CN113307971A - Polyimide precursor and application thereof - Google Patents
Polyimide precursor and application thereof Download PDFInfo
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- CN113307971A CN113307971A CN202010121146.7A CN202010121146A CN113307971A CN 113307971 A CN113307971 A CN 113307971A CN 202010121146 A CN202010121146 A CN 202010121146A CN 113307971 A CN113307971 A CN 113307971A
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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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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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
-
- 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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a polyimide precursor and application thereof, wherein the preparation raw materials of the polyimide precursor comprise a diamine monomer and a dianhydride monomer; the diamine monomer comprises 2- (diaminophenyl) benzimidazole-5 amine (BIA) and a diamine monomer A, wherein the mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the diamine monomer A is (1-4) to 1; according to the invention, BIA is introduced into a polyimide precursor raw material, the CTE of polyimide synthesized by the BIA is very low, and imidazole can form a complex with copper foil, so that good peel strength is maintained; meanwhile, the diamine monomer A containing small side groups is introduced and matched with BIA, so that the final polyimide can keep a very low CTE, the precursor polyamic acid can keep a relatively large CTE, and the contraction of an adhesive layer in the coating and heating process is reduced, thereby solving the problem that the coating and processing process is easy to turn over, and being beneficial to improving the peel strength of the flexible copper clad laminate.
Description
Technical Field
The invention relates to the technical field of flexible copper clad plates, in particular to a polyimide precursor and application thereof.
Background
Flexible printed circuit boards have been widely used in consumer electronics products such as notebook computers, mobile phones, personal digital assistants, and digital cameras, and due to the increasing technical requirements of the electronic industry, consumer electronics products are rapidly moving toward being light, thin, short, and small, and increasingly require corresponding flexible copper clad laminates to be lighter and thinner, and have high heat resistance and high reliability. The glue-free flexible copper clad laminate has been rapidly developed in recent years due to the adoption of polyimide resin with excellent mechanical property, electrical property and heat resistance.
The preparation method of the adhesive-free flexible copper clad laminate comprises a laminating method and a coating method, wherein the laminating method adopts a high-temperature roller press to roll the Thermoplastic Polyimide (TPI) composite film and the copper foil at high temperature to prepare the adhesive-free flexible copper clad laminate, and the production process is relatively simple and easy to realize; compared with the compression method, the coating method flexible copper clad laminate can be used for preparing the adhesive-free flexible copper clad laminate with more excellent mechanical property and size expansion and contraction because the polyimide formula can be regulated and controlled. At present, no matter the requirement of a Chip On Film (COF) on the low Coefficient of Thermal Expansion (CTE) of the flexible copper clad laminate without adhesive is met, or the flexible copper clad laminate without adhesive needs to seek better dimensional stability, the requirement of lower CTE is provided for the polyimide layer of the flexible copper clad laminate without adhesive. For the coating method glue-free flexible copper clad laminate, low CTE, high peel strength and excellent processability are a group of contradictions which are not easy to solve. The CTE of the polyimide is reduced, and the bonding force of the polyimide and the copper foil is reduced; the CTE of polyimide is reduced, and the CTE of precursor polyamide acid is also lower, so that the contraction of an adhesive layer is more serious in a temperature rise stage, and the problem that a flexible copper-clad plate without adhesive is easy to turn over during coating is caused.
CN107266683A discloses a thermoplastic polyimide film and a non-adhesive flexible copper-clad plate prepared from the same. The method overcomes the mutual restriction relationship between the thermoplasticity of the Polyimide (PI) film and the high Tg and the low CTE of the polyimide film, the prepared PI film has excellent comprehensive performance including good thermoplasticity, high Tg, low CTE and good bonding strength with copper foil, and the non-adhesive flexible copper clad laminate prepared from the PI film has the advantages of smooth appearance, light weight, thinness, softness, flexibility and the like, and can be applied to devices such as microelectronics, photoelectrons, wearable electronic products and the like. However, the polyimide precursor used in the present invention has a low CTE, and is likely to be folded during the coating process.
