CN101998761A - Metal lamination plate and preparation method thereof - Google Patents
Metal lamination plate and preparation method thereof Download PDFInfo
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- CN101998761A CN101998761A CN2009101896580A CN200910189658A CN101998761A CN 101998761 A CN101998761 A CN 101998761A CN 2009101896580 A CN2009101896580 A CN 2009101896580A CN 200910189658 A CN200910189658 A CN 200910189658A CN 101998761 A CN101998761 A CN 101998761A
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Abstract
The invention provides a metal lamination plate. The metal lamination plate comprises a metal layer, a thermoplastic polyimide resin layer, a thermosetting polyimide resin layer, a thermoplastic polyimide resin layer and a metal layer, wherein the thermal expansion coefficient of the thermoplastic polyimide resin layer is 10 to 50ppm per DEG C; the hygroscopic expansion coefficient of the thermoplastic polyimide resin layer is 2 to 16ppm; the thermal expansion coefficient of the thermosetting polyimide resin layer is 15 to 40ppm per DEG C; and the hygroscopic expansion coefficient of the thermosetting polyimide resin layer is 2 to 13ppm. In the metal lamination plate prepared by the provided method, the heat resistance of a copper clad laminate is improved, the peel strength is improved, and the dimensional stability of the metal lamination plate also can be improved.
Description
Technical field
The present invention relates to a kind of metal laminated plate and preparation method thereof.
Background technology
Flexible printed-circuit board (Flexible Printed Circuit-FPC) has a wide range of applications in many industries, as industries such as car industry, military project, space flight, computer, telecommunication, medical treatment and consumer electronics, flexible printed-circuit board has adapted to the needs of electronic product to light, small-sized, high density, high reliability development, has become indispensable important component part in the electronic product.The insulating barrier of flexible printed-circuit board all adopts polyimide resin all the time, but the prominent question of polyimide resin promptly is relatively poor with the adhesive force of Copper Foil.For addressing this problem, adopt adhesive with Copper Foil and the bonding preparation flexibility coat copper plate of polyimide resin, more representational two kinds of preparation methods are three-layer process and two-layer method.Three-layer process adopts epoxy resin as adhesive, and the flexibility coat copper plate of its preparation has higher peel strength, but the thermal endurance of epoxy resin itself determines its high-temperature behavior not good.And two-layer method adopts thermoplastic polyimide resin as adhesive, in the adhesive force of enhancing and Copper Foil, has improved the thermal endurance of insulating barrier integral body.
CN1764534 discloses a kind of double-sided metal laminated plates that is used for printed circuit board (PCB) and preparation method thereof.Double-sided metallic laminate wherein be included in one side metal level, be used to improve with the polyimide resin layer of metal adhesion, have 5 * 10
-6～2.5 * 10
-5Thermal coefficient of expansion the low bulk polyimide resin layer and at the metal level of another side.Its shortcoming is when having only a metal level etched, the low bulk polyimides can reduce curling of metal laminate plate, but when the two-sided circuit that carries out when printing, because the difference between the thermoplastic polyimide of improvement and metal bonding and the thermal coefficient of expansion of low bulk polyimides, still inevitable curling to a certain degree directly influences the peel strength of double-sided metallic laminate.And, metal level and polyimide layer need earlier through 350 ℃ of common curing, this process slowly heats up under nitrogen environment or vacuum and carries out, make through 300 ℃～350 ℃ press pressings again, complex process, strict to equipment and operating environment, and the adhesion between each layer of metal laminated plate a little less than.
Disclose a kind of double side flexible copper coated board and preparation method thereof in CN101420820, this double side flexible copper coated board comprises a single-side coated copper plate, coat the adhesive layer on this single-side coated copper plate and be overlaid on another Copper Foil or another single face flexibility coat copper plate on this adhesive layer.Though the double side flexible copper coated board that this invention is made folding resistance and ageing-resistant aspect be better than the double face copper that traditional three-layer process is produced, but, what its adhesive layer adopted is composition epoxy resin or acrylate modified resin combination, and the copper-clad plate that makes is lower in peel strength.
Summary of the invention
Technical problem to be solved by this invention is to obtain the high metal laminated plate of a kind of peel strength.
The invention provides a kind of metal laminated plate, wherein, the structure of metal laminated plate is metal level/thermoplastic polyimide resin layer/thermoset polyimide resin layer/thermoplastic polyimide resin layer/metal level, wherein, the thermal coefficient of expansion of thermoplastic polyimide resin layer is 10-50ppm/ ℃, and the moisture expantion coefficient is 2-16ppm; The thermal coefficient of expansion of thermoset polyimide resin layer is 15-40ppm/ ℃, and the moisture expantion coefficient is 2-13ppm.
The present invention also provides the preparation method of the described metal laminated plate of a kind of claim 1, may further comprise the steps:
A is dissolved in the first aromatic tetracarboxylic acid's dianhydride and first aromatic diamine in the polar non-solute, and reaction generates the polyamide thermoplastic acid solution;
B is dissolved in the second aromatic tetracarboxylic acid's dianhydride and second aromatic diamine in the polar non-solute, reaction generates the thermosetting polyamide acid solution, and this Thermocurable polyimide acid solution is coated on the glass plate, heating, imidization reaction takes place, and makes the Thermocurable polyimide film;
C is coated on the thermoplastic polyimide acid solution for preparing in the A step on the one side of the Thermocurable polyimide film for preparing in the B step, heating, imidization reaction takes place, make the Thermocurable polyimide layer that is covered with thermoplastic polyimide layer, again the thermoplastic polyimide acid solution is coated on the another side of Thermocurable polyimide film, imidization reaction takes place in heating, and two surfaces of system are covered with the Thermocurable polyimide film of thermoplastic polyimide layer;
D is covered with Thermocurable polyimide film, the metal level of thermoplastic polyimide layer with metal level, surface, stacks successively, and is hot-forming, obtains metal laminated plate.
