CN1960870A - Polyimide multilayer body and method for producing same - Google Patents
Polyimide multilayer body and method for producing same Download PDFInfo
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- CN1960870A CN1960870A CN 200580017730 CN200580017730A CN1960870A CN 1960870 A CN1960870 A CN 1960870A CN 200580017730 CN200580017730 CN 200580017730 CN 200580017730 A CN200580017730 A CN 200580017730A CN 1960870 A CN1960870 A CN 1960870A
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Abstract
Disclosed is a polyimide multilayer body wherein a thermoplastic polyimide layer is formed on at least one side of a highly heat-resistant polyimide layer. This polyimide multilayer body is characterized in that the highly heat-resistant polyimide layer contains a polyimide molecule having a reactive functional group, and the thermoplastic polyimide layer contains a thermoplastic polyimide molecule having a reactive functional group which is capable of forming at least one bond selected from an imide bond, amide bond and benzimidazole bond together with the reactive functional group of the polyimide molecule contained in the highly heat-resistant polyimide layer. By having such a constitution, the polyimide multilayer body is improved in the adhesion strength between the polyimides.
Description
Technical field
The present invention relates to be applicable to the polyimide multilayer body and the manufacture method thereof of flexible print circuit board, TAB band etc.More detailed saying relates to as polyimide multilayer body polyimide multilayer body, that improve each interlaminar adhesion and the manufacture method thereof that have formed thermoplastic polyimide layer in the one side at least of high-fire resistance polyimide layer.
Background technology
In recent years, along with lightweight, miniaturization, the densification of electronic products, the demand of various printed base plates is increasing, wherein, flexible layer plywood (flexible print circuit board (below, claim FPC) etc.) demand growth fast especially.The flexible layer plywood has the structure of the circuit that forms the metal forming formation on the insulating properties film.
Above-mentioned flexible layer plywood is general to use various insulating materials to form, and adopts with the insulating properties film that flexibility is arranged to be substrate, to utilize various jointing materials to pass through the method manufacturing of heating-crimping applying metal forming on the surface of this substrate.As above-mentioned insulating properties film, preferably use Kapton etc.As above-mentioned jointing material, generally use the hot setting adhesive (below, claim three layers of FPC the FPC that uses these hot setting adhesives) of epoxy system, acrylic acid series etc.
Hot setting adhesive has can be under lower temperature bonding advantage.But from now on along with the characteristic harshness of this requirement of hear resistance, bendability, electric reliability, the corresponding difficulty that becomes of three layers of FPC of estimated service life hot setting adhesive.Therefore proposed directly establishing the FPC that metal level, adhesive layer use TPI (below, also claim two layers of FPC) on the insulating properties film.This two layers of FPC compare with three layers of FPC excellent characteristic, expects demand growth from now on.
The manufacture method of the flexible metal-clad laminate that uses as two layers of FPC, can enumerate the casting method that behind curtain coating, the polyamic acid of coating on the metal forming, carries out imidizate as the precursor of polyimides, directly on Kapton, establish the metallization of metal level by sputter, coating, the laminated method of utilizing TPI that Kapton and metal forming are fitted.Wherein, the thickness range that is conceived to metal forming that can be corresponding is wideer than casting method, installation cost is than the low and preferred laminated method of metallization, as carrying out laminated device, can use the material limit of limit outlet roller shape to carry out laminated hot-rolling Laminated device or double belt formula press device etc. continuously.Consider from the viewpoint of production efficiency, more preferably use the laminated method of hot-rolling in the said method.
The polyimide multilayer body that is applicable to laminated method has the form of laminated TPI on as the Kapton of core, but the mutual cohesive of general polyimides is less high, before forming thermoplastic polyimide layer, in order to improve adhesion strength the Kapton as the core film is carried out (for example, opening 2004-51712 (patent documentation 1) with reference to the spy) such as plasma or sided corona treatment.
Yet though adopt these method cohesives to improve, because the film treatment process needs another approach, so production efficiency has problem, bonding strength itself is also still insufficient and require further improvement simultaneously.
Patent documentation 1: the spy opens 2004-51712
Summary of the invention
The problem that invention will solve
The present invention finishes in view of the above problems, its purpose is to be provided at the polyimide multilayer body that at least simultaneously forms thermoplastic polyimide layer of high-fire resistance polyimide layer, makes the polyimide multilayer body and the manufacture method thereof of the cohesive raising of high-fire resistance polyimide layer and thermoplastic polyimide layer.
Solve the method for problem
The result that the present inventor studies with great concentration in view of the above problems finds alone to adopt following novel lamilated body, novel manufacture method can improve the cohesive of high-fire resistance polyimide layer and thermoplastic polyimide layer, thereby finish the present invention.
Promptly, the present invention is a polyimide multilayer body, it is characterized in that it being the polyimide multilayer body that forms thermoplastic polyimide layer in the one side at least of high-fire resistance polyimide layer, aforementioned high-fire resistance polyimide layer contains the polyimide molecule that has reactive functional groups, and aforementioned thermoplastic polyimide layer contains the TPI molecule that the reactive functional groups that has the polyimide molecule that can be contained with the high-fire resistance polyimide layer forms the reactive functional groups that is selected from least a kind of key in imide bond, amido link, the benzimidazole key.
In the polyimide multilayer body of the present invention, the polyimide molecule that high-fire resistance polyimide layer and thermoplastic polyimide layer are contained endways can responding property functional group.In addition, above-mentioned reactive functional groups can be dicarboxylic anhydride base or amino.In addition, the polyimides that can have the polyimide molecule that above-mentioned high-fire resistance polyimide layer contains to combine with the polyimide molecule that above-mentioned thermoplastic polyimide layer contains.In addition, the polyimides that can also have the end of the polyimide molecule that polyimide molecule and above-mentioned thermoplastic polyimide layer contained that above-mentioned high-fire resistance polyimide layer contained to mutually combine.
