm/ ℃.
17. the film of claim 1, the thermal expansivity of wherein said film copper, silicon, aluminium, gold and silver, nickel, glass, pottery or The thermal expansion of polymer coefficient ± 20ppm/ ℃ in.
18. the film of claim 1, the thermal expansivity of wherein said film the thermal expansivity of copper ± 15ppm/ ℃ in.
19. the film of claim 1, the loss of wherein said film 25 ℃ are stored 24 hours in water after is less than 5% of its initial weight.
20. the film of claim 1, the loss of wherein said film 25 ℃ are stored 24 hours in water after is less than 2% of its initial weight.
21. the film of claim 1, wherein said film is a dry film, and the limiting viscosity of the solution of the 10wt% of described dry film in N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone is greater than 0.05dl/g.
22. the film of claim 1, wherein after 250 ℃ to 450 ℃ temperature is laminated to substrate, the thermal expansivity of laminated film the thermal expansivity of this film before the lamination ± 10ppm/ ℃ in.
23. the film of claim 1, wherein said film comprise the circulation polyimide of 50wt% at the most, wherein the second-order transition temperature of described circulation polyimide is 210 ℃ to 450 ℃ before circulation.
24. the film of claim 1, wherein said film comprise the circulation polyimide film of 30wt% at the most, wherein the second-order transition temperature of described circulation polyimide film is 210 ℃ to 450 ℃ before circulation.
25. the film of claim 23, the thermal expansivity of the wherein said film that comprises the circulation polyetherimide the thermal expansivity of the film that does not contain the circulation polyetherimide with same composition ± 10ppm/ ℃ in.
26. the film of claim 1, wherein said film is from comprising 1 to 30wt% solid composition curtain coating.
27. composition, it comprises the solvent cast polyimide film of claim 1, and wherein said solvent cast polyimide film is a round-robin.
28. the composition of claim 27, wherein said circulation film can be melted blend.
29. prepare the method for solvent cast polyimide film, comprising:
The polyamic acid composition curtain coating is formed film to substrate;
Heat this casting films, heat-up time and Heating temperature make can remove effectively that to desolvate and form thermal expansivity be 0.1 to 125 micron solvent cast polyimide film less than 60ppm/ ℃ and thickness; With
Thereby processing this solvent cast polyimide film is reduced to the thermal expansivity of this film and is lower than 35ppm/ ℃.
30. the method for claim 29, thereby the thermal expansivity that this solvent cast polyimide film of wherein said processing reduces this film comprises biaxial stretch-formed this solvent cast polyimide film.
31. the method for claim 29, wherein said solvent cast polyimide film comprises nanoclay.
32. the method for claim 31, wherein nanoclay is the nanoclay that peels off.
33. the method for claim 32 is wherein peeled off in the composition of the solvent system that contains 10 to 90wt% nanoclays and 10 to 90wt% and is carried out.
34. the method for claim 29 wherein after forming polyamic acid composition, is added described nanoclay in this polyamic acid composition to.
35. the method for claim 29 before described polyamic acid composition is carried out curtain coating, also comprises dianhydride component and organic diamine component are reacted in solvent system, forms polyamic acid composition.
36. the method for claim 35 comprises described dianhydride composition and organic diamine component are reacted in the presence of nanoclay.
37. the method for claim 36 also is included in and makes before described dianhydride component and organic diamine component react in solvent system, peels off the nanoclay in the described solvent system.
38. prepare the method for polyimide film, comprising:
Melt blending polymkeric substance and polyimide; With
Form film from this melt blended material, the film of wherein said formation has
Less than 60ppm/ ℃ thermal expansivity,
0.1 to 125 microns thickness and
Thermal expansivity less than 60ppm/ ℃.