By the metal laminated plate of method preparation provided by the present invention, when improving its peel strength, can also improve the dimensional stability of metal laminated plate.
Embodiment
The invention provides a kind of metal laminated plate, wherein, the structure of metal laminated plate is metal level/thermoplastic polyimide resin layer/thermoset polyimide resin layer/thermoplastic polyimide resin layer/metal level, wherein, the thermal coefficient of expansion of thermoplastic polyimide resin layer is 10-50ppm/ ℃, and the moisture expantion coefficient is 2-16ppm; The thermal coefficient of expansion of thermoset polyimide resin layer is 15-40ppm/ ℃, and the moisture expantion coefficient is 2-13ppm.
In the preferred case, the thermal coefficient of expansion of thermoplastic polyimide resin layer is 10-30ppm/ ℃, and the moisture expantion coefficient is 2-14ppm, and the thermal coefficient of expansion of thermoset polyimide resin layer is 15-30ppm/ ℃, and the moisture expantion coefficient is 2-10ppm.
The thermoplastic polyimide resin layer and the peel strength between the metal level of the metal laminated plate that is provided among the present invention are 7-9N/cm.
The thickness of thermoplastic polyimide resin layer is the 2-50 micron, and the thickness of thermoset polyimide resin layer is the 5-125 micron, and metal layer thickness is the 9-70 micron.
The present inventor finds by a large amount of tests, when three layers of flexibility coat copper plate of preparation, though, the bond layer that between metal level and polyimide layer, has added composition epoxy resin or acrylate modified resin combination conduct, can improve the adhesion between metal level and the polyimide layer, but because, the polarity of epoxy resin and polyimide resin differs bigger, so, the adhesion of bond layer and polyimide layer is limited, in addition on the one hand because the working temperature of epoxy resin is 120-200 degree centigrade, withstand high temperatures not, and the peel strength between itself and the Copper Foil is lower, and the working temperature of thermoplastic polyimide is 300-400 degree centigrade, has tangible resistance to elevated temperatures by comparison.
In addition, the present inventor also finds, by regulating the thickness coupling and control between different polyimide layers and the layer, can further improve dimensional stability.
The thickness range of monolayer thermoplastic polyimide resin layer is the 2-50 micron, and the thickness range of thermoset polyimide resin layer is the 5-125 micron, and the metal layer thickness scope is the 9-70 micron.
If all be covered with thermoplastic polyimide layer in Thermocurable polyimide layer both sides, and the thermoplastic polyimide layer thickness of Thermocurable polyimide layer both sides is respectively Pa and Pb, this moment need satisfy Pa and Pb is approaching as far as possible, and preferred thickness ratio Pa/Pb is in 1: 0.9～1.1 scopes.If thermoplastic polyimide layer thickness ratio Pa/Pb is excessive or too small in both sides, then can cause composite membrane to curl to a side.
As the thickness Po of Thermocurable polyimide during less than metal layer thickness Pc, preferred groundwork thickness is 2-12 with both sides polyimides layer thickness than Po/ (Pa+Pb): in 1 the scope; As the thickness Po of Thermocurable polyimide during greater than outer layer metal layer thickness Pc, preferred groundwork thickness and both sides polyimides layer thickness are in 3.6～26 the scope than Po/ (Pa+Pb).If than Po/ (Pa+Pb) during less than preferable range, the thickness of thermoplastic polyimide is excessive, then greatly reduces the dimensional stability that the polyimides composite bed makes copper-clad plate with both sides polyimides layer thickness for groundwork thickness.If than Po/ (Pa+Pb) during greater than preferable range, then can not give full play to by the cohesive force between itself and the metal level with both sides polyimides layer thickness for groundwork thickness, influence makes the peel strength of copper-clad plate.
The present invention also provides a kind of method of metal laminated plate, may further comprise the steps:
A is dissolved in the first aromatic tetracarboxylic acid's dianhydride and first aromatic diamine in the polar non-solute, and reaction generates the polyamide thermoplastic acid solution;
B is dissolved in the second aromatic tetracarboxylic acid's dianhydride and second aromatic diamine in the polar non-solute, reaction generates the thermosetting polyamide acid solution, and this Thermocurable polyimide acid solution is coated on the glass plate, heating, imidization reaction takes place, and makes the Thermocurable polyimide film;
C is coated on the thermoplastic polyimide acid solution for preparing in the A step on the one side of the Thermocurable polyimide film for preparing in the B step, heating, imidization reaction takes place, make the Thermocurable polyimide layer that is covered with thermoplastic polyimide layer, again the thermoplastic polyimide acid solution is coated on the another side of Thermocurable polyimide film, imidization reaction takes place in heating, and two surfaces of system are covered with the Thermocurable polyimide film of thermoplastic polyimide layer;
D is covered with Thermocurable polyimide film, the metal level of thermoplastic polyimide layer with metal level, surface, stacks successively, and is hot-forming, obtains metal laminated plate.