CN102993748A discloses a TPI film with low thermal expansion coefficient, a preparation method thereof and a method for preparing a two-layer flexible copper-clad plate by using the TPI film. When the thermoplastic polyimide film is prepared, bis (4-aminophenyl) -4- (tribromomethyl) phenylphosphine oxide and 3-phenyl-2, 6-bis (4-aminophenyl) pyridine in a certain molar ratio are combined with corresponding diamine and dianhydride to carry out solution polymerization to generate a polyamic acid copolymer, and the polyamic acid copolymer is dried to remove a solvent and then is treated by a thermal imidization method to obtain the TPI film with excellent hot melt performance and dimensional stability. The TPI film is compounded with a thermosetting polyimide film and a copper foil under certain pressure and temperature to obtain a two-layer flexible copper clad laminate material with good comprehensive performances such as stripping performance, dip soldering resistance, dimensional stability and the like. But the TPI film with lower CTE and the copper foil have poorer cohesiveness, the obtained copper-clad plate has lower peel strength, and the folding is easy to occur in the coating process of the polyimide precursor.
Therefore, there is a need in the art to develop a novel polyimide precursor, which can prepare a flexible copper clad laminate with low CTE of polyimide, while maintaining good peel strength and no folding phenomenon during coating process.
Disclosure of Invention
The invention aims to provide a polyimide precursor, in particular to a polyimide precursor applied to a flexible copper clad laminate, which can be used for preparing a glue-free flexible copper clad laminate with low polyimide CTE, simultaneously keeps good peel strength and does not turn over during coating processing.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polyimide precursor, which is prepared from raw materials including diamine monomers and dianhydride monomers;
the diamine monomer comprises 2- (diamino phenyl) benzimidazole-5 amine and a diamine monomer A;
the R is1～R8Each independently selected from-H, -F, -CH3or-CF3Provided that R is1～R4At least one of them is selected from-CH3or-CF3And R is5～R8At least one of them is selected from-CH3or-CF3；
The mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the diamine monomer A is (1-4): 1, for example, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, and the like.
According to the invention, BIA is introduced into a polyimide precursor raw material formula, the CTE of polyimide synthesized by BIA is very low, and imidazole can form a complex with copper foil, so that good peel strength is maintained; meanwhile, the diamine monomer A containing small side groups is introduced into the polyimide precursor raw material formula, and the diamine monomer A is matched with BIA, so that the final polyimide can keep a very low CTE, the precursor polyamic acid can keep a relatively large CTE, and the contraction of an adhesive layer in the coating and heating process is reduced, thereby solving the problem that the coating and processing process is easy to turn over, and being beneficial to improving the peel strength of the flexible copper clad laminate.
Preferably, the mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the diamine monomer A is (1.5-3): 1.
The invention further optimizes the proportion of the two diamine monomers, can further balance three performances of the CTE, the coating warping degree and the peel strength of the flexible copper clad laminate, controls the CTE below 10 ppm/DEG C, controls the coating warping height to be 3.2-4.8 cm, and controls the peel strength of the flexible copper clad laminate to be 1.25-1.38N/mm. Too high a content results in poor warpage and brittleness of polyimide, adversely affecting peel strength, and too high a content of diamine monomer a results in an increase in CTE value.
Preferably, the sum of the mass of the 2- (diaminophenyl) benzimidazole-5 amine and the diamine monomer A is 30 to 95% of the total mass of the diamine monomer, for example, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, etc.
Preferably, the diamine monomer a includes any one or at least two combinations of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyldiamine, 4' -diamino-3, 3' -dimethyl-5, 5' -fluoro-1, 1' -biphenyldiamine, or 4,4' -diamino-2, 2' -dimethyl-6, 6' -trifluoromethyl-1, 1' -biphenyldiamine.
Preferably, the diamine monomer further comprises 4,4' -diaminodiphenyl ether and/or p-phenylenediamine.
