CN105399950A - Polyimide resin containing cyano groups, and applications thereof in preparing copper-clad laminates - Google Patents
Polyimide resin containing cyano groups, and applications thereof in preparing copper-clad laminates Download PDFInfo
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- CN105399950A CN105399950A CN201510955100.4A CN201510955100A CN105399950A CN 105399950 A CN105399950 A CN 105399950A CN 201510955100 A CN201510955100 A CN 201510955100A CN 105399950 A CN105399950 A CN 105399950A
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- 0 C*(CC(C)(C)*(C(C1C2CCC([C@](*c(cc3*C=*)cc(*)c3OPOc(c(C)cc(C(C)(C)*(*)*)c3)c3N)O)C(CO)CC1)O)C2O)*([C@](C(CCC1[C@@](*2C(C)(C)*(C(C(CCC3C(*4C)O)/C5=C\CC3C4O)=O)C5=O)O)[C@@]3*CC1[C@@]2O)O)[C@]3O Chemical compound C*(CC(C)(C)*(C(C1C2CCC([C@](*c(cc3*C=*)cc(*)c3OPOc(c(C)cc(C(C)(C)*(*)*)c3)c3N)O)C(CO)CC1)O)C2O)*([C@](C(CCC1[C@@](*2C(C)(C)*(C(C(CCC3C(*4C)O)/C5=C\CC3C4O)=O)C5=O)O)[C@@]3*CC1[C@@]2O)O)[C@]3O 0.000 description 2
- LVHYUHYANLKDGN-NJXWOGOQSA-N C/C=C\C(\c(c(C)c1)cc(C)c1-c1ccccc1)=C/C Chemical compound C/C=C\C(\c(c(C)c1)cc(C)c1-c1ccccc1)=C/C LVHYUHYANLKDGN-NJXWOGOQSA-N 0.000 description 1
- FZBOXIHFUTWYLS-UHFFFAOYSA-N Cc(cc1)cc(-c2ccccc2)c1-c(ccc(C)c1)c1C1=CCCC=C1 Chemical compound Cc(cc1)cc(-c2ccccc2)c1-c(ccc(C)c1)c1C1=CCCC=C1 FZBOXIHFUTWYLS-UHFFFAOYSA-N 0.000 description 1
- PZCRCGZQRHMEDY-UHFFFAOYSA-N Cc(cc1)cc(C)c1-c1c(C)cc(C)cc1 Chemical compound Cc(cc1)cc(C)c1-c1c(C)cc(C)cc1 PZCRCGZQRHMEDY-UHFFFAOYSA-N 0.000 description 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N Cc(cc1)ccc1-c1ccc(C)cc1 Chemical compound Cc(cc1)ccc1-c1ccc(C)cc1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- Chemical Kinetics & Catalysis (AREA)
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- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyimide resin containing cyano groups, and applications thereof in preparing double-layer adhesive-free single-surface (double-surface) flexible copper-clad laminates (FCCL), and belongs to the technical field of copper-clad laminates. A preparation method comprises following steps: a diamine containing side chain cyano groups and rigid-flexible chain structures is mixed with a dianhydride with a different structure at a molar ratio of 1:1; a polyamide acid (PAA) solution is prepared via reaction in an aprotic polar solvent; metal substrates such as copper foil or copper plates are coated with the PAA solution uniformly, and pre-imidization is carried out at 60 to 160 DEG C so as to obtain a polyimide pre-polymer resin film material; the polyimide pre-polymer resin film material is subjected to complete thermal imidization at 180 to 350 DEG C under vacuum conditions so as to obtain the double-layer adhesive-free single-surface flexible copper-clad laminates. The polyimide resin containing side chain cyano groups and rigid-flexible chain structures possesses low linear expansion coefficient, high peel strength with copper substrates, and excellent dimensional stability and flexural endurance. The double-layer adhesive-free single-surface flexible copper-clad laminates are prepared via coating method, so that delamination caused by large difference of CTE (Coefficient Of Thermal Expansion) value among PI (polyimide resin) and TPI (thermoplastic polyimide) layers is avoided.
Description
Technical field
The invention belongs to and cover Copper Foil technical field, be specifically related to a kind of polyimide resin of cyano-containing and the application in preparation two layers of adhesive-free single or double flexible copper-clad paper tinsel thereof.