Wherein, polyamide thermoplastic acid resin above-mentioned can be by first aromatic tetracarboxylic acid's dianhydride and the synthetic thermosetting polyamide acid of first aromatic diamine, under heating condition imidization reaction takes place then, generate polyimide resin, wherein first aromatic diamine is selected from 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminobenzophenone, 1, one or more in 3 '-two (4-amino-benzene oxygen benzene); First aromatic tetracarboxylic acid's dianhydride is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,4-bis trifluoromethyl-2,3,5,6-benzene tertacarbonic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-2,4,5, the 8-tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, benzene-1,2,3, the 4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride etc., wherein preferred all benzene tertacarbonic acid's dianhydrides, 3,3, ' 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4, one or more in 4 '-benzophenone tetracarboxylic dianhydride.
In the preferred case, when the synthetic thermoplastic polyimide resin, adopted aromatic tetracarboxylic acid's dianhydride among the present invention with following structure
3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA)
Bisphenol-A two ether dianhydrides (BEPA)
Aromatic diamine is selected from one or more in the aromatic diamine with following array structure
3,4 '-diaminodiphenyl ether (3,4 '-ODA)
4,4 '-diaminodiphenyl ether (4,4 '-ODA)
3,3 '-diaminobenzophenone (3,3 '-DABP)
1,3 '-two (4-amino-benzene oxygen) benzene (TPER)
The preparation of polyamide thermoplastic acid
With the polyamic acid total weight is benchmark, according to weight ratio is the ratio of 10-30: 15-50: 100-500, take by weighing first aromatic diamine, first aromatic tetracarboxylic acid's dianhydride and the polar non-solute respectively, earlier aromatic diamine and polar non-solute are together stirred, then aromatic tetracarboxylic acid's dianhydride is added, mix, obtain polyamide thermoplastic acid.
The polar non-solute of being mentioned among the present invention is selected from N, N-dimethylacetylamide, N-methyl pyrrolidone, N, one or more in dinethylformamide, methyl-sulfoxide, oxolane, dioxanes, carrene, the chloroform.
When preparation thermoplastic poly amic acid solution, the consumption of polar non-solute solvent does not have specific (special) requirements, the solid content of solution is that 8-30% gets final product, under the preferable case 8-18%, more preferably 12%, wherein solid content refers to participate in the aromatic diamine of reaction and the ratio of quality summation with the quality of polar non-solute of aromatic tetracarboxylic acid's dianhydride.
The viscosity of thermoplastic poly amic acid is controlled in 1000CP～6000CP scope, and under the preferable case, the viscosity of thermoplastic poly amic acid is controlled in 1500CP～4000CP scope.If solution viscosity is lower than 1000CP, then can't obtain desirable coating layer thickness, and the flowability of solution is good excessively, is difficult to obtain uniform coating layer thickness.If solution viscosity is higher than 6000CP, be difficult for being coated with and controlling coating thickness.
The preparation of Thermocurable polyimide is specific as follows:
1) polyamic acid is synthetic
With the polyamic acid total weight is benchmark, according to weight ratio is the ratio of 12-25: 15-40, take by weighing second aromatic diamine, second aromatic tetracarboxylic acid's dianhydride respectively, earlier second aromatic diamine and polar non-solute together being put into mixer stirs, then second aromatic tetracarboxylic acid's dianhydride is added, be under 0 ℃-25 ℃ the condition, to mix 3-6h in temperature, the back obtains polyamide thermoplastic acid.
When the preparation Thermocurable polyimide, adopt second aromatic diamine, the second fragrant tetracarboxylic dianhydride of family, wherein, second aromatic diamine is a methoxyl group diaminobenzene, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, two methylene dianiline, 3,3 '-diaminobenzophenone, 1,3 '-two (4-amino-benzene oxygen) benzene, 1,4 '-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4, one or more in 4 '-two (3-amino-benzene oxygen) biphenyl; Second aromatic tetracarboxylic acid's dianhydride is pyromellitic acid anhydride, diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4, and one or more in 4 '-benzophenone tetracarboxylic dianhydride.
At preparation polyimides precursor solution, the consumption of solution Semi-polarity aprotic solvent solvent does not have specific (special) requirements when being polyamic acid solution, the solid content of solution is that 8-30% gets final product, under the preferable case 8-18%, more preferably 12%, wherein solid content refers to participate in the aromatic diamine of reaction and the ratio of quality summation with the quality of polar non-solute of aromatic tetracarboxylic acid's dianhydride.The aprotic polar solvent used during with preparation thermoplastic polyimide resin of the aprotic polar solvent of using identical.
With the polyamic acid solution for preparing, be coated on the glass plate, described coating process is the common various painting methods in this area, can adopt known methods such as direct blade coating, slit coating, the coating of two roller, roller coating, intaglio plate coating, the coating of curtain connection formula, spraying coating as coating process, the thickness of coating is the 15-200 micron.
To being covered with the glass plate heating of polyamic acid solution, the thermosetting polyamide sorrel carries out imidizate, the condition of imidizate can be the condition of the amic acid imidization of routine, the final Thermocurable polyimide film that obtains, and the concrete method of operation of imidizate also has been conventionally known to one of skill in the art, for example, can realize in 2-7 hour by polyamide acid film is heated down at 70-400 ℃.