In addition, the present invention is according to another kind of form, it is the manufacture method of polyimide multilayer body, it is characterized in that, the one side at least that adopts coextrusion-curtain coating rubbing method to be manufactured on the high-fire resistance polyimide layer forms the polyimide multilayer body of thermoplastic polyimide layer, this method comprises by curtain coating altogether the solution of the precursor that contains the high-fire resistance polyimides and the operation of solution casting on supporter that contains the precursor of TPI, and the precursor of high-fire resistance polyimides and the precursor of TPI have to form and be selected from imide bond, amido link, the reactive functional groups of at least a key of benzimidazole key.
In addition, the present invention is again according to another kind of form, it is the manufacture method of polyimide multilayer body, it is characterized in that, the one side at least that adopts coextrusion-curtain coating rubbing method to be manufactured on the high-fire resistance polyimide layer forms the polyimide multilayer body of thermoplastic polyimide layer, this method comprises by curtain coating altogether the solution of the precursor that contains the high-fire resistance polyimides and the operation of solution casting on supporter that contains TPI, and the precursor of high-fire resistance polyimides and TPI have to form and be selected from imide bond, amido link, the reactive functional groups of at least a key of benzimidazole key.
In the manufacture method of polyimide multilayer body of the present invention, the polyimide molecule that above-mentioned high-fire resistance polyimide layer and above-mentioned thermoplastic polyimide layer are contained endways can responding property functional group.In addition, the polyimide molecule that contained of above-mentioned high-fire resistance polyimide layer and thermoplastic polyimide layer can have the reactive functional groups that can form imide bond.
The invention effect
According to the present invention, can improve high-fire resistance polyimides in the polyimide multilayer body and the cohesive between the TPI.
The preferred plan that carries out an invention
Below, embodiment of the present invention are described.
＜1. polyimide multilayer body 〉
Polyimide multilayer body of the present invention, constitute by establishing TPI in the one side at least of high-fire resistance polyimide layer, the polyimide molecule that polyimide molecule that the high-fire resistance polyimide layer contains and thermoplastic polyimide layer contain reacts to each other, and becomes the lamilated body that improves each interlaminar adhesion.Especially, when the end of the polyimide molecule that the end of the polyimide molecule that the high-fire resistance polyimide layer contains and thermoplastic polyimide resin layer contain passes through the reaction bonded of reactive functional groups mutually, can improve the cohesive of each layer.Particularly, import reactive functional groups at end as the polyamic acid of the precursor of the contained polyimide molecule of each layer, each is fashionable layer by layer, react mutually by these reactive functional groups, can improve cohesive.Such lamilated body contains unreacted reactive functional groups.Below, describe according to an example of example.
＜1-1. high-fire resistance polyimide layer 〉
The molecular structure thickness of high-fire resistance polyimide layer of the present invention does not have particular determination, but preferably contains more than the non-thermal plasticity polyimide resin 90 weight %.The non-thermal plasticity polyimides that the high-fire resistance polyimide layer uses uses polyamic acid to make as precursor usually.Manufacture method as polyamic acid, can adopt known all methods, usually make aromatic tetracarboxylic acid's dianhydride and aromatic diamine basically equimolar amounts be dissolved in the organic solvent, under controlled temperature conditions, make until the polymerization of finishing above-mentioned acid dianhydride and diamines by stirring.These polyamic acid solution is usually with 5-35 weight %, and preferably the concentration with 10-30 weight % makes, and during the concentration of this scope, obtains suitable molecular weight and solution viscosity easily.
As polymerization, can adopt the method for all known method and these combinations.Polymerization in the polymerization of polyamic acid is characterised in that the interpolation order of monomer, by the interpolation order of control monomer, can control all rerum naturas of the polyimides that makes.Therefore, the polymerization of polyamic acid can be adopted the adding method of any monomer among the present invention.
As representational polymerization, can enumerate following method.
That is,
1) aromatic diamine is dissolved in the organic polar solvent, the method that makes this diamines and equimolar aromatic tetracarboxylic acid's two anhydride reactants basically carry out polymerization.
2) make aromatic tetracarboxylic acid's dianhydride and in organic polar solvent, react, obtain the prepolymer that two ends have anhydride group with respect to the aromatic diamine compound of the very few mole of this dianhydride.Then, use aromatic diamine compound and make aromatic tetracarboxylic acid's dianhydride and aromatic diamine compound in the full operation method that mole carries out polymerization such as become basically.
3) aromatic tetracarboxylic acid's dianhydride and aromatic diamine compound with respect to the superfluous mole of this dianhydride are reacted in organic polar solvent, after obtaining two ends amino prepolymer being arranged, in this prepolymer, remedy add aromatic diamine compound after, use aromatic tetracarboxylic acid's dianhydride and make aromatic tetracarboxylic acid's dianhydride and aromatic diamine compound in the full operation method that mole carries out polymerization such as become basically.
4) aromatic tetracarboxylic acid's dianhydride dissolved in organic polar solvent and/or disperse after, the method that mole such as use that aromatic diamine compound makes it to become basically carries out polymerization.
5) make the mixture of equimolar basically aromatic tetracarboxylic acid's dianhydride and aromatic diamine in organic polar solvent, carry out the method for reactive polymeric.
These methods can be used separately, also can partly be used in combination.
Can use the polyamic acid that adopts above-mentioned any polymerization to obtain among the present invention, polymerization does not have particular determination.
The preferred polymerization that uses two amine components that upright and outspoken structure described later is arranged to make prepolymer that adopts among the present invention.Adopt this method, exist to obtain elastic modelling quantity height, the tendency of the Kapton that the moisture expantion coefficient is little easily.The diamines that upright and outspoken structure is arranged and the mol ratio preferred 100 of acid dianhydride: the 70-100: 99 or 70: 100-99 that use when preparing prepolymer in this method: 100, preferred again 100: 75-100: 90 or 75: 100-90: 100.With respect to above-mentioned scope, rare when the ratio of acid dianhydride is high to the effect of improving elastic modelling quantity and moisture expantion coefficient, with respect to above-mentioned scope, acid dianhydride when low, produce the problem that the too little or tensile elongation of linear expansion coefficient diminishes etc. sometimes.