39. solvent cast film comprises:
The polyimide that comprises the structural unit that is derived from following material:
The dianhydride component, comprise 3,4 '-oxygen di-O-phthalic acid dianhydride, 3,3 '-oxygen di-O-phthalic acid dianhydride, 4,4 '-oxygen di-O-phthalic acid dianhydride, or its combination and
Diamine components, comprise 4,4, mphenylenediamine, Ursol D, 4,4 '-oxygen connection dianiline, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (3-amino-benzene oxygen) benzene of 3-, or its combination;
Wherein this film has
Less than 60ppm/ ℃ thermal expansivity,
0.1 to 250 microns thickness and
Residual solvent less than 5wt%; With
Wherein said polyimide has the structural unit less than the ester of the dianhydride that is derived from biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid of 15mol% or biphenyltetracarboxyacid acid.
40. solvent cast film comprises:
Comprise being derived from 4,4 '-polyimide of the structural unit of oxygen di-O-phthalic acid dianhydride and 4,4;
The second-order transition temperature of wherein said polyimide is 190 ℃ to 400 ℃; And
Wherein said film has
Less than 60ppm/ ℃ thermal expansivity,
0.1 to 250 microns thickness and
Residual solvent less than 5wt%; With
Wherein said polyimide has the structural unit less than the ester of the dianhydride that is derived from biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid of 15mol% or biphenyltetracarboxyacid acid.
41. prepare the method for circulation polyimide compositions, comprise
The solvent cast polyimide film of fusion claim 1; With
The solvent cast polyimide film and the polymer composition of fused claim 1 are merged, form the circulation polyimide compositions.
42. the method for claim 41 also comprises and extrudes the composition that comprises this fused film.
43. prepare the method for circulation polyimide compositions, comprise
Make the solvent cast polyimide film dissolving of claim 1; With
The film and the polymer composition of dissolved claim 1 are merged, form the circulation polyimide compositions.
44. the method for claim 43 also comprises and extrudes this circulation polyimide compositions.
45. goods comprise the circulation polyimide compositions of claim 41.
46. goods comprise the circulation polyimide compositions of claim 43.
47. solvent cast film comprises:
The polyimide that comprises the structural unit that is derived from dianhydride and diamines, wherein said dianhydride be selected from 3,4 '-oxygen di-O-phthalic acid dianhydride, 3,3 '-oxygen di-O-phthalic acid dianhydride, 4,4 '-oxygen di-O-phthalic acid dianhydride, and combination, described diamines is selected from 4,4, mphenylenediamine, Ursol D, and combination; Wherein
The second-order transition temperature of described polyimide is 190 ℃ to 400 ℃; Wherein
This film has the dianhydride that is selected from biphenyltetracarboxyacid acid, biphenyltetracarboxyacid acid less than 15mol%, the ester of biphenyltetracarboxyacid acid and the material of combination thereof; In addition, wherein
This film has
Less than 60ppm/ ℃ thermal expansivity, the thermal expansivity of wherein said film copper, silicon, aluminium, gold and silver, nickel, glass, pottery or The thermal expansion of polymer coefficient ± 20ppm/ ℃ in,
0.1 to 250 microns thickness and
Residual solvent less than 5wt%; Wherein
Described solvent is selected from N, the N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide, tetramethylene sulfone, tetrahydrofuran (THF), benzophenone, pimelinketone, phenol, ortho-cresol, p-cresol, meta-cresol, phenol, ethylphenol, isopropyl-phenol, tert.-butyl phenol, xylenol, pseudocuminol, chlorophenol, chlorophenesic acid, phenylphenol, in alkyl, has 1 ethylene glycol monoalkyl ether to about 4 carbon atoms, in alkyl, has 1 diglycol monotertiary alkyl oxide to about 4 carbon atoms, the glycol monomethyl aryl ethers, propylene glycol list aryl ethers, tetramethyl-urea, Phenoxyethanol, propylene glycol phenyl ether, methyl-phenoxide, veratrole, orthodichlorobenzene, chlorobenzene, trichloroethane, methylene dichloride, chloroform, pyridine, N-cyclohexyl pyrrolidone, ethyl lactate, ionic liquid, and combination.