Can directly heat up and also can adopt the program mode intensification to raise the temperature to 70-400 ℃, the present invention preferably adopts with 4-8 ℃/minute heating rate temperature programming to 70-400 ℃, so that the abundant imidization of polyamic acid generates required Thermocurable polyimide film.Further preferably make polyamide acid film be 70-200 ℃ of maintenance 0.5-4 hour down, keep realizing in 0.5-3 hour imidizate down at 200 ℃-400 ℃ in temperature by programmed temperature method.Fact proved, adopt the segmentation heating, the imidizate process is carried out fully, and help effective volatilization of polar non-solute, the Thermocurable polyimide membrane structure is stable, the performance homogeneous.
Can be among the present invention by improving reaction temperature, prolonging the conversion ratio that further raising of reaction time polyamic acid is converted into polyimides.Under the above-mentioned condition of the present invention, polyamic acid is converted into the conversion ratio of polyimides greater than 99%, therefore in the specific embodiment of the invention not the amount to polyamic acid make special requirement.In addition, the existence of a small amount of polyamic acid does not have much affect to the performance of metal laminate plate, therefore has the polyamic acid below 2% in the polyimide resin layer that allows to obtain.
Thereby improve the quality of the final metal laminated plate that is covered with polyimides that obtains for the quality that further improves polyamide acid film, under the preferable case, the polyamide thermoplastic acid solution described in the method provided by the invention, thermosetting polyamide acid solution can be the polyamic acid solution of process at 15-40 ℃ of following vacuum degassing 1-12 hour preferred 1-2 hour.In other words, under the preferable case, when method provided by the invention also is included in polyamic acid solution is applied, earlier with polyamic acid solution at 15-40 ℃ of following vacuum degassing 1-12 hour, preferred 1-2 hour, to remove the bubble that may exist in the solution.The vacuum degree of described vacuum degassing can guarantee the non-volatile or a small amount of volatilization of polyamic acid solution, and under the preferable case, described vacuum degree is the 0.001-0.1 MPa.
One skilled in the art will appreciate that because general polyimides (PI) is a kind of insoluble high molecular polymer its degree of polymerization is difficult to accurately measure, and the inherent viscosity of another the physical parameter polyamic acid directly related with the degree of polymerization is closely related.Polyamic acid is to prepare intermediate in the polyimides course of reaction by dianhydride and diamine reactant, discover, by control polyamic acid inherent viscosity within the specific limits, can obtain the polyimides of the required degree of polymerization or desired physical properties, and inherent viscosity be one with the irrelevant physical parameter that can objectively respond the polyamic acid degree of polymerization of measuring condition, so this area uses the inherent viscosity of polyamic acid to represent the degree of polymerization of polyamic acid and polyimides usually.The present invention continues to use the degree of polymerization that said method characterizes thermoplastic polyimide film at this.The present inventor discovers, as long as the viscosity of polyamide thermoplastic acid that will be corresponding with this Thermocurable polyimide film is controlled at 10000-100000cp, is preferably 15000-50000cp and gets final product.The polyamide thermoplastic acid solution for preparing in the above-mentioned steps is coated on the Thermocurable polyimide film, coating refers to the dual coating at the Thermocurable polyimide film, then the Thermocurable polyimide film that scribbles thermoplastic poly amic acid solution is heated, heating-up temperature is 50-350 ℃, be 1-7 hour heating time, obtained the two-sided Thermocurable polyimide film that is covered with thermoplastic polyimide layer
A preferred embodiment of the invention, the preparation method of metal laminated plate provided by the invention comprises the steps:
(1) with the first aromatic series tetracarboxylic dianhydride, first aromatic diamine, according to mol ratio 1.01-1.03: 1 ratio adds in the solvent, it is 5-40 weight % that the consumption of solvent makes the concentration of the polyamic acid that obtains, after 20-70 ℃ of following stirring reaction 3-7 hour, under uniform temp, obtained polyamic acid solution in vacuum degassing 1-12 hour, wherein first aromatic diamine is 1,3 '-two (4-amino-benzene oxygen) benzene, the first aromatic diacid acid anhydride is 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, solvent is N, and the N-dimethylacetylamide finally obtains the polyamide thermoplastic acid solution;
(2) with the second aromatic series tetracarboxylic dianhydride, second aromatic diamine, according to mol ratio 1.01-1.03: 1 ratio adds in the solvent, it is 10-40 weight % that the consumption of solvent makes the concentration of the polyamic acid that obtains, after 0-25 ℃ of following stirring reaction 3-10 hour, under uniform temp, obtained polyamic acid solution in vacuum degassing 1-12 hour, wherein second aromatic diamine is 4,4 '-diaminodiphenyl ether, the second aromatic diacid acid anhydride is 2,3 ', 3,4 '-biphenyl tetracarboxylic dianhydride, solvent is N, and the N-dimethylacetylamide finally obtains the thermosetting polyamide acid solution;
(3) be that 10-40 ℃, relative humidity are under the 20-80% condition in temperature, the thermosetting polyamide acid solution of preparation in the step 2 is coated on the glass plate, dry under 20-200 ℃, remove the thermosetting polyamide sorrel that obtains the 5-50 micron after desolvating, coating thickness is 50-200um;
(4) to above-mentioned thermosetting polyamide sorrel, carry out progressively imidization of gradient increased temperature, heating is converted into polyimides with polyamic acid under nitrogen, argon gas or vacuum, obtains the Thermocurable polyimide film.Wherein Jia Re temperature is 100-200 ℃ and keeps down 0.5-1.5 hour, 180-250 ℃ to keep 0.5-1.5 hour, 230-280 ℃ to keep 0.5-1.5 hour, 260-350 ℃ to keep 0.5-1.5 hour down down down.