Then, the material that polyamic acid composition of the present invention is used describes.
The suitable tetracarboxylic dianhydride who uses among the present invention comprises pyromellitic acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen connection O-phthalic acid dianhydride, 2, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2-, 3,4,9, the 10-perylenetetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) propane dianhydride, 1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1-, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) ethane dianhydride, oxygen di-O-phthalic acid dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, to benzene two (trimellitic acid monoesters acid anhydrides), ethylenebis (trimellitic acid monoesters acid anhydrides), bisphenol-A two (trimellitic acid monoesters acid anhydrides) and these analog can preferably these use or use the mixture of arbitrary proportion separately.
In these acid dianhydrides special preferred use be selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen connection O-phthalic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride at least a.
In addition, in these acid dianhydrides, use to be selected from 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen connection O-phthalic acid dianhydride, 3,3 ', 4,4 '-the preferred use amount of at least a occasion of biphenyl tetracarboxylic dianhydride, be 60 moles below the % with respect to total acid dianhydride, preferably 55 moles of % following, be more preferably 50 moles below the %.Use is selected from 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen connection O-phthalic acid dianhydride, 3,3 ', 4,4 '-at least a occasion of biphenyl tetracarboxylic dianhydride, when its use amount surpasses this scope, because so the too low and difficult system film of energy storage elastic modelling quantity the when glass transition temperature of Kapton is too low or warm sometimes is not preferred.
And to use the occasion of pyromellitic acid anhydride, preferred use amount be 40-100 mole %, be more preferably preferably 50-100 mole % of 45-100 mole %, spy.By in this scope, using pyromellitic acid anhydride, easily glass transition temperature and the energy storage elastic modelling quantity when hot are remained on the scope that is suitable for using or making film.
As the suitable diamines that in polyamic acid composition, uses as the imido precursor of heat resistant poly of the present invention, for example can enumerate 4,4 '-diamino-diphenyl propane, 4,4 '-diaminodiphenyl-methane, benzidine, 3,3 '-dichloro-benzidine, 3,3 '-dimethylbenzidine, 2,2 '-dimethylbenzidine, 3,3 '-dimethoxy benzidine, 2,2 '-dimethoxy benzidine, 4,4 '-the diamino-diphenyl thioether, 3,3 '-DADPS, 4,4 '-DADPS, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 4,4 '-the diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diamino-diphenyl ethyl phosphine oxide, 4,4 '-diamino-diphenyl-N-methylamine, 4,4 '-diamino-diphenyl N-aniline, 1,4-diaminobenzene (p-phenylenediamine), 1, the 3-diaminobenzene, 1, the 2-diaminobenzene, two { 4-(4-amino-benzene oxygen) phenyl } sulfone, two { 4-(4-amino-benzene oxygen) phenyl } propane, two { 4-(3-amino-benzene oxygen) phenyl } sulfone, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 1,3-two (3-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone and these analog etc.
As two amine components, also can will have the diamines and diamines and usefulness that soft structure is arranged of upright and outspoken structure, the ratio that this occasion is preferably used is 80/20-20/80, preferred 70/30-30/70, spy 60/40-30/70 preferably more in molar ratio.When the usage ratio of the diamines of upright and outspoken structure surpassed above-mentioned scope, the tendency that exists the tensile elongation of gained film to diminish, and when being lower than above-mentioned scope produced the problem of energy storage the elastic modelling quantity too low and difficult system film of glass transition temperature when too low or hot etc. sometimes.
There is the diamines of upright and outspoken structure to be meant the diamines that following general formula (1) is represented among the present invention.
NH
2-R
2-NH
2General formula (1)
(the R in the general formula (1)
2Be to be selected from following general formula group (1))
The group of the aromatic series base of the divalent of expression, the R among the general formula group (1)
3Identical or different, be selected from-H ,-CH
3,-OH ,-CF
3,-SO
4,-COOH ,-CO-NH
2,-Cl ,-Br ,-F and OCH
3In any group.
In addition, what is called has the diamines of soft structure, is meant the diamines of soft structures such as ether, sulfonic group, ketone group, thioether group, the diamines of preferred following general formula (2) expression.
(the R in the general formula (2)
4Be to be selected from following general formula group (2))
General formula group (2)
Group in the organic group of the divalent of expression, the R among the general formula group (2)
5Identical or different, be selected from-H ,-CH
3,-OH ,-CF
3,-SO
4,-COOH ,-CO-NH
2,-Cl ,-Br ,-F and-OCH
31 kind group.
The Kapton that uses among the present invention uses by kind, the match ratio of determining suitable aromatic acid dianhydride and aromatic diamine, can suitably make the film with desired characteristic in the above-mentioned scope.
The preferred solvent of synthesizing polyamides acid usefulness is so long as the solvent of dissolving polyamic acid, then can use any solvent, but preferred amide series solvent, be N, dinethylformamide, N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-etc., the special preferred N that uses, dinethylformamide, N, the N-dimethylacetylamide.
Polyimide multilayer body of the present invention, consider that from the fusible viewpoint that improves interlayer the thermoplastic polyimide molecule that non-thermal plasticity polyimide molecule that preferred high-fire resistance polyimide layer contains and thermoplastic polyimide layer contain reciprocally reacts.The mode that the special end that preferably becomes each above-mentioned polyimide molecule reacts mutually.Particularly, can enumerate at end and import the group that can react, the form of reacting after these are laminated as the polyamic acid of the precursor of polyimides.Therefore, obtain the polyimide molecule of the non-thermal plasticity that contains in the high-fire resistance polyimide layer, preferably import reactive functional groups at end as the polyamic acid of raw material.
