Patent Application
20080026195
In the process for preparing the polyimide composite flexible board of the present invention, a polyamic acid resin is obtained by reacting diamine of the following formula (I),
H2N—R1—NH2 (I)
[wherein R1 is phenylene (-Ph-); -Ph-X-Ph- wherein X represents a covalent bond, C1-4 alkylene which may be substituted with a halogen(s), —O-Ph-O—, —O—, —CO—, —S—, —SO—, or —SO2—; C2-14 aliphatic hydrocarbon group; C4-30 aliphatic cyclic hydrocarbon group; C6-30 aromatic hydrocarbon group; or -Ph-O—R2—O-Ph- wherein R2 represents -Ph- or -Ph-X-Ph-, and X represents a covalent bond, C1-4 alkylene which may be substituted with a halogen(s), —O-Ph-O—, —O—, —CO—, —S—, —SO—, or —SO2—]; with dianhydride of the following formula (II),
[wherein Y is a aliphatic group containing 2 to 12 carbon atoms; a cycloaliphatic group containing 4 to 8 carbon atoms; monocyclic or polycyclic C6-14 aryl; >Ph-X-Ph< wherein X represents a covalent bond, C1-4 alkylene which may be substituted with a halogen(s), —O-Ph-O—, —O—, —CO—, —S—, —SO—, or —SO2—].
In the process for preparing the polyimide composite flexible board of the present invention, the first polyamic acid resin having a glass transition temperature of from 280 to 300° C. after imidization is obtained by reacting a diamine monomer containing one benzene ring and a dianhydride moner containing one benzene ring with other diamine monomer and other dianhydride monomer, under the conditions that the mole ratio of total diamine monomer/total dianhydride monomer ranges from 0.5 to 2.0, preferably from 0.75 to 1.25, and the mole ratio of diamine monomer containing one benzene ring/other diamine monomer ranges from 60/40 to 20/80, and the mole ratio of dianhydride monomer containing one benzene ring/other dianhydride monomer ranges from 40/60 to 20/80.
In the process of the present invention, the second polyamic acid resin having a glass transition temperature of from 300 to 350° C. after imidization is obtained by reacting a diamine monomer containing one benzene ring and a dianhydride monomer containing one benzene ring with other diamine monomer and other dianhydride monomer, under the conditions that the mole ratio of total diamine monomer/total dianhydride monomer ranges from 0.5 to 2.0, preferably from 0.75 to 1.25, and the mole ratio of diamine monomer containing one benzene ring/other diamine monomer ranges from 95/5 to 80/20, and the mole ratio of dianhydride monomer containing one benzene ring/other dianhydride monomer ranges from 80/20 to 60/40.
In the process of the present invention, the third polyamic acid resin having a glass transition temperature of from 190 to 280° C. after imidization is obtained by reacting a diamine monomer containing at least two benzene rings and a dianhydride monomer containing two benzene rings with other dianhydride monomer, under the conditions that the mole ratio of total diamine monomer/total dianhydride monomer ranges from 0.5 to 2.0, preferably from 0.75 to 1.25, and the mole ratio of diamine monomer containing at least two benzene rings/other diamine monomer ranges from 60/40 to 100/0.
Embodiments of the dianhydride monomer for preparing the polyamic acid in the present invention is for instance, but not limited to, aromatic dianhydride such as pyromellitic dianhydride (PMDA), 4,4-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)-sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic dianhydride, 4,4′-(m-phenylenedioxy)diphthalic dianhydride, 2,3,6,7-naphthalene-tetracarboxylic dianhydride, 1,4,5,8-naphthalene-tetra-carboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracene-tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. The foregoing dianhydrides can be used alone or in combination of two or more. Among these, pyromellitic dianhydride (PMDA), 4,4′-oxy-diphthalic anhydride (ODPA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) are preferable.