(5) with the polyamide thermoplastic acid solution of preparation in the step 1, be coated on the two sides of the Thermocurable polyimide film of preparation in the step 4, coating thickness is 10-200um;
(6) will be coated with the Thermocurable polyimide film of polyamide thermoplastic acid solution at 70-350 ℃ of following heat drying, imidizate takes place in polyamide thermoplastic acid, finally obtains the compound polyimide film of thermoplastic polyimide layer/Thermocurable polyimide layer/thermoplastic polyimide layer;
(7) with the compound polyimide film of two metal levels and 6 steps preparation according to, the order of metal level/compound polyimide film/metal level stacks, and put into hot press, at pressure is 5-15MPa, temperature is hot pressing 2-15min under 250-330 degree centigrade the condition, finally obtains metal laminated plate provided by the present invention.
As the thickness Po of Thermocurable polyimide during less than metal layer thickness Pc, preferred groundwork thickness and both sides polyimides layer thickness are in 2～12 the scope than Po/ (Pa+Pb); As the thickness Po of Thermocurable polyimide during greater than outer layer metal layer thickness Pc, preferred groundwork thickness and both sides polyimides layer thickness are in 3.6～26 the scope than Po/ (Pa+Pb).If than Po/ (Pa+Pb) during less than preferable range, the thickness of thermoplastic polyimide is excessive with both sides polyimides layer thickness for groundwork thickness, then the dimensional stability that can make the polyimides composite bed make copper-clad plate decreases.If than Po/ (Pa+Pb) during greater than preferable range, then can not give full play to by the cohesive force between itself and the metal level with both sides polyimides layer thickness for groundwork thickness, influence makes the peel strength of copper-clad plate.
The polyamic acid solution viscosity test adopts the LVDV-I+CP type viscosimeter of U.S. BROOKFIELD company to carry out; The STA449C Jupiter type simultaneous thermal analysis instrument that the glass transition temperature of polyimide resin adopts German NETZSCH company to produce carries out.
The peel strength that makes flexible double-sided copper-clad laminated plates is peeled off mode for 90 ° according to 8.1 joints among the JIS C6471 and is carried out; Dimensional stability is carried out according to method among the JIS C6471.
To further be elaborated among the embodiment among the embodiment below to metal laminated plate provided by the present invention and preparation method thereof.
Embodiment 1
Present embodiment is used for illustrating metal laminated plate provided by the present invention and preparation method thereof
1) preparation of polyamide thermoplastic acid solution: with the solvent N of 320ml (account for total solvent consumption 80%), the N-dimethylacetylamide places reactor, is continuing to add 1 of 29.90g under the stirring condition, 3 '-two (4-amino-benzene oxygen) benzene stirs until dissolving fully.Slowly add 3,3 ', 4 of 30.10g, 4 '-biphenyl tetracarboxylic dianhydride in batches.The solvent that adds residue 20% in the process that feeds intake gradually.Stirred at ambient temperature 4 hours, and made the polyamic acid solution that viscosity is 1900CP.The solid content of this polyamic acid solution is 15%.
2) preparation of Thermocurable polyimide film: with the solvent N of 293ml, the N-dimethylacetylamide places reactor, and consumption is 100% of total solvent consumption in the reaction.Continuing to add 4 of 11.26g under the stirring condition, 4 '-diaminodiphenyl ether stirs until dissolving.The pyromellitic acid anhydride that in batches slowly adds 12.17g is to stir 4 hours under 5 degrees celsius in temperature, makes the thermosetting polyamide acid solution that viscosity is about 28000CP.The solid content of this polyamic acid solution is 8%.With above-mentioned thermosetting polyamide acid solution, directly blade coating is coated on the glass plate, and the thickness of coating is 100 microns.To being covered with glass plate heating the carrying out imidizate of thermosetting polyamide acid solution, the condition of imidizate is controlled to be with 4 ℃/minute heating rate temperature programming to 200 ℃ following maintenance 1 hour, identical heating rate and keeps realizing imidizate in 1 hour that obtaining thickness is the Thermocurable polyimide film of 25um under being warming up to 400 ℃.
3) be covered with the preparation of the Thermocurable polyimide film of thermoplastic polyimide:
The polyamide thermoplastic acid solution of gained in the step (1), adopt spreader earlier polyamic acid solution to be applied on the one side of the Thermocurable polyimide film that obtains in the step (2), coating thickness is that 50um heat-treats under 70 ℃ of temperature, and heat treatment time is 10min, makes solvent evaporates.Heat-treat the elimination solvent under above-mentioned similarity condition, coating thickness is 50um.Three layers of composite membrane after (ratio of coating thickness 1: 1) will desolventize carry out the high-temperature baking imidization, keep being warming up to 310 ℃ with the programming rate of 5 ℃/min by 80 ℃.The thickness of the polyimide composite film that obtains after the baking is about 31um.