The key that forms after the above-mentioned reaction is considered from the viewpoint of the mechanical characteristic of anti-polyimide multilayer, durability etc., must be to be selected from imide bond, amido link, more than a kind of benzimidazole key.Therefore, as the preference of reactive functional groups, can enumerate the anhydride group of hydroxyl, diamino-phenyl, amino, carboxyl, dicarboxylic acids etc.Import terminal viewpoint and consider from easy, preferably be selected from anhydride group at least a of amino, carboxyl, dicarboxylic acids.
As the concrete method that imports reactive functional groups, can enumerate
1) by the interpolation order of control monomer, make the end of polyamic acid form the method for the anhydride group of amino or dicarboxylic acids,
2) behind the formation polyamic acid, import the method for reactive functional groups etc. endways by known synthetic reaction.
If consider manufacturing cost, special preferred the use by the interpolation order of controlling above-mentioned monomer makes the end of polyamic acid form the method for amino or dicarboxylic anhydride.Adopting the occasion of this method, is the occasion of diamines at the final monomer that adds, and forms the dicarboxylic anhydride end, at tetracarboxylic dianhydride's occasion formation amino terminal.
In addition, in order to improve all characteristics of films such as sliding, conductivity of heat, electric conductivity, corona resistance, annular stiffness, also can add filler.As filler, can use any filler, and, can enumerate silica, titanium oxide, aluminium oxide, silicon nitride, boron nitride, calcium monohydrogen phosphate, calcium phosphate, mica etc. as preference.
The particle diameter of filler decides according to the kind of the film characteristics of intending upgrading and the filler that added, thus there is not particular determination, but the average particle diameter is 0.05-100 μ m, preferably 0.1-75 μ m, more preferably 0.1-50 μ m, spy 0.1-25 μ m preferably.When particle diameter was lower than this scope, difficulty presented the upgrading effect, when surpassing this scope, and injured surface or reduce mechanical property significantly significantly.In addition, the interpolation umber of filler also determines according to the film characteristics of intending upgrading or filler particle diameter etc., so there is not particular determination.The addition of general filler is 0.01-100 weight portion, preferred 0.01-90 weight portion, is more preferably the 0.02-80 weight portion with respect to polyimides 100 weight portions.When the filler addition was lower than this scope, difficulty presented the upgrading effect of filler, when surpassing this scope, might destroy the mechanical property of film significantly.
As the adding method of filler, can use
1) add method in the polymerization liquid before the polymerization or in the polymerization way to,
2) polymerization finishes the method that compounding filled dose of three rollers etc. are used in the back,
3) preparation contains the dispersion liquid of filler, be mixed into the method in the polyamic acid organic solvent solution then, Deng any method, the dispersion liquid that contains filler is mixed into the method in the polyamic acid solution, the method of especially mixing when being about to make film is because production line is filled the minimum and preferred of agent pollution.Preparation contains the occasion of the dispersion liquid of filler, the preferred use solvent identical with the polymer solvent of polyamic acid.In addition, for filler being disperseed well and making the dispersity stabilisation, also can in the scope that the film rerum natura is not had influence, use dispersant, tackifier etc.
The solution that the solution of the precursor with non-thermal plasticity polyimide resin that makes is like this called the precursor that contains the high-fire resistance polyimides.
＜1-2 thermoplastic polyimide layer 〉
Thermoplastic polyimide layer of the present invention, if adopt laminated method to have the bonding force of usefulness, then content, molecular structure, the thickness of the thermoplastic polyimide resin that contains in this layer do not have particular determination.In order to have the bonding force of usefulness, preferably contain basically more than the thermoplastic polyimide resin 50 weight %.
TPI as thermoplastic polyimide layer contains can suitably use TPI, polyamide thermoplastic acid imide, thermoplastic polyether acid imide, thermoplastic polyester acid imide etc.Wherein, have low moisture-absorption characteristics in mind, the special preferred thermoplastic polyester acid imide that uses.
The TPI that thermoplastic polyimide layer of the present invention contains can make by the conversion reaction of precursor polyamic acid by it.As the manufacture method of this polyamic acid, can be same with the precursor of high-fire resistance polyimide layer, adopt known all methods.
In addition, the laminated existing apparatus that uses, and the stable on heating viewpoint of never destroying the gained metal-clad laminate considers that the TPI among preferred the present invention has glass transition temperature (Tg) 150-300 ℃ scope.Moreover Tg can be obtained by the value of the point of inflection of the energy storage elastic modelling quantity that adopts Measurement of Dynamic Viscoelasticity device (DMA) to measure.
The polyamic acid of the precursor of the TPI that the present invention uses does not have particular determination, can use known all polyamic acids.About aforementioned base materials and aforementioned create conditions etc. also can be fully similarly used in the manufacturing of polyamic acid solution.
In addition, TPI can carry out various combinations by the raw material that will use and regulate all characteristics, when the diamines usage rate of general upright and outspoken structure was big, because glass transition temperature increases and/or the energy storage elastic modelling quantity when hot increases, cohesive, processability reduced and not preferred.Preferred 40 moles below the % of the diamines ratio of upright and outspoken structure, preferred again 30 moles below the %, preferably 20 moles below the % of spies.
As the concrete example of preferred thermoplastic polyimide resin, can enumerate and make acid dianhydride that contains the biphenyl tetracarboxylic dianhydride class and the polyimide resin that the diamine polymerization reaction system of amino-benzene oxygen is arranged.
The polyimide molecule that thermoplastic polyimide layer contains, also the polyimide molecule that contains with the high-fire resistance polyimide layer is same, must be the polyimide molecule that imports the group that can react in as the precursor polyamic acid of polyimides, made by this polyamic acid.The importing of reactive functional groups can be adopted and＜1-1. high-fire resistance polyimide layer〉the same method of described method.The polyimide molecule that thermoplastic polyimide layer contains also preferably contains the polyimide molecule that the polyamic acid of reactive functional groups makes by end.