Embodiments of the diamine monomer for preparing the polyamic acid in the present invention is for instance, but not limited to, aromatic diamine such as p-phenylene diamine (PDA), 4,4-oxydianiline (ODA), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,3-bis(3-aminophenoxy)-benzene (APB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS), 4,4′-bis(4-amino-phenoxy)-3,3′-dihydroxybiphenyl (BAPB), bis[4-(3-aminophenoxy)-phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, 2,2-bis[4-(3-aminophenoxy)phenyl]-propane, 2,2′-bis[4-(3-aminophenoxy)phenyl]-butane, 2,2-bis[4-(3-amino-phenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4′-bis(3-amino-phenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]-sulfoxide, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)-phenyl]ether, etc. The foregoing diamines can be used alone or in combination of two or more. Among these, p-phenylene diamine (PDA), 4,4′-oxydianiline (ODA), 1,3-bis(4-amino-phenoxy)benzene (TPE-R), 1,3-bis(3-aminophenoxy)benzene (APB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(4-amino-phenoxy)phenyl]sulfone (BAPS), and 4,4′-bis(4-amino-phenoxy)-3,3′-dihydroxybiphenyl (BAPB) are preferable.
The dianhydrides can react with the diamines in aprotic polar solvents. The aprotic polar solvents are not particularly limited as long as they do not react with reactants and products. Embodiments of the aprotic polar solvents are for instance N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N,N-dimethyl-formamide (DMF), tetrahydrofuran (THF), dioxane, chloroform (CHCl3), dichloromethane, etc. Among these, N-methylpyrrolidone (NMP) and N,N-dimethyl-acetamide (DMAc) are preferable.
The reaction of the dianhydrides and the diamines can be generally conducted in the range of from room temperature to 90° C., preferably from 30 to 75° C. Additionally, the mole ratio of aromatic diamines to aromatic dianhydrides ranges between 0.5 and 2.0, preferably between 0.75 and 1.25. When two or more dianhydrides and diamines are individually used to prepare the polyamic acids, their kinds are not particularly limited but depend on the final use of the polyimides as required.
Preferably, for the first polyamic acid having a glass transition temperature of from 280 to 300° C. after imidization, the used diamines at least include p-phenylene diamine (PDA) and the used dianhydrides at least include pyromellitic dianhydride (PMDA), under the conditions that the mole ratio of p-phenylene diamine monomer/other diamine monomer ranges from 60/40 to 20/80, and the molar ratio of pyromellitic dianhydride monomer/other dianhydride monomer ranges from 40/60 to 20/80.
Preferably, for the second polyamic acid having a glass transition temperature of from 300 to 350° C. after imidization, the used diamines at least include p-phenylene diamine (PDA) and the used dianhydrides at least include pyromellitic dianhydride (PMDA), under the conditions that the mole ratio of p-phenylene diamine monomer/other diamine monomer ranges from 95/5 to 80/20, and the molar ratio of pyromellitic dianhydride monomer/other dianhydride monomer ranges from 80/20 to 60/40.
Preferably, for the third polyamic acid having a glass transition temperature of from 190 to 280° C. after imidization, the used diamines include a diamine monomer containing at least two benzene rings which are selected from at least one group consisting of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(4-amino-phenoxy)-phenyl]sulfone (BAPS), 1,3-bis(3-aminophenoxy)benzene (APB), 4,4′-oxydianiline (ODA), and 4,4′-bis-(4-aminophenoxy)-3,3′-dihydroxy-biphenyl (BAPB), and the used dianhydrides include a dianhydride monomer containing two benzene rings which are selected from at least one group consisting of 4,4′-oxydiphthalic dianhydride (ODPA), 3,3′,4,4′-biphenyl-tetracarboxylic dianhydride (BPDA), and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), under the conditions that the mole ratio of diamine monomer containing at least two benzene rings/other diamine monomer ranges from 60/40 to 100/0.
According to the polyimide composite flexible board and its preparation of the present invention, the thickness of the metal foil such as copper foil is not particularly limited but depends on the final use of the obtained composite flexible board. However, the thickness of the metal foil usually ranges from 12 μm to 70 μm, and the thicknesses of the first polyimide thin layer, the second polyimide thin layer, and the third polyimide thin layer individually satisfy the following conditions.