Preferably, the dianhydride monomer comprises any one or at least two of biphenyl dianhydride, pyromellitic dianhydride or 4,4' -diphenyl ether dianhydride in combination.
The second purpose of the invention is to provide polyimide precursor glue solution, which comprises the polyimide precursor and the solvent.
Preferably, the solvent comprises N-methylpyrrolidone and/or N, N' -dimethylacetamide.
Preferably, the viscosity of the polyimide precursor glue solution is 15000-25000 cp, such as 16000cp, 17000cp, 18000cp, 19000cp, 20000cp, 21000cp, 22000cp, 23000cp, 24000cp, 25000cp and the like.
The third object of the present invention is to provide a method for preparing the polyimide precursor glue solution, the method comprising: and mixing a dianhydride monomer, a diamine monomer and a solvent to perform a polycondensation reaction to obtain the polyimide precursor glue solution.
Preferably, the preparation method of the polyimide precursor glue solution specifically comprises the following steps: and dissolving a diamine monomer in a solvent, cooling, adding a dianhydride monomer in a nitrogen atmosphere, and stirring to obtain a polyimide precursor glue solution.
Preferably, the cooling temperature is 8 to 12 ℃, such as 8.2 ℃, 8.4 ℃, 8.6 ℃, 8.8 ℃, 9 ℃, 9.2 ℃, 9.4 ℃, 9.6 ℃, 9.8 ℃, 10 ℃, 10.5 ℃, 10.8 ℃, 11 ℃, 11.4 ℃, 11.6 ℃, 11.8 ℃ and the like.
Preferably, the stirring time is 6-10 h, such as 7h, 8h, 9h and the like.
The fourth purpose of the invention is to provide polyimide, in particular to polyimide applied to a flexible copper clad laminate, wherein the polyimide is obtained by imidizing a polyimide precursor liquid in one purpose or a polyimide precursor liquid in the second purpose.
Preferably, the polyimide has a coefficient of thermal expansion of 2 to 10 ppm/deg.C, such as 2 ppm/deg.C, 3 ppm/deg.C, 4 ppm/deg.C, 5 ppm/deg.C, 6 ppm/deg.C, 7 ppm/deg.C, 8 ppm/deg.C, 9 ppm/deg.C, and the like.
Preferably, the glass transition temperature of the polyimide is 320 to 400 ℃, for example, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ and the like.
The invention aims at providing a flexible copper clad laminate, in particular to a flexible copper clad laminate without adhesive, which comprises a copper foil and an insulating layer, wherein the insulating layer contains the polyimide of the fourth purpose.
Preferably, the thickness of the insulating layer is 3 to 37 μm, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, or the like.
Preferably, the copper foil has a thickness of 9 to 70 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, or the like.
The sixth purpose of the invention is to provide a preparation method of the flexible copper clad laminate, which comprises the following steps: and coating the polyimide precursor glue solution of the second purpose on the copper foil, and imidizing to obtain the flexible copper clad laminate.
Preferably, the method of imidization comprises baking.
Preferably, the baking comprises a first baking and a second baking.
Preferably, the time of the first baking is 2-5 min, such as 2.2min, 2.4min, 2.6min, 2.8min, 3min, 3.2min, 3.4min, 3.6min, 3.8min, 4min, 4.2min, 4.4min, 4.6min, 4.8min, and the like.
Preferably, the first baking temperature is 150-180 ℃, such as 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 178 ℃ and the like.
Preferably, the time of the second baking is 20-40 min, such as 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, and the like.
Preferably, the temperature of the second baking is 350-400 ℃, such as 360 ℃, 370 ℃, 380 ℃, 390 ℃ and the like.
Preferably, the second baking is performed under the protection of nitrogen.
Preferably, the preparation method comprises:
and coating the second polyimide precursor glue solution on the copper foil, baking for 2-5 min at the temperature of 150-180 ℃, and then baking for 20-40 min at the temperature of 350-400 ℃ under the protection of nitrogen to obtain the flexible copper clad laminate.