In addition,, also can in above-mentioned high-fire resistance polyimide layer and/or thermoplastic polyimide layer, add inorganic or organic filler as required, can also add other resin in order to control the characteristic of polyimide multilayer body of the present invention.
The combination of the reactive functional groups of polyimide molecule in each layer of＜1-3. 〉
The polyimide molecule that contains in each layer as high-fire resistance polyimide layer and thermoplastic polyimide layer among the present invention can in conjunction with the combination of reactive functional groups, the combinations that can enumerate amino and dicarboxylic anhydride, diamines and carboxylic acid, amino and carboxylic acid etc.
＜2. the manufacture method of polyimide multilayer body 〉
As the method that obtains polyimide multilayer body of the present invention, can enumerate and make the high-fire resistance polyimide layer in advance, on this layer, pass through coating then, the impregnating form is as the polyamic acid solution of the precursor of TPI, add the method that hot-imide forms thermoplastic polyimide layer, make the method for the TPI of high-fire resistance polyimide layer and formation solvent soluble, make the method that high-fire resistance polyimide layer and thermoplastic polyimide layer are fitted then respectively, adopt coextrusion-curtain coating rubbing method etc. will contain that solution and the solution that contains TPI of precursor of high-fire resistance polyimides or the solution that contains the precursor of TPI are on the supporter that solution state overlapped and cast in metal drum or metal tape etc. and behind the acquisition self-supporting dry film, the method that adds hot-imide, the precursor of casting high-fire resistance polyimide layer and after obtaining the self-supporting dry film adopts coating or impregnating method to form polyamic acid solution as the TPI precursor, add the method for hot-imide etc.
Yet, consider the special preferred method that adopts coextrusion-curtain coating rubbing method to close the adhesive layer that contains TPI at least one surface layer of high-fire resistance polyimide layer from presenting effect of the present invention the most significantly.This method is because each layer is laminated under the state of polyamic acid, so can make the reactive functional groups reaction expeditiously in the operation of imidizate.
Adopt above-mentioned any method that the operation of imidizate also must be arranged.At this moment,, have and only utilize heat to carry out the hot-imide method of imidizate and the chemical imidizate method of use dehydrating agent and catalyst, can adopt any method as the method for imidizate.Adopt the occasion of any imidizate order, in order to carry out imidizate expeditiously, also heat, the temperature of this moment preferably sets in the scope of (glass transition temperature of TPI-100 ℃)-(glass transition temperature+200 ℃), more preferably be set in (glass transition temperature of TPI-50 ℃)-scope of (glass transition temperature+150 ℃) in.Because the temperature height of heat cure causes imidizate easily, thus curing rate can be accelerated, preferred aspect production efficiency.But when temperature is too high, might cause the TPI thermal decomposition.And the temperature of heat cure is when too low, even chemosetting, also difficulty is carried out imidizate, and the time that curing process needs is elongated.
The imidizate time, desirable imidizate and the dry required adequate time finished basically do not have certain qualification, and the general suitable scope of 1-600 about second of pressing set.In addition, in order to improve the fluidity of molten of adhesive layer, also can reduce acid imide rate and/or residual solvent wittingly.
The tension force that applies during as imidizate is preferably the scope of 1kg/m-15kg/m, and the spy is preferably the scope of 5kg/m-10kg/m.Tension force is less than the occasion of above-mentioned scope, produces lax when film is carried or crawls, and wrinkle take place when batching, and maybe might produce the problem that can not evenly batch etc.Otherwise greater than the occasion of above-mentioned scope, owing to carry out high temperature heating under the strong tension state applying, so the dimensional characteristic of gained flexible metal-clad laminate deterioration sometimes.
Manufacture method to polyimide multilayer body of the present invention describes particularly again.In the manufacture method of polyimide multilayer body of the present invention, so-called coextrusion-curtain coating rubbing method is to comprise to the flow casting molding machine that the flow casting molding die head more than two layers is arranged side by side supplying with the solution of the precursor that contains the high-fire resistance polyimides and containing the solution of TPI or contain the solution of the precursor of TPI, and the thin membranous body that makes two solution become two layers at least from the curtain coating mouth of above-mentioned die head carries out the manufacture method of film of the operation of curtain coating.If the method to general use describes, flow casting molding more than two layers is extruded on the level and smooth supporter continuously with above-mentioned two solution of die head curtain coating, then, obtain the plural layers of self-supporting by at least a portion solvent evaporates that makes the membranaceous body of multi-layer thin on the above-mentioned supporter.Again these plural layers are peeled off from above-mentioned supporter,, removed basically and desolvate, carry out imidizate simultaneously, obtain desired adhesive film at last by fully these plural layers being carried out heat treated at high temperature (250-600 ℃).In addition, in order to improve the fluidity of molten of adhesive layer, also can expressly reduce imidizate rate and/or residual solvent.
The precursor of general polyimides by polyimides, be that the dehydration conversion reaction of polyamic acid obtains, as the method for carrying out this conversion reaction, what the most widely know is 2 kinds of methods only utilizing heat thermal curing method that carries out and the chemosetting method of using chemical dehydrator.Yet if consider to make efficient, more preferably chemosetting method.
Here, so-called chemical curing agent is the curing agent that contains dehydrating agent and catalyst.The so-called dehydrating agent here is the dehydration closed-loop agent to polyamic acid, main component as dehydrating agent, can preferably use aliphatic anhydride, aromatic anhydride, N, N '-dialkyl group carbodiimides, lower aliphatic halide, halogenated lower aliphatic anhydride, aryl sulfonic acid dihalide, thionylhalides or these mixtures more than 2 kinds.Wherein aliphatic anhydride and aromatic anhydride effect are good especially.So-called in addition catalyst is to have to promote the composition of curing agent to the effect of the dehydration closed-loop effect of polyamic acid, for example can use aliphatic tertiary amine, aromatic nitrile base, hetero ring type tertiary amine.Wherein, the nitrogen-containing heterocycle compound of imidazoles, benzimidazole, isoquinolin, quinoline or β-picoline etc. preferably.In addition, also can suitably be chosen in the solution that dehydrating agent and catalyst form and import organic polar solvent.