4) with polyimide composite film prepared in the above-mentioned steps and two layers of thickness be 18 μ m Copper Foil according to, the order of Copper Foil/polyimide composite film/Copper Foil stacks, and carries out hot pressing in the hot press, and the hot pressing temperature is 270 ℃, pressing pressure is 12MPa, and pressing time is 2min.Make metal laminated plate sample T1, its thickness is 66 μ m, according to the method for testing test of recording and narrating among the IPC TM650 2.4.24, the thermal coefficient of expansion of thermoplastic polyimide resin layer is 38ppm/ ℃ in the T1 sample that obtains, the moisture expantion coefficient is 13ppm, the thermal coefficient of expansion of thermoset polyimide resin layer is 21ppm/ ℃, and the moisture expantion coefficient is 10ppm.
Embodiment 2
1) preparation of polyamide thermoplastic acid solution: with the solvent N of 340ml, the N-dimethylacetylamide places the glass reaction still, and consumption is 85% of total solvent consumption in the reaction.Continuing to add 4 of 22.22g under the stirring condition, 4 '-diaminodiphenyl ether stirs until dissolving fully.Bisphenol-A two ether dianhydrides that in batches slowly add 57.78g stirred 6 hours under the condition of ice-water bath, and solution viscosity makes the polyamic acid solution that viscosity is 3500CP after rising to and stablizing.The monomeric charge total amount of this polyamic acid solution and the ratio of solvent total amount are 20%.
2) preparation of Thermocurable polyimide film: the solvent N-methyl pyrrolidone of 315ml is placed reactor, and consumption is 90% of total solvent consumption in the reaction.Continuing to add 4 of 12.35g under the stirring condition, 4 '-diaminodiphenyl ether stirs until dissolving.The diphenyl ether tetracarboxylic dianhydride that in batches slowly adds 19.15g is to stir 5 hours under the room temperature condition in temperature, makes the thermosetting polyamide acid solution that viscosity is about 35000CP.The solid content of this polyamic acid solution is 10%.With above-mentioned thermosetting polyamide acid solution, directly blade coating is coated on the glass plate, and the thickness of coating is 100 microns.To being covered with glass plate heating the carrying out imidizate of thermosetting polyamide acid solution, the condition of imidizate is controlled to be with 4 ℃/minute heating rate temperature programming to 200 ℃ following maintenance 1 hour, identical heating rate and keeps realizing imidizate in 1 hour under being warming up to 400 ℃, obtains the Thermocurable polyimide film that thickness is about 25um.
3) be covered with the preparation of the Thermocurable polyimide film of thermoplastic polyimide:
The polyamide thermoplastic acid solution of gained in the step (1), adopt spreader earlier polyamic acid solution to be applied on the one side of the Thermocurable polyimide film that obtains in the step 2, coating thickness is that 100 μ m heat-treat under 70 ℃ of temperature, and heat treatment time is 15min, makes solvent evaporates.Again polyamic acid solution is applied on the another side of Thermocurable polyimide film, keeps being warming up to 310 ℃ by 80 ℃ with the programming rate of 5 ℃/min.
4) with polyimide composite film prepared in the above-mentioned steps and a layer thickness be 18 μ m Copper Foil according to, the order of Copper Foil/thermoplastic polyimide layer/Thermocurable polyimide layer stacks, carry out hot pressing in the hot press, the hot pressing temperature is 270 ℃, pressing pressure is 12MPa, and pressing time is 2min.Make metal laminated plate sample T2, its thickness is 74 μ m.Present embodiment finally makes sample T2, according to the method for testing test of recording and narrating among the IPC TM650 2.4.24, obtain in the T2 sample, the thermal coefficient of expansion of thermoplastic polyimide resin layer is 45ppm/ ℃, the moisture expantion coefficient is 14ppm, the thermal coefficient of expansion of thermoset polyimide resin layer is 27ppm/ ℃, and the moisture expantion coefficient is 11ppm.
Embodiment 3
Present embodiment is used for illustrating metal laminated plate provided by the present invention and preparation method thereof
1) preparation of polyamide thermoplastic acid solution: the solvent N-methyl pyrrolidone of 165ml (accounting for the 95%wt of total weight) is placed reactor, continuing to add 4 of 10g under the stirring condition, 4 '-diaminodiphenyl ether stirs until dissolving fully.Slowly add 3,3 ', 4 of 5.88g, 4 '-biphenyl tetracarboxylic dianhydride stirred 5 hours at 25 ℃ in batches, and solution viscosity makes the polyamic acid solution that viscosity is 4000CP after rising to and stablizing.
2) preparation of Thermocurable polyimide film: with the solvent N of 280ml, the N-dimethylacetylamide places reactor, and consumption is 80% of total solvent consumption in the reaction.Continuing to add 4 of 27.45g under the stirring condition, 4 '-diaminodiphenyl ether stirs until dissolving.The diphenyl ether tetracarboxylic dianhydride that in batches slowly adds 42.55g is to stir 7 hours under 5 degrees celsius in temperature, makes the thermosetting polyamide acid solution that viscosity is about 30000CP.The solid content of this polyamic acid solution is 25%.With above-mentioned thermosetting polyamide acid solution, directly blade coating is coated on the glass plate, and the thickness of coating is 75 microns.To being covered with glass plate heating the carrying out imidizate of thermosetting polyamide acid solution, the condition of imidizate is controlled to be with 4 ℃/minute heating rate temperature programming to 200 ℃ following maintenance 1 hour, identical heating rate and keeps realizing imidizate in 1 hour under being warming up to 400 ℃, obtains the Thermocurable polyimide film that thickness is about 12um.