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| US60/805,821 | 2006-06-26 | ||
| US11/758,782 | 2007-06-06 |
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| CN201310512834.6A Division CN103694702A (en) | 2006-06-26 | 2007-06-14 | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
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| CNA2007800316873A Pending CN101506281A (en) | 2006-06-26 | 2007-06-14 | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
| CNA2007800309174A Pending CN101506283A (en) | 2006-06-26 | 2007-06-14 | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
| CNA2007800317611A Pending CN101506282A (en) | 2006-06-26 | 2007-06-14 | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
| CNA2007800318012A Pending CN101506244A (en) | 2006-06-26 | 2007-06-25 | Methods of preparing polymer-organoclay composites and articles derived therefrom |
| CNA2007800316534A Pending CN101506288A (en) | 2006-06-26 | 2007-06-25 | Compositions and methods for polymer composites |
| CN2007800293710A Expired - Fee Related CN101501122B (en) | 2006-06-26 | 2007-06-25 | Compositions and methods for polymer composites |
| CNA2007800317838A Pending CN101506290A (en) | 2006-06-26 | 2007-06-25 | Compositions and methods for polymer composites |
| CNA2007800297482A Pending CN101501123A (en) | 2006-06-26 | 2007-06-25 | Compositions and methods for polymer composites |
| CNA200780031733XA Pending CN101506276A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
| CNA2007800309687A Pending CN101506243A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
| CNA2007800317683A Pending CN101506289A (en) | 2006-06-26 | 2007-06-26 | Phosphonium salts for polymer composites and their preparation |
| CNA2007800310078A Pending CN101506287A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
| CNA2007800318099A Pending CN101506284A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
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| CN2007800293710A Expired - Fee Related CN101501122B (en) | 2006-06-26 | 2007-06-25 | Compositions and methods for polymer composites |
| CNA2007800317838A Pending CN101506290A (en) | 2006-06-26 | 2007-06-25 | Compositions and methods for polymer composites |
| CNA2007800297482A Pending CN101501123A (en) | 2006-06-26 | 2007-06-25 | Compositions and methods for polymer composites |
| CNA200780031733XA Pending CN101506276A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
| CNA2007800309687A Pending CN101506243A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
| CNA2007800317683A Pending CN101506289A (en) | 2006-06-26 | 2007-06-26 | Phosphonium salts for polymer composites and their preparation |
| CNA2007800310078A Pending CN101506287A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
| CNA2007800318099A Pending CN101506284A (en) | 2006-06-26 | 2007-06-26 | Compositions and methods for polymer composites |
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- 2007-06-14 CN CN200780031620.XA patent/CN101627074B/en not_active Expired - Fee Related
- 2007-06-14 CN CNA2007800316873A patent/CN101506281A/en active Pending
- 2007-06-14 CN CNA2007800309174A patent/CN101506283A/en active Pending
- 2007-06-14 CN CNA2007800317611A patent/CN101506282A/en active Pending
- 2007-06-25 CN CNA2007800318012A patent/CN101506244A/en active Pending
- 2007-06-25 CN CNA2007800316534A patent/CN101506288A/en active Pending
- 2007-06-25 CN CN2007800293710A patent/CN101501122B/en not_active Expired - Fee Related
- 2007-06-25 CN CNA2007800317838A patent/CN101506290A/en active Pending
- 2007-06-25 CN CNA2007800297482A patent/CN101501123A/en active Pending
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- 2007-06-26 CN CNA2007800309687A patent/CN101506243A/en active Pending
- 2007-06-26 CN CNA2007800317683A patent/CN101506289A/en active Pending
- 2007-06-26 CN CNA2007800310078A patent/CN101506287A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101506276A (en) | 2009-08-12 |
| CN101506289A (en) | 2009-08-12 |
| CN101627074A (en) | 2010-01-13 |
| CN101501123A (en) | 2009-08-05 |
| CN101506281A (en) | 2009-08-12 |
| CN101506282A (en) | 2009-08-12 |
| CN101506243A (en) | 2009-08-12 |
| CN101501122B (en) | 2011-12-07 |
| CN101506284A (en) | 2009-08-12 |
| CN101506288A (en) | 2009-08-12 |
| CN101501122A (en) | 2009-08-05 |
| CN101506244A (en) | 2009-08-12 |
| CN101506287A (en) | 2009-08-12 |
| CN101627074B (en) | 2014-02-12 |
| CN101506290A (en) | 2009-08-12 |
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