Background technology
Flexible copper clad foil (FCCL) can be divided into three layers of flexible copper-clad paper tinsel (3L-FCCL) and two layers of flexible copper-clad paper tinsel (2L-FCCL) by structure, 3L-FCCL is by Copper Foil, sizing agent and resin basement membrane are formed, it is commercial flexible copper-clad paper tinsel classification the earliest, wherein adhesive layer is important integral part, it directly affects the performance and used life of product, in 3L-FCCL industry, sizing agent mainly divides acrylic acid or the like sizing agent and epoxy resin adhesive two major sect at present, but no matter be acrylic acid or the like sizing agent or epoxy resin adhesive, its life-time service temperature is no more than 150 degree, and high temperature is easily aging, this significantly limit the work-ing life of FCCL.2L-FCCL is only made up of Copper Foil and resin basement membrane, avoid because of sizing agent exist FCCL is occurred the high temperature situation that easily aging, work-ing life is short occurs, simplify preparation technology and the flow process of FCCL, but, this simultaneously also requires to have strong sticking power and low linear expansivity between 2L-FCCL resin basement membrane own and copper foil base material, avoids boning loosely, phenomenon generation that flexure, warpage, basement membrane come off.
Current 2L-FCCL resin base rete polyimide resin used divides thermoset polyimide resin (PI) and thermoplastic polyimide resin (TPI), the former thermostability, mechanical property are excellent, but and viscosifying power is little between metal base, sticking power is lower and snappiness not enough, the latter and metal base sticking power stronger, but the thermotolerance covering Copper Foil prepared by the existence of flexible group makes is relative with mechanical property on the low side, report that having people to adopt the mode of thermoplasticity and Thermocurable polyimide combination and be pressed into covers Copper Foil (WO2007083526A1), namely at the two sided coatings thermoplastic polyimide resin of Thermocurable polyimide, two-sided adhesive-free flexible copper-clad paper tinsel is hot pressed into two sides Copper Foil, both the sticking power between resin basement membrane and Copper Foil had been enhanced in theory, in turn ensure that the thermotolerance of resin layer self, mechanical property and dimensional stability, but adopt the mode of PI and TPI combination can only prepare double-faced flexible and cover Copper Foil, and PI and TPI interlayer thermal expansivity (CTE) difference is larger, cover Copper Foil, when soldering process, layering plate bursting phenomenon can occur.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of polyimide resin of cyano-containing, and this material has high adhesivity, low linear expansivity and good mechanical stability concurrently, extends its life cycle.
The polyimide resin of a kind of cyano-containing of the present invention, its structural formula is as follows:
Wherein a+b+c=1, and 0<a<1,0≤b<1,0≤c<1, M are the integer of 10 ~ 200;
Wherein Ar can be one of following structure,
R
1for-H or-CN, R
2for-H or-CN, and R
1and R
2one is had at least for-CN, i.e. R in group
1and R
2can not be-H simultaneously.
Wherein Ar ' is one of following structure,
Wherein X is one of following structure,
Wherein Y is one of following structure,
Second technical problem that the present invention will solve is that the polyimide resin preparation of this cyano-containing of application has two layers of adhesive-free one side (two-sided) flexible clad-copper laminate, this flexible copper-clad paper tinsel has high adhesivity and has low linear expansivity concurrently, excellent dimensional stability and thermotolerance, do not bend, the features such as resistance to bending.
Two layers of adhesive-free one side flexible copper-clad paper tinsel of the present invention, it is made up of Copper Foil and the PI resin layer be overlying on Copper Foil; Two layers of adhesive-free double-faced flexible of the present invention cover Copper Foil, its by Copper Foil, be overlying on PI resin layer on Copper Foil and the Copper Foil be overlying on PI resin layer forms; PI resin layer is the polyimide resin of cyano-containing of the present invention, and PI resin layer thickness is 20 ~ 100 μm, and Copper Foil is rolled copper foil or electrolytic copper foil, and thickness is 20 ~ 80 μm.This resin layer utilizes the adhesion property between the strong polar interaction of cyano group and soft segment raising PI layer and Copper Foil, adding of rigid chain segment, the suitable linear expansivity reducing PI layer self.