Relevant to the precursor solution of the flow casting molding more than two layers with the high-fire resistance polyimides of die head curtain coating, with the solution that contains TPI or contain solvent evaporates method in the solution of precursor of TPI, do not have particular determination, and the method for heating and/or air-supply is the easiest method.When the temperature during above-mentioned heating was too high, because solvent volatilizees rapidly, the residual trace of this volatilization became the main cause that forms tiny flaw in the adhesive film that finally makes, so preferably less than boiling point+50 of employed solvent ℃.
Embodiment
Below, illustrate in greater detail the manufacture method of polyimide multilayer body of the present invention by embodiment.In addition, the evaluation assessment of the bonding strength between the polyimides of the polyimide multilayer body in synthesis example, embodiment and the comparative example is as follows.
(bonding strength)
According to " 6.5 peel strength " of JISC6471, make sample, under the condition that 90 peel angle of spending, 50mm/ divide, peel off the wide metal forming part of 5mm, measure and peel off loading.
(synthesis example 1)
In the glass system flask of capacity 2000ml, add 780g DMF, 78.7g 3,3 ', 4,4 '-ethylene (trimellitic acid monoesters acid anhydrides) of biphenyl tetracarboxylic dianhydride (BPDA) and 5.8g is (TMEG), after stirring 1 hour under the nitrogen environment atmosphere, then under ice bath, stirred 30 minutes, add 2 of 111.7g, 2-two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP).The BAPP for preparing 3.3g in addition is dissolved in the solution among the DMF of 20g, and add this solution in the above-mentioned reaction solution at leisure on marginal not meaning viscosity limit, stirs.Viscosity stops when just having reached 2000 pools adding, stirring, and makes polyamic acid solution.
This polyamic acid solution curtain coating on the PET film (セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ corporate system) of 25 μ m, is carried out 5 minutes dryings under 120 ℃, making final thickness is 20 μ m.After peeling dried self-supporting film off from PET, be fixed on the metal pin frame, carried out drying in 5 minutes, make single sheet by 150 ℃ 5 minutes, 200 ℃ 5 minutes, 250 ℃ 5 minutes, 350 ℃.The glass transition temperature of this TPI is 240 ℃.In addition, when judging thermoplasticity, owing to produce compression set, explanation has thermoplasticity.
(synthesis example 2)
In the glass system flask of capacity 2000ml, add 780g DMF, 115.6g 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) adds 3,3 of 78.7g ' at leisure on the following stirring of nitrogen environment atmosphere, limit, 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA).Then, the ethylene (trimellitic acid monoesters acid anhydrides) of interpolation 3.8g (TMEG) stirred 30 minutes under ice bath.The TMEG for preparing 2.0g in addition is dissolved in the solution among the DMF of 20g, and add this solution in the above-mentioned reaction solution at leisure on marginal not meaning viscosity limit, stirs.When viscosity has just reached 2000 pools, stop to add, stirring, make polyamic acid solution.
This polyamic acid solution curtain coating on the PET film (セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ corporate system) of 25 μ m, is carried out 5 minutes dryings under 120 ℃, making final thickness is 20 μ m.After peeling dried self-supporting film off from PET, be fixed on the metal system pin frame, carried out drying in 5 minutes, make single sheet by 150 ℃ 5 minutes, 200 ℃ 5 minutes, 250 ℃ 5 minutes, 350 ℃.The glass transition temperature of this TPI is 240 ℃.In addition, in judging thermoplasticity, owing to produce compression set, explanation has thermoplasticity.
(synthesis example 3)
At the N that is cooled to 10 ℃, among dinethylformamide (DMF) 229kg 4 of p-phenylenediamine (PPD) (p-PDA), the 11.50kg of dissolving 6.20kg, 4 '-diaminodiphenyl ether (ODA) after, the benzophenone tetracarboxylic dianhydride (BTDA) of adding 18.50kg makes it dissolving, dissolve again 15.79kg to benzene two (trimellitic acid monoesters acid anhydrides) (TMHQ).And then add the pyromellitic acid anhydride (PMDA) of 4.01kg, stir and made it to dissolve fully in 1 hour.The DMF solution (PMDA: DMF=1.0kg: 14kg) add at leisure in the above-mentioned reactant liquor of the PMDA for preparing in addition.When reaching the 3000 pool left and right sides, viscosity stops to add.Carry out stirring in 1 hour, obtain solid branch concentration 19 weight %, at the polyamic acid solution of 23 ℃ rotary viscosities, 3400 pools.
(synthesis example 4)
At the N that is cooled to 10 ℃, the benzophenone tetracarboxylic dianhydride (BTDA) of adding 18.50kg among dinethylformamide (DMF) 240kg makes it dissolving, dissolve again 15.79kg to benzene two (trimellitic acid monoesters acid anhydrides) (TMHQ).And then the pyromellitic acid anhydride (PMDA) of interpolation 5.01kg, stirred 1 hour, make it to dissolve fully.Dissolve therein 6.20kg p-phenylenediamine (PPD) (p-PDA), 11.0kg 4,4 '-diaminodiphenyl ether (ODA) after, the DMF solution of the p-PDA for preparing in addition (p-PDA: DMF=0.22kg: 3kg) add at leisure in the above-mentioned reactant liquor, when viscosity reaches the 3000 pool left and right sides, stop to add.Carry out stirring in 1 hour, obtain solid branch concentration 19 weight %, 23 ℃ of polyamic acid solutions that rotary viscosity 3400 is down moored.
The manufacturing 1 of＜copper-surfaced laminate 〉
Below, to adopt in the manufacturing of copper-surfaced laminate behind coating thermoplastic polyamic acid on the high-fire resistance polyimide layer, the occasion of imidizate manufactured polyimide multilayer body describes.