The present invention will further illustrate by reference to the following synthesis examples and working examples. However, these synthesis examples and working examples are not intended to limit the scope of the present invention but only describe the present invention.
(a) Synthesis of Polyamic Acid-1
Into a four-neck bottle reactor equipped with a stirrer and a nitrogen gas conduit under the flow rate of nitrogen gas of 20 cc/min, 5.4 g (0.05 mole) of p-phenylene diamine (PDA) was placed and dissolved in N-methylpyrrolidone (NMP). After 15 minutes, 10 g (0.05 mole) 4,4-oxydianiline (ODA) was fed to dissolve and meantime maintained at a temperature of 15° C. 8.82g (0.03 mole) of 3,3′,4,4′-biphenyl-tetracarboxylic dianhydride (BPDA) and 15 g of NMP were fed in the first flask accompanied with a stir bar and then stirred to dissolve. Subsequently, the mixture in the first flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. 16.1 g (0.05 mole) of 3,3′,4,4′-benzophenone-tetracarboxylic dianhydride (BTDA) and 30 g of NMP were fed in the second flask and then stirred to dissolve. Subsequently, the mixture in the second flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. 4.36 g (0.02 mole) of pyromellitic dianhydride (PMDA) and 10 g of NMP were fed in the third flask and then stirred to dissolve. Subsequently, the mixture in the third flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. Afterward, the reaction was carried out at a temperature of 15° C. for further four hours to obtain the polyamic acid (PAA 1-1). 0.5 g of the obtained polyamic acid dissolved in 100 ml of NMP, and at a temperature of 25° C., was measured the intrinsic viscosity (IV) as 0.85 dl/g and the glass transition temperature (Tg) after imidization as 290° C.
According to the ingredients and their amount listed in Table 1, Polyamic Acids (PAA) 1-2 and 1-3 were synthesized by the analogous procedures and measured the intrinsic viscosity (IV) and the glass transition temperature (Tg) after imidization shown in Table 1 as well.
(b) Synthesis of Polyamic Acid-2
Into a four-neck bottle reactor equipped with a stirrer and a nitrogen gas conduit under the flow rate of nitrogen gas of 20 cc/min, 9.72 g (0.09 mole) of p-phenylene diamine (PDA) was placed and dissolved in N-methylpyrrolidone (NMP). After 15 minutes, 2 g (0.01 mole) 4,4′-oxydianiline (ODA) was fed to dissolve and meantime maintained at a temperature of 15° C. 5.88 g (0.02 mole) of 3,3′,4,4′-biphenyl-tetracarboxylic dianhydride (BPDA) and 15 g of NMP were fed in the first flask accompanied with a stir bar and then stirred to dissolve. Subsequently, the mixture in the first flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. 17.44 g (0.08 mole) of pyromellitic dianhydride (PMDA) and 30 g of NMP were fed in the second flask and then stirred to dissolve. Subsequently, the mixture in the second flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. Afterward, the reaction was carried out at a temperature of 15° C. for further four hours to obtain the polyamic acid (PAA2-1). 0.5 g of the obtained polyamic acid dissolved in 100 ml of NMP, and at a temperature of 25° C., was measured the intrinsic viscosity (IV) as 0.75 dl/g and the glass transition temperature (Tg) after imidization as 338° C.
According to the ingredients and their amount listed in Table 2, Polyamic Acids (PAA) 2-2 and 2-3 were synthesized by the analogous procedures and measured the intrinsic viscosity (IV) and the glass transition temperature (Tg) after imidization shown in Table 2 as well.