Present invention also offers a kind of preparation method of two layers of adhesive-free one side (two-sided) flexible copper-clad paper tinsel, its step is as follows:
1) copper foil surface is carried out pre-treatment, first Copper Foil is invaded and steep in CH
2cl
2in, supersound process 0.5 ~ 1h removes copper foil surface grease, is put in by the Copper Foil soaked in 0.2 ~ 1.0mol/L dilute sulphuric acid and soaks the oxide compound that 3 ~ 5h removes copper foil surface, and with distillation washing 3 ~ 4 times, dehydrated alcohol washes 2 ~ 3 times, dries;
2) under anhydrous, nitrogen environment, cyano-containing diamines, rigid structure diamines and flexible structure diamines are dissolved in polar aprotic solvent, 24 ~ 48h is stirred at adding the dianhydride 0 DEG C ~ 80 DEG C of above-mentioned three kinds of diamines molar weight sums, carry out terpolymer and obtain polyamic acid (PAA) solution, gained PAA solution is diluted, after dilution, the concentration of PAA solution is 0.074g/mL ~ 0.2g/mL, then carries out the process of elimination bubble;
3) by the PAA solution coat after dilution in step 1) on pretreated clean Copper Foil, be transferred to vacuum or inert gas environment after dry (pre-imidization) at 60 ~ 160 DEG C under (nitrogen, argon gas), at 180 ~ 350 DEG C, hot imidization is carried out in process, then Copper Foil is taken out after Temperature fall to room temperature, thus obtaining the one side flexible copper-clad paper tinsel of two layers of (copper foil layer and PI resin layer) adhesive-free, the thickness range of copper foil surface resin layer is 20 ~ 100 μm.
4) another step 1 is got) pretreated clean Copper Foil, overlay on step 3) on the resin face of the one side flexible copper-clad paper tinsel of gained, be pressed into two layers of adhesive-free double-faced flexible through pressure sintering and cover Copper Foil.
Preparing flexible copper-clad paper tinsel PI resin layer polar aprotic solvent used in the present invention is N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone wherein any one, PAA dilutes solvent for use should be identical with solvent for use during polymerization.Preparation PI resin layer diamine monomer used is cyano-containing diamines (Isosorbide-5-Nitrae-two (amino-2 cyano-benzene oxygens of 4-) biphenyl, Isosorbide-5-Nitrae-two (amino-2, the 6-dicyano phenoxy groups of 4-) biphenyl) in any one, rigid structure diamines (benzidine, terphenyl diamines, 4,4 '-diamino-2,2 '-dicyanobiphenyl, 4,4 '-diamino-2,2 '-dimethyl diphenyl etc.) in any one and flexible structure diamines (diphenyldiamine, 2,2-bis-(4 aminophenyl) propane, 2,2-bis-(4 aminophenyl) HFC-236fa, Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, 4,4-diaminodiphenylsulfone(DDS)) in any one, dianhydride used is pyromellitic acid anhydride, oxydiphthalic, 3,3 ', 4,4 '-BPDA, hexafluorodianhydride, benzophenone tetracarboxylic dianhydride, described Isosorbide-5-Nitrae-two (amino-2 cyano-benzene oxygens of 4-) biphenyl, Isosorbide-5-Nitrae-two (amino-2, the 6-dicyano phenoxy groups of 4-) biphenyl synthetic method is with reference to patent CN104277458A, and other raw materials are all buys commercial gained.
The PAA solution be polymerized is carried out eliminating bubble process and can adopt following several mode: 1) room temperature leaves standstill 10 ~ 30h in clean, dry environment, 2) in the baking oven of cleaning, keep temperature 40 ~ 50 DEG C to leave standstill 5 ~ 7h, 3) leave standstill 1 ~ 2h after supersound process 2 ~ 3h, above three kinds of modes all can eliminate bubble.
Adopt pressure sintering to prepare double-faced flexible by one side flexible copper-clad paper tinsel in the present invention and cover Copper Foil, in preparation process, keep temperature to be 300 DEG C ~ 350 DEG C, hot pressing 20 ~ 30min under 5 ~ 10MPa pressure condition, annealing cools shaping.
The present invention adopts the polyimide structures of hard and soft chain combination and successfully will be successfully applied to two layers of adhesive-free polyimide flex containing side chain cyano group and hard and soft chain structure polyimide covers Copper Foil, gained covers Copper Foil and has the following advantages: (1) polyimide resin layer and copper coin (Copper Foil) base material directly laminating and bond firmly, resin layer self has very low linear expansivity, avoid interlayer (PI resin layer and copper foil layer) CTE value and differ the demixing phenomenon caused more greatly, there is not curling, obscission with Copper Foil is laminating, extend the work-ing life covering Copper Foil.(2) polyimide resin layer self possesses excellent thermotolerance, erosion resistance, electrical insulation capability, good dimensional stability and mechanical property, and this has widened the environment for use covering Copper Foil greatly.(3) use the polyimide resin layer of cyano-containing, utilize the strong polar interaction between cyano group and metal copper ion, adopt the mode film forming directly applied at copper coin (paper tinsel) base material, easily control polyimide resin layer thickness and homogeneity.