The seventh purpose of the invention is to provide a printed circuit board, which comprises the flexible copper clad laminate of the sixth purpose.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, BIA is introduced into a polyimide precursor raw material formula, the CTE of polyimide synthesized by BIA is very low, and imidazole can form a complex with copper foil, so that good peel strength is maintained; meanwhile, the diamine monomer A containing small side groups is introduced into the polyimide precursor raw material formula, and the diamine monomer A is matched with BIA, so that the final polyimide can keep a very low CTE, the precursor polyamic acid can keep a relatively large CTE, and the contraction of an adhesive layer in the coating and heating process is reduced, thereby solving the problem that the coating and processing process is easy to turn over, and being beneficial to improving the peel strength of the flexible copper clad laminate.
Wherein the CTE of the polyimide is 3.2-12.6 ppm/DEG C, the warping height in the coating process is 1.8-5.2 cm, and the peel strength of the copper-clad plate is 1.16-1.51N/mm.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a polyimide precursor glue solution and a single-sided flexible copper-clad plate, and the preparation method comprises the following steps:
9.45 g of 2- (diaminophenyl) benzimidazole-5-amine (BIA), 2.55 g of 4,4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyldiamine (m-TB) and 1.20 g of 4,4' -diaminodiphenyl ether (ODA) were dissolved in N-methylpyrrolidone (NMP) with stirring; the resulting solution was then cooled to 10 ℃ in a water bath and 17.51 grams of biphenyl dianhydride (BPDA) was added slowly under a stream of nitrogen; stirring for 8 hours continuously to obtain the polyimide resin precursor glue solution with the viscosity of 20000 cp. Wherein the mass ratio of BIA to m-TB is 3.7: 1.
2) Coating the polyimide resin precursor glue solution on a 12-micron rolled copper foil, baking for 4min at 160 ℃, and then baking for 30min in an oven at 390 ℃ under the protection of nitrogen to finish imidization of the polyimide precursor, thereby preparing the single-sided flexible copper-clad plate with the thickness of the insulating layer of 25 microns.
Example 2
The difference from example 1 is that BIA was added in an amount of 8.77 g, m-TB was added in an amount of 3.19 g, and the mass ratio of BIA to m-TB was 2.7: 1.
Example 3
The difference from example 1 is that BIA was added in an amount of 8.10 g, m-TB was added in an amount of 3.83 g, and the mass ratio of BIA to m-TB was 2.1: 1.
Example 4
The difference from example 1 is that BIA was added in an amount of 7.42 g, m-TB was added in an amount of 4.47 g, and the mass ratio of BIA to m-TB was 1.7: 1.
Example 5
The difference from example 1 is that BIA was added in an amount of 6.75 g, m-TB was added in an amount of 5.11 g, and the mass ratio of BIA to m-TB was 1.3: 1.
Example 6
The difference from example 1 is that BIA was added in an amount of 6.07 g, m-TB was added in an amount of 5.79 g, and the mass ratio of BIA to m-TB was 1.0: 1.
Example 7
The embodiment provides a polyimide precursor glue solution and a single-sided flexible copper-clad plate, and the preparation method comprises the following steps:
9.45 g of 2- (diaminophenyl) benzimidazole-5-amine (BIA), 2.77 g of 4,4' -diamino-3, 3' -dimethyl-5, 5' -fluoro-1, 1' -biphenyldiamine and 2.47 g of 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP) are dissolved with stirring in N-methylpyrrolidone (NMP); the resulting solution was then cooled to 8 ℃ in a water bath and 12.98 g of pyromellitic dianhydride (PMDA) was added slowly under a stream of nitrogen; stirring is continued for 6 hours to prepare the polyimide resin precursor glue solution with the viscosity of 15000 cp. Wherein the mass ratio of the 2- (diamino phenyl) benzimidazole-5 amine to the 4,4 '-diamino-3, 3' -dimethyl-5, 5 '-fluoro-1, 1' -biphenyldiamine is 3.4: 1.