(c) Synthesis of Polyamic Acid-3
Into a four-neck bottle reactor equipped with a stirrer and a nitrogen gas conduit under the flow rate of nitrogen gas of 20 cc/min, 41 g (0.1 mole) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was placed and dissolved in N-methylpyrrolidone (NMP). After 15 minutes, 2.94 g (0.01 mole) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 15 g of NMP were fed in the first flask accompanied with a stir bar and then stirred to dissolve. Subsequently, the mixture in the first flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. 22.54 g (0.07 mole) of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 15 g of NMP were fed in the second flask and then stirred to dissolve. Subsequently, the mixture in the second flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. 6.2 g (0.02 mole) of 4,4′-oxydiphthalic anhydride (ODPA) and 30 g of NMP were fed in the third flask and then stirred to dissolve. Subsequently, the mixture in the third flask was added to the above reactor that the nitrogen gas was continuously charged and stirred to carry out the reaction for one hour. Afterward, the reaction was carried out at a temperature of 15° C. for further four hours to obtain the polyamic acid (PAA 3-1). 0.5 g of the obtained polyamic acid dissolved in 100 ml of NMP, and at a temperature of 25° C., was measured the intrinsic viscosity (IV) as 0.95 dl/g and the glass transition temperature (Tg) after imidization as 223° C.
According to the ingredients and their amount listed in Table 3, Polyamic Acids 3-2, 3-3, 3-4 and 3-5 were synthesized by the analogous procedures and measured the intrinsic viscosity (IV) and the glass transition temperature (Tg) after imidization shown in Table 3 as well.
According to ingredients listed in Table 4 and Table 5, the polyamic acid resin 1 obtained from the above synthesis examples was evenly applied on a copper foil with the thickness of 18 μm by a wire rod, and the thickness of the applied polyamic acid resin 1 was 3 μm. Into an oven, the copper foil was heated at a temperature of 120° C. for 3 minutes and 180° C. for 5 minutes to remove a solvent. The dried copper foil applied with the polyamic acid was taken out on which the polyamic acid resin 2 was then applied with the thickness of 17 μm. Subsequently, into an oven, the copper foil was heated at a temperature of 120° C. for 3 minutes and 180° C. for 7 minutes to remove a solvent. The applied copper foil was taken out on which the polyamic acid resin 3 was then applied with the thickness of 3 μm. Subsequently, into an oven, the copper foil was heated at a temperature of 120° C. for 3 minutes and 180° C. for 5 minutes to remove a solvent. The obtained copper foil was put into a nitrogen gas oven at a temperature of 180° C. for 1 hour, 220° C. for 1 hour, 300° C. for 0.6 hour, and 350° C. for 0.5 hour to subject the polyamic acids to imidization reaction. After cooling, the copper foil was taken out and pressed with another copper foil under a temperature of 340° C. and a pressure of 100 Kgf by using a flat pressing machine in batch or a roll calendar in continuity to produce a two-side copper-foil-pressed flexible printed circuit board. The structure of the flexible board was copper foil/polyimide 1 (280° C.<Tg<300° C. )/polyimide 2 (300° C.<Tg<350° C.)/polyimide 3 (190° C.<Tg<280° C.)/copper foil.
Generally, the two-side copper-foil-pressed flexible printed circuit board could be produced as a procedure shown in
Subsequently, the imidization equipment shown in
Finally, the pressing equipment shown in
The resultant copper foil was measured the peel strength regulated by IPC-TM650 2.2.9, the coefficient of thermal expansion by thermal gravity analyzer, and dimension stability regulated by IPC-TM650 2.2.4. The results were shown in Tables 4 and 5.
According to the present invention, the polyamic acid resins each having different glass transition temperature (Tg) after imidization were utilized. The polyamic acid resin having Tg of from 280 to 300° C. after imidization with high adhesion was firstly applied on the copper foil, and then the polyamic acid resin having Tg of 300 to 350° C. after imidization with an excellent mechanical property was applied as a support layer, and finally the polyamic acid resin having comparatively low Tg of from 190 to 280° C. after imidization with high adhesion was applied. Subsequently, the copper foil was pressed with another copper foil by using a high temperature roller or a pressing machine. At the same time, the polyamic acids conducted imidization reaction, and thus a two-side printed circuit flexible board with heat stability and dimension stability could be obtained.
| Number | Date | Country | Kind |
|---|---|---|---|
| 095127281 | Jul 2006 | TW | national |