Accompanying drawing explanation
Fig. 1: corresponding to embodiment 1, work as a=0.4, b=0.3, c=0.3, band garden circle Ar ' is 3,3 ', 4, the flexible copper-clad paper tinsel PI layer infrared spectrogram in 4 '-BPDA during structure, i.e. the structure spectrogram of PI-1;
Embodiment
Below in conjunction with embodiment, the present invention will be described, but be not limited thereto, and all equivalences done according to the content of the present patent application the scope of the claims change and modify, and all should be technology category of the present invention.
Embodiment 1
The present embodiment is preparation two layers of adhesive-free one side flexible copper-clad paper tinsel, when Ar is biphenyl structural in PI Rotating fields general formula, X is biphenyl structural, and Y is phenyl ether structure, and the Ar ' of zone circle is 3,3 ', 4,4 '-BPDA structure, a=0.4, polyamic acid (PAA) when b=0.3, c=0.3 and flexible copper clad material.
1) copper foil surface is carried out pre-treatment, first Copper Foil is invaded and steep in CH
2cl
2in, supersound process 0.5h removes copper foil surface grease, is put in by the Copper Foil soaked in 0.5mol/L dilute sulphuric acid and soaks the oxide compound that 4h removes copper foil surface, and with distillation washing 3 times, dehydrated alcohol washes 3 times, dries;
2) preparation of PAA solution
Take 1, 4-bis-(amino-2 cyano-benzene oxygens of 4-) biphenyl 0.8369g (2mmol), p-diaminodiphenyl 0.2764g (1.5mmol), diphenyldiamine 0.3004g (1.5mmol) room-temperature dissolution is in the N of 17.4mL, N-dimethylacetamide solution (15% DMAC dropped into by system quality solid content), stir 10min until completely dissolved, 3 are added to reaction flask, 3 ', 4, 4 '-BPDA (BPDA) 1.4711g (5mmol), holder ties up to anhydrous, clean and be carry out under nitrogen environment, stirring at room temperature 40h, be now the liquid of pale yellow transparent thickness in reaction flask, stir after 3h in cleaning through DMAC dilution, dry, left at room temperature 24h, obtain PAA solution, concentration is 0.074g/mL, to after gained PAA solution supersound process 2h in cleaning, dry place leaves standstill 2h to remove bubble.
3) preparation of two layers of adhesive-free flexible copper-clad paper tinsel
Get step 1) process obtain thick be the smooth rolled copper foil (electrolytic copper foil) of 20 μm, above PAA dissolution homogeneity is coated in, the two layers of adhesive-free flexible copper-clad paper tinsel PI layer thickness controlling to obtain after coating PAA liquor capacity addition makes final imidization are 20 μm, by being converted into quality with PAA liquor capacity, Copper Foil area is known, then PI layer thickness is controlled), the Copper Foil of coating PAA solution is transferred to cleaning, dry, smooth environment carries out drying by following program, 60 DEG C of dry 12h, 80 DEG C of dry 12h, 100 DEG C of dry 2h, 120 DEG C of dry 2h, 150 DEG C of dry 1h, be transferred to vacuum environment, carry out high temperature imidization program, 180 DEG C of process 0.5h, 210 DEG C of process 0.5h, 240 DEG C of process 0.5h, 270 DEG C of process 0.5h, 300 DEG C of process 0.5h, naturally cool to room temperature, obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, called after PI-1, its PI Rotating fields formula following (M is the integer of 10 to 200):
Respectively as shown in Table 1 and Table 2, the performances such as stripping strength are as shown in table 3 for its mechanical property and thermal property.
Embodiment 2
With reference to embodiment 1, take 1, 4-bis-(amino-2 cyano-benzene oxygens of 4-) biphenyl 8.369g (20mmol), p-diaminodiphenyl 2.764g (15mmol), diphenyldiamine 3.004g (15mmol) room-temperature dissolution is in the N of 174mL, N-dimethylacetamide solution (15% DMAC dropped into by system quality solid content), stir 20min until completely dissolved, 3 are added to reaction flask, 3 ', 4, 4 '-BPDA 14.711g (50mmol), holder ties up to anhydrous, clean and be carry out under nitrogen environment, 0 DEG C is stirred 48h, be now the liquid of pale yellow transparent thickness in reaction flask, stir after 4h in cleaning through DMAC dilution, dry, left at room temperature 24h, obtain PAA solution, concentration is 0.074g/ml.