Make in the precursor polyamic acid solution of the high-fire resistance polyimides that synthesis example 3,4 makes, contain the chemical curing agent that aceticanhydride/isoquinolin/DMF (weight ratio 18.90/7.17/18.93) constitutes with respect to this polyamic acid solution by weight 50%, use mixer to stir continuously, from T font die head curtain coating, curtain coating is on the stainless steel endless belt that 20mm under this die head travels.The gel mould (volatile matter content 45 weight %) of peeling off self-supporting after heating this resin molding under the condition in 130 ℃ * 100 seconds from the endless belt is fixed on the stenter folder film frame, carried out drying, imidizate by 300 ℃ * 20 seconds, 450 ℃ * 20 seconds, 500 ℃ * 20 seconds, obtains the high-fire resistance polyimide layer of 17 μ m.
Then, after the polyamic acid solution as the precursor of TPI that uses DMF that synthesis example 1 and 2 is made is diluted to solid branch concentration 10 weight %, two sides at aforesaid each high-fire resistance polyimide layer is coated with polyamic acid respectively, after a face thickness that makes thermoplastic polyimide layer (adhesive layer) is 3 μ m, 140 ℃ of heating 1 minute.Then in the FAR INFRARED HEATING stove of 390 ℃ of ambiance temperature, passed through for 20 seconds, add hot-imide, obtain polyimide multilayer body.
Both sides at the polyimide multilayer body that makes; adopt 380 ℃ of tension force 0.4N/cm, laminated temperatures, the laminated pressure 196N/cm (20kgf/cm) of polyimide multilayer body; the condition that laminated speed 1.5m/ divides is hot laminating 18 μ m rolled copper foil (BHY-22B-T continuously; Japan エ Na ジ-corporate system); as protective material, make flexible copper-surfaced laminate (FCCL) at the both sides of Copper Foil hot laminating ア ピ カ Le 125NPI (clock deep pool chemical industry Co., Ltd system) again.
The Production Example 2 of＜copper-surfaced laminate 〉
Below, the occasion that adopts coextrusion-curtain coating rubbing method to make polyimide multilayer body in the manufacturing to the copper-surfaced laminate describes.
Make the polyamic acid solution of the precursor of the high-fire resistance polyimides that synthesis example 3,4 makes contain following chemical dehydrator and catalyst.
1. chemical dehydrator: aceticanhydride is 2 moles with respect to 1 mole of the amic acid unit of the polyamic acid of the precursor of high-fire resistance polyimides
2. catalyst: isoquinolin is 1 mole for 1 mole with respect to the amic acid unit of the polyamic acid of the precursor of high-fire resistance polyimides.
Make the polyamic acid solution of the precursor of the TPI that synthesis example 1,2 makes contain following chemical dehydrator and catalyst again.
1. chemical dehydrator: aceticanhydride is 2 moles for 1 mole with respect to the amic acid unit of the polyamic acid of the precursor of TPI.
2. catalyst: isoquinolin is 2 moles for 1 mole with respect to the amic acid unit of the polyamic acid of the precursor of TPI.
Then, by 3 layers of branch manifold T font die head, be order each polyamic acid solution of curtain coating continuously of the polyamic acid solution of the polyamic acid solution of the precursor of TPI, precursor that internal layer is the high-fire resistance polyimide solution by skin, curtain coating is on the endless belt of the stainless steel that 20mm under this T pattern head travels.After heating this resin molding under the condition in 130 ℃ * 100 seconds, peel the gel mould of self-supporting from the endless belt, be fixed on the stenter folder film frame, carry out drying, imidizate by 300 ℃ * 30 seconds, 400 ℃ * 50 seconds, 450 ℃ * 10 seconds, make the polyimide multilayer body of each thermoplastic polyimide layer 3 μ m, high-fire resistance polyimide layer 17 μ m.
Both sides at the polyimide multilayer body that makes; the condition that 380 ℃ of tension force 0.4N/cm, the laminated temperatures of employing polyimide multilayer body, laminated pressure 196N/cm (20kgf/cm), laminated speed 1.5m/ divide is the rolled copper foil (BHY-22B-T of hot laminating 18 μ m continuously; Japan エ Na ジ-corporate system); as protective material, make flexible copper-surfaced laminate (FCCL) at the both sides of Copper Foil hot laminating ア ピ カ Le 125NPI (clock deep pool chemical industry Co., Ltd system) again.
(embodiment 1,2)
According to the manufacturing 1 of copper-surfaced laminate, FCCL is made in the combination that makes high-fire resistance polyimide layer and thermoplastic polyimide layer become table 1 expression.Characteristic is shown in table 1.
(embodiment 3,4)
According to the manufacturing 2 of copper-surfaced laminate, FCCL is made in the combination that makes high-fire resistance polyimide layer and thermoplastic polyimide layer become table 1 expression.Characteristic is shown in table 1.
(comparative example 1,2)
According to the manufacturing 1 of copper-surfaced laminate, FCCL is made in the combination that makes high-fire resistance polyimide layer and thermoplastic polyimide layer become table 1 expression.Characteristic is shown in table 1.
(comparative example 3,4)
According to the manufacturing 2 of copper-surfaced laminate, FCCL is made in the combination that makes high-fire resistance polyimide layer and thermoplastic polyimide layer become table 1 expression.Characteristic is shown in table 1.