2) Coating the polyimide resin precursor glue solution on a 12-micron rolled copper foil, baking for 5min at 150 ℃, and then baking for 40min at 350 ℃ in an oven under the protection of nitrogen to finish imidization of the polyimide precursor, thereby preparing the single-sided flexible copper-clad plate with the thickness of the insulating layer of 3 microns.
Example 8
The embodiment provides a polyimide precursor glue solution and a single-sided flexible copper-clad plate, and the preparation method comprises the following steps:
9.45 g of 2- (diaminophenyl) benzimidazole-5-amine (BIA), 3.32 g of 4,4' -diamino-2, 2' -dimethyl-6, 6' -trifluoromethyl-1, 1' -biphenyldiamine and 1.20 g of 4,4' -diaminodiphenyl ether (ODA) were dissolved in N-methylpyrrolidone (NMP) with stirring; the resulting solution was then cooled to 12 ℃ in a water bath and 18.46 grams of 4,4' -diphenyl ether dianhydride (ODPA) was added slowly under a stream of nitrogen; stirring for 10 hours continuously to prepare the polyimide resin precursor glue solution with the viscosity of 25000 cp. Wherein the mass ratio of the 2- (diamino phenyl) benzimidazole-5 amine to the 4,4 '-diamino-2, 2' -dimethyl-6, 6 '-trifluoromethyl-1, 1' -biphenyldiamine is 2.8: 1.
2) Coating the polyimide resin precursor glue solution on a 12-micron rolled copper foil, baking for 2min at 180 ℃, and then baking for 20min at 400 ℃ in an oven under the protection of nitrogen to finish imidization of the polyimide precursor, thereby preparing the single-sided flexible copper-clad plate with the insulating layer thickness of 37 microns.
Comparative example 1
A preparation method of a single-sided flexible copper-clad plate comprises the following steps:
1) the preparation method of the polyimide resin precursor glue solution comprises the following steps:
10.79 g of 2- (diaminophenyl) benzimidazol-5-amine (BIA) and 2.41 g of 4,4' -diaminodiphenyl ether (ODA) are dissolved with stirring in N-methylpyrrolidone (NMP); the resulting solution was then cooled to 10 ℃ in a water bath and 17.51 grams of biphenyl dianhydride (BPDA) was added slowly under a stream of nitrogen; stirring for 8 hours continuously to prepare the polyimide resin precursor glue solution, wherein the viscosity is controlled to be 20000 cp.
2) Coating the polyimide resin precursor glue solution on a 12-micron rolled copper foil, baking for 4min at 160 ℃, and then baking for 30min in an oven at 390 ℃ under the protection of nitrogen to finish imidization of the polyimide precursor, thereby preparing the single-sided flexible copper-clad plate with the thickness of the insulating layer of 25 microns.
Comparative example 2
A preparation method of a single-sided flexible copper-clad plate comprises the following steps:
1) the preparation method of the polyimide resin precursor glue solution comprises the following steps:
5.53 g of p-phenylenediamine (PPDA) and 1.81 g of 4,4' -diaminodiphenyl ether (ODA) are dissolved with stirring in N-methylpyrrolidone (NMP); the resulting solution was then cooled to 10 ℃ in a water bath and 17.51 grams of biphenyl dianhydride (BPDA) was added slowly under a stream of nitrogen; stirring for 8 hours continuously to prepare the polyimide resin precursor glue solution, wherein the viscosity is controlled to be 20000 cp.
2) Coating the polyimide resin precursor glue solution on a 12-micron rolled copper foil, baking for 4min at 160 ℃, and then baking for 30min in an oven at 390 ℃ under the protection of nitrogen to finish imidization of the polyimide precursor, thereby preparing the single-sided flexible copper-clad plate with the thickness of the insulating layer of 25 microns.
Comparative example 3
The difference from example 2 was that BIA was not added and m-TB was added in an amount of 11.96 g.