Following step, according to the operation of embodiment 1, obtains two layers of adhesive-free one side flexible copper-clad paper tinsel, gained flexible copper-clad paper tinsel performance perameter and PI layer performance perameter consistent with embodiment 1.
Embodiment 3
With reference to embodiment 1, 2) in step by N, N-N,N-DIMETHYLACETAMIDE (DMAC) solution replaces with N-Methyl pyrrolidone, add-on is 15.9mL (15% DMAC dropped into by system quality solid content), all the other operations are consistent, proceed to 3) step time, the Copper Foil being coated with PAA solution is transferred to cleaning, dry, smooth environment carries out drying by following program, 60 DEG C of dry 24h, 80 DEG C of dry 24h, 120 DEG C of dry 2h, 150 DEG C of dry 1h, all the other operations are consistent, obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, compared with embodiment 1, gained flexible copper-clad paper tinsel PI resin layer linear expansivity slightly raises, CTE value is 33.24ppm/K.
By above-mentioned gained two layers of adhesive-free one side flexible copper-clad foil resin face and thick be the smooth rolled copper foil (electrolytic copper foil of 20 μm, embodiment 1 step 1) obtain) under 20MPa pressure condition, 320 DEG C of continuous hot-press 20min obtain two layers of adhesive-free double-faced flexible and cover Copper Foil (FCCL), PI resin layer and Copper Foil adhesive property excellence, deflection degree is 0.
Embodiment 4
With reference to embodiment 1, 2) step operation is consistent with embodiment 1, 3) in step, gained pale yellow transparent PAA solution is coated in through pretreated thick be on the rolled copper foil (electrolytic copper foil) of 20 μm, control coating PAA liquor capacity addition make the final two layers of adhesive-free flexible copper-clad paper tinsel PI layer thickness obtained be 100 μm (by being converted into quality with PAA liquor capacity, Copper Foil area is known, then PI layer thickness is controlled), the Copper Foil of coating PAA solution is transferred to cleaning, dry, smooth environment carries out drying by following program, 60 DEG C of dry 12h, 80 DEG C of dry 12h, 120 DEG C of dry 2h, 150 DEG C of dry 1h, be transferred to vacuum environment and carry out high temperature imidization program, 180 DEG C of process 0.5h, 250 DEG C of process 0.5h, 300 DEG C of process 0.5h, naturally cool to room temperature, obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, its PI resin layer linear expansivity slightly raises, CTE value is 34.85ppm/K.
Embodiment 5
With reference to embodiment 1, preparation is when in PI Rotating fields general formula, and Ar is biphenyl structural, and X is biphenyl structural, and Y is phenyl ether structure, and Ar ' is 3,3 ', 4,4 '-BPDA structure, polyamic acid when a=0.4, b=0.4, c=0.2 and flexible copper clad material.
1) 1 is taken in step, 4-bis-(amino-2 cyano-benzene oxygens of 4-) biphenyl 0.8369g (2mmol), p-diaminodiphenyl 0.3685g (2mmol), diphenyldiamine 0.2002g (1mmol) room-temperature dissolution is in the DMAC of 17.8mL, stir 10-15min until completely dissolved, 3 are added to reaction flask, 3 ', 4, 4 '-BPDA 1.4711g (5mmol), holder ties up to anhydrous, clean and be carry out under nitrogen environment, stirring at room temperature 40h, be now the liquid of pale yellow transparent thickness in reaction flask, stir after 3h in cleaning through DMAC dilution, dry, left at room temperature 24h, obtain PAA solution.Flexible copper clad foil preparation process is with in embodiment 1 2) step operates consistent, and finally obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, called after PI-2, PI Rotating fields formula is as follows:
Its mechanical property and thermal property, respectively as table 1 and table 2, cover Copper Foil performance as shown in table 3.
Embodiment 6
With reference to embodiment 1, only by Ar ' by 3,3 ', 4,4 '-BPDA (BPDA) structure replaces with pyromellitic dianhydride (PMDA), its add-on is 1.0906g, the addition of system Semi-polarity aprotic solvent DMAC is 15.1mL (15% DMAC dropped into by system quality solid content), all the other operations are consistent with embodiment 1,3) in step, operation and embodiment 1 operate and are consistent, finally obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, called after PI-3, PI Rotating fields skeleton symbol is as follows:
With infrared spectra, structural characterization is carried out to it, as shown in Figure 1.
Its mechanical property and thermal property, respectively as table 1 and table 2, cover Copper Foil performance as shown in table 3.