3) be covered with the preparation of the Thermocurable polyimide film of thermoplastic polyimide:
The polyamide thermoplastic acid solution of gained in the step 1, adopt spreader earlier polyamic acid solution to be applied on the one side of the Thermocurable polyimide film that obtains in the step 2, coating thickness is that 10um heat-treats under 70 ℃ of temperature, and heat treatment time is 10min, makes solvent evaporates.Polyamic acid solution is applied on the another side of Thermocurable polyimide film again, heat-treats the elimination solvent under above-mentioned similarity condition, coating thickness is 10um.Composite membrane after (ratio of the thickness of thermoplastic polyimide layer 1: 1) will desolventize carries out the high-temperature baking imidization, keeps being warming up to 310 ℃ with the programming rate of 5 ℃/min by 80 ℃;
4) with polyimide composite film prepared in the above-mentioned steps and two layers of thickness be 18um Copper Foil according to, the order of Copper Foil/thermoplastic polyimide layer/Thermocurable polyimide layer/thermoplastic polyimide layer/Copper Foil stacks, put into hot press and carry out hot pressing, the hot pressing temperature is 270 ℃, pressing pressure is 12MPa, and pressing time is 2min.Make metal laminated plate sample T3, its thickness is 51 μ m.Present embodiment finally obtains sample T3, according to the method for testing test of recording and narrating among the IPC TM650 2.4.24, the thermal coefficient of expansion that obtains thermoplastic polyimide resin layer in the T3 sample is 41ppm/ ℃, the moisture expantion coefficient is 12ppm, the thermal coefficient of expansion of thermoset polyimide resin layer is 20ppm/ ℃, and the moisture expantion coefficient is 9ppm.
Embodiment 4
Present embodiment is used for illustrating metal laminated plate provided by the present invention and preparation method thereof.
Present embodiment adopts the method identical with embodiment 1 to prepare present embodiment metal laminated plate sample T4, the polyamide thermoplastic acid solution that different is with gained in the step 1, adopt spreader earlier polyamic acid solution to be applied on the one side of the Thermocurable polyimide film that obtains in the step 2, coating thickness is that 10um heat-treats under 70 ℃ of temperature, heat treatment time is 10min, makes solvent evaporates.Polyamic acid solution is applied on the another side of Thermocurable polyimide film again, heat-treats the elimination solvent under above-mentioned similarity condition, coating thickness is 10um.Three layers of composite membrane after (ratio of coating thickness 1: 1) will desolventize carry out the high-temperature baking imidization, keep being warming up to 310 ℃ with the programming rate of 5 ℃/min by 80 ℃.
Present embodiment finally obtains sample T4, according to the method for testing test of recording and narrating among the IPC TM650 2.4.24, the thermal coefficient of expansion that obtains thermoplastic polyimide resin layer in the T4 sample is 48ppm/ ℃, the moisture expantion coefficient is 15ppm, the thermal coefficient of expansion of thermoset polyimide resin layer is 23ppm/ ℃, and the moisture expantion coefficient is 9ppm.
Embodiment 5
Present embodiment is used for illustrating metal laminated plate provided by the present invention and preparation method thereof.
Present embodiment adopts the method identical with embodiment 3 to prepare present embodiment metal laminated plate sample T5, the polyamide thermoplastic acid solution of gained in the different step 1, adopt spreader earlier polyamic acid solution to be applied on the one side of the Thermocurable polyimide film that obtains in the step 2, coating thickness is that 40um heat-treats under 70 ℃ of temperature, heat treatment time is 10min, makes solvent evaporates.Polyamic acid solution is applied on the another side of Thermocurable polyimide film again, heat-treats the elimination solvent under above-mentioned similarity condition, coating thickness is 40um.Three layers of composite membrane after (ratio of coating thickness 1: 1) will desolventize carry out the high-temperature baking imidization, keep being warming up to 310 ℃ with the programming rate of 5 ℃/min by 80 ℃.The thickness of the polyimide composite film that obtains after the baking is about in 25um～26um scope.
Present embodiment finally obtains sample T5, according to the method for testing test of recording and narrating among the IPC TM650 2.4.24, the thermal coefficient of expansion that obtains thermoplastic polyimide resin layer in the T5 sample is 28ppm/ ℃, the moisture expantion coefficient is 7ppm, the thermal coefficient of expansion of thermoset polyimide resin layer is 24ppm/ ℃, and the moisture expantion coefficient is 7ppm.
Comparative Examples 1
The preparation technology who is recorded and narrated according to embodiment among the CN101420820 1 makes the metal laminated plate CT1 of metal laminated plate sample same size a kind of and provided by the invention.
Embodiment 6-10
These tests of every performance that present embodiment is used for detecting the prepared sample T1-T5 of embodiment 1-5 comprise:
1) the peel strength test peel strength that makes flexible double-sided copper-clad laminated sheet is peeled off mode for 90 ° according to 8.1 joints among the JIS C6471 and is carried out.
2) dimensionally stable property testing:
The dimensional stability that makes flexible double-sided copper-clad laminated sheet is carried out according to 9.6 joint methods among the JIS C6471.
Test result sees Table 1
Comparative Examples 2
This Comparative Examples is used for illustrating every performance of the sample CT1 that Comparative Examples 1 is prepared, and these test events are identical with every test event among the embodiment 6-10, and test result sees Table 1.