Comparative example 4
The difference from example 2 is that BIA was added in an amount of 9.8 g, m-TB was added in an amount of 2.16 g, and the mass ratio of BIA to m-TB was 4.5: 1.
Comparative example 5
The difference from example 2 is that BIA was added in an amount of 5.4 g, m-TB was added in an amount of 6.56 g, and the mass ratio of BIA to m-TB was 0.8: 1.
Performance testing
The invention tests the performance of the flexible copper clad laminate of the embodiment and the comparative example and records the detection result as shown in the table 1.
The test method of the characteristics is as follows:
peel Strength (PS): testing the peel strength of the metal layer at 90 degrees according to the IPC-TM-6502.4.9 method;
coefficient of Thermal Expansion (CTE): etching the copper foil of the flexible copper clad laminate to obtain a sample, and heating the sample to 350 ℃ in a Thermal Mechanical Analyzer (TMA) at the speed of 5 ℃/min in the TMA to obtain the thermal expansion coefficient between 100 ℃ and 250 ℃;
folding condition of the single-sided flexible copper clad laminate after coating and baking: the folding was visually observed and the height of the warp caused by folding was measured with a ruler.
TABLE 1
| Peel strength (N/mm) | CTE(ppm/℃) | Height of warpage (cm) | |
| Example 1 | 1.16 | 3.2 | 5.2 |
| Example 2 | 1.25 | 4.0 | 4.8 |
| Example 3 | 1.27 | 6.8 | 4.3 |
| Example 4 | 1.38 | 7.4 | 3.2 |
| Example 5 | 1.38 | 10.3 | 3.2 |
| Example 6 | 1.51 | 12.6 | 1.8 |
| Example 7 | 1.29 | 6.6 | 3.4 |
| Example 8 | 1.32 | 7.8 | 3.6 |
| Comparative example 1 | 1.13 | 2.7 | Is in the shape of a cylinder |
| Comparative example 2 | 0.87 | 17.5 | 4.6 |
| Comparative example 3 | 0.97 | 18.0 | 1.8 |
| Comparative example 4 | 1.14 | 2.8 | 7.9 |
| Comparative example 5 | 1.02 | 15.8 | 3.8 |
As can be seen from Table 1, the polyimide precursor provided by the invention can be used for preparing a glue-free flexible copper clad laminate with low CTE of polyimide, and the obtained flexible copper clad laminate has good peel strength, and can not be folded in the coating process, wherein the CTE of the polyimide is 3.2-12.6 ppm/DEG C, the warp height after coating and baking is 1.8-5.2 cm, and the peel strength of the copper clad laminate is 1.16-1.51N/mm.
Comparative example 1 coating and folding into a cylinder under the condition of using BIA alone, and the peel strength of the copper-clad plate is lower; comparative example 3, in which m-TB was used alone, the CTE of polyimide was too large and the application value was low.
In the case of comparative example 2 in which BIA and m-TB were not used, the CTE was large.
It can be seen from the comparison of examples 1 to 6 and 4 to 5 that the coating warpage is reduced with the increase of the amount of m-TB (diamine monomer A) and the decrease of the amount of BIA, but the CTE is gradually increased, and the three properties are balanced only when the ratio of the two is adjusted to (1 to 4):1 (examples 1 to 6), and particularly when the ratio is (1.5 to 3):1 (examples 2 to 4), the three properties of the CTE, the coating warpage and the peel strength of the flexible copper clad laminate can be further balanced.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A polyimide precursor is characterized in that the preparation raw materials of the polyimide precursor comprise diamine monomers and dianhydride monomers;
the diamine monomer comprises 2- (diamino phenyl) benzimidazole-5 amine and a diamine monomer A;
the R is1～R8Each independently selected from-H, -F, -CH3or-CF3Provided that R is1～R4Therein is at least provided withOne is selected from-CH3or-CF3And R is5～R8At least one of them is selected from-CH3or-CF3；
The mass ratio of the 2- (diamino phenyl) benzimidazole-5 amine to the diamine monomer A is (1-4) to 1.