Embodiment 7 (comparative example one)
The present embodiment is when Ar is biphenyl structural in preparation two layers of adhesive-free one side flexible copper-clad paper tinsel PI Rotating fields general formula, X is biphenyl structural, Y is phenyl ether structure, Ar ' is 3,3 ', 4,4 '-BPDA structure, polyamic acid (PAA) when a=0.5, b=0.5, c=0 and flexible copper clad material.
With reference to embodiment 1,2) in step 1,4-bis-(amino-2 cyano-benzene oxygens of 4-) biphenyl add-on is 1.0463g (2.5mmol), p-diaminodiphenyl add-on is 0.4606g (2.5mmol), be dissolved in the DMAC solution of 17.9mL and (calculate by 15% of system quality solid content), all the other operations are consistent with embodiment 1,3) in step, operation and embodiment 1 are consistent, finally obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, called after PI-a, its PI Rotating fields is as follows:
Its mechanical property and thermal property, respectively as table 1 and table 2, cover Copper Foil performance as shown in table 3.
Embodiment 8
With reference to embodiment 8, only by Ar ' by 3,3 ', 4,4 '-BPDA structure replaces with pyromellitic dianhydride (PMDA) structure, its add-on is 1.0906g (5mmol), the addition of system Semi-polarity aprotic solvent DMAC is 15.6mL (calculating by 15% of system quality solid content), and all the other operations are consistent with embodiment 8, finally obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, called after PI-b, its PI Rotating fields is as follows:
Its mechanical property and thermal property, respectively as table 1 and table 2, cover Copper Foil performance as shown in table 3.
Embodiment 9 (comparative example two)
The present embodiment is when Ar is biphenyl structural in preparation two layers of adhesive-free one side flexible copper-clad paper tinsel PI Rotating fields general formula, X is biphenyl structural, Y is phenyl ether structure, Ar ' is 3,3 ', 4,4 '-BPDA structure, polyamic acid (PAA) when a=0.5, b=0, c=0.5 and flexible copper clad material.
With reference to embodiment 1,2) in step 1,4-bis-(amino-2 cyano-benzene oxygens of 4-) biphenyl add-on is 1.0463g (2.5mmol), the add-on of diphenyldiamine is 0.5006g (2.5mmol), the addition of system Semi-polarity aprotic solvent DMAC is 18.2mL (calculating by 15% of system quality solid content), all the other operations are consistent with embodiment 1,3) in step flexible copper-clad paper tinsel preparation process and operation and embodiment 1 be consistent, finally obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, called after PI-c, its PI Rotating fields is as follows:
Its mechanical property and thermal property, respectively as table 1 and table 2, cover Copper Foil performance as shown in table 3.
Embodiment 10
With reference to embodiment 10, only by Ar ' by 3,3 ', 4,4 '-BPDA structure replaces with pyromellitic dianhydride (PMDA) structure, its add-on is 1.0906g (5mmol), the addition of system Semi-polarity aprotic solvent DMAC is 15.9mL (calculating by 15% of system quality solid content), and all the other operations are consistent with embodiment 10, finally obtain two layers of adhesive-free one side flexible copper-clad paper tinsel, called after PI-d, its PI Rotating fields is as follows:
Its mechanical property and thermal property, respectively as table 1 and table 2, cover Copper Foil performance as shown in table 3.
Table 1: two layers of adhesive-free flexible copper-clad paper tinsel PI layer mechanical property
As table 1, Mechanics Performance Testing adopts Shimadzu Corporation AG-I type universal testing machine, and rate of extension 8mm/min, under room temperature condition.
Table 2: two layers of adhesive-free flexible copper-clad paper tinsel PI layer thermal characteristics
Wherein Tg, Td, CTE represent 5% thermal weight loss temperature and linear expansivity under second-order transition temperature, condition of nitrogen gas respectively, wherein Tg test condition is lower 100 DEG C ~ 350 DEG C of condition of nitrogen gas, 10 DEG C/min temperature rise rate, Td test condition is lower 100 DEG C ~ 800 DEG C of condition of nitrogen gas, 10 DEG C/min temperature rise rate, CTE test condition is lower 0 DEG C ~ 350 DEG C of condition of nitrogen gas, 10 DEG C/min temperature rise rate.
Table 3: the properties of flexible copper-clad paper tinsel
As shown in table 3, in table, data test method is as follows:
(1) 90 degree of peel strength tester device is Shimadzu Corporation AG-I type universal testing machine, and detachment rate is 8mm/min, under room temperature condition.