Table 1
As can be seen from Table 1, size changing rate on the TD direction of the sample T1 that embodiment 1 is provided among the present invention is-0.044%, and the size changing rate on the MD direction is-0.038%, both are very nearly the same, and the size changing rate 0.101% on the TD direction of the sample that is provided in the Comparative Examples 1, size changing rate on the MD direction is 0.073%, differ bigger, this illustrates that metal laminated plate provided by the present invention has the characteristics of dimensional stability, and from table 1, can find, the peel strength of the sample T1 that the embodiment of the invention 1 is provided is 8.92M/cm, and the peel strength of the sample CT1 that is provided in the Comparative Examples 1 is 4.73M/cm, much smaller than the peel strength of sample provided by the present invention, illustrate that metal laminated plate provided by the invention has the peel strength height simultaneously, the advantage that dimensional stability is good.
Claims (13)
1. metal laminated plate, wherein, the structure of metal laminated plate is metal level/thermoplastic polyimide resin layer/thermoset polyimide resin layer/thermoplastic polyimide resin layer/metal level, wherein, the thermal coefficient of expansion of thermoplastic polyimide resin layer is 10-50ppm/ ℃, and the moisture expantion coefficient is 2-16ppm; The thermal coefficient of expansion of thermoset polyimide resin layer is 15-40ppm/ ℃, and the moisture expantion coefficient is 2-13ppm.
2. metal laminated plate according to claim 1, wherein, the thermal coefficient of expansion of thermoplastic polyimide resin layer is 10-30ppm/ ℃, and the moisture expantion coefficient is 2-14ppm, the thermal coefficient of expansion of thermoset polyimide resin layer is 15-30ppm/ ℃, and the moisture expantion coefficient is 2-10ppm.
3. metal laminated plate according to claim 1, wherein, the peel strength between described thermoplastic polyimide resin layer and the metal level is 7-9N/cm.
4. according to any described Metal Substrate laminate among the claim 1-3, wherein, the thickness of thermoplastic polyimide resin layer is the 2-50 micron, and the thickness of thermoset polyimide resin layer is the 5-125 micron, and metal layer thickness is the 9-70 micron.
5. metal laminated plate according to claim 1, wherein, the ratio of the thermoplastic polyimide layer thickness of described Thermocurable polyimide layer both sides is 1: 0.9～1.1.
6. metal laminated plate according to claim 1, wherein, the ratio of described Thermocurable polyimide layer and both sides thermoplastic polyimide layer sum is 2～26: 1.
7. the preparation method of the described metal laminated plate of claim 1 may further comprise the steps:
A is dissolved in the first aromatic tetracarboxylic acid's dianhydride and first aromatic diamine in the polar non-solute, and reaction generates the polyamide thermoplastic acid solution;
B is dissolved in the second aromatic tetracarboxylic acid's dianhydride and second aromatic diamine in the polar non-solute, reaction generates the thermosetting polyamide acid solution, and this Thermocurable polyimide acid solution is coated on the glass plate, heating, imidization reaction takes place, and makes the Thermocurable polyimide film;
C is coated on the thermoplastic polyimide acid solution for preparing in the A step on the one side of the Thermocurable polyimide film for preparing in the B step, heating, imidization reaction takes place, make the Thermocurable polyimide layer that is covered with thermoplastic polyimide layer, again the thermoplastic polyimide acid solution is coated on the another side of Thermocurable polyimide film, imidization reaction takes place in heating, and two surfaces of system are covered with the Thermocurable polyimide film of thermoplastic polyimide layer;
D is covered with Thermocurable polyimide film, the metal level of thermoplastic polyimide layer with metal level, surface, stacks successively, and is hot-forming, obtains metal laminated plate.
8. according to the preparation method of the metal laminated plate described in the claim 7, wherein first aromatic diamine described in the steps A is 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminobenzophenone, 1, one or more in 3 '-two (4-amino-benzene oxygen) benzene; First aromatic tetracarboxylic acid's dianhydride is 3,3 ', 4, one or more in 4 '-biphenyl tetracarboxylic dianhydride, bisphenol-A two ether dianhydrides; Wherein second aromatic diamine described in the step B is a methoxyl group diaminobenzene, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, two methylene dianiline, 3,3 '-diaminobenzophenone, 1,3 '-two (4-amino-benzene oxygen) benzene, 1,4 '-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-
Amino-benzene oxygen) one or more in the biphenyl; Second aromatic tetracarboxylic acid's dianhydride is pyromellitic acid anhydride, diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4, and one or more in 4 '-benzophenone tetracarboxylic dianhydride.
9. preparation method according to claim 7, wherein, the weight ratio of described first aromatic diamine, first aromatic tetracarboxylic acid's dianhydride and aprotic solvent is 10-30: 15-50: 100-500.
10. preparation method according to claim 7, wherein, described second aromatic diamine, second aromatic tetracarboxylic acid's dianhydride and aprotic polar solvent weight ratio be 12-25: 15-40: 100-300.
11. preparation method according to claim 7, wherein, described aprotic polar solvent is N, N-dimethylacetylamide, N-methyl pyrrolidone, N, one or more in dinethylformamide, methyl-sulfoxide, oxolane, dioxanes, carrene, the chloroform.
12. preparation method according to claim 7, wherein, the temperature of the heating in the described C step is 50-400 ℃, and the time of heating is 60-360min.
13. according to the metal laminated plate described in the claim 1, wherein, described metal level is a Copper Foil.
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Application publication date: 20110330 |