2. The polyimide precursor according to claim 1, wherein the mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the diamine monomer A is (1.5-3): 1;
preferably, the sum of the mass of the 2- (diaminophenyl) benzimidazole-5 amine and the mass of the diamine monomer A accounts for 30-95% of the total mass of the diamine monomer.
3. The polyimide precursor according to claim 1 or 2, wherein the diamine monomer a comprises any one or a combination of at least two of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyldiamine, 4' -diamino-3, 3' -dimethyl-5, 5' -fluoro-1, 1' -biphenyldiamine, or 4,4' -diamino-2, 2' -dimethyl-6, 6' -trifluoromethyl-1, 1' -biphenyldiamine;
preferably, the diamine monomer further comprises 4,4' -diaminodiphenyl ether and/or p-phenylenediamine;
preferably, the dianhydride monomer comprises any one or at least two of biphenyl dianhydride, pyromellitic dianhydride or 4,4' -diphenyl ether dianhydride in combination.
4. A polyimide precursor glue solution, which is characterized by comprising the polyimide precursor and a solvent according to any one of claims 1 to 3.
5. The polyimide precursor glue solution according to claim 4, wherein the solvent comprises N-methyl pyrrolidone and/or N, N' -dimethyl acetamide;
preferably, the viscosity of the polyimide precursor glue solution is 15000-25000 cp.
6. A preparation method of the polyimide precursor glue solution according to the claim 4 or 5, characterized by comprising the following steps: mixing a dianhydride monomer, a diamine monomer and a solvent, and carrying out polycondensation reaction to obtain a polyimide precursor glue solution;
preferably, the preparation method of the polyimide precursor glue solution specifically comprises the following steps: dissolving a diamine monomer in a solvent, cooling, adding a dianhydride monomer in a nitrogen atmosphere, and stirring to obtain a polyimide precursor glue solution;
preferably, the cooling temperature is 8-12 ℃;
preferably, the stirring time is 6-10 h.
7. A polyimide is characterized in that the polyimide is obtained by imidizing a polyimide precursor as defined in any one of claims 1 to 3 or a polyimide precursor glue solution as defined in claim 4 or 5;
preferably, the thermal expansion coefficient of the polyimide is 2-10 ppm/DEG C;
preferably, the glass transition temperature of the polyimide is 320-400 ℃.
8. A flexible copper clad laminate, characterized in that, the flexible copper clad laminate comprises a copper foil and an insulating layer, wherein the insulating layer contains the polyimide of claim 7;
preferably, the thickness of the insulating layer is 3-37 μm;
preferably, the thickness of the copper foil is 9-70 μm.
9. The preparation method of the flexible copper clad laminate according to claim 8, wherein the preparation method comprises the following steps: coating the polyimide precursor glue solution of claim 4 or 5 on a copper foil, and imidizing to obtain a flexible copper clad laminate;
preferably, the method of imidization comprises baking;
preferably, the baking comprises a first baking and a second baking;
preferably, the time for the first baking is 2-5 min;
preferably, the temperature of the first baking is 150-180 ℃;
preferably, the time for the second baking is 20-40 min;
preferably, the temperature of the second baking is 350-400 ℃;
preferably, the second baking is carried out under the protection of nitrogen;
preferably, the preparation method comprises:
coating the polyimide precursor glue solution of claim 4 or 5 on a copper foil, baking for 2-5 min at the temperature of 150-180 ℃, and then baking for 20-40 min at the temperature of 350-400 ℃ under the protection of nitrogen to obtain the flexible copper clad laminate.
10. A printed circuit board comprising the flexible copper clad laminate of claim 8.
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| CN115010923A (en) * | 2022-06-10 | 2022-09-06 | 大同共聚(西安)科技有限公司 | Preparation method of polyamide acid, polyimide and flexible copper clad laminate for 5G |
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