(2) during deflection degree test, flexible copper clad material is cut into the standard of 100 × 100cm, places in the tiling of level place, measure the curling mean value in standard four limit.
(3) water-intake rate adopts GB/T1034-2008 standard to carry out water-intake rate test, namely under room temperature, polyimide overlay film is invaded in distilled water bubble 24h, takes out and dry film surface, according to calculating water-intake rate of poor quality before and after immersion.
(4) flame retardant properties adopts UL94 standard.
(5) specific inductivity and volume specific resistance testing tool are 4294 precise impedance analysers, and by resin layer test zone surface smear silver slurry, test frequency is 10
3~ 10
7hz, under room temperature condition.
Claims (9)
1. a polyimide resin for cyano-containing, its structural formula is as follows:
Wherein a+b+c=1, and 0<a<1,0≤b<1,0≤c<1, M are the integer of 10 ~ 200;
Ar is one of following structure,
R
1for-H or-CN, R
2for-H or-CN, and R
1and R
2can not be-H simultaneously;
Ar ' is one of following structure,
X is one of following structure,
Y is one of following structure,
2. the polyimide resin of cyano-containing according to claim 1 is preparing the application in adhesive-free flexible copper-clad paper tinsel.
3. the polyimide resin of cyano-containing as claimed in claim 2 is preparing the application in adhesive-free flexible copper-clad paper tinsel, it is characterized in that: be that two layers of adhesive-free one side flexible copper-clad paper tinsel or two layers of adhesive-free double-faced flexible cover Copper Foil.
4. the polyimide resin of cyano-containing as claimed in claim 3 is preparing the application in adhesive-free flexible copper-clad paper tinsel, it is characterized in that: two layers of adhesive-free one side flexible copper-clad paper tinsel are made up of Copper Foil and the PI resin layer be overlying on Copper Foil, PI resin layer is the polyimide resin of cyano-containing according to claim 1, PI resin layer thickness is 20 ~ 100 μm, Copper Foil is rolled copper foil or electrolytic copper foil, and thickness is 20 ~ 80 μm.
5. the polyimide resin of cyano-containing as claimed in claim 3 is preparing the application in adhesive-free flexible copper-clad paper tinsel, it is characterized in that: two layers of adhesive-free double-faced flexible cover Copper Foil by Copper Foil, be overlying on the PI resin layer on Copper Foil and form the Copper Foil be overlying on PI resin layer and form, PI resin layer is the polyimide resin of cyano-containing according to claim 1, PI resin layer thickness is 20 ~ 100 μm, Copper Foil is rolled copper foil or electrolytic copper foil, and thickness is 20 ~ 80 μm.
6. the polyimide resin of cyano-containing as claimed in claim 3 is preparing the application in adhesive-free flexible copper-clad paper tinsel, it is characterized in that: the preparation process that two layers of adhesive-free one side flexible copper-clad paper tinsel or two layers of adhesive-free double-faced flexible cover Copper Foil is as follows,
1) copper foil surface is carried out pre-treatment, first Copper Foil is invaded and steep in CH
2cl
2in, supersound process 0.5 ~ 1h removes copper foil surface grease, is put in by the Copper Foil soaked in 0.2 ~ 1.0mol/L dilute sulphuric acid and soaks the oxide compound that 3 ~ 5h removes copper foil surface, and with distillation washing 3 ~ 4 times, dehydrated alcohol washes 2 ~ 3 times, dries;
2) under anhydrous, nitrogen environment, cyano-containing diamines, rigid structure diamines and flexible structure diamines are dissolved in polar aprotic solvent, 24 ~ 48h is stirred at adding the dianhydride 0 DEG C ~ 80 DEG C of above-mentioned three kinds of diamines molar weight sums, carry out terpolymer and obtain polyamic acid PAA solution, gained PAA solution is diluted, after dilution, the concentration of PAA solution is 0.074g/mL ~ 0.2g/mL, then carries out the process of elimination bubble;
3) by the PAA solution coat after dilution in step 1) on pretreated clean Copper Foil, be transferred to vacuum or inert gas environment after drying at 60 ~ 160 DEG C under, at 180 ~ 350 DEG C, hot imidization is carried out in process, then Copper Foil is taken out after Temperature fall to room temperature, thus obtaining the one side flexible copper-clad paper tinsel of two layers of adhesive-free, the thickness range of copper foil surface resin layer is 20 ~ 100 μm;
4) another step 1 is got) pretreated clean Copper Foil, overlay on step 3) on the resin face of the one side flexible copper-clad paper tinsel of gained, be pressed into two layers of adhesive-free double-faced flexible through pressure sintering and cover Copper Foil.