Table 1
| The assess sample autofrettage | Thermoplastic polyimide layer | The high-fire resistance polyimide layer | Bonding strength (N/cm) | |||
| Normality | 150℃×168hr | 121℃×100％RH×96hr | ||||
| Embodiment 1 | The manufacturing 1 of copper-surfaced laminate | Synthesis example 1 | Synthesis example 3 | 9 | 9 | 7 |
| Embodiment 2 | The manufacturing 1 of copper-surfaced laminate | Synthesis example 2 | Synthesis example 4 | 9 | 9 | 7 |
| Embodiment 3 | The manufacturing 2 of copper-surfaced laminate | Synthesis example 1 | Synthesis example 3 | 14 | 14 | 13 |
| Embodiment 4 | The manufacturing 2 of copper-surfaced laminate | Synthesis example 2 | Synthesis example 4 | 14 | 14 | 13 |
| Comparative example 1 | The manufacturing 1 of copper-surfaced laminate | Synthesis example 1 | Synthesis example 4 | 4 | 2 | 1 |
| Comparative example 2 | The manufacturing 1 of copper-surfaced laminate | Synthesis example 2 | Synthesis example 3 | 4 | 2 | 1 |
| Comparative example 3 | The manufacturing 2 of copper-surfaced laminate | Synthesis example 1 | Synthesis example 4 | 6 | 4 | 2 |
| Comparative example 4 | The manufacturing 2 of copper-surfaced laminate | Synthesis example 2 | Synthesis example 3 | 6 | 4 | 2 |
Claims (13)
1. polyimide multilayer body, it is the polyimide multilayer body that forms thermoplastic polyimide layer in the one side at least of high-fire resistance polyimide layer, it is characterized in that, aforementioned high-fire resistance polyimide layer contains the polyimide molecule of being with reactive functional groups, and aforementioned thermoplastic polyimide layer contains the TPI molecule that the reactive functional groups that has the polyimide molecule that can be contained with described high-fire resistance polyimide layer forms the reactive functional groups of at least a kind of key that is selected from imide bond, amido link, benzimidazole key.
2. the described polyimide multilayer body of claim 1 is characterized in that, previous reaction functional group is dicarboxylic anhydride base or amino.
3. the described polyimide multilayer body of claim 1 is characterized in that, the polyimide molecule that aforementioned high-fire resistance polyimide layer and aforementioned thermoplastic polyimide layer contain has previous reaction functional group endways.
4. the described polyimide multilayer body of claim 3 is characterized in that, previous reaction functional group is dicarboxylic anhydride base or amino.
5. the described polyimide multilayer body of claim 1 is characterized in that, has the polyimides that the polyimide molecule that aforementioned high-fire resistance polyimide layer contains combined with the polyimide molecule that aforementioned thermoplastic polyimide layer contains.
6. the described polyimide multilayer body of claim 5 is characterized in that, previous reaction functional group is dicarboxylic anhydride base or amino.
7. the described polyimide multilayer body of claim 5 is characterized in that, has the polyimides that the end of the polyimide molecule that polyimide molecule that aforementioned high-fire resistance polyimide layer contains and aforementioned thermoplastic polyimide layer contain mutually combines.
8. the described polyimide multilayer body of claim 7 is characterized in that, previous reaction functional group is dicarboxylic anhydride base or amino.
9. the manufacture method of polyimide multilayer body is the method that has at least simultaneously formed the polyimide multilayer body of thermoplastic polyimide layer that employing coextrusion-curtain coating rubbing method is manufactured on the high-fire resistance polyimide layer,
It is characterized in that, this method comprises that the precursor of the precursor of aforementioned high-fire resistance polyimides and aforementioned hot plastic polyimide has the reactive functional groups that can form at least a key that is selected from imide bond, amido link, benzimidazole key by curtain coating is the solution of the precursor that contains aforementioned high-fire resistance polyimides and the operation of solution casting on supporter that contains the precursor of aforementioned hot plastic polyimide altogether.
10. the manufacture method of the described polyimide multilayer body of claim 9 is characterized in that, the polyimide molecule that aforementioned high-fire resistance polyimide layer and aforementioned thermoplastic polyimide layer contain has reactive functional groups endways.
11. the manufacture method of the described polyimide multilayer body of claim 9 is characterized in that, the polyimide molecule that aforementioned high-fire resistance polyimide layer and aforementioned thermoplastic polyimide layer contain has the reactive functional groups that can form imide bond.
12. the manufacture method of polyimide multilayer body, be to adopt coextrusion-curtain coating rubbing method to be manufactured on the method that has at least simultaneously formed the polyimide multilayer body of thermoplastic polyimide layer of high-fire resistance polyimide layer, it is characterized in that, this method comprises by being total to curtain coating the solution of the precursor that contains aforementioned high-fire resistance polyimides and the operation of solution casting on supporter that contains the aforementioned hot plastic polyimide
The precursor of aforementioned high-fire resistance polyimides and aforementioned hot plastic polyimide have the reactive functional groups that can form at least a key that is selected from imide bond, amido link, benzimidazole key.
13. the manufacture method of the described polyimide multilayer body of claim 12 is characterized in that, the polyimide molecule that aforementioned high-fire resistance polyimide layer and aforementioned thermoplastic polyimide layer contain has the reactive functional groups that can form imide bond.
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| JP160729/2004 | 2004-05-31 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102939671A (en) * | 2010-04-13 | 2013-02-20 | 宇部兴产株式会社 | Heat dissipation substrate for led |
| CN113260503A (en) * | 2018-11-13 | 2021-08-13 | 杜邦电子公司 | Multilayer polymeric film |
| CN115461221A (en) * | 2020-05-29 | 2022-12-09 | 东洋纺株式会社 | Polyimide film and method for producing same |
-
2005
- 2005-05-24 CN CN 200580017730 patent/CN1960870A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102939671A (en) * | 2010-04-13 | 2013-02-20 | 宇部兴产株式会社 | Heat dissipation substrate for led |
| CN113260503A (en) * | 2018-11-13 | 2021-08-13 | 杜邦电子公司 | Multilayer polymeric film |
| CN115461221A (en) * | 2020-05-29 | 2022-12-09 | 东洋纺株式会社 | Polyimide film and method for producing same |
| CN115461221B (en) * | 2020-05-29 | 2023-12-29 | 东洋纺株式会社 | Polyimide film and method for producing same |
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