7. the polyimide resin of cyano-containing as claimed in claim 6 is preparing the application in adhesive-free flexible copper-clad paper tinsel, it is characterized in that: polar aprotic solvent is N, N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, solvent for use is diluted to PAA identical with solvent for use during polymerization, diamine monomer is cyano-containing diamines (1, 4-bis-(amino-2 cyano-benzene oxygens of 4-) biphenyl or 1, 4-bis-(4-amino-2, 6-dicyano phenoxy group) biphenyl), rigid structure diamines is benzidine, terphenyl diamines, 4, 4 '-diamino-2, 2 '-dicyanobiphenyl or 4, 4 '-diamino-2, 2 '-dimethyl diphenyl, flexible structure diamines is diphenyldiamine, 2, 2-bis-(4 aminophenyl) propane, 2, 2-bis-(4 aminophenyl) HFC-236fa, 1, 4-bis-(4-amino-benzene oxygen) benzene or 4, 4-diaminodiphenylsulfone(DDS), dianhydride is pyromellitic acid anhydride, oxydiphthalic, 3, 3 ', 4, 4 '-BPDA, hexafluorodianhydride or benzophenone tetracarboxylic dianhydride.
8. the polyimide resin of cyano-containing as claimed in claim 6 is preparing the application in adhesive-free flexible copper-clad paper tinsel, it is characterized in that: the method PAA solution be polymerized being carried out eliminating to bubble process is that room temperature leaves standstill 10 ~ 30h in clean, dry environment; Or in the baking oven of cleaning, keep temperature 40 ~ 50 DEG C to leave standstill 5 ~ 7h; Or leave standstill 1 ~ 2h after supersound process 2 ~ 3h.
9. the polyimide resin of cyano-containing as claimed in claim 6 is preparing the application in adhesive-free flexible copper-clad paper tinsel, it is characterized in that: step 4) adopt pressure sintering (under air ambient or under vacuum environment) to prepare double-faced flexible by one side flexible copper-clad paper tinsel and cover Copper Foil, at 300 DEG C ~ 350 DEG C, hot pressing 15 ~ 30min under 15 ~ 25MPa condition in preparation process, after annealing cooling, cooling is shaping.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637165A (en) * | 2021-09-01 | 2021-11-12 | 大同共聚(西安)科技有限公司 | Preparation method of double-sided conductive polyimide flexible circuit board |
| JP2022516281A (en) * | 2019-01-02 | 2022-02-25 | デリム カンパニー リミテッド | A method for producing a polyamic acid composition, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced by the method for producing the same. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007083526A1 (en) * | 2006-01-20 | 2007-07-26 | Kaneka Corporation | Polyimide film and use thereof |
| CN103193674A (en) * | 2013-03-11 | 2013-07-10 | 吉林大学 | Multi-cyandiamine monomer and preparation and application thereof |
| CN104277458A (en) * | 2014-10-14 | 2015-01-14 | 吉林大学 | High-adhesion-property low-linear-expansion-coefficient polyimide film material and preparation method thereof |
-
2015
- 2015-12-18 CN CN201510955100.4A patent/CN105399950B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007083526A1 (en) * | 2006-01-20 | 2007-07-26 | Kaneka Corporation | Polyimide film and use thereof |
| CN103193674A (en) * | 2013-03-11 | 2013-07-10 | 吉林大学 | Multi-cyandiamine monomer and preparation and application thereof |
| CN104277458A (en) * | 2014-10-14 | 2015-01-14 | 吉林大学 | High-adhesion-property low-linear-expansion-coefficient polyimide film material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XUEYING CAO, ET AL.: "Synthesis and properties of cyano group-containing polyimides with high peel strength", 《HIGH PERFORMANCE POLYMERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022516281A (en) * | 2019-01-02 | 2022-02-25 | デリム カンパニー リミテッド | A method for producing a polyamic acid composition, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced by the method for producing the same. |
| JP7317122B2 (en) | 2019-01-02 | 2023-07-28 | デリム カンパニー リミテッド | Polyamic acid composition production method, polyamic acid composition, polyimide film production method using the same, and polyimide film produced by the production method |
| CN113637165A (en) * | 2021-09-01 | 2021-11-12 | 大同共聚(西安)科技有限公司 | Preparation method of double-sided conductive polyimide flexible circuit board |
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